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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

4

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

8

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!