NATIONAL AIR TOXICS TRENDS STATIONS
QUALITY ASSURANCE ANNUAL REPORT
CALENDAR YEARS 2011 AND 2012
FINAL
December 12,2014
Environmental Protection Agency
Office of Air Quality, Planning and Standards
Air Quality Analysis Division
109 TW Alexander Drive
Research Triangle Park, NC 27711
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FORWARD
This technical report was prepared by Battelle under Contract No. GS-10F-0275K, Task Order
EP-G11D-00028. This report describes the Quality Assurance (QA) data collected for the
NATTS program during calendar years (CYs) 2011 and 2012. The report was prepared for
Margaret Dougherty, Task Order Project Officer, and David Shelow, Alternate Task Order
Project Officer at the Office of Air Quality Planning and Standards (OAQPS) in Research
Triangle Park, North Carolina.
Please note that this report contains a change to the analysis that differs from previous quality
assurance annual reports. The change pertains to the analysis of the precision data. In the
previous report for 2010, all precision data records that reported a value, whether below, equal
to, or above the method detection limit (MDL), were included in the precision calculations as
described in Section 2.5. In this report, data are utilized for the precision calculations for each
site and HAP only where both results in the replicate pair are equal to or above the reported
MDL.
This report was revised to correct the MDL measurement quality objective (MQO) for
naphthalene. The naphthalene MDL MQO was reported to be 0.029 ng/m3 in the April 17, 2014
version of report, which was in error. The correct value is 29.0 ng/m3. Applicable sections of
this report have been changed to reflect the correct MDL.
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NATIONAL AIR TOXICS TRENDS STATIONS
QUALITY ASSURANCE ANNUAL REPORT
CALENDAR YEARS 2011 AND 2012
Prepared by
Douglas J. Turner
Laura L.S. Aume
Robert T. Woodruff
Robert A. Lordo
Ian C. MacGregor
Battelle
For:
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Air Quality Analysis Division
109 TW Alexander Drive
Research Triangle Park, NC 27711
Under:
U.S. EPA Contract GS-10F-0275K
Task Order EP-G11D-00028
Battelle Contract CON00010461
Task B, Option Period III
Project # 100005824
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ACKNOWLEDGEMENTS
This report was prepared by Battelle, under Task Order EP-G11D-00028, Contract GS-10F-
0275K.
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TABLE OF CONTENTS
Section Page
1.0 INTRODUCTION 1
2.0 NATTS QUALITY ASSURANCE DATA FOR CY2011 AND CY2012 3
2.1 The NATTS Network Sites in CY2011 and CY2012 3
2.2 HAPs Measured in the NATTS Network in CY2011 and CY2012 4
2.3 Measurement Quality Objectives 5
2.4 Completeness of NATTS Data 7
2.5 Precision of NATTS Data 14
2.5.1 Analytical Precision Results 20
2.5.2 Overall Precision Results 26
2.6 Laboratory Bias Data Based on Proficiency Testing (PT) Samples 46
2.7 Flow Audit Results from Instrument Performance Audits (IPAs) 58
2.8 Method Detection Limit (MDL) Data 67
3.0 SUMMARY 86
4.0 RECOMMENDATIONS 89
5.0 REFERENCES 90
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LIST OF TABLES
Table Page
Table 1. EPA Regions, NATTS Sites, Site Type, and Air Quality Systems Site Codes 4
Table 2. The 27 NATTS Hazardous Air Pollutants and Air Quality Systems Parameter
Codes 5
Table 3. Measurement Quality Objectives for the Seven HAPs of Primary Importance
to the NATTS Program 6
Table 4. Data Sources Used to Evaluate the NATTS Data Quality Indicators 7
Table 5. Percentage Completeness Values by NATTS Site and the Seven HAPs of
Primary Importance for CY2011 9
Table 6. Percentage Completeness Values by NATTS Site and the Seven HAPs of
Primary Importance for CY2012 10
Table 7. Percentage of NATTS Sites Meeting the Completeness MQO for the Seven
HAPs of Primary Importance for CY2011 and CY2012 11
Table 8. Parameter Occurrence Codes by NATTS Site and HAP Type - CY2011 16
Table 9. Parameter Occurrence Codes by NATTS Site and HAP Type - CY2012 17
Table 10. Laboratories Performing Analyses by HAP Type for Each NATTS Site in
CY2011 and CY2012 19
Table 11. Laboratory Abbreviations and Descriptions for NATTS Laboratories 20
Table 12. Analytical Precision for Replicate Analyses > MDL - CY2011 22
Table 13. Analytical Precision for Replicate Analyses > MDL - CY2012 24
Table 14. Percentage of NATTS Sites Meeting the MQO for Overall Precision -
CY2011 and CY2012 27
Table 15. Overall Precision for Primary, Duplicate, and Collocated Samples > MDL -
CY2011 28
Table 16. Overall Precision for Primary, Duplicate, and Collocated Samples > MDL -
CY2012 30
Table 17. Percentage of NATTS Laboratories Participating in the NATTS Proficiency
Testing Program in CY2011 and CY2012 46
Table 18. Additional HAPs Contained in NATTS Proficiency Test Samples in
CY2011 and/or CY2012 47
Table 19. Non-NATTS Laboratories Analyzing Proficiency Test Samples in CY2011
and CY2012 48
Table 20. Percentages of NATTS Laboratories Meeting the Bias MQO for Proficiency
Test Samples in CY2011 and CY2012 49
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Table 21. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for VOCs - CY2011 QTR4 50
Table 22. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for Carbonyls - CY2011 QTR4 51
Table 23. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for Metals - CY2011 QTR2 52
Table 24. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for PAHs - CY2011 QTR2 53
Table 25. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for Metals - CY2012 QTR1 54
Table 26. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for PAHs - CY2012 QTR1 55
Table 27. NATTS Proficiency Testing Bias Results (Percent Difference from Target)
for Chromium (VI) - CY2012 QTR1 56
Table 28. Mean Network Flow Bias From CY2011 and CY2012 59
Table 29. Flow Audit Results from the Instrument Performance Audits - CY2011 60
Table 30. Flow Audit Results from the Instrument Performance Audits - CY2012 62
Table 31. Percentage of Audited NATTS Sites Meeting the Flow Bias MQO - CY2011
and CY2012 64
Table 32. Percentage of Sites Meeting the MDL MQO - CY2011 and CY2012 68
Table 33. Average Method Detection Limits (MDLs) by Site and Overall for VOCs
(l^g/m3) and PAHs (ng/m3) - CY2011 69
Table 34. Average Method Detection Limits (MDLs) by Site and Overall for carbonyls
(^ig/m3), metals (ng/m3), and chromium (VI) (ng/m3) - CY2011 71
Table 35. Average Method Detection Limits (MDLs) by Site and Overall for VOCs
(l^g/m3) and PAHs (ng/m3) - CY2012 72
Table 36. Average Method Detection Limits (MDLs) by Site and Overall for carbonyls
(^ig/m3), metals (ng/m3), and chromium (VI) (ng/m3) - CY2012 74
Table 37. Summary Statistics for Method Detection Limits across All Reporting
NATTS Laboratories - CY2011 75
Table 38. Summary Statistics for Method Detection Limits across All Reporting
NATTS Laboratories - CY2012 75
Table 39. Summary of NATTS Quality Assurance Results - Percentage of Sites
Meeting Measurement Quality Objectives in CY2011 and CY2012 86
Table 40. Median Completeness for the Seven HAPs of Primary Importance for
CY2011 and CY2012 86
Table 41. Ratio of the MDL Network Geometric Mean to the MQO for the Seven
HAPs of Primary Importance for CY2011 and CY2012 88
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,12
.13
.32
.33
.34
.35
.36
.37
.38
.39
.40
.41
.42
.43
.44
.45
.57
.58
.65
.66
.76
LIST OF FIGURES
Box and Whisker Plot of Percentage Complete Values for the Seven HAPs
of Primary Importance, for CY2011
Box and Whisker Plot of Percentage Complete Values for the Seven HAPs
of Primary Importance, for CY2012
Analytical and Overall Precision Summary for Acrolein > MDL at NATTS
Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for Benzene > MDL at NATTS
Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for 1,3-Butadiene > MDL at
NATTS Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for Formaldehyde > MDL at
NATTS Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for Naphthalene > MDL at
NATTS Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for PMio Arsenic > MDL at
NATTS Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for Chromium (VI) > MDL at
NATTS Sample Collection Sites in CY2011
Analytical and Overall Precision Summary for Acrolein > MDL at NATTS
Sample Collection Sites in CY2012
Analytical and Overall Precision Summary for Benzene > MDL at NATTS
Sample Collection Sites in CY2012
Analytical and Overall Precision Summary for 1,3-Butadiene > MDL at
NATTS Sample Collection Sites in CY2012
Analytical and Overall Precision Summary for Formaldehyde > MDL at
NATTS Sample Collection Sites in CY2012
Analytical and Overall Precision Summary for Naphthalene > MDL at
NATTS Sample Collection Sites in CY2012
Analytical and Overall Precision Summary for PMio Arsenic > MDL at
NATTS Sample Collection Sites in CY2012
Analytical and Overall Precision Summary for Chromium (VI) > MDL at
NATTS Sample Collection Sites in CY2012
Distribution of Laboratory Bias by HAP for Proficiency Testing Data -
CY2011
Distribution of Laboratory Bias by HAP for Proficiency Testing Data -
CY2012
Summary of Instrument Performance Flow Audit Results for NATTS Sites
CY2011
Summary of Instrument Performance Flow Audit Results for NATTS Sites
CY2012
Distribution of VOCs Average Method Detection Limits for NATTS Data -
CY2011
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Figure 22. Distribution of VOCs Average Method Detection Limits for NATTS Data -
CY2012 77
Figure 23. Distribution of Carbonyls Average Method Detection Limits - CY2011 78
Figure 24. Distribution of Carbonyls Average Method Detection Limits - CY2012 79
Figure 25. Distribution of PAHs Average Method Detection Limits - CY2011 80
Figure 26. Distribution of PAHs Average Method Detection Limits - CY2012 81
Figure 27. Distribution of Metals Average Method Detection Limits - CY2011 82
Figure 28. Distribution of Metals Average Method Detection Limits - CY2012 83
Figure 29. Distribution of Chromium (VI) Average Method Detection Limits - CY2011 84
Figure 30. Distribution of Chromium (VI) Average Method Detection Limits - CY2012 85
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ABBREVIATIONS AND ACRONYMS
AQS
Air Quality System
CV
coefficient of variation
CY
calendar year
DQI(s)
data quality indicator(s)
DQO
data quality objective
HAP(s)
hazardous air pollutant(s)
IPA(s)
instrument performance audit(s)
IQR
interquartile range
LC
local conditions
MDL(s)
method detection limit(s)
MQO(s)
measurement quality objective(s)
NATTS
National Air Toxics Trends Stations
NIST
National Institute of Standards and Technology
PAH(s)
polycyclic aromatic hydrocarbon(s)
POC(s)
parameter occurrence code(s)
PTs)
proficiency test(s)
QAAR
quality assurance annual report
QTR
quarter
RD
raw data record in AQS
RP
replicate record in AQS
STP
standard temperature and pressure
TSA
technical systems audit
VOC(s)
volatile organic compound(s)
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1.0 INTRODUCTION
As mandated under the Government Performance Results Act, the U.S. Environmental
Protection Agency (EPA) is focused on reducing the risk of cancer and other serious health
effects associated with hazardous air pollutants (HAPs) by achieving a 75% reduction in air
toxics emissions chemicals, based on 1993 levels. The current inventory of HAPs includes 188
chemicals regulated under the Clean Air Act that have been linked to numerous adverse human
health and ecological effects, including cancer, neurological effects, reproductive effects, and
developmental effects. Current Agency attention is targeting risk reduction associated with
human exposure to air toxics.
The National Air Toxics Trends Station (NATTS) network was established to create a database
of air quality data to assess progress in reducing ambient concentrations of air toxics and
concomitant exposure-associated risk. During calendar years (CY) 2011 and 2012, the NATTS
network consisted of 27 stations in the contiguous 48 states. To ensure the quality of the data
collected under the NATTS network, EPA has implemented a Quality System comprising three
primary components: (1) Technical Systems Audits (TSAs) of sample analysis laboratories and
network stations, (2) Instrument Performance Audits (IPAs) of network stations, and (3)
quarterly proficiency testing (PT) of the sample analysis laboratories. These assessments ensure
that sampling and analysis techniques are consistent with required completeness, precision, bias,
and method detection limits (MDLs) as specified by the NATTS Measurement Quality
Objectives (MQOs).
This report describes and summarizes the quality assurance (QA) data generated for the NATTS
program during CY2011 and CY2012. For data retrieved from EPA's Air Quality Systems
(AQS) database, only data input prior to November 7, 2013, are considered in this assessment.
Although this report details substantive information on 27 different HAPs of interest, it focuses
primarily on results for seven pollutants: acrolein, benzene, 1,3-butadiene, formaldehyde,
naphthalene, PMio arsenic, and chromium (VI). These pollutants represent each of the five
classes of HAPs that are analyzed within the NATTS program: VOCs, carbonyls, PAHs, PMio
metals, and hexavalent chromium. At the request of EPA, these seven pollutants were selected
as being representative of their respective constituent class and were of particular interest by
virtue of their associated health risk due to inhalation exposure and the frequency of their
occurrence at measurable concentrations. Although no HAP or group of HAPs can provide
complete representation of their respective HAP class, it is presumed that if the NATTS program
can meet the measurement quality objectives (MQOs) for these seven HAPs, the additional
20 pollutants of concern will be of comparable quality by virtue of the representativeness of the
physicochemical properties and the consistency of the collection and analysis methodologies.
The information in this Quality Assurance Annual Report (QAAR) was compiled from data
acquired from numerous sources. The following general categories of information are presented:
• Descriptive background information on the AQS sites, HAPs of interest, and MQOs;
• Assessment of the completeness of the data available in the AQS database;
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• Precision estimates for both analytical and overall sampling error computed for as
many of the 27 HAPs and for as many of the 27 NATTS sites as available in AQS for
CY2011 and CY2012;
• Evaluation of analytical laboratory bias based on results of blind audit PT samples for
many of the 27 HAPs;
• Field bias data, which are expressed as the percent difference between sampler flow
readings and a calibrated flow standard for each of four different sampler types
associated with carbonyls, PMio metals, chromium (VI), and PAHs for primary
samplers and precision (collocated or duplicate) samplers (where available) during
IPAs conducted at eight sites visited in CY2011 and five sites visited in CY2012; and
• MDL data for each site. The AQS database, specifically the ALT_MDL variable, was
used as the source of MDLs for CY2011 and CY2012.
Where possible, all data analyses were performed in SAS, version 9.3. Graphs and plots were
prepared using STATA version 13.0. Field flow audit data were transcribed into Microsoft
Excel.
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2.0 NATTS QUALITY ASSURANCE DATA FOR CY2011 AND CY2012
2.1 The NATTS Network Sites in CY2011 and CY2012
The NATTS network included 27 sites in CY2011 and CY2012. Table 1 lists these sites along
with the EPA Region in which each site is located, the site name, whether the site is located in a
predominantly urban or rural area, and the site's unique AQS identification code [1].
Although a city and state are typically used as the site name, a county name is used for the two
Florida sites on either side of Tampa Bay, for the South Carolina site, and for the site located in
Harrison County, TX. Historical consistency has been maintained for the Grand Junction, CO
site, to which two separate AQS site identification codes were assigned, one code for VOCs,
carbonyls, PAHs, and chromium (VI) (08-077-0018), and another code for PMio metals
(08-077-0017). This convention is unique to this site and is used because the organics and
metals samplers are situated at separate physical locations at the sampling site. The Bronx, NY
site had a different AQS site code starting in July 2012, when the site location changed upon
completion of renovation construction. Prior to July 2012, this site had a site code of
36-005-0080, and upon completion of the renovation, sample collection resumed under site code
36-005-0110.
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Table 1. EPA Regions, NATTS Sites, Site Type, and Air Quality Systems Site Codes
EPA Region
Site Name
Site Type
AQS Site Identification Code
I
Boston-Roxbury, MA
Urban
25-025-0042
I
Underhill, VT
Rural
50-007-0007
I
Providence, RI
Urban
44-007-0022
II
Bronx, NY
Urban
36-005-0080a, -0110b
II
Rochester, NY
Urban
36-055-1007
III
Washington, DC
Urban
11-001-0043
III
Richmond, VA
Urban
51-087-0014
IV
Chesterfield, SC
Rural
45-025-0001
IV
Decatur, GA
Urban
13-089-0002
IV
Grayson Lake, KY
Rural
21-043-0500
IV
Hillsborough County, FL
Urban
12-057-3002
IV
Pinellas County, FL
Urban
12-103-0026
V
Dearborn, MI
Urban
26-163-0033
V
Horicon, WI
Rural
55-027-0001
V
Northbrook, IL
Urban
17-031-4201
VI
Deer Park, TX
Urban
48-201-1039
VI
Harrison County, TX
Rural
48-203-0002
VII
St. Louis, MO
Urban
29-510-0085
VIII
Bountiful, UT
Urban
49-011-0004
VIII
Grand Junction, CO
Rural
08-077-0017°, -0018d
IX
Phoenix, AZ
Urban
04-013-9997
IX
San Jose, CA
Urban
06-085-0005
IX
Rubidoux, CA
Urban
06-065-8001
IX
Los Angeles, CA
Urban
06-037-1103
X
La Grande, OR
Rural
41-061-0119
X
Portland, OR
Urban
41-051-0246
X
Seattle, WA
Urban
53-033-0080
a Discontinued July 2012
b Resumed July 2012
cPMio metals only
d VOCs, carbonyls, PAHs, and Cr(VI) only
2.2 HAPs Measured in the NATTS Network in CY2011 and CY2012
The 27 HAPs measured in the NATTS program are listed in Table 2. EPA selected these air
pollutants due to their significant health concern. These include 16 VOCs, 2 carbonyls, 2 PAHs,
6 PMio metals, and chromium (VI). Succinct abbreviations of each chemical name are also
specified in this table, as they are used to identify HAPs in subsequent tables and figures
throughout this report.
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Table 2. The 27 NATTS Hazardous Air Pollutants and
Air Quality Systems Parameter Codes
HAP
HAP
Abbreviation
AQS Label
AQS Code(s)
HAP Class
benzene
BENZa
Benzene
45201
voc
1,3-butadiene
BUTAa
1,3-Butadiene
43218
voc
carbon tetrachloride
CTET
Carbon Tetrachloride
43804
voc
chloroform
CLFRM
Chloroform
43803
voc
1,2-dibromoethane
EDB
Ethylene Dibromide
43843
voc
1,2-dichloropropane
DCP
1,2-Dichloropropane
43829
voc
1,2-dichloroethane
EDC
Ethylene Dichloride
43815
voc
dichloromethane
MECL
Dichloromethane
43802
voc
1,1,2,2-tetrachloroethane
TCE1122
1,1,2,2-T etrachloroethane
43818
voc
tetrachloroethylene
PERC
T etrachloroethylene
43817
voc
trichloroethylene
TCE
T richloroethylene
43824
voc
vinyl chloride
VC
Vinyl Chloride
43860
voc
cis -1,3 -dichloropropene
cDCPEN
Cis -1,3 -Dichloropropylene
43831
voc
trans -1,3 -dichloropropene
tDCPEN
T rans -1,3 -Dichloropropylene
43830
voc
acrolein
ACROa
Acrolein
43505b43509°
voc
acrylonitrile
ACRY
Acrylonitrile
43704
voc
naphthalene
NAPHa
Naphthalene (TSP) STP
17141d
PAH
benzo[a]pyrene
BaP
Benzo[A]Pyrene (TSP) STP
17242d
PAH
formaldehyde
FORM2
Formaldehyde
43502
Carbonyl
acetaldehyde
ACET
Acetaldehyde
43503
Carbonyl
arsenic
Asa
Arsenic PMio
82103d851036
Metal
beryllium
Be
Beryllium PMio
82105d 851056
Metal
cadmium
Cd
Cadmium PMio
82110d 85110e
Metal
lead
Pb
Lead PMio
82128d 851286
Metal
manganese
Mn
Manganese PMio
82132d 851326
Metal
nickel
Ni
Nickel PMio
82136d 851366
Metal
chromium (VI)
CrVIa
Chromium (VI) TSP
12115d 14115e
Metal
a HAP is representative of other chemicals in this class.
b unverified results
c verified results
d standard conditions (STP)
e local conditions (LC)
Note that the superscript "a" in the HAP Abbreviation column of Table 2 denotes the seven
HAPs that serve as representative of their respective constituent classes for this quality
investigation: acrolein, benzene, 1,3-butadiene, formaldehyde, naphthalene, PMio arsenic, and
chromium (VI). In this document, these seven HAPs are referred to the HAPs of "primary
importance" to the NATTS program.
2.3 Measurement Quality Objectives
MQOs applicable to the various data quality indicators (DQIs) for seven HAPs of primary
importance are summarized in Table 3. The MQOs for the DQIs of completeness, precision, and
laboratory bias, as established for the NATTS program to ensure acceptable data quality within
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the network, are documented in the Technical Assistance Document [4] dated April 1, 2009. The
DQI of sensitivity is represented as the method detection limits (MDLs), and the MDL MQOs
for CY2011 and CY2012 are documented in the National Air Toxics Trends Station Work Plan
Template revised 2/09/2011 and 4/11/2012, respectively [2, 3]. The stated Data Quality
Objective (DQO) for the NATTS program is "to be able to detect a 15 percent difference (trend)
between two consecutive 3-year annual mean concentrations within acceptable levels of decision
error" [5].
Table 3. Measurement Quality Objectives for the Seven HAPs of Primary Importance to
the NATTS Program
HAP
Data Quality Indicators a
Completeness
(Section 2.4)
Analytical and
Overall Precision
(% Coefficient of
Variation)
(Section 2.5)
Laboratory
Bias
(Section 2.6)
Method Detection Limit (MDL)
(Section 2.8)
CY2011
CY2012
acrolein
benzene
1,3-butadiene
formaldehyde
naphthalene
arsenic (PMio)
chromium(VI)
>85%
< 15%
<25%
< 0.10 (xg/m3
<0.13 (xg/m3
< 0.10 (xg/m3
< 0.98 (xg/m3
< 29 ng/m3
< 0.23 ng/m3
< 0.08 ng/m3
< 0.09 (xg/m3
<0.13 (xg/m3
< 0.10 (xg/m3
< 0.08 (xg/m3
< 29 ng/m3
< 0.23 ng/m3
< 0.08 ng/m3
a. Technical Assistance Document for the National Ambient Air Toxics Trends and Assessment Program,
Revision 2, April 2009. [4]
Additional information and requirements associated with the DQIs and MQOs in Table 3 are as
follows:
1 Completeness is measured by calculating the percentage of full sample collection that
occurred, where full sample collection denotes the collection of samples every sixth
day through the entire calendar year.
2 Precision is calculated as the percent coefficient of variation (CV) for replicate
analyses, and for duplicate and collocated samples. Two types of precision are
assessed: analytical precision, and overall precision.
3 Bias denotes the assessment of laboratory performance through analysis of blind audit
PT samples.
4 MDLs inform measurement sensitivity. Sensitivity requirements are achieved if the
reported MDLs are less than or equal to target MDLs in Table 3.
5 Comparability requirements are achieved if the methods are consistent and all of the
above MQOs are met.
The MQO for flow rate, or field, bias is < 10%. Data acquired to assess compliance with the
MQOs were derived from a variety of sources. These sources are given in Table 4.
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Table 4. Data Sources Used to Evaluate the NATTS Data Quality Indicators
Data Quality Indicator
Data Source
Representativeness/Completenes s
AQS
Analytical and Overall Precision
AQS
Bias - Laboratory/analytical
Proficiency testing results reported by Wibby Environmental and Battelle
Bias - Flow rate/sampling
Audits of sampler flow rates conducted by RTI International
Sensitivity/MDL
AQS augmented with information from the analytical laboratories
For completeness, precision (analytical and overall), and MDL metrics, Battelle retrieved from
the AQS database data records corresponding to relevant samples collected from the 27 NATTS
sites during CY2011 and CY2012. Only those data present in AQS prior to November 7, 2013
were included in this report.
Analytical bias was calculated using PT sample analysis results distributed by Wibby
Environmental (in the 2nd quarter (QTR2) of 2011) and Battelle (in the 4th quarter (QTR4) of
2011 and the 1st quarter (QTR1) of 2012). Sampling bias was estimated using results from
independent measurement of sampler flow rates with National Institute of Standards and
Technology (NIST)-traceable flow standards during on-site Instrument Performance Audits
(IPAs).
2.4 Completeness of NATTS Data
Tables 5 and 6 present the completeness of NATTS data in AQS for CY2011 and CY2012 for
the seven HAPs of primary importance to the NATTS program. Based on the specified
collection frequency MQO of l-in-6 day sample collection, 61 records for the primary parameter
occurrence code (POC) represent 100% completeness. Thus, for a given HAP and site,
percentage complete was calculated by dividing by 61 the total number of records with valid
results reported to AQS. For the purposes of this completeness calculation, nondetects were
counted as valid results, but missing values or nullified results were not.
Completeness statistics were computed using records corresponding to primary measurements
or, if the primary measurement was missing, to collocated measurement(s) collected at the same
location during the same sampling period. A record was understood to be missing if no record
existed in AQS for the expected date, the record did not include a result, or the record was
nullified. Only a single record was included for each site, date, and HAP.
Sample collection at some sites was performed more frequently than others in order to meet the
requirements of other sampling networks or for other specific purposes. Thus, an algorithm was
developed to compile the AQS data so as to allow for flexibility in handling missed and
subsequent make-up samples which may not have complied strictly with the NATTS protocol of
sampling every six days. This algorithm was designed as follows:
1. RD (raw data) records in AQS corresponding to any POC were considered valid if the
"Sample Value" was not specified as missing and "Sample Duration" was equal to 7
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(corresponding to 24-hour sample collection). This included any primary, duplicate,
or collocated data in the RD dataset.
2. A maximum of one record was counted per given sampling day.
3. The first record reported in a given calendar year was always counted. The date of
this record was then used to determine the elapsed time to the next record.
4. Any record that corresponded to sampling at six or more days following the previous
record was always counted.
5. If a record corresponded to sampling at fewer than six days after the previous record,
then that record is counted only if the time interval between the record and the
immediate prior two records is 12 days or more. (This assumes that the sample serves
as a make-up for a sample that was missed prior to the last record. It eliminates the
use of back-to-back samples to make up for weeks of missing data.)
The calculated percentage complete values are presented for each NATTS site and for each of
the seven HAPs of primary importance in Table 5 and Table 6, for CY2011 and CY2012,
respectively. These tables also include the mean and median percentage complete values across
all NATTS sites for each HAP. Percentage complete values that fall below the NATTS MQO of
85% are noted in red within these tables. The percentage of NATTS sites meeting the
completeness MQO for CY2011 and CY2012 are shown in Table 7.
8
-------
Table 5. Percentage Completeness Values by NATTS Site and the Seven HAPs of Primary
Importance for CY2011
HAP Abbreviation and Parameter Code(s)
AQS Site Identification Code
Site Name
ACRO
43505
43509
BENZ
45201
BUTA
43218
FORM
43502
NAPH
17141
As
82103
85103
CrVI
12115
14115
25-025-0042
Boston, MA
98%
98%
98%
100%
100%
97%
100%
50-007-0007
Underhill, VT
0%b
92%
92%
93%
95%
80%
93%
44-007-0022
Providence, RI
89%
89%
89%
85%
92%
92%
90%
36-005-0080
Bronx, NY
98%
98%
98%
90%
98%
95%
98%
36-055-1007
Rochester, NY
85%
85%
85%
85%
93%
89%
92%
11-001-0043
Washington, DC
98%
93%
93%
97%
93%
95%
97%
51-087-0014
Richmond, VA
97%
97%
97%
95%
95%
95%
98%
45-025-0001
Chesterfield, SC
100%
100%
100%
95%
98%
98%
97%
13-089-0002
Decatur, GA
97%
97%
97%
97%
92%
93%
93%
21-043-0500
Grayson Lake, KY
98%
100%
100%
84%
100%
98%
100%
12-057-3002
Hillsborough County, FL
98%
98%
98%
98%
97%
100%
93%
12-103-0026
Pinellas County, FL
100%
100%
100%
100%
98%
97%
98%
26-163-0033
Dearborn, MI
98%
100%
100%
100%
98%
100%
98%
55-027-0001
Horicon, WI
97%
97%
97%
100%
98%
97%
100%
17-031-4201
Northbrook, IL
82%
84%
84%
98%
98%
87%
97%
48-201-1039
Deer Park, TX
100%
93%
93%
93%
100%
97%
98%
48-203-0002
Harrison County, TX
100%
98%
98%
95%
97%
98%
100%
29-510-0085
St. Louis, MO
88%
92%
92%
95%
93%
97%
93%
49-011-0004
Bountiful, UT
87%
90%
90%
97%
100%
98%
98%
08-077-0017, 0018
Grand Junction, CO
98%
98%
98%
98%
100%
95%
90%
04-013-9997
Phoenix, AZ
93%
95%
95%
80%
85%
97%
100%
06-085-0005
San Jose, CA
98%
98%
98%
100%
98%
95%
0%a
06-065-8001
Rubidoux, CA
79%
95%
79%
74%
100%
87%
98%
06-037-1103
Los Angeles, CA
79%
97%
79%
75%
97%
97%
98%
41-061-0119
La Grande, OR
50%
97%
97%
92%
95%
98%
98%
41-051-0246
Portland, OR
50%
97%
98%
100%
93%
97%
98%
53-033-0080
Seattle, WA
90%
90%
90%
89%
89%
90%
90%
Mean
90%
95%
94%
93%
96%
95%
96%
Median
97%
97%
97%
95%
97%
97%
98%
Note: Percentage complete values below 85% are specified in red.
a. Chromium (VI) was not collected at this site - this value was excluded from mean and median calculation.
b. All acrolein results were invalidated by the site administrator - this value was excluded from mean and median calculation.
9
-------
Table 6. Percentage Completeness Values by NATTS Site and the Seven HAPs of Primary
Importance for CY2012
HAP Abbreviation and Parameter Code(s)
AQS Site Identification Code
Site Name
ACRO
BENZ
BUTA
FORM
NAPH
As
CrVI
43505
45201
43218
43502
17141
82103
12115
43509
85103
14115
25-025-0042
Boston, MA
95%
95%
95%
97%
90%
100%
98%
50-007-0007
Underhill, VT
0%b
95%
95%
98%
95%
97%
100%
44-007-0022
Providence, RI
90%
92%
92%
85%
95%
93%
100%
36-005-0080,0110
Bronx, NY
98%
98%
98%
80%
82%
97%
100%
36-055-1007
Rochester, NY
92%
92%
92%
87%
95%
77%
92%
11-001-0043
Washington, DC
100%
97%
97%
100%
85%
100%
97%
51-087-0014
Richmond, VA
95%
95%
95%
95%
89%
98%
97%
45-025-0001
Chesterfield, SC
97%
97%
97%
95%
85%
95%
82%
13-089-0002
Decatur, GA
100%
100%
100%
90%
95%
93%
89%
21-043-0500
Grayson Lake, KY
97%
98%
98%
100%
93%
97%
100%
12-057-3002
Hillsborough County, FL
95%
95%
95%
98%
93%
92%
95%
12-103-0026
Pinellas County, FL
93%
93%
93%
97%
98%
90%
98%
26-163-0033
Dearborn, MI
97%
97%
97%
98%
95%
100%
97%
55-027-0001
Horicon, WI
82%
82%
82%
79%
97%
93%
97%
17-031-4201
Northbrook, IL
89%
92%
92%
98%
92%
89%
100%
48-201-1039
Deer Park, TX
100%
100%
100%
97%
100%
100%
100%
48-203-0002
Harrison County, TX
100%
98%
98%
97%
92%
97%
97%
29-510-0085
St. Louis, MO
93%
95%
95%
100%
97%
100%
98%
49-011-0004
Bountiful, UT
85%
89%
89%
85%
93%
92%
95%
08-077-0017, 0018
Grand Junction, CO
89%
89%
89%
98%
98%
92%
93%
04-013-9997
Phoenix, AZ
98%
98%
98%
100%
95%
100%
95%
06-085-0005
San Jose, CA
98%
98%
98%
100%
95%
98%
0%a
06-065-8001
Rubidoux, CA
49%
49%
49%
49%
97%
98%
98%
06-037-1103
Los Angeles, CA
48%
48%
48%
48%
93%
98%
97%
41-061-0119
La Grande, OR
69%
90%
90%
90%
93%
95%
98%
41-051-0246
Portland, OR
95%
95%
95%
93%
95%
95%
98%
53-033-0080
Seattle, WA
93%
93%
93%
98%
92%
93%
93%
Mean
90%
91%
91%
91%
93%
95%
96%
Median
95%
95%
95%
97%
95%
97%
97%
Note: Percentage complete values below 85% are specified in red.
a. Chromium (VI) was not collected at this site - this value was excluded from mean and median calculation.
b. All acrolein results were invalidated by the site administrator - this value was excluded from mean and median calculation.
10
-------
Figures 1 and 2 present "box and whisker" plots (or "boxplots") of the percentage complete
values presented in Tables 5 and 6, respectively. Thus, they represent a summary of the
distribution of percentage complete values across the 27 NATTS sites for each of the seven
HAPs of primary importance. In these figures, the bottom and top of each "box" represents the
25th and 75th percentiles, respectively; the horizontal line inside the box represents the median
value; and the diamond symbol represents the arithmetic mean. The "whiskers" emanating from
both ends of a box extend to the largest or smallest values, up to a maximum length of 1.5 times
the inter-quartile range (IQR), the distance between the 25th and 75th percentiles of the
distribution of values (i.e., the length of the box). Any values that are more than 1.5 times the
IQR in distance from the box are denoted by open circles. (The sites having percentage
complete values represented by open circles are noted in these plots.) Within both Figure 1 and
Figure 2, the dashed reference line at 85% denotes the NATTS MQO for completeness.
Table 7. Percentage of NATTS Sites Meeting the Completeness MQO for the Seven HAPs
of Primary Importance for CY2011 and CY2012
Calendar Year
VOCs
carbonyls
PAHs
metals
Acrolein3
Benzene
1,3-Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium (VI)b
2011
77%
93%
85%
78%
96%
96%
100%
2012
81%
89%
89%
78%
89%
96%
96%
a Underhill, VT site excluded from the completeness calculation.
b San Jose, CA site excluded from the completeness calculation.
11
-------
K>
100
95
®
4-i
®
Q.
E
o
O
90
85
I 80
o
_
CD
0_
75
70
65
Portland. OR and
LaGrande. OR
50% Complete
Phoenix, AZ
I
os Angeles, CA
Rubidoui, CA
Jnderhill. VT
ACRO
BENZ
BUTA FORM NAPH
AS
CrVI
HAP
Figure 1. Box and Whisker Plot of Percentage Complete Values for the Seven HAPs of Primary Importance, for CY2011
-------
100
95
90
85
c
® 80-
75-
70
65
a
T
Deer Park, IX
©
5
O Horicon.
O Horicon. •,
'.Vashington. DC _
Chesterfield. SC '
Bronx. MY
Decatur, GA
Chesterfield SC
O Rochester, NY
La Grande, OR
Rubidoux CA
[49% Cosrolete
Rubidoux CA
49% Complete
Rubidoux OA
49% Complete
Los Angeles CA Los Angeles CA Los Angeles CA.
48% Complete 48% Complete 48% Complete
Rubidoux CA
49% Complete
Los Angeles CA
48% Complete
ACRO
BENZ
BUTA
FORM
NAPH
AS
CrVI
HAP
Figure 2. Box and Whisker Plot of Percentage Complete Values for the Seven HAPs of Primary Importance, for CY2012
-------
Data completeness across the entire NATTS network met the MQO in both CY2011 and
CY2012: both the mean and median network-wide completeness for all seven priority HAPs
was greater than 85% in both CY2011 and CY2012. Failures of sites to meet the completeness
MQO were generally more prevalent for VOCs and carbonyls than for other HAP groups for
both CY2011 and CY2012. Some key findings were as follows:
• Los Angeles, CA, and Rubidoux, CA, did not achieve the MQO for acrolein,
1,3-butadiene, and formaldehyde, in both calendar years, and failed to meet the MQO
for benzene in CY2012. Horicon, WI, did not meet the MQO for these four HAPs in
CY2012, while it did in CY2011. While Northbrook, IL, did not achieve the MQO
for acrolein, benzene, and 1,3-butadiene in CY2011, it did meet the MQO for these
HAPs in CY2012.
• For both CY2011 and CY2012, chromium (VI) sampling was not conducted at the
San Jose, CA site, and acrolein results were invalidated at the Underhill, VT site.
The percentage of sites meeting the completeness MQO was 85% or greater for benzene,
1,3-butadiene, naphthalene, arsenic, and chromium (VI) in both CY2011 and CY2012. Fewer
sites met the MQO for acrolein and formaldehyde with 77% and 81% meeting the MQO for
acrolein and 78% and 78% for formaldehyde in CY2011 and CY2012, respectively.
2.5 Precision of NATTS Data
Precision of NATTS data was assessed by inspection of results in AQS from replicate anlaysis
and replicate sampling.
The term "replicate sampling" refers to the collection of duplicate and collocated sample
collections, terms that are defined as follows:
Three basic sample types are collected at NATTS sites:
• Primary sample: a single sample that represents a particular sampling event.
• Duplicate sample: a replicate sample, collected simultaneously with the primary
sample, that represents a second measurement from the same sample stream (e.g.,
the inlet stream of an outdoor air monitor) but employs an independent sample
collection device (e.g., pump or separate channel) and collection substrate (e.g.,
filter, canister, or cartridge) from the primary sample. Duplicate samples provide
the basis for assessing the aggregate variability associated with the collection
device, sampling substrate, and sample analysis.
• Collocated sample: a replicate sample, collected simultaneously with the primary
sample, that represents a second measurement from a completely independent (but
spatially close, usually 1 to 2 meters away from the primary sampler) sample
stream, collection device, and collection substrate from the primary sample.
Collocated samples provide the basis for assessing the total variability associated
with all components of the sample collection and analysis scheme. One may
assume that the atmosphere sampled by the primary and collocated samplers is
identical in its composition.
14
-------
The above sample types are differentiated within the AQS database by POC. Tables 8 and 9
provide the POCs encountered in the AQS database for each site by HAP class, for CY2011 and
CY2012, respectively.
Precision assessments associated with replicate sampling are distinctly different from those
associated with replicate analyses in the following way:
• Precision assessments associated with replicate analyses are derived from a second
chemical analysis of a single sample, be that a primary, duplicate, or collocated
sample.
• Precision assessments associated with replicate sampling are derived from
independent chemical analyses of two different sample substrates (filter, canister,
etc).
The precision for the NATTS data was assessed from both analytical (i.e., instrumental) and
overall (i.e., analytical plus sampling) perspectives:
• Analytical precision (Section 2.5.1) measures the variability in reported results due
exclusively to differences in laboratory analytical performance and is assessed by
comparing results from two analyses of a single sample, whether that sample be a
primary, duplicate, or collocated sample.
• Overall precision (Section 2.5.2), which accounts for the combined variability
associated with sample collection and laboratory analysis, is assessed by comparing
the results of paired primary and collocated samples or paired primary and duplicate
samples.
15
-------
Table 8. Parameter Occurrence Codes by NATTS Site and HAP Type - CY2011
Parameter Occurrence Codes (POCs)
EPA
Region
Site Name
AQS Site Code
P
VOCs
D
C
Carbonyls
P D
C
PAHs
P C
Metals
P C
Chromium (VI)
P D C
I
Boston, MA
25-025-0042
10
11
! 3
4
6
6
7
6
7
I
Underbill, VT
50-007-0007
1
[ 1
6
3
4
6
7
I
Providence, RI
44-007-0022
2
[ 5
7
6
1
2
6
7
II
Bronx, NY
36-005-0080
2
! 2
6
1
2
6
7
II
Rochester, NY
36-055-1007
2
! 2
6
1
6
7
III
Washington, DC
11-001-0043
4
1
2
1 2
1
1
1
2
III
Richmond, VA
51-087-0014
4
7
1 2
4
6
1
6
7
IV
Chesterfield, SC
45-025-0001
1
2
1 1
2
6
1
2
6
7
IV
Decatur, GA
13-089-0002
1,3
2,4,5
1 2
3
6
7
1
2
6
7
IV
IV
Grayson Lake, KY
Hillsborough Cty,
FL
21-043-0500
12-057-3002
6
1
7
1 1,6
! 6
2,7
6
6
7
1,6
5
2,7
6
6
6
7
7
IV
Pinellas Cty, FL
12-103-0026
1
! 6
6
5
6
7
V
Dearborn, MI
26-163-0033
1
2
[ i
2
1
2
1
9
1
2
V
Horicon, WI
55-027-0001
1
2
[ i
2
1
2
1
2
6
7
V
Northbrook, IL
17-031-4201
6
8
[ 6
6
6
6
7
VI
Deer Park, TX
48-201-1039
2
3
1 3
1
2,6
1
6
7
VI
Harrison Cty, TX
48-203-0002
1
1 1
1
1
6
VII
St. Louis, MO
29-510-0085
6
1 6
6
6
7
6
7
VIII
Bountiful, UT
49-011-0004
6
1 6
6
1
2
6
7
VIII
Grand Junction, CO
08-077-0017/-0018
6
1 6
6
3
4
6
7
IX
Phoenix, AZ
04-013-9997
6
7
' 30
31
3
1
6
7
IX
Los Angeles, CA
06-037-1103
4
5
i 4
5
6
2
3
4
5
IX
Rubidoux, CA
06-065-8001
4
5
i 4
5
6
7
2
4
4
5
IX
San Jose, CA
06-085-0005
3
5
i 3
1
1
1
X
La Grande, OR
41-061-0119
7
i 7
7
7
7
X
Portland, OR
41-051-0246
7
9
i 7
9
7
9
7
9
7
9
X
Seattle, WA
53-033-0080
6
7
i 6
7
6
7
6
6
7
P = primary
D = duplicate
C = collocated
16
-------
Table 9. Parameter Occurrence Codes by NATTS Site and HAP Type - CY2012
EPA
Region
Site Name
AQS Site Code
P
VOCs
D
C
Parameter Occurrence Codes (POCs)
Carbonyls PAHs Metals
P D C P C P C
Chromium
(VI)
P D C
I
Boston, MA
25-025-0042
10
11
3
4
6
6
7
i 6
7
I
Underhill, VT
50-007-0007
1
1
6
3
4
i 6
7
I
Providence, RI
44-007-0022
2
5
7
6
1
2
i 6
7
II
Bronx, NY
36-005-0080/-0110
2
2
6
1
2
i 6
7
II
Rochester, NY
36-055-1007
2
2
6
1
i 6
7
III
Washington, DC
11-001-0043
4
1
2
2
1
1
¦ 1
2
III
Richmond, VA
51-087-0014
4
7
2
4
6
1
i 6
7
IV
Chesterfield, SC
45-025-0001
1
2
1
2
6
1
2
! 6
7
IV
Decatur, GA
13-089-0002
1,3
2,4,5
2
3
6
7
1
2
! 6
7
IV
Grayson Lake, KY
21-043-0500
6
7
1,6
2,7
6
1,6
2,7
!6
7
IV
Hillsborough Cty, FL
12-057-3002
1
6
6
7
5
6
!6
7
IV
Pinellas Cty, FL
12-103-0026
1
6
6
5
!6
7
V
Dearborn, MI
26-163-0033
1
2
1
2
1
2
1
9
[ i
2
V
Horicon, WI
55-027-0001
1
2
1
2
1
2
1
2
[ 6
7
V
Northbrook, IL
17-031-4201
6
8
6
6
6
[ 6
7
VI
Deer Park, TX
48-201-1039
2
3
3
1
2,6
1
1 6
7
VI
Harrison Cty, TX
48-203-0002
1
1
1
1
1 6
VII
St. Louis, MO
29-510-0085
6
6
6
6
7
1 6
7
VIII
Bountiful, UT
49-011-0004
6
6
6
1
2
1 6
7
VIII
Grand Junction, CO
08-077-0017/-0018
6
6
6
3
4
1 6
7
IX
Phoenix, AZ
04-013-9997
6
7
30
31
3
1
' 6
7
IX
Los Angeles, CA
06-037-1103
4
5
4
5
6
2
3
i 4
5
IX
Rubidoux, CA
06-065-8001
4
5
4
5
6
7
2
4
i 4
5
IX
San Jose, CA
06-085-0005
3
5
3
1
1
1
X
La Grande, OR
41-061-0119
7
7
7
7
i 7
X
Portland, OR
41-051-0246
7
9
7
9
7
9
7
9
i 7
9
X
Seattle, WA
53-033-0080
6
7
6
7
6
7
6
i 6
7
P = primary
D = duplicate
C = collocated
17
-------
For the purposes of these precision assessments, the AQS database was queried for two distinct
record types: RP records and RD records. RP records contain data for various types of replicate
samples and analyses associated with a particular sampling date, site, and chemical parameter
(HAP). Different types of replicates are identified by the value of the precision ID variable
(PRECISID) according to the following scheme:
• PRECISID = 1: Collocated sample data
• PRECISID = 2: Replicate analysis of a primary sample
• PRECISID = 3: Replicate analysis of a collocated sample
Analytical precision for this report was computed from the replicate pairs of data contained in
RP records that were coded with either Precision ID 2 or 3. Overall precision was computed
from the replicate pairs of data contained in RP records that were coded with Precision ID 1 and
from paired RD records.
In addition to the replicate records, raw data (AQS RD) transactions provide a second source of
primary and collocated data in AQS. Using the POCs shown for each NATTS site listed in
Tables 8 and 9, it is possible to distinguish among primary, duplicate, and collocated sampling
events. For example, primary samples collected at the Chesterfield, SC, NATTS site are
assigned a POC of 1 for VOCs, carbonyls, and metals, while collocated samples are assigned a
POC of 2. This results in the creation of two distinct records for each sampling event at which a
collocated sample is collected. Duplicate samples are identified with a separate POC. The
assignment of a particular POC is made at the discretion of each NATTS site, thus extensive
effort was required to ensure that the POCs for each site were correctly identified. POCs for
primary, duplicate, and collocated samples of each HAP class for CY2011 and CY2012 were
determined based on POCs at each NATTS collection site in CY2007, CY2008, CY2009, and
CY2010 and discrepancies and/or uncertainties about POC assignments were resolved by direct
contact with NATTS administrators for specific collection sites.
Prior to the beginning of CY2012, ERG contacted sites for which it performs analyses to confirm
whether POCs were being appropriately assigned as collocated or duplicate based on sample
characteristics. This resulted in a number of POC assignment changes, primarily involving
POCs previously designated as duplicate sampling updated to indicate the POC represents
collocated sampling.
Multiple POCs for a given site, HAP, and sample type reflect a number of factors unique to sites
during CY2011 and CY2012, largely assigned for reasons known only to the NATTS site
administrators. Overall precision estimates were computed by comparing primary and collocated
or primary and duplicate results for a particular site, HAP, and sample collection date. To reflect
possible differences in analytical and overall precision based on the magnitude of the
contributing measurements, precision was computed as percent coefficient of variance (CV) for
each site and HAP where both replicate values were equivalent to or exceeded the reported
MDL.
18
-------
Laboratories analyzing samples for NATTS sites in CY2011 and CY2012 are listed in Table 10,
with laboratory identification codes for each laboratory shown in Table 11. Of particular note is
that several laboratories provided analytical chemistry services for multiple NATTS sites.
Table 10. Laboratories Performing Analyses by HAP Type for Each
NATTS Site in CY2011 and CY2012
Site Name
VOCs
Carbonyls
PAHs
Metals
Chromium (VI)
Boston-Roxbury, MA
RIDOH
MADEP
ERG
ERG
ERG
Underhill, VT
ERG
VTDEC
ERG
ERG
ERG
Providence, RI
RIDOH
RIDOH
ERG
RIDOH
ERG
Bronx, NY
NYSDEC
NYSDEC
ERG
RTI
ERG
Rochester, NY
NYSDEC
NYSDEC
ERG
RTI
ERG
Washington, DC
MDE
PAMSL
ERG
WVDEP
ERG
Richmond, VA
VA DCLS
VA DCLS
VA DCLS
VA DCLS
ERG
Chesterfield, SC
SCDHEC
SCDHEC
ERG
SCDHEC
ERG
Decatur, GA
GADNR
GADNR
ERG
GADNR
ERG
Grayson Lake, KY
ERG
ERG
ERG
ERG
ERG
Hillsborough County, FL
PCDEM
ERG
ERG
EPCHC
ERG
Pinellas County, FL
PCDEM
ERG
ERG
EPCHC
ERG
Dearborn, MI
ERG
ERG
ERG
MIDEQ
ERG
Horicon, WI
WSLH
WSLH
WSLH
WSLH
ERG
Northbrook, IL
ERG
ERG
ERG
ERG
ERG
Deer Park, TX
TCEQ
TCEQ
TCEQ
TCEQ
ERG
Harrison County, TX
TCEQ
TCEQ
TCEQ
TCEQ
ERG
St. Louis, MO
ERG
ERG
ERG
ERG
ERG
Bountiful, UT
ERG
ERG
ERG
ERG
ERG
Grand Junction, CO
ERG
ERG
ERG
CDPHE
ERG
Phoenix, AZ
ERG
ERG
ERG
ERG
ERG
San Jose, CAa
BAAQMD
BAAQMD
ERG
ERG
-
Rubidoux, CA
SCAQMD
SCAQMD
ERG
SCAQMD
SCAQMD
Los Angeles, CA
SCAQMD
SCAQMD
ERG
SCAQMD
SCAQMD
La Grande, OR
ODEQ
ODEQ
ODEQ
ODEQ
CHLBNT
Portland, OR
ODEQ
ODEQ
ODEQ
ODEQ
CHLBNT
Seattle, WA
ERG
ERG
ERG
ERG
ERG
aSan Jose does not collect Chromium (VI) for the NATTS program.
19
-------
Table 11. Laboratory Abbreviations and Descriptions for NATTS Laboratories
Laboratory
Laboratory Code(s)
Abbreviation
Laboratory Description
01-01-C,M,V
RIDOH
Rhode Island Department of Health
01-02-C,V
VTDEC
Vermont Department of Environmental Conservation
01-03-C
MADEP
Massachusetts Department of Environmental Protection
02-01-C,V
NYSDEC
New York State Department of Environmental Conservation
03-01-V
MDE
Maryland Department of the Environment
03-01-C
PAMSL
Philadelphia Air Management Services Laboratory
03-01-M
WVDEP
West Virginia Department of Environmental Protection
03-02-C,M,P,R,V
VADCLS
Virginia Division of Consolidated Laboratory Services
04-01-M
EPCHC
Environmental Protection Commission of Hillsborough County
04-01-V
PCDEM
Pinellas County Department of Environmental Management
04-02-C,M,P,V
SCDHEC
South Carolina Department of Health and Environmental Control
04-03-C,M,V
KYDES
Kentucky Division of Environmental Services
04-04-C,M,V
GADNR
Georgia Department of Natural Resources
05-01-M
MIDEQ
Michigan Department of Environmental Quality
05-03-C,M,P,V
WSLH
Wisconsin State Laboratory of Hygiene
06-01-C,M,P,R,V
TCEQ
Texas Commission on Environmental Quality
08-02-M
CDPHE
Colorado Department of Public Health and Environment
09-03-C,V
BAAQMD
Bay Area Air Quality Management District
09-08-C,M,P,R,V
SCAQMD
South Coast Air Quality Management District
10-02-R
CHLBNT
Chester LabNet
10-02-C,M,P,V
ODEQ
Oregon Department of Environmental Quality
11-01-C,M,P,R,V
ERG
Eastern Research Group
11-02-M
RTI
RTI International
2.5.1 Analytical Precision Results
Analytical precision was calculated from the replicate analysis results associated with either a
primary, collocated, or duplicate sample as extracted from RP records from the AQS database.
For this calculation, the two analysis results for a given sample are distinguished by referring to
one as the "principal" result and the other as the "replicate" result. The measure for analytical
precision, expressed as the percentage coefficient of variation (%CV), is defined in Eq. 1:
%CV = 100-
(Eq. 1)
20
-------
where
pi = the principal result for sample i,
n = the replicate result for sample i, and
n = the number of samples having primary-replicate result pairs.
Analytical precision was calculated only when pi > MDL and n > MDL. For those sites that did
not report MDLs into AQS, it could not be determined if the RP records exceeded the
corresponding MDLs. As a result, such data were excluded from the analytical precision
calculation.
The analytical precision for each of the 27 NATTS HAPs is presented in Table 12 and Table 13
for CY2011 and CY2012, respectively. For the seven HAPs of primary importance, analytical
precision is summarized graphically in Figures 3 through 9 for CY2011 and Figures 10 through
16 for CY2012.
For CY2011 the network mean analytical precision met the MQO of 15% for carbonyls, PAHs,
and chromium (VI), for all metals except beryllium, and for 9 of the 16 VOCs reporting
concentrations above MDLs. Analytical precision data for VOCs show some variability with no
discernible trend noted among sites or HAPs. Records for 1,2-dibromoethane and
1,2-dichloropropane did not include replicate pairs for which both results were above their
respective MDL, and are not included in Table 12. For all sites reporting metals above MDLs,
only Boston, MA met the precision MQO for all metals.
For CY2012 the network mean analytical precision met the MQO for all HAPs except for
acrylonitrile and beryllium. Moreover, all sites met the MQO for carbonyls, PAHs, and
chromium (VI). Among VOCs, sites showed close agreement with only an occasional MQO
exceedence. Records for 1,2-dibromoethane, 1,2-dichloropropane, and 1,1,2,2-tetrachloroethane
did not include replicate pairs for which both results were above their respective MDL, and are
not included in Table 13. Replicate analysis showed similar close agreement for metals, with
only two sites having analytical precision exceeding the MQO.
Overall precision comprises analytical variability and sampling variability and more fully
characterizes network-wide precision. Network achievement of the precision MQO is discussed
in Section 2.5.2.
21
-------
Table 12. Analytical Precision for Replicate Analyses > MDL - CY2011
IO
IO
AQS Site Code
Site Name
VOCs
BENZ
BUTA
CTET
CLFRM
EDC
MECL
TCE1122
PERC
TCE
VC
cDCPEN
tDCPEN ACRO
ACRY
25-025-0042
Boston, MA
-
-
-
-
-
-
-
-
-
-
-
-
-
50-007-0007
Underbill, VT
-
-
-
-
-
-
-
-
-
-
-
-
-
44-007-0022
Providence, RI
-
-
-
-
-
-
-
-
-
-
-
-
-
36-005-0080
Bronx, NY
-
-
-
-
-
-
-
-
-
-
-
-
-
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
-
-
-
-
11-001-0043
Washington, DC
-
-
-
-
-
-
-
-
-
-
-
-
-
45-025-0001
Chesterfield, SC
-
-
-
-
-
-
-
-
-
-
-
-
-
13-089-0002
Decatur, GA
-
-
-
-
-
-
-
-
-
-
-
-
-
21-043-0500
Grayson Lake, KY
6.7 (13)
6.4 (6)
6.6 (13)
6.8 (3)
6.2 (2)
4.7 (13)
-
-
-
20.2 (1)
-
4.5 (13)
4.4 (5)
12-057-3002
Hillsborough Cty, FL
4.0 (2)
21.1(1)
0.6 (2)
6.3 (2)
4.3 (2)
4.0 (2)
-
20.2 (1)
-
-
0.5 (1)
0.8 (1) 2.8 (2)
-
12-103-0026
Pinellas Cty, FL
4.4 (54)
14.1 (41)
3.5 (54)
8.5 (54)
12.7 (45)
10.3 (54)
36.8 (5)
14.3 (51)
93.4(1)
-
0(1)
22.5 (3) 10.9 (53)
9.7 (41)
26-163-0033
Dearborn, MI
6.5 (12)
7.6 (12)
6.3 (12)
6.0 (12)
5.6 (2)
4.8 (12)
-
5.2 (9)
-
-
-
6.2 (12)
-
55-027-0001
Horicon, WI
-
-
-
-
-
-
-
-
-
-
-
-
-
17-031-4201
Northbrook, IL
12.0 (24)
6.2 (12)
17.0(12)
25.4(12)
10.2 (5)
21.4(12)
-
5.0 (10)
-
-
-
21.8(12)
6.9 (4)
48-201-1039
Deer Park, TX
-
-
-
-
-
-
-
-
-
-
-
-
-
29-510-0085
St. Louis, MO
7.1 (16)
8.4 (16)
6.8 (16)
6.4 (14)
5.4 (8)
9.0(16)
-
5.5 (10)
-
-
-
26.3 (16)
-
49-011-0004
Bountiful, UT
12.6(13)
8.9 (13)
6.3 (13)
14.3 (5)
8.8 (5)
10.5 (13)
-
9.1 (4)
-
-
-
39.3 (13)
-
08-077-0017/-0018
Grand Junction, CO
4.5 (12)
5.5 (10)
17.1 (11)
6.8 (9)
2.0 (2)
16.8 (12)
-
7.2 (8)
4.3 (2)
-
-
14.4(11)
4.6 (2)
04-013-9997
Phoenix, AZ
6.6(12)
5.2 (12)
6.7 (12)
4.9 (12)
5.3 (2)
7.0(12)
-
4.8 (12)
-
-
-
5.5 (12)
2.8 (2)
06-037-1103
Los Angeles, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-065-8001
Rubidoux, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-085-0005
San Jose, CA
3.1 (31)
10.4(11)
7.1 (31)
15.9 (27)
-
7.9 (29)
-
2.4 (31)
0(4)
-
-
-
-
53-033-0080
Seattle, WA
3.1 (12)
7.4 (12)
4.6 (12)
8.4 (9)
2.9 (2)
3.2 (12)
-
3.8 (2)
-
-
-
3.6 (12)
8.0(1)
Network Mean
6.9 (201)
10.0(146)
8.0 (188)
11.8 (159)
10.7 (75)
10.4(187)
36.8 (5)
9.7 (138)
35.4 (7)
Ji > J . 1 i
0.3 (2)
19.5 (4) 17.3 (156)
8.8 (55)
Analytical precision is expressed as percentage coefficient of variation (%CV) with number of contributing data pairs (/;) shown in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Table 12. Analytical Precision for Replicate Analyses > MDL - CY2011 (continued)
IO
oo
AQS Site Code
Site Name
carbonyls
PAHs
metals
FORM
ACET
NAPH
BaP
As
Be
Cd Pb
Mn
Ni
CrVI
25-025-0042
Boston, MA
-
--
-
-
2.1 (74)
11.0(18)
6.8 (74) 1.5 (74)
1.1 (74)
1.8(72)
8.3 (10)
50-007-0007
Underhill, VT
0.7 (4)
1.7 (4)
--
-
16.4 (8)
--
5.8(9) 1.5(9)
3.4 (9)
2.9 (2)
7.7 (7)
44-007-0022
Providence, RI
-
-
-
-
-
-
-
-
-
7.2 (10)
36-005-0080
Bronx, NY
-
-
-
-
-
-
-
-
-
5.5 (12)
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
9.4 (8)
11-001-0043
Washington, DC
-
--
--
-
--
-
--
-
-
8.3 (11)
45-025-0001
Chesterfield, SC
-
-
-
-
-
-
-
-
-
7.3 (4)
13-089-0002
Decatur, GA
-
-
4.1 (12)
3.8 (2)
-
-
-
-
-
5.4(11)
21-043-0500
Grayson Lake, KY
0.7 (8)
0.9 (8)
--
-
11.2 (64)
33.3 (2)
5.0(78) 1.0(80)
0.8 (80)
33.4 (4)
5.3 (9)
12-057-3002
Hillsborough Cty, FL
2.3 (14)
1.6(14)
3.3 (12)
7.4 (3)
-
--
-
--
--
5.3 (12)
12-103-0026
Pinellas Cty, FL
2.2(12)
2.0(12)
-
--
-
--
--
--
--
5.7(10)
26-163-0033
Dearborn, MI
1.3 (12)
0.3 (12)
2.9(12)
4.4 (8)
-
--
-
--
--
4.6(12)
55-027-0001
Horicon, WI
-
-
-
-
-
-
-
-
-
3.6(10)
17-031-4201
Northbrook, IL
2.0(12)
1.7(12)
-
-
-
-
-
-
-
6.4(12)
48-201-1039
Deer Park, TX
-
-
-
-
-
-
-
-
-
5.2(12)
29-510-0085
St. Louis, MO
2.1 (12)
1.0(12)
-
--
7.2 (66)
21.0 (8)
2.8 (67) 0.6 (67)
1.2 (67)
9.6(17)
6.6(11)
49-011-0004
Bountiful, UT
4.4 (14)
1.6(14)
-
--
-
--
--
--
--
13.8(12)
08-077-0017/ -0018
Grand Junction, CO
2.2(12)
2.0(12)
-
-
-
-
-
-
-
8.0(12)
04-013-9997
Phoenix, AZ
0.9 (14)
1.2(14)
-
--
-
--
--
--
--
4.9 (14)
06-037-1103
Los Angeles, CA
-
-
--
-
5.7 (5)
-
21.1(5) 4.2(5)
21.1 (5)
3.3 (5)
--
06-065-8001
Rubidoux, CA
-
--
2.6(12)
--
8.0 (9)
--
34.8 (4) 7.2 (9)
0(5)
3.1 (9)
--
06-085-0005
San Jose, CA
0.9 (9)
1.0 (9)
-
-
-
-
-
-
-
-
53-033-0080
Seattle, WA
0.8(12)
1.3 (12)
2.5 (10)
6.3 (2)
-
--
-
--
--
5.6(14)
Network Mean
2.1 (135) 1.4(135) 3.1 (58) 5.3 (15) 8.1 (226) 16.8 (28) 7.5 (237) 1.9 (244) 3.3 (240) 7.7 (109) 7.0(213)
Analytical precision is expressed as percentage coefficient of variation (%CV) with number of contributing data pairs (/;) shown in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Table 13. Analytical Precision for Replicate Analyses > MDL - CY2012
IO
AQS Site Code
Site Name
VOCs
BENZ
BUTA
CTET
CLFRM
EDC
MECL
PERC
TCE
VC
cDCPEN
tDCPEN
ACRO
ACRY
25-025-0042
Boston, MA
-
-
-
-
-
-
-
-
-
-
-
-
-
50-007-0007
Underbill, VT
-
-
-
-
-
-
-
-
-
-
-
-
-
44-007-0022
Providence, RI
-
-
-
-
-
-
-
-
-
-
-
-
-
36-005-0080/-0110
Bronx, NY
2.5 (9)
34.1 (9)
1.3 (9)
8.1 (9)
3.6 (9)
29.6 (9)
34.5 (9)
11.4(5)
11.2 (3)
-
-
15.8 (9)
-
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
-
-
-
-
11-001-0043
Washington, DC
-
-
-
-
-
-
-
-
-
-
-
-
-
51-087-0014
Richmond, VA
-
-
-
-
-
-
-
-
-
-
-
-
-
45-025-0001
Chesterfield, SC
-
-
-
-
-
-
-
-
-
-
-
-
-
13-089-0002
Decatur, GA
-
-
-
-
-
-
-
-
-
-
-
-
-
21-043-0500
Grayson Lake, KY
5.5 (8)
13.2 (8)
6.1 (10)
18.5 (2)
8.4 (6)
25.6(10)
-
-
-
-
-
10.0(10)
73.4 (8)
12-057-3002
Hillsborough Cty, FL
4.4 (2)
6.5 (2)
1.2 (2)
2.3 (2)
0(2)
2.4 (2)
15.4(2)
-
-
-
-
9.0 (2)
-
12-103-0026
Pinellas Cty, FL
3.1 (18)
8.7 (17)
1.7 (18)
7.2 (18)
2.5 (18)
2.8 (18)
9.0(18)
-
-
1.9 (2)
2.4 (2)
7.1 (18)
14.3 (14)
26-163-0033
Dearborn, MI
7.2 (12)
5.4 (12)
5.9 (12)
20.8 (12)
5.7 (8)
5.2 (12)
4.7 (6)
-
-
-
-
10.1 (12)
-
55-027-0001
Horicon, WI
-
-
-
-
-
-
-
-
-
-
-
-
-
17-031-4201
Northbrook, IL
10.2 (28)
9.8 (15)
10.7 (14)
15.0(14)
12.2 (10)
11.1 (14)
10.6 (6)
16.0 (4)
-
-
-
30.8 (12)
-
48-201-1039
Deer Park, TX
-
-
-
-
-
-
-
-
-
-
-
-
-
48-203-0002
Harrison Cty, TX
-
-
-
-
-
-
-
-
-
-
-
-
-
29-510-0085
St. Louis, MO
7.9 (16)
7.1 (16)
15.2 (16)
8.3 (14)
12.4(10)
7.4 (16)
11.0(8)
6.2 (2)
-
-
-
11.7 (16)
-
49-011-0004
Bountiful, UT
10.2 (13)
9.3 (13)
12.0(13)
11.7 (13)
14.3 (6)
19.9(13)
7.7 (2)
-
-
-
-
8.5 (13)
-
08-077-0017/-0018
Grand Junction, CO
4.9 (12)
5.5 (12)
10.8 (12)
6.1 (8)
11.0(10)
6.5 (12)
8.3 (10)
-
-
-
-
16.9 (12)
11.1(2)
04-013-9997
Phoenix, AZ
4.0 (12)
4.1 (12)
4.5 (12)
4.2 (11)
7.1 (8)
4.0 (12)
4.3 (12)
-
-
3.8(1)
-
5.0(12)
-
06-037-1103
Los Angeles, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-065-8001
Rubidoux, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-085-0005
San Jose, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
53-033-0080
Seattle, WA
7.6 (13)
5.6 (13)
7.5 (13)
9.0(13)
5.5 (5)
15.4(13)
3.7 (2)
—
—
—
—
15.0(13)
—
Network Mean
7.3 (130)
11.8 (116)
8.9 (118)
11.3 (103)
8.7 (87)
14.2 (118)
14.4 (73)
12.6(11)
11.2 (3)
2.7 (3)
2.4 (2)
14.4(116)
43.9 (24)
Analytical precision is expressed as percentage coefficient of variation (%CV) with number of contributing data pairs (/;) shown in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Table 13. Analytical Precision for Replicate Analyses > MDL - CY2012 (continued)
AQS Site Code
Site Name
carbonyls
PAHs
metals
FORM
ACET
NAPH
BaP
As Be
Cd
Pb
Mn
Ni
CrVI
25-025-0042
Boston, MA
-
-
3.5(1)
1.9(1)
2.6 (66) 8.8 (9)
5.7 (66)
1.4 (66)
1.5 (66)
3.5 (66)
5.0(12)
50-007-0007
Underhill, VT
0.6 (9)
0.8 (9)
0.7(1)
--
28.6 (6)
20.5 (11)
0.7 (6)
1.0(12)
1.2 (4)
7.3(1)
44-007-0022
Providence, RI
-
-
3.2 (3)
4.4(1)
-
-
-
-
-
7.5 (9)
36-005-0080/-0110
Bronx, NY
-
-
6.1 (4)
2.6(1)
-
-
-
-
-
8.3 (13)
36-055-1007
Rochester, NY
-
-
1.9 (3)
2.0(1)
-
-
-
-
-
4.0 (5)
11-001-0043
Washington, DC
-
-
0.6(1)
-
--
--
-
--
-
7.1 (12)
51-087-0014
Richmond, VA
-
-
0.5 (3)
10.1(1)
-
-
-
-
-
8.0(12)
45-025-0001
Chesterfield, SC
-
-
2.5(1)
-
-
-
-
-
-
8.0 (3)
13-089-0002
Decatur, GA
-
-
2.7(11)
3.1 (2)
-
-
-
-
-
5.6(10)
21-043-0500
Grayson Lake, KY
1.7(12)
1.5(12)
2.7 (4)
2.0 (2)
13.7 (40)
9.7 (46)
0.7 (49)
1.3 (49)
1.7 (6)
12.0 (7)
12-057-3002
Hillsborough Cty, FL
9.0(10)
2.9 (10)
3.4(13)
--
-
-
-
--
-
5.6 (7)
12-103-0026
Pinellas Cty, FL
4.7(12)
3.1 (12)
0.9 (4)
3.7(1)
-
-
-
--
-
9.3 (13)
26-163-0033
Dearborn, MI
1.3 (12)
0.6(12)
2.1(15)
4.1(11)
-
-
-
--
-
4.8(14)
55-027-0001
Horicon, WI
-
-
-
-
-
-
-
-
-
10.0 (8)
17-031-4201
Northbrook, IL
3.3 (16)
2.3 (16)
-
-
1.5 (6) 10.6 (5)
1.6(6)
2.4 (6)
1.3 (6)
3.0 (6)
5.8(14)
48-201-1039
Deer Park, TX
-
-
-
-
-
-
-
-
-
3.5 (12)
48-203-0002
Harrison Cty, TX
-
-
-
-
-
-
-
-
-
4.3 (3)
29-510-0085
St. Louis, MO
1.6(12)
1.2(12)
4.8 (6)
7.4 (6)
9.2(117) 18.1 (21)
4.5 (118)
0.5 (48)
0.9(118) 10.4(107)
6.1 (12)
49-011-0004
Bountiful, UT
2.8(10)
2.7 (10)
11.0(1)
-
-
-
-
-
-
8.8(12)
08-077-0017/-0018
Grand Junction, CO
0.8(12)
0.8(12)
-
-
-
-
-
-
-
10.7 (7)
04-013-9997
Phoenix, AZ
0.9(12)
0.5 (12)
1.0 (2)
--
14.3 (4) 13.0 (4)
6.8 (4)
0.3(1)
2.4 (4)
4.0 (4)
4.3 (12)
06-037-1103
Los Angeles, CA
-
-
11.4(1)
--
-
-
-
--
-
-
06-065-8001
Rubidoux, CA
-
-
12.8 (16)
4.9 (2)
-
-
-
-
-
-
06-085-0005
San Jose, CA
0.3 (9)
42.7 (10)
1.2 (2)
--
4.6 (2)
7.7 (4)
0.5 (2)
0.7 (6)
1.4 (6)
--
53-033-0080
Seattle, WA
1.7(12)
1.5(12)
2.3 (17)
3.1 (2)
1.2(3)
3.3 (3)
1.7 (3)
1.8(3)
1.2 (3)
4.7 (12)
Network Mean
3.3 (126) 11.6 (127)
5.8 (92)
4.9 (29) 9.8 (241) 15.0 (39) 7.3 (255) 1.1 (178) 1.2 (261)
7.9 (199)
7.1 (198)
Analytical precision is expressed as percentage coefficient of variation (%CV) with number of contributing data pairs (/;) shown in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
2.5.2 Overall Precision Results
Overall precision was calculated using the (principal) results of the primary sample paired with
either the duplicate or collocated samples in the AQS database. This measure of agreement,
expressed as the % CV, is defined in Eq. 2:
pi = the result of the principal analysis performed on the primary sample within the ith
pair,
n = the result of the principal analysis performed on either the collocated or duplicate
sample within the ith pair, and
n = the number of primary-collocated and primary-duplicate sample pairs.
Overall precision was calculated only when pi > MDL and n > MDL. For those sites that did not
report MDLs into AQS, it could not be determined if the records exceeded the corresponding
MDLs. As a result, such data were excluded from the overall precision calculation.
In order to ensure all precision records were evaluated, both the RP and RD data were extracted
for precision records. The precision calculation algorithm was designed to ensure that records
that appeared both in RP and RD transactions were not represented twice in the analysis of
overall precision. Approximately half of the pairs entered into AQS for overall precision
consisted of values above the MDL for CY2011 and CY2012. Overall precision for each of the
27 NATTS HAPs is presented in Table 15 for CY2011 and in Table 16 for CY2012. For the
seven HAPs of primary importance, overall precision is presented graphically in Figures 3
through 9 for CY2011 and Figures 10 through 16 for CY2012.
As is expected given the additional variability contribution of sample collection, overall
precision for CY2011 showed much greater variability than the analytical precision: the network
mean overall precision met the MQO for carbonyls, 1 PAH, 1 metal, and 5 of 16 VOCs; the
MQO was not met for chromium (VI). Only the two carbonyl compounds met the MQO of 15%
for all sites. Those VOCs that exceeded the MQO generally showed CVs of 25% or greater.
Precision data were not available for 1,2-dichloropropane, vinyl chloride, and
cis-l,3-dichloropropene and these are not included in Table 15.
As in CY2011, CY2012 overall precision showed greater variability than CY2012 analytical
precision. The network mean overall precision met the MQO for carbonyls, 1 PAH, and 5 of 16
VOCs; the MQO was not met for any of the metals or for chromium (VI). All sites achieved the
MQO for carbonyls except for Providence, RI and LaGrande, OR; for PAHs, all sites met the
MQO except for Decatur, GA, for naphthalene, which appeared to weight the network mean
overall precision to exceed the MQO. Only Dearborn, MI, and Bountiful, UT, met the MQO for
all metals and chromium (VI). Only Pinellas County, FL, met the MQO for overall precision for
%CV = 100-"I
f (Pi-n)
(Eq. 2)
2 n
where
26
-------
all VOCs measured above the MDL. Precision data were not available for 1,2-dibromoethane
and 1,2-dichloropropane and these are not included in Table 16.
As can be seen in Figures 3 through 16, the aggregate precision associated with sample
collection and analysis varies substantially by collection site and HAP when compared to the
precision associated with analytical variability alone for both CY2011 and CY2012. Although
some of this variability may be attributable to one or more extreme values, substantial effort
would be needed to determine the extent of this impact. The fact that many sites exhibit
percentage CVs above the MQO points to a collection methodology contribution to the overall
variability, particularly for metals and VOCs.
Overall precision data analysis was limited to the number of sites reporting precision sample
pairs and corresponding MDL values into AQS. A breakdown of total sites evaluated for overall
precision is included in Table 14. The number of sites reporting precision samples with
corresponding MDLs ranged from 8 (PAHs) to 24 (chromium (VI)) in both CY2011 and
CY2012. In CY2011, all sites met the precision MQO for formaldehyde and less than 85% of
sites met the MQO for six of the remaining seven HAPs of primary importance, with less than
half of sites meeting the MQO for acrolein and arsenic. In CY2012, more than 85% of sites met
the precision MQO for benzene, formaldehyde, and naphthalene with the remaining four HAPs
of primary importance showing 84% or less of sites meeting the MQO. As in CY2011, less than
50% of sites met the precision MQO for acrolein in CY2012.
Table 14. Percentage of NATTS Sites Meeting the MQO for Overall Precision -
CY2011 and CY2012
VOCs
carbonyls
PAHs
metals
1,3-
Chromium
Metric
CY
Acrolein
Benzene
Butadiene
Formaldehyde
Naphthalene
Arsenic
(VI)
Number sites
2011
19
19
19
21
8
17
24
reporting precision
values with MDLs
2012
19
20
19
19
8
16
24
Number of sites
2011
7
16
15
21
5
8
13
meeting the
precision MQO
2012
9
18
16
18
7
9
15
Percentage of sites
2011
37%
84%
79%
100%
63%
47%
54%
meeting precision
MQO
2012
47%
90%
84%
95%
88%
56%
63%
27
-------
Table 15. Overall Precision for Primary, Duplicate, and Collocated Samples > MDL - CY2011
AQS Site Code
Site Name
VOCs
BENZ
BUTA
CTET
CLFRM
EDB
EDC
MECL
TCE1122
PERC
TCE
tDCPEN
ACRO
ACRY
25-025-0042
Boston, MA
3.4 (31)
23.7 (30)
2.9 (31)
4.9 (31)
-
7.6(19)
14.1 (31)
-
3.5 (20)
6.7(1)
-
13.3 (27)
-
50-007-0007
Underhill, VT
-
-
-
-
-
-
-
-
-
-
-
-
-
44-007-0022
Providence, RI
-
-
-
-
-
-
-
-
-
-
-
-
-
36-005-0080
Bronx, NY
-
-
-
-
-
-
-
-
-
-
-
-
-
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
-
-
-
-
11-001-0043
Washington, DC
--
75.4 (3)
6.1 (27)
10.4 (25)
-
--
31.3 (27)
-
32.0(13)
--
-
-
43.9 (5)
51-087-0014
Richmond, VA
8.1 (26)
--
5.8 (26)
--
-
--
18.3 (24)
-
10.9(1)
--
-
17.8(10)
--
45-025-0001
Chesterfield, SC
8.5 (61)
--
3.5 (57)
--
0(1)
--
65.5 (57)
0(7)
14.7(16)
0(1)
-
26.5 (49)
--
13-089-0002
Decatur, GA
25.3 (23)
-
15.0(13)
-
--
-
55.6 (7)
-
12.9(1)
--
-
-
-
21-043-0500
Grayson Lake, KY
6.1 (6)
20.1 (3)
4.3 (6)
4.8 (2)
-
4.0(1)
43.5 (6)
-
-
--
-
43.1 (6)
81.9 (2)
12-057-3002
Hillsborough Cty, FL
--
--
--
--
-
--
--
--
--
-
--
--
-
12-103-0026
Pinellas Cty, FL
9.2(11)
11.9 (8)
3.5 (11)
10.2 (11)
-
18.2(10)
23.0(11)
-
20.0(11)
--
30.3 (1)
18.0(11)
52.3 (1)
26-163-0033
Dearborn, MI
4.2 (6)
6.7 (6)
7.9 (6)
34.7 (6)
--
3.6(1)
16.6 (6)
-
5.6 (4)
--
-
10.7 (6)
--
55-027-0001
Horicon, WI
0.3 (2)
-
-
-
-
-
-
-
-
-
-
12.2 (3)
-
17-031-4201
Northbrook, IL
--
--
20.7 (6)
34.5 (6)
--
5.0 (2)
30.0 (6)
-
5.2 (5)
--
-
30.5 (6)
13.6 (3)
48-201-1039
Deer Park, TX
-
-
-
-
-
-
-
-
-
-
-
-
-
29-510-0085
St. Louis, MO
5.8(8)
5.3 (8)
6.5 (8)
3.7 (6)
-
8.9 (4)
10.9 (8)
--
11.7 (5)
-
--
40.5 (8)
--
49-011-0004
Bountiful, UT
17.9 (6)
10.6 (6)
6.5 (6)
3.6 (2)
-
10.3 (3)
13.3 (6)
-
6.7 (2)
-
-
59.9 (6)
-
08-077-0017/-0018
Grand Junction, CO
5.8 (6)
5.5 (5)
27.3 (5)
7.1 (4)
--
0(1)
21.3 (6)
-
6.9 (4)
1.2(1)
-
19.2 (5)
1.9(1)
04-013-9997
Phoenix, AZ
7.0 (6)
4.1 (6)
8.1 (6)
5.1 (6)
-
6.7(1)
58.4 (6)
-
5.5 (6)
--
-
44.9 (6)
--
06-037-1103
Los Angeles, CA
--
--
--
--
-
--
--
--
--
-
--
--
-
06-065-8001
Rubidoux, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-085-0005
San Jose, CA
14.7 (29)
46.9 (7)
15.0 (29)
29.1 (20)
--
-
31.6 (24)
-
42.8 (29)
--
-
66.6 (22)
--
41-051-0246
Portland, OR
62.1 (42)
-
14.0 (21)
-
--
-
29.3 (9)
-
70.7 (1)
--
-
36.8 (22)
--
53-033-0080
Seattle, WA
4.6 (6)
5.0 (6)
13.1 (6)
16.6 (4)
—
11.5(1)
68.5 (6)
—
0.9(1)
—
—
23.9 (6)
—
Network Mean
26.8 (263)
24.6 (82) 9.8 (258)
17.5 (119)
0(1)
11.1 (42)
41.6 (234)
0(7)
26.1 (118)
3.9 (3)
30.3 (1)
.5 (187)
46.9 (12)
Overall precision is expressed as percentage coefficient of variation (%CV) with number of contributing data pairs shown in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Table 15. Overall Precision for Primary, Duplicate, and Collocated Samples > MDL - CY2011 (continued)
carbonyls
PAHs
metals
AQS Site Code
Site Name
FORM
ACET
NAPH
BaP
As
Be
Cd
Pb
Mn
Ni
CrVI
25-025-0042
Boston, MA
12.5 (30)
13.2 (30)
-
-
4.1 (37)
20.4 (6)
18.1 (37)
6.4 (37)
3.7 (37)
4.9 (36)
27.6 (5)
50-007-0007
Underhill, VT
-
-
-
-
23.2 (3)
-
16.2 (4)
4.6 (4)
4.2 (4)
0(1)
15.5 (3)
44-007-0022
Providence, RI
9.6 (23)
10.3 (23)
--
-
16.0 (20)
--
--
14.0 (23)
13.9 (27)
37.2 (26)
17.1 (5)
36-005-0080
Bronx, NY
--
--
--
-
6.7 (51)
-
6.2 (47)
2.8(51)
4.4 (51)
4.7 (51)
8.3 (6)
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
-
19.6 (5)
11-001-0043
Washington, DC
--
--
--
-
--
-
-
-
--
-
10.3 (5)
51-087-0014
Richmond, VA
2.5 (59)
2.6 (59)
--
-
--
--
--
-
-
--
11.5 (5)
45-025-0001
Chesterfield, SC
14.6 (58)
14.7 (58)
--
--
35.3 (92)
--
37.9 (98)
37.5 (98)
32.7 (100)
57.7 (14)
8.9 (2)
13-089-0002
Decatur, GA
--
--
6.4 (6)
5.2(1)
20.0(18)
53.3 (1)
--
14.2 (22)
14.0 (22)
23.4 (22)
16.8 (5)
21-043-0500
Grayson Lake, KY
6.6(16)
6.5 (16)
--
-
20.3 (39)
0(1)
20.6 (38)
15.1 (55)
26.7 (51)
35.6 (3)
20.4 (5)
12-057-3002
Hillsborough Cty, FL
2.8 (7)
2.1 (7)
15.3 (6)
13.8 (1)
21.9 (35)
--
8.6 (9)
9.8 (36)
10.3 (59)
24.5 (53)
6.0 (4)
12-103-0026
Pinellas Cty, FL
2.6 (6)
2.6 (6)
-
-
-
-
-
-
-
-
10.8 (5)
26-163-0033
Dearborn, MI
11.7 (5)
10.1 (5)
8.6 (6)
4.4 (4)
8.4 (59)
8.7 (29)
26.0 (58)
--
26.0 (58)
33.4 (58)
10.9 (6)
55-027-0001
Horicon, WI
10.5 (4)
10.0 (4)
11.2 (3)
5.8 (2)
24.1 (5)
16.7(1)
30.2 (5)
21.6 (5)
15.6 (5)
18.3 (5)
9.1 (5)
17-031-4201
Northbrook, IL
2.9 (6)
2.2 (6)
-
-
-
-
-
-
-
-
18.2 (6)
48-201-1039
Deer Park, TX
--
--
--
-
5.3 (28)
-
12.0 (8)
14.3 (28)
4.6 (28)
8.0 (28)
11.0 (6)
29-510-0085
St. Louis, MO
3.2 (6)
1.4 (6)
--
-
11.8(32)
19.7 (3)
8.6 (33)
5.1 (33)
5.5 (33)
43.2 (7)
7.9 (6)
49-011-0004
Bountiful, UT
5.6 (7)
2.3 (7)
--
-
11.0 (3)
11.1(2)
15.7 (4)
13.1 (4)
10.4 (4)
3.1(1)
22.3 (6)
08-077-0017/-0018
Grand Junction, CO
2.2 (6)
2.1 (6)
-
-
43.2(11)
--
20.2 (3)
6.3 (10)
6.1(11)
58.4(11)
10.9 (6)
04-013-9997
Phoenix, AZ
5.8(6)
2.6 (6)
-
-
-
-
-
-
-
-
31.2 (7)
06-037-1103
Los Angeles, CA
--
--
--
-
17.1 (6)
--
6.3 (3)
7.3 (6)
0(6)
3.8 (6)
35.3 (6)
06-065-8001
Rubidoux, CA
-
-
15.5 (6)
-
12.6 (5)
-
60.1 (2)
11.4 (5)
13.2 (5)
47.9 (5)
34.7 (3)
06-085-0005
San Jose, CA
-
-
-
-
-
-
-
-
-
-
-
41-051-0246
Portland, OR
11.0 (46)
10.8 (46)
22.7 (40)
4.4 (5)
4.3 (44)
6.6 (2)
12.2 (33)
7.0 (43)
14.0 (44)
4.4 (37)
11.9 (3)
53-033-0080
Seattle, WA
4.0 (6)
1.8(6)
6.0 (5)
12.7(1)
—
—
—
—
—
—
11.0 (7)
Network Mean
9.7 (285)
9.8 (285)
18.5 (67)
6.6(13)
20.3 (488)
14.4 (45) 24.7 (382)
19.6 (460)
19.8 (545)
26.9 (364)
18.3 (115)
Expressed as percentage coefficient of variation (%CV) with number of contributing data pairs presented in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Table 16. Overall Precision for Primary, Duplicate, and Collocated Samples > MDL - CY2012
AQS Site Code
Site Name
VOCs
BENZ
BUTA
CTET
CLFRM
EDC
MECL
TCE1122 PERC
TCE
VC
cDCPEN
tDCPEN
ACRO
ACRY
25-025-0042
Boston, MA
10.1 (30)
20.8 (27)
2.7 (30)
16.8 (26)
4.1 (7)
14.1 (30)
28.0(11)
5.2 (1)
-
-
-
24.2 (23)
-
50-007-0007
Underbill, VT
-
-
-
-
-
-
-
-
-
-
-
-
-
44-007-0022
Providence, RI
-
-
-
-
-
-
-
-
-
-
-
-
-
36-005-0080/-0110
Bronx, NY
3.1 (9)
35.2 (9)
1.2 (9)
9.0 (9)
4.2 (9)
29.3 (9)
32.6(1) 35.1 (9)
11.6(5)
3.9 (3)
-
-
15.8 (9)
-
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
-
-
-
-
11-001-0043
Washington, DC
-
32.5 (8)
3.8 (23)
12.9 (26)
-
11.8 (22)
29.8 (12)
-
-
-
-
-
71.1 (4)
51-087-0014
Richmond, VA
7.1 (24)
10.9(1)
5.6 (25)
-
-
35.6(10)
0(1)
-
-
-
-
25.0 (3)
-
45-025-0001
Chesterfield, SC
7.6 (59)
-
5.4 (59)
-
-
81.7 (54)
3.4(8) 1.0(13)
-
-
-
-
59.7 (2)
-
13-089-0002
Decatur, GA
27.6 (45)
-
9.4 (46)
9.1 (3)
-
-
-
-
-
-
-
-
-
21-043-0500
Grayson Lake, KY
10.5 (4)
8.2 (3)
7.2 (5)
29.8(1)
7.3 (3)
40.0 (5)
-
-
-
-
-
14.8 (5)
102.5 (3)
12-057-3002
Hillsborough Cty, FL
-
-
-
-
-
-
-
-
-
-
-
-
-
12-103-0026
Pinellas Cty, FL
1.6 (4)
6.2 (4)
1.8 (4)
8.3 (4)
4.4 (4)
2.4 (4)
10.4 (4)
-
-
2.7(1)
0(1)
5.2 (4)
-
26-163-0033
Dearborn, MI
7.8 (6)
5.6 (6)
7.0 (6)
29.0 (6)
6.4 (4)
6.3 (6)
4.7 (3)
-
-
-
-
11.8 (6)
-
55-027-0001
Horicon, WI
1.9 (2)
-
-
-
-
-
-
-
-
-
-
11.1(2)
-
17-031-4201
Northbrook, IL
-
-
9.3 (7)
20.8 (7)
7.7 (5)
14.2 (7)
7.4 (3)
10.5 (2)
-
-
-
40.9 (6)
-
48-201-1039
Deer Park, TX
-
-
-
-
-
-
-
-
-
-
-
-
-
29-510-0085
St. Louis, MO
9.0 (8)
7.8 (8)
17.9 (8)
4.9 (7)
8.8 (5)
11.2 (8)
10.7 (4)
2.0(1)
-
-
-
15.2 (8)
-
49-011-0004
Bountiful, UT
9.0 (6)
7.8 (6)
10.9 (6)
9.3 (6)
8.0 (3)
27.7 (6)
8.8(1)
-
-
-
-
5.1 (6)
-
08-077-0017/-0018
Grand Junction, CO
6.0 (6)
4.2 (6)
15.5 (6)
7.4 (4)
7.6 (5)
8.7 (6)
5.9 (5)
-
-
-
-
23.6 (6)
15.7 (1)
04-013-9997
Phoenix, AZ
2.2 (6)
4.5 (6)
3.7 (6)
2.9 (5)
3.4 (4)
38.6 (6)
4.4 (6)
-
-
-
-
21.5 (6)
-
06-037-1103
Los Angeles, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-065-8001
Rubidoux, CA
-
-
-
-
-
-
-
-
-
-
-
-
-
06-085-0005
San Jose, CA
23.6 (41)
15.8 (7)
17.0 (43)
30.1 (28)
32.4(12)
29.4 (34)
23.9 (38)
31.5 (2)
-
-
-
35.7 (39)
24.8 (8)
41-051-0246
Portland, OR
10.5 (29)
4.4 (2)
11.1 (28)
-
-
26.3 (21)
-
-
-
-
-
33.6 (30)
-
53-033-0080
Seattle, WA
6.3 (6)
3.5 (6)
8.3 (6)
14.1 (6)
0(2)
21.7 (6)
2.3 (1)
—
—
—
—
23.4 (6)
—
Network Mean
15.7 (279)
18.8 (93)
9.6 (311)
18.9 (132)
15.2 (61)
44.4 (228)
11.3(9) 21.9(110)
16.3 (11)
3.9 (3)
2.7(1)
0(1)
28.7 (155)
59.6(16)
Expressed as percentage coefficient of variation (%CV) with number of contributing data pairs presented in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Table 16. Overall Precision for Primary, Duplicate, and Collocated Samples > MDL - CY2012 (continued)
AQS Site Code
Site Name
carbonyls
PAHs
metals
FORM
ACET
NAPH BaP
As
Be
Cd
Pb
Mn
Ni
CrVI
25-025-0042
Boston, MA
6.6(19)
5.9(15)
-
3.0 (36)
13.2 (4)
27.9 (33)
3.7 (37)
2.4 (52)
8.6 (55)
5.8(12)
50-007-0007
Underhill, VT
-
-
-
33.9 (3)
-
19.7 (6)
7.0 (3)
6.4 (6)
6.6(1)
-
44-007-0022
Providence, RI
18.9 (17)
13.1 (17)
--
11.0 (25)
--
25.3 (22)
9.6 (26)
16.5 (21)
28.8 (26)
6.2 (4)
36-005-0080/-0110
Bronx, NY
--
-
-
9.6 (54)
9.7(1)
7.1 (46)
4.3 (55)
6.4 (43)
19.6 (55)
9.7 (6)
36-055-1007
Rochester, NY
-
-
-
-
-
-
-
-
-
13.9 (4)
11-001-0043
Washington, DC
--
-
-
--
--
--
-
-
-
33.7 (10)
51-087-0014
Richmond, VA
3.9 (61)
2.4 (61)
-
--
-
-
--
-
-
13.9 (6)
45-025-0001
Chesterfield, SC
6.7 (58)
9.3 (57)
-
19.4 (88)
54.1 (52)
31.4 (90)
34.0 (92)
34.8 (96)
65.6 (24)
9.7 (2)
13-089-0002
Decatur, GA
--
-
41.1 (21)
15.8 (7)
-
-
13.0(12)
21.8(12)
11.7(12)
27.4 (7)
21-043-0500
Grayson Lake, KY
2.1 (6)
1.6(6)
-
16.9 (20)
-
29.6 (22)
4.1 (24)
3.4 (24)
1.2 (2)
5.2 (3)
12-057-3002
Hillsborough Cty, FL
12.1 (5)
4.3 (5)
10.7 (12)
29.5 (41)
-
5.9(11)
21.2 (47)
7.5 (57)
13.2 (40)
0.7 (2)
12-103-0026
Pinellas Cty, FL
5.3 (6)
4.2 (6)
-
-
-
-
-
-
-
19.5 (9)
26-163-0033
Dearborn, MI
11.2 (8)
6.3 (7)
6.0(12) 14.9(8)
10.2 (58)
10.6 (32)
10.8 (58)
-
6.8 (59)
9.3 (59)
5.6 (9)
55-027-0001
Horicon, WI
7.9 (4)
6.3 (4)
4.9 (2)
5.6 (2)
--
61.5 (2)
21.4 (2)
1.6 (2)
3.4 (2)
16.5 (8)
17-031-4201
Northbrook, IL
3.9 (8)
2.6 (8)
-
3.6 (2)
9.4(1)
5.0(1)
0.3 (2)
0.1 (2)
16.5 (2)
26.2 (13)
48-201-1039
Deer Park, TX
--
-
-
23.4 (40)
0(1)
42.5 (11)
18.0 (40)
18.1 (40)
26.2 (39)
24.8 (9)
29-510-0085
St. Louis, MO
2.5 (6)
1.8(6)
-
11.2 (58)
17.1 (11)
11.9 (59)
4.6 (25)
5.2 (59)
17.0 (53)
6.4 (8)
49-011-0004
Bountiful, UT
3.9 (5)
3.6(5)
-
11.8 (4)
14.3 (2)
10.6 (4)
5.9 (4)
9.9 (4)
11.2 (3)
9.2 (6)
08-077-0017/-0018
Grand Junction, CO
1.0 (6)
1.4 (6)
-
32.3 (11)
-
52.9 (5)
47.8(11)
57.2 (12)
68.3 (12)
15.4 (3)
04-013-9997
Phoenix, AZ
10.6 (7)
3.5 (6)
-
-
-
-
-
-
-
10.1 (6)
06-037-1103
Los Angeles, CA
--
-
-
--
--
--
-
-
-
47.5 (6)
06-065-8001
Rubidoux, CA
-
-
14.0 (12)
-
-
-
-
-
-
20.6 (5)
06-085-0005
San Jose, CA
-
-
-
-
-
-
-
-
-
-
41-051-0246
Portland, OR
20.3 (30)
16.2 (30)
12.6(23) 10.4(5)
5.0 (41)
9.4 (8)
19.3 (39)
3.9 (41)
7.0 (41)
4.3 (39)
11.7 (13)
53-033-0080
Seattle, WA
3.1 (6)
1.7 (6)
4.4(11) 12.6(2)
—
—
—
—
—
—
8.0(10)
Network Mean
10.2 (246)
8.5 (239) 21.6 (82) 13.3 (13)
16.7 (490)
37.9 (112)
:3.4 (409)
20.4 (421)
19.1 (530)
24.9 (424)
19.4(151)
Expressed as percentage coefficient of variation (%CV) with number of contributing data pairs presented in parentheses.
Values shown in red exceed the MQO of < 15% CV.
-------
Site Name
Boston, MA
Richmond, VA
Chesterfield, SC
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
Portland, OR
Seattle, WA
MQO
$/$ no data available
30 45
Percent CV
i Analytical Precision ¦ Overall Precision
Figure 3. Analytical and Overall Precision Summary for Acrolein > MDL at NATTS Sample Collection Sites
CY2011
-------
Site Name
Boston, MA
Richmond, VA
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
Portland, OR
Seattle, WA
MQO
15
30 45
Percent CV
60
75
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 4. Analytical and Overall Precision Summary for Benzene > MDL at NATTS Sample Collection Sites in
CY2011
-------
Site Name
Boston, MA
Washington, DC
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
Seattle, WA
15
30
45
Percent CV
60
75
90
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 5. Analytical and Overall Precision Summary for 1,3-Butadiene > MDL at NATTS Sample Collection Sites in
CY2011
-------
Site Name
Boston, MA
Underbill, VT
Providence, Rl
Richmond, VA
Chesterfield, SC
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
Portland, OR
Seattle, WA
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 6. Analytical and Overall Precision Summary for Formaldehyde > MDL at NATTS Sample Collection Sites in
CY2011
-------
Site Name
Decatur, GA
Hillsborough Cty, FL
Dearborn, Ml
Horicon, Wl
Rubidoux, CA
Portland, OR
Seattle, WA
* no data available
*
0 5 10 15 20 25
Percent CV
¦ Analytical Precision ¦ Overall Precision
Figure 7. Analytical and Overall Precision Summary for Naphthalene > MDL at NATTS Sample Collection Sites
CY2011
-------
Site Name
Boston, MA
Underbill, VT
Providence, Rl
Bronx, NY
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Dearborn, Ml
Horicon, Wl
Deer Park, TX
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Los Angeles, CA
Rubidoux, CA
Portland, OR
MQO
10
15
20 25
Percent CV
30
35
40
45
$ no data available
i Analytical Precision ¦ Overall Precision
Figure 8. Analytical and Overall Precision Summary for PMio Arsenic > MDL at NATTS Sample Collection Sites
CY2011
-------
oo
oo
Site Name
Boston, MA
Underbill, VT
Providence, Rl
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
Deer Park, TX
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
Los Angeles, CA
Rubidoux, CA
Portland, OR
Seattle, WA
MQO
* no data available
i Analytical Precision ¦ Overall Precision
Figure 9. Analytical and Overall Precision Summary for Chromium (VI) > MDL at NATTS Sample Collection Sites in
CY2011
-------
Site Name
Boston, MA
Bronx, NY
Richmond, VA
Chesterfield, SC
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
La Grande, OR
Seattle, WA
MQO
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 10. Analytical and Overall Precision Summary for Acrolein > MDL at NATTS Sample Collection Sites in
CY2012
-------
Site Name
Boston, MA
Bronx, NY
Richmond, VA
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
La Grande, OR
Seattle, WA
MQO
10
15
Percent CV
20
25
30
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 11. Analytical and Overall Precision Summary for Benzene > MDL at NATTS Sample Collection Sites in
CY2012
-------
Site Name
Boston, MA
Bronx, NY
Washington, DC
Richmond, VA
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Northbrook, IL H
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
La Grande, OR
Seattle, WA
MQO
10 15 20 25
Percent CV
30
35
40
$/$ no data available
I Analytical Precision ¦ Overall Precision
Figure 12. Analytical and Overall Precision Summary for 1,3-Butadiene > MDL at NATTS Sample Collection Sites
CY2012
-------
Site Name
Boston, MA
Underbill, VT
Providence, Rl
Richmond, VA
Chesterfield, SC
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
La Grande, OR
Seattle, WA
MQO
10 15
Percent CV
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 13. Analytical and Overall Precision Summary for Formaldehyde > MDL at NATTS Sample Collection Sites
CY2012
-------
Site Name
Boston, MA
Underbill, VT
Providence, Rl
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
St. Louis, MO
Bountiful, UT
Phoenix, AZ
Los Angeles, CA
Rubidoux, CA
San Jose, CA
Seattle, WA
*/* no data available
0 5 10 15 20 25 30 35 40 45
Percent CV
¦ Analytical Precision ¦ Overall Precision
Figure 14. Analytical and Overall Precision Summary for Naphthalene > MDL at NATTS Sample Collection Sites in
CY2012
-------
Site Name
Boston, MA
Underbill, VT
Providence, Rl
Bronx, NY
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
Deer Park, TX
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
San Jose, CA
La Grande, OR
Seattle, WA
MQO
10 15 20 25
Percent CV
30
35
40
$/$ no data available
i Analytical Precision ¦ Overall Precision
Figure 15. Analytical and Overall Precision Summary for PMio Arsenic > MDL at NATTS Sample Collection Sites
CY2012
-------
Site Name
Boston, MA
Underhill, VT
Providence, Rl
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Grayson Lake, KY
Hillsborough Cty, FL
Pinellas Cty, FL
Dearborn, Ml
Horicon, Wl
Northbrook, IL
Deer Park, TX
Harrison Cty, TX
St. Louis, MO
Bountiful, UT
Grand Junction, CO
Phoenix, AZ
Los Angeles, CA
Rubidoux, CA
La Grande, OR
Seattle, WA
MQO
5f / no data available
I Analytical Precision ¦ Overall Precision
Figure 16. Analytical and Overall Precision Summary for Chromium (VI) > MDL at NATTS Sample Collection Sites in
CY2012
-------
2.6 Laboratory Bias Data Based on Proficiency Testing (PT) Samples
PT analyses were performed in CY2011 QTR2 and QTR4 and in CY2012 QTR 1. Blind
"spiked" PT samples were prepared for metals and PAHs for CY2011 QTR2 by Wibby
Environmental. Battelle prepared VOC and carbonyl PT samples in CY2011 QTR4 and
prepared metals, PAH, and chromium (VI) PTs in CY2012 QTR1. Participating NATTS
analysis laboratories submitted results to the respective PT provider, which were evaluated for
acceptability by the provider, Wibby Environmental or Battelle, as appropriate.
Laboratory bias is measured by the percentage difference between the laboratory's measured
value and the target value for the PT sample for a given HAP:
Measured - Target 1\
%Differenc e = 2 100 (Eq. J)
Target
Target values were typically assigned as the average of the results of one or more confirmatory
analysis (referee) samples.
The percentage of NATTS laboratories that participated in the PT program for CY2011 and
CY2012 is shown in Table 17.
Table 17. Percentage of NATTS Laboratories Participating in the NATTS Proficiency
Testing Program in CY2011 and CY2012
PT year and quarter
VOCs
carbonyls
PAHs
metals
chromium (VI)
CY2011 QTR2
-
-
83%
69%
-
CY2011 QTR4
100%
92%
-
-
-
CY2012 QTR1
-
-
100%
100%
100%
The CY2011 and CY2012 PT samples were prepared to contain the 27 HAPs listed in Table 2
(except acrylonitrile) and many of the 11 HAPs given in Table 18. These 11 additional HAPs
include two carbonyls, six PAHs, and three metals.
46
-------
Table 18. Additional HAPs Contained in NATTS Proficiency Test Samples in
CY2011 and/or CY2012
HAP
HAP
Abbreviation
HAP Class
Spiked in
CY2011 PT
Samples?
Spiked in
CY2012 PT
Samples?
benzaldehyde
BNZD
carbonyl
Yes
No
propionaldehyde
PRPD
carbonyl
Yes
No
acenaphthene
ACEN
PAH
Yes
Yes
anthracene
ANTH
PAH
Yes
Yes
fluorene
FLUR
PAH
Yes
Yes
fluoranthene
FTHN
PAH
Yes
Yes
phenanthrene
PHEN
PAH
Yes
Yes
pyrene
PYR
PAH
Yes
Yes
cobalt
Co
metal
Yes
Yes
antimony
Sb
metal
No
Yes
selenium
Se
metal
Yes
Yes
For the two PTs performed in CY2011, the PT samples were spiked with 15 VOCs, four
carbonyls, eight PAHs, and eight metals, for a total of 35 HAPs. Tables 21 through 24 present
the PT results for these 35 HAPs for the two CY2011 PTs (one table per HAP class). Tables 25
through 27 present the PT results for the CY2012 PT for the eight PAHs, nine metals, and
chromium (VI) for a total of 18 HAPs. To reflect overall bias independent of direction, the mean
of the absolute value of the percent difference, along with the minimum and maximum values,
are presented at the bottom and in the right-most columns of these tables.
Figures 17 and 18 are box and whisker plots summarizing the percent difference values for
CY2011 and CY2012, respectively, for the seven HAPs of primary importance: acrolein,
benzene, 1,3-butadiene, formaldehyde, naphthalene, arsenic, and chromium (VI). The CY2012
PT only included PAHs, metals, and chromium (VI), hence only three of the seven HAPs of
primary importance were analyzed. A laboratory's results were included in these summaries
only if the laboratory provided analysis results for a particular sample type.
The two reference lines in Figures 17 and 18 represent the MQO of 25% for laboratory bias, in
either direction of zero bias. Thus, laboratories whose percent difference values fall within the
reference lines have achieved the MQO. Those results that fall more than 1.5 times the IQR
either above the 75th percentile or below the 25th percentile are identified by their laboratory
number (Tables 10 and 11). Figures 17 and 18 present PT results for all labs participating in the
NATTS PT program, including those labs not affiliated with NATTS sites. These non-NATTS
labs are assigned identification codes similar to those of the NATTS labs; see Table 19.
47
-------
Table 19. Non-NATTS Laboratories Analyzing Proficiency Test Samples
in CY2011 and CY2012
Laboratory
Code(s)
Laboratory Description
01-04-V
US EPA Region I Laboratory
01-05-V
Maine Department of Environmental Protection Air Laboratory
03-03-M
Pennsylvania Department of Environmental Protection, Bureau of Air Quality
04-06-V
North Carolina Department of Environment and Natural Resources
05-04-C,M,V
State of Minnesota Pollution Control Agency
05-06-M,V
Indiana Department of Environmental Management
05-07-M,V
Ohio Environmental Protection Agency Division of Environmental Services Lab
07-02-C,V
State Hygenic Laboratory at The University of Iowa
09-06-C,V
Air Pollution Control District County of San Diego
09-09-V
Joint Water Pollution Control Plant of Los Angeles County
11-03-V
US EPA National Exposure Research Laboratory
As can be seen in Tables 21 through 27, and as is summarized in Figures 17 and 18, with some
exceptions for certain laboratories and HAPs, the majority of laboratories met the laboratory bias
MQO for each of the three rounds of PTs for the seven HAPs of primary importance. In Figures
17 and 18, the central tendency of the analysis bias is best characterized by the median bias
(indicated by black horizontal lines within the IQR boxes), which lessen the effect of extreme
values.
Figure 17 shows that across laboratories, PT analyses in CY2011, based on the median bias,
tended to demonstrate a marginally low analytical bias for acrolein, formaldehyde, and arsenic, a
marginally high analytical bias for benzene, a slightly high analytical bias for 1,3-butadiene, and
a very low analytical bias for naphthalene. As shown in Table 20, percentages of NATTS
laboratories meeting the MQO for acrolein, benzene and 1,3-butadiene were 77%, 85%, and
85%, respectively. All NATTS laboratories but one met the MQO for arsenic and for
formaldehyde. For the five NATTS laboratories reporting PAH results, only two laboratories
met the MQO for naphthalene. Specifically, acceptable measurement bias was difficult to obtain
for acrolein and naphthalene; the mean absolute percent bias across all participating laboratories
was 29.5% and 26.0%, respectively. The CY2011 PAH PT results should be interpreted with
caution, as it appears that the target value may have been biased high: all reported results but one
showed a negative bias.
For the three HAPs of primary importance that were spiked for the CY2012 PT (naphthalene,
arsenic, and chromium (VI)), analytical bias was slightly high for naphthalene and arsenic and
very high for chromium (VI) as seen in Figure 18. All NATTS laboratories met the MQO for
chromium (VI) and all but one laboratory met the MQO for both naphthalene and arsenic.
CY2012 PT results are shown in Tables 25 through 27.
48
-------
Table 20. Percentages of NATTS Laboratories Meeting the Bias MQO for Proficiency Test
Samples in CY2011 and CY2012
VOCs
carbonyls
PAHs
metals
CY
Acrolein
Benzene 1,3-Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium (VI)
2011
77%
85% 85%
87%
40%
90%
-
2012
-
-
-
83%
93%
100%
49
-------
Table 21. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for VOCs - CY2011 QTR4
o
Lab Code
Laboratory Description
ACRO
BENZ
BUTA
CLFRM
CTET
DCP
EDB
EDC
MECL
PERC
TCE
TCE 1122
VC
c-DCPEN
t-DCPEN
Mean
Abs. Bias
(across HAPs)
Min
Max
01-01-V
RI Dept of Health
-10.0
15.4
1.9
-10.7
-3.6
-4.4
8.1
-15.1
-6.7
0.4
-11.9
-3.4
-7.0
1.8
14.2
7.6
-15.1
15.4
01-04-V
US EPA Region 1 Laba
-
-10.6
-4.2
-10.0
-2.0
-42.1
-16.2
-30.0
-8.5
-17.7
-28.7
-21.5
-7.2
-3.7
0.9
14.5
-42.1
0.9
01-05-V
Maine DEP Air Laba
-4.3
22.8
3.3
-3.4
3.8
-
22.1
-1.0
6.8
7.6
19.8
77.4
-3.2
-
39.3
16.5
-4.3
11A
02-01-V
New York State DEC
3.4
12.4
6.4
-11.8
2.6
0.4
3.4
-14.4
0.6
6.0
-3.6
-3.7
-4.1
7.5
26.3
7.1
-14.4
26.3
03-01-V
Maryland DOE
2.8
4.0
6.2
-14.0
-4.9
-2.3
-3.9
-13.3
-4.9
-0.4
-9.7
-13.0
-5.4
-5.9
28.6
7.9
-14.0
28.6
03-02-V
Virginia Division of
Consolidated Labs
45.9
23.8
17.9
-5.5
3.1
12.3
35.8
6.7
5.8
14.7
6.7
48.1
18.0
0.7
25.2
18.0
-5.5
48.1
04-01-V
Pinellas County DEM AQD
-12.3
6.0
3.1
-10.8
2.2
3.0
12.6
-14.4
-10.2
8.4
-1.3
-4.9
-2.1
22.5
40.0
10.2
-14.4
40.0
04-02-V
SCDHEC/DAQA
-42.6
-41.9
-42.1
-45.8
-38.6
-38.9
-29.8
-45.2
-45.4
-32.8
-38.7
-19.3
-37.7
-27.0
-14.3
36.0
-45.8
-14.3
04-04-V
Georgia DNR
-25.0
-11.3
-13.7
-25.8
-20.0
-17.2
-15.5
-21.2
-20.0
-20.8
-19.7
-22.2
-14.4
-1.5
17.8
17.7
-25.8
17.8
04-06-V
North Carolina DENRa
197.8
18.9
12.4
2.9
2.2
23.0
30.5
2.5
4.2
26.8
13.2
38.6
6.6
26.7
51.2
30.5
2.2
197.8
05-03-V
Wisconsin DNR
29.4
43.4
36.8
9.1
25.4
33.3
9.4
21.2
32.2
20.8
20.0
40.7
37.7
14.8
26.1
26.7
9.1
43.4
05-04-V
Minnesota PCAa
-
8.4
10.9
-19.1
2.4
-2.6
-4.8
-14.5
6.9
8.6
-4.9
-7.7
5.8
5.3
17.3
8.5
-19.1
17.3
05-06-V
Indiana DEM a
53.5
49.1
49.8
26.1
42.7
17.9
32.8
41.2
47.8
43.8
21.3
29.6
35.7
28.9
58.3
38.6
17.9
58.3
05-07-V
Ohio EPAa
-
32.1
19.3
-3.0
5.1
12.3
77.4
-6.1
8.5
-5.7
33.3
18.5
18.0
66.7
130.4
31.2
-6.1
130.4
06-01-V
Texas CEQ Air Laboratory
-11.8
13.2
5.3
-9.1
15.3
-12.3
20.8
-15.2
-11.9
5.7
0.0
3.7
-8.2
25.9
47.8
13.7
-15.2
47.8
07-02-V
State Hygenic Lab, Univ. of
Iowaa
27.4
32.8
-2.8
26.4
19.3
31.6
57.0
45.2
15.6
59.6
30.3
71.5
-3.0
34.4
82.2
35.9
-3.0
82.2
09-03-V
BAAQMD
19.1
20.8
17.5
3.0
32.2
-
37.7
4.5
20.3
84.9
6.7
-
6.6
-
-
23.0
3.0
84.9
09-06-V
San Diego APCDa
-13.3
13.1
2.2
-5.6
2.0
-5.2
7.7
-12.9
0.7
11.3
-2.2
3.8
2.8
15.0
48.4
9.7
-13.3
48.4
09-08-V
South Coast AQMD
Laboratory
-8.5
9.8
1.1
-12.4
-5.1
2.5
6.4
-13.6
-2.0
9.4
-11.7
9.6
-3.9
5.6
28.3
8.7
-13.6
28.3
09-09-V
JWPCP of Los Angeles3
-
17.0
8.8
-6.1
5.1
-
17.0
-6.1
5.1
13.2
6.7
-
4.9
-
-
9.0
-6.1
17.0
10-02-V
Oregon DEQ
14.7
-10.2
-23.2
-27.6
-13.2
-17.2
-9.8
-31.8
-11.9
-20.4
-18.7
-14.4
-17.0
1.5
8.3
16.0
-31.8
14.7
11-01-V
ERG
-20.3
10.2
10.9
-9.7
25.4
2.8
5.7
-11.8
6.4
0.8
-8.3
1.1
0.3
21.5
41.3
11.8
-20.3
41.3
11-03-V
US EPA NERLa
-18.5
6.4
0.4
-13.6
-3.4
-2.5
20.4
-15.8
0.7
7.9
-5.7
5.9
-5.2
10.0
40.4
10.5
-18.5
40.4
Mean Bias (across laboratories)
12.0
12.4
5.6
-7.7
4.3
-0.3
14.1
-7.0
1.7
10.1
-0.3
11.4
0.8
12.5
36.1
Mean Abs. Bias (across laboratories)
29.5
18.8
13.0
13.5
12.2
14.2
21.1
17.5
12.3
18.6
14.0
19.9
11.1
16.3
37.5
17.8
Median Bias (across laboratories)
-4.3
13.1
5.3
-9.7
2.4
-1.0
9.4
-13.3
0.7
7.9
-2.2
3.7
-3.0
8.7
28.6
Minimum
-42.6
-41.9
-42.1
-45.8
-38.6
-42.1
-29.8
-45.2
-45.4
-32.8
-38.7
-22.2
-37.7
-27.0
-14.3
Maximum
197.8
49.1
49.8
26.4
42.7
33.3
77.4
45.2
47.8
84.9
33.3
77.4
37.7
66.7
130.4
a Laboratories not performing analysis for NATTS sites
Values listed in red indicate absolute bias outside the MQO (>25%); values listed in rangi indicate absolute bias between 20-25%.
-------
Table 22. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for Carbonyls - CY2011 QTR4
Mean
Laboratory
Abs. Bias (across
Code
Laboratory Description
ACET
BNZD
FORM
PRPD
HAPs)
Min
Max
01-01-C
Rhode Island Department of Health Air Pollution Lab
0.5
-
6.8
-
3.6
0.5
6.8
01-03-C
Massachusetts Division of Environmental Protection
-7.6
-5.6
-8.4
-16.9
9.6
-16.9
-5.6
01-04-C
US EPA Region 1 Laboratory
-1.4
2.1
1.3
-4.6
2.4
-4.6
2.1
02-01-C
New York State Department of Environmental Conser
-22.8
-19.3
-25.5
-29.4
24.2
-29.4
-19.3
03-01-C
Philadelphia Air Management Services Laboratory
-5.6
-
-5.8
-15.4
8.9
-15.4
-5.6
03-02-C
Virginia Division of Consolidated Services Laboratory
-3.7
-
-0.8
-10.0
4.8
-10.0
-0.8
04-02-C
South Carolina Division of Health and Envir Control
-1.0
-
6.6
-
3.8
-1.0
6.6
04-03-C
Kentucky Division of Environmental Services
69.5
75.8
66.9
56.2
67.1
56.2
75.8
04-04-C
Georgia Department of Natural Resources
-16.5
-5.1
-21.7
-30.5
18.5
-30.5
-5.1
05-03-C
Wisconsin State Laboratory of Hygiene
-4.6
-8.9
-5.8
-15.4
8.7
-15.4
-4.6
05-04-C
State of Minnesota Pollution Control Agency
-7.6
-10.0
-9.1
-15.4
10.5
-15.4
-7.6
06-01-C
Texas Commission on Environmental Quality Air Lab
-7.6
-0.4
-5.8
-23.1
9.2
-23.1
-0.4
07-02-C
State Hygenic Laboratory at The University of Iowa
-5.6
-3.2
-6.8
-11.5
6.8
-11.5
-3.2
09-03-C
Bay Area Air Quality Management District
-6.8
-
-6.3
-
6.5
-6.8
-6.3
09-06-C
Air Pollution Control District County of San Diego
-0.4
-
-0.6
-
0.5
-0.6
-0.4
09-08-C
South Coast Air Quality Management District
-2.8
-
-2.1
-
2.5
-2.8
-2.1
10-02-C
Oregon Division of Environmental Quality
-1.8
-1.3
-3.6
-7.7
3.6
-7.7
-1.3
11-01-C
Environmental Resource Group
3.0
8.0
-3.4
-14.6
7.3
-14.6
8.0
Mean Bias (across laboratories)
-1.3
2.9
-1.3
-10.6
Mean Abs. Bias (across laboratories)
9.4
12.7
10.4
19.3
11.0
Median Bias (across laboratories)
-4.1
-3.2
-4.7
-15.4
Minimum
-22.8
-19.3
-25.5
-30.5
Maximum
69.5
75.8
66.9
56.2
a Laboratories not performing analysis for NATTS sites
Values listed in red indicate absolute bias outside the MQO (>25%); values listed in rangi indicate absolute bias between 20-25%.
-------
Table 23. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for Metals - CY2011 QTR2
Mean
Abs.
Bias
Laboratory
(across
Code
Laboratory Description
As
Be
Cd
Co
Mn
Ni
Pb
Se
HAPs)
Min
Max
01-01-M
Rhode Island Department of Health Air Pollution Laboratory
-
49
-16.1
-
5.4
1.9
-5.4
-
15.5
-16.1
49
03-02-M
Virginia Division of Consolidated Services Laboratory
-6.8
-8.2
-11.5
-
-6.5
-8.9
-7.5
-
8.2
-11.5
-6.5
04-01-M
Enviromental Protection Commission of Hillsborough County
24.7
-7
-4.6
-2.9
-1.1
-5.4
0.6
-11.1
7.2
-11.1
24.7
04-02-M
South Carolina Division of Health and Environmental Control
-15.1
-14.8
-8
10.6
12.4
3
13.7
-27.3
13.1
-27.3
13.7
04-04-M
Georgia Division of Natural Resources
-5.5
-2.5
-9.2
-2.9
-4.3
-8.1
-6.6
-14.2
6.7
-14.2
-2.5
05-03-M
Wisconsin State Laboratory of Hygiene
-2.7
3.7
-4.6
-
8.1
-5.1
-0.3
-
4.1
-5.1
8.1
06-01-M
Texas Commission on Environmental Quality Air Laboratory
2.7
10.7
5.7
-
4.3
11.4
3.3
-
6.4
2.7
11.4
09-08-M
South Coast Air Quality Management District
-15.1
-18.9
-13.8
-10.1
-14.5
-11.1
-10.4
-20.9
14.4
-20.9
-10.1
10-02-M
Oregon Division of Environmental Quality
1.4
-8.6
-5.7
-6.7
-5.4
-9.2
-3.3
-10.9
6.4
-10.9
1.4
11-01-M
Environmental Resource Group
1.4
-8.2
-5.7
-4.3
-3.8
-6.8
-6.3
-15.6
6.5
-15.6
1.4
Mean Bias (across laboratories)
-1.7
-0.5
-7.4
-2.7
-0.5
-3.8
-2.2
-16.7
Mean Abs. Bias (across laboratories)
8.4
13.2
8.5
6.3
6.6
7.1
5.7
16.7
8.8
Median Bias (across laboratories)
-2.7
-7.6
-6.9
-3.6
-2.4
-6.1
-4.3
-14.9
Minimum
-15.1
-18.9
-16.1
-10.1
-14.5
-11.1
-10.4
-27.3
Maximum
49.0
5.7
10.6
12.4
11.4
13.7
-10.9
Values listed in red indicate absolute bias outside the MQO (>25%); values listed in rangi indicate absolute bias between 20-25%.
-------
Table 24. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for PAHs - CY2011 QTR2
Laboratory
Code
Laboratory Description
ACEN
ANTH
BaP
FLUR
FTHN
NAPH
PHEN
PYR
Mean
Abs.
Bias
(across
HAPs)
Min
Max
03-02-P
Virginia Division of Consolidated Services Laboratory
-30.5
-37.0
-17.5
3.9
-29.7
-16.7
-6.9
-37.0
3.9
04-02-P
South Carolina Division of Health and Environmental Control
-29.7
-25.7
-27.4
-36.1
-27.3
-30.7
-23.3
-24.6
28.1
-36.1
-23.3
06-01-P
Texas Commission on Environmental Quality Air Laboratory
-15.9
-10.7
-11.2
-10.3
-14.3
-23.7
-5.0
-14.6
13.2
-23.7
-5.0
10-02-P
Oregon Division of Environmental Quality
-26.6
-14.3
-11.1
-24.7
-14.0
-32.0
-23.3
-13.3
19.9
-32.0
-11.1
11-01-P
Environmental Resource Group
-11.9
-13.6
-2.1
-7.2
-9.4
-13.9
-8.3
-6.9
9.2
-13.9
-2.1
Mean Bias (across laboratories)
-21.6
-19.0
-17.8
-19.2
-12.2
-26.0
-15.3
-13.2
Mean Abs. Bias (across laboratories)
21.6
19.0
17.8
19.2
13.8
26.0
15.3
13.2
18.2
Median Bias (across laboratories)
-24.1
-14.3
-11.2
-17.5
-14.0
-29.7
-16.7
-13.3
Minimum
-29.7
-30.5
-37.0
-36.1
-27.3
-32.0
-23.3
-24.6
Maximum
-11.9
-10.7
-2.1
-7.2
3.9
-13.9
-5.0
-6.9
Values listed in red indicate absolute bias outside the MQO (>25%); values listed in orange indicate absolute bias between 20-25%.
Ui
-------
Table 25. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for Metals - CY2012 QTR1
Mean
Abs.
Bias
Laboratory (across
Code
Laboratory Description
As
Be
Cd
Co
Mn
Ni
Pb
Sb
Se
HAPs)
Min
Max
01-01-M
Rhode Island Department of Health Air Pollution Laboratory
-28.8
-8.2
-
-5.2
-10.8
4.0
-2.1
-
11.5
-28.8
03-01-M
West Virginia Department of Environmental Protection
-0.1
7.2
8.5
-
5.6
-7.4
11.4
-
-
6.7
-7.4
11.4
03-02-M
Virginia Division of Consolidated Services Laboratory
12.9
14.3
8.3
-
8.9
-0.3
10.2
-
-
9.1
-0.3
14.3
03-03-M
Pennsylvania Department of Environmental Protection, Bureau of
Air Quality
-11.3
-12.5
1.5
11.6
13.7
2.8
13.3
-10.7
-45.0
13.6
-45.0
13.7
04-01-M
Enviromental Protection Commission of Hillsborough County
3.1
9.3
7.0
15.5
13.8
21.9
16.9
32.0
9.5
14.3
3.1
32.0
04-02-M
South Carolina Division of Health and Environmental Control
-11.7
-4.5
3.9
14.6
15.9
-5.0
21.8
-32.1
-33.7
15.9
-33.7
21.8
04-03-M
Kentucky Division of Environmental Services
7.8
7.6
5.7
-
8.1
2.3
7.2
-19.9
-
8.4
-19.9
8.1
04-04-M
Georgia Division of Natural Resources
4.9
7.2
4.2
16.0
11.0
2.1
10.9
-8.5
-21.8
9.6
-21.8
16.0
05-01-M
Michigan Department of Environmental Quality
-7.5
-6.0
-9.4
-2.1
-2.2
-17.5
-1.0
-
-
6.5
-17.5
-1.0
05-03-M
Wisconsin State Laboratory of Hygiene
10.8
14.7
12.0
-
16.5
5.2
16.8
-
-
12.7
5.2
16.8
05-04-M
State of Minnesota Pollution Control Agency
24.7
1.8
-4.8
8.9
2.1
-9.0
10.3
8.4
-21.7
10.2
-21.7
24.7
05-06-M
Indiana Department of Environmental Management
36.3
-1.3
10.5
-
15.4
60.2
27.6
-
-
25.2
-1.3
60.2
05-07-M
Ohio Environmental Protection Agency Division of
Environmental Services Laboratory
13.7
16.9
12.2
19.8
-
0.7
11.1
-
-25.3
14.2
-25.3
19.8
06-01-M
Texas Commission on Environmental Quality Air Laboratory
13.5
17.1
9.0
-
11.0
3.4
12.8
-
-
11.1
3.4
17.1
08-02-M
Colorado Department of Public Health and Environment,
Laboratory Services Division
17.6
17.7
15.6
29.2
141.8
7.1
31.9
7.3
-4.2
30.2
-4.2
141.8
09-08-M
South Coast Air Quality Management District
-1.6
-1.9
-1.1
11.8
8.5
-8.1
8.7
-5.1
-22.6
7.7
-22.6
11.8
10-02-M
Oregon Division of Environmental Quality
10.8
8.4
8.5
12.1
7.5
-3.3
5.0
-
-21.9
9.7
-21.9
12.1
11-01-M
Environmental Resource Group
15.7
17.5
16.6
29.8
21.5
11.4
19.9
-6.0
-7.3
16.2
-7.3
29.8
11-02-M
RTI International
6.2
14.5
7.1
11.2
5.1
-7.4
7.9
-3.4
-13.3
8.5
-13.3
14.5
Mean Bias (across laboratories)
6.2
7.9
5.6
14.9
16.6
2.5
13.0
-3.6
-18.8
Mean Abs. Bias (across laboratories)
12.6
10.6
8.1
15.2
17.4
9.8
13.1
12.3
20.6
12.7
Median Bias (across laboratories)
7.8
8.4
7.1
13.3
10.0
0.7
11.1
-5.1
-21.8
Minimum
-28.8
-12.5
-9.4
-2.1
-5.2
-17.5
-1.0
-32.1
-45.0
Maximum
36.3
21.0
16.6
29.8
141.8
60.2
31.9
32.0
9.5
a Laboratories not performing analysis for NATTS sites
Values listed in red indicate absolute bias outside the MQO (>25%); values listed in rangi indicate absolute bias between 20-25%.
-------
Table 26. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for PAHs - CY2012 QTR1
Mean
Abs.
Bias
Laboratory
(across
Code
Laboratory Description
ACEN
ANTH
BaP
FLUR
FTHN NAPH PHEN
PYR
HAPs)
Min
Max
03-02-P
Virginia Division of Consolidated Services Laboratory
-2.1
27.3
33.0
12.8
23.7
27.7
-2.1
33.0
04-02-P
South Carolina Division of Health and Environmental Control
-15.5
-22.4
17.5
-27.1
-13.2
-21.0
-1.1
-11.4
16.1
-27.1
17.5
05-03-P
Wisconsin State Laboratory of Hygiene
10.5
5.9
45.6
16.3
29.7
8.0
26.3
46.5
23.6
5.9
46.5
06-01-P
Texas Commission on Environmental Quality Air Laboratory
16.8
15.6
14.6
15.7
26.5
32.8
61.1
24.9
26.0
14.6
61.1
10-02-P
Oregon Division of Environmental Quality
-2.1
2.4
29.1
-7.6
11.1
-14.2
7.4
15.1
11.1
-14.2
29.1
11-01-P
Environmental Resource Group
19.2
4.1
25.2
9.6
15.1
18.4
17.9
16.4
4.1
25.2
Mean Bias (across laboratories)
8.7
0.6
25.4
5.7
17.0
6.6
22.6
20.1
Mean Abs. Bias (across laboratories)
14.6
8.7
25.4
17.3
21.4
18.4
23.0
23.9
19.1
Median Bias (across laboratories)
13.7
3.2
22.8
12.7
20.8
10.4
21.1
21.4
Minimum
-15.5
-22.4
14.6
-27.1
-13.2
-21.0
-1.1
-11.4
Maximum
15.6
45.6
27.3
33.0
32.8
61.1
46.5
a. Reported results were from a second PT sample which replaced the first. Sample storage integrity had been compromised during shipping.
Values listed in red indicate absolute bias outside the MQO (>25%); values listed in rangi indicate absolute bias between 20-25%.
-------
Table 27. NATTS Proficiency Testing Bias Results (Percent Difference from Target) for
Chromium (VI) - CY2012 QTR1
Laboratory Code
Laboratory Description
Chromium (VI)
Virginia Division of Consolidated Services
03-02-R
Laboratory
21.7
09-08-R
South Coast Air Quality Management District
18.0
10-02-R
Chester LabNet
14.6
11-01-R
Environmental Resource Group
19.5
Mean Bias (across laboratories)
18.5
Mean Abs. Bias (across laboratories)
18.5
Median Bias (across laboratories)
18.8
Minimum
14.6
Maximum
Values listed in oram indicate absolute bias between 20-25%.
56
-------
100
75
50-
25
0-
-25
-50
-75
-100-
04-06
198%
Difference
0 04-03
-&05-06
O05-06
0 05-03
.04-01
*
o 04-02
10 02
O04-02
gO«l.
02-01
i
r
10-02
Dashed lines indicate +/-25% WGO
ACRO BENZ BUTA FORM NAPH
HAP
AS
Figure 17. Distribution of Laboratory Bias by HAP for Proficiency Testing Data - CY2011
57
-------
40
—06-01
20-
14 I
©
g
—i—
-20- ! !
01-01
-40 - Dashed Inos indicate +/-25% MQO
As NAPH CrVI
HAP
Figure 18. Distribution of Laboratory Bias by HAP for Proficiency Testing Data - CY2012
2.7 Flow Audit Results from Instrument Performance Audits (IPAs)
Instrument performance audits (IPAs) of carbonyl, PAH, PMio, and chromium (VI) sampler
units were performed at the following NATTS field sites as follows:
• CY2011 (eight sites): Rochester, NY; Bronx, NY; Washington, DC; Richmond, VA;
Chesterfield, SC; Decatur, GA; Hillsborough County, FL; and Pinellas County, FL
• CY2012 (five sites): Horicon, WI; Northbrook, IL; Deer Park, TX; St Louis, MO;
and Portland, OR.
RTI performed the flow audits in CY2011 and CY2012. During each IPA, when flows were
sufficient for measurement, the flow rates on all sampler types at the NATTS site were
determined with certified, calibrated volumetric flow measurement devices and reported in
standard temperature and pressure (STP, 25°C and 1 atm) or ambient conditions (also referred to
as local conditions, LC) based on the typical reporting convention of the site operators. Field
bias was calculated by comparing the sampler flow reading (or setting) to the audit flow rate.
58
-------
Field bias is defined as the percentage difference between the site flow (Fs) and the audit flow
(Fa) under the same conditions (standard or ambient):
Fs — Fa
% Difference = 100 (Eq. 4)
Fa
The results from the flow audits conducted during CY2011 and CY2012 are indicated in
Tables 29 and 30 respectively. If present at the site, collocated samplers were also audited.
Carbonyl and chromium (VI) samplers may have multiple flow channels which allow for
duplicate sampling; the flow rates of any such flow channels were audited when used by the site
to collect duplicate samples. PMio metals and PAH samplers have only primary channels.
With few exceptions, most air samplers met the flow bias MQO of < 10%. The most frequent
exceedances occurred for PAH and chromium (VI) samplers. With the exception of VOC
samplers, which were not audited, the mean and mean absolute network flow bias met the MQO
for all HAP classes in CY2011 and CY2012, as indicated in Table 28.
Table 28. Mean Network Flow Bias From CY2011 and CY2012
HAP class
CY
Flow Bias (% difference)
VOC carbonyl
PAH
metals
Cr(VI)
2011
mean
-3.1
-3.7
1.4
-1.3
mean absolute
3.7
7.6
3.5
7.6
2012
mean
-1.8
2.5
-1.1
0.4
mean absolute
2.0
2.6
1.6
3.0
59
-------
Table 29. Flow Audit Results from the Instrument Performance Audits - CY2011
Site Identifier
and AQS ID
Method
Precision
Assignment
Channel
Sampler
Reading
Standard Reading
Units
Conditions
Percent
Difference
Rochester, NY
36-055-1007
voc
carbony
1
primary
primary
1
0.999
no flow readings recorded
0.984 L/min
ambient
1.5
PAH
primary
0.196
0.190
nrVmin
STP
3.2
metals
primary
16.66
17.12
L/min
ambient
-2.7
Cr(VI)
primary
15.0
15.02
L/min
ambient
-0.1
Cr(VI)
collocated
15.0
14.77
L/min
ambient
1.6
Bronx, NY
36-005-0080
VOC
carbony
1
primary
primary
1
0.999
no flow readings recorded
1.068 L/min
ambient
-6.5
PAH
primary
0.217
0.198
nrVmin
STP
9.6
metals
primary
16.65
16.85
L/min
ambient
-1.2
metals
collocated
16.68
16.92
L/min
ambient
-1.4
Cr(VI)
primary
15.0
14.35
L/min
ambient
4.5
Cr(VI)
collocated
15.0
15.13
L/min
ambient
-0.9
Washington, DC
11-001-0043
VOC
VOC
primary
duplicate
no flow readings recorded
no flow readings recorded
-
carbony
1
primary
1
0.500
0.561
L/min
ambient
-10.9
carbony
1
collocated
2
0.525
0.572
L/min
ambient
-8.2
PAH
primary
127
128.9
L/min
STP
-1.5
metals
primary
40
42.67
ftVmin
STP
-6.3
Cr(VI)
primary
15.0
12.81
IVmin
ambient
17.1
Cr(VI)
collocated
15.0
11.41
IVmin
ambient
31.5
Richmond, VA
51-087-0014
VOC
VOC
primary
collocated
no flow readings recorded
no flow readings recorded
-
carbony
1
primary
1
0.250
0.261
IVmin
ambient
-4.2
carbony
1
collocated
2
0.250
0.256
IVmin
ambient
-2.3
PAH
primary
135
134.4
IVmin
STP
0.4
PAH
collocated
144.6
144.2
IVmin
STP
0.3
metals
primary
42.05
39.21
ftVmin
STP
7.2
Cr(VI)
primary
15.0
15.89
L/min
ambient
-5.6
Cr(VI)
collocated
15.0
15.45
L/min
ambient
-2.9
Chesterfield, SC
45-025-0001
VOC
VOC
primary
collocated
no flow readings recorded
no flow readings recorded
-
carbony
1
primary
0.120
0.120
IVmin
ambient
0.0
carbony
1
collocated
0.121
0.125
IVmin
ambient
-3.2
PAH
primary
0.2
0.2290
nrVmin
STP
-12.7
PAH
collocated
0.2
0.2458
nrVmin
STP
-18.6
metals
primary
1.14
1.066
nrVmin
STP
6.9
metals
collocated
1.14
1.076
nrVmin
STP
5.9
Cr(VI)
primary
15.0
15.08
L/min
ambient
-0.5
Cr(VI)
collocated
15.0
16.26
L/min
ambient
-7.7
Percent difference values in red exceed the flow bias MQO of ±10%.
60
-------
Table 29. Flow Audit Results from the Instrument Performance Audits - CY2011
(continued)
Site Identifier
and AQS ID
Method
Precision
Assignment
Channel
Sampler
Reading
Standard Reading
Units
Conditions
Percent
Difference
Decatur, GA
voc
primary
no flow readings recorded
-
13-089-0002
voc
collocated
no flow readings recorded
-
carbony
1
primary
0.123
0.125
17min
STP
-1.6
carbony
1
collocated
0.124
0.121
IVmin
STP
2.5
PAH
primary
0.204
0.2102
nrVmin
STP
-2.9
PAH
collocated
0.198
0.1801
nrVmin
STP
9.9
metals
primary
1.05
1.058
nrVmin
STP
-0.8
metals
collocated
1.03
1.033
nrVmin
STP
-0.3
Cr(VI)
primary
1
2
14.75
14.75
16.72
15.68
L/min
IVmin
ambient
ambient
-11.8
-5.9
Cr(VI)
collocated
1
2
14.44
14.44
16.34
16.88
L/min
IVmin
ambient
ambient
-11.6
-14.5
Hillsborough County, FL
12-057-3002
VOC
carbony
1
primary
primary
1
0.725
no flow readings recorded
0.768 L/min
STP
-5.6
carbony
1
collocated
2
0.725
0.748
IVmin
STP
-3.1
PAH
primary
0.2
0.2279
nrVmin
STP
-12.2
PAH
collocated
0.2
0.2429
nrVmin
STP
-17.7
metals
primary
1.138
1.089
nrVmin
STP
4.5
metals
collocated
1.138
1.085
nrVmin
STP
4.9
Cr(VI)
primary
15.0
15.65
L/min
ambient
-4.2
Cr(VI)
collocated
15.0
14.72
L/min
ambient
1.9
Pinellas County, FL
VOC
primary
no flow readings recorded
-
12-103-0026
VOC
duplicate
no flow readings recorded
-
carbony
1
primary
1
0.670
0.685
IVnrin
STP
-2.2
carbony
1
collocated
2
0.620
0.620
IVnrin
STP
0.0
PAH
primary
0.177
0.1801
nrVmin
STP
-1.7
metals
primary
1.172
1.176
nrVmin
STP
-0.3
Cr(VI)
primary
15.0
15.85
L/min
ambient
-5.4
Cr(VI)
collocated
15.0
16.36
L/min
ambient
-8.3
Percent difference values in red exceed the flow bias MQO of ±10%.
61
-------
Table 30. Flow Audit Results from the Instrument Performance Audits - CY2012
Site Identifier
Precision
Sampler
Percent
and AQS ID
Method
Assignment
Channel
Reading
Standard Reading Units
Conditions
Difference
Horicon, WI
voc
primary
no
flow readings recorded
- flow too low to detect
-
55-027-0001
voc
duplicate
no
flow readings recorded
- flow too low to detect
-
carbonyl
primary
1
0.704
0.695
IVmin
ambient
1.3
carbonyl
duplicate
2
0.705
0.706
IVmin
ambient
-0.1
PAH
primary
0.236
0.226
nrVmin
STP
4.4
PAH
collocated
0.242
0.235
nrVmin
STP
3.0
metals
primary
1.153
1.155
nrVmin
ambient
-0.2
metals
collocated
1.148
1.152
nrVmin
ambient
-0.3
Cr(VI)
primary
15.0
13.99
IVmin
ambient
7.2
Cr(VI)
collocated
15.0
14.67
IVmin
ambient
2.2
Northbrook, IL
VOC
primary
no
flow readings recorded
- flow too low to detect
-
17-031-4201
VOC
duplicate
no
flow readings recorded
- flow too low to detect
-
carbonyl
primary
1
0.375
0.388
IVmin
ambient
-3.4
carbonyl
duplicate
2
0.414
0.444
IVmin
ambient
-6.8
PAH
primary
8.00
7.12
ft'/min
STP
12.4
PAH
collocated
sampler inoperable
metals
primary
40.0
41.46
ft'/min
STP
-3.5
metals
collocated
40.0
41.93
ft'/min
STP
-4.6
Cr(VI)
primary
15.00
14.68
IVmin
ambient
2.2
Cr(VI)
collocated
15.00
14.96
IVmin
ambient
0.3
Deer Park, TX
VOC
primary
no
flow readings recorded
- flow too low to detect
-
48-201-1039
VOC
collocated
no
flow readings recorded
- flow too low to detect
-
carbonyl
primary
2
1.102
1.11
IVmin
STP
-0.7
carbonyl
duplicate
3
1.106
1.11
IVmin
STP
-0.4
PAH
primary
8.49
8.50
ft'/min
STP
-0.1
PAH
collocated
7.60
7.54
ft'/min
STP
0.8
metals
primary
39.87
39.81
ft'/min
STP
0.2
metals
collocated
39.94
39.87
ft'/min
STP
0.2
Cr(VI)
primary
11.98
12.30
IVmin
STP
-2.6
Cr(VI)
collocated
11.99
11.21
IVmin
STP
7.0
Percent difference values in red exceed the flow bias MQO of ±10%.
62
-------
Table 30. Flow Audit Results from the Instrument Performance Audits - CY2012
(continued)
Site Identifier
Precision
Sampler
Percent
and AQS ID
Method
Assignment
Channel
Reading Standard Reading Units
Conditions
Difference
St Louis, MO
VOC
primary
no
flow readings recorded
- flow too low to detect
-
29-510-0085
VOC
duplicate
no
flow readings recorded
- flow too low to detect
-
carbonyl
primary
1
740
822
cc/min
ambient
-2.1 a
carbonyl
duplicate
2
750
840
cc/min
ambient
00
PAH
primary
0.231
0.229
m3/min
ambient
0.9
metals
primary
16.7
17.0
L/min
ambient
-0.3a
metals
collocated
16.7
17.0
L/min
ambient
-2.1a
Cr(VI)
primary
15.1"
14.83
L/min
ambient
1.8
Cr(VI)
collocated
14.0
14.56
L/min
ambient
-3.8
Cr(VI)
primaryc
15.0
15.82
L/min
ambient
-5.2
Cr(VI)
collocatedc
14.98
15.26
L/min
ambient
-1.8
Portland, OR
VOC
primary
no
flow readings recorded
- flow too low to detect
-
41-051-0246
VOC
duplicate
no
flow readings recorded
- flow too low to detect
-
carbonyl
primary
1.2
1.21
L/min
ambient
-0.8
carbonyl
collocated
0.96
0.98
L/min
ambient
-2.0
PAH
primary
222.6
226.1
L/min
STP
-1.5
PAH
collocated
221.4
220.5
L/min
STP
0.4
metals
primary
41.85
40.81
ft3/min
ambient
2.5
metals
collocated
37.17
38.14
ft3/min
ambient
-2.5
Cr(VI)
primary
14.97
15.01
L/min
ambient
-0.3
Cr(VI)
collocated
14.44
14.80
L/min
STP
-2.4
a Flow audits performed with two different flow standards; average of the two audit results reported.
b Average of flow range reported (15.0 - 15.2 L/min).
c Samplers installed to begin operation in July 2012.
Graphical summaries of the flow audit results (mean percent differences within a HAP class) are
presented by site in Figures 19 and 20 for CY2011 and CY2012, respectively.
Non-biased sampler flow rates for carbonyls, PAHs, PMio metals, and hexavalent chromium
samplers are critical for determining sample concentration. Flow rate verification for VOC
samplers is less important to determining concentration, but is important in demonstrating a
representative composite sample is collected over 24 hours.
In CY2011 all sites met the <10% flow bias MQO for metals, 7 of 8 sites met the MQO for
carbonyls, and 6 of 8 sites met the MQO for PAHs and chromium (VI). In CY2012 all sites met
the flow bias MQO for carbonyls, metals, and chromium (VI), and 4 of 5 sites met the MQO for
PAHs. Percent completeness for audited sites in CY2011 and CY2012 are shown in Table 31.
63
-------
Table 31. Percentage of Audited NATTS Sites Meeting the Flow Bias MQO -
CY2011 and CY2012
HAP class
CY
VOCs carbonyls
PAHs
metals
Chromium (VI)
2011
88%
75%
100%
75%
2012
100%
80%
100%
100%
64
-------
carbonyl
PAH
metals
Cr(VI)
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Hillsborough County, FL
Pinellas County, FL
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Hillsborough County, FL
Pinellas County, FL
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Hillsborough County, FL
Pinellas County, FL
Bronx, NY
Rochester, NY
Washington, DC
Richmond, VA
Chesterfield, SC
Decatur, GA
Hillsborough County, FL
Pinellas County, FL
-20
Dashed lines indicate MQO of +/-10%
1 1
0 10
Mean Percent Difference
20
~i—
30
Figure 19. Summary of Instrument Performance Flow Audit Results for NATTS Sites CY2011
-------
carbonyl
PAH
metals
Cr(VI)
Horicon, Wl
Northbrook, IL
Deer Park, TX
St Louis, MO
Portland, OR
Horicon, Wl
Northbrook, IL
Deer Park, TX
St Louis, MO
Portland, OR
Horicon, Wl
Northbrook, IL
Deer Park, TX
St Louis, MO
Portland, OR
Horicon, Wl
Northbrook, IL
Deer Park, TX
St Louis, MO
Portland, OR
-10
Dashed lines indicate MQO of +/-10%
1 1
0 5
Mean Percent Difference
10
~i—
15
Figure 20. Summary of Instrument Performance Flow Audit Results for NATTS Sites CY2012
-------
2.8 Method Detection Limit (MDL) Data
For CY2011 and CY2012 the AQS database, specifically the ALT_MDL variable within records
having an RD record type, served as the primary source of MDL data. AQS allows the posting
of MDL data in a variety of units, even within chemical classes; thus, for the purposes of this
report, all AQS-acquired MDLs were standardized to ng/m3 for PAHs, metals, and chromium
(VI), and to |ig/m3 for VOCs and carbonyls. Where necessary, conversion from mole fraction
(ppb) assumed conditions at STP.
The MDL results presented in this report are arithmetic means of the AQS-posted ALT_MDL
values. The MDL data for individual sites, in addition to the mean across all sites reporting data,
are indicated in Tables 33 and 34 for CY2011 and Tables 35 and 36 for CY2012. Summary
statistics for MDL data for CY2011 and CY2012 are indicated in Tables 37 and 38, respectively.
Box and whisker plots and complementary scatter plots, indicated in Figures 21 through 30,
illustrate the MDLs for VOCs, carbonyls, metals, chromium (VI), and PAHs, respectively, for
CY2011 and CY2012. Note the log scale of the y-axes in these figures. The MDL MQOs for
each HAP are added to the respective plots (as a red horizontal line) for reference. Laboratories
whose MDLs fell outside of a window defined by 1.5 x IQR in either direction of the box are
identified by circles on the graphical display. Only HAPs for which an MQO is established for
the MDL are included in Figures 21 through 30.
Because ERG serves as the analytical laboratory for numerous NATTS sites (Table 10) for
VOCs, carbonyls, metals, and particularly for chromium (VI) and PAHs, the MDLs summarized
in Tables 33 through 36 and in Figures 21 through 30 reflect a consistency in instrumental
detection limits associated with an analytical laboratory common to multiple sites. Values for
MDL MQOs remained the same for CY2011 compared to CY2010, however, several pollutants
had lower MDL MQOs in CY2012 including: acrolein, formaldehyde, lead, and
trichloroethylene. Most notably, in CY2012 the MDL MQOs for formaldehyde and lead were
lower by an order of magnitude or more compared to CY2011. Only the MDL MQO for carbon
tetrachloride increased from CY2011 to CY2012, an increase of 150%.
MDL values varied widely among sites and frequently exceeded the respective MQOs for
several HAPs. Network-wide, the geometric means met the MDL MQO for the seven HAPs of
primary importance in CY2011 and CY2012 except for acrolein in CY2011 and CY2012, as
evidenced by the ratios of the geometric mean to the MDL MQO being > 1.
The percentages of NATTS sites meeting the MDL MQOs for CY2011 and CY2012 are shown
in Table 32.
Of the sites reporting results in CY2011, only approximately one third met the MDL MQO for
acrolein. In general, the MDL MQOs for benzene, 1,3-butadiene, formaldehyde, and arsenic
were met by 70% or more of sites. All sites met the MDL MQO for chromium (VI) and
naphthalene.
In CY2012, less than 25% of sites met the MDL MQO for acrolein. Approximately half or less
of sites met the MQO for benzene and formaldehyde; approximately 80% of sites met the MDL
67
-------
MQO for 1,3-butadiene and arsenic; and all sites met the MDL MQO for chromium (VI) and
naphthalene.
Table 32. Percentage of Sites Meeting the MDL MQO - CY2011 and CY2012
VOCs
carbonyls
PAHs
metals
CY
Acrolein
Benzene 1,3-Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium (VI)
2011
35%
78% 70%
89%
100%
85%
100%
2012
23%
41% 81%
52%
100%
78%
100%
Percentage based on N = 27 NATTS sites except for acrolein and chromium (VI) where N = 26.
68
-------
Table 33. Average Method Detection Limits (MDLs) by Site and Overall for VOCs (jig/m3)
and PAHs (ng/m3) - CY2011
Site Description
AQS Site Code
VOCs
BENZ
BUTA
CTET
CLFRM
EDB
DCP
EDC
MECL
TCE1122
Boston, MA
25-025-0042
0.033
0.018
0.053
0.032
0.079
0.042
0.041
0.036
0.261
Underbill, VT
50-007-0007
0.090
0.020
0.150
0.040
0.140
0.110
0.040
0.030
0.160
Providence, RI
44-007-0022
0.033
0.018
0.053
0.032
0.079
0.042
0.041
0.036
0.261
Bronx, NY
36-005-0080
0.032
0.044
0.063
0.049
0.077
0.092
0.040
0.035
0.069
Rochester, NY
36-055-1007
0.032
0.044
0.063
0.049
0.077
0.092
0.040
0.035
0.069
Washington, DC
11-001-0043
0.032
0.022
0.095b
0.098
0.154
0.092
0.081
0.069
0.206
Richmond, VA
51-087-0014
0.080
0.114
0.195
0.189
0.240
0.283
0.105
0.189
0.234
Chesterfield, SC
45-025-0001
0.045
0.168
0.195
0.112
0.230
0.088
0.125
0.094
0.158
Decatur, GA
13-089-0002
0.102
0.081
0.075b
0.182
0.305
0.332
0.327
7.610
0.365
Grayson Lake, KY
21-043-0500
0.093
0.015
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Hillsborough Cty, FL
12-057-3002
0.029
0.033
0.044
0.034
0.046
0.046
0.036
0.017
0.027
Pinellas Cty, FL
12-103-0026
0.029
0.033
0.044
0.034
0.046
0.046
0.036
0.017
0.027
Dearborn, MI
26-163-0033
0.104a
0.020a
0.153
0.050
0.154
0.111
0.044
0.093
0.203
Horicon, WI
55-027-0001
0.319
0.221
0.629
0.488
0.768
0.462
0.404
0.347
0.686
Northbrook, IL
17-031-4201
0.105
0.060b
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Deer Park, TX
48-201-1039
-
-
-
-
-
-
-
-
-
Flarrison Cty, TX
48-203-0002
-
-
-
-
-
-
-
-
-
St. Louis, MO
29-510-0085
0.093
0.015
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Bountiful, UT
49-011-0004
0.093
0.015
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Grand Junction, CO
08-077-0017
0.093
0.015
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Phoenix, AZ
04-013-9997
0.093
0.015
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Los Angeles, CA
06-037-1103
0.160
0.088
0.126
0.098
-
-
-
0.347
-
Rubidoux, CA
06-065-8001
0.160
0.088
0.126
0.098
-
-
-
0.347
-
San Jose, CA
06-085-0005
0.097b
0.117b
0.085b
0.066
0.077
-
0.404
0.347
-
La Grande, OR
41-061-0119
0.132a
0.158b
0.197b
0.259a
-
0.245
-
0.225
-
Portland, OR
41-051-0246
0.128
0.165b
0.186b
0.244
-
0.231
-
0.216
-
Seattle, WA
53-033-0080
0.093
0.015
0.151
0.044
0.138
0.106
0.036
0.035
0.165
Arithmetic Mean
0.092
0.064
0.144
0.098
0.164
0.139
0.096
0.413
0.194
Geometric Mean
0.076
0.042
0.119
0.070
0.130
0.112
0.061
0.081
0.153
Median
0.093
0.033
0.151
0.049
0.138
0.106
0.040
0.036
0.165
Standard Deviation
0.062
0.061
0.113
0.105
0.153
0.106
0.121
1.504
0.141
MQO
0.130
0.100
0.067
0.500
-
--
-
-
-
Note: Shaded cells indicate that all reported MDLs are above the MQO and unshaded cells indicate all reported MDLs are below the MQO and
with the following exceptions indicated:
a. Some reported MDLs (less than 5%) are above the MQO
b. Between 33% and 75% of the MDLs are above the MQO
69
-------
Table 33. Average Method Detection Limits (MDLs) by Site and Overall for VOCs (jig/m3)
and PAHs (ng/m3) - CY2011 (continued)
Site Description
AQS Site Code
VOCs
PAHs
PERC
TCE
vc
cDCPEN
tDCPEN
ACRO ACRY
NAPH
BaP
Boston, MA
25-025-0042
0.069
0.048
0.017
0.040
0.026
0.123
0.260
0.107
0.060
Underbill, VT
50-007-0007
0.120
0.130
0.020
0.100
0.110
0.030
0.139
0.078
Providence, RI
44-007-0022
0.069
0.048
0.017
0.040
0.026
0.123
0.260
0.159
0.090
Bronx, NY
36-005-0080
0.068
0.054
0.026
0.045
0.045
0.069
—
0.126
0.071
Rochester, NY
36-055-1007
0.068
0.054
0.026
0.045
0.045
0.069
-
0.187
0.105
Washington, DC
11-001-0043
0.101
0.054
0.051
0.091
0.091
0.045
0.033
0.168
0.094
Richmond, VA
51-087-0014
0.191
0.107
0.136
0.175
0.068
0.428
0.131
0.185
0.104
Chesterfield, SC
45-025-0001
0.142
0.140
0.089
0.086
0.082
0.085
—
0.156
0.087
Decatur, GA
13-089-0002
0.119
0.236
0.070
0.277
0.251
0.043
—
0.142
0.080
Grayson Lake, KY
21-043-0500
0.122
0.134
0.020
0.100
0.113
0.115
0.026
0.127
0.071
Hillsborough Cty, FL
12-057-3002
0.034
0.048
0.041
0.082
0.045
0.087
0.022
0.140
0.078
Pinellas Cty, FL
12-103-0026
0.034
0.048
0.041
0.082
0.045
0.087
0.022
0.135
0.075
Dearborn, MI
26-163-0033
0.134a
0.142
0.026a
0.109
0.126
0.115
0.041
0.124
0.070
Horicon, WI
55-027-0001
0.678
0.537
0.255
0.454
0.454
0.229
—
0.133
0.136
Northbrook, IL
17-031-4201
0.122
0.134
0.020
0.100
0.113
0.115
0.026
0.147
0.072
Deer Park, TX
48-201-1039
-
-
-
-
-
-
-
0.162
0.091
Flarrison Cty, TX
48-203-0002
—
—
—
—
—
—
—
—
—
St. Louis, MO
29-510-0085
0.122
0.134
0.020
0.100
0.113
0.115
—
0.133
0.074
Bountiful, UT
49-011-0004
0.122
0.134
0.020
0.100
0.113
0.115
0.026
0.199
0.111
Grand Junction, CO
08-077-0017
0.122
0.134
0.020
0.100
0.113
0.115
0.026
0.167
0.094
Phoenix, AZ
04-013-9997
0.122
0.134
0.020
0.100
0.113
0.115
0.026
0.109
0.061
Los Angeles, CA
06-037-1103
0.068
0.107
-
0.454
0.454
0.687
-
0.130
0.072
Rubidoux, CA
06-065-8001
0.068
0.107
—
0.454
0.454
0.687
—
0.164
0.092
San Jose, CA
06-085-0005
0.046
0.072
0.255
0.454
0.454
0.403
0.217
0.140
0.078
La Grande, OR
41-061-0119
0.248b
0.285a
0.131b
-
—
0.092
-
1.035
0.262
Portland, OR
41-051-0246
0.235b
0.269
0.127b
—
—
0.092
—
2.292a
0.233
Seattle, WA
53-033-0080
0.122
0.134
0.020
0.100
0.113
0.115
0.026
0.111
0.063
Arithmetic Mean
0.134
0.137
0.064
0.160
0.155
0.178
0.078
0.262
0.096
Geometric Mean
0.106
0.111
0.041
0.117
0.107
0.129
0.047
0.172
0.089
Median
0.122
0.134
0.026
0.100
0.113
0.115
0.026
0.141
0.079
Standard Deviation
0.126
0.106
0.072
0.146
0.148
0.183
0.091
0.450
0.048
MQO
0.170
0.500
0.110
-
--
0.100
--
29.0
0.910
Note: Shaded cells indicate that all reported MDLs are above the MQO and unshaded cells indicate all reported MDLs are below the MQO and
with the following exceptions indicated:
a. Some reported MDLs (less than 5%) are above the MQO
b. Between 33% and 75% of the MDLs are above the MQO
70
-------
Table 34. Average Method Detection Limits (MDLs) by Site and Overall for carbonyls
(|ig/m3), metals (ng/m3), and chromium (VI) (ng/m3) - CY2011
Site Description
AQS Site Code
carbonyls
metals
FORM
ACET
As
Be
Cd
Pb
Mn
Ni
CrVI
Boston, MA
25-025-0042
0.103
0.069
0.060a
0.017
0.019
0.159
0.205
0.490a
0.004
Underbill, VT
50-007-0007
0.019
0.013
0.143
0.013
0.010
0.037
0.203
0.896
0.004
Providence, RI
44-007-0022
0.088
0.026
0.095
0.054
0.102
0.606
0.035
0.054
0.004
Bronx, NY
36-005-0080
0.018
0.018
0.191b
0.054
0.038
0.025
0.038
0.089
0.004
Rochester, NY
36-055-1007
0.018
0.018
0.191b
0.054
0.038
0.025
0.038
0.089
0.004
Washington, DC
11-001-0043
0.023
0.011
1.664
—
—
0.004
Richmond, VA
51-087-0014
0.097
0.180
0.023
0.013
0.017
0.064
0.029
0.143
0.004
Chesterfield, SC
45-025-0001
0.251
0.221
0.031
0.001
0.001
0.003
0.002
0.003
0.004
Decatur, GA
13-089-0002
1.165c
1.165c
0.265b
0.010
0.300
0.010
0.011
0.026
0.004
Grayson Lake, KY
21-043-0500
0.013
0.012
0.159
0.041
0.040
0.044
0.188
0.836
0.004
Hillsborough Cty, FL
12-057-3002
0.011
0.011
0.460
0.200
0.150
1.040
0.140
0.920
0.004
Pinellas Cty, FL
12-103-0026
0.011
0.011
-
-
-
-
-
-
0.004
Dearborn, MI
26-163-0033
0.010
0.009
0.039
0.014
0.028
-
0.298
0.160
0.004
Horicon, WI
55-027-0001
0.064
0.054
0.029
0.010
0.016
0.034
0.094
0.093
0.004
Northbrook, IL
17-031-4201
0.011
0.011
0.054
0.007
0.009
0.111
0.138
0.388
0.004
Deer Park, TX
48-201-1039
-
-
0.064
0.060
0.040
0.020
0.264
0.181
0.005
Flarrison Cty, TX
48-203-0002
-
-
0.069
0.060
0.040
0.020
0.272
0.188
0.005
St. Louis, MO
29-510-0085
0.012
0.011
0.124
0.008
0.009
0.045
0.421a
0.872
0.004
Bountiful, UT
49-011-0004
0.011
0.010
0.182
0.010
0.012
0.020
0.223
1.261
0.004
Grand Junction, CO
08-077-0017
0.013
0.013
0.066
0.159
0.152
0.102
0.089
0.080
0.004
Phoenix, AZ
04-013-9997
0.015
0.014
0.151
0.012
0.010
0.035
0.209
0.956
0.004
Los Angeles, CA
06-037-1103
0.123
0.180
0.100
0.100
0.100
0.100
0.100
0.100
0.020
Rubidoux, CA
06-065-8001
0.123
0.180
0.091
0.091
0.092
0.091
0.092
0.091
0.020
San Jose, CA
06-085-0005
0.068
0.075
0.160
0.010
0.010
0.020
0.200
1.130
-
La Grande, OR
41-061-0119
0.131
0.033
0.035
0.004
0.035
0.351
0.351
0.351
0.035
Portland, OR
41-051-0246
0.118
0.031
0.031
0.003
0.034
0.344
0.344
0.344
0.035
Seattle, WA
53-033-0080
0.015
0.014
0.058
0.015
0.021
0.180
0.208
0.506
0.004
Arithmetic Mean
0.101
0.096
0.174
0.041
0.053
0.145
0.168
0.410
0.008
Geometric Mean
0.038
0.031
0.096
0.020
0.028
0.059
0.109
0.213
0.005
Median
0.019
0.018
0.093
0.014
0.034
0.045
0.188
0.188
0.004
Standard Deviation
0.230
0.232
0.318
0.051
0.067
0.238
0.116
0.395
0.009
MQO
0.980
0.450
0.230
0.420
0.560
150
5.00
2.10
0.080
Note: Shaded cells indicate that all reported MDLs are above the MQO and unshaded cells indicate all reported MDLs are below the MQO and
with the following exceptions indicated:
a. Some reported MDLs (less than 5%) are above the MQO
b. Between 33% and 75% of the MDLs are above the MQO
c. Over 95% of the reported MDLs are above the MQO
71
-------
Table 35. Average Method Detection Limits (MDLs) by Site and Overall for VOCs (jig/m3)
and PAHs (ng/m3) - CY2012
VOCs
description
uitc coae
BENZ
BUTA
CTET
CLFRM
EDB
DCP
EDC
MECL
TCE1122
Boston, MA
25-025-0042
0.037
0.019
0.060
0.051
0.094
0.055
0.062
0.040
0.214
Underbill, VT
50-007-0007
0.190
0.020
0.150
0.070
0.130
0.090
0.060
0.080
0.120
Providence, RI
44-007-0022
0.043
0.024
0.105
0.080
0.149
0.076
0.074
0.055
0.178
Bronx, NY
36-005-0080
0.016
0.013
0.044
0.029
0.054
0.037
0.020
0.028
0.021
Rochester, NY
36-055-1007
0.016
0.013
0.044
0.029
0.054
0.037
0.020
0.028
0.021
Washington, DC
11-001-0043
0.061
0.022
0.126
0.049
0.077
0.092
0.081
0.104
0.137
Richmond, VA
51-087-0014
0.134
0.148
0.189
0.146
0.691
0.332
0.263
0.326
0.686
Chesterfield, SC
45-025-0001
0.115
0.221
0.226
0.205
0.200
0.162
0.133
0.132
0.185
Decatur, GA
13-089-0002
0.117
0.068
0.082
0.171
0.312
0.270
0.220
6.942
0.387
Grayson Lake, KY
21-043-0500
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.080
0.123
Hillsborough Cty, FL
12-057-3002
0.019
0.029
0.031
0.024
0.038
0.023
0.016
0.024
0.034
Pinellas Cty, FL
12-103-0026
0.019
0.029
0.031
0.024
0.038
0.023
0.016
0.024
0.034
Dearborn, MI
26-163-0033
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.080
0.123
Horicon, WI
55-027-0001
0.319
0.221
0.629
0.488
0.768
0.462
0.404
0.347
0.686
Northbrook, IL
17-031-4201
0.149b
0.066b
0.151
0.068
0.131
0.088
0.065
0.080
0.123
Deer Park, TX
48-201-1039
-
-
-
--
-
--
-
-
-
Flarrison Cty, TX
48-203-0002
-
-
-
--
-
--
-
-
-
St. Louis, MO
29-510-0085
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.080
0.123
Bountiful, UT
49-011-0004
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.101
0.123
Grand Junction, CO
08-077-0017
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.258
0.123
Phoenix, AZ
04-013-9997
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.080
0.123
Los Angeles, CA
06-037-1103
0.160
0.088
0.126
0.098
--
-
-
0.347
-
Rubidoux, CA
06-065-8001
0.160
0.088
0.126
0.098
--
-
-
0.347
-
San Jose, CA
06-085-0005
0.083b
0.042
0.046
0.071
0.038
-
0.032
0.280
--
La Grande, OR
41-061-0119
0.128
0.088
0.063
0.244
--
0.230
--
0.609
--
Portland, OR
41-051-0246
0.1343
0.093b
0.0663
0.2593
--
0.246
--
0.184
-
Seattle, WA
53-033-0080
0.195
0.024
0.151
0.068
0.131
0.088
0.065
0.080
0.123
Arithmetic Mean
0.131
0.058
0.134
0.107
0.176
0.129
0.091
0.429
0.184
Geometric Mean
0.098
0.040
0.106
0.080
0.122
0.095
0.064
0.124
0.122
Median
0.134
0.024
0.126
0.068
0.131
0.088
0.065
0.080
0.123
Standard Deviation
0.078
0.059
0.116
0.102
0.195
0.111
0.094
1.365
0.189
MQO
0.130
0.100
0.170
0.500
--
-
-
-
-
Note: Shaded cells indicate that all reported MDLs are above the MQO and unshaded cells indicate all reported MDLs are below the MQO and
with the following exceptions indicated:
a. Some reported MDLs (less than 5%) are above the MQO
b. Between 33% and 75% of the MDLs are above the MQO
72
-------
Table 35. Average Method Detection Limits (MDLs) by Site and Overall for VOCs (jig/m3)
and PAHs (ng/m3) - CY2012 (continued)
Site Description
AQS Site Code
VOCs
PAHs
PERC
TCE
vc
cDCPEN
tDCPEN
ACRO
ACRY
NAPH
BaP
Boston, MA
25-025-0042
0.108
0.068
0.023
0.058
0.058
0.174
0.274
0.141
0.053
Underbill, VT
50-007-0007
0.140
0.120
0.030
0.070
0.070
-
0.040
0.193
0.073
Providence, RI
44-007-0022
0.179b
0.090
0.035
0.070
0.106
0.265
0.284
0.217
0.082
Bronx, NY
36-005-0080
0.027
0.027
0.013
0.036
0.032
0.085
-
0.171
0.064
Rochester, NY
36-055-1007
0.027
0.027
0.013
0.036
0.032
0.085
-
0.183
0.069
Washington, DC
11-001-0043
0.136
0.054
0.077
0.045
0.045
0.069
0.043
0.232
0.087
Richmond, VA
51-087-0014
0.427
0.360
0.171
0.331
0.259
0.275
0.373
0.247
0.093
Chesterfield, SC
45-025-0001
0.183
0.193
0.146
0.122
0.082
0.108
-
0.180
0.068
Decatur, GA
13-089-0002
0.139
0.314
0.091
0.287
0.218
0.081b
-
0.090
0.034
Grayson Lake, KY
21-043-0500
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.153
0.058
Hillsborough Cty, FL
12-057-3002
0.027
0.021
0.033
0.023
0.068
0.066
0.013
0.197
0.074
Pinellas Cty, FL
12-103-0026
0.027
0.021
0.033
0.023
0.068
0.066
0.013
0.204
0.067
Dearborn, MI
26-163-0033
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.193
0.064
Horicon, WI
55-027-0001
0.678
0.537
0.255
0.454
0.454
0.229
-
0.140
0.280
Northbrook, IL
17-031-4201
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.182
0.059
Deer Park, TX
48-201-1039
-
--
--
--
--
--
--
0.179
0.067
Flarrison Cty, TX
48-203-0002
-
--
--
--
--
--
--
--
-
St. Louis, MO
29-510-0085
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.194
0.062
Bountiful, UT
49-011-0004
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.268
0.101
Grand Junction, CO
08-077-0017
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.300
0.088
Phoenix, AZ
04-013-9997
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.166
0.062
Los Angeles, CA
06-037-1103
0.068
0.107
-
0.454
0.454
0.687
-
0.234
0.065
Rubidoux, CA
06-065-8001
0.068
0.107
-
0.454
0.454
0.687
-
0.220
0.074
San Jose, CA
06-085-0005
0.031
0.075
0.015
0.454
0.454
0.399
0.024
0.184
0.069
La Grande, OR
41-061-0119
0.136
0.269
0.102
-
-
0.092
-
3.042
0.224
Portland, OR
41-051-0246
0.142a
0.286
0.107a
-
-
0.092
-
4.208
1.017a
Seattle, WA
53-033-0080
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.146
0.055
Arithmetic Mean
0.145
0.145
0.059
0.150
0.149
0.190
0.088
0.456
0.120
Geometric Mean
0.106
0.105
0.041
0.093
0.102
0.147
0.051
0.235
0.083
Median
0.136
0.118
0.028
0.068
0.073
0.137
0.043
0.193
0.069
Standard Deviation
0.137
0.122
0.061
0.160
0.152
0.172
0.113
0.948
0.190
MQO
0.170
0.200
0.110
-
-
0.090
-
29.0
0.910
Note: Shaded cells indicate that all reported MDLs are above the MQO and unshaded cells indicate all reported MDLs are below the MQO and
with the following exceptions indicated:
a. Some reported MDLs (less than 5%) are above the MQO
b. Between 33% and 75% of the MDLs are above the MQO
73
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Table 36. Average Method Detection Limits (MDLs) by Site and Overall for carbonyls
(|ig/m3), metals (ng/m3), and chromium (VI) (ng/m3) - CY2012
Site Description
AQS Site Code
carbonyls
metals
FORM
ACET
As
Be
Cd
Pb
Mn
Ni
CrVI
Boston, MA
25-025-0042
0.110
0.056
0.062
0.005
0.007
0.124
0.363
0.454
0.004
Underbill, VT
50-007-0007
0.030
0.017
0.170
0.020
0.010
0.070
0.320
0.400
0.004
Providence, RI
44-007-0022
0.305b
0.054
0.091
0.055
0.034
0.533
0.121
0.059
0.003
Bronx, NY
36-005-0080
-
-
0.140
0.058
0.036
0.025
0.028
0.053
0.003
Rochester, NY
36-055-1007
-
-
0.141
0.057
0.037
0.026
0.027
0.051
0.004
Washington, DC
11-001-0043
--
-
-
-
-
--
--
--
0.004
Richmond, VA
51-087-0014
0.073b
0.108
0.020
0.016
0.020
0.054
0.026
0.155
0.003
Chesterfield, SC
45-025-0001
0.240
0.280
0.030
0.001
0.001
0.003
0.002
0.003
0.003
Decatur, GA
13-089-0002
1.178
1.163c
0.324
0.015
0.071
0.019
0.017
0.027
0.003
Grayson Lake, KY
21-043-0500
0.007
0.007
0.170
0.020
0.010
0.070
0.320
0.400
0.003
Hillsborough Cty, FL
12-057-3002
0.012
0.012
0.460
0.200
0.150
1.040
0.140
0.920
0.003
Pinellas Cty, FL
12-103-0026
0.011
0.011
0.460
0.200
0.150
1.040
0.140
0.920
0.004
Dearborn, MI
26-163-0033
0.010
0.010
0.040
0.012
0.030
-
0.301
0.161
0.004
Horicon, WI
55-027-0001
0.062
0.070
0.029
0.010
0.016
0.034
0.094
0.093
0.004
Northbrook, IL
17-031-4201
0.017
0.017
0.065
0.005
0.007
0.130
0.379
0.474
0.004
Deer Park, TX
48-201-1039
-
-
0.065
0.056
0.040
0.019
0.237
0.158
0.004
Flarrison Cty, TX
48-203-0002
-
-
0.068
0.051
0.043
0.017
0.218
0.141
0.004
St. Louis, MO
29-510-0085
0.011
0.011
0.170
0.020
0.010
0.070
0.320
0.400
0.004
Bountiful, UT
49-011-0004
0.011
0.010
0.192
0.020
0.010
0.082
0.357
0.452
0.003
Grand Junction, CO
08-077-0017
0.012
0.012
0.083
0.253
0.075
0.046
0.094
0.070
0.003
Phoenix, AZ
04-013-9997
0.015
0.014
0.173
0.020
0.010
0.073
0.324
0.407
0.004
Los Angeles, CA
06-037-1103
0.123
0.180
-
-
-
-
-
-
0.007
Rubidoux, CA
06-065-8001
0.123
0.180
—
—
—
—
—
—
0.007
San Jose, CA
06-085-0005
0.067b
0.073
0.170
0.020
0.010
0.070
0.320
0.400
La Grande, OR
41-061-0119
0.136
0.033
0.034
0.003
0.034
0.346
0.350
0.345
0.035
Portland, OR
41-051-0246
0.124c
0.032
0.034
0.003
0.034
0.347
0.350
0.345
0.035
Seattle, WA
53-033-0080
0.016
0.014
0.065
0.005
0.007
0.129
0.377
0.472
0.004
Arithmetic Mean
0.122
0.107
0.136
0.047
0.035
0.190
0.218
0.307
0.006
Geometric Mean
0.044
0.036
0.095
0.020
0.021
0.076
0.137
0.183
0.004
Median
0.046
0.025
0.087
0.020
0.025
0.070
0.269
0.345
0.004
Standard Deviation
0.249
0.246
0.123
0.069
0.040
0.298
0.138
0.252
0.009
MQO
0.080
0.450
0.230
0.420
0.560
15
5.00
2.10
0.080
Note: Shaded cells indicate that all reported MDLs are above the MQO and unshaded cells indicate all reported MDLs are below the MQO and
with the following exceptions indicated:
a. Some reported MDLs (less than 5%) are above the MQO
b. Between 33% and 75% of the MDLs are above the MQO
c. Over 95% of the reported MDLs are above the MQO
74
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Table 37. Summary Statistics for Method Detection Limits across All Reporting NATTS
Laboratories - CY2011
VOCs
carbonyls
PAHs
metals
Acrolein
Benzene
1,3-Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium
MDL
(jig/m3)
(jig/m3)
(jig/m3)
(jig/m3)
(ng/m3)
(ng/m3)
(VI) (ng/m3)
Geometric
Mean
0.129
0.076
0.042
0.038
0.172
0.096
0.005
Arithmetic
Mean
0.178
0.092
0.064
0.101
0.262
0.174
0.008
Standard
Deviation
0.183
0.062
0.061
0.230
0.450
0.318
0.009
Minimum
0.043
0.029
0.015
0.010
0.107
0.023
0.004
Median
0.115
0.093
0.033
0.019
0.141
0.093
0.004
Maximum
0.687
0.319
0.221
1.165
2.292
1.664
0.035
MQO
0.10
0.13
0.10
0.98
29.0
0.23
0.08
Ratio of
Geometric
1.3
0.58
0.42
0.038
0.0059
0.42
0.07
Mean to MQO
Table 38. Summary Statistics for Method Detection Limits across All Reporting NATTS
Laboratories - CY2012
VOCs
carbonyls
PAHs
metals
Acrolein
Benzene
1,3-Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium (VI)
MDL
(jtg/m3)
(ng/m3)
(ng/m3)
(ng/m3)
(ng/m3)
(ng/m3)
(ng/m3)
Geometric
Mean
0.147
0.098
0.040
0.044
0.235
0.095
0.004
Arithmetic
Mean
0.190
0.131
0.058
0.122
0.456
0.136
0.006
Standard
Deviation
0.172
0.078
0.059
0.249
0.948
0.123
0.009
Minimum
0.066
0.016
0.013
0.007
0.090
0.020
0.003
Median
0.137
0.134
0.024
0.046
0.193
0.087
0.004
Maximum
0.687
0.319
0.221
1.178
4.208
0.460
0.035
MQO
0.09
0.13
0.10
0.08
29.0
0.23
0.08
Ratio of
Geometric
1.6
0.75
0.40
0.5
0.0081
0.41
0.06
Mean to MQO
75
-------
ro
E
OJ
o
1.5 x IQR
: B
~
TCE VC ACRO
Figure 21. Distribution of VOCs Average Method Detection Limits for NATTS Data -
CY2011
76
-------
1 -
.5-
ro
CD
3 .25 H
o
=0 .H
<1)
-t—'
CD
Q
o .05 H
1.5 x IQR
HAP
Figure 22. Distribution of VOCs Average Method Detection Limits for NATTS Data -
CY2012
77
-------
Figure 23. Distribution of Carbonyls Average Method Detection Limits - CY2011
78
-------
Figure 24. Distribution of Carbonyls Average Method Detection Limits - CY2012
79
-------
.4
.3
co
E
c
¦¦£ 2
c
o
—'
o
d)
"S3
Q
T3
O
-C
o>
.1
MQO = 29.0
Observations at
1.035 and 2.292
MQO = 0.91
Circles indicate MDLs > 1.5 x IQR
NAPH
BaP
HAP
Figure 25. Distribution of PAHs Average Method Detection Limits - CY2011
80
-------
.75-
c
o
—'
o
d)
"S3
Q
T3
O
-C
o>
.5
co
E
c
- .25-
.1-
.05-
MQO = 29.0
Observations at
3.042 and 4
Observation
at 1.017
MQO = 0.91
NAPH
BaP
Circles indicate MDLs > 1.5 x IQR
HAP
Figure 26. Distribution of PAHs Average Method Detection Limits - CY2012
81
-------
o
2.5
n
O)
.25
.1
o> .025
.01
.0025
.001
i
o
o
As Be
Circles indicate MDLs > 1.5 x IQR
Cd
MQO = 150 MQO = 5
O
o
0
Pb
Mn
Ni
HAP
Figure 27. Distribution of Metals Average Method Detection Limits - CY2011
82
-------
ro
a>
T3
O
1.5 x IQR
MQO = 15
o
o
o
MQO = 5
Cd Pb
HAP
Mn
Ni
Figure 28. Distribution of Metals Average Method Detection Limits - CY2012
83
-------
.05-
co
E
B)
c
o
! .025-
£=
O
o
o
1,5 x IQR
HAP
Figure 29. Distribution of Chromium (VI) Average Method Detection Limits - CY2011
84
-------
.008-
.007-
MQO = 0.08
Two observations
at 0.035
? .006-
o
<1)
•+—>
.005-
.004-
.003
Circles indicate MDLs > 1.5 x IQR
CrVI
HAP
Figure 30. Distribution of Chromium (VI) Average Method Detection Limits - CY2012
85
-------
3.0 SUMMARY
A summary of the quality assurance results for the seven HAPs of primary importance -
acrolein, benzene, 1,3-butadiene, formaldehyde, naphthalene, arsenic, and chromium (VI) is
presented in Table 39.
Table 39. Summary of NATTS Quality Assurance Results - Percentage of Sites Meeting
Measurement Quality Objectives in CY2011 and CY2012
VOCs
carbonyls
PAHs
metals
Data Quality
Calendar
1,3-
Chromium
Indicator
Year
Acrolein
Benzene
Butadiene
Formaldehyde
Naphthalene
Arsenic
(VI)
2011
77%
93%
85%
78%
96%
96%
100%
Completeness
2012
81%
89%
89%
78%
89%
96%
96%
Overall
2011
37%
84%
79%
100%
63%
47%
54%
Precision
2012
47%
90%
84%
95%
88%
56%
63%
Laboratory
2011
77%
85%
85%
87%
40%
90%
Bias
2012
--
--
--
--
83%
93%
100%
2011
88%
75%
100%
75%
Field Biasa
Not applicable
2012
100%
80%
100%
100%
Method
2011
35%
78%
70%
89%
100%
85%
100%
Dection Limit
2012
23%
41%
81%
52%
100%
78%
100%
a Field bias was determined by HAPs class - carbonyls, PAHs, and metals - not for specific HAPs (except chromium (VI))
The following summary observations are provided:
1. Completeness: Data completeness across the entire NATTS network met the MQO in
both CY2011 and CY2012: both the mean and median network-wide completeness
for all seven priority HAPs was greater than 85% in both CY2011 and CY2012.
Median network-wide completeness is indicated in Table 40 for CY2011 and
CY2012.
The percentage of sites that met the completeness MQO for CY2011 and CY2012
was 85% or greater for all of the seven HAPs of primary importance except acrolein
and formaldehyde, for which approximately 80% of sites met the MQO.
Table 40. Median Completeness for the Seven HAPs of Primary Importance for CY2011
and CY2012
VOCs
carbonyls
PAHs
metals
Acrolein
Benzene
1,3-Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium (VI)
MQO
>85%
>85%
>85%
>85%
>85%
>85%
>85%
CY2011
97%
97%
97%
95%
97%
97%
98%
CY2012
95%
95%
95%
97%
95%
97%
97%
86
-------
2. Analytical and Overall Precision: For CY2011 the network mean analytical precision
met the MQO of 15% for carbonyls, PAHs, and chromium (VI), for all metals except
beryllium, and for 9 of the 16 VOCs for reported concentrations equal to or above
MDLs.
For CY2012 the network mean analytical precision met the precision MQO for all
HAPs except for acrylonitrile and beryllium.
As is expected given the additional variability contribution of sample collection,
overall precision for CY2011 showed much greater variability than the analytical
precision: the network mean overall precision met the MQO for carbonyls, 1 PAH,
1 metal, and 5 of 16 VOCs; the MQO was not met for chromium (VI).
As in CY2011, CY2012 overall precision showed greater variability than CY2012
analytical precision. The network mean overall precision met the MQO for
carbonyls, 1 PAH, and 5 of 16 VOCs; the MQO was not met for any of the metals or
for chromium (VI).
In CY2011, all sites met the precision MQO for formaldehyde and less than 85% of
sites met the MQO for six of the seven representative HAPs, with less than half of
sites meeting the MQO for acrolein and arsenic. In CY2012, more than 85% of sites
met the precision MQO for benzene, formaldehyde, and naphthalene with the
remaining four HAPs showing 84% or less of sites meeting the MQO. As in
CY2011, less than 50% of sites met the precision MQO for acrolein in CY2012.
3. Laboratory Bias: Percentages of NATTS laboratories meeting the bias MQO for
acrolein, benzene and 1,3-butadiene were 77%, 85%, and 85%, respectively. All
NATTS laboratories but one met the MQO for arsenic and formaldehyde. For the
five NATTS laboratories reporting PAH results, only two laboratories met the MQO
for naphthalene. Specifically, acceptable measurement bias was difficult to obtain for
acrolein and naphthalene; the mean absolute percent bias across all participating
laboratories was 29.5% and 26.0%, respectively. The CY2011 PAH PT results
should be interpreted with caution, as it appears that the target value may have been
biased high: all reported results but one showed a negative bias.
For the three HAPs of primary importance that were spiked for the CY2012 PT
(naphthalene, arsenic, and chromium (VI)), all NATTS laboratories met the MQO for
chromium (VI) and all but one laboratory met the MQO for both naphthalene and
arsenic.
4. Field Bias: Sampler flows measured during IPAs conducted at NATTS field sites
indicated less than 10% absolute difference from the sampler settings with few
exceptions for both CY2011 and CY2012. The most frequent MQO exceedances
occurred for PAH and chromium (VI) samplers.
In CY2011 all sites met the <10% flow bias MQO for metals, 7 of 8 sites met the
MQO for carbonyls, and 6 of 8 sites met the MQO for PAHs and chromium (VI). In
CY2012 all sites met the flow bias MQO for carbonyls, metals, and chromium (VI),
and 4 of 5 sites met the MQO for PAHs.
87
-------
5. Method Detection Limits: MDL values varied widely among sites and frequently
exceeded the respective MQOs for several HAPs. For many HAPs the overall
network geometric mean value fell within the MQO threshold when all sites were
considered together, except for acrolein in CY2011 and CY2012. The ratios of the
network geometric means to the corresponding MQOs for the seven HAPs of primary
importance are indicated in Table 41.
Of the sites reporting results in CY2011, approximately one third met the MDL MQO
for acrolein. In general, the MDL MQOs for benzene, 1,3-butadiene, formaldehyde,
and arsenic were met by 70% or more of sites. All sites met the MDL MQO for
naphthalene and chromium (VI).
In CY2012, less than one-quarter of all sites met the MDL MQO for acrolein.
Approximately half or less of sites met the MQO for benzene and formaldehyde;
approximately 80% of sites met the MDL MQO for 1,3-butadiene and arsenic; and all
sites met the MDL MQO for naphthalene and chromium (VI).
Table 41. Ratio of the MDL Network Geometric Mean to the MQO for the Seven HAPs of
Primary Importance for CY2011 and CY2012
VOCs
carbonyls
PAHs
metals
Acrolein
Benzene
1,3-
Butadiene
Formaldehyde
Naphthalene
Arsenic
Chromium
(VI)
CY2011 MQO
<0.10 |xg/m3
< 0.13 |xg/m3
< 0.10 |xg/m3
< 0.98 (xg/m3
< 29 ng/m3
< 0.23 ng/m3
<0.08 ng/m3
ratio of
network
geometric mean
MDL to MQO
(CY2011)
1.3
0.58
0.42
0.038
0.0059
0.42
0.07
CY2012 MQO
< 0.09 |xg/m3
< 0.13 |xg/m3
< 0.10 (xg/m3
< 0.08 (xg/m3
< 29 ng/m3
< 0.23 ng/m3
<0.08 ng/m3
ratio of
network
geometric mean
MDL to MQO
(CY2012)
2
0.75
0.40
0.5
0.0081
0.41
0.06
88
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4.0 RECOMMENDATIONS
The information in the AQS database required for this report, both analytical results and site
characteristics, was acquired successfully, based on a thorough understanding of the database's
structure. Moreover, based on knowledge of POC assignments in previous years, the POCs for
the primary, duplicate, and collocated samples were assigned with greater facility than
previously. With the added AQS functionality in CY2011 that permitted MDL data to be
reported along with sample data, MDL information for CY2011 and CY2012 was taken solely
from the AQS database. Several sites still had not reported MDL data to AQS, and this report
reflects only those data in the database at the time of data extraction on November 7, 2013.
Requiring the timely reporting of MDL values to AQS would ensure the MDL results are
available so that the data user may better interpret reported results.
As stated in previous QAARs, POCs are present in the AQS database, but the associated sample
type information (e.g., primary, duplicate, or collocated) is not. There is no definitive way to
determine, from AQS alone, the relationship between specific POCs and primary, duplicate, or
collocated samples for a given site. Because POCs are assigned by either the agency monitoring
a particular NATTS site or the laboratory uploading the data to AQS, and are largely non-
standardized across NATTS sites [6, 7, 8, 9, and 10] (refer to Tables 7 and 8), the inclusion of a
field in the AQS database to specify whether a particular POC is primary, duplicate, or
collocated would be a significant benefit to the utility of the AQS data and would streamline the
analyses reported here.
Minimization of field sampler flow bias is directly correlated to improved accuracy in the
measurement of HAP concentrations. As seen in this report, relatively few samplers indicated
flow bias greater than ± 10% from the desired flow. However, flow bias for relatively few
NATTS network air monitors is assessed during any given calendar year. As most sites are
already periodically assessing flow bias, capturing this information in AQS would be beneficial.
Addition of a field in AQS to record the results of these periodic flow audits would provide a
means to minimize bias in reported results.
Lastly, AQS accepts data in a variety of units at the discretion of the agency performing the
upload. This requires careful scrutiny of the UNIT variable so that measurements can be
standardized prior to subsequent data analysis and interpretation. Standardization of the
ambiguous "ppbC" unit is particularly problematic. Implementing a requirement to report results
in mass/volume (e.g., (ig/m3) would improve the consistency of the data and facilitate
interpretation by data end-users.
To summarize, our recommendations are to:
• Require the reporting of MDLs to AQS;
• Include fields in AQS to specify the meaning of various POCs, and require the
populatation of these fields;
• Include fields in AQS to capture the results of ongoing flow audits performed by the
montoring agencies, and require the population of these fields; and
• Standardize the units of concentration used in AQS, and require that results be
uploaded in these units only.
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5.0 REFERENCES
1. U.S. Environmental Protection Agency. (October 17, 2008). AQS Data Coding Manual
(Version 2.33). Available at:
http://www.epa.gov/ttn/airs/airsaqs/manuals/AQS%20Data%20Coding%20Manual.pdf
[last accessed 11/8/2011].
2. U.S. Environ mental Protection Agency. National Air Toxics Trends Station Work Plan
Template, Revised February 9, 2011.
3. U.S. Environmental Protection Agency. National Air Toxics Trends Station Work Plan
Template, Revised April 11, 2012.
4. Eastern Research Group. Technical Assistance Document for the National Ambient Air
Toxics Trends and Assessment Program. Revision 2, April 2009.
5. U.S. Environmental Protection Agency. (July 2004). Final Draft, July 2004, National
Monitoring Strategy, Air Toxics Component. Available at:
http://www.epa.gov/ttn/amtic/files/ambient/monitorstrat/atstrat804.pdf
6. U.S. Environmental Protection Agency. (2007). National Air Toxics Trends Stations
Quality Assurance Annual Report - Calendar Year 2006. Prepared by Battelle Memorial
Institute.
7. U.S. Environmental Protection Agency. (2009). National Air Toxics Trends Stations
Quality Assurance Annual Report - Calendar Year 2007. Prepared by RTI International.
8. U.S. Environmental Protection Agency. (2010). National Air Toxics Trends Stations
Quality Assurance Annual Report - Calendar Year 2008. Prepared by RTI International.
9. U.S. Environmental Protection Agency. (2011). National Air Toxics Trends Stations
Quality Assurance Annual Report - Calendar Year 2009. Prepared by RTI International.
10. U.S. Environmental Protection Agency. (2012). National Air Toxics Trends Stations
Quality Assurance Annual Report - Calendar Year 2010. Prepared by RTI International.
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