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Quality Assurance Project Plan
for
Field Sampling Plan for Ambient Air Ethylene Oxide Monitoring
Near Sterigenics Facility, Willowbrook, EL
U.S. Environmental Protection Agency
Office of Air and Radiation
Office of Air Quality Planning and Standards
and
EPA Region 5
EPA QA Category 1
Prepared by
E PA/O AQ PS/AQ A D

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APPROVALS
I CVA/I C \A/CIMCTnPI/ Digitally signed by LEWIS WEINSTOCK
LtVVlO vVtllMO I UL/I\ Date: 2qj|^1.17 10:06:06 -05W
Lewis Weinstock, EPA OAQPS Project Manager
Vj Ohon	Digitally signed by Xi Chen
Al 
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Table of Contents
Section Page
1. PROJECT MANAGEMENT	7
1.1.	Distribution List	7
1.2.	Project Task/Organization	8
1.3.	Problem Definition/Background	10
1.4.	Project/Task Description and Schedule	11
1.5.	Data Quality Objectives and Criteria for Measurement Data	13
1.5.1.	The DQO Process	13
1.5.2.	State the Problem	14
1.5.3.	Identify the Decision	14
1.5.4.	Identify the Inputs to the Decision	15
1.5.5.	Define the Study Boundaries	16
1.5.6.	Develop a Decision Rule	16
1.5.7.	Specify Tolerable Limits on the Decision Errors	16
1.5.8.	Optimize the Design for Obtaining Data	17
1.5.9.	DQOs for this Study	17
1.6.	Measurement Quality Objectives and Performance Criteria/Acceptance Criteria	18
1.7.	Special Training Requirements/Certification	22
1.8.	Documents and Records	22
1.9.	QA Project Plan Distribution	24
1.10.	Field Documentation and Records	24
1.11.	Laboratory Documentation and Records	24

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1.12. Final Reports	25
2. DATA GENERATION AND ACQUISITION	25
2.1.	Sampling Design	25
2.1.1.	Site Selection	25
2.1.2.	Monitor Siting guidelines	32
2.2.	Sampling Methods	32
2.3.	Sample Handling and Custody	33
2.4.	Analytical Methods	36
2.5.	Field Measurements Methods	36
2.6.	Field Analyses Methods	37
2.7.	Laboratory Analyses Methods (ERG)	37
2.8.	Quality Control Requirements	38
2.9.	Field Sampling Quality Control	38
2.10.	Field Measurement/Analysis Quality Control	38
2.10.1. Field Measurement QC	38
2.11.	Laboratory Analysis Quality Control	39
2.12.	Instrument/Equipment Testing, Inspection, and Maintenance	39
2.13.	Field Measurement Instruments/Equipment	39
2.14.	Laboratory Analysis Instruments/Equipment (ERG)	41
2.15.	Instrument/Equipment Calibration and Frequency	42
2.15.1.	Field Measurement Instruments/Equipment	42
2.15.2.	Laboratory Analysis Instruments/Equipment (ERG)	42
2.16.	Inspection/Acceptance Requirements for Supplies and Consumables	42

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2.16.1.	Field Sampling Supplies and Consumables	42
2.16.2.	Laboratory Analyses Supplies and Consumables	43
2.17.	Data Acquisition Requirements (Non-Direct Measurements)	43
2.18.	Data Management	43
3.	ASSESSMENTS AND OVERSIGHT	45
3.1.	Assessments/Oversight and Response Actions	45
3.1.1.	Field and Laboratory Technical Systems Audits	45
3.1.2.	Data Quality Assessments	48
3.2.	Reports to Management	48
4.	DATA REVIEW AND USABILITY	49
4.1.	Data Review, Verification, and Validation Requirements	49
4.2.	Verification and Validation Methods	50
4.3.	Reconciliation with User Requirements	50
5.	REFERENCES	51
6.	APPENDICES	52

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TABLES	Page
Table 1-1. Quality Control Requirements for Analyses	20
Table 1-2. Project Documents and Records	23
Table 2-1. Sampling Location Details and Rationale	26
Table 2-2. Modeled stack emissions and parameters	28
FIGURES	Page
Figure 1-1. Organization Chart	9
Figure 2-1. Site Map with Sampling Locations	27
Figure 2-2. Model Domain	29
Figure 2-3. 2013-2017 seasonal wind roses for Midway	30
Figure 2-4. Monitor locations and Scoring Results	3 1
Figure 2-5. ERG's Sample Chain of Custody Form	35
Figure 2-6. ERG's Sample Tracking Tag	36
Figure 2-7. Canister setup with Passive Vacuum Regulator	40
Figure 2-8. Canisters with tripod stand setup at Willowbrook Village Hall site	41
Figure 2-9. Data management and sample flow diagram	44
Figure 3-1. ERG's corrective action report form	47

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1. PROJECT MANAGEMENT
1.1. Distribution List
Name: Lewis Weinstock
Title: OAQPS Project Manager
Organization: EPA OAQPS
Email: Weinstock.Lewis@epa.gov
Phone:919-541-3661
Name: Xi Chen
Title: OAQPS Monitoring Lead
Organization: EPA OAQPS
Email: Cheii.Xi@epa.gov
Phone:919-541-4957
Name: Jenia McBrian
Title: OAQPS QA Manager
Organization: EPA OAQPS
Email: McBrian.Jenia@epa.gov
Phone:919-541-0371
Name: Greg Noah
Title: OAQPS QA Field Coordinator
Organization: EPA OAQPS
Email: Noah.Greg@epa.gov
Phone:919-541-2771
Name: Michael Compher
Title: Region 5 Project Manager
Organization: EPA Region 5
Email: C ompher.Michael@epa.gov
Phone:312-886-5745
Name: Jacqueline Nvvia
Title: Region 5 Monitoring Lead
Organization: EPA Region 5
Email: Nvvia. Jacqueline@epa.gov
Phone:312-886-6081
Name: James Thurman
Title: OAQPS Dispersion Modeler
Organization: EPA OAQPS
Email: Thurman. James@epa.gov
Name: Julie Swift
Title: National Contract Laboratory Lead
Organization: Eastern Research Group
Email: Julie.Swift@erg.com
Phone:919-541-2703
Phone:919-468-7924

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1.2. Project Task/Organization
This project is managed and implemented by the Office of Air Quality Planning and Standards
(OAQPS) Ambient Air Monitoring Group (AAMG) of the EPA Office of Air and Radiation (OAR).
EPA Region 5 will conduct the sampling described in this QAPP, and sample analysis will be conducted
by Eastern Research Group (ERG).
OAQPS Project Manager: Lewis Weinstock will have overall responsibility for the tasks included in
this plan. These tasks include preparation of the Quality Assurance Project Plan (QAPP), serving as the
point of contact with other members of the O AQPS team handling issues such as field sampling,
laboratory analysis, stack testing and fugitives analysis at and around the source, coordination with the
analytical laboratory (through the OAQPS monitoring lead), and coordination with public affairs staff.
He will also track the project schedule and budget ensuring that activities remain on track and within
budget. He will work closely with the Regional Project Lead to address and resolve any issues that occur
with field sampling and/or other on the ground coordination activities.
OAQPS Monitoring Lead: Xi Chen will be the responsible for overseeing the overall project execution,
as well as tasking contractors with work required to complete this project. She will communicate
project needs to the contractors and coordinate laboratory services. She is responsible for the field
monitoring sampling plan; coordinating sample collection and analysis; field sampling logistics; and be
the point of contact to address any laboratory issues or concerns.
OAQPS OA Manager: Jenia McBrian will be responsible for reviewing and approving the QA Project
Plan, performing audits of data quality ( ADQ) and organizing required field and laboratory assessments.
She may provide technical QA input on the proposed sampling design, analytical methodologies, and
data review.
OAQPS Field QA Coordinator: Greg Noah will be responsible for performing the field TSA. The audit
will consist of a thorough review of the field personnel implementing the standard operating procedures
for this activity including: sample canister receipt and installation; sampler and site maintenance, quality
control checks, log book and data entry (forms); sample chain of custody and sample shipment.
Region 5 Project Manager: Michael Compher will be responsible for assigning field sample operators
their specific tasks and objectives.

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Region 5 Monitoring Lead: Jacqueline Nwia will be responsible for communicating with the Regional
Project Manager and field personnel. She will have overall responsibility for all field activities.
Contract Laboratory Lead: Julie Swift from the national contract laboratory Eastern Research Group
(ERG), will be responsible for assigning appropriate laboratory staff to perform sample preparation and
analyses specified in this plan and data reporting. She will also communicate technical issues; assist in
the resolution of technical problems; review data completeness and data quality; and review all reports.
Contract Laboratory QA Manager: Donna Tedder from ERG will be responsible for ensuring quality of
data generated in the contract laboratory. She will make QA recommendations; perform any internal
laboratory audits; evaluate the effect of technical issues on data quality; and review 10% of all data
reported.
ERG Laboratory Lead
Julie Swift
Region 5 Monitoring
Lead
Jacqueline Nwia
OAQPS QA
Coordinator
Greg Noah
ERG QA Coordinator
Donna Tedder
OAQPS Monitoring Lead
Xi (Doris) Chen
OAQPS Project
Manager
Michael Compher
OAQPS QA Manager
Jenia McBrian
OAQPS Project Manager
Lewis Weinstock
Figure 1-1. Organization Chart

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1.3. Problem Definition/Background
In December 2016, EPA's Integrated Risk Information System (IRIS)' program released an
updated assessment of the carcinogenicity of inhaled ethylene oxide (1). It concluded that ethylene oxide
is "carcinogenic to humans" by the inhalation route of exposure. The updated cancer potency
information (unit risk estimate (URE)) of ethylene oxide makes it about 60 times more potent, and more
likely to induce cancer in humans than previously thought.
Updated approximately every three years, EPA recently (August 2018) completed the National
Air Toxics Assessment2 (NATA), using the 2014 national emission inventory (NEI) \ which provides
estimates of the risk of cancer and other serious health effects from inhaling air contaminated with toxics
from large and small industrial sources, from on- and off-road mobile sources, and from natural sources
such as fires. NATA presents estimated risks at the census tract level. With the updated 2016 IRIS URE
for ethylene oxide, NATA identifies 18 areas of the country that may have elevated long-term (chronic)
cancer risks due to ethylene oxide emissions from stationary industrial sources. We define "elevated
risk" as a risk equal to or greater than 100-in-l million at a census tract. This means that for every
million people who breathe elevated levels of ethylene oxide for 70 years, 100 people may get cancer
because of that exposure. For ethylene oxide, the 2016 IRIS estimated 100-in-l million risk level
concentration is 0.01 lppb (0.02 |ig/m3).
The main use of ethylene oxide includes manufacture of ethylene glycol (antifreeze), solvents,
detergents, adhesives and other products. Also, ethylene oxide is used as a fumigant and a sterilant for
surgical equipment and plastic devices that can't be sterilized by steam (1). Chemical plants and
sterilization facilities that use ethylene oxide may present health concerns due to uncontrolled emissions
or venting to the atmosphere. Among the facilities identified as major source of ethylene oxide
emissions, Sterigenics LLC in Willowbrook, IL had a reported emission rate of -3 tons/year according
to 2014 NEI. NATA census tract chronic risks for the Willowbrook, IL area range from 100-to 300-in-l
2	https://www.epa.gOv/national-air-toxics-assessnient/2014-national-air-tox.w,, ^^jsment
3	https://www.epa.gov/air-emissiorre-iirrentories/2014-natiorial-emissioiis-iiiventorv-Pei-data

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million for 2014. In order to further assess and evaluate such elevated chronic cancer risk in the area,
ambient monitoring will help better understand and ethylene oxide emission rates as well as
concentration at breathable levels surrounding the identified facility. However, any monitoring
technology has its limitations, such as its analytical limitation for the current available method (EPA
Compendium Method TO-15(2)) that will be used for ethylene oxide. The estimated method detection
limit (MDL) established for ethylene oxide by the ERG contract laboratory is 0.045 ppbv (0.08 |ig/m3),
which translates to an around 400-in-l million cancer risk. ERG estimated MDLs using the Method
Update Rule (MUR)(3).
The established MDL will be met to evaluate the resulting data in a health-based context. The
MDLs are generally set at or below the concentrations of individual air toxics for which a lifetime,
continuous exposure would pose an excess lifetime cancer risk of one-in-one million or a hazard
quotient of 0.1. However, for ethylene oxide the laboratory analytical methodology is insufficient to
achieve such an MDL. Because the level of the MDL substantially limits our interpretation with regard
toabout potential significance of health risk-related impacts at 100-in-l million, this will be recognized
in reporting and interpreting the results.
1.4. Project/Task Description and Schedule
The ambient air monitoring efforts are intended to characterize ambient concentrations of
ethylene oxide around the Sterigenics Willowbrook, IL facility to inform the following issues:
a.	Determine the maximum and longer-term concentration(s) in proximity to the facility;
b.	Explore the relationship of ambient concentrations to facility operations (vents/fugitive) and
ethylene oxide usage;
c.	Characterize concentrations in potentially affected nearby neighborhoods to the extent possible
based on method sensitivity.
This project will follow EPA Compendium Method TO-15, "Determination of Volatile Organic
Compounds (VOCs) in Air Collected in Specially Prepared Canisters and Analyzed by Gas
Chromatography/Mass Spectrometry (GC/MS) for both sampling and analysis methodology."
A total of eight fixed sampling locations will be selected based on the EPA's latest dispersion

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modeling of the two Sterigenics buildings, community input and representative seasonal wind data. The
locations will include:
a.	Two locations at the maximum ambient air receptors in close proximity to the facility;
b.	Three locations in residential neighborhoods potentially impacted by the perimeter of the
dispersion modeling field and/or located in the predominant downwind direction during the
monitoring period;
c.	Three locations in residential neighborhoods as selected by the communities (these locations are
outside the dispersion modeling field where impact is expected).
The Region 5 office will conduct ethylene oxide ambient air sampling on a l-in-3 schedule (once
every third day), based on the national sampling calendar (Appendix A).
Sampling will begin at sampling locations 1 and 2 (see table 2-1 and Figure 2-1) on Tuesday, November
13, 2018. The remaining six sites will be deployed on Monday November 19, 2018. The only
exceptions to the national sampling calendar are the following: November 22, 2018 deployment will be
moved to November 23, 2018; December 25, 2018 deployment will be moved to December 26, 2018;
and January 21, 2019 deployment will be moved to January 22, 2019.
Unless otherwise noted, each sampling event will begin approximately at 10:00 Local Standard
Time (LST) and end at 10:00 LST the next day for a 24 hr duration. However, considering the potential
logistical delays for collecting samples, a 24±1 hr duration is required. The base (i.e., minimum
duration) sampling period is 90 days. Given the l-in-3 day sampling schedule for a period of 90 days
and a 85% sampling completeness criteria,, the base sampling period is intended to result in no less than
26 valid samples. There may be cases in which EPA shall deem the 90-day sampling period insufficient
(e.g., invalidated sample(s), insufficiently representative data, etc.) and extend sampling for a sufficient
period to achieve the goal of 26 valid samples.
It will take approximately two three weeks for EPA to determine whether the last samples are
valid. Missed or invalidated samples will only be made up on the established site-specific l-in-3 day
schedule (i .e., extend the base 90 day sampling period to include the required number of makeup
samples to achieve a minimum of 26 valid samples).
Sampling will cease upon collection of the 30th regularly scheduled (i.e., 1 -in-3 day) sample.

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with the following exception: If EPA deems any of the samples invalid as a result of problems during
sample collection or laboratory analysis, sampling will be extended for as many samples as needed to
collect 26 valid samples.
1.5. Data Quality Objectives and Criteria for Measurement Data
The primary objective for this project is to collect information on ambient air concentrations of
ethylene oxide at a selected list of sites in and adjacent to Willowbrook, IL during a defined monitoring
period. This monitoring information will be used to:
1.	Help characterize fugitive emissions from the Sterigenics Willowbrook facility;
2.	Better understand potential concentrations in Willowbrook and surrounding communities,
considering the limitations of the TO-15 method for this chemical; and
3.	Assist us in identifying locations where additional information, including additional monitoring,
may be needed to better understand potential concentrations in Willowbrook and surrounding
communities, considering the limitations of the TO-15 method for this chemical.
To do this work, EPA OAQPS along with its Region 5 partners, will facilitate the collection of
ambient air data at the identified sites. The focus will be on assessing impacts associated with the nearby
Sterigenics facility and will provide information to residents that live nearby the sites about potential air
toxics concerns from the facility.
The DQO process described in EPA's QA/G-4 (https://www.epa.gov/sites/production/files/2015-
06/documents/g4-fmal.pdf) document provides a general framework for ensuring that the data collected
by EPA or any Environmental Data Operation (EDO) meets the needs of the intended decision makers
and data users. The process establishes the link between the specific end use(s) of the data with the data
collection process and the data quality (and quantity) needed to meet a program's goals. The following
sections provide the required information for the DQO process.
1.5.1. The DQO Process
This section presents an overview of the seven steps in EPA's QA/G-4 DQO process as applied
to the objectives of this project. The purpose of this section is to provide a general discussion of the
specific issues that were used in developing the DQOs for this project.

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The DQO process is a seven-step process based on the scientific method to ensure that the data
collected by EPA meet the needs of its data users and decision makers in terms of the information to be
collected and, in particular, the desired quality and quantity of data. It also provides a framework for
checking and evaluating the program goals to make sure they are feasible, and that the data are collected
efficiently. The seven steps are usually labeled as:
1.	State the Problem
2.	Identify the Decision
3.	Identify the Inputs to the Decision
4.	Define the Study Boundaries
5.	Develop a Decision Rule
6.	Specify Tolerable Limits on the Decision Errors
7.	Optimize the Design for Obtaining Data Each of these elements is discussed in detail below.
The pollutant specific outcomes of the DQO process are contained in Section 1.7.1.8.
1.5.2.	State the Problem
The EPA project team developed the following problem statement:
Information about the updated assessment of the carcinogenicity of inhaled ethylene
oxide from EPA's IRIS Program has raised questions about outdoor air quality around
some sites near the Sterigenics LLC facility in Willowbrook, IL. Measuring the levels of
ethylene oxide in the air around these sites will help EPA better understand potential
concentrations.
EPA will use what it learns from this monitoring initiative to determine its next steps.
1.5.3.	Identify the Decision
The decision statement should provide a link between the principal study question and possible
actions. The decision that the monitoring at these sites is intended to inform is as follows:
Data will be collected from selected sites based on EPA's latest dispersion modeling for the two
Sterigenics buildings, community input, and representative seasonal wind direction data (see Section

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2.1.1). Monitoring will be performed in such a way that the resulting data will be sufficient in terms of
quantity and quality to better inform our understanding of ethylene oxide concentrations in the ambient
air at these sites. These data along will be relied upon by EPA to:
1.	Help characterize fugitive emissions from the Sterigenics Willowbrook facility;
2.	Better understand potential concentrations in Willowbrook and surrounding communities,
considering the limitations of the TO-15 method for this chemical; and
3.	Assist us in identifying locations where additional information, including additional monitoring,
may be needed to better understand potential concentrations in Willowbrook and surrounding
communities, considering the limitations of the TO-15 method for this chemical.
1.5.4. Identify the Inputs to the Decision
This section discusses the variety of inputs that are needed to make the final DQO decision for
this program. In addition to the monitoring results, other inputs potentially important to decision-
making for this project include, but are not limited to, the following items (not listed in any priority
order):
1.	List of target sampling sites;
2.	Existing ambient air sampling methods and analytical techniques;
3.	NATA estimates;
4.	Source-specific emission inventory information;
5.	Existing ambient monitoring data;
6.	Nearby meteorological monitoring data from the EPA Region 5, the National Weather Service
and/or local airport weather data;
7.	Topographical information pertaining to factors influencing pollutant transport;
8.	Health effects information, including dose-response values and information available on the
OAQPS and ATSDR web sites;
9.	Community concerns;
10.	Historical monitoring, modeling, health assessments, and other information (e.g., compliance
status, voluntary emissions reduction programs, etc.) for the area; and,
1 1. Funding Information.

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1.5.5.	Define the Study Boundaries
The specific location of the monitors will be established to represent ambient air in the proximity
of the facility, as described in this QAPP. Siting criteria that are detailed in Code of Federal Regulations
(CFR) Chapter 40 Section 58, Appendix E2 will be followed to the extent that is practical, as described
in this Plan. Any deviations from the siting criteria will be identified and documented in the final report.
Some monitors will be located in Willowbrook, IL, and others will be located in the adjacent
communities of Burr Ridge, IL and Darien, IL
1.5.6.	Develop a Decision Rule
The decision rule is an "if ... then" statement for how the various alternatives will be chosen.
If the available monitoring data and other information are insufficient to support a
conclusion, then additional data collection may be pursued. If the available monitoring
data and other information are sufficient to reach a conclusion regarding the needfor
further action and do not support the conclusion that further action is needed, then
additional data collection will not be pursued.
1.5.7.	Specify Tolerable Limits on the Decision Errors
Budgetary constraints are a consideration in describing the DQOs. The program has a finite
budget that affects the amount of monitoring performed in this program. The initial monitoring will
include samples collected from eight sites on a l-in-3 day schedule over a three-month period. It was
decided that on-site measurements will include meteorological data such as wind direction and wind
speed to help inform our consideration of this issue. The monitoring data set will need to include
samples taken when the predominant wind direction is generally from the sources in question in order to
fully support the decision making process contemplated in this exercise.
In order to understand other aspects of the quality of the data (i.e., precision and bias) the
precision estimates of the analytical method were based on the estimates from EPA's contract laboratory
(ERG) and other method estimates and is expressed in terms of coefficient of variance (CV).

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The bias was chosen from the analytical method (EPA Compendium TO-15). Data from canister
batch and trip blanks will be used to monitor method bias, which has an acceptance criteria of <3x the
method MDL.
Data completeness will be set at >85% (a minimum of 26 valid samples collected over a 90 day
period). If, due to unforeseen events, 26 valid samples are not collected in 90 days, monitoring will
continue until 26 samples are collected. Thus, >85% completeness will be achieved.
The estimated method detection limits (MDLs) will be met to evaluate the resulting data in a
health-based context. We define "elevated risk" as a risk equal to or greater than 100-in-l million at a
census tract. This means that for every million people who breathe elevated levels of ethylene oxide for
70 years, 100 people may get cancer because of that exposure. Because the level of the MDL
substantially limits our interpretation about potential significance of health risk-related impacts, this will
be recognized in reporting and interpreting the results.
1.5.8.	Optimize the Design for Obtaining Data
The team decided sampling will follow a "one every three days" schedule. A program goal of
>85% data completeness is established for the initial monitoring 90 days) since this is a short-term
program and the number of samples initially collected will be small. However, if the wind does not
come from the direction of the sources of interest impacting the sites, then the need for additional
monitoring may be indicated to evaluate the significance of source contributions.
1.5.9.	DQOs for this Study
This section combines all the information gathered and states the action that will be followed
given the scenarios that can occur.
To better evaluate potential impacts of ethylene oxide in the vicinity of the Sterigenics facility in
Willowbrook, IL, monitoring will commence at selected locations. If the following criteria are met, the
data will be considered of sufficient quantity and quality for the decision-making to commence as
described in section 1.7.1.2:
1.	Data are collected with a coefficient of variance (precision) and bias as stated in Table 1-1;
2.	Data completeness is >85% or 26 samples within a window of 90 days;

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3.	MDLs are at or below those specified in Table 1-1 and;
4.	Where applicable, sufficient samples are collected when the predominant wind direction is from
the source in question.
1.6. Measurement Quality Objectives and Performance Criteria/Acceptance Criteria
Once a DQO is established, the quality of the data must be evaluated and controlled to ensure
that it is maintained within the established acceptance criteria. Measurement Quality Objectives (MQOs)
are designed to evaluate and control various phases (i .e., sampling, preparation, and analysis) of the
measurement process to ensure that total measurement uncertainty is within the range prescribed by the
DQOs. The National Air Toxics Trends Station (NATTS) Technical Assistance Document (TAD) (4)
(see Appendix D) presents the requirements for collecting and reporting data for the NATTS network.
MQOs can be defined in terms of the following data quality indicators (DQls):
Precision - a measure of mutual agreement between individual measurements performed
according to identical protocols and procedures. This is the random component of error.
Analytical precision is calculated by comparing the differences between Replicate analyses (two
analyses of the same sample) from the arithmetic mean of the two results as shown below. Replicate
analyses with low variability have a lower Relative Percent Difference (RPD) (better precision), whereas
high variability samples have a higher RPD (poorer precision).
I*i -x21
RPD = - X 100
X
Where:
Xi = Ambient air concentration of a given compound measured in one sample;
X; = Concentration of the same compound measured during replicate analysis;
X= Arithmetic mean of Xi and X:.
Method precision is calculated by comparing the concentrations of the dupli cates/col 1 ocates for
each pollutant. The Coefficient of Variation (CV) calculation shown below is ideal when comparing
paired values, such as a primary concentration versus a duplicate concentration.

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cv =
rn
p — r
A'=i
0.5 x (p + r)
x 100
2 n
Where:
p = the primary result from a duplicate or collocated pair;
r = the secondary result from a duplicate or collocated pair;
n = the number of valid data pairs.
Bias - the systematic or persistent distortion of a measurement process that causes error in one
direction. Bias is determined by estimating the positive and negative deviation from the true value as a
percentage of the true value.
Sensitivity - the determination of the low range critical value of a characteristic that a method-
specific procedure can reliably discern (also referred to as detectability).
Completeness - a measure of the amount of valid data obtained from a measurement system
compared to the amount that was expected to be obtained under correct, normal conditions.
In theory, if these MQOs are met, measurement uncertainty should be controlled to the levels
required by the DQO. Table 1-1 lists the MQOs for ethylene oxide that will be measured for this
program. More detailed descriptions of these MQOs and how they will be used to control and assess
measurement uncertainty will be described in this QAPP. Data within these tables reflect the MQOs
needed to meet the DQOs for this program.
See Table 1-1. Quality Control Requirements for Analyses and Acceptance criteria/measurement
performance criteria for each DQ1.

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Table 1-1. Quality Control Requirements for EPA Compendium Method TO-15
QC Sample:
DQI
Frequency
Acceptance Criteria
Corrective Action
CV (collocated
sample)
Precision
1/sample event
<25%
Flag the data
RPD (replicate
samples)
Precision
1/sample event
<25%
Flag the data
Valid sample
numbers
Completeness
N/A
No less than 26 >85%
Collect make up samples
Canister batch
blank
Bias
2 batches */week
<3xMDL
Canisters put through an
additional vacuum and
pressure cleaning cycle
Canister trip blank
Bias
2/month
<3xMDL
Flag the data
MDL
Sensitivity
1/method
modification
<0.045 ppb or 0.082 ng/m5
Identify sources of
problem, eg. thoroughly
clean the system
BFB instrument
tunc performance
check
Lab QC
Daily1', prior to
sample analysis
Evaluation criteria presented in
Table 11-3 of ERG QAPP
1)	Retime
2)	Clean ion source
and/or quadrupole
Initial calibration
(ICAL) consisting
of at least 5 points
bracketing the
expected sample
concentration
Lab QC
Following any
major change,
repair or
maintenance or if
daily QC is not
acceptable.
Recalibration not
to exceed three
months.
1)	RSD of response factor <± 30%,
with two exceptions of up to ± 40%
for non-tier 1 componds only
2)	Internal Standard (IS) response
±40% of mean curve IS response
3)	Relative Retention Times (RRTs)
for target peaks ±0.06 units from
mean RRT
4)	IS RTs within 20 seconds of
mean
5)	Each calibration standard
concentration must be within + 30%
of nominal (for Tier I compounds)
1)	Repeat individual
sample analysis
2)	Repeat linearity check
3)	Prepare new
calibration standards and
repeat analysis
LCS ({ICV}
Initial/Second
source calibration
verification
check)
Lab QC
Following the
Calibration curve
The response factor < ±30%
Deviation from calibration curve
average response factor
1)	Repeat calibration
check
2)	Repeat calibration
curve
Continuing
Calibration
Verification
(CCV) of
approximately
Lab QC
Before sample
analysis on the
days of sample
analysis b
The response factor < ±30%
deviation from calibration curve
average response factor
1)	Repeat calibration
check
2)	Repeat calibration

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QC Sample:
DQI
F requency
Acceptance Criteria
Corrective Action
mid-point of the
calibration curve'1
using a certified
standard



curve
Method Blank
(MB) analysis
(zero air or N2
sample check)
Lab QC
Daily'', following
BFB and
calibration
check; prior to
sample analysis
1)	<3x MDL or 0.2 ppbv whichever
is lower
2)	IS area response ± 40% and IS
RT ± 0.33 mill, of most recent
ICAL
1)	Repeat analysis with
new blank canister
2)	Check system for
leaks, contamination
3)	Reanalyze blank
Canister cleaning
certification
Lab QC
One canister
analyzed on the
air toxics system
per batch of 8
< 3x MDL or 0.2 ppbv whichever is
lower
Reclean canisters and
reanalyze
Preconcentrator
leak check
Lab QC
Each standard
and sample
canister
connected to the
preconcentrator/
autosampler
< 0.2 psi change/minute
1)	Rctighten and re-
perform leak check
2)	Provide maintenance
3)	Re-perform leak
check test
Sampler
certification
standard
challenge with a
reference can and
a zero check with
a reference can
Lab QC
Annual
Challenge: Within 15% of the
concentration in the reference
canister.
Zero: up to 0.2 ppbV or 3x MDL
(whichever is
lower) higher than the reference can
1)	Repeat certification of
samplers, a requirement
for Tier 1 compounds
2)	Notify Program
Manager (flagging non-
Tier 1 compound data for
sampler may be an
option)
Sampling period
Field QC
All samples
24 hours ±1 hours
1)	Notify Program
Manager
2)	Flag samples with a
"Y" Hag
3)	Invalidate and
rc sample for > 24±1
hours
Retention Time
(RT)
Lab QC
All qualitatively
identified
compounds
RT within ± 0.06 RRT units of most
recent initial calibration average RT
Repeat analysis
Samples -
Internal Standards
Lab QC
All samples
IS area response within± 40% and
IS RT within ± 0.33 mi 11. of most
recent calibration
Repeat analysis
*The maximum capacity of one batch of samples to be cleaned is 12.
a The same QA criteria arc needed for SNMOC and PAMS analysis.
b Every 24 hours frequency.

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1.7.	Special Training Requirements/Certification
Field support staff from U.S. EPA Region 5 are trained and experienced on collecting the
samples, chain of custody procedures as well as process for shipping the canisters to Eastern Research
Group (ERG). No additional training is required as Region 5 field staff abide by Section 5.0 Personnel
Qual i fi cati on s/Respon si bi 1 ities of the Region 5 Standard Operating Procedure for the Collection of V OC
Samples (R5-ARD-0003-r2). ERG's "Sampling Procedures for Passive Vacuum Regulators" (see
Appendix B) will be followed to collect samples. The procedure is designed for sampling volatile
organic compounds (VOCs) in ambient air, based on the collection of whole air samples in SUM MA®
treated canisters to final pressures below atmospheric.
Experienced and trained EPA contractors will perform all necessary sample preparation and
sample analysis procedures. Each scientist participating in this project has demonstrated proficiency
with the specific analytical procedures tasked, and the EPA contracted laboratory is to maintain records
of all training and documented analyst proficiency (see Appendix C for ERG's QAPP).
1.8.	Documents and Records
Documents and records generated for this project include the QA project plan, field and
laboratory records, email correspondence, assessment reports, as well as a project final report. Table 1 -2
represents the documents and records, at a minimum, that must be filed. These documents, including
draft and intermediate versions of significant importance to the project records will be stored and
maintained consistent with EPA records management policies. In general, all the information listed in
Table 1-2 will be retained for 5 years. However, if any litigation, claim, negotiation, audit or other action
involving the records has been started before the expiration of the 5-year period, the records will be
retained until completion of the action.

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Table 1-2. Project Documents and Records
Categories
Record/Document Types
Responsible Party
Site Information
•	Network description
•	Site characterization file
•	Site maps
•	Site Pictures
EPA Region 5
Field Operations Information
•	QA Project Plan
•	Standard operating
procedures (SOPs)
•	Field and laboratory
notebooks
•	Sample handling/custody
records
•	Inspection/Maintenance
records
EPA OAQPS.
Laboratory Contractor
(ERG). EPA Region 5
Laboratory Data and Operations
Information
•	Any original data (routine
and QC data) including
data entry forms
•	Electronic deliverables of
summary analytical and
associated QC and
calibration runs per
instrument
•	Control charts
•	Chromatograms and
spreadsheets with raw
unadjusted data
•	SOPs
Laboratory Contractor
(ERG)
Quality Assurance Information
•	Network siting and
reviews
•	Data quality assessments
•	QA reports
•	Technical System Audits
•	Response/Corrective
action reports
•	QA Final Report
EPA OAQPS.
Laboratory Contractor
(ERG). EPA Region 5
Other Information
•	Final Report
•	Email correspondence
EPA OAQPS,
Region 5, ERG
Laboratory
Contractor (ERG)

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1.9.	OA Project Plan Distribution
The project manager will be responsible for ensuring that the QAPP and any revisions will be
circulated to appropriate project participants. The final approved QAPP will uploaded to the U.S.
EPA's website created for this project (https://vvvvvv.epa.gov/il/sterigenics-vvillovvbrook-facility).
1.10.	Field Documentation and Records
Each canister sample collected will be assigned a unique sample number with a sample tag. A
chain-of-custody (COC) form will be provided for each sample. The date and time sample collection
started and ended, initial and final pressure gauge readings, and site locations will be documented and
recorded on the COC form. COC forms will be scanned and saved as records on ERG's Laboratory
Information Management System (LIMS).
Field staff will maintain log books to document sampling activities and any unusual events that
may impact results. Log books will be review during technical systems audits and filed with the
OAQPS Monitoring Lead at the end of the project.
All field SOPs used in this program are included in the Appendix and will be filed with the
OAQPS Monitoring Lead
1.11.	Laboratory Documentation and Records
The laboratory contractor, ERG, has a structured records management system that allows for the
efficient archive and retrieval of records. Each laboratory archives the data from computer systems
onto a shared network drive. The paper copies of all analyses are stored on site in a secured
temperature-control 1 ed area for up to five years. All raw data required for the calculation of
concentrations and QA/QC data are collected electronically or on paper data forms. Raw data collected
will be stored in LIMS, which is equipped with an automatic digital tape backup system. Backup of the
LIMS is performed daily, weekly, and biannually. Refer to ERG's QAPP, "SUPPORT FOR THE EPA
NATIONAL MONITORING PROGRAMS," (ERG-QAPP-0344-4) section 6 in Appendix C).
All laboratory SOPs used in this program will be filed with the OAQPS Monitoring Lead. Some
of these procedures have been deemed as Confidential Business Information (CBI) but are available to
EPA personnel.

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1.12. Final Reports
The project managers and contract laboratory will compile the final report to summarize the
details of the sampling performed, the concentration results, as well as any data analysis conducted.
The report will contain the following information:
a.	Names of participating sites and corresponding metadata information;
b.	Description of the sampling and analytical methodologies used by the laboratory;
c.	Completeness of the monitoring effort for each site;
d.	Background information on the methodology used to present and analyze the data;
e.	General combined and individual site summary of the results;
f.	Variability analysis (intra-site comparisons);
g.	Pollution roses to determine predominant direction;
h.	Discussion of precision and accuracy and other QC information; and
i.	Discussions of conclusions and recommendations.
2. DATA GENERATION AND ACQUISITION
2.1. Sampling Design
2.1.1. Site Selection
A total of eight fixed sampling locations were selected based on the EPA's latest dispersion
modeling (see below for details)4 for the two Sterigenics buildings, community input, and representative
seasonal wind direction data5. However, if the wind does not come from the direction of the sources of
interest impacting the sites, then the need for additional monitoring and changes to site locations may be
indicated to evaluate the significance of source contributions. The initial sampling locations will include:
a. Two locations at the maximum ambient air receptors in close proximity to the facility;
4	Conducted by EPA/OAQPS. utilizing results from Sept 2018 source test
5	Locations based on November - April wind rose data from Midway airport

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b.	Three locations in residential neighborhoods potentially impacted by the perimeter of the
dispersion modeling field and/or located in the predominant downwind direction during the
monitoring period; and
c.	Three locations in residential neighborhoods as selected by the communities (these locations are
outside the dispersion modeling field where impact is expected).
Table 2-1 provides the list of sampling locations with latitude/longitude and rationale for site selection.
Table 2-1. Sampling Location Details and Rationale
#
Sampling Location
Latitude
Longitude
Rationale for Sampling Design
1
Willowbrook Village Hall
41.748589
-87.941090
Maximum Commercial #1
2
EPA Willowbrook Warehouse
41.747438
-87.938739
Maximum Commercial #2
3
Gower Middle School
41.743462
-87.933924
Residential 1 mpact
4
West Neighborhood
41.748763
-87.94556
Residential Impact
5
Water Tower
41.755363
-87.939163
Residential 1 mpact
6
Willow Pond Park
41.763981
-87.939845
Residential-community request
7
Hinsdale South High School
41.753685
-87.948497
Residential-community request
8
Gower Elementary School
41.748835
-87.956179
Community request
9a
Eisenhower Junior High
School
41.753003
-87.978947
Community request
a Sampling tripods have been installed at all 9 locations listed but, at least initially, monitoring wil
at the first 8 sites.
occur
Figure 2-1 provides a map with the sampling locations.

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Willowbrook EtO Ambient Sampling Sites
*to'v "'"v'vfT
— v^i, a
«
[GMea
Figure 2-1. Site Map with Sampling Locations
Air dispersion modeling of Sterigenics was conducted using the latest version of EPA's
atmospheric dispersion model, the AERMOD modeling system (version 18081), to inform monitor
placement. Information about AERMOD formulation and performance evaluation can be found in the
AERMOD Model Formulation and Evaluation document (EPA-454/R-18-003). Emissions input to the
model were based on stack test results from September 2018 and emissions were modeled with the most
recent 5 years of complete meteorological data, 2013 through 2017, using Midway International Airport
for the surface meteorological data6 and Davenport, IA for upper air data 7. Midway is located
approximately 15 km east of Sterigenics and judged adequately representative of the facility based on
guidance in Section 8.4.1 the Guideline on Air Quality Modeling. Davenport was also judged to be
representative of upper air conditions over Sterigenics. Standard hourly wind observations from Midway
were supplemented with hourly average winds calculated from 1-minute winds using the AERMINUTE
6	Integrated Surface Hourly Data (ISHD) downloaded from ftp.ncdc.noaa.gov
7	Downloaded from https://ruc.noaa.gov/raobs/

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processor (version 15272. Stack locations and parameters, building parameters for downwash, and the
2-km by 2-km receptor grid (758 receptors) with elevations were supplied by Sterigenics and no issues
were found with the source characterizations (as vertical or horizontal stacks), stack parameters and
locations. Stack parameters were modified based on the September stack tests. See Table 2-2 for stack
emissions and parameters. The receptor domain is below with the Sterigenics facility denoted by the
green squares.
Table 2-2. Modeled stack emissions and parameters
AERMOD
Source type
Emissions
Stack
Stack
Exit
Stack
ID

(g/s)
height
temperature
velocity
diameter



(m)
(K)
(m/s)
(m)
STK1
POINT
3.88E-04
8.5344
308.15
18.00707
0.1524
STK2
POINT
5.95E-04
9.7536
314.8167
18.35958
0.6096
STK4
POINT
3.68E-03
10.255
301.4833
10.18919
0.6858
STK5
POINT
1.23E-03
10.3124
301.4833
1.458640
1.3716
STK6
POINT
1.23E-03
9.5504
300.9278
1.533169
1.3716
A
POINT
2.20E-03
9.7536
312.0389
12.67323
0.70104
P
POINT
6.03E-04
10.2362
300.9278
5.409891
0.955528
0
POINT
1.21E-03
10.2362
300.9278
10.96896
0.955528
T2
POINTHOR
6.03E-04
0.9779
297.5944
4.847607
1.318398
T3
POINTHOR
6.03E-04
0.9779
297.5944
11.22017
1.318398

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. •. , -
44
m

b¦ pTyniSrffiPl ... r' :i T ;
Figure 2-2. Model Domain
Key metrics output from the model or calculated from model output to inform monitor placement
were:
a.	Maximum 24-hour concentration by receptor across the period of 2013-2017;
b.	5-year seasonal averages by receptor;
c.	5-year average by receptor.
Maximum 24-hour concentrations were considered because the monitoring would take place at
24-hour intervals. Seasonal averages were considered because the wind roses by season, exhibited
seasonal differences (Figure 2-3), especially winter, and long-term averages were chosen to be

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consistent with the annual results of NAT A. AERMOD did not directly output seasonal averages.
Monthly concentrations were output from AERMOD and seasonal averages were calculated from the
monthly averages, consistent with AERMOD's internal averaging for long term averages, i.e. including
only hours that were not calm or missing in the model output.
Winter
Spring
m
WDSfffiD
(Kftetvi
17-21
I)-17
—-J 0
•#
VWJDSPffiD
iKfttfcl
CI 4.7
~ 0-4
Ca*ns 0 00%
L_i *-i
[Hi H-A
Ca*na frMV
Summer
Fall
# a
Sr
VWDSFSED
~	«Z*
¦	17-21
|H 11-17
¦	7-11
~	4-7
f I 0-4
Cairns; 000%
w
VVINDSFfflO
~
¦	17-21
¦	11-17
7-11
~	*-r
~	0-4
C Mm 0 00%
Figure 2-3. 2013-2017 seasonal wind roses for Midway.
To inform the monitor siting, a scoring system was developed by ranking metrics (the maximum
24-hour concentrations across all receptors, ranking each 5-year average season's concentration by
receptor, and ranking the 5-year average concentration by receptor), with a receptor receiving a rank of
=1 if it had the maximum concentration for the averaging time. This resulted in six rankings for each

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receptor (24-hour, winter, spring, summer, fall, and 5-year average). The score was calculated for each
receptor by adding together its rank for each averaging time (the 24-hour ranking, each season's rank,
and the 5-year average rank of each receptor). For example, a receptor that has the highest 24-hour
average concentration, the highest winter, spring, summer, and fall average concentrations, and highest
5-year average concentration would have a score of 6 (1+1+1+1+1+1). The lower the score, the higher
the probability an area will see higher concentrations from the facility for one or more of the averaging
periods, making it more conducive for a potential monitor location. The results of the scoring, along
with the monitor locations, excluding the upwind monitor, are shown below. The monitors' locations
coincide with local minima (higher concentrations) of the receptor scores.
core
0.7 Kilometers!
Figure 2-4. Monitor locations and Scoring Results

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2.1.2. Monitor Siting guidelines
The EPA OAQPS and Region 5 office will follow the monitor siting criteria detailed in the Code
of Federal Regulations (CFR) Chapter 40 Section 58, Appendix E, to the extent possible and/or
practical. Though we do not expect strict compliance with standard siting criteria for a monitoring
exercise of this scope and with these objectives, the monitoring agencies must consider monitor
placement guidelines such as the following:
a.	Locating the sampler in an area that has an unobstructed air flow, especially in the direction of
any recognized sources of target analytes.
b.	Avoiding locations that are directly influenced by nearly adjacent, biasing emission sources (e.g.,
direct vehicle emissions, boiler stacks, backup generators).
c.	Avoiding locations where reactive surfaces may cause chemical changes in the air sampled.
d.	Placing the intake probe(s) of samplers at a representative height between 2 and 7 meters above
ground level ( AGL).
e.	Recognizing personnel and apparatus security issues, and related accessibility concerns during
both weekdays and week end s/h ol i day s.
Given the fact that cigarette or tobacco smoke and vehicle exhaust are additional potential
sources of ethylene oxide besides industrial emissions, special attention and consideration will be made
to avoid sampling those biasing emission sources.
2.2. Sampling Methods
Measurement consistency is necessary to achieve the program objectives described above. The
ability to accurately detect pollutant concentrations and evaluate the resultant data to assess the degree to
which associated health risks may be present, requires a considerable level of standardization. This
project will follow EPA Compendium Method TO-15 Determination of Volatile Organic Compounds
(VOCs) in Air Collected in Specially Prepared Canisters and Analyzed by Gas Chromatography/Mass
Spectrometry (GC/MS) for both sampling and analysis methodology.
The sampling apparatus will consist of SUM MA* 6-liter canisters and critical orifice passive
sampling kits that are calibrated for 24-hour sampling without power requirement. The inlet height will

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be approximately 2 m above ground. After 24 hours of sampling, the canister will remain under vacuum
(negative pressure),and be shipped to the analytical laboratory (EPA's VOC National Contract
Laboratory ERG with an identification tag and a COC.
All canisters are cleaned prior to reuse following ERG's SOP ERG-MOR-105 (SOP for Sample
Canister Cleaning using Wasson TO-Clean Automated System). The canisters are cleaned to <3x MDL
or 0.2 parts per billion by volume (ppbV), whichever is lower. If the canister fails the Blank criteria, it is
returned to the cleaning system bank with the other canisters that were cleaned along with it and all
canisters are put through an additional Vacuum and Pressure cycle. The same canister is analyzed again.
All canisters are cleaned by the same procedure and are entered into the canister cleanup log.
A mass flow controller (MFC) and/or critical orifice regulates the flow of ambient air into an
evacuated passivated stainless steel canister at a known, constant rate over the course of 24 hours.
Following completion of collection, the canister is transported to the contract laboratory for analysis
within 30 days of collection. Previous studies suggest that most compounds analyzed via TO-15 are
stable for up to 30 days in passivated stainless steel canisters; however, the condition of the wetted
surfaces of each individual canister is likely to influence the stability of the VOCs. Analysis of the
sample as soon as possible after collection is strongly recommended to minimize changes of the
collected sample
A 5-(.im pore size silonite stainless steel particulate filter must be installed on the sampling unit
inlet for all VOC collection. Failure to install a particulate filter allows particulates such as dust and
pollen to adhere to the interior of the sampling unit (valves, MFC, etc.) and to be pulled into the
evacuated canister during sample collection. Once inside the canister, particulate matter can form active
sites, adsorb analytes, and/or provide reactants which may degrade and form target analytes or
interferants, potentially rendering the canister irreversibly contaminated. If the particulate filter is used
in areas with high levels of particulate, which may result in decreased flows or decreased collected
pressures, it must be replaced.
2.3. Sample Handling and Custody
A color-coded, three-copy canister sample COC form (example in Figure 2-4 is shipped to the
field with each 6-liter stainless steel canister. If duplicate or collocated samples are to be taken, two

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canisters and two COC forms are sent in the shipping container(s) to the site. When a sample is
collected, the site operator fills out the form. The site operator detaches the pink copy to be retained on-
site and sends the remaining copies with the canister in the shipping container to ERG's laboratory.
Upon receipt at the analysis laboratory, the sample canister is tagged for laboratory tracking
(example figure 2-5) vacuum/pressure is measured and compared against the field documented
vacuum/pressure to ensure the canister remained airtight during transport. If the receiving vacuum
differs from the field vacuum more than 3" Hg, the laboratory program manager is notified, and sample
canister may be voided. Because there are potential differences in barometric pressures and temperatures
between the sampling site and the receiving laboratory, and different accuracies for different types of
pressure gauges, there can be a consistent difference in final field pressure and lab receipt pressure for
canister samples. This difference and other parameters are considered to determine the validity of the
canister samples. These are monitored daily, and the pressures are logged into an Excel spreadsheet.
This allows the laboratory the ability to determine if the difference is due to gauges or if the canister
leaked during transport.
Canisters will be handled with care to ensure that weld integrity is maintained, that the interior
canister surface is not compromised, and that the valve-to-canister connection remains intact. Shocks to
the surface of the canister may damage welds or create small cracks in the interior canister surface
which may expose active sites. Excessive pressure on the canister valve may cause leaks in the seal
between the canister valve and canister stem. Shipment of canisters will occur in protective hard-shell
boxes and/or sturdy cardboard boxes to ensure canister longevity. Care will be taken to replace any
boxes which have lost integrity or rigidity.
More detailed sample receipt procedures and sample acceptance policies are presented in
the SOP for Sample Receipt at the ERG Chemistry Laboratory, ERG-MOR-045 and in Appendix
C.ERG's QAPP section 9.1.

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ERG Lab ID#
ECi Kqaamt Par* Q**, Stibc 7QG,	NC 27S6C
AIR TOXICS SAMPLE CHAIN OF CUSTODY
f
-I
Site Code:
CftyV State:
AQS Code:
Canister Mumber.
Collection Date: 	
Options:
SNMOC (Y/N):_
TOXICS (Y/N):_
METHANE (Y/N):
Relinquished by:
Lab initial Ca-n. Press. {"Hg}:
Cleaning Batch # : 	
Date Can. Cleaned:
Duplicate Event (Y/N):
Duplicate Ca
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Analysis: _
Sarrple ID
Laboratory ID
~ate Sarrpled:
Canister#		
Ste: 	
Cfcrrrrent: 	
PressVac
Dup'Rep:
O
Figure 2-6. ERG's Sample Tracking Tag
2.4.	Analytical Methods
The primary objective for this project is to collect information on ambient air concentrations of
ethylene oxide at a selected list of sites in, and adjacent to, Willowbrook, IL during a defined monitoring
period, as described in Section 1.5. To this end, ambient air samples will be characterized using
analytical techniques following EPA Compendium Method TO-15
(https://www.epa.gov/sites/production/files/2015-07/documents/epa-to-15 O.pdf).
The subsections below describe both the field and laboratory methods that will be followed to
achieve project objectives.
2.5.	Field Measurements Methods
Meteorological data (e.g., wind speed and wind direction) will be obtained from a meteorological
station located on the roof of the EPA Region 5 Willowbrook warehouse, located adjacent to one of the
Sterigenics facilities. Wind speed and direction data will be collected in 1-hour intervals using a MET
One Sonic sensor, which will be mounted on a 3 meter tripod. The MET One sensor was certified for
wind speed and direction in November 2018. These local data will be supplemented with data from the
Chicago Midway airport, located 15 miles to the east. These data will be used to develop pollution
roses.

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2.6.	Field Analyses Methods
No field analysis methods will be performed for this project, this section is not applicable.
2.7.	Laboratory Analyses Methods (ERG)
The canister samples will be analyzed by ERG, the laboratory contractor. This project will
follow EPA Compendium Method TO-15, "Determination of Volatile Organic Compounds (VOCs) in
Air Collected in Specially Prepared Canisters and Analyzed by Gas Chromatography/Mass
Spectrometry (GC/MS) for both sampling and analysis methodology8" . The analysis method for
ethylene oxide will use sample pre-concentration and GC coupled with Mass spectrometer in selected
ion monitoring (SIM) mode. In general, to analyze the sample, a known volume of sample is directed
from the canister through a solid multisorbent concentrator with helium to dry water vapor in the sample
After the concentration and drying steps are completed, the VOCs in the sample are thermally desorbed,
entrained in a carrier gas stream, and then focused in a small volume by trapping on a small volume
multisorbent trap. The sample is then released by thermal desorption and carried onto a gas
chromatographic column for separation. Mass spectra for individual peaks in the total ion chromatogram
are examined with respect to the fragmentation pattern of ions corresponding to various VOCs including
the intensity of primary and secondary ions. The fragmentation pattern is compared with stored spectra
taken under similar conditions to identify the compound. And the intensity of the primary fragment is
compared with the system response to the primary fragment for known amounts of the compound
derived from calibration. The use of both gas chromatographic retention time and the generally unique
mass fragmentation patterns reduce the chances for misidentification. For ethylene oxide, characteristic
primary fragment ion mass (mass to charge, m/z) selected is 29 for quantification, while a list of
additional ions including 15, 44, 41 and 56 are also included in aiding the identification process for any
coeluting interferents. For additional details, refer to the TO-15 method.
As mentioned in section 2.1.2 since cigarette smoke is another possible source for ethylene
oxide, additional screening will be performed to examine the samples for cigarette smoke marker 2,5-
8 https://www3.epa.gov/ttTi/amtic/fiIes/ambient/airtox/to-15r.pdf

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dimethylfuran to address any influence from cigarette smoke on the samples.
2.8.	Quality Control Requirements
Evaluation of trip and laboratory blanks, calibration standards, internal standards, standard reference
materials (SRMs), continuing calibration verification (CCV), and sample replicates will be performed
throughout the study. Analytical instrument performance will be assessed daily or more frequently if
necessary (see details in ERG's QAPP, Appendix C section 11.3). Lab batch blanks will be checked for
each batch of canisters cleaned to ensure thorough cleaning; in addition, two trip blanks will be collected
each month to assess any background contamination issues during transport and deployment.
2.9.	Field Sampling Quality Control
For Quality Assurance (QA) precision and bias purposes, collocation of a minimum of one
sampling site per sampling event will be accomplished. That is, a collocated sample will be collected at
one of the sampling sites per sampling event, and this collocated sampling site shall rotate through the
sampling sites if above MDL concentrations are observed at sites other than the two maximum receptor
sites (Willowbrook Village Hall and EPA Willowbrook Warehouse). Until sufficient data are collected
to determine if there are detectable results at any of the other six sampling locations, an initial minimal
rotation of collocated sampling between the two maximum receptor sites will be conducted. The
collocated sample will require a separate sample inlet for each canister at the collocated site.
2.10.	Field Measurement/Analysis Quality Control
2.10.1. Field Measurement QC
Prior to sampling, field operators will perform a leak check on each canister/flow regulator set up
following the procedures found in ERG Sampling Procedures for Passive Vacuum Regulators (see
Appendix B).
The field staff must note any deviations from the sample plan or procedure on the sample label
and field logbook, along with anything unusual or unexpected that may influence the sample results (i.e.
markers, vehicle fuels, newly paved roads, nearby non-target activities, etc.). The field staff will also
document anything unusual in the field with photographs (stolen or damaged equipment in the field.

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toppled tripod, etc.)
2.11.	Laboratory Analysis Quality Control
Laboratory QC procedures are provided in Table 11-2, "Summary of Air Toxics Canister VOC
Quality Control Procedures", in the ERG QAPP in Appendix C. The tune of the GC/MS is verified
using a 4-Bromofluorobenzene (BFB) instrument performance check sample daily. The acceptance
criteria for the BFB are presented in Table 11-3 of the ERG QAPP. The internal standards for this
method are hexane-dl4, 1,4-difluorobenzene, and chlorobenzene-d5. The internal standard responses
must be evaluated to ensure instrument stability throughout the day. Before sample analyses, a standard
prepared at approximately 2.5 ppbV from a NIST traceable gas cylinder is used for a continuing
calibration verification (CCV). The resulting response factor for each compound is compared to the
average calibration curve response factors generated from the GC/MS. Correspondence within an
absolute value of less than or equal to 30 percent difference is considered acceptable for the quantitated
compounds. If the first CCV does not meet this criterion, a second CCV will be analyzed. If the second
CCV is acceptable, sample analysis can continue. If the second CCV does not meet acceptance criteria,
then a leak check and system maintenance are performed. If the system maintenance is completed and a
third CCV analysis meets the criterion, then analysis may continue. If the maintenance causes a change
in the system response, a new calibration curve must be analyzed before sample analyses can begin.
2.12.	Instrument/Equipment Testing, Inspection, and Maintenance
See ERG Sampling Procedures for Passive Vacuum Regulators in Appendix B.
2.13.	Field Measurement Instruments/Equipment
Six-liter stainless steel passivated canisters will be used for the project. The canisters will be
provided by ERG and fitted with particulate filters, fixed orifice flow controllers, and suitable inlets (see
Figure 2-7 and 2-8). The canisters will be placed on canister tripod stands for sampling. It is strongly
recommended that the initial canister pressure be checked prior to sample collection by measurement of
the canister vacuum with a calibrated pressure gauge or pressure transducer. If a built-in gauge on the
sampling unit cannot be calibrated, a standalone gauge will be employed for this measurement. This
initial pressure will be documented on the sample collection form. Canisters must show > 28 inches Hg

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vacuum to conduct sampling.
Once vacuum is verified, the canister is connected to the sampling unit and a leak check is
performed. A leak check may be performed by quickly opening and closing the valve of the canister to
generate a vacuum in the sampling unit. The vacuum/pressure gauge in the sampling unit will be
observed for a minimum of 5 minutes to ensure that the vacuum does not change by more than 0.2 psi
For more detail regarding the collection of samples using stainless steel canisters, refer to Section 4.2.3
of the NATTS TAD in Appendix D.
(Replacement Kit)
PN: 39-92196
Restricts
Fitting
(See chart, pg. 2)
3Q-0"Hg
Vacuum
Gauge
Mi: 39-27560
V Knurled Cap
PN 39 92194
Filtered Sample Net
	(Replacement Kit)
PN 39-92204S
V fiainguard
	Canister connection
V** tar TOV- or
Female Micro-01" Valve
PN: FQT-400S

Figure 2-7. Canister setup with Passive Vacuum Regulator.

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Figure 2-8. Canisters with tripod stand setup at Willowbrook Village Hall site.
2.14. Laboratory Analysis Instruments/Equipment (ERG)
To ensure the quality of the sampling and analytical equipment, ERG conducts performance
checks for all equipment used in each of the programs. ERG checks the sampling systems annually, and
makes repairs as needed. ERG tracks the performance of the analytical instrumentation to ensure proper
operation. ERG also maintains a spare parts inventory to shorten equipment downtime. Table 12-1
(Preventative Maintenance in ERG Laboratories) of the ERG QAPP in Appendix C includes the details
on maintenance items, how frequently they will be performed, and who is responsible for performing the
maintenance.

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2.15.	Instrument/Equipment Calibration and Frequency
2.15.1.	Field Measurement Instruments/Equipment
ERG performs a canister leak check and blank check on each canister annually. The initial
canister pressure/vacuum is checked prior to sampling. The initial pressure will be documented on the
sample collection COC form. Canisters must show > 28 inches Hg vacuum to conduct sampling. Once
vacuum is verified, the canister is connected to the sampling unit and a leak check is performed. A leak
is performed in the field by quickly opening and closing the valve of the canister to generate a vacuum
in the sampling unit. The vacuum/pressure gauge in the sampling unit will be observed for a minimum
of 5 minutes to ensure that the vacuum does not change by more than 1 in Hg. The vacuum/pressure
gauges are calibrated initially before use, and on an as needed basis, every 3-4 months. Particulate filters
are disposable and replaced if the sampling flow rate or final canister pressure/vacuum indicates a
blockage or buildup of particulates.
2.15.2.	Laboratory Analysis Instruments/Equipment (ERG)
Calibration of the GC/F ID/MS used for TO-15 analysis is accomplished quarterly (at a
minimum) by analyzing humidified calibration standards prepared in canisters generated from NIST-
traceable gas standards. The certified standards contain the VOC target compounds at approximately
500 parts per billion by volume (ppbV). Initial calibration standards are prepared at nominal
concentrations of 0.25, 0.5, 1, 2.5, 5, and 10 ppbV for the target compound (a minimum of 5 levels are
required). All standards and samples are analyzed with the following internal standards: n-hexane-d 14,
1,4-difluorobenzene, and chlorobenzene-d5. The calibration requires average response factors (RRF),
based on the internal standard, of ± 30 percent RSD. The CCV is made from a second source certified
gas at an average concentration of 2.5 ppbV. The CCV must have RRFs within ± 30% of the mean
initial calibration RRFs. Refer to Section 13 of ERG QAPP in Appendix C.
2.16.	Inspection/Acceptance Requirements for Supplies and Consumables
2.16.1. Field Sampling Supplies and Consumables
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There are no field sampling consumables other than particulate filters (see Section 2.7.1). Refer to
APPENDIX B. ERG Sampling Procedures for Passive Vacuum Regulators for required checks on the
sampling canisters to be performed in the field.
2.16.2. Laboratory Analyses Supplies and Consumables
The purpose of this element is to establish and document a system for inspecting and accepting
all supplies and consumables that may directly or indirectly affect the quality of the data. All supplies
and consumables are inspected and accepted or rejected upon receipt in the laboratory. The ERG
employee who ordered the supply is responsible for verifying that the order is acceptably delivered,
stored and dispersed upon receipt in the laboratory. The recipient's signature on the packing slip
indicates the received goods were received and are acceptable. Refer to Table 14-1 (Critical Supplies
and Consumables) and Section 14 of the ERG QAPP in Appendix C for more detailed information.
2.17.	Data Acquisition Requirements (Non-Direct Measurements)
See Section 2.1 for non-direct measurements used as inputs into AERMOD to determine sampling
locations.
2.18.	Data Management
Data management is largely managed by ERG. Field sampling operators in Region 5 will be
responsible for completion of the field COC forms (Figure 2-4). When a sample is collected, the site
operator fills out the COC form. The site operator detaches the pink copy to be retained on-site and
sends the remaining copies with the canister in the shipping container to ERG's laboratory. ERG's data
management for sample data is presented in Figure 2-7. The sample data path is shown from sample
origination to data reporting and storage. Refer to Section 15 of the ERG QAPP in Appendix C for more
detailed information.

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Yes
Willowbrook EtO QAPP
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Disposal
(14- days
	 Pap?r-!ow
	 Sample Flaw
— - 	 Computer Haw
PQk


Data Storage
(5 years)
Figure 2-9. Data management and sample flow diagram.

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3. ASSESSMENTS AND OV ERSIGHT
3.1. Assessments/Oversight and Response Actions
An assessment is defined as an evaluation process used to measure the performance or
effectiveness of the quality system and various measurement phases of the data operation. EPA and
ERG will be performing the assessments explained in this section.
3.1.1. Field and Laboratory Technical Systems Audits
A TSA is a thorough and systematic on-site qualitative audit, where facilities, equipment,
personnel, training, procedures, subcontractor systems, and record keeping are examined for
conformance to the QAPP.
A field TSA will be performed by OAQPS once all initial field sites are set up and running. It is
anticipated the audit occurring early to mid-December 2018. The audit will consist of a thorough review
of the field personnel implementing the standard operating procedures for this activity including: sample
canister receipt and installation; sampler and site maintenance, quality control checks, log book and data
entry (forms); sample chain of custody and sample shipment. If the field activity is not being
implemented correctly and the auditor feels that data quality is compromised the auditor has the
authority to halt data collection activities until corrective action is implemented. Any sample collected
prior to the audit will be qualified appropriately. A summary report will be prepared by the auditor
before existing the audit and a full report will be provided to the field personnel no later than two weeks
from the completion of the audit. Due to the simplified nature of the field activities only one audit will
be conducted unless serious findings that affect data quality are identified. As part of corrective action
and follow-up, an audit finding response letter will be generated by the Region 5 field office Program
Manager. The audit finding response letter will address what actions are being implemented to correct
the finding(s) of the TSA and in what timeframe. Audit reports and corrective action reports will be filed
with the OAQPS Monitoring Lead.
A laboratory TSA will be conducted by OAQPS in early to mid-December. The audit will
consist of a thorough review of the laboratory personnel and activities related to this QAPP and the
SOPs designated for use in this project. If the laboratory activity is not being implemented correctly and

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the auditor feels that data quality is compromised the auditor has the authority to halt sample analysis
activities until corrective action is implemented. Any sample collected prior to the audit will be flagged
appropriately. A summary report will be prepared by the auditor before existing the audit. Specific areas
will be discussed, and an attempt made to rank them in order of their potential impact on data quality. A
full report will be provided to the field personnel no later than two weeks from the completion of the
audit. Due to the timeframe for data collection, one audit will be conducted unless serious findings that
affect data quality are identified. The external TSAs will be performed by EPA at the ERG Laboratory.
The EPA audit team will prepare a brief written summary of findings for the ERG Program Manager
and Program QA Coordinator. As part of corrective action and follow-up, an audit finding response
letter will be generated by the ERG Program Manager and Program QA Coordinator. The audit finding
response letter will address what actions are being implemented to correct the finding(s) of the TSA and
in what timeframe. See figure 3-1 for a copy of ERG corrective action report form. See ERG QAPP
section 16.1 for more details (Appendix C). Audit reports and corrective action reports will be filed with
the OAQPS Monitoring Lead.
ERG has internal QA staff that perform an annual internal systems audits of laboratory analysis
activities contracted to EPA. Section 16 of the ERG NATTS QAPP explains the TSA procedure.

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CAR Number. 2018-
Correctivc Action Report
CAR Initiator	Initiation [Mr.
Area/Procedure Affected	- !ar-: <-
U Immediate Stop of Work Required?
*ERG
NWi^n>lltWTOWIf»
Dateof Dfacovery:
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Qxfc or up here to eitertt41
tmuligattoo of Non-Conformance: B»w ku the nnn afbrnsn iiv ireped>
Oitk or lap her* id enter ttit
Impact Aueumeot: What « .rfcrrtrcl tijr the rnxuxraft rmjnrr •
0*k or Up here to enter teit
Root Causae Anatyaii: WTiut caused the noraMjrtftinnance?
Okt or lip here to enter text.
Farther Analyas: Could thw tu n-i.nf rm*rxr be	in other
CVt w Up here to enter text
Corrective Action
Due Dote (or Remedial Action Completion
Immediate andyor timg-Term Remedial Corrective Actions Taken;
Ajaesunent of Corrective Action Kflertneness:
Ok* or tap here to enter tcil
QAOffictr
Project Manager:
Initiator
Signature ft Dtf e
Comment*
Click or Up here to enter text.
Olck or tap here to enter text.
Click or tap here to enter text
FoSk>w-np
Reference or attach documentation that den khui rates the return to conformance, or describe below
Oidt or tap here id enter text.
FqHow-ui) Auditor: CM or up Kerr toriter text	Date Completed:
Were corrective action procedures effective?
CHci or tap here to enter iMt
Figure 3-1. ERG's corrective action report form.

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3.1.2. Data Quality Assessments
Data quality assessment is the scientific and statistical evaluation of data to determine if data
obtained from environmental data operations are of the right type, quality, and quantity to support their
intended use. This assessment is built on a fundamental premise: data quality, as a concept, is
meaningful only when it relates to the intended use of the data.
An audit of data quality (ADQ) reveals how the data were handled, what judgments were made,
and whether uncorrected mistakes were made. Performed prior to producing a program activity's final
report, ADQs can often identify the means to correct systematic data reduction errors.
These audits involve an extensive review of all the data used to generate the final result, including a
review of instrument print-outs and other raw data, spreadsheets used to calculate and summarize data,
and field data.
For this project, an ADQ will be performed on 10% of the sample and QC data every two weeks
by EPA on data submitted by ERG. This audit may be performed at ERG to facilitate the review of
instrument data, notebooks and other laboratory and field documentation used to calculate the results.
Any issues identified will be documented and resolved before any data are released by EPA.
ERG Data Assessments
ERG, as part of the EPA NATTS contract will also provide data assessments that are described
in section 16.1.4 of the NATTS QAPP. EPA will use these assessments in final QA reports for this
project.
3.2. Reports to Management
Analytical data reports prepared by ERG are sent to the EPA OAQPS Monitoring Lead on a
biweekly basis following sample collection. These reports will be delivered in both Excel and Adobe pdf
formats. These reports will include the analytical data for each sample collected including: sample
name, lab number, target compound, canister number, sample results (ppbv and ug/m3), method
detection limit, sample matrix, sample date, sample receipt date, and other supporting laboratory
documentation. Quality control data will also be included in the reports including blanks, duplicates,
and calibration checks (continuing calibration verifications). The EPA OAQPS Monitoring Lead will

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file the reports and make them available for QA review by the EPA Quality Assurance Manager.
Regular reports to EPA provide the opportunity to identify and alert staff of data quality problems, to
implement corrective action, and to procure necessary additional resources. Biweekly meetings of ERG
personnel with EPA monitoring and QA staff, both headquarters and regional staff, will provide a means
for effective communication of sampling results, trends identified in the data, ensuring scheduled
delivery of data and reports, and identification of any deviation from the approved QAPP and plans.
A final report will also be completed following the study to summarize the details of the sampling
performed, the concentration results, as well as any data analysis conducted. Detail regarding the
contents of this report may be found in Section 1.9.4 Final Reports.
4. DATA REV IEW AND USABILITY
4.1. Data Review, Verification, and Validation Requirements
Information used to verify ethylene oxide air concentration data, includes:
a.	Sample COCs, holding times, preservation methods;
b.	Multi-point calibrations - the multipoint calibrations are used to establish proper initial
calibration and can be used to show changes in instrument response;
c.	Standards - certifications, identification, expiration dates;
d.	Instrument logs - all activities and samples analyzed are entered into the LIMS logs (batches,
sequences, etc.) to track the samples throughout the measurements procedures;
e.	Supporting equipment - identification, certifications, calibration, if needed;
f.	Blank, CCVs, replicate and spike results - these QC indicators can be used to ascertain whether
sample handling or analysis is causing bias in the data set.
The reliability and acceptability of environmental analytical information depends on the rigorous
completion of all the requirements outlined in the QA/QC protocol. During data analysis and validation,
data are filtered and accepted or rejected based on the set of QC criteria list in Table 1-1 and in section
2.5. More details can be found in ERG QAPP section 11.3 (Appendix C).

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4.2.	Verification and Validation Methods
Sample data is examined for representativeness, completeness, precision, and bias. Data
validation is performed by examination of objective evidence that the requirements for a specific
intended use are fulfilled as presented in Section 2.5. For the analytical data, the entries are reviewed to
reduce the possibility of entry and transcription errors. Once the data are transferred to the ERG LIMS
database, the data will be reviewed for routine data outliers and data outside acceptance criteria. These
data will be flagged appropriately. Prior to reporting, 100 percent of the data is reviewed by ERG Task
Leader and 10 percent of the database is checked by ERG QA Coordinator or designated reviewer.
4.3.	Reconciliation with User Requirements
A preliminary data review will be performed to uncover potential limitations to using the data, to
reveal outliers, and generally to explore the basic structure of the data. The next step is to calculate basic
summary statistics, generate graphical presentations of the data, and review these summary statistics and
graphs to determine if representativeness, comparability, completeness, precision, bias, and sensitivity,
were met. Representativeness can be assessed with site location information and is based on potential
sources and select weather station information. Comparability is based on method measure of the level
of confidence with which one data set can be compared to another. Completeness is measured by the
amount of valid sample data obtained compared to what was expected. Precision is determined from
replicate collocate analyses. Sensitivity is demonstrated through MDLs.
If the sampling design and statistical tests conducted during the final reporting process show
results that meet acceptance criteria, it can be assumed that the network design and the uncertainty of the
data are acceptable. Further use of the data will include characterizing concentrations in potentially
affected nearby neighborhoods based on method sensitivity; evaluating ethylene oxide fugitive
emissions from Sterigenics by OAQPS' Measurement Technology Group; heath risk assessment by
OAQPS's Air Toxics Assessment Group of Health and Environmental Impacts Division.

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5. REFERENCES
1.	U.S. Environmental Protection Agency. Evaluation of the Inhalation Carcinogenicity of Ethylene
Oxide (CASRN 75-21-8) In Support of Summary Information on the Integrated Risk Information
System(lRlS). National Center for Environmental Assessment, Office of Research and Development.
Washington, DC EPA/635/R-l 6/350Fa. 2016.
https://cfpub.epa.gov/ncea/iris/iris_documents/documents/toxrevievvs/1025tr.pdf
2.	EPA Compendium Method TO-15, Determination of Volatile Organic Compounds (VOCs) in Air
Collected in Specially Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry
(GC/MS) for both sampling and analysis methodology, 1999.
https://vvvvvv.epa.gov/sites/production/files/2015-07/documents/epa-to-15_0.pdf
3.	ENVIRONMENTAL PROTECTION AGENCY 40 CFR Part 136 [EPA-HQ-OW-2014-0797; FRL-
9957-24- OW] RIN 2040-AF48 Clean Water Act Methods Update Rule for the Analysis of Effluent.
2017. https://vvvvvv.gpo.gov/fdsys/pkg/FR-2017-08-28/pdf/2017-17271 pdf
4.	National Air Toxics Trends Stations (NATTS) program's Technical Assistance Document, 2016.
fattps://www3.epa.gov/ttn/amtic/files/ambient/airto\;N A i"l'S%20T \D°- o20Revision%203 FINAL%20Q
ctober%202016.pdf

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6. APPENDICES
APPENDIX A. Ethylene Oxide Sampling Calendar
APPENDIX B. ERG Sampling Procedures for Passive Vacuum Regulators
APPENDIX C. ERG's QAPP, "SUPPORT FOR THE EPA NATIONAL MONITORING
PROGRAMS," (ERG-Q APP-0344-4).
APPENDIX D TECHNICAL ASSISTANCE DOCUMENT FOR THE NATIONAL AIR TOXICS
TRENDS STATIONS PROGRAM, Revision 3
APPENDIX E. Standard Operating Procedure for Collection of VOC Samples (R5-ARD-0003-r5)

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APPENDICES
APPENDIX A. Ethylene Oxide Sampling Calendar
2018/2019 3-Day Sampling Calendar - EtO
November
Sun
Mon
Tue
Wed
Thu
Fri
Sat











1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
TB
17
18
19
20
21
22
23
24
25
26
27
TB
29
30

December
Sun
Mon
Tue
Wed
Thu
Fri
Sat


LJ


-J
2
3
n
5
6
mm <3
9
10
ii
12
TB
14 15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
TB





January
Sun
Mon
Tue
Wed
Thu
Fri
Sat








1
2
3
4
5
6
7
8
9
10
11
12
13
14
TB | 16
17
18
19
20
21
22
23
24
25
26
27
28
29
TB
31

February
Sun
Mon
Tue
Wed
Thu
Fri
Sat












1
2
3
4
5
6
7
8
9
10
11
12
13
TB
15
16
17
18
19
20
21
22
23
1 24
25
TB
27
28

1
Standard Sample Collection
Field Blank Collection

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APPENDIX B. ERG Sampling Procedures for Passive Vacuum
Regulators

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Region 5 Air Toxics Study
October 2018
Sampling Procedures for Passive Vacuum Regulators
The procedure presented is designed for sampling volatile organic compounds
(VOCs) in ambient air, based on the collection of whole air samples in SUMMA®
treated canisters to final pressures below atmospheric. The samples are then
analyzed using EPA Compendium Method TO-15 Determination of Volatile
Organic Compounds (VOCs) in Air Collected in Specially Prepared Canisters
and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) and the
EPA National Monitoring Program's contract laboratory (i.e. ERG following the
Category 1, EPA approved "Support for the EPA National Monitoring Programs"
QAPP).
Laboratory Analysis Methodology using the TO-15 method may be referenced
by contacting the Eastern Research Group (ERG) directly at 919-468-7824 or by
email to Julie.Swift@erq.com.
I. INSTALLATION
A.	Sampler Siting
Designate the address or GPS coordinates on the Chain of Custody (COC)
form.
The sampler should be mounted in a location that is unobstructed on all
sides. There should be no tree limbs or other hanging obstructions above
the sampler. It is suggested that the horizontal distance from the sampler to
the closest vertical obstruction higher than the sampler be at least twice the
height of the vertical obstruction. The inlet of the sampling system must be
positioned at least 2 meters above grade (ideal), but not more than 5 meters
above grade.
B.	Sampler Installation
1. The sampling system consists of two components: a sample canister and
a passive vacuum regulator (Veriflow vacuum regulator with gauge and
sample inlet probe). The canisters have been cleaned, tested for
contamination (blanked) and evacuated, the passive collection assemblies
will have been cleaned, tested for contamination (blanked), and calibrated
for 24-hour integrated sampling.
Page I of 4

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Region 5 Air Toxics Study
October 2018
2.	The complete sampling system must be securely mounted on a support
structure which ensures that the sample inlet meets the siting criteria (at
least 2 meters above grade, but not more than 5 meters above grade).
3.	For collocated samplers, horizontal spacing should be between 0 and 4
meters, and inlet heights within 1 meter vertically.
II. OPERATING PROCEDURE
A.	Equipment and Supplies
•6-liter sample collection canister
•Veriflow vacuum regulator/gauge/inlet probe (passive collection assembly)
• ERG COC form
B.	Sampler and Sample Media Receipt Activities
Complete Sampling System
1.	Check parts and components to ensure none is damaged.
2.	Ensure all fittings are present and in good condition.
3.	Prior to sampling keep all sampling system components in a clean
area free of contamination.
Sample Collection Canister
1.	The sample collection canister and associated sample COC will arrive
via air freight from ERG in a cardboard box.
Note: The canisters do not need to be refrigerated after receipt or
during return shipping.
2.	Ensure the canister is not damaged. Confirm that the valve remained
in the closed position during shipping and that the top plug is secured
on the bellows valve inlet fitting.
Page 2 of 4

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Region 5 Air Toxics Study
October 2018
C. Preparing for a Sampling Event
1.	Prepare sample paperwork. On the ERG Toxics/SNMOC COG, supply
all required information in the "Lab Pre-Sampling" section. Record any
pertinent observations in the "Comments" section at the bottom of the
form.
2.	Remove the plug attached to the bellows valve inlet. Retain the plug in
a clean place so that it can be used to reseal the bellows valve inlet
after the sampling event.
3.	Assemble the complete sampling system.
a.	Attach the outlet fitting of the Veriflow vacuum controller to the
canister bellows valve inlet fitting.
Note: Do not over tighten the fitting nut. When the fitting nut
feels snug by hand, another quarter turn should be sufficient to
secure the controller inlet to the can.
b.	Ensure that the plug at the inlet of the Veriflow remains tight in
order to perform a leak check.
Perform a leak check by opening and then immediately closing the
canister valve. Observe the vacuum reading on the Veriflow
gauge. If the vacuum changes by more than 1 in Hg over 5
minutes, ensure that all fittings are tight. If all fittings are tight, then
assemble another sampling system using another canister and
repeat steps 2 and 3.
D. Sampling and Data Collection
1.	Record the initial collection start time and date in "Setup Date:" in the
"Field Setup" section on the COC form. Fully open the canister
bellows valve. Observe the pressure (i.e., "Hg vacuum) indicated on
the gauge.
2.	After 24 hours, read the gauge and record the remaining pressure left
in the can on the ERG Toxics/SNMOC Sample Data Sheet and record
the reading in the "Field Recovery", "Field Final Can. Press. ("Hg)"
Page 3 of 4

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Region 5 Air Toxics Study
October 2018
blank. If the pressure is zero, note the lack of pressure in the
"Comments" section of the form.
3.	Close the canister bellows valve fully.
4.	Disconnect the canister from Veriflow vacuum controller by unfastening
the Veriflow outlet fitting from the canister bellows valve inlet fitting.
5.	Replace and secure the retained plug on the canister bellows valve.
6.	On the ERG Toxics/SNMOC Sample Data Sheet, supply all required
information in the "Field Recovery" section. Be sure to record any
observations that were made during the run period in the "Comments:"
section.
E. Sample Shipping
a.	Remove the pink copy of the ERG Toxics/SNMOC Sample Data Sheet
and file in a site record.
b.	Pack the can and the completed white/yellow copy of the ERG Toxics/
SNMOC Sample Data Sheet in the original cardboard shipping box and
tape it closed. The can does NOT need to be shipped cold.
c.	Use the pre-filled out UPS label provided by ERG, and fill out the Sender"
section with the sampling agency's address and phone number. Send
priority overnight to ERG at the address below.
ERG
601 Keystone Park Drive
Suite 700
Morrisville, NC 27560
919-468-7924
Note: if the shipping form is lost, use the address above for shipping to
ERG, and contact them directly for the UPS accounting number.
Page 4 of 4

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APPENDIX C. ERG's QAPP9 "SUPPORT FOR
THE EPA NATIONAL MONITORING
PROGRAMS," (ERG-QAPP-0344-4).

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ERG-QAPP-0344-4
SUPPORT FOR THE EPA NATIONAL
MONITORING PROGRAMS
(UATMP, NATTS, CSATAM, PAMS, and NMOC
Support)
Contract No. EP-D-14-030
2018
Quality Assurance Project Plan
Category 1
Eastern Research Group, Inc.
601 Keystone Park Drive, Suite 700
Morrisville, NC 27560

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Date
Page
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4
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ii of xvi
2018 Quality Assurance Project Plan, Category 1
UATMP, NATTS, CSATAM, PAMS, and NMOC Support (Contract No. EP-D-14-030)
Approved by:
U.S. EPA Project Officer:
U.S. EPA QA Manager:
U.S. EPA Delivery Order Manager:
ERG Program Manager:
ERG Deputy Program Manager:
ERG Program QA Officer:
Date:
Date:
Date: W*
C|olJUj< ( ,	Date: ^ (Z"7-( t-g
fe" (Lu K/i I Id A'i f/IAJDate: F ^7 ^
I As .. f		 Date: 7' lz~7(/ P
ERG Deputy Program QA Officer:

Date: 1 /3l/i9
DISCLAIMER
This Category 1 Quality Assurance Project Plan has been prepared specifically to address the
operation and management of the U.S. EPA National Monitoring Programs (UATMP, NATTS,
CSATAM, PAMS and NMOC). The contents have been prepared in accordance with Level I
Specifications of the EPA Requirements for Quality Assurance Project Plans, EPA QA/R-5 and the
EPA Guidance for Quality Assurance Project Plans, EPA QA/G-5.

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Project No.	0344.00
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Revision No.	4
Date	March 2018
Page	iii of xvi
TABLE OF CONTENTS
Section
PROJECT MANAGEMENT
1	Project/Task Organization	1 of 8
1.1 Assignment of Program Personnel	1 of 8
1.1.1	Program Manager	2 of 8
1.1.2	Deputy Program Manager	2 of 8
1.1.3	Program Technical Adviser	3 of 8
1.1.4	Program QA Coordinator	3 of 8
1.1.5	Deputy Program QA Coordinator	3 of 8
1.1.6	Task Leaders	4 of 8
2	Problem Definition/Background	1 of 3
3	Project/Task Description	1 of 4
3.1	PAMS, NMOC and SNMOC	1 of 4
3.2	UATMP, NATTS and CSATAM	2 of 4
4	Data Quality Objectives and Criteria for Measurement Data	1 of 5
5	Special Training Requirements/Certification	1 of 2
5.1	Field Activities Training Personnel	1 of 2
5.2	Analytical Laboratory Personnel	2 of 2
6	Documentation and Records	1 of 6
6.1	Data Management	1 of 6
6.2	Preliminary Monthly Data Reports	1 of 6
6.3	Quarterly QA Report	2 of 6
6.4	Annual Summary Reports Submitted to EPA	2 of 6
6.5	Records and Supporting Data	3 of 6
6.5.1	Notebooks	4 of 6
6.5.2	Electronic Data Collection	5 of 6
6.6	Data Reporting Package Archiving and Retrieval	5 of 6
6.7	Quality System Document Control	5 of 6
MEASUREMENT DATA ACQUISITION
7	Sampling Process Design	1 of 10
7.1	NMOC and SNMOC Canister Samplers	1 of 10
7.2	VOC and Carbonyl 24-Hour Samplers	4 of 10
7.3	Carbonyl Only 24-Hour Samplers	5 of 10
7.4	Hexavalent Chromium Samplers	8 of 10
7.5	PAMS Sampling	10 of 10
7.6	HAPS Sampling	10 of 10
8	Sampling Method Requirements	1 of 1

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Element No.	A2
Revision No.	4
Date	March 2018
Page	iv of xvi
TABLE OF CONTENTS (Continued)
Section
9	Sample Handling and Custody Requirements	1 of 16
9.1	Canister Sample Custody	1 of 16
9.1.1	Canister Custody	1 of 16
9.1.2	Canister Analytical Routing Schedule	6 of 16
9.1.3	Canister Cleanup	6 of 16
9.2	Carbonyl Sample Custody	9 of 16
9.2.1 Carbonyl Analytical Routing Schedule	9 of 16
9.3	HAPs Sample Custody	11 of 16
9.4	Invalid Samples	1 1 of 16
9.5	Analytical Data	16 of 16
9.6	Sample Monitoring Data	16 of 16
10	Analytical Methods Requirements	1 of 13
10.1	Canister Cleanup System	1 of 13
10.1.1	Heated Canister Cleaning System	2 of 13
10.1.2	Unheated Canister Cleaning System	4 of 13
10.2	VOC and Concurrent Analytical Systems	7 of 13
10.3	Carbonyl Analytical Systems	9 of 13
10.4	Poly cyclic Aromatic Hydrocarbons Analytical Systems	10 of 13
10.5	Metals Using an Inductively Coupled Argon Plasma Mass
Spectrometry Analytical System	1 1 of 13
10.6	Hexavalent Chromium Analytical System	12 of 13
11	Quality Control Requirements	1 of 40
11.1 Sample Canister Integrity Studies	1 of 40
1 1.2 Standard Traceability	1 of 40
11.3	Accuracy and Acceptance	2 of 40
1 1.3.1 SNMOC Analysis	2 of 40
1 1.3.2 VOC Analysis	3 of 40
1 1.3.3 Carbonyl Compound Analysis	8 of 40
1 1.3.4 PAH Analysis	9 of 40
1 1.3.5 Metals Analysis	21 of 40
1 1.3.6 Hexavalent Chromium Analysis	28 of 40
11.4	Precision	3 1 of 40
11.5	Completeness	3 1 of 40
1 1.6 Representativeness	32 of 40
1 1.7 Sensitivity (Method Detection Limits)	32 of 40
12	Instrument/Equipment Testing, Inspection, and Maintenance Requirements	1 of 4
12.1	SNMOC, VOC, and PAMS	3 of 4
12.2	Carbonyls	3 of 4
12.3	HAPs	3 of 4

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Date	March 2018
Page	v of xvi
TABLE OF CONTENTS (Continued)
Section
13	Instalment Calibration and Frequency	1 of 7
13.1	SNMOC Calibration	1 of 7
13.2	VOC Calibration	2 of 7
13.3	Carbonyl Calibration	4 of 7
13.4	HAPs Calibration	5 of 7
13.5	Laboratory Support Equipment Calibration	6 of 7
14	Inspection/Acceptance for Supplies and Consumables	1 of 5
14.1	Purpose	1 of 5
14.2	Critical Supplies and Consumables	1 of 5
14.3	Acceptance Criteria	1 of 5
15	Data Management	1 of 7
15.1	Data Recording	1 of 7
15.2	Data Validation	3 of 7
15.3	Data Reduction and Transformation	3 of 7
15.4	Data Transmittal	4 of 7
15.5	Data Summary	5 of 7
15.6	Data Tracking	6 of 7
15.7	Data Storage and Retrieval	7 of 7
ASSESSMENT/OVERSIGHT
16	Assessments and Response Actions	1 of 7
16.1	Assessment Activities and Project Planning	1 of 7
16.1.1	External Technical Systems and Data Quality Audits	1 of 7
16.1.2	Internal Technical Systems Audits	2 of 7
16.1.3	Proficiency Testing	3 of 7
16.1.4	Data Assessment for Final Report	4 of 7
16.2	Documentation of Assessments	4 of 7
16.2.1	TSA, Data Quality Audit, and PT Documentation	4 of 7
16.2.2	Internal Data Review Documentation	4 of 7
16.3	Corrective Action Reports	5 of 7
17	Reports to Management	1 of 2
17.1 Frequency, Content, and Distribution of Reports	1 of 2
17.1.1	Monthly and Annual Reports	1 of 2
17.1.2	Internal Technical System Audit Reports	2 of 2
DATA VALIDATION AND USABILITY
18	Data Review and Verification	1 of 1 1
18.1	Data Review Design	1 of 1 1
18.2	Data Verification	2 of 1 1
18.3	Data Review	2 of 1 1
18.4	Data Reduction and Reporting	3 of 1 1
18.5	Data Validation	4 or 1 1

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Date	March 2018
Page	vi of xvi
18.6 Air Quality System	5 of 11
18.6.1 AQS Flagging and Reporting	6 of 1 1
19	Data Validation, Verification and Analysis	1 of 2
19.1	Process for Validating and Verifying Data	1 of 2
19.1.1	Verification of Data	1 of 2
19.1.2	Validation of Data	1 of 2
19.2	Data Analysis	2 of 2
20	Reconciliation with Data Quality Objectives	1 of 1
20.1	Conduct Preliminary Data Review	1 of 1
20.2	Draw Conclusions from the Data	1 of 1
21	References	1 of 2
APPENDICES
A Exemptions Table
B 2018 Sampling Schedule
C ERG Standard Operating Procedures
ERG-MOR-003B Field Procedure for Collecting Ambient Air Toxics and
Carbonyl Compounds Samples Using the ERGAT/C Sampling
System (with O3 Denuder Scrubber)
ERG-MOR-003C Field Procedure for Collecting Ambient Air Toxics and
Carbonyl Compounds Samples Using the ERG(C):AT/C
Sampling System (with O3 Denuder Scrubber)
ERG-MOR-003D Field Procedure for Collecting Ambient Air Toxics and
Carbonyl Compounds Samples Using the ERG AT/C Sampling
System (with O3 Denuder Scrubber and Mass Flow Meter)
ERG-MOR-005 Standard Operating Procedure for the Concurrent GC/FID/MS
Analysis of Canister Air Toxic Samples using EPA
Compendium Method TO-15 and EPA Ozone Precursor
Method
ERG-MOR-013
Field Procedure for Collecting Ambient Air Hexavalent
Chromium Samples Using the ERG CR6 Sampling System
ERG-MOR-017
Standard Operating Procedure for Developing, Documenting,
and Evaluating the Accuracy of Spreadsheet Data
ERG-MOR-022
Standard Operating Procedure for the Preparation of Standards
in the ERG Laboratory
ERG-MOR-024
Standard Operating Procedure for Preparing, Extracting, and
Analyzing DNPH Carbonyl Cartridges by Method TO-1 1A

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Page
ERG-MOR-030
ERG-MOR-033
ERG-MOR-039
ERG-MOR-044*
ERG-MOR-045
ERG-MOR-046*
ERG-MOR-047B
ERG-MOR-047C
ERG-MOR-049
ERG-MOR-057
ERG-MOR-060
ERG-MOR-061
Standard Operating Procedure for Canister Sampling System
Certification Procedures
Standard Operating Procedure for Hazardous Waste
Standard Operating Procedure for Maintaining Laboratory
Notebooks
Standard Operating Procedure for Method 8270C - GC/MS
Analysis of Semi volatile Organics
Standard Operating Procedure for Sample Receipt at the ERG
Chemistry Laboratory
Field Procedure for Collecting Speciated and/or Total
Nonmethane Organic Compounds Ambient Air Samples Using
the ERGS/NMOC Sampling System
Field Procedure for Collecting Ambient Carbonyl Compounds
Samples Using the ERG:C Sampling System
Field Procedure for Collecting Ambient Carbonyl Compounds
Samples Using the ERG:C Sampling System (new timer)
Standard Operating Procedure for analysis of Semivolatile
Organic Compounds (Polynuclear Aromatic Hydrocarbons)
Using EPA Compendium Method TO-13 A. & ASTM D
6209-13
Standard Operating Procedure for Project Peer Review
Standard Operating Procedure for PDFID Sample Analysis by
Method TO-12
Standard Operating Procedure for Standard Preparation Using
Dynamic Flow Dilution System
ERG-MOR-062
Standard Operating Procedure for Sample Canister Cleaning

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TABLE OF CONTENTS (Continued)
ERG-MOR-063
ERG-MOR-079
ERG-MOR-084
ERG-MOR-085
ERG-MOR-095
ERG-MOR-097
ERG-MOR-098
ERG-MOR-099
ERG-MOR-100
Standard Operating Procedure for the Preparation and Analysis
of Ambient Air for Hexavalent Chromium by Ion
Chromatography
Standard Operating Procedure for Sample Login to the
Laboratory Information Management System
Standard Operating Procedure for the Preparation and
Extraction of High Volume Quartz and Glass Fiber Filters for
Metals by ICP-MS using Method 10 3.1 and FEM Method
EQL-0512-201
Standard Operating Procedure for the Preparation and
Extraction of 47mm Filters for Metals by ICP-MS using
Method IO 3.1 and FEM Method EQL-05 12-202
Standard Operating Procedure for the Analysis of High Volume
Quartz, Glass Fiber Filters, and 47mm Filters for Metals by
ICP-MS using Method 10-3.5, FEM Method EQL-05 12-201,
and FEM Method EQL-05 12-202
Standard Operating Procedure for Manual Integration of
Chromatographic Peaks
Standard Operating Procedure for the Preparation of Monitoring
Data for AQS Upload
Standard Operating Procedure for the Laboratory Information
Management System
Standard Operating Procedure for Carbonyl System
Certification
ERG-MOR-105
Standard Operating Procedure for Sample Canister Cleaning
using the Wasson TO-Clean Automated System
* These SOPs are not current because they are not in need. Once EPA/State/Local or Tribal agency
requests this work, the SOP will be updated and provided to the EPA before work begins.
D
Subcontractor Q APPs will be added if they are initiated

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Page	ix of xvi
LIST OF TABLES
Table
I-1	Program Organization	5 of 8
1-2 QC Responsibilities and Review Functions	7 of 8
3-1	List of Analytical and Support Services	3 of 4
4-1	Measurement Quality Objectives for the National Program (UATMP, NATTS,
C SAT AM, PAMS, NMOC)	4 of 5
6-1 Data Documentation and Records	3 of 6
8-1	EPA Methods and ERG SOPs for each Sampling System	1 of 1
9-1	Example of Canister Pressure Check Spreadsheet	4 of 16
10-1	VOC GC/FID/MS Operating Conditions	8 of 13
1 1-1	Summary of SNMOC Quality Control Procedures	4 of 40
1 1 -2	Summary of Air Toxics Canister VOC Quality Control Procedures	5 of 40
I	1-3	BFB Key Ion Abundance Criteria	8 of 40
II-4	Summary of Carbonyl Quality Control Procedures	10 of 40
11-5	DFTPP Key Ions and Ion Abundance Criteria	15 of 40
II	-6	Internal Standards and Associated PAHs	16 of 40
1 1-7	Summary of Quality Control Procedures for Analysis of SVOC Samples for PAHs	17 of 40
1 1-8	Instrument Mass Calibration & Performance Specifications	22 of 40
11-9	Summary of Quality Control Procedures for Metals Analysis	24 of 40
1 1-10	Summary of Quality Control Procedures for Hexavalent Chromium	29 of 40
11-11	2018 SNMOC Method Detection Limits	33 of 40
1 1-12	2018 Air Toxics Method Detection Limits	35 of 40
1 1-13	2018 Carbonyl Method Detection Limits (Underivatized Concentration)	36 of 40
11-14	2018 PAH Method Detection Limits	37 of 40
1 1-15 2018 Metals Method Detection Limit	39 of 40
1 1-16 Target MDLs for the N ATTS Program	40 of 40
12-1	Preventive Maintenance in ERG Laboratories	1 of 4
13-1	Relative Response Factor Criteria for Initial Calibration of Common Semi volatile
Compounds	5 of 7
14-1	Critical Supplies and Consumables	2 of 5
15-1	Report Equations	6 of 7
15-2 Data Archive Policies	7 of 7

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Page	x of xvi
LIST OF TABLES (Continued)
Table
18-1 Qualifier Codes	7 of 11
18-2 Null Codes	9 of 11
18-3 Summary of Quantitation and Detection Limit Flags and Applications	11 of 11

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Page	xi of xvi
LIST OF FIGURES
Figure
1-1 National Monitoring Programs Organizational Chart	6 of 8
3-1 Duplicate/Col 1 ocate and Replicate Analysis Schematic	4 of 4
7-1	NMOC, SNMOC, and 3-Hour Air Toxics Sampling System Components	2 of 10
7-2	VOC/Carbonyl Sampler Training Form	3 of 10
7-3	24-Hour Integrated Air Toxics Sampling System Components	6 of 10
7-4	Carbonyl Sampling System Components	7 of 10
7-5	Hexavalent Chromium Sampling System Components	9 of 10
9-1	Example NMOC COC	2 of 16
9-2	Example Air Toxics COC	3 of 16
9-3	Example ERG L1MS Login Page	5 of 16
9-4	Canister Tag	5 of 16
9-5	Canister Cleanup Log for the ERG Heated Cleaning System	7 of 16
9-6	Canister Cleanup Log for the ERG Unheated Cleanup System	8 of 16
9-7	Example Carbonyl Compounds COC	10 of 16
9-8	Example SVOC Sample COC	12 of 16
9-9	Example Ambient Hexavalent Chromium COC	13 of 16
9-10	Example Metals COC	14 of 16
9-11	ERG Blank COC Record	15 of 16
10-1	Heated Canister Cleanup System Schematic	3 of 13
10-2	Unheated Canister Cleanup System Schematic	5 of 13
10-3	Gas Chromatograph/Mass Spectrometer/FID System	9 of 13
10-4	HPLC System	1 1 of 13
13-1 Dynamic Flow Dilution Apparatus	4 of 7
15-1	Data Management and Sample Flow Diagram	2 of 7
16-1	ERG Response/Corrective Action Report Form	7 of 7

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Page
SYMBOLS AND ABBREV IATIONS
AAC
AMTIC
AQS
ASTM
BFB
BLK
BS/BSD
CAA
CAR
CCB
CCV
CFR
coc
C SAT AM
cv
DFTPP
DNPH
DPR
DQOs
DUP
DVD
EPA
ERG
FACA
FB
FC-43
FEM
FID
GC
GPRA
HAPs
He
H2
Atmospheric Analysis and Consulting
Ambient Air Monitoring Technical Information Center
Air Quality Subsystem
American Society for Testing and Materials
4-Bromofluorobenzene
Blank
Blank Spike/Blank Spike Duplicate
Clean Air Act
Corrective Action Report
Continuing calibration blank
Continuing calibration verification
Code of Federal Regulations
Chain of Custody
Community Scale Air Toxics Ambient Monitoring
Coefficient of Variation
Decafl uorotri phenyl phosphi ne
2,4-Dinitrophenylhydrazine
Daily Performance Check
Data Quality Objectives
Duplicate
Digital Versatile Disk
U.S. Environmental Protection Agency
Eastern Research Group, Inc.
Federal Advisory Committee Act
Field Blank
pert! uorotri butyl am i ne
Federal Equivalency Method
Flame Ionization Detector
Gas Chromatograph
Government Performance and Results Act
Hazardous Air Pollutant(s)
Helium
Hydrogen

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Page
Hg
HPLC
HSV
IC
IC
ICAL
ICB
ICP-MS
ICS A/IF A
ICSAB/IFB
ICV
ID
IS (or ISTD)
KED
LCS
LCV
LIMS
LOQ
LRB
m
MB
MDLs
mL
mm
mM
MQOs
MS
MS/MSD
MUR
Hg
|ig/mL
M-g/m3
(.iL
|im
SYMBOLS AND ABBREV IATIONS (Continued)
Mercury
High Performance Liquid Chromatography
High standard verification
Ion Chromatography
Initial Calibration Standards (for ICP-MS)
Initial Calibration
Initial Calibration Blank
Inductively Coupled Plasma/Mass Spectrometer
Interference Check Standard A
Interference Check Standard B
Initial calibration verification
Identification
Internal Standard
Kinetic Energy Discrimination
Laboratory Control Standard
Low Calibration Verification
Laboratory Information Management System
Limit of Quantitation
Laboratory Reagent Blank
Meter(s)
Method Blank
Method Detection Limit(s)
Milliliter
Millimeter
Millimolar
Measurement Quality Objective
Mass Spectrometer
Matrix Spike/Matrix Spike Duplicate
Method Update Rule
Micrograms
Micrograms per milliliter
Microgram per cubic meter
Microliters
Micrometer

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Page
(.ig/mL
N2
NAAQS
NATTS
NELAC
NELAP
NIST
NIOSH
ng
ng/m3
nm
NMOC
NMP
NOx
03
OAQPS
OD
OSHA
PAHs
PAMS
PCBs
PDF
PDFID
PDS
PE
POC
ppbC
ppbv
ppmC
psig
PT
PUF
QA
QAPPs
SYMBOLS AND ABBREV IATIONS (Continued)
Micrograms per milliliter
Nitrogen
National Ambient Air Quality Standard
National Ambient Toxics Trends Stations
National Environmental Laboratory Accreditation Conference
National Environmental Laboratory Accreditation Program
National Institute of Standards and Technology
National Institute for Occupational Safety and Health
Nanogram
Nanogram per cubic meter
Nanometer
Nonmethane Organic Compounds
National Monitoring Program
Oxides of Nitrogen
Ozone
Office of Air Quality Planning and Standards
Outer Diameter
Occupational Safety and Health Administration
Poly cyclic Aromatic Hydrocarbons
Photochemical Assessment Monitoring Stations
Polychlorinated biphenyls
Portable Document Format
Preconcentration Direct Flame Ionization Detection
Post digestion spike
Performance Evaluation
Parameter Occurrence Code
Parts per Billion as Carbon
Parts per Billion by volume
Parts per Million as Carbon
Pounds per square inch gauge
Proficiency Testing
Polyurethane Foam
Quality Assurance
Quality Assurance Project Plan(s)

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Page
QC
QL
RE
RF
RPD
RRF
RRTs
RSD
RT
RTP
SB
SIM
SIP
SNMOC
SOPs
SQL
SRD
SRM
SSQC
STI
svoc
TAD
TSAs
TSP
UAM
UATMP
UPS
UV
VOCs
SYMBOLS AND ABBREV IATIONS (Continued)
Quality Control
Quantitation Limit
Relative Error
Response Factor
Relative Percent Difference
Relative Response Factor
Relative Retention Times
Relative Standard Deviation
Retention Time
Research Triangle Park
Solvent Blank
Selected Ion Monitoring
State Implementation Plan
Speciated Nonmethane Organic Compounds
Standard Operating Procedure(s)
Sample Quantitation Limit
Serial dilution
Standard Reference Material
Second Source Quality Control
Sonoma Technology, Inc.
Semivolatile Organic Compounds
Technical Assistance Document.
Technical System Audits
Total Suspended Particulate
Urban Airshed Model
Urban Air Toxics Monitoring Program
United Parcel Service of America
Ultraviolet
Volatile Organic Compound

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DISTRIBUTION LIST
Copies of this plan and all revisions will be provided to:
•	Jeff Yane, Work Assignment Manager, U.S. EPA, C404-02, RTP, NC
•	Dave Shelovv, Delivery Order Manager, U.S. EPA, C339-02, RTP, NC
•	Greg Noah, AT QA Coordinator, U.S. EPA, C304-06, RTP, NC
U.S. EPA Regional contacts may obtain a copy of the QAPP by contacting the ERG Program
Manager. It is the responsibility of each Regional contact to make copies of the plan for appropriate
State personnel or to refer them to ERG Program Manager. The ERG staff working on this contract
will receive a copy of this QAPP and all revisions.

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PROJECT MANAGEMENT
SECTION 1
PROJECT/TASK ORGANIZATION
1.1 Assignment of Program Personnel
Table 1-1 presents the program organization listing the program assignment and responsible
person for each aspect of the Environmental Protection Agency (EPA) National Monitoring Programs
(NMP). The program organizational chart is presented in Figure 1-1. All Eastern Research Group,
Inc. (ERG) staff working on this contract are provided access to a current electronic copy of this
signed, EPA approved Quality Assurance Project Plan (QAPP).
ERG's primary support on this contract includes Nonmethane Organic Compounds (NMOC),
Speciated Nonmethane Organic Compounds (SNMOC), Volatile Organic Compounds (VOCs),
Poly cyclic Aromatic Hydrocarbons (PAHs), Metals, Hexavalent Chromium, and other Hazardous Air
Pollutants (HAPs). Subcontracting services are extended by Chromlan for on site technical assistance
for Photochemical Assessment Monitoring Stations (PAMS) analysis, Sonoma Technology, Inc.
(ST1) for data validation. Atmospheric Analysis and Consulting, Inc. (AAC) Lab for VOCs by
Method TO-17, pesticides/Polychlorinated biphenyls (PCBs), anions, diisocyanates, and
4,4'-methylenedianiline, and RT1 International for metals analysis, in the event of a large workload.
ERG is responsible to the client for the work of the subcontractor and choosing subcontractors
that meet the applicable requirements for the methods and contracts. The subcontractor should meet
the Data Quality Objectives (DQOs) requirements for the appropriate method. ERG shall maintain a
record of subcontractor compliance, including documentation of subcontractor's Method Detection
Limits (MDLs), QAPPs, etc. Sample analysis will not begin with the subcontractor until MDLs,
QAPPs, etc., have been approved by EPA and ERG. Before sample analysis, the subcontractor may
perform Proficiency Testing (PT) samples and/or Technical System Audits (TS As) if they are
available through Office of Air Quality Planning and Standards (OAQPS). If such measures are not

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available, ERG will request audit reports performed with the subcontract lab and will supply PT
audits if requested by the EPA when analysis is contracted with the laboratory.
1.1.1	Program Manager
Ms. Julie Swift, an ERG Vice President, serves as the Program Manager for EPA's NMP. In
this role, she has the primary responsibility for understanding program level needs, both EPA's and
their clients" (i.e.. State, Local, and Tribal agencies). Ms. Swift is ultimately accountable for
providing timely, cost effective, and high-quality services that meet the needs of the NMP efforts.
Her responsibility is ensuring EPA/client satisfaction by verifying that all components necessary for
effective management are in place and active during the contract performance period. Ms. Swift
coordinates with the ERG Quality Assurance (QA) Officer, and task leaders to provide EPA/client
perspective, communicate technical issues and needs, and ensure the program staff facilitates
decisions appropriate to their roles on Contract EP-D-14-030. She prepares budgetary and schedule
information and prepares all information for presentation to EPA at scheduled program meetings. As
the Program Manager, Ms. Julie Swift is responsible for the technical operation and the quality of the
program on a day-to-day basis. She leads the analytical tasks and provides technical direction and
support. She assists in the resolution of technical issues and serves as a resource for Task Leaders
regarding any project issues. Ms. Swift also performs an overall review of the data that is reported
monthly.
1.1.2	Deputy Program Manager
As the Deputy Program Manager, Ms. Laura Van Envvyck assists the Program Manager for
EPA's NMP. She assists the Program Manager in all aspects of the technical operation and the
quality of the program on a day-to-day basis. She assists the analytical Task Leaders and provides
technical direction and support. She assists in the resolution of technical issues and serves as a
resource for Task Leaders regarding project issues. Ms. Van Envvyck is also the Carbonyl and HAPs
Support Task Leader.

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1.1.3	Program Technical Adviser
The Program Technical Adviser, Mr. Dave Dayton assists in the resolution of technical issues.
He communicates with ERG management and the technical staff for discussion of real and potential
technical problems. He peer reviews draft and final program report products and provides oversight
of efforts to evaluate and characterize data.
1.1.4	Program OA Coordinator
Ms. Donna Tedder, the Program and Laboratory QA Coordinator, is responsible for ensuring
the overall integrity and quality of project results. Ms. Tedder, or her designee, will do a 10 percent
QA review for all sample analyses delivered for reporting by the Program Manager. In the case of
subcontracted work, 20 percent of data from subcontractor will be reviewed. The lines of
communication between management, the Program QA Coordinator, and the technical staff are
formally established and allow for discussion of real and potential problems, preventive actions, and
corrective procedures. The key Quality Control (QC) responsibilities and QC review functions are
summarized in Table 1-2. On major quality issues, Ms. Tedder reports independently to Ms. Jan
Connery, ERG's corporate QA Officer.
1.1.5	Deputy Program QA Coordinator
The Deputy Program QA Coordinator, Ms. Jennifer Nash, is responsible for ensuring the
integrity and quality of project results. The Deputy QA Coordinator will assist the Program QA
Coordinator with the QA review for sample analyses delivered for reporting by the Program
Manager. The major QC responsibilities and QC review functions are summarized in Table 1-2. The
Deputy QA Coordinator will work closely with the Program QA Coordinator to ensure the overall
quality of the Program.

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1.1.6 Task Leaders
ERG Task Leaders are responsible for meeting the project objectives, meeting report
schedules, and directing the technical staff in execution of the technical effort for their respective
task(s). The Task Leaders will review 100 percent of all sample analyses. The Program QA
Coordinator will request 10 percent of that data for review prior to data reporting by the Program
Manager. The Task Leaders manage the day-to-day technical activities on delivery orders for this
program. They assess and report on the project's progress and results (e.g., recordkeeping, data
validation procedures, sample turnaround time) and ensure timely, high-quality services that meet the
requirements in this QAPP.

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Table 1-1
Program Organization
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Program Assignment
Program Personnel Assigned
Phone Number
Email Address
Program Manager
Julie Swift
(919)468-7924
inlie
Deputy Program Manager
Laura Van Enwyck
(919)468-7930
l.niin i nuorv, rkfi'erg.eoiii
Task Leader - Network Site Coordination
Randy Bower
(919)468-7928
i.incb b^YUTi?, crs.com
Task Leader - Shipping and Receiving
Randy Bower
(919)468-7928
randv. bowerfo),erg .com
Task Leader - Air Toxics
Randy Bower
(919)468-7928
randv. bowerfoierg .com
Task Leader - Carbonyl Analysis
Laura Van Enwyck
(919)468-7930
l.iinj.vimeii\\\ ck®ere.com
Task Leader - Hexavalent Chromium
Glenn Isom
(919)468-7940
2lenn.1somficr2.com
Task Leader - Metals
Randy Mercurio
(919)468-7922
randy. mercurio filerg. com
Task Leader - NMOC Analysis
Mitchell Howell
(919)468-7915
mitch. howell (Stare .com
Task Leader - Semivolatiles
Scott Sholar
(919)468-7951
scott. sholarfiiere.com
Task Leader - SNMOC Analysis
Mitchell Howell
(919)468-7915
mitch. ho wellfiere .com
Task Leader - PAMS Support *
Julie Swift
(919)468-7924
iulie.swift(3lerg.com
Task Leader - HAPs Support **
Laura Van Enwyck
(919)468-7930
laiira.vaneirwyekfiie:
Task Leader - Data Characterization
Regi Oommen
(919)468-7829
reei. oommenfiterg.o
Task Leader - Annual Report/AQS Entry
Jaime Hauser
(919)468-7813
iaime.haiiser@erg.com
Program Technical Adviser
Dave Dayton
(919)468-7883
dave. day toiifiierg .com
Program QA Coordinator
Donna Tedder
(919)468-7921
donna, tedderfiierg .com
Deputy QA Coordinator
Jennifer Nash
(919)468-7881
i etmifer.na shfiere .com
Project Administrator
Kerry Fountain
(919)468-7962
:ainfi)erg.com
~Subcontracting support when requested from Chromian and Sonoma Technology. Inc.
~~Subcontracting support when requested from AAC and RTI International (miscellaneous H APs).

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Deputy Program Manager
Laura Van Enwyck
Project Administrator
Kerry Fountain
EPA Project Officer
JeffYane
Contracts Manager
Serena Vetere
Program Manager
Julie Swift
Program Technical Advisor
Dave Dayton
EPA QA Officer
Greg Noah
Air Toxics Analysis
Task Lead
Randy Bower
SNMQC Data Analysis
Task Lead
Mitchell Howell
Metals Analysis
Task Lead
Randy Mercuric
Shipping^ Receivini
Task Lead
Randy Bower
Data Characterization
Task Lead
RegiOommen
Carbonyl Analysis
Task Lead
Laura Van Enwyck
NMOC Analysis
Task Lead
Mitchell Howell
Subcontractors
AACLab
RTI International
Subcontracted HAPs
Task Lead
Laura Van Enwyck
EPA Delivery Order Manager
DaveShelow
Subcontractors
Chramian
Sonoma Technologies, Inc.
QA Audit & PAMS Support
Task Lead
Julie Swift
Annual Reports/AQS Entry
Task Lead
Jaime Hauser
Network Site Coordination
Taskbead
Randy Bower
Semiwolatile (PAH) Analysis
Task Lead
Scott Sholar
Hexavalent
Chromium Analysis
Task Lead
Glennlsom
Program QA Coordinator
DonnaTedder
Deputy QA Coordinator
Jennifer Nash
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Figure 1-1. National Monitoring Programs Organizational Chart

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Table 1-2
QC Responsibilities and Review Functions
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Responsible Person
Major Responsibilities
Ms. Julie Swift,
Program Manager
•	Ensure overall timely performance of high quality technical services
•	Communicate technical issues and needs
•	Assist in the resolution of technical problems
•	Track all management systems and tools
•	Track deliverables and budget performance
•	Ensure appropriate level of staffing and committed resources exist to
perform work
•	Communicate daily with the EPA/State/Local/Tribal agencies
•	Ensure data quality
•	Check information completeness
•	Review data completeness and quality before reporting to client
•	Review all reports
•	Report project performance (budget and deliverables) to EPA at
scheduled meetings and in monthly progress reports
•	Day-to-day management of task leaders
Ms. Laura Van Enwyck,
Deputy Program
Manager
•	Assist Program Manager where needed
•	Ensure overall timely performance of high quality technical services
•	Communicate technical issues and needs
•	Assist in the resolution of technical problems
•	Ensure appropriate level of staffing and committed resources exist to
perform work
•	Communicate with the EPA/State/Local/T ribal agencies
•	Ensure data quality
•	Check information completeness
•	Review data completeness and quality before reporting to client
•	Day-to-day management of task leaders
Mr. Dave Dayton,
Program Technical
Adviser
•	Assist in the resolution of technical problems
•	Communicate potential technical issues and needs
•	Review draft and final data reports
Ms. Donna Tedder.
Program QA
Coordinator
•	Make QA recommendations
•	Review QAPP
•	Audit laboratory
•	Review QA reports
•	Evaluate the effect of technical issues on data quality
•	Review 10% of all data for reporting
•	Review documentation (SOPs. reports, etc.)

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Table 1-2
QC Responsibilities and Review Functions (Continued)
Responsible Person
Major Responsibilities
Ms. Jennifer Nash,
Deputy Program QA
Coordinator
•	Assist QA Coordinator where needed
•	Make QA recommendations
•	Review QAPP
•	Assist with laboratory audit(s)
•	Evaluate the effect of technical issues on data quality
•	Review 10% of all data for monthly reporting
•	Review documentation (SOPs. reports, etc.)
Task Leader*s)
•	Review documentation
•	Review 100% of analytical data generated by analysts
•	Develop analytical procedures
•	Propose procedural changes
•	Train and supervise analysts
•	Meet task report schedules
•	Manage day-to-day technical activities
•	Check information completeness
•	Review instrument and maintenance log books
•	Review calibration factor drift
•	Perform preventive maintenance
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SECTION 2
PROBLEM DEFINITION/BACKGROUND
The Clean Air Act (CAA) Amendments of 1990 required EPA OAQPS to set National
Ambient Air Quality Standard (NAAQS) for the "criteria" pollutant ozone (O3). In areas of the
country where the N A AQS for O3 was being exceeded, additional measurements of the ambient
NMOC were needed to assist the affected States in developing/revising O3 control strategies.
Measurements of ambient NMOC are important to the control of VOCs that are precursors to
atmospheric O3. Due to previous difficulty in obtaining accurate NMOC concentration
measurements, EPA started a monitoring and analytical program in 1984 to provide support to
the States. ERG has continuously supported EPA for the NMOC programs since 1984.
In 1987, EPA developed the Urban Air Toxics Monitoring Program (UATMP) to help
State, Local and Tribal air monitoring agencies characterize the nature and extent of potentially
toxic air pollution in urban areas. Since 1987, several State and local agencies have participated
in the UATMP by implementing ambient air monitoring programs. These efforts have helped to
identify the toxic compounds most prevalent in the ambient air and indicate emissions sources
that are likely to be contributing to elevated concentrations. Studies indicate that a potential for
elevated cancer risk is associated with certain toxic compounds often found in ambient urban
air(1). As a screening program, the UATMP also provides data input for models used by EPA,
State, local and risk assessment personnel to assess risks posed by the presence of toxic
compounds in urban areas. The UATMP program is a year-round sampling program, collecting
24-hour integrated ambient air samples at urban sites in the contiguous United States every 6 or
12 days.
The SNMOC program was initiated in 1991 in response to requests by State agencies for
more detailed speciated hydrocarbon data for use in O3 control strategies and Urban Airshed
Model (UAM) input.

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Title I, Section 182 of the CAA Amendments of 1990 requires States to establish PA MS
as part of their State Implementation Plan (SIP) for O3 nonattainment areas. The rule revises the
ambient air quality surveillance regulations to include enhanced monitoring of O3 and its
precursors. The regulations promulgated in 1993 require monitoring of O3, oxides of nitrogen
(NOx), selected carbonyl compounds, and VOCs. The required monitoring is complex and
requires considerable lead time for the agencies to acquire the equipment and expertise to
implement their PA MS network. Under the PA MS program, each site may require a different
level of support with respect to sampling frequency, sampling equipment, analyses, and report
preparation. Presampling, sampling, and analytical activities are performed according to the
guidance provided in the Technical Assistance Document (TAD)'2', for Sampling and Analysis
of Ozone Precursors, 1998 revision. The program objective of PAMS is to provide data that are
consistent with the proposed rule for ambient air quality surveillance regulations in accordance
with Code of Federal Regulations Title 40, Part 58 (40 CFR Part 58). The ERG team offers site
support to any State that needs to set up a PAMS site and/or provide technical help. The specific
analytical methodology applicable to the PAMS program will be discussed in this QAPP.
In 1999, EPA expanded this program to provide measurements of additional C A A H APs
to support the Government Performance and Results Act (GPRA). As required under the GPRA,
EPA developed a Strategic Plan that includes a goal for Clean Air. Under this goal, there is an
objective to improve air quality and reduce air toxics emissions to levels 75 percent below 1993
levels by 2010 in order to reduce the risk to Americans of cancer and other serious adverse
health effects caused by airborne toxics.
In 2001, EPA designed a national network for monitoring air toxics compounds present
in ambient air entitled the National Ambient Toxics Trends Station (NATTS). The primary
purpose of the NATTS network is tracking trends in ambient air toxics levels to facilitate
measuring progress toward emission and risk reduction goals. The monitoring network is
intended for long term operation for the principle purpose of discerning national trends in air
toxics ambient concentrations.

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Beginning in 2003/2004, EPA conducted periodic Community Scale Air Toxics Ambient
Monitoring (CSATAM) grant competitions. The resultant 1- to 2-year grants are designed to help
State, Local, and Tribal communities identify and profile air toxics sources, characterize the
degree and extent of local air toxics problems, and track progress of air toxics reduction
activities. Grants have been awarded across the United States, in large, medium, and small
communities. The ERG team can offer site support and analysis to any agency for the UATMP,
NATTS and CSATAM programs.
The data obtained by following this QAPP will be used by EPA, State, Local, Tribal and
risk assessment personnel to determine prevalent O3 precursors and air toxics in the urban air.
The data collected from the continuous yearly sites gives the data analyst consistent high quality
analytical results. Sampling and analytical uncertainties are determined through this program by
performing 10 percent sampling duplicate (or collocated) and analytical replicate samples for
each of the ambient air sites.
This QAPP defines the preparation, sampling, laboratory analyses and QA/QC
procedures conducted by ERG for EPA's NMP to deliver data of sufficient quality to meet the
programs" objectives. Many of these procedures described in this QAPP are based on
experiences obtained during previous National Program Studies.

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SECTION 3
PROJECT/TASK DESCRIPTION
This section describes the activities performed under each of the major EPA NMP
components (NMOC, SNMOC, UATMP, CSATAM, NATTS, and PAMS). ERG dedicates
passivated canisters, sampling equipment and expendable sampling media to the program to
maintain known quality that meets the program objectives. An applicable measurement methods
list is presented in Table 3-1. Sampling and analysis are determined when delivery orders are
provided by EPA.
3.1 PAMS, NMOC and SNMOC
The program objective of PAMS is to provide data that are consistent with the proposed
rule for Ambient Air Quality Surveillance in accordance with 40 CFR Part 58. The ERG team
can offer site support to any State that needs to set up a PAMS site and/or maintain it with
technical help. Canister and/or carbonyl samples are collected typically every 3 days by
State/Local/or Tribal agency personnel starting on the first of June through the end of September
at each of the designated sites.
The NMOC and SNMOC programs require collection of ambient air samples over a
3-hour period. This sample collection period occurs from 6:00 - 9:00 a.m. local time to capture
mobile source pollutants during the morning "rush hour" simultaneously with sunrise, which
provides the energy necessary for many photochemical reactions. Weekday sampling will be the
responsibility of the individual States involved in this program. Canister and/or carbonyl samples
are collected by State/Local/or Tribal agency personnel every weekday, typically starting on the
first Monday of June through the end of September at each of the designated sites.
ERG can provide sampler, sampler training, and any technical assistance needed
throughout the monitoring program. At least one week before each sample collection episode,
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with the field chain of custody (COC) forms. The time-integrated ambient samples are then
collected and shipped to ERG for analysis.
3.2 UATMP, NATTS and C SAT AM
The UATMP program was initiated as an analytical/technical support program focused
on ascertaining ambient air levels of organic toxic species. The program has since expanded to
provide for the measurement of additional HAPs and the standard sample collection frequency
was increased to 1 in 6 days, with some sites continuing at 1 in 12 days.
The NATTS Network is intended for long term operation for the principle purpose of
discerning national trends. The primary purpose of the NATTS network is tracking trends in
ambient air toxics levels to facilitate measuring progress toward emission and risk reduction
goals. The monitoring network is intended to be able to detect a 15 percent difference (trend)
between two successive 3-year annual mean concentrations within acceptable levels of decision
error. The standard sample collection frequency is 1 in 6 days.
The program objective of the C SAT AM Program is designed to help State, Local, and
Tribal communities identify and profile air toxics sources, characterize the degree and extent of
local air toxics problems, and track progress of air toxics reduction activities. Grants have been
awarded across the entire United States, in large, medium, and small communities. Awarded
grants fall into one of three categories: community-scale monitoring, method
development/evaluation, and analysis of existing data. The sample collection frequency may be
1 in 6 days or 1 in 12 days. Targeted pollutants generally reflect the NATTS core compounds,
criteria pollutants, and/or pollutants related to diesel particulate matter.
The ERG team can offer site support and analysis to any State that needs VOC, carbonyl,
or other analyses for the PA MS, UATMP, NATTS and CSATAM programs, as shown in
Table 3-1. Relevant Standard Operating Procedures (SOPs) are also referenced in the table.

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Table 3-1
List of Analytical and Support Services


SOP
Analysis
Based on Method
(ERG-MOR-
XXX)
Analysis
Total NMOC
TO-12®
-060
Speciated NMOC/PAMS Hydrocarbons via
GC/FID
TAD for O/one Precursors':'
-005
VOCs via GC/MS
TO-15'4'
-Qp5
Concurrent SNMOC and VOC via GC/MS/FID
TAD for O/one Precursors': /TO-15':4i
-005
Carbonyls via HPLC
TO-11 A:5:
-024
PMio HAP Metals via ICP-MS
IO-3.5(6)/EQL-0512-201 (7V
EQL-0512-202'Si
-095
TSP Hexavalent Chromium via IC
ASTM D7614(9)
-063
SVOC analysis via GC/MS (SCAN)
TO-13A(10) / Method 8270D(n>
-044***
PAH analysis via GC/MS (SIM)
TO-13A(10) / ASTM D6209-13(12)
-049
PCB/Pesticides via GC *
TO-4A(13)
*
Anions via IC *
NIOSH 7903(14) **
*
VOCs via GC/MS (from cartridge) *
TO-17(15)
*
Diisocyanates *
OS H A Methcxl 42^16)
*
4.4"-Meth\ lenedianiline *
NIOSH Methcxl 5029<17)
*
Site Support
NMOC/SNMOC
TAD for O/one Precursors'
-046***
VOC
TO-15 4
-003 or -021
Carbonyls
TO-11 A'S|
-003 or-047
Hexavalent Chromium
ASTM D7614-12(9)
-013
PA MS Technical
NA
NA
PA MS QA
NA
NA
Other Services
Performance Samples for VOC
TO-15 4
-061
Performance Samples for Carbonyls
TO-11 A'S|
-024
Performance Samples for PAH
TO-13A(10) / ASTM D6209-13(12)
-049
Performance Samples for PM10 HAP Metals
IO-3.5 (6)/EQL-0512-201(7)/
EQL-0512-202'Si
-095
Performance Samples for TSP Hexavalent
ASTM D7614-12(9)
-063
Chromium


Sampler Certification for Carbonyls
TO-11 A'S|
-100
Sampler Certification for VOC
TO-15 4
-030
Uniform Calibration Standards
TO-15 4
-061
AQS Data Entry (per pollutant group)
NA
-098
Report Development/Data Characterization
NA
NA
* Will be supplied by subcontractor when analysis is requested.
**NIOSH Method 7903 was replaced with 7906, 7907 and 7908.
***SOP is currently archived but will be updated if needed for sample analysis.

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ERG can provide sampler, sampler training, and any technical assistance needed
throughout the monitoring program. Canister and/or carbonyl samples are collected by
State/Local/or Tribal agency personnel every 6 or 12-days at each of the designated sites. At
least one week before each sample collection episode, ERG ships the necessary clean, certified
canisters and/or carbonyl cartridges to the site along with the field COC forms. The time-
integrated ambient samples are then collected and shipped to ERG for analysis.
ERG then prepares the program data for a final annual report describing sampling and
analysis procedures, results, discussion of results, compilation of statistics, and
recommendations. To determine the overall precision of analysis for the programs, replicate
analyses (10 percent of the total number of samples) are used following the schematic shown in
Figure 3-1. After the final data report receives approval by the EPA Project Officer and Delivery
Order Manager, ERG distributes the final report to designated recipients. ERG provides the final
data summaries to the associated agencies electronically in Excel® and Adobe* formats. ERG
staff finalizes and uploads the data into the Air Quality Subsystem ( AQS) database.
Figure 3-1. Duplicate/Collocate and Replicate Analysis Schematic
Primary
Sample
(Designated
D1 or C1)
Duplicate or
Collocate
Sample
(Designated
D2 or C2)
Replicate
Analysis of
Primary
Sample (R1)
Replicate
Analysis of
Duplicate or
Collocate
Sample (R2)

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SECTION 4
DATA QUALITY OBJECTIV ES AND CRITERIA FOR MEASUREMENT DATA
As ERG performs measurement services only, DQOs for defining a toxics network
program are not identified in this QAPP. A well-prepared description of the Measurements
Quality Objectives (MQOs) can be found in the TAD for the NATTS Program prepared for EPA
in October 2016(18). This section will discuss the MQOs of the ERG laboratory analyses,
emphasizing the levels of uncertainty the decision maker is willing to al low/accept from the
analytical results. The DQOs for the four programs - NMOC, UATMP, PAMS, and CSATAM -
are similar but are not identical. Therefore, the programs are discussed separately.
The NATTS TAD presents the requirements for collecting and reporting data for the
NATTS network. Eighteen compounds have been identified as major risk drivers based on a
relative ranking performed by EPA and have been designated as NATTS Core or "Tier I"
compounds. All other reported compounds, for any NMP, are considered compounds of interest,
but do not necessitate the NATTS MQOs. The Tier I compounds are acknowledged throughout
this document. ERG exemptions from the NATTS TAD are listed in Appendix A.
Once a DQO is established, the quality of the data must be evaluated and controlled to
ensure that data quality is maintained within the established acceptance criteria. MQOs are
designed to evaluate and control various phases (sampling, preparation, analysis) of the
measurement process to ensure that the total measurement uncertainty is within the range
prescribed by the DQOs. MQOs can be defined in terms of the following data quality indicators:
Precision - a measure of mutual agreement between individual measurements performed
according to identical protocols and procedures. This is the random component of error.
Bias - the systematic or persistent distortion of a measurement process that causes error in
one direction. Bias is determined by estimating the positive and negative deviation from
the true value as a percentage of the true value.

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Representativeness - a measure of the degree to which data accurately and precisely
represent a characteristic of population, parameter variations at a sampling point, a
process condition, or an environmental condition.
Detectabilitv - the determination of the low range critical value of a characteristic that a
method-specific procedure can reliably discern.
Completeness - a measure of the amount of valid data obtained from a measurement
system compared to the amount that was expected to be obtained under correct, normal
conditions. Data completeness requirements are included in the reference methods (see
References, Section 21).
Comparability - a measure of the level of confidence with which one data set can be
compared to another.
Bias has been the term frequently used to represent closeness to "truth" and includes a
combination of precision and bias error components. The MQOs listed will attempt to separate
measurement uncertainties into precision and bias components. Table 4-1 lists the MQOs for
pollutants to be measured in all areas of the UATMP, NATTS, C SAT AM, PAMS, and NMOC
program.
Analytical Precision is calculated by comparing the differences between Replicate
analyses (two analyses of the same sample) from the arithmetic mean of the two results as shown
below. Replicate analyses with low variability have a lower Relative Percent Difference (RPD)
(better precision), whereas high variability samples have a higher RPD (poorer precision).
*1 -*2
RPD = - x 100
Where:
Xi = Ambient air concentration of a given compound measured in one sample;
X; = Concentration of the same compound measured during replicate analysis;
X = Arithmetic mean of Xi and X:.

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Method precision is calculated by comparing the concentrations of the
duplicates/col 1 ocates for each pollutant. The Coefficient of Variation (CV) calculation shown
below is ideal when comparing paired values, such as a primary concentration versus a duplicate
concentration.

CV = 100 x
O - r)
0.5 x (p + r)_
2 n
Where:
p = the primary result from a duplicate or collocated pair;
r = the secondary result from a duplicate or collocated pair;
n = the number of valid data pairs (the 2 adjusts for the fact that there are two
values with error).

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Tier I. see
NATTSTAD
Table 4.1-1
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0.0038 ng/m3
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>85%
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GC-PDFID
EPA Compendium
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GC-FID
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analysis of
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(RPD)
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determined upon
need
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determined upon
need
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determined upon
need
Completeness
>85%
>85%
>85%
>85%
>85%
>85%
Bias
± 25%
± 25%
± 25%
± 25%
± 25%
± 25%
Comparability/
Based on Method
GC/MS
EPA Compendium
Method TO-13A(10)
and ASTM D6209-
13(12), (or SW-846
Method 8270D(11))
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cartridge
Diisocyanates
4,4'-
Methylene-
dianiline

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SECTION 5
SPECIAL TRAINING REQUIREMENTS/CERTIFICATION
The activities of EPA's NMP are performed using accepted EPA, National Institute for
Occupational Safety and Health (NIOSH), and Occupational Safety and Health Administration
(OSHA) sampling and analytical protocols for the field sampling training personnel and
analytical laboratory staff.
5.1 Field Activities Training Personnel
Field activities training personnel involved in this project have over 30 years of
experience in the duties they will be performing in the field. The training of ERG field activities
personnel is recorded in the ERG Training Records files. Special certification is not needed for
an operator to set up the sampling systems. Each State should document and record the training
of their personnel on the field testing procedures provided by ERG.
The States" field testing staff will be subject to on-site surveillance by EPA. ERG's Task
Leader will provide appropriate corrective action enforcement, if necessary, for the ERG
personnel setting up the sampling equipment and the field testing staff. ERG provides on-the-job
training in the field on sampler use and maintenance, for supervisors and field site operators. The
appropriate SOPs used during training are presented in Appendix C. ERG does not provide SOPs
for sampling systems that are not maintained by ERG. Sampling System Training forms used
during operator training in the field is presented in Figure 7.2 for VOC/Carbonyl and Carbonyl
samplers. The forms will only be provided when new site personnel are trained on the sampling
systems. After training is completed and signed in the field, the yellow copy is retained for site
records. The original copy is scanned in the laboratory and stored by the QA coordinator.
The sampling equipment for monitoring sites may be inside a sampling building or
outside. There are no hazards inherent to the samplers and no special safety training or
equipment will be required. Site hazards should be addressed on a site-by-site basis by the site

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operator"s SOPs. All ERG field activities training personnel will follow the ERG Corporate
Health and Safety Plan.
5.2 Analytical Laboratory Personnel
Analytical laboratory personnel involved in this project have been trained in their tasks
and have up to 30 years of experience in the duties they will be performing in the analytical
laboratory. Training of ERG laboratory personnel is recorded in ERG Training Records in an
Excel® database and filed as a hardcopy. It is the responsibility of the trainee and the laboratory's
Project Administrator to keep the Training Records up to date. It is the responsibility of the
Program Manager and Quality Assurance Coordinator to approve analysis training records.
Normal training and overview is provided to the analyst by the Task Leader for that analysis.
Technical training includes general techniques and specific training based on the appropriate
SOP, method, and program QAPP. The trainee first observes the task, then performs the task
under supervision of the trainer, then performs the task under supervision of the Task Lead (if
the Task Lead is not the trainer). After training, demonstration of each personnel's ability to
perform an analytical task involves repeated measurements of a standard, which is described in
more detail in each analytical SOP. Currently, no special certifications are needed for the
analysis of the ambient samples received for these programs.
ERG maintains appropriate SOPs for each of the analytical methods. These SOPs are
presented in Appendix C. All SOPs document equipment and/or procedures required to perform
each specific laboratory activity. Laboratory staff will be subject to on-site surveillance by the
QA staff and periodic performance evaluation (PE) samples. These audits will assure the
program that the appropriate analysts and analytical procedures are being used. The samples
involved in this program are generated by monitoring air emissions. Health and Safety training is
performed annually. The laboratory personnel will adhere to the ERG Corporate Health and
Safety manual.

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SECTION 6
DOCUMENTATION AND RECORDS
The EPA NMP are a collection of individual ambient monitoring programs that generate
documents and records that need to be retained/archived. All ERG staff working on this contract
are provided access to a current electronic copy of this signed, EPA approved QAPP. Annually,
the staff is required to sign a form to document that they read and understood the QAPP. In this
QAPP, ERG's reporting package (information required to support the analytical results) includes
all data required to be collected as well as support data deemed important by ERG/EPA.
6.1	Data Management
ERG has a structured records management system that allows for the efficient archive
and retrieval of records. Each laboratory archives the data from the computer systems onto the
shared network drive. The laboratory paper copies of all analyses are stored on site in a secured
temperature-control 1 ed area for up to five years after the close of the contract. The laboratory
also archives the data in the Laboratory Information Management System (LIMS) data server
which is backed up weekly, monthly, and biannually. The Program Manager has final authority
for the storage, access to, and final disposal of all records kept for the EPA NMP.
6.2	Preliminary Monthly Data Reports
Preliminary monthly summary data reports are sent in Adobe Portable Document Format
(PDF) and Excel formats to EPA and appropriate State/Local/Tribal agencies. The monthly data
reports will include analytical results, associated MDL, final units, associated QC samples, and
data qualifiers.

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6.3	Quarterly QA Report
A QA report for each type of data analysis is sent to EPA and appropriate
State/Local/Tribal agencies on a quarterly basis in the form of control charts including initial
calibration verifications, continuing calibration verifications, method blanks, initial calibration
blanks, continuing calibration blanks, and blank spikes.
6.4	Annual Summary Reports Submitted to EPA
Hard copies of the final report are presented to EPA contacts at the end of the sampling
period. State/Local/Tribal agencies receive electronic copies (i.e., PDF). The final report is
submitted for the data collected from January 1 to December 3 1 of the previous year. The report
can contain the following information:
•	Names of participating sites and corresponding metadata information, including city
name, location and the AQS codes;
•	Description of the sampling and analytical methodologies used by the laboratory;
•	Completeness of the monitoring effort for each site;
•	Background information on the methodology used to present and analyze the data;
•	General combined and individual site summary of the year's results;
•	Discussion of different trends for the select H APs chosen for analysis;
•	Risk screening evaluations using toxicity factors (e.g., UREs or RfCs);
•	Variability analysis (intra-site and seasonal comparisons);
•	Pollution roses to determine predominant direction for select compounds;
•	Discussion of precision and accuracy and other prevalent QC concerns; and
•	Yearly discussions of conclusions and recommendations.

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If corrections are needed after the final report is presented to EPA, the report is easily
retrieved, and corrections are sent to all relevant personnel.
6.5 Records and Supporting Data
All raw data required for the calculation of air toxics concentrations, submission to the
EPA/AQS database, and QA/QC data are collected electronically or on data forms that are
included in the field and analytical methods sections. All hardcopy information is filled out in
indelible ink. Corrections are made by inserting one line through the incorrect entry, initialing
the correction (ERG maintains a signature log), and placing the correct entry alongside the
incorrect entry, if this can be accomplished legibly, or by providing the information on a new
line. Table 6-1 presents the location of the data records for field and laboratory operations stored
at the ERG laboratory.
Table 6-1. Data Documentation and Records
Item
Record
Short Term
Location Storage
Long Term
Location Storage
Field Operations
Sampling System Training
Sampling System
Training Form
ERG
Copy scanned and
hardcopy stored
by ERG
coc
ERG C OCs
Field gets "pink"
copy, ERG gets
"yellow" and
"white" copy
Copy scanned and
stored on ERG
LIMS
QC Sample Records (field blanks,
duplicate/ collocated, sample integrity,
etc.)
COC
Field
Copy scanned and
stored on ERG
LIMS
General Field Procedures
COC
Field
Copy scanned and
stored on ERG
LIMS
Laboratory Records
Sample Prep Data
Bench sheets
Hardcopy filed.
LI MS. shared
network drive
Hardcopy
archived. LIMS,
shared network
drive

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Table 6-1. Data Documentation and Records, Continued
Item
Record
Short Term
Location
Storage
Long Term
Location Storage
Laboratory Operations
Sample Management Records (sample
receipt, handling, storage, etc.)
COCs
LI MS. with
sample analytical
data
LI MS. with
sample analytical
data
Test Methods
SOPs
Hardcopy filed,
shared network
drive
Shared network
drive
QA/QC Reports (General QC records,
MDL information, calibration, etc.)
Individual records for
each analysis
Hardcopy filed,
shared network
drive
Hardcopy
archived, shared
network drive
Corrective Action Reports
Individual records for
each analysis
Hardcopy filed, a
copy in data
package if
appropriate
All copies
archived
Data Reduction, Verification, and Validation
Electronic Data (used for reporting and
AQS)
Excel® and Access®
Shared network
drive
Shared network
drive
6.5.1 Notebooks
ERG issues laboratory notebooks upon request. These notebooks are uniquely numbered
and associated with the laboratory personnel. Notebooks are archived upon completion for at
least 5 years from the end of a project. Although L1MS data entry forms are associated with all
routine environmental data operations, the notebooks can be used to record additional
information about these operations. The procedures for maintaining notebooks are presented in
SOP for Maintaining Laboratory Notebooks (ERG-MOR-039) in Appendix C.
Field Notebooks - Field notebooks are the responsibility of EPA, States, Local or Tribal
agencies as ERG is not responsible for the collection of samples.
Laboratory Notebooks - Notebooks are associated with general procedures such as
calibration of analytical balances, standard preparation logs, etc., used in this program.

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Logbooks are generated and bound by the laboratory's Project Administrator for
procedures such refrigerator/freezer temperatures, canister cleaning, etc. Logbook pages have a
unique version identifier. Upon completion, logbooks are archived indefinitely, at a minimum at
least 5 years from the end of a project.
6.5.2 Electronic Data Collection
To reduce the potential for data entry errors, automated systems are utilized (where
appropriate) and record the same information that is found on data entry forms. In order to
provide a back-up, hardcopy data collected on an automated system will be stored for 5 years
after the end of the closed EP A NMP contract.
6.6	Data Reporting Package Archiving and Retrieval
In general, all the information listed above will be retained for at least 5 years from the
date of the end of the closed contract with EPA. However, if any litigation, claim, negotiation,
audit, or other action involving the records has been started before the expiration of the 5-year
period, the records will be retained until completion of the action and resolution of all issues
which arise from it, or until the end of the regular 5-year period, whichever is later. The long-
term storage is on-site in a locked climate-controlled file room with limited-access. The Project
Administrator keeps a record of documents entering and leaving long-term storage. Access to the
facility storage area is limited to authorized personnel only.
6.7	Quality System Document Control
To ensure the use of the most current version of quality system documents, all quality
documents (QAPP, SOPs, etc.) generated at the ERG Laboratory must be uniquely identified.
Original documents shall include the date of issue, revision number, page number, the total
number of pages, and appropriate signatures. Copies of quality documents shall be controlled
and include the date of issue, revision number, page number, the total number of pages, and copy

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control number. When an original quality document is updated, the QA Coordinator or designee
will ensure that the copy documents are also updated, and old versions are destroyed. During the
project, revised QAPPs will be circulated to appropriate EPA personnel and ERG's laboratory
staff. For copies of documents out of the laboratory's control, a stamp or watermark stating
"Uncontrolled" or "Draft", if applicable, will be applied. Each approved QAPP will be posted on
EPA's Ambient Air Monitoring Technical Information Centers (AMTIC) Website without the
associated SOPs.

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MEASUREMENT DATA ACQUISITION
SECTION 7
SAMPLING PROCESS DESIGN
Sampling procedures for the NMOC, SNMOC, UATMP, NATTS, and C SAT AM
programs are discussed in this section. ERG provides site-specific support for the PA MS and
HAPs sampling. All parameters listed in this section are necessary for the sampling systems
listed below. ERG is not responsible for the collection of samples nor the design of these
programs.
7.1 NMOC and SNMOC Canister Samplers
Sampling for NMOC and SNMOC takes place each workday from the beginning of June
to the end of September at designated NMOC and SNMOC sites from 6:00 a.m. to 9:00 a.m.
local time. Sampling procedures have been discussed in detail in other documents.(1,2)
Figure 7-1 is a diagram of the ERG sampling system used for collecting the ambient air samples.
Clean, evacuated passivated stainless-steel canisters are shipped daily from ERGs Research
Triangle Park (RTF) Laboratory to the NMOC and SNMOC sites. Canisters are connected to the
sampling system by local operators. The digital timer automatically activates the pump and
solenoid valve to start and stop sample collection. The pump pressurizes air samples during the
sampling period to about 15 pounds per square inch gauge (psig), and the flow control valve
(variable orifice) ensures a constant sampling rate over the 3-hour period. A 2-micron stainless
steel filter is installed in the sampling line to remove particulate from the ambient air that may
damage or plug the variable orifice. The sample probe inlet is positioned from 2 to 10 meters (m)
above ground level.
ERG installs the sampling systems at the site location and trains associated local
operators on site. Operator training is documented on the Sampler Training Form (Figure 7-2). It
is the responsibility of the local operators to operate the sampling apparatus and complete the
field sample COC form that ERG supplies with each canister. ERG staff maintain telephone

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Inlet to Sample Manifold or
Direct to Atmosphere
Sample Line
Bellows
Valve
Flow
Control
Valve
Duplicate
Sample
Canister
Bellows
Valve
Sample
Rotameter
Primary
Sample
Canister
Receptacle
Outlet
(Optional Use)
Channel 2
Channel 1
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Figure 7-1. NMOC, SNMOC, and 3-Hour Air Toxics Sampling System Components

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VOC/Carbonyl Sampling System Training
Installation Date:	Trainer:
Site ID: 		Copy of SOP on Site: (Y/N)
Installed Sampler ID #:	Replaced Sampler ID #:
Time Set:	Carb Line Replaced: (Y/N)
Timer Set:	VOC Line Replaced: (Y/N)
Trainee:	Signature:	Date:
NOTES:
ERG assumes no personal and/or property liability realized by the user from the use of ERG provided
equipment. The user, by virtue of accepting the ERG equipment for use, undertakes any/all personal and/or
property liabilities that could be associated with its use (including operational, housing, and/or safety).
Figure 7-2. VOC/Carbonyl Sampler Training Form

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and/or email contact throughout the project to provide whatever assistance is needed to resolve
technical issues that arise during the sampling program.
For a 3-hour ambient air sample, NMOC, SNMOC, and VOC measurements may all be
performed from the same canister. Refer to Section 7.2 for sampler certification.
7.2 VOC and Carbonyl 24-Hour Samplers
ERG provides the sites with a sampling schedule each year. A total of 3 1 sampling days
will be scheduled per site for a 12-day sampling schedule and 61 sampling days for the 6-day
sampling schedule. Days for duplicate (or collocated) sampling will also be designated. The
2018 Sampling calendar is presented in Appendix B
Prior to installation of an ERG sampler at a UATMP, NATTS or CSATAM site, the
sampler is certified at the ERG laboratory. Certification establishes that the system is functioning
correctly and provides for the appropriate level of specified compound recovery and cleanliness.
To certify the sampling system, cleaned, humidified nitrogen (N2) is first flushed through the
sampler for at least 24 hours to remove the potential for organic contaminants in the system. The
canister sub-system of the samplers is then challenged with a mixture of representative VOCs at
known concentrations to qualify the sampler recovery characteristics (as recommended in the
NATTS TAD)1'*'. A Sampling System Blank is then collected in canisters and on carbonyl
cartridges and is analyzed based on EPA Compendium Method TO-15'4' and Method TO-1 1A«
to verify that the system meets the required cleanliness criteria and can produce non-biased
samples (as required by the NATTS TAD1'*1). These results are documented in a file specific to
each sampler by system identification number. The certification procedures are presented in SOP
for Canister Sampling System Certification Procedures (ERG-MOR-030) and SOP for Carbonyl
System Certification Procedures (ERG-MOR-100) in Appendix C.
Integrated ambient air samples are collected in 6-liter passivated stainless-steel canisters
(SUMMA, Silonite®, TO-Can, etc.) and carbonyl cartridges for a 24-hour period beginning at

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midnight for each scheduled sampling event. Carbonyl cartridges are shipped cold and the
cleaned, quality-controlled canisters are shipped under vacuum to the site from the ERG
laboratory. After sampling, the final pressure in the canister should ideally be between 2 to
8 inches of Mercury ("Hg) vacuum. The sampling assembly for the sample collection is shown in
Figure 7-3.
The physical mechanism for filling the canister is vacuum displacement. The vacuum
pump shown in Figure 7-3 is used to purge the mass flow controller and the sample inlet lines. A
second vacuum pump is used to draw ambient air through the carbonyl sampling probe and
cartridges. Ozone is removed from the sample stream prior to collection on the
2,4-Dinitrophenylhydrazine (DNPH) sampling cartridge. To accomplish O3 removal, the sample
stream (ambient air) is drawn through a potassium iodide-coated denuder O3 scrubber which is
an internally integrated component of the sampler. Carbonyl sampling can occur at sites at the
same time as the canister samples are taken or on separate samplers.
7.3 Carbonyl Only 24-Hour Samplers
Carbonyl samples are collected using D N PH -impregnated sampling cartridges with an
integrated sampling system (e.g., vacuum pump, capillary critical orifices, and O3 scrubbers),
shown in Figure 7-4. Ambient air is drawn through the cartridges via a separate sampling probe.
A potassium iodide-coated denuder O3 scrubber is an internally integrated component of the
sampler that removes O3 from the sample stream prior to the DNPH sampling cartridge.
Prior to installation of an ERG sampler at a UATMP, NATTS or CS ATAM site, the
sampler is certified at the ERG laboratory. Certification establishes that the system is functioning
correctly and provides for the appropriate level of cleanliness. To certify the sampling system,
cleaned, humidified N2 is first flushed through the sampler for at least 12 hours to remove the
potential contaminates from the system. A Sampling System Blank and a reference blank are
then collected on carbonyl cartridges and are analyzed based on EPA

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Inlet to Sample Manifold or
Direct to Atmosphere
enuder
Ozone
rubber
Primary
Duplicate
Plumbing Connections
¦ Electrical Connections
Rotameter
Sample
Air Source
Sample
Air Source
2-Micron
Fi ter
DNPH
Cartridge
DNPH
Cartridge
by-Pass
Capillary
Vacuum
Source
vacuum
Source
Mass
Flow
Orifice/fiter
Assembly
Orifice/fiter
Assembly
Controller
10-20 seem)
Bellows
valve
acuum
~ uplKate
Sample
Canister
Relief
Capillary
Gauge
^luxtron
Relief
Capillar/
Solenoid
Be ows
valve
(m)
Elapsed Timer
Primary
Thermocouple
MassFlov.-
Control
Display


Digital Timer

Channel 1
Channel 2
TemperatureControlier
RecepracleOutlet
Figure 7-3. 24-Hour Integrated Air Toxics Sampling System Components

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inlet to Sample Manifold or Direct to Atmosphere
Di
Primary
Denuder
Oione
Jcrubtmi
Dupiraie
Key
Plumbing Connections
Elenncal Connections
Digital Timet

Channel 1
Channel 2

Sample
AirSounjgl
DNPH |
Carer idgeL
Vacuum,
Lource'
! Retainers
I Tube
Orifice/f iter
Assembly1-
I
Rotarnerei
1
Sample
Aii 5ouite
iDMPH
J Cartridge
.Vacuum
Source
Griflee/fiter
Assembly
vacuum
Relief
Capillary
Elapsed Timer
i ernperatureContro'ier
Thermocouple
ReceptaUeOuHet
Figure 7- 4. Carbonyl Sampling System Components

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Compendium Method TO-1 1 A'5' to verify that the system meets the required cleanliness criteria
and can produce non-biased samples as required by the NATTS TAD1'*1. These results are
documented in a permanent file specific to each sampler by system identification number. The
certification procedure is presented in the SOP for Carbonyl Sampling System Certification
(ERG-MOR-100) in Appendix C.
A total of 3 1 sampling cartridges for a 12-day sampling schedule and 61 sampling
cartridges for a 6-day sampling schedule will be collected and analyzed per site. Duplicate (or
collocated) samples and field blanks will be collected monthly and are designated in the 2018
Sampling calendar presented in Appendix B.
7.4 Hexavalent Chromium Samplers
Sodium bicarbonate-impregnated cellulose filters are connected to the Hexavalent
Chromium sampler as shown in Figure 7-5 and ambient air is drawn through the filters through a
glass sampling probe using Teflon sampling lines. Prepared filters are shipped to each site for the
hexavalent chromium sampling. ERG ships the bicarbonate-impregnated sodium cellulose filters
to each site in coolers (chilled with blue ice packs). The samples are collected for a 24-hour
period. Disposable polyethylene gloves are used by the field operators when handling the filters
to reduce background contamination. After sampling, the filters are removed from the sampling
apparatus, sealed, and returned to the ERG laboratory in the coolers and ice packs in which they
were received. Additional qualifying information for the hexavalent chromium sampling and
analysis techniques is presented in the American Society for Testing and Materials (ASTM)
D7614-12(9) method and specific details are provided in ERG's SOI'for the Preparation and
Analysis of Ambient Air for Hexavalent Chromium by Ion Chromatography (ERG-MOR-063)
presented in Appendix C.

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Outside
Filter
Teflon
Fitter
Holder
Sample Air
In From
Atmosphere
/ / / j /
CheVj"
Key
Plumbing Connections
Electrical Connections
Receptacle Outlet
(Optional Use)
Inside
Connecting
Tube
Sample
Flow
Rotameter
Digital Timer
Channel 1
Channel 2
Elapsed
Timer
Figure 7-5. Hexavalent Chromium Sampling System Components

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7.5	PA MS Sampling
PAMS sampling is performed completely by the PA MS sites in accordance with the
Ozone Precursors TAD121 with ERG only supplying support as requested (e.g., sampling system
and training for automated gas chromatograph (GC) systems). ERG ships cleaned canisters and
prepared carbonyl cartridges to the PAMS sites on the appropriate schedule to support the
sampling program, and the samples are shipped to the ERG laboratory for analysis. The need for
support of automated GC systems is site specific.
7.6	HAPs Sampling
HAPs sampling is performed by the sites in accordance with the methods listed in
Table 3-1, with the exception of hexavalent chromium sampling (see Section 7.4). ERG provides
the hexavalent chromium sampling systems and media and receives the samples from the sites
for analysis.

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SECTION 8
SAMPLING METHOD REQUIREMENTS
The sampling methods that are used in this program are described in this Section. Since
there are four separate sampling systems and subsequently four separate analytical techniques,
each of the sampling methods is different.
The SOPs for each method are reviewed annually and updated as necessary. The QA
Coordinator, Program Manager and Writer/Editor will review, sign and date SOPs before
distributing to the laboratories satellite file areas. The previous copies will be replaced with the
revised edition. The appropriate users are notified of the updated procedure. The original, and all
previously revised edits, are stored in an archive file maintained by ERG's Project
Administrator.
As ERG is not responsible for actual execution of the field sampling in this program, the
ERG SOPs list general sampling guidelines needed for the NMOC, UATMP, Carbonyl, and
Hexavalent Chromium sampling. Table 8-1 identifies the different methods and SOP numbers
for operation of each type of sampler ERG provides. Some HAPs sampling is not addressed in
the NMP Support contract (Metals, PAHs, etc.), and are not discussed in this QAPP.
Table 8-1
EPA Methods and ERG SOPs for each Sampling System
Sampling System
Based on Applicable Method
ERG SOP Number
NMOC
EPA Compendium Method TO-12(3)
ERG-MOR-046
voc
EPA Compendium Method TO-15 4
ERG-MOR-003
Carbonyl
EPA Compendium Method TO-11A(5)
ERG-MOR-047
Hexavalent Chromium
ASTM D7614-12 Method""
ERG-MOR-013
0344.00
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March 2018
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Page
SECTION 9
SAMPLE HANDLING AND CUSTODY REQUIREMENTS
Similar sample custody procedures are followed for all monitoring programs. However,
program-specific differences exist because the analytical requirements for the programs vary. As
these activities are conducted under one EPA contract. United Parcel Service of America (UPS)
with Overnight Delivery will handle all shipping to and from the sites. Unless specified below,
samples taken in the field should not require any extra special precautions for shipping.
The Shipping and Receiving Task Leader will ensure that sample media that leaves and
field samples that are received in the laboratory follow all procedures listed in this QAPP and the
individual SOPs. The Task Leader will also advise the Project Manager of any issues or
obstacles regarding sample shipping, receipt, login and storage. The sample custodian working
under the Shipping and Receiving Task Leader will ship sample media to the field and receive
custody of samples, complete COC receipt information, document sample receipt, and enter
COC information into LIMS to create a work order.
9.1 Canister Sample Custody
9.1.1 Canister Custody
A color-coded, three-copy canister sample COC form (Figures 9-1 and 9-2) is shipped
with each 6-liter canister for the NMOC, SNMOC, UATMP, NATTS, C SAT AM, or PAMS
sites. If duplicate or collocated samples are to be taken, two canisters and two COC forms are
sent in the shipping container(s) to the site. When a sample is collected, the site operator fills out
the form per the instructions in the on-site notebook. The site operator detaches the pink copy to
be retained on-site and sends the remaining copies with the canister in the shipping container to
ERG's laboratory.

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t&ERG
ERG Lab ID #
: Keystone Park Drive. Suite 700, Morrisviile. NO 271560
NMOC SAMi CHAIN 0>: OUSiOL:;

Site Code:
Canister Number:
Ui
C
City/State;
Lab Initial Can. Press.
AOS Code:
Date Can. Cleaned:
o.
•£ £
Collection Date:
Cleaning Batch #:

Options

£
NMOC (Y/N):


SNMOC (Y/N):
Duplicate Event (Y/N):
TOXICS (Y/N):
Duplicate Can #:
—	a
a	s
.2	5
•-	i/>
Operator: 		
Setup Date: ________
Field Initial Can. Press. ("Hg):
Sys, #:
Rotameter Setting: 	
Elapsed Timer Reset (Y/N):
Canister Valve Opened (Y/N):
Recovery Date: 	
Field Final Can. Press, (psig):
Sample Duration (3 or 24 hr):
Elapsed Time: 	
Canister Valve Closed (Y/N):
Lab Final Can. Press, (psig):
si
a
cc
Received by: _	
Status. Valid
If void, why:	
Date:
Void
(Circle one)
•MR
O
¦W.
Analyst: 	
Date: 	
NMOC I nstrument
Inj. 1 (AC)
Inj. 2 (AC)
Inj. 3 (AC)
Average AC:
Database entry by:
Batch ID
Date:
(ppmC)

(ppmC)

(ppmC)

Standard Dev. (AC):	
Average Cone. (ppmC):
Standard Dev. (ppmC):
V c
.s
5 s.
v O
II
¦5 £¦
i- O
lyst:
Batch ID
Analyst:
Batch ID
Date:
Date:
Comments:
White: Sample Traveler
Canary: Lab Copy
Pink: Field Copy
Figure 9-1. Example NMOC COC

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ERG SO #
T£.	z~ s-SC
AIR TOXICS SAMPLE CHA.N OF CUSTODY
5
W
is.
I
ft
5
f
I
r
Site Code:
Cityi'Startr
AOS Code:
Collection Date:
Options:
SNMOC
TOXICS (Y/NV.
METHANE {YW]c_
Relinquished by.
R*oefv«0 by	
Canister Number 	
Ljfc trWW Car Press. fHiJ:
Cleanine Batch#: 	
Bale Con. GfeBneti;	
| * JTOJ,
Duplicate Can#: 	
Me:
Date:
MFCSetSna:
System#:
5o«up Date:
~«td Initial Can Press.:
Reoowery 0*::
OpetalDt 	
9—|	T!•»»» Docoi /VJWV
I IrtlGr »»GS€lv ^ WfSi |»
Canister Valve Opened (Y/tQ: .
_ps<0 psla "Wg |Cirefe one)
Sample OumScrt <3 or 24 hi}: _
EtspeesJ Tirrte:
F»nal Can. :Fiess»:
VMJD
Rrfiwpishal by.	
		psig psi» "tig ICirefe niwj
VO® (Qfcte ams) Canister Valve Closed
	 Date:	
Beeeiweif by.
Lab Find- Can. Ptess.:
Itatas: VALID
Dstt:
¥£»
	*W| tCiijW on*) OpffP*BrtBtilP p»a:	
(Circle one)	Gauge: 1 2 (Code aw)

Comments:
*W.* Sample Traveler
Canary: Lab Cope
Pink Field Copy
Figure 9-2. Example Air Toxics COC

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Upon receipt, the sample canister vacuum/pressure is measured and compared against the
field documented vacuum/pressure to ensure the canister remained airtight during transport. If
the receiving vacuum differs from the field vacuum more than 3"Hg, the program manager is
notified, and sample canister may be voided. Because there are potential differences in
barometric pressures and temperatures between the sampling site and the receiving laboratory
(such as those sites at high altitudes), and different accuracies for different types of pressure
gauges, there can be a consistent difference in final field pressure and lab receipt pressure for
canister samples. This difference and other parameters are considered to determine the validity of
the canister samples. These are monitored daily and the pressures are logged into an Excel
spreadsheet. This allows the laboratory the ability to determine if the difference is due to gauges
or if the canister leaked en route. A sample of the spreadsheet is presented in Table 9-1.
Table 9-1
Example of Canister Pressure Check Spreadsheet
Date Received
Site
Field Pressure
Reading
Lab Pressure
Reading
Difference
8/30/16
NBIL
2 "Hg
6 "Hg
4 "Hg
9/7/16
NBIL
1 "Eg
4 "Hg
3 "Hg
9/14/16
NBIL
3 "Hg
7 "Hg
4"Hg
9/16/16
NBIL
4 "Hg
7 "Hg
3 "Hg
8/30/16
BLKY
5 "Hg
5 "Hg
0 "Hg
9/7/16
BLKY
5 "Hg
3.5 "Hg
1.5 "Hg
9/13/16
BLKY
5 "Hg
5 "Hg
0 "Hg
9/16/16
BLKY
5 "Hg
4 "Hg
1 "Hg
The canister should be cleaned no more than 30 days before sampling. If the canister is
older than 30 days, a note will be made in LIMS and a flag will be added to the sample results in
AQS. More detailed sample receipt procedures and sample acceptance policies are presented in
the SOP for Sample Receipt at the ERG Chemistry Laboratory, ERG-MOR-045 in Appendix C.
The sample specific information from the COC is then entered into LIMS (example login page is
shown in Figure 9-3) following the SOP for Sample Login to the Laboratory Information
Management System, ERG-MOR-079 found in Appendix C. The sample is given a unique LIMS

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identification (ID) number and tagged (see Figure 9-4), noting the site location and the sample
collection date.
II Samples - 6012504 [0LS. Environmental Protection Agency, Region 9 - PXSS]
TT7T7	a Sample Information Containers I Qualifiers!
3341 items
|<12 Months ~
irwii 22
Work Order	
16012904 T|
Samples	
6012304-02
6012304-03
Name
| Field Data | Field Info ] Field Info | Memos
~N
|PXSS
Sample | Details "j Location ] Well Data

Alias


r
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Regulatory ID



| Air -r 1101 ^25/16 00:00 H
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IField Sample
f"~ QC Source Cross-Table | iHI j



Work Analyses
Modify | Analyses included for this sample
Metals Analysis
SNMOC 2016
T0-11A 2016
47mm

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| TAT ] Due
I Hold
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TQ-15 2016

45 03/13/1G 12:00
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T0-13A 2016
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Add
Edit
Copy | Delete |
Group Edit | Field Data |
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Done
Figure 9-3. Example ERG LI MS Login Page
Aralysis:

Sarrple ID

Laboratory ID

~ete Sarrpled:

Qarister #:
Ress/Vac:
3te:
Djp'Ffep:
Ctrrrnerit:

O
Figure 9-4. Canister Tag
The LIMS ID number is recorded on the canister tag and on all ERG copies of the COC.
The remaining copies of the canister sample COC are separated. The white copy is scanned (the

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PDF is stored in the LIMS system) and is kept with the canister sample until analysis is
complete. After sample analysis, the white copy goes into the data package with the sample data.
The yellow copy is stored chronologically in a designated file cabinet for one year. The file
cabinet is in Room 102 in the Laboratory building.
9.1.2	Canister Analytical Routing Schedule
Each canister has a unique canister identification number inscribed on the canister. This
number is used during can cleaning, field collection, laboratory receipt, and laboratory sample
analysis and is included on the individual Toxics/SNMOC COCs and entered into the LIMS.
The canister sample analysis hold time is 30 days from the sampling date. The samples
are sent to the ERG Air Toxics Laboratory for VOC and SNMOC/PAMS GC/Flame Ionization
Detector/Mass Spectrometer (FID/MS) analysis. The canister sample is analyzed and kept in the
laboratory until after the analyst reviews the relevant analytical data.
9.1.3	Canister Cleanup
All canisters are cleaned prior to reuse following SOP ERG-MOR-105 (SOP for Sample
Canister Cleaning using Wasson TO-Clean Automated System) as shown in Appendix C. The
canisters are cleaned using the procedure described in Section 10.1.1. The unheated system
(following SOP ERG-MOR-062, SOP for Sample Canister Cleaning) is maintained as a backup,
if needed, and is described in Section 10.1.2. The canisters are cleaned to <3x MDL or 0.2 parts
per billion by volume (ppbV), whichever is lower, and 20 parts per billion as Carbon (ppbC) for
T otal SNMOC. If the canister fails the Blank criteria, it is returned to the cleaning system bank
with the other canisters that were cleaned along with it and all canisters are put through an
additional Vacuum and Pressure cycle. The same canister is analyzed again. All canisters,
whether used for NMOC, SNMOC, UATMP, NATTS, CS ATAM, or PAMS, are cleaned by the
same procedure and are entered into the canister cleanup log, shown in Figure 9-5 for the heated
systems and in Figure 9-6 for the unheated systems.

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3

Upper
Heated Canister Cleaning Systems Logbook
2016-2
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Rear



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Rear



Oven Temperature {°CJ
Final Evac Date
Front



Leak Check



Upper
Healed System 2
Pass
Fail
Rear



Batch ID



Front



Cleaning Date





Initials
Extra Cycle Date

Lower

Program


Rear



Oven Temperature (°C)
Final Evac Date
Front



Leak Check





Review Initials & Date


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V	P
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Req. Cycle 3 pass
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Opt. Cycle 4 pass
V	P or
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Req. Cycle 1	Req. Cycle 2 Req. Cycle 3 pass
V	P	V	P	V	P or
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Page
9.2 Carbonyl Sample Custody
Figure 9-7 shows the color-coded, three-copy COC form used for all carbonyl sampling
documentation. A COC is shipped to the site with the carbonyl cartridges. After sampling, the
COC form is completed by the site operator and the pink copy is retained for site records. The
carbonyl sample cartridges and remaining COC copies are shipped to ERG's analytical
When samples are received, they are logged into the LIMS database and given a unique
LIMS ID number following the SOP for Sample Login to the Laboratory Information
Management System, SOP ERG-MOR-079, found in Appendix C. The remaining copies of the
COC are separated. The white copy of the COC is scanned (the PDF is stored in the LIMS
system) and is labeled with the LIMS ID number, site code, sampling date, individual sample
designations, and date of receipt and initials of receiving personnel and put into a bag. The
sample bag is stored in a refrigerator designated for carbonyl samples only. The yellow copy is
stored chronologically in a designated file cabinet for one year. The file cabinet is in Room 102
in the Laboratory building. More detailed sample receipt procedures and sample acceptance
policies are presented in the SOP for Sample Receipt at the ERG Chemistry Laboratory,
ERG-MOR-045.
9.2.1 Carbonyl Analytical Routing Schedule
laboratory.
The carbonyl cartridge samples are extracted within 14 days of the sampling day and
analyzed within 30 days after extraction. The extracts are kept in the designated extract
refrigerator until after the analyst and the Task Leader reviews all the relevant analytical data.

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feERG
t h
.-± ID
Swim	IC-
C4RBONYL COMPOUNDS CHAIN OF CUSTODY
j& S
3 
2 §
£ o
$
a
Cacfe,
'State:
Code:
Cotectim Date:	
CastndgsLol#' 		
Dupficsia Evern !Y«;
RainquishetS by:,
-¦aoBVMityf	
-Up Date:	
Date:,
Date;
Operator
Sys.C
Sampling ftolawwlsr Raiding toe'min):
Elapsed Traaf Rases (Y.Wf
¦way Date:
Operator:	
i-i Sampfcrifl Rotameter Raatfing ftc'min):
r'ridges Gappsci j»J):	
Rafmqufehed by:	
Sample Duration (3 or 24 tw> 	
ElapsaiTiwse: 	
Siilus VALID VOID (Circle onai
Date:
¦o $

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Page
9.3	HAPs Sample Custody
Samples collected on prepared sample media (i.e., XAD-2®, Polyurethane Foam (PUF),
hexavalent chromium filters, etc.) use supplied three-copy COC forms to document sample
collection. Field testing personnel will record applicable collection data (such as time, date,
location, meteorological parameters) on the appropriate COC forms (Figures 9-8, 9-9 and 9-10)
and keep the pink copies for site records. The COCs are then shipped to ERG with the prepared
sample media.
Because the sites supply the filters used for metal analysis, COC forms are normally
supplied by the State, Local or Tribal agency for these samples. If needed, however, COC forms
can be supplied by ERG electronically inputting multiple filters for metal analysis (Figure 9-11).
Samples are received at ERG's laboratory as presented in the SOP for Sample Receipt at ERG
Chemistry Laboratory, ERG-MOR-045.
All HAPs samples received at the ERG laboratory will be logged into the LIMS as
described in the SOP for Sample Login to the Laboratory Information Management System,
ERG-MOR-079.
9.4	Invalid Samples
The sample COC form may indicate that the sample sent from a site is invalid. The
sample can be determined invalid at the site or in the laboratory. SOP ERG-MOR-045 describes
the sample receiving procedure and sample acceptance. Individual sites will be contacted if there
are any questions about the samples upon receipt. When a sample is designated as invalid, the
assigned LIMS ID number is notated as a void and is invalidated on the individual respective
COC form. Another sample media will be sent to the site with the COC designated to make up
on non-standard sampling days. If the site has repeated invalid samples, normally three voids in a
row, the ERG site coordinator Task Leader will work with the site personnel to diagnose and
correct the problem. The sites will also be notified in the monthly analytical reports of any
invalid samples.

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feERG
Ewi Lab ID ,
i I. >1 . I ••
8D» Kr-iMr-? Dnw "X "isrfSfis* i-jC
SVOC SAMPLE CHAIN OF CUSTODY
Container #r
I
a.
£
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AOS Cede:
Cartftige Ceritftealten Drts
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SUR: ID:	
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Site Operator:
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	 Dale:	
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RbbbubuI by:	
State: Valid
BwQKt.Whjf 	
Date:
Container#:
Void (Ckcte one) Uncorrected Temperature:
	 Cocectetl Temperature:
TnefmometeK 1R1 R2
(Girdle QFie|
Samples stoned in gefr*a#rator # 1
Ccmuiiciita.
W»> 1«. Sample Traider	G*wy: Lab Copy
Pink: Field Copy
Figure 9-8. Example SVOC Sample COC

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„at> iQ 9
•5-	Fs?*iua -as	sic
AMBIENT HEXAVALENT CHROMIUM.CHAIN Of .CUSTODY FORM
a
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Calfecfian Date:	
Prim*y E*ni;C¥Mli
-Data:
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2
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b Operator. 	
i-Up Date: 	
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InlfiBi Wauwter Setting (G.O: BJ:_
Programmed Start Time: 	
System*	
Elapsed Timer Reset (YiMJr;
_ {Alter 5 minutes warm-up)
Programmed End Time:
Recovery Dale: _________
Site Operator: 	
Final Rotameter Reading (C O B
Elapsed Tune: 	
Relinquished by.	
Recovwy Time:
	I After 5 minutes warm-up j
Status Valid Void (Circle one)
Date:
»
o

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Tot at
Tjme
System £
i eta* V->l
Lab ID







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f-.-J
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ft¥p
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Comments;	
Whte Sample Travels'
Canary Lab Copy
Figure 9-10. Example Metals COC
Pink: fteM Copy

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%ERG*	Chain of Custody Record
j&fM	Far* Dfme. Sii ¦
PROJECT

ANALYSES
STORAGE LOCATION
CITE
1





ERG L'IMS ID
REWWKS (FErS»U&^a*Tlf|
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'Canary. Lsfo copy
Figure 9-11. ERG Blank COC Record
Rnfc: flew Copy

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Page
9.5	Analytical Data
After analysis, the laboratory will provide narratives describing any anomalies and
modifications to analytical procedures, data and sample handling records, and laboratory notes
for inclusion in the final report. All laboratory electronic records will be stored for archive on
Digital Versatile Disk (DVD), or shared network drive. DVDs are stored in Room 102 in the
Laboratory building and the shared network has limited access. Raw data will be stored on the
shared network for at least 5 years after the end of the closed contract.
All records generated by measurement activities are signed or initialed by the person
performing the work and reviewed by an appropriate Task Leader. Measurement results become
part of a proj ect report, of which 10 percent is requested by the QA Coordinator (or a reviewer
designated by the QA Coordinator) for review.
9.6	Sampling Monitoring Data
All COC forms from the monitoring sites will be stored with the analytical results. The
forms are also scanned and stored in the LIMS as described in the SOP for Sample Login to the
Laboratory Information Management System, SOP ERG-MOR-079. The COC forms will be
reviewed by the sample custodian(s). Task Leaders and Program Manager. The laboratory will
contact the individual site if necessary information is not completed on the COC forms. The
original field data will remain in ERG custody and will eventually be stored on file with the final
report until 5 years after the end of the closed contract.

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SECTION 10
ANALYTICAL METHODS REQUIREMENTS
Analytical procedures are program-specific because the instrumentation and the target
compounds of the four programs differ. The primary analytical instrument is GC/F ID/MS for
SNMOC, VOCs and PA MS hydrocarbons; High Performance Liquid Chromatography (HPLC)
for carbonyls; GC/MS for Sentivolatiles (SVOC); Inductively Coupled Plasma/Mass
Spectrometer (ICP-MS) for Metals; and Ion Chromatography (1C) for Hexavalent Chromium.
All samples taken for SNMOC, VOCs, or PAMS hydrocarbons can be evaluated by GC/F ID/MS
because the instrumentation is collecting all of the data at the same time. Corrective action for
analytical system failures realized at time of analyses is initiated by the Analyst and supported by
the Task Leader for that method. All analytical method SOPs are provided in Appendix C. The
methods used for NMOC and other individual HAPs analysis not currently discussed will be
added to this QAPP when the individual States request the analyses. Samples will not be
analyzed until ERG receives approval from EPA.
The SOPs for each method are reviewed annually and updated as necessary. The QA
Coordinator, Program Manager and Writer/Editor will review, sign and date SOPs before
distributing to the laboratories satellite file areas. The previous copies will be replaced with the
revised edition. The original, and all previously revised edits, are stored in a historical file
maintained by ERG's Project Administrator.
10.1 Canister Cleanup System
The canisters are cleaned using a Wasson TO-Clean Model TO 0108 heated canister
cleaning system and is explained in Section 10.1.1. The unheated system is used as backup and is
described in Section 10.1.2. A bulk liquid N2 devvar is located external to the ERG laboratory
facility. This devvar continuously produces a volume of ultrapure gaseous N2 in its headspace
area (-100 psig) that is more than adequate to accommodate all in-lab gaseous N2 applications.
Ultrapure gaseous N2 is extracted from the devvar headspace and delivered to the cleaning

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systems. Transport of the gas is accomplished through a 3/8" outer diameter (OD) pre-cleaned
stainless-steel tubing.
10.1.1 Heated Canister Cleaning System
The TO-Clean heated cleaning systems are commercially available systems manufactured
by Wasson-ECE (Figure 10-1). These systems can clean up to twelve canisters per system at a
selected temperature from ambient to 100°C. Each system consists of an oven that holds the
canisters, an Edwards RV8 vacuum pump, a stainless-steel humidifi cation chamber for the
dilution gas, and a control unit. The procedure for cleaning canisters is the SOP for Sample
Canister Cleaning using the Wasson-ECE, ERG-MOR-105 in Appendix C.
The cleaning system oven has enough capacity to clean up to 12 canisters at a time. Two
racks hold up to six canisters each. Canisters are connected to a 12-port, two-level manifold with
compression fittings and flexible stainless-steel tubing. Ultra-pure N2 is the dilution gas and is
applied to the manifold via an electrically actuated valve. Vacuum is applied to the manifold
through a pneumatically-actuated vacuum valve. The oven is heated to 40°C during the cleaning
cycles.
The control unit controls the pressure, vacuum, and vent valves and houses the front
panel control unit and oven temperature controller. The touchscreen front panel control stores
and executes the cleaning programs, provides manual valve control and leak check diagnostics,
and displays vacuum, pressure, and program time information. The oven temperature controller
is separate from the front panel control within the control unit and regulates the oven temperature
to a preset value.
The Edwards RV8 vacuum pump is separated from the system by a cryogenic trap. This
trap removes contaminants and water vapor from the canisters before reaching the pump, and it
prevents the sample canisters from being contaminated by back-diffusion of hydrocarbons from
the vacuum pump into the cleanup system. The humidifier system is a modified SUMMA®-
treated 6-liter canister partially filled with HPLC-grade water. The ultra-pure N2 dilution gas is

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Controller
Box
V2
INC
J Vacuum Actuator Valve
Vacuum
(15 mToriy ^j.
V3
i
j Pressure Valve
vi L
Purge
Vent '
Purge Valve
x z x i r-
¦ JU 4 X
"BT
Vacuum Valve
Humidifier
Cold Trap
(Liquid Argon)
Hard
Vac.
Pump
UHP
- w-- Nitrogen
(or Air)
Heated 40°C
Figure 10-1. Heated Canister Cleanup System Schematic

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bubbled through the water prior to entering the manifold, achieving an estimated relative
humidity of 75 percent.
After sample analyses and data review are completed, 12 canisters are connected to the
manifold in the oven. The bellows valve on each canister is opened. The vacuum pump is started
and one of the vacuum routing valves is opened, drawing a vacuum on the canisters connected to
the corresponding manifold. The canisters are evacuated to a vacuum reading of 400 millitorr
and held for 45 minutes. The vacuum valve is then closed and the ultrapure gaseous N2 that has
been humidified is introduced into the evacuated canisters at a rate of 5.0 liters per minute until
the pressure in the canisters reach approximately 20 psig. This evacuation and pressurization of
the canisters constitutes one Cleanup Cycle.
The Cleanup Cycle is repeated twice more to facilitate a complete canister cleanup
procedure. Following the third pressurization, the canister bellows valves are closed and one
canister (out of the 12 cleaned) is selected for cleanliness verification analysis. The cleanliness of
the canister is qualified by GC/MS and FID analysis. The pass/fail results of the analyses are
documented on a shared network so that the pass/fail rate can be monitored. The cleanliness
criterion for each bank of 12 canisters is < 3x MDL or 0.2 ppbV for each individual VOC,
whichever is lower, and 20 ppbC for Total SNMOC. If the canister does not pass the cleanliness
criteria, the canister is reconnected to the cleanup manifold with the other 1 1 canisters it was
cleaned with and another cleaning cycle is performed, and the same canister is analyzed again.
Upon meeting these criteria, the canister is reconnected to the cleanup manifold with the other 1 1
canisters constituting the original bank of 12. All 12 canister bellows valves are opened, and the
canisters are evacuated to a vacuum reading of 50 millitorr. The bellow valves are closed, and
canisters are ready to be packaged and shipped to each network site.
10.1.2 Unheated Canister Cleaning System
A canister cleanup system (Figure 10-2) has been developed and is used to prepare
sample canisters for use in collecting representative whole air samples (SOP for Sample Canister

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Headspace
at 100 psig
U1 ^
Liquid N2
Dewyer
N2 Flow
Rotameter
Flow
Controller
Pressure
Regulator
Moisture_
Indicator
Catalytic
Oxidizer

5.0|j Filter
Assembly
Dry
Rotameter
tcsr I
N2
Humidifier
Wet
Rotameter
Absolute
Pressure
Guage
^^-^Vacuum ^
Source*—
Selector
Valve
Vacuum
Cryotrap
Rotary Vane Pump
N2
Bypass
Cryotrap
Purge Valve
x'
£
A B
Routing
Valve
8-Port
Manifold
Roughing
Pump
DDDDDDDDDDDDDDDD
Port
Manifold
To
Ambient
A.	Man
B.	Man
C.	Man
D.	Man
fold Air Pressure Valve
fold Vacuum Valve
fold Pressure Release Valve
fold Port for Connecting Canisters to be Cleaned
Figure 10-2. Unheated Canister Cleanup System Schematic

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Cleaning, ERG-MOR-062 in Appendix C). This cleaning system is used as a backup to the
heated canister cleaning system explained in Section 10.1.1.
A single-stage regulator controls the final N2 pressure in the canisters and a metering
valve is used to control the flow rate at which the canisters are filled during a cleanup cycle. The
flow direction is controlled by a separate flow meter, installed in the N2 gas line. A shutoff valve
exists between the N2 gas line and the humidifier system (which is a modified SUM MA*-treated
6-liter canister partially filled with H PLC-grade water). One rotameter and flow-control valve
direct the gaseous N2 into the humidifier where it is bubbled through the H PLC-grade water. A
second flow-control valve and flow meter allow gaseous N2 to bypass the humidifier system, if
desired. By setting the flow-control valves separately, the downstream relative humidity can be
regulated. Approximately 75 percent relative humidity is used for canister cleaning. This is
accomplished by routing 100 percent of the gaseous N2 flow through the humidifier. Another
shutoff valve is located between the humidifier and each 8-port manifold where the canisters are
connected for cleanup.
The vacuum system consists of a Precision Model DD-310 vacuum pump, a cryogenic
trap, a vacuum and pressure gauge, and a manifold vacuum valve connected as shown in
Figure 10-1. The cryogenic trap prevents the sample canisters from being contaminated by back-
diffusion of hydrocarbons from the vacuum pump into the cleanup system. The manifold vacuum
valves enable isolation of the vacuum pump from the system without shutting off the vacuum
pump.
After sample analyses and data review are completed, a bank of eight canisters is
connected to each manifold as shown in Figure 10-1. The canister bellows valve on each canister
is opened. The vacuum pump is started and one of the vacuum routing valves is opened, drawing
a vacuum on the canisters connected to the corresponding manifold. The bank of eight canisters
is evacuated to a vacuum reading of 29.5" Hg (as indicated by the pressure gauge), and held for
30 minutes. The vacuum routing valves are then closed and the ultrapure gaseous N2 that has
been humidified is introduced into the evacuated canisters at a rate of 4.0 liters per minute until

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the pressure in the canisters reach approximately 20 psig. This "Evacuation and Pressurization"
of the canisters constitutes one Cleanup Cycle.
The Cleanup Cycle is repeated twice more to facilitate a complete canister cleanup
procedure. Following the third pressurization, the canister bellows valves are closed and one
canister (out of the eight cleaned) is selected for cleanliness verification analysis. The cleanliness
of the canister is qualified by GC/MS and FID analysis. The pass/fail results of the analyses are
documented on a shared network so that the pass/fail rate can be monitored. The cleanliness
criterion for each bank of eight canisters is < 3x MDL or 0.2 ppbV for each individual VOC,
whichever is lower, and 20 ppbC for Total SNMOC. If the canister does not pass the cleanliness
criteria, the canister is reconnected to the cleanup manifold with the other seven canisters it was
cleaned with and another cleaning cycle is performed, and the same canister is analyzed again.
Upon meeting these criteria, the canister is reconnected to the cleanup manifold with the other
seven canisters constituting the original bank of eight. All eight canister bellows valves are
opened and the canisters are evacuated to a vacuum reading of approximately 29.5" Hg for a
fourth time. The bellow valves are closed, and the canisters are ready to be packaged and shipped
to each network site.
10.2 VOC and Concurrent Analytical System
The VOC GC/FID/MS analyses are performed on a 250-milliliter (mL) sample from the
canister with an Agilent 6890 GC/F ID and an Agilent 5975 MS with Selected Ion Monitoring
(SIM) using a 60 m by 0.32-millimeter (mm) Inner Diameter and a 1-micrometer (.mi) film
thickness Restek Rxi-lms capillary column followed by a Y-union connector that splits the mobile
phase between the MS and the FID. Table 10-1 shows the GC/F ID/MS operating conditions.
Figure 10-3 shows the GC/F ID/MS system arrangement. Canister samples must be analyzed
within 30 days from sample collection. The analytical SOP for the Concurrent GC/FID/MS
Analysis of Canister Air Toxic Samples using EPA Compendium Method TO-15 and EPA Ozone
Precursor Method (ERG-MOR-005) is presented in Appendix C.

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Table 10-1
VOC GC/FID/MS Operating Conditions
Parameter
Operating Value
Sample Volume
250 mL
Restek RXi-lms Capillary Column:
Length:
Inside diameter:
Film thickness:
Oven temperature:
60 m
0.32 mm
1 \im
-50°C for 5 minutes. 15°C/min to 0°C then
5°C/min to 150°C, then 25°C/min to 220°C
for 1 minute then 25°C/min to 150°C for
4 minutes
Temperatures:
FID:
Injector Oven Temperature:
MS Quad Temperature:
MS Source Temperature:
300°C
220°C
200°C
280°C (350°C 5975)
Gas Flow Rates:
Column Carrier Gas (Helium (He)):
FID Make-up (He):
FID (Hydrogen (H;)):
FID (Air):
2 m L/min
30 m L/min
30 mL/min
300 mL/min
Entech Sample Interface Conditions:
Module 1 - Glass Bead/Tenax® Trap Initial
Temperature:
Module 2 - Tenax® Trap Initial Temperature:
Module 3 - Cryofocuser Temperature:
-150°C
-50°C
-196°C
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6L Sample Canisters
Silica Coated
Guard Column
Agilent ChemStation*
Software for Mass Spectra
And FID Peak Identification
& Entech Software
FID
Gas Chromatograph
Mass
Spectrometer
Detector
8-port
Low Dead Volume
Stainless-Steel
Y-Union Connector
Rji-1^5 Column
16-port Entech
Autosampler
Figure 10-3. VOC GC/MS/FID System
10.3 Carbonyl Analytical System
Carbonyl samples are stored in the refrigerator after they are received from the field prior
to analysis. The carbonyl cartridge samples are extracted within 14 days of the sampling day and
analyzed within 30 days after extractions. Sample preparation is performed by removing the
DNPH sampling cartridge from its shipping container and attaching it to the end of a 5 mL
Micro-Mate® glass syringe. Five mL of acetonitrile are added to the syringe and allowed to drain
through the cartridge into a 5 mL Class A volumetric flask and diluted to the 5 mL mark with
acetonitrile. This solution is then transferred to a 2 mL autosampler vial fitted with a Teflon-
lined, self-sealing septum and a 4 mL vial with a Teflon-lined cap and both vials are stored in a
refrigerator at 4°C until analysis.
The analytical separation of carbonyls is performed using a Waters HPLC configured
with a reverse-phase 250 mm by 4.6 mm C-18 silica analytical column with a 5-micron particle
size. A typical HPLC system is shown in Figure 10-4. ERG's system uses an Agilent HPLC
chromatographic data software system. Typically, 15-microliters (|iL) samples are injected with
an automatic sample injector. A mobile phase gradient of water, acetonitrile, and methanol is

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used to perform the analytical separation at a flow rate of 1.0 mL/minute. A multi wavelength
Ultraviolet (UV) detector is operated at 360 nanometer (nm). The complete SOP for Preparing,
Extracting, and Analyzing DNPH Carbonyl Cartridges by Method TO-11A (ERG-MOR-024) is
presented in Appendix C. Sample and waste disposal procedures are outlined in ERG-MOR-
033, the SOP for Hazardous Waste.
10.4 Polycyclic Aromatic Hydrocarbons Analytical Systems
Sampling modules containing PUF/XAD-2®, petri dishes containing glass microfiber
filters, and COC forms and all associated documentation will be shipped to the ERG laboratory
from the field. Each filter should be folded in quarters, placed inside the cartridge (with the
XAD/PUF) and capped before shipment. Upon receipt at the laboratory, samples will be logged
into the LIMS system and stored in the refrigerator. Sample preparation and analysis procedures
are based on EPA Compendium Method TO-13 A1"" and ASTM D6209-13l ,2) method. The hold
time is 14 days after sampling for extraction and 40 days after extraction for analysis.
Sample extracts will be analyzed for PAHs using GC/MS in SIM. The MS will be tuned
and mass-calibrated as required using perfluorotributylamine (FC-43), per the analytical
procedures presented in the SOP for analysis of Semivolatile Organic Compounds (Polynuclear
Aromatic Hydrocarbons) Using EPA Compendium Method TO-13A and AS I'M 1)6209 fERG-
MOR-049) (see Appendix C). Sample and waste disposal procedures are outlined in ERG-MOR-
033, the SOI' for Hazardous Waste.

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Injection
Valve
Column
Data
System
Mobile
Phase
Pump
Variable
Wavelength
UV
Detector
Mobile
Phase
Reservoir
Data
Output
Figure 10-4. HPLC System
10.5 Metals Using an Inductively Coupled Argon Plasma Mass Spectrometry Analytical
System
Upon receipt from the field, the samples are checked against the COC forms and then
logged into the LIMS system. Each sample component is examined to determine if damage
occurred during travel. Color, appearance, and other sample particulars are noted. Sample
preparation and analysis procedures are based on EPA Compendium Methods IO-3.1(22) and
IO-3.5(6), respectively for the Determination of Metals in Ambient Particulate Matter using ICP-
MS techniques. A complete description of the preparation and analytical procedures are

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presented in the SOPs for quartz and glass fiber (8x10") filter prep (ERG-MOR-084) and for
Teflon 47mm filter prep (ERG-MOR-085) and analysis (ERGMOR-095) in Appendix C. These
procedures were approved as NAAQS Federal Equivalency Methods (FEM) for the analysis of
Lead for Total Suspended Particulate (TSP) on quartz and glass fiber filters (EQL-0512-201'7')
and for PMio on Teflon filters (EQL-05 12-202|S|). Analysis hold time for metals filters is
180 days.
The ICP-MS consists of an inductively coupled plasma source, ion optics, a quadrupole
MS, a recirculator and an autosampler. The MS will be mass calibrated and resolution checked.
Resolution at low mass is indicated by magnesium isotopes 7Li, 24, 25, and 26Mg, 59Co, 1 15In,
206, 207, and 208Pb and U238. Instrument stability must be demonstrated by running a tuning
(daily performance check) solution [ 1 micrograms per liter (|ig/L of barium, bismuth, cerium,
cobalt, indium, lead, lithium and uranium, and 15 |ig/L of magnesium] 10 times with a resulting
Relative Standard Deviation (RSD) of absolute signals for all analytes less than 2 or 5 percent,
depending on element and instrument acquisition mode. Sample and waste disposal procedures
are outlined in ERG-MOR- 033, the SOP for Hazardous Waste.
10.6 Hexavalent Chromium Analytical System
Hexavalent chromium filter samples are stored in the freezer after they are received from
the field prior to analysis. Internal studies have shown that the hexavalent chromium does not
degrade for up to 21 days if the samples are stored in the freezer before extraction. Upon receipt
from the field, the samples are checked against the COC forms and then logged into L1MS. Due
to oxidation/reduction and conversion between the trivalent and hexavalent chromium, the
extraction is performed immediately prior to analysis. Therefore, it is important that the IC be
equilibrated, calibrated and ready for analysis before filters are extracted. Sample preparation is
performed by removing the filter from the filter holder and placing it into a 14 mL polystyrene
tube. The filters are extracted in 10 mL of a 20 millimolar (mM) sodium bicarbonate solution.
The tubes are shaken for 45 minutes using a wrist action shaker before a 2.5 mL aliquot is
removed for analysis on the IC. All analysis is completed within 24 hours of the filter extraction.

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The analytical separation for the hexavalent chromium is performed using a Dionex-600
IC or Dionex ICS-5000 with a Dionex LC 20 Chromatography Enclosure with a post-column
reagent delivery device and an advanced gradient pump configured with an IonPac AS7
analytical column and an IonPac NG1 guard column. Both of ERG's ICs use the Dionex
Chromeleon® data system. For the Dionex-600 IC, samples are injected using a Dionex AS40
autosampler. The samples analyzed with the Dionex ICS-5000 are injected using an AS-DV
autosampler. A mobile phase is used to perform the analytical separation at a flow rate of
1.0 mL/min, and a post-column reagent flow rate of 0.3 mL/min. The multiwavelength UV
detector is set at 530 nm. The samples are prepped and analyzed following ASTM D7614-12(9)
method and the SOP for the Preparation and Analysis of Ambient Air for Hexavalent Chromium
by Ion Chromatography (ERG-MOR-063) that is presented in Appendix C. Sample and waste
disposal procedures are outlined in ERG-MOR- 033, the SOP for Hazardous Waste.

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SECTION 11
QUALITY CONTROL REQUIREMENTS
This section describes the quality control requirements for each of the major program
components (NMOC, SNMOC, VOC, Carbonyls, PA MS, HAPs - SVOC, Metals and
Hexavalent Chromium). As there is not a current need for some of the HAPS (SVOC analysis
following TO-13A(10)/SW 846 Method 8270E1"', PCB/Pesticides1'V|, inorganic acids1'4', etc.),
this information is not provided. As soon as these analyses are requested by EPA or States,
however, the QAPP will be modified and a new set of MDLs will be completed and presented to
EPA. The 2018 MDLs are presented in this section.
11.1	Sample Canister Integrity Studies
Before any SNMOC or VOC samples are collected for a program, all stainless-steel
sample canisters are checked for leaks. The canisters are evacuated to less than 25" Hg. The
canister vacuum, measured on a Heise gauge, and the barometric pressure is recorded. After
7 days, the canister vacuum and barometric pressure is remeasured. The canisters are considered
leak-free if there is less than 1" Hg difference in vacuum (adjusted for differences in the
barometric pressure). The canisters are then cleaned using the procedure described in Section 10.
For the canister to be used without further cleanup, an analysis must show that it meets the
quality objective for cleanliness.
11.2	Standard Traceability
The standards used for all analytes are vendor-supplied National Institute of Standards
and Technology (NIST) standards or vendor-supplied referenced to a NIST standard. All
analytical methods are also certified by comparison to a second source NlST-traceable standard.
The ERG-MOR-022 SOP for the Preparation of Standards in the ERG Laboratory, provides
direction for preparing standards from solid or liquid chemicals. The SOP used to prepare
canister standards is SOP for Standard Preparation Using Dynamic Flow Dilution System, ERG-
MO R-06 1 (Appendix C).

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Element No. Section 11 - B5
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11.3 Accuracy and Acceptance
As ambient air measurements encompass a range of compounds and elements whose
individual concentrations are unknown, defining absolute accuracy is not possible. Instead,
accuracy is determined by comparing the analysis of duplicate samples and of standards of
known concentration. The criteria for the analysis of duplicate (or collocated) samples and their
replicate analyses are found in Section 4. Accuracy of analysis is based on the accuracy of the
calibration, including the accuracy of the calibration standards. Each instrument calibration is
discussed by method in Section 13 of this QAPP. Accuracy is monitored throughout the program
using QC samples. Required QC samples and their criteria and corrective actions are discussed
by the methods listed below.
1 1.3.1 SNMOC Analysis
Prior to sample analysis for SNMOC, a continuing calibration verification (CCV)
standard of hydrocarbons, prepared using either a NIST-traceable Linde or Air Environmental
high pressure gas, is analyzed daily to ensure the validity of the current Response Factors (RF).
This standard will have an approximate concentration range from 5 ppbC to 400 ppbC. The
concentrations are compared to the calculated theoretical concentrations of the CCV. The
standard analysis is considered acceptable if the percent recovery is 70-130 percent for 10
selected compounds.
If the CCV does not meet the percent recovery criterion, a second CCV is analyzed. If the
second CCV meets the criterion, the analytical system is considered in control. If the second
CCV does not meet acceptance criteria, a leak test and system maintenance are performed.
Following these maintenance procedures, a third CCV analysis can be performed. If the criterion
is met by the third analysis, the analytical system is considered in control. If maintenance causes
a change in system response, a new calibration curve is required.

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A system blank of cleaned, humidified N2 is analyzed after the CCV and before the
sample analysis. The system is considered in control if the total NMOC concentration for the
system blank is less than or equal to 20 ppbC.
CCV requirements are presented in Table 1 1 -1. If both the hydrocarbon and TO-
15W
parameters are requested from same sample, the instrument must conform to the standard QC
procedures listed in both Tables 1 1-1 and 1 1 -2 (for VOC QC requirements).
1 1.3.2 VOC Analysis
The tune of the GC/MS is verified using a 4-Bromofluorobenzene (BFB) instrument
performance check sample daily. The acceptance criteria for the BFB are presented in
Table 11-3. The internal standards for this method are hexane-du, 1,4-difluorobenzene, and
chlorobenzene-d?. The internal standard responses must be evaluated to ensure instrument
stability throughout the day.
Before sample analyses, a standard prepared at approximately 2.5 ppbV from a NIST-
traceable Linde or Air Environmental gas cylinder is used for a CCV. The resulting response
factor for each compound is compared to the average calibration curve response factors
generated from the GC/MS using the Agilent ChemStation® Software. Correspondence within an
absolute value of less than or equal to 30 percent difference is considered acceptable for the
quantitated compounds. If the first CCV does not meet this criterion, a second CCV will be
analyzed. If the second CCV is acceptable, sample analysis can continue. If the second CCV
does not meet acceptance criteria, then a leak check and system maintenance are performed. If
the system maintenance is completed and a third CCV analysis meets the criterion, then analysis
may continue. If the maintenance causes a change in the system response, a new calibration
curve must be analyzed before sample analyses can begin.

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Project No.	0344.00
Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	5 of 40
Tabic 11-2
Summary of Air Toxics Canister VOC Quality Control Procedures
QC Check
Frequency
Acceptance Criteria
Corrective Action
BFB Instrument Tune
Performance Check
Dailyb, prior to sample
analysis
Evaluation criteria presented in Section 16.1.1 of
the SOP and Table 11-3 of this QAPP.
1)	Retune
2)	Clean ion source and/or
quadrupole
Initial calibration (ICAL)
consisting of at least 5 points
bracketing the expected
sample concentration.
Following any major
change, repair, or
maintenance or if daily
QC is not acceptable.
Recalibration not to
exceed three months.
1)	% RSD of Response Factors < 30% RSD (with
two exceptions of up to ± 40% for non-Tier I
compounds only)
2)	Internal Standard (IS) response ±40% of mean
curve IS response
3)	Relative Retention Times (RRTs) for target
peaks ±0.06 units from mean RRT
4)	IS RTs within 20 seconds of mean
5)	Each calibration standard concentration must
be within ±30% of nominal (for Tier I
compounds)
1)	Repeat individual
sample analy sis
2)	Repeat linearity check
3)	Prepare new calibration
standards and repeat
analysis
LCS ({ICV! Second source
calibration verification
check)
Follow ing the
calibration curve
The response factor < 30% Deviation from
calibration curve average response factor
1)	Repeat calibration check
2)	Repeat calibration curve
Continuing Calibration
Verification (CCV) of
approximately mid-point of
the calibration curve'1 using a
Certified Standard
Before sample analysis
on the days of sample
analy sis b
The response factor < 30% Deviation from the
calibration curve average RRF (Relative Response
Factor)
1)	Repeat calibration check
2)	Repeat calibration curve
a The same QA criteria arc needed for SNMOC and PAMS analysis.
b Every 24 hours frequency.

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Tabic 11-2
Summary of Air Toxics Canister VOC Quality Control Procedures (Continued)
Project No.
Element No.
Revision No.
Date
Page
QC Check
Frequency
Acceptance Criteria
Corrective Action
Method Blank Analysis
(Zero Air or N2 Sample
Check)
Dailyb, follow ing BFB
and calibration check;
prior to sample analysis
1)	<3x MDL or 0.2 ppbV. whichever is lower
2)	IS area response ± 40% and IS RT ± 0.33 min.
of most recent IC AL
1)	Repeat analysis with
new blank canister
2)	Check system for leaks,
contamination
3)	Reanalvze blank
Duplicate and Replicate
Analysis
All duplicate and
collocate field samples
<25% RPD for compounds greater than 5 x MDL
1)	Repeat sample analysis
2)	Flag data in LIMS; Flag
in AQS as permitted
Canister Cleaning
Certification
One canister analyzed
on the Air Toxics
svstem per batch of 12
<3x MDL or 0.2 ppbV. whichever is lower
Reclean canisters and
reanalyze
Preconcentrator Leak Check
Each standard and
sample canister
connected to the
preconcentrator/
autosampler
< 0.2 psi change/minute
1)	Retighten and re perform
leak check
2)	Provide maintenance
2) Re-perform leak check
test
a The same QA criteria arc needed for SNMOC and PAMS analysis.
b Every 24 hours frequency.

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	7 of 40
Table 11-2
Summary of Air Toxics Canister VOC Quality Control Procedures (Continued)
QC Check
Frequency
Acceptance Criteria
Corrective Action
Sampler Certification -
Standard Challenge with a
reference can and a Zero
Check with a reference can
Annual
Challenge: Within 15% of the concentration in the
reference canister.
Zero: up to 0.2 ppbV or 3x MDL (whichever is
lower) higher than the reference can
1)	Repeat certification of
samplers, a requirement for
Tier I compounds
2)	Notify Program
Manager (flagging non-
Tier I compound data for
sampler mav be an option)
Sampling Period
All samples
24 hours ± 1 hours
1)	Notify Program
Manager
2)	Flag samples 22-23
hours and 25-26 hours in
AQS with a "Y" flag
3)	Invalidate and re-sample
for > 24±2 hours
Retention Time (RT)
All qualitatively
identified compounds
RT within ± 0.06 RRT units of most recent initial
calibration average RT
Repeat analysis
Samples - Internal Standards
All samples
IS area response within ± 40% and IS RT within ±
0.33 min. of most recent calibration average IS
response
Repeat analysis
a The same QA criteria arc needed for SNMOC and PAMS analysis.
b Every 24 hours frequency.

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
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Table 11-3. BFB Key Ion Abundance Criteria
Target Mass
Rel. To Mass
Lower Limit %
Upper Limit %
50
95
8
40
75
95
30
66
95
95
100
100
96
95
5
9
173
174
0
2
174*
95
50
120
175
174
4
9
176
174
93
101
177
176
5
9
* alternate base peak
After acceptable analysis of the daily standard has been demonstrated, a system blank
consisting of clean, humidified air or N2 is analyzed. A concentration per compound of
< 3x MDL or 0.2 ppbV, whichever is lower (as outlined in Table 1 1-2) indicates that the system
is in control. If a concentration greater than the acceptance criterion is detected, a second system
blank is analyzed. If the second system blank fails, system maintenance is performed. Another
system blank can be analyzed and if it is in control, ambient air samples are analyzed. All other
QC procedure acceptance criteria and corrective actions are presented in Table 11-2.
11.3.3 Carbonyl Compounds Analysis
Daily CCVs prepared from NIST traceable stocks are performed to ensure that the
analytical procedures are in control. CCVs are performed every 12 hours or less when samples
are analyzed. Compound responses in the CCVs must have a percent recovery between
85-115 percent. Compound retention time drifts are also measured from this analysis and tracked
to ensure that the HPLC instruments are operating within acceptable parameters.
If one of these CCV does not meet the criterion, analysis of a second injection of the
CCV is performed. If the second CCV does not pass or if more than one CCV does not meet the
criterion, a new standard is prepared and analyzed. If it fails a third time, a new calibration curve

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(at least 5 concentration levels) is analyzed. All samples analyzed with the unacceptable CCV
will be reanalyzed.
Crotonaldehyde tautomerizes into two chromatographical 1 y separate peaks after it is
spiked onto the DNPH cartridge. The best analytical recovery for crotonaldehyde is determined
when both the peaks are integrated together for all samples and QC.
Acetaldehyde elutes with its stereoisomer. The best analytical recovery for acetaldehyde
is determined when both peaks are integrated together for all samples and QC.
Acetonitrile system blanks (or solvent blanks) bracket each sequence, with one at the
beginning of the sequence and one at the end. The system is considered in control if target
compound concentrations are less than the current laboratory MDLs. Quality procedures
determined for the carbonyl analysis ensure that ambient air samples are collected in the
prescribed manner and that compound quantitative analyses are performed with known bias and
precision. The quality procedures for carbonyl analysis are presented in Table 11-4.
1 1.3.4 PAH Analysis
Every 12 hours, the mass spectrometer used for PAH analysis must have an acceptable
Decafluorotriphenylphosphine (DFTPP) instrument performance tune check meeting the criteria
listed in Table 11-5 when 1 (.iL or less of the GC/MS tuning standard, depending on instrument
sensitivity, is injected through the GC (50 nanogram (ng) on column).
Samples should be received with filters folded and inserted into the glass thimble
cartridge with the sorb en t media. It will be noted on the COC and extraction bench sheet if a
filter is received in a petri dish, instead of a glass thimble. Prior to sample analyses, a daily CCV
must be analyzed, usually a standard prepared at approximately the midpoint of the calibration
curve from NlST-traceable PAH stock solution. The resulting response factor for each

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Table 11-4
Summary of Carbonyl Quality Control Procedures
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Page
Parameter
QC Check
Frequency
Acceptance Criteria
Corrective Action
HPLC
Efficiency
Analyze Second
Source QC
(SSQC) sample
Once per 12 hours or
less
1)	Resolution between acetone and
propionaldehyde > 1.0
2)	Column efficiency > 5,000 plate counts
1)	Eliminate dead volume
2)	Back flush
3)	Replace the column repeat
analysis
DNPH Peak
All samples
Every chromatogram
from an extracted
cartridge (field sample,
method blank, lot blank,
and BS/BSD)
DNPH must be > 50% of the DNPH are in
the laboratory QC samples
1) Sample concentration will
be flagged as estimate ("E")
Sampler
Certification
Zero Challenge
cartridge with a
reference cartridge
Annual
Each compound must be < 0.2 ppbV above
the reference cartridge
1)	Repeat certification of
samplers, a requirement for
Tier I compounds
2)	Notify Program Manager
(flagging non-Tier I
compound data for sampler
mav be an option)
ICAL
Run a 5-point
calibration curve
At setup or when
calibration check is out
of acceptance criteria (at
least every 6 months)
1)	Correlation coefficient at least 0.999,
relative error for each level against
calibration curve < 20%
2)	The absolute value of the intercept/slope
of the calibration curve must be less than
the MDL for each compound
1)	Check integration
2)	Reanalyze
3)	Reprepare standards and
recalibrate
ICV
Analyze SSQC
sample
After calibration in
triplicate
85-115% recovery
1)	Check integration
2)	Recalibrate
3)	Reprepare standard

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Table 11-4
Summary of Carbonyl Quality Control Procedures (Continued)
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Element No.
Revision No.
Date
Page
Parameter
QC Check
Frequency
Acceptance Criteria
Corrective Action
Retention Time
Analyze SSQC
Once per 12 hours or
less
Each target compound within ± 2.5% of the
mean calibration standards RT (set in
Agilent® software)
1)	Check integration.
2)	Check for plug in LC
3)	Check column temperature
in LC
ccv
Analyze SSQC
sample
Once per 12 hours or
less
85-115% recovery
1)	Check integration
2)	Reanalyze, reprepare
standard, or recalibrate
3)	Reanalyze samples not
bracketed by acceptable
standard
Solvent Blank
(aka Continuing
calibration blank
(CCB), System
Blank, or
Laboratory
Reagent Blank
(LRB))
Analyze
acetonitrile
Bracket sample batch. 1
at beginning and 1 at
end of batch
Measured concentration must be < MDL for
each compound
1)	Locate contamination
and correct
2)	Flag associated data
Sampling Period
All samples
All samples
24 hours ± 1 hours
1)	Notify Program Manager
2)	Flag samples 22-23 hours
and 25-26 hours in AQS with
a "Y" flag
3)	Invalidate and re-sample for
> 24±2 hours

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Table 11-4
Summary of Carbonyl Quality Control Procedures (Continued)
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Element No.
Revision No.
Date
Page
Parameter
QC Check
Frequency
Acceptance Criteria
Corrective Action
Lot Blank
Check
Analyze blank for
new lots received
Analyze 1.0 % of total
lot or a minimum of 3
cartridges, whichever is
greater
Compounds must be less than values listed:
Formaldehyde
<0.15 (.ig/cartridge (0.03 (.ig/mL
Acetaldehyde
<0.10 (.ig/cartridge (0.02 (ig/mL
Acetone
<0.30 (.ig/cartridge (0.06 (ig/mL
Others
<0.10 (.ig/cartridge (0.02 (ig/mL
1)	Reanalyze an additional set
of cartridges from the new lot
2)	Notify vendor if lot blank
continues to fail and acquire
new lot if possible
3)	Flag data associated with
bad lot
Extraction
Solvent Method
Blank (ESMB)
Aliquot of
extraction solvent
prepared with
samples during
extraction
First extraction per
month and when
acetonitrile lot changes
All target compounds must be < MDL
1)	Check integration
2)	Reanalyze
3)	Locate and resolve
contamination in extraction
glassware/solvent
4)	Flag batch data
Field Blank (FB)
Check
Field blank
samples collected
in the field
Monthly (if provided by
site)
Underivatized compound concentrations
must be less than values listed:
Formaldehyde
<0.3 fig/cartridge (0.06 (ig/mL
Acetaldehyde
<0.4 fig/cartridge (0.08 (ig/mL
Acetone
<0.75 fig/cartridge (0.15 (ig/mL
Others
<7.0 (ig/cartridge (1.4 ng/mL
1)	If FB fails, notify site
coordinator, schedule another
FB. Additional FBs are
collected until the problem is
corrected and data are
acceptable
2)	Flag samples since the last
acceptable FB

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Table 11-4
Summary of Carbonyl Quality Control Procedures (Continued)
Project No.
Element No.
Revision No.
Date
Page
Parameter
QC Check
Frequency
Acceptance Criteria
Corrective Action
Duplicate or
Collocate
Samples
Analysis of
duplicate and
collocated samples
As collected (10% of
sampling schedule)
< 20% RPD for concentrations > 0.5
(.ig/cart ridge
1)	Check integration
2)	Check instrument function
3)	Reanalyze duplicate
samples
4)	Flag data in LIMS (and
AQS as permitted)
Replicate
Analyses
Replicate
injections
One per batch.
Performed on every
duplicate and collocate
sample or if none
available, on a field
sample
< 10% RPD for concentrations >0.5
(.ig/cartridge
1)	Check integration
2)	Check instrument function
3)	Reanalyze sample
MB (BLK)
Analyze MB
One per batch of 20
samples
Underivatized compound concentrations
must be less than values listed:
Formaldehyde
<0.15 (ig/cartridge (0.03 (.ig/mL)
Acetaldehyde
<0.10 (.ig/cartridge (0.02 (.ig/mL)
Acetone
<0.30 (.ig/cartridge (0.06 (.ig/mL)
Others
<0.10 (.ig/cartridge (0.02 (.ig/mL)
1)	Reanalyze MB
2)	Check extraction
procedures
3)	Flag batch data

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Project No.	0344.00
Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	14 of 40
Table 11-4
Summary of Carbonyl Quality Control Procedures (Continued)
Parameter
QC Check
Frequency
Acceptance Criteria
Corrective Action
Blank
Spike/Blank
Spike Duplicate.
(BS/BSD or
LCS/LCSD)
Analyze BS/BSD
(or LCS/LCSD)
One BS/BSD
(LCS/LCSD) per batch
of 20 samples
80-120% recovery for Formaldehyde and
Acetaldehyde and 70-130% for all other
compounds.
BSD (LCSD) precision <20% RPD of BS
(LCS)
1)	Reanalyze BS/BSD
(LCS/LCSD)
2)	Check calibration
3)	Check extraction
procedures
Note: Crotonaldchydc tautomerizes into two chromatographically separate peaks after it is spiked onto the DNPH cartridge. The best analytical recovery is
determined when both peaks arc integrated together for all samples and QC. Acctaldchydc elutes with its stereoisomer. The best analytical recovery for
Acctaldchydc is determined when both peaks arc integrated together for all samples and QC. Breakthrough cartridges arc not submitted or analyzed as
specified by Compendium Method TO-11 A.

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Date	March 2018
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compound will be compared to the average calibration curve response factors. Correspondence
within an absolute value of less than or equal to 30 percent difference is considered acceptable. If
the first CCV does not meet this criterion, a second CCV will be analyzed. If the second CCV is
acceptable, sample analysis can continue. If the second CCV does not meet acceptance criteria,
then a leak check and system maintenance are performed. If the system maintenance is
completed and a third CCV analysis meets the criterion, then analysis may continue. If the
maintenance causes a change in the system response, a new calibration curve must be analyzed
before sample analyses can begin.
EPA Compendium Method TO-13A1"" employs and spikes two different types of
surrogates. The Field Surrogates, fluoranthene-dio and benzo(a)pyrene-d12, are spiked onto the
PUF media prior to shipment to the field; acceptable recoveries for these field surrogates are in
the range of 60 to 120 percent. The laboratory surrogates, fluorene-dio and pyrene-dio, are spiked
into the PUF immediately before extraction; acceptable recoveries for these laboratory surrogates
are 60 to 120 percent.
Table 11-5. DFTPP Key Ions and Ion Abundance Criteria
Mass
Ion Abundance Criteria
51
10 to 80% of base peak
68
< 2% of mass 69
69
Present
70
< 2% of mass 69
127
10 to 80% of base peak
197
< 2% of mass 198
198
Base peak (100% relative abundance) or >50% of mass 442
199
5 to 9% of mass 198
275
10 to 60% of base peak
365
> 1.0% of mass 198
441
Present but < 24% of mass 442
442
Base peak, or >50% of mass 198
443
15 to 24% of mass 442
Note: All ion abundances must be normalized to the nominal ba.se peak. 198 or 442. This
criterion is based on the tunc criteria for Method 8270D.

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
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Internal standard responses and retention times must also be evaluated for stability. The
SIM procedures of EPA Compendium Method TO-13 A1"" preclude the use of guidelines for
qualitative analysis of mass spectra, since complete mass spectra are not acquired when SIM
procedures are used. Quantitative analysis for each compound is performed relative to the
assigned internal standard. The following internal standard assignments are suggested for PAH
analysis are presented in Table 1 1-6. All method criteria and MQOs for ERG's PAH analysis are
listed in Table 1 1-7.
Table 11-6. Internal Standards and Associated PAHs
Internal Standard
Associated Compound
Naphthalene-dx
Naphthalene
Acenaphthelene-dio
Acenaphthylene
Acenaphthene
Fluorene
9-Fluorenone
Pyrene
Retene
Fluoranthene
Phenanthrene-dio
Phenanthrene
Anthracene

Chrysene-di;
Cyc 1 ope n ta( c .d )py re ne
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Chrysene
Perylene-di;
Perylene
Indenof 1,2,3 -cd)pyrene
Dibenz(a.h (anthracene
Benzo(g,h,i)perylene
Coronene

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Table 11-7
Summary of Quality Control Procedures for Analysis of SVOC Samples for PAHs
Project No.
Element No.
Revision No.
Date
Page
Quality Control
Check
Frequency
Acceptance Criteria
Corrective Action
DFTPP instrument
tunc check
Daily prior to calibration check and
sample analysis; every 12 hours if
instrument is operated 24 hours/day
Evaluation criteria presented in
Section 11. Table 11-5
1)	Re-analyze
2)	Prepare new tune check standard;
analyze
3)	Re-tune instrument; reanalyze
4)	Clean ion source; re-tune
instrument; reanalyze
Solvent Blank (SB)
Prior to ICAL
All target compounds < MDL
1)	Reanalyze
2)	Perform maintenance on GC;
reanalyze
Five-point (minimum)
calibration (ICAL)
Following any major change, repair,
or maintenance if daily quality
control check is not acceptable.
Minimum frequency every six weeks
< 30% RSD of the RRFs for
each compound; Avg Relative
Response Factor (RRF) above or
equal to minimum RRF limit for
each pollutant; < 30% the
nominal concentration required
for Tier I compounds
RRTs within ± 0.06 RRT units
of mean RRT of calibration
IS RT within ± 20.0 sec of mean
RT of calibration
1)	Repeat individual calibration
standard analyses
2)	Check integrations and calculations
3)	Prepare new calibration standards
and repeat analysis
4)	Perform maintenance on GC,
especially leak check and repeat
analysis
5)	Clean ion source and repeat analysis

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	18 of 40
Table 11-7
Summary of Quality Control Procedures for Analysis of SVOC Samples for PAHs (Continued)
Quality Control
Check
Frequency
Acceptance Criteria
Corrective Action
Retention Time (RT)
All qualitatively identified
compounds and internal standard
RRT set in software to be no
larger than + 0.25 minutes
Repeat analysis
Secondary Source
Calibration Verification
(SCV)
Immediately after each ICAL
< 30% Difference for each
compound RRF compared to the
mean RRF of the calibration
curve.
1)	Repeat SCV analysis
2)	Check calculations
3)	Prepare a new SCV standard and
repeat analysis
4)	Perform maintenance on GC,
especially leak check; reanalyze
5)	Clean ion source; reanalyze
Continuting Calibration
Verification (CCV)
Standard
Daily (or every 12 hours)
Above or equal to RRF
minimum and < 30% Difference
for each compound RRF
compared to the mean RRF of
the calibration curve.
1)	Repeat individual sample analyses
2)	Check calculations
3)	Prepare a new CCV standard and
repeat analysis
4)	Perform maintenance on GC,
especially leak check; reanalyze
5)	Clean ion source; reanalvze
Solvent Method Blank
(SMB)
One with every extraction batch of
20 or fewer field-collected samples.
All target compounds < MDL
1)	Check integration
2)	Reanalyze
3)	Flag samples
4)	Remove solvent lot from use
Method Blank (MB)
With every extraction batch < 20
samples
All analytes < 2x MDL
1)	Repeat analysis
2)	Flag data
Blank Spike (BS) or
(LCS)
BSD (or LCSD)
One BS (or LCS) with every
extraction batch < 20 samples.
BSD (or LCSD) once per quarter.
60-120% recovery of nominal
for all compounds
< 20% RPD compared to BS (or
LCS)
1)	Repeat analysis
2)	Flag data

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Project No.	0344.00
Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	19 of 40
Table 11-7
Summary of Quality Control Procedures for Analysis of SVOC Samples for PAHs (Continued)
Quality Control
Check
Frequency
Acceptance Criteria
Corrective Action
Surrogate compound
recoveries:
Laboratory surrogates
fluorene-dio
pyrene-dio
Field Surrogates
fluoranthene-dio
benzo(a)pyrene-di 2
Every sample/blank/BS
60-120% Recovery
1)	Repeat analysis
2)	Check calculation
3)	Flag surrogate data
4)	Flag sample data if both field or both
lab surrogates fail
Internal Standard
Response:
naphthalene-ds
acenaphthylene-di 0
chrysene-di2
perylene-di2
Every sample/blank/BS
Within 50% to 200% of the ISs
in the most recent initial
calibration CAL4
1)	Repeat analysis
2)	Invalidate or flag data if unable to
reanalyze
Cartridge Lot Blank
One cartridge (and filter) for each
batch of prepared cartridges for a
particular sample date.
All target compounds < 2 times
the MDL
1)	Repeat analysis
2)	Invalidate or flag data if unable to
reanalyze prior to cartridge shipment
Field Blank
Monthly (or as provided by site)
Target compounds < 5 times the
MDL
1)	If FB fails, notify site coordinator,
schedule another FB. Additional FBs
are collected until the problem is
corrected and data are acceptable
2)	Flag samples since the last
acceptable FB when input in AQS
Replicate Analysis
Replicate sample, on each collocate
or at a minimum one per sequence
< 10% RPD for concentration >
0.5 ng/(.iL or lowest cal point,
whichever is less.
1)	Check integration
2)	Check instrument function
3)	Reanalyze
4)	Flag replicate samples

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
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Table 11-7
Summary of Quality Control Procedures for Analysis of SVOC Samples for PAHs (Continued)
Quality Control
Check
Frequency
Acceptance Criteria
Corrective Action
Collocate Samples
Collocated samples, 10% of field
samples, or as collected
< 20% RPD for concentration >
0.5 ng/(.iL or lowest ICAL level,
whichever is less
1)	Check integration
2)	Check instrument function
3)	Reanalyze
4)	Flag collocated samples
Sampling Period
All samples
24 hours ± 1 hours
1)	Notify Program Manager
2)	Flag samples 22-23 hours and 25-26
hours in AQS with a "Y" flag
3)	Invalidate and re-sample for > 24±2
hours
NOTE: Matrix Spikes are not performed as required by Compendium Method TO-13A. Matrix spikes are not required by ASTM D2609.

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4
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11.3.5 Metals Analysis
The mass spectrometer used for metals analysis must have an acceptable daily
performance check using the tuning solution before each analysis. Daily performance checks are
done in both standard and kinetic energy discrimination (KED) mode to verify instrument
performance in both modes. Performance specifications are presented in Table 1 1-8. Analysis of
the metals will be performed by ICP-MS for antimony, arsenic, beryllium, cadmium, total
chromium, cobalt, lead, manganese, mercury, nickel, and selenium. The internal standards for
this method are lithium, scandium, germanium, yttrium, indium, terbium, holmium, and bismuth.
Internal standard responses must be evaluated for stability. Gold is added to each of the standards
before analysis to prevent the loss of mercury on lab ware or instrument tubing in the ICP-MS.
Daily calibration, using a calibration blank and at least 5 non-zero standards prepared
from NlST-traceable stock solutions, is performed to ensure that the analytical procedures are in
control. To be considered acceptable, the calibration curve must have a correlation coefficient
> 0.998. Replicate analysis of the calibration standards must have an RSD < 10 percent, except
for the second calibration standard (CAL2). This standard uses the same concentrations as the
Limit of Quantitation (LOQ) standard, which are near or less than that of the MDL, therefore an
RSD > 10 percent is acceptable. After calibration, an Initial Calibration Verification (ICV),
Initial Calibration Blank (ICB), High Standard Verification (HSV), Interference Check Standard
A (ICSA), and Interference Check Standard B (ICSAB) are analyzed to ensure quality before the
analysis of the samples.
If the initial calibration check does not meet criteria, a second calibration check analysis
is performed. If the second set does not pass, or if one or more of the daily QC checks do not
meet criteria, a new calibration curve is prepared and analyzed. All samples analyzed with the
unacceptable QC check will be reanalyzed or flagged appropriately when necessary. During the
analysis of the samples, the Continuing Calibration Verification (CCV) and Continuing
Calibration Blank (CCB) are analyzed immediately before the analysis of samples, every 10

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Date	March 2018
Page	22 of 40
samples, and at the end of every analysis batch, he ICS A and ICSAB are analyzed once per
analysis day. Quality procedures for metals analysis are shown in Table 1 1-9.
Table 11-8 Instrument Mass Calibration & Performance Specifications
Parameter
Peak Width
Sensitivity/Criteria*
RSD
IT Is' -
Standard Mode
Bkg4.5
NA
< 1.0 cps
N/A
7Li
0.65-0.85
> 50,000 cps
< 2% RSD
24Mg
0.65-0.85
> 500,000 cps
< 2% RSD
25 Mg
0.65-0.85
> 70,000 cps
< 2% RSD
26Mg
0.65-0.85
> 80,000 cps
< 2% RSD
59Co
0.65-0.85
> 100,000 cps
< 2% RSD
1 15 In
0.65-0.85
> 220,000 cps
< 2% RSD
206Pb
0.65-0.85
> 70,000 cps
< 2% RSD
207Pb
0.65-0.85
> 60,000 cps
< 2% RSD
208Pb
0.65-0.85
> 100,000 cps
< 2% RSD
238U
0.65-0.85
> 300,000 cps
< 2% RSD
140Cel60/140Ce
NA
<0.02
N/A
13 7Ba++/13 7Ba+
NA
<0.03
N/A
Bkg220.7
NA
< 2.0 cps
N/A
Analyzer Pressure
NA
< 10"6 mbar
NA
KED Modef
Bkg4.5
NA
< 0.5 cps
N/A
24Mg
0.65-0.85
> 3,000 cps
< 5% RSD
25Mg
0.65-0.85
> 500 cps
< 5% RSD
26Mg
0.65-0.85
> 600 cps
< 5% RSD
59Co
0.65-0.85
> 30,000 cps
< 2% RSD
1 15 In
0.65-0.85
> 30,000 cps
< 2% RSD
206Pb
0.65-0.85
> 60,000 cps
< 2% RSD
207Pb
0.65-0.85
> 50,000 cps
< 2% RSD
208Pb
0.65-0.85
> 80,000 cps
< 2% RSD
238U
0.65-0.85
> 80,000 cps
< 2% RSD
140Cc 160/140Ce
NA
<0.01
N/A
59Co/35C1160
NA
> 18.0
N/A
Bkg220.7
NA
< 2.0 cps
N/A
*cps - Counts per second
t - There are no vacuum requirements for KED mode

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Table 11-8 Instrument Mass Calibration & Performance Specifications (Continued)
Parameter
Peak Width
Sensitivity/Criteria*
RSD
i( i rii^riji
Standard Mode
Bkg4.5
NA
< 1.0 cps
N/A
7Li
0.65-0.85
> 55,000 cps
< 2% RSD
24Mg
0.65-0.85
> 500,000 cps
< 2% RSD
25Mg
0.65-0.85
> 80,000 cps
< 2% RSD
26M.o
0.65-0.85
> 100,000 cps
< 2% RSD
59Co
0.65-0.85
> 100,000 cps
< 2% RSD
1 15 In
0.65-0.85
> 240,000 cps
< 2% RSD
206Pb
0.65-0.85
> 80,000 cps
< 2% RSD
207Pb
0.65-0.85
> 70,000 cps
< 2% RSD
208Pb
0.65-0.85
> 160,000 cps
< 2% RSD
238U
0.65-0.85
> 330,000 cps
< 2% RSD
140Cc 160/140Ce
NA
<0.02
N/A
13 7Ba++/13 7Ba+
NA
<0.03
N/A
Bkg220.7
NA
< 2.0 cps
N/A
Analyzer Pressure
NA
< 10"6 mbar
NA
KED Modef
Bkg4.5
NA
< 0.5 cps
N/A
24Mg
0.65-0.85
> 10,000 cps
< 5% RSD
25 Mg
0.65-0.85
> 2,000 cps
< 5% RSD
26Mg
0.65-0.85
> 3,000 cps
< 5% RSD
59Co
0.65-0.85
> 30,000 cps
< 2% RSD
1 15 In
0.65-0.85
> 35,000 cps
< 2% RSD
206Pb
0.65-0.85
> 100,000 cps
< 2% RSD
207Pb
0.65-0.85
> 90,000 cps
< 2% RSD
208Pb
0.65-0.85
> 200,000 cps
< 2% RSD
238U
0.65-0.85
> 85,000 cps
< 2% RSD
140Cel60/140Ce
NA
<0.01
N/A
59Co/35C1160
NA
> 18.0
N/A
Bkg220.7
NA
< 2.0 cps
N/A
*cps - Counts per second
f - There are no vacuum requirements for KED mode

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Table 11-9
Summary of Quality Control Procedures for Metals Analysis
Project No.
Element No.
Revision No.
Date
Page
Quality Control Check
Frequency
Acceptance Criteria
Corrective Action
Daily Performance
Check (DPR) STD
Mode
Before each analysis
See Table 11-8
1)	Repeat analysis of DPR
2)	Re-optimize instrument tuning parameters
3)	Reprepare DPR standard
4)	Perform instrument maintenance
Daily Performance
Check (DPR) RED
Mode
Before each analysis
See Table 11-8
1)	Repeat analysis of DPR
2)	Re-optimize instrument tuning parameters
3)	Reprepare DPR standard
4)	Perform instrument maintenance
Initial Calibration
Standards (IC)
Daily before each analysis, at
least 5 non-zero calibration
points and a blank
Correlation coefficient (R) > 0.998
replicate %RSD <10. RSDs >
10% are acceptable for the target
elements in the CAL2 standard (at
LOQ concentration).
1)	Repeat analysis of calibration standards
2)	Reprepare calibration standards and
reanalyze
ICV
Immediately after calibration
Recovery 90-110%
1)	Repeat analysis of ICV
2)	Reprepare ICV standard
3)	Recalibrate and reanalyze
ICB
Immediately after ICV
Absolute value must be < MDL
1)	Locate and resolve contamination
problems before continuing
2)	Reanalyze or recalibrate failing elements
for the entire analvsis when appropriate
HSV
After ICB and before ICS
Recovery from 95-105%
1)	Repeat analysis of HSV
2)	Reprepare HSV
ICSA/IFA
Following the HSV
Within ±3 times LOQ from zero or
from the stock standard background
contamination when present
1)	Repeat analysis of ICS A
2)	Reprepare ICSA and analyze
3)	Recalibrate or flag failing elements as
necessary

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Table 11-9
Summary of Quality Control Procedures for Metals Analysis (Continued)
Project No.
Element No.
Revision No.
Date
Page
Quality Control Check
Frequency
Acceptance Criteria
Corrective Action
ICSAB/IFB
Following each ICS A
Recovery 80-120% of true value
plus standard background
contamination when present
1)	Repeat analysis of ICSAB
2)	Reprepare ICSAB and analyze
3)	Recalibrate or flag failing elements as
necessary
CCV
Analyze before samples, after
every 10 samples, and at the end
ofeach run
Recovery 90-110%
1)	Reanalyze CCV
2)	Reprepare CCV
3)	Recalibrate and reanalyze samples since
last acceptable CCV
Low Calibration
Verification (LCV)
After the first and last CCV
Recovery 70-130% for Pb only
1)	Reanalyze LCV
2)	Reprepare LCV
3)	Recalibrate and reanalyze samples since
last acceptable LCV
CCB
Analyzed after each CCV
Absolute value must be < MDL
1)	Reanalyze CCB
2)	Reanalyze samples since last acceptable
CCB
Laboratory Reagent
Blank (LRB)/Blank
(BLK1)
1 per batch of < 20 samples
Absolute value must be < MDL
1)	Reanalyze for verification
2)	If > 5x MDL, failing elements for all batch
QC and samples must be flagged
3)	When enough sample filter remains (for
quartz and glass fiber filters), a reextraction
and analysis of the batch should be
considered
MB/BLK2
1 per batch of < 20 samples
Absolute value must be < MDL.
Flag the failing elements in the MB. Note:
This QC sample is not required by the IO-
3.5 method and there is no further corrective
action
Standard Reference
Material (SRM)
1 per batch of < 20 samples
Recovery 80-120% for Pb only
1)	Reanalyze
2)	Flag sample data
3)	Re-extract batch if possible

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Table 11-9
Summary of Quality Control Procedures for Metals Analysis (Continued)
Project No.
Element No.
Revision No.
Date
Page
Quality Control Check
Frequency
Acceptance Criteria
Corrective Action
LCS/BS (and
LCSD/BSD for 47mm
Teflon filters only)
1 per batch of < 20 samples
Recovery 80-120%, < 20% RPD for
BS/BSD
1)	Reanalyze
2)	Flag data if recovery for only one or two
elements fail criteria
3)	Reprepare sample batch if recovery for
most elements fail criteria, when possible
Duplicate (DUP1)
(Laboratory Duplicate)
1 per batch of < 20 samples, for
quartz/TSP/Glass fiber filters
only
< 20% RPD for sample and
duplicate values > 5x MDL
1)	Check for matrix interference in the case
of DlJPl.
2)	Repeat duplicate analysis
3)	Flag data
Replicate Analysis
(Analytical Duplicate)
1 per batch of < 20 samples
< 20% RPD for sample and
duplicate values > 5x MDL
1)	Repeat replicate analysis
2)	Flag data
Collocated Samples
(C1/C2)
10% of samples annually (for
sites conducting collocated
sampling)
< 20% RPD of samples and
collocated values > 5x MDL
1)	Repeat C1 and/or C2 analyses if replicate
analyses fail
2)	Flag CI and C2 data if associated
replicate reanalvses vcrifv failure
Matrix Spike (MS) and
Matrix Spike Duplicate
(MSD) for 8x10"
Quartz/TSP/Glass fiber
filters only
1 per batch of < 20 samples
Recovery 80-120% when the parent
sample concentration is less than 4
times the spike concentration.
Not applicable to Teflon method
1)	Flag data if recovery for only one or two
elements fail criteria, or when a matrix
interference is confirmed by Serial Dilution
(SRD) and/or Post Digestion Spike (PDS)
results
2)	Reanalyze
3)	Reprepare sample batch if recovery for
most elements fail criteria or contamination
is evident
4)	Sb failures must be flagged on MS/MSD
and all samples

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Table 11-9
Summary of Quality Control Procedures for Metals Analysis (Continued)
Project No.
Element No.
Revision No.
Date
Page
Quality Control Check
Frequency
Acceptance Criteria
Corrective Action
MS/MSD RPD for
8x10" Quartz/TSP/Glass
filters only
1 per batch of < 20 samples
RPD <20%
Not applicable to Teflon method
1)	Check for 4x spike concentration and
non-homogenous matrix, flag as necessary
2)	Reanalyze for verification
PDS
1 per batch of < 20 samples
Recovery 75%-125%
1)	Flag failed elements for parent
sample and PDS
2)	Reprepare PDS if preparation issue is
suspected reason for failure
SRD
1 per batch of < 20 samples
10% RPD of undiluted sample if the
element concentration is > 25x
MDL
1)	Reprepare dilution if preparation
issue is suspected reason for failure
2)	Flag failed analytes
Field Blank
All Field Blanks as received
from field
<5x MDL
1) Flag failed elements in FB
Internal Standards
(ISTD)
Every Calibration. QC and Field
Sample
Recovery 60-125% of the measured
intensity of the calibration blank
1)	If drift suspected, stop analysis and
determine cause, recalibrate if necessary
2)	Reprepare sample
3)	If recovery > 125% due to inherent
ISTD, dilute sample and reanalyze
Sampling Period
All samples
24 hours ± 1 hours
1)	Notify Program Manager
2)	Flag samples 22-23 hours and 25-26
hours in AQS with a "Y" flag
3)	Invalidate and re-sample for > 24±2
hours

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1 1.3.6 Hexavalent Chromium Analysis
CCVs prepared from NIST-traceable stocks are performed each analysis day to ensure
that the analytical procedures are in control. During the analysis of the samples, the ICV and ICB
are analyzed immediately before the analysis of samples, a CCV and CCB after every ten
injections, and at the end of every analysis batch. The acceptance criteria are between
90-1 10 percent recovery for the ICVs and CCVs and less than MDL for the ICBs and CCBs.
If these daily CCVs (and/or CCBs) do not meet the criterion, a second analysis of the
same standard is performed. If the second CCV does not pass or if more than one daily CCV
does not meet the criterion, a new standard is prepared and analyzed. If it fails a third time, a new
calibration curve (with at least 5 concentration levels) is analyzed. All samples analyzed with the
unacceptable CCV will be reanalyzed. The quality procedures for hexavalent chromium analysis
are presented in Table 11-10.

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Table 11-10
Summary of Quality Control Procedures for Hexavalent Chromium
QC Check
Frequency
Acceptance Criteria
Corrective Action
Initial 6-point calibration
standards
Before every sequence
Correlation coefficient > 0.995;
Relative Error (RE) < 20%
1)	Repeat analysis of calibration standards
2)	Reprepare calibration standards and reanalyze
ICV
Before every sequence,
following the initial
calibration
Recovery 90-110%
1)	Repeat analysis of initial calibration
verification standard
2)	Repeat analysis of calibration standards
3)	Reprepare calibration standards and reanalyze
ICB
One per batch, following
the ICV
Analyte must be < MDL
1)	Reanalyze
2)	Reprepare blank and reanalyze
3)	Correct contamination and reanalyze blank
4)	Flag data of all samples in the batch
ccv
Every 10 injections and at
the end of the sequence
Recovery 90-110%
1)	Repeat analysis of CCV
2)	Reprepare CCV
3)	Flag data bracketed by unacceptable CCV
Laboratory Control Sample
(LCS/LCSD)
Two per sample batch of <
20 samples
Recovery 90-110%
1)	Reanalyze
2)	Reprepare standard and reanalyze
3)	Flag data of all samples since the last
acceptable LCS
MB
One per batch
Analyte must be < MDL
1)	Reanalyze
2)	Flag data for all samples in the batch
Replicate Analysis
Duplicate. Collocate.
BS/BSD and/or replicate
samples only
RPD < 20% for concentrations
greater than 5 x the MDL
1)	Check integration
2)	Check instrument function
3)	Flag samples
CCB
After every CCV and at the
end of the sequence
Analyte must be < MDL
1)	Reanalyze
2)	Reprepare blank and reanalyze
3)	Correct contamination and reanalyze blank
4)	Flag data of all samples in the batch


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Table 11-10
Summary of Quality Control Procedures for Hexavalent Chromium (Continued)
Project No.
Element No.
Revision No.
Date
Page
QC Check
Frequency
Acceptance Criteria
Corrective Action
Retention Time (RT)
For identification of analyte
RT must be within 5% window of
the average RT of initial calibration
standards
1)	Check integration/identification
2)	Reanalyze
Sampling Duration
All samples
24 hours ± 1 hours
1)	Notify Program Manager
2)	Flag samples 22-23 hours and 25-26 hours in
AQS with a "Y" flag
3)	Invalidate and re-sample for > 24±2 hours

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11.4 Precision
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Analytical precision is estimated by repeated analysis of approximately 10 percent of the
samples. The second analysis is performed in the same analytical batch as the first analysis.
Duplicate and collocated samples are reanalyzed once each to determine overall precision,
including sampling and analysis variability.
Precision estimates are calculated in terms of absolute percent difference. Because the
true concentration of the ambient air sample is unknown, these calculations are relative to the
average sample concentration.
Precision is determined as the RPD using the following calculation:
RPD
X,
- X,
X
100
Where:
Xi is the ambient air concentration of a given compound measured in one sample;
X; is the concentration of the same compound measured during
duplicate/col 1 ocate/replicate analysis; and
X is the arithmetic mean of Xi and X:.
11.5 Completeness
Completeness, a quality measure, is calculated at the end of each year. Percent
completeness is calculated as the ratio of the number of valid samples received to the number of
scheduled samples (beginning with the first valid field sample received through the last field
sample received). This quality measure is presented in the final report. The completeness criteria
for all parameters were previously presented in Table 4-1.

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Completeness is determined using the following calculation:
Number of valid samples
Completeness = —	;	;	:			;— x 100
Total expected number of samples
11.6	Representativeness
Representativeness measures how well the reported results reflect the actual ambient air
concentrations. This measure of quality can be enhanced by ensuring that a representative
sampling design is employed. This design includes proper integration over the desired sampling
period and following siting criteria established for each task. The experimental design for sample
collection should ensure samples are collected at proper times and intervals for their designated
purpose per the data quality objectives. For example, SNMOC samples are collected to gain
information about PA MS volatile hydrocarbons. Therefore, collection of 3-hour samples from
6:00 a.m. to 9:00 a.m. each weekday is appropriate. Quality measures for duplicate sample
collection and replicate analyses are included. ERG is not responsible for the sampling design;
therefore, representativeness is beyond the scope of this QAPP. The state and local areas should
designate the representativeness following EPA guidelines, however a copy of the 2018 EPA
sampling schedule is presented in Appendix B.
11.7	Sensitivity (Method Detection Limits)
Based on changing EPA guidance on MDL determination procedures, the NATTS
program has adopted two MDL procedures, a modified Method Update Rule (MUR) for CFR
Part 136, Appendix B1'91 and the Federal Advisory Committee (FAC) Single Laboratory
Procedure (v2.4)(20). In the modified MUR, the MDLs are determined using spiked sample and
blank sample data, using the larger value for the new MDL. The MDLs determined from spiked
samples are verified by analyzing standards at one to four times the newly determined limits. For
the FAC, the historic blank sample data is used to determine the MDL and spiked samples are
used if the blank data does not meet requirements. VOC, carbonyl, SVOC, metals and hexavalent
chromium analyses follow one of the two methods for MDL determination.

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For SNMOC and hexavalent chromium (non-NATTS program), the MDLs of the target
compounds are determined by analyzing at least seven spiked samples at one concentration on
the appropriate collection media (ex.- for SNMOC, 7 spiked samples in 7 individual canisters).
The concentration of the spiked samples should be within five times the expected detection limit.
The samples should be prepared in a minimum of three different preparation batches and
analyzed over 3 non-consecutive days (minimum). This procedure follows the method listed in
the 1987 CFR Part 136, Appendix The MDLs determined from spiked samples are verified
by analyzing standards at one to four times the newly determined limits.
The MDL for NMOC has not been determined in 2018. If this method is needed, a
detection limit study will be performed before analysis begins. The MDLs for the SNMOC are
listed in Table 11-11, for VOCs in Table 11-12, and carbonyl compounds (based on a sample
volume of 1000 L) in Table 11-13. The PAH MDLs, based on a sampling volume of 300 m3, are
presented in Table 11-14.
Table 11-11. 2018 SNMOC Method Detection Limits
Target Compound
MDL
(ppbC)
SQL
(ppbC)
Target Compound
MDL
(ppbC)
SQL
(ppbC)
1,2.3-T rimethylbenzene*
0.172
0.546
Cyclopentene
0.515
1.64
1.2.4-Trimethylbenzene*
0.185
0.588
Ethane*
0.993
3.16
1,3,5 -T rimethylbenzene *
0.173
0.549
Ethylbenzene*
0.096
0.305
1,3-Butadiene*
0.123
0.390
Ethylene*
2.35
7.46
1-Butene*
0.125
0.396
Isobutane*
0.051
0.161
1 -Decene
0.185
0.588
Isobutene
0.131
0.417
1 -Dodecene
0.611
1.943
Isopentane*
0.060
0.191
1 -Heptene
0.082
0.262
Isoprene*
0.055
0.176
1-Hexene*
0.085
0.272
Isopropylbenzene*
0.089
0.284
1-Nonene
0.127
0.404
m,p-X ylene*
0.220
0.701
1 -Octene
0.096
0.305
w-Diethylbenzene *
0.446
1.42
1-Pentene*
0.060
0.190
Methylcyclohexane *
0.070
0.222
1-Tridecene
0.288
0.914
Methylcyclopentane *
0.115
0.365
1-Undecene
0.390
1.24
w-Ethyltoluene *
0.219
0.696
2,2,3-T rimethylpentane
0.057
0.182
«-Butane*
0.076
0.241
* PAMS compounds
NOTE: MDL's reported arc from Instrument 1. New MDLs will be reported for Instrument 4 if required.

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Project No.	0344.00
Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	34 of 40
Table 11-11. 2018 SNMOC Method Detection Limits
Target Compound
MDL
(PPbC)
SQL
(PPbC)
Target Compound
MDL
(PPbC)
SQL
(PPbC)
2,2,4-Trimethylpentane*
0.132
0.419
«-Decane*
0.238
0.755
2,2-Dimethylbutane *
0.084
0.267
/7-Dodecane*
0.445
1.41
2,3,4-T rimethvlpentane *
0.060
0.190
/7-Heptane*
0.075
0.239
2.3 -D i methyl butane *
0.057
0.182
«-Hexane*
0.175
0.558
2.3 -D i methyl pentane *
0.119
0.377
/7-Nonane*
0.095
0.302
2.4-Dimethylpentane *
0.096
0.305
/7-Octane*
0.062
0.197
2-Ethyl-l-butene
0.060
0.190
/7-Pentane*
0.081
0.256
2-Methyl-1 -Butene
0.089
0.283
/7-Propylbenzene *
0.121
0.385
2-Methyl-1 -Pentene
0.091
0.288
n-Tridecane
0.296
0.942
2-Methyl-2-Butene
0.287
0.912
/7-lJndecane*
0.339
1.08
2 -Methy lheptane *
0.199
0.631
o-Ethyltoluene*
0.152
0.483
2-Methylhexane*
0.136
0.431
o-Xylene*
0.131
0.417
2-Methylpentane *
0.189
0.600
/j-Diethvlbenzene*
0.191
0.609
3 -Methyl-1 -Butene
0.222
0.706
/;-Ethyltoluene*
0.203
0.644
3 -Methy lheptane *
0.134
0.426
Propane*
0.611
1.94
3 -Methy lhexane *
0.262
0.833
Propylene*
0.162
0.515
3 -Methy lpentane *
0.075
0.239
Propyne
0.056
0.177
4-Methyl-1 -Pentene
0.078
0.248
Styrene*
0.246
0.781
Acetylene*
0.044
0.139
Toluene*
0.609
1.94
Benzene*
0.080
0.255
/ra/7.v-2-Butene*
0.036
0.114
c7.v-2-Butene*
0.032
0.102
/ra/7.v-2-He\ene
0.038
0.120
c7.v-2-He\ene
0.063
0.200
rra/7.v-2-Pentene*
0.050
0.159
c7.v-2-Pentene*
0.055
0.175
a-Pinene*
0.189
0.602
Cyclohexane*
0.081
0.257
/>'-Pinene*
0.443
1.41
Cyclopentane*
0.055
0.175



* PAMS compounds
NOTE: MDL's reported arc from Instrument 1. New MDLs will be reported for Instrument 4 if required.

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	35 of 40
Table 11-12. 2018 Air Toxics Method Detection Limits

MDL
SQL

MDL
SQL
Target Compounds
(p.g/m3)
(p.g/m3)
Target Compounds
(p.g/m3)
(p.g/m3)
1.1.1 -T richloroethane
0.0750
0.238
cis-1.3-Dichloropropene
0.0894
0.284
1,1,2,2-Tetrachloroethane
0.144
0.457
Dibromochloromethane
0.131
0.417
1,1.2-T richloroethane
0.104
0.330
Dichlorodifluoromethane
0.135
0.430
1,1 -Dichloroethane
0.0578
0.184
Dichlorotetrafluoroethane
0.0938
0.298
1,1 -Dichloroethene
0.0473
0.150
Ethvl Acrvlate
0.0964
0.306
1.2.4-T richlorobenzene
1.85
5.89
Ethvl ferf-Butyl Ether
0.0458
0.146
1.2.4-T rimethylbenzene
0.132
0.420
Ethylbenzene
0.112
0.357
1.2-Dibromoethane
0.145
0.462
Hexachloro-1.3-Butadiene
0.293
0.931
1.2 -D i ch 1 o roethane
0.0564
0.179
m,p-X ylene
0.157
0.498
1.2-Dichloropropane
0.0941
0.299
w-Dichlorobenzene
0.110
0.348
1,3,5 -T rimethylbenzene
0.167
0.532
Methyl Isobutyl Ketone
0.0975
0.310
1,3-Butadiene*
0.0429
0.136
Methyl Methacrylate
0.411
1.31
Acetonitrile
0.0275
0.0873
Methvl terf-Butyl Ether
0.0371
0.1 18
Acetvlene
0.0421
0.134
Methylene Chloride
0.0500
0.159
Acrolein*
0.516
1.64
//-Octane
0.151
0.481
Acrylonitrile
0.0232
0.0736
o-Dichlorobenzene
0.124
0.394
Benzene*
0.0463
0.147
o-Xylene
0.1 17
0.371
Bromochloromethane
0.0703
0.223
//-Dichlorobenzene
0.121
0.384
Bromodichloromethane
0.111
0.352
Propylene
0.110
0.351
Bromoform
0.183
0.583
Stvrene
0.155
0.493
Bromomethane
0.0448
0.143
tert-Amyl Methyl Ether
0.0518
0.165
Carbon Disulfide
0.239
0.762
T etrachloroethylene *
0.0992
0.315
Carbon Tetrachloride*
0.0840
0.267
Toluene
0.493
1.57
Chlorobenzene
0.0887
0.282
trans-1.2-Dichloroethylene
0.0533
0.169
Chloroethane
0.0659
0.209
trans-1.3-Dichloropropene
0.0807
0.257
Chloroform*
0.0633
0.201
T richloroethylene*
0.0806
0.256
Chloromethane
0.0961
0.306
T richlorofluoromethane
0.0654
0.208
Chloroprene
0.0469
0.149
T richlorotrifluoroethane
0.0749
0.238
cis-1.2-Dichloroethylene
0.0740
0.235
Vinyl Chloride*
0.0327
0.104
*NATTS Tier I compounds

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Table 11-13. 2018 Carbonyl Method Detection Limits
(Underivatized Concentration)
Compound
MDL
(|ig/m3)
SQL
(jig/m3)
2,5-Dimethylbenzaldehyde
0.0163
0.05171
2-Butanone (Methyl Ethyl Ketone)
0.136
0.432
Acetaldehyde *
0.0389
0.124
Acetone
0.408
1.30
Benzaldehyde
0.00952
0.03029
Butyraldehyde
0.0576
0.183
Crotonaldehyde
0.00809
0.02571
Formaldehyde *
0.0739
0.235
Hexaldehyde
0.00742
0.02361
Isovaleraldehyde
0.01 12
0.03565
Propionaldehyde
0.00469
0.01493
Tolualdehydes
0.0169
0.05361
Valeraldehyde
0.00746
0.02372
NOTE: Assumes 1000 L sample volume. MDLs determined in June 2018.
*NATTS Tier I compounds
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Element No.	Section 11 - B5
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Date	March 2018
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Table 11-14. 2018 PAH Method Detection Limits

MDL
SQL
Compounds
(ng/m3)
(ng/m3)
9-Fluorenone
0.0607
0.193
Acenaphthene
0.0743
0.236
Acenaphthylene
0.0147
0.0466
Anthracene
0.0134
0.0426
Benzo(a)anthracene
0.0104
0.0330
Benzo(a)pyrene *
0.0106
0.0337
Benzo(b)fluoranthene
0.0213
0.0677
Benzo(e)pyrene
0.0105
0.0334
Benzo(g,h,i )perylene
0.0130
0.0413
Benzo(k)fluoranthene
0.01 16
0.0369
Chrysene
0.00805
0.0256
Coronene
0.00467
0.0148
Cyclopenta(c,d)pyrene
0.00711
0.0226
Dibenz(a,h)anthracene
0.0150
0.0477
Fluoranthene
0.0248
0.0790
Fluorene
0.0693
0.220
lndeno( 1,2,3-cd)pyrene
0.0133
0.0424
Naphthalene *
1.82
5.77
Perylene
0.00929
0.0295
Phenanthrene
0.125
0.398
Pyrene
0.0126
0.0400
Retene
0.0617
0.196
NOTE: Assumes a 300 m3 sample volume. MDLs determined in May 2018.
*NATTS Tier I compounds
Two MDLs are determined for the metals analysis. One is determined for quartz filters,
and the other for Teflon filters. The detection limits for metals the determined by the FAC(20)
method using compiled method blank data. If the resulting MDL for any element does not meet
criteria, then seven to 10 replicate blank filter strips should be spiked at a concentration of two to
five times the estimated MDL, digested, and analyzed to determine the MDL values using the
method described in 40 CFR Part 136(18), Appendix B. Both procedures should be prepared

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following the entire analytical method procedure. The metals MDLs are shown in Table 11-15
and are based on a sampling volume of 2000 m3 for the quartz filters and 24.04 m3 for the Teflon
filters. For 2018, the FACA procedure was used to determine the MDLs for the quartz and
Teflon filters. The hexavalent chromium MDL is also included in Table 11-15 and is based on a
sampling volume of 21.6 m3.
The Sample Quantitation Limit (SQL) is also reported in Table 11-13 through
Table 11-15. The SQL is defined as the lowest concentration an analyte can be reliably measured
within specified limits of preci si on and bias during routine laboratory operating conditions. The
SQL is defined by EPA as a multiplier (3.18) of the MDL and is considered the lowest
concentration that can be accurately measured, as opposed to just detected. ERG submits this
data into AQS using flags to show where the data is in respect to the detection level.
The NATTS Program requires sampling and analysis for 18 target air toxic analytes.
Hexavalent chromium is no longer required by the NATTS program, but was given a target
MDL in the latest NATTS TAD"" and the NATTS Work Plan Template'2". The NATTS
program uses sensitivity to assess quantification from a monitoring site with the appropriate level
of certainty. In order to meet this objective, target MDLs have been established for the NATTS
Program and are compared to the current 2018 ERG MDLs in Table 11-16.

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Element No.	Section 11 - B5
Revision No.	4
Date	March 2018
Page	39 of 40
Table 11-15. 2018 Metals Method Detection Limit
Element
47 mm Teflon
8x10" Quartz
MDL
(ng/m3)
SQL
(ng/m3)
MDL
(ng/m3)
SQL
(ng/m3)
Antimony *
0.15 1
0.479
0.0336
0.107
Arsenic *
0.0362
0.1 15
0.00879
0.0280
Beryllium *
0.00142
0.00453
0.00130
0.00414
Cadmium *
0.00487
0.0155
0.00544
0.0173
Chromium *
3.27
10.4
1.13
3.61
Cobalt *
0.0842
0.268
0.0183
0.0582
Lead *
0.0657
0.209
0.0855
0.272
Manganese *
0.194
0.616
0.816
2.60
Mercury
0.0153
0.0485
0.00498
0.0158
Nickel *
1.21
3.85
0.436
1.39
Selenium *
0.0582
0.185
0.0101
0.0321

Hexavalent Chromium MDL (47mm Cellulose)

Hexavalent Chromium
0.0040
0.0127

NOTE: For total metals: Assumes total volume of 24.04 m3 for Teflon fi
ters and 2000 m3 for Quart/ filters.
For hexavalent chromium: Assumes total volume of 21.6 m\
*NATTS Tier I Compounds

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Table 11-16. Target MDLs for the NATTS Program
Pollutant
NATTS
Target
MDL
(ng/m3)
ERG 2018
MDL
(ng/m3)
Is ERG
MDL <
Target
MDL?
NATTS Tier I VOCHAPs
Acrolein
0.09
0.516
NO
Benzene
0.13
0.0463
YES
1,3-Butadiene
0.10
0.0429
YES
Carbon Tetrachloride
0.17
0.0840
YES
Chloroform
0.50
0.0633
YES
T etrachloroethylene
0.17
0.0992
YES
T richloroethylene
0.20
0.0806
YES
Vinyl Chloride
0.11
0.0327
YES
NATTS Tier I Car bony I HA
Ps
Acetaldehyde
0.45
0.0389
YES
Formaldehyde
0.080
0.0739
YES
Pollutant
NATTS
Target
MDL
(ng/m3)
NATTS Tier IPAHHAPs
Benzo(a)pyrene
Naphthalene
0.91
29
ERG 2018
MDL
(ng/m3)
0.0106
1.82
NATTS Tier I Metal HAPs
Is ERG
MDL <
Target
MDL?
YES
YES
(Low Vol PMio)
(High Vol PM10)
Arsenic (PMio)
0.23
0.0362
YES
0.00879
YES
Beryllium (PMio)
0.42
0.00142
YES
0.00130
YES
Cadmium (PMio)
Lead (PMio)
0.56
15.0
0.00487
0.0657
YES
YES
0.00544
0.0855
YES
YES
Manganese (PMio)
Nickel (PMio)
5.0
2.1
0.194
1.21
YES
YES
0.816
0.436
YES
YES
NOTE: Target MDL's were obtained from the NATTS Work Plan Template (March 2015), Section 3.1 and the
NATTS TAD, Revision 3ll8>

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SECTION 12
INSTRUMENT/EQUIPMENT TESTING, INSPECTION, AND MAINTENANCE
REQUIREMENTS
To ensure the quality of the sampling and analytical equipment, ERG conducts
performance checks for all equipment used in each of the programs. ERG checks the sampling
systems annually, and makes repairs as needed. ERG tracks the performance of the analytical
instrumentation to ensure proper operation. ERG also maintains a spare parts inventory to
shorten equipment downtime. Table 12-1 details the maintenance items, how frequently they will
be performed, and who is responsible for performing the maintenance. All checks, testing,
inspections, and maintenance done on each instrument are recorded in the appropriate
Maintenance Logbook or LIMS Instrument Maintenance Logs for each instrument.
Table 12-1
Preventive Maintenance in ERG Laboratories
Item
Maintenance Frequency
Responsible Party
For Analytical Systems
Multipoint Calibration
As needed or at least at intervals
specified in Section 11
Analyst
Comparison to Continuing
Calibration Standard
Daily
Analyst
Replace GC/LC/IC- Column
As necessary (i.e., observe
peaks tailing, retention time
shifts, increased baseline noise,
etc.)
Analyst
Detector Maintenance
As necessary
Analyst
Computer Backup
Biweekly, Daily preferred
Analyst
Accelerated Solvent Extractor
Piston Rinse Seal
Quarterly, or as needed
Analyst
Standard Rinse Seal
Quarterly, or as needed
Analyst

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Table 12-1
Preventive Maintenance in ERG Laboratories (Continued)
Project No.
Element No.
Revision No.
Date
Page
Item
Maintenance Frequency
Responsible Party
High Performance Liquid Chromatography
In-line filter
As necessary (when pressure
increases above 2500 psi)
Analyst
Inspect Delivery System Motor
Annually
Service Technician
Replace Teflon Delivery Tubing
Annually
Service Technician
Ion Chromatography
Rinse Post Column Reagent
lines with methanol
As necessary
Analyst
Rinse Eluent Lines with
Deionized water
After every sequence
Analyst
Sonicate Inlet and Outlet Check
Valves
As necessary
Analyst
Rinse Autosampler Injector
As necessary
Analyst
Inorganic Laboratory
Flush system for 5 minutes with
the plasma on with a rinse blank
After every sequence
Analyst
Cleaning cones, torch, injector,
spray chamber
Quarterly, or as needed for
analysis quality
Analyst
Change Roughing Pump Oil
Annually
Service Engineer
Replace Air Filters
Annually
Service Engineer
For Sampling Field Equipment (UATMP, Carbonyl, NMOC/SNMOC, and Hexavalent
Chromium)
Inspect/Replace vacuum pump
diaphragms and flapper valves
At each system certification
effort
ERG
Inspect Sampler (overall)
At each system certification
effort and prior to each
scheduled collection event
ERG/Field Operator
Inspect/Replace Cartridge
Connectors
Prior to each collection event,
replace as needed
ERG/Field Operator
Replace Ozone Scrubber
At each system certification
effort
ERG
MFM Check or Flow check
At each system certification
effort
ERG
Inspect/Replace Fans
At each system certification
effort
ERG

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Page
12.1	SNMOC, VOC, and PA MS
The GC/FID/MS systems are maintained under a service agreement. ERG personnel
perform minor maintenance, such as filament changes, carrier gas filter replacements, column
maintenance, and source cleaning. The following spare parts should be kept in the lab: traps,
filament, column, and split for the column. All procedures, checks, and scheduled maintenance
checks for V OC GC/F ID/MS analysis are provided in ERG's SOP (ERG-MOR-005) presented
in Appendix C.
12.2	Carbonyls
The carbonyl HPLC analytical systems are maintained under a service agreement. ERG
personnel perform minor maintenance, such as column and detector maintenance, on an
as-needed basis. The following spare parts should be kept in the lab: solvent frit, column, in-line
filter and guard column. All procedures, checks, and scheduled maintenance checks are provided
for carbonyl HPLC analysis in ERG's SOP (ERG-MOR-024) presented in Appendix C.
12.3	HAPs
The GC/MS systems for PAH and VOC analysis are maintained under the same service
agreement. ERG personnel perform minor maintenance as needed. The following spare parts
should be kept in the lab: injector sleeve, filament, and column.
For the HAPs sample analyses performed on the ICP-MS and IC, routine preventive
maintenance is performed by the Analyst or Task Lead. ERG personnel perform minor
maintenance, such as column and detector maintenance, on an as-needed basis. Contracted
service agreements are in place for non-routine maintenance. Spare pump tubing, focusing lens,
gem tips, and o-rings should be kept in the lab for the ICP-MS. A spare guard and analytical
column, piston seals, reaction coil, and reservoir frits should be kept in the lab for the IC. More
procedures, checks, and scheduled maintenance checks are provided in ERG's SOP

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(ERG-MOR-049) for PAH analysis by GC/MS, ERG-MOR-095 for metals analysis by ICP-MS,
and ERG-MOR-063 for hexavalent chromium by IC presented in Appendix C.

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SECTION 13
INSTRUMENT CALIBRATION AND FREQUENCY
The programs are discussed separately in this section because the requirements for
analytical system calibrations differ. Analytical instruments and equipment are calibrated when
the analysis is set up, when the laboratory takes corrective action, following major instrument
maintenance, or if the continuing calibration acceptance criteria have not been met. Appropriate
standards are prepared by serial dilutions of pure substances or accurately prepared concentrated
solutions. Many analytical instruments have high sensitivity, so calibration standards must be
extremely dilute solutions. In preparing stock solutions of calibration standards, great care is
exercised in measuring weights and volumes, since analyses following the calibration are based
on the accuracy of the calibration.
Each calibration analysis is stored, electronically and hardcopy, with traceability for the
samples analyzed using that calibration. Each of the analytical systems is calibrated for all
reported target analytes, except for the NMOC and SNMOC calibrations. The NMOC calibration
is based on propane and the SNMOC calibration is based on propane, hexane, benzene, octane,
and decane average response factors. NMOC calibration will be discussed in more detail when
the analysis is requested by a State.
13.1 SNMOC Calibration
For the SNMOC method, average carbon response factors are obtained quarterly (at a
minimum) based on the analysis of humidified calibration standards prepared in canisters. The
Dynamic Flow Dilution System (SOP Number ERG-MOR-061, Appendix C) is used to dilute
certified Linde or equivalent alkanes into clean, evacuated SUMMA®- treated canisters. The gas
standards are traceable via the gravimetric preparation using NIST-traceable weights. These gas
standards are recertified annually. HPLC grade water is used to humidify the standard to
approximately 50 percent. The standard is diluted with scientific-grade air to achieve the desired
concentrations for the calibration. The response factors generated from the calibration are used to

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determine concentrations of detected compounds, on the assumption that FID response is linear
with respect to the number of carbon atoms present in the compound.
At least five calibration standards are prepared in ranges from 5 to 400 ppbC
concentrations. The average response factors for propane, hexane, benzene, octane, and decane
are determined using the response correlated to concentration. Individual concentrations for the
C; through C13 compounds detected on the FID are calculated using one of the five response
factors, with a similar Carbon number. The calibration is considered representative if the average
RF RSD for the curve is within ±20 percent. Daily, before sample analysis, a CCV standard
(such as Air Environmental gas standard), is analyzed to ensure the validity of the current
response factors. Ten selected hydrocarbons, ranging from C; through C10, from the QC standard
are compared to the calculated theoretical concentrations. A percent recovery of 70-130 percent
is considered acceptable showing the analytical system is in control.
A blank of cleaned, humidified air or N2 is analyzed after the CCV and before sample
analyses. The system is considered in control if the total NMOC concentration for the blank is
less than or equal to 20 ppbC.
13.2 VOC Calibration
Calibration of the GC/F ID/MS is accomplished quarterly (at a minimum) by analyzing
humidified calibration standards prepared in canisters generated from NIST-traceable Linde or
Air Environmental (or equivalent) gas standards. The certified standards contain the VOC target
compounds at approximately 500 ppbV. Although the MS is the primary quantitation tool,
responses on the FID are recorded to detect and quantify hydrocarbon peaks and can be used for
SNMOC or PA MS results. The calibration for these hydrocarbon peaks should be accomplished
as explained in Section 13.1.

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Calibration standards are prepared with a dynamic flow dilution apparatus (Figure 13-1,
see Standard Operating Procedure ERG-MOR-061, Appendix C). The gases are mixed in a
SUM MA*-treated mixing sphere and bled into evacuated canisters. One dilution air stream is
humidified by routing it through a SUM MA*- treated bubbler containing HPLC-grade water; the
other stream is not humidified. The dilution air streams are then brought together for mixing with
the streams from the certified cylinders. Flow rates from all streams are gauged and controlled by
mass flow controllers. The split air dilution streams are metered by "wet" and "dry" rotameters
(-50 percent relative humidity) from the humidified and unhumidified dilution air streams,
respectively.
The system is evacuated with a vacuum pump while the closed canister is connected. The
lines leading to the canister and to the mixing sphere are flushed for at least 20 minutes with
standard gas before being connected to the canister for filling. A precision pressure gauge
measures the canister pressure before and after filling.
Initial calibration standards are prepared at nominal concentrations of 0.25, 0.5, 1, 2.5, 5,
and 10 ppbV for each of the target compounds (a minimum of 5 levels are required). All
standards and samples are analyzed with the following internal standards: //-hexane-du,
1,4-difluorobenzene, and chlorobenzene-ds. The calibration requires average response factors,
based on the internal standard, of ± 30 percent RSD, however per Compendium Method TO-15'4'
acceptance criteria, up to two compounds can have ± 40 percent RSD (non-Tier I compounds).
The CCV is made from a second source certified gas at an average concentration of 2.5 ppbV.
The CCV must have RRFs within ± 30% of the mean initial calibration RRFs.

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Atmosphere
atmosphere
vacuum
Pump Start
F1 Purge/FloodVafoe
2 Purge/Flo odVahe
BeHows
SeJlcws
Valve
va vs
MFC \
0-10Lpm
KF2
(61 )
xamster/
fc=d
amst
MFC
0-1 Lp 1*1
Chan
Select
Isolations Valve 4!so,a:ion
Vaive^i	A Valve
MFC
0-50 stem
Active V - "
/Tempers tureV
LsnLrolief /
MK
0" 20 seem
MFC than
MFC
0-500 seem
ay-Pass
O-biOstcm
Rotamete'
MFC
G-lOsccm
MFC /
0-10 stem
O.bl SUMMA ! rested Mixing Chamber
aellcws
Valve
H
Diluent	Diluent
Rotameter Rotameier
[wet:	(dry
0-10 Lprn
MFC
0-1 Lpm
New
Control
Valve
LEGEND
D = Diluent
P = Pollutant
F = Fill
MFC = Mass Flow Controller
TC = Thermccouple
HeatTraced Line
&LSJMMA	pJgv,
TreatedHumjdrfie- contra '
Valve "
Figure 13-1. Dynamic Flow Dilution Apparatus
13.3 Carbonyl Calibration
For the carbonyl analyses, the HPLC instrument is calibrated using an acetonitrile
solution containing the derivatized targeted compounds. The calibration curve consists of six
concentration levels ranging from 0.01 to 3.0 microgram per milliliter (ng/mL) (underivatized
concentration), and each is analyzed in triplicate. The standard linear regression analysis
performed on the data for each analyte must have a correlation coefficient greater than or equal
to 0.999. The Relative Error (RE) for each compound at each level against the calibration curve
must be < 20 percent. As a QC procedure to verify the calibration and check HPLC column
efficiency, a SSQC sample solution containing target carbonyl compounds at a known
concentration is analyzed in triplicate after every calibration curve, with an 85-115 percent
recovery criterion.

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In each sequence, a CCV (a second source standard) is analyzed every 12 hours or less
while samples are analyzed (meeting the 85-115 percent recovery criterion). A system blank
brackets the analytical batch, by analyzing one blank at the beginning and one at the end of each
sequence.
13.4 HAPs Calibration
The GC/MS system in SIM mode is calibrated for PAH analysis at a minimum every six
week. The average calibration RRF must be greater than or equal to the minimum RRF presented
in Table 13-1. For the other HAPs sample analyses, calibration is performed on the ICP-MS and
IC. Calibration requirements for the HAPs analytical methods are in Tables 1 1-7, 11-9 and
11-10.
Table 13-1.
Relative Response Factor Criteria for Initial Calibration of Common Seniivolatile
Compounds
Seniivolatile Compounds
Minimum RRF
Maximum
%RSD
Maximum
% Difference
Naphthalene
0.700
30
30
Acenaphthylene
1.300
30
30
Acenaphthene
0.800
30
30
Fluorene
0.900
30
30
Phenanthrene
0.700
30
30
Anthracene
0.700
30
30
Fluoranthene
0.600
30
30
Pyrene
0.600
30
30
Benz(a)anthracene
0.800
30
30
Chrysene
0.700
30
30
Benzo(b)fluoranthene
0.700
30
30
Note - The ASTM method includes no minimum RRF criteria, therefore none arc listed here for the ASTM(12)
compounds.

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Tabic 13-1.
Relative Response Factor Criteria for Initial Calibration of Common Seniivolatile
Compounds (Continued)
Seniivolatile Compounds
Minimum RRF
Maximum
%RSD
Maximum
% Difference
Benzo(k)fluoranthene
0.700
30
30
Benzo(a)pyrene
0.700
30
30
Indcnof 1,2,3 -cd)pyrene
0.500
30
30
Dibenz(a,h)anthracene
0.400
30
30
Benzo(g.h.i (pcrylcnc
0.500
30
30
Perylene
0.500
30
30
Coronene
0.700
30
30
Benzo(e)pyrene
--
30
30
Cyclopenta(c,d)pyrene
--
30
30
Retene
~
30
30
9-Fluorenone
~
30
30
Note - The ASTM method includes no minimum RRF criteria, therefore none arc listed here for the ASTM(12)
compounds.
13.5 Laboratory Support Equipment Calibration
Analytical balances are serviced and calibrated annually with NIST traceable weights by
a vendor service technician. The certificate of Weight Verification (ISO9001) is kept on file by
the QA Coordinator. The balance calibrations are checked daily on days of use with Class 1
weights and recorded. The data loggers used for temperature/humidity/pressure have calibration
checks annually performed by the vendor. The infrared (IR) thermometers are annually vendor
calibrated with NIST-traceable standards. The calibration of the thermometers used in the metals
sample digestion procedure are checked against a thermometer with a NIST traceable vendor
calibration. The pressure gauges used for measuring sample canister pressure at receipt are
calibrated annually by a certified vendor. Other pressure gauges, used in canister cleaning or
canister sample dilution, are checked against a "transfer standard" gauge that is calibrated
annually by a certified vendor. MFCs used in the canister dynamic dilution standard system are
calibrated annually and the calibrations are checked quarterly.

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Pipette calibrations are checked and recorded quarterly. If a pipette fails a calibration
check they are rechecked. If it continues to fail, it is sent back to the manufacturer for
recalibration. If recalibration is not possible it will be repaired or replaced with a new pipette.
Syringe calibrations are checked and recorded annually. If a syringe fails the calibration check, it
will be replaced with a new one. Class A volumetric glassware is used throughout the laboratory
for bringing sample extracts up to final volume.

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SECTION 14
INSPECTION/ACCEPTANCE FOR SUPPLIES AND CONSUMABLES
14.1	Purpose
The purpose of this element is to establish and document a system for inspecting and
accepting all supplies and consumables that may directly or indirectly affect the quality of the
NMP. By having documented inspection and acceptance criteria, consistency of the supplies can
be assured. This section details the supplies/consumables, their acceptance criteria, and the
required documentation for tracing this process.
14.2	Critical Supplies and Consumables
Table 14-1 details the various components for the field and laboratory operations.
14.3	Acceptance Criteria
Acceptance criteria for supplies/consumables must be consistent with overall project
technical and quality criteria. As requirements change, so do the acceptance criteria. Knowledge
of laboratory equipment and experience are the best guides to acceptance criteria. It is the
laboratory analyst's responsibility to update the criteria for acceptance of consumables. Other
acceptance criteria such as observation of damage due to shipping can only be performed once
the equipment has arrived on site.
All supplies and consumables are inspected and accepted or rejected upon receipt in the
laboratory. The ERG employee who ordered the supply is responsible for verifying that the order
is acceptably delivered, stored and dispersed upon receipt in the laboratory. The recipient's
signature on the packing slip indicates the received goods were received and are acceptable.
Some supplies or consumables listed in Table 14-1 must be deemed acceptable through testing or
blanking, such as with the carbonyl DNPH cartridges. Any changes in standards and sample

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media must meet the acceptance criteria outlined in Section 11 for that particular method. Such
testing and blanking data is kept with the sample data. Staff should not use supplies or
consumables of different model numbers or grades without first discussing it with the Program
Manager and specific Task Leader and testing the supply or consumable. Staff should keep any
certificate of analysis or cleanliness that arrives with the suppl y/con sum abl e on file. For specific
information on reagents and standards used, see applicable method SOP.
Table 14-1
Critical Supplies and Consumables
Area
Item
Description
Vendor
Model
Number
Field Supplies and Consumables (Fabrication Lab)
All Samplers
Various
Swagelok®
fittings
All Samplers
Swagelok
Various
NMOC Sampler
Pump
Metal Bellows
KNF Ncwbcrger
UN 05-SV.91
VOC Sampler
Vacuum Pump
VOC System
Thomas
2107VA20
Canisters
VOC Canisters
Entech
6-liter
Silonite®
Canisters
Carbonyl Sampler
DNPH Cartridges
DNPH coated plastic
cartridges
Waters
WAT 037500
Hexavalent
Chromium
Sampler
Pump
High Vacuum
Thomas
VA-21 10
Laboratory Supplies and Consumables (Laboratories listed below)
All Laboratories
Powder Free
Gloves
Polyethylene
VWR
32915-246
All Laboratories
Gloves
Nitrile
Expotech,Therm
oFisher. VWR
1461558
(Expotech)
Liquid
Chromatography
Guard column
Zorbax ODS
Agilent
820950-902
Liquid
Chromatography
Chromatographic
Column
Zorbax ODS
Agilent
880952-702
Liquid
Chromatography
UV Lamp
For 2487 detector
Waters
WA 5081142
GC/MS - VOC
Chromatographic
Column
0.32 x 1 (.i - 60 m
column
Restek
Rxi-lms
GC/MS - SVOC
Chromatographic
Column
0.25 x 0.25 f.i-30 m
column
Agilent J&W
HP-5MS UI
GC/MS - SVOC
Inject seal
Injection port seal
Expotech
2264837
GC/MS - SVOC
Liner
Injection port liner
Expotech
2377232

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Table 14-1
Critical Supplies and Consumables (Continued)
Project No.
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Page
Area
Item
Description
Vendor
Model
Number
GC/MS & Liquid
Chromatography
Helium
Carrier Gas
Air Gas
UHP
GC/MS
Hydrogen Gas
FID Gas
Air Gas
UHP
GC/MS
Liquid Nitrogen
Coolant Gas
Air Gas
Bulk
GC/MS
Liquid Argon
Coolant Gas
Air Gas
Bulk
GC/MS
Air
FID Gas
Air Gas
Zero
GC/MS
T raps
Glass bead/Tenax
Trap
Entech
01-04-11340
GC/MS
Trap Heater
Sample Trap Heater
Entech
01-09-13010
GC/MS
Cryogenic Valve
Cryogenic Valve
Entech
01 -01 -71760
I CP-MS
Liquid Argon
Coolant Gas
Air Gas
Bulk
I CP-MS
Acid
High Purity Nitric
Fisher/SCP
Science
A200-
212/Plasma
Pure Plus
I CP-MS
Acid
Hydrochloric Acid
Fisher/SCP
Science
A466-1/Plasma
Pure Plus
I CP-MS
Hydrogen
Peroxide
Hydrogen Peroxide,
30%
SCP Science
Plasma Pure
Plus
I CP-MS
Whatman 8"xl 1"
Quartz/Glass
Fiber Filters
MTL 47mm
Teflon™ Filters
Filters
GE Healthcare
Life Sciences &
MTL
1851-8531
1882-8532
PT47-EP
IC
Reaction Coil
Knitted Reaction Coil
ThermoFisher
04263 1
IC
Guard Column
Dionex Ion Pac NG1
ThermoFisher
039567
IC
Analytical
Column
Dionex Ion Pac AS7
ThermoFisher
035393
IC
Methanol
Solvent
Expotech, Fisher.
VWR
HPLC grade
IC
Sample vials 14
mL. polystyrene
with caps
Sample containers
ThermoFisher
352057
IC
Whatman Filters
Filters-47mm ashless
cellulose
Expotech, Fisher
09-850H
Prep
Water Filter
Ultrapure Ion
Exchange Cartridge
Expotech
1425973
Prep
Water Filter
Cartridge submicron
Expotech
1425977
Prep
Water Filter
Pretreatment
Cartridge
Expotech
1426051
Prep
Whatman Filters
Filters-110mm GFA
Expotech
1422153

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Table 14-1
Critical Supplies and Consumables (Continued)
Area
Item
Description
Vendor
Model
Number
Prep
PUF
Pre-cleaned PUF
Cen-Med,
Expotech
824-20038,
2256468
Prep
XAD®
XAD®
Expotech
2255045
Prep
Petri Dish
Filter container
Expotech
1426833
Prep
Acetonitrile
Solvent
Expotech, Fisher.
VWR
HPLC grade
Prep
Methylene
Chloride
Solvent
Expotech. Fisher,
VWR
Optima grade
Prep
Hexane
Solvent
Expotech. Fisher.
VWR
95% (Optima
grade)
Prep
Toluene
Solvent
Expotech. Fisher.
VWR
Optima Grade
Prep
Nitrogen
Evaporation gas
Air Gas
UHP (or Bulk)
Prep
Amber glass
bottles 250 mL
Sample containers
Expotech
2373176
Prep
Extraction cells
Sample containers
Thermo Electron
068077
Prep
Ottawa sand
Extraction filler
Expotech
2262138
Prep
Seals
ASE Vespel Seals
Fisher
056776
Prep
Disposable pi pets
Disposable pipets
Expotech
1405717
Prep
4 mL amber
sample vials
Sample containers
Expotech, Fisher.
VWR
66030-734
(VWR)
Prep
4 mL sample
Teflon lined caps
Sample containers
Expotech, Fisher.
VWR
66030-771
(VWR)
Prep
Autosampler
snap-it vials
Sample containers
Waters
WAT 094220
Prep
Autosampler
snap-it caps
Sample containers
Waters
18000303
Consumables and supplies with special handling and storage needs must be handled and
stored as suggested by the manufacturer. Consumables with expiration dates, such as solvents
and standards, must be labeled with a receipt date, date opened, and the initials of the person that
opened the consumable and standard expiration dates must be entered into the standards section
of LIMS. To decrease waste, the oldest supplies or consumables should be used first.

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SECTION 15
DATA MANAGEMENT
15.1 Data Recording
Data management for sample data is presented in Figure 15-1. The sample data path is
shown from sample origination to data reporting and storage. The LIMS allows the laboratory to
manage and track samples, instrument workflow, and reporting. The LIMS stores the raw
instrument data and performs the conversion calculations to put the data into final reporting
units. These calculations are reviewed and documented annually by the QA coordinator and kept
in the QA files in Room 102. The main procedures are described in the SOP for the Laboratory
Information Management System (ERG-MOR-099). The main functions of the LIMS system
include, but are not limited to:
•	Sample login;
•	Sample scheduling, and tracking;
•	Sample processing and quality control; and
•	Sample reporting and data storage.
All LIMS users must be authorized by the LIMS Administrator and permitted specified
privileges. The following privilege levels are defined:
•	Data Entry Privilege - The individual may see and modify only data within the LIMS
that he or she has personally entered.
•	Reporting Privilege - Without additional privileges.
•	Data Administration Privilege - Data Administrators for the database are allowed to
change data as a result of QA screening and related reasons. Data Administrators are
responsible for performing the following tasks on a regular basis:
- Merging/correcting the duplicate data entry files;
- Running verification/validation routines, correcting data as necessary.

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Sample Prep
Assigned
sample
Collection
Sample Transfer
Chain af Custody
Forms
Sample
Login/Storage
Laboratory
Receipt
Datsba
Monthly Data
Quarterly aqs
Data Review
OaiaTransrer
To AQS
\
Sample

Preparation

1
1
4 <
|
' t

Sample

Analysis


1
I
' ~


OA


Review



l
> 1


X



/ Accept \
No

\ \ Data

\
I
g T
Yes
Data Entry
and
Historical
Database
Post Sample
Sample
Disposal
(i ¥ear)
	 PaperFlow
	Sample Flow
		 Computer Flow
Data Storage
(5 years]
Figure 15-1. Data Management and Sample Flow Diagram

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15.2	Data Validation
Data validation is a combination of checking that data processing operations have been
carried out correctly and of monitoring the quality of the field operations. Data validation is
confirmed by examination of objective evidence that the requirements for a specific intended use
are fulfilled as presented in Section 4. This data validation is performed prior to the annual final
report. The data reported monthly are considered preliminary until the data is validated, entered
into the AQS database, and reported in the annual final report. Data validation is discussed in
more detail in Section 18.5.
15.3	Data Reduction and Transformation
Data generated on an instrument is reduced by the analyst via instrument
chromatographic software. Any manual integration to chromatographic data follows SOP
ERG-MOR-097, the SOP for Manual Integration of Chromatographic Peaks. Specific equations
used by the instrument chromatographic software to calculate concentration are documented in
the individual analytical SOPs found in Appendix C. The equations for transforming raw data are
set up to automatically calculate to final concentrations in the LIMS system. The initial and final
reporting units for SNMOC are ppbC. All other analyses are reported in units different from their
raw data. The initial units for the Carbonyl Compounds analysis are microgram per milliliter
(|ig/mL), while the final reporting units are in either ppbV or microgram per cubic meter
(|ig/m3), per site request, however the NATTS sites are to be reported in |ig/m3 per the NATTS
TAD(18). The initial units for VOC are ppbV and the LIMS data reports are in ppbV and |ig/m3.
The PAH initials units are ng/|iL with final reporting units of nanogram per cubic meter (ng/m3).
The initial units for metals are ng/L with final reporting units of ng/m3. The initial units for the
hexavalent chromium analysis are ng/mL with final reporting units of ng/m3. The associated
MDLs are reported in final reporting units with the final concentrations. MDLs are adjusted for
dilution and actual prep volumes, and sample collection volume where applicable, before
reporting.

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The electronic data file is uploaded onto a network server (which is backed-up daily) and
into the LIMS. Once the data is in LIMS, the Task Leader reviews it following the checklists
presented in the SOPs using instrument software and the method-specific control limits set up in
LIMS. Ten percent of all data is reviewed by the QA Coordinator or designee following the
checklist and method specific acceptance criteria in the summary quality control procedure tables
outlined in Section 11. After data has successfully completed both reviews and the checklists
have been signed, it is available for reporting by the Program Manager.
The SOP for Project Peer Review uses manual calculations and visual verification to
review all data reported to EPA and State/Local/Tribal agencies following guidelines outlined in
SOP ERG-MOR-057 (see Appendix C). SOP for Developing, Documenting, and Evaluating the
Accuracy of Spreadsheet Data, presented in SOP ERG-MOR-O17 (see Appendix C), is consulted
in special cases where the calculations are performed via spreadsheets instead of the LIMS
Reporting formats are designed to fulfill the program requirements and to provide
comprehensive, conventional tables of data. The LIMS data reporting format includes any
required data qualifiers, footnotes, detection limits for each analyte, and appropriate units for all
measurements. The LIMS can produce Adobe and Excel data reports, which is standard for this
program. Each report is reviewed by the Program Manager or designee before it is sent to the
client.
15.4 Data Transmittal
Data transmittal occurs when data are transferred from one person or location to another
or when data are copied from one form to another. Some examples of data transmittal are
copying raw data from a notebook onto a data entry form for keying into a computer file and
electronic transfer of data over a computer network. Each individual SOP listed in Appendix C
discusses the procedures for determining the calculations of concentrations as well as data entry.
system.

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ERG will report all ambient air quality data and information specified by the AQS User's
Guide and other documents located at the website http://www.epa.go\ 'tin' itrs/airsags/manuals/
coded in the AQS format. Such air quality data and information will be fully screened and
validated and will be submitted directly to the AQS database via electronic transmission, in the
format of the AQS, and in accordance with the annual schedule. The SOP for the Preparation of
Monitoring Data for AOS Upload is presented in Appendix C (SOP ERG-MOR-098).
15.5 Data Summary
ERG is implementing the data summary and analysis program in the form of a final
annual report. The following specific summary statistics will be tracked and reported for the
network:
•	Single sampler bias or accuracy (based on laboratory audits if available);
•	Analytical precision (based on analytical replicates);
•	Sampler precision (based on collocated data);
•	Network-wide bias and precision; and
•	Data completeness.
Equations used for these reports are given in Table 15-1.

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Table 15-1. Report Equations
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Criterion
Equation
Coefficient of Variation (CV)-p and r are
concentrations from the primary and duplicate
samplers, respectively. This equation is also used
for collocated samples and replicate analysis.
Ivn r (p~r) 1
CV = 100 x I=lLo-5 x (p+r)J
yj 2 n
Percent Completeness
, N valid . 		
Completeness 	*100
]M theoretical
Where, N valid is the number of valid samples analyzed in the
sampling year and N theoretical is the number of valid samples
that should be taken within that same sampling year
15.6 Data Tracking
The ERG LIMS database contains the necessary input functions and reports appropriate
to track and account for the status of specific samples and their data during processing
operations. The following input locations are used to track sample and sample data status:
•	Sample Control
-	Sample collection information (by Work Order);
-	Sample receipt/custody information;
-	Unique sample number (LIMS ID);
-	Storage location;
-	Required analyses;
•	Laboratory
-	Batch/bench assignment;
-	Sequence assignment (if needed);
-	Data entry/review;
-	Query/update analysis status;
-	Standards/calibration information.

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15.7 Data Storage and Retrieval
Data archival policies for hardcopy records are shown in Table 15-2.
All data are stored on the ERG LIMS server. This system has the following
specifications:
•	Operating System: Windows 2008 Server
•	Memory: 6GRAM
•	Hard Drives: Three drives of 450G each configured as RAID 5;
•	Network card: Gigabit card (10/100/1000)
•	Tape Drives for Backup: Two tape drives are daisy chained (HP StorageWorks,
1/8 G2 Tape Autoloader). Symantec Backup Exec Software ver. 12.5
•	Security: Network login password protection on all workstations; Additional
password protection applied by application software.
Security of the data in the database is ensured by the following controls:
•	Password protection on the data base that defines three levels of access to the data;
•	Logging of all incoming communication sessions, including the originating
telephone number, the user's ID, and connect times; and
•	Storage of media, including backup tapes, in an alternate location that is at a
locked, restricted access area.
Table 15-2. Data Archive Policies
Data Type
Medium
Location
Retention Time
Final Disposition
Laboratory
notebooks
Hardcopy
Laboratory
5 years after close
of contract
N/A
LIMS Database
Electronic (on-
line)
Laboratory
Backup media
after 5 years
Backup tapes
retained
indefinitely
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ASSESSMENT/OVERSIGHT
SECTION 16
ASSESSMENTS AND RESPONSE ACTIONS
An assessment is defined as an evaluation process used to measure the performance or
effectiveness of the quality system or the establishment of the monitoring network and sites and
various measurement phases of the data operation.
The results of QA assessments indicate whether the control efforts are adequate or need
to be improved. Documentation of all QA and QC efforts implemented during the data
collection, analysis, and reporting phases are important to data users, who can then consider the
impact of these control efforts on the data quality. Both qualitative and quantitative assessments
of the effectiveness of these control efforts will identify those areas most likely to impact the
data quality. ERG will perform the following assessments to ensure the adequate performance of
the quality system.
16.1 Assessment Activities and Project Planning
16.1.1 External Technical Systems and Data Quality Audits
A TSA is a thorough and systematic on-site qualitative audit, where facilities, equipment,
personnel, training, procedures, subcontractor systems, and record keeping are examined for
conformance to the QAPP. The TSAs will be performed by EPA or its designee at the ERG
Laboratory. The TSAs for the contract are conducted approximately every 3 years. The EPA QA
Office will implement the TSA either as a team or as an individual auditor. ERG will participate
in any data quality audits by EPA or designee at the discretion of the EPA QA Coordinator.
The EPA audit team will prepare a brief written summary of findings for the Program
Manager and Program QA Coordinator. Problems with specific areas will be discussed and an
attempt made to rank them in order of their potential impact on data quality. ERG will work with

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EPA to solve required corrective actions. As part of corrective action and follow-up, an audit
finding response letter will be generated by the Program Manager and Program QA Coordinator.
The audit finding response letter will address what actions are being implemented to correct the
finding(s) of the TSA. This summary from EPA and the following response from ERG are filed
in the QA/QC file in Room 102. The findings and the follow-up corrective actions are discussed
in the annual QA Management Systems Review.
As part of ongoing National Environmental Laboratory Accreditation Conference
(NELAC) certification, TSAs are performed at ERG by Florida Department of Health or
designee every two years. A summary of findings is sent to ERG, specifically the Q A
Coordinator. The QA Coordinator sends its response of corrective actions which is either
accepted or denied by Florida Department of Health. This documentation is stored in the QA/QC
file in Room 102. The findings and the follow-up corrective actions are discussed in the annual
QA Management Systems Review.
16.1.2 Internal Technical Systems Audits
An internal TSA is performed examining facilities, equipment, personnel, training,
procedures, and record keeping for conformance to the individual SOPs and this QAPP. The
TSAs will be performed by the Program QA Coordinator and will be conducted at least once per
year. The checklists for the internal TSAs are based on the NATTS TSA or National
Environmental Laboratory Accreditation Program (NELAP) checklists with additional areas
addressing the individual SOPs and this QAPP. The content of the checklists vary episode to
episode to ensure comprehensive in-depth coverage of procedures over time. Such elements will
be included in the checklists:
•	Criteria listed in Section 1 1 of this QAPP
•	SOP specifications
•	Method specifications
•	Supporting equipment specifications
•	Other laboratory wide QA systems in place (ex. Satellite SOP notebooks)

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The Program QA Coordinator will report internal audit findings to the Program Manager
within 30 days of completion of the internal audit in the form of a report. The EPA Delivery
Order Manager will be informed if issues from the internal audit impact the quality of this
program. The report is filed in the QA/QC file in Room 102. All corrective actions are addressed
and implemented as soon as they are determined. The findings and the follow-up corrective
actions are discussed in the annual QA Management Systems Review to assess effectiveness of
the corrective actions.
16.1.3 Proficiency Testing
The PT is an assessment tool for the laboratory operations. 'Blind" samples are sent to the
laboratory, where they follow the normal handling routines that any other sample follows. The
results are sent to the Program Manager and Program QA Coordinator for final review and
reporting to the auditing agency. The auditing agency prepares a PT report and sends a copy of
the results to the Program Manager, Program QA Coordinator, and the EPA QA Office(s). Any
results outside the acceptance criteria are noted in the PT report. Repeated analyte failures are
investigated to determine the root cause and documented on a CAR. The PT reports are filed in
the QA/QC file in Room 102. The performance on these audits is discussed in the annual QA
Management Systems Review.
Currently, there is one audit program supported by this contract. This is provided through
the NATTS program for carbonyl, metals, VOC, and PAH audits. These audits are provided to
ERG from EPA (or an EPA contractor) throughout the year. The acceptable limits are provided
on the annual reports presented to the participating States and EPA.
ERG participates in round robin studies, such as Regional EPA round robin studies, when
available for VOC, metals, carbonyls, and SNMOC. In these studies, each participating
laboratory result is compared against the calculated average. Reports from these studies are kept
in the QA/QC file in Room 102. The performance on these studies is discussed in the annual QA
Management Systems Review.

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16.1.4 Data Assessment for Final Report
A data quality assessment is the statistical analysis of environmental data to determine
whether the quality of data is of adequate quality, based on the MQOs. The data assessment in
the final report is presented to EPA and State agencies and includes the following:
•	Review of the MQOs of the program, which includes completeness, precision and
accuracy.
•	Present the results of the data quality assessment using summary statistics, plots
and graphs while looking for and discussing any patterns, relationships, or
anomalies.
•	Qualify the data that does not meet the MQO for completeness for each
monitoring site and for site-specific summary statistics.
16.2 Documentation of Assessments
16.2.1	TSA. Data Quality Audit, and PT Documentation
All reports from EPA or designated contractors regarding ERG's performance on TSAs,
Data Quality Audits, and PTs are filed in the QA/QC file in Room 102. PT reports are dispersed
and discussed with contributing staff.
Reports from internal TS As are prepared and discussed with the contributing staff and
Program Manager and filed in the QA/QC file in Room 102.
16.2.2	Internal Data Review Documentation
Internal data review is performed on 100 percent of the data by the Task Leader and
10 percent of the data by the Program Q A Coordinator or designee against the criteria in the
individual SOPs and this QAPP prior to being reported each month. The assessment is
documented on the data review checklist, which is returned to the Task Leader for minor

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correction action and inclusion in the data package. The checklists used for analyses are shown
in their respective SOPs (Appendix C) as follows:
•	VOC - ERG-MOR-005, SOP for the Concurrent GC/FID/MS Analysis of Canister
Air Toxic Samples using EPA Compendium Method TO-15 and EPA Ozone
Precursor Method.
•	Carbonyl - ERG-MOR-024, SOI' for Preparing, Extracting, and Analyzing DNPH
Carhonyl Cartridges by Method TO-11A.
•	SVOC/PAH - ERG-MOR-049, SOP for Analysis of Semivolatile Organic
Compounds (Polynuclear Aromatic Hydrocarbons) Using EPA Compendium Method
TO-13A & ASTMD6209.
•	Metals - ERG-MOR-095, SOP for the Analysis of High Volume Quartz, Glass Fiber
Filters, and 47 mm Filters for Metals by ICP-MS using Method 10 3.5 andFEM
Method EQL-0512-201 and FEM Method EQL-0512-202.
•	Hexavalent chromium - ERG-MOR-063, SOP for the Preparation and Analysis of
Ambient Air for Hexavalent Chromium by Ion Chromatography.
•	SNMOC - ERG-MOR-005, SOP for the Concurrent GC/FID/MS Analysis of
Canister Air Toxic Samples using EPA Compendium Method TO-I5 and EPA Ozone
Precursor Method.
During the internal data review, major QC problems identified are brought to the attention of the
Program Manager and are documented on a CAR. The final project report also addresses QA
considerations for the whole project.
16.3 Corrective Action
The Response/Corrective Action Report (CAR) will be filed whenever a problem is
found such as an operational problem, or a failure to comply with procedures that affects the
quality of the data. A CAR is an important ongoing report to management because it documents
primary QA activities and provides valuable records of QA actions. A CAR can be originated by
anyone on the project but must be sent to the Program QA Coordinator and Program Manager.
Any problem that affects the quality of the overall program will be discussed with EPA.

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On the numbered CAR, the description of the problem, the cause of the problem, the
corrective action, and the follow-up are documented. The follow-up assists the QA coordinator
in determining if the corrective action was successful and if it was handled in a timely manner.
The CAR is recorded on a three-part form, the white copy goes into the project file, the yellow
copy goes into the QA file (Room 102), and the pink copy goes to the facilitator. A copy of the
ERG CAR Form is shown in Figure 16-1.
Each recommendation addresses a specific problem or deficiency and requires a written
response from the responsible party. The Program QA Coordinator will verify that the corrective
action has been implemented. A summary of the past years" CARs are discussed during the
annual QA Management Systems Review.
The following actions are taken by the laboratory QA Coordinator and Program Manager
when any aspect of the testing work, or the results of this work, does not conform to the
requirements of the quality system or testing methods:
•	Identify nonconforming work and take actions such as halting of work or withholding
test reports;
•	Evaluate of the impact of nonconforming work on quality and operations;
•	Take remedial action and make decision about the acceptability of the nonconforming
work (resample, use as is with qualification, or unable to use);
•	Notify the client, and if necessary, recall the work; and
•	Authorize the continuation of work.
ERG and its subcontractors are responsible for implementing the analytical phase of this
program and are not responsible for the overall DQOs. Therefore, this QAPP tries to ensure that
analytical results are of known and adequate quality to ensure the achievement of the various
program DQOs.

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CAR Number; 201B-
Corrective Action Report
CAR Initiator	Initiation Date:
Area/Procedure Affected:	r terns »d - r ft- ¦
la Immediate Stop of Work Required? ji ii en
Non-Conformancc
Date of Discovery:
Description cA Noo-OctflforDiance: Wlaa happened? Haw ij that a rvYnTcna&iZBlicng erenrt t
Q«i of lap liere to after teat
IftveStigfitJOU of No&-CoEliuniL&Jloe: *as the nnn-^rcfrannnnnfi dik^ni^td?
0*4 W lip 'wre to EffWr 
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SECTION 17
REPORTS TO MANAGEMENT
This section describes the quality-related reports and communications to management
necessary to support monitoring network operations and the associated data acquisition,
validation, assessment, and reporting. Important benefits of regular monthly reports to EPA
provide the opportunity to alert of data quality problems, to propose viable solutions to problems,
and to procure necessary additional resources.
Effective communication among all personnel is an integral part of a quality system.
Regular, planned quality reporting provides a means for tracking the following:
•	Adherence to scheduled delivery of data and reports;
•	Documentation of deviations from approved QA and test plans, and the impact of
these deviations on data quality; and
•	Analysis of the potential uncertainties in decisions based on the data.
17.1 Frequency, Content, and Distribution of Reports
Frequency, content, and distribution of reports for monitoring are shown below.
17.1.1 Monthly and Annual Reports
Analytical data reports prepared by the Program or Deputy Program Manager are sent to
EPA, State, Local and Tribal agencies monthly. These reports include the analytical data for each
sample collected monthly including sample results, MDLs, sample information (canister ID,
sample volume, etc.) and a QA report (could include duplicates, MB, CCB, CCV, MS/MSD,
etc., depending on the analysis). Quarterly QA reports are distributed which include a summary
of analyte specific quality control charts (ICV, ICB, CCB, CCV, BLK, BS/BSD, etc.). An annual
data report, containing a summary of the monthly reported data and a yearly assessment of the
air toxics data, is reported to EPA and State agencies by the Program Manager. This report

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documents the statistical analysis and quality assessment for the measurement data and how the
objectives for the program were met.
The annual report includes the quality information for each toxic monitoring network in
each state. Each report includes:
•	Program overview and update;
•	Quality objectives for measurement data;
•	Data quality assessment;
•	Collocated and duplicate sampling estimates for precision and bias; and
•	PTs that were performed during the study, if applicable.
17.1.2 Internal Technical System Audit Reports
The Program QA Coordinator or designee performs an internal technical system audit at
least once a year for the monitoring network for EPA, State, and NATTS contracts. The findings
are listed in reports which are presented to the Program Manager and filed in the QA/QC storage
file cabinet located in Room 102. These reports are available to EPA personnel during their TSA.
More detail on internal TSAs is provided in Section 16.

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DATA V ALIDATION AND USABILITY
SECTION 18
DATA REVIEW AND V ERIFICATION
Data verification is a two-stage process to determine if the sampling and analytical data
collection process is complete, consistent with the DQOs discussed in this QAPP and associated
SOPs, and meets the program requirements. First the data is reviewed for completeness,
accuracy, and acceptability. Then the data is verified to meet the quality requirements of the
program.
18.1 Data Review Design
Information used to verify air toxics data, includes:
•	Sample COCs, holding times, preservation methods.
•	Multi-point calibrations - the multipoint calibrations are used to establish proper
initial calibration and can be used to show changes in instrument response.
•	Standards - certifications, identification, expiration dates.
•	Instrument logs - all activities and samples analyzed are entered into the LIMS logs
(batches, sequences, etc.) to track the samples throughout the measurements
procedures.
•	Supporting equipment - identification, certifications, calibration, if needed.
•	Blank, CCVs, replicate and spike results - these QC indicators can be used to
ascertain whether sample handling or analysis is causing bias in the data set.
•	Review Checklists - these record data quality review performed on all data by Task
Leader and on 10 percent of the data by the QA Coordinator or designee. The
checklists used to review data is presented in the SOPs.
•	Summary Reports - monthly summary data reports present the preliminary data to
EPA and respective State/Local/Tribal representatives including data qualifiers.

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The reliability and acceptability of environmental analytical information depends on the
rigorous completion of all the requirements outlined in the QA/QC protocol. During data
analysis and validation, data are filtered and accepted or rejected based on the set of QC criteria
listed in the individual SOPs included in Appendix C.
The data are critically reviewed to locate and isolate spurious values. A spurious value,
when located, is not immediately rejected. All questionable data, whether rejected or not, are
maintained along with rejection criteria and any possible explanation. Such a detailed approach
can be time-consuming but can also be helpful in identifying sources of error and, in the long
run, save time by reducing the number of outliers.
18.2	Data Verification
Data verification by examination confirms that specified method requirements have been
fulfilled. The specific requirements are QC checks, acceptable data entry limits, etc. as presented
in Section 1 1. The analytical procedures performed during the monitoring program will be
checked against those described in the QAPP and the SOPs for the UATMP, PA MS, and NMOC
support included in Appendix C. Deviations from the QAPP will be classified as acceptable or
unacceptable, and critical or noncritical. During review and assessment, qualifiers will be applied
to the data as needed; data found to have critical flaws (such as low spike for surrogate
recoveries, contaminated blanks, etc.) will be invalidated and a CAR filled out and implemented,
if needed. All data management guidelines followed for this contract are presented in Section 15.
18.3	Data Review
The COC forms are checked to ensure accurate transcription. The data are scrutinized
daily to eliminate the collection of invalid data. The analyst records any unusual circumstances
during analysis (e.g., power loss or fluctuations, temporary leaks or adjustments, operator error)
on the LIMS bench sheet and notifies the analytical Task Leader.

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QC samples and procedures performed during the monitoring program will be checked
against those described in Section 11 of the QAPP. If QC is found unacceptable, corrective
actions are implemented (as described in the same section). Prior to reporting, 100 percent of the
data is reviewed by the Task Leader(s). To verify accuracy, at least 10 percent of the database is
checked by the QA Coordinator or designated reviewer. Items checked can include original data
sheets, checks of all calculations (from calibration to sample analysis), and data transfers. As the
data are checked, corrections are made to the database as errors or omissions are encountered. If
major errors are found, a greater percent of the data is checked to verify data quality. The
Program Manager reviews all data before it is reported to EPA or the State/Local/Tribal
agencies.
18.4 Data Reduction and Reporting
Monthly site-specific data summaries for the NMP are distributed to the participating
EPA technical staff, administrators, and to the administrators of the State/Local/Tribal agencies
involved in the study. NATTS, CSATAM, and UATMP data consists of any toxics including
VOC, SNMOC, carbonyl, or other HAPs (metals, sentivolatiles, etc.) requested by the program
participants. Each report is prepared after 45 days from the end of the sampling month.
Cumulative listings are periodically generated upon request. This timely turnaround of data
assists in planning, preliminary modeling, and program development for the participating
State/Local/Tribal agencies. Any changes made in the preliminary data because of subsequent
data validation processes performed by EPA and/or State/Local/Tribal agencies are noted in the
cumulative project data summaries for each specific sampling site. The data summaries include:
•	Site code;
•	Sample identifications;
•	Sample dates;
•	Target compound list;
•	Concentrations (ppbv, ppbC, ng/m3 and/or p,g/m3); and

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• Method detection limits.
Preliminary monthly data summaries are emailed to the program participants. These data
summaries are considered preliminary until the data is validated and entered into the AQS
database, as detailed in Section 18.6.
The Program Manager reviews all data before they are reported to EPA and/or the
State/Local/Tribal agencies. ERG prepares a final report containing all aspects of the individual
programs including data summaries, QA, QC, and data analysis results for EPA, and distributes
site-specific summaries of the final data to designated personnel.
18.5 Data Validation
Data validation is confirmed by examination of objective evidence that the requirements
for a specific intended use are fulfilled as presented in Section 4. Intended use deals with data of
acceptable quality to permit making decisions at the correct level of confidence. This data
validation is performed prior to the annual final report. The data reported monthly are considered
preliminary until the data is validated, entered into the AQS database, and reported in the annual
final report.
The Precision from analysis of replicate samples in CV is determined by site, by
compound, and as an average for the method. These precisions are based on analytical analyses
only. Precision from the analysis and collection of duplicate/collocate samples in CV is
determined by site, by compound, and as an average for the method. These precisions are based
on analytical precision and sampling precision. The method average precision also includes
collocated samples which can increase precision results. This measure the complete data set is
compared against the data quality objective for the NATTS program, even though the other
programs are not as stringent. This is accomplished prior to the preparation of the annual final
report.

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Representativeness can be assessed with site location information and is based on
potential sources and select weather station information. This is accomplished while preparing
the annual final report. Comparability is based on method measure of the level of confidence
with which one data set can be compared to another. Ongoing data review and adherence to the
data quality objectives keeps the data quality con si stent and therefore comparable over the
project. This is an ongoing data quality review followed by a data assessment prior to the
preparation of the annual final report.
Completeness is measured by the amount of valid sample data obtained compared to
what was expected. This is determined by counting the number of valid samples based on the
sampling schedule for a that site. Eighty-five percent is considered complete for all the programs.
This is an ongoing assessment used to facilitate make-up sampling in the same quarter when
possible.
To ensure that the data is reliable in the ranges of concern, the minimum detection limit
targets are those specified for the NATTS program, even though the other programs are less
stringent. This is an ongoing assessment since detection limits are determined annually.
18.6 Air Quality System
ERG submits data collected for the NMOC, UATMP, NATTS, CSATAM, PAMS, and
other air toxics programs to the AQS database.
Prior to ERG's submittal of data to AQS, the State/Local/Tribal agency submits, at a
minimum, Basic Site Information transactions (Type A A) for each sampling site, and Site Street
Information (Type AB) and Site Open Path Information (Type AC), if necessary. ERG then
submits monitor transactions (Types M A through MN, as applicable) to prepare the AQS
database for data upload. Data that are uploaded into AQS include Raw Data transactions (Type
RD), QA transactions (Type Duplicate and Replicate, and Pb Analysis Audit) and Blank
transactions (Type RB). ERG follows the NATTS TAD1'*' to code data for the AQS database.

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The submittal process involves the following steps:
•	The raw data are formatted into pipe-delimited (|) coding that is accepted by AQS.
Raw data, data generated by single sample episodes, by the primary sample (D1) of a
duplicate episode, or by collocates (C1 and C2), are submitted using RD transactions.
Precision data, data generated by Duplicate and Replicate samples (Rl, D2, and/or
R2), are submitted using QA transactions, specifically Duplicate and Replicate
transactions. Accuracy data, generated for lead-FEM audit results, are also submitted
using QA transactions.
•	The RD QA (specifically duplicate, replicate and Pb Analysis Audit), and RB coding
is generated and reviewed following guidelines specified in the SOP for the
Preparation of Monitoring Data for AQS Upload (ERG-MOR-098) to ensure that the
proper monitor ID (including state, county, site, parameter, and Parameter Occurrence
Code (POC) codes), sampling interval, units, method, sample date, start time, and
sample values are correct. The transactions are stored as text files for upload into the
AQS database.
•	Transaction files are primarily loaded under the Monitoring and Quality Assurance
screening group.
•	Transactions are edited to correct any errors found by AQS and then resubmitted.
This step is repeated until the transactions are free of errors.
•	AQS performs a statistical check on the data submitted to validate the data and
determines if there are any outliers based on past data.
•	Raw data (RD) transactions are then posted into the AQS database.
18.6.1 AQS Flagging and Reporting
Air toxics data submittals may be submitted with flags to indicate additional information
related to the sample. There are two qualifier flag types that may be applied: Null codes and
Qualifier codes.
•	Null Code — assigned when a scheduled sample is not usable (e.g., canister leaked,
canister damaged in shipment, etc.).
•	Qualifier Code — used to note a procedural or quality assurance issue that could
possibly affect the concentration of the value or the uncertainty of the result. These
flags can also be applied to indicate atypical field conditions (e.g., nearby fires,
construction in the area).

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Qualifier Codes can be used in combination, with up to 10 possible codes applied. If a
Null code is used, no other flag should be used since no results are reported. Table 18-1 presents
the Qualifier codes and Table 18-2 presents the Null codes available to AQS users. These flags
are applicable to the various steps of sample collection and analysis such as field operations,
chain of custody, and laboratory operations.
Blank issue flags are qualifier flags used if reported blank values are above the limits set
by the method SOPs or QAPP. If high blank values are associated with samples, the sample
values are reported but appropriately flagged as described in the NATTS TAD1'*'. Samples will
not be invalidated due to high blank values. Blank issue flags are included in Table 18-1.
Table 18-1
Qualifier Codes
Qualifier Code
Qualifier Description
1
Deviation from a CFR/Critical Criteria Requirement
IV
Data reviewed and validated
2
Operational Deviation
3
Field Issue
4
Lab Issue
5
Outlier
6
QAPP Issue
7
Below Lowest Calibration Level
9
Negative value detected - zero reported
CB
Values have been Blank Corrected
CC
Clean Canister Residue
CL
Surrogate Recoveries Outside Control Limits
DI
Sample was diluted for analysis
DN
DNPH peak less than NATTS TAD requirement, reported value should be

considered an estimate
EH
Estimated; Exceeds Upper Range
FB
Field Blank Value Above Acceptable Limit
FX
Filter Integrity Issue
HT
Sample pick-up hold time exceeded
LA
African Dust
IB
Asian Dust
IC
Chemical Spills & Industrial Accidents
ID
Cleanup After a Major Disaster
IE
Demolition
IF
Fire - Canadian
IG
Fire - Mexico/Central America

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Table 18-1
Qualifier Codes, Continued
Qualifier Code
Qualifier Description
IH
Fireworks
II
High Pollen Count
IJ
High Winds
IK
Infrequent Large Gatherings
IL
Other
IM
Prescribed Fire
IN
Seismic Activity
10
Stratospheric Ozone Intrusion
IP
Structural Fire
IQ
Terrorist Act
IR
Unique Traffic Disruption
IS
Volcanic Eruptions
IT
Wildfire-U. S.
J
Construction
LB
Lab blank value above acceptable limit
LJ
Identification of Analyte Is Acceptable; Reported Value Is an Estimate
LK
Analyte Identified; Reported Value May Be Biased High
LL
Analyte Identified; Reported Value May Be Biased Low
MD
Value less than MDL
MS
Value reported is V* MDL substituted
MX
Matrix Effect
ND
No Value Detected. Zero Reported
NS
Influenced by nearby source
QP
Pressure Sensor Questionable
QT
Temperature Sensor Questionable
QX
Analyte does not meet QC criteria
SQ
Values Between SQL and MDL
ss
Value substituted from secondary monitor
sx
Does Not Meet Siting Criteria
TB
Trip Blank Value Above Acceptable Limit
TT
Transport Temperature is Out of Specs
V
Validated Value
VB
Value below normal; no reason to invalidate
W
Flow Rate Average out of Spec.
X
Filter Temperature Difference out of Spec.
Y
Elapsed Sample Time out of Spec.
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Table 18-2
Null Codes
Null Code
Qualifier Description
AA
Sample Pressure out of Limits
AB
Technician Unavailable
AC
Construction/Repairs in Area
AD
Shelter Storm Damage
AE
Shelter Temperature Outside Limits
AF
Scheduled but not Collected
AG
Sample Time out of Limits
AH
Sample Flow Rate out of Limits
AI
Insufficient Data (cannot calculate)
AJ
Filter Damage
AK
Filter Leak
AL
Voided by Operator
AM
Miscellaneous Void
AN
Machine Malfunction
AO
Bad Weather
AP
Vandalism
AQ
Collection Error
AR
Lab Error
AS
Poor Quality Assurance Results
AT
Calibration
AU
Monitoring Waived
AV
Power Failure
AW
Wildlife Damage
AX
Precision Check
AY
Q C Control Points (zero/span)
AZ
Q C Audit
BA
Maintenance/Routine Repairs
BB
Unable to Reach Site
BC
Multi-point Calibration
BD
Auto Calibration
BE
Building/Site Repair
BF
Precision/Zero/Span
BG
Missing ozone data not likely to exceed level of standard
BH
Interference/co-clution/misidentification
BI
Lost or damaged in transit
BJ
Operator Error
BK
Site computer/data logger down
BL
QA Audit
BM
Accuracy check
BN
Sample Value Exceeds Media Limit
BR
Sample Value Below Acceptable Range
CS
Laboratory Calibration Standard
DA
Aberrant Data (Corrupt Files. Aberrant Chromatography, Spikes, Shifts)
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Table 18-2
Null Codes (Continued)
Project No.
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Page
Null Code
Qualifier Description
DL
Detection Limit Analyses
EC
Exceeds Critical Criteria
FI
Filter Inspection Flag
MB
Method Blank (Analytical)
MC
Module End Cap Missing
QV
Qualitv Control Multi-point Verification
SA
Storm Approaching
sc
Sampler Contamination
ST
Calibration Verification Standard
sv
Sample Volume out of Limits
TC
Component Check & Retention Time Standard
TS
Holding Time or Transport Temperature Is Out Of Specs.
XX
Experimental Data
ERG submits data to AQS using qualifier flags to show where the data are with respect to
the detection level. A variety of terms and acronyms are used for defining the lowest level that
can be detected for each analytical method. These terms and applications are derived from EPA's
TAD for the NATTS program and are presented below:
•	Quantitation Limits (QL) — the lowest level at which the entire analytical system
must provide a recognizable signal and acceptable calibration point for the analyte.
•	Detection Limits (DL) — the minimum concentration of an analyte that can be
measured above instrument background.
•	MDL — the minimum concentration of a substance that can be measured and
reported with 99 percent confidence that the analyte concentration is greater than zero
and is determined from analysis of a sample in each matrix containing the analyte
(Part 136, A pp. B).
•	SQL — the lowest concentration of an analyte reliably measured within specified
limits of precision and accuracy during routine laboratory operating conditions.
Normally, the SQL is determined as a multiplier of the method detection limit
(e.g., 3.18 times) and is considered the lowest concentration that can be accurately
measured, as opposed to just detected.
The qualifier flags associated with quantitation and detection limits are also included in
Table 18-1, while Table 18-3 summarizes how they are applied to the data.

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Table 18-3
Summary of Quantitation and Detection Limit Flags and Applications
If Concentration is:
Value to
Report
Flag Applied
> SQL
Value
None
> MDL and < SQL
Value
SQ
< MDL
Value
MD
Not Detected
0
ND
Project No.
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Date
Page

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SECTION 19
DATA V ALIDATION, V ERIFICATION METHODS
Many of the processes for verifying and validating the measurement phases of the data
collection operation have previously been discussed in Section 18. If these processes are
followed, and the sites are representative of the boundary conditions for which they were
selected, one would expect to achieve the DQOs. However, exceptional field events may occur,
and field and laboratory activities may negatively affect the integrity of samples. In addition, it is
expected that some of the QC checks will fail to meet the acceptance criteria. This section will
outline how ERG will take the data to a higher level of quality analysis by performing software
tests, plotting, and other methods of analysis.
19.1 Process for Validating and Verifying Data
19.1.1	Verification of Data
For the analytical data, the entries are reviewed to reduce the possibility of entry and
transcription errors. Once the data are transferred to the ERG LIMS database, the data will be
reviewed for routine data outliers and data outside acceptance criteria. These data will be flagged
appropriately. Prior to reporting, 100 percent of the data is reviewed by the TL(s) and 10 percent
of the database is checked by the QA Coordinator or designated reviewer. The PM also reviews
the data prior to the preliminary report. After a preliminary reporting batch is completed, a
review of 10 percent of the data will be conducted for completeness and manual and electronic
data entry accuracy by the Annual Report/AQS TL.
19.1.2	Validation of Data
Data validation is performed by examination of objective evidence that the requirements
for a specific intended use are fulfilled as presented in Section 4. Data is examined for
representativeness, completeness, precision, and bias. This data validation, some of it performed

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with summary statistical analysis, is performed prior to the annual final report. Data validation is
discussed in more detail in Section 18.5.
19.2 Data Analysis
Data analysis refers to the process of interpreting the data that are collected. Although
there are a large number of parameters to analyze, many of these parameters present similar
characteristics, (i.e., VOC, SVOC, and particulate metals, grouped according to their physical
and chemical properties).
ERG will employ software programs, described below, to help analyze the data.
Spreadsheet - Select ERG employees perform analysis on the data sets using Excel®
spreadsheets (analysts. Task Leaders, and QA reviewers) and Access* databases (AQS data
entry). Spreadsheets and databases allow the user to input data and statistically analyze, graph
linear data. This type of analysis will allow the user to see if there are any variations in the data
sets. In addition, various statistical tests such as tests for linearity, slope, intercept, or correlation
coefficient can be generated between two strings of data. Time series plots and control charts can
help identify the following trends:
•	Large jumps or dips in concentrations;
•	Periodicity of peaks within a month or quarter; and
•	Expected or unexpected relationships among species.

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SECTION 20
RECONCILIATION WITH DATA QUALITY OBJECTIV ES
The project management team, QA Coordinator, and sampling and analytical team
members are responsible for ensuring that all measurement procedures are followed as specified
and that measurements data meet the prescribed acceptance criteria. Prompt action is taken to
correct any problem that may arise.
20.1	Conduct Preliminary Data Review
A preliminary data review will be performed as discussed in Sections 16 and 18 to
uncover potential limitations to using the data, to reveal outliers, and generally to explore the
basic structure of the data. The next step is to calculate basic summary statistics, generate
graphical presentations of the data, and review these summary statistics and graphs to determine
if the program requirements in Section 4, representativeness, comparability, completeness,
precision, bias, and sensitivity, were met. Representativeness can be assessed with site location
information and is based on potential sources and select weather station information.
Comparability is based on method measure of the level of confidence with which one data set
can be compared to another. Completeness is measured by the amount of valid sample data
obtained compared to what was expected. Precision is determined from replicate analyses for a
given method. Laboratory bias is demonstrated through PT samples and second source standards.
Sensitivity is demonstrated through minimum detection limits.
20.2	Draw Conclusions from the Data
If the sampling design and statistical tests conducted during the final reporting process
show results that meet acceptance criteria, it can be assumed that the network design and the
uncertainty of the data are acceptable. This conclusion can then be reported to EPA and the
States/Local/Tribal agencies, who then decide whether to perform risk assessments and analyze
the data to determine whether these data can be used to address health effects.

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SECTION 21
REFERENCES
2.
3.
4.
5.
6.
7.
8.
McAllister, R. A., D-P. Dayton, and D. E. Wagoner. 1985 Nonmethane Organic
Compounds Monitoring Assistance for Certain States in EPA Regions I, III, V, 17, and
VII. Radian Corporation, DCN No. 85-203-024-35-01, prepared for Dr. Harold G.
Richter, Research Triangle Park, NC: U.S. Environmental Protection Agency, 1986.
Technical Assistance Document for Sampling and Analysis of Ozone Precursors. U.S.
Environmental Protection Agency, National Exposure Research Laboratory, Research
Triangle Park, NC. EPA 600-R-98/161. September 1998. Can be found at
i w\ »,s i vww 3. epa.gov/ttn/amtic/files/amhient/pams/neM /»n\ t't
Compendium Method TO-12, Determination of Non-Methane Organic Compounds
(NMOC) in Ambient Air Using Cryogenic Pre-Concentration Direct Flame Ionization
Detection (PDF1D), 1999. Can be found at
https://www3.epa.80v/itnamtil/files/amhient/airtox/to- 12.pdf.
Compendium Method TO-15, Determination of Volatile Organic Compounds (VOCs) In
Air Collected In Spedal 1 y-Prepared Canisters And Analyzed by Gas Chromatography/
Mass Spectrometry (GC/MS), 1999. Can be found at
https://www3.epa.gov/ttnamtil/files/ambient/airtox/to-15r.pdf.
Compendium Method TO-1 1 A, Determination of Formaldehyde in Ambient Air Using
Adsorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC),
1999. Can be found at https://www3.epa.gov/ttnamtil/files/ambient/airtox/to-llar.pdf.
Compendium Method 10-3.5, The Determination of Metals in Ambient Particulate
Matter Using Inductively Coupled Argon Plasma/Mass Spectrometry (ICP-MS), 1999.
Can be found at imp irn w.epa.gov/ttn/amtic/files/ambient/inorginn•. dt
EQL-05 12-201, Standard Operating Procedure for Determination of Lead in TSP by
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) with Hot Block Dilute Acid
and Hydrogen Peroxide Filter Extraction, 2012. Can be found at
https://www3.epa.sov/ttn/amtic/files/ambient/pb/EQL-0512-201 pJf
EQL-0512-202, Standard Operating Procedure for the Determination of Lead in PM 10 by
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) with Hot Block Dilute Acid
and Hydrogen Peroxide Filter Extraction, 2012. Can be found at
https://www3.epa.gOv/ttn/amtic/files/ambierit/pb/EOL-0512-202:pdf
ASTM D7614, Standard Test Method for Determination of Total Suspended Particulate
(TSP) Hexavalent Chromium in Ambient Air Analyzed by Ion Chromatography (IC) and
Spectrophotometric Measurements, 2012. Can be found at
https://www. astrn. org/Standards/1 htm.

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10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
Compendium Method TO-13 A, Determination of Poly cyclic Aromatic Hydrocarbons
(PAHs) in Ambient Air Using Gas Chromatography/Mass Spectrometry (GC/MS), 1999.
Can be found at https://www3.epa.sov/ttnamtil/files/ambient/airtox/to-13arr.pdf
SW-846, Method 8270D, Semivolatile Organic Compounds by Gas Chromatography/
Mass Spectrometry (GC/MS), 1996. Can be found at
http://www.epa.zov/epawaste/hazard/testmethods/sw846/pdfs/8270d.pdf.
ASTMJD6209 Standard Test Method for Determination of Gaseous and Particulate
Poly cyclic Aromatic Hydrocarbons in Ambient Air (Collection on Sorbent-Backed
Filters with Gas Chromatographic/Mass Spectrometric Analysis). Can be found at
https://www. astm. org/Standards/D6209. htm.
Compendium Method TO-4A, The Determination of Pesticides and Polychlorinated
Biphenyls in Ambient Air Using High Volume Polyurethane Foam (PUF) Sampling
Followed by Gas Chromatographic/Multi-Detector Detection (GC/MD), 1999. Can be
found at http://www.epa.zov/ttnamiil/files/amMent/airtox/to-4ar2r.pdf.
NIOSH 7903, Acids, Inorganic, 1994. Can be found at
http://www.cdc.sov/niosh/docs/2003-154/pdfs/7903.pdf.
Compendium Method TO-17, The Determination of Volatile Organic Compounds in
Ambient Air Using Active Sampling Onto Sorbent Tubes, 1999. Can be found at
https://www3.epa.gov ttnamtil files ambient air/ox to-17r.pdf
OSHA Method 42, Diisocyanates (1,6-Mexamethylene Diisocyanate (HDI), Toluene-2,6-
Diisocyanate (2,6-TDI), Toluene-2,4-Diisocyanate (2,4-TDI), 1989. Can be found at
http://www.osha.sov/dis/slic/methods/orsanic/ors042/ors042.html.
NIOSH Method 5029, 4,4 -Methylenedianiline, 1994. Can be found at
http://www.cdc.sov/niosh/docs/2003-154/pdfs/5029.pdf.
Technical Assistance Document for the National Air Toxics Trends Station Program.
U.S. Environmental Protection Agency. Office of Air Quality Planning and Standards,
Research Triangle Park, NC, October 2016. Can be found at
https://www3.epa.gov/ttnamtil/files/ambient/airtox/NATTS%20TAD%20Revision%203
FINAL %2 OOctober%202016.pdf.
U.S. Environmental Protection Agency. Code of Federal Regulations. Title 40, Chapter 1,
Part 136, Appendix B. Office of the Federal Register, July 1, 1987. Can be found at
https://www .ecfr. sov/csi-bin/text-
idx?SID=dfbcc3c558942b0766bcldba02b7Id72&mc=true&node=ap40.25.136 17.b&r
sn=div9.
U.S. Environmental Protection Agency. Federal Advisory Committee Act (FACA). Can

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Appendix A
ERG Exemptions from the NATTS TAD, Revision 3 & 4

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2017 Quality Assurance Project Plan, Category 1
UATMP, NATTS, CSATAM, PAMS, and NMOC Support
(Contract No. EP-D-14-030)
The proposed ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3, listed in Appendix
A of the QAPP have been deemed acceptable as noted by the signatures below.
U.S. EPA QA Manager:
U.S. EPA Delivery Order Manager:
ERG Program Manager:
ERG Deputy Program Manager:
ERG Program QA Officer:
Appapved by:
r
r-
Z7
Date:
Date:
:1kd 17
L ,	Date: % (/l3-
i|z4i>
Vl^CL.	t-LU-— Date:

Date: ffz-^lt?

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ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/or experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
Anal* i'.-
VO Ox
."f
'JfV/
TAIt Ri-k-miiT
I.HCllI i'HI
4.2.2, pg fif>
, J, -w j-
: -#*
! ...
ecM"ii
l»au- Mu-I»m Ik-liu-n
> irih'i Mair.iiii'n \
V-ali -:y.V Man-.i^t'i'l
Approved at June 2017 F,PA/ERG
meeting (.Tune 23. 2017)
VOCs
4.2.4.1.1.1, pg 74
Oanisters with leak rales > 0.1 psi/day
must be. removed from service and
repaired.
ERG evacuates the canisters to -25" Ilg
and measured again in seven days. Our
acceptance criteria is <1" Hg (QAPP
section 11,1). This more accurately mimics
the vacuum of the canisters shipped to the
field when Ihere is greater potential of
major leak affecting the sample
concentration.
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
VOCs
4.2.4 2 4. pa 77
Table 4 2 3. pa 93
Stales on canister per batch cleaned in
Section 4.2.4.2,4. but in Table 4.2-3 it
states that the canister chosen must
represent no more than 10 total
canisters.
FRG heated canister cleaning systems are
12-port svstems. We propose to continue
vei l t ying cleanliness on one canister for
each batch of 12. Historical data can be
provided it needed.
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
VOCs
4.2.6, pg 80
The recommended tolerance is a
pressure change of <0.5 psia.
Because of the wide variety of sites,
gauges, operators, ERG has created a
spreadsheet to track the, pressure
differences between field and laboratory.
If these values differ by historical
differences > 3", the samples arc
invalidated
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
lofS

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ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/or experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
A ii.il i lo
VOCs
TAI • Krii-icnci-
i.iidil imi"
4 2 X 2 2. pg 87
iable 4.2 3, pg 93
iji' IVir.inieii-r
Analysis of swept carrier gas through
the Preeuneenlralor to demonstrate the
instrument is sufficiently clean to begin
analysis (IB).
i:i«; Lv.vp!i>>!'.
This is listed as a recommendation in
Section 4.2.8.5.2.2 but as a requirement in
Table 4.2-3. Because (he samples are
checked with the analysis of blank
samples, ERG will analyze the IB only for
trouble shooting purposes.
lil'A Appmval.'lk'dsi'ii!
OmrSliiliiH il.PA Ik-lit i-r>
"nlri Manager! \-
'•n-ji V'Uli '.()A Miiiu^i-n
Approved al June 2017 EPA/ERG
meeting (June 23, 2017)

Carbonyls
4.3.2, pg 97
The sample must be kept cold during
shipment such thai, the temperature
remains < 4~C, and the temperature of
the shipment must be determined upon
receipt at the laboratory.
This requirement will be extremely
difficult to achieve during summer months
and is not required in Method TO-11A
i'lie vendor does not ship the cartridges to
the laboratory in cixders but the samples
are shipped overnight with receipt in the
laboratory Tuesday through Friday. ERG
will conduct a summer study to determine
the necessity of this requirement and
present it to the EPA in 2017.
Study presented to the EPA on
August 25, 2017 validating F.RG's
exemption. The exemption was
approved at this meeting.
O-arbonyls
4 3.9.4, pg 115
'I able 4.3-4. pa
121
F.MSR - For batch si/.es of more than 20
field-collected cartridges, n such QC
samples ci each type must be added to
the batch, where n = batch size / 20, and
where n is rounded to the next highest
integer.
F.RG has previously only performed this
type of ert action to see if there w ere
problems in a new lot of solvents. Our
procedure will perform this extraction oxicc
a month, in Ihe first batch of samples
prepared each month.
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
2 of S

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ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/a- experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain ill effect throughout the current contract.
Anakli.-
TAI • Uvk-miiT
i. "ical i--il
' I'aijuiekr
i!K(; iXivjjIit'ii
I-I'A Appnival.'l>ccl>i"ii
lhi>i- Sin-In" iM'A IH-liUTi
'¦ 'rili-i- \I;iii:iuit> Jv-
Grt'ii S..:ih -'(JA Mhii.i-jiti
Carbouyls
4.3.9.5.2. pg 117
For positive identification, the RT of a
derivatizedcarbonyl must be within
three standard deviations (3 s) or ± 2%,
whichever is smaller, of its mean RT
from the ICAL
ERG's Carbonyl software (Agilent®)
allows a +2.5% window, not +2.0%, but
will automatically check if compounds arc
outside of this window. ERG believes the
automatic function is advantageous and
will perform LC maintenance checks if the
RT fall outside this RT window.
Approved at June 2017 EPA/HRG
meeting (June 23, 2017)





Metais
4.4.5, pg 128
Field blank analysis must demonstrate
all target elements < MDL,
ERG does not get filters from the same lot
thai are provided to the field for sampling.
Our filters are purchased and we determine
the MDLs based on (he background in that
particular lot. Because of llu; wide variety
of filter lots coming in from the different
sites, and until the manuLvi urers of the
filters provide clean enough samples, die
majority of the elements could potentially
be flagged. "ERG proposes U> flag only
those elements over 5xMDL in order to
better accommodate the potential lot
differences.
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
3 of 8

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5 of 10
ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/or experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
A mil vi i-
TAD Uiliienci-
i.iicai i--ii ~
" I'ai anifii1!"
Lv.vpiii':"!
Ml* \ ^ppn.ival.'l >ed>i"ii
1 >isvi- Slu|i>« il'1'A IK-lhcn
)rder Mananeri \
Grej: ,N.»:ili ;QA M;in.i^i'i-l
Melals
4.4.10.5, pg 137
RT5S- spiked digestion solution only (no
filler strip - ensures proper spike
recovery without the filter matrix)
ERG will prepare Standard Reference
Material samples (required by NAAQS
lead) and perforin Post Digestion Spike,
analysis lo ensure proper spike recovery
without the filter matiix, instead of
preparing and analyzing the RBS,
Approved al June 2017 EPA/ERG
meeting (June 23, 2017)
Metals
4.4.10.5.2.1, pg
139
Each filter strip must, be accordion
folded or coiled and placed into
separate digestion vessels.
ERG does not use accordion folding fa* the
QFF filters. The digestion procedure is
detailed in SOP 0S4. Historical data for
over 10 years show acceptable recoveries
using this method. ERG proposes to keep
current folding procedures in place.
Approved at June 2017 EPA/ERG
meeting (June 23. 20P)
Metals
4,4.11,7,1, pg 142
Replicate analyses tt tt libration
slandards muni xho\ KSD _£ 10%
ERG's lowest calibration point is at the
LOQ concentration. Our standard practice
is to have all cai points atRSD „1()',;,
but the low cal pomt at %RSD *>20%. litis
standard uses die same concentrations as
the Limit ot Quantitation (LOQ) standard,
which are near or less than that of the
YTDl . therefore an RSD i 20 percent is
acceptable.
Added text in QAPP Section
11.3.X "Replicate analysis of the
calibration standards must have
an RSD 5 10 percent, except tor
the second calibration standard
(CAL2). lliis standard uses the
same concentrations as the Limit
of Quantitation (LOQ) standard,
which are near or less than that of
the VIDE, therefore an RSD i 20
percent is acceptable,"
Approved at June 2017 EPA/ERG
meeting lJune 23.2017»
4 of 8

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ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/or experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
AlKiJviv
Mclals
TAI t lii'leri'iici-
1.iicai i'>ii
4.4.11.7,3, pg 143
4.4.11-7.fi, pg 144
4.4.11.S, pg 145
Table 4.4-3
/ '/ w / / '/
" iViraiiieU-i1
The ICR is again analyzed following
the ICV: all element responses must be
less than the laboratory's established
MDLsp lor MDLs determined via
Section 4.1.3.1 or Ihc portion of the
MDL represented by s-K for MDLs
determined via Section 4.1.3,2, Also
for CCB, negative values, BLK1, and
Rfl.
i:k<; r v_vpii"ii
ERG references the MDL for the IC.D,
CCB, negative values, reagent Wanks and
method blanks, not lhe.s * K. F.RG docs
not believe there should be 2 different sets
of criteria for instrument/batch QC, These
are all < MDL,
Kl'A .\ppi-iivj|,'lk'cMi-n
Ibur S!ii|i>« l)clhrr>
'• )rd>T Miiuanen &
tiros: V'iili Miiii.rjm
Approved at .Tunc 2017 EPA/F.RG
meeting (June 23, 2017)
Metals
4.4.11.7,4, pg 143
Table 4,4-3. pg
147
ICSA - All tarset elements < MDLsp
(refer lo Section 4.1.3.1) or s-K (refer to
Section4.1.3.2) -may be subtracted for
ICS A certificate of analysis
ERG's critieria is for the results to be
within +3 times LOQ from zero or from
the stock standard. This allows us to take
into account the background in the
interference solution when present.
Approved at June 2017 EPA/F.RG
meeting (June, 23, 2017)
Melals
4.4.9.5.1, pg 132
4.4.10.5.1, pg 137
Table 4.4-3. pg
148
LCS - Recovery within 80-120% of
nominal for all target elements, Sb
recovery 75-125%.
ERG does not currently flag Sb if it is over
80-120%. ERG will monitor Sb with
conlrol charts for 6 months or gather
existing data to allow us to statistically
determine reasonable acceptance criteria.
Historical control charts presented
and it was decided to flag QC and
sample data starting 11/1/17.
Discussed at the September 2017
EPA/ERG meeting
(September 22, 2017)
Metals
4.4.10.5.1,pg 137
Table 4.4-3, pg
148
MS/MSD - Recovery within 80-120%
of the nominal spiked amount for all
target elements, Sb recovery 75-125%.
ERG does not currently flag Sb if it is over
80-120%. ERG will monitor Sb with
conlrol charts for 6 months or gather
existing data to allow us to statistically
determine reasonable acceptance criteria.
Historical control charts presented
and it was decided to flag QC and
sample data starting 11/1/17.
Discussed at the September 2017
EPA/ERG meeting
(September 22, 2017)
5 of 8

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Project No.
Element No.
Revision No.
Date
Page
0344.00
Appendix A
4
March 2018
7 of 10
ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of liistoricai data and/a- experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
AmUu-
TAI i Ri-k-mici-
i.m'alii'ii::
"
yi11'iirann-iir
i.K<; r; v.vpii"ii
MI'A ^ppin-.ali'iK'cM'.ii
Ihm- Slu-lnM lH'.\ l)eliur>
Oidei MjiiauenA-
Gi t li .Si-all V M:ni.i'_:LTl
PAII
4.5.3, pg 152
Table 4.5-3
Lot Blank - Regardless of the source of
materials or the specific cleaning
procedures each agency adopts, the
QFF and PI JF/XAD-2/PT IF present in
cartridges must meet the batch blank
acceptance criteria of < 10 ng each for
all target compounds. One cartridge for
each batch of 20 or fewer prepared
cartridges
ERG's procedure has been to prepare one
filter per preparation shipment day.
Background contamination (even when
precleancd before preparing cartridges by
[he laboratory) show targets > 10 ng per
target compound. ERG's criteria is to flag
only those compounds which have
recoveries > 5x MTIL. ERG will monitor 6
months of lot blank data loproviil i 11
EPA to justify exemption.
Historical control charts presented
and it was decided to allow a new
exemption criteria to be less than
theMDL starting 11/1/17.
Discussed at the September 2017
EPA/ERG meeting
(September 22, 2017)
PAH
4.53.3, pg 153
Field surrogates are added no sooner
tlian two weeks prior to (he scheduled
sample collection date.
ERG will be unable to provide sites with
an extra sample media on each sampling
day (standard practice) if we arc not
allowed to have cartel aes spiked no
sooner than two weeks. This practice is
not listed in TO-13A or the AS I'M 6209.
ERG will perform a study or gather
existing data to determine how long the
spiked surrogates are stable on the
cartridges (up to 3 months) and present it
to the EPA to ju-lily exemption.
Study presented to the EPA on
August 25, 2017 validating ERG's
exemption. The exemption was
approved at this meeting.
6 of 8

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Project No.
Element No.
Revision No.
Date
Page
0344.00
Appendix A
4
March 2018
8 of 10
ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/or experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
AimIi It
T.VH RHi-i'i-iicl-
i.'icjl ii>n
^ / ! '''
tj! ' I'il I'iM lieK'l-
I.K<; L\cep!i'-n
\ V\ Appno ¦il.'IKvKi"ii
Ibiu- Slii-li>« il\l'A IMiut.x
'• )rdei- Manaiicri \
(•n-g V>:ili ;y.\ M;iii.i£i-ri
PAH
4.5.4.11), pg 154
Samples which are shipped overnight
should be packed with sufficient cold
packs oi ice to ensure they arrive at the
laboiatorj al _ 4 C.
This requirement will be extremely
difficult to achieve during summer months,
F,RG will conduct a summer study to
determine the necessity of (his requirement
and present it to the EPA in 2017,
Study presented to the EPA on
August 25, 2017 validating ERG's
exemption. The exemption was
approved al (Ms meeting.
PAII
4.5.5.S.2, pg 160
Tuning the MS. Table 4.5-2
IRt i currently uses the version from
S270D Rev5 July 2014 version which is
the updated tune (able for where the TO-
13 A method originally lifted their tune
criteria. Tt is our opinion the original table
listed (in Table 4.5-2) was created for older
machines with less capability. The 2014
revision gives the operator the ability? to
tune to the heavier masses and gel. better
resolution on the complex compounds.
ERG proposes to continue using the 827((D
criteria.
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
PAH
4.5.5.5.3, pg 161
An SB which is not fortified with IS
must be analyzed just prior to
calibration (o ensure Ihe instrument is
sufficiently clean to continue analysis.
Analysis of the SB must show all target
compounds, IS, and surrogate
compounds are not detected
Table 4.5-3 states that the SB must be
analyzed before each DFTPP tune, Section
4.5.5,5.3 states before each calibration,
ERG will analyze the SB prior to the 1CAL
which is required in our DQOs not to
exceed 6 weeks.
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
7 of 8

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Project No.
Element No.
Revision No.
Date
Page
0344.00
Appendix A
4
March 2018
9 of 10
ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 3 (2017 QAPP, Contract EP-D-14-030)
ERG has provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/a- experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
A mil vie
TAI l Ui-k-mici-
i.lii'jlii'll "
' I'jIMIIIOllT
I RC L
l-:i'\ Approval,'IK'iMi-n
1 »ii*i- Slii ln" iM'A IK'liu n
¦ li der M Jiianon &¦
t Iron Ni'jili :: 162
The RRTs of each surrogate or target
compound across the 1CAI. ;ii: tli.n
averaged to determine the ICAL RRT,
All RRTs must be within ± 0.06 RRT
units of RRT.
I'.KG's VOC software (ChemStation)
allow* different time deltas for lower and
upper lime limits'. For inslanee, Ihe
window for acenaplithylene is RT - 0.175
and RT + 0.25. The largest delta in the
database is RT + 0.25, and if s used for
several compounds. These windows for
each compound are well within those
required using the mean RRI. A table
presenting RRTs to ERG* s current
procedure of tracking RT 's is presented in
Appendix B.
Approved at June 2017 F.PA/ERG
meeting (June 23,2017)

VOC Table 7.1,
pg iw



All
Analytcs
Car bony 1,
4.3.8.1.3, pg 110
The sampling period for all field
samples collected should be 1380-1500
minutes (24+1 hour) stalling and ending
at midnight.
ERG has reported any sample that was 22-
23 hours or 25-26 hours, but flagged them
Approved at June 2017 EPA/ERG
meeting (June 23, 2017)
Metals, 4.4.9,4.1 &
4.4.10.4.1,
|>v 1 ~ 1 & pg 137
with a "Y" (Elapsed Sample Time out of
Spec,). Anything greater than ±2 hours is
invalidated.

PAH, 4.5.4,1,
Pg I"1!



8 of 8

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Project No.
Element No.
Revision No.
Date
Page
0344.00
Appendix A
4
March 2018
10 of 10
ERG EXEMPTIONS FROM THE NATTS TAD, REVISION 4 (2018 QAPP, Contract EP-D-14-03Q)
ERG lias provided the documentation to demonstrate that ERG meets the standard, in the form of historical data and/or experimental study results. These
exemptions from Revision 3 NATTS TAD were approved and will remain in effect throughout the current contract.
\n.ih It-
VOCs
T \li Kcli'i i iiri'
1.m';!( inll
4.2.3.5. Lpg 71
y ' I'aramcli-r _
The zero check is performed by
simultaneously providing humidified
(50 to 70% RH) hydrocarbon- and
o:\idanl-lree a.tu air (must lii^cl tlw
cleanliness criterion t>l'< 0.2ppbv or <
3x MDL. whichever is lower) or UIP
nitrogen to the sampling unit for
collection into a canister and to a
separate reference canister connected
directly to the supplied IICT zero air
gas source.	
I.I«i I'ACi'lilinil 	
For the compound aeetonitrile, F.RG will
use the previous criteria from TAD, Rev 2
of <0.2 ppbv.
1.1 "A \rini'"1. al/DccMim
Da'.f Shi-lim • l-.l1 \ l.k-lnen
< !i ili-r \l:m;i:jtn
< ii t-j .Nn.ih ((,> V Mjn.i-jcr)
Approved at My 2018 EPA'ERG
meeting (July 27,2018)
lofl

-------
Appendix B
2018 Sampling Schedule

-------
2018 6-Day Sampling Calendar
January
sun
Mon
Tue
Wed
Thu
Fri
Sat


rn


1 1 1

1
I2
3
4
5
6
7

9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
FB

28
29
30
31

1 1 1

April
Sun
Mon
Tue
Wed
Thu
Fri
Sat
I I



1 1 1
nn
HE9
3
4
! 5
6
m

9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
FB
27
23
29
30





February	March
Sun Mon Tue Wed Ttiu Fri Sat II Sun Mon Tue wed Thu Fri sat
May 1
Sun
Mon
Tue
Wed
Thu
Fri
Sat



1H




	
HI

2
3
4
5
6
7
¦a
9
10
11
12
13
14
15
16
17
IB
19
20
21
22
23
24
25
FB
27
28
29
30
31


July

August !
Sun
Mon
Tue
Wed
Thu
Fri
Sat

Sun
Mon
Tue
Wed
Thu
Fri
sat
II



I

rn






ET^
3
4
5
1 6 |
7

LJ


1
2
3
4
8
9
10
11
12
M7M
14

M
Hi
7
8
9
10
11
15
16
17
18
19
20
21


13
14
15
16
17
IB
22
23
24
25|
26
27
28

1—isl
20
21
22
23
D
25
29
30
FB
1 1 1



QT|
27
28
29
FB
~3

October

November
sun
Mon
Tue
Wed
Thu
Fri
Sat

Sun
Mon
Tue
Wed
Thu
Fri
Sat





I I I

rn







1
2
3
4
Is
6

rn



1
2
1 3 1
7
8
9
10
O
12
13

n
5
6
7
8
9

14
15
16
17
18
19
20

ii
12
13
14
15 nvm
17
21
22
23|
24
25
26
27

is
19
20
21

liL
24
28
FB
30
31




25
26
27
FB
p*H


¦Standard Sample Collection
| FB | Field Blank Collection
Duplicate Sampling Collection
September
Sun
Mon
Tue
Wed
Thu
Fri
sat


1 1 1


1
2
3
-
5
6
7
8
9
10

12
13
14
15
16
P*
18
19
20
21
22
|23
24
25
26
27
J*]
FB
1 30 | |






December
Sun
Mon
Tue
Wed
Thu
Fri
Sat
1





1
2 |
3
4
5
6
7 :
8
9
O
11
12
13
14
15
16
17
18
19
20
21

23
24
25
26
27
FB
L 29
30
31





Makeup Duplicate Collection
or normal sample

-------
Appendix C
Relevant ERG Standard Operating Procedures
The information contained herein is confidential and proprietary
And may not be used in any manner or form without the express
Written permission of the Program Manager.

-------
Appendix D
Subcontractors
Quality Assurance Project Plan
RTI Laboratories
Will be provided when work is initiated.
The information contained herein is confidential and proprietary
And may not be used in any manner or form without the express
Written permission of the Program Manager.

-------
APPENDIX D. TECHNICAL ASSISTANCE
DOCUMENT FOR THE NATIONAL AIR TOXICS
TRENDS STATIONS PROGRAM, Revision 3

-------
TECHNICAL ASSISTANCE DOCUMENT
FORTHE
NATIONAL AIR TOXICS TRENDS STATIONS PROGRAM
Revision 3
Prepared for:
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards (C3 04-06)
Research Triangle Park, NC 2771 1
Prepared by:
Battel le
505 King Avenue
Columbus, OH 43201
October 2016

-------
DISCLAIMER
This document has been reviewed in accordance with U.S. Environmental Protection Agency
policy and has been approved for publication. Mention of trade names or commercial products
does not constitute endorsement or recommendation for use.
11

-------
CONTENTS
LIST OF FIGURES	xi
LIST OF TABLES	xi
ACRONYMS AND ABBREVIATIONS	xiii
1.0: INTRODUCTION	1
1.1	Background	1
1.2	Target Analytes: Analytes of Critical Concern/Risk Drivers	 1
1.3	Importance of Adherence to Guidelines	4
1.4	Overview of TAD Sections	5
1.5	Critical Changes and Updates from Revision 2 of the NATTS TAD	6
1.6	Good Scientific Laboratory Practices	7
1.6.1 Data Consistency and Traceability	7
1.7	NATTS as the Model for Air Toxics Monitoring	7
1.8	References	8
2.0: IMPORTANCE OF DATA CONSISTENCY	9
2.1	Data Quality Objectives and Relationship to the Quality Assurance Project
Plan 	9
2.1.1	Representativeness	 11
2.1.2	Completeness	 11
2.I.2.1 Make-up Sample Policy	 1 1
2.1.3	Precision	 12
2.1.4	Bias	13
2.1.4.1	Assessing Laboratory Bias - Proficiency Testing	13
2.1.4.2	Assessing Field Bias	 14
2.1.5	Sensitivity	 14
2.2	NATTS Workplan	15
2.3	Quality System Development	15
2.4	Siting Considerations	 17
2.4.1	Sampling Instrument Spacing	 17
2.4.2	Interferences to Sampling Unit Siting	 18
2.4.3	Obstructions	 18
2.4.4	Spacing from Roadways	19
2.4.5	Ongoing Siting Considerations	19
2.5	References	20
3.0: QUALITY ASSURANCE AND QUALITY CONTROL	21
3.1	NATTS Quality Management Plan	21
3.2	NATTS Main Data Quality Objective, Data Quality Indicators, and
Measurement Quality Objectives	21
3.3	Monitoring Organization QAPP Development and Approval	2 1
3.3.1 Development of the NATTS QAPP	22
3.3.1.1	NA ITS QAPP - Program DQOs, DQIs, and MOOs	22
3.3.1.2	NA ITS QAPP - Performance Based Method Criteria	22
in

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3.3.I.3 NA TTS QAPP - Incorporating Quality System Elements	23
3.3.1.3.1	Standard Operating Procedure Documents	23
3.3.1.3.2	Corrective Action Process	24
3.3.1.3.3	Quality Assurance Unit and Internal Audit
Procedures	26
3.3.1.3.4	Calibration of Instruments	27
3.3.1.3.4.1 Calibration Verification (Checks)	31
3.3.1.3.5	Document Control System	31
3.3.1.3.6	Training Requirements and Documentation, and
Demonstration of Capability	32
3.3.1.3.6.1	Initial Demonstration of Capability	33
3.3.1.3.6.2	Ongoing Demonstration of Capability	33
3.3.1.3.7	Sample Custody and Storage	34
3.3.1.3.8	Traceability of Reagents and Standard Materials	34
3.3.1.3.9	Labeling	35
3.3.1.3.10	Early Warning Systems - Control Charts	35
3.3.1.3.11	Spreadsheets and Other Data Reduction Algorithms	36
3.3.1.3.12	Software Validation, Testing, Updating, and
Upgrading	36
3.3.1.3.12.1	Software Validation	36
3.3.1.3.12.2	Software Testing	37
3.3.1.3.12.3	Software Updating and Upgrading	37
3.3.1.3.13	Review of Records	37
3.3.1.3.14	Data Verification and Validation	38
3.3.1.3.14.1	Data Verification	38
3.3.1.3.14.2	Data Validation	39
3.3.1.3.15	Reporting of Results to AQS	40
3.3.1.3.15.1 Corrections to Data Uploaded to AQS	45
3.3.1.3.16	Records Retention and Archival, and Data Backup	45
3.3.1.3.17	Safety	45
3.3.2 Standard Operating Procedures	45
3.4 References	47
4.0: COLLECTION AND ANALYSIS METHODS	48
4.1	Method Detection Limits	48
4.1.1	Frequency of Method Detection Limit Determination	51
4.1.2	MDL Measurement Quality Objectives	51
4.1.3	Determining MDLs	52
4.1.3.1	MDLs via 40 CFR Part 136 Appendix B - Method Update Rule	53
4.1.3.2	MDLs via DQ FA C Single Laboratory Procedure v 2.4	59
4.1.4	References	61
4.2	VOCs - Overview of EPA Compendium Method TO-15	62
4.2.1	General Description of Sampling and Analytical Methods	62
4.2.1.1	Sampling Pathway	65
4.2.1.2	Particulate Filtration	65
4.2.2	Precision - Sample Collection and Laboratory Processing	65
iv

-------
4.2.2.1	Sample Collection and Analysis Precision	66
4.2.2.2	Laboratory Analytical Precision	67
4.2.3 Sample Collection Procedures	68
4.2.3.1	Sampling Equipment Specification	68
4.2.3.2	Sample Collection, Setup, and Retrieval	68
4.2.3.2.1	Sample Setup	68
4.2.3.2.2	Subambient Sample Collection	69
4.2.3.2.3	Superambient (Positive) Pressure Sampling	69
4.2.3.2.4	Sample Retrieval	70
4.2.3.3	Sampling Schedule and Duration	70
4.2.3.4	Sampling Train Configuration and Presample Purge	70
4.2.3.5	Sampling Unit Non-Biasing Certification	70
71
72
72
73
73
4.2.3.5.1	Zero Check	
4.2.3.5.2	Known Standard Challenge	
4.2.4	Canister Hygiene	
4.2.4.1	Qualification of Canisters	
4.2.4.1.1 Canister Bias	
4.2.4.1.1.1	Canister Integrity and Zero Air Check	73
4.2.4.1.1.2	Known Standard Gas Check	74
4.2.4.2	Canister Cleaning	75
4.2.4.2.1	Heated Canister Cleaning	75
4.2.4.2.2	Cycles of Evacuation and Pressurization	76
4.2.4.2.3	Gas Source for Canister Cleaning Pressurization	76
4.2.4.2.4	Verification of Canister Cleanliness	77
4.2.4.3	Canister Maintenance and Preventive Maintenance	78
4.2.4.3.1	Collection of Whole Air Samples into Canisters	78
4.2.4.3.2	Overtightening of Valves	78
4.2.4.3.3	General Canister Handling	78
4.2.5	Method Detection Limits	79
4.2.6	Canister Receipt	79
4.2.7	Dilution of Canisters	80
4.2.8	GC/MS Tuning, Calibration, and Analysis	80
4.2.8.1	Interferences	80
4.2.8.2	Specifications for the Preconcentrator and GC/MS	81
4.2.8.3	Standards and Reagents	82
4.2.8.3.1	Calibration Standards	82
4.2.8.3.2	Secondary Source Calibration Standards	82
4.2.8.3.3	Internal Standards	82
4.2.8.3.4	Diluent Gases	83
4.2.8.3.5	MS Tuning Standard - BFB	83
4.2.8.3.6	Reagent Water for Humidification of Gases	83
4.2.8.4	Preparation of Calibration Standards and Quality Control
Samples	84
4.2.8.4.1	Calibration Standards	84
4.2.8.4.2	Second Source Calibration Verification Sample	85
4.2.8.4.3	Method Blank	85
v

-------
4.2.8.4.4 Laboratory Control Sample	85
4.2.8.5 Analysis via GC/MS	86
4.2.8.5.1	Tuning of the MS	86
4.2.8.5.2	Leak Check and Calibration of the GC/MS	86
4.2.8.5.2.1	Leak Check	86
4.2.8.5.2.2	Initial Calibration of the GC/MS	87
4.2.8.5.2.3	Secondary Source Calibration
Verification	88
4.2.8.5.2.4	Continuing Calibration Verification	89
4.2.8.5.2.5	Analysis of Laboratory QC Samples
and Field Samples	89
4.2.8.5.3	Compound Identification	89
4.2.8.5.4	Internal Standards Response	91
4.2.9	Data Review and Concentration Calculations	92
4.2.10	Summary of Quality Control Parameters	93
4.2.11	References	95
4.3 Carbonyl Compounds via EPA Compendium Method TO-1 la	96
4.3.1	General Description of Sampling Method and Analytical Method	96
4.3.2	Minimizing Bias	96
4.3.3	Carbonyls Precision	97
4.3.3.1	Sampling Precision	97
4.3.3.1.1	Collocated Sample Collection	97
4.3.3.1.2	Duplicate Sample Collection	98
4.3.3.2	Laboratory Precision	99
4.3.4	Managing Ozone	99
4.3.4.1	Copper Tubing Denuder/Scrubber	99
4.3.4.2	Sorbent Cartridge Scrubbers	100
4.3.4.3	Other Ozone Scrubbers	101
4.3.4.3.1	Cellulose Filter Ozone Scrubbers	101
4.3.4.3.2	Modified Dasibi™ Ozone Scrubber	101
4.3.5	Collection Media	101
4.3.5.1	Lot Evaluation and Acceptance Criteria	 102
4.3.5.2	Cartridge Handling and Storage	 102
4.3.5.3	Damaged Cartridges	103
4.3.5.4	Cartridge Shelf Life	103
4.3.6	Method Detection Limits	103
4.3.7	Carbonyls Sample Collection Equipment, Certification, and
Maintenance	 104
4.3.7.1	Sampling Equipment	 104
4.3.7.1.1	Sampling Unit Zero Check (Positive Bias Check)	 104
4.3.7.1.2	Carbonyls Sampling Unit Flow Calibration	105
4.3.7.1.3	Moisture Management	 107
4.3.7.2	Sampling Train Configuration andPresample Purge	 108
4.3.7.3	Carbonyl Sampling Inlet Maintenance	 108
4.3.8	Sample Collection Procedures and Field Quality Control Samples	108
4.3.8.1 Sample Collection Procedures	 108
vi

-------
4.3.8.1.1	Sample Setup	109
4.3.8.1.2	Sample Retrieval	109
4.3.8.1.3	Sampling Schedule and Duration	110
4.3.8.2 Field Quality Control Samples	110
4.3.8.2.1	Field Blanks	110
4.3.8.2.2	Trip Blanks	Ill
4.3.8.2.3	Collocated Samples	Ill
4.3.8.2.4	Duplicate Samples	112
4.3.8.2.5	Field Matrix Spikes	112
4.3.8.2.6	Breakthrough Samples	112
4.3.9	Carbonyls Extraction and Analysis	113
4.3.9.1	Analytical Interferences and Contamination	113
4.3.9.1.1	Analytical Interferences	113
4.3.9.1.2	Lahware Cleaning	113
4.3.9.1.3	Minimizing Sources of Contamination	113
4.3.9.2	Reagents and Standard Materials	 114
4.3.9.2.1	Solvents	 114
4.3.9.2.2	Calibration Stock Materials	 114
4.3.9.2.3	Secondary Source Calibration Verification Stock
Materials	 114
4.3.9.2.4	Holding Time and Storage Requirements	 114
4.3.9.3	Cartridge Holding Time and Storage Requirements	 114
4.3.9.4	Cartridge Extraction	 1 15
4.3.9.4.1	Laboratory Quality Control Samples	115
4.3.9.4.2	Cartridge Extraction Procedures	 1 16
4.3.9.5	Analysis by HPLC	 1 16
4.3.9.5.1	Instrumentation Specifications	 1 16
4.3.9.5.2	Initial Calibration	 1 17
4.3.9.5.3	Secondary Source Calibration Verification
Standard	 1 18
4.3.9.5.4	Continuing Calibration Verification	 1 18
4.3.9.5.5	Replicate Analysis	 1 18
4.3.9.5.6	Compound Identification	 1 18
4.3.9.5.7	Data Review and Concentration Calculations	119
4.3.10	Summary of Quality Control Parameters	 121
4.3.11	References	 123
4.4 PMio Metals Sample Collection and Analysis	 124
4.4.1	Summary of Method	 124
4.4.2	Advantages and Disadvantages of High Volume and Low Volume
Sample Collection	125
4.4.2.1	Low Volume Sampling	125
4.4.2.2	High Volume Sampling	125
4.4.3	Minimizing Contamination, Filter Handling, and Filter Inspection	 126
4.4.3.1	Minimizing Contamination	 126
4.4.3.2	Filter Handling	 126
4.4.3.3	Filter Inspection	 127
vii

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4.4.4	Precision - Sample Collection and Laboratory Processing	127
4.4.4.1	Sample Collection Precision	127
4.4.4.2	Laboratory Precision	 127
4.4.4.2.1	Low Volume Teflon® Filter Laboratory Precision	 127
4.4.4.2.2	High Volume QFF Laboratory Precision	 127
4.4.5	Field Blanks	 128
4.4.6	Lab ware Preparation for Digestion and Analysis	 128
4.4.7	Reagents for Metals Digestion and Analysis	129
4.4.8	Method Detection Limits	129
4.4.8.1	Teflon® Filter MDL	129
4.4.8.2	QFF MDL	129
4.4.9	Low Volume Sample Collection and Digestion	130
4.4.9.1	Air Sampling Instruments	130
4.4.9.2	Flow Calibration	130
4.4.9.3	Filter Media	131
4.4.9.3.1 Lot Background Determination	131
4.4.9.4	Filter Sampling, Retrieval, Storage, and Shipment	131
4.4.9.4.1 Sampling Schedule and Duration	131
4.4.9.5	Teflon® Filter Digestion	131
4.4.9.5.1	Laboratory Digestion QC Samples	131
4.4.9.5.2	Digestion Procedure	132
4.4.9.5.2.1	Hot Block Digestion	132
4.4.9.5.2.2	Microwave Digestion	133
4.4.9.5.2.3	AcidSonication	134
4.4.10	High Volume Sample Collection and Digestion	135
4.4.10.1	A ir Sampling Instruments	135
4.4.10.2	Flow Calibration	135
4.4.10.3	Filter Media	135
4.4.10.3.1 Lot BackgroundDetermination	135
4.4.10.4	Filter Sampling, Retrieval, Storage, and Shipment	136
4.4.10.4.1 Sampling Schedule and Duration	137
4.4.10.5	QFF Digestion	137
4.4.10.5.1	Laboratory Digestion QC Samples	137
4.4.10.5.2	Digestion Procedure	138
4.4.10.5.2.1	Hot Block Digestion	139
4.4.10.5.2.2	High Volume QFF Microwave
Digestion	139
4.4.10.5.2.3	High Volume QFF Acid Sonication	139
4.4.11	PMio Metals Analysis by ICP/MS - EPA 10-3.5	139
4.4.11.1	ICP/MS Instrumentation	139
4.4.11.2	ICP/MS Interferences	139
4.4.11.3	Preparation of Calibration Standards for ICP/MS Analysis	 140
4.4.11.3.1	Primary Calibration Standards	 140
4.4.11.3.2	Secondary Source Calibration Verification
Standard	 140
4.4.11.4	Internal Standards	141
viii

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4.4.11.5	Tuning Solutions	 141
4.4.11.6	ICP/MS Warm Up, MS Tuning, and Setup	 141
4.4.11.7	ICP/MS Calibration and Analytical Sequence Batch	 142
4.4.11.7.1	Initial Calibration	 142
4.4.11.7.2	Initial Calibration Verification	143
4.4.11.7.3	Initial Calibration Blank	143
4.4.11.7.4	Interference Check Standard	143
4.4.11.7.5	Continuing Calibration Verification	143
4.4.11.7.6	Continuing Calibration Blank	 144
4.4.11.7.7	Laboratory Digestion Batch Quality Control
Samples	 144
4.4.11.7.H Serial Dilution	 144
4.4.11.7.9 Replicate Analysis	 144
4.4.11.8	ICP/MS Data Review and Concentration Calculations	 144
4.4.11.8.1	Concentration Calculations for Low Volume
Sampling	145
4.4.11.8.2	Reporting of Concentrations for High Volume
Sampling	145
4.4.12	Summary of Method Quality Control Requirements	 146
4.4.13	References	149
4.5 Collection and Analysis of PAHs via EPA Compendium Method TO-13 A.	150
4.5.1	Summary of Method	150
4.5.2	Sample Collection Equipment	150
4.5.2.1	Sampler Flow Calibration and Verification	151
4.5.2.2	Sampling Unit Maintenance	151
4.5.3	Sampling Media and Their Preparation	152
4.5.3.1	Glassware Cleaning	153
4.5.3.2	Cartridge Preparation	153
4.5.3.3	Field Surrogate Addition	153
4.5.4	PAH Sampling	154
4.5.4. la Sampling Schedule and Duration	154
4.5.4.1b Retrieval, Storage, and Transport of QFFs and Cartridges	154
4.5.4.2	Field Blanks	155
4.5.4.3	Collocated Sampling	155
4.5.5	PAH Extraction and Analysis	156
4.5.5.1	Reagents and Standard Materials	156
4.5.5.1.1	Solvents	156
4.5.5.1.2	Calibration Stock Materials	156
4.5.5.1.2.1 Secondary Source Calibration
Verification Stock Material	156
4.5.5.1.3	Internal Standards	156
4.5.5.1.4	Surrogate Compounds	156
4.5.5.1.4.1	Field Surrogate Compounds	157
4.5.5.1.4.2	Extraction Surrogate Compounds	157
4.5.5.2	Hold Times and Storage Requirements	157
4.5.5.3	Extraction, Concentration, and Cleanup	157
IX

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4.5.5.3.1	Soxhlet Extraction	157
4.5.5.3.2	,4ccelerated Solvent Extraction	157
4.5.5.3.3	Extract Concentration and Cleanup	158
4.5.5.3.3.1	Extract Concentration	158
4.5.5.3.3.1.1	Concentration via Kuderna-Danish	158
4.5.5.3.3.1.2	Concentration via Nitrogen Blowdown	159
4.5.5.3.3.2	Extract Cleanup	159
4.5.5.4	PAH Method Detection Limits	159
4.5.5.5	PAH Analysis via GC/MS	 160
4.5.5.5.1	GC/MS Instrumentation	 160
4.5.5.5.2	Tuning of the MS	 160
4.5.5.5.3	Calibration of the GC/MS	 160
4.5.5.5.4	Secondary Source Calibration Verification	 162
4.5.5.5.5	Continuing Calibration Verification	 162
4.5.5.5.6	Analysis of QC Samples and Field Samples	 162
4.5.5.5.7	Compound Identification	 162
4.5.5.5.8	Internal Standards Response	163
4.5.5.5.9	Surrogate Evaluation	163
4.5.5.5.10	Data Review and Concentration Calculations	163
4.5.6	Summary of Quality Control Parameters	 164
4.5.7	References	 166
5.0: METEOROLOGICAL MEASUREMENTS	 167
6.0: DATA HANDLING	 168
6.1	Data Collection	 168
6.2	Data Backup	 168
6.3	Recording of Data	169
6.3.1	Paper Records	169
6.3.2	Electronic Data Capture	169
6.3.3	Error Correction	169
6.3.3.1 Manual Integration of Chromatographic Peaks	169
6.4	Numerical Calculations	 170
6.4.1	Rounding	 170
6.4.2	Calculations Using Significant Digits	 170
6.4.2.1	Addition and Subtraction	 170
6.4.2.2	Multiplication and Division	 171
6.4.2.3	Standard Deviation	 171
6.4.2.4	Logarithms	 171
6.5	In-house Control Limits	171
6.5.1	Warning Limits	 172
6.5.2	Control Limits	 172
6.6	Negative Values	 172
6.6.1	Negative Concentrations	 172
6.6.2	Negative Physical Measurements	 172
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7.0: DATA VALIDATION TABLES	173
7.1	VOCs via EPA Compendium Method TO-15	 174
7.2	Carbonyls via EPA Compendium Method TO-1 1A	 181
7.3	Metals via EPA Compendium Method 10 3.1 and 10 3.5	 187
7.4	PAHs via EPA Compendium Method TO-13 A.	196
LIST OF FIGURES
Figure 3.1-1. Example Corrective Action Report	26
Figure 4.1-1. Graphical Representation of the MDL and Relationship to a Series of Blank
Measurements in the Absence of Background Contamination	48
Figure 4.1-2. Graphical Representation of the MDL and Relationship to a Series of
Measurements at the MDL Value	49
Figure 4.2-1. Collocated and Duplicate VOC Canister Sample Collection	67
Figure 4.2-2. Qualitative Identification of GC/MS Target Analytes	90
Figure 4.2-3. Determination of Chromatographic Peak Signal-to-Noise Ratio	91
Figure 4.4-1. Portioning of QFF Strips for Digestion	 138
LIST OF TABLES
Table 1.2-1. Analytes of Principle Interest for the NATTS Program	3
Table 2.1-1. Assessments of Precision through Field and Laboratory Activities	 13
Table 2.4-1. Sampling Unit Inlet Vertical Spacing Requirements	 18
Table 2.4-2. Sampling Unit Inlet Required Minimum Distances from Roadways	19
Table 3.3-1. Calibration and Calibration Check Frequency Requirements for Standards
and Critical Instruments	28
Table 3.3-2. AQS Qualifier Codes Appropriate for NATTS Data Qualification	42
Table 3.3-3. Required AQS Quality Assurance Qualifier Flags for Various
Concentrations Compared to an Agency's MDL and SQL	43
Table 4.1-1. Concentrations of the NATTS Core Analytes Corresponding to a 10"6
Cancer Risk, a Noncancer Risk at a HQ of 0.1, and to the MDL MQO	52
Table 4.1-2. One-sided Student's T Values at 99% Confidence Interval	55
Table 4.1-3. K-values for n Replicates	60
Table 4.2-1. VOC Target Compounds and Associated Chemical Abstract Service (CAS)
Number via Method TO-15	64
Table 4.2-2. Required BFB Key Ions and Ion Abundance Criteria	86
Table 4.2-3. Summary of Quality Control Parameters for NATTS VOCs Analysis	93
Table 4.3-1. Carbonyl Target Compounds and Associated Chemical Abstract Service
(CAS) Number via Method TO-1 1A	96
Table 4.3-2. Maximum Background per Lot of DNPH Cartridge	 102
Table 4.3-3. Carbonyls Field Blank Acceptance Criteria	 1 1 1
Table 4.3-4. Summary of Quality Control Parameters for NATTS Carbonyls Analysis	 121
Table 4.4-1. NATTS Program Metals Elements and Associated CAS Numbers	125
XI

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Table 4.4-2.	Example ICP/MS Analysis Sequence	 142
Table 4.4-3.	Method Criteria Parameters for NATTS Metals Analysis	 147
Table 4.5-1.	PAHs and Associated Chemical Abstract Numbers (CAS)	151
Table 4.5-2.	DFTPP Key Ions and Abundance Criteria	 160
Table 4.5-3.	Summary of Quality Control Parameters for NATTS PAH Analysis	164
APPENDICES
Appendix A Draft Report on Development of Data Quality Objectives (DQOs) For The
National Ambient Air Toxics Trends Monitoring Network	202
Appendix B NATTS AQS Reporting Guidance for Quality Assurance Samples	235
Appendix C EPA Rounding Guidance Provided By EPA Region IV	243
xii

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ACRONYMS AND ABBREV IATIONS
ACN
acetonitrile
ADQ
audit of data quality
AIRS
Aerometric Information Retrieval System
amu
atomic mass unit
ANP
annual network plan
ANSI
American National Standards Institute
AQS
Air Quality System
ASE
accelerated solvent extraction
ASQ
American Society for Quality
BFB
bromofluorobenzene
CAA
Clean Air Act
CAL
calibration
CAR
corrective action report
CARB
California Air Resources Board
CAS
Chemical Abstracts Service
CCB
continuing calibration blank
CCV
continuing calibration verification
CDCF
canister dilution correction factor
CDS
chromatography data system
CFR
Code of Federal Regulations
COA
certificate of analysis
COC
chain of custody
Cr6+
hexavalent chromium
CV
coefficient of variation
DART
Data Analysis and Reporting Tool
DB
dilution blank
DFTPP
decafl uorotri phenyl phosphi ne
DL
detection limit
DNPH
2,4-dinitrophenylhydrazine
DOC
demonstration of capability
DQI
data quality indicator
DQ FAC
Federal Advisory Committee on Detection and Quantitation Approaches and Uses in

Clean Water Act Programs
DQO
data quality objective
ECTD
extended cold trap dehydration
EPA
United States Environmental Protection Agency
ESMB
extraction solvent method blank
eV
electron volt
Xlll

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FAA
FAEM
FID
FRM
g
GC
GC/MS
GFAA
GPRA
HAP
HCF
Hg
HPLC
HQ
IB
IC
ICAL
ICB
ICP/AES
ICP/MS
ICS
ICV
ID
D3CF
in.
IS
K-D
KI
L
LCS
LCSD
LFB
LIMS
LPM
M
m
3
m
m/z
MB
MDL
flame atomic absorption
flexible approaches to environmental measurement
flame ionization detector
federal reference method
gram(s)
gas chromatograph
gas chromatograph/mass spectrometry
graphite furnace atomic absorption spectrometry
Government Performance Results Act
hazardous air pollutant
hydrocarb on-free
mercury
high performance liquid chromatograph
hazard quotient
instrument blank
ion chromatograph
initial calibration
initial calibration blank
inductively coupled plasma/atomic emission spectroscopy
inductively coupled plasma/mass spectrometer
interference check standard
initial calibration verification
identifier
instrument dilution correction factor
inch(es)
internal standard
Kuderna-Danish
potassium iodide
liter(s)
laboratory control sample
laboratory control sample duplicate
laboratory fortified blank
laboratory information management system
liter(s) per minute
molar
meter(s)
cubic meter(s)
mass to charge
method blank
method detection limit
xiv

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MFC	mass flow controller
mg	milligram(s)
min	minute(s)
mL	milliliter(s)
mm	millimeter(s)
mM	millimolar
MPT	microscale purge and trap
MQO	measurement quality objective
MS	mass spectrometer or matrix spike
MUR	method update rule
jug	microgram(s)
|iL	microliter(s)
jim	micrometer(s)
n	number
NAAQS	national ambient air quality standards
NATTS	National Air Toxics Trends Station
ng	nanograms(s)
nni	nanometer(s)
O;	oxygen molecule
O3	ozone molecule
OAQPS	Office of Air Quality Planning and Standards (EPA)
OH"	hydroxide ion
PAH	poly cyclic aromatic hydrocarbon
PM	particulate matter
PM2.5	particulate matter with aerodynamic diameter < 2.5 microns
PM10	particulate matter with aerodynamic diameter < 10 microns
POC	parameter occurrence code
ppb	part(s) per billion
ppbv	part(s) per billion by volume
ppm	part(s) per million
ppmv	part(s) per million by volume
psi	pound(s) per square inch
psia	pound(s) per square inch absolute
psig	pound(s) per square inch gauge
PT	proficiency test
PTFE	polytetrafluoroethylene
PUF	polyurethane foam
QA	quality assurance
QAPP	quality assurance project plan
QC	quality control
QFF	quartz fiber filter
QL	quantitation limit
xv

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QMP
quality management plan
QSA
quality systems audit
RB
reagent blank
RBS
reagent blank spike
RH
relative humidity
RPD
relative percent difference
RRF
relative response factor
RRT
relative retention time
RSD
relative standard deviation
RT
retention time
SB
solvent blank
SIM
selective ion monitoring
SLT
state, local, or tribal agency
SMB
solvent method blank
SOP
standard operating procedure
SQL
sample quantitation limit
SSCV
second source calibration verification
STP
temperature and pressure
SVOC
semi-volatile organic compound
TAD
technical assistance document
TOF
time of flight
TSA
technical systems audit
UP
through the probe
UATS
urban air toxics strategy
UV
ultraviolet
voc
volatile organic compound
v/v
volume per volume
xvi

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1.0: INTRODUCTION
1.1	Background
Hazardous air pollutants (HAPs), or air toxics, are regulated under the Clean Air Act (CAA) as
amended in 1990 and include a list of 189 toxic pollutants associated with adverse health effects.
Such HAPs are emitted by numerous stationary and mobile sources. The U.S. Environmental
Protection Agency (EPA) Government Performance Results Act (GPRA) commitments specify a
goal of reducing air toxics emissions by 75% from 1993 levels to significantly reduce the
potential for human health risk.
The National Air Toxics Trends Station (NATTS) Program was developed to fulfill the need for
long-term ambient air toxics monitoring data required to assess attainment of GPRA
commitments. The NATTS network was designed to generate data of a known, consistent, and
standardized quality sufficient to enable the identification of spatial, and, more importantly,
long-term temporal trends in the concentrations of air toxics. This technical assistance document
(TAD) presents best practices and sets forth requirements for the collection and reporting of
NATTS network air toxics data and is intended as an aid to the agencies responsible for
implementing the NATTS Program. EPA recognizes that the partnership between the EPA and
state and local air monitoring agencies is intrinsic to attaining the goal of the NATTS Program to
generate high quality data needed to accomplish the end goal of trends detection. This TAD
includes information on the implementation and maintenance of the necessary quality system, on
the collection and analysis of air samples, and on the reporting of results to EPA's Air Quality
System (AQS) database.
1.2	Target Analytes: Analytes of Critical Concern/Risk Drivers
While it is impractical to measure all HAPs at all monitoring sites, HAPs have been assigned by
analyte class to a tiered system according to their relative toxicity. The 1990 CAA amendments
required EP A to develop a subset of the 189 toxic pollutants identified in Section 1 12 that have
the greatest impact on the public and the environment in urban areas. The resulting subset of air
toxics consisted of 33 HAPs which are identified in the Integrated Urban Air Toxics Strategy
(UATS)1, commonly referred to as the Urban HAP List. This subset of 33 HAPs covers a
variety of inhalation exposure periods (acute/chronic), exposure pathways (inhalation, dermal,
ingestion), and associated adverse health effects (cancer/non-cancer). However, the NATTS
Program is primarily concerned with traditional inhalation pathway exposures of more
ubiquitous HAPs, and is focused on measuring HAPs which have available and cost-effective
measurement methods. As such, 18 of the 33 U ATS H APs were selected as core H APs for the
NATTS Program. HAPs omitted from the UATS list include those for which analysis methods
are less cost-efficient or less reliable and those HAPs deemed to have a lesser impact on
inhalation exposure but a greater impact on the welfare of watersheds and water bodies through
airborne deposition. Also omitted from the NATTS program were those HAPs which are
categorized as persistent bio-accumulative compounds (PBTs) such as pesticides, mercury,
polychlorinated bi phenyls (PCBs), and dioxins.2
1

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Hexavalent chromium was removed from the list of NATTS core HAPs due to it being a local
source-driven pollutant (and not ubiquitous) and due to the preponderance of non-detect results
on a national scale which provided little useful data. Sites are not required to, but may elect to,
collect and report hexavalent chromium data. With the removal of hexavalent chromium, the 17
remaining UATS HAPs included poly cyclic organic matter (POM), which was added later (in
2007) as speciated poly cyclic aromatic hydrocarbons (PAHs). The replacement of POM with
naphthalene and benzo(a)pyrene brought the list of required NATTS core HAPs to 18.
Sixty of the 189 HAPs have been selected as "Analytes of Principle Interest" for the NATTS
Program; these 60 belong to one of four different analyte classes according to the method by
which they are typically measured, i.e. volatile organic compounds (VOCs), carbonyls, metals,
and (PAHs). These 60 "Analytes of Principle Interest" include 17 (18 when replacing POM with
naphthalene and benzo(a)pyrene) of the UATS HAPs (mentioned previously) and are listed in
Table 1.2-1 along with their analyte classes and concentrations corresponding to a 10"6 cancer
risk and a noncancer risk at a hazard quotient (HQ) of 0.1. Of these 60 HAPs, 18 have been
identified as major risk drivers based on a relative ranking performed by EPA and have been
designated NATTS Core, or Tier I, analytes; these compounds must be measured at all NATTS
sites. The remaining 42 Tier II HAPs are highly desired and should be measured and reported.
EPA recognizes that additional resources are required to provide quality-assured data for the
additional Tier II analytes; however, given that these methods are already conducted to measure
the Tier I Core analytes, data for many of Tier II analytes can be reported with modest additional
resource input.
2

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Table 1.2-1. Analytes of Principle Interest for the NATTS Program
HAP
Analytc Class and
Collection and
Analysis Method
Tier
10 6 Cancer Risk
Concentration
(fig/m3)
Noncancer Risk
|Hazard Quotient = 0.1]
Concentration (jig/m3)
acrolein

1 (UATS)
-
0.002
tctrachlorocthylcne

1 (UATS)
3.8 a
4 a
benzene

1 (UATS)
0.13
3
carbon tetrachloride

1 (UATS)
0.17
19
chloroform

1 (UATS)
-
9.8
trichlorocthvlcne

1 (UATS)
0.21a
0.2 a
1,3-butadiene

1 (UATS)
0.03
0.2
vinyl chloride

1 (UATS)
0.11
10
acetonitrile

II
-
6
acrylonitrile

11 (UATS)
0.015
2
bromoform

II
0.91
-
carbon disulfide

II
-
70
chloroben/cne

II
100
-
chloroprene

II
-
0.7
p-dichlorobenzenc

II
0.091
80
cis-1,3 -dichloropropcne
VOC by
11 (UATS)
0.3
2
trans-1,3 -dichloropropene
TO-15
11 (UATS)
0.3
2
ethyl aery late

II
0.071
-
ethyl benzene

II
-
100
hexachloro-1,3 -butadiene

II
0.0022
9
methyl ethyl ketone

II
-
500
methyl isobutyl ketone

II
-
300
methyl methacrylate

II
-
70
methyl tert-butyl ether

II
3.8
300
methylene chloride

11 (UATS)
2.1
100
styrene

II
-
100
1,1,2,2-tetrachloroethane

11 (UATS)
0.017
-
toluene

II
-
40
1.1.2-trichlorocthane

II
0.063
40
1,2,4-trichlorobcn/cne

II
-
20
m&p-xylenes

II
-
10
o-xylene

II
-
10
formaldehyde
carbonyl by
1 (UATS)
0.08 a
0.08 a
acctaldchyde
TO-11A
1 (UATS)
0.45
0.9
3

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Table 1.2-1. Analytes of Principle Interest for the NATTS Program (Continued)
HAP
Analyte Class
and Collection
and Analysis
Method
Tier
10 6 Cancer Risk
Concentration
(fig/m3)
Noncancer Risk
|Hazard Quotient =
0.11 Concentration
(fig/m3)
nickel

1 (UATS)
0.0021
0.009
arsenic

1 (UATS)
0.00023
0.003
cadmium

1 (UATS)
0.00056
0.002
manganese

1 (UATS)
-
0.005
beryllium
metal by IO-3.1
1 (UATS)
0.00042
0.002
lead
and 10-3.5
1 (UATS)
-
0.015
antimony

II
-
0.02
chromium

II (UATS)
0.00008
0.01
cobalt

II
-
0.01
selenium

II
-
2
naphthalene

1 (UATS b)
0.029
0.029
benzo(a)pyrene

1 (UATS b)
0.00091
0.3
acenaphthene

II (UATS b)
-
0.3
acenaphthylene

II (UATS b)
-
0.3
anthracene

II (UATS b)
-
0.3
benz(a)anthracene

II (UATS b)
0.0091
0.3
bcn/o(b)fluoranthcnc

II (UATS b)
0.0091
0.3
benzo(e)pyrene
PAH by T0-13A
II (UATS b)
-
0.3
ben/o(k)fluoranthcnc
II (UATS b)
0.0091
0.3
chrysene

II (UATS b)
0.091
0.3
dibenz(a,h)anthracene

II (UATS b)
0.0091
0.3
fluoranthenc

II (UATS b)
-
0.3
fluorene

II (UATS b)
-
0.3
indeno( 1,2,3 -cd)pyrene

II (UATS b)
0.0091
0.3
phenanthrene

II (UATS b)
-
0.3
pyrene

II (UATS b)
-
0.3
a These values are per the NATTS Workplan Template, March 2015 3
b PAHs compounds included in the UATS list as poly cyclic organic matter (POM)
1.3	Importance of Adherence to Guidelines
The overall data quality objective (DQO) of the NATTS Program is to detect trends in HAP
concentrations covering rolling three-year periods with uniform certainty across the 27-site
network with a coefficient of variation (CV) not to exceed 15 percent.4 Stated another way, the
DQO is to be able to detect a 15% difference (trend) in non-overlapping three-year periods
within acceptable levels of decision error. This is accomplished by generating representative
concentration data for the various HAPs with appropriate sensitivity within acceptable limits of
imprecision and bias. For overall trends to be discernable, concentration data must be generated
with methods which meet minimum performance criteria. The DQO, data quality indicators
4

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(DQIs), and their associated measurement quality objectives (MQOs), or acceptance criteria, are
presented in detail in Sections 2.1 and 3.2. EPA recognizes there is a disconnect in the NATTS
bias MQO, which may not exceed 25%, and bias criteria in individual methods, notably TO-13A
and TO-15, which exceed 25%. These methods are currently undergoing refinement by EPA's
Office of Research and Development (ORD). For information regarding the determination of the
DQO, DQIs, and MQOs, please refer to the following background reports and 2013 DQO
reassessment report:
•	Air Toxics Monitoring Concept Paper, Revised Draft February 29, 2000:
https://www3.epa.. \ tmamti 1/files/ambient/airtox/cncp-sab.pdf
•	Draft Report on Development of Data Quality Objectives (DQOs) for the National
Ambient Air Toxics Trends Monitoring Network, September 27, 2002
(Appendix A of this TAD)
•	Analysis, Development, and Update of the National Air Toxics Trends Stations
(NATTS) Network Program-Level Data Quality Objective (DQO) and Associated
Method Quality Objectives (MQOs), Final Report, June 13, 2013
https://www3.epa. gov/ttnamti l/fi1es/ambient/airtox/nattsdqo20130613.pdf
Together, these documents provide a roadmap for determining and verifying the NATTS DQO
and supporting MQOs.
A review of data during Phase I of the NATTS pilot project identified that variations in
sampling, analysis, data reporting, and quality assurance resulted in a large amount of data
inconsistency.2 This TAD was developed and revised to increase consistency across the network
and facilitate attainment of the NATTS DQO. Failure to attain the prescribed NATTS MQOs
limits the ability to detect trends. Trends must be assessed so that EPA, as outlined in the EPA's
Integrated Urban Air Strategy, may verify that the cumulative health risks associated with air
toxics are in fact decreasing.5
1.4	Overview of TAD Sections
This document is organized so as to present guidance and requirements in the likely order in
which they are needed when establishing a network site or network sites and laboratory, i.e.,
planning, implementation, and data verification. Background information, the NATTS DQO,
and the framework and requirements for quality systems are addressed first, followed by
collection and analysis of air samples, with data handling and validation tables completing the
document. Each section is briefly described below.
1.	Background - Brief overview of the history of the NATTS Program, NATTS
analytes, and critical changes from Revision 2
2.	Metrics Defining Data Quality for the NATTS Program - Importance of data
consistency, NATTS monitoring objectives, quality systems, and siting criteria
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3.	Quality Assurance and Quality Control - Quality Assurance Project Plan (QAPP)
development, QAPP elements including standard operating procedures (SOPs),
corrective action, equipment calibration, document control, training, chain of custody
(COC), traceability, labeling, control charting, software, records review, data
verification and validation, and air quality subsystem (AQS) reporting
4.	Collection and Analysis Methods - method detection limit (MDL) procedures, VOCs,
carbonyls, PMio metals, and PAHs
5.	Meteorology - Brief description of required meteorological measurements
6.	Data Handling - Procedures and policies for collection, manipulation, backup,
archival, and calculations
7.	Data Validation Tables - A series of tables detailing method specific critical criteria
1.5	Critical Changes and Updates from Revision 2 of the NATTS TAD
With this revision, the NATTS TAD has not only been reorganized and streamlined, but it has
been substantially updated compared to Revision 2. Specific changes include:
Specification of detailed requirements and recommendations for quality system
development and implementation
Specification of calibration requirements and recommendations for all instruments,
including support equipment
•	Recommendations for conducting and documenting of training
•	Revision to the MDL determination procedure to be inclusive of the contribution
from the collection media background
Clarification of precision for sample collection and analysis
•	Relaxation of certain VOCs sample collection requirements
•	Provision of updated guidance on collection and analysis of VOCs, carbonyls, PMio
metals, and PAHs
•	Exclusion of hexavalent chromium sampling and analysis methods
Clarification on data handling practices
•	Provision of data validation templates
Updating the guidance and requirements for the air sampling and analysis methods is the primary
goal of this TAD revision. The secondary goal is to provide a more user-friendly guidance
document with discrete sections organized in a manner so as to allow users to quickly locate the
desired information. Of note, data validation template tables have been provided as an appendix
in Section 7.
With the removal of hexavalent chromium as a NATTS core HAP in June 2013, guidance for
sample collection and analysis for this analyte are not provided within this TAD revision.
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1.6	Good Scientific Laboratory Practices
Good scientific practices, including instrument calibration and proper recording of observations,
measurements, and instrument conditions, are equally important in both the field and in the
laboratory. Such practices are necessary to generate data which are consistent, comparable,
standardized, traceable, and defensible. Appropriate aspects of good laboratory and field
practices are to be detailed in each agency's NATTS quality system. The need for, and examples
of such practices are given below and in Section 2.
1.6.1 Data Consistency and Traceability. To be able to verify that the NATTS network
generates data of quality sufficient to evaluate the main NATTS Program DQO, data collection
and generation activities must be traceable to calibrated instruments, certified standards, and to
activities conducted by individuals with the appropriate and documented training. Traceability
in this case refers to ensuring the existence of a documentation trail which allows reconstruction
of the activities performed to collect and analyze the sample and to the certified standards and
calibrated instrumentation employed to determine analyte concentrations. To specifically ensure
attainment of overall network bias requirements, each reported concentration must be traceable
to a measurement of known accuracy, be it from an analytical balance, volumetric flask, gas
chromatography/mass spectrometer (GC/MS), mass flow controller, critical orifice calibration
plate, etc. Maintaining this traceability from sample collection to final results reporting assures
that NATTS data are credible and defensible, and that the root cause of nonconformances may be
found and corrected which thereby enables continuous improvement in NATTS program
activities. Instrument calibration specifications and frequencies are provided in Section 3.
1.7	NATTS as the Model for Air Toxics Monitoring
Air toxics monitoring is an important, but often secondary, consideration for many air quality
agencies. One reason for such is that there are no national ambient air quality standards
(NAAQS) for air toxics for which regulatory compliance efforts would be required. Guidance
for conducting air toxics sample collection and analysis is not as widely available as for criteria
pollutants and is limited to performance-based compendium methods as compared to Federal
Reference Methods (FRMs). This TAD is intended to primarily provide guidance and delineate
requirements for NATTS sites and their associated laboratories; however, aspects of sampling,
analysis, and quality assurance could be applied by agencies conducting air toxics monitoring
outside of the NATTS network. This TAD incorporates feedback provided by the air toxics
community with vast and varied experience conducting air toxics measurements. Feedback and
input provided by the air toxics community were carefully reviewed and considered by a small
workgroup of EPA and state/local/tribal (SLT) stakeholders in reviewing and revising this TAD.
The NATTS network is a collaboration of SLT monitoring organizations with EPA. With an
extensive network of experienced site operators and laboratory staff, the NATTS network strives
to be the exemplar of air toxics monitoring.
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1.8	References
1.	Smith, R.L.; French, C.L.; Murphy, D.L.; Thompson, R. Selection of HAP s under Section
112(h) of the Clean Air Act: Technical Support Document, Integrated Urban Air Toxics
Strategy (UATS), July 28, 1999.
2.	National Monitoring Strategy Air Toxics Component, Final Draft. United States
Environmental Protection Agency, July 2004. Available at (accessed October 18, 2016):
https://www3.epa.gOY/ttnamtil/files/ambient/monitorstrat/atstrat804.pdf
3.	National Air Toxics Trends Station Work Plan Template. United States Environmental
Protection Agency, Revised: March 2015. Available at (accessed October 18, 2016):
https ww3.epa.gov/ttn/amtic/files/ambient/airtox/nattsworkplantemplate.pdf
4.	Quality Management Plan for the National Air Toxics Trends Stations. Quality Assurance
Guidance Document, EPA 454/R-02-006. September 2005. Available at (accessed October
18,2016): https://www3.epa.gov/ttriamtil/files/ambient/airtox/nattsqmp.pdf
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2.0: IMPORTANCE OF DATA CONSISTENCY
As the main goal of the NATTS Program is to detect long-term trends in ambient air toxics
concentrations across the continental United States, sample data collected at each site must be
comparable over time and from one site to the next. The ability to detect and evaluate trends on
a nationwide basis requires the standardized operation of the NATTS Program based upon four
key components:
-	Known and specific MQOs for the program;
Specified measurement (collection and analysis) methods performed in a standardized
and consistent manner across the network;
-	Known and specific acceptance criteria for various aspects of the specified
monitoring methods; and
Stability of monitoring sites including location and operation over the required period
of time.
In short, each site's concentration data must meet the MQOs and be generated with standardized
methods that are appropriately sensitive, show minimal bias, and are sufficiently precise.
Moreover, the collected samples taken together must be representative of the ambient conditions
at the site over the course of a year and the annual dataset must be adequately complete. If
program MQOs are not attained at each site, the network data will not be consistent across all
sites and the ability to detect concentration trends will be compromised. MQOs related to each
of the specific DQls are discussed in more detail in Section 2.1.
This TAD is written such that requirements are described as "must" and recommendations are
described as "should." It is expected that monitoring agencies will make good faith efforts to
comply with the requirements and adopt recommendations, where feasible.
2.1	Data Quality Objectives and Relationship to the Quality Assurance Project Plan
The DQO process ensures that the type, quantity, and quality of data used in decision making are
appropriate to evaluate the overall DQO of the NATTS Program. Discussion of the
determination of the NATTS DQO is addressed in the NATTS Quality Management Plan
(QMP)1 and is not reproduced here. Background information on the development of the NATTS
DQO process is detailed in the initial DQO report2 and a follow up assessment was completed in
20133 to verify that the DQO and supporting MQOs remained applicable and suitable to attain
network goals.
Each monitoring organization must develop a QAPP that describes the framework of the
resources, responsible individuals, and actions to be taken to attain the NATTS DQO. QAPP
development is described further in Section 3.3.
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There is a single main DQO for the NATTS Program, which is:
To be able to detect a 15% difference (trend) between two successive 3-year annual mean
concentrations (rolling averages) within acceptable levels of decision error.
This main DQO is directly related to demonstrating a reduction in health-based risk related to air
toxics inhalation exposure. To achieve this main DQO, the NATTS Program network was
designed to meet the following primary monitoring objectives, which are to:
•	Measure concentrations of the NATTS Tier I core analytes and Tier II analytes of
interest in ambient air at each NATTS site. These analytes are listed in Table 1.2-1.
•	Generate data of sufficiently high and known quality that are nationally consistent.
Such requires the implementation and maintenance of a robust and functional quality
system, the proper execution of the applicable sampling and analysis methods, and
that the specified methods provide sufficient sensitivity to obtain a limit of detection
at or lower than that at which adverse health effects have been determined.
•	Collect sufficient data to represent the annual average ambient concentrations of air
toxics at each NATTS site. Collection of one sample every six days results in 60 or
61 samples per year exclusive of additional quality control (QC) samples such as
blanks, collocated samples, duplicates, etc.
In addition to these primary monitoring objectives, the NATTS network was designed to address
the following secondary monitoring objectives, which are to:
•	Complement existing programs. The NATTS network is integrated with existing
programs such as criteria pollutant monitoring. Photochemical Assessment
Monitoring Stations (PAMS), National Core (NCore), etc., and to take advantage of
efficiencies of scale to the extent that methodologies and operations are compatible.
Establishment of NATTS sites at existing sites leverages the existing resources of
experienced operators and infrastructure to achieve program objectives.
•	Reflect community-oriented population exposure. Stationary monitors are sited to be
representative of average concentrations within a 0.5- to 4-kilometer area (i.e.,
neighborhood scale). These neighborhood-scale measurements are more reflective of
typical population exposure, can be incorporated in the estimation of long-term
population risk, and are the primary component of the NATTS Program. Note that
some NATTS sites may no longer truly represent neighborhood scale due to source or
infrastructure changes. While new near-field sources may impact the measured
concentrations, stability of the site location is necessary to detect trends which may
still be discernable even when sites are impacted by such sources.
•	Represent geographic variability. A truly national network must represent a variety
of conditions and environments that will allow characterization of different emissions
sources and meteorological conditions. The NATTS Program supports population
risk characterization and the determination of the relationships between emissions and
air quality under different circumstances, and allows for tracking of changes in
emissions.4 National assessments must reflect the differences among cities and
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between urban and rural areas for selected HAPs, so the network:
o Includes cities with high population risk (both major metropolitan areas and other
cities with high or potentially high anticipated air toxics concentrations);
o Distinguishes differences within and between geographic regions (to describe
characteristics of areas affected by high concentrations (e.g. urban areas) versus
low concentrations (e.g. rural areas);
o Reflects the variability among pollutant patterns across communities; and
o Includes background monitoring (i.e., sites without localized sources).
The above monitoring objectives are supported by the DQls as described in the following
subsections:
2.1.1	Representativeness. To adequately characterize the ambient air toxics
concentrations over the course of a year, sample collection must occur every six days per the
national sampling calendar for a 24-hour period beginning and ending at midnight local standard
time (without correction for daylight savings time, if applicable). This sample collection
duration and frequency provides a sufficient number of data points to ensure that the collected
data are representative of the annual average daily concentration at a given site. Collection
methods are designed to efficiently capture airborne HAPs over this time period in order to
measure concentrations representative of the ambient air during sample collection.
2.1.2	Completeness. Compari son of concentration data across sites and over time requires
that a minimum number of samples be collected over the course of each calendar year. The
MQO for completeness prescribes that > 85% of the annual air samples must be valid, equivalent
to 52 of the annual 61 expected samples (51 during years when there are only 60 collection
events).
A valid sample is one that was collected, analyzed, and reported to AQS without null flags. If a
collected sample is voided or invalidated for any reason, a make-up sample collection should be
attempted as soon as practical according to the make-up sampling policy below.
2.1.2.1 Make-up Sample Policy. Samples and sample results may be invalidated for a
number of reasons. In all cases, the concentration data are entered in AQS flagged with a null
code indicating the data are invalid. In order to increase the likelihood of attaining the
completeness MQO of > 85%, make-up samples should be collected when a sample or sample
result is invalidated.
A replacement sample should be collected as close to the original sampling date as possible, and
preferably before the next scheduled sampling date. When scheduling make-up sample
collection, consideration should be given to minimize bias introduced to the annual concentration
average due to differences in concentration from the originally scheduled sample date. Such
considerations include concentration differences due to sample collection on a particular day of
the week (weekday versus weekend) and potential seasonal effects. If it is not feasible to collect
the make-up sample prior to the next scheduled sampling date, the sample should be collected
within 30 days of the original sampling date. In all cases, the make-up sample should be
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collected within the calendar year averaging period that starts January 1 and ends December 3 1.
Note: For sampling units employing six-day timers, failure to reset the timer following a make-
up sample can result in mistakenly collecting samples on dates that do not follow the national
sampling calendar.
To summarize, make-up samples should be collected as close to the original sampling date as
possible, and should be collected according to the following, in order of most preferable to least
preferable:
1.	Before the next scheduled sampling date
2.	Within 30 days of the missed collection date
3.	Within the calendar year.
In order to be temporally representative of the annual concentration at a given site, the sample
dates must be as evenly distributed as possible to capture concentrations that fluctuate seasonally
or according to weather patterns. It is not acceptable to delay make-up sampling until the end of
the calendar year, as this may bias the data to be more seasonally than annually representative.
2.1.3 Precision. Reproducibility is a key component of ensuring concentration results at
one site are comparable to those at other sites and are comparable over time. For the NATTS
Program, precision of field and laboratory activities (inclusive of extraction and analysis) may be
assessed by collection of collocated and/or duplicate field samples; the precision of laboratory
handling and analysis may be estimated by the subdivision of a collected sample into preparation
duplicates which are separately taken through all laboratory procedures (digestion or extraction
and analysis) and includes instances in which target analytes may be added to a sub sample to
prepare matrix spike duplicates; and analytical precision is assessed by the replicate analysis of a
sample or sample extract/digestate. Note that the previous revision of this TAD required that
collocated and duplicate samples be analyzed in replicate. This has been relaxed to permit
replicate analysis on any sample chosen by the laboratory. A summary of possible precision
assessments is shown in Table 2.1-1. Precision sample collection and replicate analysis
requirements will be detailed in each site's annual NATTS workplan.
The network MQO is based on an evaluation of at least an entire year's data. In all cases a
coefficient of variance (CV) of < 15% must be met. For more information on how the CV is
calculated, see the 2011 -2012 NATTS Quality Assurance Annual Report.5 Note that this
precision MQO is different than the precision acceptance criteria for the individual collection
and analysis methods; imprecision of the latter may be permitted to be larger than 15%. Such
method-specific precision requirements apply to comparing two measurements and do not apply
to larger (N > 2) sample sets.
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Table 2.1-1. Possible Assessments of Precision through Field and Laboratory Activities
HAP Class
Collocation
*
Duplicate
Field
Samples *
Preparation
(Digestion/
Extraction)
Duplicate
Matrix
Spike
Duplicate
Analysis
Replicate
VOCs
yes
yes
no
no
yes
Carbonyls
yes
yes
no
no
yes
PMio metals -





high volume
collection
yes
no
yes
yes
yes
PMio metals -





low volume
yes
no
no
no
yes
collection





PAHs
yes
no
no
no
yes
*Note: Collection of collocated and duplicate field samples is highly desired, but not required, and
will be detailed in the site's annual workplan.
2.1.4 Bias. Bias is the difference of a measurement from a true or accepted value and can
be negative or positive. As much as possible, bias should be minimized as biased data may
result in incorrect conclusions and therefore incorrect decisions. Bias may originate in several
places within the sample collection and analysis steps. Sources of sample collection bias
include, but are not limited to, incorrectly calibrated flows or out-of-calibration sampling
instruments, elevated and unaccounted for background on collection media, poorly maintained
(dirty) sampling inlets and flow paths, and poor sample handling techniques resulting in
contamination or loss of analyte. Sources of sample analysis bias include, but are not limited to,
poor hygiene or technique in sample preparation, incorrectly calibrated or out of tolerance
equipment used for standard materials preparation and analysis, and infrequent or inappropriate
instrument maintenance leading to enhanced or degraded analyte responses.
2.1.4.1 Assessing Laboratory Bias - Proficiency Testing. Each laboratory analyzing
samples generated at NATTS sites must participate in the NATTS proficiency testing (PT)
program. PT samples for each of the four sample classes, VOCs, carbonyls, PMio metals, and
PAHs, are generated at a frequency determined by EP A Office of Air Quality Planning and
Standards (OAQPS), typically twice annually for each class. Participating laboratories are blind
to the spiked concentrations and analyze the PT samples via methods and procedures identical to
those employed for field-collected air samples.
PT target analytes, which include all Tier I analytes, among others, are identified in the following
tables in Section 4:
VOCs
Carbonyls
PMio Metals
PAHs
Table 4.2-1
Table 4.3-1
Table 4.4-1
Table 4.5-1
Each laboratory's PT results, on an analyte-by-analyte basis, must be within ± 25% of the
assigned target value, defined as the NATTS laboratory average, excluding outliers. In the event
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there is a problem with the NATTS laboratory average such as a contamination issue, the
assigned target value may be changed to the nominal concentration or referee laboratory average,
as applicable, and will be detailed in the PT results. Laboratories which fail to meet the bias
acceptance criterion on an analyte-by-analyte basis must identify the root cause of the bias for
the failed analyte, take corrective action, as appropriate, to eliminate the cause of the bias, and
must evaluate the potential for bias in reported field sample data going back to last acceptable PT
result. In the event of two consecutive failed PTs for a given analyte, laboratories must qualify
field collected sample results as estimated when reported to AQS. EPA recognizes that the
NATTS MQO bias criterion of ± 25% established through the DQO process is narrower than the
bias criteria for some of the analytical methods, namely TO-15 and TO-13 A. In order for the
main NATTS DQO to be achieved, the bias MQO criterion must be achieved.
2.1.4.2 Assessing Field Bias. The direction of the flow rate bias in carbonyl s, PMio metals,
and PAHs samplers is opposite that to the bias introduced in the reported concentrations. That is,
flow rates which are biased low result in overestimation of air concentrations whereas flow rates
which are biased high result in underestimation of air concentrations. As VOCs collection
methods involve collection of whole air into the canister, the flow rate accuracy is of less
importance and does not directly correlate to errors in measured concentrations. Rather, it is
important that the flow rate into the canister be constant over the entire 24-hour collection period
so as to best characterize the average burden of VOCs over the entire sampling duration.
Indicated flow rates for carbonyl s and P AHs must be within ± 10% of both the flow transfer
standard and the design flow rate (where applicable). The indicated flow rate for the low volume
PMio metals method must be within ± 4% of the flow transfer standard and within ± 5% of the
design flow rate. The indicated flow rate for the high volume PMio metals method must be
within ± 7% of the transfer standard and within ± 10% of the design flow rate. Failure to meet
these criteria must result in corrective action including, but not limited to, recalibration of the
sampling unit flow or resetting of flow linear regression response, where possible. Sampling
units which cannot meet these flow accuracy specifications must not be utilized for sample
collection. Additionally, following a failing calibration or calibration check, agencies must
evaluate sample data collected since the last acceptable calibration or calibration check, and such
data may be subject to invalidation. Corrective action is recommended for flow calibration
checks which indicate flows approaching, but not exceeding the appropriate flow acceptance
criterion. Calibration flow checks must be performed at minimum quarterly; however, to
minimize risk of invalidation of data, monthly flow calibration checks are recommended.
Sampling bias for VOCs and carbonyls is also characterized by evaluating sample media
collected by providing analyte-free zero air or nitrogen to the sampling unit (zero checking) and
by providing a known concentration analyte stream to VOCs sampling units (known standard
check). These zero checks and known standard checks are discussed further in Sections 4.2.5.5
and 4.3.7.1.1, for VOCs and carbonyls, respectively.
2.1.5 Sensitivity. Following promulgation of the C A A and its amendments, ambient air
toxics concentrations have been decreasing. As concentrations decrease, they become
increasingly difficult to measure and, as a result, measurement methods must become
increasingly sensitive. Concurrent with decreases in ambient air toxics concentrations, health
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risk assessments for exposures to air toxics are driving health risk-based concentrations lower,
which also precipitates a need to increase method sensitivity. In order to ensure that methods are
sufficiently sensitive, MDL MQOs have been established which prescribe the maximum
allowable MDL for each required NATTS core/Tier I analyte. As concentrations for HAPs
decrease in the ambient atmosphere and are measured closer to the MDL or below the MDL, this
results in a decrease in the accuracy (decrease in precision and increase in bias) of the percent
change estimate in evaluating a trend.
The MDL and sample quantitation limit ([SQL], defined as 3.18 times the MDL concentration)
provide information on the concentration at which both positive identification and accurate
quantification is expected, respectively. While all measured concentrations (even those less than
the MDL) must be reported to AQS, the confidence associated with each reported concentration
is correlated to its relationship to the corresponding MDL and SQL.
The SQL is equivalent to ten-fold the standard deviation of seven measurements of MDL
samples, which was defined in draft EPA guidance in 19946 as the minimum level (ML). The
3.18-fold was derived by dividing 10 standard deviations by 3.14 (the student's T value for 7
replicates). The MDL process in 40 Code of Federal Regulations (CFR) Part 136 Appendix B is
protective against reporting false positives such that 99% of the measurements made at the
determined MDL value are positively detected (determined to be different from the detectors
response in the absence of the analyte), but does not attempt to characterize precision or address
accuracy at the determined MDL concentration. The SQL (ML) concentration provides more
confidence to the accuracy of the measurement with precision that is well-characterized.
MDL MQOs that must be met (as of the promulgation of this document in October 2016) are
given in Table 4.1-1. Further discussion of MDL background, determination, and importance are
discussed in in Section 4.1.
2.2	NATTS Workplan
Each year the EPA will submit a workplan to each agency conducting NATTS Program work
covering the grant period from July 1 through June 30 of the following calendar year. This
workplan details the sample collection, sample analysis, and data reporting responsibilities and
the associated budget with which each agency must comply. The workplan briefly describes the
NATTS main DQO and associated outputs and outcomes as related to the EPA's strategic goals.
The workplan will prescribe the quantity of quality assurance samples (collocated, duplicate, or
analysis replicate) to be collected at each site for the grant funding year. The workplan also
specifies the required MDL MQOs for the Tier I Core analytes.
2.3	Quality System Development
There are 1 1 quality management specifications defined in EPA Order CIO 2105.0
(https://www.epa.gov/sites/prodiiction/files/2015-Q9/documents/epa order c 50.pdf)
for all EPA organizations covered by the EPA Quality System. It is EPA policy that each agency
conducting NATTS Program work must have a quality system that conforms to the minimum
specifications of the American National Standards Institute (ANSI)/American Society for
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Quality (ASQ) E4 "Specifications and Guidelines for Quality Systems for Environmental Data
Collection and Environmental Technology Programs.7 ASQ E4 is based on the general principle
that the quality system provides guidelines for quality assurance (QA) and quality control (QC)
based on the continuous cycle of planning, implementation, documenting, and assessment.s
Each agency's quality system must also comply with the requirements as given in this TAD,
which complements the requirements in ASQ E4. The purpose of defining the quality systems
requirements in this manner is to provide a single source for developing or revising quality
systems for NATTS Program work. Quality systems documents, including QAPPs and SOPs,
must be revised to reflect the requirements. The quality system and associated functions are
described in the plan-do-check-act feedback loop to ensure continuous improvement to ensure
NATTS MQOs are met.
Plan - The planning portion of the quality system incorporates development of quality systems
documents such as a QMP, QAPP, and SOPs which define the activities to be conducted, who
they are conducted by, when activities are conducted, and how they must be documented. These
documents must adapt and incorporate adjustments to procedures and policies when changes are
needed or when procedures and policies become obsolete. Quality systems documents serve a
dual purpose in that they describe how activities will be conducted and serve to document
policies and procedures for reconstructing past activities.
Do - Activities described in the quality systems documents must be implemented and executed as
prescribed. Staff training is a necessary element of a functional quality system, ensuring that
each individual conducting activities has the experience and skills required to generate work
product of a known and adequate quality. Appropriate training combined with up-to-date quality
systems documents ensure that staff have both the skills and procedures to conduct activities as
required.
Check - Assessments are conducted during and after planning and implementation to ensure that
work products meet the objectives and needs of the program as defined during planning.
Additionally, assessments ensure that quality systems documents sufficiently describe the
activities to be performed, that measurements and calculations are accurate, that staff perform
activities per the current quality systems documents, that staff training is up to date, and that
nonconformances are communicated to those ultimately responsible for the program.
Act - Following assessments, root cause analysis is performed and corrective action is taken to
address nonconformances such that the NATTS program may be continuously improved.
Each agency must have a robust and fully-functioning quality system to ensure that NATTS
Program MQOs for the various DQls are met. When MQOs are met across the entire network,
the NATTS program DQO will be attained. A fundamental part of a functional quality system is
the QAPP, which each agency must develop and maintain for NATTS program work. Details
and specific quality system elements that must be incorporated in the NATTS QAPP are
presented in Section 3.
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2.4
Siting Considerations
Urban concentration data are needed to address the range of population exposures across and
within urban areas. Conversely, rural concentration data are needed for characterization of
exposures of non-urban populations, to establish non-source impacted concentrations (as
practicable), and to better assess environmental impacts of emissions of air toxics. The NATTS
network at the time of this TAD revision consists of 20 urban sites and seven rural sites. Each of
these sites has been established since 2008, and only modest modifications involving relocation
within a small geographic area have occurred over the past several years. Long-term monitoring
needed to measure average concentrations over successive three-year periods requires that sites
are maintained at, or in very close proximity to, their current location. This long-term data
generation from each site is integral to discerning trends in air toxics concentrations.
For each of the 27 sites currently in the NATTS network, sampling unit siting may have changed
little, if at all, from when sample collection for the NATTS Program began at the specific site.
Nonetheless, site operators should evaluate instrument siting annually to ensure that
requirements continue to be met consistently across the network. Siting criteria to consider
relate to changes at the site such as tree growth, construction or development on property near
the site, new sources, and other changes which may impact sample collection and the resulting
measured concentrations. Particular attention should be paid to vertical placement of inlets,
spacing between sampling inlets, proximity to vehicle traffic (especially where traffic levels have
increased due to housing or business development), and proximity to obstructions or other
interferences. Additionally, monitoring agencies should be aware of changes in sources,
population, and neighborhood make-up (businesses, industry, etc.) which may impact sampler
siting or sample concentrations.
Monitoring unit inlet placement must conform to the specifications listed in 40 CFR Part 58
Appendix E and the additional guidance given below.
2.4.1 Sampling Instrument Spacing. Requirements for sampler spacing are relative to the
sampling unit inlet (edge) and must conform to the criteria listed in Table 2.4-1.
As an example, per the table above, an inlet to a carbonyls sampler must be no less than 2 m and
no more than 15 m above the ground and it may be no closer than 2 m to any high volume
sampler. Moreover, the inlets of collocated samplers may be no further than 4 m in the
horizontal direction, and no more than 3 m apart vertically.
Note that for gaseous HAPs (VOCs and carbonyls) there is no minimum collocation distance as
gases are much more homogeneous in the ambient air than particulate matter, and are not likely
to influence one another, particularly at the low flow rates utilized.
17

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Table 2.4-1. Sampling Unit Inlet Vertical Spacing Requirements


Inlet Above Ground
Horizontal
Vertical
Parameter
Flow Rate
Level Height
Collocation
Collocation


Requirement"
Requirement
Requirement
VOCs
Low volume
(< 1000 iiiL/min)
2-15 in
0-4 in
< 3 ill
Carbonyls
Low volume
(~ 1 L/iiiin)
2-15 ill
0-4 in
< 3 ill

Low volume
2-15 in
1-4 illb
< 3 ill
PMio Metals
(-16.7 L/min)
High volume 0
(~ 1.1 iivVmin)
2-15 ill
2-4 mb
< 3 ill
PAHs
High volume c' d
(> 0.139 mVillin)
2-15 in
2-4 in
< 3 ill
a Many standalone sampling unit inlets do not meet the minimum height and must be installed on a support
structure such as a riser or rooftop to elevate the inlet to the proper height.
b 40 CFR Part 58 Appendix A Section 3.3.4.2(c).
0 These high volume sampling units must be minimally 2 m from all other sampling inlets.
d 40 CFR Part 58 Appendix E states that high volume sampling units arc those with flow > 200 L/minutc.
However the regulations arc silent on high volume PAHs sampling units, which operate > 139 L/minutc; in this
T AD they arc conservatively being treated as high volume sampling units such that they must minimally be 2 m
horizontally from other instrument inlets.
2.4.2	Interferences to Sampling Unit Siting. Interference from other samplers,
particularly high volume sampling units for PAHs and PMio metals, must be avoided by ensuring
that all inlets are minimally 2 meters from any high volume inlet. Additionally, to eliminate
recollection of already sampled "scrubbed" air, exhausts (when so equipped) from high volume
sampling units must be directed away from air samplers in the primary downwind direction via
hose that terminates minimally 3 meters in distance from any sampler.
PMio metal sampling unit sites must not be in an unpaved area unless covered by vegetation year
round, so the impacts of wind-blown dusts are kept to a minimum.9
Tarred or asphalt roofs should be avoided for the install of inlets for carbonyls, VOCs, and P AHs
air samplers as these materials may emit target analytes during warmer sampling periods. If
installation is performed on such a roof, it is recommended that the tar or asphalt be encapsulated
or sufficiently weathered and that collected samples be evaluated for marker compounds
indicative of contamination or influence from the tar or asphalt.
2.4.3	Obstructions. An inlet of standalone sampling units and inlet probes must be at least
1 meter vertically or horizontally away from any supporting structure, wall, parapet, or other
obstruction. If the probe is located near the side of a building, it should be located on the
windward side relative to the prevailing wind direction during the season of highest
concentration potential.
Inlets must have unrestricted airflow and be located away from obstacles so that the distance
from the obstacle to the inlet is at least twice the height difference the obstacle protrudes above
the inlet. For instance, if a monitoring trailer is 4 meters above the inlet of a PMio metals
sampling unit, the inlet must be minimally 8 meters from the monitoring trailer.
18

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All sampling inlets must be minimally 10 meters from the dripline (end of the nearest branch) of
any tree.
2.4.4 Spacing from Roadways. Sampling unit inlets for VOCs, carbonyls, PMio metals,
and PAHs must meet or exceed the minimum distance from roadways according to Table 2.4-2.
Table 2.4-2. Sampling Unit Inlet Required Minimum Distances from Roadways
Roadway Average Daily Traffic (ADT), Vehicles
per Day
Minimum Distance to Inlet (m)"
< 15,000
15
20,000
20
40,000
40
60,000
60
80,000
80
> 100,000
100
a Distance from the edge of the nearest traffic lane. The distance for intermediate traffic counts should be
interpolated from the table values based on measured traffic counts. Values in this table taken from 40 CFR
Part 58 Appendix E, Figure E-l for neighborhood scale sites.
2.4.5 Ongoing Siting Considerations. Agencies must be mindful of conditions at the site
that may impact siting criteria.
Infrequent, non-characteristic, or non-representative sources such as road and building
construction may impact measured sample concentrations due to increased dust, emissions from
materials utilized (paints, paint strippers, asphalt, etc.), and heavy machinery operation. Other
such sources include demolition operations (e.g. buildings or roadways) generating dust which
may impact PMio metals concentrations. Application of fresh pavement and painting of traffic
lanes generates substantial concentrations of PAHs and VOCs. For sites in residential areas,
storage of fuels, operation of charcoal grills, backyard fire pits, and fireplaces can contribute to
elevated measured concentrations of PAHs and PM. Concentrations of HAPs measured at rural
sites may be affected by forest fires, logging operations, etc. Observation of such conditions
must be noted on the sample collection records or site log and may require qualification of
results.
Fast growing trees, newly constructed buildings or traffic routes, and other interferences must be
noted and recorded in the site log and data must be qualified, as appropriate. When these items
negatively impact the siting criteria, the obstruction or interference must be addressed. Such
necessary changes to instrument siting should be included in each site's annual network plan.
For unavoidable impacts to the site (such as a business acting as a significant source), these
should be addressed in the network plan and may require relocation of the site. Such
interferences and potential relocation should be discussed and addressed in concert with the EPA
Region office.
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2.5 References
1.	Quality Management Plan for the National Air Toxics Trends Stations. Quality Assurance
Guidance Document, EPA 454/R-02-006. September 2005. Available at (accessed October
2.	Draft Report on Development of Data Quality Objectives (DQOs) for the National Ambient
Air Toxics Trends Monitoring Network, September 27, 2002
(Appendix A of this TAD)
3.	Analysis, Development, and Update of the National Air Toxics Trends Stations (NATTS)
Network Program-Level Data Quality Objective (DQO) and Associated Method Quality
Objectives (MQOs), Final Report, June 13, 2013. Available at (accessed October 18, 2016):
https://www3.epa.gov/ttnamtil/files/ambient/airtox/riattsdqo20130613.pdf
4.	National Air Toxics Program: The Integrated Urban Strategy, Report to Congress, EP A
453/R-99-007, July 2000. Available at (accessed October 18, 2016):
https://www.epa.gOv/sites/production/files/2014-08/documents/072000-urban-air-toxics-
report-conaress.pdf
5.	National Air Toxics Trends Stations Quality Assurance Annual Report, Calendar Years 2011
and2012, Final, December 12, 2014. Available at (accessed October 18, 2016):
6. National Guidance for the Permitting, Monitoring, and Enforcement of Water Quality-based
Effluent Limitations Set Below Analytical Detection Quantitation Levels, Draft Report.
United States EPA, 1994
7.	Specifications and Guidelines for Quality Systems for Environmental Data Collection and
Environmental Technology Programs, American National Standards Institute
(ANSI)/American Society for Quality (ASQ) E4, 2004.
8.	Overview of the EPA Quality System for Environmental Data and Technology.
EPA/240/R-02/003; U.S. Environmental Protection Agency: Office of Environmental
Information. Washington, DC. November 2002. Available at (accessed October 18, 2016):
https://www.epa.gov/sites/production/files/2015-08/dociiments/overview-final.pdf
9.	Ambient Air Quality Surveillance, Probe and Monitoring Path Siting Criteria for Ambient
Air Quality Monitoring, 40 CFR § 58 Appendix E, 201
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3.0: QUALITY ASSURANCE AND QUALITY CONTROL
3.1	NATTS Quality Management Plan
EPA OAQPS developed the NATTS Program QMP to provide a set of minimum requirements
that must be followed by all monitoring organizations (state, local, or tribal organization; or
company) conducting NATTS Program work. Development of the QMP began in 2002 and was
completed, approved, and implemented in 2005. Essential QA and QC elements are defined
within the NATTS QMP1 and are excerpted and presented in this document.
3.2	NATTS Main Data Quality Objective, Data Quality Indicators, and
Measurement Quality Objectives
There is a single main DQO for the NATTS Program, which is stated as:
To be able to detect a 15% difference (trend) between two successive 3-year annual mean
concentrations (rolling averages) within acceptable levels of decision error.
To achieve this primary DQO, the DQls of representativeness, completeness, precision, bias, and
sensitivity must meet specific MQOs, or acceptance criteria. The MQOs for each of the DQls
are as follows:
•	Representativeness: Sampling must occur at one-in-six day frequency, from
midnight to midnight local time, over 24 ± 1 hours
•	Completeness: At least 85% of all data available in a given quarter must be reported
•	Precision: The CV must be no more than 15%
•	Bias: Measurement error must be no more than 25%
•	Sensitivity: MDLs must meet the network requirements.
Each entity supporting NATTS Program data collection must ensure that these MQOs are met
for each of the DQls. Implementation of a robust quality system is part of the process to attain
such.
3.3	Monitoring Organization QAPP Development and Approval
As discussed in Section 2.3, the monitoring organization quality system is the framework that
ensures that defensible data of appropriate quality - those that meet the network MQOs for the
various DQls - are generated and reported to EPA so that the NATTS DQO is attained. The
NATTS QAPP is the roadmap for design of each organization's quality system.
Given the importance of the QAPP, each monitoring organization operating a NATTS
monitoring site and/or laboratory performing analysis of NATTS Program samples must have an
up-to-date and fully approved QAPP which covers all aspects of the sample collection, analysis.
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and QA/QC activities performed by the specific agency and at the associated laboratory at which
samples are analyzed. All major stakeholders involved in the monitoring organization's and/or
laboratory's NATTS Program work should provide input to and review the QAPP to ensure that
aspects of the QAPP for which they are responsible are accurately and adequately described.
The QAPP must minimally be approved and signed by the monitoring organization's NATTS
Program Manager (however named) and the EPA Regional office (or EPA Regional office
delegate as defined in the grant language) in which the monitoring site and/or laboratory exists
and the QAPP must be on-file.
The NATTS QAPP must provide an overview of the work to be conducted, describe the need for
and objectives of the measurements, and define the QA/QC activities to be applied to the project
such that the monitoring objectives are attained. The QAPP should include information for staff
responsible for project management, sample collection, laboratory analysis, QA, training, safety,
data review, and data reporting.
The NATTS QAPP for each monitoring organization is the starting point or roadmap to ensure
that the NATTS MQOs, and therefore NATTS monitoring objectives, are achieved. Review of
the NATTS QAPP on an annual basis (or as required by the Region), conduct of audits and
assessments, and implementation of effective corrective action ensure that NATTS sites and
supporting labs are in fact achieving NATTS program objectives, and, if not, are implementing
corrective actions, as needed.
The NATTS QAPP for each monitoring organization must include the NATTS DQO, DQls, and
MQOs listed above in Section 3.2, and should include elements listed in Section 3.3.1.3 to ensure
that data of sufficient quality are generated over time such that concentration trends may be
successfully detected and that monitoring data of comparable quality are generated across the
entire NATTS network. The NATTS Program DQO, DQls, and MQOs take precedent over
regional, state, local, or tribal monitoring objectives for the associated air toxics sampling that is
performed unless the SLT requirements are more stringent than those indicated for NATTS.
Monitoring agencies are free to prescribe more conservative acceptance criteria (e.g. lower blank
acceptance concentrations, tighter recovery ranges, etc.).
3.3.1 Development of the NATTS QAPP. EPA has developed a model QAPP as
described in EPA QA/R-5, EPA Requirements for Quality Assurance Project Plans2 and the
accompanying document, EPA OA (7-5, Guidance for Quality Assurance Project Plans ,3 This
model QAPP may be a useful starting point in the development of the QAPP for each monitoring
agency conducting NATTS Program work.
3.3.1.1	NATTS QAPP — Program DQOs, DQls, and MQOs. The NATTS DQOs, DQls, and
MQOs, which are given in Section 3.2 of this TAD, must be included in the NATTS QAPP.
3.3.1.2	NA TTS QAPP - Performance Based Method Criteria, N ATTS Program work must
comply with the requirements listed in this TAD and with the collection and analysis methods
specified in Section 4. Acceptance criteria specified in the methods must be met as prescribed;
however, method deviations are permitted provided the acceptance criteria for precision and bias
are met and can be demonstrated to be scientifically sound and defensible. The NATTS Program
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is designed according to the EPA's Flexible Approaches to Environmental Measurement
(FAEM). The FAEM is a performance-based measurement systems approach which prescribes
specific methods or approaches to be implemented, but permits deviations in the manner in
which the specified methods are performed provided that the resulting data meet the data quality
acceptance criteria for precision and bias.
Planned method deviations must be described in the monitoring organization's QAPP and must
be approved by the cognizant EPA regional office (or delegate as detailed in the grant language).
Adjustments to storage conditions and holding times are not permitted, nor are deviations which
permit exceedances to the specified method acceptance criteria or to NATTS MQOs as such
would allow data of a quality lower than, and not comparable to, that required to be generated in
the NATTS network per the NATTS QMP and per this TAD. Agency QAPPs should
incorporate much of the guidance listed in this TAD.
3.3.1.3 NA TTS QAPP - Incorporating Quality System Elements. In addition to the
example information contained in the model QAPP listed in Section 3.3.1, monitoring
organizations should develop and prescribe within the QAPP the following quality system
elements which are described in more detail in the following sections:
•	Pertinent SOP documents
•	Corrective action procedures
•	QA unit and internal audit procedures
•	Calibration of instruments
•	Document control
•	Training requirements and documentation, and demonstration of capability
•	Sample custody and storage
•	Traceability of reagents and standard materials
•	Labeling
•	Early warning systems - control charts
•	Spreadsheets and data reduction algorithms
•	Software validation, updating, and upgrading
•	Review of records
•	Data verification and validation
•	Reporting of results to AQS
•	Records retention and archival
•	Safety
3.3.1.3.1 Standard Operating Procedure Documents. The NATTS QAPP must list
the pertinent SOPs, however named, to be followed to conduct all NATTS Program work. SOPs
must prescribe the details of the activities applicable to sample collection in the field, preparation
and analysis of the samples in the laboratory, and data review, reduction, and reporting. SOPs
must minimally cover the following aspects of the NATTS program:
•	Sample collection for VOCs, carbonyls, PMio metals, and PAHs;
•	Sample preparation and analysis for VOCs, carbonyls, PMio metals, and PAHs;
23

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•	Calibration, certification, and maintenance of each type of sample collection and
analysis instrument;
•	Calibration of critical support equipment; and
•	Data review.
Additional SOPs should be prepared as necessary to cover routine procedures and repetitive
tasks which, if performed incorrectly, could affect data quality such as COC and performing
numerical calculations (describing rounding, significant figures, etc.).
Refer to Section 3.3.2 for further guidance on preparation of SOPs.
For portions of the sample collection and analysis which are contracted or otherwise performed
elsewhere (not by the cognizant NATTS monitoring agency), the monitoring organization must
reference the SOP of the third party in its NATTS QAPP and if the laboratory is other than the
national contract laboratory (which are maintained by EPA), must maintain a current, approved
copy of the third party's SOP(s) on file. Monitoring agencies must ensure that third-party
laboratory QAPPs and SOPs are available.
3.3.1.3.2 Corrective Action Process. Each monitoring organization must have a
corrective action process in place that is executed upon discovery of nonconformances to the
NATTS TAD, NATTS agency QAPP, and/or applicable agency SOPs. Each monitoring
organization should ideally have a corrective action tracking procedure so that all corrective
actions are available in a single location (e.g., binder, database, etc.) and may be readily
referenced. Corrective actions are taken to remedy nonconformances found during audits or
assessments; however, corrective action must also be performed and documented for
nonconformances or problems noted during routine, everyday operations.
For each nonconformance, a corrective action report should be prepared which includes the
following components:
•	Unique corrective action report (CAR) identifier
•	Identification of the individual initiating the CAR (staff person's name)
•	Date of discovery of nonconformance
•	Date of C AR initiation
•	Area or procedure affected (e.g., PMio metals sample collection)
•	Description of the nonconformance (what happened and how it does not conform)
•	Investigation of the nonconformance (how discovered, what is affected by the
nonconforming work)
•	Root cause analysis (what caused the nonconformance)
•	Investigation for similar areas of nonconformance
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•	Immediate and long-term (if needed) remedial corrective actions (and documentation
of when completed)
•	Due date for remedial action completion
•	Impact assessment of nonconformance
•	Assessment of corrective action effectiveness
•	Demonstration of return to conformance
•	Follow up audit to ensure corrective actions were effective (with date completed)
Situations which would require a corrective action report include, but are not limited to:
•	Repeated calibration failure
•	Incorrect sample storage conditions
•	Blank contamination
•	Incorrect procedures followed
•	Repeated QC acceptance criteria failures
Root cause analysis should be performed as soon as possible so remedial actions may be taken to
correct the problem before it affects other procedural areas or additional samples and to
minimize recurrence of the problem. For problems where the root cause is not immediately
obvious, a stepwise approach should be taken to isolate the specific cause(s) of the
nonconformance(s). Incorrect conclusions may result if too many variables are altered at one
time, rendering the corrective action process ineffective.
An example CAR form is shown below in Figure 3.1-1.
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Corrective Action Report


Corrective Action Report ID (CAR-YYYYMMDD-XXX):


Initiated By;


Area(s) or Proceduref s) Affected:


Description of Nonconformance:


Investigation of Nonconformance:


Root Cause:


Investigation for Similar Instances of Nonconformance:


Immediate Corrective Action(s):
Date(s) completed


Impact Assessment of Nonconformance:


Long-term Corrective Action(s):
Date(s) completed


Assessment of Effectiveness of Coll ective Action:


Additional Corrective Action Necessary:
(optional - Provide CAR ID)
Date(s) completed


Return To Conformance (if applicable):
Date(s) completed


Follow-up Actions (if any):
Date(s) completed


Corrective Action Completion Date:


Approval of Corrective Action Completion


QA Manager Representative:



Figure 3.1-1. Example Corrective Action Report
3.3.1.3.3 Quality Assurance Unit and Internal Audit Procedures. Each
monitoring organization should have a QA group, or, minimally, an individual quality assurance
officer (however named). This quality assurance unit is typically responsible for performing
assessments (audits) of sample collection procedures, sample analysis procedures, data records,
and the quality system as well as managing and overseeing the corrective action process,
managing document control, performing QA training, and reviewing QC data as applicable.
Monitoring organizations which contract laboratory analysis should ensure that the laboratory
operates a QA program to oversee and conduct audits of these aspects for which the laboratory is
responsible.
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QA staff should be independent from project management to best ensure that nonconformances
are addressed and remedied and to maximize the likelihood that data of sufficient quality are
generated. Moreover, independent QA oversight is integral to ensuring that internal audits are
objective. For agencies which may not have sufficient resources to dedicate an independent QA
staff member, an individual not affiliated with a given activity may serve to perform QA
functions. The quality assurance staff should conduct three types of audits:
•	Technical systems audits (TSAs): An on site review and inspection of the monitoring
agency's monitoring program to assess compliance with the established regulations
governing the collection analysis, validation, and reporting of ambient air quality
data.4 The auditor observes staff conducting sample collection and analysis activities
and compares the activities performed against procedures codified in the agency
QAPP and applicable SOPs, ensures proper documentation practices, verifies staff
training records, verifies proper data reporting, and ensures all operations are
performed in accordance with appropriate safety practices.
•	Audits of Data Quality ( ADQs): The auditor reviews reported data to ensure
traceability of all measurements and calculations from initial receipt of sample
collection media through to the final reported results. Calculations and data
transformations are verified to be accurate.
• Quality Systems Audits (QSAs): The auditor reviews quality systems documents
such as the agency QMP, QAPP, and SOPs to ensure they are current and to assess
compliance with program requirements, such as those stipulated in this TAD.
The monitoring organization QAPP, SOP, or other suitable controlled document should define
the schedule for audit frequency, the scope of each type of audit (i.e., which operational areas
must be observed, which records must be reviewed, etc.), the timeline for following up on audit
nonconformances, the timeline for conducting follow-up audits that ensure that
nonconformances are being remedied in a satisfactory and timely manner, and the method for
reporting audit outcomes to agency management and staff. For monitoring organizations which
utilize contract laboratory analysis services, the laboratory QAPP, QMP, or similar controlled
document should define these frequencies.
3.3.1.3.4 Calibration of Instruments. Each agency must define in the NATTS
QAPP, SOP, or similar controlled document the frequency at which critical instruments must be
calibrated and the acceptable tolerance for such calibrations. Critical instruments are defined as
those whose measurements directly impact the accuracy of the final reported concentrations.
The calibration of such instruments must be traceable to a certified standard and a standard
calibration process. Critical instruments include, but are not limited to:
•	Flow transfer standards
•	Mass flow controllers, mechanical flow controllers, and meters generating flow
readings for calculating total collected sample volumes and diluting standard gases
•	Thermometers and barometers
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•	Volumetric delivery devices such as fixed and adjustable pipettes, bottletop
dispensers, etc.
•	Balances
•	Pressure gauges and transducers when measuring pressures for dilution or standard
preparation
Such critical instruments must be calibrated initially and the calibration verified (checked)
periodically to ensure the calibration remains valid. Instruments must be recalibrated (or
removed from service and replaced with a properly calibrated unit) when calibration verifications
fail. Data generated with the failing equipment since the last acceptable calibration or calibration
verification must be examined and considered for qualification. Monitoring agencies are
encouraged to perform more frequent calibration checks (identified as recommendations) to limit
the amount of data subject to qualification when calibration checks fail acceptance criteria.
Frequency of calibration verifications must conform to Table 3.3-1 and must be addressed within
the agency NATTS QAPP, SOPs, or similar controlled document.
Table 3.3-1. Calibration and Calibration Check Frequency Requirements for Standards
and Critical Instruments
instrument or
Standard
Area of Use
Required Calibration Check"
Frequency and Tolerance
Required
Calibration b Frequency
Balances
Laboratory - Weighing
standard materials, calibration
of pipettes, determining mass
loss for microwave metals
digestion, weighing PAHs
sorbent resin (XAD-2)
Each day of use with certified
calibration check weights
bracketing the balance load;
Must be within manufacturer-
specified tolerance covering the
range of use
Initially, annually, and when
calibration checks
demonstrate an out of
tolerance condition
Certified Weights
Laboratory - Calibration
verification of balances
Check not required.
Annual certification by
accredited metrology
laboratory; Must be within
manufacturer-specified
tolerance
Mechanical
Pipettes
Laboratory - Dispensing
liquid volumes
Minimally quarterly,
recommended monthly, by
weighing delivered volumes of
dcioni/cd water bracketing
those dispensed; Must be within
manufacturer-specified
tolerance covering the range of
use
Initially and when calibration
checks demonstrate an out of
tolerance condition
Bottletop
Dispensers
Laboratory - Dispensing
critical liquid volumes
Each day of use by delivery
into a To Contain (TC)
graduated cylinder
Must be within ± 5%
When delivery volumes arc
set and when calibration
checks fail criteria
Thermometers -
Laboratory
Laboratory - Temperature
monitoring of water baths,
metals digestion, refrigerated
storage units, canister
cleaning ovens, and water for
pipette calibration
Check not required.
Annual at temperature range
of use or at not-to-exceed
temperature - Correction
factors applied to match
certified standard
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Table 3.3-1. Calibration and Calibration Check Frequency Requirements for Standards
and Critical Instruments (Continued)
instrument or
Standard
Area of Use
Required Calibration Check*
Frequency and Tolerance
Required
Calibration b Frequency
Thermometers -
Meteorological
Field - Recording
environmental conditions
during sample collection
Minimally quarterly, monthly
recommended
Must be w ithin
± 0.5°C of certified standard at
working temperature
Initially and when calibration
checks indicate readings out
of tolerance
Barometers
Field - Recording
environmental conditions
during sample collection
Laboratory - Recording
environmental conditions
during instrument calibration
Minimally quarterly, monthly
recommended
Must be w ithin
±10 nun Hg of certified
standard at typical barometric
pressure
Initially and when calibration
checks indicate readings out
of tolerance
Flow Transfer
Standards
Field - Critical flow orifices
and volumetric flow meters
for calibrating and verifying
sampling unit flows
Built-in thermometers and
barometers must be calibrated
Check not required.
Annual; Must be within
manufacturer-specified
tolerance and cover the range
of use
Pressure Gauges
or Transducers
Field and Laboratory -
Measure canister
pressure/vacuum before and
after collection, measure final
canister vacuum following
cleaning
Annual. Must be w ithin 0.5 psi
or manufacturer-specified
tolerance and cover the range of
use
Initially and when calibration
checks show out of tolerance.
Must cover the range of use
Flow Controllers
and Meters -
Laboratory
Laboratory - Mass flow
controllers (MFCs), flow
rotameters, or similar devices
for measuring/metering gas
flow rates for critical
measurements (standard gas
mixing)
Minimally quarterly, monthly
recommended
Flow w ithin ± 2% of certified
standards
Initially and when calibration
checks demonstrate flows are
out of tolerance
VOCs Sampling
Units
Field - Collection of VOCs in
canisters
Flow control (such as MFC)
Pressure gauge/transducer
If performed, minimally
quarterly, for flow control,
annually for pressure
gauge/transducer
Flow control (check is optional)
w ithin ±10% of certified flow
If needed for critical
measurements (canister
starting/ending pressure),
pressure gauge/transducer
w ithin ±0.5 pounds per square
inch (psi) of certified standard
Flow control - Initially and
when components affecting
flow arc adjusted or replaced,
or when calibration checks
demonstrate flows arc out of
tolerance
Pressure gauges/transducers -
initially and when calibration
checks demonstrate flows arc
out of tolerance
Carbonvls
Sampling Units
Field - Collection of
carbonvls on 2,4-
dinitrophcnylhydrazinc
(DNPH) sorbent cartridges
Flow control (such as MFC)
Minimally quarterly, monthly
recommended
Flow w ithin ±10% of certified
flow and design flow
Initially , when calibration
checks demonstrate flows are
out of tolerance, and w hen
components affecting flow
arc adjusted or replaced
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Table 3.3-1. Calibration and Calibration Check Frequency Requirements for Standards
and Critical Instruments (Continued)
Instrament or
Standard
Area of Use
Required Calibration Check*
Frequency and Tolerance
Required
Calibration b Frequency
PMio Metals
Sampling Units
Field - Collection of PMio on
filter media for metals
analysis
Flow control must be within
tolerance
If equipped, thermometer and
barometer must be within
field tolerances specified
above
Minimally quarterly, monthly
recommended
Low volume flows within ±4%
of transfer standard and ±5% of
design flow
High volume flows within±7%
of transfer standard and ±10%
of design flow
Initially, when calibration
checks demonstrate flows are
out of tolerance, and when
components affecting flow
arc adjusted or replaced
PAHs Sampling
Units
Field - Collection of
carbonyls on QFF, PUF, and
XAD-2 media sampling
modules
Flow control must be within
tolerance
If equipped, thermometer and
barometer must be within
field tolerance specified
above
Minimally quarterly, monthly
recommended
Flow within ±10% of certified
flow and design flow
Initially, when calibration
checks demonstrate flows are
out of tolerance, and when
components affecting flow
arc adjusted or replaced
GC/MS for
VOCs analysis
Laboratory - Analysis of
VOCs from stainless steel
canisters
Refer to Table 4.2-3
Initially, following failed
continuing calibration
verification (CCV) check,
following failed
bromofluorobcnzcne (BFB)
tune check, or when
changes/maintenance to the
instrument affect calibration
response
HPLC for
carbonyls
analysis
Laboratory - Analysis of
carbonyl-DNPH extracts
Refer to Table 4.3-4
Initially, following failed
continuing calibration
verification (CCV) check, or
when changes/maintenance to
the instrument affect
calibration response
I CP/MS for
metals analysis
Laboratory - Analysis of
PMio digestates for metals
Refer to Table 4.4-3
Each day of analysis
GC/MS for
PAHs analysis
Laboratory - Analysis of
polyurcthane foam
(PUF)/resin/quartz fiber filter
(QFF) extracts for PAHs
Refer to Table 4.5-3
Initially, following failed
continuing calibration
verification (CCV) check,
following failed
decafluorotriphenylphosphine
(DFTPP) tune check, or when
changes/maintenance to the
instrument affect calibration
response
a Calibration verification checks arc a comparison to a certified standard, typically at a single point at which the
instrument is used, to ensure the instrament or standard remains within a prescribed tolerance. Instruments or
standards which exceed the tolerance must be adjusted to be within prescribed tolerances or replaced.
b Calibration refers to resetting the reading or setting or applying a correction factor to the instrument or standard
to match a certified standard, typically at three or more points bracketing the range of use.
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3.3.1.3.4.1 Calibration Verification (Checks)
Following instrument calibration, critical instruments must undergo periodic calibration
verification (check) to ensure bias meets the assigned acceptance criterion. Calibration checks
typically challenge the instrument at a single point typical of use or toward the middle of the
calibration range. Calibration checks may also include multiple points bracketing the range of
use. Instruments for which calibration checks are required include, but are not limited to:
•	Mass flow controllers, mechanical flow controllers, and meters generating flow
readings for calculating total collected sample volumes and diluting standard gases
•	Volumetric delivery devices such as fixed and adjustable pipettes, bottletop
dispensers, etc.
•	Balances
•	Analytical instruments generating concentration data (e.g. GC/MS, HPLC, ICP-MS)
3.3.1.3.5 Document Control System. Each monitoring organization must have a
prescribed system defined in its NATTS QAPP or QMP for control of quality system documents
such as QMPs, QAPPs, and SOPs. A properly operating document control system ensures that
all documents integral in defining performance criteria and prescribing procedures are current,
and that outdated or superseded documents are not available for inadvertent reference. All such
controlled documents must minimally be approved by a cognizant manager (however named)
who is ultimately responsible for the conduct of the work (e.g., monitoring agency director for an
agency QMP, NATTS program manager for the NATTS QAPP, monitoring manager or
laboratory manager for a field or analytical SOP, etc.), and by a QA staff member responsible for
overseeing the work. Current versions of controlled documents must be readily available to each
staff member conducting NATTS Program work.
To increase the likelihood that all applicable NATTS activities are performed according to
current, approved procedures, the distribution of controlled documents should be managed and
tracked such that only the current, approved versions are available in areas in which such
documents are needed (for example, at field sites and in laboratories) and that outdated versions
are removed once superseded. With the proliferation of networked computers at monitoring sites
and within laboratories, it is convenient to have electronic versions of controlled documents
available which are write-protected. Printing privileges of such read-only electronic documents
should be disallowed, or, if printing is permitted, such documents should be identified via
watermark with the date of printing and their expiration.
Procedures and frequency for changing and updating controlled documents should be clearly
described in the QAPP, SOP, or similar controlled document. Preparing amendments is an
efficient way to address minor changes to controlled documents. An amendment describes the
change and rationale for the change, and may be appended to the document without requiring a
complete revision of the document. Such amendments should be approved minimally by the
cognizant manager (field operations manager or laboratory manager) responsible for the conduct
of the work, and by a member of Q A staff responsible for the document and overseeing the
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work. For major changes to controlled documents, such as those required for a new sampling
unit or updated laboratory information management system (LIMS), a new revision should be
prepared and approved by all required signatories. A system for identifying revisions should be
prescribed to allow tracking of versions. A typical example system uses whole numbers to
designate major revisions and decimals to indicate minor revisions. For example, the first
version of a QAPP would be version 1.0, a minor revision would update to version 1.1, and the
next major revision would be version 2.0, and so on.
An effective date must be included on all controlled documents and they should include an issue
date if this is different from the effective date. A period between the issue date and effective
date permits staff to become familiar with the SOP prior to its becoming effective. A header or
footer should indicate the effective date, version number, page number, and total number of
pages included in the document. A best practice is to include a revision history section for each
controlled document so that readers can quickly and efficiently ascertain changes from the
previous version of the document.
Monitoring agencies (and laboratories) should forbid uncontrolled excerpts to be printed from
controlled documents such as operation instructions or calibration standard preparation tables.
These excerpts are then uncontrolled and may inadvertently be referenced when the version of
origin is no longer effective. For the same reason, unless permitted by the agency's controlled
document policy, uncontrolled shortcut procedural summary documents (summarizing SOP
procedures) similarly should not be permitted. Such procedure summaries may be included in
the NATTS QAPP or applicable SOP to ensure they are updated when the document is revised.
Similarly, notes should not be recorded on controlled document hard copies unless permitted by
the monitoring organization's controlled document revision or amendment process.
The review frequency for controlled documents should be described within the QMP, QAPP, or
similar controlled document. Periodic review of controlled documents must be performed to
ensure that they adequately describe current agency policies and procedures. Each such review
and outcome of the review (e.g., adequate, minor revision needed, major revision needed, etc.)
should be documented. The agency NATTS QAPP must be reviewed annually and associated
SOPs are recommended to be reviewed annually, but must minimally be reviewed every three
years. SOPs must be reviewed following major changes to network guidance to ensure they are
compliant with the updated guidance.
3.3.1.3.6 Training Requirements and Documentation, and Demonstration of
Capability. The training required for each staff member who conducts NATTS Program work
must be prescribed in the agency NATTS QAPP, SOP, or similar controlled document, and the
completion of each required training element must be documented. Specifically, staff must read,
and document that they have read and understood, the most recent versions of the NATTS
quality system documents (QAPP, SOPs, etc.) pertaining to their responsibilities.
Each monitoring organization must have minimum requirements for staff position experience
including a combination of education and previous employment experience. In addition to
documented experience, each staff member must be approved by cognizant management to
conduct the activities for which they are responsible. Such approval should be granted initially
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before beginning work and periodically thereafter, and should be minimally based on successful
completion of a demonstration of capability (DOC) process. DOCs are described in the
subsections below.
Each staff member must have training documented which indicates the staff member's training is
current for each procedure performed, as required by the agency QMP, NATTS QAPP, SOP, or
similar controlled document. Training documentation can consist of hard copy or electronic
documentation and may be located in numerous files or locations, provided it can be retrieved for
auditing purposes. In addition to relevant DOC documentation, the training records should
include items related to experience such as a resume or curriculum vitae, certificates from
training coursework, and a job description specific to the monitoring organization.
3.3.1.3.6.1	Initial Demonstration of Capability
Once the staff member has read the relevant current SOP, and documented such, the staff
member must demonstrate proficiency with a given procedure prior to performing activities to
generate or manipulate NATTS program data. One method by which such could be
accomplished is as follows. First, the staff member observes an experienced staff member
performing the procedure. Next, the trainee conducts the activity under the immediate
supervision of and with direction from an experienced staff member. Finally, the trainee
performs the activity independently while being observed by an experienced staff member. To
ensure all aspects of a procedure are captured in the initial DOC, it is recommended that a
checklist be developed that includes all required steps consistent with the applicable quality
system document(s) to perform the activity. Regardless of the actual initial DOC process
selected for implementation, the process to be implemented and its acceptance criteria must be
defined in the QAPP, SOP, or similar controlled document.
3.3.1.3.6.2	Ongoing Demonstration of Capability
Each staff member performing NATTS Program field work must demonstrate continued
proficiency with tasks for which they are responsible, minimally every three years, but
recommended to be annually. The staff member should be observed by a QA staff member (as
part of an audit), experienced staff member, or responsible manager.
Laboratory staff must annually demonstrate continued proficiency by completing one of the
following:
•	Repeat of the I DOC procedure.
•	Acceptable performance on one or more blind samples (single blind to the analyst)
following the approved method for each target analyte. Acceptable performance is
indicated by demonstrating recovery within limits of the method LCS for each target
analyte.
•	Analysis of at least four consecutive LCSs with acceptable levels of bias. Acceptable
performance is indicated by demonstrating recovery within limits of the method LCS
for each target analyte.
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• Acceptable performance on a PT sample. Acceptable performance is defined by the
provider of the PT sample, as indicated by no results marked as "Unacceptable" or
equivalent, for target analytes.
As with the initial demonstration of capability, the continuing DOC process and its applicable
process acceptance criteria must be prescribed in the agency NATTS QAPP, SOP, or similar
controlled document.
3.3.1.3.7	Sample Custody and Storage. Procedures and details related to sample
custody and sample storage must be included in each monitoring organization's NATTS QAPP
or similar document such as a sample handling SOP.
The COC is a documented trail of who had possession of a sample or group of samples at any
specific point from collection through receipt at the laboratory. Custody records must include
details of transfers of possession between individuals, between individuals and shippers (when
applicable), and to storage at the laboratory and any pertinent details such as storage location and
conditions. It is strongly recommended to maintain sample integrity that samples be protected
and access to the samples be limited to those responsible for the samples.
Sample custody begins when media are readied for dispatch to the field monitoring site. At this
point, a COC form, sample collection form with portions dedicated to documenting custody
transfers, or other form as defined by the monitoring agency, must accompany the sampling
media until they are received at the laboratory for analysis. Each time the sampling media are
transferred, the individual relinquishing the sample and receiving the sample, the date and time,
and the storage conditions (for carbonyls and PAHs samples) should be documented so the
history of the sample is traceable and can be reconstructed. Storage conditions for carbonyls and
PAHs samples must be monitored with a calibrated thermometer and storage records should
include unique identifiers for the thermometers monitoring the storage units.
Sample collection forms or other forms as defined by the monitoring agency may double as a
COC form provided they include sufficient space for documenting all sample transfers and
storage conditions.
If not already assigned prior to dispatching to the field, upon receipt at the laboratory each
specific field-collected sample medium (cartridge, filter, canister, etc. including all field QC)
must be uniquely identified for tracking within the laboratory. This unique identifier allows each
sample to be tracked to ensure proper storage within the laboratory and to avoid switching of
samples which can invalidate sample data.
3.3.1.3.8	Traceability of Reagents and Standard Materials. Each monitoring
organization must prescribe in its NATTS QAPP, or similar controlled document, the
information to be recorded and maintained for traceability of reagents and standard materials and
must codify the requirements for their labeling.
All reagents and standard materials utilized in the preparation and analysis of NATTS Program
samples must be of known concentration or purity as documented by a certificate of analysis
34

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(COA) or similar certification. Such certification documents must be retained. The one
exception to this is for deionized water which is sourced from a water polisher, for which records
of the maintenance must be maintained to demonstrate that the water is of appropriate quality.
When prepared in the laboratory, the source of all reagents must be documented (in a logbook or
similar) and be traceable to the certificates of analysis. Lot or batch numbers for each reagent
(acid, solvent, etc.) must be documented for all preparations. Critical volume measurements
(e.g. delivered volumes of stock standards, final volumes of diluted standards) must be
documented in the preparation log when used for reagent or standard preparation, including
unique identifiers (where applicable) for measurements by way of volumetric syringes,
mechanical pipettes, and volumetric flasks, among other methods. The conditions at which the
reagents and standards are stored must be documented, particularly for those reagents and
standards which require special conditions such as refrigeration or protection from light. If
maintenance of a specific temperature range or not-to-exceed temperature is required, the
temperature(s) of storage containeds) must be measured and documented at a prescribed
frequency (recommend minimally daily during normal working hours) and the calibration of
thermometers must be certified and traceable at the critical temperature (e.g. for a carbonyls
sample storage refrigerator, the thermometer must be calibrated at 4°C). A calibrated min-max
type thermometer or continuous monitoring is recommended to ensure that the not-to-exceed
temperature is maintained.
Expiration dates must be assigned to reagents and standards and must be set as the earliest
expiration date among any component comprising the reagent or standard. If the expiration date
is given as a month and year, the date after which the reagent or standard may not be used is
understood to be the last day of the indicated month. For reagents or standards which were not
assigned an expiration by the supplier, the monitoring agency may assign an expiration
(recommended not to exceed five years). The policy for assigning the expiration date when not
provided by the manufacturer must be prescribed in the monitoring agency QAPP, SOP, or
similar controlled document.
3.3.1.3.9	Labeling. Each NATTS monitoring organization must have a prescribed
procedure for labeling of all samples, standards, and reagents. Each must be uniquely identified
and the identifier clearly labeled on the applicable container (e.g., VOCs canister tag, DNPH
cartridge foil pouch, metals filter holder, PAHs cartridge transport jar, GC vial containing
solvent, etc.).
Standards and reagents must be minimally labeled to identity the contents (e.g., 69-component
VOC blend in nitrogen, 2 |ig/mL benzo(a)pyrene in hexane, 2% v/v nitric acid, etc.), and should
include the preparation date and expiration date. All standards and reagents prepared or mixed in
the laboratory must be traceable to a preparation log.
3.3.1.3.10	Early Warning Systems - Control Charts. Laboratories should employ
control charting where practical to track QC parameters. If used, the process of control charting
should be described in the NATTS QAPP, SOP, or similar controlled document. Parameters
suitable for control charting include concentrations measured in QC samples such as blanks,
laboratory control spikes, matrix spikes, secondary source calibration standards, internal
standards, and proficiency test results. Control charts may be prepared with spreadsheets and
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many LIMS incorporate control charting capabilities. Once implemented, control charts are
simple to maintain and are a valuable tool for evaluating trends and may provide an alert before
nonconformances occur. Control charts should be periodically updated and reviewed to ensure
data inputs are current and that associated control limits meet method-specified criteria. The
update frequency should be prescribed in the applicable controlled document.
3.3.1.3.11	Spreadsheets and Other Data Reduction Algorithms. While spreadsheets
and other automated or semi-automated data reduction algorithms, for instance, those contained
in LIMS software, are valuable tools for transforming and reducing data generated by sampling
and analysis instruments, they have limitations and may be sources of error. If a NATTS agency
in fact employs such processes it should prescribe the NATTS QAPP, SOP, or similar controlled
document the details for preparation, review, and control of data reduction spreadsheets or of
other non-commercial automated and/or semi-automated data transformation and reduction
algorithms and processes. Implementation of such processes will require an initial time
investment, but should minimize errors and subsequently increase the efficiency and speed of
data reporting. If an agency were to implement such processes, it should codify the relevant
procedures into its QAPP or other quality system document and may consider adoption of the
following best practices.
Where possible, manual entry of instrument data into spreadsheets and/or non-commercial
automated data transformation/reduction algorithms must be minimized. Rather, the direct
importation of data outputs from instruments into such systems is preferable so as to avoid
transcription errors. Furthermore, data reduction spreadsheets or other non-commercial
algorithms must be validated and locked/non-editable to ensure that critical formulas are not
inadvertently altered. The process of validation of the spreadsheet or non-commercial algorithm
must be codified in the quality system document such that it is known and verifiable that all
critical aspects of the data reduction procedure have been confirmed to be technically defensible,
valid, and error-free. This validation should be performed when the spreadsheet or non-
commercial algorithm is revised.
3.3.1.3.12	Software Validation, Testing, Updating, and Upgrading. Each agency
performing NATTS Program work should have prescribed within the agency NATTS QAPP,
SOP, or similar controlled document policies and procedures for testing, updating, and upgrading
computer software systems employed for data generation and manipulation such as
chromatography data systems (CDSs), LIMS, and other instrument software where applicable.
The policies and procedures should detail the responsible individuals, testing required, and
documentation to be maintained.
3.3.1.3.12.1 Software Validation
Off-the-shelf software packages such as spreadsheet programs are presumed to be validated. It is
strongly recommended that individual spreadsheets should be validated as described in Section
3.3.1.3.11. Other software packages such as CDS should undergo validation by manually
calculating values to ensure that software outputs match the expected result. Due to the
differences in algorithms or limitations to how software packages handle calculations, there may
be slight differences between commercial software package outputs and spreadsheets or other
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software systems. Such differences should be noted and addressed where possible if they impact
digits which are significant in the calculations. Records of software validation must be
maintained.
3.3.1.3.12.2	Software Testing
Once validated, software packages should be tested minimally annually and when updated or
upgraded to ensure that calculations are being performed as expected. This may be performed by
processing a previous dataset through the software and comparing the outputs for parity. The
rationale behind such testing is to ensure that software systems and calculation regimes have not
become corrupted. Discrepancies in outputs must result in corrective action to rectify the
discrepancies.
3.3.1.3.12.3	Software Updating and Upgrading
Software manufacturers periodically release software updates to correct bugs, improve the user
interface, or include new functionality, etc. Updates or upgrades installed should be documented
in a log and be verified for proper operation by the testing regime prescribed in Section
3.3.1.3.12.2. Agencies should verify that upgrades were performed and the date they were
performed.
3.3.1.3.13 Review of Records. To ensure that sample collection and analysis
activities were performed as prescribed, are documented completely and accurately, and to
identify potential nonconformances that may invalidate data, all logbooks, forms, notes, and data
must be reviewed by a second individual who has familiarity with the procedure but who did not
generate the record. Field site notebooks, site equipment maintenance logs, sample collection
forms, COC forms, laboratory preparation logs, analysis instrument logs, storage temperature
logs, and all other critical information must be reviewed on a periodic basis by an individual who
did not record the documentation. Each record should minimally be reviewed for legibility,
completeness, traceability, and accuracy (including hand calculations not performed by a
validated spreadsheet). It is also recommended that reviews should determine if the procedures
followed were codified and appropriate. These reviews must be documented, either within the
records themselves, or in a separate review notebook or form indicating the individual
performing the review, the materials reviewed, and when the review was performed. Details of
the review scope, schedule, responsible individuals, and required documentation must be
described in the NATTS QAPP, SOP, or similar controlled document. These reviews should
occur minimally quarterly and a best practice would be to conduct reviews monthly.
If documentation errors are noted during review, they should be corrected as soon as practical.
Correction of handwritten entries must be performed with a single line, the correct entry must be
made nearby or be traceable to an annotated footnote, the individual making the correction must
be identified by signature or initials, the notation must include the date the correction was made,
and the notation should include the rationale for the correction. Corrections to electronic logs
must likewise not overwrite the original record, must identify the individual making the
correction, must include the date of the correction, and should include the rationale for the
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correction. Further guidance on maintaining electronic logs is available in the EPA Technical
Note - Use of Electronic Logbooks for Ambient Air Monitoring. 5
Note that reviewing records as described in this section is a component of the data verification
process described in the next section, but should not be substituted for the data verification
process.
3.3.1.3.14 Data Verification and Validation. Data verification is the systematic
process for evaluating objective evidence (data) for compliance with requirements for
completeness and for correctness as stipulated by a specific method. Objective evidence consists
of the records such as sample collection forms, sample storage records, laboratory preparation
records, calibration records, analysis results, etc. Validation is the confirmation that verified data
have met specific intended use requirements, i.e., meeting DQO requirements prescribed in the
NATTS QAPP.6
Spurious data have an outsized influence on statistical analysis and modeling; thus, data must be
closely examined to ensure that concentration values accurately reflect air quality conditions at
the monitoring site through verification and validation. Monitoring organizations must not
censor (invalidate) data they consider to be anomalous or spurious. Data should only be
invalidated if they do not meet the critical specifications in the validation tables in Section 7 or
when there is a known problem with the data which would invalidate them. For data suspected
to be spurious or anomalous, they should be qualified appropriately when entered into AQS so
the end data user can decide the most suitable manner for handling the data.
Each monitoring organization must have processes and policies which must be described within
its NATTS QAPP or other quality systems document for data verification, data validation, and
the associated documentation that is generated and retained during the processes of verification
and validation of data. It is a best practice that NATTS agencies perform data verification in
accordance with the tables in Section 7 of this TAD where method-specific criteria may be
found. Additional information on implementing and structuring data validation and verification
policies and procedures is available in Guidance on Environmental Data Verification and Data
Validation, EPA QA/G-8, EPA/240/R-02-004 6
3.3.1.3.14.1 Data Verification
The data verification process begins when sample media are dispatched to the field for collection
and ends following final review of a completed data package. Verification includes many of the
aspects of data review discussed in Section 3.3.1.3.13 as well as additional QC checks such as
verification of proper sample handling and verification of calculations. Once data verification is
completed, data validation is conducted. Given in this section is a generic data verification
process that a NATTS agency may adopt. Data verification is not required, but is strongly
recommended.
Upon retrieval of samples in the field, the field operator verifies that sample collection
parameters comply with SOPs and documents the collection details on the field sample
collection form. At the laboratory, custody documentation is reviewed to ensure that sample
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collection documentation meets specification and does not exhibit anomalies which would
invalidate the collected sample. Laboratory analysts ensure that media have been stored properly
and that QC samples are prepared according to method specifications. Following acquisition of
the analytical data, the analyst reviews QC results as well as the acquired data to ensure proper
analyte identification and to verify that method-specified acceptance criteria are met. A peer
then reviews the entire data package beginning with sample collection and custody
documentation through preparation, analysis, and concentration calculations so as to ensure that
method procedures were properly followed, calculations are correct, and method-specific
acceptance criteria are met. At any point during the initial and/or peer review, errors must be
corrected and additional notes added to describe problems or anomalies in the sample collection
and analysis processes. QC failures or method deviations must be documented and appropriate
flags applied to the results so staff performing data validation may be alerted regarding data
which may be com prom i sed or require invalidation.
3.3.1.3.14.2 Data Validation
Data validation is performed following the data verification process and is a separate process
from the network-wide assessments made by data users to evaluate trends and assess whether
data meet MQOs. During validation data are evaluated by the monitoring agency for compliance
with specific use requirements which may include comparison of collocated sample results,
examination of meteorology data, sample collection notes, and custody forms, and review of
historical data for trends analysis and identification of outlier data. Attainment of the NATTS
MQOs should also be assessed by monitoring agencies to determine if the data will support
attainment of the NATTS DQO. Failure to attain the NATTS MQOs must prompt corrective
action. Given in the remainder of this section is a generic data validation process that a NATTS
agency may adopt. Note that data are not being validated if the monitoring agency is not
performing data validation since he EPA does not perform subsequent data validation.
An appropriate starting point for validating data involves preparing summary statistics by
calculating the central tendency of the data set along with the standard deviation and relative
standard deviation of the concentrations of each HAP. The central tendency may be calculated
as the arithmetic mean, geometric mean, median, or mode:
•	Arithmetic mean: The sum of the measured concentration values divided by the total
number of samples in the dataset.
•	Geometric mean: The nth root of the product of n concentration values.
•	Median: The concentration value represented by the midpoint of the dataset when the
concentration values are placed in numerical order. Fifty percent of the resulting
concentration values will be above this value and 50% will be below.
•	Mode: The concentration value with the highest frequency.
Once the summary statistics have been prepared, each HAP and combination of HAPs may be
evaluated using graphical techniques to identify anomalous data and outliers. Graphical
techniques permit comparison of concentrations of each H AP to the expected concentrations and
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relative concentrations of other HAPs to inspect for values which stand out. Time series plots,
scatter plots, and fingerprint plots, described below, are valuable tools for validating data.
•	Time series plots: Concentrations are plotted on the y-axis against collection date
(time) on the x-axis. Extreme or anomalous values are immediately identifiable in
individual HAP plots, and may be more powerful when multiple HAPs are plotted
together. HAPs which are typically emitted from the same type of source (i.e.,
benzene and toluene from mobile sources) and from different sources (i.e.,
formaldehyde and PMio nickel) can provide insight on whether concentration
anomalies are realistic to the collected sample or may be an artifact of the collection
or analysis of the sample.
•	Scatter plots: Concentrations of pairs of H APs are plotted such that each H AP (e.g.,
benzene and toluene) is dedicated to the y-axis or x-axis such that the coordinates of
each plotted point are set by the benzene and toluene concentrations measured during
a given sampling event. The resulting plots generally show points which are clumped
together such that they have a well-defined relationship. Points which lie outside of
the well-defined area are then generally identifiable and can be further investigated.
•	Fingerprint plots: Concentrations of all HAPs within a given class (e.g., VOCs,
carbonyls, etc.) are plotted on the y-axis against the molecular weight, alphabetical
order, or some other consistent order on the x-axis which enable discerning patterns
or identifying anomalies. Fingerprints prepared for each sampling event are
compared and will typically be very similar among events. Plots which show
markedly different patterns may indicate anomalous results. For instance, during a
specific sampling event a HAP may be observed at a concentration much higher or
much lower than expected given the typically observed pattern between concentration
and molecular weight (alphabetical order, etc.), and such is evidence of a spurious
result for this HAP for this sampling event.
Confidence is increased for concentration data which do not appear anomalous when plotted
using these graphical tools. For data which appear to be anomalous, they should be flagged for
follow up and the root cause investigated.
The free Data Analysis and Reporting Tool (DART) software was developed with EPA funding
and incorporates preparation of the graphical displays mentioned above. DART is available at
airnowtech.org at the following URL: fattp://airnowtech.org/dart/dartwelc m (all users must
have an account with username and password).
3.3.1.3.15 Reporting of Results to AQS. Each monitoring organization must
prescribe procedures and policies for the reporting of all applicable information generated in the
conduct of the NATTS Program to the EPA AQS database. AQS is a repository of data from
state, local, and tribal agencies as well as federal organizations. The stored data consist of
descriptions of monitoring sites and associated monitoring equipment, reported concentrations of
air pollutants, data flags, and calculated summary and statistical information.
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This section discusses reporting of data to AQS and provides details on the following monitoring
agency requirements. Monitoring agencies must:
•	Report NATTS data to AQS within 180 days from the end of the calendar quarter in
which samples were collected
•	Report concentration data for all Tier I NATTS required HAPs
•	Verify and validate data according to the monitoring agency policies
•	Report QA data (field blanks, trip blanks, collocated, duplicate, replicate analysis, and
lot blanks)
•	Qualify data appropriately in relation to the MDL (EPA plans to implement automatic
flagging for measured concentrations)
•	Add other qualifiers as necessary when data do not meet acceptance criteria
•	Report MDLs with the sample data
•	Report data in appropriate units in standard conditions (except PMio metals)
•	Verify data were input to AQS properly
The concentrations of all HAPs measured during the execution of the NATTS Program must be
input into AQS within 180 days from the end of the calendar quarter during which the applicable
air samples were collected. All data uploaded to AQS must have been previously verified and
validated per the requirements codified in the cognizant monitoring agency's quality system.
Data preparation and entry are also the responsibility of each participating monitoring
organization.
AQS permits entry of qualifier codes consisting of the following four different types:
Informational Only, Null Data Qualifier, QA Qualifier, and Request Exclusion. Request
Exclusion qualifiers do not apply to NATTS data. All uploaded data must be appropriately
qualified, as necessary, in AQS. More than one qualifier may be reported with a concentration
value to provide additional information regarding the applicable concentration result. However,
the null data qualifier flag must not be entered with other flags, as such a flag indicates that no
concentration data are reported. Invalidation of concentration results and the subsequent
assignment of a null qualifier code in AQS require careful consideration and should be consistent
with data review and reporting procedures in the monitoring agency QAPP. Data which do not
meet method QC requirements may still be of use and should be entered with the appropriate QA
qualifier code. AQS qualifier codes appropriate for qualification of NATTS data are listed in
Table 3.3-2 (excludes Null Data Qualifier codes).
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Table 3.3-2. AQS Qualifier Codes Appropriate for NATTS Data Qualification
Qualifier Code
Qualifier Description
Qualifier Type Code
1
Deviation from a CFR/Critical Criteria Requirement
QA
2
Operational Deviation
QA
3
Field Issue
QA
4
Lab Issue
QA
5
Outlier
QA
6
QAPP Issue
QA
7
Below Lowest Calibration Level
QA
CC
Clean Canister Residue
QA
CL
Surrogate Recoveries Outside Control Limits
QA
DI
Sample was diluted for analysis
QA
EH
Estimated; Exceeds Upper Range
QA
FB
Field Blank Value Above Acceptable Limit
QA
FX
Filter Integrity Issue
QA
HT
Sample pick-up hold time exceeded
QA
IC
Chem. Spills & Indust Accidents
INFORM
ID
Cleanup After a Major Disaster
INFORM
IE
Demolition
INFORM
IH
Fireworks
INFORM
II
High Pollen Count
INFORM
IJ
High Winds
INFORM
IK
Infrequent Large Gatherings
INFORM
IM
Prescribed Fire
INFORM
IP
Structural Fire
INFORM
IQ
Terrorist Act
INFORM
IR
Unique Traffic Disruption
INFORM
IS
Volcanic Eruptions
INFORM
IT
Wildfire-U. S.
INFORM
J
Construction
INFORM
LB
Lab blank value above acceptable limit
QA
LJ
Identification Of Analyte Is Acceptable; Reported Value Is An Estimate
QA
LK
Analyte Identified; Reported Value May Be Biased High
QA
LL
Analyte Identified; Reported Value May Be Biased Low
QA
MD
Value less than MDL
QA
MX
Matrix Effect
QA
ND
No Value Detected
QA
NS
Influenced by nearby source
QA
QX
Does not meet QC criteria
QA
SQ
Values Between SQL and MDL
QA
ss
Value substituted from secondary monitor
QA
sx
Does Not Meet Siting Criteria
QA
TB
Trip Blank Value Above Acceptable Limit
QA
XT
Transport Temperature is Out of Specs
QA
V
Validated Value
QA
VB
Value below normal; no reason to invalidate
QA
W
Flow Rate Average out of Spec.
QA
The most up-to-date AQS codes and descriptions, including qualifier codes and definitions, are
available at the following URL:
https://www.epa.gov/aqs/aqs-code-list
42

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Concentrations of HAPs uploaded to AQS must be flagged according to whether they are above
or below the sample quantitation limit (SQL) or method detection limit (MDL) thresholds.
Concentration data less than the laboratory MDL must be flagged with the QA qualifier code
MD, data greater than or equal to the MDL but less than the SQL (3.18-fold the MDL) must be
flagged using the QA qualifier code SQ. All concentration values for qualitatively identified
analytes, even those less than MDL, must be reported to AQS and must not be censored by
substitution of one half the MDL, by replacement with 0, or by any other method. Negative
concentrations must not be translated to zero for reporting purposes. Where qualitative
identification acceptance criteria are not met for a given HAP, its concentration must be reported
as zero and flagged as ND. The convention for reporting concentration data and the associated
QA flags are shown in Table 3.3-3.
Table 3.3-3. Required AQS Quality Assurance Qualifier Flags for Various
Concentrations Compared to a Laboratory's MDL and SQL
Concentration Level
Reported Value
Associated QA Flag
> SQL
measured concentration
no flag
> MDL but < SQL
measured concentration
SO
< MDL
measured concentration
MD
H AP not qualitatively identified
0
ND
The MDL for a given HAP must be reported to AQS along with the HAP's concentration or
AQS will reject the submission. The reported MDL should ideally be normalized to the
collected air volume for the respective air sample. Normalization of the MDL to the collected air
volume is required when the collected air volume for the sample is greater than 10% different
from the target collected air volume. If the total collected air volume is not within 10% of the
target collected air volume, the monitoring organization should take corrective action which may
involve troubleshooting the sampling unit and verifying calculations. For example, the target
collected air volume for carbonyls sampling at 0.75 L/min is 1.08 m3 and the formaldehyde
MDL is 0.052 |ig/m3 for this target volume. For a total collected sample volume of 0.95 nr\ the
collected volume is -12% lower than the target, and requires normalization of the formaldehyde
MDL as follows (MDL increases by the -12% to account of the reduced sample volume):
0.052 mg/m3 • 1.08 m3 = 0.059 (ig/m3
0.95 m3
Reporting units must be consistent across the NATTS network to ensure that data may be
statistically combined with minimal manipulation. HAPs must be reported in the following unit
conventions:
•	VOCs - parts per billion by volume (ppbv)
•	Carbonyls - mass per unit volume (e.g. |ig/m3 or ng/m3)
•	PAHs - mass per unit volume (e.g. |ig/m3 or ng/m3)
•	Metals - mass per unit volume (e.g. |ig/m3 or ng/m3)
All concentrations, with the exception of those for PMio metals, must be reported to AQS
corrected to the standard conditions of 760 mm Hg and 25°C. PMio metals data must minimally
43

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be reported in local conditions but may also be reported in standard conditions at the discretion
of the monitoring organization. Except for PMio metals, this requires that sites calibrate
sampling unit instruments in standard conditions or that conversion to standard conditions is
performed with average temperature and barometric pressure readings taken during sample
collection.
Sample collection must be performed from midnight to midnight local standard time (no
correction for daylight savings time) which may require adjustment of recorded collection times
generated by sampling unit clocks to ensure values are accurately input into AQS. Clock timers
controlling sampling unit operation must be adjusted so that digital timers are within ±5 minutes
of the reference time (cellular phone, GPS, or similar accurate clock) and mechanical timers
within ±15 minutes.
NATTS agencies are required to report data for each of the Tier I analytes listed in Table 1.2-1
and are also encouraged to report data collected for Tier II analytes. Careful attention must be
paid to coding of data uploaded to AQS to ensure that the five-digit parameter code is accurate
and that the associated units comply with those listed above.
NATTS sites may have numerous monitors collecting data for programs besides NATTS. Each
individual monitor of a given type (VOCs, carbonyls, PMio metals, and PAHs) and duplicate
samples collected from a single monitor are to be assigned a parameter occurrence code (POC)
by the state, local, or tribal agency (SLT). There is no guidance on how POCs are assigned by
SLTs and a survey of NATTS sites indicates that several monitors can be assigned the same
POC. Data uploaded to AQS indicate the assigned POC, but the POC does not indicate whether
the associated data are from a primary monitor, duplicate sample from the primary monitor,
duplicate sample from a duplicate monitor, or collocated sample. Due to the ambiguous nature
of POC assignment, each NATTS agency must prescribe and maintain a legend of POCs for
minimally each of the four monitor types required for NATTS in the annual network plan (ANP)
or other controlled document. The recommended convention is to assign a lower POC to the
primary monitor and a higher POC to the duplicate and/or collocated monitor.
QA data including, but not limited to, field QA samples such as field and trip blanks and
collocated and duplicate test samples, laboratory QA results from replicate analyses (as required
by the workplan), and lot blanks must be reported to AQS. AQS also accepts laboratory blanks
and laboratories are not required to, but may, report method blank data to AQS. Guidance for
reporting QA samples (blanks and precision samples - collocated, duplicate, and replicate
samples) is included in Appendix B.
Prior to submission of data to AQS, all data must be reviewed to ensure the parameter code,
POC, unit code, method code, and any associated qualifier or null codes are properly assigned. In
addition, the reported parameters should specify the NATTS network affiliation.
AQS instructions for data upload are described in the AQS User Guide and additional AQS
manuals and guides available at the following URL:
http://www3.epa.gin/ttn airs/airsags/manuals/
44

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Additional assistance is available by calling the AQS help line at (866) 41 1-4372.
3.3.1.3.15.1 Corrections to Data Uploaded to A QS
If it discovered during data validation, as a result of corrective action, or through other means
that erroneous data have been reported to AQS, the erroneous data must be deleted, and the
corrected data uploaded to AQS. EPA Region staff must be notified when the erroneous data are
discovered and SLTs must notify the EPA Region to correct the records in AQS when changes
are needed to large swaths of data (e.g. a calendar quarter) or data from previous calendar years
are to be altered. Monitoring agencies should also notify data users which may have provided
notification of data query (as is done for AQS data pulls for conducting the NATTS assessments
and data analysis for preparing the NAT A), as the updated data may impact the data user's
analysis outcomes.
3.3.1.3.16	Records Retention and Archival, and Data Backup. All records required
to reconstruct activities to generate the concentration data for NATTS Program samples must be
retained for a minimum of six years. The basis for the six-year retention period is that this
covers the two successive three-year periods over which trends in HAP concentrations are
determined. If problematic or anomalous data are observed during trends analysis, the archived
records will be available for review to investigate the suspicious data. Quality system documents
such as QMPs, QAPPs, and SOPs, sample collection and analysis records, maintenance logs,
reagent logs, etc. must also be retained for at least six years. Requirements for records retention,
including electronic records, must be prescribed in the QMP, agency NATTS QAPP, or similar
controlled policy document.
Electronic data must also be retained for a minimum of six years. Data generated by sampling
and analysis instruments, including all QA/QC data, as well as data stored in databases and/or in
a LIMS must be backed up on a periodic basis as defined in an applicable quality system
document such as the QAPP. Archived electronic data must be stored in a manner such that they
are protected from inadvertent alteration. Additionally, monitoring agencies must maintain
accessibility to the archived data which may include maintaining legacy software systems or
computers or may involve conversion of the data to a format which is compatible with current
computers and software systems. Monitoring agencies should consider the compatibility of the
archived data when upgrading or replacing computer systems and software to ensure the
archived data remain accessible.
3.3.1.3.17	Safety. While not strictly a quality system element, safety is integral in
ensuring the continued collection of quality data. Each monitoring organization must codify
appropriate safety requirements and procedures within the NATTS QAPP or similar controlled
policy document. For monitoring organizations with existing safety plans or programs, these
may be referenced within the QAPP. Safety plans should include information regarding safety
equipment, inspection frequency of safety equipment, and safety training frequency.
3.3.2 Standard Operating Procedures. Each monitoring organization conducting
NATTS Program work must develop and maintain SOPs, however named, which must describe
in detail the procedures for performing various activities needed to execute air sampling, sample
45

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analysis, data reduction, and data reporting, among others, for the NATTS program. It is not
acceptable to simply cite a method document (e.g., EPA Compendium Method TO-1 1 A) or
instrument manual as the SOP, although these documents may serve as the basis for an SOP and
may be referenced in the SOP. Instrument manuals and the compendium methods do not include
sufficient detail on the specific procedures and/or equipment information necessary to perform
the procedures and generally offer several different procedures or conventions for performing
activities or operating equipment. SOPs must reflect current practice and the work performed
must be in accordance with SOPs. SOPs must be written with sufficient detail to enable an
individual with limited experience with or knowledge of the procedure, but with basic
understanding of the procedure, to successfully perform the procedure when unsupervised.
Production, review, revision, distribution, and retirement of SOPs must conform to the
requirements prescribed by the monitoring organization's document control system as discussed
in Section 3.3.1.3.5.
SOPs can be developed in many formats but should minimally contain information regarding the
following, where applicable:
•	Title (e.g.. Collection of Ambient VOCs Samples in Stainless Steel Canisters)
•	Scope and Objectives (e.g., covers sample collection but not analysis)
•	References (e.g., EPA Compendium Method TO-11 A)
•	Definitions and Abbreviations
•	Procedures - instructions (usually step-by-step) for performing activities within the
scope of the SOP including information on required materials, reagents, standards,
and instruments; sample preparation; instrument calibration and analysis, and data
analysis and reporting procedures, among other information, as required
•	Interferences
•	Calculations
•	Quality control acceptance criteria with associated corrective actions
•	Safety information
•	Revision history
The author of each SOP must be an individual knowledgeable with the activity and the
organization's internal structure who has the responsibility for the veracity and defensibility of
the document's technical content. A team approach may be followed to develop the SOP,
especially for multi-tasked processes where experience of a number of individuals is critical to
the procedure. SOPs must be approved in accordance with Section 3.3.1.3.5 of this TAD and
must be revised when they no longer reflect current practices. At a minimum, SOPs are to be
reviewed by the author and a member of QA to determine if revisions are needed and these
reviews and revisions must be documented. The frequency for review is recommended to be
annually, but must not exceed three years, and the period must be prescribed in the monitoring
agency's NATTS QAPP, QMP, or similar controlled document. Once a new version is effective,
the previous version must be retired and may not be referenced for conducting procedures.
46

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3.4 References
1.	Environmental Protection Agency. (September 2005). Quality Assurance Guidance
Document. Quality Management Plan for the National Air Toxics Trends Stations. (EPA
Publication No. EPA/454/R-02-006). Office of Air Quality Planning and Standards.
Emission, Monitoring, and Analysis Division. Research Triangle Park, North Carolina.
Available at (accessed October 19, 2016):
https://www3.epa.gov/ttnamtil/files/ambieiit/airtox/iiattsqmp.pdf
2.	Environmental Protection Agency. (March 2001). EPA Requirements for Quality Assurance
Project Plans. EPA QA/R-5 (EPA Publication No. EPA/240/B-01 -003). Office of
Environmental Information, Washington, DC. Available at (accessed October 19, 2016):
hit; t >!\\ \\ \\ epa.gov/sites/prodiictioii/files/2016-06/documeiits/r5--firial 0 p»lf
3.	Environmental Protection Agency. (December 2002). Guidance for Quality Assurance
Project Plans. EPA QA/G-5 (EPA Publication No. EPA/240/R-02-009). Office of
Environmental Information, Washington, DC. Available at (accessed October 19, 2016):
https://www.epa.gov/sites/prodiiction/files/2015-06/dociiments/g5-firial.pdf
4.	Environmental Protection Agency. (May 2013). Quality Assurance Handbook for Air
Pollution Measurement Systems, Volume II. (EPA Publication No. EPA-454/B-13-003).
Office of Air Quality Planning and Standards, RTF, NC. Available at (accessed October 19,
2016): https://www3.epa.gov/ttnamtil/files/ambient/pm25/qa/QA.-Handbook-Yol4l ixlf
5.	Environmental Protection Agency. (April 20, 2016). Technical Note - Use of Electronic
Logbooks for Ambient Air Monitoring. Office of Air Quality Planning and Standards, RTF,
NC. Available at (accessed October 19, 2016):
https://www3.epa.gov/ttnamtil/files/policv/Electronic Logbook Final %204 20 16.pdf
6.	Environmental Protection Agency. (November 2002). Guidance on Environmental Data
Verification and Data Validation. EPA QA/G-8 (EPA Publication No. EPA/240/R-02-004).
Office of Environmental Information, Washington, DC. Available at (accessed October 19,
2016): https://www.epa.gov/sites/prodiiction/files/2015-06/documents/g8-final.pdf
47

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4.0: COLLECTION AND ANALYSIS METHODS
4.1	Method Detection Limits
The MDL as prescribed in 40 CFR Part 136 Appendix B was initially developed and applied to
wastewater analyses.1 Since then, this procedure has been applied to a variety of other matrices
and analysis methods to approximate the lowest concentration (or amount) of analyte that can be
reported with 99% confidence that the actual concentration (or amount) is greater than zero. As
can be seen below in Figure 4.1-1, the Gaussian curve represents analysis of contamination-free
method (matrix) blanks and the distribution of their concentration values around zero. The small
area of the blank values to the right of the MDL value (indicated by the vertical dashed line)
represent the 1% of values which would be considered false positives.
C
O
"<4—'
O
Q)
4—>
O
o
c
0
3
O"
a>
w
(1 % chance oi
I false positive
LL
Not drawn to scale
0 MDL
Concentration
Figure 4.1-1. Graphical Representation of the MDL and Relationship to a Series of Blank
Measurements in the Absence of Background Contamination
(Credit: Reference 2 as adaptedfrom Reference 3)
In practical terms, this MDL procedure provides a conservative detectability estimate and aims to
ensure that there is a 1% false positive rate - incorrectly reporting the presence of an analyte
when it is in fact absent - at the determined MDL concentration. In many cases the analyte will
be qualitatively identified (per, for example, the criteria given for the various analytical methods
in Section 4.2) at concentrations below the MDL with a signal distinguishable from instrumental
48

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noise. That is to say, the MDL procedure is not protective of false negatives, which is
incorrectly concluding that the analyte is absent when it is in fact present; in fact, 50% of the
time the analyte present at the MDL concentration will be measured at less than the MDL (the
compound will not be 'detected').4 This can be seen in Figure 4.1-2 - the solid Gaussian curve
represents a series of measurements at the MDL concentration. The measurements in the shaded
portion of the curve to the left of the MDL value are false negatives or values measured at less
than the MDL. Such values may be properly qualitatively identified despite being less than the
MDL value. Therefore, if an analyte is measured at the MDL concentration, the analyte is
present 99% of the time; however, for analytes measured at or less than the MDL concentration,
50% of the time the analyte may also be present.
50 % chance of
false negative •
sx t
0 MDL
	Concentration	
Figure 4.1-2. Graphical Representation of the MDL and Relationship to a Series of
Measurements at the MDL Value
(Credit: Reference 2 as adaptedfrom Reference 3)
In summary:
•	99% of the results measured > MDL are in fact greater than zero (there is a 1% false
positive rate, or chance that such measurements are not actually greater than zero)
•	50% of actual concentrations at the MDL will be reported as > MDL
•	50% of actual concentrations at the MDL will be reported as < MDL (they will be
false negatives) even though they may still be qualitatively identified and may still in
fact be valid identifications
49

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The MDL as described in 40 CFR Part 136 App B and in Reference 1 is a statistical estimate of
the lowest concentration at which there is a 99% chance that the concentration is greater than
zero. The MDL procedure is not simply a characterization of the noise of the instrument nor is it
a known level of accuracy ensured at the MDL concentration. The MDL is also not an estimate
of the precision or variability of the method. Moreover, the MDL is not simply a representation
of the analysis instrument sensitivity, also known as the instrument detection limit (1DL), as the
latter does not incorporate the potential effect of the matrix for samples taken through the
preparation process (such as extraction or digestion). The IDL establishes the lowest
concentration that may be measured with a defined confidence by the instrument, and knowing
the IDL is particularly helpful when troubleshooting the MDL process; however, the IDL does
not, and must not, replace the MDL.
There are known limitations to the 40 CFR Part 136 Appendix B MDL procedure, not the least
of which is that it is a "compromise between statistical respectability and requirements of cost
and time."2'3 More specifically for the NATTS program, the MDL procedure prescribed in this
TAD of spiking sample collection media in the laboratory does not explicitly take into account
the functionality of all portions of the method from collection through analysis. In particular,
conducting an MDL study through the probe is impractical for gases and not currently possible
for PMio metals and PAHs. To the extent feasible the impact of the sampling process on
detectability is minimized by strongly recommending that bias checks (zero and known standard
checks) are performed for carbonyls and VOCs field samplers.
The MDL concentration, as defined in 40 CFR Part 136 Appendix B, is determined statistically
by preparing and analyzing minimally seven separate aliquots of a standard spike prepared in the
method matrix. All portions of the method and matrix are to be included in the preparation and
analysis such that any matrix effects and preparation variability are taken into account. The
MDL procedure is an iterative process and, to be meaningful, the MDL procedure must be
performed as prescribed.
The MDL procedure adopted for the NATTSs program, which is described in detail in Section
4.1.3.1, builds upon the 40 CFR Part 136 Appendix B by adding some aspects of the proposed
method update rule (MUR).5 The MUR recognizes that the CFR procedure assumes that blank
values are centered around a concentration of zero and does not take into account the potential
for background contamination to be present in the sample collection media. If there is a
consistent background level of contamination on the sample collection media, as is typical for
carbonyls on DNPH cartridge media and metals elements on QFF media, measured blank values
will not be centered around zero; rather, they will be centered on the mean blank value. In such
cases the MDL must be defined as the value that is statistically significantly greater than the
blank value and the 40 CFR Part 136 Appendix B procedure will underestimate the MDL. This
occurs since the resulting standard deviation of the MDL replicates (and thus the calculated
MDL concentration) prepared in the presence of background contamination will not be different
than if there was no discernable background (standard deviation simply evaluates the difference
in the spread of the values, not the magnitude of the individual values). The MUR takes into
account the media background and adjusts for matrix blanks levels that are not centered around
zero.
50

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The MDL procedure prescribed in Section 4.1.3.1 adds few additional steps than those required
in the 40 CFR Part 136 Appendix B procedure. The net effect is that if there is little or no
contribution of background contamination on the sampling media, the MDL will be no different
than that determined previously by 40 CFR Part 136 Appendix B. If the sampling media (or
other aspects of the standard preparation of instrumental analysis procedures) contributes blank
contamination, the determined MDL will incorporate this average blank background
concentration. In all cases, the new MDL will be the concentration at which there is a 99%
chance that the actual reported concentration is statistically greater than the mean levels found in
blanks.
The DQ FAC Single Laboratory Procedure v 2.4 described in Section 4.1.3.2 is a similar
procedure to determine the MDL which takes into account the media background and other
potential background contributions. This procedure is more involved and is better suited to
laboratories with high sample throughput; however, laboratories may opt to determine MDLs via
this procedure.
The MlJR-modified 40 CFR Part 136 Appendix B method still has a 50% false negative rate,
which is generally recognized as unacceptable for the purposes of environmental monitoring.2'3
As a result, concentrations measured at less than the MDL, so long as the qualitative
identification criteria have been met, are valid and necessary for trends analysis and substituting
or censoring concentrations measured at less than MDL is not permitted. EPA recognizes that
many laboratories are not comfortable reporting concentrations measured less than the MDL as
these concentrations are outside of the calibrated range of the instrument and are associated with
an unknown and potentially large uncertainty. However, actual values reported at less than the
MDL are more valuable from a data analyst's standpoint and far superior than censored or
substituted values. Addition of qualifiers as prescribed in Section 3 .3 .1.3 .15 and in Table 3 .3-1
indicates when values are near, at, and below detection limits and are therefore associated with
larger uncertainties.
4.1.1 Frequency of Method Detection Limit Determination. MDLs must be determined
minimally annually or when changes to the instrument or preparation procedure result in
significant changes to the sensitivity of the instrument and/or procedure. Examples of situations
where redetermination of the MDL is required include, but are not limited to:
-	Detector replacement
-	Replacement of the entire analytical instrument
-	Replacement of a large (e.g. > 50%) portion of an agency's canister fleet
Changing the cleaning procedure for sample collection media or lab ware which
results in a marked reduction in contamination levels
4.1.2 MDL Measurement Quality Objectives. In order to ensure that measurements of
air toxics in ambient air are sufficiently sensitive to assess trends in concentrations which may
result in health effects due to chronic exposures, a minimum required method sensitivity, or
MDL MQO, has been established for each of the core NATTS analytes. Though few changes
have been made to MDL MQOs since the beginning of the NATTS Program, as new toxicology
data are available, MDL MQOs may be adjusted. The annual NATTS network workplan
51

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template includes the most up-to-date MDL MQO for each core analyte. Laboratories must meet
(be equal to or less than) the MDL MQO listed in the most recent NATTS workplan.
The NATTS MDL MQOs are based on concentrations to which chronic exposures may result in
unacceptable health risks. While analytical methods prescribed in this TAD are capable of
meeting the MDL MQOs, MDLs may be elevated above the MDL MQOs due to background
contamination. The convention listed in 40 CFR Part 136 Appendix B accounted for
instrumental limitations during the determination of MDLs but did not consider the background
or interferences, which, in certain instances, may be several-fold higher than the MDL MQO. As
a result, the MUR MDL procedure has been adopted by the NATTS program to provide a more
realistic threshold of detection given the limitations of the method and background
concentrations attributable to the collection media and analytical instrumentation. The decision
to include portions of the MUR for MDL determination for the NATTS Program was carefully
weighed by examining historical data from the NATTS network and comparing typical media
background levels to evaluate the percentage of data which would additionally be coded as less
than the laboratory MDL. The results of the examination indicated that a minimum additional
amount of concentration data would be marked as less than the MDL when reported to AQS.6
NATTS Tier I core analytes and the concentrations as of March 2015 that correspond to 10"6
cancer risk levels, to noncancer risk hazard quotients (HQs) of 0.1, and to MDL MQOs are listed
in Table 4.1-1. Refer to the latest NATTS workplan template for the most up-to-date values.
Table 4.1-1. Concentrations of the NATTS Core Analytes Corresponding to
a 10"6 Cancer Risk, a Noncancer Risk at a HQ of 0.1, and to the MDL MQO
Core Analyte
Cancer Risk 10 6
Gig/m3)
Noncancer Risk at
HQ = 0.1
(Hg/m3)
MDL MQO
(Hig/m3)
(ppbv)
Acrolein
-
0.0020
0.090
0.039
Benzene
0.13
3.0
0.13
0.041
1,3-Butadiene
0.030
0.20
0.10
0.050
Carbon tetrachloride
0.170
19
0.17
0.027
Chloroform
-
9.8
0.50
0.10
T ctrachlorocthvlcne
3.8
4.0
0.17
0.025
T richloroethylene
0.21
0.20
0.20
0.037
Vinyl chloride
0.11
10
0.11
0.043
Acctaldchvde
0.45
0.90
0.45
0.25
Formaldehyde
0.080
0.080
0.080
0.065
Benzo(a)pyrene
0.00091
0.30
0.00091
NA
Naphthalene
0.029
0.029
0.029
NA
Arsenic (PMio)
0.00023
0.0030
0.00023
NA
Beryllium (PMio)
0.00042
0.0020
0.00042
NA
Cadmium (PMio)
0.00056
0.0020
0.00056
NA
Lead (PMio)
-
0.015
0.015
NA
Manganese (PMio)
-
0.0050
0.0050
NA
Nickel (PMio)
0.0021
0.00081
0.0021
NA
4.1.3 Determining MDLs. MDLs may be determined via one of two procedures. The first
procedure in Section 4.1.3.1 is adopted from updates pending at the time this document was
revised, an update to the MDL procedure described in 40 CFR Part 136 Appendix B, the MUR. 5
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The second procedure in Section 4.1.3.2 is to determine MDLs via the procedure described in the
December 2007 Report of the Federal Advisory Committee on Detection and Quantitation
Approaches and Uses in Clean Water Act Programs.' Both methods incorporate media blank
background levels in the determination of analyte-specific MDLs.
MDL studies must be determined for each instrument employed to analyze samples for the
NATTS Program. For laboratories utilizing multiple instruments for a given method, MDL
studies must be performed for each instrument (the same samples or extracts may be used for all
instruments). In instances where multiple instruments are employed for reporting NATTS
Program results for the same analyte class (e.g., two or more HPLC-ultraviolet [UV]
instruments), there are two conventions for how to report the MDLs. The preferred convention
is to maintain an MDL for each instrument and report the respective MDL from the instrument
on which a given sample was analyzed. Alternatively, the most conservative (highest) MDL
from the multiple instruments can be reported - though this may not reflect the MDL associated
with the sample analysis. It is not appropriate to average the MDL values for reporting.
4.1.3.1 MDLs via 40 CFR Part 136 Appendix B - Method Update Rule. The MDL
procedure described in this section is adopted from the procedure as given in 40 CFR Part 136
Appendix B with several changes, based on those proposed in the CFR on February 19, 2015, to
explicitly include in the MDL the background (i.e. contamination) contribution of the sample
collection media and to incorporate temporal variability in laboratory preparation and instrument
performance.5 The preliminary work on the MUR identified measuring metals on air filters as an
example of where the 40 CFR Part 136 Appendix B method did not generate a realistic
concentrations level for the MDL value due to the elevated background contamination on the
filter media.
A minimum of seven spiked samples and seven method blanks must be prepared in matrix over
the course of a minimum of three different preparation batches. A batch is defined as a group of
samples prepared on one day, therefore three different preparation batches would require
preparation on three separate days. To properly characterize the variability in preparation, the
dates of preparation should be spread out such that they are not consecutive. Analysis of these
blanks and spikes must similarly be conducted over the course of three different analysis batches
where each sample is only analyzed once. Again, a batch is defined as a group of samples
analyzed on one day. Spreading the preparation and analysis over multiple preparation batches
and across analysis days is intended to incorporate the variability of both sample preparation and
analytical instrumentation that occurs over time. It is preferable to determine an MDL that is
representative of the laboratory's capability than to have an unreal istically low MDL determined
by selecting the best sampling media (i.e. canisters) and attempting to generate the lowest MDL
value possible. Two MDL values are calculated, one MDL for the spiked samples according to
the convention in 40 CFR Part 136 Appendix B (MDLsp) and one MDL for the method blanks
which includes the media background contribution (MDLb).
The first step is to select a spiking level for preparing the MDL spiked samples. If too low of a
spiking level is chosen, the analyte may not be reliably detected. If too high of a spiking level is
chosen, the variability of the method near the actual limits of detection may not be properly
53

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characterized. An appropriate spiking level may be selected by considering the following (in
order of importance):
1.	The concentration at which the instrument signal to noise ratio is three- to five-fold
for the analyte.
2.	The concentration at which qualitative identification criteria for the analyte are lost
(note that this will be approximately the concentration determined from the MDL
process absent of blank contamination).
3.	Analysis of a suite of blank samples - calculate the standard deviation of the
measured concentration and multiply by 3.
4.	Previously acceptable MDL studies and related experience.
Note that the MDL spiking level should not be within the calibration curve; rather, the MDL
spiking level should be less than the lowest calibration standard in order to best approximate the
MDL. Concentrations within the calibration curve are required to meet precision and bias
acceptance criteria and are of a high enough concentration that qualitative identification is
certain.
The second step is to prepare the seven or more separate spiked samples (at the level determined
in the first step) and seven or more method blank samples. In order to best mimic field-collected
samples, each spiked and blank sample must include, to the extent feasible, all portions of the
sample matrix and be subjected to the same procedures performed to process field samples in
preparation for analysis. Prepare method blanks and spiked samples over the course of three
different preparation batches preferably on non-consecutive days.
An efficient method to determine the MDL following this convention is to prepare and analyze
an MDL sample on a continuous basis with typical sample batches prepared over the course of
several weeks or months. In this scenario, one (or up to three) spikes would be prepared at the
time of sample batch preparation and after seven or more data points have been collected for the
MDL spikes and for the associated method blanks (which are already required with each
analytical batch), the MDL could be calculated. This would alleviate the need to dedicate a
significant contiguous block of time to preparing and analyzing MDL samples and method
blanks. The following must be taken into consideration during preparation of the MDL samples:
1.	Spiked samples must be prepared in matrix (DNPH cartridge, canister, PAH cartridge
with quartz fiber filter, or metals Teflon* filter or QFF strip).
2.	Selection of media should include as much variety as possible (e.g., different canister
manufacturers or individual DNPH cartridges selected from different boxes or lots) to
best characterize the variability of the method attributable to the use of media
representative of field-collected samples.
3.	Blank media which do not meet cleanliness criteria for a given analyte should trigger
root cause analysis to determine the source of the contamination and should not be
used to determine the method blank portion of the MDL. Cleanliness criteria are
given in Tables 4.2-3, 4.3-4, 4.4-2, and 4.5-3 for VOCs, carbonyls, metals, and PAHs
54

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collection media, respectively. Of particular concern are background levels of
contaminants in canisters and on PUF/XAD cartridges resulting from insufficient
cleaning. For DNPH cartridges, media background levels should meet the criteria
specified in Method TO-11A (duplicated in Table 4.3-2). Metals quartz fiber filter
media typically show elevated background levels of certain elements such as
chromium, nickel, manganese, and lead. It is not possible to decrease the background
levels of these three elements on QFFs, though EPA is working with manufacturers to
reduce the amount of background contamination on the filter media.
The third step is to analyze the samples against a valid calibration curve. QC criteria for the
analytical sequences must be met (blanks, laboratory control sample [LCS], calibration checks,
etc.). Analyze the samples over the course of minimally three different analytical batches.
1.	Perform all MDL calculations in the final units applicable to the method.
2.	Calculate the MDL of the spiked samples, MDLsp:
a.	Following acquisition of the concentration data for each of the seven or more
spiked samples, calculate the standard deviation of the calculated
concentrations for the spiked samples (%>). Include all replicates unless a
technically justified reason can be cited (faulty injection, unacceptably low
internal standard response, etc.), or if a result can be statistically excluded as
an outlier.
b.	Calculate the MDL for the spiked samples (MDLsp) by multiplying ssp by the
one-sided student's T value at 99% confidence corresponding to the number
of spikes analyzed according to Table 4.1-2. Other values of T for additional
samples (n > 13) may be found in standard statistical tables.
MDLsp = Asp * T
Table 4.1-2. One-sided Student's T Values at 99% Confidence Interval
number of MDL
samples (n)
degrees of
freedom
v(n-1)
student's T
value
7
6
3.143
8
7
2.998
9
8
2.896
10
9
2.821
11
10
2.764
12
11
2.718
13
12
2.681
c. Compare the resulting calculated MDLsp value to the nominal spiked amount.
The nominal spiked level must be greater than MDLsp and less than 10-fold
MDLsp, otherwise the determination of MDLsp must be repeated with an
adjusted spiking concentration. For MDLsp values greater than the nominal
spike level, the MDL spiking level should be adjusted higher by
55

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approximately two or three-fold. For nominal spike levels which are greater
than the 10-fold the MDLsp, the MDL spiking level should be adjusted lower
by approximately two or three-fold.
Calculate the MDL of the method blanks, MDLt>:
a.	If none of the method blanks provide a numerical result for the analyte, the
MDLb does not apply. A numerical result includes both positive and negative
results for analytes which are positively identified. Non-numeric values such
as "ND" would result when the analyte is not positively identified. Only
method blanks that meet the specified qualitative criteria for identification
(signal to noise, qualifier ion presence, etc.) are to be given a numerical result.
b.	If the method blank pool includes a combination of non-numeric (ND) and
numeric values, set the MDLb to equal the highest of the method blank results.
If more than 100 method blank results are available for the analyte, set the
MDLb to the level that is no less than the 99th percentile of the method blanks.
In other words, for n method blanks where n > 100, rank order the
concentrations. The value of the 99th percentile concentration (n-0.99) is the
MDLb. For example, to determine MDLb from a set of 129 method blanks
where the highest ranked method blank concentrations are ... 1.10, 1.15, 1.62,
1.63, and 2.16, the 99th percentile concentration is the 128th value (129 0.99 =
127.7, which rounds to 128), or 1.63. Alternatively, spreadsheet programs
may be employed to interpolate the MDLb more precisely.
c.	If all concentration values for the method blank pool are numeric values,
calculate the MDLb as follows:
i.	Calculate the average concentration of the method blanks (xb).
ii.	Calculate the standard deviation of the method blank concentrations, Sb.
iii.	Multiply Sb by the one-sided student"s T value at 99% confidence
corresponding to the number of blanks analyzed according to Table 4.1-2.
Other values of T for additional samples (n > 13) may be found in
standard statistical tables.
iv.	Calculate MDLb as the sum of Xb and the product of Sb and the associated
student's T value:
MDLi, = Xb+ si, T
Compare MDLsp and MDLb. The higher of the two values is reported as the
laboratory MDL for the given analyte.
If the MDL is determined as the MDLsp, laboratories should perform verification of
the determined MDL by:
a. Preparing one or more spiked samples at one to five-fold the determined MDL
and analyze the sample per the method to ensure the determined MDL is
reasonable. Recall that at the MDLsp concentration there is a 50% chance that the

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analyte will not be detected; however, the analyte should be detected at two- to
five-fold the determined MDL.
b.	Developing reasonable acceptance criteria for the MDL verification. For
example, an MDL verification that recovers 2% of the nominal amount is not
realistic, nor is one that recovers 300%. An appropriate starting point for
acceptance limits is to double or triple the acceptance window prescribed by the
method for the given analyte. For example, TO-15 normally permits benzene
LCS recoveries to be 70 to 130% (± 30% error), therefore doubling the MDL
verification acceptance limits would permit 40 to 160% recovery. Note that for
collection media with a significant background contamination, blank subtraction
may be necessary to evaluate the recovery of the MDL verification sample.
c.	Examining the MDL procedure for reasonableness if the verification sample is
outside of the laboratory-defined acceptance criteria. Such an examination might
include investigating the signal-to-noise ratio of the analyte response in the spiked
samples, comparing the MDL to existing instrument detection limits (if known -
discussed below), and relying on analyst experience and expertise to evaluate the
MDL procedure and select a different spiking level. The MDL study should then
be repeated with a different spiking level.
Troubleshooting may include determination of the instrument detection limit
(1DL) to evaluate whether the poor or elevated recovery is due to the instrument.
The IDL is determined by analyzing seven or more aliquots of a standard,
calculating the standard deviation of the measurements, and multiplying the
standard deviation by the appropriate student's T value. IDL samples are to be
prepared in the same matrix as calibration standards and are not processed
through sample collection media as is done for MDL spiked samples (e.g. for
TO-1 1A and TO-13 A, the standard would be in solvent, for TO-15 the standard
would be typically in a single canister, and for 103.5 metals analysis the standard
would be prepared in the aqueous acid matrix).
Example calculation:
A laboratory is determining the MDL for formaldehyde by TO-1 1A by spiking commercially-
prepared DNPH cartridges. The analyst spiked eight cartridges with formaldehyde-DNPH at
0.030 |ig/cartridge (in terms of the amount of the free formaldehyde) over three separate
preparation batches. These eight spiked cartridges and eight additional method blank cartridges
were extracted over three different dates. Results were analyzed over three different analysis
batches per Method TO-1 1A yielding the following results:
57

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Method
Cartridge
Number
Preparation Batch
and Date
Analysis Batch
and Date
Spikes
(jig/cartridge)
Blanks
(jig/cartridge)
1
A - September 12, 2015
QR9 - September 13
0.1685
0.1412
2
A - September 12, 2015
QR9 - September 13
0.1651
0.1399
3
A - September 12, 2015
QR9 - September 13
0.1701
0.1402
4
B - September 19, 2015
QR12 - September 21
0.1673
0.1405
5
B - September 19, 2015
QR12 - September 21
0.1692
0.1408
6
C - September 28, 2015
QR16 - September 29
0.1686
0.1403
7
C - September 28, 2015
QR16 - September 29
0.1705
0.1402
8
C - September 28, 2015
QR16 - September 29
0.1696
0.1410
The average (x) and standard deviation (s) of measured formaldehyde mass were determined for
both the spikes and the method blanks (all in units of |ig/cartridge):
xSp = 0.1686
xi, = 0.1405
.s'sp = 0.0017
Sb = 0.0004
To calculate the MDLsp, the standard deviation of the spiked aliquots is multiplied by the
associated student's T. The student's T value for eight aliquots is 2.998, corresponding to seven
degrees of freedom (8 - 1 = 7):
MDLsp = 0.0017 |ig/cartridge • 2.998
= 0.0051 |ig/cartridge
The MDLSp is subsequently verified to be less than the spike level, and the spike level is
confirmed to be less than 10-fold the MDLsp:
MDLsp < spike level < 10-fold MDLsp
0.005 1 |ig/cartridge < 0.030 |ig/cartridge < 0.05 1 |ig/cartridge
Observe that the determinedMDLsp is less than the background level offormaldehyde (5c h
0.1405 jug cartridge) on the DNPH cartridge media; such indicates that the MDLsp is biased low
and that background levels must be taken into account.
To calculate the MDLb, the standard deviation of the blank measurements is multiplied by the
associated student's T and this product is added to the average blank value, Xb:
MDLb = 0.0004 |ig/cartridge • 2.998 + 0.1405 |ig/cartridge
= 0.1417 |ig/cartridge
58

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The MDLSp and MDLb are compared to determine which is greater, and the greater of the two
values is reported as the laboratory MDL for the specific analyte.
0.1417 |ig/cartridge > 0.0051 |ig/cartridge
In this case, the formaldehyde MDLb of 0.1417 |ig/cartridge is greater than the MDLsp of 0.0051
|ig/cartridge, and is reported as the laboratory MDL for formaldehyde as measured by Method
TO-11A.
4.1.3.2 MDLs via DQ FACSingle Laboratory Procedure v 2.4J The MDL procedure
described in this section involves examination and manipulation of historical method blank data
to derive the MDL. This procedure must be performed only with method blanks that include all
media contributions and processing procedure elements. Also, method blank analyses which
were the result of laboratory preparation or analysis errors must not be included.
The DQ FAC procedure requires that historical method blank data be examined to verify that at
least 50% of the results are a numerical value (zero, positive concentration, or negative
concentration). If fewer than 50% of the method blank values are numerical, or, stated another
way, if 50%) or more of the values are reported as nondetects, use the procedure described above
in Section 4.1.3.1. Once it is determined that the DQ FAC method is applicable, assign method
blanks without a numerical value (i.e., non-detect) as zero. Calculate the standard deviation of
the included method blanks. A minimum of seven method blanks meeting these criteria is
required within the calendar year. If results of more than seven method blanks within the year
meet these criteria, all such method blank data should be included in the evaluation.
Calculate the MDL as follows:
MDL = xmb + s K
where:
xmb = mean result of the method blanks
s = standard deviation of the method blanks
K = is a multiplier for a tolerance limit based on the 99th percentile for n-1
degrees of freedom according to Table 4.1-3.
Note that if xmb is a negative value, substitute zero for this value.
If 5% or more of the blank results are greater than the MDL, raise the MDL as follows:
1.	To the highest method blank result if less than 30 method blank results are available.
2.	To the next to highest method blank result if 30 to 100 method blank results are
available.
3.	To the 99th percentile, or the level exceeded by 1% of all method blank results, if there
are more than 100 method blank results available.
59

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Only method blanks that meet the specified qualitative criteria for identification (signal to noise,
qualifier ion presence, etc.) are to be given a numerical result.
Table 4.1-3. K-values for 11 Replicates
n
K
n
K
n
K
n
K
7
6.101
30
3.317
53
2.993
76
2.855
8
5.529
31
3.295
54
2.977
77
2.851
9
5.127
32
3.273
55
2.970
78
2.847
10
4.829
33
3.253
56
2.963
79
2.843
11
4.599
34
3.234
57
2.956
80
2.839
12
4.415
35
3.216
58
2.949
81
2.836
13
4.264
36
3.199
59
2.943
82
2.832
14
4.138
37
3.182
60
2.936
83
2.828
15
4.031
38
3.167
61
2.930
84
2.825
16
3.939
39
3.152
62
2.924
85
2.821
17
3.859
40
3.138
63
2.919
86
2.818
18
3.789
41
3.125
64
2.913
87
2.815
19
3.726
42
3.112
65
2.907
88
2.811
20
3.670
43
3.100
66
2.902
89
2.808
21
3.619
44
3.088
67
2.897
90
2.805
22
3.573
45
3.066
68
2.892
91
2.802
23
3.532
46
3.055
69
2.887
92
2.799
24
3.494
47
3.045
70
2.882
93
2.796
25
3.458
48
3.036
71
2.877
94
2.793
26
3.426
49
3.027
72
2.873
95
2.790
27
3.396
50
3.018
73
2.868
96
2.787
28
3.368
51
3.009
74
2.864
97
2.784
29
3.342
52
3.001
75
2.860
98
2.782
60

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4.1.4
References
1.	Glaser, J. A., Foerst, D. L., McKee, G. D., Quave, S. A., & Budde, W. L. (1981). Trace
analyses for wastewaters. Environmental Science and Technology, I5{ 12), 1426-1435.
2.	Boyd, R. K., Basic, C., & Bethem, R. A. (2008). Trace Quantitative Analysis by Mass
Spectrometry. West Sussex, England: John Wiley and Sons.
3.	Childress, C. J. O., Foreman, W. T., Connor, B. F., & Maloney, T. J. (1999). New Reporting
Procedures Based on Long-Term Method Detection Levels and Some Considerations for
Interpretations of Water-Quality Data Provided by the U.S. Geological Survey National
Water Quality Laboratory - Open-File Report 99-193. US Geological Survey. Available at
http://water.usgs.gOY/owq/QFR 99-193/, accessed October 12, 2016.
4.	Keith, L.H. (1992). Environmental Sampling and Analysis: A Practical Guide. Chelsea, MI:
Lewis Publishers, pp. 93-1 19.
5.	Proposed Method Update Rule to 40 CFR Part 136, Federal Register Volume 80, No. 33.
February 19, 2015. Available at https w w w.gpo.go \ i \ s/pkg/FR-2015-02-19/pdf/201
02841.pdf, accessed October 12, 2016.
6.	Turner, D. J. and MacGregor, I. C., (2016). How Adoption of the Method Detection Limit
Method Update Rule Will Impact the Reporting of Concentrations of Air Toxics in Ambient
Air. Paper presented at the Air and Waste Management Association Air Quality
Measurement Method and Technology Conference, Chapel Hill, NC, March 15, 2016.
7.	Report of the Federal Advisory Committee on Detection and Quantitation Approaches and
Uses in Clean Water Act Programs, Submitted to the US Environmental Protection Agency,
Final Report 12/28/07. Appendix D, pages D-1 through D-9.
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4.2
VOCs - Overview of EPA Compendium Method TO-15
Each agency must codify in an appropriate quality systems document, such as an SOP, or
equivalent, its procedures for performing VOC sampling, canister cleaning, and analysis.
Various requirements and best practices for such are given in this section. Note that regardless
of the specific procedures adopted, the method performance specifications as given in Section
4.2.12 must be met.
Of the 188 HAPs listed in Title 111 of the CAA Amendments of 1990, 97 of these are VOCs.
VOCs are defined as organic compounds having a vapor pressure greater than 10"1 Torr at 25°C.1
VOC air toxics ambient air concentrations are typically measured at the single part per trillion
(ppt) to single ppb level. Measurement of these VOCs is based on the techniques described in
EPA Compendium Method TO-151'2, which describe collection of whole air samples into
evacuated stainless steel canisters followed by preconcentration of the volatiles for analysis via
GC/MS. When initially released, TO-15 indicated the lower limit for concentration
measurement was approximately 0.5 ppbv. However, with newer more sensitive mass
spectrometer detectors, much lower detection limits are achievable such that the MDL MQOs
listed in Table 4.1-1 can be attained. Due to the lack of current and specific guidance for
measuring low (sub-ppbv) levels of VOCs in ambient air, at the time of this TAD's release, EPA
was collecting public comments to revise TO-15 to include techniques and instrumentation that
permit sub-ppbv measurements of VOCs in ambient air. Much of the guidance listed in this
section are anticipated to be included in EPA's update of TO-15.
4.2.1 General Description of Sampling and Analytical Methods. An MFC and/or
critical orifice regulates the flow of ambient atmosphere into an evacuated passivated stainless
steel canister at a known, constant rate over the course of 24 hours. Following completion of
collection, the canister is transported to a laboratory for analysis within 30 days of collection.
Previous studies suggest that most compounds analyzed via TO-15 are stable for up to 30 days in
passivated stainless steel canisters;3,4 however, the condition of the wetted surfaces of each
individual canister is likely to influence the stability of the VOCs. Analysis of the sample as
soon as possible after collection is strongly recommended to minimize changes of the collected
sample, especially for HAPs such as acrolein, 1,3-butadiene, and carbon tetrachloride, among
others.
VOCs are identified and quantified via cryogenic preconcentration GC/MS and a typical analysis
scheme is as follows. A known volume of the whole air (an air parcel from which gases have not
been removed and are completely captured for sample collection) is passed through and the
VOCs are cryogenically trapped onto a sorbent bed while N2, O2, Ar, CO:, and to the extent
possible, H2O are selectively removed. The volume trapped is measured via MFC or by the
change in pressure of a known volume downstream of the sorbent trap. The sample introduction
pathway and sorbent bed are then swept with dry inert gas (such as helium) to remove water,
while the VOCs are retained on the cold sorbent. After the preconcentration and dehydration,
the sorbent is heated to desorb the VOCs and the VOCs entrained in a carrier gas stream where
they are refocused and subsequently introduced onto the GC column for separation. After
separation on the column, VOCs are ionized in a quadrupole, ion trap, or time of flight (TOF)
MS which detects the ion fragments according to their mass to charge (m/z) ratio. The responses
62

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of the ion fragments are plotted against the retention time and compared to the standard
chromatogram to identify the compounds in the sample based on retention times and ion
fragments of standards analyzed under the same chromatographic and MS conditions.
Method TO-15 addresses sampling of VOCs such that integration of the sample results in a final
canister pressure is subambient (< 14.7 psia, or less than the typical ambient atmospheric
pressure at the field location) or above ambient (> 14.7 psia, or above the typical ambient
atmospheric pressure at the field location). Previous versions of this TAD have disallowed
superambient sampling since such is thought to result in depressed recoveries of hydrophilic
polar VOCs due to their dissolution into condensed water. However, many of the sites in the
NATTS network collect canisters at superambient pressures. Due to a lack of definitive studies
demonstrating one method to be superior, this revision of the TAD permits pressurized sampling
but strongly recommends that collected canister pressures remain less than or equal to 3 psig
(-17.7 psia) to minimize the potential for water condensation. Regardless of the chosen final
canister pressure, each agency is responsible for ensuring that method performance specifications
are met, and specifically that method precision and bias are acceptable for their selected
combination of sampling instrument; final canister pressure; canister type; and preconcentration,
water management, and analysis techniques.
A previous study by McClenny et al.5 indicates that ambient air samples collected above
atmospheric pressure may exhibit condensation on the interior canister surfaces. Liquid water
inside the canister decreases precision from canister reanalysis since the amount of condensation
decreases as air is removed from the canister, and the pressure decreases, which changes the
equilibrium of analytes between the liquid and gas phases. For monitoring agencies collecting
samples to superambient pressure, samples should not be pressurized above 3 psig to minimize
the condensation of liquid water inside the canister.
The calibration and tuning of the MS must be monitored and compensated for by the analysis of
internal standards (IS) with each injection and analysis of continuing calibration standards
minimally every 24 hours of analysis (recommended every 10 sample injections and concluding
each sequence).
The VOCs including, but not limited to, those in Table 4.2-1 may be determined by this method.
63

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Table 4.2-1. VOC Target Compounds and Associated Chemical Abstract
Service (CAS) Number via Method TO-15
Target Compound
CAS #
acetone
67-64-1
acrolein a b
107-02-8
acrylonitrile
107-13-1
benzene ab
71-43-2
bcn/vl chloride
100-44-7
bromodichloro methane
75-27-4
bromoform (tribromomethane)
75-25-2
1,3-butadiene a b
106-99-0
2-butanone (methyl ethyl ketone)
78-93-3
carbon disulfide
75-15-0
carbon tetrachloride (tetrachloromethane)a b
56-23-5
chlorobenzenc
108-90-7
chloroform (trichloromethane)a b
67-66-3
cyclohexane
110-82-7
dibromochloro methane
124-48-1
1,2-dibromoethane b
106-93-4
1,2-dichlorobenzene
95-50-1
1,3 -dichlorobenzene
541-73-1
1,4-dichlorobenzene
106-46-7
dichlorodinuoromethane (Freon-12)
75-71-8
1,1-dichloroethane
75-34-3
1.2-dichlorocthane b
107-06-2
1,1 -dichloroethene
75-35-4
cis-1.2-dichloroethcnc
156-59-2
trans-1,2-dichloroethene
156-60-5
1.2-dichloropropane b
78-87-5
cis-1.3-dichloropropcne b
10061-01-5
trans-1.3-dichloropropcne b
10061-02-6
1,2-dichlorotetrafluoroethane (Freon-114)
76-14-2
1,4-dioxane
123-91-1
ethanol
64-17-5
ethyl acetate
141-78-6
ethyl chloride (chlorocthanc)
75-00-3
cthvlbcnzcne
100-41-4
4-ethyl toluene
622-96-8
heptane
142-82-5
hexachloro-1,3-butadienc
87-68-3
hexane
110-54-3
2-hexanone (methyl butyl ketone)
591-78-6
isoprene
78-79-5
isopropyl alcohol
67-63-0
methanol
67-56-1
methyl bromide (bromomethane)
74-83-9
methyl chloride (chloromethane)
74-87-3
methyl isobutyl ketone (4 -met hy 1 -2 -pentanone)
108-10-1
methyl methacrvlate
80-62-6
methyl tert-butyl ether
1634-04-4
methylene chloride (dichloromethane)b
75-09-2
propene
115-07-1

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Table 4.2-1. VOC Target Compounds and Associated Chemical Abstract Service (CAS)
Number via Method TO-15 (Continued)
Target Compound
CAS #
sty re ik
100-42-5
1,1,1.2-tctrachloroctlianc
630-20-6
1,1,2,2-tetrachloroethane b
79-34-5
tctrachlorocthcnc a b
127-18-4
tetrahydrofuran
109-99-9
toluene
108-88-3
1,2,4-trichlorobenzene
120-82-1
1,1.1 -trichloroethane
71-55-6
1,1,2-trichloroethane
79-00-5
trichlorofluoromethane (Frcon 11)
75-69-4
1.1.2-trichloro-1,2.2-trifluorocthanc (Frcon-113)
76-13-1
1,2.4 -t ri met hy lbc n/c nc
95-63-6
1,3,5-trimcthvlbcn/cnc
108-67-8
trichlorocthcnc a b
79-01-6
vinyl acetate
108-05-4
vinyl bromide
593-60-2
vinyl chloride (chloroethene)a b
75-01-4
m&p-xylene
108-38-3 (m)/106-42-3 (p)
o-xylenc
95-47-6
a NATTS Tier I core analvtc
'NATTS PT target analyte
4.2.1.1	Sampling Pathway. All wetted sampling surfaces that contact the sampled
atmosphere, including the inlet probe, must be of chromatographic grade stainless steel or
borosilicate glass. Stainless steel tubing may be additionally fused silica lined which increases
the inertness of the flow path. While PTFE Teflon is permitted, its use is not recommended as
high molecular weight compounds may adsorb to the surface. Use of other materials such as
copper, FEP Teflon*, or rubber is not permitted, as they have active sites or provide
opportunities for VOCs to adsorb and later desorb.
4.2.1.2	Particulate Filtration. A 2-|im pore size sintered stainless steel particulate filter
must be installed on the sampling unit inlet for all VOC collection. If employing a standalone
VOC inlet probe, a particulate filter placed further upstream in the sampling pathway may permit
a longer period between sampling inlet pathway cleaning. Failure to install a particulate filter
allows particulate residue such as dust and pollen to adhere to the interior of the sampling unit
(to valves, MFC, etc.) and to be pulled into the evacuated canister during sample collection.
Once inside the canister, particulate matter can form active sites, adsorb analytes, and/or provide
reactants which may degrade and form target analytes or interferants, potentially rendering the
canister irreversibly contaminated. The particulate filter must be replaced minimally annually or
more frequently if in areas with high airborne PM levels which may result in decreased flows or
decreased collected pressures.
4.2.2 Precision - Sample Collection and Laboratory Processing. Each agency must
prescribe procedures that it will follow to assess VOCs precision in the NATTS QAPP, SOP, or
similar controlled document. Given below are the various types of precision and associated
frequency requirements for VOCs.
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Precision between duplicate, collocated, and replicate analysis samples must be < 25% relative
percent difference (RPD) for target compound concentrations > five-fold the laboratory MDL.
Both sample results must be qualified when entered into AQS for instances in which collocated
or duplicate samples fail this precision specification. For precision criteria failures of replicate
analyses, the value reported as the RD transaction must be qualified. Root cause analysis must
be performed to investigate and correct the failure. If a root cause cannot be identified, results
should be qualified as estimated. Please refer to the list of qualifiers in Table 3.1-1.
4.2.2.1 Sample Collection and Analysis Precision. Collocated and duplicate samples are
compared to the primary sample to determine the precision inclusive of all sample collection and
analysis procedures.
For samples to be collocated, each sampling unit must have its own pathway to the ambient
atmosphere. If collected from a manifold, each sampling unit must have a dedicated manifold
for it to be collocated; otherwise this configuration is defined as duplicate. The rationale behind
this distinction is that there is potential non-homogeneity of the sampled atmosphere in the
manifold when compared to the ambient atmosphere. Any effect of the manifold impacts both
sampling units and they are not sampling truly independently from the ambient atmosphere. If
both sampling unit inlets connect to the same inlet manifold, the samples are duplicate, not
collocated, as shown in Figure 4.2-1. To summarize,
•	Collocated samplers must have two separate flow control devices and two separate
discrete inlet probes to the ambient atmosphere. If applicable, each sampling unit
must connect to a separate manifold. Collocated sampling inlet probes must be
within 1 to 4 meters of the primary sampling inlet probe.
•	Duplicate sampling is performed in situations where two canisters are collected
through a single inlet probe, which includes a common inlet manifold.

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COLLOCATED
standalone inlet probes
manifold A
manifold B
DUPLICATE
standalone inlet probe
manifold inlet
probe
manifold inlet
probe
sampling unit
sampling unit
sampling unit
sampling unit
Figure 4.2-1. Collocated and Duplicate VOC Canister Sample Collection
Collocated or duplicate VOC sampling, if performed (as detailed in the workplan), must be
conducted at a minimum frequency of 10%. This is equivalent to a minimum of six collocated
samples per year, or roughly one every other month, for sites conducting one-in-six days
sampling for a total of 61 primary samples annually. More frequent collocated sample collection
provides additional sample collection precision and is encouraged where feasible.
4.2.2.2 Laboratory Analytical Precision. Several analysis aliquots can be removed from a
collected canister which affords replicate analysis to evaluate analytical precision. The same
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sample is injected twice and the results are evaluated for precision as RPD. The required
frequency for replicate analyses reported to AQS is prescribed in the workplan, but is
recommended to be performed on a one-per-batch frequency or one-in-20 sample injections,
whichever is more frequent. Monitoring organizations are encouraged to report all replicate
analysis results to AQS.
4.2.3 Sample Collection Procedures
4.2.3.1	Sampling Equipment Specification. Various sampling instruments are commercially
available. Such systems may permit simultaneous collection of VOCs canisters and carbonyl
cartridges or include secondary channels for collection of duplicate VOCs canister samples.
Regardless of the additional features, each sampling unit must minimally include the following
options:
•	Elapsed time indicator
•	Multi-day event control device (timer)
•	Latching solenoid valve with a low temperature rise coil
•	Pressure gauge or pressure transducer to perform leak checking of canister
connection
•	MFC (preferred) or critical orifice to control sampling flow
All wetted surfaces of the flow path in the sampling unit must be constructed of chromatographic
grade stainless steel or borosilicate glass. Stainless steel may be additionally deactivated with
fused silica linings. Use of PTFE Teflon is discouraged as it can behave as a sorbent for high
molecular weight VOCs. Inclusion of glass-lined stainless steel is discouraged as it is prone to
breakage which can cause flow restrictions.
4.2.3.2	Sample Collection, Setup, and Retrieval
4.2.3.2.1 Sample Setup. It is strongly recommended that the initial canister
pressure be checked prior to sample collection by measurement of the canister vacuum with a
calibrated pressure gauge or pressure transducer. If a built-in gauge on the sampling unit cannot
be calibrated, a standalone gauge should be employed for this measurement. This initial pressure
should be documented on the sample collection form. Canisters must show > 28 inches Hg
vacuum to conduct sampling.
Once vacuum is verified, the canister is connected to the sampling unit and a leak check is
performed. A leak check may be performed by quickly opening and closing the valve of the
canister to generate a vacuum in the sampling unit. The vacuum/pressure gauge in the sampling
unit should be observed for a minimum of 5 minutes to ensure that the vacuum does not change
by more than 0.2 psi. Commercially-available canister sampling units may include a leak check
routine. For onboard leak check routines, the leak check criteria should be equivalent or better
than those listed above. If a leak is detected, fittings should be tightened to locate the source of
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the leak. Sample collection must not commence until a successful leak check is attained. Leak
check pressure change and duration is documented on the field collection form.
Following successful leak check, the sample collection program is verified and the canister valve
is opened.
4.2.3.2.2	Subambient Sample Collection. Subambient pressure sample collection
results in a canister pressure that is approximately 10 to 13 psia (2 to 10 inches Hg vacuum).
Sample collection must be performed at a constant flow rate over the 24-hour collection period.
Flow rates are typically 2.5 to 3.5 mL/minute for 6-L canisters.
As discussed earlier in Section 4.2.1, the management of water in sample collection is important
to the ability to remove air from the canister that is representative of the atmosphere initially
collected. At subambient pressures, the partial pressure of water vapor does not typically exceed
the equilibrium vapor pressure at the typical analysis temperature, thus water generally will not
condense on the interior surfaces of the canister.
Subambient sample collection does not include a pump in the sampling pathway. With fewer
components, moving parts, seals, and surfaces, there is generally less risk of contaminating a
collected sample. A less complex sampling system has fewer parts to wear out and break,
simplifying maintenance.
Two disadvantages with subambient sample collection relate to contamination due to leaking and
a smaller overall volume of collected gas for analysis. A canister leak on a subambient pressure
sample will cause ambient air to enter the canister and contaminate the sample, invalidating the
sample. Moreover, a canister at subambient pressure contains less air than an equivalent
superambient sample, which limits the number of aliquots that may be effectively removed from
the canister before there is insufficient gas remaining for analysis.
4.2.3.2.3	Superambient (Positive) Pressure Sampling. Superambient pressure
sampling (positively pressurized sampling) involves collection of samples above atmospheric
pressure utilizing a pump to push air into the canister. As discussed earlier in Section 4.2.1,
sample collection at pressures above ambient pressure may result in water condensation on the
interior walls of the canister.5 It is theorized that this condensation may lead to poor
representation of hydrophilic polar compounds in the aliquot of gas removed from the canister
for analysis. An advantage of superambient pressure sample collection is that if the canister
leaks slightly, the sample will not become contaminated so long as the canister pressure remains
greater than atmospheric pressure.
A disadvantage of superambient sample collection is that it requires incorporation of a pump and
additional valves in the sampling pathway, which provide additional opportunities for
contamination over time when compared to subambient sampling methods which do not require
the additional pumps and valves.
Some sampling systems are susceptible to condensation in the flow pathway during high-
dewpoint conditions. This condensation manifests in the high pressure area between the pump
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and the bypass valve and is evidenced by rough pressure responses when the bypass valve is
operating. To alleviate this condensation, the bypass valve should be kept as open as possible to
maximize the air flow through the sampler and minimize the condensation.
4.2.3.2.4 Sample Retrieval Following completion of sample collection, it is
strongly recommended that the final canister pressure be measured with a calibrated pressure
gauge and recorded on the sample collection form. If an on-board gauge on the sampling unit
cannot be calibrated, a standalone calibrated gauge should be used. The sample start and stop
times as well as the elapsed collection time must also be recorded on the sample collection form.
The sample custody form must be completed and accompany the collected sample at all times
until relinquished to the laboratory. COC documentation must comply with Section 3.3.1.3.7.
Sampling units which incorporate computer control of the sampling event with associated data
logging may provide the above information which should be printed and attached to the sample
collection form or transcribed. If transcribed, the transcription must be verified by another
individual. For such sampling units, the data logged should be reviewed to ensure the sample
collected appropriately and there are no flags or other collection problems that may invalidate the
collected sample. Collected data should be downloaded and provided to the analysis laboratory.
4.2.3.3	Sampling Schedule and Duration. VOC sample collection must be performed
according to the national sampling schedule at one-in-six days for 24 ± 1 hours beginning at
midnight and concluding on midnight of the following day, standard local time, unadjusted for
daylight savings time. For missed or invalidated samples, a make-up sample should be
scheduled and collected per Section 2.1.2.1. Clock timers controlling sampling unit operation
must be adjusted so that digital timers are within ±5 minutes of the reference time (cellular
phone, GPS, or similar accurate clock) and mechanical timers within ±15 minutes.
4.2.3.4	Sampling Train Configuration andPresample Purge. Sampling unit inlets may be
connected to a standalone inlet probe or may be connected to a sampling inlet manifold with a
single inlet probe. If connected to a manifold inlet, the VOC sampling line must be connected to
the port closest to the manifold inlet probe. Inlet manifolds must incorporate a blower to pull
ambient air through the manifold; the manifold flow rate should be minimally two times greater
than the total demand of the systems connected to the manifold. An exit flow meter should be
installed to ensure excess air flow which reduces residence time and ensures that a fresh supply
of ambient air is available for sampling. Refer to Section 2.4 for sampler siting requirements.
For either inlet system listed above, the inlet line to the sampling unit must be purged with
ambient air such that the equivalent of a minimum of 10 air changes is completed just prior to
commencing sample collection. This purge eliminates stagnant air and flushes the inlet line.
4.2.3.5	Sampling Unit Non-Biasing Certification. Prior to field deployment and annually
thereafter, each V OC sampling unit must be certified as n on-biasing by collection over 24 hours
of both a sample of hydrocarbon-free (HCF) zero air (or equivalent VOC- and oxidant-free air)
or zero grade nitrogen and known concentration VOC standard in air.
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This certification may be performed as part of an internal audit, however, this certification is best
performed following annual maintenance which includes calibration (or calibration checks) of
MFCs and pressure gauges and other preventive maintenance, as needed, to ensure the sampling
unit is non-biasing prior to field deployment. Equipment such as dynamic dilution systems,
connecting tubing, and MFCs should be purged with humidified zero air or nitrogen for
sufficient time (typically one hour) to ensure the challenge delivery system is clean.
A best practice is to perform this procedure through the probe (TTP) where the entire sampling
train is assessed for bias. Conducting the TTP procedure requires equipment such as portable
zero air generators and portable gas-phase dynamic dilution systems and staff familiar with their
operation. While the TTP procedure is the best practice, each sampling unit must minimally be
bench tested. Suitable test procedures are described below.
Recommended certification check procedures are described below. For agencies which cannot
perform the annual maintenance and challenge in-house, manufacturers, the national contract lab,
or third party vendors may offer certification services. Regardless of the exact procedure
adopted, the performance specifications listed below must be met.
4.2.3.5.1 Zero Check. The zero check is performed by simultaneously providing
humidified (50 to 70% RH) hydrocarbon- and oxidant-free zero air (must meet the cleanliness
criterion of < 0.2 ppbv or < 3x MDL, whichever is lower) or UHP nitrogen to the sampling unit
for collection into a canister and to a separate reference canister connected directly to the
supplied HCF zero air gas source. The reference canister collects the challenge gas directly and
is the baseline for comparison of the challenge sample. Compounds which show increased
concentrations in the challenge sample compared to the reference sample indicate contamination
attributable to the sampling unit.
The humidified zero gas flow is provided to a challenge manifold constructed of
chromatographic stainless steel. The manifold should include three additional ports for
connections to the sampling unit inlet, reference MFC, and a rotameter which acts as a vent to
ensure that the manifold remains at ambient pressure. The reference MFC flow is set to
approximately the same flow rate as the sampling unit. Zero gas is to be supplied such that there
is excess flow to the manifold as indicated by the rotameter on the vent port. Sampling is
performed over 24 hours, to simulate real world conditions, into the reference canister and
through the sampling unit into the zero challenge canister. Sampling for 24 hours best replicates
conditions in the field, however, shorter sampling durations for these challenges are also
acceptable.
Analysis by GC/MS for target compounds must show all Tier I core compounds in the zero
challenge canister are not greater than 0.2 ppbv or 3x MDL (whichever is lower) higher than the
reference canister and the remaining core compounds should also meet these criteria. Where
exceedances are noted in the zero challenge canister for Tier I core compounds, corrective action
must be taken to remove the contamination attributable to the sampling unit and the sampling
unit zero challenge repeated to ensure criteria are met before sampling can be conducted.
Subsequent collected field sample results for non-Tier I compounds that fail this criterion must
be qualified when input to AQS.
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4.2.3.5.2 Known Standard Challenge. The known standard challenge is performed
by simultaneously providing a humidified (50 to 70% RH) known concentration standard of
target VOCs (at approximately 0.3 to 2 ppb each) in air or UHP nitrogen to the sampling unit for
collection into a canister and to a separate reference canister connected directly to the supplied
standard gas stream. The reference canister collects the challenge gas directly and is the baseline
for comparison of the challenge sample. Compounds which show enhanced or decreased
concentrations in the challenge sample compared to the reference sample indicate bias
attributable to the sampling unit.
It is recommended that the challenge gas contain all target VOCs, however, a smaller subset of
compounds is sufficient provided that each target compound type is represented in the gas
mixture (e.g. low molecular weight, fluorinated, chlorinated, brominated, high molecular weight,
etc.).
The standard challenge gas is supplied to the challenge manifold by dilution of a gas mixture of
VOCs via dynamic dilution with humidified HCF zero air. The manifold should be constructed
of chromatographic stainless steel and should include three additional ports for connections to
the sampling unit inlet, reference canister, and a rotameter acting as a vent to ensure that the
manifold remains at ambient pressure. The reference canister may be collected via MFC, other
constant flow device, or a grab sample to characterize the plenum manifold concentrations.
Challenge gas is to be supplied such that there is excess flow supplied to the challenge manifold
as indicated by the rotameter on the vent port. Samples are collected simultaneously for 24
hours to simulate real world conditions. Sampling for 24 hours best replicates conditions in the
field, however, shorter sampling durations for these challenges are also acceptable.
Analysis by GC/MS for target compounds must demonstrate that each VOC in the challenge
sample is within 15% of the concentration in the reference sample. All Tier I core compounds in
the challenge gas must meet this criterion. For Tier I core compounds exceeding these criteria,
corrective action must be taken to address the bias in recovery attributable to the sampling unit.
Subsequent collected field sample results for non-Tier I compounds that fail this criterion must
be qualified when input to AQS.
Following completion of the known standard challenge, the sampling unit should be flushed with
humidified HCF zero air or ultra-high purity (UHP) nitrogen for a minimum of 24 hours.
Once shown as non-biasing, a best practice to assess ongoing bias is to compare fingerprint plots
(discussed in Section 3.3.1.3.14.2) of each sample from the site.
4.2.4 Canister Hygiene. At the time of this TAD revision, measuring VOCs in ambient air
using passivated stainless steel canisters is approximately a 40-year old technology. While
measurement systems have become more sensitive with the advent of selected ion monitoring
(SIM) and TOF detection, many agencies are unable to achieve sufficient sensitivity to measure
VOCs at ambient concentrations in collected air samples due to the inability to properly clean
and maintain canisters. The following sections present requirements and best practices for
assessing background levels in canister media and maintaining sufficiently low background
levels to the measurement of VOCs in ambient air.
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4.2.4.1 Qualification of Canisters. When new canisters are received, it is strongly
recommended that they be qualified appropriately prior to use for sample collection or for
preparation of standards and blanks. New canisters may contain residues such as cutting oils,
pump oils, or coating byproducts from the manufacturing process and/or residual contamination
from compounds added by manufacturers to perform QC checks on the canisters prior to release
to customers. Additionally, new canisters may have defects making them unsuitable for use even
after the canisters have been cleaned and treated for the residual contaminants. Such defects may
relate to poor valve sealing, active sites from incomplete coating or surface deactivation, or poor
canister integrity due to inadequate welds.
Following new canister receipt and before use and annually thereafter, it is strongly
recommended that canisters be properly cleaned, tested for leaks, and evaluated for bias such that
the requisite canister performance specifications are met. As with new canisters, existing
canisters in agency fleets may exhibit some of the same problems over time and it is strongly
recommended that they be qualified on an annual basis to verify they are non-biasing. All
canisters in a given fleet need not be qualified at the same time, rather a subset can be qualified
on a rolling basis such that all canisters are qualified within the period of a year. For monitoring
agencies with large canister fleets, it may not be feasible to assess each canister within a year. In
such cases, the monitoring agency should prepare a schedule to assess canisters in a reasonable
timeframe (e.g. every 18 months). Suitable procedures are described in the following sections.
4.2.4.1.1 Canister Bias. It is strongly recommended that all canisters be evaluated
for bias when newly purchased (prior to use for field sample collection or use for laboratory QC
sample preparation) and annually thereafter. Assessment for bias of newly purchased canisters
or canisters from an existing fleet is performed identically. Canisters which exhibit a positive or
negative bias exceeding the criteria below should be segregated and reconditioned before reuse
or discarded. Some commercial canister manufacturers offer reconditioning services for their
canisters. Consult the manufacturer for methods to clean or recondition cans which fail these
bias criteria.
4.2.4.1.1.1 Canister Integrity and Zero Air Check
Within two days following cleaning, preferably the same day, canisters should be pressurized
with humidified HCF zero grade air (or UHP N2). This short duration following cleaning is
intended to characterize the canister condition before analytes have a chance to "grow" in the
canister. In order to assess leak tightness of the canisters and to best represent the contamination
potential from collected field samples, pressurization should be performed so that the final
canister pressure closely matches that of the typical pressure of field sample canisters.
Subambient pressurization provides less diluent and may provide more measurable target
compound mass per injection aliquot. Pressurization above ambient pressure permits removal of
larger aliquots of sample gas, and as such affords more opportunities for reanalysis. In either
case, canisters must be approximately 2 psi above or below ambient pressure to permit
assessment of canister leaks. The leak check process given here is one example for a method to
determine canister leak tightness. Other equivalent methods can be performed provided they
meet the leak criteria of < 0.1 psi/day. Leak checks are recommended to be performed annually.
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however the frequency of performing leak checks must be prescribed in the NATTS QAPP,
SOP, or similar controlled document.
Immediately upon pressurization, each canister's pressure is measured with a calibrated gauge
for establishment of a baseline. After a minimum of 7 days and after as long as 30 days, each
canister's pressure is again measured. Canisters with leak rates >0.1 psi/day must be removed
from service and repaired. This leak rate permits 5% of the sample volume to leak over 7 days
and a 20% sample volume leak over 30 days.
The canister should be analyzed within two days of initial pressurization and all Tier I core
analytes must be < 3x MDL or < 0.2 ppb, whichever is lower, and non-Tier I compounds should
meet this criterion. Note that following this analysis, the canister pressure must be remeasured
to accurately assess the canister leak rate as the aliquot removed for analysis changes the canister
pressure. Subsequent analysis may be performed minimally at 14 days after pressurization and is
highly recommended to be performed at 30 days after initial pressurization. Laboratories may
tailor this later timepoint to be representative of the maximum holding time experienced by the
laboratory (e.g. 21 days if all samples are analyzed within this time frame from sample
collection). Analyses at these later timepoints must show all Tier I core analytes < 3x MDL or
< 0.2 ppb, whichever is lower, and non-Tier I compounds should meet this criterion.
Intermediate timepoints less than 30 days will likely indicate if there is a problem with a
particular canister. Canisters which meet criteria at intermediate timepoints should be analyzed
at the 30-day timepoint to verify they are bias free for the 30-day period. If analysis can be
performed at only one timepoint after initial pressurization, it is recommended to be at 30 days.
Laboratories have reported growth of oxygenated compounds (e.g. ketones, alcohols, aldehydes)
in canisters. Of particular concern in the canister zero air checks is acrolein, which evidence
suggests may "grow" in canisters that are stored for extended periods. The mechanism for
acrolein growth is not well understood; however, such is widely regarded as problematic in
performing ambient concentration analysis. Suggested pathways of acrolein growth are
decomposition of particulate residue, slow time-release of acrolein from interstitial spaces within
the canister, breakdown of cutting oil residues in valves, or decomposition of other volatile
constituents within the canister. Concentrations of target compounds above twice the laboratory
MDL should be closely scrutinized as they indicate the presence of canister background
concentrations which may cause issues with future sample collection measurements.
4.2.4.1.1.2 Known Standard Gas Check
Following the canister zero air check in Section 4.2.6.1.1.1, it is strongly recommended that
canister bias be assessed by filling a cleaned canister with a low-level (0.3 to 2 ppb) humidified
standard gas and analyzed 30 days following the initial pressurization. Intermediate timepoints
minimally 14 days after pressurization may be added and may indicate a bias problem,
eliminating the need to perform the 30-day timepoint analysis. Canisters which meet criteria at
intermediate timepoints should be analyzed at the 30-day timepoint to verify they are bias free
for the 30-day period. Laboratories may tailor this later timepoint to be representative of the
maximum holding time experienced by the laboratory (e.g. 21 days if all samples are analyzed
within this time frame from sample collection). The initial analysis should show that target
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analytes are within 30% of nominal and not show significant degradation beyond 30% of
nominal for subsequent timepoints over the 30-day evaluation period.
While not a substitute for performing canister bias checks, an additional method to assess
canister bias is to collect an ambient air sample, analyze it immediately, and analyze it again
following an extended period (e.g. 30 days) and look for changes in analyte concentration which
exceed 30% from the initial analysis.
4.2.4.2 Canister Cleaning. Cleaning of canisters for ambient sample collection may be
performed in a variety of ways which may result in acceptably low background levels in the
canister. Systems are commercially available from a variety of manufacturers or may be custom-
built. Many incorporate the following elements:
1.	Manifold for connection of several canisters (typically 4 to 8)
2.	Rough vacuum pump to achieve vacuum of approximately 1 inch Hg
3.	High vacuum pump (such as a molecular drag pump) to achieve a final canister
vacuum of approximately 50 mTorr or less
4.	Heating oven, heating bands, or heating jackets
5.	Humidifi cation system
6.	Automated switching between evacuation and pressurization
7.	A pressure release valve to minimize the likelihood of system overpressurization
8.	Trap (cryogenic or molecular sieve) to eliminate backstreaming of contaminants
into canisters (only necessary for systems with a non-oil free vacuum pump - note
use of such pumps is not recommended)
9.	Chromatographic grade stainless steel tubing and connections - recommend
minimizing system dead volume to minimize pressurization/evacuation time and
provide less surface area for contaminants
10.	Source of clean purge gas such as zero air or UHP nitrogen
11.	Absence of butyl rubber. Teflon*, or other materials that may adsorb and/or
offgas compounds of interest or other potential interferences
Regardless of how canisters are cleaned, canister cleanliness criteria must be met.
Monitoring agencies must prescribe a policy for holding time for cleaned canisters, which must
not exceed 30 days unless objective evidence indicates that the additional time does not
negatively impact measured sample concentrations.
4.2.4.2.1 Heated Canister Cleaning. Heating of canisters during cleaning is
strongly recommended. Various methods of heating canisters during cleaning may be employed.
The temperature applied to the canister should depend on whether the canister is silica-lined or
electropolished, the temperature rating of the valve and vacuum gauge (if so equipped), and the
heating method employed.
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Heating bands often cause hot spots on the canister, do not evenly heat canister surfaces further
from the bands, and may not adequately heat the valve. Heating jackets and ovens heat the
canister evenly, but may not be able to isolate the valve from the heat source, which may cause
damage to the valve if cleaning is performed at high heat (> SOT). Some heating jackets or
ovens allow the valve to protrude from the jacket or oven and allow the valve to only be exposed
to radiant heat.
If employing humidified HCF zero grade air during canister cleaning (specifically the canister
pressurization steps), silica-lined canisters should not be heated above 80°C as oxidation of the
surface may occur which leads to active sites within the canister.
Heating is recommended for cleaning of ambient concentration canisters, however higher
temperatures are not always better. For canisters of known history used for ambient sample
collection, heating to approximately 75°C during cleaning is generally sufficient. Canisters used
for collection of source level (part per million) samples or samples with matrices including high
molecular weight compounds with high boiling points should be heated to a higher temperature
(100°C or higher), if permitted by the canister and valve. Typically such canisters cannot be
sufficiently cleaned and should be sequestered from use for collecting ambient samples.
4.2.4.2.2	Cycles of Evacuation and Pressurization. Canisters containing standards
or unknown contents with pressures above ambient pressure should be vented into a fume hood
or other exhaust outlet prior to connection to the canister cleaning manifold. In general, the
greater the number of evacuation and pressurization cycles, the more effective the cleaning.
Also, longer holds of vacuum generally result in more effective cleaning. Canisters should be
evacuated to > 28 inches Hg vacuum during each evacuation cycle.
While TO-15 recommends three cycles of evacuation and pressurization, minimally five cycles
of evacuation and pressurization are recommended and ten or more have been shown to be
effective in removing stubborn oxygenated compounds (e.g. acetone, methyl ethyl ketone, and
isopropanol). 7 Following the principle of extraction efficiency where each cycle recovers a
specific percentage of each compound (i .e. 85%), additional evacuation and pressurization cycles
(up to 20) are highly recommended to achieve sufficiently clean canisters. Vacuum of > 28
inches Hg should be maintained for minimally 5 minutes before the pressurization step. Final
evacuation to < 50 mTorr and maintaining this vacuum for minimally 5 minutes is
recommended. Longer final vacuum holds up to approximately an hour are recommended if
feasible. Automated canister cleaning systems may be advantageous as including additional
cycles or extending vacuum hold times can easily be programmed.
An alternative to performing the final evacuation at the end of the cleaning cycles, canisters may
be stored pressurized with humidified zero air or other clean purge gas. When stored
pressurized, canisters are evacuated to < 50 mTorr just prior to field deployment.
4.2.4.2.3	Gas Source for Canister Cleaning Pressurization. If canisters are heated
during cleaning, pressurization of canisters to approximately 5 psig is recommended to avoid
rupture of the canister when heat is applied. For canisters which are not heated during cleaning,
pressurization up to approximately 30 psia is recommended. The purge gas for canister cleaning
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should be high purity zero air or nitrogen. Scrubbing of purge gas with additional hydrocarbon
traps, moisture traps, and/or catalytic oxidation may be necessary to obtain sufficiently clean
purge gas which should be < 0.2 ppbv or < 3x MDL, whichever is lower. When using zero air as
the purge gas, lower temperatures should be maintained during the cleaning process (as
compared to temperatures possible with UHP N2) in order to avoid oxidation of interior canister
surfaces. UHP nitrogen may be sourced from cylinders or may be the headspace gas from a
liquid nitrogen devvar. Regardless of the purge gas selected, its cleanliness should be verified by
analysis to ensure that contaminants are not introduced into the canisters during the cleaning
process.
The source gas should be humidified to approximately 30 to 70% as practical, generally higher
humidity levels are considered to be more effective. The water assists in removal of polar
compounds which may otherwise remain adsorbed to interior canister surfaces. Most
commercial canister cleaning systems incorporate a type of humidifier, however these typically
do not provide a sufficient level of humidity. Humidifi cation systems may be constructed which
incorporate a diptube in deionized water which humidifies by bubbling the purge gas through the
deionized water or via an impinger placed above the surface of the water in the humidifying
chamber. If a bubbler type humidifier is employed, care should be taken to ensure the
downstream pressure is lower than the humidifier upstream pressure to avoid backflow of the
water. It is recommended that the RH of the purge gas be measured with a calibrated hygrometer
to ensure the desired RH is attained.
4.2.4.2.4 Verification of Canister Cleanliness. Following completion of canister
cleaning activities, minimally one canister per batch cleaned must be pressurized to
approximately the pressure of field collected samples with humidified purge gas, held minimally
overnight, and analyzed to ensure all target compounds are < 3x MDL or < 0.2 ppbv, whichever
is lower. Cleanliness criteria must be lowered for agencies which dilute field samples such that
the cleanliness criteria are met for undiluted samples. For instance, if a laboratory dilutes all
samples by two-fold by addition of gas to the collected sample canister, the cleanliness criteria
are not doubled, but are cut in half. A detected concentration of benzene at 0.15 ppbv (assuming
3x MDL is higher) at the instrument would not pass criteria, as the concentration adjusted for
dilution is 0.30 ppbv which exceeds the 0.2 ppbv criterion.
Analysis of more than one canister from each batch is highly recommended and should be no
less than one out of every ten canisters. A best practice is to survey every canister in a cleaning
batch. Following analysis, canisters are re-evacuated to < 50 mTorr. If only a subset of the
canisters in the batch is able to be analyzed, the selected canisters should be those which
indicated the highest total VOC concentration or the highest single target compound
concentration in the previous sample. Other conventions for selecting the batch blank canister
include random selection or evaluating high molecular weight compounds or oxygenated
compounds which are more difficult to completely remove from canisters.
A composite batch blank sample may be prepared by closing the valve of a chosen canister
(which is still under vacuum). The manifold is then pressurized with clean purge gas such that
the other connected canisters are pressurized. The chosen batch blank canister is then opened to
fill the canister with the composite gas from all of the canisters connected to the manifold.
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Actions must be taken to further investigate failure of batch blanks to meet the cleanliness
criteria. If each cleaned canister from the batch is surveyed, only those canisters which fail the
criteria must be recleaned. If one canister representing the batch fails, either the entire batch can
be recleaned (recommended) or two canisters from the batch can be selected and analyzed to
confirm the batch does not pass criteria. If both of these canisters pass, only the failing canister
must be recleaned, otherwise, the batch must be recleaned. Continued failure of batch blanks
may indicate that the manifold or other parts of the system has become contaminated.
4.2.4.3 Canister Maintenance and Preventive Maintenance. Maintenance of canisters
involves a combination of preventive actions and best practices related to initial canister
qualification, sample collection, cleaning, and general handling.
4.2.4.3.1	Collection of Whole Air Samples into Canisters. Whole air sampling into
canisters must be performed with a particulate filter as discussed in Section 4.2.3.3 as once
particulates have been drawn into a canister, they are difficult to remove. Particulate residue
inside of a canister creates active sites and adsorption sites which may have a detrimental effect
on sample compound recovery. Particulates may deposit into canister valves, potentially leading
to the damage of the threads and seals, resulting in leaks. Furthermore, general cleaning of
canisters does little to remove particulate residue interferences which may be indistinguishable
from degradation of the interior surface of the canister. For canisters which cannot be
remediated successfully, the canister may require retirement. Alternatively, canister
manufacturers offer canister reconditioning services which can restore canisters to brand new
condition.
When not connected to a system for cleaning, sample collection or analysis, the canister opening
should always be capped with a brass cap to ensure particulates do not deposit into the valve
opening. To avoid galling the threads of the connection, the brass cap should be installed finger
tight then snugged gently, no more than 1/8 turn with a wrench.
4.2.4.3.2	Overtightening of Valves. The amount of torque required to close a valve
depends on the particular type of valve and overtightening will likely damage the valve. Canister
valves should never be closed with excessive force or by using a wrench. Damaged valves may
not seal appropriately resulting in leaks. Valves with damaged threads or seals should be
replaced.
4.2.4.3.3	General Canister Handling. Canisters should be handled with care to
ensure that weld integrity is maintained, that the interior canister surface is not compromised,
and that the valve-to-canister connection remains intact. Shocks to the surface of the canister
may damage welds or create small cracks in the interior canister surface which may expose
active sites. Excessive pressure on the canister valve may cause leaks in the seal between the
canister valve and canister stem.
Shipment of canisters in protective hard-shell boxes and/or sturdy cardboard boxes is
recommended to ensure canister longevity. Care should be taken to replace any boxes which
have lost integrity or rigidity.
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4.2.5	Method Detection Limits. MDLs for VOCs must be determined minimally annually
by following the procedures in Section 4.1. To ensure that the variability of the media is
characterized in the MDL procedure, separate spiked canisters (it does not suffice to simply
analyze a low-concentration level standard) and method blanks must be prepared, carried out
with canisters in use for field collection. It is recommended that canisters are chosen randomly
and that each type of canister employed for field sample collection be represented. It is not
acceptable to "cherry pick" the best performing canisters for determining MDLs. For example,
laboratories determining the MDL following Section 4.1.2.1 must prepare a minimum of seven
method blank canisters and a minimum of seven spiked canisters over the course of three
different batches (different calendar dates - preferably non-consecutive). These samples must be
analyzed in three separate analytical batches (different calendar dates - preferably non-
consecutive). The MDL is then determined by calculating the MDLsp and MDLh and selecting
the higher of the two concentrations as the laboratory MDL. Please refer to section 4.1.2 for
specific details on selecting a spiking concentration, procedures, and calculations for determining
MDLs.
While the MDL capabilities of each laboratory may vary due to a number of factors (canister
hygiene, condition of equipment, cleanliness of diluent gases, etc.), spiking concentrations for
VOCs MDLs of approximately 0.05 to 0.125 ppbv are typical to achieve the required MDL
MQOs.
All steps performed in the preparation and analysis of field sample canisters (such as dilution)
must be included in the MDL procedure. Canisters must be prepared at the selected spiking
concentration with humidified diluent gas. It is not appropriate to prepare a higher concentration
spike and analyze a smaller aliquot than analyzed for field collected samples. For example, for
laboratories which analyze 500 mL of field collected sample, a spike concentration of 0.06 ppbv
was chosen. The spiked canisters should be prepared at 0.06 ppbv with humidified diluent gas
and 500 mL analyzed. It would not be acceptable for the laboratory to prepare spikes at 0.30
ppbv and analyze only 100 mL of the sample as this would not be representative of the procedure
for field collected samples.
Note that at very low levels approximating the MDL, the qualitative identification criteria related
to qualifier ion abundance ratio and/or signal-to-noise ratio listed in Section 4.2.10.5.3 may not
be strictly met when determining the MDL. As the MDL spikes are prepared in a clean matrix
with standard materials, the presence of the analyte is expected.
Determined MDLs for Tier I core analytes must meet (be equal to or lower than) those listed in
the most current workplan template.
4.2.6	Canister Receipt. When received at the laboratory, canister samples must be
accompanied by a COC form. The sample custodian must sign and date the custody form
indicating transfer of custody and examine the sample collection documentation. Sample
custody is further described in Section 3.3.1.3.7.
Canister pressure for canisters collected to subambient pressure must be measured with a
calibrated gauge or pressure transducer when received at the laboratory to ensure that the sample
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has not leaked. This is a best practice for canisters collected to pressures above ambient
pressure. An acceptable pressure change for subambient pressure samples between the measured
pressure at sample retrieval in the field and the pressure upon receipt in the laboratory must be
defined in an SOP or similar quality systems document. The recommended tolerance is a
pressure change of < 0.5 psia (ensure the measurement is in absolute pressure to account for
differences in altitude which contribute to error when measured in psig). Pressurized samples
must be measured prior to analysis to ensure that they have not leaked down to atmospheric
pressure. Subambient pressure samples which demonstrate pressure changes exceeding criteria
should be invalidated.
4.2.7	Dilution of Canisters. Canister samples collected at subambient pressures may
require pressurization with HCF zero air or UHP nitrogen to provide sufficient pressure for
analysis. When such dilution is performed, the diluent gas must be collected in a separate
certified clean canister as a dilution blank (DB) and analyzed to ensure that the dilution process
does not contaminate collected samples.
The canister pressure must be measured with a calibrated pressure gauge or pressure transducer
just prior to dilution and immediately following dilution. A canister dilution correction factor
(CDCF) is calculated from the two absolute pressure readings as follows:
Pd
CDCF = j-
where:
Pd = The pressure of the canister following dilution (psia)
Pi = The pressure of the canister immediately preceding dilution (psia)
Diluted canisters should be allowed to equilibrate minimally overnight, and preferably 24 hours
before analysis.
4.2.8	GC/MS Tuning, Calibration, and Analysis
4.2.8.1 Interferences. Moisture in the sample gas may interfere with VOC analysis by
GC/MS. Poor water management can cause peak broadening and retention time shifts resulting
in peak misidentification, particularly for hydrophilic polar compounds. Carbon dioxide in the
collected sample can coelute with more volatile VOCs and interfere with their quantitation. A
properly configured moisture management system (as discussed below) can reduce or eliminate
the interference of water and carbon dioxide.
Preconcentration systems employ moisture management techniques to eliminate most of the
water in the concentrated sample. Instrument manufacturers utilize different methods to manage
water removal as well as carbon dioxide such as extended cold trap dehydration (ECTD) or
microscale purge and trap (MPT) techniques.
ECTD removes most of the water in the sampled gas by passing the sample gas through an
empty first trap cooled to approximately -50°C. This low temperature immediately freezes the
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water and allows the VOCs to pass through to a second trap consisting of a weak adsorbent
where the VOCs are then trapped. To ensure complete transfer of the VOCs, the first trap is
warmed to just above the freezing point of water and a small volume of dry inert gas is employed
to sweep any higher boiling point VOCs to the second trap while retaining the water on the first
trap.8
MPT typically permits a larger amount of water to pass through to the second trap and ultimately
to the analytical column than ECTD, potentially resulting in peak broadening and retention time
shifts. For MPT, the first trap containing sorbent and/or deactivated glass beads is cooled to
approximately -160 to -110°C where all the water and VOCs are retained. The first trap is then
heated to several degrees above the freezing point of water and purged with dry inert gas to
sweep the VOCs to the second sorbent trap.8 The purge of the first trap at a higher temperature
may permit more water onto the column compared to ECTD.
Artifacts in chromatograms such as silanol compounds formed from the breakdown of fused
silica linings of canisters and siloxane compounds from the breakdown of the stationary phase in
an analytical column can interfere with quantitation of less volatile VOCs.
4.2.8.2 Specifications for the Preconcentrator and GC/MS. The analysis instrument must
employ detection via mass spectrometer (MS). The MS may be a quadrupole, ion trap, TOF
detector. Detection via flame ionization detector (FID) does not permit positive compound
identification. Flame ionization detection may be performed by way of splitting the column
effluent with the MS and quantitation can be performed from the FID signal. However due to
the non-specific nature of FID detectors, analytes must be qualitatively identified via the MS.
Sample introduction and concentration should be handled by an automated cryogenic
preconcentration system capable of cooling to as low as -190°C and capable of quantitatively
transferring target analytes to the GC column. For cryogenic systems, the target VOCs are
isolated from the whole air matrix by passage of the matrix onto a series of traps packed with
deactivated glass beads or with a polymer or graphitized sorbent; in some systems, water
management is performed by passage of the gas stream through a cryocooled, empty trap.
Typically the final step in the cryogenic preconcentration routine is to refocus the VOCs onto
another low-volume trap for introduction as a tight band onto the head of the GC column.
The GC should be temperature programmable with cryogenic cooling capabilities. VOCs should
be separated with a 60 m by 0.32 mm capillary column with 1 |im lining of 100%
dimethylpolysiloxane (e.g., DB-1), or with a column capable of separating the target analytes
and ISs so that method performance specifications are attained. The transfer line to the MS
should be capable of maintaining 200°C.
The MS detector is operated in electron ionization mode at 70 electron volt (eV) in full scan,
SIM, or SlM/scan mode. If operated in full scan or SIM/scan mode, the MS must be capable of
completing an entire scan in < 1 second. The MS must be capable of scanning from 45 to 250
atomic mass unit (amu) and producing a mass spectrum of BFB compliant with the ion
abundances listed in Table 4.2-2 (for instruments operating in SCAN or SIM/SCAN mode). For
laboratories performing analysis of lower molecular weight analytes such as acetonitrile ( ACN),
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methanol, acetylene, etc., a lower MS scan range capable of 25 to 250 amu may be necessary.
Note that the lower scan range often increases the presence of low mass interferences in the
chromatogram.
Sample and standard introduction to the preconcentrator is preferably performed via autosampler
which allows connection of many canisters that permits unattended analysis of anywhere from
four to 16 or more canisters and permits unattended operation. Ports are also typically available
on the preconcentrator for internal standard and/or standard introduction.
4.2.8.3	Standards and Reagents
4.2.8.3.1	Calibration Standards. Stock calibration gases may be procured at
concentrations ranging from approximately 50 to 1000 ppb of each target VOC in UHP nitrogen.
Target VOCs in this concentration range are generally stable in high pressure passivated
cylinders for at least one year, although some vendors certify their mixtures for longer time
periods. Calibration gases should be recertified by the supplier or third party annually unless a
longer expiration period is assigned by the supplier. Alternatively, a new stock standard or set of
stock standard gases may be procured; however, this is typically several-fold more expensive
than recertification. Dilution of the stock calibration gas by approximately 400-fold permits
preparation of working range calibration standards in canisters at single digit ppb concentrations.
Off-the-shelf stock mixes are available containing approximately 65 target VOCs including the
NATTS core VOCs at 1 ppm, and gas mixtures with tailored compound lists and concentrations
are available as custom orders from certain suppliers. It may be necessary to procure multiple
stock gases to acquire all desired VOCs.
Calibration stock gases must be purchased from a supplier that provides a CO A. stating each
target VOCs concentration with associated uncertainty. An expiration must be assigned to each
standard gas mixture. Uncertainty of the certified concentrations must be specified as within no
more than ± 10%.
4.2.8.3.2	Secondary Source Calibration Standards. Secondary source stock
calibration gases must be procured from a separate supplier and meet the criteria listed above in
Section 4.2.10.3.1. A standard prepared with a different lot of source material from the same
supplier as the primary calibration stock is only acceptable if it is unavailable from another
supplier. As with the calibration stock gases, the secondary source stock must be recertified
annually.
4.2.8.3.3	Internal Standards. IS gases should be procured including a minimum of
three VOCs covering the early, middle, and late elution range of the target VOC elution order.
At minimum a single IS compound must be used. ISs must either be deuterated VOCs or VOCs
which behave chromatographically similarly to, but are not, target VOCs. Three typical VOCs
internal standards are 1,4-difluorobenzene, chlorobenzene-ds, and bromoch 1 oromethane.
IS stock gases are commercially available at 100 ppb in UHP nitrogen, or may be purchased with
a custom suite of compounds at desired concentrations. IS stock gases should be evaluated upon
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receipt for the presence of contaminants. Compounds whose response increases with an
increasing volume of IS analyzed are present in the IS mixture. IS gas standards which
contribute unacceptable levels of target VOCs, such that, for instance, system blanks fail
acceptance criteria, must not be employed for analysis and must be replaced. Typical
contaminants in IS mixtures include methylene chloride and carbon disulfide.
The IS must be added to and analyzed with each injection at the same concentration in order to
monitor instrument sensitivity and assess potential matrix effects. ISs are not added directly to
the sample canister, rather they are introduced through a different dedicated non-sample port in
the preconcentrator and trapped along with the sample aliquot on the first trapping module in the
preconcentrator. The concentration of IS added to each injection should be chosen such that the
IS compounds provide a peak which is on scale and approximates the area response of the highest
calibration standard.
4.2.8.3.4	Diluent Gases. Diluent gases may consist of zero air or UHP nitrogen.
Zero air is typically sourced from a zero air generator and may be further scrubbed by treatment
with activated carbon scrubbers or oxidizers. Zero air is also commercially available in
cylinders, however may be cost prohibitive to procure meeting cleanliness specifications or may
require further cleanup to remove impurities which affect analysis. Nitrogen gas must be from
an UHP source (purity > 99.999%) or from the headspace of a liquid nitrogen devvar. Regardless
of which gas is chosen as a diluent, it must be analyzed to demonstrate to verify that levels of
target VOCs are acceptably low (< 3x MDL or 0.2 ppb, whichever is lower). For diluent gas
contained within a cylinder or from discrete liquid nitrogen tanks, the gas must be analyzed prior
to preparing dilutions with the gas. For zero air generators or replenished on site fixed liquid
nitrogen Devvars, the diluent gas must be analyzed monthly.
4.2.8.3.5	MS Tuning Standard - BFB. 4-bromofluorobenzene (BFB) may be
purchased as a standalone gas at approximately 30 to 100 ppb in UHP nitrogen or may be
purchased as a component in the IS mixture.
4.2.8.3.6	Reagent Water for Humidification of Gases. Reagent water for
humidification of gases must be ASTM Type I (> 18 MO-cm). Additional purifying steps, such
as sonication, helium sparging, or boiling may be necessary to reduce or eliminate dissolved
gases potentially present in the water.
Humidification is most efficiently performed by bubbling the gas to be humidified through a
bubbler via a diptube submerged in the reagent water or passing the gas across the surface of the
reagent water via an impinger. Analysts should be aware of the potential for water to enter the
bubbler tube and be sucked into the gas supply tubing if the pressure downstream of the bubbler
becomes greater than the upstream pressure. Passing of the gas to be humidified through the
headspace of a vessel containing water typically achieves a RH of 20 to 30%, which is
insufficient to maintain the desired RH level of approximately 50% for serving as a diluent gas in
standards preparation or as a humidified blank. Laboratories should measure the RH of the
resulting humidified gas stream to ensure it reaches approximately 50%. If this RH level cannot
be reached with an inline humidification system, liquid water should be added to the canister.
Approximately 75 |iL of deionized water can be added to the canister to increase the RH to
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approximately 40-50% at room temperature and 30 psia. Adding water to canisters with a
syringe via rubber septum is not recommended, as the syringe needle can core the septum
resulting in deposits of rubber into the canister and valve, leading to later bias problems with the
canister. For direct injection of water into a canister with a syringe, a high pressure Teflon
sealed septum (such as a Merlin Microseal®) should be installed on the canister. For canisters
which are connected to a gas source for pressurization via a dynamic or static dilution system,
the water can be added to the valve opening prior to connecting the outlet tubing. Once the
tubing is connected, the valve is opened and the water is pulled into the canister along with the
diluted standard gas.
4.2.8.4 Preparation of Calibration Standards and Quality Control Samples
4.2.8.4.1 Calibration Standards. Working calibration standards are typically
prepared by diluting the calibration stock gas with humidified zero air by dynamic dilution or
calibrated automated static dilution. In these types of dilution, flows of the stock gas(es) and
diluent gas are carefully metered and the gases may be blended in a mixing chamber to ensure
complete mixing. Such systems are commercially available which permit the mixing of multiple
standard gases with a diluent gas. The homogenous, diluted gas mixture is then collected into a
cleaned canister. Working level concentrations are tailored to provide standards covering
approximately 0.1 to 5 ppb.
Calibration standard canisters may be prepared according to two conventions for calibrating the
GC/MS. The first convention consists of preparing a separate canister for each calibration
concentration level such that a total of five different calibration standard canisters are prepared to
establish the calibration curve with the required minimum five points. For this procedure, the
same volume is analyzed from each canister to establish the calibration curve. The second
convention consists of preparing two separate canisters at a low and high concentration.
Different volumes of each of the two canisters are analyzed to prepare the five-point calibration
curve. It is also acceptable to prepare the calibration curve by injecting different volumes from a
single canister provided the calibration curve is verified with an independent second source
quality control standard.
MFCs in dynamic dilution systems must be calibrated initially and the calibration verified
minimally quarterly. Mass flow controllers which fail the calibration check criterion of 2% must
be calibrated. Removal of the MFC from the dynamic dilution system to be calibrated by the
manufacturer is inconvenient and expensive. Instead, a regression calibration can be generated
by challenging the MFC with gas and recording the MFC setting and measuring the flow with a
flow calibrator for a minimum of five points covering the 10% to 100% of the flow range of the
MFC. The resulting regression slope and intercept is then employed to provide the MFC setting
for a given desired flow.
Dynamic dilution systems should be powered on and diluent and stock gases flowing through the
MFCs for minimally one hour prior to use. Warm-up flows should be the desired settings
necessary to prepare the working calibration standards. This warm-up period allows passivation
and equilibration of gases to ensure the concentration of the blended gas is stable prior to
transferring to the canister. When changing stock gas flow rate to prepare a different
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concentration, calibration gas should flow through the system for a minimum of 30 minutes prior
to preparation of the working calibration canister. These warm-up and equilibration times are
particularly important for laboratories analyzing compounds with higher boiling points such as
hexachlorobutadiene and 1,2,4-trichlorobenzene. Extended equilibration times may be necessary
to fully passivate the flow path and mixing chamber of the dynamic dilution system when these
compounds are desired.
Note that final pressures of calibration standard canisters must not exceed the maximum pressure
permitted by the preconcentrator unit. Closely matching the pressure of the calibration standard
canisters to the expected pressure of the collected field samples is recommended when analysis is
performed with preconcentrators that measure volumes with MFCs. Consult the preconcentrator
instrument manual for further guidance on matching canister pressures.
The preferred procedure for preparing calibration standards is dynamic dilution; however, static
dilution by way of syringe injection of calibration stock gases may also be employed. Syringe
dilution requires excellent technique to accurately and reproducibly prepare calibration
standards.
Calibration standard canisters must be humidified to approximately 50% RH by either
humidifying the diluent or by addition of liquid water to the canister. For diluent gases which
are humidified to approximately 25% RH, approximately 100 |iL of reagent water should be
added to the canister prior to pressurization with standard gas to approximately 30 psia. For
standard canisters prepared at lower pressures, a smaller volume of water should be added.
Standard canisters must be allowed to equilibrate minimally overnight (recommended 24 hours)
before analysis.
4.2.8.4.2	Second Source Calibration Verification Sample. A second source
calibration verification (SSCV) is prepared in a canister at approximately the mid-range of the
calibration curve by dilution of the secondary source stock standard. The SSCV verifies the
accuracy of the calibration curve. The SSCV must minimally contain all Tier I core compounds
and it is recommended that the SSCV also contain at least one compound representative of each
type of compound in the calibration (e.g. low molecular weight, chlorinated, fluorinated,
brominated, high molecular weight, etc.). It is strongly recommended that the SSCV contain all
compounds in the calibration mix.
4.2.8.4.3	Method Blank. The MB canister is prepared by filling a cleaned canister
with humidified diluent gas. For laboratories using a dilution system (dynamic or automated
static), the method blank should be pressurized with the dilution system. The MB verifies the
diluent gas is sufficiently clean. To best represent canisters which are sent to the field for sample
collection, the MB should be prepared in a clean canister which was verified by batch blank
analysis. Analysis of a canister cleaning batch blank as the MB complicates the corrective action
process to locate the source if the MB canister analysis indicates contamination.
4.2.8.4.4	Laboratory Control Sample. The LCS is prepared at approximately the
lower third of the calibration range by dilution of the calibration stock gas. While not required,
preparation and analysis of the LCS is recommended. The LCS may serve as the CCV and the
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volume of LCS analyzed should be the same volume as that taken from sample canisters for
routine analysis. The LCS serves to both verify that calibration standards were prepared
correctly and that the instrument remains in calibration.
4.2.8.5 A nalysis via GC/MS
4.2.8.5.1 Tuning of the MS. Prior to initial calibration and every 24 hours of
analysis thereafter, the MS tune of quadrupole MS detectors must be verified to meet the
abundance criteria in Table 4.2-2 by injection and analysis of approximately 50 ng of BFB when
operating in SCAN or simultaneous SIM/SCAN mode.
Failure to meet the BFB tuning criteria requires corrective action which may include adjusting
MS tune parameters or cleaning of the ion source. The instrument must be recalibrated
following adjustments or maintenance which impacts the MS tune.
To the extent possible for ion trap and TOF MS detectors, tune the MS such that the m/z
abundance sensitivities are maximized for the lower mass range, m/z < 150. TOF and ion traps
should be tuned per the manufacturer specifications.
Table 4.2-2. Required BFB Key Ions and Ion Abundance Criteria
Mass (m/z)
Ion Abundance Criteria *
50
8.0 to 40.0% of m/z 95
75
30.0 to 66.0% of m/z 95
95
Base peak, 100% relative abundance
96
5.0 to 9.0% of m/z 95 (see note)
173
Less than 2.0% of m/z 174
174
50.0 to 120.0% of m/z 95
175
4.0 to 9.0% of m/z 174
176
93.0 to 101.0 of m/z 174
177
5.0 to 9.0% of m/z 176
* All abundances must be normalized to m/z 95, the nominal base
peak, even though the ion abundance of m/z 174 may be up to
120% of m/z 95.
4.2.8.5.2 Leak Check and Calibration of the GC/MS
4.2.8.5.2.1 Leak Check
Prior to beginning an analytical sequence, including an initial calibration (ICAL) sequence, each
canister connection must be verified as leak-free through the preconcentrator. During the leak
check, canisters are connected to the autosampler or sample introduction lines and the canister
valves are kept closed. Each port of the autosampler or sample introduction line is evacuated
and the pressure monitored over 30 seconds or 1 minute for a change in pressure. Connections
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which show a pressure change of > 0.2 psi/minute or exceed manufacturer criteria must be
corrected by tightening the fittings. Leak check criteria in automated leak check routines should
be equivalent to or better than those listed above and should be prescribed in the analysis SOP.
Analysis must not be performed on any canister connection which does not pass the leak check.
Canisters which do not pass leak check may leak to atmospheric pressure allowing laboratory air
into the analyzed sample stream. Many preconcentration control software systems include a leak
check function which provides standard QC reports. Following the leak check all autosampler
ports or sample introduction lines are evacuated and the canister valves are opened. Leak checks
must be documented in the analysis records.
4.2.8.5.2.2 Initial Calibration of the GC/MS
The GC/MS instrument must be calibrated initially, following failure of CCV checks, and
following adjustments or maintenance which impact the performance of the GC/MS system
including, but not limited to: cleaning of the ion source, trimming or replacing the capillary
column, or adjustment of MS tune parameters.
The MS must meet BFB tune criteria listed in Section 4.2.10.5.1 before calibration may begin.
An instrument blank (IB) is recommended to be analyzed prior to analysis of calibration
standards to demonstrate the instrument is free of target VOCs and potential interferences. The
IB is an injection of carrier gas taken through the preconcentration steps without introduction of
sample gas into the preconcentrator. Analysis of the IB must show all target compounds are < 3x
MDL or < 0.2 ppb, whichever is lower.
The ICAL curve is prepared by analysis of different concentration levels covering approximately
0.03 to 5 ppbv. At minimum five levels must be included in the ICAL and more are
recommended, especially in the lower end of the calibration curve if the lowest standard
concentration is in the tens of pptv. Calibration curves may be established on the instrument by
two conventions. The first convention is to prepare a separate canister for each level of the
calibration curve and inject the same volume from each canister. The second convention
involves preparation of one to three canisters at different concentrations from which different
volumes are analyzed to establish the calibration curve. An example of this second convention
with two separate canisters follows:
For a typical analysis volume of 400 mL, an eight-point calibration curve is constructed
utilizing two standard canisters prepared at 0.25 ppbv and 5.0 ppbv. The curve is
established at 0.03, 0.05, 0.075, 0.1, 0.25, 0.75, 1.5, and 5.0 ppb by analysis of 48, 80,
120, 160, and 400 mL from the 0.25 ppb canister and analysis of 60, 120 and 400 mL
from the 5.0 ppb canister.
For measuring low (tens of pptv) levels of VOCs as is needed for ambient air analysis, it is
important to characterize the lower end of the calibration curve by loading the number of
calibration points toward the bottom of the curve (as shown in the example above). Including
more points in the lower end of the curve minimizes calibration error at the low end of the curve
as the upper end of the curve has an outsized influence on the curve model when calibration
levels are evenly distributed across the calibration range.
87

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When the second calibration convention is utilized (analyzing different volumes out of one to
three canisters), checking the calibration of the MFC quarterly is recommended to ensure
accurate volumes are metered for analysis.
Following analysis of all calibration standards, a calibration curve is prepared for each target
analyte by determining the relative response factor of each concentration level. Following data
acquisition for the calibration standards, the relative response factor (RRF) of each target
compound in each calibration level is determined as follows:
where:
As =	peak area for quantitation ion of the target compound
A is =	peak area for quantitation ion of the assigned internal standard compound
Cs =	concentration of the target compound
Cis =	concentration of the assigned internal standard compound
If the method of RRFs is selected for construction of the calibration curve, the relative standard
deviation (RSD) of the RRFs for each Tier I Core target V OC must be < 30% and all other
compounds should meet this specification. For Tier II compounds which do not meet this
criterion, results should be qualified when reported to AQS. Alternatively, a calibration curve
may be prepared by linear or quadratic regression of the ratios As/Ais as the dependent variables
and the ratios Cs/Cis as the independent variables. The correlation coefficient for linear or
quadratic curves must be > 0.995 for target VOCs. Irrespective of the curve fit method selected,
the calculated concentration for each V OC at each calibration level must be within 30% of the
nominal concentration when quantitated against the resulting calibration curve. Exclusion of
calibration standard levels is not permitted unless justifiable (for example, a known error in
standard preparation). Sample analysis must not be performed, and if performed, results must
not be reported when calibration acceptance criteria are not met for Tier I core analytes. Rather,
corrective action, possibly including recalibration, must be taken.
Relative retention times (RRTs) are calculated for each concentration level of each target
compound by dividing the target compound retention time (RT) by the associated IS compound
RT. The RRTs of each target compound are then averaged to determine the mean RRT (RRT) of
the ICAL. RRT at each concentration level must be within ± 0.06 RRT units of RRT.
4.2.8.5.2.3 Secondary Source Calibration Verification
Following each successful initial calibration, a SSCV standard must be analyzed to verify the
ICAL. Each target V OC in the SSCV must recover within ± 30% of nominal or the RRF must
be within ± 30% of the mean ICAL RRF. Periodic reanalysis of the SSCV is recommended once
the ICAL has been established.
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4.2.8.5.2.4	Continuing Calibration Verification
Once the GC/MS instrument has met tuning and calibration criteria, a CCV must be analyzed
after every 24 hours of analysis immediately following the BFB tune check and is recommended
to be analyzed after every ten sample injections and at the end of each analytical sequence. Each
target VOC's concentration in the CCV must be within ± 30% of nominal or the RRF must be
within 30% of the average RRF from the ICAL. Corrective action must be taken to address CCV
failures, including, but not limited to, preparing and analyzing a new CCV, trimming or
replacing the column, retuning the MS, or preparing a new ICAL.
4.2.8.5.2.5	A nalysis of Laboratory QC Samples and Field Samples
The following laboratory QC samples are required with each analysis batch containing 20 or
fewer field-collected canisters:
-	MB
-	Replicate sample analysis
Each target VOC's concentration in the MBs must be < 3x MDL or < 0.2 ppb, whichever is
lower. The precision of the replicate analysis must be such that < 25% RPD is achieved for each
target VOC having a concentration > 5x MDL. Samples should be reanalyzed to confirm the out
of criteria result(s) and if confirmed, should be a trigger for corrective action. Sample data
associated with these failures must be qualified appropriately when reported to AQS.
An LCS is recommended to be analyzed with each analysis batch, and must recover within 70 to
130%.
4.2.8.5.3 Compound Identification. Four criteria must be met in order to positively
qualitatively identify a target compound:
1.	The signal-to-noise ratio of the target and qualifier ions must be > 3:1, preferably
> 5:1.
2.	The target and qualifier ion peaks must be co-maximized (peak apexes within one
scan of each other)9
3.	The RT of the compound must be within the RT window as determined from the
ICAL average.
4.	The abundance ratio of the qualifier ion response to target ion response for at least
one qualifier ion must be within ± 30% of the average ratio from the ICAL.
Please refer to Figure 4.2-2 for an example of the qualitative identification criteria listed above
and the following discussion. The RT is within the retention time window defined by the
method (red box A), and the abundance ratios of the qualifier ions are within 30% of the ICAL
average ratio (red box B). The signal-to-noise ratio of the peak is shown to be greater than 5:1
(red oval C) and the target and qualifier ion peaks are co-maximized (dotted purple line D).
89

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Abundance Scan 1043 (7.660 min): 03191404.D\data.ms (-1032) (-)
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methylene chloride
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BT ¦	7 £,&f, Tn-iri
Tgt Ion: 84 Resp: 65009
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B
Abundance
30000'
20000
10000
Time-*
Figure 4.2-2. Qualitative Identification of GC/MS Target Analytes
Please refer to Figure 4.2-3 for the following example for determining the signal-to-noise ratio.
To determine signal-to-noise, the characteristic height of the noise of the baseline (A) just before
the peak and the height of the analyte peak (B) are measured. The ratio of the analyte peak
height (B) is divided by the noise height (A) to calculate the S:N ratio. In the example below,
the peak at 17.0 minutes is discernable from the noise, but is not well-resolved and is very close
to a S:N of 3. In the example, the peak heights of the noise and analyte peak (at approximately
17.0 minutes) are approximately 700 units and 1700 units, respectively, for a S:N of 2.4.
Determination of the S:N is somewhat subjective based on the individual analyst and their
characterization of the noise and analyte peak. Some chromatography systems include S:N
functions which require the analyst to assign the noise and target peak. For well-resolved peaks,
the S:N will greatly exceed 5:1, and does not need to be measured. For peaks with low S:N that
are questionable as to whether they meet the criteria in item #1 above, the 3:1 S:N criterion is a
guideline; it is unnecessary to measure each peak, rather the experienced analyst's opinion
should weigh heavily on whether the peak meets the S:N criterion.
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TIC: D1231503.D\data.ms
—I—i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i—|—i—i—i—i
5.5C 16.DC 16.53 17. DO 17.50
Figure 4.2-3. Determination of Chromatographic Peak Signal-to-Noise Ratio
As with the S:N determination, evaluation of whether target and qualifier ion peaks are co-
maximized does not need to be rigorously evaluated with each peak. Rather the interpretation of
the experienced analyst should weigh heavily on whether the qualifier ion peaks are co-
maximized with the target ion. Items 3 (retention time) and 4 (relative ion abundances) above
may be automated by the analysis software such that they are automatically flagged. It is
important that the RT windows and ion abundances be updated with each new ICAL.
If any of these criteria are not met, the compound may not be positively identified. The only
exception to this is when in the opinion of an experienced analyst the compound is positively
identified. The rationale for such an exception must be documented.
4.2.8.5.4 Internal Standards Response. The response of the ISs must be monitored
for each injection (except for the instrument blank immediately preceding the ICAL or daily
CC V). Area responses of each IS must be within ± 40% of its mean area response in the five-
point ICAL. Each IS must elute within 0.33 minutes of its average RT from the five-point ICAL.
Note: Comparing the IS response to the most recent CCV is not appropriate as this permits the
IS response to drift by as much as 64% from the five-point ICAL before corrective action is
necessary. For example, if the average IS response in the ICAL is 10000 area counts, the CCV
IS response may decrease to as low as 6000 area counts (a decrease of -40% from the five-point
ICAL average) and still meet criteria. Comparing sample IS response to this CCV permits the IS
to drift as low as 3600 area counts (a decrease of -40% from the CCV response), a drift of -64%
from the five-point ICAL average IS response.
The IS response tends to decrease over time as the MS ion optics age and become dirty. If an IS
response is nonconformant and appears to be isolated to a specific sample, the possibility of a
matrix interference should be investigated by analysis of a smaller volume of the air sample. If
an IS response in the dilution remains nonconformant, corrective action should be taken which
91

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may include investigating problems with the preconcentrator, autosampler, or other parts of the
sample introduction path. The MS tune should also be evaluated for a degradation or
enhancement of sensitivity.
4.2.9 Data Review and Concentration Calculations. Each chromatogram must be
closely examined to ensure chromatographic peaks are appropriately resolved and integration
does not include peak shoulders or inflections indicative of a coelution.
The concentrations of target compounds detected in the analyzed aliquot are quantitated by
relating the area response ratio of the target compound and assigned IS in the unknown sample to
the average RRF (RRF) of the initial calibration curve as follows:
__ At ¦ C|S
D ~ AIS ¦ RRF
where:
Cd = instrument detected analyte concentration (ppb)
At = area response of the target compound quantitation ion
Cis = concentration of assigned internal standard (ppb)
A is = area response of the assigned internal standard quantitation ion
RRF = average relative response factor from the initial calibration
If a smaller aliquot was analyzed from the sample canister than the typical analysis volume, an
instrument dilution correction factor (IDCF) must be calculated:
V
y-v op nom
dcf= —
vinj
where:
Vnom = nominal volume of sample injected (typical volume analyzed)
Vinj = reduced volume of the sample injected
The final in air concentration (Cf) of each target compound is determined by multiplying the
instrument detected concentration by the canister dilution correction factor and the instrument
dilution correction factor:
CF = CD¦CDC ¦ DC
where:
Cf =	concentration of the target compound in air (ppb)
CDCF = canister dilution correction factor
IDCF = instrument dilution correction factor
92

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MDLs reported with the final concentration data must be corrected by multiplying the MDL by
the canister and instrument dilution correction factors applied to the sample concentrations. For
example, if the benzene MDL is 0.0091 ppbv for an undiluted sample and the sample was diluted
by 2.5, the MDL becomes 0.023 ppbv.
4.2.10 Summary of Quality Control Parameters. A summary of QC parameters is shown
in Table 4.2-3.
Table 4.2-3. Summary of Quality Control Parameters for NATTS VOCs Analysis
Parameter
Description and Details
Required Frequency
Acceptance Criteria
Instrument Blank (IB)
Analysis of swept carrier gas
through the preconcentrator to
demonstrate the instrument is
sufficiently clean to begin analysis
Prior to IC AL and daily
beginning CCV
Each target VOC s
concentration < 3x MDL or
0.2 ppb. whichever is lower
BFB Tunc Check
50 ng injection of BFB for tune
verification of quadrupole MS
detector
Prior to initial calibration
and every 24 hours of
analysis thereafter
Abundance criteria listed in
Table 4.2-2
Initial Calibration
(ICAL)
Analysis of a minimum of five
calibration levels covering
approximately 0.1 to 5 ppb
Initially, following failed
BFB tune check, failed
CCV, or when
changes/maintenance to
the instrument affect
calibration response
Average RRF < 30% RSD
and each calibration level
must be within ± 30% of
nominal
For quadratic or linear
curves. r> 0.995, each
calibration level must be
within ± 30% of nominal
Secondary Source
Calibration
Verification (SSCV)
Analysis of a secondary source
standard at the mid-range of the
calibration curve to verify ICAL
accuracy
Immediately after each
ICAL
Recovery within
± 30% of nominal or RRF
within ±30% of the mean
ICAL RRF
Continuing
Calibration
Verification (CCV)
Analysis of a known standard at
the mid-range of the calibration
curve to verify ongoing instrument
calibration
Following each daily
BFBtune check and
every 24 hours of
analysis; recommended
after each ten sample
injections and to
conclude each sequence
Recovery within
± 30% of nominal or RRF
within ±30% of the mean
ICAL RRF
Canister Cleaning
Batch Blank
A canister selected for analysis
from a given batch of clean
canisters to ensure acceptable
background levels in the batch of
cleaned canisters
One canister from each
batch of cleaned
canisters - Canister
chosen must represent no
more than 10 total
canisters.
Each target VOC s
concentration < 3x MDL or
0.2 ppb. whichever is lower
(All Tier I Core analytes
must meet this criterion)
Internal Standards
(IS)
Dcutcrated or not naturally
occurring compounds co-analy/cd
with samples to monitor
instrument response and assess
matrix effects
Added to all calibration
standards. QC samples,
and field-collected
samples
Area response for each IS
compound within
± 40% of the average
response of the IC AL
Preconcentrator Leak
Check
Pressurizing or evacuating the
canister connection to verify as
leak-free
Each standard and
sample canister
connected to the
instrument
< 0.2 psi change/minute or
manufacturer
recommendations
93

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Table 4.2-3. Summary of Quality Control Parameters for NATTS VOCs
Analysis (Continued)
Parameter
Description and Details
Required Frequeney
Acceptance Criteria
Method Blank (MB)
Canister filled with clean diluent
gas
One with every analysis
batch of 20 or fewer
field-collected samples
Each target VOC s
concentration < 3x MDL or
0.2 ppb. whichever is lower
Laboratory Control
Sample (LCS)
Canister spiked with known
amount of target anal vte at
approximately the lower third of
the calibration curve
(Recommended) One
with every analysis batch
of 20 or fewer field-
collected samples
Each target VOC s recovery
must be 70 to 130% of its
nominal spiked amount
Duplicate Sample
Field sample collected through the
same inlet probe as the primary
sample
10% of primary samples
for sites performing
duplicate sample
collection (as prescribed
in workplan)
Precision < 25% RPD of
primary sample for
concentrations
> 5xMDL
Collocated Sample
Field sample collected through a
separate inlet probe from the
primary sample
10% of primary samples
for sites performing
collocated sample
collection (as prescribed
in workplan)
Precision < 25% RPD of
primary sample for
concentrations
> 5xMDL
Replicate Analysis
Replicate analysis of a field-
collected sample (chosen by
analyst)
Once with every analysis
sequence (as prescribed
in workplan)
Precision < 25% RPD for
target VOCs with
concentrations
> 5xMDL
Retention Time (RT)
RT of each target compound and
internal standard
All qualitatively
identified compounds
and internal standards
Target VOCs within
± 0.06 RRT units of mean
ICALRRT
IS compounds within
± 0.33 minutes of the mean
ICALRT
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4.2.11	References
1.	Spicer, C.W., S. M. Gordon, et al. (2002). Hazardous Air Pollutants Handbook:
Measurement. Properties, and Fate in Ambient Air. Boca Raton, Lewis Publishers.
2.	Determination of Volatile Organic Compounds (VOCs) in Air Collected in Specially
Prepared Canisters and Analyzed by Gas Chromatography/Mass Spectrometry (GC/MS);
EPA Compendium Method TO-15; U.S. Environmental Protection Agency: 1999. Available
at (accessed October 19, 2016):
3.	Standard Operating Procedures for the Determination of Acrolein and other Volatile Organic
Compounds (VOCs) in Air Collected in Canisters and Analyzed by Gas Chromatography/
Mass Spectrometry (GC/MS), U.S. Environmental Protection Agency, Office of Air Quality
Planning & Standards, Research Triangle Park, NC, November 2006.
4.	Herrington, J.S.: Storage Stability of 66 Volatile Organic Compounds (VOCs) in Silicon-
Lined Air Canisters for 30 Days. Literature Catalog # EVAN2066-UNV, Restek Corporation.
2015. Available at (accessed October 19, 2016):
http:.""v\uu restek cont/pdl-. t-\ ¦ \N2P66-UNY pdf
5.	McClenny, W.A.; Schmidt, S.M.; Kronmiller, KG. Variation of the Relative Humidity of
Air Released from Canisters After Ambient Sampling. In Proceedings of the Measurement of
Toxic and Related Air Pollutants International Symposium, Research Triangle Park, NC,
1997.
6.	Restek Technical Guide: "A Guide to Whole Air Canister Sampling. Equipment Needed
and Practical Techniques for Collecting Air Samples." Literature Catalog # EVTG1073A.
Available at (accessed October 19, 2016): http://www.icstck.com/pdfs/EVTG1073A.pdf
7.	EPA NATTS Proficiency Testing Results Calendar Year 2016 Quarter 1 - Referee Results
from EPA Region V
8.	Entech Application Guide: "3-Stage Preconcentration is Superior for TO-14A and TO-15 Air
Methods." August 25, 2015. Available at (accessed October 19, 2016):
http://www.entechinst.com/3-stage-preconcentration-is-superior-for-to-14a-and-to-15-air-
methods/#
9.	Identification and Confirmation of Chemical Residues in Food by Chromatography-mass
Spectrometry and Other Techniques. Lehotay, S.J ., et al, TrAC- Trends in Analytical
Chemistry. December 2008. pp. 1070-1090

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4.3	Carbonyl Compounds via EPA Compendium Method TO-11A
Each agency must codify in an appropriate quality systems document, such as an SOP, or
equivalent, its procedures for collection of airborne carbonyl s onto cartridges, extraction of the
cartridges, and analysis of the extracts. Various requirements and best practices for such are
given in this section. Note that regardless of the specific procedures adopted, method
performance specifications as given in Section 4.3.10 must be met.
4.3.1 General Description of Sampling Method and Analytical Method. Carbonyl
compounds such as aldehydes and ketones may be collected and analyzed via EPA Compendium
Method TO-11 A. The atmosphere to be characterized is drawn at a known flow rate for a known
duration of time through an ozone denuder and through a sorbent cartridge coated with DNPH,
where the carbonyl compounds react with the DNPH and are derivatized to form carbonyl -
hydrazones. These carbonyl-hydrazones are solids at typical ambient temperatures and are
retained on the cartridge sorbent bed until eluted with acetonitrile ( ACN). Eluted extracts are
analyzed by HPLC with a UV detector at a wavelength 360 nm.1
The carbonyls including, but not limited to, those in Table 4.3-1 may be determined by this
method.
Table 4.3-1. Carbonyl Target Compounds and Associated Chemical
Abstract Service (CAS) Number via Method TO-11A
Target Carbonyl
CAS #
acctaldchyde ab
75-07-0
acetone
67-64-1
benzaldehyde b
100-52-7
butyraldchydc
123-72-8
cratonaldchydc
4170-30-3
2,5-dimethylbenzaldehyde
5779-94-2
formaldehyde ab
50-00-0
hcptaldchydc
111-71-7
hcxaldchydc
66-25-1
isovalcraldchydc
590-86-3
m&p-tolualdehyde
(m) 620-23-5/(p) 104-87-0
methyl ethyl ketone
78-93-3
methyl isobutyl ketone
108-10-1
o-tolualdchydc
529-20-4
propionaldehyde b
123-38-6
valcraldchydc
110-62-3
a NATTS required core analytcs
b NATTS PT analytcs
4.3.2 Minimizing Bias. The sampling of airborne carbonyls onto DNPH cartridges is
potentially affected by a variety of interferences. For example, nitrogen oxides react with the
DNPH derivative to form compounds which may coleute with carbonyl-hydrazone derivatives.
Moreover, ozone reacts with DNPH to form possible coeluting interferences and also reacts with
and causes negative bias in the measurement of various carbonyl-hydrazones. (More
information on ozone management is given in Section 4.3.4.) To minimize introduction of
96

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contamination and to keep bias to a minimum, manage ozone per Section 4.3.4 and handle
cartridges as in Section 4.3.5.2. Clean lab ware and select high-purity reagents as in
Section 4.3.9.
The cartridge inlet and outlet caps must be installed when the cartridge is not in use so as to
isolate it from the ambient atmosphere where carbonyl compounds and interfering compounds
may be passively sampled. Further, cartridges must be stored sealed in the foil pouch or similar
opaque container, as light may degrade the DNPH derivatives. Finally, DNPH cartridges must
be stored at < 4°C after sampling as such slows the reaction of contaminants. Cartridges should
only be handled while wearing powder-free nitrile or vinyl gloves.
4.3.3 Carbonyls Precision
4.3.3.1 Sampling Precision. Depending on the configuration of the sampling unit or units at
the monitoring site, sampling precision may be assessed by way of the collection and analysis of
collocated or duplicate cartridges. Sampling precision is a measure of the reproducibility in the
sampling, handling, extraction, and analysis procedures. Monitoring agencies are encouraged to
collect collocated and duplicate samples. For monitoring agencies collecting collocated and/or
duplicate samples (as detailed in each site's workplan), they must be collected at a minimum
frequency of 10% of primary samples.
4.3.3.1.1 Collocated Sample Collection. A collocated sample is a sample for which
air is drawn through a co-collected cartridge from an independent inlet probe via a separate
discrete sampling unit. If two cartridges are collected together with a single sampling
instrument, to be collocated the air passing onto each cartridge must flow through wholly
separate channels, where each channel must have a discrete inlet probe, plumbing, pump, and
flow controller such as an MFC or rotameter. For sites which employ a manifold inlet to which
one or more carbonyl sampling unit inlets is connected, samples co-collected with the primary
sample will be designated as duplicate, as shown in Figure 4.3-1.
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COLLOCATED
standalone inlet probes
manifold B
manifold A
sampling unit
sampling unit
sampling unit
sampling unit
DUPLICATE
standalone inlet probe
manifold inlet
probe
manifold inlet
probe
sampling unit
sampling unit
sampling unit
sampling unit
Figure 4.3-1. Collocated and Duplicate Carbonyls Sample Collection
More information on collocated samples is given in Section 4.3.8.2.3.
4.3.3.1.2 Duplicate Sample Collection. Duplicate sampling assumes that both the
primary and duplicate sampling inlets are connected to the same inlet probe to the atmosphere
whether connected to a manifold or a standalone inlet probe.
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A duplicate sample may be collected, for example, by splitting (with a tee, or similar) the
primary sample flow path onto two separate cartridges, where each cartridge has its own discrete
and separate flow channel and/or flow control device (MFC, orifice, or rotameter) located within
a single sampling unit.
More information on duplicate samples is given in Section 4.3.8.2.4.
4.3.3.2 Laboratory Precision. Laboratory precision for field-collected carbonyls cartridges
is limited to replicate analysis of a single extract. Each DNPH cartridge is extracted as a discrete
sample which does not permit assessing precision through the extraction process. Replicate
analysis of a given extract is required with each analysis sequence and must show < 10% RPD
for concentrations > 0.5 |ig/cartridge.
Precision incorporating both the extraction and analysis procedures may be assessed by
preparation, extraction, and analysis of duplicate LCSs. An LCS and LCS duplicate (LCSD)
must be prepared minimally quarter, and are recommended with each extraction batch at a
concentration in the lower third of the calibration range. The LCS/LCSD pair must show
precision of < 20% RPD.
4.3.4 Managing Ozone. Ozone is present in the atmosphere at various concentrations
ranging from approximately 20 ppb at rural sites to as much as 150 ppb at peak times in urban
environments. Ozone is a strong oxidant and may impact the sampling and analysis in various
ways. Ozone which is not removed from the sampled air stream may react directly with the
DNPH reagent thereby making the DNPH unavailable for derivatizing carbonyl compounds.
Ozone may also react with carbonyl-hydrazones on the sampled cartridge to degrade these
compounds, leading to underestimation of carbonyl concentrations. These degradation
byproducts may also be difficult or impossible to separate chromatographical 1 y from desired
target compounds, resulting in overestimation or false positive detection of target compounds.
In order to mitigate the impact of ozone on carbonyl measurements, an ozone denuder/scrubber
must be installed in the sampling unit flow path upstream of the DNPH cartridge(s). Typically,
the removal of ozone by potassium iodide (KI) is effected by the oxidation of the iodide ion to
iodine in the presence of water, as follows:
O3 —* O2 ~t~ 0
+ 2K + 20 + 0 -> 2KO + 2
O3 + 2K + 2O 2 O2 2KO
Several different KI ozone scrubbers are described in the following sections. For the NATTS
program, ozone must be removed during the collection of carbonyls with the denuder in
Section 4.3.4.1.
4.3.4.1 Copper Tubing Denuder/Scrubber. Method TO-11A describes an ozone
denuder/scrubber and this is the preferred ozone removal method for the NATTS program. The
scrubber is fashioned from coiled copper tubing whose interior has been coated with a saturated
KI solution and which is heated to approximately 50°C or above to eliminate condensation.
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Heating prevents the deposition of liquid water to the denuder walls which may both dissolve the
KI coating and may clog the silica gel pores in the DNPH cartridge with KI as it recrystallizes.
As this type of scrubber/denuder operates via titration, its efficacy over time is related to the
amount of deposited KI, the total volume of sampled air, and the average ozone concentration of
the sampled air. In general, it is presumed that this type of denuder/scrubber should be effective
for up to 100,000 ppb-hours at flow rates of less than 1 L/minute.' A study not yet published at
the time of this TAD's release has found that such copper tubing ozone scrubbers are effective
for the 100,000 ppb-hours cited in TO-1 1 A; they were able to efficiently remove 150 ppb O3
over 30 consecutive days when operated at a flow rate of 1 L/min at relative humidities ranging
from 10 to 85% at a nominal temperature of 25°C.2 Given an average ozone concentration of
approximately 70 ppb, this type of denuder/scrubber should effectively scrub ozone from the
sampled air stream for all 61 annual 24-hour samples required by the NATTS Program without
depleting the KI reagent. If the average concentration of ozone is greater than 70 ppb over the
course of the year or the sampling frequency is increased from one-in-six days, or if duplicate
sampling is performed more frequently than every other month such that the flow rate through
the denuder is doubled during most sampling events (thereby exposing the scrubber to twice the
burden of ozone), the life span of the KI denuder/scrubber will be proportionately reduced.
The denuder/scrubber must be replaced or recharged with KI minimally annually to ensure there
is sufficient KI substrate to eliminate co-sampled ozone; they should also be recharged if ozone
breakthrough is observed as decomposition products of O3 attacking the DNPH and the
formaldehyde hydrazone derivative (see reference 1 for more information). Denuders are
commercially available or they may be recharged by recoating the copper tubing with a saturated
solution of KI in deionized water (144 grams KI in 100 mL deionized water). The solution is
maintained inside the copper tubing for minimally 15 minutes (some agencies suggest 24 hours
or more), then the solution drained. The emptied tubing is then dried by a gentle stream of dry
UHP nitrogen for minimally one hour.
When a sampling instrument is removed from service for recharging the KI denuder/scrubber
and/or for calibration/maintenance, a best practice is to challenge the denuder with ozone at
120% of the maximum measured ozone concentration for several hours and measure the
resultant downstream concentration. Such will demonstrate the ozone scrubber's efficacy prior
to removal from the field. For denuders shown to be less than fully effective upon removal from
the field, defined as downstream ozone concentration > 10 ppb or a breakthrough > 5%,
chromatograms from recent sampling events should be examined for indications of ozone
interference. Following recharge/replacement of the KI denuder/scrubber, the 120% ozone
concentration challenge should be repeated to demonstrate effective ozone removal prior to its
deployment for field use. The zero challenge of the sampling unit prescribed in Section 4.3.7.1.1
must be performed following recharging of the denuder/scrubber.
4.3.4.2 Sorbent Cartridge Scrubbers. Sorbent cartridges, such as silica gel, coated with KI
are commercially available, but their use is not permitted due to their sorption of water vapor.
Sampling in humid environments results in the sorbent bed becoming saturated with water,
resulting in clogging of the cartridge substrate which substantially reduces or eliminates sample
flow. While inexpensive and convenient for use, sorbent bed KI cartridges must not be
employed for the NATTS Program sampling.
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4.3.4.3 Other Ozone Scrubbers. Agencies may opt to develop custom-made KI ozone
scrubber/denuders. The efficiency of ozone removal must be demonstrated for such custom
systems. To demonstrate efficiency of ozone removal, the homemade scrubber/denuder must be
challenged over a contiguous 24-hour period with a minimum of 100 ppb ozone at the flow rate
for the carbonyl instrument sampler (typically approximately 1 L/min) and demonstrate
breakthrough of < 5%. Agencies must also quantify the capacity of such scrubbers (for example,
in ppb-hours) and with such data they must determine and codify in their quality system the
minimum required recharge/replacement frequency of the scrubbers.
4.3.4.3.1	Cellulose Filter Ozone Scrubbers. The California Air Resources Board
(CARB) removes ozone with cellulose filters coated with KI on the RM Environmental Systems
Incorporated 924 and Xonteck 924 sampling units. These samplers are standalone and not
installed in a separate shelter, so do not allow the ready installation of a heated copper tubing
ozone scrubber. The DNPH cartridge is installed in close proximity (several millimeters) from
the inlet probe, which is open to the atmosphere. The Kl-coated filter is installed at the inlet
probe, just upstream of the DNPH cartridge.
4.3.4.3.2	ModifiedDasibi™ Ozone Scrubber. In the Dasibi ™ scrubber fifteen 2-
inch diameter copper mesh screens are arranged in a stacked formation. The magnesium oxide
coated screens provided with the unit are exchanged for copper screens which are coated with
KI. To coat the screens, they are immersed in a saturated KI solution in deionized water and air
dried. The coated screens are assembled in the Dasibi enclosure with a fiberglass particulate
filter at each end, the O-rings installed, and the enclosure secured with the supplied screws. This
procedure imparts approximately 4 mmoles or 700 mg of KI over the fifteen 2-inch diameter
screens. With this mass of KI, the scrubber should effectively remove ozone for approximately
300 sampling dates assuming 24 hours of sampling at 1 L/minute with ozone concentrations of
100 ppb.
In order to ensure that condensation does not impact the scrubber's performance, it should be
maintained at a minimum temperature of 50°C.
4.3.5 Collection Media. EPA Compendium Method TO-1 1A specifies DNPH-coated
silica gel sorbent cartridges for the collection of carbonyl compounds from ambient air. These
DNPH cartridges may be prepared in house or purchased from commercial suppliers. Most
NATTS sites utilize one of two commercial brands of media, specifically the Waters
WAT037500 or Supelco S-10 cartridges. These cartridges are specified to meet the background
criteria of TO-1 1A and typically exhibit proper flow characteristics. Examination of background
concentrations and proficiency test data do not indicate an obvious difference in the performance
between the two brands of cartridges. Laboratories may prepare DNPH cartridges in house;
however, preparation is a time- and labor-intensive process which requires meticulous detail to
cleanliness to ensure the resulting media are contaminant-free. The expense and resources
involved in preparation of DNPH media in house is generally greater than the cost of purchasing
com m erciall y-a vai 1 abl e DNPH cartridge media. Regardless of the type of cartridge selected, the
method performance specifications in Section 4.3.10 must be met.
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4.3.5.1 Lot Evaluation and Acceptance Criteria. For each lot or batch of
purchased or prepared DNPH cartridge, a representative number of cartridges must be analyzed
to demonstrate that the lot or batch is sufficiently free of contamination. Most commercially-
available DNPH cartridges are accompanied by a COA indicating the lot or batch background of
various carbonyls. While a COA provides a level of confidence that the lot or batch is
sufficiently clean, laboratories must verify the background levels of carbonyls in each batch or
lot of cartridges.
For commercia 11 y-purchased cartridges, a minimum of three cartridges, or 1% of the total lot,
whichever is greater from each lot or batch, must be extracted and analyzed. For cartridges
prepared in house, a minimum of three cartridges per each preparation batch must be extracted
and analyzed. Each cartridge tested in the lot or batch must meet the criteria listed in
Table 4.3-2. Ongoing analysis of method blanks permits continual assessment of the lot's
contamination levels.
Additionally, agencies may elect to perform flow evaluations of the lot(s) to ensure cartridges do
not overly restrict sampling flows.
Table 4.3-2. Maximum Background per Lot of DNPH Cartridge
Carbonyl Compound
Not-to-Excecd Limit (jig/cartridge)
Acctaldchvde
<0.10
Formaldehyde
<0.15
Acetone a
<0.30
Other Individual Target Carbonyl Compounds
<0.10
a Acetone is not a target compound and should not be grounds for lot disqualification unless it interferes with
other target anal vies in the chromatogram.
If any cartridge tested exceeds these criteria, an additional three cartridges, or 1% of the total lot,
whichever is greater, must be tested to evaluate the lot. If the additional cartridges meet the
criteria, the lot or batch is acceptable for sampling. If any of the additional cartridges fail
criteria, the lot or batch must not be used for NATTS sampling and should be returned to the
provider.
4.3.5.2 Cartridge Handling and Storage. DNPH sampling cartridge media are typically
shipped unrefrigerated by the supplier. DNPH cartridges must be stored refrigerated at < 4°C
upon receipt. Un sampled cartridges must be maintained sealed in their original packaging and
protected from light (foil pouch or similar opaque container) until installed for sample collection
or prepared as QC samples as light may degrade the DNPH derivatives. Cartridges which are
not stored appropriately may suffer from degradation of the DNPH reagent and may show
increased levels of contaminants from passive sampling of target compounds and interferants.
DNPH cartridges should only be handled by staff wearing powder-free nitrile or vinyl gloves or
equivalent. Measures must be taken to avoid exposure of DNPH cartridges (unsampled or
collected samples) to exhaust fumes, sunlight, elevated temperatures, and laboratory
environments where carbonyl compounds such as acetone may contaminate sampling media.
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As soon as possible after sample collection, cartridges must be capped (if caps are provided),
sealed in the foil pouch (to protect from light and the ambient atmosphere), and transported
(shipped) and stored refrigerated at < 4°C. Cartridges must be transported in coolers with ice,
freezer packs, or equivalent method for providing refrigeration during transport to and from the
laboratory. Monitoring the shipping temperature with a calibrated min-max type thermometer is
a best practice.
4.3.5.3	Damaged Cartridges. DNPH cartridges are susceptible to water damage and to
physical damage. Unused or sampled cartridges, including blanks, must not indicate clumping of
the silica gel sorbent which is indicative of water condensation inside the cartridge sorbent bed.
Physical damage to cartridges such as cracks, broken inlet or outlet fittings, or openings into the
sorbent bed are pathways for the ingress of contamination. Cartridges which indicate such
damage must not be used in the NATTS Program, or if already used for sample collection, must
be voided and a make-up sample should be collected per Section 2.1.2.1, where possible.
4.3.5.4	Cartridge Shelf Life. DNPH cartridges that are commercially purchased typically are
provided with an expiration from the manufacturer specifying storage conditions. Agencies must
comply with the manufacturer expiration, if given. Degradation of the DNPH reagent or silica
gel sorbent bed which may reduce collection efficiency to unacceptable levels may occur after
the assigned expiration date. Additionally, as DNPH cartridge media age, their levels of
background contamination are likely to have increased, perhaps to unacceptable levels, due to
passive sampling and uptake from the ambient atmosphere. For cartridges which are not
assigned an expiration date or are assigned an arbitrary expiration date (i.e. six months from time
of receipt) by the manufacturer, agencies should work within this expiration period as practical.
For such cartridges which have exceeded the arbitrary expiration period, they may be shown to
be acceptable if levels of contaminants meet the criteria in Table 4.3-2 and there remains
sufficient DNPH to conduct sampling and ensure excess DNPH levels remain following sample
collection. This level of DNPH on unsampled cartridges is recommended to be a reduction of
DNPH area counts of no more than -15% from the original lot acceptance analysis.
4.3.6 Method Detection Limits. MDLs for carbonyls must be determined minimally
annually by following the procedures in Section 4.1. To ensure that the variability of the media
and the extraction process is characterized in the MDL procedure, separate cartridges must be
spiked and extracted (it does not suffice to simply analyze a low-concentration solution of
derivatized carbonyls). For example, laboratories determining the MDL following Section
4.1.2.1 must prepare a minimum of seven method blank cartridges and a minimum of seven
spiked cartridges over the course of three different batches (different calendar dates - preferably
non-consecutive). These samples must be analyzed in three separate analytical batches (different
calendar dates - preferably non-consecutive). The MDL is then determined by calculating the
MDLsp and MDLh and selecting the higher of the two concentrations as the laboratory MDL.
Please refer to section 4.1.2 for specific details on selecting a spiking concentration, procedures,
and calculations for determining MDLs.
All steps performed in the preparation and analysis of field sample cartridges (such as dilution of
extracts) must be included in the MDL procedure. Cartridges should be spiked and the solvent
permitted to dry prior to extraction.
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Determined MDLs for Tier I core analytes must meet (be equal to or lower than) those listed in
the most recent workplan.
4.3.7 Carbonyls Sample Collection Equipment, Certification, and Maintenance.
Carbonyls are collected by drawing the ambient atmosphere through a DNPH cartridge at a
known flow rate of approximately 0.25 to 1.25 L/minute over the 24-hour collection period. An
ongoing EPA funded study not yet published at the time of this TAD's release indicated that at
1.25 L/minute there was no breakthrough at aldehyde concentrations of 5 ppbv. Collection of
samples with flow rates of approximately 1 L/minute represents an appropriate compromise
between maximizing collection efficiency and sensitivity.
4.3.7.1 Sampling Equipment. The sampling unit may control flow rate by a MFC or by a
combination critical orifice and flow rotameter. Advantages of MFCs include that they provide
real-time control of a specified flow, adjusting for changes in backpressure and sampling
conditions. Additionally, MFC flow data may be continuously captured and recorded so as to
permit calculation of a total sampled volume. Such is in contrast with sampling units with
rotameters for which only beginning and ending flow rate measurements are available for total
volume calculations. Another limitation of rotameters is that their indicated flows must be
manually corrected to standard conditions using the barometric pressure and temperature at the
site on the day of sample collection. Rotameters are less complicated and expensive than MFCs.
A variety of commercial and custom-built sampling instruments is available. These range from
simple flow pumps controlled via critical orifice and flow rotameter to multi-channel/multi-
pump systems connected through multiple MFCs and operated by touch screen control. Some
units are also able to simultaneously collect VOC canisters or allow remote computer login to
monitor sampling events and download sample collection data. Note that such options are
advantageous, but not required.
Regardless of the additional features, each sampling unit must minimally include the following
options:
•	Elapsed time indicator
•	Multi-day event control device (timer)
•	MFC (preferred) or critical orifice and flow rotameter to control sampling flow
•	Ozone denuder
Each sampling unit must be flow calibrated annually and shown to be free of positive bias.
4.3.7.1.1 Sampling Unit Zero Check (Positive Bias Check). It is required that prior
to field deployment and minimally annually thereafter each carbonyl sampling unit be certified
to be free of positive bias by collection over 24 hours of a sample of humidified HCF zero air (or
equivalent carbonyl - and oxidant-free air) or UHP nitrogen. Each channel of each carbonyl
sampling instrument should be so verified. A best practice is to perform this procedure TTP
where the entire in-situ sampling train is tested. As many agencies do not possess the resources
to perform TTP procedures, the zero check may be performed in the laboratory where as much of
the flow path as possible must be included. Minimally the portion of the flow path comprising
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the ozone denuder/scrubber and sampling unit into which the DNPH cartridge is installed should
be verified as non-biasing. The positive bias check should be performed following the recharge
or replacement of the ozone scrubber/denuder, is ideally performed following the annual
recalibration of the flow control device, and ideally includes the length of tubing that connects
the instrument to the manifold or the entire new or cleaned inlet probe.
A recommended zero check procedure is described below. For agencies which cannot perform
the annual maintenance (ozone scrubber/denuder recharge, flow control calibration) and
challenge in house, manufacturers, the national contract laboratory, or third party laboratories
may perform this service. Regardless of the exact procedure adopted, when performed, the
performance specifications listed below must be met.
The zero check is performed by simultaneously providing humidified (50 to 70% RH)
hydrocarbon- and oxidant-free zero air or UHP nitrogen to the sampling unit for collection onto a
cartridge and to a separate reference cartridge connected directly to the supplied zero gas source.
As closely as possible, sample collection parameters for the ozone scrubber/denuder, flow rate,
etc., should mimic those for field sample collections.
The humidified zero gas flow is provided to a challenge manifold constructed of
chromatographic stainless steel. The manifold should include three additional ports for
connections to the sampling unit inlet, reference sample, and a rotameter to serve as a vent to
ensure that the manifold remains at ambient pressure during sample collection. The reference
sampling flow is set to approximate the flow rate of the sampling unit with an MFC, mechanical
flow device, or needle valve downstream from the reference cartridge. Zero gas is supplied such
that there is excess flow to the manifold as indicated by the rotameter on the vent port. Sampling
is performed over 24 hours to simulate real world conditions, into the reference cartridge and
through the sampling unit and into the zero challenge cartridge.
Another method to provide the sampling unit with carbonyl-free gas is to install a DNPH
sampling cartridge on the inlet to sampling unit. This cartridge traps the carbonyl compounds
and replaces the zero gas source. A zero challenge cartridge collected in this manner should be
compared to a field blank as the reference cartridge.
Analysis for target compounds in the zero challenge cartridge must show that each compound is
< 0.2 ppbv greater than the reference cartridge. Comparison to the reference cartridge permits
evaluating the contribution of the sampling unit irrespective of cartridge background
contamination. Where exceedances are noted for the zero challenge cartridge, corrective action
must be taken to remove the contamination attributable to the sampling unit and the sampling
unit zero challenge repeated to ensure criteria are met before sampling may be conducted.
4.3.7.1.2 Carbonyls Sampling Unit Flow Calibration. Initially prior to field
deployment and whenever independent flow verification indicates the flow tolerance has been
exceeded, the flow control device (MFC or flow rotameter) must be calibrated against a
calibrated flow transfer standard and the flow control device (or regression for a flow rotameter)
adjusted to match the transfer standard (or the regression characterizing its response must be
reset to match the transfer standard).
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Note that manufacturer procedures for calibration may be followed if flows can be calibrated at
standard conditions. A suitable calibration procedure for MFCs is as follows. The sampling unit
pump(s) and MFC should be warmed up and run for approximately five minutes to ensure the
MFC is stable. A blank DNPH cartridge should be installed into the air sampler to provide a
pressure drop to the pump, and airflow through the cartridge commenced. The calibrated flow
transfer standard should be connected at the upstream end of the sampling unit so as much of the
flow path is included as possible in order to identify potential leaks in the flow path that may not
otherwise be evident. MFC calibration should be performed at minimally three flow rates: the
typical flow rate for sample collection, approximately 30% less than the typical flow of sample
collection, and approximately 30% higher than the typical flow of sample collection. Particular
attention should be paid to ensure that the correct calibration conditions are compared - that both
the reading on the flow transfer standard and MFC are in standard (25°C and 760 mm Hg)
conditions.
Calibration of flow rotameters is more complex than calibration of MFCs. The temperature and
barometric pressure both at the time of calibration and during sample collection are needed to
correct the indicated rotameter flow rate to the actual flow rate.3 A suitable rotameter calibration
procedure is given below.
The flow rotameter should be challenged with a flow of air which is simultaneously measured by
a calibrated flow transfer standard. At each flow rate set point, the flow reading from the flow
transfer standard and the corresponding reading from the flow rotameter are recorded. The
challenged flow range should include a minimum of five flow rates that span the useful scale of
the flow rotameter and include the expected indicated flow rate during field operation. A linear
regression is then generated by plotting the flow transfer (known) readings on the x-axis and the
flow rotameter readings (unknown) on the y-axis. The resulting linear regression equation
allows the rotameter's indicated flow (on the y-axis) to be related to the known calibrated flow of
the rotameter on the x-axis at the specific conditions of ambient temperature and barometric
pressure at which the flow calibration is performed.
To calculate the actual flow rate during operation of the rotameter in the field, the rotameter flow
rate during calibration is found by way of cross reference with the indicated flow from the
rotameter calibration plot. Stated another way, the rotameter is read, and this indicated flow is
found on the y-axis of the calibration plot and the corresponding flow rate during calibration is
read from the x-axis (or the regression equation is solved for x). This flow rate during
calibration, Qc, along with the ambient temperature and pressure during calibration and during
sample collection are input into the following equation to calculate the flow during sample
collection:
Q a = Qc
where:
Qa = volumetric flow rate at ambient (or local) conditions where the rotameter is
operated
Qc = volumetric flow rate at ambient (or local) conditions during rotameter calibration
Pc = barometric pressure during rotameter calibration
c-a
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Pa = barometric pressure at ambient (or local) conditions where the rotameter is operated
Ta = absolute temperature at ambient (or local) conditions where the rotameter is
operated
Tc = absolute temperature during rotameter calibration
For flow rotameters which are calibrated by delivery of a known flow measured at standard
conditions, the calculation of the ambient flow at standard conditions is performed according to
the following equation:
Qa,std - Qc,std Jf£y~
where:
Qa,std = flow rate where the rotameter is operated, in standard conditions (760 mm Hg,
25°C)
Qc.std = flow rate where the rotameter was calibrated, in standard conditions
Tc, Pc, Ta, and Pa are as above.
As an example, assume that a rotameter is calibrated - its indicated flow is cross-referenced to a
calibrated flow - by delivery of known flows measured at standard conditions. Assume as well
that the calibration is performed near sea level at a typical laboratory temperature such that Pc =
750 mm Hg and Tc = 20° C = 293.15 K, and that a field sample is collected in the summer in
Grand Junction, Colorado, such that Pa = 650 mm Hg, Ta = 35° C = 308.15 K. Assume the
indicated rotameter flow is 800 mL/min, which from the calibration plot corresponds to a known
flow rate at standard conditions of 750 mL/min. The actual flow rate, in standard conditions, for
this carbonyl sample in Grand Junction is equal to 750 mL/min • V (650/750 • 293.15/308.15) =
681 mL/min.
To perform a flow calibration verification on the sampling unit flow, the sampling unit pump(s)
should be warmed up and run for approximately five minutes to ensure flows are stable. A blank
DNPH cartridge should be installed into the air sampler to provide a pressure drop to the pump,
and airflow through the cartridge commenced. The calibrated flow transfer standard should be
connected at the upstream end of the sampling unit so as much of the flow path is included as
possible in order to identify potential leaks in the flow path that may not otherwise be evident.
The sample flow is then set to the flow setting of typical sample collection and the flow
compared to the transfer standard. Ensure that both the sampling unit and flow transfer standard
are set to report flows at standard conditions of 25°C and 760 mm Hg. Rotameter flows must be
converted to standard conditions (Qa. std) with the temperature and barometric pressure measured
at the time of the calibration check via the equation above. The sampling unit flow in standard
conditions must be within 10% of the flow indicated by the transfer standard. If outside of this
range, the MFC must be recalibrated or the regression equation for the flow rotameter must be
re-established.
4.3.7.1.3 Moisture Management. Humidity plays several roles with regard to
sample collection. Water vapor can condense on interior portions of the sample flow path
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potentially resulting in a low measurement bias due to carbonyls dissolving in the liquid water.
To minimize the condensation of liquid water onto the interior surfaces of the flow path, the
ozone scrubber is maintained at a minimum of 50°C. Additionally, connecting tubing may be
insulated to maintain the elevated temperature and discourage condensation. High humidity in
sampled atmospheres may also lead to somewhat lower carbonyl collection efficiencies due to
the possible back reaction of the DNPH-carbonyl derivative with water to form the free carbonyl.
The reverse reaction is less likely for aldehydes due to their higher reactivity, however can lead
to lower collection efficiencies for ketones. 4
4.3.7.2	Sampling Train Configuration andPresample Purge. The carbonyl sampling inlet
probe may be standalone or connected to a manifold inlet. For either configuration, components
comprising the wetted surfaces of the flow path must be constructed of borosilicate glass, PTFE
Teflon, or chromatographic grade stainless steel. Due to the reactivity of materials such as
copper or adsorpti ve/desorpti ve properties of materials such as FEP Teflon*, rubber, or plastic
tubing, these materials must not be utilized within the flow path.
For sites having a common inlet manifold, it must be constructed of borosilicate glass. A bypass
pump is connected to the manifold to continuously pull ambient air though the manifold. The
flow rate of the bypass pump must be minimally double the total maximum sampling load for all
sampling units connected to the manifold. Where the carbonyls sampling unit has its own inlet
probe separate from the manifold, no additional bypass pump is necessary.
Regardless of how the ambient air is introduced into the sampling instrument, it is strongly
recommended that the inlet line to the sampling unit be purged with ambient air such that the
equivalent of a minimum of 10 air changes is completed just prior to commencing sample
collection. This purge eliminates stagnant air and flushes the inlet line.
4.3.7.3	Carbonyl Sampling Inlet Maintenance. Over time, the carbonyl inlet probe and
connecting tubing will become laden with particulate residue. This particulate residue may scrub
target analytes from the gas stream and may act as sites for adsorption/desorption. Wetted
surfaces of inlet probes and connecting tubing must be cleaned and/or replaced minimally
annually, and preferably every six months, particularly if operated in an urban environment
where there is a higher concentration of PM.
Only deionized water should be used to clean inlet lines. If the lines are short enough, a small
brush can be employed in concert with the deionized water to effectively clean the interior of the
tubing. It may be more effective to simply replace the tubing on a prescribed basis. Many
carbonyl sampling units utilize Teflon® particulate filters upstream of the denuder to alleviate
particulate loading of internal parts (valves and MFCs) of sampling units. Such particulate filters
must be replaced periodically, recommended to be replaced after six months but must not exceed
annually.
4.3.8 Sample Collection Procedures and Field Quality Control Samples
4.3.8.1 Sample Collection Procedures. Prior to beginning sample collection, all DNPH
cartridge lot characterization must be completed as described in Section 4.3.5.1. The sampling
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unit must have passed the zero check in the previous 12 months, the sampling inlet line cleaned
or replaced in the previous 12 months, the flow control device calibrated within the past 12
months, and, if so equipped, the particulate filter must have been changed in the previous year.
In addition to the procedures described below, all cartridges must be handled as prescribed in
Section 4.3.5.2.
4.3.8.1.1	Sample Setup. Blank DNPH cartridge media are transported to the site in
a cooler on ice packs where they are either stored on site in a refrigerator or freezer (with
calibrated temperature monitoring), or installed into the sampling unit for sample collection.
Appropriate blank, non-exposed DNPH cartridge(s) are installed into the sampling unit and the
sample collection program verified to comply with Section 4.3.8.1.3. The flow rate of collection
should be set to a known calibrated flow rate of approximately 0.7 to 1.5 L/minute (at standard
conditions) for a total collection volume of 1.0 to 2.2 m3 at standard conditions. Method
sensitivity is linearly proportional to the total collection volume, and the latter should be adjusted
within the specified range so that MDL MQOs are attained. An ongoing EPA funded study not
yet published at the time of this TAD's release indicated that at these flow rates there was no
breakthrough at aldehyde concentrations of 5 ppbv. Flow rates greater than 1.5 L/minute may
result in decreased in collection efficiency.
For sampling units which permit a leak check function on the sample pathway, a leak check must
be initiated prior to sample collection. A successful leak check indicates no flow through the
sampling unit.
The initial flow rate, date and time of sample initiation, and cartridge identification information
must be recorded on the sample collection form.
4.3.8.1.2	Sample Retrieval. The collected cartridges must be retrieved as soon as
possible after the conclusion of sampling in order to minimize degradation of the carbonyl-
DNPH derivatives, preferably within 72 hours of the end of sample collection. The ending flow
rate, total flow (if given), and sample duration must be documented on the sample collection
form. The cartridges are removed from the sampling unit, the caps installed on the inlet and
outlet of each cartridge, each cartridge sealed in its separate foil pouch, and the pouches
immediately placed in cold storage. The sample must be kept cold during shipment such that the
temperature remains < 4°C, and the temperature of the shipment must be determined upon
receipt at the laboratory. A best practice to minimize contamination is to transport the sealed foil
pouch in an outer zipperlock bag containing activated carbon.
Sampling units which incorporate computer control of the sampling event with associated data
logging may provide the above information which must be printed and attached to the sample
collection form or transcribed. For such sampling units, the data logged should be reviewed to
ensure the sample was collected appropriately and there are no flags or other collection problems
that may invalidate the collected sample. Collected data should be downloaded and provided to
the analytical laboratory. The sample custody form must be completed and accompany the
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collected sample at all times until relinquished to the laboratory. COC documentation must
comply with Section 3.3.1.3.7.
4.3.8.1.3 Sampling Schedule and Duration. Carbonyl sample collection must be
performed on a one-in-six days schedule per the national sampling calendar for 24 ± 1 hours
beginning at midnight and concluding on midnight of the following day, local time unadjusted
for daylight savings time. For missed or invalidated samples, a make-up sample should be
scheduled and collected per Section 2.1.2.1. Clock timers controlling sampling unit operation
must be adjusted so that digital timers are within ±5 minutes of the reference time (cellular
phone, GPS, or similar accurate clock) and mechanical timers within ±15 minutes.
4.3.8.2 Field Quality Control Samples. QC samples co-collected with field samples include
field and trip blanks, collocated and duplicate samples, field matrix spikes, and breakthrough
samples. Blank cartridges provide information on the potential for field-collected samples to be
subjected to positive bias, whereas spiked cartridges assess the potential for the presence of both
positive and negative bias.
4.3.8.2.1 Field Blanks. Field blanks must be minimally collected once per month;
however, it is a best practice to increase this frequency, ideally to collect a field blank with each
collection event. Field blanks must be handled in the same manner as all other field-collected
samples, transported in the same cooler and stored in the same refrigerator/freezer storage units.
Field blanks are exposed to the ambient atmosphere for approximately five to ten minutes by
installation of the blank cartridge into the sampling position on the primary sampling unit with
no air drawn through the cartridge. The field blank cartridge is then removed from the sampling
unit and placed immediately into cold storage. Collection of the field blank in this manner
characterizes the handling of the blank cartridge in the sampling position in the primary sampling
unit and standardizes field blank collection across the NATTS network for carbonyls and with
metals and PAHs field blank collection.
An exposure blank is similar to a field blank, but is not required, and may be collected via
several protocols. The exposure blank includes opening the cartridge pouch, removing the caps
exposing the cartridge to the ambient atmosphere briefly, and exposing it to the temperature
conditions of the primary sampling cartridge for the same duration as the co-collected field
samples. Like a field blank, air is not drawn through the exposure blank cartridge. Some
sampling units have a dedicated "field blank" channel for installation of the exposure blank
through which air is not permitted to flow. For multi-channel sampling units, the exposure blank
may be installed in channel which is not activated for sample flow. For sampling units which
have neither a dedicated blank channel nor unused channel available on the sampling unit, the
exposure blank cartridge may be removed from the foil pouch, installed in the sampling unit for
five to ten minutes, the cartridge uninstalled and the end caps reinstalled, and the cartridge
placed near the sampling unit for the duration the primary sample is installed in the sampling
unit.
Field blanks and exposure blanks may passively sample ambient air throughout the time of
exposure, and as a result may have somewhat higher background levels as compared to lot
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blanks, trip blanks, or laboratory method blanks. Field blanks must meet and exposure blanks
should meet the following criteria listed in Table 4.3-3.
Table 4.3-3. Carbonyls Field Blank Acceptance Criteria
Carbonyl Compound
Not-to-Exceed Limit (ng/cartridge)
Acctaldchvde
<0.40
Formaldehyde
<0.30
Acetone a
<0.75
Sum of Other Target Carbonyls
<7.0
a Acetone is not a target compound and should not be grounds for field blank criteria failure unless it interferes
with other target analvtes in the chromatogram.
Failure to meet the field blank criteria indicates a source of contamination and corrective action
must be taken as soon as possible. For agencies which collect associated trip blanks, comparison
of the field blank to trip blank values may provide meaningful insight regarding the
contamination source. Field-collected samples associated with field blanks which do not meet
these criteria must be flagged/qualified when input to AQS. For field blanks which fail criteria
and are collected with each sampling event, the co-collected field sample results must be
flagged/qualified when input to AQS. For failing field blanks which are collected on a less
frequent basis (i.e. monthly basis), field collected samples since the last acceptable field blank
must be flagged/qualified when input to AQS.
Field samples must not be corrected for field blank values. Field blank values must be reported
to AQS so that data users may estimate field and/or background contamination.
4.3.8.2.2	Trip Blanks. Trip blanks are a useful tool to diagnose potential
contamination in the sample collection and transport of carbonyl samples. Trip blanks are not
required, but are a best practice. A trip blank consists of a blank unopened cartridge which
accompanies field sample cartridges at all times to and from the laboratory. The trip blank
cartridge is stored in the same refrigerator/freezer, transported in the same cooler to and from the
site, and kept at ambient conditions during sample collection. The cartridge must remain sealed
in the foil pouch and not removed from its pouch until extracted in the laboratory.
Background levels on the trip blank should be comparable to the lot blank average determined as
in Section 4.3.5.1 and must not exceed the values listed in Table 4.3-2. Exceedance of these
thresholds must prompt corrective action and the results of the associated field-collected samples
must be appropriately qualified when input to AQS.
4.3.8.2.3	Collocated Samples. Collocated sampling is described in detail in
Section 4.3.3.1.1. Where such is performed, it must be done at a frequency of no less than 10%,
meaning approximately one collocated sample every other month.
Following extraction and analysis the collocated cartridge results are compared to evaluate
precision. Precision must be < 20% RPD for results > 0.5 |ig/cartridge. Root cause analysis
must be performed for instances in which collocated samples fail this preci si on specification and
the results for both the primary and collocated samples must be qualified when entered into
AQS.
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4.3.8.2.4 Duplicate Samples. Duplicate sampling is described in detail in
Sections 4.3.3.1.1 and 4.3.3.1.2. Where such is performed, it must be done at a frequency of no
less than 10%, meaning approximately one duplicate sample every other month.
Following extraction and analysis the duplicate cartridge results are compared to evaluate
precision. Precision must be < 20% RPD for results >0.5 |ig/cartridge. Root cause analysis
must be performed for instances in which duplicate samples fail this precision specification and
the primary and duplicate results must be qualified when entered into AQS.
4.3.8.2.5 Field Matrix Spikes. Performance of field matrix spiked sample
collection is a best practice, but is not required. Field matrix spikes are prepared by spiking a
blank DNPH cartridge with a known amount of analyte (either derivatized or underivatized)
prior to dispatching to the field for collection. The field matrix spike is handled identically to
field samples; sample storage, transport, and extraction are identical. Field matrix spiked
samples are collected concurrently with a non-spiked primary sample as a duplicate sample per
Section 4.3.8.2.3 via duplicate channel or split sample flow.
The primary field sample and matrix spiked sample analysis results are evaluated for spike
recovery based on the amount spiked prior to shipment to the field as follows:
CField Matrix Spike Result — Primary Sample Result)
%Recovery = 		£	:—, „ ,, ^ 4						 ¦ 100
Nominal Spiked Amoun t
Spike recovery should be within ± 20% (80 to 120% recovery) of the nominal spiked amount. In
the event of an exceedance, root cause analysis should be performed to determine sources of
negative or positive bias, as needed, for example, sources of contamination or reasons for the
loss of analyte. High recoveries may indicate contamination in the matrix spike sample
collection channel or loss in the primary sample collection channel. Low recoveries may
indicate a poorly functioning ozone denuder, which permits ozone to pass through the sample
collection flow path and degrade the spiked analytes.
4.3.8.2.6 Breakthrough Samples. While not required, collection of breakthrough
samples is a best practice. A breakthrough sample is a second DNPH cartridge connected
immediately downstream of the primary sample cartridge. Periodic collection of breakthrough
samples provides a level of assurance that the primary sample cartridge is efficiently trapping
target carbonyls. For sites conducting breakthrough sampling the recommended frequency is
once per month which should be described in the agency NATTS QAPP, SOP, or similar
controlled document.
Note that this breakthrough cartridge will increase the pressure drop in the sampling system and
may require an adjustment in the operation of the sampling unit to achieve the desired flow rate.
Breakthrough sample results must meet the field blank criteria listed in Table 4.3-3.
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4.3.9 Carbonyls Extraction and Analysis. Target carbonyls collected on the DNPH
cartridges are extracted and analyzed per EPA Compendium Method TO-11A' according to the
following guidance.
4.3.9.1 A nafytical Interferences and Contamination
4.3.9.1.1	Analytical Interferences. The carbonyl-hydrazone derivatives are
separated with a HPLC system and are typically detected at 360 nm with a photodiode array or
similar detector operating at UV wavelengths. Identification is based on retention time matching
with known standards. MS and photodiode array (PDA) detectors are also an option if more
definitive identification and quantification are desired or required. Minimally, analysis by
HPLC-UV must be performed.
Interferences from co-eluting peaks may result from hydrazones formed by co-collected
compounds or reactions with co-collected compounds which form artifacts. Such co-el uting
peaks may form as dimers or trimers of acrolein or be the result of chemical reactions with
nitrogen oxides. Target analyte peaks which indicate shoulders, tailing, or inflection points
should be investigated to ensure these chromatographic problems are not related to a co-el uting
interference.
4.3.9.1.2	Labware Cleaning. Lab ware must be thoroughly cleaned prior to use to
eliminate potential interferences and contamination. Regardless of the specific procedures
implemented, all method performance specifications for cleanliness must be met. Volumetric
labware used for collection of cartridge eluent can show buildup of silica gel residue over time,
requiring aggressive physical cleaning methods with laboratory detergent and hot water. Clean
all associated labware by rinsing with ACN, washing with laboratory detergent, rinsing with
deionized water, rinsing with ACN or methanol, and air drying or drying in an oven at no more
than 80 to 90°C. 5 Heated drying of volumetric ware at temperatures > 90°C voids the
manufacturer volumetric certification.
4.3.9.1.3	Minimizing Sources of Contamination. Several target analytes in this
method are typically present in ambient air and may contaminate solvents and the DNPH reagent
if appropriate preventive measures are not in place. ACN used for sample extraction, standards
preparation, and mobile phase preparation must be carbonyl-free HPLC grade or better (as
indicated by the supplier or on the CO A) and must be stored tightly capped away from sources of
carbonyls. DNPH cartridges must be handled properly per Section 4.3.5.2.
Laboratories which process environmental samples for organic compounds such as pesticides
typically employ extraction with acetone or other solvents which may contaminate DNPH
cartridge media and carbonyl extraction solvents. Laboratory areas in which cartridges are
stored, extracted, and analyzed should be free of contaminating solvent fumes. Carbonyls
handling areas should have heating, ventilation, and air conditioning systems separate from such
laboratory operations.
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4.3.9.2 Reagents and Standard Materials
4.3.9.2.1	Solvents. Solvents employed for extraction, preparation of standards
solutions, and preparation of mobile phase must be high-purity carbonyl-free, HPLC grade, and
shown by analysis to be free of contaminants and interferences. Such solvents include ACN,
methanol, and deionized water. Deionized water must be ASTM Type 1(18 MO-cm).
4.3.9.2.2	Calibration Stock Materials. Calibration source material must be of
known high purity and must be accompanied by a CO A. Calibration materials should be neat
high purity solids or sourced as certified single component or component mixtures of target
compounds in an appropriate solvent (i.e., ACN or methanol).
Neat solid material must be weighed with a calibrated analytical balance with the appropriate
sensitivity for a minimum of three significant figures in the determined standard mass. The
calibration of the balance must be verified on the day of use with certified weights bracketing the
masses to be weighed. Calibration standards diluted from stock standards must be prepared by
delivering stock volumes with mechanical pipettes or calibrated gastight syringes and the
volumes dispensed into Class A volumetric lab ware to which ACN is added to establish a known
final dilution volume.
4.3.9.2.3	Secondary Source Calibration Verification Stock Materials. A
secondary source standard must be prepared to verify the calibration of the HPLC on an ongoing
basis, minimally immediately following each ICAL. The secondary source stock standard must
be purchased from a different supplier than the calibration stock material or, only if unavailable
from a different supplier, may be of a different lot from the same supplier as the calibration
material.
4.3.9.2.4	Holding Time and Storage Requirements. Unopened stock materials are
appropriate for use until their expiration date provided they are stored per manufacturer
requirements. Once opened, stock materials may not be used past the manufacturer
recommended period or, if no time period is specified, not beyond six months from the opened
date. To use the standard materials past this time period, standards must have been demonstrated
to not be degraded or concentrated by comparison to freshly opened standards. Unopened stock
materials must be stored per manufacturer recommendations. All stock and diluted working
calibration standards must be stored at < 4°C in a separate refrigeration unit from sample
cartridges and sample extracts.
4.3.9.3 Cartridge Holding Time and Storage Requirements. All field-collected cartridges
must be stored at < 4°C and extracted within 14 days of the end of collection. These conditions
similarly apply to laboratory-prepared QC samples, which must be stored at < 4°C and extracted
within 14 days of preparation. Extracts must be analyzed within 30 days of extraction. Results
input to AQS must be appropriately qualified for failure to meet the holding time and/or storage
criteria.
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4.3.9.4 Cartridge Extraction
4.3.9.4.1 Laboratory Quality Control Samples. With each extraction batch of 20 or
fewer field-collected cartridges, which may include the various field QC samples such as those
listed in Section 4.3.8.2, the following negative and positive laboratory QC samples must be
prepared (except LCS/LCSD which must be prepared/analyzed minimally quarterly -
recommended with each batch). For batch sizes of more than 20 field-collected cartridges, n
such QC samples of each type must be added to the batch, where n = batch size / 20, and where n
is rounded to the next highest integer. Thus for batch sizes of 30, two of each of the following
QC samples would be included in each batch. A best practice would be to process field-
collected cartridges in batches of no more than 20 at a time.
-	Extraction Solvent Method Blank (ESMB): An ESMB is prepared by transferring the
extraction solvent into a flask just as an extracted sample. The purpose of this
negative control is to demonstrate that the extraction solvent is free of interferences
and contamination and that the lab ware washing procedure is effective. Analysis
must show target compound responses are less than the laboratory MDLsp for MDLs
determined via Section 4.1.3.1 or the s K portion of the MDL for MDLs determined
via Section 4.1.3.2.
-	Method Blank (MB): The MB is a negative control that may also be referred to as the
cartridge blank. The MB is a blank unopened cartridge (that has not left the
laboratory) which is extracted identically to field samples. All target analytes must
meet criteria specified in Table 4.3-2.
-	Laboratory Control Sample (LCS): The LCS, also referred to as the laboratory
fortified blank (LFB), is a positive control prepared by spiking a known amount of
underivatized or derivatized DNPH-carbonyl target analyte onto a cartridge such that
the expected extract concentration is in the lower third of the ICAL range. The
spiked cartridge is allowed to sit for minimally 30 minutes to allow the solvent to dry
following addition of the DNPH-carbonyl in solution. The LCS is then extracted with
the same extraction solvent and method employed for field samples to assess bias in
matrix of the extraction and analysis procedures. Recovery of the LCS must be
within 80 to 120% of nominal for formaldehyde and 70 to 130% of nominal for all
other target carbonyls.
-	Laboratory Control Sample Duplicate (LCSD): The LCSD is prepared and extracted
identically to the LCS. The LCSD assesses precision through extraction and analysis.
Recovery of the LCSD must be within 80 to 120% of nominal for formaldehyde and
70 to 130%) for all other target carbonyls. The LCS and LCSD results must show
RPD of <20%.
All field-collected and laboratory QC samples in a given extraction batch must be analyzed in
the same analysis batch (an analysis batch is defined as all samples analyzed together within a
24-hour period).
Laboratories must take corrective action to determine the root cause of laboratory QC
exceedances. Field-collected sample results associated with failing QC results (in the same
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preparation batch or analysis batch) must be appropriately qualified when input into AQS. In
order to simplify troubleshooting when experiencing QC failures, QC sample cartridge media
and extraction solvent lots should be the same, where possible.
4.3.9.4.2 Cartridge Extraction Procedures. Cartridges are extracted with carbonyl-
free HPLC grade ACN. Field-collected cartridges must be removed from cold storage and
allowed to equilibrate to room temperature, approximately 30 minutes, prior to extraction.
Cartridges are removed from the foil pouch, the end caps are removed, and the cartridges are
installed in a holding rack with the inlet of the cartridge pointed down to facilitate elution. Field-
collected samples and associated field and laboratory QC samples discussed in Section 4.3.9.4.1
must be extracted in the same batch.
The ACN extraction solvent must be added to the cartridge so that elution occurs in the direction
opposite of sample air flow (unless the laboratory can demonstrate that reverse elution is not
necessary). Luer syringe barrels or other commercial 1 y-avai 1 able funnels are available for use as
solvent reservoirs for extraction, if needed. Elution may be performed by gravity or vacuum
methods. The cartridge eluent is collected in a clean volumetric flask or other appropriate
volumetrically certified vessel. Once the eluent is collected, the extract is brought to a known
final volume with ACN extraction solvent.
A minimum 2-mL extraction volume is necessary to ensure complete elution of the target
analytes from the sorbent bed. An extraction volume up to 5 mL may be employed, however
larger volumes do not increase the extraction efficiency and may overly dilute the extract.
Once brought to volume, it is highly recommended that an aliquot of the extract is transferred to
an autosampler vial for analysis and the remaining extract stored in a sealed vial protected from
light at < 4°C. The stored extract affords reanalysis if there are problems during analysis (up to
40 days from extraction).
4.3.9.5 Analysis by HPLC
4.3.9.5.1 Instrumentation Specifications. For separation of the DNPH-carbonyls
by HPLC, the analytical system must have the following components:
Separations module capable of precise pumping of ACN, methanol, and/or deionized
water at 1 to 2 m L/min
Analytical column, C18 reversed phase, 4.6 x 50-mm, 1.8-|im, or equivalent
Guard column
Absorbance detector set to 360 nm or mass selective detector capable of scanning m/z
range of 25 to 600
Column heater capable of maintaining 25-35 ± 1 °C-
- Degassing unit
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4.3.9.5.2 Initial Calibration. On each day that analysis is performed, the
instrument must be calibrated (meaning an ICAL must be performed) or the ICAL must be
verified by analysis of a CCV according to the following guidance.
ICAL of the HPLC must be performed initially, when continuing calibration checks fail criteria,
and when there are major changes to the instrument which affect the response of the instrument.
Such changes include, but are not limited to: change of guard or analytical column (if analyte
retention times change), backflushing of the analytical column (if analyte retention times
change), replacement of pump mixing valves and/or seals (if analyte retention times change,
replacement of the detector and/or lamp, and cleaning of the MS source (if HPLC/MS).
Working calibration standards are prepared in ACN at concentrations covering the desired
working range of the detector, typically from approximately 0.01 to 3.0 |ig/mL of the free
carbonyl. In order to avoid confusion or error in concentration calculation, it is recommended
that all concentrations be expressed as the free carbonyl and not the DNPH-carbonyl. The ICAL
must consist of a minimum of five calibration standard levels which cover the entire calibration
range.
Prior to calibrating the HPLC, the instrument must be warmed up and mobile phase should be
pumped for a time sufficient to establish a stable baseline. All solutions to be analyzed must be
removed from cold storage and equilibrated to room temperature prior to analysis.
Once a stable baseline is established, minimally one solvent blank (SB, an aliquot of extraction
solvent dispensed directly into a vial suitable for the HPLC autosampler, or similar) must be
analyzed to demonstrate the instrument is sufficiently clean, after which analysis of calibration
standard solutions may commence. The SB must show target compound responses are less than
the laboratory MDLsp for MDLs determined via Section 4.1.3.1 or the s K portion of the MDL
for MDLs determined via Section 4.1.3.2.
To establish the ICAL, each standard solution must be injected minimally once and preferably in
triplicate. The instrument response (area units) is plotted on the y-axis against the nominal
concentration on the x-axis and the calibration curve generated by linear regression for each
target compound. The calibration curve correlation coefficient (r) must be > 0.999 for linear fit
and the curve must not be forced through the origin. The calculated concentration of each
calibration solution must be within 20% of its nominal concentration.
The absolute value of the concentration equivalent to the intercept of the calibration curve
(|intercept/slope|) converted to concentration units (by division by the slope) must be less than
the laboratory MDLsp for MDLs determined via Section 4.1.3.1 or the s K portion of the MDL
for MDLs determined via Section 4.1.3.2. When this specification is not met, the source of
contamination or suppression must be corrected and the calibration curve reestablished before
sample analysis may commence.
RT windows are calculated from the ICAL by determining the mean RT for each target
compound. For positive identification the RT of a derivatized carbonyl must be within three
standard deviations (3s) or ± 2%, whichever is smaller, of its mean RT from the IC AL. Note that
1 17

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heating the column to a constant temperature of approximately 25 to 30°C promotes consistent
RT response by minimization of column temperature fluctuations.
4.3.9.5.3	Secondary Source Calibration Verification Standard. Following each
successful ICAL, a second SSCV must be analyzed to verify the accuracy of the ICAL. The
SSCV is prepared in ACN at approximately the mid-range of the calibration curve by dilution of
the secondary source stock standard. Alternatively, two or more concentrations of SSCV may be
prepared covering the calibration range. All SSCVs must recover within ± 15% of nominal.
4.3.9.5.4	Continuing Calibration Verification. Once the HPLC has met ICAL
criteria and the ICAL verified by the SSCV, a CCV must be analyzed prior to the analysis of
samples on days when an ICAL is not performed, and minimally every 12 hours of analysis. The
CCV is also recommended to be analyzed after every 10 sample injections and at the end of the
analytical sequence. On days when an ICAL is not performed, a SB must be analyzed prior to
the CCV to demonstrate the instrument is sufficiently clean to commence analysis.
At a minimum, a CCV must be prepared at a single concentration recommended to be at
approximately the mid-range or lower end of the calibration curve, must be diluted from the
primary stock or secondary source stock material, and CCV recovery must be 85 to 115% for
each target compound. As a best practice, two or more concentrations of CCV may be prepared
and analyzed so as to better cover instrument performance across the range of the calibration
curve.
Corrective action must be taken to address CCV failures, including, but not limited to, preparing
and analyzing a new CCV, changing the guard or analytical column, backflushing of the
analytical column, replacement of the detector and/or lamp (if HPLC/UV), and cleaning of the
MS source (if HPLC/MS).
4.3.9.5.5	Replicate Analysis. For each analytical sequence of 20 or fewer field-
collected samples, at least one field-collected sample extract should be selected for replicate
analysis (as prescribed in the workplan). For sequences containing more than 20 field-collected
samples, n such replicates must be analyzed, where n = batch size / 20, and where n is rounded to
the next highest integer. Thus, for batch sizes of 30, two replicate analyses would be performed.
Replicate analysis must demonstrate precision of < 10% RPD for concentrations >0.5
|ig/cartridge.
4.3.9.5.6	Compound Identification. The following criteria must be met in order to
positively identify a target compound:
1.	The signal-to-noise (S:N) ratio of the target compound peak must be > 3:1, preferably
> 5:1. Refer to Section 4.2.5.10.3 for more information on S:N.
2.	The RT of the compound must be within the acceptable RT window determined from
the ICAL average (see Section 4.3.9.5.2).
3.	**HPLC-MS only ** - The target and qualifier ion peaks must be co-maximized
(peak apexes within one scan of each other). Refer to Section 4.2.5.10.3 for more
information on co-maximization.
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4. **HPLC-MS only ** - The abundance ratio of the qualifier ion response to target ion
response for at least one qualifier ion must be within ± 30% of the average ratio from
the ICAL. Refer to Section 4.2.5.10.3 for more information on ion abundances.
Item 1 above does not need to be evaluated closely with each identified peak. Rather the
interpretation of the experienced analyst should weigh heavily on whether the peak meets the
minimal signal-to-noise ratio. Item 2 above may be automated by the analysis software such that
it is automatically flagged. RT windows must be updated with each new ICAL.
If any of these criteria (as applicable) are not met, the compound may not be positively
identified. The only exception to this is when in the opinion of an experienced analyst the
compound is positively identified. The rationale for such an exception must be documented.
4.3.9.5.7 Data Review and Concentration Calculations. Each chromatogram must
be closely examined to ensure chromatographic peaks are appropriately resolved and integration
does not include peak shoulders or inflections indicative of a coelution. The HPLC method may
require modification to employ mobile phase gradient programming or other methods to resolve
coeluting peaks.
Each chromatogram of an extracted cartridge (MB, LCS, LCSD, or any field-collected sample)
must be examined to ensure a DNPH peak is present. Chromatograms in which the DNPH peak
area is < approximately 50% of the typical peak area of the laboratory QC samples must be
investigated for potential compound misidentification due to the likely appearance of additional
chromatographic peaks as a result of formation of side products from the consumption of the
DNPH. This verification can be estimated and should be prescribed within the SOP or similar
controlled document. Once sample identification is confirmed, field-collected samples must be
qualified as estimated concentrations when entered into AQS since depletion of the DNPH to
below 50% of typical levels indicates the potential for negative bias in the measured
concentrations.
The concentrations of target carbonyls in unknown samples are calculated by relating the area
response of the target carbonyl to the relationship derived in the calibration curve generated in
Section 4.3.9.5.2.
Concentration results which exceed the instrument calibration range must be diluted and
analyzed such that peak within the calibration range. The diluted result must be reported and the
associated MDL adjusted accordingly by the dilution factor (the MDL multiplied by the dilution
factor).
While TO-1 1A allows for blank subtraction, this is not an acceptable practice and results must
not be corrected for solvent blank or MB levels. Concentrations exceeding acceptance criteria
for these blanks must prompt investigation as to the source of contamination and associated field
collected sample results may require qualification.
For sampling units which do not provide an integrated collection volume, the beginning and
ending flows are averaged to calculate the collected air volume. For computer controlled
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sampling units, the integrated collected volume is typically available from the data logging
system. Sampled air volumes must be in standard conditions of temperature and pressure (STP),
25°C and 760 mm Hg. Sampling unit flows should be calibrated in flows at standard conditions
so conversion from local conditions to standard flows is not necessary.
The air concentration in |ig/m3 of each target carbonyl is determined by multiplying the
concentration in the extract by the final extract volume and dividing by the collected sample air
volume at standard conditions of 25°C and 760 mm Hg:
Ca =	concentration of the target carbonyl in air (|ig/m3)
Ct =	concentration of the target carbonyl in the extract (|ig/mL)
Ve =	final volume of extract (mL)
V,v = volume of collected air at STP (m3)
Carbonyls concentrations can also be calculated in ppbv by multiplying by a conversion factor
based on the molecular weight of the target carbonyl at STP is calculated as follows:
where:
MW
0.082059 • 298.15
where:
CF = conversion factor (|.ig m"3 ppb"')
MW = molecular weight of the target carbonyl (g/mol)
The air concentration of the target carbonyl in ppb is then calculated as follows:
where:
concentration of the target carbonyl in air (ppb)
concentration of the target carbonyl in air (|ig/m3)
conversion factor (|.ig m"3 ppb"')
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4.3.10 Summary of Quality Control Parameters. A summary of QC parameters is shown
in Table 4.3-4.
Table 4.3-4. Summary of Quality Control Parameters for NATTS Carbonyls Analysis
Parameter
Description and Details
Required Frequeney
Acceptance Criteria
Solvent Blank
(SB)
Aliquot of ACN analyzed to
demonstrate instrument is
sufficiently clean to begin
analysis
Prior to ICAL and daily
beginning CCV
All target carbonyls
< MDLSp (referto Section
4.1.3.1) or.vR (refer to
Section 4.1.3.2)
Initial Calibration
(ICAL)
Analysis of a minimum of five
calibration levels covering
approximately 0.01 to 3.0
Hg/mL
Initially, following failed
CCV, or when changes to the
instrument affect calibration
response
Linear regression
:r> 0.999, the concentration
of each target carbonvl at
each calibration level must be
within ± 20% of nominal
Second Source
Calibration
Verification
(SSCV)
Analy sis of a second source
standard at the mid-range of the
calibration curve to verify
curve accuracy
Immediately following each
ICAL
Recovery of each target
carbonvl within
± 15% of nominal
Continuing
Calibration
Verification
(CCV)
Analysis of a known standard
at the mid-range of the
calibration curve to verify
ongoing instrument calibration
Prior to sample analysis on
days when an ICAL is not
performed, and minimally
every 12 hours of analysis.
Recommended following
every 10 sample injections,
and at the conclusion of each
analytical sequence
Recovery of each target
carbonvl within
± 15% of nominal
Extraction Solvent
Method Blank
(ESMB)
Aliquot of extraction solvent
analyzed to demonstrate
extraction solvent is free of
interferences and contamination
One with every extraction
batch of 20 or fewer samples,
at a frequency of no less than
5%
All target carbonyls
< MDLSp (referto Section
4.1.3.1) or vK. (refer to
Section 4.1.3.2)
Method Blank
(MB)
Unexposed DNPH cartridge
extracted as a sample
One with every extraction
batch of 20 or fewer samples,
at a frequency of no less than
5%
Criteria in Table
4.3-2 must be met
Laboratory
Control Sample
(LCS)
DNPH cartridge spiked with
known amount of target anal vte
at approximately the lower
third of the calibration curve
Minimally quarterly.
Recommended: One with
every extraction batch of 20
or fewer samples, at a
frequency of no less than 5%
Formaldehyde recovery 80-
120% of nominal spike
All other target carbonyls
must recover 70-130% of
nominal spike
Laboratory
Control Sample
Duplicate (LCSD)
Duplicate LCS to evaluate
precision through extraction
and analysis
Minimally quarterly.
Recommended: One with
every extraction batch of 20
or fewer samples, at a
frequency of no less than 5%
Must meet LCS recovery
criteria
Precision < 20% RPD of LCS
Replicate Analy sis
Replicate analysis of a field-
collected sample
Once with every analysis
sequence of 20 or fewer
samples, at a frequency of no
less than 5% (as required by
workplan)
Precision < 10% RPD for
concentrations
>0.5 ng/cartridge
Retention Time
(RT)
RT of each target compound in
each standard and sample
All qualitatively identified
compounds
Each target carbonvl within
± 3.v or ± 2% of its mean
ICAL RT
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Table 4.3-4. Summary of Quality Control Parameters for NATTS
Carbonyls Analysis (Continued)
Parameter
Description and Details
Required Frequency
Acceptance Criteria
Lot Blank
Evaluation
Determination of the
background of the DNPH
cartridge media
Minimum of 3 cartridges or
1% (whichever is greater) for
each new lot of DNPH
cartridge media
All cartridges must meet
criteria in Table 4.3-2
Zero Certification
Challenge
Clean gas sample collected
over 24 hours to demonstrate
the sampling unit docs not
impart positive bias
Annually
Each target carbonvl in the
zero certification < 0.2 ppb
above reference sample
Field Blank
Blank DNPH cartridge exposed
to field conditions for
minimally 5 minutes in the
primary sampling location
Monthly
Must meet criteria in Table
4.3-3
Duplicate Sample
Field sample collected through
the same inlet probe as the
primary sample
10% of primary samples for
sites performing duplicate
sample collection (as
required by workplan)
Precision < 20% RPD of
primary sample for
concentrations
>0.5 ng/cartridge
Collocated Sample
Field sample collected through
a separate inlet probe from the
primary sample
10% of primary samples for
sites performing collocated
sample collection (as
required by workplan)
Precision < 20% RPD of
primary sample for
concentrations
>0.5 ng/cartridge
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4.3.11 References
1.	Determination of Formaldehyde in Ambient Air using Adsorbent Cartridges Followed by
High Performance Liquid Chromatography (HPLC) [Active Sampling Methodology]; EPA
Compendium Method TO-11A; U.S. Environmental Protection Agency: January 1999.
Available at (accessed October 19, 2016):
fattps ¦> v w3.epa.gov/ttaamtil/files/ambient/airtox/fo-llarpdf
2.	MacGregor, I. C., Hanft, E. A., and Shelovv, D. M. (2015). Update on the Optimization of
U.S. EPA Method TO-11A for the Measurement of Carbonyls in Ambient Air. Paper
presented at the National Ambient Air Monitoring Conference, St. Louis, MO, August 10,
2016.
3.	Urone, P., & Ross, R. C. (1979). Pressure change effects on rotameter air flow rates.
Environmental Science & Technology, J3(6), 732-734. doi: 10.1021 /es60154a003
4.	Steven Sai Hang Ho, Ho Sai Simon Ip, Kin Fai Ho, Wen-Ting Dai, Junji Cao, Louisa Pan
Ting Ng. "Technical Note: Concerns on the Use of Ozone Scrubbers for Gaseous Carbonyl
Measurement by DNPH-Coated Silica Gel Cartridge." Aerosol and Air Quality Research, 13:
1 151-1 160, 2013.
5.	Care and Safe Handling of Laboratory Glassware. Coming Incorporated. RG-C1-101-REV2.
2011. Available at (accessed October 19, 2016):
imp tsmedia2.corning.com/LiteScierices/media/pdt/Care and Sate Handling .Lab Glass%\
oi e Rfi-CI-101Rev2.pdf

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4.4
PMio Metals Sample Collection and Analysis
Each agency must codify in an appropriate quality systems document, such as an SOP, or
equivalent, its procedures for performing PMio metals sampling, filter digestion, and digestate
analysis. Various requirements and best practices for such are given in this section. Note that
regardless of the specific procedures adopted, method performance specifications as given in
Section 4.4.13 must be met.
4.4.1 Summary of Method. PMio metals are collected onto a filter by either a low volume
or high volume air sampling method. Following completion of either sampling procedure, the
filter, or portion thereof, is digested to liberate (dissolve) the desired elements by heating in acid,
and the digestate is analyzed via ICP/MS per EPA Compendium Method IO-3.5.1 Briefly,
digestates are introduced to the ICP/MS through pneumatic nebulization into a radio frequency
argon plasma where the elements in solution are desolvated, atomized, and ionized. The ions are
extracted from the plasma by vacuum and separated on the basis of their mass-to-charge ratio by
a quadrupole or TOF MS capable of a resolution of 1 amu at 5% peak height. An electron
multiplier is applied to the ions transmission response and the resulting signal information
recorded and processed by the data system.
The particle-bound metals in the air are collected with a commercial 1 y-avai 1 able standalone air
sampler fitted with a size-selective inlet (SSI) such that only particulate matter (PM) with a mass
median aerodynamic diameter less than 10 |im is captured. Particles are deposited on either
47-mm Teflon* filter (low volume) or 8 inch x 10 inch QFF media over the 24-hour collection
period. The low volume sampling method flow is set to 16.7 liters per minute (LPM; at local
conditions) for a total collection volume of 24.05 m3. The high volume method flow is set to
approximately 1.13 nrVmin (at local conditions) for a total collection volume of approximately
1627 m3. For both low volume and high volume methods, the SSls require a closely regulated
flow rate to ensure PM cut points are accurate and temporally stable.
Following the completion of any desired gravimetric measurements for determining total PMio
gravimetric concentration, the filters are digested for metals analysis. Following collection,
filters should be stored at ambient conditions and must be digested and analyzed within 180
days.
The target metals of interest to the NATTS Program are listed in Table 4.4-1.

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Table 4.4-1. NATTS Program Metals Elements and Associated CAS Numbers
Element
CAS Number
Antimony b
7440-36-0
Arsenic a b
7440-38-2
Berylliuma b
7440-41-7
Cadmiuma b
7440-43-9
Chromium
7440-47-3
Cobaltb
7440-48-4
Leada b
7439-92-1
Manganese a b
7439-96-5
Nickela b
7440-02-0
Seleniumb
7780-49-2
a NATTS Tier I core analyte
' NATTS PT target analyte
4.4.2 Advantages and Disadvantages of High Volume and Low Volume Sample
Collection. Summarized below are some of the advantages and disadvantages of the high and
low volume air sampling for PMio metals.
4.4.2.1	Low Volume Sampling
Advantages
•	Many low volume samplers are already in use at PM monitoring sites to assess
compliance with the National Ambient Air Quality Standards. As a result, many
monitoring agencies are familiar with and have the infrastructure to support low
volume PM sampling.
•	Teflon* filters, as compared to QFFs, typically have lower background levels of
metals such as chromium, nickel, manganese, and cobalt. As a result, MBs are
cleaner and MDLs that account for MB levels are lower.
•	Low volume instruments are available into which several filters may be
simultaneously loaded so as to permit collection of several sampling events in
sequence without the need for operator intervention.
Disadvantages
•	The extraction and analysis method must have greater sensitivity and background
contamination must be more strictly limited in order to achieve MDLs equivalent to
high volume sampling, due to the lower total sample volume collected.
•	The entire Teflon* filter is digested for analysis, thus error in preparation may require
invalidation of results, and it not possible to prepare duplicate and/or spike duplicate
field collected samples for QC purposes.
4.4.2.2	High Volume Sampling
Advantages
•	At the listed flow rates, the high volume sampling method collects approximately 67
times more mass on the filter than low volume sampling, thereby providing greater
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sensitivity (approximately seven-fold) for metals analysis even after taking into
consideration that only a portion (typically approximately 1/9) of the QFF is digested
for analysis.
•	In the event of loss of the primary sample and when assessment of method precision
and bias is desirable, duplicate and spike duplicate samples may be readily prepared
by extraction and analysis of another filter field collected sample strip.
Disadvantages
•	QFFs typically have higher background levels of target metals, such as chromium,
nickel, manganese, and cobalt.
•	Sequential sampling is not possible with high volume filter sampling instruments.
4.4.3 Minimizing Contamination, Filter Handling, and Filter Inspection
4.4.3.1	Minimizing Contamination. Careful handling of the filter media is required to
ensure that metals measured on the filter are present as a result of sampling the ambient
atmosphere, rather than due to contamination. Each agency must codify into an appropriate
quality system document, such as an SOP, procedures that it will follow to minimize the
introduction of metals contamination during filter handling, processing, extraction, and
subsequent analysis of digestates. What follows in this section are practices either that are
required or are recommended for adoption into an agency's quality system.
See also Section 4.4.6 for guidance on minimizing contamination during the preparation of
lab ware.
4.4.3.2	Filter Handling. Filters must only be handled with gloved hands or plastic or
Teflon*-coated forceps, and filter media must not be manipulated with metal tools. Tools for
portioning filter strips must be ceramic or plastic. Forceps and work areas should be routinely
decontaminated using a dilute nitric acid solution followed by rinses with deionized water. Use
of volumetric syringes with metal needles must be avoided.
Teflon* filter media should be transported to and from the field in non-metallic cassettes which
must be kept tightly capped except during installation of filters into sampling units. Placement
of filters into, and subsequent removal of filters from cassettes should be performed in the
laboratory in a clean area where measures are taken to control the levels of airborne particulate
matter, such as a conditioning room for filter weighing. Such filter weighing rooms typically
employ dust-reduction methods such as high efficiency particulate air (HEPA) filtration to
minimize potential deposition contamination.
QFFs should be transported and maintained in manila or glassine envelopes which protect the
filter from dust deposition and from physical damage. The filter should be placed into, and
subsequently removed from, the cassette while the cassette is in a clean area, one without
obvious dust contamination, away from visible sources of PM, and with minimal air movement.
Following removal from the cassette after the conclusion of sampling, the filter must be folded
lengthwise in half (with gloved hands) with the particulate matter inward, and placed into a
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protective manila envelope or folder, or within a glassine envelope to protect the filter from loss
of PM or from deposition of dust.
4.4.3.3 Filter Inspection. Filter media must be inspected for pinholes, discolorations,
creases, thin spots, and other defects which would make them unsuitable for sample collection.
Teflon* filters must additionally be inspected for separation of the support ring. Filters should
be inspected on a light table or similar apparatus which allows backlighting of the filter to aid in
the identification of defects. Any surface (such as the light table) coming into contact with the
filter media must be decontaminated from dust and residue prior to use with deionized water and
lint-free wipes. All filter handling requirements given in Section 4.4.3.2 must be followed.
4.4.4 Precision - Sample Collection and Laboratory Processing. Each agency must
codify in an appropriate quality systems document, an SOP, or similar, procedures that it will
follow to assess precision. Given below are the various types of precision and guidance on how
to measure each.
4.4.4.1	Sample Collection Precision. Given that each PMio metals instruments consists of a
discrete inlet and sampling pump, collection of duplicate samples is not possible. Thus,
evaluation of the precision of the entire PMio metals sampling technique, from collection through
extraction and analysis, may only be performed by way of collocated sampling.
For monitoring sites conducting collocated PMio metals sampling, collocated samples must be
collected as minimally 10% of the primary samples collected (as prescribed in the workplan).
This is equivalent to a minimum of six collocated samples for sites conducting one-in-six days
sampling for a total of 61 primary samples annually. More frequent collocated sample collection
provides additional sample collection precision and is encouraged where feasible.
Collocated sample results must show precision of < 20% RPD compared to the primary sample
for concentrations > 5x MDL. Root cause analysis must be performed for instances in which
collocated samples fail this precision specification and the results of the primary and collocated
sample must be qualified when entered into AQS.
4.4.4.2	Laboratory Precision
4.4.4.2.1	Low Volume Teflon® Filter Laboratory Precision. Teflon* filters must
be extracted in their entirety. As a result, duplicate samples may not be prepared by subdividing
a filter. However, the precision of filter digestion and analysis should be assessed by the
preparation and analysis of duplicate LCSs. A sample digestate may be selected with each
digestion batch to be analyzed in replicate to determine analytical precision. To summarize,
•	A duplicate LCS informs the precision of digestion and analysis procedures, and
•	Replicate analysis of a sample digestate provides precision for the analysis only.
4.4.4.2.2	High Volume QFFLaboratory Precision. Sample processing and
analysis precision may be evaluated in several different ways with QFFs. For example, to
evaluate the precision of the filter preparation, digestion, and analysis processes, duplicate strips
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may be portioned from a field collected QFF filter and digested separately and duplicate LCSs
may be prepared. Preparation, digestion, and analysis of a matrix spike (MS) and matrix spike
duplicate (MSD) duplicate pair can additionally be performed to evaluate the matrix effects on
precision of field collected samples. Finally, to determine analytical precision, a sample
digestate may be analyzed in replicate. To summarize:
•	Duplicate sample filter strips and duplicate LCSs provide precision of digestion and
analysis procedures;
•	Duplicate matrix spike filter strips provide information on the precision of digestion
and analysis procedures, and include an assessment of potential matrix effects of that
specific sample; and
•	Replicate analysis of a sample digestate provides precision for the analysis only.
4.4.5	Field Blanks. For both high volume and low volume sampling methods, field blank
samples must be collected minimally monthly for each primary sampling unit (total of 12 per
year for a total of 18% of samples [12 out of 61]). For collocated sampling units, field blank
samples should be collected minimally twice per year (two out of six) or for 18% of collocated
samples collected, whichever is greater.
Field blanks must be generated by installing the field blank filter into the sampling unit to
simulate a field sample, however the field blank does not experience sample flow. After
minimally 5 minutes have elapsed (or the duration of sample switching required by the sampling
unit, as applicable), the filter is retrieved and stored at the field site until the associated field
sample can be retrieved and transported to the laboratory.
Field blank analysis must demonstrate all target elements < MDL.
An exposure blank is similar to a field blank, but is not required, and may be collected via
several protocols. The exposure blank includes exposing the filter to the ambient conditions by
installation in a sampling unit, and just like a field blank, air is not drawn through the exposure
blank cartridge. The exposure blank filter sample may be installed in the primary sampling unit
on non-sample collection days or could be installed in a collocated sampling unit during
collection of the primary sample.
4.4.6	Labware Preparation for Digestion and Analysis. Regardless of how filters are
digested, labware cleaning is essential to ensure background contamination is minimized. As
with other contamination minimization procedures, each agency must codify in an appropriate
quality systems document, such as an SOP, or equivalent, its procedures for effective cleaning
and decontamination of labware. Regardless of the procedures adopted, method performance
specifications as given in Section 4.4.13 must be met.
Labware for hot block digestions is typically single use; however, labware for microwave
digestion and volumetric labware for preparation of standards and reagents must be effectively
cleaned before each use. To do so, labware should be rinsed with tap water to remove as much
of the previous contents as possible. Following this tap water rinse, labware should be soaked
minimally overnight in a > 10% HNO3 (v/v) aqueous solution. Soaking should be followed by a
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minimum of three rinses with deionized water and air drying. Alternatively, lab ware cleaning
instruments are commercially available which may be programmed to provide washing, rinsing,
and soaking cycles in various detergent and acid solutions.
Volumetric lab ware must not be heated above 80 to 90°C as this voids the volumetric
certification. 2 Clean lab ware should be stored in a contaminant-free area, upside down or capped
to minimize introduction of contamination. Elevated levels in calibration blanks and digested
reagent blanks indicate the presence of contamination. Additional cleaning and acid rinsing
steps should be considered when blanks exceed the specified acceptance criteria.
4.4.7	Reagents for Metals Digestion and Analysis. Due to the sensitivity of 1 CP/MS
instruments, the purity of reagents and standards is paramount. Reagents and standards must be
certified and traceable with COAs, and it is recommended that all reagents and standards be of
the greatest purity possible and have minimal background levels of target elements. Regardless
of the reagents and standards selected, calibration and reagent blanks must be meet method
specifications as given in Section 4.4.13.
Reagent water for the preparation of digestion solutions and for dilution of standard materials
should be ASTM Type I or equivalent (having an electrical resistivity greater than 18 MO-cm).
Acids should be trace metals grade, ACS spectroscopic grade, UHP grade, or equivalent. Further
polishing of reagent water and redistillation of acids may be necessary to achieve blank
acceptance criteria. Borosilicate glass volumetric flasks and storage containers should be
avoided. Teflon* or plastic (polyethylene, polypropylene, etc.) certified volumetric flasks and
storage bottles are preferable as they do not leach contaminants into stored solutions. Solutions
prepared in borosilicate glass volumetric flasks should be transferred as soon as possible to a
Teflon® or plastic storage container.
4.4.8	Method Detection Limits. MDLs must be determined per the guidance provided in
Section 4.1. Furthermore, MDLs must be determined with reagents, media, and sample handling
techniques identical to those employed for the processing of field samples. Determined MDLs
for Tier I core analytes must meet the requirements listed in the most recent workplan.
4.4.8.1	Teflon® Filter MDL. If the 40 CFR Part 136 Appendix B guidance in Section 4.1.3.1
is followed. Teflon® filter MDLs must be determined by digesting minimally seven spiked filters
and seven method blank filters (all selected from the same lot of filters) in three temporally-
separated and unique digestion and analytical batches. Both the MDLsp and MDLb must be
tracked and documented. QC blanks, which are not prepared with the filter matrix, are compared
to the MDLSp regardless of whether it is reported as the laboratory MDL. Alternatively, MDLs
may be determined following the procedure in Section 4.1.3.2. For laboratories determining
MDLs according to Section 4.1.3 .2, laboratories must track the portion of the MDL determined
by s K for comparison to QC blanks which are not prepared with the filter matrix.
4.4.8.2	QFF MDL. If the updated 40 CFR Part 136 Appendix B procedure in Section 4.1.3.1
is followed, QFF MDLs must be determined by digesting seven spiked filter strips and seven
method blank filter strips in three temporally-separated and unique digestion and analytical
batches. The filter strips should be from a different filter (from the same lot of filters) for each
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batch. Both the MDLsp and MDLb must be tracked and documented. QC blanks, which are not
prepared with the filter matrix, are compared to the MDLsp regardless of whether it is reported as
the laboratory MDL. Alternatively, MDLs may be determined following the procedure in
Section 4.1.3.2. For laboratories determining MDLs according to Section 4.1.3.2, laboratories
must track the portion of the MDL determined by s K for comparison to QC blanks which are
not prepared with the filter matrix.
4.4.9 Low Volume Sample Collection and Digestion
4.4.9.1	Air Sampling Instruments. Low volume sample collection instruments must comply
with the Low-Volume PMio FRM requirements as listed in 40 CFR Part 50 Appendix L, i.e.,
they must operate at the design flow rate of 16.67 L/min (at local conditions), utilize 47-mm
Teflon* filter collection media, and be fitted with the "pie plate" PMio inlet or the louvered inlet
specified in 40 CFR 50 Appendix L, Figures L-2 through L-19, configured as in the PMio
reference method. The following instruments are among those that comply with these
specifications:
•	Andersen Model RAAS10-100
•	Andersen Model RAAS10-200
•	Andersen Model RAAS 10-300
•	BG1 Incorporated Model PQ100
•	BG1 Incorporated Model PQ200
•	Opsis Model SM200
•	Thermo Scientific or Rupprecht and Pataschnick Parti sol Model 2000
•	Thermo Scientific Parti sol 2000-FRM
•	Thermo Scientific Parti sol or 2000i
•	Rupprecht and Patashnick Parti sol-FRM 2000
•	Thermo Scientific Parti sol-PIus Model 2025
•	Thermo Fisher Scientific Parti sol 2025i
•	Rupprecht and Patashnick Parti sol-Plus 2025
•	Tisch Environmental Model TE-WilburlO
Sampler siting requirements are listed in Section 2.4.
4.4.9.2	Flow Calibration. Sampling unit flow calibration must be performed minimally
annually against a traceable calibrated flow transfer standard by adjusting the sampling unit flow
to match the certified standard.
Moreover, the instrument flow should be checked minimally quarterly, recommended to be
monthly, and per 40 CFR Part 50 Appendix L, the flow adjusted if it is not within ± 4% of the
transfer standard or within ± 5% of the design flow rate. Prior to performing flow checks,
sampling units should be leak checked to ensure that flow path integrity is maintained. A leak
check should be performed minimally every five sample collection events. A successful leak
check indicates a total flow of less than 80 mL or loss of less than 25 mm Hg.
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4.4.9.3	Filter Media. Low volume PMio metals must be collected onto a 46.2-mm Teflon*
filter substrate with a polypropylene support ring, 2-|im pore size, and a particle deposit area of
1 1.86 cm2. Filters must be stamped or printed with a unique identifier on either the support ring
or on the filter substrate/ EPA typically annually sends agencies the filter media.
4.4.9.3.1 Lot Background Determination. For each lot of filters, the concentration
of metals in the lot background must be determined by digesting and analyzing five separate
filters from a given lot.
While there is no prescribed threshold for the lot background concentration for each element, the
lot blank concentrations must be reported to AQS. Note that the previous version of this TAD
permitted lot blank subtraction provided results were flagged in AQS with the QA data qualifier
"CB", however lot blank subtraction is not permitted. AQS guidance is provided in Section
3.3.1.3.15.
4.4.9.4	Filter Sampling, Retrieval, Storage, and Shipment. Teflon® filters will likely arrive
at the field site already installed in a cassette. The filter must be installed per the requirements of
the specific low volume instrument. A leak check may then be performed followed by
verification of the correct sampling date, duration, and target flow rate.
Upon sample retrieval, instrument performance information including the average temperature,
barometric pressure, average flow, total collected volume, collection duration, and any flags
indicating a problem during collection should be recorded, downloaded, or otherwise recorded,
as appropriate. Following removal from the instrument, the covers are placed back onto the filter
cassette, and the cassette sealed into a resealable plastic bag. Filters need not be shipped or
stored refrigerated. Filters must be handled per the procedures in Section 4.4.3.1. The sample
custody form must be completed and accompany the collected sample at all times until
relinquished to the laboratory. COC documentation must comply with Section 3.3.1.3.7.
4.4.9.4.1 Sampling Schedule and Duration. Metals sample collection must be
performed on a 1 -in-6 days schedule for 24 ± 1 hours beginning at midnight and concluding at
midnight of the following day, standard time (unadjusted for daylight savings time), as per the
national sampling calendar. For missed or invalidated samples, a make-up sample should be
scheduled and collected per Section 2.1.2.1. Clock timers controlling sampling unit operation
must be adjusted so that digital timers are within ±5 minutes of the reference time (cellular
phone, GPS, or similar accurate clock) and mechanical timers within ±15 minutes.
4.4.9.5	Teflon® Filter Digestion
4.4.9.5.1 Laboratory Digestion QCSamples. Each sample digestion batch must
consist of 20 or fewer field-collected filters (primary samples, collocated samples, and field
blanks). The following laboratory QC is required with each digestion batch:
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-	Negative Control Samples (Blanks), one each:
o Reagent Blank (RB) - digestion solution with no filter
o MB - blank filter with digestion solution
-	Positive Control Samples (Spikes), one each:
o Reagent Blank Spike (RBS) - spiked digestion solution with no filter
o LCS - spiked blank filter with digestion solution
o LCSD - duplicate spiked blank filter with digestion solution
Laboratory QC samples must be processed, digested, and analyzed identically to field-collected
samples, including, if applicable, filtration and/or centrifugation of digestates.
4.4.9.5.2 Digestion Procedure. Filter must be digested with one of three possible
methods: hot block digestion, microwave digestion, or heated sonication. The three different
techniques are described in the following sections.
4.4.9.5.2.1 Hot Block Digestion
The hot block digestion wells must be checked to ensure each reaches and is able to maintain the
target digestion temperature initially when put into use and annually thereafter. To do so, the hot
block is set to the target temperature (typically 95°C) and, after the temperature has been
reached, a digestion vessel filled with deionized water, known as a temperature blank, is placed
into each well. After approximately 5 minutes (or long enough for the temperature to stabilize),
the temperature of the water in each temperature blank is measured. Temperatures across the
block should be within ± 5°C of the target temperature setting.
To perform digestion of Teflon* filters, each is placed into a separate digestion vessel. Certified
single-use metals-free vessels with certified volumetric graduations are commercially available
for hot block digestions and other vessels may be utilized provided they meet the required blank
specifications. The lot and manufacturer of the digestion vessels must be documented with each
batch. Sufficient digestion solution must be added to each vessel so as to completely submerge
the filter. Digestion solutions typically consist of approximately 2% (v/v) nitric acid (HNO3) and
0.5% (v/v) hydrochloric acid (HC1). To assist in the recovery of antimony, it may be necessary
to add 0.1% hydrofluoric acid (HF) to the digestion solution.
The hot block digester is powered on and warmed to the desired temperature (~95°C) prior to
placing each digestion vessel into a digestion well. Each digestion vessel should be covered with
a precleaned ribbed watch glass and the batch of filters should be digested for a recommended
for 2.5 hours, though digestion must be for a minimum of 30 minutes. Note that this duration of
digestion must be consistent from batch to batch. An automatic shutoff timer can ensure
consistent digestion duration. A temperature blank must be included with each batch to ensure
that the proper temperature is reached during the digestion period. Digestion vessels should be
observed periodically throughout digestion to ensure none go to dryness and that the filters
remain submerged. Deionized water should be added to digestion vessels to avoid going to
dryness. Filters which float should be resubmerged with a clean plastic or Teflon* stirring rod.
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Once digestion has completed, digestion vessels are removed from the block and cooled to room
temperature (approximately 30 minutes). Once cooled, the walls of the digestion vessel should
be rinsed down with approximately 10 mL of deionized water and the digestates should be
allowed to settle for minimally 30 minutes. Following settling, digestates must be brought to
their final volume with deionized water. The final volume may be measured with the
graduations on the vol urn etri cal 1 y-certi fi ed digestion vessel. Otherwise, digestates must be
transferred to a Class A volumetric vessel and the digestion vessel must be rinsed several times
with small (2 to 3 mL) volumes of deionized water to ensure a quantitative transfer. The
transferred digestates must be then brought to volume with deionized water.
For transfer of aliquots for analysis, filtration or centrifugation may be necessary to eliminate
particulate interference on the ICP/MS. All such processing steps must be performed on both the
field-collected and laboratory batch QC samples.
4.4.9.5.2.2 Microwave Digestion
Microwave digestion has several disadvantages when compared to hot block digestion. For
example, microwave digestion equipment and accessories are expensive. Digestion vessels and
associated caps must be cleaned and decontaminated after each use. Microwave oven power
must be calibrated on a specified, periodic basis to ensure that the digestion energy is
appropriate, comparable, and stable from batch to batch. Calibration frequency should not
exceed six months and a best practice is to verify microwave power monthly. To ensure the
appropriate amount of heat is imparted to vessels in an incompletely filled digestion rack, blank
vessels may need to be added or the microwave power may need to be reduced. Due to the
higher pressure and temperature, digestion vessels may overpressurize and explode, resulting in
loss of sample and possible injury to laboratory staff. While such is possible, modem microwave
digestion units typically employ temperature and pressure monitoring to adjust the power to
reduce the likelihood of explosion.
The advantages of microwave compared to hot block digestion are that digestion may be
performed more quickly (in approximately 30 minutes), digestions are more reproducible due to
the even heating, the closed digestion vessels ensure no loss of volatile analytes such as mercury
and lead and decrease the likelihood of the introduction of external contamination, and digestions
are more complete as a result of the increased temperature and pressure.
To digest air filter samples by microwave digestion the microwave program should permit
ramping the temperature to 180°C over 10 minutes and holding at 180°C for 10 minutes
followed by a 5-minute cool down. Other programs are also acceptable provided the requisite
batch QC criteria are met.
For digestion, each Teflon* filter must be placed into a separate microwave digestion vessel.
Sufficient digestion solution must be added to each vessel so as to completely submerge the
filter. Digestion solutions typically consist of approximately 2% (v/v) HNO3 and 0.5% (v/v)
HC1. Addition of a small amount (~0.1%) of hydrofluoric acid (HF) to the digestion solution
may be needed to maintain antimony in solution.
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The vessel caps and pressure relief valves are installed on the microwave digestion vessels and
each vessel weighed to the nearest 0.01 g with a calibrated analytical balance. Weighed
digestion vessels are then installed in the carousel in the microwave. The microwave digestion
program is run concluding with a cool down. At the end of the program, the microwave status
should be checked to verify the program completed appropriately and the digestion vessel
carousel is carefully removed from the microwave oven and allowed to cool in a fume hood.
Once cooled, vessels must be weighed to the nearest 0.01 g to ensure no loss of sample. Vessels
which exhibit mass loss of > 0.01 g must be invalidated or, minimally, their analysis results must
be flagged. Once cooled and weighed, vessels may be opened. Caution must be used when
opening vessels as the contents may still be under pressure.
After cooling, the walls of the digestion vessel should be rinsed down with approximately 10 mL
of deionized water and the digestates should be allowed to settle for minimally 30 minutes.
Following settling, digestates must be transferred to a Class A volumetric vessel and the
digestion vessel rinsed several times with small (2 to 3 mL) volumes of deionized water to
complete the quantitative transfer. The digestates are brought to volume with deionized water.
For transfer of aliquots for analysis, filtration or centrifugation may be necessary to eliminate
particulate interference on the ICP/MS. All such processing steps must be performed on both the
field-collected and laboratory batch QC samples.
4.4.9.5.2.3 A cid Sonication
Each filter is placed into a separate digestion vessel. Certified single-use metals-free vessels
with certified volumetric graduations are commercially available and other vessels may be
utilized provided they meet the required blank specifications. The lot and manufacturer of the
digestion vessels must be documented with each batch. Sufficient 4% (v/v) HNO3 digestion
solution is added to each vessel so as to completely submerge the filter. Addition of a small
amount (~0.1%) of hydrofluoric acid (HF) to the digestion solution may be needed to maintain
antimony in solution.
The sonication bath is powered on and warmed to the desired temperature (~69°C) prior to
placing the digestion vessels into the bath. Each digestion vessel should be capped and sonicated
for a minimum of 3 hours. Digestion vessels should be observed periodically throughout
digestion to ensure the filter remains submerged. Filters which float should be resubmerged with
a clean plastic or Teflon* stirring rod.
Once the digestion program has completed, digestion vessels are removed from the bath and
cooled. Once cooled, the walls of the digestion vessel should be rinsed down with
approximately 10 mL of deionized water and the digestates should be allowed to settle for
minimally 30 minutes. Following settling, digestates must be brought to their final volume with
deionized water. The final volume may be measured with the graduations on the volumetrically-
certitied digestion vessel. Otherwise, digestates are transferred to a Class A volumetric vessel
and the digestion vessel are rinsed several times with small (2-3 mL) volumes of deionized water
to ensure a quantitative transfer. The transferred digestates are then brought to volume with
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deionized water.
For transfer of aliquots for analysis, filtration or centrifugation may be necessary to eliminate
particulate interference on the ICP/MS. All such processing steps must be performed on both the
field-collected and laboratory batch QC samples.
4.4.10 High Volume Sample Collection and Digestion
4.4.10.1	Air Sampling Instruments. High volume sample collection instruments must comply
with the High-Volume PMio FRM requirements in 40 CFR Part 50 Appendix J, i.e., they must
operate at a design flow rate of 1.13 m3 (at local conditions), utilize 8 inch x 10 inch QFF
collection media, and be fitted with the PMio inlet per EPA Reference Method RFPS-0202-141,
RFPS-1287-063, or equivalent. The following sampling units are among those that comply with
these specifications:
•	Ecotech Model 3000
•	Graseby Andersen/GMW Model 1200
•	Graseby Andersen/GMW Model 321 -B
•	Graseby Andersen/GMW Model 321 -C
•	Tisch Environmental Model TE-6070 or New Star Environmental Model NS-6070
•	Wedding and Associates or Thermo Environmental Instruments Inc. Model 600
Sampler siting requirements are listed in Section 2.4.
4.4.10.2	Flow Calibration. Sampling unit flow calibration must be performed minimally
annually against a traceable calibrated flow transfer standard by adjusting the sampling unit flow
to match the certified standard.
Moreover, the instrument flow should be checked minimally quarterly, recommended to be
monthly, and the flow adjusted if it is not within ± 7% of the transfer standard or within ± 10%
of the design flow rate. Prior to performing flow checks, sampling units should be leak checked
to ensure that flow path integrity is maintained. Leak checks are performed by installing a piece
of polycarbonate or other suitable substrate to seal off the filter plate and briefly operating the
sampling unit motor. If a high-pitched whistle is heard, there is a leak in the flow path which
must be remedied before sample collection can commence. Leak checks should be performed
approximately every fifth sample collection event.
4.4.10.3	Filter Media. Sampling media consist of 8 inch x 10 inch QFF substrate with a 2-|im
pore size, capable of 99% particle sampling efficiency for particles 0.3 |im in diameter or larger.
Filters must be stamped or printed with a unique identifier on the corner of the filter and are
typically provided annually by EPA.4
4.4.10.3.1 Lot Background Determination. For each lot of filters, the concentration
of metals in the lot background must be determined by digesting and analyzing five filter strips,
each cut from a separate filter from a given lot of filters. For monitoring agencies contracting
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analysis, filters for lot blanks should be supplied to the laboratory to determine the lot
background.
QFFs typically have background levels higher than Teflon* filters; chromium, cobalt, lead,
manganese, and nickel may be routinely found. Note that the previous version of this TAD
permitted lot blank subtraction provided results were flagged in AQS with the QA data qualifier
"CB", however lot blank subtraction is not permitted.
While there is no prescribed threshold for the lot background concentration for each element, the
lot blank concentrations must be reported to AQS. Information on reporting to AQS may be
found in section 3.3.1.3.15.
4.4.10.4 Filter Sampling, Retrieval, Storage, and Shipment. Filter media may be installed in
a sampling cassette at the laboratory before shipment to the field, or the site operator may be
required to install the filter into the cassette. Installation of the filter into the cassette must be
performed in a clean (minimal dust) indoor environment, preferably protected from air
movement, with the filter identifier oriented downward. A cover should be attached to the top of
the cassette to protect the filter sampling surface. Storing the assembled filter and cassette in a
sealed plastic bag during transport and storage is a best practice.
The cam-lock bolts of the size-selective inlet on the sampling unit are loosened to allow the inlet
to open on the hinge and the inlet locked open using a prop. The swing bolts are then loosened
to allow the assembled cassette and filter to be installed. Installation must be performed
carefully to ensure that the rubber gasket on the base of the sampling unit forms a tight seal
around the cassette. The swing bolts are then tightened in a diagonal pattern to ensure even
pressure is applied to the cassette. Each time a sample is set up, the inside of the sampling head
and mating surfaces should be given a quick visual inspection for loose debris or corrosion
which could impact the filter and the integrity of the gasket on the size-selective inlet. Once the
cassette is installed, the inlet is closed and secured to the body of the sampling unit using the
cam-lock bolts.
If the sampling unit is equipped with electronic flow control to automatically adjust flow rate
based on ambient temperature and pressure, the sample schedule program must be verified
before the sampling unit is ready for collection. If the sampling unit is not equipped with
electronic flow control, the sampling unit must be powered on and allowed to run for minimally
five minutes (ten minutes are recommended) before a reading of the pressure drop across the
flow venturi, which must be cross-referenced to a corresponding calibrated flow. The unit is
then powered off and the sample schedule program verified.
Upon sample retrieval, instrument performance information including the average temperature,
barometric pressure, average flow, total collected volume, collection duration, and any flags
indicating a problem during collection should be recorded, downloaded, or otherwise recorded,
as appropriate. For sampling units without electronic flow control, the sampling unit must be
powered on and allowed to run for minimally five minutes (ten minutes are recommended)
before recording the reading of the pressure drop across the flow venturi. The filter sample
cassette is then removed from the sampling unit and the cover placed on the cassette (it is a best
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practice to place the filter cassette into a resealable plastic bag) until the filter may be removed
from the cassette in a clean area, free of obvious contamination, and with minimal air movement.
When removed from the cassette, the filter must be folded in half, lengthwise, with the
particulate matter inward. Folding the filter lengthwise is the best way to ensure that the
portioned filter strips include a portion of the fold. The folded filter must then be placed within a
manila or glassine envelope for transportation to the laboratory. Alternatively, the cover may be
replaced on the filter cassette and the cassette placed in a resealable plastic bag for transportation
to the laboratory where the filter is removed. Filters need not be shipped or stored cold. Filters
must be handled per the procedures in Section 4.4.3.1. The sample custody form must be
completed and accompany the collected sample at all times until relinquished to the laboratory.
COC documentation must comply with Section 3.3.1.3.7.
4.4.10.4.1 Sampling Schedule and Duration. Metals sample collection must be
performed on a 1 -in-6 days schedule for 24 ± 1 hours beginning at midnight and concluding at
midnight of the following day, standard local time (unadjusted for daylight savings time), per the
national sampling calendar. For missed or invalidated samples, a make-up sample should be
scheduled and collected per Section 2.1.2.1. Clock timers controlling sampling unit operation
must be adjusted so that digital timers are within ±5 minutes of the reference time (cellular
phone, GPS, or similar accurate clock) and mechanical timers within ±15 minutes.
4.4.10.5 QFF Digestion
4.4.10.5.1 Laboratory Digestion QCSamples. Each sample digestion batch must
consist of 20 or fewer field-collected filters (primary samples, collocated samples, and field
blanks). The following laboratory QC is required with each digestion batch:
-	Negative Control Samples (Blanks), one each:
o Reagent Blank - digestion solution only (no filter strip)
o Method Blank - blank filter strip with digestion solution
-	Positive Control Samples (Spikes), one each:
o RBS - spiked digestion solution only (no filter strip - ensures proper spike
recovery without the filter matrix)
o LCS - spiked blank filter strip with digestion solution (evaluates proper spike
recovery with blank filter matrix)
o LCSD - (optional) duplicate spiked blank filter strip with digestion solution
(evaluates precision of proper spike recovery with blank filter matrix)
-	Matrix QC Samples, one each:
o Duplicate Sample Strip - An additional strip cut from a collected field sample
(evaluates precision of the sample result and digestion process)
o Matrix Spike - An additional strip cut from a collected field sample which is
spiked at the same concentration as the LCS (provides information on matrix
effects on spike recovery)
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o Matrix Spike Duplicate - An additional strip cut from a collected field sample
which is spiked at the same concentration as the LCS (provides precision
information on matrix effects on spike recovery)
4.4.10.5.2 Digestion Procedure. Prior to digestion, filter samples must be examined
for damage to the filter or other defects (presence of insects, large visible particulates, etc.)
which may affect sample integrity or analysis results. Following inspection, the requisite
number of filter strips is to be cut from each filter to complete the digestion batch as listed above
in Section 4.4.10.5.1.
Sampled 8 inch < 10 inch QFF media have an exposed filter area of 7 inch x 9 inch, leaving a
!4-inch border of unsampled area around the entire filter. Strips for digestion should be cut
perpendicular to the fold line for filters folded lengthwise as shown in Figure 4.4-1 and must not
include the unsampled V% inch x 8 inch border section at each end (left and right in Figure 4.4-1).
This results in a 1 inch « 7 inch exposed section of the filter for each strip, equivalent to 1/9 of
the 63 in2 exposed filter area. Other conventions for portioning filter strips are acceptable so
long as they include 7 in2 of exposed filter area and a portion of the fold.
fold line
1/2" unexposed border
exposed filter area
		 x 9")
filter strips for digestion (1" x 8")
exposed area = 1" x 7"
Figure 4.4-1. Portioning of QFF Strips for Digestion
Filter sample strips may be digested using one of three methods: hot block digestion, microwave
digestion, or heated sonication.
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4.4.10.5.2.1 Hot Block Digestion
Each filter strip must be accordion folded or coiled and placed into separate digestion vessels.
Otherwise follow procedures as given in Section 4.4.9.5.2.1. Note that HF acid is not
recommended for digestion of QFFs.
4.4.10.5.2.2	High Volume QFF Microwave Digestion
Each filter strip must be accordion folded or coiled and placed into separate digestion vessels.
Otherwise follow procedures as given in Section 4.4.9.5.2.2. Note that HF acid is not
recommended for digestion of QFFs.
4.4.10.5.2.3	High Volume QFF Acid Sonication
Each filter strip must be accordion folded or coiled and placed into separate digestion vessels.
Otherwise follow procedures as given in Section 4.4.9.5.2.3. Note that HF acid is not
recommended for digestion of QFFs.
4.4.11	PMio Metals Analysis by ICP/MS - EPA IO-3.5
4.4.11.1	ICP/MS Instrumentation. In order to achieve the necessary sensitivity, PMio metals
for NATTS Program work must be analyzed via ICP/MS. Analysis via ICP-atomic emission
spectroscopy (ICP-AES), graphite furnace atomic absorption (GFAA), or flame atomic
absorption (FAA) is insufficiently sensitive and not permitted. ICP/MS instruments may be
equipped with either a quadrupole MS or a TOF MS. For either system of MS, the general
operation of the ICP is common and subject to the same interferences. The chosen instrument
must have the capability to minimally scan for masses ranging from 7 to 238 amu.
4.4.11.2	ICP/MS Interferences. ICP/MS instruments are susceptible to interferences which
can result in bias or saturation effects which overload the detector and require an extended period
to bring detector response back into the acceptable sensitivity range. Such interferences are
explained in more detail below.
Isobaric interferences are caused by isotopes of different elements which have the
same mass number as a target element. This results in a high bias for the target
element, but such biases may be corrected with standard equations in ICP/MS
software.
- Polyatomic, or molecular interferences are caused by combination of ions to form
molecular ions which have the same mass as a target element. These interferences
can result in high or low bias depending on the target element. Use of a collision
reaction cell to remove polyatomic interferences upstream of the MS detector can
greatly reduce or completely eliminate the effect of the interference.
Transport interferences are a result of matrix effects which alters aerosol formation
and results in changes to solution nebulization at the plasma. These interferences are
typically not an issue with air filter analysis as the concentration of dissolved solids in
digestates is fairly consistent from sample to sample.
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-	Matrix interferences are due to a chemical component in the solution which causes
suppression or enhancement of the measured signal. This interference can be
addressed by utilization of an internal standard or by diluting the sample digestate to
minimize the impact of the interference.
-	Memory, or carryover, interferences can occur when solutions of very high
concentrations are analyzed. The high concentration may be difficult to effectively
rinse from the ICP/MS sample introduction pathway resulting in contamination of
subsequent solutions or in the electron multiplier becoming saturated resulting in a
"burn in" where response factors of the ICP/MS are affected requiring substantial
time for sensitivity to return. Extensive rinsing times and/or recalibration may be
necessary to resolve such interferences.
4.4.11.3 Preparation of Calibration Standards for ICP/MS Analysis. Due to the instrument
sensitivity effects of dissolved solids, the matrix of standard solutions must exactly match that of
the final analyzed digestates. For example, if the final concentrations of acids in the analyzed
digestates are 2% (v/v) nitric acid, 0.5% (v/v) hydrochloric acid, and 0.1% (v/v) hydrofluoric
acid when samples are brought to volume, the acid concentrations in standard solutions must also
be 2%, 0.5%, and 0.1%, respectively.
Aliquots of the stock standard solutions must be delivered with a Class A pipette or calibrated
mechanical pipettor. All standard solutions must be brought to final volume in a Class A
volumetric flask or equivalent Class A lab ware.
Stock single or multi-element solutions may be purchased commercially at certified
concentrations in dilute nitric acid (typically 3% v/v) which are conveniently diluted to working
concentration levels. Alternatively, stock solutions may be prepared gravimetric ally by
weighing appropriate amounts of high purity element solids and dissolving them into dilute nitric
acid.
4.4.11.3.1	Primary Calibration Standards. Multi-element calibration standard
solutions are prepared by diluting primary certified stock standard solutions in dilute nitric acid
(typically 2% v/v). Calibration standard levels must cover a minimum of three non-zero
concentrations spanning the desired concentration range (typically 0.1 to 250 |ig/L depending on
the element), however five levels are strongly recommended. These standard solutions are
analyzed to generate the ICAL.
4.4.11.3.2	Secondary Source Calibration Verification Standard. A SSCV standard
solution, also referred to as the QC sample, must be prepared by dilution of the secondary source
stock standard solution with nitric acid (typically 2% v/v) to minimally a single concentration
approximately at the mid-range of the curve. Preparation of the SSCV at three different
concentrations covering approximately the lower third, mid-range, and upper third of the
calibration range is a best practice and is recommended. This secondary source standard must be
purchased from a different supplier. The SSCV stock may only be a different lot from the same
supplier if unavailable from another supplier.
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4.4.11.4	Internal Standards. ICP/MS analysis must include the evaluation of ISs to monitor
ion response of analyzed solutions and to correct for instrumental drift and matrix interferences.
A minimum of three IS elements must be co-analyzed with each solution. Suggested IS elements
include Bi, Ge, In, 6Li, Sc, Tb, 69Ga, Rh, and Y.
As relative responses of the target elements and IS elements are used to determine the final
concentration of the elements in solution, the concentration of the IS must be the same for each
analyzed solution. To achieve such, a known volume of the IS at a known concentration may be
added to a known volume of each solution to be analyzed, or the IS may be added to each
analyzed solution via a mixing coil on the ICP/MS sample introduction system. Further, IS
concentrations should approximate those in the analyzed samples. A concentration of no more
than 200 |ig/L is recommended.
As with the calibration stocks, acids, and reagent water, the IS stock solution must be from a
high purity source so as to minimize background levels of target elements.
IS responses must be monitored throughout the analysis and must be within 60 to 125% of the
response of the initial calibration blank (ICB). For samples or solutions which show responses
outside of this range, the instrument should be investigated to be sure the response change is not
due to instrument drift. Instrument drift causing failures in IS response require retuning of the
instrument and recalibration prior to continuing sample analysis.
4.4.11.5	Tuning Solutions. A tuning solution must contain elements covering the mass range
of interest so that the ICP/MS may be tuned and mass calibration and resolution checks may be
performed. A typical tuning stock solution contains isotopes of Li, Mg, Y, Ce, Tl, and Co at
approximately 10 mg/L and is diluted so that final concentrations are approximately 100 |ig/L or
less for each element.
4.4.11.6	ICP/MS Warm Up, MS Tuning, and Setup. The ICP/MS must be warmed up for a
minimum of 30 minutes, or a duration prescribed by the manufacturer, prior to use. The tuning
solution must be analyzed to perform mass calibration and resolution checks, which may be
performed during the warm up period. The MS must be optimized to provide a minimum
resolution of approximately 0.75 amu at 5% peak height and mass calibration within 0.1 amu of
unit mass. At a minimum five aliquots of the tuning solution must be analyzed and absolute
signal relative standard deviation for each analyte of < 5% must be achieved. Manufacturer
tuning recommendations may also be followed.
Standard, blank, and sample solutions should be aspirated for a minimum of 30 seconds to
equilibrate the ICP/MS response prior to acquiring data. Accelerated sample introduction
systems may lessen this equilibration time. The ICP/MS must be set up such that three replicate
integrations are performed for each analyzed solution. Each analysis result must be the average
of these replicate integrations.
A rinse blank of 2% nitric acid in deionized water should be used to flush the system between
analyzed solutions. The rinse blank solution should be aspirated for a sufficient time to ensure
complete return to baseline before the next sample, standard, or blank introduction. Depending
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on the sample introduction system, this may take approximately 60 seconds. Sample
introduction systems that increase the rinse blank speed are available to decrease rinse times.
4.4.11. 7 ICP/MS Calibration and Analytical Sequence Batch. On each day that analysis is
performed, the instrument must be calibrated and the analysis batch QC samples listed in the
following subsections must be analyzed. Calibration acceptance criteria are given in the
following sections and are summarized in Section 4.4.13.
An example analysis sequence is given in Table 4.4-2.
Table 4.4-2. Example ICP/MS Analysis Sequence
Sequence
Number
Solution Analyzed

Sequence
Number
Solution Analyzed
1
Tuning solution

26
field sample 6
2
ICB

27
field sample 7
3
ICAL 1 (lowest concentration)

28
field sample 8
4
ICAL 2

29
field sample 9
5
ICAL 3(highest concentration)

30
field sample 7
6
ICV

31
field sample 8
7
ICB

32
field sample 9
8
ICS B

33
field sample 10
9
ICS A

34
field sample 11
10
ccv

35
field sample 12
11
CCB

36
field sample 13
12
RB

37
CCV
13
MB

38
CCB
14
LCS

39
field sample 14
15
LCSD

40
field sample 15
16
field sample 1

41
field sample 16
17
duplicate (field sample 1)

42
field sample 17
18
matrix spike (field sample 1)

43
field sample 18
19
matrix spike duplicate (field
sample 1)

44
field sample 19
20
field sample 2

45
replicate analysis (field sample 16)
21
field sample 3

46
1:5 serial dilution (field sample 19)
22
CCV

47
ICS B
23
CCB

48
ICS A
24
field sample 4

49
CCV
25
field sample 5

50
CCB
4.4.11.7.1 Initial Calibration. Once the mass calibration and tuning have met the
criteria listed in Section 4.4.1 1.6, the response of the instrument must be calibrated for the
elements of interest. Analyze the initial calibration blank (ICB, an undigested reagent blank)
followed by the calibration standard solutions. The calibration curve must include the ICB as the
zero concentration standard. Linear regression must be performed on the calibration solution
responses and must show appropriate linearity and the curve fit must have a correlation
coefficient (r) of 0.995 or greater. Replicate analyses of the calibration standards must show
%RSD < 10%.
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4.4.11. 7.2 Initial Calibration Verification. Once the calibration curve is established,
the SSCV (or QC sample) must be analyzed as the initial calibration verification (ICV) and must
recover within ± 10% of the nominal value.
4.4.11.7.3	Initial Calibration Blank. The ICB is again analyzed following the ICV;
all element responses must be less than the laboratory's established MDLsp for MDLs determined
via Section 4.1.3.1 or the portion of the MDL represented by s K for MDLs determined via
Section 4.1.3.2. If the ICB does not meet this criterion, the analysis sequence must be stopped
and the source of the contamination found before analysis may continue.
4.4.11.7.4	Interference Check Standard. Once the instrument has been calibrated,
the calibration verified by analysis of the ICV, and the system shown to be free of contaminants
by analysis of the ICB, the instrument must be shown to be free of interferences by analysis of an
interference check standard (ICS). The ICS must be analyzed immediately following the ICB,
every 8 hours of continuous operation, and at the conclusion of the analysis sequence just prior
to the final CCV.
Analysis of the ICS allows for the explicit demonstration that known isobaric and/or polyatomic
interferences do not impact concentration results. Two types of ICS should be analyzed. A Type
A ICS contains elements known to form interferences, and a Type B ICS consists of a standard
solution of target elements subject to interferences from elements in ICS Type A. ICS Type A
solutions should contain high levels of elements such as Al, Ca, CI, Fe, Mg, Mo, P, K, Na, S, and
Ti at 20 to 20,000 mg/L which are known interferences to target elements such as As, Cd, Cr,
Co, Cu, Mn, Ni, and Se. These target elements should be present in ICS Type B solutions at
concentrations of approximately 10 to 20 mg/L, or lower concentrations, as appropriate,
anticipated to interfere with the analysis.
Analysis of ICS Type A must demonstrate that concentrations of all target analytes are less than
3x MDLsp (for MDLs determined by Section 4.1.3.1) or three-fold the portion of the MDL
represented by s K for MDLs determined via Section 4.1.3.2. Note that ICS Type A solutions
typically contain target analytes at quantifiable concentrations. ICS certificates of analysis
should be examined to determine whether observed concentrations above this criterion are due to
contaminant levels in the ICS Type A solution. Background subtraction of these levels may be
necessary if observed concentrations exceed the acceptance criterion. The ICS Type B solution
must show recovery of target elements of 80 to 120%. Concentrations of target elements in
samples which exceed the concentrations in ICS Type B solutions should be diluted and
reanalyzed.
ICP/MS equipped with reaction collision cells are less susceptible to isobaric and polyatomic
interferences than those without and may demonstrate little to no measureable interferences
when analyzing Type A ICS solutions. However, to ensure the collision reaction cell is
operating properly, the ICS Type A and Type B solutions must be analyzed minimally once each
day of analysis to ensure proper operation of the cell.
4.4.11.7.5	Continuing Calibration Verification. At a minimum, a CCV must be
prepared at a single concentration at approximately the mid-range of the calibration curve, must
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be diluted from the primary stock or secondary source stock solution, and must be analyzed
following the ICS, prior to the analysis of samples, after the analysis of every 10 digestates, and
at the end of the analytical sequence. CCV recovery must be 90 to 110% for each target element.
As a best practice, two or more concentrations of CCV may be prepared and analyzed so as to
better cover instrument performance across the range of the calibration curve.
4.4.11.7.6	Continuing Calibration Blank. The CCB is from the same solution as the
ICB and must be analyzed after each CCV to ensure the instrument background remains
acceptably low. A CCB is not required after the CCV concluding the analysis sequence. CCB
analysis must show that the absolute value of the instrument concentration response for each
target element is less than the laboratory's established MDLsp for MDLs determined via Section
4.1.3.1 or the portion of the MDL represented by s K for MDLs determined via Section 4.1.3 .2.
If the CCB does not meet this criterion, the analysis sequence must be stopped and the source of
the contamination found before analysis may continue. Samples analyzed since the last
acceptable CCB require reanalysis.
4.4.11.7.7	Laboratory Digestion Batch Quality Control Samples. Laboratory
digestion batch QC samples for low volume Teflon* and high volume QFF media described in
Sections 4.4.9.5 and 4.4.10.5, respectively, are analyzed with each analysis batch. Laboratory
QC samples (consisting of RBs, MBs, RBSs, and LCSs) are analyzed after the first CCV and
CCB pair and should be analyzed prior to the analysis of field samples in the same digestion
batch. Duplicate digested samples, matrix spikes, and matrix spike duplicates similarly should
be analyzed immediately following their parent field sample. In order to minimize reanalysis if
more than one digestion batch is included in an analysis batch, each digestion batch should be
analyzed altogether and separated by a CCV and CCB prior to analysis of the next digestion
batch.
4.4.11.7.8	Serial Dilution. A sample must be chosen for each analysis batch for
serial dilution. A sample digestate should be diluted five-fold and fortified with IS (so that the
concentration of the IS is the same as in the parent sample). Element concentrations for elements
> 5x MDL in the serially diluted sample must recover within 90 to 110% of the undiluted
sample.
4.4.11.7.9	Replicate Analysis. A replicate of digestate from a field-collected sample
must be analyzed at the minimum rate of one for every 20 field-collected samples in the analysis
batch. Precision of the replicate analysis must be < 10% RPD for elements > 5x MDL.
4.4.11.8 ICP/MS Data Review and Concentration Calculations. The concentration for each
field-collected sample must be reported in ng/m3 in local conditions. Results may additionally
be reported by correction to standard atmospheric conditions of 25°C and 760 mm Hg.
Conversion of collected volume in local conditions to standard conditions is performed as
follows:
Qs = ^ n' ^
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where:
Qs =	flow at standard conditions (760 mniHg and 25°C)
Ps =	standard barometric pressure = 760 mniHg
Ts =	standard temperature in K = 298.15K
Qa =	flow at ambient conditions
Pa =	ambient barometric pressure in mmHg
Ta =	ambient temperature in K
Results must not be corrected for calibration blank or MB levels. Concentrations exceeding
acceptance criteria for these blanks must prompt investigation as to the source of contamination.
Concentration results which exceed the instrument calibration range must be diluted and
analyzed within the calibration range. The diluted result must be reported and the associated
MDL adjusted accordingly by the dilution factor. For example, if the sample is diluted by a
factor of two to analyze nickel within the calibration curve, the MDL should be increased by a
factor of two when reporting to AQS.
Negative concentration results which exceed the absolute value of the laboratory's established
MDLsp for MDLs determined via Section 4.1.3.1, or the portion of the MDL represented by s K
for MDLs determined via Section 4.1.3.2. MDLsp for field-collected samples indicate the likely
existence of contamination problems in the reagents, standards, or lab ware used to prepare the
calibration curve. Negative concentrations should not be qualified as "9" when entered in AQS
as this qualifier indicates that negative concentrations were replaced with zero. Overly negative
concentrations are further discussed in Section 6.6.1.
4.4.11.8.1 Concentration Calculations for Low Volume Sampling. To calculate the
airborne concentration of each element measured on the Teflon* filter, the ICP/MS measured
concentration in |ig/mL is multiplied by the sample digestate final volume in mL and by the
dilution factor (if dilution of the digestate was performed), and is divided by the sampled air
volume in nr\ as follows:
__ Qcp/MS " Vdig " D
Lair —
1000 ¦ vair
where:
Cair = Concentration of the element in air at local conditions (ng/m3)
Cicp/ms = Concentration measured in the sample digestate (|ig/mL)
Vdig = Volume of digestate (mL)
DF = Dilution factor
Vair = Volume of air sampled (m3)
4.4.11.8.2 Reporting of Concentrations for High Volume Sampling. To calculate
the airborne concentration of each element measured on the QFF, the ICP/MS measured
concentration in |ig/mL is multiplied by the final digestate volume in mL, by the fraction of the
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filter digested for analysi s, and by the dilution factor (if dilution of the digestate was performed),
then is divided by the sampled air volume in nr\ as follows:
r __ Qcp/ms " Vdig ' D ¦ Ff
air ~~ 1000 ¦ vair
where:
Cair ~~
Concentration of the element in air at local conditions (ng/m3)
ClCP/MS =
Concentration measured in the sample digestate (|ig/mL)
Vdig =
Volume of digestate (mL)
DF =
Dilution factor
Ft =
Fraction of exposed filter digested a
Vair —
Volume of air sampled (m3)
a For a 1 inch x 8 inch strip portioned as described in Section 4.4.11.5.2, this is equivalent to 1/9 by dividing the
exposed area of the portioned strip by the area of the exposed filter.
(1 inch x 7 inch = 7 in.2)/(7 inch x 9 inch = 63 in.2) = 1/9
4.4.12 Summary of Method Quality Control Requirements. QC requirements are
summarized in Table 4.4-3.
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Table 4.4-3. Method Criteria Parameters for NATTS Metals Analysis
Parameter
Description and Details
Required Frequency
Acceptance Criteria
ICP/MS Tuning
ICP/MS mass calibration and
resolution checks
Analysis of a minimum of
five aliquots of the tuning
solution each day of
analysis prior to IC AL
Absolute signal of five replicates
RSD < 5%
Mass calibration within 0.1 amu
of unit mass
Resolution check within
0.75 ainu at 5% peak height
Alternatively, must meet
manufacturer tuning criteria
Internal Standards
Addition
Elements other than target
elements used to monitor
instrument performance and
correct for matrix effects
Added to each analyzed
solution
Recovery within 60-125% of the
response of the initial calibration
blank
Rinse Blank
2% (v/v) HNO; aspirated to
eliminate memory effects
between solutions
Following each analyzed
solution
Duration of aspiration sufficient
to eliminate element carryover
as evidenced by successful
CCVs and CCBs
Initial Calibration
(ICAL)
Minimum of three levels
covering the desired
concentration range plus the
calibration blank
Each day analysis is
performed
Correlation coefficient (r)
>0.995
Initial Calibration
Verification (ICV)
Second source calibration
verification (SSCV) or QC
standard analyzed to verify the
ICAL
Each day of analysis
immediately following the
ICAL
Recovery within 90-110% of
nominal for all target elements
Initial Calibration
Blank (ICB)
Calibration blank analv/cd to
ensure instrument is sufficiently
clean to continue analysis
Each day of analysis
immediately following the
ICV
All target elements
< MDLSp (refer to Section
4.1.3.1)	or s-K (refer to Section
4.1.3.2)
Interference Check
Standard (ICS) A
Solution containing known
interferences analv/cd to
demonstrate that the effect of
such interferences is
sufficiently low
Following the ICB. after
every 8 hours of analysis,
and just prior to the
concluding CCV
Once daily for ICP-MS
equipped with collision
reaction cell
All target elements
< MDLsp (refer to Section
4.1.3.1)	or.vK (refer to Section
4.1.3.2)	- may be subtracted for
ICS A certificate of analysis
1 ntcrfcrence Check
Standard (ICS) B
Solution containing target
elements at high concentrations
to demonstrate acceptable
recovery
Following the ICB. after
every 8 hours of analysis,
and immediately
preceding ICS A
Once daily for ICP-MS
equipped with collision
reaction cell
Recovery within 80-120% of
nominal for all target elements
Continuing Calibration
Verification (CCV)
Calibration or second source
standard analyzed to v erify
instrument remains in
calibration
Immediately following
the initial ICS, after ev ery
10 samples and at the
conclusion of the analysis
sequence
Recovery within 90-110% of
nominal for all target elements

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Table 4.4-3. Method Criteria Parameters for NATTS Metals Analysis (Continued)
Parameter
Description and Details
Required Frequency
Acceptance Criteria
Continuing Calibration
Blank (CCB)
Analysis of the calibration
blank solution to ensure
instrument is sufficiently clean
to continue analysis
After each CCV except at
the conclusion of the
analysis sequence
All target elements
< MDLsp (refer to Section
4.1.3.1)	or ,s"K (refer to Section
4.1.3.2)
Reagent Blank (RB)
Aliquot of digestion solution
taken through the digestion
process
One per digestion batch of
20 or fewer field-
collected samples
All target elements
< MDLsp (refer to Section
4.1.3.1)	or s-K (refer to Section
4.1.3.2)
Method Blank (MB)
Blank filter or filter strip taken
through the digestion process
One per digestion batch of
20 or fewer field-
collected samples
All target elements
< MDL
Reagent Blank Spike
(RBS)
Aliquot of digestion solution
spiked with known amount of
target elements and taken
through the digestion process
One per digestion batch of
20 or fewer field-
collected samples
Recovery within 80-120% of
nominal for all target elements
Laboratory Control
Sample (LCS)
Filter or filter strip spiked with
a known amount of each target
element and taken through the
digestion process
One per digestion batch of
20 or fewer field-
collected samples
Recovery within 80-120% of
nominal for all target elements,
Sb recovery 75-125%.
Laboratory Control
Sample Duplicate
(LCSD)
Duplicate filter or filter strip
spiked with a known amount of
each target element and taken
through the digestion process
(Optional) One per
digestion batch of 20 or
fewer field-collected
samples
Recovery within 80-120% of
nominal for all target elements,
Sb recovery 75-125%,
precision < 20% RPD of LCS
Duplicate Sample
Strip
Additional strip from a field-
collected filter taken through
the digestion process
*QFF only*
One per digestion batch of
20 or fewer field-
collected samples
Precision < 20% RPD for
elements > 5x MDL
Matrix Spike
Strip from a field-collected
filter spiked with a known
amount of each target element
and taken through the digestion
process
*QFF only*
Once per analysis batch of
20 or fewer samples
Recovery within 80-120% of the
nominal spiked amount for all
target elements, Sb recovery 75-
125%.
Matrix Spike
Duplicate
Additional strip from the same
field-collected filter as the MS,
and spiked with the same
amount of each target element
as the MS, and taken through
the digestion process
*QFF only*
One per digestion batch of
20 or fewer field-
collected samples
Recovery within 80-120% of the
nominal spiked amount for all
target elements, Sb recovery 75-
125%,
precision < 20% RPD of MS
Collocated Sample
Sample collected from a
separate sampling unit
concurrently with the primary
sample
10% of primary samples
for sites conducting
collocated sampling (as
required by workplan)
Precision < 20% RPD of primary
sample for elements > 5x MDL
Serial Dilution
Five-fold dilution of a sample
digestate to assess matrix
effects
One per digestion batch of
20 or fewer field-
collected samples
Recovery within 90-110% of
undiluted sample for elements >
25x MDL
Replicate Analysis
Second aliquot of a sample
digestate chosen for replicate
analysis
One per digestion batch of
20 or fewer field-
collected samples
Precision < 20% RPD for
elements > 5x MDL
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4.4.13	References
1.	Determination of Metals in Ambient Particulate Matter Using Inductively Coupled
Plasma/Mass Spectrometry (ICP/MS); EPA Compendium Method 10-3.5; Compendium of
Methods for the Determination of Inorganic Compounds in Ambient Air; EPA/625/R-
96/010a; U.S. Environmental Protection Agency: Center for Environmental Research
Information. Office of Research and Development. Cincinnati, OH. June 1999. Available at
(accessed October 19, 2016):
https://www3.epa.gov/ttnamtil/files/ambient/inorganic/mthd-3-5.pdf
2.	Care and Safe Handling of Laboratory Glassware. Coming Incorporated. RG-CI-101-REV2.
2011. Available at (accessed October 19, 2016):
http://csmedia2.coming.com/LifeSciences/media/pdf/Care and Safe Handlirig Lab Glassw
are RG-CI-101Kev2~pdf
3.	Sampling of Ambient Air for PM 10 Concentration using the Rupprecht and Pataschnick
(R&P) Low Volume Parti sol ® Sampler; EP A Compendium Method 10-2.3; Compendium of
Methods for the Determination of Inorganic Compounds in Ambient Air, EPA/625/R-
96/010a; U.S. Environmental Protection Agency: Center for Environmental Research
Information. Office of Research and Development. Cincinnati, OH. June 1999. Available at
(accessed October 19, 2016):
luif j://www3.epa.gov/ttnamtil/files/ambient/inorgamc/mthd-2-3.pdr
4.	Section, Preparation, and Extraction of Filter Material; EPA Compendium Method 10-3.1;
Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air,
EPA/625/R-96/01 Oa; U.S. Environmental Protection Agency: Center for Environmental
Research Information. Office of Research and Development. Cincinnati, OH. June 1999.
Available at (accessed October 19, 2016):
https://www3.epa.gov/ttn/amtic/files/ambient/inorganic/mthd-3-l.pdf
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4.5	Collection and Analysis of PAHs via EPA Conipendiiim Method TO-13A
Each agency must codify in an appropriate quality systems document, such as an SOP, or
equivalent, its procedures for performing PAHs sampling, media extraction, and extract analysis.
Various requirements and best practices for such are given in this section. Note that regardless
of the specific procedures adopted, method performance specifications as given in Section 4.5.6
must be met.
4.5.1	Summary of Method. PAHs, which are semi volatile organic compounds (SVOCs),
are collected per the guidance given in EPA Method TO-13 A. 1 and ASTM D6209.2 These two
methods are similar and share collection media specifications: utilizing a quartz fiber particulate
filter and glass thimble containing PUF and styrene-divinylbenzene polymer resin sorbent
(XAD-2 or equivalent) to collect PAHs from ambient air.
Approximately 200 to 350 m3 of ambient air is drawn through a quartz fiber particulate filter and
cartridge containing a "sandwich" of PlJF-resin-PlJF over 24 hours. The QFF and contents of
the cartridge are extracted by way of accelerated solvent extraction ( ASE)3 or in a Soxhlet
apparatus, and the extract is analyzed by GC/MS. Concentrations of PAHs in ambient air are
generally low (0.02 to 160 ng/m3), thus a large volume of air must be collected to ensure
sufficient mass is present for quantification with a typical quadrupole MS in SIM mode.
The more volatile PAHs, such as naphthalene, are subject to potential loss from the cartridges
due to, for example, volatilization and decomposition from exposure to light. 4> 5 Thus, PAH
cartridges should be collected from the sampling unit, protected from light, and brought to < 4°C
as soon as possible after the end of the sampling period. Shipment and storage at refrigerated
temperatures will further minimize evaporative losses of the more volatile PAHs. PAHs with
higher volatility may also be lost from the sorbent cartridge during sampling due to migration out
of the cartridge outlet (breakthrough) or from volatilization from the QFF, especially during
warm weather. 6'7
The PAHs including, but not limited to, those in Table 4.5-1 may be determined by this method.
4.5.2	Sample Collection Equipment. A high volume PS-1 style sampler, or equivalent,
which is able to maintain a minimum flow rate of 140 L/min over a 24-hour sampling period is
required. Such sampling units are commercially available with various conveniences. The most
basic units are equipped with an event timer and an elapsed time counter to control and indicate
duration of sample collection. Flow rate is controlled by the fan motor speed, ball valve, or
combination. A manometer (such as a magnehelic) is attached to the ports on a venturi located
between the sampling inlet and the fan motor to indicate the pressure differential which
correlates to the flow rate. Computer control is available on more expensive systems; such units
have an automatic start/stop timer, indicate elapsed sampling time, monitor and record flow rates
over the course of the collection event, indicate start and stop times, and monitor the pressure
differential and adjust the blower speed to ensure a user defined flow setpoint is maintained.
Each high volume sampler should have an extension tube for the motor exhaust to ensure that the
sampled atmosphere is not resampled. If so equipped, the exhaust tube must terminate in the
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predominant downwind direction minimally 3 meters away from the unit. Care should be taken
to ensure that the exhaust does not interfere with other sampling units at the site. The sampling
unit inlet must minimally be 2 meters from all other sampling inlets. Sampler siting
requirements are listed in Section 2.4.
Table 4.5-1. PAHs and Associated Chemical Abstract Numbers (CAS)
Target Compound
CAS Number
Acenaphthene b
83-32-9
Accnaphthylcne
208-96-8
Anthracene b
120-12-7
Benzo(a)anthracene
56-55-3
Benzo(a)pyrene a b
50-32-8
Benzo(e)pyrene
192-97-2
Dibcn/o(g.h.i)pcrylcnc
191-24-2
Benzo(b)fluoranthene
205-99-2
Benzo(k)fluoranthene
207-08-9
Chryscnc
218-01-9
Coroncnc
191-07-1
Dibcn/o(a.h)anthracene
53-70-3
Fluoranthcnc b
206-44-0
Fluorcnc b
86-73-7
9-Fluorene
486-25-9
Indenol 1,2,3 -cdlpyrene
193-39-5
Naphthalene a b
91-20-3
Perylene
198-55-0
Phenanthrene b
85-01-8
Pyrcne b
129-00-0
Retene
483-65-8
a NATTS Tier I core analytc
b NATTS PT target analytc
4.5.2.1	Sampler Flow Calibration and Verification. Sampler flow must be calibrated
initially and when flow verification checks indicate flows deviate by more than 10% from the
flow transfer standard flow or design flow. Flow verification checks must be performed
quarterly, and are recommended to be performed monthly. Flow verifications must be
performed at approximately the setting utilized to collect field samples.
Flow calibration of a non-mass flow controlled sampler (those without computer control) must
be performed with a traceable, calibrated flow transfer standard capable of inducing various
backpressures to generate different sampling unit flow rates that bracket the target flow rate.
Such may be accomplished with an electronic flow meter, a variable orifice, or a series of fixed
plate orifices, or similar. The known inlet flows must then be correlated to the measured
manometer readings at the flow venturi. Computer controlled units must be electronically
adjusted so the flow settings correlate to the calibrated flow rate as indicated by the flow transfer
standard.
4.5.2.2	Sampling Unit Maintenance. Each site must have a defined maintenance schedule
for the PAHs sampling units, recommended to be monthly, but may not exceed quarterly.
Included in this maintenance must be the schedule for the periodic cleaning of the sampling
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heads. Sampling heads should be washed with chromatographic grade hexane, acetone, or other
suitable solvent to ensure subsequent samples are not contaminated. Use of such solvents should
be performed with proper ventilation (e.g. fume hood) and with proper personal protective
equipment (PPE - such as solvent impermeable gloves, lab coat, and safety glasses). Other
maintenance items should include: inspection of sampling unit electrical connections, check of
timers for proper operation, replacement of motors and motor brushes, removal of debris from
underneath the gable and inside the upper portion of the sampling unit, and inspection of sealing
gaskets.
4.5.3 Sampling Media and Their Preparation. Regardless of the source of materials or
the specific cleaning procedures each agency adopts, the QFF and PUF/XAD-2/PUF present in
cartridges must meet the batch blank acceptance criteria of < 10 ng each for all target
compounds. A batch blank is a complete cartridge (including a QFF) selected from among those
purchased in a single lot or from among each batch of cartridges prepared with a specific batch
of cleaned media. Note that media components may be analyzed separately, but must meet the
cleanliness criterion.
Particulate filters for sample collection are quartz fiber, 102 to 104 mm diameter with 2-|im pore
size. All filters must be inspected on a light table or similar for pinholes, discolorations, tears, or
other defects such as thin spots; air samples must not be collected with those found to be
unsuitable. After inspection, filters should be baked (in a muffle furnace) at 400°C for a
minimum of 4 hours to remove potential impurities and interferences. Once cooled, the filters
should be stored in a sealed container to ensure they do not become contaminated prior to sample
collection.
PUF plugs are available commercially, or they may be prepared by cutting plugs of the proper
diameter (2 3/8 inch) from PUF sheets of 1.5-inch thickness. PUF plugs may be purchased raw
and cleaned by the laboratory prior to use, or may be purchased precleaned. Some precleaned
PUF plugs do not meet cleanliness criteria for target analytes or may contain interferences which
require subsequent cleaning procedures prior to use for sample collection. Precleaned PUF plugs
are typically shipped with a certificate of analysis listing the contaminant levels for common
PAHs. Following sample extraction, used PUF plugs may be cleaned for reuse, if so desired.
Styrene-divinylbenzene polymer resin, such as XAD-2, is commercially available and may be
purchased with or without precleaning. As with precleaned PUF, some precleaned resins do not
meet cleanliness criteria for target analytes or may contain interferences which require
subsequent cleaning procedures before use for sample collection. Precleaned resin sorbent is
generally shipped with a certificate of analysis listing the contaminant levels for common PAHs.
Following sample extraction, used resin may be cleaned for reuse. The resin physically degrades
and disintegrates over time, requiring periodic replacement.
PUF and/or resin sorbents should be cleaned before reuse with a specialized solvent extraction
program that is slightly different than the method by which the QFF, PUF, and resin from a
sample cartridge are extracted. A more aggressive solvent or combination of solvents such as
methylene chloride (not suitable for PUF cleaning), toluene, hexane, and/or acetone should be
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employed to remove target analytes and interferences from the PUF and resin media for
cleaning.
All clean media should be stored in sealed containers protected from light (aluminum foil, amber
glass, etc.).
4.5.3.1	Glassware Cleaning. Glass thimbles, extraction glassware, and volumetric glassware
for preparing standard solutions must be thoroughly cleaned and contaminant-free prior to use
such that blank criteria are met as given in Section 4.5.6. Aggressive washing with hot water and
laboratory grade soap, tap water rinsing, deionized water rinsing, acid or base rinsing, and
solvent (methylene chloride) rinsing may be necessary to ensure that contaminants and
interferences are removed from lab ware prior to use. Non-volumetric glassware may be baked at
400°C for 4 hours. Volumetric glassware must not be heated above 80 to 90°C unless otherwise
indicated by the manufacturer as such heating voids the volumetric certification.* Following the
final solvent rinse, clean lab ware should be capped or covered (as appropriate) with solvent
rinsed foil to prevent contamination with dust, etc.
4.5.3.2	Cartridge Preparation. If cartridges are assembled in house, they must be assembled
in batches, and the lots of media contained in the cartridges must be traceable so as to maintain
the ability to track potential contamination. One assembled cartridge from each batch of 20 or
fewer assembled cartridges must be extracted as a batch blank. The batch blank ensures the
cleaned media and preparation results in acceptably low background levels of target PAHs.
The following procedure should be followed to prepare cartridges. Tools contacting sampling
media are solvent rinsed and technicians must wear gloves during cartridge preparation. One
1.5-inch thick PUF plug is placed into the inlet of the cartridge and pushed down to contact the
support screen. Note that glass thimble cartridges equipped with a glass frit support are not
suitable for NATTS sample collection. The glass frit creates an excessive flow restriction
resulting in pre-mature wear and failure of motors and brushes. A 15-gram aliquot of clean resin
is then added to the cartridge on top of the PUF plug and distributed evenly. The second 1.5-
inch thick PUF plug is then placed on top of the resin layer to retain the resin layer in place.
For storage, cartridges should be wrapped in solvent rinsed foil, sealed in a resealable plastic bag
or other container, and kept at < 4°C.
4.5.3.3	Field Surrogate Addition. Prior to dispatching sample cartridges to the field, field
surrogate compounds must be added to the sorbent media. The recovery of field surrogate
compounds is evaluated to assess the retention of PAHs during air sampling as well as the
performance of the sample media handling, extraction, and analysis procedures.
Field surrogates should be added by spiking 1 jug (e.g., 100 |iL of a 10 |ig/mL solution in
methylene chloride, toluene, hexane, or other suitable solvent) of, for example, fluoranthene-dio
and benzo(a)pyrene-di2 directly into the PUF and resin sorbent. Field surrogates are added no
sooner than two weeks prior to the scheduled sample collection date.
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4.5.4 PAH Sampling. Sample media must be installed into the sampling unit as close to
the sampling date as possible to minimize positive bias due to passive sampling of the sorbent
media. At the time of installation, sampling units without computerized flow control must be
allowed to warm up for minimally five ten minutes (ten minutes are recommended) prior to
recording the initial flow rate, i.e., the manometer reading. Computer-control 1 ed sampling
instruments do not require this warm-up period to record the initial flow. The ambient
barometric pressure and temperature must be measured with calibrated instruments and recorded.
The QFF and cartridge are loaded into a sampling head. At the head's outlet is a cam-lock
connection which connects the head to the PS-1 sampling unit, and at the head inlet is a threaded
ring filter holder to accept the QFF. The head may be unscrewed in the middle such that the
glass cartridge may be inserted inside into a cartridge body. Inert gaskets (such as silicone
rubber) are placed in the top and bottom of the cartridge body inside the sampling head. A filter
is placed onto the support screen of the filter holder, and an inert gasket (such as
polytetrafluoroethylene [PTFE]) seals the filter to the top filter retaining ring. The filter is
protected during handling by a cover secured to the filter holder with three swing bolts.
4.5.4.1a Sampling Schedule and Duration. PAHs sample collection must be performed
on a l-in-6 days schedule for 24 ± 1 hours beginning at midnight and concluding on midnight of
the following day, local time unadjusted for daylight savings time, per the national sampling
calendar. For missed or invalidated samples, a make-up sample should be scheduled and
collected per Section 2.1.2.1. Clock timers controlling sampling unit operation must be adjusted
so that digital timers are within ±5 minutes of the reference time (cellular phone, GPS, or similar
accurate clock) and mechanical timers within ±15 minutes.
4.5.4.1b Retrieval, Storage, and Transport of QFFs and Cartridges. The QFF and glass
cartridge must be retrieved as soon as possible after the conclusion of sampling in order to
minimize the evaporative loss of the more volatile PAHs, preferably within 24 hours, but not to
exceed 72 hours of the end of collection. Such is particularly important during warm weather.
As with sample setup, units without computerized flow control must be allowed to warm up for
minimally five minutes (ten minutes are recommended) prior to recording the manometer
reading, which is recorded as the ending flow setting. Computer-control 1 ed sampling units do
not require this warm-up period. The ambient barometric pressure and temperature must be
measured with calibrated instruments and recorded.
To retrieve a sample, the following procedure should be followed. It is recommended that the
operator dons non-latex powder-free gloves to place the filter cover onto the filter inlet and
secure the cover with the swing bolts. The operator then releases the cam-locks, disconnects the
sampling head from the sampling unit, and covers the outlet end of the sampling head with foil
or suitable plug. The assembled sampling head is transported to a clean indoor environment, free
of obvious PAHs sources, for disassembly. If the disassembly is to occur more than 10 minutes
following sample retrieval, the sampling head is stored and transported refrigerated.
For sampling head disassembly, gloves must be donned, the filter cover removed, and the filter
carefully retrieved and folded into fourths with the particulate matter inward. The folded filter is
then inserted into the glass thimble cartridge with the sorbent media. It is not acceptable to place
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the folded filter into a secondary container such as a petri dish, as jostling of the filter inside the
petri dish may result in loss of PM to the inside of the dish. Storage inside the glass cartridge
minimizes disturbance of PM to ensure that PM is either on the filter or within the PUF inside
the glass thimble. The glass thimble cartridge is removed from the sampling head, wrapped in
solvent-rinsed foil, and placed within a protective jar or case for shipment.
The protective jar or case containing the cartridge must be stored at < 4°C until shipment to the
laboratory. The sample should be kept cold during shipment such that the temperature remains
< 4°C, and the temperature of the shipment must be determined upon receipt at the laboratory.
For transport of samples which are retrieved at a site and delivered to the laboratory on the day
of retrieval, it may be difficult to sufficiently cool samples to < 4°C by the time they are received
at the laboratory. It is imperative that samples be placed into cold storage for transport as soon
as possible after retrieval, so samples arrive at the laboratory chilled. Samples which are shipped
overnight should be packed with sufficient cold packs or ice to ensure they arrive at the
laboratory at < 4°C. The sample custody form must be completed and accompany the collected
sample at all times until relinquished to the laboratory. COC documentation must comply with
Section 3.3.1.3.7. If cartridges are broken, resin has escaped, or the sampling media otherwise
compromised, the sample must be voided.
4.5.4.2	Field Blanks. Field blanks must be collected minimally monthly. A field blank is a
complete blank cartridge and QFF fortified with field surrogates and assembled in a sampling
head identically to a field-collected sample except that there is no sample flow. To collect a field
blank, the assembled sampling head is minimally installed into the sampling unit and the filter
cover removed for minimally 5 minutes. The field blank is then retrieved as a regularly collected
field sample and placed into cold storage until the co-collected field sample is
transported/shipped to the laboratory for analysis.
Field blanks must show that all target PAHs are < 5x MDL. Results for field collected samples
associated with the failing field blank and collected since the last acceptable field blank must be
appropriately qualified when entered into AQS.
An exposure blank is similar to a field blank, but is not required, and may be collected via
several protocols. The exposure blank includes exposing the filter and sorbent media to the
ambient conditions by installation in a sampling unit, and just like a field blank, air is not drawn
through the exposure blank sampling head. The exposure blank sample may be installed in the
primary sampling unit on non-sample collection days or may be installed in a collocated
sampling unit during collection of the primary sample.
4.5.4.3	Collocated Sampling. Collocated samples must be collected at a frequency of 10%
of the primary samples for sites conducting collocated sampling (as required by the workplan).
A collocated sample is a second assembled sampling head (cartridge and QFF) collected via a
separate PAHs sampling unit. The collocated sampling unit inlet must be between 2 to 4 meters
from the primary sampling inlet.
Collocated samples must demonstrate precision < 20% RPD for instrument measured
concentrations >0.5 |ig/mL. Root cause analysis must be performed for instances in which
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collocated samples fail this precision specification and the results of the primary and collocated
samples must be qualified when entered into AQS.
4.5.5 PAH Extraction and Analysis
4.5.5.1 Reagents and Standard Materials
4.5.5.1.1	Solvents. Solvents employed for extraction and preparation of standards
solutions must be high-purity chromatographic grade, and shown by analysis to be free of
contaminants and interferences. Suitable solvents include dichloromethane, n-hexane, methanol,
diethyl ether, and acetone.
4.5.5.1.2	Calibration Stock Materials. Calibration source material must be of
known high purity and must be accompanied by a CO A. Calibration materials should be neat
high purity solids or sourced as certified single component or component mixtures of target
compounds in solvent.
Neat solid material must be weighed with a calibrated analytical balance with the appropriate
sensitivity for a minimum of three significant figures in the determined standard mass. The
calibration of the balance must be verified on the day of use with certified weights bracketing the
masses to be weighed. Calibration standards diluted from stock standards should be prepared by
delivering stock volumes with mechanical pipettes (preferably positive displacement) or gastight
syringes calibrated and the volumes dispensed into Class A volumetric glassware to which
solvent is added to establish a known final dilution volume.
4.5.5.1.2.1 Secondary Source Calibration Verification Stock Material
A secondary source standard must be prepared to verify the calibration of the GC/MS on an
ongoing basis. This secondary source stock standard must be purchased from a different supplier
than the calibration stock. The SSCV stock may only be a different lot from the same supplier if
unavailable from another supplier.
4.5.5.1.3	Internal Standards. ISs are required to correct for both short-term
variability in GC/MS performance and for potential matrix effects. ISs must be added to all
analyzed solutions at the same concentration. IS compounds should be chemically and
chromatographical 1 y similar to the target compounds.
Deuterated analogs of target compounds are recommended as ISs. Suggested deuterated
standards include: naphthalene-ds, acenaphthene-dio, perylene-di:, phenanthrene-dio, and
chrysene-di2. These ISs should be purchased as high purity single or multi-component mixtures
in solvent. Note that deuterated standards also contain small amounts of the target compound
which may appear as contamination if the concentration of IS added is too high.
4.5.5.1.4	Surrogate Compounds. Surrogate compounds are required to monitor and
assess the retention of PAHs on the adsorbent media and the performance of the sample media
handling, extraction, and analysis procedures. Two types of surrogate compounds are prescribed
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for the subject method, field surrogates and extraction surrogates. As with ISs, deuterated
analogs of target compounds are recommended for surrogate compounds.
4.5.5.1.4.1	Field Surrogate Compounds
Field surrogates are required and were previously described in Section 4.5.3.3. Fluoranthene-dm
and benzo(a)pyrene-di2 are the recommended field surrogate compounds. Stock standard
solutions of these two surrogate compounds in solvent are commercially available and are
diluted to working concentrations in suitable solvent (i.e., hexane).
4.5.5.1.4.2	Extraction Surrogate Compounds
Extraction surrogate compounds must be added to the sample media just prior to extraction and
their recoveries are evaluated to assess the performance of the extraction and analysis
procedures. Fluorene-dio and pyrene-dio are the recommended extraction surrogate compounds
and 1 jug should be added to the media (e.g., 10 |iL of 10 |ig/mL solution). Stock standard
solutions of these two surrogate compounds in solvent are commercially available and are
diluted to working concentrations in suitable solvent (i.e., hexane).
4.5.5.2	Hold Times and Storage Requirements. Collected samples must be transported and
stored at < 4°C until extraction, and must be extracted within 14 days of collection. Extracts
must be stored in amber or foil-wrapped vials at < 4°C, however storage in a freezer at < -10°C is
preferable. Extracts must be analyzed within 40 days of extraction. Working standards and open
ampules of stock standards must be stored protected from light at < -10°C in Teflon sealed amber
vials in a storage unit separate from sampled cartridges and sample extracts.
4.5.5.3	Extraction, Concentration, and Cleanup. Extraction of samples may be performed
by Soxhlet or ASE; these techniques are described in more detail below.
4.5.5.3.1	Soxhlet Extraction. Each Soxhlet extraction batch must include 20 or
fewer field-collected samples and a MB. An LCS, and LCSD are required quarterly, but
recommended with each extraction batch. Prior to extraction, each field-collected sample and
QC sample must be fortified with extraction surrogate standards (typically fluorene-dio and
pyrene-dio). Extraction should be performed by combining the QFF, PUF plugs, and resin
sorbent into the soxhlet extraction vessel and extracting with sufficient 90:10 hexane:diethyl
ether to cover the sample media. Extraction should be performed for a minimum of 18 hours and
the temperature of heating mantle should be set such that reflux occurs at a rate of at least three
cycles per hour.
Extracts must be capped, protected from light, and stored refrigerated at < 4°C if they are not to
be concentrated immediately following extraction.
4.5.5.3.2	Accelerated Solvent Extraction. To perform ASE, a 100 mL ASE cell
should be packed as follows: QFF, top PUF plug, resin, bottom PUF plug, and clean Ottawa
sand to fill the cell. Each extraction batch must include 20 or fewer field-collected samples and
an MB. An LCS and LCSD are required quarterly, and recommended with each batch. Prior to
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extraction, each field sample and quality control sample must be fortified with extraction
surrogate standards (typically fluorene-dm and pyrene-dio). To ensure the cell seals properly,
stray resin grains should be removed from the threads with a horsehair brush or compressed air.
The following procedure should then be followed: install the cells into the extractor, install the
clean extract collection bottles, verify that the solvent reservoirs are full, and start the extraction
program. A recommended solvent combination for ASE is 2:1 or 3:1 hexane:acetone (v:v).3 An
example ASE program follows:
temperature:
cycles:
purge:
static time:
flush:
60°C
minimum of 3
60 seconds
5 minutes
50%
Extracts must be capped, protected from light, and stored refrigerated at < 4°C if they are not to
be concentrated immediately following extraction.
4.5.5.3.3 Extract Concentration and Cleanup
4.5.5.3.3.1 Extract Concentration
Refrigerated extracts are equilibrated to room temperature prior to concentration. It is
recommended that extracts be dried by passage through approximately 10 g of sodium sulfate,
where the eluate is collected into a concentration flask or tube. The extraction flask and sodium
sulfate are then rinsed three times with extraction solvent and the rinsate collected into the
concentration vessel.
Prior to use, sodium sulfate should be solvent rinsed and placed in an oven at 400°C for a
minimum of 4 hours to remove impurities. Muffled sodium sulfate should be cooled and stored
in a desiccator to minimize contact with humidity in ambient air.
Extracts should be concentrated by either Kuderna-Danish (K-D) or nitrogen blowdown
techniques. The extracts must not be allowed to evaporate to dryness.
4.5.5.3.3.1.1 Concentration via Kuderna-Danish
To concentrate via K-D, the following procedure should be followed. Attach a Snyder column to
the K-D apparatus and concentrate to approximately 5 mL on a water bath set to 30 to 40°C.
Rinse the Snyder column and concentrator flask with several mLs of n-hexane and allow the
solvent to drain into the concentrator tube. Concentrate to < 1 mL final volume via nitrogen
blow-down or via micro-Snyder column. Bring the extract to 1.0 mL final volume via syringe,
rinsing the concentration tube with n-hexane as the extract is drawn into the syringe.
Following concentration to 1 mL, the extract is ready for analysis unless further cleanup is
required. Extract cleanup is explained in Section 4.5.5.3.3.2.
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4.5.5.3.3.1.2 Concentration via Nitrogen Blowdown
Several nitrogen blowdown evaporator concentrator instruments are commercially available. As
the release of large volumes of solvent is detrimental to air quality, systems which capture the
evaporated solvent are preferable.
The solvent should be concentrated to < 1 mL final volume in a water bath set to 30-40°C and
the final volume of the extract should be established as 1.0 mL with a calibrated syringe. The
concentration tube should be rinsed with GC-grade n-hexane as the extract is drawn into the
syringe.
Following concentration to 1 mL, the extract is ready for analysis unless further cleanup is
required. Extract cleanup is explained in Section 4.5.5.3.3.2.
4.5.5.3.3.2 Extract Cleanup
A cleanup step may be required in order to clarify cloudy extracts or remove interfering
compounds from extracts showing significant chromatographic interferences.
To clarify cloudy extracts, they are passed through a packed column of 10 g of silica gel as
detailed in EPA Compendium Method TO-13 A. and ASTM D6209. Ambient air matrices
typically do not result in cloudy extracts and therefore likely do not require additional cleanup.
4.5.5.4 PAH Method Detection Limits. MDLs for PAHs must be determined minimally
annually by following the procedures in Section 4.1. To ensure that the variability of the media
and the extraction process is characterized in the MDL procedure, cartridges and QFFs must be
extracted (it does not suffice to simply analyze a low-concentration solution of PAHs) and blank
and spiked cartridges with QFFs must be prepared. For example, laboratories determining the
MDL following Section 4.1.2.1 must prepare and extract a minimum of seven method blank
cartridges and QFFs and a minimum of seven spiked cartridges and QFFs over the course of
three different dates (preferably non-consecutive). The resulting extracts must be analyzed in
three separate analytical batches (three different calendar dates - preferably non-consecutive).
All steps performed in the preparation and analysis of field sample cartridges must be included in
the MDL procedure.
Note that at very low levels approximating the MDL, the qualitative identification criteria related
to qualifier ion abundance ratio and/or signal-to-noise ratio listed in Section 4.5.5.5.7 may not be
strictly met when determining the MDL. As the MDL spikes are prepared in a clean matrix with
standard materials, the presence of the analyte is expected.
As discussed in Section 4.1.3.1, one MDL spike sample can be added to analysis periodically.
Together with the MB from each batch, once results for seven or more MDL spike samples and
method blanks are available, the MDL can be calculated.
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4.5.5.5 PAH Analysis via GC/MS
4.5.5.5.1	GC/MS Instrumentation. The GC should be capable of temperature
programming such that the temperature may be ramped from 25°C to 290°C at a rate of
8°C/minute or faster. A 30 to 50 m by 0.25 mm fused silica capillary column coated with 0.25
|im crosslinked or bonded 5% phenyl methylsilicone film, or equivalent suitable column capable
of separating the target analytes, surrogates, and ISs with appropriate resolution, should be
installed in the GC. The carrier gas should be helium or hydrogen. Injector and transfer line
should be capable of maintaining 275-300°C. GC injection volume should be 1.0 |iL.
Electron ionization should be performed at 70 eV and the MS should be operated in SIM mode
to maximize sensitivity to ions of the target compounds of interest. Alternatively, for
instruments which are capable, operation in combination SlM/scan mode is preferred.
Spectrometers operating in full scan mode may lack sufficient sensitivity. If full scan is
performed, the MS should be capable of scanning from 35-500 amu in < 1 second.
4.5.5.5.2	Tuning of the MS. The GC/MS must be tuned prior to calibration and
every 12 hours of analysis thereafter via analysis of 5 to 50 ng of DFTPP.
If operated in full scan mode or SIM/scan mode, the MS tune must be optimized to achieve the
ion abundances below in Table 4.5-2.
For instruments operated in SIM mode, the above ion abundance criteria do not apply. Tuning
for SIM instruments is optimized to maximize the signal for DFTPP masses greater than 150
amu. The SIM MS tune must maximize the signal for masses 198, 275, 265, and 442 while
maintaining unit resolution between masses 197, 198, and 199 as well as 441, 442, and 443.
Table 4.5-2. DFTPP Key Ions and Abundance Criteria
mass
ion abundance criteria
51
30-60% of mass 198
68
< 2% of mass 69
70
< 2% of mass 69
127
40-60% of mass 198
197
< 1% of mass 198
198
base peak, assigned 100% relative abundance
199
5-9% of mass 198
275
10-30% of mass 198
365
> 1% of mass 198
441
present, but < mass 443
442
> 40% of mass 198
443
17-23% of mass 442
4.5.5.5.3 Calibration of the GC/MS. All solutions to be analyzed, including
calibration standards, should be removed from refrigerated storage for sufficient time (typically
one hour) to equilibrate to ambient temperature prior to analysis.
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Calibration standard solutions must be prepared at minimally five separate concentration levels
in hexane covering approximately 0.1 to 2.0 |ig/mL and must contain surrogate compounds at
concentrations bracketing those expected in the sample extracts.
ICAL must be established initially, when continuing calibration criteria are not met, or when an
instrument change (ion source cleaning, column trim or change, etc.) may affect instrument
calibration (including alteration of retention times). Calibration is recommended every six
weeks.
An SB which is not fortified with IS must be analyzed just prior to calibration to ensure the
instrument is sufficiently clean to continue analysis. Analysis of the SB must show all target
compounds, IS, and surrogate compounds are not detected.
A known volume of each standard should be transferred to a GC analysis vial and fortified with
IS just prior to analysis. Recommended quantitation and secondary ions are listed in Table 5 of
method TO-13 A. Each compound must be assigned to the IS compound with the nearest
retention time.
Following data acquisition for the calibration standards, the relative response factor (RRF) of
each surrogate and target compound in each calibration level is determined as follows:
As ¦ Cjs
RRF =
Ais " Cs
where:
As =	peak area for quantitation ion of the surrogate or target compound
A is =	peak area for quantitation ion of the assigned internal standard compound
Cs =	concentration of the surrogate or target compound
Cis =	concentration of the assigned internal standard compound
The RSD of the RRFs for each surrogate and target compound must be < 30%. Alternatively, a
calibration curve may be prepared by linear or quadratic regression. The correlation coefficient
for linear or quadratic curves must be > 0.995 for target compounds. Irrespective of the curve fit
method selected, the calculated concentration of each calibration level must be within 30% of the
nominal concentration when quantitated against the resulting calibration curve. Exclusion of
calibration standard levels is not permitted unless justifiable (for example, a known error in
standard preparation). Sample analysis must not be performed, and if performed, results must
not be reported when calibration acceptance criteria are not met. Rather corrective action,
possibly including recalibration, must be taken.
The absolute value of the concentration equivalent to the intercept of the calibration curve
((intercept/slope or equivalent!) converted to concentration units (by division by the slope or
equivalent) must be less than the laboratory MDL. When this specification is not met, the source
of contamination or suppression must be corrected and the calibration curve reestablished before
sample analysis may commence.
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RRTs are calculated for each concentration level of each surrogate and target compound by
dividing the surrogate or target RT by the associated IS compound RT. The RRTs of each
surrogate or target compound across the ICAL are then averaged to determine the ICAL RRT.
All RRTs must be within ± 0.06 RRT units of RRT.
4.5.5.5.4	Secondary Source Calibration Verification. Following each successful
initial calibration, a SSCV must be analyzed to verify the initial calibration. The SSCV is
prepared at approximately the mid-range of the calibration curve. Alternatively, two or more
concentrations of SSCV may be prepared covering the calibration range. All SSCVs must
recover within ± 30% of nominal or demonstrate an RRF within ± 30% of the average RRF of
the calibration curve.
4.5.5.5.5	Continuing Calibration Verification. Once the GC/MS instrument has
met tuning and calibration criteria, a CCV must be analyzed every 12 hours of analysis following
the 12-hour DFTPP tuning check standard. The CCV must recover within ± 30% of nominal or
demonstrate RRF within 30% of the mean ICAL RRF for all target PAHs. Corrective action
must be taken to address CCV failures, including, but not limited to, preparing and analyzing a
new CCV, cleaning or replacing the injector liner, trimming or replacing the column, retuning
the MS, or preparing a new initial calibration.
4.5.5.5.6	Analysis of QC Samples and Field Samples. The MS must be tuned and
the calibration determined or verified prior to the analysis of field samples. ISs should be added
to each extract just prior to analysis. Note that a best practice is not to add IS to the entire 1 mL
of extract. An aliquot of the extract should be taken for fortification with ISs to preclude loss of
the entire extract in the event of IS spiking errors.
The following QC samples are required with each analysis sequence:
Solvent method blank (SMB)
-	MB
-	Replicate extract analysis
Prior to analysis of laboratory QC samples or field-collected samples, a SMB consisting of an
aliquot of the batch extraction solvent fortified with IS must be analyzed and demonstrate target
compounds are < MDL.
Target PAHs must not be present in MBs at concentrations > 2x MDL. Replicate analysis must
demonstrate precision of < 10% RPD for all measured concentrations > 0.5 |ig/mL.
An LCS/LCSD pair is required quarterly and recommended with each extraction batch to
monitor recovery and precision in matrix. Target PAHs in the LCS and LCSD must recover
within 60 to 120% of nominal and the LCSD must demonstrate precision of < 20% RPD for all
target PAHs.
4.5.5.5.7	Compound Identification. Four criteria must be met in order to positively
identify a surrogate compound or target PAH:
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1.	The signal-to-noise ratio of the target and qualifier ions must be > 3:1, preferably >
5:1.
2.	The target and qualifier ion peaks must be co-maximized (peak apexes within one
scan of each other).
3.	The RT of the compound must be within the acceptable RT window determined from
the ICAL average.
4.	The abundance ratio of the qualifier ion response to target ion response for at least
one qualifier ion must be within ± 15% of the average ratio from the ICAL.
If any of these criteria are not met, the compound may not be positively identified. The only
exception to this is when in the opinion of an experienced analyst, the compound is positively
identified. The rationale for such an exception must be documented. For examples of the
qualitative identification criteria and calculation of S:N, refer to Section 4.2.10.5.3.
4.5.5.5.8	Internal Standards Response. IS response must be monitored for each
injection (except for the SB immediately preceding the initial calibration or 12-hour tune check).
Area responses of the IS must be 50 to 200% of the area responses in the initial calibration mid-
level standard and they must elute within ± 20 seconds (± 0.33 minute) of the mean RT of the
initial calibration. Extracts which do not meet these response acceptance criteria should be
diluted, and the dilution analyzed to examine for matrix interferences. If the IS still does not
meet criteria in the dilution, the MS tune should be evaluated for a degradation or enhancement
of sensitivity and corrective action taken to address the failure. Sample results calculated from
IS criteria failures must be appropriately qualified when entered into AQS.
4.5.5.5.9	Surrogate Evaluation. Following calibration, each analyzed extract
should be evaluated to ensure the recovery of each surrogate compound is within 60 to 120% of
the nominal spiked value. Results which fall outside of these limits indicate potential analyte
loss or enhancement either through sample collection and handling and/or extraction process and
must be qualified appropriately when reported to AQS.
4.5.5.5.10	Data Review and Concentration Calculations. For sampling units
without computerized flow control, the beginning and ending flows are averaged to calculate the
collected air volume. For computer controlled sampling units, the integrated collected volume is
typically available from the data logging system. Sampled air volumes must be in STP, 25°C
and 760 mm Hg. Sampling unit flows should be calibrated in flows at standard conditions so
conversion from local conditions to standard flows is not necessary. For units which do not have
computerized flow control, temperature and barometric pressure at sample setup and take down
must be recorded.
Each chromatogram must be closely examined to ensure chromatographic peaks are
appropriately resolved and integration does not include peak shoulders or inflections indicative
of a coelution.
The concentrations of target PAHs in unknowns are calculated by relating the area response ratio
of the target PAH and internal standard in the unknown to the relationship derived in the
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calibration curve selected in Section 4.5.5.5.3. The final air concentration of each target PAH is
determined by multiplying the concentration in the extract by the final extract volume and
dividing by the collected sample air volume at standard conditions of 25°C and 760 mm Hg:
1000 ¦ ct ¦ ve
where:
Ca =	concentration of the target compound in air (ng/m3)
Ct =	concentration of the unknown sample in the extract (|ig/mL)
Ve =	final volume of extract (mL)
V,v =	volume of collected air volume at STP (m3)
4.5.6 Summary of Quality Control Parameters. A summary of QC parameters is shown
in Table 4.5-3.
Table 4.5-3. Summary of Quality Control Parameters for NATTS PAHs Analysis
Parameter
Description and Details
Required Frequency
Acceptance Criteria
Solvent Blank
(SB)
Aliquot of solvent (without IS)
analyzed to ensure the GC/MS is free
of interferences and of compounds of
interest (target PAHs, internal
standards, and surrogates)
Prior to each DFTPP tunc
check
No target compound. IS.
or surrogates
qualitatively detected
DFTPP Tunc
Check
5 to 50 ng injection of DFTPP for
tuning of MS detector
Prior to initial calibration
and every 12 hours of
analysis thereafter
Abundance criteria listed
in table 4.5-2 must be
met
Initial Calibration
(ICAL)
Analysis of a minimum of five
calibration levels covering
approximately 0.1 to 2 ng/mL
Initially, following failed
DFTPP tunc check, failed
CCV, or when changes to
the instrument affect
calibration response.
Recommended every six
weeks.
Average RRF
< 30% RSD and each
calibration level must be
within ± 30% of nominal
For quadratic or linear
regression, r > 0.995,
each calibration level
must be within ± 30% of
nominal
Secondary Source
Calibration
Verification
(SSCV)
Analysis of a second source standard
at the mid-range of the calibration
curve to verify curve accuracy
Immediately after each
ICAL
Recovery within
± 30% of nominal or
RRF within 30% of
mean ICAL RRF
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Table 4.5-3. Summary of Quality Control Parameters for NATTS PAHs
Analysis (Continued)
Parameter
Description and Details
Required Frequency
Acceptance Criteria
Continuing
Calibration
Verification
(CCV)
Analysis of a known standard at the
mid-range of the calibration curve to
verify ongoing instrument calibration
Following each DFTPP
tunc check not followed by
ICAL and recommended at
the conclusion of each
sample sequence
Recovery within
± 30% of nominal or
RRF within 30% of
mean ICAL RRF
Cartridge Batch
Blank
A cartridge (and QFF) selected for
analysis to ensure acceptable
background levels in the batch of
cartridges
One cartridge for each
batch of 20 or fewer
prepared cartridges
All target compounds
each <10 ng/cartridge
Field Surrogate
Compounds
Deutcrated P AHs which assess
recovery during sample collection,
handling, and analysis
Added to every cartridge
prior to field deployment
Recovery 60-120% of
nominal spiked amount
Internal Standards
(IS)
Deutcrated PAHs added to extracts to
assess the impact of and correct for
variability in instrument response
Added to all calibration
standards. QC samples,
and field sample extracts
except the SB
Area response within 50-
200% of the response of
the mid-level calibration
standard in the ICAL.
Extraction
Surrogate
Compounds
Deutcrated P AHs which assess
recovery during sample extraction
and analy sis
Added to media before
extraction
Recovery 60-120% of
nominal spiked amount
Solvent Method
Blank (SMB)
Aliquot of extraction solvent fortified
with IS to ensure extraction solvent is
free of interferences and target
compounds
One with every extraction
batch of 20 or fewer field-
collected samples
Target compounds
< MDL
Method Blank
(MB)
Blank cartridge and QFF taken
through all extraction and analy sis
procedures
One with every extraction
batch of 20 or fewer field-
collected samples
Target analyte amounts
< 2x MDL
Laboratory
Control Sample
(LCS)
Cartridge spiked with known amount
of target analyte
Minimally quarterly.
Recommended as one with
every extraction batch of
20 or fewer field-collected
samples
Recovery 60-120% of
nominal spiked amount
Laboratory
Control Sample
Duplicate (LCSD)
Duplicate cartridge spiked with
known amount of target analyte
Minimally quarterly.
Recommended as one with
every extraction batch of
20 or fewer field-collected
samples
Recovery 60-120% of
nominal spiked amount
and precision
< 20% RPD compared to
LCS
Replicate Analysis
Replicate analy sis of a field sample
extract
Once with every analy sis
sequence
Precision < 10% RPD
for concentrations
> 0.5 ng/mL
Field Blank (FB)
Blank cartridge and QFF assembly
exposed to ambient atmosphere for
minimally five minutes
One per month
Target analyte amounts
< 5xMDL
Collocated
Samples
Sample collected concurrently with
the primary sample
10% of primary samples
for sites conducting
collocated sampling (as
required by workplan)
Precision < 20% RPD
for concentrations
> 0.5 ng/mL
Retention Time
(RT)
RT of each target P AH, surrogate
compound, and internal standard
All qualitatively identified
compounds
Target analytes within ±
0.06 RRT units of mean
ICALRRT
Internal standards within
± 0.33 minutes of mean
ICAL RT
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4.5.7
References
1.	Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Ambient Air Using Gas
Chromatography/Mass Spectrometry (GC/MS); EPA Compendium Method
TO-13 A. In Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air (Second Edition)', EPA 625/R-96/010b; U.S. Environmental Protection Agency,
Center for Environmental Research Information. Office of Research and Development.
Cincinnati, OH, January 1999. Available at (accessed October 19, 2016):
https://www3.epa. gov/ttnamti 1/files/ambient/airtox/to-13arr.pdf
2.	ASTM D6209-13, Standard Test Method for Determination of Gaseous and Particulate
Polycyclic Aromatic Hydrocarbons in Ambient Air (Collection on Sorbent-Backed Filters
with Gas Chromatographic/Mass Spectrometric Analysis), ASTM International, West
Conshohocken, PA, 2013, www.astm.org.
3.	Accelerated Solvent Extraction for Monitoring Persistent Organic Pollutants in Ambient Air.
White Paper 71064. Aaron Kettle, Thermo Fisher Scientific, Sunnyvale, CA. 2013.
4.	Chuang, J.C.; Hannan, S.W.; Koetz, J. R. Stability of Polynuclear Aromatic Compounds
Collectedfrom Air on Quartz Fiber Filters andXAD-2 Resin, EPA-600/4-86-029; U.S.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, Methods
Development and Analysis Division: Research Triangle Park, NC, September 1986.
5.	Feng, Y.; Bidleman, T.F. Influence of Volatility on the Collection of Polynuclear Aromatic
Hydrocarbon Vapors with Polyurethane Foam. Environ. Sci. Technol. 1984, 18, 330 -333.
6.	Yamasaki, H.; Kuvvata, K.; Miyamoto, H. Effects of Ambient Temperature on Aspects of
Airborne Polycyclic Aromatic Hydrocarbons. Environ. Sci. Technol. 1982, 16, 89-194.
7.	Galasyn, J.F.; Hornig, J.F.; Soderberg, R.H. The Loss of PAH from Quartz Fiber High
Volume Filters. J. Air Pollut. Contr. Assoc. 1984, 34, 57-59.
8.	Care and Safe Handling of Laboratory Glassware. Coming Incorporated. RG-CI-101-REV2.
2011. Available at (accessed October 19, 2016):
are RG-CI-101 Rev2.pdf

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5.0: METEOROLOGICAL MEASUREMENTS
A goal of the NATTS network is to leverage existing monitoring sites (such as those conducting
criteria pollutant monitoring, PA MS sites, and NCore sites, etc.) to conduct NATTS Program
sample collection. Many of the existing 27 NATTS sites conduct site-specific meteorological
measurements.
While such site-specific meteorological measurements such as wind speed, wind direction, solar
radiation, precipitation, etc. are highly desirable and complement collected NATTS data, only
temperature and barometric pressure measurements are required for NATTS sample collection
events. If temperature and barometric pressure measurements are not recorded from calibrated
temperature and barometric pressure functions on sampling units themselves, they must be
recorded from site-specific calibrated meteorological instruments. If site-specific meteorological
monitoring is not performed, each site must acquire the applicable temperature and barometric
pressure from the closest off-site meteorological monitoring station (i.e.. National Weather
Service, local airport, etc.). For sites collecting additional meteorological parameters beyond
temperature and barometric pressure, please consult EPA's Quality Assurance Handbook for Air
Pollution Measurement Systems, Volume IV Meteorological Measurements for more
information, available at (accessed October 19, 2016):
https://www3.epa.gov/ttnamtil/files/ambient/met/draft-volume-4.pdf
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6.0: DATA HANDLING
6.1	Data Collection
All records must be documented in detail sufficient to reconstruct the activities and
transformations to generate reported concentration data. If such records are not available,
validity of the data cannot be determined. Such records minimally include observations,
laboratory measurements, and photographs as well as instrument calibration records and COAs.
Records related to manipulation of data such as through data reduction spreadsheets, peak
integrations, hand calculations, or calculations handled by a LIMS must be maintained and must
be transparent so the transformations may be verified.
6.2	Data Backup
Electronic data acquired from laboratory instruments, field instruments, databases, and data
manipulation software in support of NATTS Program work must be maintained for a minimum
of six years following acquisition. As previously discussed, this six-year period is needed to
cover two consecutive three-year periods needed to assess trends for the NATTS DQO. In order
to maintain electronic records for this duration, it is necessary to prevent data loss and corruption
by ensuring data redundancy. Each NATTS agency must prescribe data redundancy policies and
procedures, which may be included in the NATTS QAPP, SOP, or similar controlled document.
For data acquisition software systems such as CDSs, ICP-MS control and operation software,
and environmental control tracking software systems which are connected via computer network,
a best practice is to enable automated nightly backups of data to a separate physical hard drive or
server, preferably one at a different physical location. Backing up of data to a separate partition
on the same hard drive provides little additional security if the hard drive fails. For software
systems which are not networked to a server, a best practice is to manually back up the data after
completion of each day's activities to removable media (thumb drive, external hard drive, etc.)
for transfer to a networked computer or server.
These daily backups must be protected from inadvertent alteration and compiled on a regular
frequency, recommended weekly but not to exceed monthly, to an archival system such as a tape
drive, DVD, additional external server, cloud storage, etc. This archival must be access-limited
by password and/or other security means to a select few individuals as deemed responsible by
cognizant management.
Archived electronic data must remain accessible such that retired computer or software systems
must be maintained to access data, or archived data converted such that it remains accessible and
legible until the archival period has lapsed.
Once archived, archived data should be reviewed or tested to ensure complete records are
maintained and data have not been corrupted. Such a review is recommended every six months,
but should not exceed annually.
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6.3	Recording of Data
Data generated as in Section 6.1 must be recorded so that it is clear who performed the activity,
when the activity was performed, and, if applicable, who documented performance of the
activity.
6.3.1	Paper Records. Data entries created on paper records such as field collection forms,
COC forms, or laboratory notebooks, must be recorded in legibly in indelible ink and must
identify the individual creating the entry. Measurements must clearly indicate appropriate units.
Individuals creating paper data records must be identified by way of signature or initials unique
to the individual and in such a manner that unambiguous identification is possible. One method
by which such may be accomplished is to create a cross-reference for each staff person that
shows each staff person's printed name, signature, and initials.
6.3.2	Electronic Data Capture. Electronic data recording systems such as electronic
logbooks, LIMS, and instrumental data acquisition software generally require a user to log in
with a username and password to utilize the system. Each action (entry, manipulation,
instrument operation) recorded by such software systems must be attributable to an individual
and the corresponding date and time recorded. If so equipped, audit trails must be enabled on
software systems in order to record changes made to electronic records.
6.3.3	Error Correction. Changes to recorded data or data manipulation may be required
due to calculation errors, incorrectly recorded measurements, or errors noted during data
verification and validation. When records are amended, whether paper or electronic, the original
record must remain legible or otherwise intact, and the following information must be recorded:
the identity of the individual responsible for making the change, the date the change was made
and the rationale for the change. For example, hand-written data records may be corrected by a
single line through the entry with the correction, the initials of the responsible individual, the
date of correction, and the rationale for change documented in close proximity to the correction
or identifiable by annotated footnote. For common corrections such as those for incorrect date,
illegible entry, calculation errors, etc., a list of abbreviations may be developed to document
change rationale. Any such abbreviations must be defined in a quality systems document such as
an SOP, or in the front of a logbook, etc.
6.3.3.1 Manual Integration of Chromatographic Peaks. Automated functions for the
integration of chromatographic peaks are included in the chromatography data systems (CDS)
that control all GC/MS and HPLC instruments. These integration functions should be configured
such that little intervention or correction is needed by the analyst, so as to best ensure that peak
integration is as reproducible and introduces as little human error as possible. While these
functions ensure consistent integration practices, subtle differences in peak shape, coeluting
peaks, and baseline noise may result in inconsistent or incorrect peak integration.
Analysts must be properly trained to review and adjust peak integration performed by CDS
automated functions, and specific procedures must be codified into each agency's quality system.
All manual changes to automated peak integration must be treated as error corrections. Typical
corrections to peak integration may include: adjustment of the baseline, addition or removal of a
169

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vertical drop line, or peak deletion if the requisite compound identification criteria are not met.
The identification criteria for the chromatography methods are listed as follows:
VOCs:	Section 4.2.10.5.3
Carbonyls: Section 4.3.9.5.6
PAHs:	Section 4.5.5.5.7
Manual peak deletion, that is, effectively reporting that the compound was not detected, is not
permitted in instances in which the peak specified identification criteria are met.
For each adjustment to chromatographic peak integration (manual integration), the record of the
original automated integration must be maintained and it is strongly recommended that the
adjustment be justified with the documented rationale (signal-to-noise too low, incorrect
retention time, incorrectly drawn baseline, etc.), analyst initials, and date.
6.4	Numerical Calculations
Numerous calculations and manipulations are necessary to determine the target analyte
concentration of a given field-collected sample or QC sample or to determine evaluate whether
data generated during calibration verifications meet acceptance criteria.
6.4.1	Rounding. Rounding of values must be avoided until the final step of a calculation.
Rounding during intermediate steps risks the loss of fidelity of the calculation which may lead to
significant calculation error.
EPA Region IV SESD has developed guidance for rounding which is adopted into the revision of
the Volume II of EPA" s QA Handbook. This guidance is included in Appendix C of this TAD.
6.4.2	Calculations Using Significant Digits. Final reported results should be rounded to
the correct number of significant digits per the rules below. To the extent feasible, carry the
maximum number of digits available through all intermediate calculations and do not round until
the final calculated result. Non-significant digits that are carried through calculations may be
represented using subscripted numerals. (For example, 2.321 has three significant figures, with
the final 1 being non-significant and carried through to avoid unnecessarily introducing
additional error into the final result.)
6.4.2.1 Addition and Subtraction. The number of significant digits in the final result is
determined by the value with the fewest number of digits after the decimal place. For example:
A 5.6
B 63.71
C + 9.238
78.5
170

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The final result is limited to one decimal place due to the uncertainty introduced in the tenths
place by measurement A.
6.4.2.2	Multiplication and Division. The number of significant digits in the final result is
determined by the value with the fewest number of significant digits. For example, acrolein was
measured by the GC/MS at a concentration of 2.72 1 ppb from a canister that was diluted with
zero air resulting in a dilution factor of 1.41. The dilution factor is applied to the measured result
to calculate the in air concentration:
2.721 ppb • 1.41 = 3.837 ppb
3.84 ppb
The final result is limited to three significant digits due to the dilution factor containing three
significant digits.
6.4.2.3	Standard Deviation. Standard deviation in a final result must not display digits in a
place that the sample average does not have a significant digit. Take, for example, the following
average and standard deviation of the form x ± .v:
107.2 ± 2.3J_ is reported as 107.2 ± 2.3
The standard deviation is rounded to the appropriate significant digit of the sample average.
6.4.2.4	Logarithms. For converting a value to its logarithm, retain as many places in the
mantissa of the logarithm (to the right of the decimal point in the logarithm) as there are
significant figures in the number itself. For example (mantissa underlined):
login 24.5 = 1.389
For converting antilogarithms to values, retain as many places in the value as there are digits in
the mantissa of the logarithm. For example (mantissa underlined):
anti log (1.131) = 13.5
6.5	In-hoiise Control Limits
The analysis methods detailed in Section 4 specify acceptance criteria for routine QC samples.
These acceptance criteria are the maximum allowable ranges permitted, however, laboratories
may find that they rarely or never exceed the acceptance criteria. As each laboratory and the
associated analyst, instruments, and processes are unique, development of in-house control limits
is recommended to evaluate trends and identify problem situations before exceedances to method
acceptance criteria occur.
In-house control limits may be generated to evaluate the bias of quality control samples such as
the LCS, CCV, SSCV, and to evaluate precision of LCSD, matrix spike duplicate, etc. Warning
171

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limits and control limits are established following acquisition of sufficient data points, generally
more than seven, per the guidance in the subsequent sections. Under no circumstances may data
be accepted which exceeds method specified acceptance criteria even if in-house warning or
control limits have not been exceeded.
6.5.1	Warning Limits. Warning limits are established as a window of two standard
deviations surrounding the mean (x ± 2.v). Exceedance of the warning limit should prompt
monitoring of the parameter for values which remain outside the warning limits. For repeated
values exceeding the warning limits, corrective action should be taken to address the trend.
6.5.2	Control Limits. Control limits are established as a window of three standard
deviations surrounding the mean (x ± 3s). Corrective action is required when control limits are
exceeded.
6.6	Negative Values
In general, negative values of small magnitude may be expected from certain analytical
platforms in the NATTS program, specifically those which do not apply calibration regressions
which are forced through the origin. However, depending on the situation, negative numbers can
be problematic and indicative of bias due to faulty sensors, contamination in reagents and
lab ware, improper calibration, or calculation errors.
Negative values must be evaluated to ensure that their magnitude does not significantly impact
the resulting measurements.
Minimum values will be updated in AQS to permit the reporting of negative values for NATTS
parameters. Negative values for all qualitatively identified analytes must be reported to AQS as-
is without censoring or replacing with zero.
6.6.1	Negative Concentrations. For analysis measurements, a negative concentration
result generated by a positive instrument response (i.e., positive area count) must be investigated
to ensure that the negative concentration is of small magnitude such that the absolute value of the
concentration is less than the MDLsp (for MDLs determined via Section 4.1.3.1) or s K for
MDLs determined via Section 4.1.3.2. Where negative concentrations fail this criterion,
corrective action must be taken to determine and remediate the source of the bias.
6.6.2	Negative Physical Measurements. For physical measurements such as mass,
absolute pressure, and flow, negative values generated by an instrument must be evaluated to
ensure they do not adversely impact future measurements.
For example, a VOCs sampling unit pressure transducer reads -0.4 psia upon connection to a
canister at hard vacuum. The acceptable canister pressure threshold is 0.5 psia. Since negative
absolute pressures are impossible, the -0.4 psia reading is significant, especially when compared
to an acceptance criterion of 0.5 psia. Due to the -0.4 psia bias, the pressure in another canister
at 0.8 psia would be read 0.4 psia and would incorrectly meet the acceptance criterion for sample
collection due to the incorrect calibration of the pressure transducer.
172

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7.0: DATA V ALIDATION TABLES
The following tables are a distillation of the general quality control guidance and requirements in
Section 3 and of the individual methods described in Section 4. More information on each data
validation parameter can be located within the text identified in the reference column. Each
parameter is assigned a category of importance. The categories in order of decreasing
importance are:
1.	Critical - Criteria must be met for reported results to be valid - Samples for which
these criteria are not met are invalidated.
2.	MQO - Required NATTS Measurement Quality Objective which must be attained -
Failure to meet these criteria does not necessarily invalidate data, but may
compromise data and result in exclusion from trends analysis.
3.	Operational - Failure to meet criteria does not invalidate reported results; the results
are compromised and on a case-by-case basis may require qualification - refer to
Section 3.3.1.3.15 for the list of AQS qualifiers
4.	Practical - Failure to meet criteria does not invalidate reported results; results may be
compromised but do not require qualification.
The validation tables in the following sections will be available on AMTIC in Microsoft Excel®
format so the parameters may be sorted according to importance.
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7.1	VOCs via EPA Coinpendiiim Method TO-15
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Field Readiness Checks and Collection Activities
Canister Cleaning
Batch Blank
Minimally one canister selected for analysis from a given
batch of clean canisters to ensure acceptable background
levels in the batch of cleaned canisters - must represent no
more than 10 canisters
Each target VOC s concentration
< 3x MDL or 0.2 ppb, whichever is
lower
Section 4.2.6.2.4
TO-15 Section
8.4.1.6
Critical
Canister Viability
All canisters
Canister must be used within 30
days from final evacuation
Section 4.2.6.2
TO-15 Section 1.3
Operational
Sampling Unit
Clock/Timer Check
Verified with each sample collection event
Clock/timer accurate to ±5 minute
of reference for digital timers, ±15
minutes for mechanical timers, set
to local standard time
Sample collection period verified
to be midnight to midnight
Section 4.2.5.3 and
Table 3.3-1
Operational
Canister Starting
Pressure
Determination
Each canister prior to collection of a field sample or
preparation of a calibration standard or laboratory QC sample
Vacuum > 28" Hg as determined
w ith calibrated pressure gauge or
transducer
Section 4.2.5.2.1
Critical
Sample Setup Leak
Check
Each canister prior to collection - draw vacuum on canister
connection
Leak rate must be < 0.2 psi over 5
minutes
Section 4.2.5.2.1
Critical
Sampling Frequency
One sample every six days according to the EPA National
Monitoring Schedule
Sample must be valid or a make-up
sample should be scheduled (refer
to Section 2.1.2.1)
Section 4.2.5.3
Critical and
MQO
Sampling Period
All field-collected samples
1380-1500 minutes (24 ± 1 hr)
starting and ending at midnight
Section 4.2.5.3
Critical and
MQO
Pre-Sample
Collection Purge
Each sampling event
Minimum of ten air changes just
prior to sample collection
Section 4.2.5.4
Practical
Field-collected
Sample Final
Pressure
All field-collected samples
Must be determined w ith a
calibrated pressure gauge or
transducer per agency quality
system specification
Section 4.2.5.2.4
Operational
Sample Receipt
Chain-of-custody
All field-collected samples including field QC samples
Each canister must be uniquely
identified and accompanied by a
valid and legible COC w ith
complete sample documentation
Sections 3.3.1.3.7
and 4.2.5.2.4
Critical

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7.1 VOCs via EPA Coinpendiiim Method TO-15 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Sample Holding
Time
All field-collected samples, laboratory QC samples, and
standards
Analysis within 30 days of end of
collection (field-collected samples)
or preparation (QC samples or
standards)
Section 4.2.1
TO-15 Sections
1.3, 2.3, and 9.2.8.1
Operational
Canister Receipt
Pressure Check
All field-collected samples upon receipt at the laboratory -
measured with calibrated pressure gauge or transducer
Pressure change of < 0.5 psi from
the final pressure at retrieval
Section 4.2.8
Critical for
subanibient
sample
collection.
operational
for
pressuri/cd
sample
collection
GC/MS Analysis
Instrument Blank
(IB)
Analysis of swept carrier gas through the preconccntrator to
demonstrate the instrument is sufficiently clean prior to
analysis of ICAL or daily beginning CCV
Each target VOC s concentration
< 3x MDL or 0.2 ppb, whichever is
lower
Section
4.2.10.5.2.2
Operational
BFB Tunc Check
50 ng injection of BFB for tune verification of MS detector
analyzed prior to initial calibration and every 24 hours of
analvsis thereafter (for quadrupole MS only)
Must meet abundance criteria
listed in Table 4.2-2
Section 4.2.10.5.1
TO-15 Section
10.4.2
Critical
GC/MS Multi-Point
Initial Calibration
(ICAL)
Analysis of a minimum of five calibration levels covering
approximately 0.1 to 5 ppb
Initially and minimally every three months thereafter,
following failed BFB tunc check, failed CCV, or when
changes to the instrument affect calibration response
Average RRF < 30% RSD and
each calibration level must be
within ± 30% of nominal
For linear regression (with either a
linear or quadratic fit),
r > 0.995 and each calibration level
must be within ± 30% of nominal
Section
4.2.10.5.2.2
TO-15 Section
10.5.5.1
Critical
Secondary Source
Calibration
Verification (SSCV)
Analysis of a secondary source standard at the mid-range of
the calibration curve to verify ICAL accuracy immediately
after each ICAL
Recovery within ± 30% of nominal
Section
4.2.10.5.2.3
Critical
Continuing
Calibration
Verification (CCV)
Analysis of a known standard at the mid-range of the
calibration curve to verify ongoing instrument calibration;
following each daily BFB tune check and at the conclusion of
each analytical sequence
Each target VOC must recover
within 70-130% of the nominal
spiked amount or the RRF must be
within 30% of the mean IC AL
RRF
Section
4.2.10.5.2.4
TO-15 Section
10.6.5
Critical

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7.1 VOCs via EPA Coinpendiiim Method TO-15 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Internal Standards
(IS)
Deutcrated or non-naturally occurring compounds co-
analyzed with all calibration standards, laboratory QC
samples, and field-collected samples so as to monitor
instrument response and assess matrix effects
Area response for each IS
compound within ± 40% of the
average response of the ICAL
Section 4.2.10.5.4
TO-15 Section
10.7.5
Critical
Preconcentrator
Leak Check
Pressurizing or evacuating each canister connection to the
preconcentrator to verify as leak-free prior to analysis
< 0.2 psi change/minute or
manufacturer specifications
Section
4.2.10.5.2.1
Operational
Method Blank (MB)
Canister filled with clean humidified diluent gas (gas
employed for dilution of standards and /or samples)
One with every analysis batch of 20 or fewer field-collected
samples
Each target VOC s concentration
< 3x MDL or 0.2 ppb. whichever is
lower
Section 4.2.10.4.3
TO-15 Section
10.7.5
Operational
Laboratory Control
Sample (LCS)
Canister spiked with known amount of target analyte at
approximately the lower third of the calibration curve
Recommended: One with every analysis batch of 20 or fewer
field-collected samples
Each target VOC s recovery must
be 70 to 130% of its nominal
spiked amount
Section
4.2.10.5.2.5
Operational
Retention Time
(RT)
RT of each target compound and internal standard for all
qualitatively identified compounds and internal standards
Each target VOC s RRT must be
within ± 0.06 RRT units of its
mean ICAL RRT
Each IS RT must be within± 0.33
minutes of its mean IC AL RT
Sections
4.2.10.5.2.2 and
4.2.10.5.4
TO-15 Sections
10.5.5.2. 10.5.5.3.
and 10.5.5.4
Critical


Signal-to-noise >3:1




RT within prescribed window


Compound
Identification
Qualitative identification of each target VOC in each
standard, blank. QC sample, and field-collected sample
(including field QC samples)
Ion abundances of at least one
qualifier ion within 30% of IC AL
mean
Peak apexes co-maximized (within
one scan for quadrupole MS) for
quantitation and qualifier ions
Section 4.2.10.5.3
Critical
Replicate Analysis
A single additional analysis of a field-collected canister
Once with every analysis sequence (as prescribed in
vvorkplan)
Precision < 25% RPD for target
VOCs with concentrations
> 5xMDL
Section
4.2.10.5.2.5
TO-15 Section
11.1.1
Operational

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7.1 VOCs via EPA Coinpendiiim Method TO-15 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Duplicate Sample
Field sample collected through the same inlet probe as the
primary sample
10% of primary samples for sites performing duplicate
sample collection (as prescribed in workplan)
Precision < 25% RPD of primary
sample for concentrations
> 5xMDL
Sections 4.2.4;
4.2.4.1
Operational
Collocated Sample
Field sample collected through a separate inlet probe as the
primary sample
10% of primary samples for sites performing duplicate
sample collection (as prescribed in workplan
Precision < 25% RPD of primary
sample for concentrations
> 5xMDL
Sections 4.2.4 and
4.2.4.1
Operational
Laboratory Readiness and Proficiency
Method Detection
Limit
Determined initially and minimally annually thereafter and
when method changes alter instrument sensitivity
MDL determined via 4.1 must be:
Acrolein < 0.09 ng/m;
Benzene < 0.13 ng/m;
1,3-Butadiene < 0.10 ng/m;
Carbon Tetrachloride < 0.017
Hg/m;
Chloroform < 0.50 ng/m5
Tctrachlorocthylcne < 0.17 ng/m;
Trichlorocthylcne < 0.20 ng/m;
Vinyl Chloride < 0.11 ng/m;
These MDL MQOs current as of
October 2015. Refer to current
workplan template for up-to-date
MQOs.
Sections 4.1 and
4.2.7
MQO
Stock Standard
Gases
Purchased stock standard gases for each target VOC
All standards
Certified and accompanied by
certificate of analysis
Recertified or replaced annually
unless a longer expiration is
specified by the supplier
Section 4.2.10.3.1
Critical

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7.1 VOCs via EPA Coinpendiiim Method TO-15 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category


Each target compound within
± 25% of the assigned target value


Proficiency Testing
Blind sample submitted to each laboratory to evaluate
laboratory bias
Two per calendar year1
Failure of one PT must prompt
corrective action. Failure of two
consecutive PTs (for a specific
core analyte) must prompt
qualification of the analyte in field
collected samples until return to
conformance.
Section 2.1.4.1
Operational
andMQO
Canister and Sampling Unit Testing and Maintenance

Testing of the leak tightness of each canister in the agency
fleet
Annually, may be performed simultaneously with canister
zero air check



Canister Leak Test
Leak rate must be < 0.1 psi/day
Section 4.2.6.1.1.1
Operational
Canister Zero Check
Verification that a canister docs not contribute to positive
bias over an approximate 30-day period
Strongly Recommended: Each canister in the agency fleet
once annually (or as defined by agency policy) or after major
maintenance such as replacement of valve
All Tier 1 core target compounds
must be < 0.2 ppb or < 3x MDL,
whichever is lower
Section 4.2.6.1.1.1
TO-15 Section
8.4.3
Operational
Canister Known
Standard Gas Check
Verification that a canister docs not contribute to bias over an
approximate 30-day period
Strongly Recommended: Each canister in the agency fleet
once annually (or as defined by agency policy) or after major
maintenance such as replacement of valve
All Tier 1 core target compounds
must be within ± 30% of nominal
Section 4.2.6.1.1.2
Operational
Sampling Unit Flow
Calibration
Calibration of sampling unit flow controller
Initially and when calibration checks demonstrate flows are
out of tolerance, or when components affecting flow are
adjusted or replaced
Flow set to match the certified
flow primary or transfer standard
Table 3.3-1
TO-15 Section
8.3.5
Practical

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7.1 VOCs via EPA Coinpendiiim Method TO-15 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Sampling Unit Non-
biasing Certification
Verification that the sampling unit docs not contribute to bias
Prior to field deployment and annually thereafter, or when
flow path components are repaired or replaced
Sampling units must be subject to a Zero Check and Known
Standard Challenge
Zero Check - All Tier 1 core target
analytes < 0.2 ppb or < 3x MDL,
whichever is lower
Known Standard Challenge - All
Tier 1 core target analytes within
±15% of the reference sample
Section 4.2.5.5
Operational
Sampling Unit Flow
Calibration Check or
Audit
Verification of sampling unit flow rate
Minimally quarterly, monthly recommended
Flow within ±10% of certified
primary or transfer standard flow
and design flow
Table 3.3-1
Practical
Site Specifications and Maintenance


270° unobstructed probe inlet
Inlet 2-15 meters above-ground
level


Sampling Unit
Siting
Verify conformance to requirements
Annually
>10 meters from drip line of
nearest tree
Collocated sampling inlets spaced
within 4 meters of primary
sampling unit inlet
Section 2.4
Operational
Sample Probe and
Inlet
Sample probe and inlet materials composition
Annually
Chromatographic grade stainless
steel or borosilicate glass
Section 4.2.3.2
Operational
Sample Inlet Filter
Particulate filter maintenance
Minimally annually
Clean or replace the 2-^m sintered
stainless steel filter
Section 4.2.3.3
TO-15 Section
7.1.1.5
Operational
Sampling Inlet and
Inlet Line Cleaning
Sample inlet and inlet line cleaning or replacement
Minimally annually - More often in areas with high airborne
particulate levels
Cleaned with distilled water or
replaced
Section 4.2.3.1
Operational
Data Reporting
Data Reporting to
AQS
Reporting of all results a given calendar quarter
Quarterly, within 180 days of end of calendar quarter
All field-collected sample
concentrations reported including
data less than MDL.
Field QC sample and laboratory
replicates must also be reported (as
required by workplan).
Section 3.3.1.3.15
Operational

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7.1 VOCs via EPA Coinpendiiim Method TO-15 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
AQS Reporting
Units
Units must be as specified with each submission to AQS
ppbv
Section 3.3.1.3.15
Critical
Data Completeness
Valid samples compared to scheduled samples
Annually
> 85% of scheduled samples
Section 3.2
MQO
Dependent upon EPA contract with PT provider

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7.2
Carbonyls via E PA Compendium Method TO-11A
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Field Readiness Checks and Collection Activities
Collection Media
All field-collected samples and matrix quality control
samples
Cartridge containing silica gel solid
sorbent coated with DNPH
Section 4.3.5
TO-11A
Section 8.2
Critical


Sample retrieval as soon as possible, not
to exceed 72 hours post-sampling.
Sections
4.3.5.2,
4.3.5.3,	and
4.3.8.1.2
TO-11A
Sections 6.5
and 10.12

Media Handling
All field-collected samples and all quality control samples
Retrieved sample shipped and stored at
< 4°C, protected from light until
extraction.
Damaged cartridges (water damage or
cracked) must be voided.
Critical



Section

Cartridge Lot
Blank Check
Analysis of a minimum of 3 cartridges or 1% of the total lot.
whichever is greater, for each new lot
Formaldehyde < 0.15 jig/cartridge,
Acctaldchydc < 0.10 jig/cartridge,
Acetone < 0.30 jig/cart ridge,
all others < 0.10 jig/cart ridge
4.3.5.1 and
Table
4.3-4
TO-11A
Section
9.2.5.17
Critical
Sampling Unit
Clock/Timer Check
Verified with each sample collection event
Clock/timer accurate to ±5 minute of
reference for digital timers and ±15
minutes for mechanical timers, set to
local standard time
Sample collection period verified to be
midnight to midnight
Table 3.3-1
Operational
Sampling Unit
Leak Check
Pressurization or evacuation of internal sampler flow paths
to demonstrate as leak-free
Prior to each sample collection
Must show no indicated flow
Section
4.3.8.1.1
Operational
Sampling
Frequency
One sample every six days according to the EPA National
Monitoring Schedule
Sample must be valid or a make-up
sample should be scheduled (refer to
Section 2.1.2.1)
Section
4.3.8.1.3
Critical and
MQO
Sampling Period
All field-collected samples
1380-1500 minutes (24 ± 1 hr) starting
and ending at midnight
Section
4.3.8.1.3
Critical and
MQO

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7.2 Carbonyls via EPA Coinpendiiim Method TO-11A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Pre-Sample
Collection Purge
Each sampling event
Minimum of ten air changes just prior to
sample collection
Section
4.3.7.2
Practical
Sample Receipt
Chain-of-custody
All field-collected samples
Each cartridge must be uniquely
identified and accompanied by a valid
and legible COC with complete sample
documentation
Section
3.3.1.3.7
Critical
Sample Holding
Time
All field-collected samples, laboratory QC samples, and
standards
Extraction: 14 days from sample
collection (cartridge storage < 4 °C)
Analysis: 30 days from extraction
(extract storage < 4 °C)
Section
4.3.9.3
TO-11A
Sections
11.1.2 and
11.2.5
Operational



Section

Sample Receipt
Temperature Check
All field-collected samples upon receipt at the laboratory
Must be < 4°C
4.3.8.1.2
TO-11A
Section
10.12
Operational
HPLC Analysis
Solvent Blank (SB)
Prior to ICAL and daily beginning CCV
All target compounds < MDLsp (referto
Section 4.1.3.1) or vK (refer to Section
4.1.3.2)
Section
4.3.9.5.2
Operational
HPLC Initial
Multi-Point
Calibration (ICAL)
Initially, following failed CCV, or when changes to the
instrument affect calibration response
Injection of a minimum of 5 points covering approximately
0.01 to 3.0 (ig/mL
Correlation coefficient (r) > 0.999;
relative error for each level against
calibration curve < 20%. Absolute value
of intercept divided by slope must not
exceed MDLsp (MDLs determined by
Section 4.1.3.1) or.v-R (MDLs
determined by Section 4.1.3.2)
Section
4.3.9.5.2
TO-11A
Section
11.4.3
Critical
Secondary Source
Calibration
Verification
(SSCV)
Secondary source standard prepared at the mid-range of the
calibration curve, analyzed immediately after each IC AL
85 to 115% recovery
Section
4.3.9.5.3
TO-11A
Section
11.4.4
Critical
Continuing
Calibration
Verification (CCV)
Prior to sample analysis on days when an ICAL is not
performed and minimally every 12 hours of analysis;
recommended following analysis of every 10 field-collected
samples and at the conclusion of each analytical sequence
85 to 115% recovery
Section
4.3.9.5.4
TO-11A
Section
11.4.5
Critical

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7.2 Carbonyls via EPA Coinpendiiim Method TO-11A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Extraction Solvent
Method Blank
(ESMB)
An aliquot of extraction solvent delivered to a volumetric
flask. One with each extraction batch of 20 or fewer fie Id-
collected samples.
Each target carbonyl's concentration
< MDLSp (referto Section 4.1.3.1) or
v K (refer to Section4.1.3.2)
Section
4.3.9.4.1
Operational
Method Blank
(MB)
Unexposed DNPH cartridge extracted as a sample
One with every extraction batch of 20 or fewer field-
collected samples
Formaldehyde < 0.15 jig/cart ridge.
Acctaldchydc < 0.10 jig/cart ridge.
Acetone < 0.30 jig/cartridge,
all others < 0.10 jig/cart ridge
Section
4.3.9.4.1
Operational
Laboratory Control
Sample (LCS)
DNPH cartridge spiked with known amount of target analyte
at approximately the lower third of the calibration curve,
minimally quarterly, one recommended with every
extraction batch of 20 or fewer field-collected samples
Formaldehyde recovery 80-120% of
nominal spike
All others recovery 70-130% of nominal
spike
Section
4.3.9.4.1
Operational
Laboratory Control
Sample Duplicate
(LCSD)
Duplicate LCS to evaluate precision through extraction and
analysis, minimally quarterly, one recommended with every
extraction batch of 20 or fewer samples
Formaldehyde recovery 80-120% of
nominal spike
All others recovery 70-130% of nominal
spike
Precision < 20% RPD of LCS
Section
4.3.9.4.1
Operational
Retention Time
(RT)
Every injection
Each target carbonyl's RT within ± 3s or
± 2% of its mean IC AL RT
Section
4.3.9.5.2
Critical
Replicate Analysis
A single additional analysis of a field-collected sample
extract
Once with every analysis sequence of 20 or fewer samples
Precision < 10% RPD for concentrations
>0.5 ng/cartridge
Section
4.3.9.5.5
TO-11 A
Section
13.2.3
Operational
Field Blank
Minimally monthly, sample cartridge installed in primary
sampling position and exposed to field conditions for
minimally 5 minutes
Formaldehyde < 0.30 jig/cart ridge.
Acctaldchydc < 0.40 jig/cart ridge.
Acetone < 0.75 jig/cart ridge.
Sum of all other target compounds < 7.0
jig/cartridge
Section
4.3.8.2.1
TO-11A
Section
13.3.1
Operational
Collocated Sample
Collection
Field sample collected through a separate inlet probe from
the primary sample
10% of primary samples for sites performing collocated
sample collection (as prescribed in workplan)
Precision < 20% RPD of primary sample
for concentrations > 0.5 ng/cartridgc
Section
4.3.8.2.3
TO-11A
Section
13.4.1
Operational

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7.2 Carbonyls via EPA Coinpendiiim Method TO-11A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Duplicate Sample
Collection
Field sample collected through the same inlet probe as the
primary sample
10% of primary samples for sites performing collocated
sample collection (as prescribed in workplan)
Precision < 20% RPD of primary sample
for concentrations > 0.5 ng/cartridge
Section
4.3.8.2.4
TO-11 A
Section
13.4.1
Operational
DNPH
Chromatography
Evaluation
All cartridges
DNPH peak must be present
Section
4.3.9.5.7
Critical
For all field-collected cartridges
DNPH must be > 50% of the DNPH
area in the laboratory QC samples
Critical
Laboratory Readiness and Proficiency
Proficiency Testing
Blind sample submitted to each laboratory to evaluate
laboratory bias
Two per calendar year1
Each target compound within ± 25% of
the assigned target value
Failure of one PT must prompt
corrective action. Failure of two
consecutive PTs (for a specific core
analvte) must prompt qualification of the
analvte in field collected samples until
return to conformance.
Section
2.1.4.1
Operational
andMQO
Method Detection
Limit
Determined initially and minimally annually thereafter, and
when method changes alter instrument sensitivity
MDL must be:
Formaldehyde < 0.08 ng/m;
Acctaldchydc < 0.45 ng/m;
These MDL MQOs current as of
October 2015. Refer to current workplan
template for up-to-date MQOs.
Sections 4.1
and 4.3.6
MQO
Stock Standard
Solutions
Purchased stock materials for each target carbonvl
All standards
Certified and accompanied by certificate
of analysis
Section
4.3.9.2.2
Critical
Working Standard
Solutions
Storage of all working standards
Stored at < 4°C, protected from light
Section
4.3.9.2.4
TO-11A
Section 9.4.3
Critical

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7.2 Carbonyls via EPA Coinpendiiim Method TO-11A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Sampling Unit Testing and Maintenance
Field Sampler Flow
Rate Calibration
Calibration of sampling unit flow controller
Initially and following failure of flow verification checks
Flow set to match a certified flow
transfer standard
Table 3.3-1
and 4.3.7.1.2
Critical
Ozone Scmbber
Recharge
Recharge o/one scrubber w ith KI
Minimally annually
Scrubber capacity sufficient to be
effective (o/one removal > 95%) for 12
months of 24-hour sampling every sixth
day
Section
4.3.4.1
TO-11 A
Section 10.1
Critical
Sampling Unit
Non-biasing
Certification
Verification with humidified zero air or nitrogen that the
sampling unit docs not contribute to positive bias
Prior to field deployment and annually thereafter, or when
flow path components arc repaired or replaced
Difference between challenge and
reference cartridge < 0.2 ppbv for each
target carbonyl
Section
4.3.7.1.1
Operational
Sampling Unit
Flow Calibration
Check or Audit
Verification of sampling unit flow rate
Minimally quarterly, monthly recommended
Flow w ithin ± 10% of certified primary
or transfer standard flow and design
flow
Table 3.3-1
Critical
Site Specifications and Maintenance


270° unobstructed probe inlet


Sampling Unit
Siting
Verify conformance to requirements
Annually
Inlet 2-15 meters above-ground level
> 10 meters from drip line of nearest tree
Collocated sampling inlets spaced no
more than 4 meters from primary
sampling unit inlet
Section 2.4
Operational
Sample Probe and
Inlet
Sample probe and inlet materials composition
Annually
Chromatographic grade stainless steel.
PTFE Teflon, orborosilicate glass
Section
4.3.7.2
Critical
Sample Inlet Filter
Particulate filter maintenance
Minimally annually, if equipped
Clean or replace the inline particulate
filter (if equipped)
Section
4.3.7.3
Operational

Sample inlet and inlet line cleaning or replacement



Sampling Inlet and
Inlet Line Cleaning
Minimally annually - More often in areas with high airborne
particulate levels
Cleaned with distilled water or replaced
Section
4.3.7.3
Operational

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7.2 Carbonyls via EPA Coinpendiiim Method TO-11A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Data Reporting
Data Reporting to
AQS
Reporting of all results a given calendar quarter
Quarterly, within 180 days of end of calendar quarter
All field-collected sample
concentrations reported including data
less than MDL.
All data must be in standard conditions.
Field QC sample and laboratory
replicates must also be reported.
Section
3.3.1.3.15
Operational
AQS Reporting
Units
Units must be as specified with each quarterly submission to
AQS
mass/volume (ng/m3 or ng/m3)
Section
3.3.1.3.15
Critical
Data Completeness
Valid samples compared to scheduled samples
Annually
> 85% of scheduled samples
Section 3.2
MQO

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7.3	Metals via EPA Compendium Method IO 3.1 and IO 3.5
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Field Readiness Checks and Collection Activities
Collection Media
All field-collected samples and matrix quality control
samples
Low volume collection:
47-mm Teflon filters with
polypropylene support ring and
2-nm pore si/c
Section 4.4.9.3
40CFR Part 50
Appendix Q
Section 6.2.3
Critical
High volume collection:
8"xl0" quart/ fiber filter (QFF)
filters with 2-^im pore si/c
Section 4.4.10.3
103.1 Section 4.1.6
Critical
Media Inspection
Filters inspected for pinholes, tears, or other
imperfections unsuitable for sample collection
All filters
Filters with defects must be
discarded
Section 4.4.3.3
103.1 Section 4.2
102.3 Section 7.2
Critical
Media Handling
All field-collected samples and quality control samples
Low volume: Plastic or Teflon
coated forceps or powder-free
gloves
Section 4.4.3.2
103.1 Section
5.2.1.1
102.3 Section 7.2
Practical
High volume: Plastic or Teflon
coated forceps or powder-free
gloves
Practical
Lot Background
Determination
For each new lot of media:
•	As part of the MDL process when determining
MDLs via Section 4.1.3.1
or
•	Five separate filters digested and analyzed
Low volume: No acceptance
criterion
Lot blank subtraction is not
permitted
Section 4.4.9.3.1
Practical
High volume: No acceptance
criterion
Lot blank subtraction is not
permitted
Section 4.4.10.3.1
103.1 Table 9
Practical
Sampling Unit
Clock/Timer
Check
Verified with each sample collection event
Clock/timer accurate to ±5
minute of reference for digital
timers and within ±15 minutes
for mechanical timers, set to local
standard time
Sample collection period verified
to be midnight to midnight
Table 3.3-1
Operational

-------
7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Sampling Unit
Leak Check
Verification that sampling train is leak tight
Every five sample collection events
Low volume: Leak rate of < 25
ininHg over 30 seconds or 80
mL/min
Section 4.4.9.4
EPA QA
Handbook Vol 11
Appendix D
Practical
High volume: absence of a
whistle
Section 4.4.10.4
102.1 Section
7.3.1.6
Practical
Sampling
Frequency
One sample every six days according to the EPA
National Monitoring Schedule
Sample must be valid or a make-
up sample should be scheduled
(refer to Section 2.1.2.1)
Sections 4.4.9.4.1
and 4.4.10.4.1
Critical and
MQO
Sampling Period
All field-collected samples
1380-1500 minutes (24 ± 1 hr)
starting and ending at midnight
Sections 4.4.9.4.1
and 4.4.10.4.1
Critical and
MQO
Pre-Sample
Collection Warm-
up
Only for high volume sampling units without computer
controlled flow
Minimum of five minutes (ten
minutes recommended) after
filter installation but before
sample collection
Section 4.4.10.4
102.1 Section
7.4.2.9
Operational
Post-Sample
Collection Warm-
up
Only for high volume sampling units without computer
controlled flow
Minimum of five minutes (ten
minutes recommended) before
filter retrieval
Section 4.4.10.4
102.1 Section
7.4.2.9
Operational
Sample Receipt
Chain-of-custody
All field-collected samples
Each filter must be uniquely
identified and accompanied by a
valid and legible COC with
complete sample documentation
Section 3.3.1.3.7
Critical
Sample Holding
Time
All field-collected samples and laboratory QC samples
Digestion: within 180 days from
sample collection or preparation
Analysis: within 180 days from
sample collection
Section 4.4.1
103.1 Section 6.1.2
Operational
Acid Digestion and ICP/MS Analysis
Microwave
Calibration
Standardization of microwave power output
Output calibration not to exceed six months; monthly
recommended
Level of output should differ by
no more than 10% across batches
Section 4.4.9.5.2.2
Operational

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7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Hot Block
Temperature
Verification
Reagent water blank with thermometer to ensure
digestion temperature consistent for all wells
Initially and annually thereafter for each well in the hot
block digester
Within ± 5°C of desired
temperature
Section 4.4.9.5.2.1
Operational
Hot Block
Temperature
Check
Reagent water blank with thermometer to monitor
digestion temperature
Each digestion batch
Within ± 5°C of desired
temperature
Section 4.4.9.5.2.1
Operational
I CP/MS Warm Up
Warm up of ICP torch and MS detector
Each day of analysis
Minimum of 30 minutes (or
according to manufacturer
specifications) prior to
performing initial calibration
Section 4.4.11.6
103.5 Section
10.1.1
Practical
I CP/MS Tuning
Analysis of tuning solution containing low (e.g. Li), and
medium (e.g. Mg), and high (e.g. Pb) mass elements
Each day of analysis during or immediately following
warm up
•	Minimum resolution of
0.75 a mil at 5% peak
height
•	Mass calibration within
0.1 amu of unit mass
•	Five replicates of tuning
solution with %RSD <
5%
•	Manufacturer
specifications may be
followed
Section 4.4.11.6
103.5 Section
10.1.1
Critical
Initial Calibration
Blank (ICB)
Analysis of undigested reagent blank
Each day of analysis prior to initial calibration (ICAL)
and immediately following the initial calibration
verification (ICV)
ICB following ICV: each target
element's concentration
< MDLSp (refer to Section
4.1.3.1)	or.vR (refer to Section
4.1.3.2)
Sections 4.4.11.7.1
and 4.4.11.7.3
103.5 Section
11.3.3
Critical
I CP/MS Initial
Multi-Point
Calibration (ICAL)
Minimum of three standard concentration levels plus
ICB covering approximately 0.1 to 250 ng/L
Each day of analysis, following failed CCV, or retiming
of the MS
Linear regression correlation
coefficient (r) > 0.995
Replicate integrations RSD <
10%
Section 4.4.11.7.1
Critical

-------
7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Initial Calibration
Verification (ICV)
Analysis of second source calibration verification
Each day of analysis immediately following ICAL
Within ± 10% of nominal
Section 4.4.11.7.2
103.5 Section
11.3.2
Critical
1 ntcrfcrcncc Check
Standard (ICS)
Each day of analysis following the second ICB and
every 8 hours of analysis thereafter. Once daily for 1 CP-
MS with collision reaction cells
Analysis of two solutions which contain interfcrants
(ICS A) and target elements with known interferences
(ICS B)
ICS A: all target elements
< 3x MDLSp (refer to Section
4.1.3.1) or 3x,s"K (refer to
Section 4.1.3.2) - may be
subtracted for background
indicated on certificate of
analysis
ICS B: 80 to 120% recovery
Section 4.4.11.7.4
103.5 Section
11.3.5
Operational
Continuing
Calibration
Verification (CCV)
Each day of analysis immediately following the ICS.
following every 10 sample injections, and at the
conclusion of each analytical sequence
90 to 110% recovery
Section 4.4.11.7.5
103.5 Section
11.3.6
Critical
Continuing
Calibration Blank
(CCB)
Each day of analysis immediately after each CCV
all target elements < MDLsp
(refer to Section 4.1.3.1) or .v K,
(refer to Section 4.1.3.2)
Section 4.4.11.7.6
103.5 Section
11.3.7
Critical
Reagent Blank
(RB)
Digested reagent blank
Once with each extraction batch of 20 or fewer samples
Low volume: All target elements
< MDLsp (refer to Section
4.1.3.1)	or s-K (refer to Section
4.1.3.2)
Sections 4.4.9.5.1,
4.4.11.7.7, and
Table 4.4-3
Operational
High volume: All target
elements
< MDLSp (refer to Section
4.1.3.1)	or s-K (refer to Section
4.1.3.2)
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
Operational
Method Blank
(MB)
Low volume: Digested blank filter
Once with each extraction batch of 20 or fewer samples
High volume: Digested blank filter
Once with each extraction batch of 20 or fewer samples
Low volume: All target elements
< MDL
Sections 4.4.9.5.1.
4.4.11.7.7, and
Table 4.4-3
Operational
High volume: All target
elements
< MDL
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
103.5 Section
11.3.8
Operational
Reagent Blank
Spike (RBS)
Spiked digested reagent blank (no filter)
Low volume: Recovery within
80-120% of nominal for all target
elements
Sections 4.4.9.5.1.
4.4.11.7.7, and
Table 4.4-3
Operational

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7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category

Once with each digestion batch of 20 or fewer field-
collected samples
High volume: Recovery within
80-120% of nominal for all target
elements
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
Operational
Laboratory Control
Sample (LCS)
Low volume: Digested spiked filter
Once with each extraction batch of 20 or fewer field-
collected samples
High volume: Digested spiked filter strip
Once with each extraction batch of 20 or fewer field-
collected samples
Low volume: Recovery within
80-120% of nominal for all target
elements
Sections 4.4.9.5.1,
4.4.11.7.7, and
Table 4.4-3
Operational
High volume: Recovery within
80-120% of nominal for all target
elements
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
103.5 Section
11.3.9
Operational
Laboratory Control
Sample Duplicate
(LCSD)
Low volume: Duplicate digested spiked filter
Once with each extraction batch of 20 or fewer field-
collected samples
High volume: Duplicate digested spiked filter strip
Once with each extraction batch of 20 or fewer field-
collected samples
Low volume: Recovery within
80-120% of nominal for all target
elements and precision < 20%
RPDofLCS
Sections 4.4.9.5.1,
4.4.11.7.7, and
Table 4.4-3
Operational
High volume: Recovery within
80-120% of nominal for all target
elements and precision < 20%
RPD of LCS - Not required if
batch contains MSD
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
Operational
Duplicate Digested
Filter Strip
High volume only
Digested duplicate field-collected filter strip
Once with each extraction batch of 20 or fewer field-
collected samples
Precision < 20% RPD for
elements
> 5xMDL
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
103.5 Section
11.3.11
Operational
Matrix Spike (MS)
High volume only
Digested spiked field-collected filter strip
Once with each extraction batch of 20 or fewer field-
collected samples
Recovery within 80-120% of the
nominal spiked amount for all
target elements - 75-125% for Sb
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
103.5 Section
11.3.10
Operational

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7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Matrix Spike
Duplicate (MSD)
High volume only
Duplicate digested spiked field-collected filter strip
Once with each extraction batch of 20 or fewer field-
collected samples
Recovery within 80-120% of the
nominal spiked amount for all
target elements - 75-125% for Sb
and precision < 20% RPD of MS
Sections
4.4.10.5.1,
4.4.11.7.7, and
Table 4.4-3
103.5 Section
11.3.11
Operational
Serial Dilution
Five-fold dilution of a field-collected sample digestate
Once with every analysis sequence of 20 or fewer field-
collected samples
Recovery of 90-110% of
undiluted sample for elements >
25x MDL
Section 4.4.11.7.8
103.5 Section
11.3.12
Operational
Replicate Analysis
A single additional analysis of a field-collected sample
digestate
Once with every analysis sequence of 20 or fewer field-
collected samples
Precision < 10% RPD for
concentrations > 5x MDL
Section 4.4.11.7.9
Operational
Internal Standards
(IS)
Non-target elements added to each analyzed solution at
the same concentration
60 to 125% recovery
Section 4.4.11.4
103.5 Section 11.5
Critical
Field Blank
Sample filter installed in primary sampling unit for
minimally 5 minutes
Minimally monthly for primary sampling units, as 18%
(approximately 1 out of 5) of collocated samples
All target elements < MDL
Section 4.4.5
Operational

Field sample collected with a separate sampling unit
between 2 and 4 meters from primary sampling unit



Collocated Sample
Collection
10% of primary samples for sites performing collocated
sample collection (as prescribed in workplan)
Precision < 20% RPD of primary
sample for concentrations > 5x
MDL
Section 4.4.4.1
Operational

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7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Laboratory Readiness and Proficiency


Each target compound element
within ± 25% of the assigned
target value


Proficiency
Testing
Blind sample submitted to each laboratory to evaluate
laboratory bias
Two per calendar year1
Failure of one PT must prompt
corrective action. Failure of two
consecutive PTs (for a specific
core analvte) must prompt
qualification of the analvte in
field collected samples until
return to conformance.
Section 2.1.4.1
Operational and
MQO
Method Detection
Limit
Determined initially and minimally annually thereafter,
with each new lot of filter media, and when method
changes alter instrument sensitivity
MDL must be:
Arsenic < 0.00023 ng/m;
Beryllium < 0.00042 ng/m;
Cadmium < 0.00056 \iglm3
Lead <0.15 ng/m;
Manganese < 0.005 ng/m5
Nickel < 0.0021 ng/m;
These MDL MQOs current as of
October 2015. Refer to current
workplan template for up-to-date
MQOs.
Sections 4.1 and
4.4.8
MQO
Stock Standard
Solutions
Purchased stock materials for each target element
All standards
Certified and accompanied by
certificate of analysis
Section 4.4.7
Critical
Working Standard
Solutions
Storage of all working standards
Stored in Teflon or suitable
plastic bottles
Section 4.4.7
103.5 Section
7.2.4
Practical
Sampling Unit Testing and Maintenance
Field Sampler
Flow Rate
Calibration
Calibration of sampling unit flow controller
Initially and when flow verification checks fail criteria
Flow set to match a certified
transfer flow standard
Table 3.3-1 and
4.4.9.2 and
4.4.10.2
Critical

-------
7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Sampling Unit
Flow Calibration
Check
Verification of sampling unit flow rate
Minimally quarterly, monthly recommended
Low volume:
Within ± 4% of certified transfer
standard flow and within ± 5% of
design flow
Table 3.3-1 and
40 CFR 58
Appendix A
Section 3.3.3 -
EPA QA Guidance
Document 2.12
Operational
High volume:
Within ± 7% of certified transfer
standard flow and within ± 10%
of design flow
Table 3.3-1 and
40 CFR 58
Appendix A
Section 3.3.3 EPA
QA Handbook
Section 2.11.7
Operational

-------
7.3 Metals via EPA Compendium Method IO 3.1 and IO 3.5 (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Site Specifications and Maintenance


270° unobstructed probe inlet




Inlet 2-15 meters above-ground
level
> 10 meters from drip line of


Sampling Unit
Siting
Verify conformance to requirements
Annually
nearest tree
Low volume collocated sampling
inlets spaced 1-4 meters from
primary sampling unit inlet
High volume collocated sampling
inlets spaced 2-4 meters from
primary sampling unit inlet
Section 2.4
40 CFR Part 58
Appendix E
Operational
Data Reporting


All field-collected sample
concentrations reported including
data less than MDL.


Data Reporting to
AQS
Reporting of all results a given calendar quarter
Quarterly, within 1820 days of end of calendar quarter
All data must be in local
conditions and may additionally
be reported in standard
conditions
Field QC sample and laboratory
replicates must also be reported
(as prescribed in workplan)
Section 3.3.1.3.15
Operational
AQS Reporting
Units
Units must be as specified
With each quarterly submission to AQS
mass/volume (ng/m3 or ng/m3)
Section 3.3.1.3.15
Critical
Data Completeness
Valid samples compared to scheduled samples
Annually
> 85% of scheduled samples
Section 3.2
MQO

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7.4	PAHs via EPA Coinpendiiim Method TO-13A
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Field Readiness Checks and Collection Activities
Collection Media
All field-collected samples and matrix quality control
samples
Glass cartridge containing two PUF plugs
totaling 3" in height, 15 g styrcnc-divinyl
polymer resin. 104-mm quart/ fiber filter
with 2-fim pore si/c
Section 4.5.3
TO-13A
Section 9.1
Critical
Media Handling
All field-collected samples and laboratory quality control
samples
Sample retrieval as soon as possible
recommended, preferably within 24 hours,
not to exceed 72 hours post-sampling
Retrieved sample shipped and stored at
< 4°C, protected from light until extraction
Damaged cartridges (leaking resin) must
be voided.
Section
4.5.4.1
TO-13A
Section
11.3.4.10
Operational
Cartridge Lot
Blank Check
Analysis of a cartridge from each lot to demonstrate
appropriate media cleanliness
Minimum of 1 cartridge for each new lot
All target P AHs < 10 ng/cartridge
Section 4.5.3
TO-13A
Section
14.2.1
Critical
Sampling Unit
Clock/Timer
Check
Verified with each sample collection event
Clock/timer accurate to ± 5 minutes of
reference for digital timers, within ±15
minutes for mechanical timers, set to local
standard time
Sample collection period verified to be
midnight to midnight
Table 3.3-1
Operational
Sampling
Frequency
One sample every six days according to the EPA National
Monitoring Schedule
Sample must be valid or a make-up sample
scheduled (refer to Section 2.1.2.1)
Section
4.5.4.1
Critical and
MQO
Sampling Period
All field-collected samples
1380-1500 minutes (24 ± 1 hr) starting and
ending at midnight
Section
4.5.4.1
Critical and
MQO
Sample Flow Rate
All field-collected samples
0.140 to 0.245 nvVminute for total
collection volume of 200 to 350 m3 (at
standard conditions of P = 1 atm and T =
25°C)
Section 4.5.1
Critical
Pre-Sample
Collection Warm-
up
Only for sampling units without computer controlled flow
Minimum of five minutes (ten minutes are
recommended) after sampling head
installation but before sample collection
Section 4.5.4
TO-13A
Section
11.3.3.3
Practical

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7.4 PAHs via EPA Coinpendiiim Method TO-13A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Post-Sample
Collection Warm-
up
Only for sampling units without computer controlled flow
Minimum of five minutes (ten minutes are
recommended) before sampling head
retrieval
Section
4.5.4.1
Practical
Sample Receipt
Chain-of-custody
All field-collected samples including field QC samples
Each cartridge/QFF must be uniquely
identified and accompanied by a valid and
legible COC with complete sample
documentation
Section
3.3.1.3.7
Critical
Sample Holding
Time
All field-collected samples and laboratory QC samples
Extraction: 14 days from sample
collection (cartridge storage < 4 °C)
Analysis: 40 days from extraction (extract
storage < 4 °C)
Section
4.5.5.2
TO-13A
Section
11.3.4.10
Operational
Sample Receipt
Temperature
Check
Verification of proper shipping temperature for all field-
collected samples upon receipt at the laboratory
Must be < 4°C unless delivery time from
field site is < 4 hours
Section
4.5.4.1
Operational
Extraction and GC/MS Analysis
DFTPP Tuning
5-50 ng injected to tune MS prior to IC AL and every 12
hours of analysis thereafter
For GC/MS operated in full scan or
SIM/full scan must meet criteria listed in
Table 4.5-2
GC/MS operated in SIM mode must tune
to meet criteria in Section 4.5.5.5.2
Section
4.5.5.5.2
TO-13A
Section
13.3.3
Critical
Solvent Blank
(SB)
Aliquot of solvent analyzed to demonstrate the instrument
is sufficiently clean to begin analysis
Prior to IC AL and daily beginning CCV
All target, surrogate, and IS compounds
not qualitatively detected
Section
4.5.5.5.3
TO-13A
Section
14.1.2
Critical
GC/MS Initial
Multi-Point
Calibration
(ICAL)
Minimum of 5 points covering approximately 0.1 to 2.0
(ig/mL
Initially, following failed CCV, following failed DFTPP
tunc check, or when changes to the instrument affect
calibration response
Average RRF < 30% and each calibration
level must be within ± 30% of nominal
For linear regression (with either a linear
or quadratic fit) correlation coefficient (r)
> 0.995 and each calibration level within ±
30% of nominal
Section
4.5.5.5.3
TO-13A
Section
13.3.4.5
Critical
Secondary Source
Calibration
Verification
(SSCV)
Secondary source standard prepared at the mid-range of
the calibration curve, analyzed immediately after each
ICAL
70 to 130% recovery of nominal or RRF
within ±30% of IC AL average RRG
Section
4.5.5.5.4
Critical

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7.4 PAHs via EPA Coinpendiiim Method TO-13A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Continuing
Calibration
Verification
(CCV)
Mid-range standard analyzed prior to sample analysis on
days when an ICAL is not performed, every 12 hours of
analysis following the DFTPP check, and at the conclusion
of each analytical sequence
70 to 130% recovery of nominal or RRF
within ±30% of ICAL average RRG
Section
4.5.5.5.5
TO-13A
Section
13.3.5.5
Critical
Method Blank
(MB)
Unexposed PUF/resin cartridge and QFF extracted as a
sample
One with every extraction batch of 20 or fewer field-
collected samples
All target P AHs < 2x MDL
Section
4.5.5.5.6
TO-13A
Section
13.3.6
Operational
Laboratory
Control Sample
(LCS)
PUF/resin cartridge and QFF spiked with known amount
of target anal vie at approximately the lower third of the
calibration curve
Minimally quarterly; recommended one with every
extraction batch of 20 or fewer field-collected samples
All target P AHs 60-120% recovery of
nominal spike
Section
4.5.5.5.6
TO-13A
Section
13.3.7
Operational
Laboratory
Control Sample
Duplicate (LCSD)
Duplicate LCS to evaluate precision through extraction
and analysis
Minimally quarterly, recommended one with every
extraction batch of 20 or fewer field-collected samples
All target P AHs 60-120% recovery of
nominal spike
Precision < 20% RPD of LCS
Section
4.5.5.5.6
Operational
Internal Standards
Deutcrated homologues of target P AHs added to every
injection except beginning SB
50-200% of the area response of the mid-
level ICAL standard from IC AL
Section
4.5.5.5.8
TO-13A
Section
13.4.7
Critical
Field Surrogate
Compounds
Deutcrated homologues of target P AHs added to each
cartridge before field deployment, also added to cartridges
for laboratory and field QC
Recovery 60-120%
Sections
4.5.3.3 and
4.5.5.5.9
TO-13A
Section
13.4.6.3
Operational
Extraction
Surrogate
Compounds
Deutcrated homologues of target P AHs added to each
extracted field sample, field QC sample, and laboratory
QC sample
Recovery 60-120%
Sections
4.5.5.1.4.2
and 4.5.5.5.9
TO-13A
Section
13.4.6.3
Operational

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7.4 PAHs via EPA Coinpendiiim Method TO-13A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Retention Time
(RT)
Every injection
Target and surrogate compound RT within
± 0.06 relative retention time units (RRT)
of mean ICAL RRT
Internal standard RT within ±0.33 minute
of the most recent CCV
Section
4.5.5.5.3
TO-13A
Sections
13.4.6.3 and
13.3.4.5
Critical

A single additional analysis of a field-collected sample



Replicate
Analysis
extract
Once with every analysis sequence of 20 or fewer field-
collected samples (as required by workplan)
Precision < 10% RPD for concentrations >
0.5 ng/mL
Section
4.5.5.5.6
Operational
Field Blank
Blank sample cartridge installed in sampling unit for
minimally five minutes
Minimally monthly
All target PAHs < 5x MDL
Section
4.5.4.2
TO-13A
Section
11.3.4.9
Operational
Collocated
Sample
Collection
Field sample collected with a separate sampling unit
between 2 and 4 meters from primary sampling unit
10% of primary samples for sites performing collocated
sample collection (as required by workplan)
Precision < 20% RPD of primary sample
for concentrations > 0.5 ng/mL
Section
4.5.4.3
Operational


Signal-to-noise >3:1




RT within prescribed window
Section

Compound
Identification
Qualitative identification of each target P AH in each
standard, blank. QC sample, and field-collected sample
(including field QC samples)
At least one qualifier ion abundance within
15% of IC AL mean
Peak apexes co-maximized (within one
scan for quadrupole MS) for quantitation
and qualifier ions
4.5.5.5.7
TO-13A
Section
13.4.3
Critical

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7.4 PAHs via EPA Coinpendiiim Method TO-13A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Laboratory Readiness and Proficiency


Each target compound within ± 25% of the
assigned target value


Proficiency
Testing
Blind sample submitted to each laboratory to evaluate
laboratory bias
Two per calendar year1
Failure of one PT must prompt corrective
action. Failure of two consecutive PTs (for
a specific core analvte) must prompt
qualification of the analvte in field
collected samples until return to
conformance.
Section
2.1.4.1
Operational
and MQO
Method Detection
Limit
Determined initially and minimally annually thereafter and
when method changes alter instrument sensitivity
MDL must be:
Benzol a Ipyrene < 0.00091 ng/m;
Naphthalene < 0.029 ng/m;
These MDL MQOs current as of October
2015. Refer to current workplan template
for up-to-date MQOs.
Sections 4.1
and 4.5.5.4
MQO
Stock Standard
Materials
Purchased stock materials for each target P AH
All standards
Certified and accompanied by certificate of
analysis
Section
4.5.5.1.2
Critical
Working Standard
Solutions
Storage of all working standards
Stored at < -10°C, protected from light
Section
4.5.5.2
Critical
Sampling Unit Testing and Maintenance
Field Sampler
Flow Rate
Calibration
Calibration of sampling unit flow controller
Initially, when flow verification checks fail criteria, or
when instrument maintenance changes flow characteristics
of the sampling unit
Flow set to match a certified flow transfer
standard
Table 3.3-1
and 4.5.2.1
Critical
Sampling Unit
Flow Calibration
Check or Audit
Verification of sampling unit flow rate
Minimally quarterly, monthly recommended
Flow within ± 10% of certified primary or
transfer standard flow and design flow
Table 3.3-1
Critical
Site Specifications and Maintenance


270° unobstructed probe inlet


Sampling Unit
Siting
Verify conformance to requirements
Annually
Inlet 2-15 meters above-ground level
> 10 meters from drip line of nearest tree
Collocated sampling inlets spaced 2-4
meters from primary sampling unit inlet
Section 2.4
Operational

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7.4 PAHs via EPA Coinpendiiim Method TO-13A (Continued)
Parameter
Description and Required Frequency
Acceptance Criteria
Reference
Category
Data Reporting


All field-collected sample concentrations


Data Reporting to
AQS
Reporting of all results a given calendar quarter
Quarterly, w ithin 180 days of end of calendar quarter
reported including data less than MDL.
All data must be in standard conditions.
Field QC sample and laboratory replicates
must also be reported.
Section
3.3.1.3.15
Operational
AQS Reporting
Units
Units must be as specified
With each quarterly submission to AQS
mass/volume (ng/m3 or ng/m3)
Section
3.3.1.3.15
Critical
Data
Completeness
Valid samples compared to scheduled samples
Annually
> 85% of scheduled samples
Section 3.2
MQO

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Appendix A
APPENDIX A
DRAFT REPORT
ON
DEVELOPMENT OF DATA QUALITY OBJECTIVES (DQOS) FOR
THE NATIONAL AMBIENT AIR TOXICS TRENDS
MONITORING NETWORK
SEPTEMBER 27, 2002
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Appendix A
September 27, 2002
DRAFT REPORT
on
DEVELOPMENT OF DATA QUALITY OBJECTIVES (DQOS) FOR THE
NATIONAL AMBIENT AIR TOXICS TRENDS MONITORING NETWORK
Contract No. 68-D-98-030
Work Assignment 5-12
for
Sharon Nizich
Work Assignment Manager
Vickie Presnell
Project Officer
Office of Air Quality Planning and Standards
Emissions, Monitoring, and Analysis Division
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park, North Carolina 27711
Prepared by
BATTEL LE
505 King Avenue
Columbus, Ohio 43201-2693
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Appendix A
BATTELLE DISCLAIMER
This report is a work prepared for the United States Environmental Protection
Agency by Battelle Memorial Institute. In no event shall either the United States
Environmental Protection Agency or Battelle Memorial Institute have any
responsibility or liability for any consequences of any use, misuse, inability to
use, or reliance upon the information contained herein, nor does either warrant or
otherwise represent in any way the accuracy, adequacy, efficacy, or applicability
of the contents hereof.
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Appendix A
TABLE OF CONTENTS
Page
EXECUTIVE SUMMARY	 v
1.0 INTRODUCTION	 1
2.0 THE GENERAL DQO PROCESS	 1
2.1	State the Problem	 2
2.2	Identify the Decision	 3
2.3	Identify the Inputs to the Decision	 3
2.4	Define the Study Boundaries	 4
2.5	Develop a Decision Rule	 4
2.6	Specify Tolerable Limits on the Decision Errors	 5
2.7	Optimize the Design	 6
3.0 DQOS FOR THE SIX STUDY COMPOUNDS	 6
3.1	DQOs for Measuring the Percent Decrease of Benzene at Urban Locations	 9
3.2	DQOs for Measuring the Percent Decrease of Benzene at Rural Locations	 10
3.3	DQOs for Measuring the Percent Decrease of 1,3-Butadiene at Urban Locations	11
3.4	DQOs for Measuring the Percent Decrease of 1,3-Butadiene at Rural Locations	12
3.5	DQOs for Measuring the Percent Decrease of Arsenic at Urban Locations	13
3.6	DQOs for Measuring the Percent Decrease of Arsenic at Rural Locations	14
3.7	DQOs for Measuring the Percent Decrease of Chromium	15
3.8	DQOs for Measuring the Percent Decrease of Acrolein	16
3.9	DQOs for Measuring the Percent Decrease of Formaldehyde at Urban Locations	17
3.10	DQOs for Measuring the Percent Decrease of Formaldehyde at Rural Locations	18
APPENDIX A: ESTIMATES OF THE DQO PARAMETERS MEASURING ENVIRONMENTAL
VARIABILITY	A-1
List of Tables
Table 3.1.1 DQO input parameters for benzene at urban locations	 9
Table 3.1.2 DQO output parameters for benzene at urban locations	 9
Table 3.2.1 DQO input parameters for benzene at rural locations	10
Table 3,2.2 DQO output parameters for benzene at rural locations	10
Table 3.3.1 DQO input parameters for 1,3-butadiene at urban locations	11
Table 3.3.2 DQO output parameters for 1,3-butadiene at urban locations	11
Table 3.4.1 DQO input parameters for 1,3-butadiene at rural locations	12
Table 3.4.2 DQO output parameters for 1,3-butadiene at rural locations	12
Table 3.5.1 DQO input parameters for arsenic at urban locations	13
Table 3.5.2 DQO output parameters for arsenic at urban locations	13
Table 3.6.1 DQO input parameters for arsenic at rural locations	14
Table 3.6.2 DQO output parameters for arsenic at rural locations	14
Table 3,7.1 DQO input parameters for chromium	15
Table 3.7.2 DQO output parameters for chromium	15
Table 3.8.1 DQO input parameters for acrolein	16
Table 3.8.2 DQO output parameters for acrolein	16
Table 3.9.1 DQO input parameters for formaldehyde at urban locations	17
Table 3.9.2 DQO output parameters for formaldehyde at urban locations	17
Table 3.10.1 DQO input parameters for formaldehyde at rural locations	18
Table 3.10.2 DQO output parameters for formaldehyde at rural locations	18
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Appendix A
List of Figures
Figure 3.1.1 Power curve for detecting a 15 percent decrease between 3-year means
of benzene concentrations based on the data verification found in urban
locations of the Pilot Study	 9
Figure 3.2.1 Power curve for detecting a 15 percent decrease between 3-year means
of benzene concentrations based on the data variation found in rural
locations of the Pilot Study	10
Figure 3.3.1 Power curve for detecting a 15 percent decrease between 3-year means
of 1,3-butadiene concentrations based on the data variation found in urban
locations of the Pilot Study	11
Figure 3.4.1 Power curve for detecting a 15 percent decrease between 3-year means
of 1,3-butadiene concentrations based on the data variation found in rural
locations of the Pilot Study	12
Figure 3.5.1 Power curve for detecting a 15 percent decrease between 3-year means
of arsenic concentrations based on the data variation found in urban
locations of the Pilot Study	13
Figure 3.6.1 Power curve for detecting a 15 percent decrease between 3-year means
of arsenic concentrations based on the data variation found in rural
locations of the Pilot Study	14
Figure 3.7.1 Power curve for detecting a 15 percent decrease between 3-year means
of chromium concentrations based on the data variation found in
the Pilot Study	15
Figure 3.8.1 Power curve for detecting a 15 percent decrease between 3-year means
of acrolein concentrations based on the data variation found in
the Pilot Study	16
Figure 3.9.1 Power curve for detecting a 15 percent decrease between 3-year means
of formaldehyde concentrations based on the data variation found in urban
locations of the Pilot Study	17
Figure 3.10.1 Power curve for detecting a 15 percent decrease between 3-year means
of formaldehyde concentrations based on the data variation found in rural
locations of the Pilot Study	18
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Appendix A
EXECUTIVE SUMMARY
The Data Quality Objective (DQO) process described in EPA's QA/G-4 document
provides a general framework for ensuring that the data collected by EPA meets the needs of
decision makers and data users. The process establishes the link between the specific end use(s)
of the data with the data collection process and the data quality (and quantity) needed to meet a
program's goals. This process was applied to one of the primary goals of the National Air
Toxics Monitoring Network, namely to establish trends and evaluate the effectiveness of HAP
reduction strategies. This report documents the results of the DQO process for the local
monitoring data requirements for: benzene, 1,3-butadiene, arsenic, chromium, acrolein, and
formaldehyde.
The technical approach used followed the conceptual model developed for the PM25
Federal Reference Method (FRM) DQOs. This conceptual model of simulating daily deviations
from a seasonal curve was followed mainly due to its success in use with PM2.5 and the
flexibility of the conceptual model. It is a quite general model for simulating the characterization
of ambient concentrations in terms of annual or multi-year averages from 1 in n day sampling.
The model incorporates several sources of variability: seasonal variability, natural day-to-day
variability, sampling incompleteness, and measurement error. The measurement error was
restricted to a precision component without a bias component, because the mathematical form of
the assessment of trends is robust to multiplicative bias. Pollutant specific parameters were used
in the modeling. The parameters describing the natural variation of the pollutants were based on
data analyses of the Pilot City data and EPA's Air Toxics Data Archive. Finally, separate urban
and rural DQOs were established for the pollutants that were sufficiently measured in rural
locations of the Pilot Study.
While there are pollutant specific requirements with respect to measurement detection
limits, the DQOs established all fall into the same framework. Each pollutant needs to be
measured on a schedule of at least once every six days with at least an 85 percent quarterly
completeness. The measurement precision needs to be controlled with a coefficient of variation
no more than 15 percent. Under these conditions, true decreasing trends of 30 percent or more
can be detected at least 90 percent of the time between successive three-year periods. Moreover,
the error rate for when there is no true change between successive three-year periods is
controlled to be at most 10 percent. Sampling frequency and natural or environmental
day-to-day variation are the primary factors affecting these error rates.
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Appendix A
1.0 INTRODUCTION
The Data Quality Objective (DQO) process described in EPA's QA/G-4 document
provides a general framework for ensuring that the data collected by EPA meets the needs of the
intended decision makers and data users. The process establishes the link between the specific
end use(s) of the data with the data collection process and the data quality (and quantity) needed
to meet, a program's goals. This process was applied to one of the primary goals of the National
Air Toxics Monitoring Network, namely to establish trends and evaluate the effectiveness of
HAP reduction strategies. This report documents the results of the DQO process for the local
monitoring data requirements for: benzene, 1,3-butadiene, arsenic, chromium, acrolein, and
formaldehyde.
The technical approach used followed the conceptual model developed for the PM25
FRM DQOs. This conceptual model was followed mainly due to its success in use with PM2.5
and the flexibility of the conceptual model. It is a quite general model for simulating the
characterization of ambient concentrations in terms of annual or multi-year averages from
1 in n day sampling. The model incorporates several sources of variability: seasonal variability,
natural day-to-day variability, sampling incompleteness, and measurement error. The
measurement error was restricted to a precision component without a bias component because
the final mathematical form of the assessment of trends is robust to multiplicative bias. Pollutant
specific parameters were used in the modeling. The parameters describing the natural variation
of the pollutants were based on data analyses of the Pilot City data and the Air Toxics Archive.
Finally, separate urban and rural DQOs were established for the pollutants that were sufficiently
measured in rural locations of the Pilot Study.
A workgroup organized by EPA/OAQPS/EMAD provided representatives of data users,
decision makers, state and local parties, and monitoring and laboratory personnel. Battelle
provided technical statistical support throughout the process with examples and data analyses.
The workgroup guided the DQO development and made the decisions that were not driven by
data analyses in the DQO development during a series of conference calls. These decisions
included items such as establishing a specific mathematical form for measuring trends and
establishing limits 011 the sampling rate. B attelle and EPA also held a meeting in Research
Triangle Park, North Carolina, on June 17, 2002 to discuss the development details.
2.0 THE GENERAL DQO PROCESS
This section presents an overview of the seven steps in EPA's QA/G-4 DQO process as
applied to one of the primary goals of the National Air Toxics Monitoring Network, namely to
establish trends and evaluate the effectiveness of HAP reduction strategies (see
www.epa.gov/quality/qa_docsJitml). The purpose of this section is to provide general discussion
on the specific issues that were used in developing the DQOs as they relate to the general DQO
process.
The DQO process is a seven-step process based 011 the scientific method to ensure that
the data collected by EPA meet the needs of its data users and decision makers in terms of the
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Appendix A
information to be collected, in particular the desired quality and quantity of data. It also provides
a framework for checking and evaluating the program goals to make sure they are feasible and
that the data are collected efficiently. The seven steps are usually labeled as:
State the Problem
Identify the Decision
Identify the Inputs to the Decision
Define the Study Boundaries
Develop a Decision Rule
Specify Tolerable Limits on the Decision Errors
Optimize the Design.
This section has general discussion for each of these items. The pollutant specific outcomes of
the DQO process are contained in Section 3.
2.1
State the Problem
Characterize the ambient concentrations in the region represented by the monitor to
establish any significant downward trend (measured by a percent change between
successive 3-year means of the concentrations).
The ability to characterize the trends was statistically modeled. The statistical model was
designed by starting with a model similar to the one used for PM2.5 FRM data. The ambient
concentrations are modeled as deviations from a sine curve, where the sine curve represents
seasonality. This sine curve represents long-term daily averages of the concentrations that one
would observe at the site. The form used is as follows:


/' 1 \
r-1
A
1 +
vr + l


day
sm | — 2 ic
365
where
A = the long term annual average and
1* = the ratio of the highest point on the sine curve to the lowest point. A value of
r = 1 indicates no seasonality.)
The natural deviations from the sine curve are assumed to follow a lognormal distribution
with a mean that is given by the particular point on the sine curve. (For example, the value of the
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Appendix A
sine curve for Day 100 is the mean for all Day 100s across many years.) The coefficient of
variation (CV) of the lognomial distribution is assumed to be a constant. The general model
considered also allows for the day-to-day deviations from the sine curve to be correlated, but the
current DQOs are based on a correlation of zero, (The correlation effectively measures how
quickly the concentrations can change from one deviation from the sine curve to another. A
correlation of zero indicates that it can change fast enough that values measured on consecutive
days would be completely independent. A value of 0.2 would say that a positive deviation from
the curve is somewhat more likely to be followed by another positive deviation than a negative
deviation. A value of 0.9 would indicate that positive deviations are almost always followed by
another positive deviation.) Filially, the measured values are modeled with a normally
distributed random measurement error with a constant coefficient of variation (CV). The
specific values for the various parameters are pollutant specific.
The population parameters (the degree of seasonality, the autocorrelation, and the CV of
the deviations from the sine curve) were estimated from the Pilot City data (and in the case of
benzene compared with estimates from the Air Toxics Data Archive). (See Appendix A.) A
near worst-case choice was made for each of the parameters. The power curves and decision
errors are established via Monte-Carlo simulation of the model with the particular parameters for
various combinations of truth and observed percent changes in three-year mean concentrations.
The power curves are plotted as functions of the true percent change in the three-year annual
means for compound specific combinations of the sampling frequency, completeness, and
precision. Decision errors are stated for these worst-case scenarios.
Note; It was decided by the workgroup from budgetary considerations that the proposed
DQOs should be constrained to no more than one in six day sampling.
2.2	Identify the Decision
The decision statement should provide a link between the principal study question and
possible actions. The potential actions associated with achieving or failing to achieve a
particular percent decrease in the observed three-year mean concentration were not defined by
the workgroup. However, it was decided that any decision would be based on whether or not a
15 percent decrease was observed. Hence the form of the decision was fixed, and may be
specified as follows:
Significant decreases (15 percent or more) between successive three-year mean
concentration levels will result in ... Insignificant decreases, (increases, or decreases of
less thai 15 percent) will trigger alternate actions of.
2.3	Identify the Inputs to the Decision
Only six HAPs (benzene, 1,3-butadiene, arsenic, chromium, acrolein, and formaldehyde)
were considered in the DQO development. It is assumed that the other pollutants will be
represented by at least one of these six. The statements included here apply implicitly to the
other HAPs.
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It is assumed that the analytical techniques used in the Pilot study will be used throughout
the program. Most importantly for the DQOs the Method Detection Limits (MDLs) will not
increase. The pollutant specific MDLs assumed are listed in Section 3. Those values were
identified as pollutant-site maximums that were achieved by at least two of the pilot sites in each
pollutant's case.
Among the key decisions made as a part of the DQO process was that each pollutant will
need to be measured on a schedule of at least once every six days with a quarterly completeness
of 85 percent for six consecutive years. The completeness criterion was checked against the pilot
data, and was generally achieved. All valid measurements count toward the completeness goal,
including non-detects. The analysis of the trends at the site level will be based on a percent
difference between the mean of the first three annual concentrations and the mean of the last
three annual concentrations. Hence for each year the annual average concentration, Xj, needs to
be found, i = 1, 2, ... 6. Next find the mean, X, for the first three years and the mean, Y, for
years 4 through 6 as follows:
Then the downward trend, T, is the percent decrease from the first three-year period to the
second three-year period. Namely,
The Action Level is the cutoff point that separates different decision alternatives. Based
on the assumed budgetary constraint of one in six day sampling and the natural variation
exhibited by the six compounds considered, an action level of 15 percent was chosen. Hence at
least a 15 percent decrease between the two distinct three-year mean concentrations will need to
be observed in order to be considered a significant decrease. This assumes that the mean
concentrations are above the health standards, and hence it makes sense to consider trends.
(Note that characterizing the mean concentrations is a separate goal of the Air Toxics program
that has not yet been considered and could result in different DQOs.)
2.4	Define the Study Boundaries
It is desired that the specific location of the monitors be constrained so that they represent
neighborhood scale assessment for each of the two three-year periods under consideration. The
details of how to ensure this goal have not yet been determined. Some guideline is provided by
the Air Toxics Monitoring Concept Paper (see http://www,epa,gov/ttn/antic/airtxfil.html),
2.5	Develop a Decision Rule
The decision rale is an "if... then" statement for how the various alternatives will be
chosen. As noted above the specific alternative actions have not been formalized yet, just the
form of the decision rule.
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X4 + Xs + X6
3
X —Y
T =	100.
X
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If the percent- change between successive three-year average concentration levels
is greater than or equal to 15 percent, then ... Otherwise ...
2.6 Specify Tolerable Limits on the Decision Errors
Since the program will not generate complete, error-free data, there will be some
probability of making a decision error. The main goal of the DQO process is to find a workable
balance between how complete and error free the data are with acceptable levels of decision
errors. To find the balance, the possible errors need to be carefully defined. This usually needs
to be done with the recognition that there will be a range, often called the gray zone, where it is
impractical to control decision errors.
The QA/G-4 guidance recommends using 0.01 as the starting point for setting decision
error rates. However, such a limit would generally require a sampling rate that is not feasible.
The workgroup decided on the following limits:
If there is no true decrease in the three-year average concentrations, then the
probability of observing a mean concentration for years four through six that is at
least 15 percent below the observed mean concentration from years one through
three should be no more than 10 percent.
If there is a true decrease in the three-year average concentrations of at least 30
percent, then the probability of observing a mean concentration for years four
through six that is less than 15 percent below the observed mean concentration
from years one through three should be no more than 10 percent.
Equivalently, the second statement could read that:
If there is a true, decrease in the three-year average concentrations of at least 30
percent, then the probability of observing a mean concentration for years four
through six that is at least 15 percent below the observed mean concentration
from years one through three should be at least 90 percent.
The power curves shown in Section 3 show the probability of observing at least a
15 percent decrease as a function of the true decrease. In terms of the above goals this
means that the power curve graphs should start below 10 percent for a true percent
change of 0 and end above 90 percent for a true percent change of 30 percent. Since
there is a particular interest in the error rates for no true change and for a true change of a
30 percent decrease, this associated x-axis (horizontal axis) range is shown for each
curve. Also, it is sometimes useful to know when the two target error rates are achieved.
The range of "truth" between these values is referred to as the gray zone, i.e., the range of
true percent decreases that cannot be reliably detected by the sampling scheme. These
are also given for each curve (and indicated with vertical dotted lines).
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2.7 Optimize the Design
In each pollutant's case, a sampling schedule of once every six days is set forth with a
quarterly completeness criteria of 85 percent. Pilot City study participants were surveyed and
almost all were collecting and obtaining valid data values at a rate that exceeded 85 percent for
each of the six compounds considered (valid non-detects counted toward completeness). Hence,
the target rate of 85 percent was selected, instead of the more common 75 percent completeness
goal. This should make the power curves more representative of the network's expected
monitoring conditions.
3.0 DQOS FOR THE SIX STUDY COMPOUNDS
This section states the design values, namely it gives the expected maximum error rates,
gray zones, and power curves for each of the six compounds considered explicitly. The
parameters describing the natural state of the ambient conditions used to construct the power
curves, error rates and gray zone are compound specific based on data from the Pilot Study. (See
Appendix A.) In each case, the Pilot City data yielded a range of estimates. The specific values
used were the extremes (or nearly so) that would make detecting a downward trend more
difficult. Actual performance in almost all cases should be better than that indicated by the
power curves, since specific sites would not be characterized by these extremes in each of these
parameters. However, since the sensitivity to the different parameters is not the same, the DQOs
need to protect against a combined set of extremes. Hence, the use of extremes for network
design purposes is conservative.
Since the rural sites can be quite different from urban sites, separate DQOs are shown in
those cases where there were sufficient data to support investigating a separate set of DQOs. In
the case of formaldehyde, the urban and rural DQOs are essentially the same.
There are twelve input parameters shown in each section. They are:
1.	Tl. This is the target error rate for when there is no change. It is always 10 percent.
2.	T2. This is the target error rate for when there is a 30 percent decrease. It is always
10 percent.
3.	The action limit. This is the minimum observed percent change from the mean
concentration of the first three years to the mean concentration from the last three
years that would be used to indicate that the concentrations have decreased.
Decreases less than this amount would not be considered significant decreases in the
mean concentration.
4.	The sampling rate. It is set to one in six day sampling in each case.
5.	The quarterly completeness criterion. This was set to 85 percent based on the
recommendation of ERG and a review of the Pilot Study data completeness.
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6.	Measurement error Coefficient of Variation (CV), This was assumed to be
15 percent for each compound. (A sensitivity analysis showed that the DQOs are
robust to moderate changes in this value.)
7.	Seasonality ratio. This is a measure of the degree of seasonality. Specifically, it is
the ratio of the highest point on the seasonal curve to the lowest point. A value of 1
indicates no seasonality. Larger values make it more difficult to estimate an annual
or three-year mean concentration, and hence larger values make it more difficult to
measure the percent change.
8.	Autocorrelation. This is a measurement of how quickly day-to-day deviation from
the seasonal curve can occur. A value of 0 indicates that changes occur quickly
enough that each day is independent of the preceding day, Values greater than 0
indicate that the changes are generally slower, so that days with concentrations above
the seasonal curve are more likely to be followed by another day above the seasonal
curve. Values greater than 0 increase the precision of the three-year means and the
percent change between the three-year means. Hence, a value of 0 is the most
conservative choice for the DQOs. Zero was used in all cases, because many daily
measurements are required to obtain a reliable estimate of this parameter.
9.	Population CV. This is a measurement of the natural variation about the seasonal
curve. Larger values decrease the precision of the three-year mean concentration
estimates and the percent change between them. The power curves are strongly
dependent on this parameter, but the estimates can be strongly influenced by a few
outlier values. Generally the 90th percentile of the estimates from the Pilot study was
used as a balance between these competing forces. This value was then rounded up
to be a multiple of 5 percent for the urban DQOs. For the rural DQOs an additional
5 percent was added, since there were fewer rural sites on which to base the
estimates,
10.	MDL. This is the MDL used in the simulations. The value was chosen to be a
reasonably attainable maximum for a site and compound.
11.	Initial mean concentration. This is the mean concentration of the first three years in
the simulations. Values closer to the MDL decrease the precision of the percent
change estimate. The value chosen was approximately equal to the 25th percentile of
the site-compound means from the Pilot study.
12.	Health Risk Standard. This value is shown for reference only. It was not used in the
simulations.
In addition to the power curves, there are three sets of output values.
1. Eitoi'o is the percent of the simulations with no change in the true three-year means
that in fact generated at least a 15 percent decrease in the observed three-year means.
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2. Errorso is the percent of the simulations with a 30 percent decrease in the true three-
year means that generated less than a 15 percent decrease in the observed three-year
3. The gray zone is the interval of the true decreases that cannot be detected with
confidence by the study design. In this range, the probability of observing at least a
15 percent decrease is greater than 10 percent, but less than 90 percent.
In summary, based on variability and uncertainty estimates from the ten-city Pilot Study,
the following Sections 3,1 through 3.10 suggest that the specified air toxics trends DQOs will be
met for monitoring sites that satisfy the goals of 1 in 6 day sampling, 85 percent completeness,
and 15 percent measurement CV. These results were explicitly developed for benzene (urban
and rural); 1,3-butadiene (urban and rural); arsenic (urban and rural); chromium (urban only);
acrolein (urban only); and formaldehyde (urban and rural).
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3.1 DQOs for Measuring the Percent Decrease of Benzene at Urban Locations
Table 3.1.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of benzene at
urban locations. Table 3.1,2 shows the output values from the simulations. Figure 3.1,1 shows
the associated power curve, which is the probability of observing a 15 percent difference
between successive three-year means as a function of the true percent difference in the distinct
three-year means. In summary, based on variability and uncertainty estimates from the ten-city
Pilot Study data. Table 3.1.2 suggests that the specified air toxics trends DQOs will be met for
benzene at urban monitoring sites that satisfy the goals of one in six-day sampling. 85 percent
completeness, and 15 percent measurement CV. (See section 3.0 for definitions of the input
parameters and output values.)
Table 3.1.1 DQO input parameters for benzene at urban locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (ng/m3)
10%
15%
1 in 6 day
4.5
85%
1.0
T2
Measurement CV
Completeness
Autocorrelation
MDL (ng/nr)
Risk Standard (ug/mJ)
10%
15%
85%
0
0.044
0.128
Table 3.1.2 DQO output parameters for benzene at urban locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
6%
97%
3% - 26%
|
c!
Tj
oS
5
tiD
C
'S
I
j=>
a!
True percent difference
Figure 3.1.1 Power curve for detecting a 15 percent decrease between successive
three-year means of benzene concentrations based on the data variation
found in urban locations of the Pilot Study
DQOs for Trends - Draft Report	9	September 27, 2002
i
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
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3.2 DQOs for Measuring the Percent Decrease of Benzene at Rural Locations
Table 3.2.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of benzene at
rural locations. Table 3.2.2 shows the output values from the simulations. Figure 3.2.1 shows
the associated power curve, which is the probability of observing a 15 percent difference
between successive three-year means as a function of the true percent difference in the distinct
three-year means. In summary, based on variability and uncertainty estimates from the ten-city
Pilot Study data. Table 3.2.2 suggests that the specified air toxics trends DQOs will be met for
benzene at rural monitoring sites that satisfy the goals of one in six-day sampling. 85 percent
completeness, and 15 percent measurement CV. (See section 3.0 for definitions of the input
parameters and output values.)
Table 3.2.1 DQO input parameters for benzene at rural locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (ng/m3)
10%
15%
1 in 6 day
4.0
60%
1.0
T2
Measurement CV
Completeness
Autocorrelation
MDL (iig/nr)
Risk Standard (ng/mJ)
10%
15%
85%
0
0.044
0.128
Table 3.2.2 DQO output parameters for benzene at rural locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
2%
99%
7% - 23%
15	20
True percent difference
Figure 3.2.1 Power curve for detecting a 15 percent decrease between successive
three-year means of benzene concentrations based on the data variation
found in rural locations of the Pilot Study
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3.3 DQOs for Measuring the Percent Decrease of 1,3-Butadiene at Urban
Locations
Table 3.3.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of 1.3-
butadiene at urban locations. Table 3.3.2 shows the output values from the simulations. Figure
3.3.1 shows the associated power curve, which is the probability of observing a 15 percent
difference between successive three-year means as a function of the true percent difference in the
distinct three-year means. In summary, based on variability and uncertainty estimates from the
ten-city Pilot Study data. Table 3.3.2 suggests that the specified air toxics trends DQOs will be
met for 1,3-butadiene at urban monitoring sites that satisfy the goals of one in six-day sampling.
85 percent completeness, and 15 percent measurement CV. (See section 3.0 for definitions of
the input parameters and output values.)
Table 3.3.1 DGO input parameters for 1,3-butadiene at urban locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (uq/m3)
10%
15%
1 in 6 day
7.0
100%
0.1
T2
Measurement CV
Completeness
Autocorrelation
MDL (iq/nr)
Risk Standard (nq/mJ)
10%
15%
85%
0
0.02
10~'
Table 3.3.2 DQO output parameters for 1,3-butadiene at urban locations
Error rate for no true chanqe
Error rate for 30% decrease
Gray zone
10%
94%
0% - 28%
1
cJ
!
cs
CD
5
on
a
•E?
i
CJ-.
o
6
Figure 3.3.
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0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
10
0
5
15
20
25
30
True percent difference
1 Power curve for detecting a 15 percent decrease between successive
three-year means of 1,3-butadiene concentrations based on the data
variation found in urban locations of the Pilot Study
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3.4 DQOs for Measuring the Percent Decrease of 1,3-butadiene at Rural
Locations
Table 3.4.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of 1.3-
butadiene at rural locations. Table 3.4.2 shows the output values from the simulations. Figure
3.4.1 shows the associated power curve, which is the probability of observing a 15 percent
difference between successive three-year means as a function of the true percent difference in the
distinct three-year means. In summary, based on variability and uncertainty estimates from the
ten-city Pilot Study data. Table 3.4.2 suggests that the specified air toxics trends DQOs will be
met for 1,3-butadiene at rural monitoring sites that satisfy the goals of one in six-day sampling.
85 percent completeness, and 15 percent measurement CV. (See section 3.0 for definitions of
the input parameters and output values.)
Table 3.4.1 DGO input parameters for 1,3-butadiene at rural locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (uq/m3)
10%
15%
1 in 6 day
6.0
75%
0.1
T2
Measurement CV
Completeness
Autocorrelation
MDL (uq/nr)
Risk Standard (nq/nr)
10%
15%
85%
0
0.02
10°
Table 3.4.2 DQO output parameters for 1,3-butadiene at rural locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
4%
98%
4% - 25%
i
GO
-s
True percent difference
Figure 3.4.1 Power curve for detecting a 15 percent decrease between successive
three-year means of 1,3-butadiene concentrations based on the data
variation found in rural locations of the Pilot Study
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3.5 DQOs for Measuring the Percent Decrease of Arsenic at Urban Locations
Table 3.5.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of arsenic at
urban locations. Table 3.5.2 shows the output values from the simulations. Figure 3.5.1 shows
the associated power curve, which is the probability of observing a 15 percent difference
between successive three-year means as a function of the true percent difference in the distinct
three-year means. In summary, based on variability and uncertainty estimates from the ten-city
Pilot Study data. Table 3.5.2 suggests that the specified air toxics trends DQOs will be met for
arsenic at urban monitoring sites that satisfy the goals of one in six-day sampling, 85 percent
completeness, and 15 percent measurement CV. (See section 3.0 for definitions of the input
parameters and output values.)
Table 3.5.1 DQO input parameters for arsenic at urban locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (ng/m3)
10%
15%
1 in 6 day
5.0
85%
0.002
T2
Measurement CV
Completeness
Autocorrelation
MDL (ng/nr)
Risk Standard (|jg/mJ)
10%
15%
85%
0
0.000046
0.0043
Table 3.5.2 DQO output parameters for arsenic at urban locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
8%
95%
2% - 27%
1
a
a
0.4
<4-
o
True percent difference
Figure 3.5.1 Power curve for detecting a 15 percent decrease between successive
three-year means of arsenic concentrations based on the data variation
found in urban locations of the Pilot Study
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3.6 DQOs for Measuring the Percent Decrease of Arsenic at Rural Locations
Table 3.6.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of arsenic at
rural locations. Table 3.6.2 shows the output values from the simulations. Figure 3.6.1 shows
the associated power curve, which is the probability of observing a 15 percent difference
between successive three-year means as a function of the true percent difference in the distinct
three-year means. In summary, based on variability and uncertainty estimates from the ten-city
Pilot Study data. Table 3.6.2 suggests that the specified air toxics trends DQOs will be met for
arsenic at rural monitoring sites that satisfy the goals of one in six-day sampling, 85 percent
completeness, and 15 percent measurement CV. (See section 3.0 for definitions of the input
parameters and output values.)
Table 3.8.1 DQO input parameters for arsenic at rural locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (ng/m3)
10%
15%
1 in 6 day
4.0
65%
0.001
T2
Measurement CV
Completeness
Autocorrelation
MDL (i.g/m')
Risk Standard (ug/mJ)
10%
15%
85%
0
0.000046
0.0043
Table 3.6.2 DQO output parameters for arsenic at rural locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
3%
99%
5% - 24%
a
o
i 0.7
0£|
0.4
True percent difference
Figure 3.6.1 Power curve for detecting a 15 percent decrease between successive
three-year means of arsenic concentrations based on the data variation
found in rural locations of the Pilot Study
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3.7 DQOs for Measuring the Percent Decrease of Chromium
Table 3.7.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of chromium.
Table 3.7.2 shows the output values from the simulations. Figure 3.7.1 shows the associated
power curve, which is the probability of observing a 15 percent difference between successive
three-year means as a function of the true percent difference in the distinct three-year means. In
summary, based on variability and uncertainty estimates from the ten-city Pilot Study data. Table
3.7.2 suggests that the specified air toxics trends DQOs will be met for chromium at monitoring
sites that satisfy the goals of one in six-day sampling, 85 percent completeness, and 15 percent
measurement CV. (See section 3.0 for definitions of the input parameters and output values. )
Table 3.7.1 DQO input parameters for chromium
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (jiq/m*1)
10%
15%
1 in 6 dav
5.0
90%
0.0015
T2
Measurement CV
Completeness
Autocorrelation
MDL (jjq/ma)
Risk Standard (uq/m1)
10%
15%
85%
0
0.00018
0.012
Table 3.7.2 DQO output parameters for chromium
Error rate for no true change
Error rate for 30% decrease
Gray zone
7%
96%
2% - 27%
True percent difference
Figure 3.7.1 Power curve for detecting a 15 percent decrease between successive
three-year means of chromium concentrations based on the data variation
found in of the Pilot Study
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3.8 DQOs for Measuring the Percent Decrease of Acrolein
Table 3,8,1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year me an concentrations of acrolein.
Table 3,8,2 shows the output values from the simulations. Figure 3,8,1 shows the associated
power curve, which is the probability of observing a 15 percent difference between successive
three-year means as a function of the true percent difference in the distinct three year means, hi
summary, based on variability and uncertainty estimates from the ten-city Pilot Study data. Table
3,8,2 suggests that the specified air toxics trends DQOs will be met for acrolein at monitoring
sites that satisfy the goals of one in six-day sampling. 85 percent completeness, and 15 percent
measurement C V, ( See section 3,0 for definitions of the input parameters and output values,)
Table 3.8.1 DQO input parameters for acrolein
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (uq/m1)
10%
15%
1 in 6 day
4.0
105%
0.4
T2
Measurement CV
Completeness
Autocorrelation
MDL (uq/m5)
Risk Standard (np/m1)
10%
15%
85%
0
0 14
-
Table 3.8.2 DQO output parameters for acrolein
Error rate for no true change
Error rate for 30% decrease
Gray zone
10%
S1%
0% - 29%
DQOs for Trends - Draft Report	tS	September 37,
	i	l	i	i	l	:	
5	10	15	20	25	30
True percent difference
Power curve for detecting a 15 percent decrease between successive
three-year means of acrolein concentrations based on the data variation
found in the Pilot Study
Figure 3.8.1
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3.9 DQOs for Measuring the Percent Decrease of Formaldehyde at Urban
Locations
Table 3.9.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of
formaldehyde at urban locations. Table 3.9.2 shows the output values from the simulations.
Figure 3.9.1 shows the associated power curve, which is the probability of observing a
15 percent difference between successive three-year means as a function of the true percent
difference in the distinct three-year means. In summary, based on variability and uncertainty
estimates from the ten-city Pilot Study data. Table 3.9.2 suggests that the specified air toxics
trends DQOs will be met for formaldehyde at urban monitoring sites that satisfy the goals of one
in six-day sampling, 85 percent completeness, and 15 percent measurement CV. (See
Section 3.0 for definitions of the input parameters and output values.)
Table 3.9.1 DGO input parameters for formaldehyde at urban locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration fug/m3)
10%
15%
1 in 6 day
7.0
90%
2.5
T2
Measurement CV
Completeness
Autocorrelation
MDL Liq/m ')
Risk Standard (nq/m')
10%
15%
85%
0
0.014
1.3 10'
Table 3.9.2 DQO output parameters for formaldehyde at urban locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
8%
95%
2% - 27%
S
a
0.4
d.
True percent difference
Figure 3.9.1 Power curve for detecting a 15 percent decrease between successive
three-year means of formaldehyde concentrations based on the data
variation found in urban locations of the Pilot Study
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3.10 DQOs for Measuring the Percent Decrease of Formaldehyde at Rural
Locations
Table 3.10.1 shows the input parameters used in the simulation model in developing the
DQOs for measuring the percent decrease between three-year mean concentrations of
formaldehyde at rural locations. Table 3,10.2 shows the output values from the simulations.
Figure 3.10.1 shows the associated power curve, which is the probability of observing a
15 percent difference between successive three-year means as a function of the true percent
difference in the distinct three-year means. In summary, based on variability and uncertainty
estimates from the ten-city Pilot Study data. Table 3.10.2 suggests that the specified air toxics
trends DQOs will be met for formaldehyde at rural monitoring sites that satisfy the goals of one
in six-day sampling, 85 percent completeness, and 15 percent measurement CV. (See
Section 3.0 for definitions of the input parameters and output values.)
Table 3.10.1 DGO input parameters for formaldehyde at rural locations
T1
Action Limit
Sampling Rate
Seasonality
Population CV
Initial
Concentration (jiq/m')
10%
15%
1 in 6 day
7.0
90%
2.1
T2
Measurement CV
Completeness
Autocorrelation
MDL Liq/m ')
Risk Standard (nq/m')
10%
15%
85%
0
0.014
1.3 10'
Table 3.10.2 DGO output parameters for formaldehyde at rural locations
Error rate for no true change
Error rate for 30% decrease
Gray zone
8%
95%
1%- 27%
•g
Ci
I
0J
5
bp
%
8
n-i
o
O
CU
True percent difference
Figure 3.10.1 Power curve for detecting a 15 percent decrease between successive
three-year means of formaldehyde concentrations based on the data
variation found in rural locations of the Pilot Study
DQOs for Trends - Draft Report	18	September 27,2002
i
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
225

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NATTS TAD Revision 3
Appendix A
APPENDIX A:
ESTIMATES OF THE DQO PARAMETERS MEASURING
ENVIRONMENTAL VARIABILITY
226

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NATTS TAD Revision 3
Appendix A
Appendix A: Estimates of the DQO Parameters Measuring Environmental
Variability
The DQO parameters that measure the natural environmental variability of a pollutant are
generally uncontrollable parameters that have a strong effect on the decision errors. The
simulation model described in Section 2.1 uses these parameters. This appendix describes both
the parameters and the method for estimating the parameters from the Pilot data. The basic
simulation model is that the true concentration levels vary about a sinusoidal curve with one full
oscillation in each year. Four parameters describe characteristics of the sine curve and the
natural deviations from the sine curve.
Seasonality Ratio
The ratio parameter is a measure of the degree of seasonality in the data. It is the ratio of
the high point to the low point on the sine curve. The model assumes that the amplitude of the
sine curve is proportional to the mean. The parameter was estimated by finding the monthly
averages and taking the ratio of the highest average to the lowest average. The site estimates are
restricted to those sites that had at least 3 measurements in each of at least six months.
Population CV
This parameter measures the amount of random, day-to-day variation of the true
concentration about the sine curve. This parameter was estimated as follows. Starting with
every 6th day measurements (deleting if needed), the natural log of each measurement was found.
Next, a new sequence of numbers was created equal to the differences of successive pairs in the
sequence of the log-concentrations that were from measurements taken six days apart. Finally,
terms were removed from this sequence so that each term in the remaining sequence was based
on distinct numbers. Let S be the standard deviation of this set of numbers. The estimate for the
population CV is^/(exp(s2/2)-l), The site estimates are restricted to those with at least ten
terms being used in the estimates.
Autocorrelation
The final parameter describing the natural variation of the true concentrations is
autocorrelation. This is a measurement of the similarity between successive days. Consider two
sets of measurements. First, suppose you had measured the concentrations on every July 15th for
the p ast five years. You would expect those five values to be rather spread out. The
population CV should capture how different these measurements are from each other. On the
other hand, suppose instead you measure the concentrations each day from July 15, 2002, to July
20, 2002. These values may not be as spread out as the other set, simply because they are nearer
in time to each other. Autocorrelation measures this effect. A good way to think of
autocorrelation is it measures how quickly the local concentrations can change. The value of the
autocorrelation ranges between 0 and 1. A value of 0 means that the local concentrations can
change very rapidly from day-to-day. A value of 1 means that the local concentrations are
constant.
DQOs for Trends - Draft Report	A-1	September 27,2002
227

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NATTS TAD Revision 3
Appendix A
Estimating autocorrelation is more difficult than estimating the population CV. Unless a
site had daily measurements, a value of 0 was used. Realistically, 0 is the most conservative case
and can always be used. Assuming a site had daily measurements, let S6 be the standard
deviation computed as in the section on population CV, based on differences of the logs from
every 6th day measurements. Let 51 be the same thing using differences of logs from daily
measurements. If 56 > 51, then the autocorrelation was estimated with (562 - 512)/562. This
method adjusts for seasonality, but still tends to slightly over estimate the truth. There were too
few sites with sufficient daily measurements to obtain distributions of the pollutant
autocorrelations, so a value of 0 was used for all pollutants.
Initial concentration.
This is simply the mean concentration for the site.
Table A-l gives the pollutant and site estimates for the seasonality ratio and the initial
mean concentrations. Table A-2 gives the pollutant and site population CV estimates.
DQOs for Trends - Draft Report	A-2	September 27,2002
228

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NATTS TAD Revision 3
Appendix A
Table A-1. Estimates of the seasonality ratio and initial mean by pollutant ji a site
Pollutant
Site ID
Urban / Rural
Mean
(ng/m3)
Seasonality Ratio
1,3-BUTADIENE
2616300051
Urban
0.3190
3.60
1,3-BUTADIENE
4400700261
Urban
0.2600
3.15
1,3-BUTADIENE
2616300331
Urban
0.2067
2.65
1,3-BUTADIENE
2616300271
Urban
0.2032
2.03
1,3-BUTADIENE
2612500101
Urban
0.2027
1.36
1,3-BUTADIENE
4400700221
Urban
0.1789
5.86
1,3-BUTADIENE
1210300181
Urban
0.1732
4.41
1,3-BUTADIENE
4400700251
Urban
0.1431
4.07
1,3-BUTADIENE
1205710751
Urban
0.1382
5.43
1,3-BUTADIENE
1210310081
Urban
0.1272
3.31
1,3-BUTADIENE
5303300321
Urban
0.1250
6.51
1,3-BUTADIENE
1210350021
Urban
0.1164
2.50
1,3-BUTADIENE
5303300801
Urban
0.1148
5.76
1,3-BUTADIENE
5303300241
Urban
0.1141
7.10
1,3-BUTADIENE
4400700241
Urban
0.1041
4.64
1,3-BUTADIENE
4400710101
Urban
0.1019
5.35
1,3-BUTADIENE
5303300201
Urban
0.1010
10.03
1,3-BUTADIENE
5303300101
Urban
0.0916
10.39
1,3-BUTADIENE
5303300381
Urban
0.0809
5.51
1,3-BUTADIENE
4400300021
Urban
0.0358
5.38
1,3-BUTADIENE
0807700131
Rural
0.2192
6.00
1,3-BUTADIENE
0807700161
Rural
0.1810
4.06
1,3-BUTADIENE
1311300391
Rural
0.1182
3.23
1,3-BUTADIENE
1311300371
Rural
0.0886
1.22
ACROLEIN
4400700261
Urban
0.5904
2.04
ACROLEIN
4400700221
Urban
0.5866
3.36
ACROLEIN
4400700241
Urban
0.5366
2.36
ACROLEIN
4400700251
Urban
0.5366
2.18
ACROLEIN
4400710101
Urban
0.3637
3.34
ACROLEIN
4400300021
Urban
0.3509
3.69
ARSENIC TSP
1205710751
Urban
0.0038
5.01
ARSENIC TSP
2616300271
Urban
0.0033
2.06
ARSENIC TSP
2616300331
Urban
0.0028
3.13
ARSENIC TSP
1210350021
Urban
0.0027
2.94
ARSENIC TSP
1205700811
Urban
0.0027
1.59
ARSENIC TSP
1205710651
Urban
0.0026
1.40
ARSENIC TSP
2616300151
Urban
0.0024
2.68
ARSENIC TSP
1210300181
Urban
0.0024
2.41
ARSENIC TSP
2616300051
Urban
0.0023
2.82
ARSENIC TSP
1210310081
Urban
0.0022
1.56
ARSENIC TSP
2616300011
Urban
0.0021
4.50
ARSENIC TSP
2616300191
Urban
0.0019
2.97
ARSENIC TSP
5303300241
Urban
0.0015
4.48
ARSENIC TSP
2612500101
Urban
0.0014
14.99
DQOs for Trends - Draft Report	A-3	September 27,2002
229

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NATTS TAD Revision 3
Appendix A
Table A-1. Estimates of the seasonality ratio and initial mean by pollutant and site (Cont'd.)
Pollutant
Site ID
Urban / Rural
Mean
Mg/m3)
Seasonality Ratio
ARSENIC TSP
5303300201
Urban
0.0010
3.80
ARSENIC TSP
5303300381
Urban
0,0009
3.13
ARSENIC TSP
5303300101
Urban
0.0008
4.94
ARSENIC TSP
0807700161
Rural
0.0016
2.11
ARSENIC TSP
0807700131
Rural
0.0008
3.54
BENZENE
2616300271
Urban
18.8411
12.42
BENZENE
2616300051
Urban
2.2038
1.92
BENZENE
2612500101
Urban
2.0860
1.59
BENZENE
2616300331
Urban
2.0710
1.55
BENZENE
5303300321
Urban
1.7124
3.97
BENZENE
5303300241
Urban
1.6500
2.76
BENZENE
4400700261
Urban
1.4416
2.43
BENZENE
1210300181
Urban
1.2763
3.09
BENZENE
4400700221
Urban
1.2648
3.49
BENZENE
5303300801
Urban
1.1697
1.71
BENZENE
5303300101
Urban
1.1466
2.08
BENZENE
5303300381
Urban
1.1161
2.30
BENZENE
4400700251
Urban
1.1123
3.30
BENZENE
1205710751
Urban
1.0364
2.98
BENZENE
5303300201
Urban
1.0229
2.03
BENZENE
1210310081
Urban
0.9283
2.62
BENZENE
1210350021
Urban
0.8940
1.94
BENZENE
4400700241
Urban
0.8849
3.06
BENZENE
1205710651
Urban
0.8791
2.47
BENZENE
4400710101
Urban
0.8006
4.15
BENZENE
1205700811
Urban
0.6451
2.37
BENZENE
4400300021
Urban
0.4190
5.05
BENZENE
0807700131
Rural
2.7088
2.36
BENZENE
0807700161
Rural
1.8649
3.16
BENZENE
1311300391
Rural
1.1701
2.68
BENZENE
0606530111
Rural
1.0166
3.10
BENZENE
1311300371
Rural
0,9221
1.66
BENZENE
0606530121
Rural
0.7622
2.71
CHROMIUM TSP
2616300271
Urban
0.0075
1.70
CHROMIUM TSP
2616300331
Urban
0.0061
1.68
CHROMIUM TSP
2616300151
Urban
0.0059
2.09
CHROMIUM TSP
2616300051
Urban
0.0049
1.90
CHROMIUM TSP
2616300011
Urban
0.0036
2.31
CHROMIUM TSP
2612500101
Urban
0.0034
1.79
CHROMIUM TSP
2616300191
Urban
0.0031
2.45
CHROMIUM TSP
1205710651
Urban
0.0019
1.62
CHROMIUM TSP
1210350021
Urban
0.0017
3.68
CHROMIUM TSP
5303300201
Urban
0.0017
6.25
CHROMIUM TSP
1210300181
Urban
0.0016
2.51
DQOs for Trends - Draft Report	A-4	September 27,2002
230

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NATTS TAD Revision 3
Appendix A
Table A-1. Estimates of the seasonality ratio and initial mean by pollutant and site (Cont'd.)
Pollutant
Site ID
Urban / Rural
Mean
(ng/m3)
Seasonality Ratio
CHROMIUM TSP
1205700811
Urban
0.0014
1.87
CHROMIUM TSP
1210310081
Urban
0.0014
2.99
CHROMIUM TSP
1205710751
Urban
0.0014
1.88
CHROMIUM TSP
5303300241
Urban
0.0011
4.23
CHROMIUM TSP
5303300381
Urban
0.0009
3.02
CHROMIUM TSP
5303300101
Urban
0.0009
3.17
FORMALDEHYDE
2616300331
Urban
7.2980
70.55
FORMALDEHYDE
1210300181
Urban
4.1605
2.36
FORMALDEHYDE
4400710101
Urban
4.0325
2.80
FORMALDEHYDE
1205710651
Urban
3.8291
2.25
FORMALDEHYDE
4400700251
Urban
3.6958
2.53
FORMALDEHYDE
2616300271
Urban
3.5940
1.64
FORMALDEHYDE
4400700261
Urban
3.4373
2.36
FORMALDEHYDE
1205700811
Urban
3.4311
2.38
FORMALDEHYDE
4400700221
Urban
3.3888
2.01
FORMALDEHYDE
1210310081
Urban
3.2569
2.56
FORMALDEHYDE
1205710751
Urban
2.9991
2.73
FORMALDEHYDE
2612500101
Urban
2.8279
2.21
FORMALDEHYDE
1210350021
Urban
2.8150
2.31
FORMALDEHYDE
2616300191
Urban
2.7887
4.43
FORMALDEHYDE
4400700241
Urban
2.6769
3.25
FORMALDEHYDE
2616300011
Urban
2.4937
2.98
FORMALDEHYDE
5303300801
Urban
1.7148
2.97
FORMALDEHYDE
5303300321
Urban
1.4839
3.56
FORMALDEHYDE
5303300381
Urban
1.3536
2.53
FORMALDEHYDE
5303300201
Urban
1.3236
3.78
FORMALDEHYDE
5303300241
Urban
1.1373
2.48
FORMALDEHYDE
5303300101
Urban
1.0165
9.43
FORMALDEHYDE
0807700131
Rural
7.3046
6.72
FORMALDEHYDE
0807700161
Rural
7.0664
2.15
FORMALDEHYDE
1311300371
Rural
2.3401
5.10
FORMALDEHYDE
1311300391
Rural
2.1613
3.02
FORMALDEHYDE
0606530121
Rural
2.1246
2.83
FORMALDEHYDE
0606530111
Rural
1.6840
1.90
DQOs for Trends - Draft Report	A-5	September 27,2002
231

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NATTS TAD Revision 3
Appendix A
Table A-2. Population CV estimates by pollutant and site
Pollutant
SITE ID
Urban /
Rural
State
County
Population
CV
1,3-BUTADIENE
530330032
Urban
WA
King County
109.2%
1,3-BUTADIENE
530330024
Urban
WA
Kinq County
106.7%
1,3-BUTADIENE
530330010
Urban
WA
King County
97.4%
1,3-BUTADIENE
530330038
Urban
WA
King County
85.8%
1,3-BUTADIENE
440070025
Urban
Rl
Providence County
84.2%
1,3-BUTADIENE
530330020
Urban
WA
King County
79.6%
1,3-BUTADIENE
261630027
Urban
Ml
Wayne County
78.0%
1,3-BUTADIENE
261250010
Urban
Ml
Oakland County
74.7%
1,3-BUTADIENE
440071010
Urban
Rl
Providence County
74.1%
1,3-BUTADIENE
530330080
Urban
WA
King County
72.4%
1,3-BUTADIENE
261630033
Urban
Ml
Wayne County
67.8%
1,3-BUTADIENE
121030018
Urban
FL
Pinellas County
67.5%
1,3-BUTADIENE
440070024
Urban
Rl
Providence County
64.5%
1,3-BUTADIENE
440070022
Urban
Rl
Providence County
63.8%
1,3-BUTADIENE
120571075
Urban
FL
Hillsborough County
62.9%
1,3-BUTADIENE
440070026
Urban
Rl
Providence County
61.7%
1,3-BUTADIENE
261630005
Urban
Ml
Wayne County
59.5%
1,3-BUTADIENE
121031008
Urban
FL
Pinellas County
57.9%
1,3-BUTADIENE
120571065
Urban
FL
Hillsborough County
57.6%
1,3-BUTADIENE
121035002
Urban
FL
Pinellas County
55.7%
1,3-BUTADIENE
440030002
Urban
Rl
Kent County
54.1%
1,3-BUTADIENE
120570081
Urban
FL
Hillsborough County
32.7%
1,3-BUTADIENE
080770013
Rural
CO
Mesa County
69.8%
1,3-BUTADIENE
080770016
Rural
CO
Mesa County
67.1%
1,3-BUTADIENE
131130039
Rural
GA
Fayette County
34.5%
1,3-BUTADIENE
131130037
Rural
GA
Fayette County
13.4%
ACROLEIN
440030002
Urban
Rl
Kent County
100.3%
ACROLEIN
440071010
Urban
Rl
Providence County
80.7%
ACROLEIN
440070024
Urban
Rl
Providence County
66.4%
ACROLEIN
440070022
Urban
Rl
Providence County
58.7%
ACROLEIN
440070026
Urban
Rl
Providence County
53.4%
ACROLEIN
440070025
Urban
Rl
Providence County
39.9%
ARSENIC TSP
530330024
Urban
WA
King County
99.6%
ARSENIC TSP
261630001
Urban
Ml
Wayne County
83.8%
ARSENIC TSP
261630019
Urban
Ml
Wayne County
78.2%
ARSENIC TSP
261630033
Urban
Ml
Wayne County
74.3%
ARSENIC TSP
530330010
Urban
WA
King County
72.1%
ARSENIC TSP
261630005"1
Urban
Ml
Wayne County
68.4%
ARSENIC TSP
530330038
Urban
WA
King County
67.2%
ARSENIC TSP
530330020
Urban
WA
King County
64.0%
ARSENIC TSP
261630027
Urban
Ml
Wayne County
64.0%
ARSENIC TSP
261630015
Urban
Ml
Wayne County
61.1%
ARSENIC TSP
121035002
Urban
FL
Pinellas County
47.3%
ARSENIC TSP
120571075
Urban
FL
Hillsborough County
44.3%
DOOs for Trends - Draft Report	A-6	September 27,2002
232

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NATTS TAD Revision 3
Appendix A
Table A-2. Population CV estimates by pollutant and site (Cont'd.)
Pollutant
SITE ID
Urban /
Rural
State
County
Population
CV
ARSENIC TSP
120570081
Urban
FL
Hillsborouqh County
27.9%
ARSENIC TSP
121031008
Urban
FL
Pinellas County
27.2%
ARSENIC TSP
121030018
Urban
FL
Pinellas County
26.5%
ARSENIC TSP
120571065
Urban
FL
Hillsborough County
22.7%
ARSENIC TSP
080770016
Rural
CO
Mesa County
56.4%
ARSENIC TSP
080770013
Rural
CO
Mesa County
37.0%
BENZENE
261630027
Urban
Ml
Wayne County
221.2%
BENZENE
530330032
Urban
WA
K
ng County
93.5%
BENZENE
530330020
Urban
WA
K
ng County
82.2%
BENZENE
530330010
Urban
WA
K
ng County
66.2%
BENZENE
530330024
Urban
WA
K
ng County
64.7%
BENZENE
261630005
Urban
Ml
Wayne County
55.1%
BENZENE
121031008
Urban
FL
Pinellas County
49.8%
BENZENE
121030018
Urban
FL
Pinellas County
49.6%
BENZENE
261250010
Urban
Ml
Oakland County
48.7%
BENZENE
261630033
Urban
Ml
Wayne County
46.2%
BENZENE
440071010
Urban
Rl
Providence County
45.8%
BENZENE
121035002
Urban
FL
Pinellas County
41.9%
BENZENE
440070024
Urban
Rl
Providence County
41.6%
BENZENE
120571075
Urban
FL
Hillsborough County
41.6%
BENZENE
530330080
Urban
WA
King County
40.1%
BENZENE
530330038
Urban
WA
Kinq County
39.4%
BENZENE
440070025
Urban
Rl
Providence County
37.7%
BENZENE
120571065
Urban
FL
Hillsborough County
36.1%
BENZENE
120570081
Urban
FL
Hillsborough County
35.8%
BENZENE
440030002
Urban
Rl
Kent County
34.6%
BENZENE
440070022
Urban
Rl
Providence County
33.9%
BENZENE
440070026
Urban
Rl
Providence County
29.1%
BENZENE
131130037
Rural
GA
Fayette County
54.2%
BENZENE
060653011
Rural
CA
Riverside County
53.7%
BENZENE
131130039
Rural
GA
Fayette County
52.1%
BENZENE
060653012
Rural
CA
Riverside County
49.1%
BENZENE
080770016
Rural
CO
Mesa County
45.8%
BENZENE
080770013
Rural
CO
Mesa County
32.2%
CHROMIUM TSP
530330010
Urban
WA
King County
98.5%
CHROMIUM TSP
530330020
Urban
WA
King County
87.0%
CHROMIUM TSP
530330038
Urban
WA
King County
84.9%
CHROMIUM TSP
530330024
Urban
WA
King County
84.6%
CHROMIUM TSP
121035002
Urban
FL
Pinellas County
61.5%
CHROMIUM TSP
120571065
Urban
FL
Hillsborough County
51.2%
CHROMIUM TSP
120571075
Urban
FL
Hillsborough County
44.6%
CHROMIUM TSP
261630033
Urban
Ml
Wayne County
43.9%
CHROMIUM TSP
261630019
Urban
Ml
Wayne County
42.7%
CHROMIUM TSP
261630005
Urban
Ml
Wayne County
42.0%
DQOs for Trends - Draft Report	A-7	September 27,2002
233

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NATTS TAD Revision 3
Appendix A
Table A-2, Population CV estimates by pollutant and site (Cont'd.)
Pollutant
SITE ID
Urban /
Rural
State
County
Population
CV
CHROMIUM TSP
261630015
Urban
Ml
Wayne County
39.8%
CHROMIUM TSP
121031008
Urban
FL
Pinellas County
39.5%
CHROMIUM TSP
121030018
Urban
FL
Pinellas County
35.6%
CHROMIUM TSP
120570081
Urban
FL
Hillsborough County
34.5%
CHROMIUM TSP
261630027
Urban
Ml
Wayne County
33.0%
CHROMIUM TSP
261630001
Urban
Ml
Wayne County
31.8%
FORMALDEHYDE
121031008
Urban
FL
Pinellas County
84.9%
FORMALDEHYDE
120570081
Urban
FL
Hillsborough County
80.1%
FORMALDEHYDE
261630033
Urban
Ml
Wayne County
78.0%
FORMALDEHYDE
530330032
Urban
WA
K
ng County
72.2%
FORMALDEHYDE
530330024
Urban
WA
K
ng County
59.7%
FORMALDEHYDE
530330020
Urban
WA
K
ng County
57.9%
FORMALDEHYDE
120571075
Urban
FL
H
llsborough County
55.8%
FORMALDEHYDE
530330010
Urban
WA
K
ng County
53.9%
FORMALDEHYDE
440070024
Urban
Rl
Providence County
52.3%
FORMALDEHYDE
530330080
Urban
WA
King County
52.2%
FORMALDEHYDE
261630019
Urban
Ml
Wayne County
52.0%
FORMALDEHYDE
530330038
Urban
WA
King County
48.9%
FORMALDEHYDE
261630001
Urban
Ml
Wayne County
44.0%
FORMALDEHYDE
121035002
Urban
FL
Pinellas County
40.9%
FORMALDEHYDE
120571065
Urban
FL
Hillsborough County
38.2%
FORMALDEHYDE
440070022
Urban
Rl
Providence County
37.4%
FORMALDEHYDE
261630027
Urban
Ml
Wayne County
35.8%
FORMALDEHYDE
121030018
Urban
FL
Pinellas County
32.7%
FORMALDEHYDE
261250010
Urban
Ml
Oakland County
31.1%
FORMALDEHYDE
440070026
Urban
Rl
Providence County
28.3%
FORMALDEHYDE
440071010
Urban
Rl
Providence County
26.6%
FORMALDEHYDE
440070025
Urban
Rl
Providence County
26.6%
FORMALDEHYDE
060653011
Rural
CA
Riverside County
84.3%
FORMALDEHYDE
131130037
Rural
GA
Fayette County
57.2%
FORMALDEHYDE
060653012
Rural
CA
Riverside County
39.3%
FORMALDEHYDE
131130039
Rural
GA
Fayette County
35.1%
FORMALDEHYDE
080770013
Rural
CO
Mesa County
27.6%
FORMALDEHYDE
080770016
Rural
CO
Mesa County
23.7%
DQOs for Trends - Draft Report	A-8	September 27,2002
234

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NATTS TAD Revision 3
Appendix B
APPENDIX B
NATTS AQS REPORTING GUIDANCE FOR
QUALITY ASSURANCE SAMPLES
BLANKS AND PRECISION SAMPLES
(COLLOCATED, DUPLICATE, AND REPLICATE REPORTING)
235

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NATTS TAD Revision 3
Appendix B
NATTS QA Data Reporting to AQS
Blanks and Precision Samples (Collocated, Duplicate, and Replicate reporting)
Blank Sample Reporting
Blank samples in the NATTS program consist of field blanks, trip blanks, lot blanks, laboratory
method blanks, and exposure blanks. Monitoring agencies are required to report field blank, trip
blank, and lot blank data to AQS. Optionally, monitoring agencies may also report laboratory
method blanks and exposure blanks.
To report blank data, submit a raw blank (RB) transaction for each blank sample. The Blank
Type for the various blanks are:
To create an RB transaction for a field blank, the Blank Type field is entered as "FIELD" (bold
below) as in the following example:
RB|I|11|222|3333|44444|9|7|454|888|FIELD|2015 0101|00:00|0.04 63||||||||||||0.0001|
Precision Sample Background
Duplicate and replicate analyses are defined and reported in the NATTS program. Collocated
data reporting is used in both the SLAMS and NATTS programs. The purpose of this section is
to clarify how data from these assessments should be reported to AQS using the new QA
transaction formats. (Please note, the old AQS "RA" and "RP" transactions have been retired
and can no longer be used to report data.) The goal is to provide consistent reporting terms and
procedures to allow the data to be universally understood.
Simplified schematics are included in this article for illustrative purposes and do not address
specifics related to different sampling approaches or methodologies.
The AQS transaction formatting descriptions are not repeated herein this document. Please refer
to the, but may be found on the AQS web site for those (accessed October 19, 2016):
https://aqs.epa. gov/aq sweb/documents/T ran sacti onF orm ats.html
Field blank:
Trip blank:
Lot blank:
FIELD
TRIP
LOT
LAB
Laboratory Method Blank:
Exposure Blank:
FIELD 24HR
236

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NATTS TAD Revision 3
Appendix B
Collocated Samples
Collocated samples are samples collected simultaneously at the same location using two
completely separate sampling systems, each with a separate inlet probe to the ambient sampled
atmosphere. The allowable distance between inlet probes is defined in regulations or in program
guidance. Both of the monitors (each designated by a separate AQS Parameter Occurrence Code
- POCs) have been established in AQS already. The samples are collected and analyzed
separately. Each is reported as a sample value for the appropriate monitor.
Schematic
Collocated Samples
Primary
Monitor N
0
Collocated samples are samples collected simultaneously at the same
location using two completely separate sampling systems, each with a
separate inlet probe to the ambient sampled atmosphere.
Collocated
Monitor C
Two completely separate sampling systems at same location, two different samples analyzed.
Collocated Sample Reporting Instructions
For AQS to automatically create the 'precision pair' for the primary and collocated samples, the
monitors must be identified to the system as QA collocated. One monitor must be designated as
the QA primary. If using transactions, the Monitor Collocation Period (MJ) transaction is used.
(If using the AQS application, the "QA Collocation" tab on the Maintain Monitor form may be
used to enter thesis data). The collocation data must be entered for both monitors, with one
indicated as the primary, and the other indicated as the collocated (not the primary). In the
example below, the primary monitor is indicated by the bolded 'Y' (yes, this is the primary) in
the Primary Sampler Indicator in the first MJ string and the collocated monitor by the bolded 'N'
(no, this is not the primary) in the Primary Sampler Indicator in the second MJ string.
Once the monitors have been identified as collocated this is done, there are no additional
reporting requirements; simply report the raw data from each monitor (From the schematic, value
'a' from the primary monitor 'N' and value 'b' from the collocated monitor 'C'). Once this is
done, AQS will know to pair data from these two monitors for the date range specified.
A set of transactions must be created for each time period the monitors are operating together.
The transactions have a begin date and end date for the operational period. The end date may be
left blank if the collocation period is still active (as indicated in the example below). To define a
collocation, submit two MJ transactions (example below with differences bolded and where
primary monitor TSP is POC 5 and collocated monitor 'C' is POC 9):
237

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NATTS TAD Revision 3
Appendix B
MJiI I 11!222|3333|44444!5|20150101 | i 3|Y
MJ|I|11|222 I 3333|44444|9|20150101| |3|N
Report two Raw Data (RD) transactions for each time sample data are to be reported from both
monitors; one for each monitor (POC). (In this example, sample 'a' is 0.0463 from monitor 'N'
(POC 5) and sample "b* from monitor 'C' (POC 9) is 0.0458):
RD|I|11|222|3333|44444|5|7|454 M
RD|I I 11 I 222|3333|44444 j 9|7 I 454 i!
58 I 20150101|00:00|0.0463| 6 I I I I I I I I I I I 0 . 00 01 | 0. 0005
58|20150101|00:00!0.0458! [B] 1 I [ [ I I I I I ( I 0.0001|0.0005
Since there are two monitors involved, each sample is reported for its appropriate POC and there
will be an RD transaction for every time there is a valid sample from each monitor (e.g., two per
day in this scenario). If the sample value from one POC is not available, report a null data code
for that monitor (that is, do not report the sample value from the collocated monitor as being
from the primary POC).
Duplicate Samples
Duplicate samples are two (or more) samples collected simultaneously using one or more
sampling units sharing a common inlet probe to the ambient atmosphere and the collected
samples are analyzed separately. This simultaneous collection may be accomplished by "teeing'
the line from the flow control device (sampling unit) to the media (e.g. canisters), and then
doubling the collection flow rate, or may be accomplished by collecting one discrete sample via
two separate flow control devices (sampling units) connected to the same inlet probe.
Schematic
Duplicate Samples
Monitor N
Duplicate samples are two (or more) samples collected simultaneously
using one or more sampling units sharing a common inlet probe to the
ambient atmosphere and the collected samples are analyzed separately
or
Primary
Monitor IM
Collocated
Monitor C
Q
Q
One sampling system inlet probe, two different samples analyzed.
238

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NATTS TAD Revision 3
Appendix B
Duplicate Sample Reporting Instructions
In this case, there is only one inlet probe involved but with multiple samples. Since only one
inlet probe is involved, all data should be reported for the same POC.
First, report the raw data as you normally would via the RD transaction. Report just one value,
the one for the sample obtained through the 'primary" hardware (the normal flow path or normal
canister, etc. as defined by the monitoring organization convention - typically this would be
sample 'a'). In this case, if sample 'a' comes from the primary hardware and has a value of
54.956, you would report:
RD|I|11|222|3333|44444|5|7|454|888|20150101|00:00|54.956||6||||||||||||0.0001|0.0005
If the primary value is null for some reason, the duplicate value may be reported as the sample
value for this POC in the RD transaction. In this case, there is not a valid duplicate assessment
to report. If all duplicates are null, an RD transaction with no sample value and a null data code
should be reported.
Each of the duplicate sample values is then also reported via the QA - Duplicate transaction.
This transaction has room for up to 5 duplicate sample values. Report them in any order, starting
with 1 and proceeding through the number of samples. In the schematic, there are two samples
(a 'primary" and a 'duplicate") so sample value 'a" would be reported as Duplicate Value 1 and
sample value 'b" would be reported as Duplicate Value 2. The same value reported on the Raw
Data transaction must be one of the values reported on the Q A - Duplicate transaction.
Note that there is no sampling time reported on the QA - Duplicate transaction. Instead, there is
an Assessment Date and an Assessment Number. If multiple duplicate samples are performed on
the same day, label the first with Assessment Number = 1, the second with Assessment Number
= 2, and so on. Also note that all values must be reported in the same units of measure.
Here is an example QA - Duplicate transaction (with sample 'a" = 54.956 and sample 'b" =
51.443 - Assessment Number ' 1' bolded):
QA| I|Duplicate|999|11|222|3333|44444|5|20150101|11454|888|54.956|51. 443 | | | |
239

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NATTS TAD Revision 3
Appendix B
Replicate Analysis
A replicate assessment is a separate analysis or multiple separate analyses of one discrete sample
(VOCs) or prepared sample (a sample extract [carbonyls or PAHs] or digestate [PMio metals]) to
yield multiple measurements from the same sample.
Schematic
A replicate assessment is a separate analysis or multiple separate
analyses of one discrete sample (VOCs) or prepared sample (a sample
extract [carbonyls or PAHs] or digestate [PM10 metals]) to yield multiple
measurements from the same sample.
Monitor N
One sampling system, one sample, multiple analyses.
Replicate Sample Reporting Instructions
Again in this case, there is only one AQS monitor (POC) involved and one single sample,
however multiple analyses of the sample.
First, report the raw data as you normally would via an RD transaction. Report just one value,
according to your laboratory's convention for reporting replicate data (e.g. the first replicate). In
this case, if you have chosen replicate 'a' as your raw data value and it has a value of 0.844, you
would report:
RD|I|11|222|3333|44444|5|7|454|888|20150101|00:00|0.844| |6| | | | | | | | | | | |0 . 000110.0005
If the normally reported value is null for some reason, one of the other replicate values may be
reported as the sample value for this POC in the RD transaction. If only one of the replicate
values remains valid, there is not a valid replicate assessment to report. If all replicates are null,
an RD transaction with no sample value and a null data code should be reported.
Once the RD transaction is completed, if two or more replicates are valid, these are reported via
the QA - Replicate transaction. This transaction has room for up to 5 replicate sample values.
Report them in any order, starting with 1 and proceeding through the number of samples. In the
schematic above there are three replicates 'a', 'b', and 'c', thus analytical value 'a' would be
reported as Replicate Value 1, analytical value 'b' would be reported as Replicate Value 2, and
analytical value 'c' would be reported as Replicate Value 3.
Note that there is no sampling time reported on this transaction. Instead, there is an Assessment
Date and an Assessment Number. If multiple replicate samples are collected on the same day,
label the first with Assessment Number = 1 (indicated below in bold), the second with
Replicate Samples
240

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NATTS TAD Revision 3
Appendix B
Assessment Number = 2, and so on. Also note that all values must be reported in the same units
of measure
Here is a sample QA - Replicate transaction (if sample values 'a', "b\ and "c" are 0.844, 0.843,
and 0.792, respectively):
QA|I|Replicate|999|11|222|333|44444|5|2 0210101|1|454|888|0.844|0.843|0.7 92|||
Combining Duplicates and Replicate Analysis
It is possible to collect duplicate samples simultaneously and perform replicate analyses of these
duplicate samples. This is often referred to as a duplicate/replicate sample. In this case (see
schematic below), there are two duplicate samples, '1' and '2'. Duplicate Sample '1' has three
replicates: 'a', 'b', and 'c\ Duplicate Sample '2' has three replicates: 'd', and T.
Schematic
Duplicate / Replicate Samples

It is allowable {but not a requirement) to perform replicate analyses of
duplicate samples. In this case two duplicate samples are collected,
and each is "replicate" analyzed three times.
One sampling system, two samples, multiple analyses of each.
Duplicate/Replicate Reporting Instructions
This scenario requires the reporting of an RD transaction, a QA - Duplicate transaction, and a
QA - Replicate transaction to AQS.
For the RD transaction, follow the same rules to report the value from the primary (normal)
hardware (this would typically be sample '1', replicate 'a') and operations procedure path if
possible; follow the convention established by the laboratory. If the normal hardware path yields
sample 'la' you would report (in this case the value is represented by the "a" in the appropriate
place, with spaces for clarity):
RD|I|11|222 I 3333|44444|5|7|454|888|20150101|00:00| a | |6| I I I I I I I I I I I 0 . 000110.0005
For the QA - Duplicate transaction: select one of the replicate analyses each from the primary
and duplicate sample (using the convention established by the laboratory) and report those on the
QA — Duplicate transaction. If the values to be reported are 'la' and '2d', the record would look
like this (again, values are represented by 'a' and 'd', spaces added for clarity):
241

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NATTS TAD Revision 3
Appendix B
QAiI I Duplicate|999|11|222|333|44444|5|20210101!1|454|888 i a j d. MM
There are only two duplicate samples (one pair) in this case because only two paths were
assessed. (That is, you are not allowed to cross-multiply the replicate analyses to create
additional duplicate assessments [pairs].)
For the replicate transaction: report this as two assessments. Assessment Number 1 for the day
would include the values for replicates 'a', 'b', and 'c\ Assessment Number 2 for the day would
include values for replicates'd', 'e', and 'f.
The example transactions, using letters in place of the values:
QA|I|Replicate|999|11|222|333|44444|5|20210101|1|454|888| a ] b | c I J]
QA|I|Replicate|999|11|222|333|44444|5|20210101|2|454|888 I d I e | f | ! |
Combining Collocated Samples and Replicate Analysis
It is also possible to make replicate analyses of collocated samples. Theseis is are sometimes
referred to as collocated replicate samples.
Schematic
Collocated Replicate Samples
Primary
Monitor N
Collocated
Monitor C
	.
M

1
It is also possible to make replicate analyses of collocated samples.
Two completely separate sampling systems, two different samples analyzed multiple times.
Collocated Replicate Reporting Instructions
Since collocated monitors report all data independently, report these data for each monitor (e.g.,
under its own POC) according to the replicate reporting instructions.
242

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NATTS TAD Revision 3
Appendix C
APPENDIX C
EPA ROUNDING GUIDANCE
Provided by EPA Region IV
243

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NATTS TAD Revision 3
Appendix C
Rounding Policy for Evaluating NAAQS QA/QC Acceptance Criteria
The following outlines EPA's Rounding Policy for evaluating Quality Assurance / Quality
Control (QA/QC) acceptance criteria. This policy is being provided to air monitoring
organizations in order to ensure consistency across the country in the validation of monitoring
data that is used for demonstrating compliance with the National Ambient Air Quality Standards
(NAAQS).
EPA's interpretation of standard rounding conventions is that the resolution of the measurement
device or instrument determines the significant figures used for rounding. The acceptance
criteria promulgated in the appendices of 40 CFR Part 50, or otherwise established in EPA
guidance documents, are not physical measurements. As an example, the quality control (QC)
acceptance criterion of ±5% stated in the fine particulate matter regulations (40 CFR Part 50,
Appendix L, Section 7.4.3.1) is not a measurement and, as such, does not directly contribute to
either the significant figures or to rounding. However, the flow rate of the sampler - measured
either internally by the flow rate control system or externally with a flow rate audit standard - is
a measurement, and as such, will contribute to the significant figures and rounding. EPA's
position is that it is not acceptable to adjust or modify acceptance criteria through rounding or
other means.
Example using PM2.5 Sampler Design Flow Rate
40 CFR Part 50, Appendix L, Section 7.4.3.1 defines the 24-hour sample flow rate acceptance
criterion as ±5% of the design flow rate of the sampler (16.67 liters per minute, LPM). The QC
acceptance criterion of ±5% stated in regulation is not a measurement and, therefore, does not
contribute towards significant figures or rounding. The measurement in this example is the flow
rate of the sampler. PM2.5 samplers display flow rate measurements to the hundredths place
(resolution) - e.g., 16.67 LPM, which has 4 significant figures. Multiplying the design flow rate
(16.67 LPM) by the ±5% acceptance criterion defines the acceptable flow regime for the
sampler. By maintaining 4 significant figures - with values greater than 5 rounding up - the
computations provide the following results:
•	The low range is -5% of the design flow: 0.95 16.67= 15.8365 = 15.84
•	The upper range is +5% of the design flow: 1.05 16.67= 17.5035-17.50
Rounding in this manner, the lower and upper acceptance limits for the flow rate measurement
are defined as 15.84 and 17.50 LPM, respectively.
40 CFR Part 58, Appendix A, Section 3.2.1 requires monthly PM2.5 flow rate verifications. The
verification is completed with an independent audit standard (flow device). The monthly check
includes a calculation to ensure the flow rate falls within ±5% of the design flow rate (see
244

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NATTS TAD Revision 3
Appendix C
Method 2.12, Section 7.4.7). Therefore, flow rates obtained during monthly flow rate
verification checks should measure between 15.84 - 17.50 LPM, as defined above.
Measurements, in general, are approximate numbers and contain some degree of error at the
outset; therefore, care must be taken to avoid introducing additional error into the final results.
With regards to the PM2.5 sampler's design flow rate, it is not acceptable to round the ±5%
acceptance criterion such that any calculated percent difference up to ±5.4% is acceptable -
because rounding the acceptance criterion increases the error in the measurement. It is important
to note that the PM2.5 sampler must maintain a volumetric flow rate of approximately 16.67 LPM
in order for its inertial separators to appropriately fractionate the collected ambient air particles.
Flow rates greater than 5% of the nominal 16.67 LPM will shift the cut point of the inertial
separator lower than the required aerodynamic diameter of 2.5 microns and, thus, block the
larger fraction of the PM2.5 sample from being collected on the sample filter. Conversely, as the
sampler's flow rate drops below -5% of the nominal 16.67 LPM, the inertial separator will allow
particulate matter with aerodynamic diameters unacceptably larger than 2.5 microns to be passed
to the sample filter. Therefore, it is imperative that the flow rate of the sampler fall within the
±5% acceptance criterion.
A Note 011 Resolution and Rounding
Measurement devices will display their measurements to varying degrees of resolution. For
example, some flow rate devices may show measurements to tenths place resolution, whereas
others may show measurements to the hundredths place. The same holds true for thermometers,
barometers, and other instruments. With this in mind, rounding should be based on the
measurement having the least number of significant figures. For example, if a low-volume PM10
sampler displays flow rate measurements to the tenths place (3 significant figures), but is audited
with a flow device that displays measurements to the hundredths place (4 significant figures), the
rounding in this scenario will be kept to 3 significant figures.
Table 1 below lists some examples of N A AQS regulatory QA/QC acceptance criteria with
EPA's interpretation of the allowable acceptance ranges, as well as a column that identifies
results that exceed the stated acceptance limits. Table 1 is not a comprehensive list of ambient
air monitoring QA/QC acceptance criteria. Rather, Table 1 is provided to demonstrate how EPA
evaluates acceptance criteria with respect to measurement resolution.
The validation templates in the QA Handbook Vol II will be revised to meet this policy.
If you have any questions regarding this policy or the rounding conventions described, please
contact your EPA Regional Office for assistance.
245

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NATTS TAD Revision 3
Appendix C
Table 1: Examples of Quality Control Acceptance Criteria
Regulatory
Method
Requirement
Method
Acceptance
Criteria
Typical
Measurement
Resolution
Acceptance Range
(Passing Results)
Exceeding
QA/QC Check
Shelter
Temperature
20 to 30°C or
FEM op. range
1 Decimal, 3
SF*
20.0 to 30.0°C or
FEM op. range
< 19.9°C
> 30.rc
PM2.5 Design
Flow (16.67 Ipm)
±5%
2 Decimal, 4 SF
15.84 to 17.50 Ipm
< -5.1%
> +5.1%
PM2.5 Transfer
Standard
Tolerance
±4%
2 Decimal, 4 SF
-4% Audit
Std
Sampler
Display
+4% Audit
Std
< -4.1%
> +4.1%

15.84
16.47
16.00
16.67
17.34
16.80
17.50

PM2.5 Lab:
Mean Temp
24-hr Mean
20 to 23°C
1 Decimal, 3 SF
20.0 to 23.0°C
< 19.9°C
> 23.1°C
PM2.5 Lab:
Temp Control
SD over 24-hr
±2°C
1 Decimal, 3 SF
±2.0°C
<-2.rc
> +2.1°C
PM2.5 Lab:
Mean RH
24-hr Mean
30% to 40%
1 Decimal, 3 SF
30.0% to 40.0%
< 29.9%
>40.1%
PM2.5 Lab:
RH Control
SD over 24-hr
±5%
1 Decimal, 3 SF
±5.0%
< -5.1%
> +5.1%
PM2.5 Lab:
Difference
in 24-hr RH
Means
±5%
1 Decimal, 3 SF
±5.0%
< -5.1%
> +5.1%
*SF = Significant Figures
246

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APPENDIX E. Standard Operating Procedure
for Collection of YOC Samples (R5-ARD-0003-
r2)

-------
Page 1 of 16
Document No.: R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
^tDSX
f a
W/
*4 PRO"*
U.S. Environmental Protection Agency, Region 5
Field Quality Procedures
TECHNICAL FIELD
STANDARD OPERATING PROCEDURE
Standard Operating Procedure for collection of VOC samples
Effective Date
Number
9/29/2017
R5-ARD-0003-1-2
Author
Name: Scott Ilamilton
Title: Authc
Signature/
Date:
Hj2*1 If
Review & Approvals
Name: Jackie Nwia
Title: Reviewer
Signature:
Date
; f/W/
7
Name: Bilal Qazzaz
Title: Quality A^ujiance Coordinator
Signature: **).
Name: Michael Compher
Title: Air Monitoring and Analysis Section Chief
Date:
Signature:
A'.. Ll S.	
Date:
1/^/17
if** I »

-------

-------
Document No.: R5-ARD-Q003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 2 of 15
REVISION/CHANGE HISTORY
The table below identifies changes to this controlled document aid the respective effective
date(s) over time.
Revision
Number
History/Change Description
Document
Author/Owner
Management
Approver
Effective
Date
0
Original Document
Chad McEvoy
Michael
Compher
03-31-2015
1
Updated to include Canister
Sampling Field Test Data Sheet,
more specific instructions for
conducting the sample
collection, and other minor edits
Jacqueline
Nwia
Michael
Compher
05-03-2017
2
Added language on evidence
tampering and deleted option to
ship samples.
Scott Hamilton
Michael
Compher
9-29-2017
















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Document No.: R5-ARD 0003r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 3 Of 15
Document No.: R5-ARD 0003 r2
Title: VOC Sampling
Effective Date: 09/29/2017
TABLE OF CONTENTS
I.0	PURPOSE			4
2.0 APPPLIC ABILITY/SCOPE							4
3.0 DEFINITIONS..						4
4.0 SUMMARY OF METHOD/PROCEDURE		....4
5.0 PERSONNEL QUALIFICATIONS/RESPONSIBILITES	.5
6.0 EQUIPMENT AND SUPPLIES					5
7.0 REAGENTS AND STANDARDS			5
8.0 HEALTH AND SAFETY CONSIDERATIONS							6
9.0 INTERFERENCES..			6
10.0 PROCEDURE					6
II.0	WASTE MANAGEMENT						10
12.0 DATA AND RECORDS MANAGEMENT	10
13.0 QUALITY CONTROL & QUALITY ASSURANCE					11
14.0 REFERENCES							.11
15.0 ATTACHMENTS	11

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Document No R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 4 of 15
1.0 PURPOSE
1.1 This standard operating procedure describes steps for collecting air samples in the
field for later analysis at Region 5 Chicago Regional Laboratory (CRL). TMs SOP is
intended for use by field technicians so samples are collected consistently and
documented properly.
2.0 APPLICABILITY/SCOPE
2.1	TMs document, applies to the collection of air samples in the field. Field technicians
should follow this SOP to ensure samples are collected properly and consistently, and
that all documentation is completed.
2.2	The official signed copy of this SOP will be stored in the QA Tracking system under
the folder "VOC SOP" and will be available to all field sampling staff. The SOP
should be reviewed annually.
2.3	This document outlines obtaining the sampling vessels (i.e. bottles or canisters) from
CRL, collecting and documenting the sample in the field, completing the chain- of
custody, and returning the samples to CRL.
2.4	This SOP is written to provide general instruction for collecting samples; individual
projects will have specific needs and processes. Refer to. the project specific Quality
Assurance Project Plan (QAPP) or sampling plan for details.
3.0 DEFINITIONS
COC	Chain of Custody
CRL	Chicago Regional Laboratory
GMAP	Geospatial Monitoring of Air Pollutants
PID	Photo Ionization Detector
QAPP	Quality Assurance Project Plan
VOC	Volatile Organic Compounds
4 J SUMMARY OF METHOD/PROCEDURE
4.1 Field staff will use containers supplied by CRL to collect air samples by opening the

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Document No : R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 5 of 15
valve on the canister, allowing the sample to enter the canister or bottle and then closing
the valve. Samples may be grab samples or composite samples collected over a period of
time. Staff will document relevant information on the sample labels (supplied by CRL),
Canister Sampling Field Test Data Sheet (from Compendium Method TO-15) and chain
of custody form (supplied by CRL). Labelled samples, Field Test Data Sheet and the
chain of custody form(s) are then returned to CRL's sample custodian.. Results will be
reported by CRL at a future date.
5.0 PERSONNEL QUALIFICATION/RESPONSIBILITIES
5.1 Personnel involved in the collection of samples must meet the minimum training
requirements for safety and technical expertise. Minimum training will include a
background in air programs and hands on training with CRL or air monitoring
personnel. The field staff is also responsible for reviewing this SOP prior to
conducting sampling using passive canisters. Approved copies of this SOP and the
project-specific air monitoring Quality Assuran.ce Project Plan (QAPP) will, be
available to field staff throughout the duration of sampling activities.
6.0 EQUIPMENT AND SUPPLIES
6.1	Equipment used for the collection of VOC samples will vary depending on the
objective of the project and the compounds of interest. Metal canisters or glass
bottles could be used to hold the sample, and different volumes of containers are
available. Both factors are dictated by the compounds of interest, project goals, and
resource availability. Regulators/orifices (obtained from CRL and provided with the
vessels) may be attached to the vessels to restrict the flow, allowing for a longer
and/or specific sampling time.
6.2	Sample labels and chain of custody form will be supplied by CRL to document
sample information.
7.0 .REAGENTS AND STANDARDS
7.1	No reagents or standards are used during sample collection.
7.2	All reagents and standards used as part of the laboratory analysis can be found in
section 7 (Reagents & Standard Gas Mixtures) of the Central Regional Laboratory's
"SOP for VOCs in Air from TO-15" CRL SOP MS-005 Revision 6, Dated
06/04/2013.

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Document No.: R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 6 of IS
8.0 HEALTH AND SAFETY CONSIDERATIONS
8.1 Field staff must complete the minimum safety training as required by the US EPA.
Minimum safety trainings include the USEPA 24-hour field safety course and annual
8 hour refresher courses as required. Any necessary health and safety equipment
needs for specific projects must be made in coordination with the Regional Safety
Manager.
9.0 INTERFERENCES
9.1	The possibility of contamination of canister samples exists due to the improper
handling and wear of canister valves.
9.2	Special attention must be given to canisters with QT valves; QT valves are normally
in a closed position to minimize leakage, a protective cover should be placed over the
valve to minimize leakage and prevent contamination of the canister. Bottles with QT
valves should be evacuated using a dual stage pump in the field on the day of
sampling, or as close to the day of sampling as possible. The dual stage pump should
be capable of creating a strong vacuum within the bottle.
9.3	Additional possibilities of laboratory and storage contamination and preventative
procedures can be found in section 5 (Caution & Interferences) of the Central
Regional Laboratory's "SOP for VOCs in Air from TO-15" CRL SOP MS-005
Revision 6, Dated 06/04/2013.
10.0 PROCEDURE
10.1 Instrument or Method Calibration and Standardization
1.	No instrument or method calibrations are expected for sample collection.
2.	Steps should be taken to standardize sample collection as much as possible. Field
technicians should consider the following:
a)	Avoid wearing perfumes, lotions, or hand sanitizers prior to or during sample
collection.
b)	Record data (GPS values, time, etc) from the same source each time.
c)	If taking grab samples, hold away from the body.
d)	Note any nearby activity that may influence the sample on the sample label and in
field notes.

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Document No.: RS-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 7 of 15
e) An upwind or background sample may be helpful; refer to the project QAPP or
sampling plan.
f} Copy or photograph sample labels and the completed chain of custody form.
10.2	General field or equipment procedures
1.	Field staff must request VOC sample bottles or canisters from CRL's sample
coordinator (Amanda Wroblc) by completing "CRL Form 008 Rev 1.1-
November 2013". CRL chemists are available to discuss, and recommend,
possible lab analyses. The lab may need some time to ensure sufficient,
appropriate sample containers are available, and may need time to prepare the
analysis equipment. Field staff should also be familiar with the sample return
process in order to efficiently return the samples to the sample custodian (Rob
Snyder 312-353-9083). Information on shipping samples are available on
CRL Form 008 Rev 1.1- November 2013.
2.	Field personnel that collect potential evidence for enforcement purposes, must
follow established procedures or guidance to document and demonstrate
custody and integrity of the sample of the samples.
3.	Field samples and appropriate environmental data shall be maintained under
custody at all tim.es during field activities. Samples and data are in custody if
they are:
a.	Within the direct possession or the control (i.e. within the view) of an
individual designated to have sample handling responsibilities; or
b.	Placed in a designated area to prevent tampering; or
c.	Maintained in a manner that ensures the integrity of the samples is not
compromised when placed in an unsecured area.
10.3	Sample Collection
a. Grab sample Procedure:
1.	Choose canister and gather COC and canister sticker (if applicable).
2.	Record all information on the sample label provided by CRL and place the
label on the canister.
3.	Record all information on the COC as follows. If errors are made on the
form strike through with one line, initial and date the error. Then write the
correct information on the form, A sample COC form is in Appendix C. It
is acceptable to use two lines for one canister to record information if
needed. Be sure to draw a full line through the row in the areas where
additional space was not needed.
a.	PROJECT NAME = Project name should be a unique name for you to
identify this group of samples.
b.	SAMPLER NAME = Write the samplers name and signature.

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Document No.: R5-ARD-G003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 8 of 15
c.	ST A. NO. = Station Number. For the first canister write "1" for the
second canister write "2", etc.
d.	DATE = write the date.
e.	TIME = write the time the sample was taken. This should be filled out
last since it will take some time to complete all paperwork before the
sample is actually taken,
f.	COMP/GRAB _ "Composite or Grab Sample". Check the box under
Grab sample.
g.	STATION LOCATION - Write the GPS coordinates of where the
sample was taken.
h.	NO. OF CONTAINERS = "1"
4.	Remove the Ya inch cap from the inlet of the canister.
5.	Hold the canister out away from the sampler's body facing the direction
where the air is coming from and in the direction of the air you want to
sample. Hold the canister as far as possible with the inlet facing away
from you, above your head, if possible.
6.	Open the canister valve (righty-tighty, lefty loosey). The sampler should
hear a distinct hiss for 5-10 seconds. This sound is the sample canister
filling up with sample air.
7.	Leave the valve open until the hissing stops and then close the valve
tightly. Replace the % inch cap and tighten.
8.	Record the sample time on the COC.
9.	Place the canister back in the box and store it in a safe spot under lock and
key. Sample should be delivered to CRL as soon as possible. Ensure that
the sampler signs and dates the COC under ''"'relinquished by" and that the
sample custodian signs and dates the COC under "received by". The pink
copy should be given to the sampler.
10.	Additional notes may be helpful such as pressure, temperature, other
meteorological conditions and distinct odors.
b. Composite sample Procedure:
1.	Choose canister and gather COC, canister sticker (if applicable) and field
data form.
2.	Record all information on the sample label provided by CRL and place the
label on the canister.
3.	Record all information oil the COC as follows. If errors are made on the
form strike through with one line, initial and date the error. Then write the
correct information on the form. A sample COC form is in Appendix C. It
is acceptable to use two lines for one sample to record information if
needed. Be sure to draw a full line through the row in the areas where
additional space was not needed.

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Document No.: R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 9 of 15
a.	PROJECT NAME = Project name should be a unique name for you to
identify this group of samples.
b.	SAMPLER NAME ~ Write the samplers name and signature. Each
sampler must utilize their own COC.
c.	STA. NO. = Station Number. For the first canister write "1" for the
second canister write "2", etc.
d.	DATE - write die date.
c. TIME = write the time the sample begins.
f.	COMP/GRAB - "Composite or Grab Sample". Check the box under
Composite sample.
g.	STATION LOCATION = Write the GPS coordinates of where the
sample was taken.
h.	NO. OF CONTAINERS - "1"
4.	Remove the Vainch cap from the inlet of the canister.
5.	Install the sample Met assembly and tighten snugly with a 9/16" wrench.
6.	Place the canister in the desired sampling position.
7.	Record the following information on the Canister Sampling Field Test
Data Sheet (Appendix D). Note that not all information requested oil the
general TO -15 form is needed.
a.	Site Location
b.	Sampling Date
c.	Canister SN
d.	Operator
e.	Temperature Start Ambient
f.	Canister Pressure start
g.Local	Time start
h.Leave	all of Section C blank
8.	Open the canister valve (righty-tighty. lefty loosey).
9.	The canister is now filling. It is a good idea to return to the station in a
few hours to observe the pressure. It is imperative that the canister still be
under slight vacuum at the conclusion of the sampling time.
10.	At the conclusion of the sampling time close the valve tightly, remove the
sample inlet assemble and replace the lA inch cap and tighten.
11.	Record the following information on the Canister Sampling Field Test
Data Sheet (Appendix D). Note that not all information requested on the
general TO-15 form is needed.
a.	Temperature End Ambient
b.	Canister Pressure End
c.Local	Time Stop
d.Leave	all of Section C blank

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Page 10 of 15
Document No.: R5-ARD-QQ03-r2
Title; VOC Sampling
Effective Date: 09/29/2017
12.	Place the canister back in the box and store it in a safe spot under lock and
key. Sample should be delivered to CRL as soon as possible. Ensure that
the sampler signs and dates the COC under "relinquished by" and that the
sample custodian signs and dates the COC under "received by". The pink
copy should be given to the sampler.
13,	Additional notes may be helpful such as other meteorological conditions
and distinct odors.
10,4 Sample Handling and Preservation
1.	Samples should be handled gently and packed to prevent breakage. Ensure all
information has been recorded on sample labels.
2.	Immediately transport samples back to CRL's sample custodian with completed
Canister Sampling Field Test Data Sheet and COC.
10.5	Sample Preparation and Analysis
Samples will not be prepared or analyzed in the field. Samples will be prepared
and analyzed by CRL following their procedures in the laboratory.
10.6	Troubleshooting
1.	Field technicians should inspect sample vessels before collecting a sample to be
sure the vessel hasn't been compromised prior to use. Do not use any vessel
suspected of having a leak prior to sample collection.
2.	Technicians may hear a hiss or pop as air rushes into a vessel (especially for a
grab sample). No sound may indicate the vessel leaked prior to use.
3.	Record all information onto the sample label at the time of collection.
10.7	Data Acquisition, Calculations, and Data Reduction
N/A
10.8	Data Review and Acceptance
Ensure all fields on the sample label(s). Canister Sampling Field Test Data Sheet
and chain of custody form(s) have been completed.
11.0 WASTE MANAGEMENT
N/A
12.0 DATA AND RECORDS MANAGEMENT
12.1 All COC forms and other field notes will be submitted to the project manager and

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Document No.: R5 ARD 0003 r2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 11 of 15
13.0
14.0
15.0
will be stored with other data associated with the project (i.e. GMAP data). The CRI,
will complete analysis of the canisters or bottles as soon as possible after sampling. CRL
will submit validated data to the project manager.
QUALITY CONTROL & QUALITY ASSURANCE
The field staff must note any deviations from the sample plan or procedure on the sample
label and field notes. Also note anything unusual or unexpected that may influence the
sample results (i.e. markers, vehicle fuels, newly paved roads, nearby non-target
activities, etc.).
REFERENCES
SOP for VOCs in Air from TO-15 CRL SOP MS-005 Revision 6, Dated 06/04/2013
ATTACHMENTS
APPENDIX A
CRL Form 008 Rev 3- March 2017
APPENDIX B
CRL Sample Label
APPENDIX C
CRL Chain of Custody
APPENDIX D
COMPENDIUM METHOD TO-15 CANISTER
SAMPLING FIELD TEST DATA SHEET

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Document No.: R5-ARD-0003-/2
Title: VOC Sampling
Effective Date: 09/29/2017
Page 12 of 15
APPENDIX A
CRL Form 008 Rev 3- March 2017

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, ' ' . U.S. ENVIRONMENTAL PROTECTION AGENCY-REGION 5
| Q CHICAGO REGIONAL LABORATORY
\*	ANALYTICAL REQUEST FORM
Ht
This analytical request form should be completed before sending samples to CRL for analysis. The requester should
complete all relevant fields and email the form and electronic copy of the quality assurance project plan (QAPP)
and/or sampling plan to the CRL Sample Coordinator Rob Thompson (Thompson.robert(a>epa.gov).
GENERAL PROJECT INFORMATION
Requester:

Request Date:

Title:

Division/Office
:
Address:

Phone:

E-mail:

1 I One-time or Q Continuous request (check one)
A continuous request is defined as a standing request for the same analytical service (analyses and sample matrices)
that may span several sites/projects/sampling events. Please note that submission of this analytical request form is
only required once for a continuous request. However, QAPPs and/or sampling plans should still be submitted for
every site/project.
Site Name and Location:

Expected Arrival Date at CRL:

Turnaround Time Requested (standard TAT is 45 days):

CRL ANALYTICAL SERVICES
Disclaimer:
The effective versions of all Standard Operating Procedures (SOPs) are available in pdf format on the R5 Intranet. By
submitting an analytical request form, the requestor is implying consent for the use of the appropriate effective
SOPs. It is the responsibility of the requester to check the intranet for SOP deviations (known at CRL as Pen&lnk
changes) and version updates. Should the CRL suspect that an SOP deviation affect the data, the CRL Sample
Coordinator will contact the requester via email or phone to obtain a Pen&lnk consent. As defined by CRL, SOP
deviations "affect the data" when there is a change in the laboratory's ability to identify or quantify the analytes in
the SOP or when there is a deviation in the regulatory method.
Form Instructions:
1.	In the table below, select the appropriate checkbox to request an analysis and enter the proposed number
of samples of each matrix type. An analysis is not currently available for a matrix where the box is shaded.
2.	For other/waste, briefly describe the matrix in the space provided. Additional space for a detailed matrix
description is available at the end of the table, if needed.
3.	For multi-analyte tests, list specific classes/subsets (e.g., PAHs, RCRA metals, etc.) in the space given at the
end of this table, if requested.
Page 1 of 4
CRL Form 008 Rev 3—March 2017

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General Chemistry
Analysis Request
Sample Matrix and Number
Analysis
L
Check to Request
soil/sediment
water/liquid
other/waste*
acidity
1 ....



! |
C $'
j i
iii
, i'"
4 ,
j. •"
:
! *'


alkalinity





ammonia-N






anions**






biochemical oxygen demand-S day (BOD)





t.
I 11
¦, ii



carbonaceous BOD-5 day (CBOD)



i' 'i
! ')
!', -li
. . . . i'i:


corrosivity by pH





cyanide, amenable to chlorination





cyanide, total






dissolved organic carbon (DOC)



¦•1
,1 I



fluoride






grain size




!n m .

ignitability by flashpoint



i ' ' ! ];
»ii 1 :i, j;
ii
v •!
,f..;!
.* * j


nitrate-nitrite-N



-I'll!!
, j!
'*! :


paint filter liquid test



,
!!
J -if


pH






residue, filterable (TDS)



'.! i
¦'
j|{!


residue, non-filterable (TSS)





solvent ID



iri


total Kjeldahl nitrogen (TKN)






total organic carbon (TOC)






total phosphorus (TP)






total dissolved phosphorus (TDP)



i: i
i '!•'
' lii
. .1 : .
|:'i11
ii
i: i
•! i s
1;¦"
if:.:
|
.''11
		

total solids (TS)
~
!! i|l
i< l.li


total volatile solids (TVS)



1
1.1
¦' .ii


turbidity



1 i;
||!!!
I-


water content



i' 1 iv-
If
¦"iiiils:


Page 2 of 4
CRL Form 008 Rev 3—March 2017

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Metals
Analysis Request
Sample Matrix and Number
Analysis
Check to Request
soil/sediment
water/liquid
other/waste*
chromium (VI)






dissolved metals** (except Hg & Cr (VI))






hardness






mercury (Hg)






total metals** (except Hg & Cr (VI))





wipe/filter
Organics
Analysis Request
Sample Matrix and Number
Analysis
Check to Request
soil/sediment
water/liquid
other/waste*
air toxics**
~


air
1,4-dioxane, low level






oil & grease






polychlorinated biphenyls (PCB) congeners






perfluorinated compounds** (PFCs)






pesticides, chlorinated**






PCB aroclors**






semi-volatiles** (SVOCs)






total petroleum hydrocarbons
(TPH as DRO/ORO)

~




(tri-n-butyl)-n-tetradecylphosphonium
chloride (UPC)

c




volatiles** (VOCs)

L




Toxicity Characteristic Leaching Procedure (TCLP)
Analysis Request
Sample Matrix and Number
Analysis
Check to Request
soil/sediment
water/liquid
other/waste*
' TCLP Hg

~




TCLP metals

~




TCLP pesticides






TCLP SVOCs






TCLP VOCs






Page 3 of 4
CRL Form 008 Rev 3—March 2017

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^Additional Matrix Description
- - - 	— —			 -- 	. 	:			
Please describe other/waste matrix, if not specified above:
**Specific Analyte Class/Subset Request
Please list or attach specific class/subset for multi-analyte test, if requested:
NON-STANDARD REQUESTS
For analyses/matrices not listed above or to obtain analyte lists, quality control limits, and/or reporting limits, please contact
the CRL Sample Coordinator to discuss. (Thompson.robert@epa.gov, 312-353-9078)
CRL DATA FORMAT
The CRL standard data deliverable includes: 1) a pdf of the work order 2) a pdf of the final Level II report and 3) an electronic
data deliverable (EDD) that includes batch quality control sample data. EDD typically refers to an Excel spreadsheet of the data,
but EDDs are available in a variety of formats and can be customized upon request. A full data package (Level IV) is also
available upon request and will be transmitted electronically via the CRLSharePoint. Contact Sylvia Griffin, CRL Data
Coordinator, for additional details. (Griffin.svlvia(5>epa.gov. 312-353-9073)
CRL SAMPLE DISPOSAL POLICY
Due to space limitations in a controlled temperature environment, samples are relocated to secure room temperature storage
six months after the analysis completion of the project. Notification of the intent to relocate the samples is given to the
customer with sufficient time for the customer to respond with any objections. Samples remain in secure room temperature
storage until the case/project is completed and the samples are no longer needed. Notification is given to the customer with
sufficient time for customer response prior to sample disposal.
CRL SAMPLE SHIPMENT REQUIREMENTS
Before collecting samples, please refer to the attached table for sample sizes, containers, and preservatives. Notify the CRL
Sample Custodian (312.353.9083, Snyder.robert(5>epa.gov) and the CRL Sample Coordinator (312.353.9078,
Thompson.robert(5)epa.gov) before shipping any samples and to arrange for sample receipt.
When packing samples for shipment:
¦S Seal individual samples in plastic bags, preferably Ziploc bags.
S The temperature of samples requiring refrigeration during transport MUST be maintained at or below 6°C.
Ice in a sealed plastic bag or reusable ice substitute freeze packs are acceptable cooling media.
S Chain of custody forms MUST be sealed in a large Ziploc bag and taped to the inside of the cooler lid.
S Include the address to which the cooler should be returned.
After items are packed for shipment, secure the cooler with tape and attach a custody seal across the seam of the cooler lid.
All samples MUST be shipped overnight to arrive Monday thru Friday or hand-delivered. No deliveries are accepted on weekends
or Federal holidays. Exceptions may be made on a case by case basis depending on sampling priority/emergency status.
Send all samples to:
Robert Snyder
US EPA Region 5
Chicago Regional Laboratory
536 S. Clark Street, 10th Floor
Chicago, IL 60605
Page 4 of 4
CRL Form 008 Rev 3-March 2017

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U.S. EPA CHICAGO REGIONAL LABORATORY
	 HOLDING TIME AND CONTAINER REQUIREMENTS FOR WATER / AQUEOUS SAMPLES	
DISCLAIMER: This table represents The Chicago Regional Laboratory's (CRL) recommended guidelines. Additional containers may be required for laboratory quality control samples (see
notes section). There are non-routine analytes (reported upon request) that may require modification to the specifications detailed in this table. It is the client's responsibility to confirm
container, preservation, and holding time requirements for a project prior to initiating sampling. This includes any equipment procurements, if applicable. No brand endorsements are
made or implied.
General Chemistry
CRL SOP(s)
Reference Method
Holding Time (days)
Min. Volume (mLs)'
Container'

Preservation
Acidity
AIG004A
SM Z310
14
50
500 mL Poly

<6 C
Alkalinity
AIG005
SM 2320 B
14
50
500 mL Poly

<6 C
Ammonia (Nitrogen, NH3) Distilled
AIG029B
SM 4500-NH3 B/H
28
50
500 mL Poly

pH<2, H2S04, <6 C
Anions (Br, CI, F, NOa, NO;, P04*, S04)
AIG045A
EPA 300.0
2b or 28
10
250 mL Poly

<6C
Biochemical Oxygen Demand (BOD) 5-day
AIG006, A
SM 5210 B
2
60
1 L Poly

<6 C
BOD, Carbonaceous (cBOD)
AIG006, A
SM 5210 B
2
60
1L Poly

<6 C
Corrosivity
AIG003
EPA 9040C
365
20
250 mL Amber

<6 C
Cyanide, Amenable
AIG025A
SM 4500 CN' G
14
50
500 mL Poly

dechlorinatec
NaOH, pH>l0, <6 C
Cyanide, Total
AI6025C
EPA 335.4
14
50
500 mL Poly

dechlorinate0
NaOH, pH>10, <6C
Ignltabllity (Flashpoint)
AIG048A, B
EPA 1010A, 1020B
365
100
250 mL Clear
<6 C
Nitrogen, Nitrate+Nitrite
AIG031B
ASTM D7781-14
28
10
500 mL Poly

pH<2, HjSO*, <6 C
Nitrogen, Total Kjeldahl (TKN)
AIG035B
EPA 351.2
28
10
500 mL Poly

pH<2, H2S04, <6 C
Organic Carbon, Dissolved (DOC)
AIG021D
EPA 5310B
28
20
500 mL Poly

field filteredd
pH<2, H2504, <6 C
Organic Carbon, Total (TOC)
AIG021D
EPA 5310B
28
20
500 mL Poly

pH<2, H2SOfl, <6 C
Paint Filter Liquid Test
AIG010
EPA 9095B
30
100
250 mL Amber

<6 C
pH
AIG0Q2
SM 4500-H* B
15 min
50
250 mL Poly

TCLP ext. (In days): 14for organics, 28for Hg, 180for metals
c Dechlorinate with ascorbic acid	J Contact CRL for additional details and/or options
d Field filtering should use a 0.45 pm filter	' Applicable to method 608 only
* All containers must be filled completely and maintained on ice at < 6 C	Per sample. Does not include amount needed for QC samples or excess
f 40 day holding time post extraction	needed for dilutions/reanalysis
8 28 day holding time post extraction	m Extra containers needed for MS/MSD location. Frequency = 1/20 field samples
page 1 of 2
CRL Sample Requirements Table
Version 3
July 2017

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1# /

U.S. EPA CHICAGO REGIONAL LABORATORY


HOLDING TIME AND CONTAINER REQUIREMENTS FOR SOIL / SOLID SAMPLES

DISCLAIMER: This table represents The Chicago Regional Laboratory's (CRL) recommended guidelines. Additional containers may be required for laboratory quality
control samples (see nates section). There are non-routine analytes (reported upon request) that may require modification to the specifications detailed in this table. It
is the client's responsibility to confirm container, preservation, and holding time requirements for a project prior to initiating sampling. This includes any equipment
procurements, if applicable. No brand endorsements are made or implied.




General Chemistry
CRLSOP(s)
Reference Method
Holding Time (days)
Min. Mass (g)1
Contained
Preservation11
Ammonia (Nitrogen, NH3)
AIG029B, 22A
SM 4500-NH3 B/H
28
1
4 oz. jar
<6 C
Anions (Br, CI, F, N03, NOa, P04, S04)
AIG039, 45A
EPA 300.0
2a,b or 28b
10
4 oz. jar
<6 C
Chemical Oxygen Demand (COD)
AIG007A, 22A
410.4
28"
10
4 02. jar
<6 C
Cyanide, Total
AIG025B, C
EPA 335.4
14
1
4 oz. jar
<6 C
Nitrogen, Total Kjeldahl (TKN)
AIG022A, 35B
EPA 351.2
28h
1
4 02. jar
<5 C
Organic Carbon, Total (TOC)
AIG009A
ASA-SSSA
28b
1
4 oz. jar
<6 C
Particle Size
AIG038, 38A
ASTM D2487-93
365
100
16 oz. jar
<6 C
PH
AIG008
EPA 9045D
365
20
4 oz. jar
<6 C
Phosphorus, Total (TP)
AIG022A, 34B
EPA 365.4
28b
1
4 oz. jar
<6 C
% Solids
AIG019
SM 2540 G
7
10
4 oz, jar
<6 C
Metals
CRLSOP(s)
Reference Method
Holding Time [days)
Min. Mass (g)1
Container
Preservation
Chromium (VI)
AIG033A
EPA 7199/3060A
30
2.5
4 02. jar
<6 C
Mercury (Hg)
AIG043C,D,E
EPA 245.5/747IB
EPA 7473
28
1
4 oz. jar
<6 C
Metals, Total
MetalsOOl,
003A, 004
EPA 200.7/200.8
EPA 6010C,D/6020B
180
100
4 oz. jar
<6 C
Organics
CRL SOP(s)
Reference Method
Holding Time (days)
Min. Mass (g)'
Container
Preservation
Pesticides, Chlorinated
GC001
EPA 8081B
14m
10
8 oz. jar
<6 C
Polychlorinated Biphenyls (PCBs)
GC002, 003
EPA 8082A
365m
10
8 oz. jar
<6 C
PCB Congeners
MS034
NA
365
30
8 oz. jar
<6 C





50 mL

Perfluorinated Compounds (PFCs)
OM013
NA
28
2
Polypropylene
Tubek
<6 C
Petroleum Hydrocarbons (TPH as DRO/ORO)
GC034
EPA 8015C
14m
30
8 oz. jar
<6 C
Poiycydic Aromatic Hydrocarbons, Alkylated
MS026
NA
14m
30
8 oz.'jar
<6 C
Semi-Volatile Organic Compounds (SVOCs)
MS026
EPA 8270D
14m
30
8 02. jar
<6 C
Tetradecylphosphonium chloride (TTPC)
OM017
NA
NA
2
4 02. jar
<6 C





3 Encores™0 or

Volatile Organic Compounds (VOCs)
MS001
EPA 8260C
2
5
3 VOA vials
w/ stir bar8^"1
<6 C
Waste Characterization
CRLSOP(s)
Reference Method
Holding Time (days)
Min. Mass (g)1
Container
Preservation
Toxicity Characteristic Leaching Procedure (TCLPf
GEN019
EPA 1311
Variesh
Varies1
16 oz. jar
<6 C
HOLDING TIME AND CONTAINER REQUIREMENTS FOR FILTERS / WIPE SAMPLES
Organics
CRL SOP(s)
Reference Method
Holding Time (d ays)
Num. of Wipes
Container
Preservation
Polychlorinated Biphenyls (PCBs)
GC0Q2, 003
EPA 8082A
365m
1 wipe w/hexane
4 oz. jar
<6 C
Semi-Volatile Organic Compounds (SVOCs)
MS026
EPA 8270D
14m
1 wipe w/
isopropanol
4oz.jar
<6C
HOLDING T ME AND CONTAINER REQUIREMENTS FOR AIR / VAPOR SAMPLES
Volatile*
CRL SOP(s)
Reference Method
Holding Time (days)
Pressure
Vessel
Preservation
Air Toxics
MS005
TO-15
30
approx. -7"Hg
2.7 LSumma'
Ambient
Notes:
' Nitrite, nitrate, and ortho-phosphate have a 48 hour holding time
b Holding time after extraction
c All jars should be wide mouthed and have a Teflon lid
d All containers must be filled completely and maintained on ice at<6C
e If no additional organics are requested, a 4 oz. jar must be submitted for % solids. For
MS/MSD locations, 3 extra encores/VOA vials are need. Frequency = 1/20 field samples
Dispensed in preweighed 40 rnL VOA vials with stir bar.
Preferred over Encore™ or similar. Mo brands are endorsed bv CRL.
s Can be requested for metals, Hg, Pesticides, SVOCs and VOCs
h Field collection->TCLP ext. (in days): 14 for organics, 28 for Hg, 180 for metals
1 Contact CRL for additional details and/or options
J Collected w/aS gram coring device (e.g. Terracore™ or similar)
k Must be preweighed
1 Per sample. Does not include amount needed for QC samples or excess needed
for dilutions/reanalysis
ra40 day holding time post extraction
CRL Sample Requirements Table
Version 3
page 2 of 2	July 2017

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Document No.: R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
APPENDIX B	CRL Sample Label
1, Completed CRL Sample Label - Example
K< ,
Start Time |^| £- ^
End Time |t| j
Site Name
Sampler

:t3ftOate <\ >. H
cjrt Pressure pJA-
re
on/Speed pT]}
Aind Direct)
A\f
N
" S7' ll" Vv/

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Page 14 of 15
Document No.: R5-ARD-0003-r2
Title: VOC Sampling
Effective Date: 09/29/2017
APPENDIX C
CRL Chain of Custody
1. Completed CRL Chain of Custody Form - Example
A U & GOsfEHMWfcHT
>» :r"l
¦iAj 0 IIP ("¦¦ , )
CC 1-1 [V. I
4M i}'lS"4>'i?.
5 fitt >'<

H1M V?Z.S°I ,-8! « iH HH i.
Oil I 3 DW
£*/ <3(098 DW

>M -\ O
MM ¦n«53HS
W oHoo 0^'-m
fS?f, X
Sr1 CC
^	-?7 V^O^bC-;
Ship fa"
Received by:
n/l'fiqj shed by: (SfgrwfureJ
7JL/1 '511
Received by: iS/crawe,)
D/Jlo Time
quisnfrd by' (Signature)
ATTN:
Date.' Time
Airbill Number
Dale > Time
Received for Laboratory by
(Signature}
Helinqu.shed by • Signature/
Chair of Custody Seal Numbers
5f.^no-.l: P riK Coordinator F&d File>:"Yeaow -1 at»r?.50--y File
;{|»0>a'<.n vVfite Ax
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Page 15 of 15
Document No.: R5~ARD-G0Q3-r2
Title: VOC Sampling
Effective Date: 09/29/2017
APPENDIX D COMPENDIUM METHOD TO-15 CANISTER SAMPLING FIELD TEST DATA
SHEET
jrocs
Method TO-IS
COMPENDIUM METHOD TO-15
CANISTER SAMPLING FIELD TEST DATA SHEET
A .CEHERAi DiFORmTIOH
SITEIDCAHOH: .
SITE .REDRESS: _
SAMPLING DATE:
SfflPPIHS DATE:	
CANISTER SERIA1 HO.: .
SAMPLER©: 	
OPERATOR:
CAMSTERUEAK
CHECK PATE:.
B. SAMFLIKC MFURMAIION
HMEERATIISE

ffiTEPJOR
AMBIENT
MAMAUM
imwm&
START




STOP




PRESSURE
C AHIS TER P RE SSURE




SAMPLING TIMES
FLOW MIES

LOCAL HME
ELAPSED miSE
MEIER READ IN#

MANIFOLD
FLOW RATE
CANISTO.
FLOW RATE
now
CONTROLLER
READOUT
START






STOP






SAMPLKO SYSTEM CERTDI CATION DATE: ,
QTXARECELYEECKEIIFICATIOWDAIE: _
C, LAB ORATORY INFORMATION
DATA RECEIVED: 	
HE CHIVED 3¥:	
ffitTIAL ERESSUKE:	
ICTJU. H3ESSTOE:	
DH.tr nt)H FACTOR:	
AHALYSIS
CfC-JIB-ECD DATE:	
&C-MSD-SCAH DATE:
OC-MSD SIUDATE: _
BEStTLTS*: 	
IS 0IXT' -ECD:	
SC.USD- SCAH:
C'CMSD-SIU: _
SIGNATURE TITLE
Figurs 9. Canister sampling field test data sheet (FIDS),
January J 991
Comprndiian of Methods for Toxic Organic Mr Polluisnis
Page 15-55

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