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NATTS Quality AssuranceMulti-Year Assessment
QA Conference2009
Dennis K. Mikel EPA–OAQPS-AQAD
Outline
The NATTS Program QA IndicatorsEvolution of the NATTS Program and CompoundsData Quality ObjectivesMeasurement Quality Objectives
Meeting our Stated ObjectivesPrecision CompletenessDetectabilityBias
What’s New? Summary/Recommendations
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•Underhill, VT•Hazard, KY•Chesterfield, SC•Grand Junction, CO•La Grande, OR•Harrison County, TX
•Chicago, IL•Houston (Deer Park), TX•St. Louis, MO•Bountiful, UT•San Jose. CA•Phoenix, AZ•Seattle WA•Richmond, VA
•E. Providence, RI•Boston (Roxbury), MA•New York, NY•Rochester, NY•Washington, DC•Decatur, GA•Tampa, FL•Detroit, MI•Los Angeles, CA•Rubidoux, CA
•Rural•Urban Sites
NATTS QA Objective
Data Quality Objectives (DQOs) are tied to the GPRA goal of reduction of Air Toxics by 75% (1993 levels) by 2010:
“To be able to detect a 15% difference (trend) between two successive 3-year annual mean concentrations within acceptable levels of decision error.”
To meet these DQOs we need:
1-in-6 day sampling frequency with at least an 85% quarterly completeness;
precision controlled to a Coefficient of Variance (CV) of no more than 15%;
detectability based on 2001 Pilot Study Minimum Detection Limits (MDLs);
bias for the data set of less than 25%.
These are our Measurement Quality Objectives (MQOs)!
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NATTS QA Program
Measurement Quality Objectives (MQOs)
> 85%0.014 ug/m3< 25%< 15%Formaldehyde
> 85%0.020 ug/m3< 25%< 15%1,3-Butadiene
> 85%0.044 ug/m3< 25%< 15%Benzene
> 85% 0.046 ng/m3< 25%< 15%Arsenic
CompletenessDetectabilityBias(Lab)
Precision(CV)
Compound
Meeting Objectives: Precision Results 2004 - 2007
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13
14
‘06
1021metals
1355aldehydes
1447vocs
’07‘05‘04
Four Year Average:
Benzene: 19%
1,3 Butadiene 17%
Formaldehyde: 14%
Arsenic: 12%
No. of collocated sites
NATTS DQO Compounds - Precision
0
5
10
15
20
25
30
35
40
2004 2005 2006 2007
Years
% C
V
Benzene
1,3 Butadiene
Formaldehyde
Arsenic
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Precision by Site 2007
Arsenic Formaldehyde
Precision by Site 2007
Benzene1,3 Butadiene
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Meeting Objectives: Data Completeness 2004 – 2007
0
10
20
30
40
50
60
70
80
90
100
2004 2005 2006 2007
Years
% C
ompl
eten
ess
Benzene1,3 ButadieneFormaldehydeArsenic
Meeting Objectives: Mean MDLs 2004 - 2007
0.010
0.100
1.000
10.000Benzene 1,3 BD Formaldehyde Arsenic
ug/m
3/(n
g/m
3 fo
r Ars
enic
)
Mean MDL 2004
DQO MDL
RBC 1/10-6
Mean MDL 2005
Mean MDL 2006
Mean MDL 2007
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Identifying Problems: DQO compounds 2004 – 2007
0
0.2
0.4
0.6
0.8
1
1.2
2004 2005 2006 2007
Years
(ug/
m3
- ng/
m3)
Benzene1,3 Butadieneformaldehydearsenic
MDLs Reported - Arsenic
CMPDNUM=Arsenic
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MDLs Reported - Benzene
CMPDNUM=Benzene
MDLs Reported - FormaldehydeCMPDNUM=Formaldehyde
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NATTS PT - Metals Performance
-75.0
-50.0
-25.0
0.0
25.0
50.0
75.0
100.04th Q tr 0
4
1st Qtr 0
5
2nd Q tr 05
3rd Q tr 05
4th Q tr 05
1s t Qtr 0
6
2nd Q tr 06
3rd Q tr 06
4th Q tr 06
1st Qtr 0
7
2nd Q tr 07
3rd Q tr 07
4th Q tr 07
1st Qtr 0
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Avg
% D
iffer
ence
s
As
Be
Cd
Pb
Mn
Ni
NATTS PT - VOC Performance
-75.0
-50.0
-25.0
0.0
25.0
50.0
75.01s
t Qtr 0
5
2nd Q
tr 05
3rd Q
tr 05
4th Q
tr 05
1st Q
tr 06
2nd Q
tr 06
3rd Q
tr 06
4th Q
tr 06
1st Q
tr 07
2nd Q
tr 07
3rd Q
tr 07
4th Q
tr 07
1st Q
tr 08
Avg
% D
iffer
ence
Benzene
1,3 Butadiene
Carbon Tet
Chloroform
1,2 DBM
1,2 DCP
DCMDCE
1122, TCE
PERC
TCE
Vinyl Chloride
cis-1,3 DCP
Trans 1,3 DCP
Acrolein
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NATTS PT - Carbonyls Performance
-75.0
-50.0
-25.0
0.0
25.0
50.0
75.01st Q
tr 05
2nd Qtr 0
5
3rd Qtr 0
5
4th Qtr 0
5
1st Qtr 0
6
4th Qtr 0
6
1st Qtr 0
7
3rd Qtr 0
7
1s t Qtr 0
8
% D
iffer
ence
Formaldehyde
Acetaldehdye
Acetone
Crotonaldehyde
What’s New
•Hexavalent Chromium (Cr+6)
•Started in earnest in 2007
•At this time, haven’t pulled the collocated data
•We have no PT samples yet
•Polycyclic Aromatic Hydrocarbons
•Started collecting data in earnest in 2008
•Created two PT samples so far
•Most recent PT 1st Qtr 2009
•Results look excellent
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PAH compounds by Concentration
SVOC Concentration(ng/m3)
Fluorene 4.2
Fluoranthene 2.8
Chrysene 0.17
Phenanthrene 12.51
Other Compounds* 0.457Pyrene 1.48
Acenaphthene 5.012Anthracene 0.514
Naphthalene 64.45
AcenaphtheneAnthraceneChryseneFluorantheneFluoreneNaphthalenePhenanthrenePyreneOther Compounds*
* Other Compounds include: Benzo (a)anthraceneBenzo (a) pyreneBenzo (k) fluorantheneBenzo (b) fluorantheneBenzo (g,h,I)peryleneIndo (1,2,3, cd) Pyrene
PAH Precision Data 2007
Precision Results of SVOC TCEQ and ERG Combined
2007
0
5
10
15
20
25
30
35
40
% C
oeff
icie
nt o
f Var
ianc
e
Compound
Acenaphthene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (k) fluoranthene
Benzo (b) fluoranthene
Benzo (g,h,i) perylene
Chrysene
Fluoranthene
Fluorene
Indo (1,2,3,cd) Pyrene
Naphthalene
Phenanthrene
Pyrene
24.3%0.0743Indo (1,2,3,cd) Pyrene
22.4%0.08647Benzo (g,h,i) perylene
22.4%0.06947Benzo (b) fluoranthene
28.0%0.09447Benzo (k) fluoranthene
37.7%0.06943Benzo (a) pyrene
26.5%0.06950Benzo (a) anthracene
19.3%1.4857Pyrene
13.6%12.5157Phenanthrene
15.7%64.4557Naphthalene
13.4%4.257Fluorene
13.6%2.857Fluoranthene
19.8%0.1757Chrysene
19.2%0.51445Anthracene
16.3%5.01254Acenaphthene
Coefficient of Variance (%)
Average Concentration
(ng/m3)# of
PairsCompound
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PAH PT Study: 2009
Summary: Is the Program Able to Meet the DQOs?
Yes and No
The data completeness (2007) is above he required 85%. Good Job everyone!
The detectability for the 4 DQO compounds does not meet the MDLs stated in the DQOs, it appears that this has leveled out. However, one to two labs drive up the MDLs.
The CV data from the collocated/duplicate data illustrates that Overall, we are not meeting CV of less than 15% with the exception of Arsenic. Perhaps, 15% CV is too high, the program can meet 20%
The laboratories are meeting the 25% Bias requirement.
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Summary: What’s Next?
We have added Hexavalent Chromium to the NATTS program - need to create PT samples and begin looking at the PrecisionWe have added PAH compounds to the program and we know the P/B and things look good We are beginning to understand the realistic quality of HAPS data!