Update on Manual Method for Update on Manual Method for Sampling and Analysis of Sampling and Analysis of Condensable ParticulateCondensable Particulate

Ray Merrill Ray Merrill –– ERGERGRon Myers Ron Myers –– EPAEPA

OverviewOverviewMethods backgroundMethod 202 performance (bias)Methods Comparison– Hardware & preparation– Sampler operation– Recovery requirements– Analytical finish

Dry Impinger Method performance– Bias– precision

Schedule

BackgroundBackgroundWhat is Condensable PM ?What is Condensable PM ?

Vapors and gases at stack temperature that form liquid or solid aerosols upon coolingAll condensable PM <1μM

BackgroundBackgroundHow was Condensable PM Measured?How was Condensable PM Measured?

Existing Method 202– Promulgated in 1991– Over 6 options in method– Artifact issue

BackgroundBackgroundWhatWhat’’s Changing with Condensable PM Measurement?s Changing with Condensable PM Measurement?

Dry Impinger Method (OTM-28)– Originally proposed by John Richards

(Method 202 variant)– Single standard procedure (no options)– Minimizes SO2 artifact– Low level blank management– Will replace EPA Method 202

Method 202 Artifact (bias)Method 202 Artifact (bias)

Artifact Mass (mg)SO2

ppmTest

durationH2O

volume No Purge Purge

300 1 Hr 400 ml 180 ± 6 10 ± 0.5

300 3 Hr 800 ml 400 ± 25 20 ± 5

50 6 Hr 1400 ml 200 ± 10 20 ± ??

OTMOTM--28 Sampling Train28 Sampling TrainDry Impinger GlasswareDry Impinger Glassware

OTMOTM--28 CPM Filter Media28 CPM Filter Media

Method Comparison:Method Comparison:Glassware PreparationGlassware Preparation

Existing Method 202 Dry Impinger MethodSoap & Tap Water WashTap Water Rinses

Acetone RinseMeCl Rinse

Soap & Tap Water WashTap Water RinsesUltrafilter water rinseAcetone RinseMeCl RinseHeat @ 300 Heat @ 300 °C C –– 6 Hrs6 Hrs

Method Comparison:Method Comparison:Glassware Set UpGlassware Set Up

Existing Method 202 Dry Impinger MethodMethod 23 Condenser

2 G/S Impingersw/ tipped stems100ml DI water

G/S Impinger w/ short stem, no water

1 G/S Impinger w/ 100 ml DI water

G/S Impinger w/ stem w/o water

Optional filter Filter

G/S Impinger w/ 100 ml water

G/S Impingerw/ Silica Gel

G/S Impinger w/ Silica Gel

Opt

ion

#1

Method Comparison:Method Comparison:Sampling TemperatureSampling Temperature

Existing Method 202 Dry Impinger Method

Maintain ALL four impingers in ice water bath

First two impingers in ≈ 85° F water bath

Filter Gas @ ≤ 85° F

Last two impingers in ice water bath

Method Comparison:Method Comparison:Post Test RecoveryPost Test Recovery

Existing Method 202 Dry Impinger MethodNitrogen PurgeAir PurgeNo Purge

Mandatory Purge with filtered UHP NitrogenOptional}

Option #2

Recovery Requirements:Recovery Requirements:Reagent Quality RequirementsReagent Quality Requirements

Existing Method 202 Dry Impinger MethodDI Water – ASTM Type II

Acetone – not usedMeCl – ACS Grade

<0.001% residueNH4OH – 14.8 Molar

DI Water –Ultra filteredASTM Type II

Acetone - < 1 ppm residueMeCl – ACS Grade

< 1 ppm residueNH4OH – NIST traceable

0.1 Normal

Dry Impinger MethodDry Impinger MethodSampling

Verify Sample Validity

Valid? Discard

Measure sample

volumes Dry &

W eigh filters

Extract samples

Evaporate organic

W eigh Residue

No

Yes

Organic Fraction

Oven & ambient evap

Reconst. 100 mL

Titrate w/NH 4OH

Correct M ass for NH 4 Added

Oven & ambient evap

W eigh pan & measure Inorganic

CPM

Inorganic Fraction

Method OTMMethod OTM--28 Comparisons28 Comparisons

OTM – 28 Compared to– Method 202– Controlled Condensate– Low Temperature Filter Train

OTM OTM –– 28 to Method 202 Comparison28 to Method 202 Comparison(EPA Laboratory Study)(EPA Laboratory Study)

OTM OTM -- 28 vs. M202 28 vs. M202 (Gravimetric Comparison)(Gravimetric Comparison)

Source: Electric Power Research Institute, 2008Source: Electric Power Research Institute, 2008

0 .0

2 .0

4 .0

6 .0

8 .0

1 0 .0

1 2 .0

1 4 .0

1 6 .0

1 2 3 4 5 6 7 8 9 1 0 1 1 1 2

mg/

DSC

M

1 5 0 p p m S O 2

~ 1 5 % H 2 02 1 3 - 2 1 6 OF

5 0 0 p p m S O 2

~ 1 5 % H 2 02 4 8 - 2 8 6 O F

A v e B la n k

5 0 0 p p m S O 2

~ 1 0 % H 2 0

3 0 0 - 3 4 0 O F

2 5 p p m S O 2

~ 1 5 % H 202 0 5 - 2 1 5 O F

M - 2 0 2 D r y Im p in g e r

OTM OTM -- 28 vs. M202 28 vs. M202 (Titration for Acid Artifact)(Titration for Acid Artifact)Source: Electric Power Research Institute, 2008Source: Electric Power Research Institute, 2008

0 .0

5 .0

1 0 .0

1 5 .0

2 0 .0

2 5 .0

1 2 3 4 5 6 7 8 9 1 0 1 1 1 2R u n N u m b e r

mg/

dscm

Sul

fate

~ 1 5 % H O2 5 p p m S O 2

2 0 5 - 2 1 5 F O

~ 1 0 % H O5 0 0 p p m S O 2

3 0 0 - 3 4 0 FO

~ 1 5 % H O1 5 0 p p m S O 2

2 1 3 - 2 1 6 F

~ 1 5 % H O5 0 0 p p m S O 2

2 4 8 - 2 8 6 FO

M -2 0 2 O T M 2 8

O

2

2 2

2

OTM OTM –– 28 Method Performance28 Method Performance

OTM OTM –– 28 Method Performance28 Method Performance(EPA Laboratory Replicate Study)(EPA Laboratory Replicate Study)

Run Organic (mg/dscm)

Inorganic (mg/dscm)

Filter (mg/dscm)

Total(mg/dscm)

1 0.12 2.36 -0.36 2.342 0.16 2.99 -0.06 3.033 0.09 1.44 0.00 1.464 0.31 1.98 0.00 2.225 0.17 1.65 0.07 1.776 0.39 2.58 -0.20 2.527 0.08 1.24 0.31 1.568 0.02 1.94 0.18 2.06Blank -0.02 mg 0.21 mg 0.00 mg 0.68 mgAverage 0.17 2.02 -0.01 2.18Std Dev 0.12 0.59 0.21 0.53MDL 0.37 1.78 0.63 1.60

OTM OTM –– 28 Method Performance28 Method PerformanceAmmonia and Sulfur DioxideAmmonia and Sulfur Dioxide

(EPA Laboratory Replicate Study)(EPA Laboratory Replicate Study)

Phase I Test Run

Method 5 filter

(160 °C) (μg)

Low-temp filter

(71 °C) (μg)

Aqueous (μg)

Organic (μg)

Ambient filter

(30 °C) (mg) Total (μg)

NH3 16 ND ND ND NA ND** ND 17 ND ND ND NA ND** ND 18 ND ND ND NA ND** ND

Train Blank 1 ND NA ND NA NR ND Train Blank 2 ND NA ND NA NR ND Train Blank 3 ND NA ND NA NR ND Reagent Blank NA NA ND NA NR ND

SO4 16 180 160 ND NA ND* 340 17 146 201 ND NA ND* 347 18 181 156 ND NA ND* 337

Train Blank 1 147 142 ND NA NR 289 Train Blank 2 147 102 ND NA NR 249 Train Blank 3 150 NA ND NA NR 150*

Reagent Blank NA NA ND NA NR ND ND = Not detectable above 27.6 total micrograms ND** = Not detected in gravimetric analysis of filter NR = Not run

OTM OTM -- 28 vs. Controlled Condensate28 vs. Controlled CondensateSOSO44 RecoveryRecovery

Source: Electric Power Research Institute, 2008Source: Electric Power Research Institute, 2008

0 .0

5 .0

10 .0

15 .0

20 .0

25 .0

30 .0

35 .0

40 .0

45 .0

31 32 33 19 2 0 21 34 35 36 22 23 24

mg/

dscm

150 ppm S O 2

0 ppm S O 2 150 ppm S O 2

0 ppm S O4

6 .9 m g /dscm S O 3 S p ike

34 .4 m g/dscm S O 3 S p ike

C on tro lled C ondensa te S OO T M -28 S O by ICO T M -28 C P M res idue w e igh t

24

Dry Impinger Method RecapDry Impinger Method Recap

No OptionsMinor glassware changesNo water at start of testShort stem impinger insert replaced with tipped insert for purgingDegassed Type III water added if neededBoth organic & inorganic evaporations at room temperatureSignificant reduction of sulfate artifact

Schedule UpdateSchedule Update

FR Proposal – April 2009Comment Period Close – June 2009FR Promulgation – December 2009

QUESTIONSQUESTIONS