PB87-119897
EPA/600/2-S6/100
October 1986
TEST METHOD EVALUATIONS AND EMISSIONS TESTING
FOR RATING WOOD STOVES
Lc.\reice E Cottone
Engineering -Science
Two -'Int hill
10521 Rosenaven Stree:
Fairfax. Vi-gm'C 22030
Co-.trcct 68-02-3996, '.York Assignme-i-.s 7. 12, 13. and 15
end
Messer
Rcdicn Coroorction
P.O 3ox 13000
Research Triangle Park, Nortn Caro^nc 27/09
EPA Contract 68-02-399^-, Work Assignment 38
EPA Contract 68-02-3850, Work Assignment 22
EPA Project Officers:
Robert C. McOillis
Air and Energy Engineering Research Laboratory
Research Tnangle Park. North Carolina 2771 1
and
Peter R. Westlin
Emission Standards and Engineering Division
Office of Air Quality Planning end Standards
Research Triangle Park. North Carolina 27711
AIR AND ENERGY ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
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TECHNICAL REPORT DATA
(Pt eaie ,ecd IAII.r.Jctjcm$ on the ,e.ene befoee comp!enn:)
REPORT NO 2 13 RECIP’ENrS ACCESSI P 0
EPA/600/2-86/100 I jPB87 11 9 7IAS
4 TItLE A’ O S B!TLE 15 REPORT DATE
Test Method Evaluations and Emissions Testing for [ October 1986
Rating Wood Stoves PERFORMNG ORGANIZATION CODE
1 AI. TM Ri
Lawrence E. Cottone (ES) and Edward Messer
(Radian)
PERFORMING ORGANIZATION REPORT NO
9 P(AFoRMip OROANIZATIOP. NAME AND AOORESS
Engineering Science, 10521 Rosehaven St.. Fairfax 1
VA 22030; and Radian Corp.. p. 0. Box 13000.
Research Triangle Park, NC 27709
10 PROGRAM ELEMENT NO
11 CONFRACtfGRANT o
68-02-3996. Tasks 7, 12. 13.
15; 68-02-3994. Task 38
12 SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air and Energy Engineering Research Laboratory
Research Triangle Park, NC 27711
13 TYPE OF REPOR1 AND PERIOD COVERED
EPA/600/13
1 SUPPLEMENTARY P.IOTESAEERL project officer is Robert C. McCrillis . Mail Drop 65, 919/
541-2733. (*) Also 68-02-3850. Task 22. Cofunded by EPA/OAQPS: project officer
Peter R. Westlin. Mail Drop 19. 919/541-2237 .
16 ABSTRACT The report gives results of a comparison of three sampling methods for
wood burning stoves: the EPA Modified Method 5 (MM5). the Oregon Me’rod 7 (0M7),
and the ASTM proposed Method P180. It also addresses the effect that e .iL sion for-
mat (grams per hour, grams per kilogram wood burned, micrograms “ joule heat
output) has on the intermethod correlations. (The comparison was used a basis
for the selection of an emission sampling method and stove operating procedure
which are, in turn, being used by EPA to develop a New Source Performance Stan-
dard (NSPS) for wood burning stoves.) Five stoves (two catalytic, one noncatalytic
generic, one noncatalytic high efficiency, and one catalytic fireplace insert) were
tested. Test results showed good correlations between the total train emissions ob-
tained with each method. The strength of the correlations varied with the emission
format: the grams per hour format showed the strongest correlation. POM emis-
sions showed a general (but weak) correlation with total emissions when the grams
per hour formz t was used; there were no correlations when the emissions were ex-
pressed in either of the other two formats.
7 KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS lb IDENTIFIERS/OPEN ENDED TERMS
C. COSATI F ld/G eup
Pollution Evaluation
Stoves Sampling
Wood
Combustion
Emission
Tests
Pollution Control
Stationary Sources
Wood Stoves
13B
13A
ilL
2 1B
14G
l4B
IS O STRI8UTION STATEMENT
Release to Public
19 SECURITY CLASS (Th&iRepo,tj
Unclassified
21 NO OF PAGES
148
° SECURITY CLASS (flzipqv
Unclassified
22 PRICE
£PA Form 222 0 -I (E-73)
I
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NOT ICE
This document has been reviewed in accordance with
U.S. En ironmental Protection Agency policy and
app oved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
ii
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ABSTRACT
The U. S. Environmental Protection Agency ha decided to
develop a New Source Performance Stdndard (NSPS) for wood burning
stoves. During the development prouss several issues must be
resolved. One of the more cr. tica1 issues is the selection of an
emission sampling method and stove operating procedure. This
report addresses the comparison of three candidate sampling
methocts: the EPA Modified Method 5 (MM5), the Oregon Method 7
(0M7), and the ASTN proposed Method P180. it also addresses the
effect emission format (g/hr. g/kg wood burned, ug/J heat output)
has on the intermethod correlations.
Five stoves (i.e., two catalytic, one noncotalytic generic,
one noncatalytic high efficiency, and one catalytic fireplace
insert) were tested. The stoves were nominally operated
according to the State of Oregon’s certification procedure.
Simultaneous teats were conducted using MM5 and 0M7 in the stove
flue and MM5, 0117, and ASTM in the (ASTN) dilution tunnel.
Quality assurance tests using duplicate sampling trains were
also conducted. Proportional sampling, using S02 as a tracer
gas, was conducted in the flue, end isokinetic sampling was
conducted in the dilution tunnel.
Results ehowed good correlations between the total train
emissions obtained with each method. The strength of the
correlations varied with the emission format; the grams per hour
format showed the strongest correlation. PUN emissions showed a
general (but weak) correlation with total emissions when the
grams per hour format was used; there were no correlations when
the emissions were expressed in either of the other two formats.
iii
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CONTENTS
Ficjures
Tables vi
Abbreviations vii
1. Introduction 1
2. Summary or Results 3
3. Test Facility and Stove Descriptions 25
4. Sampling Procedures 28
5. Quality Assurance and Spec al Considerations 37
Appendix
Analytical Results Al
FIGURES
Number Page
1 Schematic of Stove haust and Dilution System With
Sample Locations 26
2 Schematic of Modified Method S Sampling Train 30
3 Schematic of DM7 Sampling Train 31
4 Schematic of ASTh Sampling Train 32
V
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TABLES
Number Page
la Summary of Woodstove Bniston Test Results Using Oregon Can—
bustion Program and Actual Dilution Tunnel Gas Flows - Grams
perHour
lb Summary of Woodstove Emission Test Results Using Oregon Wood—
stove Combustion Program and Actual Dilution Tunnel Gas Flows —
GransperKilOgram 6
ic Summary of Woodstove Emission Test Results Using Oregon Wood—
stove Combustion Program and Actual Dilution Tunnel Gas Flows -
p.Iicrograms per Joule 8
2a Summary of Woodstove Emission Test Results Using Oregon Method
7 to Standardize Dilution Tunnel Flow — Grams per Hour 10
2b Summary of Woodstove Emission Test Results Using Oregon Method
7 to Standardize Dilution Tunnel Flow — Grams per Kilogram . . . . 12
2c Summary of Woodstove Emission Test Results Using Oregon Method
7 to Standardize Dilution Tunnel Flow — Microgram per Joule . . . 14
3a Summary of Woodstove Emission Test Results Using Orsat Data
andF _GramsperHour 16
3b Summary of Woodstove flniscion Test Results Calculated and Fc —
Grams per Kilograms 18
3c summary of Woodstove Emission Test Results Calculated Orsat
Data and Fc — Mic ograms per Joule 20
4 Average eLssion rates per stove — Arithmetic Average 23
5 Validation Criteria — Sampling Trains 38
6 Validation Criteria — Woodstove Operation . . . . . 39
7a Su. mary o Timber—Eze Sampling Condtions • 40
lb Summary of Blaze King Sampling Conaitions 41
lc Summary of Lakewood Sampling conditions 42
vi
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Tables (Cont.)
Number
7d Summary of Bosca Sampling Conditions 43
7e Summary of Fisher Sampling Conditions 44
8 Results of Train Blank Sample Analyses Gravimetric Residue,
Milligrams 46
9 Results of Train Blank Analyses for Organics and Modified
Method S Samples 47
10 Summary of Duplicate Samples (Grams/Hour) 49
11 Comparison of Average CEMS C0 2 , 02, and CO With Concurrent
Orsat Results 50
12 Heat Input and Gas Flow Calculated Using Fc Factors and Wood
Heat Content Compared to Heat Output and Gas Flows Calculated
by Oregon Stove Combustion Program 52
13 Comparison of Moisture Determinations in the Stack Gas as
Measured by MM5, Wet Bulb/Dry Bulb, and 0M7 53
vii
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LIST OF ABBREVIATIONS AND SYM DLS
ABBREVIATIONS
ACF —— Actual Cubic Feet
ASTh —— A nerican Society of Testing Materials
Btu —— British thermal units
CEMS —— continuous em ssion monitoring System
DB —— dry bulb t nperature
g -- grams
j —— )oules
kg —— kilograms
mg —— milligrams
MM5 —- Modified Method 5
ng —— nanograms
0M7 —- Oregon Method 7
POM —— polycyclic organic matter
s m 3 —— standard cubic meters (200 centigrade, 60 millimeters
mercury)
TCO —- total chromatographable organics
WB —- wet bulb tenperature
SYMBOLS
CO —- carbon monoxide
CO 2 —- carbon dioxide
02 —- oxygen
Me d 2 —- methylene chloride
ii
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SECTION 1
INTRODUCTION
The purpose of this test program was to collect emission testing data
for the Environmental Protection Agency (EPA) to evaluate emission measurement
procedures that have been applied to certification of odstoves and to de-
velop an acceptable procedure for app] ication to a New Source Performance
Standard (NSPS) for the woodstove source category.
The primary objectives of the project as defined by EPA were:
o To collect emission testing data for evaluating the effectiveness
of the Oregon Department of Environmental Quality (DEQ) emission
sampling method (0147) in distinguishing between low and high emis-
sions of total particulate matter, condensible organic matter, and
polycyclic organic matter POM, using EPA Modified Method 5 (MMS) as
the reference.
o To collect emission testing data for evaluating the accuracy and pre-
cision of the Oregon DEQ (0M7) sampling method and the applicability
of the dilution tunnel emission sampling approach (as used with the
American Society for Testing Materials (ASTM) home heating appliance
emission sampling method) to the Oregon DEQ ()47 sampling method.
o To collect emission testing data for evaluating the representativena’,s
of the ASIM emission sampling method using MMS as the reference.
SAMPLING METHODS
The three sampling methods (MM5, 0147, and ASD4) have slightly different
objectives which may account for slight differences in the actual emissions
measured. EPA 14145 was designed to collect isokinetic samples of particulate
and condensible and semi-volatile organic components. The method captures
the semi—volatile organic fraction on a sorbent resin.
The Oregon sampling method was designed for the collection of particles
and condensible organ c mattEr. Isokinetxc sampling is not required for samp-
ling woodstove emission5, but the method does require proportional sampling.
The AS’DI method makes tnt assumption that the particles in the diluted
gas stream are small and behave a a gas. The sample rate is held constant
(+ 2%) throughout the test and gas measurements are taken at varying time
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intervals depending on the burn rate. Since the sample is collected at
basically ambient temperature and moisture conditions the .ample train fil ’.er
is not heated. The AS Th1 method specifies that the sample rate be based on
the filter loading and the filter face velocity (2 to 30 ft/nun). During
these tests, all sampling trains were operated at fixed points in the stack
or dilution tunnel as appropriate.
DESCRIPTION OF FACILITIES
The five stoves tested included three catalytic stoves (a Timber-eze
Model 477, a Blaze King Catalyst Stove — King Model KEJ—11O1, and a Fisher—
Tech IV fireplace insert), one conventional non-catalytic stove (Lakewood),
and one low emission non-catalytic stove (BOSCA).
PROJECT PARTICIPANTS
Project participants and their goals and responsibilities included:
o EPA AEERL — to evaluate stove emissions and available control strat-
egies for the purpose of standards development.
o EPA OAQPS - to eva] ’Ia’o the procedures used in the collection of
existing data and select a representative end reliable procedure Fn.
future testing of woodstove emissions.
o Radian Corporation - to specify odstoVe design and operating param-
eters that should be tested in order to provide the necessary infor-
mation for this program and to perform analyses on all samples col-
lected by the MM5, 0M7, and ASTM sampling methods.
o Engineering—SCience — to develop a detailed stove operation and nis—
sion test and quality assurance approach to fulfill the goals of
AEERL and OAQPS; to operate the woodstoves and collect ø iission sam-
ples according to those plans; and, to summarize the conditions,
methodologies, and results of the test program.
TEST LOCATION
All tests were conducted at the ES test facility in Research Triangle
Park, North Carolina. An air conditioned traiL. r was used to house the con—
tinuous analyzers and data recorders.
2
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SECTION 2
SUMMARY OF’ RESULTS
Sampling problems and i consi.stencies (discussed in Section 5) resulted
in each data point being calculated using three different approaches.
Briefly, those approaches are as follows:
Tables la, lb and ic: The stove heat outputs and stack flows were
calculated using the Oregon woodstove test method of carbon, hydrogen,
oxygen balance (CHO balance). The dilution tunnel flows and moisture
contents were determined for each of the samples collected at that
location. Possible problems with the CEMS data and definite problems
with the tracer gas method made the CHO balance results suspect. Diffe-
rences in the methods for measuring dilution tunnel flows and moisture
specified by the different sampling methods introduced minor differences
in calculations of the emission rates measured aimultaneously in the
dilution tunnel.
Tables 2a, 2b and 2c: The stove heat outputs and stack flows were
calculated as described for Tables Ia, lb and ic. The dilution tunnel
flows and moisture contents were standardized to those results of the
0M7 train, which uses EPA Reference Method 4 for moisture c easurements.
Tables 3a, 3b and 3c: The stove heat input was determined fran the
kilograms of dry wood burned per hour and the analyzed heat content
of the fuel. The stack flow rate was calculated using Fc, and F factor
for wood (40 CFR 60.45, July 1985). Dilution tunnel flows and moisture
contents were standardized to the CM7 train as in Tables 2a, 2b and 2c.
The results of the 22 test burns are prasented in three emission formats:
grams per hour (Tables la, 2a and 3a, grains per kilogram of wood burned (Ta-
bles lb, 2b and 3b) and micrograms per joule (Tables ic, 2c and 3c). Dupli-
cate sample results are included below the matching sample run.
Some of the data have been qualified in the summary tables. Those data
include the following:
o All sample runs conducted during test barns “Blaze King” 3 and “BOSCA”
—3 (High Efficiency —3). These burns could not be sampled to comple-
tion. This prohibited calculations according to the Oregon woodstove
test procedure and did not provide an emission measurement represen-
tative of a ccinplete burn. Results were calculated using the F
factor and are reported in Tables 3a, 3b and 3c.
3
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TArn E le • SIIMMAHY 1W l .1\N M 19S1 1)ll TI-,T 8F3 )I T’ 4 t*. 1444. 0RIX.(I44 W(1t )I ls15)VE C )44 13 1’,Tll)H lil )K..IA.M Nill
ALTIJAL Ill) (441044 T(INI4LL ( AS 10W . I T (J )M1N I) bY k ALI’ SAI4I ’I THAI)) - ( .NAM ’. I ’ I ) 4411(3 )
Stove I et
burn th lt4’Ut
I 111111
hr)
T1ehere e
I A
2A
our n
R to
(.lr y
hr I
40,712 0.913
15,0,16 4.22
35.006 1.22
9.38
20.2
D l I
Stdl .k 1LII,I ,t1
1)140-
4 1, 141
54-ack lu Iiii ,_l
M M ’.
p . .rttc ,i1.tte Ito Il lei lol ION
St , .ck P o.tesio ,le t 1ut4on ‘1 ’ui floI I’i!lLbl llOflS
D l lu—
4-14,1 1
DM7 14)45 DM1 A’,TM StacIl Tunnel
4
4.
I.
S
S.
2
I.akewood
2
4
4.
10.4
12. ’)
4.’)L)
3.13
b.29
3.36
0.154
0.0. UU
0.112
0.993
17 • 4
5.19
6.02
3.73 g
30.7
11.0
1. IHQ
L OS
4.13
4.OU
2.54
9.55
2.15
4.22
3.40
I). 071.2
0,04t .1
0. 0)06
0.11515
0.41241)
0.0244 ’
0.04 I
(. 1)4)41
3.36
2.50
9.1b
3.00)0.’
43.3
9.
4.90
4.17
3.54
0.345
0.0990
11.00)7
11.0120
44•49
I 5.2
2.29
3.t .3
0.140
0.413
0.4)1)0
11.07)15
0. UI
21.1
40. 1
1.943
4.98
6.62
0.31)4
(I. 295
I I . 4(14 4.)?)
1.224)
7.22)
11,185
H, 465
22, .1141
22, 7111
32.1 iii
32,110
9.032
13,211
13,211
I 6,581
96,474
96,4 74
0. 4 )
1.4)9
I 09
3.04
I .04
2.7?
2.77
0.89
1.17
1.17
I • 51
7.31
1.17
7.54Q
23. OQ
24. SQ
2n.1
39.
52. OQ
44.5
42. ’)
32.9
184.
304.
75.3
27.1)
33.0
20.0
29.5
0.338
0.741
0.474
53.9
24.9
D.b 99
0.5°
54.4
28.5
22.4
13.8
23.9
0.5b9
4.10
(4.245
0.492
160.0
94.5
99.0
92.5
80.8
1.71
3.116
46.4
I 2.6
88.34 )
130.0
5.49
34.4
(Cot , I 4 nun ’I I
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TAIII.F la (conttnuu,i)
I irn I’4rttc Ildt TCO phenol lUM
Stove Ih at H , te Stack I3, te ’ iofl3 ill lotion Tunnel IStiet 0 !
Horn Output (Jcy DUo. lOb—
Number (Htu/ kj/ tbol’ tl ,,n th ,n
hr) hr) 0M7 MRS 0141 ASIM Stack Tunnel Stack Tunnel Stack bonnel
u’
2 7.972 0.54 30.5 21.2 10.5 0.26 12.) 12.1 6.21 0.194 0.0557 0.092) 0.0342
p 7.972 0.54 12. 1 3 13
4 13.999 1.08 16.0 9.26 24.4 8.64.1 ) 9.93 6.55 1.76 0.303 0.249 0.4)2 0.384
19.511 1.46 20.6 15.4 33.0 10.1 10.1 9.36 5.94 0.327 0.225 0.8)3 0.80!
In 19.511 I... 11.6 43.913
5 40.59! ). !U 50.3 25.9 61.1 37.1 20.5 24.2 2!.) 3.32 1.40 4.5!) 4.4!)
3k
3.,.
Fiaher
2 0,752 0.55 9.94 5.36 22.61. 10.1 4.17 4.97 3.221. 0.0637 0.031!!. 0.0202 0.04*15
8.7:2 0.55 14.9 7.4.8 0.0220 0.04.4!
4 14.273 0.95 17.3 11.8 23.011 13.1 6.12 5.!) 3.9911 0.140 0.0244.44 0.0451 0.075011
14,273 0.95 27.5 3.0 0.0312 0.105
3 23.570 1.58 19.6 16.0 47.1 21.4 13.6 5.53 6.4.1 0.183 0.123 0.083) 0.23!)
29.223 2.02 40.5 30.4 71.9 37.1 31.2 12.6 13.0 0.4)2 0.14b 0.155 0.415
* Indicatee renulta of du ’l bate rune
(3 — Data reuontei hut quality be eacertain d,w, to low fflter box te !flperatur*B
X — Hack filter torn
I. — Saziipla rate bubow 90’. ienkinetice
II — Sample rate above 110% tuoktIleti ! .U
A — Teat burn wan not conuintent with o 1 ncified atove operattnq proee.lures
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TAUI.E lb. SUMMARY 0i W0Ou ,T(JVE 194 I ’ ,stON Th . ’l ’ R1 .UI.TS US lOt. 0P X ()N W00l)STDVE WMUt0.T IUN Uti(LIIA )4 ANt)
ACTUAL UlLlfl ’IOH TUNNEl. GAS VL(a45 I6.T6H?41NU) bY FALII SAI4PI.6 TRAIN - (.HA?8 ,/Kll.CL.RA NS
Stove
8irn
I ,at
Output
I Sirn
Rate
(dry
p a rt lcul ato
flhlu—
tion
l)tl )l—
Stack tion
I lilU—
tion
StaCk Elnt*eLonU
Dilutton Tunnel oulone
)luuber
(Rtu/
k.j/
St
ck Tunnel
Stack
Tunflel
Stack T innui
SrI
hr)
1455
0147
MM5 —
0 ’ .
Tiebereze
16 ¶0,772 0.90 ¶0.4 4.92 12.81. 6.1451. 4.79 3.76 4.641. 0.0630 0.05671. 0.0596 0.091 31.
26 15,006 1.22 16.6 8.55 10.5 4.02 2.57 5.16 2.75 0.126 0.0236 0.0)21 0 0299
28 15.006 1.22 0.781
4 7,220 0.60 29.0 10.0 17.8 13.30 6.80 ¶5.9 7.03 0.127 0.151 0.1)41)1. 11.11 ‘.1)1
7,220 0.60 6.58
I ¶1,185 1.09 5.28 3.405 10.1 3.79 2.33 1.97 3.12 0.0428 0.0521 0.026 ) 0.0352
I ’ 11,105 1.09 3.00 2.29
S 22, 201 1.64 5.95 I .O3XQ 8. 13 S.67Q 2.99 2.54 2.15 0.0UU7 0.0604 0.04911 0.044)
5’ 22,281 1.64 6.18 9.24 I.U2 2.21 0.0852 0.0678 0.0401 0.0419
2 32. 170 2.17 5.62 2.91 4.56 3.87 2.80 1.80 2.39 0.0644 0.0919 0.0376 0.0625
7 ’ 32,170 2417 2.76Q
36
1 . 08 ewood
1 9,812 0.89 50.0 26.7Q 60.6 27.3Q 30.8 17.6 21.8 0.376 0.517 0.136 0.200
3 13,271 1.17 36.7 20.9Q 64.4 23.1 28.2 17.1 25.2 0.289 0.639 0.149 0.460
3’ 13, 217 1. 17 22.9 45.7 21.2 0.563 0.432
2 16,587 1.51 21.8 i3.0Q 36.0 10.9 14.8 9.12 ¶5.8 0.377 0.729 0.162 0.326
4 96,474 7.11 25.6 7.26Q 23.5 7.60 13.8 12.9 ¶1.3 1.08 0.538 2.28 1.76
4 96,474 7.11 25.6 12.311 11.3 0.765 2.01
(cont I relel)
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tAIII .E lb (continued)
l S4rn particulate TCO phenol 14344 -—
Stove lk at Sate Stack l3eixxtons - t)tlutiOfl Tunnel F3nhiaslona
Sure Output (dry Ditu— Ollu— Dilu—
Number (Ntu/ k .j/ tioui Stack tion tion
hr) hr) 8145 0447 8445 0447 ASTM Stack Tunnel Stack Tunnel Stack Tunnel
Rosca
2 7.972 0.54 56.4 39.3 34.2 15.3 22.8 22.4 11.5 0.359 0.103 0.171 0.063)
7.972 0.54 23.7Q
4 I 3.999 1.08 14.8 8.58 26.3 A.O2ç 9.20 6.06 7.18 0.355 0. 31 0.400 0.355
1 49. 511 1.46 14.1 13.4, 22.6 7.30 6. O 6.41 4.07 0.224 0.154 0.571 0.549
j x 19.544 1.46 7.98 6.15
S 40.594 3.40 46.2 8.37 24.7 42.0 6.63 7.80 6.06 0.74 0.416 1.45 4.44
3A
3A
Fixhor
2 41,752 0.55 18.4 9.79 4 1.2L 49.5 7.59 5.40 5.861. 0.116 0.06745 0.0367 0.44411.
2 8,752 0.55 27.1 4.87 0.0404 0.117
4 14. 271 0.95 48.2 42.4 25.441 43.8 6.45 5.40 4.2011 0.147 0.O2’ 4ll 0.0475 0.0744911
4 44.273 0.95 29.0 4.04 0.0320 0.440
3 23.570 1.58 42.4 10.4 30.2 43.5 0.58 3.50 4.22 0.446 0.0780 0.0527 0.151
1 29,223 2.02 20.4 15.4 35.6 19.3 45.4 6.22 6.42 0.244 0.0724 0.0767 0.205
Indicatex runulte of duplicate rune
Q - Data p euented but quality Is lmcortaln duo to low filter box t nporature8
S — Hock filter torn
1. - Sample rate below 90% iooklnet(ru
ii — ,)amplx rate abuva 110% lxukisrntic.x
A - Text burn wax not consiutent with 8 1 -.301f103 stove operattnq ‘rocedurea
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TMILE Ic. SUMMARY 01’ WOOUS )OVE 94!SS!ON 1 ’6$P RI:suI.’rs 115190 ( 1XON W000ST0V WMUU 1’I0N I I4Ali P440
ACTUAL PILUD1ON i ’Jl1N1 . (.AS 114M9 UBT4kMIN 2) BY IACII Ml’L TRAIN - NiL .X . 8A14’ ,/JOiJ Ik ’
Stove
Burn
Buat
Output
Burn
Rate
(dry
Utlution
Tunnel
ISninotOn _
Dilu—
Stack tion
Dilu-
tion
Stack
Buim9ioflB
Dilu—
tlon
Number
(Btu/
k ’j/
0147
14145
0147
A5TH Ste
ck Tunnel
Stock
Tunnol St
ack Tunnel
Br)
Br)
14145
Timberere
IA 10,772 0.90 0.826 0.390 1.011. 0.5431. 0.379 0.296 0. 3671. 0.00499 0.004491. 0.00472 0.007241.
2?. 15.006 1.22 1.287 0.659 0.clI 0.3)0 0.196 0.396 0.212 0.00973 0.0U182 0.00710 0.0023)
2A 15.006 1.22 0.0603
Blaze king
4 7.220 0.60 2.29 0.790 1.4(3 1.059 0.536 1.26 0.554 0.0100 0.0119 0.00315 0.00621
7,220 0.60 0.518
1 11,105 1.09 0.488 0. 3 )48 0.935 0.350 0.215 0.162 0.280 0.00396 0.00407 0.00243 0.00325
11,185 1.09 0.285 0.212
3 22.281 1.64 0.4)5 0.128XQ 0.568 0.3969 0.209 0.177 0.151 0.00619 0.00422 0.00349 0.00309
22,281 1.64 0.361 0.645 0.127 0.154 0.00595 0.00473 0.00340 0.0033..
2 32, 170 2.77 0.459 0.238 0.69 0.316 0.235 0.147 0.195 0.00526 0.00751 0.00307 0.00510
2 ’ 32.170 2.77 0.2259
3?.
Lakewood
I 9,812 0.89 4.31 2. 3t9 5.2) 2. 359 2.65 1.52 1.88 0.0324 0.0444 0.01)7 0.017’)
3 13.277 1.17 3.07 I .759 5.38 1.93 2.36 1.43 2.11 0.024) 0.0534 0.0)24 0.0385
3 13,277 1.17 1.91 3.82 1.78 0.047) 0.036)
2 16,567 1.51 1.08 I • 129 3.11 1.64 1.28 0.787 I • 36 0.0325 0.0b30 0.0140 0.0281
4 96,474 7.17 1.6) 0.5)29 1.65 0.536 0.973 0.910 0.794 0.0760 0.03 9 0.161 0.124
4 96.474 7.17 1.81 0.136U 11 (1.795 0.0539 0.141
(continued)
-------
TABLK lc (continued)
Rim Particulate ¶ O phenol poji
Stove I6iat Itita Stack Bulsajona Dilution Tunnel 13,ikasione
Burn Output (dry Dilu— DUo- DUe—
Nuober (Btuf ky, tion Stack tion tion
- hr) Br) MIlS 0M7 liNt, DM1 ASTI4 Stack Tunnel Stac.k tunnel Stack Tunuti
2 7,972 0.54 3.62 2.53 2.20 0.982 l.47 1.44 0.739 0.0231 0.00663 0.0110 0.00406
7,972 0.54 1. 52Q
4 13,999 1.08 1.09 0.629 1.92 0.5B7Q 0.673 0.444 0.526 0.0260 0.0169 0.0292 0.0260
I 19,511 1.46 1.00 0.749 1.60 0.518 0.490 0.455 0.289 0.0159 0.0109 0.0405 0.0390
l• 19.511 1.46 .1.566 0.437
5 40,591 3.10 1.18 0.606 1.57 O.8b8 0.460 0.565 0.497 0.0541 0.0345 0.105 0.105
3A
3A
Fisher
2 8,752 0.55 1.08 0.583 2.45t. 1.18 0.452 0.322 0.3496 0.00690 O.D040 0.00219 0.008831.
2 8.752 0.55 1.62 0.290 0.00239 0.00695
4 14,273 0.95 1 • 15 0.783 1.5811 0.868 0.407 0.341 0.2659 0.00928 0.00164H 0.00300 0.0049011
4 14,273 0.95 1.83 0.253 0.00207 0.00696
3 23,570 1.58 0.789 0.643 1.92 0.860 0.546 0.222 0.268 0.00738 0.00496 0.00135 0.00959
1 29,223 2.02 1.32 0.988 2.34 1.20 1.01 0.407 0.421 0.0140 0.00474 0.00503 0.0135
• Indicates results of duplicate runs
Q — Data p eaented Dut quality is .xicertain due to low filter bo tenl reture8
X — Buck filter torn
6 — Seeple rate below 90 iaokir,ettca
H — Saisple rate abo o 1 10k ieokinntic . ,
P. — Teat burn Wa , not conatetent with ..çacLfi .&tovu operatiaj .rocedures
-------
TABLE 2a. SUMMARY OF W000SIOVE I)4ISSION lEST RE 3ILTS USING 0R1X014 METHOD 7 TO
STANDAIWIZE DIL(JF ION TU’0l .L FLCM NGI1 ,TIINE CON1’ .NT CRAIIS PER IIOUS
Stove
Burn
Heat
Output
Burn
Rate
(dry
Particulate
TCO
phenol
Duo-
tion
Dilu-
tion
Stack
*3ninaions
Dilution
Tuned
iaeiuiB
Dilu—
tion
Number
(Btu/
kg/
Tunnel
by)
hr)
EMS
0147
14)45
0147
ASTM SLack Tunnel
Stack
o Tiebereze
1k *0,772 0.90 9.36 4.43 1I.4L 6.161. 4.26 3.39 4.12 0.0567 0.0507 0.0537 0.0B’6
2A 15,006 1.22 20.2 10.4 13.2 4.89 3.37 6.29 3.44 0.154 0.1.298 0.112 0.0376
2k 15,006 1.22 0.999
Blaze King
4 7,220 0.60 17.4 6.02 10.7 7.99Q 4.50 9.55 4.22 0.0762 0.0906 0.0240 O.O4 4
4 7,220 0.60 3.96
1 11,185 1.09 5.75 3. fiX 10.9 4.15 2.66 2.15 3.39 0.0467 0.0570 0.07136 0.0301
11,185 1.09 3.36 2.34
S 22,291 1.64 9.76 3.(IOXQ 13.4 9. 27Q 4.9’ 4.17 3.56 0.145 0.0996 0.0817 0.0731
22,281 1.64 8.49 *5.3 2.99 3.65 0.140 0.112 0.0798 0.0790
2 32,170 2.77 15.6 ,j.07 24,1 10.7 6. 5 . 4.98 6.75 0,178 0.258 0.104 0.176
2 32,170 2.77 7.640
Lakewood
9,812 0.89 44.5 23.8Q 54.1 24.40 27.2 *5.7 19.4 0.335 0.46* 0.121 0.186
3 13,277 1.17 42.9 24. SQ 74.8 27.0 33.1 20.0 29.2 0.338 0.74* 0.174 0.534*
3 *3,277 1.17 26.7 53.2 24.8 0.655 0.503
2 *6,587 l.5l 32.9 19.6Q 54.5 28.5 22.1 13.8 23.9 0.569 1.10 0.245 0.492
4 96,474 7.17 184. 52.OQ 170. 54.6 97.1 92.5 81.8 7.73 3.90 16.4 12.8
4 96,474 7.17 *64. 89.OH 80.8 5.49 14.4
(continued)
-------
TABLE 2a (continued)
Stove
Burn
Biat
Output
Rate Stack
(dry
——
Raisetons Dilution Tunnel beissiOns
Dilu—
tion
Dilu—
tion
Duo-
tion
flunbcr
(Btu/
hr)
hr) p 045
0147 14145 0147 ASTh Stac
Ii Tunnel
Stack Tunnel Ste
ek Tunnel
B e e ca
2 7.972 0.54 30.5 21.2 18.5 6.27 12.2 12.1 6.21 0.194 0.0558 0.0923 0.0343
2 7.972 0.54 12.BQ
4 13.999 1.08 16.0 9.26 28.6 8.66Q 9.10 6.55 7.85 0.383 0.251 0.432 0.385
1 19,511 1.46 20.6 15.4 32.7 10.7 9.85 9.36 5.90 0.327 0.222 0.833 0.791
19,511 1.46 11.6 8.76
5 40,591 3.10 50.3 25.9 68.3 37.2 20.4 24.2 21.6 2.32 1.50 4.50 4.55
Fisher
2 8.752 0.55 9.94 5.78 22.61. 10.7 4.17 2.97 3.25 0.0637 0.0815 0.0202 0.0371
2 8.752 0.55 14.9 2.70 0.0641 0.0220
4 14,273 0.95 17.3 11.8 23.914 13.0 6.23 5.13 4.03 0.140 0.0753 0.0451 0.0247
4 14,273 0.95 28.3 3.94 0.108 0.0320
3 23,570 1.58 19.6 16.0 48.0 21.3 13.4 5.53 6.73 0.183 0.240 0.0833 0.124
29,223 2.02 40.5 30.4 71.6 37.0 30.3 12.6 12.9 0.432 0.413 0.155 0.146
Indicatee results of duplicate rune
Q — Data çreaented but quality is ulcertatn do, to ow filter L- ,c tesperatures
X — Back filter torn
I , — Se ple rate below 90% isokinetice
H — Saaple rate above 110% isokinotics
A — Test burn was not con lstent with specified stove .perating procedures
-------
TABL.E 2b. SUMMARY OF WOODS OVE D4ISSION TEST RESUI.TS US!NG ORiZON METHOD 7 TO STANDARDIZE
DILUTION TUNNEl. RL( S MOISTURE CONTENT CRAM2 PER KIWGRAJ4
Stove
Burn
Number
I at
Output
(Btu/
h )
Burn
Rate
(dry)
(kg/
hr)
Particulate
O
Phenol - POM
Dilu— Dilu—
tion tion
Stack
E ,ieaions
Dilution
Tunnel
l3 i 9ton5
Dilu—
tion
ASTh Stack
MRS
0M7
1 1 ) 1 5
OH7
Tlmbereze
lA 10,772 0.90 10.4 4.92 12.6 6.84 4.73 3.76 4.58 0.0630 0.0563 0.0596 0.0906
2A 15,006 1.22 16.6 8.55 10.9 4.0) 2.76 5.16 2.82 0.126 0.0244 0.092) 0.0308
2A 15,006 1.22 0.818
Blaze King
4 7,220 0.60 29.0 10.0 17.8 13.1 7.50 15.9 7.04 0.l27 0.15: 0.0400 0.0790
4 7,220 0.60 6.61
1 11,185 1.09 5.28 3.40X 10.0 3.81 2.44 1.97 3.11 0.0428 0.0523 0.0263 0.0350
11,185 1.09 3.08 2.15
S 22,281 1.64 5.95 1.83XQ 8.17 5.66 3.03 2.54 2.17 0.0887 0.0607 0.0498 (‘.0446
22,281 1.64 5.18 9.31 1.82 2.22 0.0852 0.0682 0.0487 0.0482
2 32,170 2.77 62 2.91 8.72 3.81 3.09 1.80 2.44 0.0644 0.093) 0.0376 0.0635
2 32,170 2.77 2.76Q
Lakewood
1 9,812 --0.89 50.0 26.70 60.7 27.4 30.6 17.6 21.8 0.376 0.518 0.136 0.209
3 13,277 1.17 36.7 20.90 63.9 23.1 28.3 17.1 25.0 0.289 0.633 0.149 0.457
3 13,277 1.17 22.9 45.5 21.2 0.560 0.430
2 16.587 1.51 21.8 13.OQ 36.1 18.8 14.6 9.12 15.9 0.377 0.730 0.162 O.32o
4 96,474 7.17 25.6 7 .26Q 23.7 7.61 13.5 12.9 11.4 1.08 0.545 2.28 1.78
4 96,474 7.17 25.6 12.4 11.3 0.765 2.01
(continued)
-------
TABLE 2b (continued)
Stove
Burn
(blat
Output
jrn
Rate
(dry)
Particulate
TCO
phenol
Stack
Ra18910n8
Diluttot’
Tunnel
Dni 3iofla
DILU—
Ditu—
tion
Dilu—
tion
Number
(Btu/
(kq/
ck Tunnel
Stack
Tunnel Ste
c l i Tunnel
hr)
hr)
7045
0747
7045
0747
P.STN
Boaca
2 7.972 0.54 56.4 39.3 34.3 15.3 22.5 22.4 11.5 0.359 0.103 0.171 0.0635
2 ° 7,972 0.54 23.7
4 13,999 1.08 14.8 8.59 26.4 8.02 8.43 6.06 7.27 0.355 0.232 0.400 0.357
19,511 1.46 14.1 10.6 22.4 7.30 6.75 6.41 4.04 0.224 0.152 0.571 0.542
I 19,511 1.46 7.99 6.00
5 40.591 3.10 16.2 8.37 22.0 -12.0 6.59 7.80 6.91 0.147 0.483 1.45 1.47
Fiaher
2 8.752 0.55 18.1 9.79 41.0 19.5 7.58 5.40 5.91 0.116 0.148 0.0367 0.0675
2 8.752 0.55 27.1 4.91 0.117 0.0400
4 14,273 0.95 18.2 21.4 25.2 13.7 6.57 5.40 4.24 0.147 0.0792 O.047 0.02b0
4* 14.273 0.95 29.8 4.15 0.114 0.0331
3 23.570 1.58 12.4 10.1 30.4 13.5 8.45 3.50 4.26 0.116 0.152 0.0527 0.0783
1 29.223 2.02 20.7 15.1 35.4 18.3 15.0 6.22 6.38 0.214 0.204 0.0767 0.0721
* Indicates results of duplicate tuna
Q — Date esentod but quality to uicertain du e to low filter box tmnperatures
X — Buck filter torn
L — Sample rato below 90% isokinetica
H — Sa ple rate above 110% isokinetiCs
A — Teat burn web not consiotont U) th e 1 uctfiod utovo oporatir*j procodurea
-------
TABLE 2c • SUMMARY W000ST(WE 194 ISSION TEST RESdLTS (SING 0RR ON METhOD 7 TO STM%DARDIZE
DIIA7rION TuNNEl. FLQ4 & )VIbIURE Q)NTENT PER MICROGRAMS/JOULE
Stove
Burn
l at
Output
Burn
Rate
(dry)
particulate
TCO
Phenol
POM -
Stack
Dnicsions
Dilution
Tunnel
Buissions
Dilu—
Dilu-
tion
Dilu—
tian
‘lueiber
(Btu/
(kg/
Tunnel
Stack Tunnel
lit)
hr)
14145
0147
14115
‘)M7
ASTM
Stack
Tunnel
Tinbereze
1A 10,772 0.90 0.826 0.390 1.00 0.542 0.375 0.298 0.363 0.00499 0.00446 0.00472 0.00718
2A 15,006 1.22 1.287 0.659 0.837 0.309 0.213 0.398 0.217 0.00973 0.00188 0.00710 0.00237
2A 15,006 1.22 0.0631
Blaze Ktn
4 7,220 0.60 2.29 0.790 1.4% 1.05 0.591 1.26 0.555 0.0100 0.0119 0.00315 0.00623
4 7,220 0.60 0.52%
I 11,185 1.09 0.408 O.3 14X 0.928 0.352 0.226 0.182 0.287 0.00396 0.00483 0.00243 0.00323
1. 11.185 1.09 0.285 0.199
S 22, 281 1.64 0.415 0.1 2SXQ 0.57% 0.395 0.211 0.177 0.151 0.00619 0.00424 0.00348 0.003% 1
22,281 1.64 0.361 0.650 0.127 0.155 0.00595 0.00476 0.00340 0.00336
2 32.170 2.77 0.459 0.238 0.712 0.316 0.252 0.147 0.199 0.00526 0.00761 0.00307 0.00518
2 32. 170 2.77 0. 225Q
Lakevood
1 9.812 0.89 4.31 2.30Q 5.23 2.36 2.63 1.52 1.88 0.0324 0.0445 0.0117 0.0180
3 13.277 1.17 3.07 l.75Q 5.34 1.93 2.37 1.43 2.09 0.0241 0.0529 0.0124 0.0382
3 13.277 1 • 17 1.91 3.80 1.77 0.04GB 0.0359
2 16.587 1.51 1.88 1.1 2Q 3.12 1.63 1.26 0.787 1.37 0.0325 0.0631 0.0140 0.0281
4 96.474 7.17 1.81 0.51 2Q 1.67 0.537 0.955 0.910 0.804 0.0760 0.0384 0.161 0.126
4* 96.474 7.17 1.81 0.875 0.195 0.0539 0.141
(continued)
-------
TABLE 2c (continued)
Stove
Burn
at
Output
Burn
Rate
(dry)
particulate
Dsis iOns
Dilu-
tion
Ditu—
tion
DL
ti
u—
.
Stack
siestons
Dilution
Nwnber
(btu/
‘q/
OH?
ASTH Ste
ck Tunnel
Stack
Tunnel Ste
ck ru.,
nel
hr)
hr)
pw5
0M7
Fisher
2 6.752 0.55 1.08 0.563 2.45 1.16 0.452 0.322
2 . 6.752 0.55 1.62
4 14,273 0.95 (.15 0.783 1.59 0.867 0.415 0.341
4* 14.273 0.95 1.89
3 23.570 (.58 0.789 0.643 1.93 0.859 0.537 0.222
1 29.223 2.02 1.32 0.988 2.32 1.20 0.982 0.407
* Indicatea-resultq of duplicate runs
Q — Data rcnCflted but quality is uncertain due to low filter box tee .peratures
X — Back filter torn
I. - Sampto rate below 901 ieokinetice
Ii — Sezsple rate above (10% isoktnetica
A — Test burn was not consistent with e cified stove operating procedures
0.352 0.00690 0.00883
0.292 0.00695
0.268 0.00926 0.00500
0.262 0.007(7
0.271 0.00738 0.00965
0.418 0.0140 0.0134
0.00219 0.00402
0. 00239
0.00300 0.00164
0.00213
0.00335 0.00499
0.00503 0.00412
Bosca
0.01(0
0.00408
U i
2
7,972
0.54
3.62
2.53
2.20
0.983
1.45
1.44
0.739
0.0231
2
7.972
0.54
1.52
0.532
0.0260
0.0170
0.0292
0.0261
4
13,999
1.08
1.09
0.628
1.94
0.567
0.617
0.455
0.287
0.0159
0.0108
0.0405
0.0385
1
(9.511
1.46
(.00
0.749
1.59
0.518
0.479
I
19,511
(.46
0.566
0.478
0.565
0.505
0.0541
0.0350
0.105
0.106
5
40,591
3.10
(.18
0.606
1.60
-------
TABLE 3a. SUMMARY 01’ WOODSTOVE 124 1SS1011 TEST RESULTS USING ORSAT DATA AND 1’ c - GMAMS PER HOUR
Burn
P Factor
Buat
Input
Burn
Rate
(dry
Parttculate
ItO —
Dilu—
— Phenol
ION
Stack
r ,Lmsions
Dilutior’
TUnnel
E1nissjong
Number
(Btu/
kg/
tinn
Dilu—
Dilu-
hr)
hr)
14145
0147
14145
0117
tion
tion
Timbereza
IA 17.285 0.90 17.0 8.01 11.41. 6.161. 4.26 6.13 4.121. 0.103 0.05071. 0.0971 0.08161.
2A 23.218 1.22 14.6 7.S5 13.2 4.89 3.37 4.55 3.44 0.111 0.0298 0.0813 0.0376
26 23.218 1.22 0.999
Blaze King
4 11.607 0.60 23.3 7.99 10.7 7.99Q 4.50 12.1 4.22 0.101 0.0908 0.0319 0.0474
4 11.607 0.60 3.96
1 20.898 1.09 7.13 4.591 10.9 4.5 2.66 2.66 3.39 0.0S76 0.0570 0.0355 0.0301
20,89U 3.09 4.36 2.34
SF 33.964 1.64 10.5 3.22xQ 13.4 9.27Q 4.96 4.47 3.56 0.156 0.0996 0.0877 0.0731
31,964 1.64 9.11 15.3 3.21 3.65 0.150 0.312 0.0856 0.0790
2 53.615 2.77 20.8 30.8 24.1 10.7 8.55 (..66 6.75 0.239 0.258 0.139 0.176
53.615 2.77 l0.3Q
3A? 6,620 0.34 5.45 2.50 15.933 9.43 2.91 2.18 2.9911 0.0223 0.049311 0.0316 0.04’
1.ake od
1 17,148 0.89 54.7 29.2Q 54.1 24.4Q 27.2 19.3 19.4 0.411 0.463 0.148 I. ,.186
3 22.667 1 • 17 56.4 33. IQ 74.8 27.0 33.1 26.3 29.2 0.444 0.741 0-228 0.5341
3 22.667 1 • 17 35.0 52.2 24.8 0.655 0.503
2 29.004 1.51 45.3 26.9Q 54.5 28.5 22.1 18.9 23.9 0.782 1.10 0.337 0.492
4 339.443 17.17 216. 61.3Q 170. 54.6 97.1 109. 81.8 9.11 3.90 19.3 12.8
139.443 17.17 216. 89.011 95.1 6.46 16.9
(continued)
-------
TA6LE Se (continued)
Burn
F Faet ’ r
ibiat
Input
Burn
Rate
(dry
Particulate
Phenol
PO II
Stack
l]uissions
TCO
Tunnel
k3 iastong
Nwsber
(Otuf
k j/
Dtlu—
Dilu—
Dilu—
hr)
hr)
1845
0 (47
tion
tion
tion
Bosca
2 10.466 0.54 27.3 19.0 18.5 8.27 12.2 10.9 6.21 1.74 0.0558 0.0827 0.0343
2 10.466 0.54 12.8Q
4 21,299 1.00 14.7 6.49 28.6 8.66Q 9.10 6.00 7.85 0.351 0.251 0.396 0.365
28.082 1.46 12.6 9.39 32.7 10.7 9.85 5.70 5.90 0.199 0.222 0.508 0.791
1’ 28,082 1.46 7.10 8.76
S 64.001 3.10 22.3 11.5 68.3 37.2 20.4 10.7 21.6 (.02 1.50 1.90 4.55
3AP 11.447 0.60 (7.2 6.97 56.4 20.2(4 19.7 7.50 14.0 0.402 0.549 0.476 1.06
3 ’A P 11.447 0.60 16. 7Q 59.6Q 7.OSQ 20. 4Q 0.252Q 0.81 SQ 0.252Q 1 .47Q
Fisher
2 10.621 0.55 8.54 4.63 22.61. 10.7 4.17 2.55 . 251. 0.0547 0.08151. 0.0173 0.037L
2’ 10,621 0.55 14.9 2.70 0.0641 0.022C
4 18.501 0.95 15.9 10.8 23.9(4 13.1 6.24 4.72 4.03(4 0.128 0.0753(4 0.0415 0.024711
4 18.501 0.95 26.3 3.94 0.108 0.0320
3 30.279 1.58 19.7 16.1 48.0 21.3 13.4 5.55 6.73 0.184 0.240 0.0836 0.124
1 38.911 2.02 38.9 29.2 71.6 37.0 30.3 12.0 12.9 0.4(5 0.413 0.149 0.146
‘ Indica tCs results of duplicate runs
Q — Data presented but quality is ‘mcertatn di to low filter temperatures
X — Secorel filter torn
I I — Sample rate in cess of 110 percent im kinetic
1. — Sample rate below 90 percent i okinetic
A — Test burn was not consistant with specified stove operutln procedures
— F calculated using CI3IS data because of bed orsat
-------
TAIi1,I. lb. SUNMAKY 1* WOObS I’OVF M I ‘, ‘,!I N T 1.T K1 ’ .IIITS LAI CIlIA i-W MI, I , — C W ’ i’i t I I KkM ’ ,
Burn
V Vartur
l&,at
input
hint
P4t6
(dry)
Stack
hyticuLOfle
I’articu hatu
I)ilutton
Tunnel
1S ,Ili LOflu
‘I to
Ohlu—
I ’henol
t)tlu—
I’OM
tutu—
Nu nber
tutu/
(k .j/
tion
tion
tiun
hi-)
hi P
$1145
087
1145_
0)47
h.,T . Stack Tunnel
Stack Tunnel
Stack ‘lunnel
Theboreze
IA l7.2U . 0.90 113.9 8.90 12.61. 6.841. 4.73 6.81 4.581. 0.114 0.05631 0.108 11.09061.
21). 23. 218 1.22 2.0 6.19 10.9 4.01 2.76 3.73 2.82 0.0913 0.0244 0.0067 0.0)08
26* 23.218 1.22 0.818
Blaze King
4 11.607 0.60 38.5 13.3 17.8 13.IQ 7.50 21.2 7.04 0.1C.9 0.151 0.0332 0.0790
11.607 0.60 6.61
I 20.098 1.09 6.54 4.2111 10.0 3.111 2.44 2.44 3.11 0.0530 0.0523 0.0325 0.0)50
1 * 20.898 1.09 1.82 2.15
5 ? 11.964 1.64 6.3’) I.97Q11 8.17 5.66Q 3.03 2.13 2.17 0.0952 0.0607 0.0534 0.0446
31.964 1.64 5.5’, 9.31 1.95 2.22 0.0914 0.0682 0.0522 0.1)182
2 53.615 2.77 7. 2 3.90 8.72 3.87 3.09 2.41 2.44 0.0861 0.09)1 0.050) 0.On3S
2 ’ 53.615 2.77 3.69 ( 1
3k 6.620 0.34 16.0 7.34 46.611 27.7 8.56 6.41 8.7911 0.0656 0.1 .3 ’ I 0.0429 0.11911
Lake t O .i
1 - 17,148 0.1)9 61.4 32.8 (1 60.7 21.4(1 30.6 21.6 21.8 0.461 0.518 0.167 0.20’)
3 22.667 1.17 40.2 27. SQ 63.’) 23.1 28.11 22.5 2t.0 0.379 0.633 0. 195 (1.4)7
3’ 22.667 1.17 30.0 45.5 21.2 0.560 0.430
2 29.004 1.51 30.0 17.8(1 36.1 18.8 14.6 12.5 $5.9 0.518 0.730 0.223 0. )26
4 139,441 7.17 30.2 hl, 55i 1 23.1 7.bI 13.5 15.2 11.4 1 • .17 0.545 2.61 1.70
4’ $31.44) 7.U 30.2 I 2.4 ?, I 3. .1 U.’JI 1 I .1. it
Ii tnt I nite’))
-------
TAIILt 31. (continued)
Hoaca
2
2
4
I.
5
31.
3A
35.2 34.3 15.3
23.7
7.86 26.4
6.43 22.4 7.30
4.86
3.70 22.0 I 2.0
11.6 94.0 33.711
99. 3Q
6.43
6.75
6.00
6.59
32.8
0.639 1.41
0.793 1.76
0.420tj 2.45 )2
a Indicatea reaulta of duplicate runo
Q — L ta peaented but quality Ia uncertain ‘ue to low filter teml .eraturea
X — Second filter torn
14 — Sample rate in excuas of *10% taokinetic
I . — Zampte rate below 90% teokinetlc
A — Teat burn wee not conutotent with ap.cl find atuva operatiraj procudurea
Burn
F Factor
Iwot
Input
£k .rn
Rate
(dry)
Particulate
— —
¶.. .nnel l) ,iaaiona
‘ IV O
Dilu—
Phenol
Dilu—
10 , 4
I l ilu—
Stack FS,tauiona
Dilution
Number
(Htu/
(k9/
t.i n
tion
Ito ..
hr)
hr)
MJ45_ ON?
14145 —
0747
A 1M Stack Tunnel
Stack Tunnel
Stack
Tunnel
10, 466
10,406
2* • 299
28.082
28 • 082
o4,00l
11.44?
11,447
10,621
10,621
18, 501
18,501
30. 279
30. 911
0.54
0.54
1.08
1.46
I • 46
3.10
0.60
0.60
u.55
0.55
0.95
0.95
1.58
2.02
22.5 20.1 11.5 0.322 0.103
50.5
13.6
8.61
7.18
20. 7
27.9)2
15.5
16.0
12.5
19.2
Ytaher
2
4
4.
3
0.153 0.0635
5.56 7.21 0.325 0.232 0.366 0.357
3.91 4.04 0.137 0.l 2 0.348 0.542
3.45 6.97 0.330 0.483
12.5 23.3 0.669 0.913
1l.7Q 34.05) 0.420Q l.36çj
8.41 41.01.
27.1
11.4 25.21.
29.41
10.2 30.4
*4.4 35.4
19.5 7.50 4.64 5.91L
4.9’
13.7 6.57 4.96 4.2414
4.15
13.5 11.45 3.5* 4.26
111.3 15.0 5.96 6.38
0.0995 .148L
0.111
0.135 0.010211
0.114
0.1*1 0.152
0.205 0.204
0.0315 0.u .7Sl .
0.0400
0.0437 0.021 ,01’
0. 0 33 7
0.0529 0.07113
0.0136 0.0721
-------
TA6LE 3t.. SUMMARY OI WOO0S13JVI M81 .St0N TEST RIOOJLT’. CALCIILATI3I OISAD L1 TA £ - MICRIX.F IAMS I’LK J0ULI
Burn
Mumbo
Ti ,nbercze
1A
2A
2A
Blaze Kin j
4
4.
I.
5?
2
2
3A
Lake ood
3.
2
4
F I’actor I*irn
rtic llatn
TCO
Phenol — PO l l ——
Dilu— [ lila— Olin—
Meet Rat ’
Stack
Fellootons Dilution
Tunnel k2 iooionu
Input (dry)
(Rtu/ (kg/
tion l Ion lion
hr) hr)
MRS
OR? MRS
ON?
ASTM
Steck
Tunnel Sta . k Tunnel Stecii Tune)
11,285 0.90
0.932
0.440 0.624
0.33111.
(.234
0.336
0.2261. 0.00563 0.001781. 0.0053 0.0044 11
23,218 l.22
0.597
0.308 0.541
0.200
0.1)7
0.1116
0.141 0.00455 0.00122 O.003) 0.00153
23,’l8 1.22
0.041
11,607 0.60
1.8)
0.653 0.814
0.653Q
0.368
1.04
0.345 0.008211 0.00742 0.00261 0.003117
1 1,oO7 0.60
0.324
20,898 1.09
0.323
0.208X 0.497
0.188
O.l21
0.121
0.154 0.00262 U.C 59 0.00’ I 0.00173
20.8911 1.09
0.189
0.106
31,964 1.64
0.311
0.O956XQ 0.398
0.275Q
0.147
31,964 l.64
0.270
0.4 53
0.0953
0.108 0.00445 0.00332 0.00254 0.00234
53,61S 2.77
0.369
0.191 0.427
0.150
0.151
0.118
0.119 0.00422 0.00456 0.0024b 0.00311
53.615 2.77
O.lUlQ
6,620 0.34
0.781
0.358 2.211)
1.35
0.417
0.312
0.4211 )1 0.00319 0.007U.II 0.00452 0.005 ’9 1 1
Il, 148 0.89
3.02
I .i .2l) 2.99
1 .3 5 Q
1.51
1.07
1.07 0.0221 0.0255 0.00921 0.0103
22.661 1.17
2.3o
I.34Q 3.13
1.13
1.39
1.10
1.42 0.0186 0.0 10 0.0095b 0.0224
22,667 1.17
1.47 2.2)
1.04 0 u27 ’ 0.0210
29,004 1.51
1.48
0.IJHOQ 1.18
0.9)1
0.721
0.6)9
0,183 0.0256 0.031. 0.0110 0.0161
139,443 1.17
1.47
0.417Q 1.16
0.371
0.661
0.741
0.556 0. G19 0.0266 0.131 0.0868
139.443 1.11
1.47
O.oO SII
0.b47
0.0439 (1.115
(coot. I e 1)
-------
TABI.E 3c (conttnuu.t)
• Indicates results of duplicate nina
Q — Data preaentrd but quality is uncertain due to low fitter temp ratures
X — Secor fitter tarn
H — Sample rate in excess of 1 10% isokinetic
1. — Sample rate below 90% isokinetic
A — Test burn was not coue latent with a eci I ied a tow. operatinçj proce0ures
Particulato TC O Phenol P09
Dilution Tunnel Emissions
burn
Number
flosCa
2
I’) 2
— 4
I ’
S
36
3 ’A
F ’I sher
2
2’
4
4’
3
F factor
Burn
heat
Input
R ,te
Idry )
Stack
Emissions
L)ilu—
Dhlu—
Dilu—
(Btu/
(kij/
tion
tion
thon
hr)
hr)
8145
0141
14145
(1 (47
ASTE.
Stack
Tunnel
Stack Tunnel
Stack lonnol
10.466
0.54
2.47
1.72
1.68
0.748
1.10
0.984
0.561
0.0158 0.00506
0.00749 0.00311
10.466
0.54
l.l6Q
21.299
1.08
0.654
0.318
1.27
O. 386 Q
0.405
0.267
0.350
0.0156 0.0112
0.0116 0.0172
28.082
1.46
0.425
0.317
1.10
0.360
0.333
0.19)
0.199
0.00674 0.00750
0.0171 0.J2b7
28.082
1.46
0.240
0.296
64.001
3.10
0.330
0.170
1.01
0.552
0.303
0.158
0.320
0.0152 0.0222
0.0293 0.Uh74
11,447
0.60
1.43
0.518
4.67
I .6811
1.63
0.622
1.16
0.03)3 0.0455
0.0394 0.01171
11.447
0.60
l. 39 Q
4. 9 4Q
0. 5 84Q
I.69Q
0. 0 20’JQ 0.0675Q
0.0201(0 0.122 ._I
10.621
0.55
0.762
0.413
2.021.
0.957
0.312
0.228
0.290L
0.00489 0.007281.
0.00155 0.0033(1.
10.621
0.55
1.33
0.241
0.00512
0.O OI Ob
18.501
(1.95
0.816
0.556
1.2311
0.669
0.320
0.242
0.20111
0.00650 0.0038611
0.01 ,213 0.0(11 2 ( 11
18.501
0.95
1.45
0.202
0.00553
0.00164
30,279
1.58
0.617
0.503
1.50
0.669
0.4(8
0.174
0.211
0.00577 0.00751
0.00262 0.00)88
38.911
2.02
0.947
0.711
1.74
0.902
0.738
0.293
0.314
0.0101 0.0101
0.00362 0.00355
-------
o P .nlsokifletic sampling conducted for a47 and MMS sample runs in the
dilution tunnel were designated with an “H” when sample rates were
over 110 percent of isokinetiC and an “L” when sampling rates were
below 90 percent of isokinetiC.
o Two torn second filters ifl CM7 sample trains (located between the
third and fourth impingerS) were identified with an “x.
o TwO test burns were not adequately conducted under the Oregofl wood—
stove test procedure stove operating guidelines. The doors were
opened during sampling and the coals and woodpieCeS stirred during
t .o rxmber-eZ test burns.
o several cM7 and MM5 sample runs were conducted with the heated filter
box temperature below the specified lover limit of 223°F. In all of
those cases except BD-0M7-5 the average t nperabireS were between 200
and 223°F.
These conditions are thscussed in greater detail in Section 5.
Total gravimetriC enu.ssioflS for each of the sampling methods are com-
prised of the combined individual analyses of the following fractions:
o MM5 — front half Med 2 rinse drydown residue
filter catch
X .D extraction
9 i volatile organics (extracted from back—halt ater) by CC
plus water drydown residue
s i volati orcjanics (in rinse solvent) by CC plus solvent
drydown residue condensate extraction semi—volatile organics
by CC plus drydown residue
o 0M7 — front half solvent rinse drydown residue
front filter catch
back half extraction drydown residue
back half weter drydown residue
back half rinse drydown residue
back filter catch
o AS 4 — front half and between—filter solvent rinse drydown residue
front filter catch
back filter catch
The summarY tables also include results of organic sampling and analyses
conducted on MM5 samples for total omatographable organics (TCO), phenol
and POM. rC0 .,eze determined on the combined back half fractions of the MM5
samples. POA and phenol were analyzed in combined aliquots from all front
and back half fractions of the MM5 samples.
Table 4 presents arithmetic averages on a per stove basis for the
results presented in Tables 3a through 3c. iwerageS were calculated for all
22
-------
‘TAULE 4. AVEKAGr l24I ,5lON RATL.S PER STOVE ARITH4ETIC 6VER LE
Burn
bar Stove
4 Blaze King
4 LakewOOd
4 BoaCa
4 Fiohar
4 Blazo King
4 LakawOOd
4 BoaCa
4 Fiohor
CRAMS PER KIWGRAM OF DRY WOOD DIIRNFD
Particulate -- TOO
Stack ioaiOna Dilution Tunnel 5n1egiOflO
Dilu-
tion
14i45 0 )47 - )4)45 0)47 P . 5TH Stack Tunnul Stack
CRAMS PER HOUR
*4.1 (5) 7.65(3) 14.9 (5) 6.27(3)
117. (5) 35.0 (1) P1.3 (5) 36.7 (3)
*9.2 (4) 11.1 (5) 37.0 (4) 18.7 (3)
20.8 (4) 15.2 (4) 40.7 (4) 20.5 (4)
Dilu-
tion
Tunnel Stack
4.60(5)
44.9 (4)
*2.1 (5)
13.5 (4)
4 Blaze King
4 LaltOwOOd
4 BoeCa
4 Fishor
Ut Lu-
tton
Tunnel
3,54(5) 4.31(5)
53.7 (5) 35.8 (5)
8.33(4) 10.4 (4)
6.2 (4) 6.57(4)
( .I)AMS PFR HOUR
0.141(5)
3.44 (5)
0.828(4)
0.195(4)
0.1 23(5)
1.37 (5)
0.507(4)
0.206(4)
12.9 (5) 8.15(3) 10.8 (5) 4.76(3)
40.0 (5) 30.0 (1) 46.0 (5) *6.5 (3)
20.0 (5) 11.6 (5) 26.5 (4) *4.6 (4)
16.0 (4) 11.10(4) 30.7 (4) 16.3 4)
AVERAGE MICROGRAMS PER JOULE
0.07 59(5)
7.38 (5)
0.742 (4)
0.0729(4)
3.94(4)
21.9 (4)
13.9 (6)
9.4 (4)
6.15(5)
*7.0 (5)
8.26(4)
4.77(4)
3.40(5)
*9.1 (5)
7.45(4)
4.93(4)
0. 082 7
2.90 (5)
1.44 (4)
0.08)0(4)
0.0541(5)
0.640 (5)
0.608 (4)
0.0560(4)
0.0989(5) 0.0851(5) 0,0483(5)
0.706 (5) 0.597 (5) 1.1.) (5)
0.279 (4) 0.243 (4) 0.377 (4)
0.139 (4) 0.147 (4) 0.0504(4)
MICROGRAMS P R JOULE
0.633(5) 0.344(3) 0.530(5) 0.234 (3) 0. 179(5) 0.344(4) 0.182(4) 0.004P9(4) 0.00447(4) 0.00231(4) 0.00276(4)
1.96 (5) 1.47 ( I) 2.27 (4) 0.81) (3) 1.07 (4) 0.835(5) 0.934(5) 0.0345 (5) 0.0293 (5) 0.0549 (5) 0.03*3 (5)
0.970(4) 0.565(5) 1.27 (4) 0. 54 (3) 0.487(5) 0.401(4) 0.358(4) 0.0133 (4) 0.0*15 (4) 0.0*79 (4) 0.0286 (4)
0.786(4) 0.546(4) 1.51 (4) 0.799 (4) 0.462(4) 0.234*4) 0.242(4) 0.00684(4) 0.0072 (4) 0.00248(4) 0.0216 (4)
-------
pollutants medsured by each method. None of the data qualified with Q, X, U,
L or A in Tables 3a through 3c were used in calculating the arithmetic aver-
age. The number of samples used to determine each average is in parentheses
in the table.
24
-------
SECTION 3
TEST FACILITY AND STOVE DESCRIPTIONS
The test facility was designed to conform as closely as practicable to
both the Oregon and ASTM facility requirements (Figure 3). The test stove
was mounted on a platform scale. The accuracy of the scale used for most of
these test ’ was 0.2 pounds. The 8—inch stove pipe was equipped with a water
seal which isolated the sampling location fr the stove and scale. This
minimized interference with the weight measurements by sampling activities
in the stack.
The AS1}1 dilution hoed was located above the stove pipe exit. The draft
was measured on several occasions at the top of the stack to insure that less
than 0.005 inches of water draft was induced on the stack with no fire in the
stove. The dilution tunnel was constructed of r— nch stove pipe. Sampling
was conducted in a downcaner upstream of the blower. The blower was operated
at a constant rate during the test program.
APPLICANCE TESTFD AND TEST NDITIONS
Five stoves were tested under this test program. The units are identi-
fied below:
o Timber-eze Model 477 Catalytic Heator
o Blaze King Catalyst Stove - King Model KEJ—1101
o Lakewood Cottager (non-catalytic)
o Bosca — Model 500 (high efficiency noncatalyst stove)
o Fisher Tech IV Fireplace Insert (catalytic)
Test charges for the Timber—eze were approximately 8.2 kg, Blaze King 13.7
kg, Lakewood 7.9 kg, Bosca 4.2 kg, and Fisher 7.6 kg. Fuel noisture was
checked prior to each test. Air dried Douglas fir having a moisture content
between 19 and 25% on a dry basis was used for all tests.
Stove operation followed the Oregon procedures with a few exceptions.
Those exceptions are presented in Section 5 under “Other Considerat1ons .
SELECTION OF SAMPLING L XATION
The test locations were selected according to the cr47 and AS 4 criteria.
The stove pipe test location was 8 feet above the scale platform (Figure 3).
The MM5 and the C147 trains sampling in the stack re located at the same
25
-------
S:m
SCALE
SO 2
—ANALYZER
STOVE PI’
0.20 DIA
..,- ——
INJECTION
—
0.81
0M7—
L’ 1
2.44
STATIC
PRESSURE
r
SCALE
— 2 CO. CO 2
WET/DRY BULB TEMP
—MM S
1
WATER SEAL
0M7-
ASTM
D 1LUTION
FAN
Figure 1. SchematIc of stove exhaust and dilution system with sample locations.
SCALE
0.15
I
1 14
3.05
PITOT— J
1.
STOVE
41
—FLOW—
26
-------
elevation to avoid any possible discrepancies in results becduse of loss of
particulate on the stack wall or other reasons. No traverse was attem} ced
due to the small duct diameter aixi multiple sample probes (0M7 and PIMS) being
located at the same elevation.
The wet bulb ar.d dry bulb thermometers were located approximately 10
inches downstream of the sampling probes. The continuous analyzer sample
probe was at the same elevation as the thermocouples.
The SO 2 tracer gas injection was 36 inches downstream of the CP47 and MMS
sampling points as specified in the method. The stack height allowed the SO 2
gas sample to be extracted at a point 46 inches downstream of the injection
point which does not meet the 8 duct diameters criteria of the method.
The test location in the dilution tunnel was selected to meet STh cri-
teria except that the sampling trains were 8 duct diameters downstream of
the pitot tube. Three sample probes were at the same elevation (ASm, 0M7,
and P4145) in the thnnel. The ASIM method specifies that the pitot tube be lo-
cated approximately 2 tunnel diameters (16 inches) downstream of the pitot
tt’be. The various draf EPA procedures (LA, 2C, SC) .t ich deal with sampling
small ducts dictate 8 duct diameters of undisturbed flow upstream of both the
pitot and probe locations. EPA criteria were followed for selecting the di-
lution tunnel test points. The sample probes were inserted at 900 angles to
each other. Nozzles were inserted 2 inches into the stack. The thermocouple
was inserted 6 inches downstream of the sample probe.
27
-------
SECTION 4
SAMPLING PR(XEDURES
Due to the nature of the test program and the source category to be
tested, some compromises were required between the specifics of the various
test procedures. The basic procedures followed were:
o Modified Method 5 prepared for EPA, 01W, EPA Project Officer Raymond
Merrill.
o Oregon D partment of Environmental Quality Standard Method for Mea-
suring the Emissions and Efficiencies of Woodstoves, June 8, 1984.
o AS 4 Standard Test Method for Heating Performance and Emissions of
Residential Wood-Fired Closed C nbustion Chamber Heating Appliances,
Revised November 1984.
Those methods are referred to in this document as MM5, 0M7, and ASIM, re—
spectively. Certain other reference and draft procedures were used in con-
junction with those basic n thods. The specific ancillary methods used
varied with the test location.
o Stack M i-IS — EPA Met’ od 3 — molecular weight
EPA Method 4 — moisture
EPA Method 5C — particulate matter in small ducts
o Stack 0M7 - 0M4 — moisture
cti5 — particulate matter emissions
0H7 — condensibla matter emissions
EPA Method 10 — co, co 2
EPA Method 20 — oxygen
AST4 D3286.77 — higher heating value
or ASTM D201 5.77 — higher heating value
0M4 — alternate, jet bulb/dry bulb
o Dilution Tunnel MI-lb — EPA-2C — velocity in small ducts
EPA - 3 - molecular weight
EPA—4 — moisture
EPA-5C - particulate matter in small ducts
o Dilution Tunnel 0M7 — 0M4 - moisture
C. l5 — particulate emissions
0M7 — condensible matter emissions
28
-------
o Miution Tunnel AST4 — as specified in the method
Figures 2, 3, and 4 illustrate the MM5, 0M7 , and ASTM sample
trains, respectively.
The anissions sampling on the Timber-eze stove began within 5 minutes
after the stove was loaded with the fuel charge. This was a deviation from
the Oregon procedure and was corrected for all subsequent burns. All other
test burns were conducted with the emissions sampling starting one minute
or less before the stove test charge was placed in the firebox.
SAMPLE RECOVERY
ihe solvents specified for CM7 sample recovery are acetone (front half)
and acetone and water (back half). For the ASTh method acetone and methanol
are specified. Those recoveries were made according to the procedures. In
addition, a methylene chloride rinse of the 0M7 front and back halves was
made and recovered separately.
The MMS train was recovered using methylene chloride. Methanol was used
on runs 11—2, H—3, H—4, and H—5 after the Med 2 ri. se because the Med 2 did not
seem to clean the trains satisfactorily. Those fractions were recovered sepa-
rately.
Following sample recovery, all samples were sealed and safely stored
until transportcJ to the laboratory for analysis. Samples were delivered to
the lab within 1 week of their collection.
Sample containers were borosili ’ ate glass bottles with Teflon lined
caps. Prior to the test program all sai’ple containers and sample train glass-
ware were washed with soap and water rinced iith disi..i.iled water and a final
rinse with methylene chloride.
ilters for the test program were tare weighed by ES. Tare weights were
given to Radian for determination of final weights.
EPA- MM 5
Two front half fractions and four back half fractions were collected
for the MM5 sample trains. The fractions were:
o rront half
— inethylene chloride probe and front half
rinse
— filter
o Back half
— condensate, including rinse of all glassware between the filter
and the XAD-2 Lrodule and the Med 2 rinse of the condensate impinger
bottle
29
-------
Stack Wall
Filter Holder
Figure 2. SchematIc of Modified Method S Sample Train
Jacketed Condenser
Water Jacketed
XAD Sorbent Module
Dry Gas Meter
Vacuum Line
3fl
-------
H3ated Filter Holder
Thermocouple
lmpin er Train
,—Unheated Filter Holder
Thermocouple
Check Valve
impinger
ium Gauge
Orifice or
Dry Gas
Main
By-Pass
Air-Tight
Valve
Valve
Valve
Figure 3. Schematic of 0M7 Sampling Train
-------
Thermomatars
Orifice
Dry Gas Meter
Thermocouple
impinger Train
Check Valve
Impinger
Ice Bath
Sacoi d Filter
First Filter
C.)
Main Valve
By-Pass Valve
Air-Tight Pump
Figure £6. Schematic of ASTM Sample Train
-------
- XAD-2 nodule
- back half water frc n the second and third impir ers including
a rinse
- .ilica qel
0M7
The 47 sample reccvery resulted in the following fractions (0M7, 8.0):
o Frc,nt half
— acetone rinse of probe and front half
— filter
— Med 2 rinse of probe and front half (in addition to C -l7 procedure)
o Back half
- water catch and impinger water wash
— acetone rinse f back half
- Med 2 rinse of back ha f (in addjtjcn to CM7 procedure)
— filter
— silica gel
ASTh
Sample fractions fran each ASIM train included (AS1M, 10.11, 11.12):
o Front half:
— acetone/methanol rinse of probe and front half
— first filter
— second filter
— Med 2 rinse of front half (in addition to ASIM procedure)
o Back half
— none
Although the ASThi method does not specify, the glass surfaces exposed to the
sample between the two filters were rinsed with acetone then methanol and
both rinses added to the front half acetone/methanol rinse bottle.
SAMPLE WENTZFICATION AND LOG
Each sample fraction was given an identifying code number which desig-
nated the sa?ple location, stove number, method type, sample fraction and run
number. Application of the code simplified tracking samples throughout the
collection, handling, enalysis and reporting processes.
The sample numbering syste.n had 5 canponents ihich were applied in the
following order:
o Stove ID - Sample Location — Method — Fraction — Run Number
33
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The specific codes are listed below:
o Stove ID: B — Blaze King
T - T mber-eze
G — Generic (Lahe ,ood)
H — High Efficiency (Bosca)
F — Fisher
o Sample locations: S - Stack
0 — Dilution Tunnel
o Method: Mr45 - Modified Method S
c 1 47 - Oregon Method 7
AST - ASt 4
o Fraction: PR — Probe and Front Half Rinse
F — Filter
F2 — Second Filter (ASTh and cr47)
C — Condensate and Glassware Rinse
BH — Rack Half Water Rinse (with Med 2 impinger
rinse for pluS)
BR — Back Half Acetone Rinse (0147 only)
Xl — XAD Module
PM — Probe and Front Half MeC12 Rinse (0H7 only)
RH — Rack Half Med 2 Rinse (DM7 only)
o Run Numbers: 1 — First Burn Rate
2 - Second Birn Rate
3 — Third Burn Rate
4 — Fourth Burn Rate
5 — Fifth Burn Rate
B - Blank
SAMPLE ANALYSES
All sample analyses ware conducted by the Radian Corporation under a
stparate contract. A copy of the laboratory report is provide i in Appendix
D. Analytical Methodo are described there.
CO/C0 2 , OXYGEN AMALYZERS
Carbon mono a de (CO) and carbon dioa de (do 2 ) ware monitored using an
Anarad Model AR—412 infrared analyzer. The analyzer has a 0 to 5 percent CO
range and a 0 to 20 percent CO 2 range. The 02 analyzer was an MSA stack gas
analyzer which uses a ft.El cell detector. That instrument has a r?nge of 0 to
20.9 percent. The gas sample was extracted using a stainless steel probe
bent into the gas flow. A glass fiber filter was used to i enove particulate
material. A gas sample conditioner including two impingers with water in an
ice bath, was upstrean of the filter.
The instruments ware calibrated with gases certified to be within ± 2
percent of the specified cylinder value. The gases ware in concentrations to
34
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generate analyzer responses of approximately 20—30%, 45-55% and 70—80% of
full scale. Daily pre— and post—test calibrations were conducted by direct
introduction of the zero and span gases to the analyzers. The analyzer
operation was acceptable if the analyzer response was ± 2% of the cylinder
value. After the pretest multipoint calibration, a single span gas was
introduced t the sample probe acc3rdlng to EPA Method 20, Figure 20—1. This
latter calibration theck demonstrated performance of the systes. If any
calibration checks did not comply with the + 2 percent criteria, corrections
to the systun were made and the calibrations repeated. Span d ecks were made
using a single gas every 2 to 3 hours during each test and after eacn test.
An evaluation of the C )iS, 2’ 02, and C X) data is presented in Section 5.
Dr,.ft problems did occur during mst test burns. Corrections were made for
each span or zero drift but the accuracy of the CP2IS data remains suspect
based upon a f l factor test as described in A eference Method 3, 40 CFR
60 Appendix A, July 1985. This is discussed further in Section 5.
SO 2 TRACER GAS
SO 2 was injected into the stack 32 inthes (4 duct diameters) downstream
of the c147 sample point. The SO 2 was injected at a rate that resulted in a
downstream concentration of less than 5000 ppo (0M7 6.3). A critical orifice
was used to control the injection rate. The orifice was calibrated using bub-
ble meters prior to the test prcgram.
The procedure followed for the tracer gas analyzer calibration was sim-
ilar to that followed for CO. CO 2 and 02. Span gases were on hand to cal-
ibrate the instrument to 1000 ppm. Calibration gases were certified by the
manufacturer to be ± 2 percent of the cylinder value.
Problems with the tracer gas system were identified after the first test
but it was not witil an audit was conducted that the problem was determined
to be apparent reactions of the SO 2 in the system. The SO 2 was used as a guide
for proportional sampling but the accuracy of the actual values collected are
S us pact.
TD4PERATURES
Type K thermocouples were used to n nitor flue gas tenperatures in both
the stack and the dilution tunnel. The ASTM procedure specifies measuring
the stack gas t nperature 8 feet above the top of the scale using an array of
5 thermocouples (ASTM 6.12). That array would interfere with the 0147 and 14145
sample syst ns and was not used for this test program.
Flue gas temperatures were measured at the center of the stack approx-
imately 1 duct diameter downstream of the sampling location. The dilution
tunnel temperature was measured at a similar point in that duct.
Thermocouples were calibrated as per PA Method 2.
35
-------
MOISTURE MEA JREMENTS
The Oregon test Metbud specifies use of an alternate moisture determining
technique, which is based on wet bulb/dry bulb tenperatures. Wet bulb and dry
bulb ter peratures were monitored and recorded every 5 minutes at a location 1
ct dian eter downstream of the stack sample collection pint (OH 3.3, 3.8).
Moisture catch in the 0P47 and MM5 sample trains were also used to deter-
mine stack gas moisture according to EPA Method 4 and Oregon Metbod 4. A
comparison of stack gas moisture measurements resulting from the three methods
is presented in Section 5.
The dilution tunnel noisture content was measured using the Gt7 and M145
samples.
FUEL HEAT Q)NTENT I ND DENSITf
The heat content of the fuel was determined for each piece of wood burned
during the test program. Sawdust was collected when the wood was cut to build
fuel cribs. The shavings were placed in plastic bags and labeled to identify
the specific cribs constructed from that particular board. Blocks of wood
were also collected at the same time and sealed in plastic bags.
The dust and wood blocks were submitted t a subcontract laboratory for
heat content and density analysis respectively. The heat contents for each
crib were used in the Fc calculations discussed in Section 2. The laboratory
repnrt is provided in Appendix D.
36
-------
SECTION 5
Q LITY A3SURANCE/QUALITI CONTROL
QAPP VALIDATION CRITERIA
This test program required an AEERL Level 1 Quality Assurance Program
Plan (QP .PP), which was prepared by Engineering—Science and approved by EPA.
The Radian Corporation prepared a separate plan for the laboratory analysis
portion of the program. In addition to adhering as closely as possible to
the test procedure described in Section 4, validation criteria were identified
for the sampling program. Validation criteria for sampling train and wood—
stove operation are presented in Tables 5 and 6 respectively.
A systems audit was conducted by Research Trianc4e Institute (Rn) at the
woodstove test facility during the sampling program. Following submittal of
the first draft report RTI conducted a data quality audit. The draft audit
report gave this sampling program and the resulting data an acceptable rating
with qualifications.
The qualification was lifted fran the audit rating after ES responded to
the draft audit report indicating that the validation criteria specified in
the QAPP would be canpared to the actual sampling and stove operating condi-
tions. The comparison must be made with an understanding of the relative
importance of the cr3 terj.a in order to make valid qualifications of the data.
A brief discussion of the criteria is included at the end of Appendix E in
response to canments made in the auditors report.
Tables 7a through 7e present a summary of sampling conditions for each
of the samples collected. The parameters considered ncst critical were
included in the table and used to characterize the data from each sample run.
No isokinetic sampling was considered to make the results of the corresponding
sample unacceptable (u). Average filter box temperatures outside the 248°F
plus or minus 25°F were considered sufficient deviation fran the cJ47 and MMS
procedures to require qualification of those data. A total mass catch of
less than 30 milligrams was considered significant enough to require qualifying
the data if the sample volume was below the criteria volume. If either the
mass catch was in excess of 30 milligrams or the sample volume was larger
than the criteria volume then the results were considered acceptable.
Several of the sample train validation criteria were satisfactory for
all samples collected. These included post test leak rate, condenser outlet
temperature, and orsat leak rate.
37
-------
TABLE 5. VALIE TION CRITERIA - SAMPLING TRAINS
MM5 Stack — Leak Rate < 0.001 cfrr’
Filter Temperature 248°F + 25°F
Condenser Outlet Temperature <70°F
Sample Volume >30 cf (meter cond.)
Sample Rate = approximately 1—3 liters/minute
Orsat Leak Rate = 0
0M7 Stack — Leak Rate < 0.005 cfm
Filter Temperature 250°F + 25°F
Sample Volume >30 cr (meter cond.)
Sample Rate = approximately 0.1 cfm
MM S
Dilution
Tunnel — Leak Rate < 0.02 cfm
Filter Temperature 248°F ÷ 25°F
Condenser Outlet Temperature <70°F
Sample Volume >120 cf
Orsat Leak Rate = 0
0M7
Dilution
Tunnel — Leak Rate < 0.02 cfm
Filter Temperature 250°F ÷ 25°F
Sample Volume >120 cf
ASfl4
Dilution
Tunnel - Leak Rate < 0.02 cfm
Filter Temperature 70—90°F
Sample Rate 0.1 — 1.5 cfm
Continuous
Analyzers — zero Drift 5% of scale
Span Drift 2% of scale
38
-------
TABLE 6. VALIDATIC 4 CRITERIA - WOODSTOVE OPERATION
Fuel Moisture
Fuel Crib Photo
Fuel Load — Blaze King
— Timbereze
Fuel Density
Ambient Temperature in Roan
Surface Temperature
Low &irn
Low Mid Birn
High Mid Birn
High Burn
Dilution Tunnel Temperature
Dilution Tunnel Flow
16—20% (19—25% dry)
27—3 3 Lx unds
17—20.8 pounds
28.7—37/4 pounds/cubic foot
65—90°F
X+ 125°F
<10,000 Btu/hr
10,000—15,000 Btu/hr
15,000—25,000 Btu/hr
Maximum heat output
<125°F
1 00-4 00 pounds/pound wood
39
-------
TABLE 7a. A SUMMARY OF TIMBER-EZE SAMPLING CONDITIONS
Sample
Number
Sample
Duration
(Minutes)
Sample
Volume
(ACF)
Filter
Tempera
(°F)
Box
ture
Percent
Isokinetics
Total Mass
Collected
(mg)
Evaluation
Rat ng
TS—MM5—l
TS—MMS—2
297.5
307.5
14.039
24.722
250
248
213
179
A
A
TD—MM —1
TD—MMS —2
400
320
391 .642
160.96
230
249
79
104
135
70
U
A
TS— 47—l
TS—0M7—2
297.0
207.5
13.189
46.086
257
256
170
92
A
A
TD—0M7—1
TD—0M7—2
377
320
370.893
155.562
245
249
83
100
70
26
U
A
TD—AST—1
TD—AST—2
TD—AST—2
366
320
317
244.725
195.828
194.230
85
8C
4
32
22
7
A
A
A
(a) A — Acceptable
Q — Qualified
U — Unacceptable
40
-------
TABLE 7b. SUMMARY OF BLAZE KING SAMPLING CONDITIONS
Sample
Sample
Duration
Sample
Volume
Filter Box
Temperature
Percent
Total Mass
Collected
Evaluation(a)
Number
(Minutes)
(ACF)
(°F)
Isokinetics
BS—MMS—1 640 60.998 249 448 A
BS—MM5—2 238 17.529 251 197 A
BS—MM5—3 221 16.052 257 130 A
BS—M145—4 1,185 103.320 263 2,263 A
BS—MMS—5 415 24.481 245 210 A
BS—MM5—5Q 415 18.524 256 159 A
BD—M145—1 640 306.077 248 105 120 A
BD—MM5—2 238 119.033 233 103 94 A
BD—MM5—3 222 112.356 248 111 57 U
BD—MM5—4 1,185 523.820 244 97 185 A
BD—MMS—5 350 160.874 249 105 74 A
BD—MM5—Q 350 154.754 235 102 81 A
BS—0M7—1 640 44.226 263 232 A
BS—0M7—1Q 640 84.428 242 363 A
BS—0M7—2 238 22.734 249 133 A
BS—0M7—2Q 238 14.430 250 87 A
BS—0M7—3 221 15.740 262 57 A
BS—0t17—4 1,185 103.150 254 779 A
BS—0M7—5 415 24.528 220 68 Q
BD—0M7—1 640 277.088 248 96 41 A
BD—0M7—2 232 193.758 247 100 41 A
BD—0M7—3 222 117.213 245 102 35 A
BD—0M7—4 1,185 594.102 203 109 156 Q
BD—0M7—4Q 1,185 543.834 248 108 76 A
BD—0M7—5 345 171 .306 178 105 54 Q
BD—AST—1 639 397.303 39 A
BD—AST—1Q 639 389.082 33 A
BD—AST—2 236 144.810 42 A
BD—AST—3 230 134.056 13 A
BD—AST-4 1,185 562.049 84 A
BD—AST—5 411 174.566 30
(a) A — Acceptable
Q — Qualified
U — Unacceptable
41
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TABLE 7c. SUMMARY OF LAKEWOOD SAMPLING CONDITIOflS
Sample
Sample
Duration
Sample
Volume
Filter Box
Temperature
Percent
Total Mass
Collected
Evaluation ’
Number
(Minutes)
(ACF)
(°F)
Isokinetics
(mg)
Rating
BS—MM5—1 640 60.998 249 448 A
GS—MM5—1 410 22.269 245 2,478 A
GS—MM5—2 260 15.852 250 888 A
GS—MN5• 3 340 18.379 245 1,455 A
GS—MM5—4 60 3.099 253 262 A
GS—M145--4Q 60 2.452 244 227 A
GD—14M5—1 410 188.778 249 98 325 A
GD—M145—2 260 123.279 252 98 223 A
GD—MM5—3 340 161 .956 249 96 401 A
GD—MM5—3Q 340 169.199 247 102 297 A
GD—MMS—4 58 27.258 250 109 159 A
GS—0M7—1 415 22.933 222 1,351 Q
GS-0M7—2 260 15.884 221 526 Q
GC—0M7—3 340 18.007 223 809 Q
GS—0M7—Q3 340 13.322 252 726 A
CS—0M7—4 60 2.989 223 71 Q
GD—a47—1 405 212.500 211 108 171 Q
GD—0M7—2 260 118.459 256 102 113 A
GD—0M7—3 340 155.727 233 102 140 A
GD—0M7—4 57 25.696 250 99 49 A
GD-0M7—Q4 57 29.034 251 119 90 U
GD—AST—1 408 204.141 70 186 A
GD—AST—2 251 132.681 68 100 A
GD—AST—3 235 172.604 70 193 A
GD—AST—4 53 17.531 72 60 A
(a) A — Acceptable
Q — Qualified
U Unacceptable
42
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TABLE 7d. SUMMARY C ’? BOSCA SAMPLING CONDITIONS
Sample
Sample
Duration
Sample
Volume
Filter Box
Temperature
Percent
Total Mass
Collected
Evaluation(a)
Number
(Minutes)
(AcF)
(°F)
Isokinetics
HS—MP45—1 145 6.499 247 109 A
HS—MM5—2 360 20.83 246 1,061 A
HS—MMS—3 90 7.72 253 419 A
HS—MM5—3Q 90 1.92 219 111 Q
HS—MM5—4 200 15.345 249 395 A
HS—MM5—5 65 5.853 251 243 A
IID-41M5—1 150 67.77 242 100 74 A
HD—MM5—2 360 162.70 243 94 101 A
FID—MM5—3 90 39.934 244 91 75 A
HD—MMS—3Q 80 36.345 246 101 73 A
HD—MM5-4 200 86.952 240 100 85 A
HD—MN5—5 65 28.861 245 98 64 A
HS— 47—1 145 3.298 246 45 A
HS—0M7—1Q 145 13.30 254 126 A
HS—0M7—2 360 21.57 250 765 A
HS—0M7—3 90 8.207 259 179 A
HS—0M7—4 200 15.889 239 234 A
HS—0M7—5 65 6.065 246 128 A
HD—ct47—1 150 69.299 257 104 25 A
HD—0M7—2 360 187.88 250 109 52 A
IID—0M7—2Q 360 166.12 217 95 71 Q
IID—0M7—3 91 47.05 244 115 32 U
HD-0M7—4 200 89.765 202 96 27 Q
tiD—0M7—5 65 30.193 242 102 37 A
HD—ASTM—1 149 74.673 70 25 A
HD—ASThI—1Q 150 78.224 75 24 A
HD—ASN—2 359 182.49 70 75 A
HD—ASTh—3 89 45.895 76 31 A
HD—ASIM—4 200 100.067 71 32 A
HD—ASTh— 66 33.010 72 23 A
(a) A — Acceptable
Q — Qualified
U — Unacceptable
43
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TABLE 7e. SUMMARY OF FISHER SAMPLING CONDITIONS
Sample
Number
Sanpie
Duration
(Minutes)
Sample
Volume
(ACF)
Filter Box
Temperature
(°F)
Percent
sokinetics
Total
Collec
(mg)
Mass
ted
EvaluatiOn
Ratln9 —
FS—MMS—1
190
14.013
250
429
A
FS-MMS—2
FS—MM5—3
620
220
26.035
17.076
‘251
257
483
334
A
A
FS—MMS—4
375
14.954
251
310
A
FD-MMS—1
190
86.131
249
100
205
A
FD—MMS—2
610
256.632
237
36
190
U
FD—MM5—2Q
620
289.182
236
19
142
A
FD-MM5—3
220
100.739
248
105
159
A
FD—MM5—4
375
190.196
246
154
U
FD—MMS—4Q
375
165.545
250
2
159
A
FS— 47—1
190
14.530
246
333
A
FS—0M7—2
620
31.293
243
313
A
FS—0M7—3
220
17.573
248
277
A
FS—0M7—4
375
15.814
249
223
A
FD—0M7—1
190
87.884
255
97
109
A
FD—0M7—2
610
283.173
249
106
100
A
FD—OM7—3
220
103.014
250
103
73
A
FD—0M7—4
375
168.749
246
1Ô1
74
A
FD—AS IM—1
190
99.940
—
103
A
FD—ASTh—2
609
322.743
—
44
A
FD—ASTh—3
220
118.053
—
52
A
FD—ASTM—4
305
190.709
—
40
A
(a) A — Acceptable
Q — Qualified
U - Unacceptable
44
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COntinUoUs enission monitor zero and spar, checks were done at approxi—
rnately 2 to 3 hour intervals during each test burn. At least one of the
analyzers monitoring 02, or co had one or more periods of instrument
drift in excess of 2 percent during all test burns except High Efficiency
(BOSCA) —4 and F .sher —3. Zero and span drift corrections were made assunu.ng
a gradual linear drift between the two span checks showing the drift. These
data were entered into the woodstove program (Appendix C).
Several test burns that do not reliably reflect actual anisslons accord-
ing to Oregon stove operating procedures must be qualified. Those are listed
below with an explanation for the reason for their qualification
o Timber—eze —1 Stove doors were opened during the test burn.
o Timber—eze —2 Stove doors were opened during the test burn.
o Blaze King -3 Fire died after less than 3 pounds of wood were
burned. Sampling stopped after 220 minutes.
o High Efficiency (BOScA) —3 Regional power failure ended sampling
after 70 minutes.
These data were not entirely deleted fran the results because they can be con-
sidered useful for test method evaluation.
The dilution tunnel flow criteria were neglected during this test program.
Most flows were greatly in excess of the 100:1 to 400:1 range of air to wood
rat1c specified in the 1 S ’Di procedure. This criteria was not used to qualify
or invalidate any samples.
BLANKS
Two types of blanks were Collected in the field and subn’itted to the
laboratory for analysis. Solvent blanks were collected for each solvent and
sample media (filters, XAD—2 modules) used for sample collection and recovery.
Those blanks were for use by the lab in making blank corrections.
Train blanks were collected to demonstrate the efficiency of sample recov-
ery and possible contamination of samples in the stove test facility environment.
Those blanks were obtained by charging a sample train as if it were a actual
sample. The sample train was then leak checked, sealed, allowed to sit over-
night and leak checked again. The train blank wes then recovered following
sample recovery procedures for the appropriate train types (MMS, 0M7 or ASTM).
Tables 8 and 9 present the results of analyses of train blanks. Many of the
train blank results are higher than normal acceptable levels. The MM5 water
fraction was consistenfly I’igh. Since the water used for charging the MMS
trains was from the same container as the water used to charge the 0M7 trains
that source of contamination can be eliminated as pDssibility. As mentioned
in Section 4, the methylane chloride did not appear to be a satisfactory sol-
vent for the materia collected during sampling. Ineffect)ve sample recovery
using MeC1 2 may have left residue in the sample trains which would then
result in high train blanks.
45
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TABLE 6. RE JLTS OF TRAIN BLANK SAMPLE ANALYSES
GRAVEMETRIC RESIDUE, MILLIGRAMS
Front
Rinse
Filter
Back
Rinse
Back Back
Water Filter
TS—0M7
1.0
0.9
0.1
4.3 0.3
TD—G 7
0.7
0.5
1.1
1.7 2.2
BS—0M7
1.9
0.7
2.5
17.2 0.9
BD—ct47
2.6
1.3
2.4
9.8 0.3
GS—0M7
1.4
1.3
0.2
0.3 0.2
GD—Q47
1.1
0.0
0.9
1.5 1.0
HS—0M7
1.1
0.9
0.1
4.3 0.3
HD—047
2.3
0.0
0.7
0.4 0.3
Front
Rinse
Filter
Extract
XAD, TC0
Condensate, Rinse
Back Water
TS—MM5
1.2
14.2
0.0
27
TD-MM5
0.5
0.3
0.0
16
BS-MM5
NA
NA
NA
NA
BD-MM5
NA
NA
NA
NA
GS—MM5
1.2
2.2
0.0
31
GD-MM5
0.3
0.0
0.0
23
HS—Mit5
1.3
0.8
0.0
140
HD-MMS
0.9
0.0
0.0
16
FS-B
NA
NA
NA
NA
FS-B
NA
NA
0.3
119
Front
Rinse
Filter
it 1
Filter
it 2
TD-ASN
NA
NA
NA
BD-AS l
NA
NA
NA
GD—P.STM
1.3
0.1
0.2
HD—AS l
1.3
0.6
0.4
NA = no analysis or no sample collected
46
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TBLE 9. RESULTS OF TRAIN BLANK ANALYSES Ft R ORGANICS
AND MODIFIED METHOD 5 SAMPLES
TCO
(mg)
Phenol
(mlcroqrams)
POM
(mi crograms)
TS-BM7
TD-B
0.0
0.0
9.4
0.0
0.0
0.0
BS-B
BD-B
NA
NA
NA
NA
NA
NA
GS-B
GD—B
0.0
0.0
26.2
7.2
0.0
0.0
MS-B
MD—B
0.0
0.0
26.4
13.1
0.0
0.0
FS—B
FS—B
0.3
NA
0.0
NA
1U09.5
NA
NA = no analysis or no sample collected
47
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DUPLICATE SAMPLES
Duplicate samples were collected to demonstrate the precision of the
sampling methods at each location. Table 10 presents the results of the
duplicate samples in units of grams per hour except for the samples collected
in the stack during test burn 1 1-3. That burn was not completed and no stack
flow rate could be calculated using the Oregon woodatove program. Those
results were calculated using the F calculations.
DATA PR( ESSING QC/QA
One hundred eighteen individual sample runs were conducted during this
program. The large amount of resulting data underwent multiple checks to
minimize the number of errors. All data reduction was done twice by two
different data handlers. The two sets of data were then compared. Any in-
consistencies resulted in a third check of that particular portion of the
data to resulve the discrepancy.
The example calculations were prepared by the field team leader and given
to the data processor for input to the computer. Calculations were then done
using a calculator by an engineer not familiar with the project, and the re—
suits compared to the computer output.
EVALUATION (P C1 4S DATA - 02, 2’ A D CO
During the sampling program, the CE7IS data were reduced as five minute
averages. As an added QA check, the fuel factor (F 0 ) was calculated accord-
ing to EPA Reference Method 3 (40 CFR 60, Appendix A, July 1985). Reference
Method 3 specifies a range for F 0 of 1.)00 to 1.120 for wood. Table 11
presents the average CRIS a 2 02, and O values for each test horn and the
corresponding orsat analyses. F 0 was cai.ulated for both CE 4 and Orsat data
for each horn. The F 0 for ITost of the C 4S data were outside the acceptable
range specified in the Reference Method. Some of the project participants
are concerned with the accuracy of these data since they are the basis for
calculating stack gas flow rates and heat outputs which are used to calculate
emission rates.
This F 0 meas e had not been identified as one of the validation criteria
in the QAPP. The CD4S criteria were a 5 percent zero drift and a 2 percent
span drift. The effect of these drift allowances on the F 0 can be signifi-
cant. Eor example for the test burn for B—4 the CO 2 was 5.5 percent and the
02 was 14.6 percent. The worst case span drift situations allowable under the
validation criteria would be for a negative 1.9 percent 02 span drift and a
negative 1.9 percent CO 2 span drift. In this case the average 02 and CO 2
values would have been 14.2 percent and 5.1 percent respectively, resulting
in an F 0 of 1.298 rather than the calculated 1.079. Thus, it appears that
the F 0 calculation is highly sensitive to instrument drift.
The F 0 is an oxygen balance evaluation. The instrument used for this
test program uses a zirconium oxide detector which operates at a t nperathre
of 7600 C. Oxygen is consumed by combustibles in the sample gas at that
48
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TAULE 10. SJMKARY 1*’ DUPLICATE SAI4PLES CORk S/H0t1k )
Stack
Particulata Eaie iono
KisS 0147
Dilution
Participate
KHS 0147
Tt nnol
L inuionu Dilution
ASTpI Stack Tunnel
Dilution
Stack Tunnel
Dilution
Stack Tunn 1
T—2 3.37
(0.99))
7.99Q
(3.96)
a—i 4.5j 2.66
(4.16) (7.34)
8-5 10.5 13.4 4.47 3.56 0.156 0.0996 0.0877 0.073
(9.11) ( 15.3) (3.21) (3.65) (0.150) (0.1 12) (0.0856) (0.079)
10.8
(30.3)
0—3 32.1 74.8 29.2 0.741 0.534
(35.0) (53.2) (24.8) (0.655) (0.503)
0—4 2 1C 54.6 109 9.11 19.3
(216) (89.0)11 (95.1) (6.46) (16.9)
11-2 8.27
((2.11)
11-1 9.39 9.85
(7.10) (8.76)
11—3 17.2 56.4 7.50 14.0 0.402 0.549 0.476 1.06
(16.7) (59.6)Q (7.05)Q (20.4)Q (0.252)Q (0.815) (0.252)Q (1.47)Q
22.61. 3.25 0.08 (51. 0.0371L
(14.9) (:.70) (0.064;) (0.0220)
23.911 4.0311 0.075311 0.0247H
(28.3) (3.94) (0.108) (0.0)20)
(a) All data fr Table 3a SectiOn 2.
-------
TABLE II • COMPARISON OF AVERAGE CI2IS 02, MiD CO WITH Q) CURRENT ONSAT RESULTS (b
(a Calculated according to 40 CFR
60,
Appendix A, Reference Method 3.
F 0 —
20.9 —(% 0 —
0.5%
CO)
(% CO + % 0)
(b CDIS data were corrected for zero and span drifts.
NA Insufficient data were collected to ccinplete these calculations.
7I
0
Heat
Stack Output
(Btu/Hour)
%
Woodstove CHO
C buation
Efficiency
CEM 1%) CEM (a
O CO F, CO ,
Orsat (P.)
Orsat
(a
CO 2
0
CO
F ,.
‘ F—i
T—2
10,772
15.006
81.9
130.2
4.5
2.3
16.7
18.0
0.1 0.942
0.1 1.126
3.0
2.3
17.9
18.6
0.0
0.0
1.000
1.000
8—1
8—2
8—3
8—4
B—S
1 1.185
32.170
NA
7.220
22.281
74.5
79.9
NA
103.4
96.1
4.1
6.3
NA
3.2
5.5
16.9
15.3
NA
17.3
14.6
0.1 0.836
0.2 0.912
NA NA
0.3 1.177
0.1 1.079
4.4
5.8
1.0
2.0
1.0
16.4
14.8
19.6
18.6
19.6
0.0
0.0
0.0
0.0
0.0
1.023
1 .052
1.300
1.150
1.300
C—I
G—2
0—3
0—4
9.812
16.587
13.277
96.474
71.6
74.3
75.7
93.8
5.6
6.7
5.9
11.0
14.5
14.1
14.4
7.3
1.8 0.980
1.4 0.941
1.5 0.980
1.8 1.141
5.4
6.0
5.1
8.9
13.9
14.0
14.3
11.2
1.6
0.9
1.4
0.0
1.114
1.065
1.123
1.090
H—i
11—2
H-3
11—4
H—S
19.511
7.912
NA
13.999
40.591
106.7
115.9
NA
87.3
87.7
4.7
3.8
NA
5.5
7.7
14.5
15.2
NA
14.3
11.8
0.8 1.232
1.0 1 .310
NA NA
1.1 1.091
1.0 1.047
6.8
3.0
6.4
6.7
10.1
12.8
15.3
.2.7
13.6
8.2
0.7
1.0
1.0
0.9
1.7
1.127
1.525
1.176
1.020
1.148
F—i
F—2
F—3
F—4
29.223
8.752
23,570
14.273
100.3
110.9
96.5
105.9
5.9
4.5
5.9
4.7
14.1
15.4
14.4
15.2
0.3 1.128
0.2 1.201
0.2 1.082
0.3 1.176
7.0
5.4
6.1
4.1
13.6
14.6
13.4
14.2
0.1
0.1
0.1
0.4
1.043
1.155
1.218
1.533
-------
temperature which results in low oxygen readings. Preliminary testing done
showed C 1 through C 7 hydrocarbons on catalyst and non—catalyst equipped
woodstoves averaging 1.0 iralligram per liter of flue gas. This could esu1t
in a 1:1 decrease in detected 02 for each carbon combusted in the detector
furnace. Errors in tne CT 4 measurements uld result in errors in the stack
gas flows calculated using the CHO balance which would result in a proportional
and direct error in the calc ated MM5 and cti7 stack emission rates. Since the
dilution tunnel flows were measured using a standard pitot tube, errors in
the CEMS would not cause an error in those emission rates. It can be assumed
that combustible levels in emissions from non—catalyst stoves would be signifi-
cantly higher than t} se from catalyst-equipped stoves.
EVALUATION OF SO 2 TRACER GAS MEASUREMENTS
The Oregon DEQ Standard Method for Measuring the E nissions and Efficiencies
of Woodstoves (June 8, 1984) recommends the use of sulfur dioxi 1 e as a tracer
gas for determining the stack gas flow rate and for maintaining proportional
sampling in the stack. Many problems were experienced with span checks of the
• racer gas analyzer. It was finally determined that the SO 2 was apparently
reacting with other components of the flue gas including material condensed in
the SO 2 sample Line or material collected on the filter. Span d ecks were
erratic. The SO 2 concentrations have an effect on the output of the Oregon CR0
balance calculation. Increasing the SC 2 concentration entered into the calcula-
tion increases the stove heat output, the percent oxygen and overall combustion
efficiency while decreasing the wood combustion efficiency, stack gas flow rate,
and percent CO 2 . Inaccurate SO 2 measurements precluded reliable proportional-
sampling in the stack.
RESULTS CALCULPIT US 1MG ORSAT DP.TA AND F FAC I’OR
Table 12 compares the stack flow and heat output data used for calculating
results presented in Section 2 tables la, lb and lc with the stack flow and
heat input values calculated using F factor calculations as presented in 40
CFR 60.45. The dry fuel composition was assumed to be 51 percent carbon, 7.3
percent hydrogen, and 41 percent oxygen as described in the Oregon procedure.
PC wag calculated using the heat content determined for each crib used during
the test program (Appetidix D). The resulting heat input and stack flows were
used to calculate the results summarized in tables 3a, 3b and 3c of Section 2.
MOISWRE DETERMINATIONS IN THE STACK
Moisture determinations were made in conjunction with MM5 and CM7 using
procedures following EPA Reference Method 4 (40 CFR 60, Appendix A). In ad-
dition, wet bulb/dry bulb measurements were made as required by the Oregon
procedure. Table 1 3 summarizes the moistures for each run.
OTHER CONSIDERATIONS
Following is a list of events which occurred during the sampling program
and which should be considered when evaluating the results.
51
-------
TAI3LE 1 2 • H EAT INP UT N D GAS FLGIJS CP.LCULATfD USING Fc FACTORS N D
WOOD HEAT CONTENT CCMPARED TO HEAT OUTPUT AND GAS FL S
CALCULATED bY OREX OH STOVE (DMBUSTION PROGRN4
— Oregon Program Fr. Factor
Run Heat Output Stack Flow Heat Input Stack Flow
Stove Number (Btu/hr) ( SM 3 /hr) (l3tu/rir) (SM 3 /hr )
T imbereZe 1 10,772 16.4 17,285 29.7
2 15,006 71.8 23,218 52.0
Blaze K.tng 1 11,185 19.8 20,898 24.5
32.170 35.3 53,615 47.2
3 a a 6,620 17.4
4 7,220 20.1 11,607 26.7
5 22,281 27.9 31,964 29 • 9 b
LakewoCd 1 9,312 10.3 17,148 12.6
2 16,587 15.2 29,004 20.9
3 13,277 13.8 22,667 18.1
4 96,474 58.2 139,443 68.5
Bosca 1 19,511 32.2 28,082 19.6
2 7,972 15.4 10,466 13.8
a a 11,447 8.3
4 13,999 16.3 21,299 14.2
5 40,5 1 32.0 64,001 28.5
sher 1 29,223 34.7 38,911 33.3
2 8,752 13.9 10,621 12.0
3 23,570 26.4 30,279 26.5
4 14,273 21.6 18,500 19.8
a Test burn was not complete. No Oregon Program run.
b Calculated using average CO 2 and CO fr an CE 4S because Orsat had apparently
leaked during the test.
C F sm 3 C 20.0 (% C in wood )
a v
where: GCV = higher heating value of wood
Fc stack flow = F X J X — 100%
hour %C 0 2 +%CO
52
-------
“ABLE 1 3. COMPARISON OF t IS JRE DETERMINATIONS IN TdE STACK GAS AS
ME1 SUR D BY MMS, WET BULB/DRY BULB, AND
Burn
Number
Stove
Heat Output
(Btu/hour)
Burn Rate
(dry) g/hr)
Stack
Moisture
(%)
M!45
WB/DB
0M7
1
Timber—eze
10,772
0.9
6.6
5.0
7.1
2
T mber—eze
15,006
1.22
3.8
4.0
8.9
4
Blaze King
7,220
0.60
6.8
2.0
8.1
1
Blaze King
11,185
1.06
8.1
7.1
7.2
(7.1)
5
Blaze King
22,281
1.64
6.2
(7.9)
7.0
9.5
2
Blaze King
32,170
2.77
6.8
4.0
10.8
(9.3)
3
Blaze King
NC
NC
3.9
NC
5.5
1
Lakewood
9,812
0.89
6.8
5.0
8.6
3
Lakewood
13,277
1.17
8.7
7.0
9.9
(11.8)
2
L.akewood
16,587
1.51
9.4
5.0
11.0
4
Lakewood
96,474
7.17
18.5
(14.0)
12.0
19.5
2
Bosca
7,972
0.54
6.5
5.0
9.1
4
Bosca
13,999
1.08
10.2
3.0
9.3
1
Bosca
19,511
1.51
9.6
6.0
18.6
(8.7)
5
Bosca
40,591
3.10
13.1
3.0
14.5
3
Bosca
NC
NC
13.5
(27.6)
NC
9.6
2
Fisher
8,752
0.55
5.7
9.6
6.8
4
Fisher
14,273
0.95
4.5
6.8
7.9
3
Fisher
23,570
1.58
5.5
7.9
7.9
1
Fisher
29,223
2.02
5.5
7.9
9.6
a Numbers in parentheses indicate results of duplicate runs.
NC — Not calculated because of insufficient data fros partial test burn.
53
-------
1. TS-MM5—1: ‘rube caine loose frcm meter box coarse adjust valve. Sam-
pling ended immediately. Tube repaired and train leak
checked.
2. TD—MM5—1: Silica gel spent.
3. TD— 7—1 Lost cower 3 times for a total of 16 minutes. Test ‘Ut
short due to a fourth power loss.
4. ‘ rD—ASP—i Data recorded at 5 minute intervals rather than on a
percent of fuel burned basis.
5. TD—AST—2: Data recorded at 5 minute intervals rather than on a
percent of fuel burned basis.
6. BS—(*17—1: Second filter tore during run, probably during pretest
leak check.
7. ss—c 47-2Q: Second filter installed backwards in sample train.
8. 5ø—0M7—2: Pump failed .tfter 134 minutes. A second meter box was
used for the duration of the test. six minutes of sample
time were lost. Meter gamma was corrected by proportion-
ing the bio calibrations based on percent of the respec-
tive gas volumes.
9. BD-M145-5
BD—a17 -5
BD—AST-5
BD—Mt45—SQ: ct.17 filter heater failed. All dilution tunnel samplers
shutdown for 70 minutes while repairs ware made. Sam-
pling restarted simultaneously. Stack samplers continued
operat:ng during the shutdown.
10. BD—MM5—5Q: Operator failed to record meter temperature. Meter tem-
perature estimated to be 950 for the test.
11. BD—0M7—5: Operator failed to record meter temperature for first 13
readings of 35 reading test. Average recorded readings
used for calculations.
12. GD—0M7—1: Lost power after 5 minutes of sampling. Power restored
and testing resumed after 5 minutes downtime.
13. HS—MM5-1: After testing was completed the elbow between the con-
denser and XAD module was broken as the operator was
removing the sample train from the stack. No post—test
leak check was conducted.
14. H—3: Lost power to samplers and stove scale. Test ended after
70 minutes of burn.
1 5. T—i: Stove charged, doors were closed then testing started.
Sixty minutes into the test, power was lost to the scale
54
-------
and the scale automatically rezeroed itself. Readings
continued adding the final weight, prior to the power
lcss, to the scale reading. Stove doors were opened for
S minutes after 6 minutes of burn. Stove doors were
opened zor 6 mirutes after 90 minutes of burn. Stove
doors were opened for 1 minute after 400 minutes of burn.
16. T-2: Stove doors open for first 10 minutes of test. Stove
doors opened for 5 minutes after 65 minutes of burn.
Stove docrs opened for 5 minutes after 125 minutes of
burn. Stove doors opened for 3 minutes after 161 min-
utes of burn. Stove doors opened for 1 minute after
305 minutes of burn.
17. B—3: Fire died after 220 minutes. Less than 3 punds of wood
burned.
55
-------
APPENDIX
ANAL I’T ICAL RESULTS
A- I
-------
TABLE OF CONTENTS
Section Page
LISI OF FIGURES A-3
LIST OF TABLES A-4
1.0 INTRODUCTION A-5
2.0 PROJECT ORGANIZATION A-6
3.0 TECHNICAL APPROACH A-8
3.1 Sample Preparation A-8
3.2 Analysis A-12
3.3 Sample Preparation Protocol A—18
4.0 ANALYTICAL RESULTS A-33
5.0 QUALITY ASSURANCE AND QUALITY CONTROL A-53
A-2
-------
LIST OF FIGURES
Number Page
2—1 Radian project organization A—7
3-1 Oregon Method 7 sample fractions and ana yt1ca1 matrix A-lO
3-2 ASTM sample fractions and analytical matrix A-li
3—3 EPA N?15 sample fractions and analytical matrix A-13
5—1 TCO QC standard analysis A-55
5-2 Arti ct peak of GC/MS analysis A-64
5—3 GRAV aialysls modification A-66
5-4 ModifIcation to woodstove QAPP A-68
5-5 TCO calibration modification A-69
5—6 GRAY analysis corrections A—70
5—7 GC/MS unit correction A—fl
5—8 Systems audit checklist A—72
A-3
-------
LIST OF TABLES
Number Page
3—1 Sample Preparation A-9
3-2 Target Compounds for Quantitative Analysis by GC/MS A-14
3—3 GC,’MS Analytical Conditions A-16
3-4 Estimated Quantifiable Limit A—17
3-5 Sample RS-2 A— 19
3—6 Sample GS-2 A—25
4-1 Woodstove Gravijnetric Results A-34
4-2 Total Chromatographable Orcianics A-41
4-3 Amount of Target Compr.undc In Sample, ng A-44
5—1 Woodstoves Response Factor Database A—56
5-2 Linear Regression, Woodstove Database A-58
5-3 Daily Calibration Checks A—59
5-4 Analyses of Check Sample A-60
5-5 Daily Percent Recoveries (Check Sample) A-61
5-6 Woodstove Duplicates A-62
5-7 QA/QC Audit GC/MS Samples • A-81
5-8 QA/QC Audit TCO and GRAY A—83
A- 4
-------
1 .0 INTRODUCTION
In an effort to provide heating at a cost lower than the combustion
of fossil fuels, woodstoves are becoming increasingly popular. However,
when woodstoves are used, products of both complete and Incomplete
combustion of wood are emitted. Three sampling methods are currently
being use i to collect samples to characterize woodstove emissions:
1) the EPA Modified Method 5 (MM5) sampling traIn; 2) the Oregen
Method 7 (0M7) for sampling condensible emissions from stationary
sources apparatus; and 3) the draft ASTM dilution tunnel method. The
first two methods both collect a sample directly from the stdck, while
the third method requires dilution of the entire stack flow first, with
subsequent collection of a sample from these diluted gases. For the
Moditled Method 5 sampling train, the following components are analyzed;
probe wash, filters, XAD—2 resin, XAD—2 cartridge rinse, condensate,
condensate impinger rinse, impinger water, and impinger rinse. For
Oregon Method 7, the following com2onents are analyzed: probe wash,
filters, Impinger water, and impinger rinse. For the ASTM dilution
tunnel, filters and probe wash are analyzed. The analytical
determinations will be GRAV (gravimetric analysis), T (determination
of total chrornatographable organic content), and
qualitative/quantitative determination of polynuclear organic materials
(POMs) u5ing capillary GC/LIS techniques.
A-5
-------
2.0 F 3ECT 0f ANIZATI0N
The organization of the personnel Involved In the woodstoves
project Is depicted In Figure 2—1. The Radian Pr grain Manager w is Susan
Fernandes, and the Project Director was Edward Messer. The Project
Dlre.tor was responsible for coordinating all analytical tasks through
the direct Involvement of task leaders. The task leaders served
complementary roles in areas of project coordination overseeing sample
preparations gas chromatography (TOO) and gravimetric (GRAY) analysis,
GCIMS, quality control, and data analysis and validation. The three
task leaders were Joann Rice (GC/T O) Ed Messer (GRAY/Sample Prep) and
Joan Bursey (GC/MS). The task leaders also enacted quality assurance
procedures described in the Quality Assurarna Project Plan with
supervision by and coordination with both the Project Director and
Quality Assurance (Q.A) officer. The Quality Assurance Staff consisted
of Donna Holder (GA Officer) with assistance from Deborah Benson (QA
Assistant). The overall laboratory project was reviewed periodically by
Jim McGaughey and Denny Wa ner , who served as Senior Technical Advisors
for this project.
A-6
-------
Robert C. I ’cCrl1fls
U.S. EPA
Project Officer
_I_
Division Manager
Stan Dzlerlenga \\\ Donna HoHer
QA Officer
James Kamas
Susan Fernandes Deborah Benson
Program Managers QA Assistant
— Edtsard Messer
Project Director
Denny Wagone-
_ 4 aughe
Senior Technical Adv
_______________________ __________________________________________________ ______________________
Bursey, Task Leader
I Edward Messer, Task Leader I IJoann Rice. Task
L Samp’e Preparation I itO
_____________________________ __________________________ GC/MS
Tade Joan
L
Porch
Co e
.
IJ. Cassidy
FIgure 2-1. Radian project organization.
A-?
-------
3.0 TECHNICAL APPROACH
3.1 SAIbIR.E PREPARATION
The sample preparation was performed as shown in Table 3—1. The
samples were provided by Engineering Science and consisted of the
following:
1odifled Method 5 — MeC1, and MeC*1 probe washes, filter(s), XAD—2
resin, MeCl rinse of XAD-2 cartridge, conde sato, Med 2 rinse of
condensate 1mpinger, Impinger water, and Med 2 rinse of the
Impingers.
Oregon Method 7 — Probe wash (acetone), front filter(s), Impinger
water, impinger rinse (acetone), and back filter(s).
— Filters and probe rinses.
The field saznpl Ing program consi sted of four burns from each of
five stoves for a total of twenty burns; additional duplicate burns
Increased the total to a maxirntsn of twenty—four. Each burn produced one
M and 0147 taken in the stack, and one M , OM7, and ASTM taken in the
dilution tunnel for a total of five sample sets. For QA purposes
selected burns employed dual H1 6s In the stack which resulted In as many
as seven sample sets for analysis. The sample collection period was
during the months of September, Octobc. and November. EngIneering
Science recovered the samples at the test facility and delivered than,
with the proper docunentation, to Radian’s RTP laboratory.
The analysis of 0147 samples followed procedures published by the
state of Oregon as shown In Figurt 3-1. Analysis of ASTM samples
followed the procedures defined In the draft standard method and as
depicted in Figure 3—2. Analysis of the M 5 samples followed published
AEE .. Level 1 procedures with the following exceptions:
A-8
-------
Table 3 -1. SAMftE FREPARATION
IRA IN
COMPONENT OREGON I EThOD 7 EPA MODIFIED METhOD 5 ASTM
FRCOE DESICCATE AND DESICCATES WEIGH
WASHES WEIGH EXTRACT WITh FILTER DESICCATE AND WEIGH
DESICCATE, WEIGH
FRONT DESICCATE AND EXTRACT WITH FRC8E
FILTER WEIGH RESICIJE DESICCATE AND WEIGH
XAD—2
NA
SO) HLET
LEVEL 1
EXTRACTION
FROCEDJRE
BY
NA
CONDENSATE
LIQUID
PARTITION
mc i. rinse
NA
EXTRACTION BY LEVEL
1
NA
IMPINGERS EXTRACT BY EXTRACT WITH
mci. rinse OREGON FROCEDURE CONDENSATE NA
BACK DESICCATE AND
FILTER WEIGH NA NA
Sampling
Method
Analysis Matrix
for Stack Samp1e
ICC
GRAY
POM
Level 1
Soxhiet
Weighing Extraction
Level 1 Oregon
Partition Partition
Extraction Extraction
M1 6
0 147
25 50
50 ——
25 ——
- - 25
25
-—
25
25
25
——
M 16
OM7
ASTt4
Analysis Matrix for
Dilution Tunnel Samples
25
-—
--
25
25
--
25
-—
-—
25 50
25 ——
75 --
25 ——
—— 25
-- —-
Total 200 100 50 50 50 100 50
A-9
-------
Oregon Method 7 (OM-7)
lExtract Water with
Chi Groform/Ether
0M7 Method
PR-
PM-
F 1 —
BR-
Probe Rinse Acetone
Probe Rinse MeC1 2
Front Filter
Back Filter
Back—half Impin er Water
Back—half MeCL, Impinger Rinse
Back—half Acetbne Impinger Rinse
Figure 3—1. Oregon Method 7 sample fraction and analytical matrix.
A-JO
-------
ASTM Method
[ _ 3nt Half Probe Rinse/Filters j
ASTM €1HOD
Acetone/MeOH probe rinse
MeCl ., probe rinse
First Filter
Second Filter
Figure 3-2.
ASTM sample fractions and analytical matrix.
L9J
We
Mass
, \
Mass
PR-
PM -
F ! 1 —
F 2 —
A-li
-------
1. Probe washes were desiccated at roan tomperature and weighed.
2. The filters were desiccated at room temperature and weighed.
3. The dried probe residues and filters were combined and Soxhiet
extracted with methylene chloride.
4. The XAD—2 resin and XAD—2 cartridge rinse were placed in a
Soxhlet and extracted according to Level 1 procedures.
5. The condensate, condensate Impinger rinse, impinger water, and
impinger rinse were combined and extracted by the Level 1
partition procedure.
6. The extracts from steps 4 and 5 were combined and then
analyzed for TcO, GRAY organics, and selected polynuclear
organics as shown in Figure 3—3.
3.2 ANALYSIS
The Total Chronlatographable Organics (TCO) method was used to
provide senl—quantitatjve data on the sample extracts for organic
compounds with boiling points between 100°C and 300°C. This method is
based on separating the components of a mixture In a GC column and
measuring thd separated components with a Flame Ionization Dectec-tor
(FID). Quantitative calibration of the T 0 procedure for the purpose of
mass determination was accomplished by the use of mixtures of known
concentration of the normal hydrocarbons decane, dodecane, and
tetradecane. The peak area due .o the FID response of the sample
extract was summed over a T O retention time window (Cl to Cl i) and a
corresponding TcO value (mg/ri) was determined from the calibration
curve.
The gravimetric (GRAY) method was used for the quantitation of
organic compounds with boiling points of 300°C and greater. This method
is applicable to organic liquids, solid sample extracts, aqueous
extracts, and extracts from the Modified Method 5 sampling train sorbent
module. The analysis was performed after the sample material was
concentrated in order to have sufficient GRAY material to weigh in an
accurate manner.
Qualitative and quantitative analysis was performed by high
resolution capillary gas chromatography/mass spectrometry for the target
compound listed In Table 3—2. Quantitatjon standards were
d 10 —phenanthrene and d 12 —chrysene; these compounds were added to the
samples Immediately pr,or to analysis.
A-i 2
-------
e
[ DRY1
Iw i
LM4 J
PR M.C1 2 PROBE RINSE
F FILTER
X XAD 2 RESIN AND MeCI2 RINSE
C CONDENSATE AND M.CI2 flINSE
I4 BACk.HALF IMPINOER U 2 AND
M.C 1 2 RINSE
PU Me0 14 PROBE RINSE..ONLY FEW
SAMPLES COLlECTED
ADJUST VOL
IF NECESSARY.
REPEAT ORAV
MM6 FRACTIONS
Figure 3-3 EPA MMS sample fractions end analyticel matrix.
-------
Table 3—2. TARGET COMPOUNDS FOR QUANTITATIVE ANALYSIS BY GC/MS
acenaphthene 1—nltronaphthalene
anthracene 9—rnethylchol anthrene
benzo(a)anthracene carbazole
benzo(a)pyrene acridine
benzo ( b) fl uoranthene 9— phenanth rol
benzo(g,h.i)perylefle pyrenequl none
benzo(k) fl uoranthene
ch rysene
dlbenzo(a,h)anthraCefl e
fl uoranthene
fl rene
lndeno(1,2,3—cd)pyrefl e
naphtha ene
ph enanth rene
phenol
pyrene
A-t 4
-------
Samples were analyzed by a Finnigan 4500 GC/MS data system with a
DB—5 fused silica capillary column (30 rn, 0.32 mm ID, 1 u film
thickness). Chromato rapnic conditions were selected to optimize both
peak resolution and analysis time. The mass spectrometer was tuned to
meet criteria for decafluorotriphenyiphosphine (DFTPP). No samples were
analyzed until tune criteria were met. Target compounds were Identified
using characteristic ions and retention t1. es established by the
analysis of standards. The analysis was performed In the full scan
mode. Analytical conditions are shown in Table 3—3.
The GC/MS was calibrated by analyzing a solution containing
quantitation standards and target compounds. The target compounds were
put into the calibration solution at five concentration levels and each
sol ution was analyzed to estabi Ish a response factor database.
Quantitation of compounds was performed by the method of relative
response factors. An estimated quantifiable limit for the compounds of
interest is shown In Table 3—4. This is a quantifiable limit for the
GC/MS instrumentation only, not for the method. The numbers in the
table were obtained by looking at the system response for the
lowest—level calibration sample and determining the nirber of area units
obtained per nanogram of compound (assuming linearity of system response
from 5 to 1 ng). The number of area units per nanogram was then
multiplied by an appropriate factor (I.e., number of nanograms) to
obtain a value In the range of 1000—1500 area units, which is usually
readily reproducible upon repeated injection by the analytical system.
Note that the number is representative of the Quantifiable Limit, not
the Limit of Detection. A determination of the quantifiable limit for
the overall method would require a determination of compound recoveries
over the range of interest and Incorporation of this recovery factor
into the determination. Daily analysis included a demonstration of
DFTPP tune, daily calibration check, a quality control sample, and
analytical sampi es.
I i addition to the qualitative/quantitative analyses performed for
the list of target compounds, two of the sample extracts were
characterized In order to obtain an indication of the types of compounds
present in the samples. The qualitatlvta analysis was performed by a
semi—automated method. The sample peaks were selected by a computer
program developed by Lynn Wright (EPA, RTP). The peaks selected by
A-i 5
-------
Table 3—3. C C/MS ANALYTICAL CONDITIONS
Instrument: Finnigan MAT 5100
Column: 3Cm 00—5 wide bore (0.32mm), thIck
fIlm (1 u) fused silica capillary
GC Program: 450 (4 mm), 290°C at 10°/mm, hold
at 290°C
Emission Current: 0.3 mA
Electron Energy: 70 eV
Separator Oven Temperature: 290°C
Transfer Line Temperature: 290°C
Injector Temperature: 290°C
tAanlfold Temperature: 105°C
Injection Mode: Splltless 0.6 mm, then 10:1 split
Scan Cycle: 0.95 s scan, 0.05 hold
Column Head Pressure: e psi
A-iC
-------
Table 3—4. ESTIMATED QUANTIFIABLE LIMIT
Compound C tantif1able Limit ,
phenol 0.8
naphthalene 0.5
acenaphthylene 0.6
acenaphthene 0.9
fluorene 0.9
nitronaphtha lene 3.0
phenanthrene 0.7
anthracene 0.6
acridlne 0.7
carbazole 0.7
fluoranthene 0.8
phenanthrol 6.0
pyrene 0.7
benzo( a) anth racene 0.8
chrysene 0.9
benzo( b) fi uoranthene 1.0
benzo(k) fluoranthene 1.0
benzo(a)pyrene 1.2
methyicholanthrene 3.0
benzo(g,h,i)perylene 1.1
dlbenzo(a,h)anthracene 1.4
lndeno(1 ,2,3 —cd)pyrene 1.3
A-li
-------
Dr. Wright’s program were plotted in an automated mode and a library
search against the 40,000 compound NBS reference library was obtained.
The spectra and results of the library search were Inspected and manual
Interpretation was cuperlirposed upon the automated computerized
Interpretation. The data are reported as scan number, compound(s)
Identified at that elution time 1 and three parameters reported from the
NBS library search algorithm which aid In estimating the quality of the
identification. However, 1 a compound was not Identified In the
library search, the results are reported as (ma:iual). It Is a’so
Important to keep In mind that the Purity and Rflt criteria are
determined by the spectral Integrity. That Is, if components coelute,
these parameters can be quite low because the spectrum does not
represent a pure component. However, the Identification can still be
entirely valid. Results of the qualitative analysis are reported In
Tables 3—5 and 3—6.
3.3 SAMPLE PREPARATION PROTOCOL
Each of the three sampling methods (0M7, ASTM , and M S) have
specific analytical schemes which are outlined as flow diagrams in
Figures 3—1 through 3—3.
Flow diagram (Figure 3—1) shows the analytical matrix of the Oregon
Method 7 (0M7). As Illustrated this method matrix Is comprised oc five
major components: 1) front—half probe rinses (PR and PM); 2) front
filter (F 1 ); 3) back—half Impinger water/Me d 2 rinses (BH and BM);
4) back—half lrnpinger acetone rinse (BR); arid 5) back filter (F 2 ). The
front—half probe rinses (PR and PM) were comb1 ,ed and evaporated to
dryness In a tared beaker, then put In the desiccator for 24 hours. The
samples were weighed and checked every 2 hours until constant weight was
establ Ishod.
The back—half impinger rinse (BR) was treated in the same manner as
the PR and PM rinses — desiccated, dried, and weighed until constant.
The back—half impinger solutions (BH and AM) were combined and put Into
separatory funnels (the bottles rinsed with distilled H 2 0 and this
added) and vigorously shaken with 25 rnL of chloroform (CHC1 3 ) for one
minute. Fractions were allowed to separate, ani tho lower chloroform
A- 18
-------
Table 3—5. SAMP1E BS—2
compound Piirit E.tt £U.
186 cyclohexene 854 987 863
199 trichioroethylene 954 990 960
232 3—penten—2—one 965 991 965
240 C 9 H 20 734 876 762
242 2—niethylfuran 785 930 809
253 2,3—butanedjone 709 951 739
258 unknown
270 methyl butenoate 262 879 286
275 methyl 2—oxopropanoate 939 972 946
288 toluene 952 993 952
297 cyclopentanone 865 977 879
330 furfural 729 856 832
359 C 5 H 6 0 (manual)
363 tetrachioroethylene 845 874 966
367 C 5 H 4 0 2 867 894 964
374 C 6 H 10 0 (manual)
381 C 6 H 12 0 2 621 845 654
409 C 7 H 16 0 (manual)
430 cyclohexenone 710 874 756
435 methyl 2—oxobutanoate 203 931 203
441 ethylbenzene 789 990 789
455 xylene 280 910 302
phenylacetylene (manual)
472 methylcyclohexenone 406 878 439
480 styrene 694 934 699
488 1—(2—furanyl)ethanone 782 986 790
xylene (manual)
494 2,5—hexanedione 903 932 950
499 2 3—dlhydro—2i5—d1methylfuran 777 883 804
511 pyranone 326 950 373
continued
A-% 9
-------
Table 3—5. conttnued
Compoun 1 Purity Eli Lilt
520 5,5—dlmtheyl—2(5H)furanone 737 530 871
535 tetramethylcyclohexadlene 762 974 762
551 1—(acetyloxy)—2—butanone 769 808 816
555 C 6 I l 10 0 3 906 978 919
560 rnethylfurancarboxaldehyde 590 922 624
benzaldehyde (manual)
582 C 10 H 16 528 934 545
benzonitrlle (manual)
587 C 3 —alkylbenzene (manual)
C 8 H 12 0 (manual)
595 phenol 909 988 919
616 C 10 H 15 709 994 709
622 benzofuran 803 948 840
627 C 10 H 15 798 993 798
635 unknown
642 C 6 H 8 0 2 862 998 862
655 cyclohexenylethanone 604 615 674
658 C 6 H 14 716 901 716
662 C 3 —alkylbenzene (manual)
Indane (manual)
666 C 4 —alkylbenzene 613 982 613
hydroxybenzaldehyde 411 969 422
678 C 10 11 16 841 971 841
684 cresol 578 976 587
indene (manual)
693 acetophenone 637 941 658
C 8 H 12 0 (manual)
698 rnethylbenzaldehyde 856 993 861
708 cresol 697 987 897
713 methylbenzaldehyde (manual)
continued
A-20
-------
Table 3—5. continued
Purfty EJ.t RLit
723 trimethy lcyclopenteflOfle 784 942 792
738 dimethy lstyrene 432 930 454
hydroxymethylpyranofle 419 920 438
745 dlmethyiphenol 461 957 472
751 methylbenzofuran 695 961 718
756 phenyipropenal 547 959 567
769 C 8 H 12 0 (manual)
776 ethyiphenol 416 909 433
C 4 —alkylbenzene 413 959 420
methylhydroxybenzaldehyde (manual)
783 C 10 H 16 797 978 807
789 d lmethyiphenol 886 995 886
798 propyiphenol 500 944 511
804 benzolc acId 412 937 432
methylindan (manual)
809 dlrnethyiphenol (manual)
methylindan (manual)
814 pentanolc acid (7) 287 905 299
C 4 —alkylbenzene (manual)
619 dimethyiphonOl 367 938 387
826 methylacetophenone 756 935 806
836 ethylbenzenedtol 781. 927 781
639 naphtha lene 880 974 895
845 C H. 403 912 430
C 10 H 18 0 531 942 561
654 phenylpropenal 752 973 752
869 dimethylbenzofuran 616 951 633
879 C 3 —alkylphenol 670 985 670
895 ethylbenzoic acid 747 843 770
continued
A-21
-------
Table 3—5. continued
Compnurni Purity f.it Rf it
907 methylbenzenedicarboxaldehyde 561 937 596
hexanoic acid C’?) 229 894 236
915 indanone 734 980 746
921 ci lhydroxyacetophenone 671 994 67].
930 hydroxybenzaldehyde 782 925 844
948 rnethylnaphthalene 737 959 765
963 methylnaphthalene 791 981 794
972 dimethoxyphenol 348 868 401
990 methoxypropenyiphenol 744 997 744
995 C 6 —alkylbenzene (manual)
decanoic acid 488 976 491
1002 C 13 H 10 (manual)
1013 hydroxymethoxybenzaldehyde 885 993 888
1019 b lphenyl 611 995 811
1029 C 9 H 8 0 (manual)
C 7 —alkylbenzene (manual)
1036 d lmethylbenzofuranone 410 951 420
dimethyl naphthal ene (manual)
1042 carboxyllc acid (manual)
1050 acenaphthone 367 882 400
benzopyranone 378 932 404
1060 dimethyltetral ln 332 953 339
C 13 H 10 (manual)
1063 d lmtheylnaphthalene 459 885 513
1077 ethyltetralln 302 744 381
dtmethylnaphthalene 305 736 386
1084 acenaphthy lene 595 945 618
C 10 H 11 C0 2 H (manual)
1089 hydroxymethoxyacetophenone 804 980 817
1093 C 6 —alkylbenzene 615 974 620
continued
A-2 2
-------
Table 3—5. cofltinued
Corn pound
1108 naphthofuran 128 93 134
1115 naphthalenecarLo’ aldehyde 483 968 483
1123 hydroxyrrethoxyphenyipropanone 740 912 801
1139 d lbenzofuran 9 5 97k’ 917
1159 dodecanolc acid 786 998 Th8
1167 C 11 H 16 0 2 (manual)
1172 phthdlate est r (manual)
1180 naphthofuran 392 957 392
1192 fluorene 629 946 652
1203 C 3 —alkylnaphthalene (manual)
1216 hydroxymethoxybenzeneacetic acid 724 947 724
1221 rnethyldibenzofuran 696 964 719
1232 blphenylcarboxaldehy i 8 B 936 ‘9
1300 fluorenone 824 953 862
1303 tetradecanolc acId 749 989 750
1335 d 10 —phenanthrene (manual)
1338 phenanthrene 863 987 870
1.345 anthracene (manual)
1.350 dinethylacetophenone 378 948 ?88
1389 heptaciecanol 824 9S 826
1430 phthalate ester 904 991 905
1437 hexadecanolc acid (manual)
1440 C 14 HflCHO (manual)
1485 unknown
1504 C 16 H CHO (manual)
1.516 hexadecanol 803 991 805
1524 pyr ne (manual)
1538 C 17 H 31 CHO (manual)
fluoranthen€ (manual)
contin . .d
A-2 3
-------
Table 3—5. concluded
_______ Purity EJ.t &t.it
1546 C 18 H 33 0H (manaul)
1562 dodecanediol 791 986 797
1590 hydrocarbon
1606 N—pheny lnaphthylamlne 830 971 830
1615 C 4 —alkylphenanthrene 618 877 684
1619 CtBH 33 CHO (manual)
1632 oxygenated compound
1645 oxygenated compound
1698 docosane 808 960 837
1751 d 12 —chrysene (manual)
1768 d i isooctyl phthalate 918 977 937
1855 naphthalenylbeflzOthiOPhefle 308 670 425
A-24
-------
Table 3—5. SA iP1E ( S—2
____ Purity E.lt RLLt
190 C 5 H 10 902 990 902
210 2,5 — imeth :lfuran 831 902 912
223 methyl butan ate 816 898 894
234 3—penten—2—one 968 992 968
242 C 9 1’4 20 737 889 765
256 2, 3—butanedione 721 947 759
261 2,2—dlmethylpropanolc acid 674 843 723
278 methyl 2—oxoprc anoateEC 4 H 5 0 3 ] 891 916 900
291 toluene 955 994 9 5
302 2—rnethyltetrahydrofurar)20 1 718 821 860
333 furfural 7)3 864 807
361 metFi lfuran 431 947 431
367 C 5 I 4 0 2 C2H—pyran—2—oe] 818 880 818
377 unknown
383 1—(1—rnethylethoxy)—2—prOpaflOflo 541 791 632
391 cresol (7 ci’ tion too soonl) 406 884 431
404 2—cycloheen— —one 470 843 492
411 1,2—ethaned 1 diacetate 848 956 886
424 2,4—hexadienal 718 882 759
433 cyclohexenone 723 903 747
437 C 6 H 1 0 (manual)
442 ethylbenzene 820 992 820
456 xylene 501 978 509
phenylacetylene (manual)
464 peitenoic acid (manual
474 663 740 734
481 styrene 685 984 690
C 6 H 8 (manual)
489 xylene (manual)
1,(2—furanyl)ethanOfle 683 964 705
continued
A-2 5
-------
Table 3—6. ContInued
Comoound RudI EJ..t &U.t
496 2 ,5—hexanedlone 899 930 950
501 cyclohexanone 849 884 896
522 S..S—d imethy l—2(5H) —furanone 790 852 902
533 C 7 H 10 0, C 7 H 12 0 (manual)
551 C 8 H 18 0 (manual)
555 l—acetyloxy—2—butanone 932 978 944
560 S—methyl—2—furancarboxaldohydo 583 921 620
benzaldehycie 291 850 319
588 C 3 —a lky lbenzene 542 976 551
C 8 H 12 0 (manual)
596 phenol 939 999 939
608 methylstyrene 602 942 633
C 3 —alky lbenzene 470 889 474
616 C 7 H 11 CHO (manual)
623 benzofuran 767 936 816
629 methyistyrene 775 995 775
C 3 —alkylbenzene (manual)
636 C 9 H 14 0 (manual)
642 C 6 H 8 0 2 875 997 875
(2—hydroxy—3—methyl —2 —cycl openten—]—one)
649 methylantsole 825 991 825
655 l —(l—cyclohexen—1—yl)ethanone 686 851 761
659 C 7 H 10 0 (manual)
663 benzeneacetaldehy-le 393 843 464
methyl sty rene (manual)
667 hydroxybenzaldehyde 616 994 616
C 4 —alkylbenzene 404 937 410
678 C 10 H 15 474 970 474
C 8 H 12 0 (manual)
685 cresol 746 9Y6 746
Indene (manual)
continued
-------
Table 3—6. contInued
Campound Purity Lit au.t
693 acetophenone 716 943 741
unsaturated C 4 —alkylbenzene (manual)
698 methylbenzaldehyde 795 991 799
708 cresol 914 988 914
713 methylbenzaldehycle 552 935 589
723 trimethylcyclopentenone 786 938 795
729 C 10 H 12 408 840 470
732 methyl benzoate 485 935 511
unsaturated C 4 —alkylbenzene (manual)
739 hydroxymethylpyranone 859 986 859
unsaturated C 4 —alkylbenzene 811 975 826
745 d imethylphenol 623 990 623
propynyloxybenzene 452 983 452
751 3—phenyl—2—propenal 772 991 772
756 rnethylbenzofuran 838 968 862
761 C 10 H 10 330 835 381
C 9 11 10 0 (manual)
769 C 9 H 18 0 584 926 584
776 ethylphenol 563 971 570
C 4 —alkybenzene (manual)
methoxybenzaldehyde (manual)
83 C 3 —alkylphenol 435 909 458
C 4 —alkylbenzene (manual)
C 9 H 16 (manudi)
789 d lmethyiphenol 902 992 902
796 propyiphenol 562 955 569
802 trlmethyiphenol 725 757 929
805 ethyl phenol 15 926 880
809 d lmethyiphenol 712 988 712
C 10 H 10 (manual)
continued
A-27
-------
Table 3—6. contInued
Coinp und Puri .y - EJ.t Rt.tt
813 C 10 H 16 0 (manual)
methyl acetophenone 562 865 617
820 dlmethylphenol 437 942 4 0
826 methylacetophenone 791 933 841
836 demethoxybenzene 681 959 691
839 naphthalene 946 980 963
843 5—(hydroxymethyl)furancarboxaldehyde 844 976 854
849 tr methylphenol 756 955 787
854 C 9 H 8 0 432 966 432
861 dlmethylbonzofuran 572 888 592
869 dlmethylbenzofuran 655 970 663
879 ethylmethylphenol 811 997 811
883 blfurart 531 969 537
891 dlhydrobenzopyranol 434 845 471
897 3—methyl—1,2—benzenedfol 716 947 716
C 3 —alkylphenol (n-anual)
907 2—methyl—1,4—benzenedicarboxaldehyde 773 982 784
915 indanone 838 979 851
921 dlhydroxyacetophenone 697 985 702
924 methylbenzenedlol 783 974 794
929 hydroxybenzaldehyde 693 969 712
935 C 4 —alkylphenol (manual)
948 2—methylnaphthalene 757 958 786
950 hydroxymethylacetophenone 801 887 882
959 unsaturated C 6 —alkylbenzene 316 961 327
963 1—methylnaphthalene 781 972 793
990 methoxypropenyiphenol 670 995 67C
996 C 6 —alkylbenzene (manual)
C 10 H 14 0 2 (‘nanual)
1002 methoxypropyiphenol 788 923 819
ccr.t lnued
A-28
-------
Table 3—6. contInued
$ . onip und Purit E.Lt RIJ..t
1007 hydroxybenzoic acId 359 921 .b9
1014 hydroxymethoxybeflZaldehYde 869 994 869
1019 b iphenyl 708 975 719
1029 trimethy lbeflzaldehYde 426 955 426
1039 C 8 H 15 CO 2 H (manual)
1050 C 12 H 10 378 860 408
1060 dimethylnaphthalefle 464 908 487
dimethyldecalin (manual)
unsaturated C 5 —alkylbenzene (manual)
1063 dln;ethylnaphthalefle (manual)
C 5 —alkylbenzene (manual)
1.065 ethenylnaphthalefle 876 924 932
1069 methoxypropenylcheflOl 798 986 798
1075 C 9 H 19 C0 2 H (manual)
1084 blphenylene 735 977 740
1089 hydroxymethoxyaCetoPheflOfle 789 993 793
1093 C 5 —alkylbenzefle 584 949 600
1108 d lphenylmethafle 39]. 873 433
1118 naphthaleneCarbOXaldehYd e 515 978 520
1124 C 12 H 20 0 (manual)
1139 dibenzofuran 878 979 892
11.56 dlniethylbeflzeflebUtaflolc acid 721 968 721
116]. methyl ketone (manual)
1167 C 8 H 7 —benzene (manual)
1189 C 7 - .alkylbenzene (manual)
1192 fluorene 767 958 783
1208 methylfluorene 361 824 373
1216 hydroxymethoxyPheflYlaCetiC acid 695 939 703
1221 methyldibe f iZofuran 672 959 694
1232 9H—xanthene 720 929 750
ccr.tI rued
A-29
-------
Table 3-6. concluded
Comp und Purity EJ.t &U.t
1238 naphthofuran 445 991 445
1261 blphenylol 745 859 657
1275 anthracene (manual)
1301 fluorerione 578 96S 591
1309 rnethoxyfluorene 378 766 434
1317 dlbenzodtoxln 729 956 756
1324 oxygenated compound
1335 diOphenanthrene
1345 phenanthrene 756 970 773
1376 nonanediol 594 983 594
1389 pentadecanol 749 969 765
1404 C 9 H 12 0 462 872 505
1408 benzoclnno line 834 953 867
1416 methylanthracene 647 898 710
1430 phthalate ester (manual)
1437 methylanthracene (manual)
1440 C 12 H 3 CHO (manual)
1453 phenanthrenedlone 575 871 645
1459 phenylnaphthalerie 450 860 515
1497 etheuyloxyoctadecane 389 835 453
1502 C 16 H 29 CH0 (manual)
1516 alkene or alcohol
1524 fluoranthene 781 964 802
1538 pyrene 918 958 953
1613 tetramethyiphenanthrene 750 823 874
1619 aldehyde
1644 benzo(c)fluorene 242 749 257
1695 C 10 H 12 0 2 418 894 457
1751 d 12 —chrysene
1768 phthal ate ester
1985 benzo(a)pyrene 454 565 795
A-30
-------
layer was transferred into a tared beaker. The chloroform extraction
was repeated twice more with addition of the bottom CHC1 3 layers to the
tared beaker. Extraction was repeated three times on the BR and BM
fractions using diethyl other in place of chloroform. The ether layers
were transferred to the same beaker used for chloroform. The combined
solvent extract was evaporated to dryness and desiccated 24 hours.
Samples were weighed until constant (<0.5 mg change for two weighings).
The extracted water layers were transferred to separate tared beakers
and evaporated at 105°C to dryness. Samples were next desiccated for
24 hours and weighed until constant. Solvent blanks were determined by
evaporatIng 75 mL of both chlor3forni and diethyl ether to a dry constant
weight (<0.5 mg change). The two filters (F 1 and F 2 ) were also
desiccated at room temperature for 24 hours and weighed to constant
value (<0.5 mg change). All data were rmcorded in the sample log
notebook and entered Into the Sa nple and Analysis Management (SAM)
computer program.
Flow diagram (Figure 3—2) shows the analytical matrix of the ASTM
method. As illustrated this method matrix consists of three major
fractions: 1) the probe rinses (PR); 2) the first filter (F 1 ); and
3) the second filter (F 2 ). In this scheme ar additional probe ruse of
Med 2 (PM) was included, and these were ana’yzed separately In the same
manner as the original probe rinse (PR). The probe rinses were put into
tared beakers and desiccated at room temperature. After reaching
complete dryness the samples ‘tore desiccated for S hours. After
obtaining the Initial weight 1 the samples were weighed every 2 hours or
until constant (<0.5 mg change). The filters were left at room
temperature for 24 hours and weighed. Then the filters were desiccated
16 hours, weighed1 desIccated 2 hours and reweighed. All data were
entered into sample log notebook and the SAM computer program.
The final flow diagram (Figure 3—3) shows the analytical matrix for
t! e Modifhi Method 5 (M ) procedure. As shown this method matrix
includes five major sample components: 1) probe rinse Med 2 (PR);
2) filter (F); 3) XAO—2 resin CX); 4) condensate solutions (C); and 5)
Impinger solutions (OH). The condensate (C) and impinger rinses (BH)
were combined and 1 ethod 3530 A/SN extraction performed.
A- 31
-------
The XAD—2 resin (X) and NeC1 2 rinses wero Soxhiet extracted for 16
hours using MeCl 2 as the solvent. The XAD extracts were added to the
organic fraction fran the Method 3530 ExtractIon (BH and C), and tho
final volune adjusted to 10 nL. Preliminary Gravimetric Analysis (GRAV)
was done on the combined extracts CX, C, and BR) to determine if the
GRAV value was less than 30 mg/mL. If necessary, the volume was
adjusted with MeC1 2 until the GRAV value was between 0.1 and 30 ng/rnL.
After reaching an acceptable GRAV value, GC/T O analysis was done.
Again, the volume of the extract was adjusted to maximize the GC/TO
results. The values frar the GC/TCO analyses were used to determine
correct dilution volumes for the GC/MS samples. This GC/T O screen also
indicated that a column chromatography step was not warranted. The
probe rinse (PR) in MaC1 2 was evaporated at roan tomperature In a tared
beaker, desiccated, and weighed to the nearest 0.5 mg. The weighing was
repeated every 2 hours until a constant (<0.5 mg change) value vas
reached. The filter was desiccated for 24 hours and weighed. Weighing
was repeated every 2 hours until constant (within C.5 mg) weight was
reached. The probe rinse (PR) and filter (F) were combined in a Soxhlet
apparatus nd extracted with MeC1 2 for 16 hours. The fiiial volume was
adjusted to 10 mL and this fraction was combined In equal parts with the
organic fractions of the XAD—condensate-’impinger CX C, and BH)
extractions.
The final step Involves adding quantitation standards before the
sample was su ni . d for GC/MS analysis. Since column chromatography
was not performed, no surrogate compounds were added.
A-32
-------
4.0 ANALYTICAL RESULTS
The rel lability and acceptabil ity of envlrorTnental analytical
Information depends upon the rigorous canpletioi; of all requirccents
outlined in the QA/ protocol.
The data were carefully logged into sample notebooks on a daily
basis by the analysts to minimize the collection of invalid data. Daily
control checks consisted of examination of reproduc1t iltty of duplicate
Irijoctions, sample blanks, and quality control samples that were
analyzed during the daily analysis cycle. The analysts recorded any
unusual instances In the daily cycles (such us power loss or
fluctuations, tanporary leaks or adjustments, or operator error).
Probl ns were documented as detected and appropriate corrective action
taken to maximize the validity of the database.
The analysts on each task double checked all data entries to ensure
accurate transcriptions and calculations. The data were then reviewed
by each respective Task Leader and corrections made If necessary.
Finally, all data were reviewed and calculations spot—checked by QA
Officer to verify the Integrity of the data. After validation of the
database, data tables were prepared and are shown In Summary Tables 4—1 .
4—2, and 4—3.
A-33
-------
Table 4—1. Woodstove Gravlmetrtc Results
MODIFIED METHOD 5
XAD, C, & 6Ff
SAMPLE ID PMeOH PR FILTER TCO GRAV
(mg) (mg) Cmg) (mg) (mg)
BD—i NA 1.0 6.3 37.4 76
BD—QC1 NA NA NA NA NA
BD—2 NA 0.5 7.8 26.5 60
BD—3 NA 1.0 9.9 10.7 35
BD—4 NA 1.2 8.5 73.1 102
BD—QC4 NA NA NA NA NA
BD—5 NA 0.5 7.7 19.5 46
BD—QC5 NA 1.0 7.2 19.4 54
BD—B NA NA NA NA NA
BS—1 NA 32.0 52.6 168.0 195
BS—aC l NA NA NA NA NA
BS—2 NA 5.8 28.9 62.9 99
BS—QC2 NA NA NA NA NA
BS—3 NA 1.4 14.3 51.5 62
BS—4 NA 51.1 249.4 1240.0 723
BS—5 NA 11.8 32.0 89.6 76
BS—QC5 NA 15.9 12.1 56.0 75
BS—B NA NA NA NA NA
GD—i NA 1.9 134.0 117.0 72
GD—2 NA 1.6 53.8 97.7 70
GD—3 NA 1.5 128.6 157.0 114
GD—QC3 NA 0.9 31.5 138.0 127
GD—4 NA 0.7 30.6 76.5 52
GD—QC4 NA NA NA NA NA
GD—B NA 0.3 0.0 0.0 23
GS—1 NA 48.7 699.0 872.0 858
GS—2 NA 39.5 215.6 371.0 262
GS—3 NA 23.9 260.6 680.0 490
GS—QC3 NA NA NA NA NA
GS—4 NA 8.4 37.6 132.0 84
GS—QC4 NA 9.8 38.2 99.6 79
GS—B NA 1.2 2.2 0.0 31
G—LOADING BLANK NA NA NA NA NA
continued
A-34
-------
Table 4—1. Woodstove Gravimetric Results continued
MODIFIED METHOD 5
XAD, C, & BH
SAMPLE ID PMeOR PR FILTER TCO GRAY
(mg) (mg) (mg) (mg) (mg)
MD—i NA 0.7 5.0 13.4 55
HD—QC1 NA NA NA NA NA
HD—2 1.1 0.2 7.4 33.7 59
HD—QC2 NA NA NA NA NA
HD—3 1.7 0.2 11.3 18.6 44
HD—QC3 1.2 0.3 9.4 25.0 38
1 10—4 1.6 0.2 17.6 23.3 24
lID—S 1.6 0.9 9.5 20.4 32
lID—B 0.4 0.9 0.0 0.0 16
HS—1 NA 3,7 14.1 49.2 42
HS—QC 1 NA NA NA NA NA
IIS—2 11.6 13.6 147.1 422.0 478
HS—3 17.7 8.0 91.1 183.0 137
HS—QC3 8.5 9.2 17.0 46.7 38
11 5—4 15.2 10.0 100.7 161.0 123
HS—5 10.0 10.4 45.8 117.0 70
MS—B 1.1 1.3 0.8 0.0 140
ID—i NA 1.7 12.8 49.2 72
10—2 NA 1.8 6.4 18.3 44
TD-QC2 NA NA NA NA NA
ID—B NA 0.5 0.3 0.0 16
TS—1 NA 12.5 35.1 76.7 88
TS—2 NA 15.0 21.9 56.2 86
TS—3 NA 8.3 130.5 186.0 176
TS—QC3 NA NA NA NA NA
TS—B NA 1.2 14.2 0.0 27
BLANK XAD MODULE NA NA NA 0.0 ii
continued
A-35
-------
Table 4—1. Woodstove Gravimotric Results continued
MODIFIED METHOD 5
XAD, C. 6 BH
SAMPLE ID PMeOH PR FILTER TCO GRAY
(mg) (mg) (mg) (mg) (mg)
FD—1 1.0 3.6 26.5 36.9 138
FD—2 1.5 0.2 3.5 27.2 159
FD—QC2 2.7 0.3 5.2 25.5 110
FD—3 0.0 1.3 10.6 22.3 125
FD—4 1.2 1.0 4.4 26.0 123
FD—QC4 2.7 3.6 21.3 22.1 112
FS—l 32.1 14.0 81.7 133.0 200
FS—2 17.2 28.3 98.3 144.0 212
FS—3 13.4 12.0 30.4 94.3 198
FS—4 13.8 7.9 32.6 92.3 178
FS—B NA NA NA 0.3 119
contInued
A-36
-------
Table 4—1. Woodstoye Gravimetric Results continued
OREGON METHOD 7
BH BM
CHC13/ETHER EXTRACTION
FRONT WMER CHC13/ETHER BACK
SAMPLE ID PR & PM FILTER FRACTION FRACTION BR FILTER
(mg) (mg) (mg) (mg) (mg) (mg)
BD—1 1.3 7.3 16.2 14.9 1.0 0.7
BD—QC1 NA NA NA NA NA NA
BD-2 0.8 5.8 21.1 7.9 2.1 2.8
BD—3 0.5 4,8 20.8 5.4 1.0 2.4
BD—4 61.2 11.7 35.2 41.2 2.4 3.8
BD—QC4 1.5 13.7 45.4 13.2 2.2 0.0
BD—5 4.8 18.0 18.4 8.8 0.8 2.9
BD—QC5 NA NA NA NA NA NA
BD—B 2.6 1.3 9.8 1.8 0.6 0.3
BS—i 31.1 34.7 64.2 35.2 43.0 24.0
BS—QCL 46.9 59.4 122.7 61.2 54.8 17.9
BS—2 29.0 19.2 34.9 11.2 19.4 19.3
BS—QC2 23.0 15.7 26.2 12.6 4.6 5.3
BS—3 9.5 7.5 10.9 2.0 11.3 16.2
BS—4 49.4 78.2 184.0 117.0 144.8 205.2
BS—5 24.4 10.1 13.5 5.3 11.4 2.9
9S -QC5 NA NA NA NA NA NA
BS—B 1.9 0.7 17.2 1.1 1.4 0.9
GD—i 5.6 101.7 46.2 13.6 3.2 0.6
GD—2 2.4 24.7 37.8 38.9 5.6 3.8
GD—3 8.2 103.1 19.5 7.3 2.3 0.0
GD—QC3 NA NA NA NA NA NA
GD—4 1.0 27.6 10.6 4.7 4.7 0.5
GD—QC4 0.7 50.5 20.1 9.8 8.2 0.7
GD-B 1.1 0.0 1.5 0.0 0.9 0.1
GS—i 160.1 731.4 161.3 98.6 125.7 73.9
GS—2 132.8 289.3 28.0 59.4 11.5 4.7
GS—3 164.8 381.6 45.1 36.1 144.3 37.3
GS—QC3 174.0 424.1 35.2 45.5 19.0 2 .1
GS—4 23.2 34.8 5.0 3.1 4.6 0.6
GS—QC4 NA NA NA NA NA NA
GS—B 1.4 1.3 0.3 0.0 0.2 0.2
G—LOADING BLANK NA 0.0 NA NA NA NA
continued
A-37
-------
Table 4—1. Woodstove Gravimetric Results continued
OREGON METHOD 7
BH & BM
CHC13/ETHER EXTRACTION
FRONT WATER CHC13/ETHER BACK
SAMPLE ID PR & PM FILTER FRACTION FRACTION BR FILTER
(mg) (mg) (mg) (mg) (ing) ( mg )
HD—1 1.8 3.9 14.8 2.8 1.6 0.0
HD QC1 NA NA NA NA NA NA
HD—2 2.6 16.3 25.5 4.3 2.2 1.0
HD—QC2 1.8 34.9 14.2 19.4 0.5 0.3
HD—3 1.5 5.5 16.5 3.0 1.7 3.8
HD—QC3 NA NA NA NA NA NA
HD—4 1.2 12.8 8.8 0.6 2.2 1.1
HO—S 2.6 7.2 16.6 7.9 1.4 1.4
HO—B 2.3 0.0 0.6 0.4 0.1 0.3
HS—1 18.6 12.7 3.7 1.4 5.7 3.2
HS—QC I 42.4 20.5 9.3 4.6 19.4 29.7
HS—2 70.4 334.6 60.4 189.2 29.3 81.0
HS—3 44.0 77.6 11.9 34.8 8.3 2.8
HS—QC3 NA NA NA NA NA NA
HS—4 76.0 74.1 19.6 6.5 29.6 26.2
HS—5 27.3 67.4 7.8 18.0 4 ,3 3.2
HS—B 1.1 0.5 0.4 3.8 0.0 0.7
TO—i 3.6 10.0 24.4 25.9 2.1 4.2
TD—2 2.7 6.2 0.0 13.5 2.5 0.6
TD—QC2 NA NA NA NA NA NA
TO—B 0.7 0.5 1.7 0.9 0.2 2.2
TS—1 12.4 12.5 7.5 21.1 17.0 21.5
TS—2 19.4 33.0 38.3 202 32.8 26.6
TS—3 23.9 170.6 45.4 30.0 78.6 47.0
TS—QC3 11.4 90.6 54.4 120.4 30.0 103.6
TS—B 1.0 0.9 4.3 0.0 0.1 0.3
FD—1 2.0 37.1 28.4 21.6 18.9 1.4
FD—2 4.3 9.7 55.5 14.9 12.1 3.0
FD—3 2.2 5.0 18.5 14.4 21.7 10.9
FD—4 2.2 10.0 39.4 9.3 11.7 1.8
FS—i 69.6 66.9 41.3 39.2 58.0 57.7
FS—2 33.6 37.3 57.0 39.1 92.0 53.8
FS—3 61.8 39.7 45.9 39.6 58.1 32.3
FS—4 36.6 27.2 28.7 26.7 50.3 53.5
cant I nued
A-38
-------
Table 4—i. Woodstove Gravimetric Results continued
ASTM
FILTER FILTER
SAMPLE ID PR PM ONE TWO
(mg) (mg) Cmg) (mg)
BD—1 3.2 1.9 32.7 1.1
BD—QC1 0.7 0.4 30.4 1.6
BD—2 1.4 1.6 38.0 0.8
BD—3 0.0 2.2 9.9 0.5
BD—4 3.3 1.6 77.6 1.4
BD—QC4 NA NA NA NA
BD—5 4.8 1.9 22.5 0.4
BD—QCS NA NA NA NA
BD—8 NA NA NA NA
BS—i NA NA NA NA
BS—QC1 NA NA NA NA
BS—2 NA NA NA NA
BS—QC2 NA NA NA NA
BS—3 NA NA NA NA
BS—4 NA I JA NA NA
BS—5 NA NA NA NA
BS—QC5 NA NA NA NA
BS—B NA NA NA NA
GD—i 2.7 1.4 180.3 1.2
GD—2 0.2 0.7 98.3 0.7
GD—3 2.2 1.7 187.6 1.3
( 2 D—QC3 NA NA NA NA
2.8 1.1 55.8 0.6
UD—QC4 NA NA NA NA
GD—B 0.0 1.3 0.1 0.2
GS—i NA NA NA NA
GS—2 NA NA NA NA
GS—3 NA NA NA NA
GS—QC3 NA NA NA NA
GS—4 NA NA NA NA
GS—QC4 NA NA NA NA
GS—B NA NA NA NA
G—LOADING BLANK NA NA NA NA
continued
A-39
-------
Table 4—1. Woodstove Gravimotric Results conc udod
ASTM
FILTER FILTER
SAMPLE ID PR PM ONE TWO
(mg) mg) (mg) (mg)
HD—QC1 0.0 0.6 21.8 1.1
HD—2 1.8 0.1 73.0 0.0
HD—QC2 NA NA NA NA
HD—3 0.6 0.1 30.1 0.0
HD—QC3 NA NA NA NA
HD—4 0.6 0.1 31.3 0.0
HD—5 0.8 0.9 20.8 0.0
HD—B 0.0 1.3 0.6 0.4
HS—1 NA NA NA NA
HS—QC1 NA NA NA NA
HS—2 NA NA NA NA
HS—3 NA NA NA NA
HS—QC3 NA NA NA NA
HS—4 NA NA NA NA
HS—5 NA NA NA NA
MS—B NA NA NA NA
10—1 0.7 0.4 29.2 1.6
TD—2 3.0 0.0 17.6 1.7
TD—QC2 2.9 0.3 1.3 2.0
TO—B NA NA NA NA
TS—1 NA NA NA NA
TS—2 NA NA NA NA
TS—3 NA NA NA NA
TS—QC3 NA NA NA NA
TS—B NA NA NA NA
FD—1 2.3 2.1 97.8 0.4
FD—2 4.2 1.2 37.8 0.6
FD—3 5.7 0.8 45.0 0.8
FD—4 2.9 * 37.2 0.0
* sample was contaminated
A-40
-------
Tøble 4-2. TOTAL CHROHATOGRAPIIADLE ORGANICS (TCO)
6.76192
0.790004
1.47312
0.9067 27
5.43253
0.4 07916
SAMPLE
1.0. I
AREA
COUNTS
AREA
COUNTS
PERCENT
DIFF.
MEAN
AREA CTS.
TCO
HG/HL •
lCD
MG/)QML
DILUTION
FACTOR
TOTAL HG
(MINUS BLANK)
80—1-9472
806693
753929
730311.00
3.74
Z .0
2.50
37.4
00—2—9621
655360
650203
652781.50
3.10
12.4
2.14
26.5
80—3-9653
320854
316162
318508.00
1.42
5.67
1.88
10.7
60—4-9657
523689
518962
521325.50
2.44
9.75
7.50
73.1
BO—5—9869
502905
476307
469606.00
2.28
9.11
2.14
19.5
8 0—QC S—9863
583475
580577
582026.00
2.74
11.0
1.76
19.4
ND—B-10343
36308.00
—0.00205
—0.00820
1.67
0.00
1 10—1—10095
480931.00
2.23
0.93
1.50
110—2—9982
1040800.00
5.05
20.2
1.67
33.7
110—3—10249
653463.00
3.10
12.4
1.50
18.6
HD—QC3—10247
866729.00
4.17
16.7
1.50
25.0
HD 4—1J345
729167.50
3.48
13.9
1.67
23.3
110—5—10347
781688.00
3.75
15.0
1.36
20.4
C D — 2CC21
45374.00
0.0433
0.174
2.14
0.00
68—1—0875
816389.00
3.92
IS.7
7.50
117.0
60—2—9979
62209f. so
2.94
11.8
8.33
97.7
60—3—10097
869563.00
4.19
16.8
9.40
157.0
GD— 0C3—1 0 0 98
661397.00
4.15
16.6
8.33
138.0
60—4—10094
393526.00
1.79
7.18
10.7
76.5
10—8—9622
105159.50
0.344
1.38
1.50
0.00
10—1—9380
1227760.00
5.99
24.0
2.14
TO—2—9897
712619.00
3.40
13.6
1.50
18.3
10251—B
27637
26923
2.6173
27280.00
—0.0474
—0.190
1.50
0.00
38510
482961
1041390
658221
070733
744691
787064
45549
e22436
625690
800337
876839
394087
106738
1239730
712)25
34106
476901
1040210
648705
862725
713644
776312
43 19
810342
618503
858769
045955
392965
103581
12 15 790
712513
12.130
0.844196
0.1133743
1. 456 24
0.923934
4.25 707
1.37548
I • 77 37
1. 4 8140
1.15529
2 .47 80
3 .5 8534
0.285 115
3.00211
1. 949 892
0. 0 297 494
Continued
DETERMINE THE
• TCO ag/mi VALUES ARE MULTIPLIED 81 4.0 IN ORDER TO
TOTAL eg IN THE ORIGINAL 10 ml SAMPLE VOLUME.
-------
T4b14 4—2. TOTAL CHROMATOGRAPHABLE ORGANICS (TCO)
SAMPLE
1.0. S
AREA
COUNTS
AREA
COUNTS
PERCENT
01FF.
MEAN
AREA CIS.
TCO
NG/ML
ICO
MG/1OML
DILUTION
FACTOR
TOTAL MG
(MINUS ULANK)
es—l— 9473
1159930
11’6520
1.162826
11 5322.OO
5.61
56.1
3.00
160.0
BS—2—9619
1208290
1285310
0.2315822
1286800.00
6.29
62.9
1.00
62.9
05—3—9654
1066210
1056260
0.9375869
1051235.00
5.15
51.5
1.00
51.5
8S—4—9655
2278920
2274590
0.1901830
2276755.00
11.26
113.0
11.0
1240.0
05—5—9900
1824090
1812090
0.6600333
1818090.00
0.96
89.6
1.00
89.6
BS—OC S—987 0
1208019
1091780
10.10788
1149895.00
5.60
56.0
1.00
56.0
GS—B—10 092
54836
51986
5.3360
53411.00
0.0839
0.839
1.00
0.00
GS—1—9871
1619120
1611780
0.4543626
1615450.00
7.94
79.4
11.0
872.0
05—2—9978
1096410
2090610
0.5304021
1093510.00
5.31
53.1
7.00
371.0
05—3—10090
1269700
1264480
0.4119675
1261090.00
8.19
61.9
11.0
680.0
05—4—10099
700054
C;ioii
1.18359
695935.50
3.31
33.1
4.00
132.0
GS—QC4—10096
610215
605054
0.849359
607634.50
2.87
28.7
3.50
99.6
1 15—6—10344
35982
33563
6.9565
34772.50
—0.00977
—0.098
2.50
0.00
1 15—1—10093
1017040
1012350
0.5408361
1015095.00
4.92
49.2
1.00
49.2
HS—2—9981
1459520
1409550
3.463352
1434535.00
7.03
70.3
6.00
422.0
11 5—3—10250
968215
923908
4.683311
946061.50
4.57
45.7
4.00
163.0
HS—QC3—10248
965806
964448
0.140107
965127.00
4.67
46.7
1.00
46.7
HS—4—10346
837083
835220
0.222807
036151.50
4.02
40.2
4.00
151.0
HS—S—10346
617263
616897
0.0593116
617080.00
2.92
29.2
4.00
117.0
TS—8—9620
50905
49940
1.0978
50426.50
0.0689
0.689
1.00
0.00
15—1—9378
1653150
1499350
9.757335
1576250.00
7.14
77.4
1.00
76.7
15—2—9898
1180350
1155300
2.145013
1167825.00
5.69
56.9
1.00
56.2
15—3—9901
981629
944681
3.63614
963155.00
4.66
46.6
4.00
186.0
Continued
-------
1.b . 4—2. TOTAL CHROMATOGRAPHABLE ORGANICS (TCO)
SAMPLE AREA AREA PERCENT MEAN TCO TCO DILUTION TOTAL MG
1.0. I COUNTS COUNTS 01FF. AREA CIS. MG/Mt MG/1OML FACTOR (MINUS BLANK)
FS—1—11003 1029080 1026140 0.28610 1027610 5.32 133.0 I 1.00 133.0
FS—2—10997 1107000 1117390 0.93419 1112195 5.78 144.0 I 1.00 144.0
FS—3—10999 738797 740158 0.18405 739418 3.77 94.3 S 1.00 94.3
FS—4— 10995 725312 123700 0.23077 124536 3.69 92.3 5 1.00 92.3
FS—X—8—11002 41768 44274 5.82506 43021 0.03 0.3 1.00 0.3
FD—l—1l001 713030 73S121 3.04391 724101 3.69 36.9 3.00 36.9
P0 —2—11005 526761 560554 6.21586 543658 2.72 27.2 1.00 27.2
FD—0C2—1l000 513078 513878 0.23416 512478 2.55 25.5 1.00 25.5
FD—3—11004 452527 454417 0.41678 453472 2.23 22.3 1.00 22.3
P0—4—10998 521)25 520283 0.16170 520704 2.60 26.0 1.00 26.0
FD—0C4—10996 454640 444136 2.33740 449388 2.21 22.1 1.00 22.3
concluded
I Indicates rg/25 m
-------
Table 4-3. AMOUNT OF TARGET COMPOUNDS IN SAMPLE. MICROGRAMS
SAMPLE
ION BD-1 BD—2 80—3 BD-4 8D—S 800C-5
94 phenol 629.8 1018.0 176.3 1567.5 547.8 596.5
128 naphthalane 290.4 470.3 93.8 490.0 235.6 238.7
152 acenaphthylene 55.0 /6.2 24.9 100.7 53.3 57.6
154 acenaphthene 6.0 5.7 Trace Trace 4.5 4.5
166 fluorene 17.2 19.7 5.4 37.6 15.6 16.9
173 nltronaphthalene
178 phenanthrene 52.0 62.7 16.4 105.0 58.6 63.1
178 anthracene 6.7 Trace 17.4 7.1 6.3
174 acrldine
167 cerbazole
202 fluoranthene 17.3 3.5 35.2 14.4 15.7
194 pP e. anth.ol
202 pyrone 13.1 Trace 31.9 8.5 13.8
228 benzo(a)anthracene
228 .hrysene 4.0
252 benzc(b)fluoranthene
252 benzo(k)fluoranthene
252 berzo(a)pyrene
263 3—methyicholanthrene
276 benzo(g.h,1)perylene
278 dlbonzo(a. ti)anthracuno
276 Indeno(1.2.3cd)pyrene
continued
-------
Tible 4—3. AMOUNT Q TARGI1 COMPOUNDS IN SAMPLE, MICROGRAMS
SAHPL C
ION COMPOUND OS—i 0 5-2 OS—3 05—4 BS—5 DSOC-5
94 phono 3656.6 2246.8 526.9 9934.2 3131.7 261.9
120 naphthalens 1359.7 671.6 172.0 2084.3 1071.1 947.0
152 aconaphthylono 281.3 131.7 55.5 486.2 210.6 170.2
154 acor.phthono 7.6 19.1 17.1
166 fluoreno 104.7 56.4 23.2 189.4 61.7 54.1
173 nltronaphthclOflo
170 phononthr.ne 277.0 165.1 50.6 363.6 212.7 174.1
178 anthracone 44.7 15.1 20.7 Trace 31.0 25.4
174 icridIno
167 corbazo o
202 iü?êi thO 90 ,3 57.1 24.9 Trace 64.6 51.3
194 phonanthrol
202 pyrono 80.9 41.0 23.7 Trace 52.9 45.9
228 bonzo(a)anthracene 34.9
228 chryseno 35.2 18.7 15.5
252 bonzo(b)fluoranth3flo 41.5
252 bonzo(k)fluoronthene 43.9
252 bsnzo(.)pyrcno 50.9
263 3—oethy cho OAthrOflO
276 benzo(g.h.t)perylSflS 52.5
216 dlbsnze(a,h).nthraC eflo 53.7
276 lndono(1.2.3Cd)pyrOfle 55.9
cont Inuod
-------
Table 4—3. AMOUNt OF TARGET COMPOUNDS IN SAMPLE 1 MICROGRAMS
SAMPLE
ION COMPOUND GD—i 60—2 60-3 GDOC-3 D-4 GD—a
94 phenol 2168.2 4512.5 3978 3659 3653 7.2
128 naphthalene 752.6 1359.9 1796 1794 7026
252 ccenaphthylane 139.8 235.0 360.5 346.9 1638
154 acenaphtheno Trace 21.1 30.5 29.2 72.9
166 fluorono 48.9 73.0 123.4 107.4 379.3
173 nltronaphttieleno
178 phonanthrono 107.1 199.4 305.5 280.3 1299
178- anthraceno 16.5 28.8 43.3 45.3 189.2
174 acridjn.
167 carbaxolo
202 f r; thara 53.0 92.2 200.3 630
194 phonanthrol
202 pyrono 22.3 41.5 65.9 77.5 Trace
228 bonzo(a)anthracone 22.2 151.8
228 chryseno 27.6 26.0 146.6
252 bonzo(b)f)uorantheno 239.8
252 bonzo(k)fluoranthon,
252 benzo(s)pyrono 177.0
263 3—oethylcholanthr,no
276 bonzo(g.h,1)poryleno
278 dibenzo(a,h)anthracen .
276 indorotl.2.3cd)pyrono
continued
-------
Tabis 4—3. AMOUNT OF TARGET COMPOUNDS IN SAMPLE. MICROGRAMS
SAMPLC
ION COMPOUND GS-1 GS—2 GS-3 GS-4 GSQC-4 GS-B
94 phono 18618.2 15328.6 11466.6 11041.6 6765.0 26.2
128 naphtti 1.ne 4168.2 4391.0 4364.9 11016.9 9165.9
152 aconaphthylons 862.9 713.4 905.5 3891.0 2910.8
354 acenaphthene Traco 208.9 152.9
166 fluorone 291.6 244.5 289.2 931.0 679.4
173 flltronaphthalene
178 phonanthrono 626.6 669.3 2873.3 1760.1
178 anthracene Trace 101.8 496.3 328.9
174 OcrIdine
167 carbazolo
202 1uorenthena 228.6 218.9 193.0 1254.e
194 phonanthrol
202 OflO 224.5 174.6 157.9 1136.9 763.3
228 bonzo(a)anthraceno 264.3
228 chrysone 309.0 92.3 273.3 196.7
252 benzo(b)fluoranthone 500.5 374.0
252 benao(k)f1uor nthane
252 benzo(a)pyreno 271.1
263 3—asthylcholOnthreio
276 bonao(g,h.f)pory onc 213.0 145.9
278 djbenzo(o,h)anthrecon,
276 Indono(1.2,3c4)pyrono 251.7 171.3
Continued
-------
Tabi. 4—3. AMOUNT OF IARG(T COMPOUNDS IN SAMPLE. MICROGRAMS
SAMPLE
ION COMPOUND HO-i HD—2 P 10-3 HDQC-3 P10-4 HO-S HO-B TO—i 10-2 TD-O
94 phenol 505.5 302.4 731.7 994.4 747.8 1415.6 13.1 604.3 158.2
120 nephthelerio 872.0 103.3 824.9 1008.7 676.1 2303.1 627.0 117.4
152 aconaphthyl .n . 292.5 28.3 204.9 306.3 170.6 649.1 92.6 23.5
154 •c.naphthene 10.2 9.3 13.6 Trace 22.0 22.4 6.6
166 fluorons 77.6 Tr co 47.0 72.8 44.3 145.7 36.9 0.5
173 nltronaphthalefl .
178 phenanthren. 250.1 41.1 135.6 194.0 126.5 494.4 111.2 29.4
176 anthracons 37.1 TraCe 24.2 30.1 17.6 75.7 Trace
174 acridlns
167 csrbazolO
202 fluoranthons 103.6 12.8 67.4 75.9 36.1 175.5 34.2 7.7
194 phonanthrol
202 pyran . 83.9 Trec. 52.2 59.0 29.6 132.1 29.3 6.9
228 b.nzo(a)anthraCena 17.4 13.6 11.4 Trace 47.7 6.2
220 chryasno 16.2 12.3 19.0 Trace 42.8 7,8
252 benzo(b)fluoranthsfls 20.0 17.4 Trøco 19.7
252 benzu(k)fluoranthofle
252 benzo(a)pyrefl . 11.5 Trace 46.5
263 3—m.thylcholanthrofl s
276 b.nzo(g.h.I)porylIflO
270 dlbenze(a,h)anthraC efll
276 ndeno(1.2.3Cd)pyrOflS
Continued
-------
Table 4-3. AMOUNT OF TARGET COMPOUNDS IN SAMPLE, MICROGRAMS
SAMPLE
ION COMPOUND HS—1 HS—2 145—3 HSOC-3 HS—4 HS - 5 HS—B
94 phenol 1726.0 6763.5 9759.7 1674.1 9446.4 11194.2 26.4
125 naphthalono 2273.6 1659.0 6910.4 1638.6 6133.7 11378.1
152 ecenapbthylono 808.3 494.7 1777.2 457.6 1588.6 3457.3
154 ecenaphthone 31.1 101.2 25.3 89.1 150.9
166 fluore ’e 191.6 169.2 464.0 110.1 365.4 515.5
173 nltro .iaphthaleno
178 phenanthronc 505.3 462.6 1086.2 232.9 982.6 2414.1
178 anthraceno 96.6 91.7 208.9 45.3 176.0 446.1
174 acridlno
167 carba ole
207 f1yorantI ene 1835 179.’ 370.9 90.4 342.1 1018.
194 phononthrol
202 pyrene 153.6 161.5 275.9 66.8 265.1 062.5
228 benzo(a)antbrecene 87.8 19.9 110.2
228 chrysene 44.7 96.5 21.3 116.5 219.5
252 benao(b)fluoranthone 64.8 137.3 33.0 244.3 378.3
252 benzo(k)f lsjoranthon.
252 bonzo(a)pyrene 40.4 81.6 135.8 244.8
263 3— ethylcholantbrene
276 bsnze(g ,h.1)p.rylone 81.0 128.8
275 d$bonzo(a,b)enthracone
276 indono(1.2.3cd)pyrene 136.9
confl nuod
-------
Table 4—3. AMOUNT OF TARGET COMPOUNDS IN SAMPLE. MICROGRAMS
SAMPLE
ION COMPOUND TS—1 TS—2 TS—3 BLANK
94 phenol 1283.5 1368.1 1946.7 9.4
128 naphthalene 737.9 572.4 482.9
152 acenaph’hylene 164.6 112.7 84.5
154 acenaphtheno 38.7 37.6 Trace
166 fluorene 56.4 45.0 Trace
173 nltronaphthalene
178 phenanthreno 117.8 106.4
178 anthracene 14.7 17.6 77.2
174 acridlne
167 carbazole 3.1
202 fluorantheno 40.9 33.7 Trace
194 phenanthrol
202 pyrene 37.3 32.9
228 benzo(a)anthrecene
228 chryseno 9.2 15.6
252 benzo(b)fluoranthene 22.8
252 bunzo(k)fluoranthene
252 bonzo(o)pyrone
263 3—ziethylcholanthreno
276 benzo(g,h .1)per lc o
278 dlbenzo(e,h)anthracene
276 Indeno(1.2,3cd)pyrene
conttnued
-------
Table 4—3. AMOUNT OF TARGET COMPOUNDS IN SAMPLE. NICROGRAMS
SAMPLE Duplicate SOLVENT
ION COMPOUND FD—1 FDQC—2 FD—2 FD—3 FD-3 FD-4 FDOC—4 BLANK +
94 phenol 1181.6 608.4 683.9 794.5 788.2 486.5 604.4 Q
TARGETS
128 naphthalene 258.6 158.1 233.0 274.9 252.1 114.4 135.6 DETECTED
152 acenaphthylena 40.7 24.8 27.4 50.0 46.2 19.2 21.8
154 acenaphthene Trace Trace
166 fluoreno 15.6 Trace is.i 17.4 16.6 Trace Trace
173 nitr3naphtha lone
178 phenanthrene 52.0 26.5 61.7 40.5 39.6 26.1 21.4
178 anthracone Trace Trace 11.2 Trace Trace Trace Trace
174 acrldtne 1 .8
167 Carbazole
202 fluoranthono 17.9 Trace 33.4 14.0 13.8 Trace Trace
194 phen n p ... 0 i
202 Pyrone 15.8 Trace 29.1 13.9 13.0 Trace rece
228 benio(a)anthracone Trace Ti ace Trace Trace
228 chryaeno Traro Trace Trace Trace Trace Trace Trace
252 bOrizo(b)fluoranthene
252 benzo(k)fluoraflthefle
252 benzo(apyrene
263
276 bonzo(g,h,1Jpery 0 0
278 dIbenzo(a.h)anthracon.
276 inaune(1,2,3cd)pyreno
Continued
-------
Table 4-3. AMOUNT OF TARGET COMPOUNDS IN SAMPLE, MICROGRAMS
SAMPLE DuplIcate ANALYT. BLANK
ION COMPOUND FS -1 FS—2 FS —3 FS—4 FS—4 BLANK + XADI
94 phenol 4572.6 3087.4 3125.7 2500.4 2357.2 NO
TARGETS
128 naphttialone 995.7 607.4 978.8 554.8 524.0 DETECTED 614.3
152 acenaphthyleno 166.0 94.0 126.1 70.3 73.2
154 acenephthono 15.9 11.2 14.2 321.2
166 fluerune 72.3 51.6 58.3 38.9 36.4
173 nltronaphthalene
170 phenanthrene 215.6 108.1 127.5 75.0 76.4 402.8
178 anthracene 42.4 18.8 V.4 17.0 18.2
174 acrldine
167 carbazole
202 fluoranthene 71.8 35.9 38.1 27.1 27.9
194 phenanthrol
202 pyrene 24.2 32.8 33.4 26.0 23.5
228 benze(a)anthracene 15.7 10.8 10.1 Trace Trace
228 chrysene 16.2 9.9 9.4 Trace Trace 406.1
252 benzo(b) fluoranthene
252 bonzo(k)fluoranthene
252 benzo(e)pyrene 65.1
263 3—a ethylcho1ar,throne
276 bonzo(g,h,I)perylene
278 d lbenzo(a.h)anthreceno
276 Indeno(1 ,Z ,3cd)pyreno
COnCluded
• S1gnIf1ca t quantitlea of targets detected In Blank 11002
• Solvent and Analytical Blanks are Solvent Lot IAN319
-------
5.0 CXJALITY ASSURANCE AND QUIiLITY CONTROL
Supporting quality control and quality assurance data for the
analytical determinations are reported In this section.
5.1 GRAVIP .ETRIC ANALYSIS
As requested in the QA/OC protocol the accuracy of the gravimetric
(GRAY) analysis must be ± 20% of the actual value. Proficiency tests
were administered to the analyst using prepared standards containing
known amounts of stearic acid, elcosane, and triphenylmethane In a total
voUine of 100 mL of methylene chloride. The results for the GRAY tests
are as follows:
Actual Experiment 1 Accuracy
GRAY Test 1 1.21 mg/mI 1.20 mg/mL —0.8% 2.4%
GRAY Test 2 1.21 mg/mI 1.16 mg/mL —4.1%
GRAY Test 3 1.04 mg/mI 1.05 mg/mI 1.0%
GRAY Test 3 1.04 mg/mI 1.10 mg/mI 5.a%
The results of the GRAY Audit were within the precision and accuracy
specification outlined in the SOP. It should be noted that the same
analyst performed all GRAY analyses.
A GRAY value for duplicate method blanks was determined f or each
now lot of solvent and/or set of samples. Also, a reagent blank was
analyzed for GRAY every ten samples (listed in Table 4—1). These
reagent (solvent) blanks consisted of the same volume of solvent used In
analyzing the samples. Any unusually hi reagent blanks were noted and
the blanks reanalyzed. The reported GRAY values were determined by
subtracting the ‘alues of the solvent blanks from the samples, including
the method blanks.
A-53
-------
5.2 TOTAL Q1Rc 4ATOGRAFHABLE ORGANICS (TOO)
The gas chromatograph (GC) was calibrated using solutions prepared
by diluting a stock solution of C 7 to C 17 hydrocarbons. The stock
solution contained approximately 37 mg (C 7 to C 17 )/mL. Linear
regression analysis of the calibration curve resulted in a correlation
coefficient of 0.9999. C 7 and C 19 peaks were not Included in the
regression analysis. One calibration standard in the middle of the
linear working range was used as the daily QC standard.
Duplicate injections of the QC standard were performed daily prior
to sample analysis. If the QC standard duplicates differed by more than
15% the Injections were repeated. If the mean QC standard response
differed by more than 15% from the original value obtained, a new
standard was prepared and then analyzed. If the new standard failed to
meet the criteria, the 1nstrt nent was recalibrated. A plot of the QC
standard results Is shown in Figure 5—1.
The GC Injector septum was changed daily, along with a colunn
bake—out at 300°C for twenty minutes. If the detector response was not
stable after column bake—out, this procedure was repeated until
stability was obtained.
Duplicate Injections were performed for all samples analyzed. The
TCO results from both injections could not differ by more than 15%. The
T values were calculated by subtracting the appropriate field blanks
from the total values.
5.3 GC/MS CALIBRATION AND TUNING DATA
The gas chranatograph/mass spectrometer system was tuned to meet
DFTPP criteria every day prior to analysis. Daily analysis was
initiated by a check of DFTPP to verify that the Instrumental tune as
acceptable prior to the analysis of samples. Tuning data are Included
as Appendix J.
The Instrument was calibrated by analysis of five calibration
samples at a concentration of 5, 10, 50. 100, and 200 ng/uL. These
points were Incorporated Into a database and the mean, standard
deviation, and per cent coefficient of variation calculated. The
database Is shown in Table 5—1. A linear regression was performed for
each of the ions for each compound in the calibration standard, with the
A-54
-------
DAILY OC STAN D,A, RD
TUT4L H Ur TUGF APIV RE O t’’
1 — — ____________________ — __________________ ———— — —
________________-— — —-_____________ +15%
0
I.LI (1
-o 2’:’:’
Lii-
ri’ i : ’
rn
UI
ii: ’:
LL
Cs 4
Relative %
Day FID Response Difference
0 256020.5
1 251064.5 1.954702
3 261676.0 2.1848/1
3 264540.5 3.273392
5 290394.5 12.58164
5 280126.0 8.992132
Figure 5—1. ICO QC standard analysis.
A-55
-------
Table 5—1 WCODSTOVES RESPONSE FACTOR DATABASE
Compound SD L ±Z
dln...phenanthrene 188 1.000 0 0
p no1 94 1.203 0.081 6.7 1.041 1.365
naphthalene 128 1.786 0.238 13.3 1.310 2.262
acenaphthylene 152 1.548 0.198 12.8 1.152 1.944
acenaphthene 154 0.940 0.116 12.3 0.708 1.172
fluorene 166 1.010 0.122 12.1 0.756 1.254
nltronaphthalene 127 0.311 0.025 8.0 0.261 0.361
173 0.210 0.022 10.4 0.166 0.254
phenanthrene 178 1.273 0.150 12.6 0.953 1.593
anthracene 178 1.537 0.182 11.8 1.173 1.901
acrldine 179 1.227 0.075 6.1 1.077 1.377
carbazole 167 1.260 0.080 6.3 1.100 1.420
DFTPP 127 0.080 0.004 5.0 0.072 0.088
198 0.161 0.009 5.4 0.143 0.179
fluoranthene 202 1.134 0.147 13.0 0.084 1.428
phenanthrol 194 0.177 0.033 18.4 0.111 0.243
pyrene 202 1.167 0j63 14.0 0.841 1.493
di,...chrysene 240 1.000 0 0
bêiizo(a)anthracene 228 2.054 0.213 10.4 1.628 2.480
chrysene 228 1.816 0.192 10.6 1.432 2.200
benzo(b)fluoranthene 252 1.687 0.185 11.0 1.317 2.057
benzo(k)fluoranthene 252 1.591 0.185 11.6 1.221 1.961
benzo(a)pyrene 252 1.394 0.148 10.6 1.098 1.690
3—methyicholanthreno 268 0.694 0.092 13.3 0.51 0.878
benzo(g,h,1)perylene 276 1.502 0.167 11.1 1.168 1.836
dlbenzo(a,h)anthracene 278 1.192 0.129 10.8 0.934 1.450
lndeno(1,2,3,c,d)pyi-ene 276 1.209 0.151 12.5 0.907 1.511
A-56
-------
exception of pyrenequinone, which could not be chromatographed under the
analytical conditions used. Correlation coefficients are shown In
Table 5—2. The linear plots are Included as Appendix K. Calibration
checks were performed daily prior to sample analysis. Values for the
response factors obtained In the daily calibration checks are shown in
Table 5—3, and compared to the i atabase values. The precision of the
analysis is illustrated by the eight daily analyses of the same standard
(100 mg/uL) , with only phenol exhibiting % CV above 2C and all of the
rest of tne compounds showing % CV less than 15 (Table 5—3).
A check sample containing naphthaleno, phenanthrene, fluoranthene,
pyrene, and chrysene was analyzed daily. The results of the first two
analyses, with relative percent difference, are shown in Table 5—4.
Results for the subsequent days are shown In Table 5—5. DuplIcate
analyses were performed for four samples. These samples were injection
duplicates, not process duplicates, since an entire sample (e.g., the
entire XAD—2 module) was extracted to prepare the sample. Results are
shown In Table 5—6. The GC/MS values for all Blank Runs (field and
solvent) were reported separately. All reported GC/MS sample values
were reported independently of the blank values.
A peak Is observed at approximately 1500 scans In the sample
chromatograms. The mass spectrum, shown in Figure 5—2, is
characteristic of an unsaturated aldehyde. This compound Is not
observed in the solvent blanks (Appendix I, Figures Ii and 12) but
appears to be an artifact associated with the extraction of XAD—2.
Field exposure of the XAD—2 Is not essential, since the compound appears
also In the chranatograms of the internal audit samples consisting of
spiked XAD—2 which was not sent to the field.
5.4 SYSTEMS AND PERFORMANCE AUDIT
A systans and performance audit of the Woodstove Project was
performed by Donna Holder as part of the Internal R.dlan quality
assurance progran. Joann Rice, Nancy Cole and Melinda Dilda provided
input for the systems audit. Denny Wagoner, Joan Bursey, Ed Messer and
Joann Rice were responsible for coordinating the performance audit
analysis.
A-57
-------
Table 5-2. LINEAR REGRESSION, W000STOVE DATABASE
Compound orre1at1on Coefflclent
phenola 94 0.964
naphthalenea 128 0.936
acenaphthy Ienea 152 0.930
acenaphthenea 154 0.922
fluorenea 166 0.923
nltronaphtha lenea 127 0.928
173 0.928
phenanthrenea 178 0.911
anthracene 178 0.903
acrldinea 179 0.886
carbazo ea 167 0.907
fluorantheneâ 202 0.891
phenanthrolä 194 0.924
pyrenea 202 0.884
benzo(a) nthraceneb 228 0.883
chryseneL) b 228 0.875
benzo(b)f luoranthenob 252 0.847
benzo(k)fluoragthene 252 0.901
benzo(a)pyrene b 252 0.886
3—methyl chol anthreneb 268 0.874
benzo(g,h ,1)perylene 276 0.856
blbenzo(a,h)anthraceneb 278 0.862
lndeno(1 ,2 ,3—c d) pyreneb 276 0.853
aRelative to d 10 —phenanthrene.
bRelative to d 12 —chrysene.
A-SB
-------
Table 5-3. DAILY CALIBRATION CHECKS
.I. n tabase 11/12 11/13 11/14 11/15 11/18 U.L19 11/20 11/21 J?& n SD %CV
phenol 94 1.203 1.092 1.258 1.247 ..2l4 1.139 1.000 0.673 0.607 1.029 0.255 24.8
naphthaleno 128 1.786 1.529 1.677 1.657 1.663 1.681 1.544 1.142 1.118 1.501 0.237 15.8
aconaphthylono 152 1.548 1.395 1.422 1.445 1.4U 1.445 1.335 1.158 1.041 1.332 0.151 11.3
acenaphthono 154 0.940 0.849 0.872 0.850 0.881 0.884 0.844 0.747 0.667 0.828 0.079 9.5
fluorene 166 1.010 0.927 0.911 0.943 0.932 0.907 0.889 0.823 0.772 0.888 0.060 6.7
nltronaphthal one 173 0.210 0.227 0.231 0.226 0.230 0.223 0.216 0.198 0.180 0.216 0.018 8.4
phonanthrene 178 1.273 1.178 1.196 1.208 1.221 1.207 1.207 1.189 1.166 1.197 0.010 1.5
anthraceno 178 1.537 1.453 1.496 1.478 1.504 1.521 1.529 1.507 1.518 ].501 0.025 1.7
acridlne 179 1.227 1.238 1.331 1.302 1.329 1.315 1.346 1.337 1.315 1.320 0.019 1.4
carbazole 167 1.260 1.306 1.374 1.289 1.304 1.346 1.277 1.181 1.171 1.281 0.071 5.6
fl.jorantheno 202 1.134 1.116 1.150 1.011 1.098 1.174 1.154 1.260 1.261 1.161 0.070 6.0
phenanthrol 194 0.177 0.216 0.262 0.215 0.211 0.205 0.194 0.201 0.210 0.214 0.021 9.6
pyrene 202 1.167 1.118 1.195 1.104 1.128 1.213 1.223 1.341 1.368 1.211 0.099 8.2
be r.zc C a) Anth
cone 228 2.054 1.888 1.917 1.883 1.662 1.947 1.844 1.744 1.722 1.8S1 0.079 4.3
chrysono 228 1.816 1.684 1.683 1.699 1.723 1.670 1.631 1.630 1.639 1.670 0.034 2.0
benzo(b)fluor—
antheno 252 1.687 1.576 1.557 1.659 1.741 1.645 1.386 1.635 1.830 1.628 0.132 8.1
bonzo(k) fluor—
anthene 252 1.591 1.527 1.411 1.453 1.538 1.355 1.358 1.444 1.703 1.474 0.115 7.8
benzo(a)pyreno 252 1.394 1.381 1.271 1.357 1.411 1.252 1.160 1.307 1.492 1.329 0.104 7.8
3-methyichol—
anthrene 268 0.694 0.872 0.756 0.802 0.863 0.618 0.616 0.641 0.839 0.751 0.111 14.7
benzo(g .h. 1)
poryleno 276 1.502 1.599 1.353 1.451 1.572 1.208 1.241 1.416 1.696 1.442 0.173 12.0
d l be nzo( a. h)
anthraceno 278 1.192 1.314 1.096 1.170 1.297 0.891 1.007 1.199 1.411 1.173 0.171 14.6
Indenoll .2.3—
c,d)pyrene 276 1.209 1.283 1.175 1.186 1.330 1.049 1.006 1.211 1.424 1.209 0.139 11.5
-------
Table 5-4. ANALYSES OF CHECK SAP i_E
F8 50540 F850533
Mean CLC. Q.C.
Response Sample Sample *
Comcound Factor flu.aJ1 Run #2
naphthalene 1.786 1.803 (101) 1.752 (98) 2.9
phenanthrene 1.273 1.320 (104) 1.300 (102) 1.5
fluoranthene 1.134 1.065 (94) 1.027 (91) 3.6
pyrone 1.167 1.176 (101) 1.134 (97) 3.6
chrysene 1.816 1.514 (83) 1.426 (79) 6.7
C )=%Recovery.
‘RPD = Relative % difference between QC Sample Run #1 and Run 2.
+ QC x 100
A-60
-------
Table 5—5. DAILY PER( NT RECOVERIES (CHECK SAMPLE)
C npound
11113
11/14
11/15
11/18
11/19
11/2i
11/21
J? .n
SD
% CV
naphthalene
98
101
100
99
98
73
68
91
14.1
15.5
phenanthrene
102
104
103
103
105
102
102
103
1.2
1.1
fluoranthene
91
94
92
99
98
106
107
98
6.4
6.5
pyrene
97
101
99
107
107
122
122
108
10.4
9.6
chrysene
79
83
83
80
82
79
79
81
1.9
2.3
0 .
-d
-------
Table 5—6. WOODSTOVE DUFtICATES
Total ng Total g
F850530 F650606 BEQ
phenol 2249 1339 50.7
naphthalene 872 654 28.6
acenaphthylene 132 91 36.8
fluorene 36 19 61.8
phenanthrene 165 140 16.4
anthra ne 15
fi uorantheno 57 43 28.0
pyrene 41 32 24.7
F85054]. F850607
phenol 15,329 6,692 75.1
naphthalene 4,391 2,610 50.9
acenaphthylene 713 390 58.5
acenaphthene 77 ——— ——
fluorene 244 95 87.9
phenanthrene 669 508 27.4
anthracene 102
fi ucrantheno 219
pyrene 175
chrysene 92
(continued)
A-6 2
-------
1UNNEL DUPLICATES
F850581 F850570
phano 1568 1452 7.7
naph ha ene 490 461 6.1
acenaphthylene 101 101 0
acenaphthene 10 10 0
fluorene 38 39 2.6
phenanthrene 105 108 2.8
anthra ne 17 18 5.7
fluoranthene 35 38 8.2
pyrene 32 33 3.1
F850594 F850560
pheno 853 506 51.1
naphthaThne 911 872 4.4
acenaphthy ene 335 2 13.4
acenaphthene 13 10 26.1
fluorene 92 78 16.5
phenanthrene 282 258 8.9
anthracene 40 38 5.1
fluorarrthene 99 104 4.9
pyrene 75 84 11.3
benzo(a)anthracefle 21 17 21.1
chrysene 19 16 17.1
benzo(b)fluoranthene 25 20 22.2
benzo(a)pyrene 13 12 8.0
A-63
-------
MASS SPECTRUM
11/14/85 10:49:08 + 25:02
SAMPLE: WOCDSTOUE CS—2 1:10 DILUTION
CONDS.: —
ENHANCED (S 158 2N 01)
55
DATA: F850541 p1502
CAL !: FC43RP *7
BASE P1/2: 55
RIC: 145664.
41
82
15552.
0
67
96
50.0
11/2
103
II
I.
II
124
..ll .
It
158
FIgure 5—2. Artifact peak of GC/MS ana’ysiS.
-------
The systems audit focused on observing the procedures and
techniques used by the laboratory team, a check of dociguentatlon
completeness and a review of team adherence to the QC protocol
prescribed by the Quality Assurance Project Plan (QAPP). Several
modifications to the analytical procedures were made (based on EPA
approval). The memoranda docunenting these changes are Included in this
section as Figures 5—3, 5—4 and 5—5. No other significant procedural
problems were noted. Upon thorough examination of the original and
revised Draft WoodstoveS Report several modifications were made in the
previously reported data. The docunentation of these changes are
addressed via Corrective Action Memoranda that are Included In this
section as Figures 5—6 and 5—7. The systems audit checkli5t is
presented as Figure 5—8.
The performance audit for T O and (iC/MS consisted of six audit
samples submitted blindly to the laboratory for analysis. The first set
of three audit samples were submitted and analyzed simultaneously with
the first set of woodsteve burns. The second set of three audit samples
were submitted at a later date and analyzed along with the last sot of
voodsteve burns. The samples were prepared by spiking approximately
25 grams of XAD—2 packed in resin tubes with a knewn amount of POMs and
PiAs. Two additional blind samples were prepared by Candace Blackley
according to the QAPP for Gravimetric analysis. The overall results of
the performance audit are presented in Tdbles 5—7 and 5-8. The average
recovery for target compounds (PNAs and POMs) was 85 percent for the
Initial set of three audit samples. The final set of three audit
samples showed an average recovery (target compounds) of 89 percent for
both low and high spiked concentrations.
In s mmary. the performance audit showed that the accuracy targets
were met well within the acceptance range. The systems audit confirmed
the laboratory team to be competent and knowledgeable in their tasks,
doc nontation to be completed and current, chain—of-CustOdY procedures
sati sfactory and the prescribed QC protocol to be met to sati sfy the
program objectives.
A-65
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ORANDUM
DATE: November 7. 1985
TO: Robert McCrilIis (EPA—ERC), Raymond Merrill (EPA—ERC),
RlchardCrums (RTI)
F 4: Donna Molder1 *
SUBJECTs Gravinetric Analysis (GRAY) Modifications for Analysis of Vood
Stove En iss1on Samples
Per a phone conversation bett een Ed I4esser (Radian) and Ray Merrill
(EPA) on November 1. 1985, the Gravimetric (GRAY) analysis for the Wood
Stove Emission Samples wifl be modif led as followsi
The Soxhiet methylone chloride end the contents of the separatory
funnel (condensate, tie Cl, Rinse Condensate Impinger, Impinger 1120.
and Me Cl, Rinse Impinger? will be combined and sdjusted to 10.0 ii
total voltne, Instead of the original 250.0 a . total volume. The
minimum requirement for total mass of sample t.as also been changed
from 10.0 og to 1.0 n total weight. This procedure Is depicted in
the attached figure.
This modification was a result of analyzing three Radian Audit
Samples and screening several eoodstove extracts at the original 250 i .
volume. The Audit Samples t ere submitted to the laboratory to evaluate
the method performance. These were prepared and analyzed upfront prior
to actual samDle analyses. Preliminary GRAY and TCO (Total
Chromatographable Organics) analyses tiero unable to detect the spiked
concentrations within the linear working range of the standard curves,
1n iIcat1ng the need for further concentration of the samples.
Figure 5—3. Gravimetric analysis (GRAy) modifications
-------
Figure 5-3. Continued
A-67
Preflminary ICO
0.1 — 10 mg/mL
Preliminary GRAy,
Mlnmum 1.0 my
Total Weight
-------
MEMORANDUM
DATE: November 19, 1985
TO: Ray Merr,fl (EPA), Robert McCrllIls (EPA), and Richard Crume (Rh)
FROM: Donna J. Holder
SUBJECT: Modification to Woodstoves QAPP
The procedure for the calibration of the gas chromatograph/maSS spectrometer
should be amended to read as follows:
A five—point calibration, with a single value at each concentration level,
will be used to calibrate the gas chromatograph/maSS spectrometer system.
Triplicate values for one of the calibration points (one analysis cn each of
three successive dais) will be used to assess analytical precision; rn an,
standard deviation, and percent coefficient of variation will be calculated.
A linear regression will be performed for each of the points of the or 4 glnal
calibration curve and the value of the correlation coefficient will be
reported.
If you have any questions please call J. I3ursey or E. Messer at 481—0212.
Figure 5-4. Modification to woodstove QAPP.
A-68
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TO: Dr. Ray Merrill (EPA), Dr. Robert McCrillis (EPA),
Richard rume (RI!)
FROM: Donna Holder (Radian)
DATE: December 2, 1985
SUBJECT: Gas chromatograph Calibration for Total ChromatograPhable Organics
(TCO) Analysis (Modification to Calibration Curve).
As per the standard operating procedure for TCO analysis, a multi-point
calibration curve was performed that covered the range from 0.37 mg/rnL to
37.04 mg/mL total chromatograPhable organicS. A five point calibration curve
was used. A linear regression calculation was performed using the five GC
responses obtained for the five concentrations on the curve. The results are
given below:
Slope 156960.1
Intercept 153969.9
Corr. Coefficient 0.9949
The intercept generated from the regression calculation was relatively large
(153969.9). The Intercept is used to calculate TCO amounts by subtracting it
from the GC response for a particular sample. TCO analysis of sample blanks
resulted In small GC response values. Therefore, when the intercept wds
subtracted from blank values to determine TCO amounts, negative values were
obtained.
The TCO linear regression line was plotted to determine if any of he points
were significantly skewed. The highest concentration point were significantly
skewed. The highest concentration point analyzed deviated noticeably from the
regression line and was causing the intercept of this line t3 be large. Since
few samples had TCO values In this range, th. highest point was dropped and
the linear regression was repeated. The v Iues are given below:
Slope 181284.5
Intercept 20327.5
Corr. Coefficient 0.9999
All TCO values were calculated and reported using the slope and intercept of
the four point calibration. The sample blank values obtained were
approximately zero mg/mi.
Figure 5—5. Modification to TCO analysis.
A-69
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MEMORANOIJM
DATE: December 13, 1985
TO: Dr. Ray Merrill (EPA), Dr. Robert McCrlllis (EPA) , and Joe
Evans (RTI)
FROM: Donr 1 a Holdert ’k
SUBJECT: Gravimetric (GRAV) Analysis Corrections
In reviewing the GRAY filter data. two changes were made that
resulted In ne values for several samples. The changes are as follows:
1) Due to a number of blank samples with unusually high
values, the GRAY filters were reweighed. It was noticed
that labels with the Radian number and sample ID were
placed on the petri dish bottom. This resulted In the dish
weights approximately 100 mg higher. All petri dishes with
labels on the bottom were reweighed three times (without the
fllters)——first with the labels on them; second, after the
labels were removed and the petri dish bottom was cleaned with
acetone (NOTE: The filter number from Engineering Science was
NOT removed.); and third, after two hours to reach constant
weight (wIthin 0.5 mg). The second and third weights were
averaged and then subtracted from the first weight to get the
1 .bal’s weight. The label weight was then subtracted fran the
GRAY value to get the correct filter weight.
2) Upon ox vninatiofl of filter tare weights provided by
Engineering Science. Radian found several tare weights that
had been miscalculated. As a result. all filter tare weights
were chocked and any necessary corrections made.
If you have any questions, please call Melinda Dilda or Ed Messer
at (919) 481—0212.
Figure 5—6. GRAV analysis corrections.
A-7 0
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ME RAND11M
los Donna Holder (Radian QW )
From: Joan Bursey (PFK GC/P’IS)
Subject: GC/14S Unit Correction In olving Woodstoves Program
Dates January 10, 1986
For the first series of analyses of P014 and phenol. an error was made In
the calculations. The value as originally obtained from the GC/HS
determination Is expressed as ng/uL. which is equivalent to ug/zL. This
value is then multiplied by the total number of ml In the sample to
obtain a value of micrograms per total sample. In order to perform a
calculation Involving the number of ml. of sample to obtain the total
weight of material per sample, a conversion of units must take place.
Otherwise, the multiplication should be by a factor of 10,000. for
example, for a 10 ml 5ample. Hot ever. the multiplication was performed
but the units written after the multiplication were consistently
nanograms rather than micrograms. The result Is that the digits as
reported In the data tables are correct but the units are Incorrect:
the units should be reported as micrograms per total sample . not
nanograms.
cc: Ed I4esser
Denny Wagoner
Iigure 5—7. GC/MS Unit Correction.
A- il
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ANALYSIS OF U000 STOVE EMISSION SAMPLES
TECHNICAL SYSTEMS AUDIT
CHECKLIST
Site: PPK Laboratory Date: December 2. I9
Contract: 203-0Z3-38-OI Auditor: 0. J. Holder
YES NO CO IENTS ITEM
ORGANIZATION AND PERSONNEl. .
1. Project Manager: Susan Fernandes
Project Director: £d Messer
2. Task Leaders:
Sample PreparatIon: J. McGauahev
GC/TCO: J. Rice____________
GC/MS: J. Bi.irsey
GRAV: N. Oildp
SAMPLE HANDLING/STORAGE
1. Are SOPS available for sample
custody?
• logging samples
- storing samples
- dispersement
x 2. All samples logged In manually and
through SAM?
3. All samples labelled appropriately
(log-In date, disposal date, client,
etc.) before refrigeration?
_____ Bottles are 4. All completely analyzed samples
marked with an stored separately In the refrigerator
eXD to indicate with holding time requirements?
that they have
been analyzed.
_____ Stored in the 5. Are all TCO samples stored In
freezer. refrigerator at or below 4 0 C?
_____ All GRAY samples 6. Are all dry GRAY samples stored
are stored in a in a dessicator?
dessicator until
weighed.
Figure 5—a. Systems audit checklist.
A-72
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YES NO COMNENTS ITEM
7. Are all CC/MS samples stored
in a refrigerator or freezer?
8. Are all diluted samples labelled
with diluted sample container
label containing the appropriate
information (date, solvent,
Radian ID number, dilution
factor, new concentration,
analyst’s Initials)?
9. Are standards stored separately
in the refrigerator?
10. Is the refrigerator checked
monthly for expired sample dates?
CA1I8RJ TION PROCEDURES
_ x _ C 7 - C 17 1. QuantitatIve calibration using
stock solution of decane,
dodecane, and tetradecane?
0.99 usually the 2. CalibratIon curve linear with
standard. correlation coefficient O.97 for
acceptance?
_____ Daily QC standard 3. CalIbration frequency documented?
calibration records.
4. CalibratIons recorded In a
permanent record?
GRAY
1. AnalytIcal balance calibrated
to tO.1 mg accuracy against a
certified standard?
2. Frequency of calibration well
documented?
3. Balance calibrations recorded
in a permanent record?
Figure D—8. Continued
A-i 3
-------
YES NO CO11MEI’ TS ITEM
4. Is all apparatus that contacts
a COncer trated or evaporated
residue sample glass, teflon,
aluminum, or steel?
1. Is calibration curve verified
daily by measuring one or more
calibration standards ( ±15% of
true value as acceptable)?
2. Frequency of calibration well
documanted?
3. Are calibration data kept in a
permanent record?
QU UTY CONTROL PROCEOURE
T(Qj çhec ks
1. Is a daily bakeout done and a
QC sample analyzed to test for
Contamination?
2. If contamination is Suspected,
or duplicates of a sample show
increasing concentration 15%, is
a reagent blank analyzed?
3. If contamination Is fou 8 d, is the
column baked out at 270 C for 20
Lilnutes and Is a blank check
repeated?
4. Is a QC sample run daily (to
check C 7 -C 17 window)?
5. Is a reagent sample run for each
new reagent batch?
Auto-sampler used. 6. Is the needle flush2d with
Place a flush vial solvent (Oichloromethane) between
between samples but Injections?
not between duplicates.
Figure 5—8. Continued
A-74
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YES NO COMMENTS ITEM
7. Is the GC Inlet septum changed
daily?
GRAV DC Check.s
1. Is analyst proficiency
demomstrated prior to testing
(following SOP guidelines)?
Opens from the top. 2. Is the dessicating cabinet have a
Sealing around It. sealtight door with gum rubber
(no silicon sealant)?
_____ Done in the hood. 3. Is the evaporation of samples
carried out in an area clean of
airborne dust and organic vapors?
_____ Entire sample is used 4. ? re all samples analyzed In
much of the time, duplicate by the same analyst?
5. Is a method blank analyzed In
duplicate ’ for each new solvent
lot or sample set?
6. Are 2 reagent blanks analyzed
each day samples are run?
7. If a sample needs to be re-
analyzed but insufficient sample
remains, Is the initial resilt
reported with a qualifying
statement?
CC/MS DC Checks
1. Does each sample set
( lO samples) include a method
blank and sample duplicate?
2. Are the following QC samples
analyzed:
-surrogates
-Internal standards
-duplicates
-glassware blank
-matrix spike
-system performance standard (MS)
Figure 5.8. Continued
A-i 5
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YES NO COt ’ 1ENTS LIE u
3. Is the GC column and sample inlet
system evaluated using the
appropriate standards?
4. Is the MS performance evaluated
using the following:
- standards
-daily response factors (using
standards)
-Peak width evaluation ( 5 scans
wide at a concentration of 50
ug/mL)
5. Are at least 10% of all samples
spiked and analyzed to monitor
data quality?
6. Are at least 10% of all samples
analyzed QC checks?
7. Are all QC data accessible for
all GC/f4S analytical result)?
8. Are QC results kept in a
permanent record?
GENERAL OC Checks
x 1. Uave standards been analyzed
periodically to verify that each
analytical method Is In control?
2. Do QC records Indicate corrective
action taken on data that has
been rejected?
3. Are questionable results
considered acceptable by
authorized persons (chemist,
engineer, etc.)?
4. Are all QC data accessible for
all analytical results?
Figure 5.8. Continued
A-76
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YES NO COM?IENTS ITEM
PREVENTIVE 1AINTENANCE
GENERAL PROCEDURES
1. Are system operating
(manufacturer’s) manuals
available?
_____ Maintenance logbcok 2. Are preventive maintenance
for each Instrument, activities (service calls)
documented in standard forms?
_____ Maintained by the 3. Are permanent service records
Task Leader, for all instruments available and
maintained (logbooks)?
Project Director and 4. Do s the laboratory supervisor
Task Leader. moiiitor supplies and maintain a
purchase order file?
5. Is a storeroom available for
Inventory of spare parts?
6. Are the following general on-
hand laboratory supplies
maintained?
-printer paper
-printer/plotter supplies
-magnetic tapes
-ultrasonic bath
-centrifuge
-olgital voltmeter
-electrical connectors and
supplies
7. Are the following GC supplies
Inventoried:
-fused silica capillary columns
-glass packed columns
-carrier gas
•secondary gases
-glass%.are
Figure 5.8. Continued
-------
YES NO COMMENTS ITEM
-dilution glassware
-drurnmond pipettes
-syringes with replacement parts.
8. Are the following MS maintenance
procedures performed:
-Evaluation of ion source
performance (history profile,
routine cleaning)
-quadruple performance (mass
peak shape, isotope abundance
and ratios)
-Electron Multiplier Performance
(history profile, replacement)
-Overall performance (repeller
voltage, high mass peak shape,
operating vacuum, ultimate
sensitivity, background noise,
signal-to-noise ratio, etc.)
DOCUMENTATION PROCEDURES
GENERA1
1. Are all samples accompanied by
sample tracking form and
appropriate signatures?
N/A 2. Do sample worksheets contain all
pertinent information, including
methods of dilution or
concentrati cm?
3. Do all instruments have
documented troubleshooting
procedures?
4. Are Instrument modifications
well -documented?
Figure 5.8. Continued
A-78
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YES NO COMMENTS ITEM
I. Q TORY NOTEBOOKS
1. Is permanent ink used for all
entries and sample worksheets?
2. Are changes In entries iade by a
single line drawn though the
incorrect Information, dated and
Initialized?
3. Are reporting units for data
specified where appropriate?
4. Are repeat analyses recorded
properly?
_____ Maintained In a 5. Do lab notebooks contain all
general project pertinent Information such as:
file.
-chromatograms
-spectra information
-Instrument parameters
-copies of simple log-in sheet
-calculations
-dilution factors
- instrument probl ems
-maintenance measures
-hardware changes
6. Is electronic data storage
available?
N/A 7. Are all Internal standards and
surrogate spikes documented on
sample worksheet forms?
N/A 8. Are all sample worksheets
reviewed, signed, and dated by
appropriate member of the GC/MS
group?
9. Are all notebooks for the project
maintained in one central file?
Figure 5.8. Continued
A-79
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YES NO CO IENTS ITEM
_____ x Information is 10. Are all problem . encountered
recorded in documented on standard forms?
appropri ate logbook.
____ _____ 11. Is a corrective action file
maintained?
Figure 5.8. Concluded
A-80
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Tab’e 5—7. QA/QC AUDIT GC/MS SAMPLES
Audit 1 (9872) Audit 2 (9873) Audit 3 (9874)
True Measured Percent True Measured Percent True Measured Percon
TARGET Conc. Conc. Recovery Conc. Conc. Rocovery Conc. Conc. Rocovery
COMPOUND (ng/uL) (ng/uL) (S) (ng/uL) (ng/uL) (%) (ng/ul) (ng/uL) (%)
Phenol 0 Trace 200 132.0 66 1,000 725.9 73
Napthalene 0 Trace 200 142.1 71 1,000 721.0 72
Acenephylene 0 0 200 161.3 81 1,000 811.9 81
Acenephthene 0 0 200 163.6 82 1.000 821.9 82
Fluorone 0 0 200 171.0 86 1,000 824.5 92
N ltron aphthalene 0 0 — — — — — —
Phenanthrene 0 0 200 187.0 94 1,000 661.9 86
Anthrocene 0 0 200 120.7 60 1,000 714.6 71
Acridlne 0 0 — — — — — —
Carbezole 0 0 — — — — —
Fluoranthene 0 0 200 130.3 65 1.000 670.8 87
Phenanthrol 0 0 — — - — — —
Pyrene 0 0 200 123.7 62 1,000 85
Benzo(a)enthracere 0 0 200 182.0 91 1.000 869.5 87
Chrysene 0 0 200 157.6 79 1.000 824.1 82
Benzo(b)fluoranthene 0 0 200 198.3 99 1,000 863.8 66
Oenzo(k)fluoranthene 0 0 200 185.4 93 1,000 911.0 91
Benzo(a)pyrene 0 0 200 208.5 104 1.000 927.3 93
3—Lethyichelanthrene 0 0 — — — — — —
Bonzo(g,h.1)pery lene 0 0 200 211.6 106 1.000 921.1 92
D lbenzo( a,h)anthracene 0 0 200 222.2 111 1,000 992.7 99
Indeno(1,2.3—cd)pyrene 0 0 200 227.3 114 1.0u3 946.9 95
Continued
-------
Table 5 —7. tLA/QC AUDIT GC/MS SAMPLES
AudIt 4 (11165) Audit 5 (11166) ‘ Audit 6 (11167) +
Truo Measured Porcent True Measured Percent True Measured Percent
TARGET Conc. Conc. Recovery Cooc. Conc. Recovery Conc. Conc. Rocovery
COMPOUND (ng/uL) (ng/uL) ( 5) (ng/uL) (ng uL) CS) (nc/ui) (ng/uL) ( 5)
Phenol 0 0 201.3 127.2 63.2 2013 1378 68.4
Napthalene 0 0 300.0 336.0 112 1000 1054 105
Acenaphylene 0 0 300.0 266.3 60.8 1000 910.0 97.0
Acenaphthene 0 0 300.0 262.1 87.4 1000 787.8 76.8
Fluorone 0 0 300.0 287.7 95.9 1000 1065 107
Nitronaphthalono 0 0 201.4 262.1 130 2014 1574 78.2
Phonanthrene 0 0 300.0 292.9 97.6 1000 1079 108
Anthracecie 0 0 300.0 245.5 81.8 1000 861.2 86.1
Acr1o no 0 0 402.0 400.5 101 1500 1132 115
Carbazole 0 0 404.8 389.7 96.3 1518 1491 98.2
Fluoranthene 0 0 300.0 278.0 92.7 1000 1029 103
P enenthrol 0 0 400.2 — 0.0 1501 47.6 3.2
r’yrene 0 0 300.0 301.1 100 1000 1062 106
Bonzo(a)anthracone 0 0 300.0 290.0 96.1 1000 988.0 98.8
Chrysene 0 0 300.0 293.0 97.7 1000 1008 101
Bonzo(b)fluoranthene 0 0 300.0 275.5 91.8 1000 1026 103
Benzo(k)fluoi-anthene 0 0 300.0 254.6 64.9 1000 945.3 94.5
Benzo(a)pyrene 0 0 300.0 234.2 78.1 1000 811.5 81.2
3—methylcholanthrene 0 0 200.8 85.2 42.4 2006 449.1 22.4
Benzo(g.h.1)perylone 0 0 300.0 287.0 95.7 1000 1095 110
Dlbenzo(a,h)anthracene 0 0 300.0 310.2 103 1000 1131 113
Indeno(1.2.3—cd)pyrene 0 0 300.0 284.2 94.7 1000 1108 111
concluded
* All PAN’s S 300
+ All PAN’s 5 1000
-------
Tsble 5—8. QAIQC AUDIT TCO AND GRAY
SAMPLE AREA AREA PERCENT 1 1EA4 SAMPLE TOTAL
1.0.1 COUNTS — COUNTS 01FF. AREA CTS. Hg/Fl VOL (sl)
10251—B 14000 12124 14.362 13062 + I
Audit 1 6222 5800 1.020 6011 0.03 * 1 0.03 *
(9812)
Audit 2 116196 115812 2.038 111)04 0.62 • 1 0.62 ‘
(9873)
Audit 3 499919 454941 9.433 477460 2.54 U 1 2.54 ‘
(9874)
Audit 4 50314 55860 10.447 53087 0.08 ‘ S 0.04 •
(11165)
Audit S 109225 105423 3.543 107324 0.37 • 5 1.85
(11166)
Audit 6 311201 322811 3.662 317006 1.50 ‘ S 7.50 U
(11167)
+ So’vent Blank
a Total ag/aL calculated using daily response factor.
GRAY
TEST
1
THEORETICAL
mg/aL
1.21
EXPERIMENTAL
og/mi
1.20
ACCURACY
—
—0.83
2
1.21
1.16
—4.13
3
1.04
LOS
0.96
4
1.04
1.10
5.77
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