» jv i * 1 i /
^fV-
wV-
•^"LdxA.
. X^
Vi^
f^/?
.66?
-------
Page
2 of 5
Date
R - Reconnended
H « Mandatory
4. M-3 sampling train check:
^nitiai \nj
(should bold
1U in* vacuuni tznaz \nj
for- 1/2* mm.)
PntTjje sample train* with* stack* gas
• • ' Constant* rate* sampling l- -jar
5. Time* test- started- • *
• Time tear ended
6. Dry gas (* • )j5ort* initial
meter ...... ffrM,^
volume: (• * * )• port- initial *.-• *
final • * •
( * )• port- initial
• • * final
'")-'•)•> Q*
/ yj'lo
Test
/n*** 7i» /
•AJ/4
-A) /A •
• • yf/yp
LL»_>»
• -vT^c^
'/ft'ZLJD ^M
fStfK
Test
Pitn
/ i^^y »J
so/rf-
•fi)//r -
• 'A) f ft •
' ' u'^>1 ' '
• • •Kfoji'
• SofLb'Ad
Test
Run
3
/^Zo'3/9
• •^->--
• •—•• • •
ft*9', 6/1-
1 "*""*.'!'
. . . ._._. .
Test
Run
4
^.'..' : : ::H
BVVii-seisU-IMHIUBiHM
7. Train operation Nozzle changed
during run during run —
AtO
pitch- and- yaw of- probe- o*.k-. j- -s~te& '
nozzle* not scraped* on* nipple
effective- seal- around- probe
prooe moved- at- proper- tune
probe .heated* * • • • •
calculator constants or nomograph
changed when TS and /or TM
changea- significantly*
average time to set
isokenetics after probe
Average values:
impinger temperature
should* be-< 70T
from filter holder while in
stack?
" **?*&' '
~ ~<**L>*' '
•^Pexj
- -->*lj>_A
V
\ / t*1***-
>•
^ .
**MZS —
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• '^t^LA '1
' -ty*A '
i ....
t • - • •
< AoJiit
.^.
**,
-
398 t J?^ h .,-.
/JO
AJ o
Ad
*Jfi '
-------
Page
uUsHwwSi,
3 of 5
Dace
R • Recommended
M - Mandatory
Check on filter holder loosening of
damning device holder
was silica gel changed
during run?
was any partieuiate lost?
Accurate /IP
readine of? AH
-Q-CA*£) '
Test
Run
Af-3-lf
-/oo
Tesc
Run
3
t
. AA/Miniamm sample tine of • • • y- mia. nee
' <*VN. Minimum sample volume of • \y- dacf collected
8. Post test: -• Al' openings- sealed
- recovery area- clean- sheltered .........
- filter handled- with- gloves-.- foreens- •
- petri- dish sealed, labeled
- anv samoe lose
vater- measured-
grad cyl.
weighed
si,
v nee-
- condition - color-
4.
tHLw_*^
0
- probe- cooled- surtlcienely
- nozzle* removed- and* br«*h«d
• probe brushed* 6- cin»«
— nozzle* brushes* clean
. , - vash bottles clean*
r-> - M-8 15- mxnnte- -ouree
"^-^ - blank taken: acetone-, vacer- other* *
cao-ped-
l-aoeied
Sealed
*-M
•ji
•^
"A
•^
*
• ^
r%T
jW *
iJ»' "
•64 ' *
Sh1
77"
•
• A
Ji
>ra*/j
**iJi "
s&a '
if*-
4"! '
^
jU • •
***"
* • • • • •
•
• •
...
. . . .
•
euw^ kartO
— «--»>U-uuJl OS&
-------
-
Dace
R " Reconaended
M " Mandatory
9. Post test Orsat Analysis of Initial (M*
analyzer - Analyzer leak check
(levels should not fall below Final (M)
0.2 mL in- bnrrette for- 2- min-.) •
Orsaf samples? • Each bar analyzed- 3- times-
Z CO-> agrees- trir.nin- Q-.2I
S- CO- agrees- within- 0-.2X
checked against air- (20; 9- +• 0-.3)
COoZ
cox-"r
' Z C0»»
^range-for- fuel
Orsat- analysis- valid
Orsac aoluciona changed
«hen calcalated F0
exceeds fuel type -range •
All samoiing* comoonents* clem- anrf- •••4o«4- • •
- Orsac "
- Run- isoicenetic TeaWobmerver-
1-m
Test
Run
$W
v
• VLM
a
-rfn
l^e^- -
-*f-
UJ2>4
V
A>/A
cfA: ^-J
-^
?-JfW
Test
Run
3 ^
•M-3t*
]W
V-U^
UJL/ • •
:%**::
"v^~
•d,?. •
-^-
•ti/A •
•/J//f- •
UU>, '
•^M.
w-«--p_^
Page
Test
Run
3
.
'•
1
f
r
\
'• r
!•
y it IT?*
4 of 5
Test
4
l
• -
K • •
. ...
1^
*-v^Ai<
RT I f
U
-------
Page
o of 5
J. NOTES: Care should be taken, when sampling for organic compounds, to
follow stringent quality control guidelines to avoid contamination of the
sample and sampling train. Take note of any occurences which could bias
the sample in any manner.
Include: (1) General comments; (2) Changes to pretest agreement vith
justification; (3) Identify (manufacturer) and describe condition of
sampling equipment; (4) any abnormal occurrences during test program.
(Additional page(s) attached: Yes _; , No
Signature of Observer
CD
~ K /j_
Affiliation of Observer
Date
-------
APPENDIX G
PARTICIPANTS
-------
PROJECT PARTICIPANTS
Affiliation
USEPA
EMC
BSD
PES
ATS
DEECO
ERG
FAL
Quanterra
LabCorp
RTI
ABC Coke
Name
John C. Bosch, Jr.
Alfred E. Vervaert
Lula H. Melton
John T. Chehaske
Franklin Meadows
Daniel F. Scheffel
Dennis P. Holzschuh
Ron Kolde
Dennis P. Becvar
Dennis D. Holzschuh
Troy A. Abernathy
Gary M. Gay
Amanda Richcreek
Steven B. Blaine
Paul T. Siegel
Steve Terrell
Richard Durham
Marc Hamilton
Joan T. Bursey
William H. Wadlin
Robert Weidenfeld
Marvin Branscome
Sandy George
Stacy Molinich
John Pearson
Mark Poling
Bruce Wise
Responsibility
Work Assignment Manager
Group Leader
Process Monitor and Observer
Program Manager
Project Manager
Field Team Leader
QA Coordinator
Sample Recovery
Laboratory Audit
Field Team Member
Field Team Member
Field Team Member
Field Team Member
Field Team Member
Field Team Member
CARB Method 429 Sample Transport
Sample Recovery
QAPP
PM/MCEM Analysis
Metals Analysis
PAH Analysis
NIOSH PAH Analysis
EPA/ESD Contractor
EPA/ESD Contractor (Observer)
EPA/ESD Contractor (Observer)
President
Manager, Engineering Environmental Compliance
Facility Testing Coordinator
-------
APPENDIX H
SAMPLING AND ANALYTICAL PROCEDURES
-------
EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
Method 1 - Sample and Velocity Traverses for Stationary Sources
1. PRINCIPLE AND APPLICABILITY
1.1 Principle. To aid in the representative measurement of
pollutant emissions and/or total volumetric flow rate from a
stationary source, a measurement site where the effluent stream is
flowing in a known direction is selected, and the cross-section of
the stack is divided into a number of equal areas. A traverse
point is then located within each of these equal areas.
1.2 Applicability. This method is applicable to flowing gas
streams in ducts, stacks, and flues. The method cannot be used
when: (1) flow is cyclonic or swirling (see Section 2.4), (2) a
stack is smaller than about 0.30 meter (12 in.) in diameter, or
0.071 m2 (113 in.2) in cross-sectional area, or (3) the measurement
site is less than two stack or duct diameters downstream or less
than a half diameter upstream from a flow disturbance.
The requirements of this method must be considered before
construction of a new facility from which emissions will be
measured; failure to do so may require subsequent alterations to
the stack or deviation from the standard procedure. Cases
involving variants are subject to approval by the Administrator,
U.S. Environmental Protection Agency.
2. PROCEDURE
2.1 Selection of Measurement Site. Sampling or velocity
measurement is performed at a site located at least eight stack or
duct diameters downstream and two diameters upstream from any flow
disturbance such as a bend, expansion, or contraction in the stack,
or from a visible flame. If necessary, an alternative location may
be selected, at a position at least two stack or duct diameters
Prepared by Emission Measurement Branch EMTIC TM-001
Technical Support Division, OAQPS, EPA
-------
EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
downstream and a half diameter upstream from any flow disturbance.
For a rectangular cross section, an equivalent diameter (De) shall
be calculated from the following equation, to determine the
upstream and downstream distances:
p= 2LW
e (L + W)
Eq. 1-1
Where
L = Length and W = width.
An alternative procedure is available for determining the
acceptability of a measurement location not meeting the criteria
above. This procedure,
determination of gas flow angles at the sampling points and
comparing the results with acceptability criteria, is described in
Section 2.5.
2.2 Determining the Number of Traverse Points.
2.2.1 Particulate Traverses. When the eight- and two-diameter
criterion can be met, the minimum number of traverse points shall
be: (1) twelve, for circular or rectangular stacks with diameters
(or equivalent diameters) greater than 0.61 meter (24 in.); (2)
eight, for circular stacks with diameters between 0.30 and 0.61
meter (12 and 24 in.); and (3) nine, for rectangular stacks with
equivalent diameters between 0.30 and 0.61 meter (12 and 24 in.).
When the eight- and two-diameter criterion cannot be met, the
minimum number of traverse points is determined from Figure 1-1.
Before referring to the figure, however, determine the distances
from the chosen measurement site to the nearest upstream and
downstream disturbances, and divide each distance by the stack
Prepared by Emission Measurement Branch EMTIC TM-001
Technical Support Division, OAQPS, EPA
-------
EMTIC TM-001 EMTIC NSPS TEST METHOD Page 3
diameter or equivalent diameter, to determine the distance in terms
of the number of duct diameters. Then, determine from Figure 1-1
the minimum number of traverse points that corresponds: (1) to the
number of duct diameters upstream; and (2) to the number of
diameters downstream. Select the higher of the two minimum numbers
of traverse points, or a greater value, so that for circular stacks
the number is a multiple of 4, and for rectangular stacks, the
number is one of those shown in Table 1-1.
2.2.2 Velocity (Non-Particulate) Traverses. When velocity or
volumetric flow rate is to be determined (but not particula'te
matter) , the same procedure as that used for particulate traverses
(Section 2.2.1) is followed, except that Figure 1-2 may be used
instead of Figure 1-1.
2.3 Cross-Sectional Layout and Location of Traverse Points.
2.3.1 Circular Stacks. Locate the traverse points on two
perpendicular diameters according to Table 1-2 and the example
shown in Figure 1-3. Any equation (for examples, see Citations 2
and 3 in the Bibliography) that gives the same values as those in
Table 1-2 may be used in lieu of Table 1-2.
For particulate traverses, one of the diameters must be in a plane
containing the greatest expected concentration variation, e.g.,
after bends, one diameter shall be in the plane of the bend. This
requirement becomes less critical as the distance from the
disturbance increase's; therefore, other diameter locations may be
used, subject to the approval of the Administrator.
In addition, for stacks having diameters greater than 0.61 m (24
in.), no traverse points shall be within 2.5 centimeters (1.00 in.)
of the stack walls; and for stack diameters equal to or less than
0.61 m (24 in.), no traverse points shall be located within 1.3 cm
(0.50 in.) of the stack walls. To meet these criteria, observe the
procedures given below-
2.3.1.1 Stacks With Diameters Greater Than 0.61 m (24 in.). When
any of the traverse points as located in Section 2.3.1 fall within
2.5 cm (1.00 in.) of the
stack walls, relocate them away from the stack walls to: (1) a
distance of
2.5 cm (1.00 in.); or (2) a distance equal to the nozzle inside
diameter, whichever is larger. These relocated traverse points (on
each end of a diameter) shall be the "adjusted" traverse points.
-------
EMTIC TM-001 EMTIC NSPS TEST METHOD Page 4
Whenever two successive traverse points are combined to form a
single adjusted traverse point, treat the adjusted point as two
separate traverse points, both in the sampling (or velocity
measurement) procedure, and in recording the data.
2.3.1.2 Stacks With Diameters Equal To or Less Than 0.61 m (24
in.). Follow the procedure in Section 2.3.1.1, noting only that
any "adjusted" points should be relocated away from the stack walls
to: (1) a distance of 1.3 cm (0.50 in.); or (2) a distance equal to
the nozzle inside diameter, whichever is larger.
2.3.2 Rectangular Stacks. Determine the number of traverse points
as explained in Sections 2.1 and 2.2 of this method. From Table 1-
1, determine the grid configuration. Divide the stack cross-
section into as many equal rectangular elemental areas as traverse
points, and then locate a traverse point at the centroid of each
equal area according to the example in Figure 1-4.
If the tester desires to use more than the minimum number of
traverse points, expand the "minimum number of traverse points"
matrix (see Table 1-1) by adding the extra traverse points along
one or the other or both legs of the matrix; the final matrix need
not be balanced. For example, if a 4 x 3 "minimum number of
points" matrix were expanded to 36 points, the final matrix could
be 9 x 4 or 12 x 3, and would not necessarily have to be 6 x 6.
After constructing the final matrix, divide the stack cross-section
into as many equal rectangular, elemental areas as traverse points,
and locate a traverse point at the centroid of each equal area. The
situation of traverse points being too close to the stack walls is
not expected to arise with rectangular stacks. If this problem
should ever arise, the Administrator must be contacted for
resolution of the matter.
2.4 Verification of Absence of Cyclonic Flow. In most stationary
sources, the direction of stack gas flow is essentially parallel to
the stack walls. However, cyclonic flow may exist (1) after such
devices as cyclones and inertial demisters following venturi
scrubbers, or (2) in stacks having tangential inlets or other duct
configurations which tend to induce swirling; in these instances,
the presence or absence of cyclonic flow at the sampling location
must be determined. The following techniques are acceptable for
this determination. Level and zero the manometer. Connect a Type
S pitot tube to the manometer. Position the Type S pitot tube at
each traverse point, in succession, so that the planes of the face
openings of the pitot tube are perpendicular to the stack cross-
-------
EMTIC TM-001 EMTIC NSPS TEST METHOD Page 5
sectional plane; when the Type S pitot tube is in this position, it
is at "0° reference." Note the differential pressure (Ap) reading
at each traverse point. If a null (zero) pitot reading is obtained
at 0° reference at a given traverse point, an acceptable flow
condition exists at that point. If the pitot reading is not zero
at 0° reference, rotate the pitot tube (up to ±90° yaw angle),
until a null reading is obtained. Carefully determine and record
the value of the rotation angle (a) to the nearest degree. After
the null technique
has been applied at each traverse point, calculate the average of
the absolute values of a; assign a values of 0° to those points for
which no rotation was required, and include these in the overall
average. If the average value of a is greater than 20°, the
overall flow condition in the stack is unacceptable, and
alternative methodology, subject to the approval of the
Administrator, must be used to perform accurate sample and velocity
traverses. The alternative procedure described in Section 2.5 may
be used to determine the rotation angles in lieu of the procedure
described above.
2.5 Alternative Measurement Site Selection Procedure. This
alternative applies to sources where measurement locations are less
than 2 equivalent or duct diameters downstream or less than one-
half duct diameter upstream from a flow disturbance. The
alternative should be limited to ducts larger than 24 in. in
diameter where blockage and wall effects are minimal. A
directional flow-sensing probe is used to measure pitch and yaw
angles of the gas flow at 40 or more traverse points; the resultant
angle is calculated and compared with acceptable criteria for mean
and standard deviation.
NOTE: Both the pitch and yaw angles are measured from a line
passing through the traverse point and parallel to the stack axis.
The pitch angle is the angle of the gas flow component in the plane
that INCLUDES the traverse line and is parallel to the stack axis.
The yaw angle is the angle of the gas flow component in the plane
PERPENDICULAR to the traverse line at the traverse point and is
measured from the line passing through the traverse point and
parallel to the stack axis.
2.5.1 Apparatus.
2.5.1.1 Directional Probe. Any directional probe, such as United
Sensor Type DA Three-Dimensional Directional Probe, capable of
measuring both the pitch and yaw angles of gas flows is acceptable.
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EMTIC TM-001 EMTIC NSPS TEST METHOD Page 6
(NOTE: Mention of trade name or specific products does not
constitute endorsement by the U.S. Environmental Protection
Agency.) Assign an identification number to the directional probe,
and permanently mark or engrave the number on the body of the
probe. The pressure holes of directional probes are susceptible to
plugging when used in particulate-laden gas streams. Therefore, a
system for cleaning the pressure holes by "back-purging" with
pressurized air is required.
2.5.1.2 Differential Pressure Gauges. Inclined manometers, U-tube
manometers, or other differential pressure gauges (e.g., magnehelic
gauges) that meet the specifications described in Method 2, Section
2.2.
NOTE: If the differential pressure gauge produces both negative
and positive readings, then both negative and positive pressure
readings shall be calibrated at a minimum of three points as
specified in Method 2, Section 2.2.
2.5.2 Traverse Points. Use a minimum of 40 traverse points for
circular ducts and 42 points for rectangular ducts for the gas flow
angle determinations. Follow Section 2.3 and Table 1-1 or 1-2 for
the location and layout of the traverse points. If the measurement
location is determined to be acceptable
according to the criteria in this alternative procedure, use the
same traverse point number and locations for sampling and velocity
measurements.
2.5.3 Measurement Procedure.
2.5.3.1 Prepare the directional probe and differential pressure
gauges as recommended by the manufacturer. Capillary tubing or
surge tanks may be used to dampen pressure fluctuations. It is
recommended, but not required, that a pretest leak check be
conducted. To perform a leak check, pressurize or use suction on
the impact opening until a reading of at least 7.6 cm (3 in.J H20
registers on the differential pressure gauge, then plug the impact
opening. The pressure of a leak-free system will remain stable for
at least 15 seconds.
2.5.3.2 Level and zero the manometers. Since the manometer level
and. zero may drift because of vibrations and temperature changes,
periodically check the level and zero during the traverse.
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EMTIC TM-001 EMTIC NSPS TEST METHOD Page 7
2.5.3.3 Position the probe at the appropriate locations in the gas
stream, and rotate until zero deflection is indicated for the yaw
angle pressure gauge. Determine and record the yaw angle. Record
the pressure gauge readings for the pitch angle, and determine the
pitch angle from the calibration curve. Repeat this procedure for
each traverse point. Complete a "back-purge" of the pressure lines
and the impact openings prior to measurements of each traverse
point .
A post-test check as described in Section 2.5.3.1 is required. If
the criteria for a leak-free system are not met, repair the
equipment, and repeat the flow angle measurements.
2.5.4 Calculate the resultant angle at each traverse point, the
average resultant angle, and the standard deviation using the
following equations. Complete the calculations retaining at least
one extra significant figure beyond that of the acquired data.
Round the values after the final calculations.
2.5.4.1 Calculate the resultant angle at each traverse point:
R.. = arc cosine [ (cosineYi) (cosinePi) ]
Eq. 1-2
Where:
RA = resultant angle at traverse point i, degree.
Yi = yaw angle at traverse point i, degree.
Pi = pitch angle at traverse point i, degree.
2.5.4.2 Calculate the average resultant for the measurements:
Eq. 1-3
Where:
Ravg = average resultant angle, degree.
n = total number of traverse points.
2.5.4.3 Calculate the standard deviations:
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 8
(n-1)
Where:
standard deviation, degree.
2.5.5 The measurement location is acceptable if Ravg
s 10°.
B3[. 1-4
20° and Sd
2.5.6 Calibration. Use a flow system as described in Sections
4.1.2.1 and 4.1.2.2 of Method 2. In addition, the flow system
shall have the .capacity to generate two test-section velocities:
one between 365 and 730 m/min (1200 and 2400 ft/min) and one
between 730 and 1100 m/min (2400 and 3600 ft/min) .
2.5.6.1 Cut two entry ports in the test section. The axes through
the entry ports shall be perpendicular to each other and intersect
in the centroid of the test section. The ports should be elongated
slots parallel to the axis of the test section and of sufficient
length to allow measurement of pitch angles while maintaining the
pitot head position at the test-section centroid. To facilitate
alignment of the directional probe during calibration, the test
section should be constructed of plexiglass or some other
transparent material. All calibration measurements should be made
at the same point in the test section, preferably at the centroid
of the test section.
2.5.6.2 To ensure that the gas flow is parallel to the central
axis of the test section, follow the procedure in Section 2.4 for
cyclonic flow determination to measure the gas flow angles at the
centroid of the test section from two test ports located 90° apart.
The gas flow angle measured in each port must be ±2° of 0°.
Straightening vanes should be installed, if necessary, to meet this
criterion.
2.5.6.3 Pitch Angle Calibration. Perform a calibration traverse
according to the manufacturer's recommended protocol in 5°
increments for angles from -60° to +60° at one velocity in each of
the two ranges specified above. Average the pressure ratio values
obtained for each angle in the two flow ranges, and plot a
-------
EMTIC TM-001 EMTIC NSPS TEST METHOD Page 9
calibration curve with the average values of the pressure ratio (or
other suitable measurement factor as recommended by the
manufacturer) versus the pitch angle. Draw a smooth line through
the data points. Plot also the data values for each traverse
point. Determine the differences between the measured datavalues
and the angle from the calibration curve at the same pressure
ratio. The difference at each comparison must be within 2° for
angles between 0° and 40° and within 3° for angles between 40° and
60°.
2.5.6.4 Yaw Angle Calibration. Mark the three-dimensional probe
to allow the determination of the yaw position of the probe. This
is usually a line extending the length of the probe and aligned
with the impact opening. To determine the accuracy of measurements
of the yaw angle, only the zero or null position need be calibrated
as follows: Place the directional probe in the test section, and
rotate the probe until the zero position is found. With a
protractor or other angle measuring device, measure the angle
indicated by the yaw angle indicator on the three-dimensional
probe. This should be within 2° of 0°. Repeat this measurement
for any other points along the length of the pitot where yaw angle
measurements could be read in order to account for variations in
the pitot markings used to indicate pitot head positions.
BIBLIOGRAPHY
1. Determining Dust Concentration in a Gas Stream, ASME
Performance Test Code No. 27. New York. 1957.
2. DeVorkin, Howard, et al. Air Pollution Source Testing Manual.
Air Pollution Control District. Los Angeles, CA. November
1963.
3. Methods for Determining of Velocity, Volume, Dust and Mist
Content of Gases. Western Precipitation Division of Joy
Manufacturing Co. Los Angeles, CA. Bulletin WP-50. 1968.
4. Standard Method'for Sampling Stacks for Particulate Matter.
In: 1971 Book of ASTM Standards, Part 23. ASTM Designation D
2928-71. Philadelphia, PA. 1971.
5. Hanson, H.A., et al. Particulate Sampling Strategies for
Large Power Plants Including Nonuniform Flow. USEPA, ORD,
ESRL, Research Triangle Park, NC. EPA-600/2-76-170. June
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EMTIC TM-001 EMTIC NSPS TEST METHOD Page 10
1976.
6. Entropy Environmentalists, Inc. Determination of the Optimum
Number of Sampling Points: An Analysis of Method 1 Criteria.
Environmental Protection Agency. Research Triangle Park, NC.
EPA Contract No. 68-01-3172, Task 7.
7. Hanson, H.A., R.J. Davini, J.K. Morgan, and A.A. Iversen.
Particulate Sampling Strategies for Large Power Plants
Including Nonuniform Flow. USEPA, Research Triangle Park, NC.
Publication No. EPA-600/2-76-170. June 1976. 350 p.
8. Brooks, E.F., and R.L. Williams. Flow and Gas Sampling
Manual. U.S. Environmental Protection Agency. Research
Triangle Park, NC. Publication No. EPA-600/2-76-203. July
1976. 93 p.
9. Entropy Environmentalists, Inc. Traverse Point Study. EPA
Contract No. 68-02-3172. June 1977. 19 p.
10. Brown, J. and K. Yu. Test Report: Particulate Sampling
Strategy in Circular Ducts. Emission Measurement Branch.
Emission Standards and Engineering Division. U.S.
Environmental Protection Agency, Research Triangle Park, NC
27711. July 31, 1980. 12 p.
11. Hawksley, P.G.W., S. Badzioch, and J.H. Blackett. Measurement
of Solids in Flue Gases. Leatherhead, England, The British
Coal Utilisation Research Association. 1961. p. 129-133.
12. Knapp, K.T. The Number of Sampling Points Needed for
Representative Source Sampling. In: Proceedings of the Fourth
National Conference on Energy and Environment. Theodore, L.
et al. (ed). Dayton, Dayton Section of the American Institute
of Chemical Engineers. October 3-7, 1976. p. 563-568.
13. Smith, W.S. and D.J. Grove. A Proposed Extension of EPA
Method 1 Criteria. Pollution Engineering. XV (8):36-37.
August 1983.
14. Gerhart, P.M. and M.J. Dorsey. Investigation of Field Test
Procedures for Large Fans. University of Akron. Akron, OH.
(EPRI Contract CS-1651) . Final Report (RP-1649-5). December
1980.
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EMTIC TM-001 EMTIC NSPS TEST METHOD Page 11
15. Smith, W.S. and D.J. Grove. A New Look at Isokinetic Sampling
Theory and Applications. Source Evaluation Society
Newsletter. VIII(3):19-24. August 1983.
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 12
Table 1-1. CROSS-SECTION LAYOUT FOR
RECTANGULAR STACKS
Number of traverse points
Matrix layout
9
12
16
20
25
30
36
42
49
3x3
4x3
, 4x4
5x4
5x5
6x6
, 7x6
7x7
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 13
TABLE 1-2
LOCATION OF TRAVERSE POINTS IN CIRCULAR STACKS
(Percent of stack diameter from inside
wall to traverse point)
Traverse
Point
Number on a
Diameter
1
2
3
4
5
6 .....
7
8
9
10 ....
11 ....
12 ....
13 ....
Number of traverse points on a diameter
2
14
.6
85
.4
4
6.
7
25
.0
75
.0
93
.3
6
4.
4
14
.6
29
.6
70
.4
85
.4
95
.6
8
3.
2
10
.5
19
.4
32
.3
67
.7
80
.6
89
.5
96
.8
10
2.6
8.2
14.
6
22.
6
34.
2
65.
8
77.
4
85.
4
91.
8
97.
4
•
12
2.1
6.7
11.
8
17.
7
25.
0
35.
6
64.
4
75.
0
82.
3
88.
2
93.
3
97.
9
14
1.8
5.7
9.9
14.
6
20.
1
26.
9
36.
6
63.
4
73.
1
79.
9
85.
4
90.
1
94.
3
16
1.6
4.9
8.5
12.
5
16.
9
22.
0
28.
3
37.
5
62.
5
71.
7
78.
0
83.
1
87.
5
18
1.
4
4.
4
7.
5
10
.9
14
.6
18
.8
23
.6
29
.6
38
.2
61
.8
70
.4
76
.4
81
.2
20
1.
3
3.
9
6.
7
9.
7
11
2.
9 .
16
.5
20
.4
25
.0
30
.6
38
.8
61
.2
69
.4
75
.0
22
1.1
3.5
6.0
8.7
11.
6
14.
6
18.
0
21.
8
26.
2
31.
5
39.
3
60.
7
68.
5
24
1.1
3.2
5.5
7.9
10.
5
13.
2
16.
1
19.
4
23.
0
27.
2
32.
3
39.
8
60.
2
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 14
14 ....
15 ....
16 ....
17 ....
18 ....
19 ....
20 ....
21 ....
22 ....
^ O • • • •
24 ....
98.
2
91.
5
95.
1
98.
4
85
.4
89
.1
92
.5
95
.6
98
.6
79
.6
83
.5
87
.1
90
.3
93
.3
96
.1
98
.7
73.
8
78.
2
82.
0
85.
4
88.
4
91.
3
94.
0
96.
5
98.
9
67.
7
72.
8
77.
0
80.
6
83.
9
86.
8
89.
5
92.
1
94.
5
96.
8
98.
9
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 15
50
0.5
Dud Diameters Upstream from Row Disturbance* (Distance A)
1.0 1.5 2.0
2.5
40
30
20
10
Higher Number i» for
Rectangular Stacks or Duds
* From Point of Any Type of
Dlsturbanc* (B«nd, Expansion, Contraction. «tc.)
I
I
J_
I
S. ^^Diaturtanca
J I MaMurament
1 L si-
T
B
Disturbance
16 Slack Diameter > 0.61 m (24 in.)
I «
Stack Diameter » 0.30 to 0.81 m (12-24 in.)
I I I
345678
Duct Diameters Downstream from Flow Disturbance* (Distance B)
0
10
Figure 1-1. Minimum number of traverse points for
particulate traverses.
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 16
50
40
30
20
10
0.5
Duct Diameters Upstream from Flow Disturbance* (Distance A)
1.0 1.5 2.0
2.5
II I I I I
8 Higher Number is for
Rectangular Stacks or Ducts
16 Stack Die
I
_X
j.
1
1
\
/Disturbance
Measurement
Site
Disturbance
-
imeter > 0.61 m (24 in.)
12
— * From Point of Any Type of
Disturbance (Bend, Expansion, Contraction, etc.)
Stack Diameter
I I I I I I
8or9a
•0.30 to 0.61 m (12-24 in.)
|
3 4 5 6 78
Duct Diameters Downstream from Flow Disturbance* (Distance B)
10
Figure 1-2. Minimum number of traverse points for velocity
(nonparticulate) traverses.
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 17
Traverse
Point
1
2
3
4
5
e
Distance
% of diameter
4.4
14.7
29.5
70.5
85.3
95.6
Figure 1-3. Example showing circular stack cross section
divided into 12 equal areas, with location of traverse
points indicated.
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EMTIC TM-001
EMTIC NSPS TEST METHOD
Page 18
o
o
o
o
1 1
o
I 4
0
o
1
o
I- 1
o
0
o
o
Figure 1-4. Example showing rectangular stack cross section
divided into 12 equal areas, with a traverse point at centroid
of each area.
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EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
Method 2 - Determination of Stack Gas Velocity and Volumetric
Flow Rate (Type S Pitot Tube)
1. PRINCIPLE AND APPLICABILITY
1.1 Principle. The average gas velocity in a stack is determined from the gas
density and from measurement of the average velocity head with a Type S
(Stausscheibe or reverse type) pitot tube.
1.2 Applicability. This method is applicable for measurement of the average
velocity of a gas stream and for quantifying gas flow.
This procedure is not applicable at measurement sites that fail to meet the
criteria of Method 1, Section 2.1. Also, the method cannot be used for direct
measurement in cyclonic or swirling gas streams; Section 2.4 of Method 1 shows
how to determine cyclonic or swirling flow conditions. When unacceptable
conditions exist, alternative procedures, subject to the approval of the
Administrator, U.S. Environmental Protection Agency, must be employed to make
accurate flow rate determinations; examples of such alternative procedures are:
(1) to install straightening vanes; (2) to calculate the total volumetric flow
rate stoichiometrically, or (3) to move to another measurement site at which the
flow is acceptable.
2. APPARATUS
Specifications for the apparatus are given below. Any other apparatus that has
been demonstrated (subject to approval of the Administrator) to be capable of
meeting the specifications will be considered acceptable.
2.1 Type S Pitot Tube. Pitot tube made of metal tubing (e.g., stainless steel)
as shown in Figure 2-1. It is recommended that the external tubing diameter
(dimension Dt, Figure 2-2b) be between 0.48 and 0.95 cm (3/16 and 3/8 inch).
There shall be an equal distance from the base of each leg of the pitot tube to
its face-opening plane (dimensions PA and PB, Figure 2-2b); it is recommended
that this distance be between 1.05 and 1.50 times the external tubing diameter.
The face openings of the pitot tube shall, preferably, be aligned as shown in
Figure 2-2; however, slight misalignments of the openings are permissible (see
Figure 2-3) .
The Type S pitot tube shall have a known coefficient, determined as outlined in
Section 4. An identification number shall be assigned to the pitot tube; this
number shall be permanently marked or engraved on the body of the tube. A
standard pitot tube may be used instead of a Type S, provided that it meets the
specifications of Sections 2.7 and 4.2; note, however, that the static and impact
pressure holes of standard pitot tubes are susceptible to plugging in
particulate-laden gas streams. Therefore, whenever a standard pitot tube is used
to perform a traverse, adequate proof must be furnished that the openings of the
Prepared by Emission Measurement Branch EMTIC M-002
Technical Support Division, OAQPS, EPA
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EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
pitot tube have not plugged up during the traverse period; this can be done by
taking a velocity head (Ap) reading at the final traverse point, cleaning out the
impact and static holes of the standard pitot tube by "back-purging" with
pressurized air, and then taking another Ap reading. If the Ap readings made
before and after the air purge are the same (±5 percent), the traverse is
acceptable. Otherwise, reject the run. Note that if Ap at the final traverse
point is unsuitably low, another point may be selected. If "back-purging" at
regular intervals is part of the procedure, then comparative Ap readings shall
be taken, as above, for the last two back purges at which suitably high Ap
readings are observed.
2.2 Differential Pressure Gauge. An inclined manometer or equivalent device.
Most sampling trains are equipped with a 10-in. (water column) inclined-vertical
manometer, having 0.01-in. H20 divisions on the 0- to 1-in. inclined scale, and
0.1-in. H20 divisions on the 1- to 10-in. vertical scale. This type of manometer
(or other gauge of equivalent sensitivity) is satisfactory for the measurement
of Ap values as low as 1.3 mm (0.05 in.) H20. However, a differential pressure
gauge of greater sensitivity shall be used (subject to the approval of the
Administrator), if any of the following is found to be true: (1) the arithmetic
average of all Ap readings at the traverse points in the stack is less than
1.3 mm (0.05 in.) H20; (2) for traverses of 12 or more points, more than 10
percent of the individual Ap readings are below 1.3 mm (0.05 in.) H20; (3) for
traverses of fewer than 12 points, more than one Ap reading is below 1.3 mm
(0.05 in.) H20. Citation 18 in the Bibliography describes commercially available
instrumentation for the measurement of low-range gas velocities.
As an alternative to criteria (1) through (3) above, the following calculation
may be performed to determine the necessity of using a more sensitive
differential pressure gauge:
i. +K
Where:
Api = Individual velocity head reading at a traverse point, mm (in.)
H20.
n = Total number of traverse points.
K = 0.13 mm H20 when metric units are used and 0.005 in. H20 when
English units are used.
Prepared by Emission Measurement Branch EMTIC H-002
Technical Support Division, OAQPS, EPA
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EMTIC TM-002 NSPS TEST METHOD Page 3
If T is greater than 1.05, the velocity head data are unacceptable and a more
sensitive differential pressure gauge must be used.
NOTE: If differential pressure gauges other than inclined manometers are used
(e.g., magnehelic gauges), their calibration must be checked after each test
series. To check the calibration of a differential pressure gauge, compare Ap
readings of the gauge with those of a gauge-oil manometer at a minimum of three
points, approximately representing the range of Ap values in the stack. If, at
each point, the values of Ap as read by the differential pressure gauge and
gauge-oil manometer agree to within 5 percent, the differential pressure gauge
shall be considered to be in proper calibration. Otherwise, the test series
shall either be voided, or procedures to adjust the measured Ap values and final
results shall be used, subject to the approval of the Administrator.
2.3 Temperature Gauge. A thermocouple, liquid-filled bulb thermometer,
bimetallic thermometer, mercury-in-glass thermometer, or other gauge capable of
measuring temperature to within 1.5 percent of the minimum absolute stack
temperature. The temperature gauge shall be attached to the pitot tube such that
the sensor tip does not touch any metal; the gauge shall be in an interference-
free arrangement with respect to the pitot tube face openings (see Figure 2-1 and
also Figure 2-7 in Section 4). Alternative positions may be used if the pitot
tube-temperature gauge system is calibrated according to the procedure of Section
4. Provided that a difference of not more than 1 percent in the average velocity
measurement is introduced, the temperature gauge need not be attached to the
pitot tube; this alternative is subject to the approval of the Administrator.
2.4 Pressure Probe and Gauge. A piezometer tube and mercury- or water-filled
U-tube manometer capable of measuring stack pressure to within 2.5 mm (0.1 in.)
Hg. The static tap of a standard type pitot tube or one leg of a Type S pitot
tube with the face opening planes positioned parallel to the gas flow may also
be used as the pressure probe.
2.5 Barometer. A mercury, aneroid, or other barometer capable of measuring
atmospheric pressure to within 2.5 mm (0.1 in.) Hg. See NOTE in Method 5,
Section 2.1.9.
2.6 Gas Density Determination Equipment. Method 3 equipment, if needed (see
Section 3.6), to determine the stack gas dry molecular weight, and Reference
Method 4 or Method 5 equipment for moisture content determination; other methods
may be used subject to approval of the Administrator.
2.7 Calibration Pitot Tube. When calibration of the Type S pitot tube is
necessary (see Section 4), a standard pitot tube for a reference. The standard
pitot tube shall, preferably, have a known coefficient, obtained either (1)
directly from the National Bureau of Standards, Route 70 S, Quince Orchard Road,
Gaithersburg, Maryland, or (2) by calibration against another standard pitot tube
with an NBS-traceable coefficient. Alternatively, a standard pitot tube designed
according to the criteria given in Sections 2.7.1 through 2.7.5 below and
illustrated in Figure 2-4 (see also Citations 7, 8, and 17 in the Bibliography)
may be used. Pitot tubes designed according to these specifications will have
baseline coefficients of about 0.99 ± 0.01.
2.7.1 Hemispherical (shown in Figure 2-4) ellipsoidal, or conical tip.
2.7.2 A minimum of six diameters straight run (based upon D, the external
diameter of the tube) between the tip and the static pressure holes.
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EMTIC TM-002 NSPS TEST METHOD Page 4
2.7.3 A minimum of eight diameters straight run between the static pressure
holes and the centerline of the external tube, following the 90-degree bend.
2.7.4 Static pressure holes of equal size (approximately 0.1 D), equally spaced
in a piezometer ring configuration.
2.7.5 Ninety-degree bend, with curved or mitered junction.
2.8 Differential Pressure Gauge for Type S Pitot Tube Calibration. An inclined
manometer or equivalent. If the single-velocity calibration technique is
employed (see Section 4.1.2.3), the calibration differential pressure gauge shall
be readable to the nearest 0.13 mm (0.005 in.) H20. For multivelocity
calibrations, the gauge shall be readable to the nearest 0.13 mm (0.005 in.) H20
for Ap values between 1.3 and 25 mm (0.05 and 1.0 in.) H20, and to the nearest
1.3 mm (0.05 in.) H20 for Ap values above 25 mm (1.0 in.) H20. A special, more
sensitive gauge will be required to read Ap values below 1.3 mm (0.05 in.) H20
(see Citation 18 in the Bibliography).
3. PROCEDURE
3.1 Set up the apparatus as shown in Figure 2-1. Capillary tubing or surge
tanks installed between the manometer and pitot tube may be used to dampen Ap
fluctuations. It is'recommended, but not required, that a pretest leak-check be
conducted as follows: (1) blow through the pitot impact opening until at least
7.6 cm (3 in.) H20 velocity pressure registers on the manometer; then, close off
the impact opening. The pressure shall remain stable for at least 15 seconds;
(2) do the same for the static pressure side, except using suction to obtain the
minimum of 7.6 cm (3 in.) H20. Other leak-check procedures, subject to'the
approval of the Administrator, may be used.
3.2 Level and zero the manometer. Because the manometer level and zero may
drift due to vibrations and temperature changes, make periodic checks during the
traverse. Record all necessary data as shown in the example data sheet
(Figure 2-5).
3.3 Measure the velocity head and temperature at the traverse points specified
by Method 1. Ensure that the proper differential pressure gauge is being used
for the range of Ap values encountered (see Section 2.2). If it is necessary to
change to a more sensitive gauge, do so, and remeasure the Ap and temperature
readings at each traverse point. Conduct a post-test leak-check (mandatory), as
described in Section 3.1 above, to validate the traverse run.
3.4 Measure the static pressure in the stack. One reading is usually adequate.
3.5 Determine the atmospheric pressure.
3.6 Determine the stack gas dry molecular weight. For combustion processes or
processes that emit essentially C02, 02, CO, and N2, use Method 3. For processes
emitting essentially air, an analysis need not be conducted; use a dry molecular
weight of 29.0. For other processes, other methods, subject to the approval 6>f
the Administrator, must be used.
3.7 Obtain the moisture content from Reference Method 4 (or equivalent) or from
Method 5.
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EMTIC TM-002 NSPS TEST METHOD Page 5
3.8 Determine the cross-sectional area of the stack or duct at the sampling
location. Whenever possible, physically measure the stack dimensions rather than
using blueprints.
4. CALIBRATION
4.1 Type S Pitot Tube. Before its initial use, carefully examine the Type S
pitot tube in top, side, and end views to verify that the face openings of the
tube are aligned within the specifications illustrated in Figure 2-2 or 2-3. The
pitot tube shall not be used if it fails to meet these alignment specifications.
After verifying the face opening alignment, measure and record the following
dimensions of the pitot tube: (a) the external tubing diameter (dimension Dt,
Figure 2-2b); and (b) the base-to-opening plane distances (dimensions PA and PB,
Figure 2-2b) . If Dt is between 0.48 and 0.95 cm (3/16 and 3/8 in.), and if ^
and PB are equal and between 1.05 and 1.50 C\., there are two possible options:
(1) the pitot tube may be calibrated according to the procedure outlined in
Sections 4.1.2 through 4.1.5 below, or (2) a baseline (isolated tube) coefficient
value of 0.84 may be assigned to the pitot tube. Note, however, that if the
pitot tube is part of an assembly, calibration may still be required, despite
knowledge of the baseline coefficient value (see Section 4.1.1).
If Dt, PA, and g are outside the specified limits, the pitot tube must be
calibrated as outlined in Sections 4.1.2 through 4.1.5 below.
4.1.1 Type S Pitot Tube Assemblies. During sample and velocity traverses, the
isolated Type S pitot tube is not always used; in many instances, the pitot tube
is used in combination with other source-sampling components (thermocouple,
sampling probe, nozzle) as part of an "assembly." The presence of other sampling
components can sometimes affect the baseline value of the Type S pitot tube
coefficient (Citation 9 in the Bibliography); therefore an assigned (or otherwise
known) baseline coefficient value may or may not be valid for a given assembly.
The baseline and assembly coefficient values will be identical only when the
relative placement of the components in the assembly is such that aerodynamic
interference effects are eliminated. Figures 2-6 through 2-8 illustrate
interference-free component arrangements for Type S pitot tubes having external
tubing diameters between 0.48 and 0.95 cm (3/16 and 3/8 in.). Type S pitot tube
assemblies that fail to meet any or all of the specifications of Figures 2-6
through 2-8 shall be calibrated according to the procedure outlined in Sections
4.1.2 through 4.1.5 below, and prior to calibration, the values of the
intercomponent spacings (pitot-nozzle, pitot-thermocouple, pitot-probe sheath)
shall be measured and recorded.
NOTE: Do not use any Type S pitot tube assembly which is constructed such that
the impact pressure opening plane of the pitot tube is below the entry plane of
the nozzle (see Figure 2-6B).
4.1.2 Calibration Setup. If the Type S pitot tube is to be calibrated, one leg
of the tube shall be permanently marked A, and the other, B. Calibration shall
be done in a flow system having the following essential design features:
4.1.2.1 The flowing gas stream must be confined to a duct of definite cross-
sectional area, either circular or rectangular. For circular cross sections, the
minimum duct diameter shall be 30.5 cm (12 in.); for rectangular cross sections,
the width (shorter side) shall be at least 25.4 cm (10 in.).
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EMTIC TM-002 NSPS TEST METHOD Page 6
4.1.2.2 The cross-sectional area of the calibration duct must be constant over
a distance of 10 or more duct diameters. For a rectangular cross section, use
an equivalent diameter, calculated from the following equation, to determine the
number of duct diameters:
D - 2LW
e (L + W)
Eq. 2-1
Where:
De = Equivalent diameter.
L = Length.
W = Width.
To ensure the presence of stable, fully developed flow patterns at the
calibration site, or "test section," the site must be located at least eight
diameters downstream and two diameters upstream from the nearest disturbances.
NOTE: The eight- and two-diameter criteria are not absolute; other test section
locations may be used (subject to approval of the Administrator), provided that
the flow at the test site is stable and demonstrably parallel to the duct axis.
4.1.2.3 The flow system shall have the capacity to generate a test-section
velocity around 915 m/min (3,000 ft/min). This velocity must be constant with
time to guarantee steady flow during calibration. Note that Type S pitot tube
coefficients obtained by single-velocity calibration at 915 m/min (3,000 ft/min)
will generally be valid to ±3 percent for the measurement of velocities above 305
m/min (1,000 ft/min) and to ±5 to 6 percent for the measurement of velocities
between 180 and 305 m/min (600 and 1,000 ft/min). If a more precise correlation
between Cp and velocity is desired, the flow system shall have the capacity to
generate at least four distinct, time-invariant test-section velocities covering
the velocity range from 180 to 1,525 m/min (600 to 5,000 ft/min), and calibration
data shall be taken at regular velocity intervals over this range (see Citations
9 and 14 in the Bibliography for details).
4.1.2.4 Two entry ports, one each for the standard and Type S pitot tubes, shall
be cut in the test section; the standard pitot entry port shall be located
slightly downstream of the Type S port, so that the standard and Type S impact
openings will lie in the same cross-sectional plane during calibration. To
facilitate alignment of the pitot tubes during calibration, it is advisable that
the test section be constructed of plexiglas or some other transparent material.
4.1.3 Calibration Procedure. Note that this procedure is a general one and must
not be used without first referring to the special considerations presented in
Section 4.1.5. Note also that this procedure applies only to single-velocity
calibration. To obtain calibration data for the A and B sides of the Type S
pitot tube, proceed as follows:
4.1.3.1 Make sure that the manometer is properly filled and that the oil is free
from contamination and is of the proper density. Inspect and leak-check all
pitot lines; repair or replace if necessary.
4.1.3.2 Level and zero the manometer. Turn on the fan, and allow the flow to
-------
EMTIC TM-002 NSPS TEST METHOD Page 7
stabilize. Seal the Type S entry port.
4.1.3.3 Ensure that the manometer is level and zeroed. Position the standard
pitot tube at the calibration point (determined as outlined in Section 4.1.5.1),
and align the tube so that its tip is pointed directly into the flow. Particular
care should be taken in aligning the tube to avoid yaw and pitch angles. Make
sure that the entry port surrounding the tube is properly sealed.
4.1.3.4 Read Apstd, and record its value in a data table similar to the one shown
in Figure 2-9. Remove the standard pitot tube from the duct, and disconnect it
from the manometer. Seal the standard entry port.
4.1.3.5 Connect the Type S pitot tube to the manometer. Open the Type S entry
port. Check the manometer level and zero. Insert and align the Type S pitot
tube so that its A side impact opening is at the same point as was the standard
pitot tube and is pointed directly into the flow. Make sure that the entry port
surrounding the tube is properly sealed.
4.1.3.6 Read Ap5, and enter its value in the data table. Remove the Type S
pitot tube from the duct, and disconnect it from the manometer.
4.1.3.7 Repeat Steps 4.1.3.3 through 4.1.3.6 above until three pairs of Ap
readings have been obtained.
4.1.3.8 Repeat Steps 4.1.3.3 through 4.1.3.7 above for the B side of the Type
S pitot tube.
'4.1.3.9 Perform calculations, as described in Section 4.1.4 below.
4.1.4 Calculations.
4.1.4.1 For each of the six pairs of Ap readings (i.e., three from side A and
three from side B) obtained in Section 4.1.3 above, calculate the value of
the Type S pitot tube coefficient as follows:
C =C
^p(s) p(std),
Eq. 2-2
Where:
Cp(s) = Type S pitot tube coefficient.
Cp,,td) = Standard pitot tube coefficient; use 0.99 if the
coefficient is unknown and the tube is designed according
to the criteria of Sections 2.7.1 to 2.7.5 of this
method.
ApBtd = Velocity head measured by the standard pitot tube, cm
(in.) H20.
Ap, = Velocity head measured by the Type S pitot tube, cm (in.)
H20.
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EMTIC TM-002
NSPS TEST METHOD Page 8
4.1.4.2 Calculate Cp (side A), the mean A-side coefficient, and C"p (side B), the
mean B-side coefficient; calculate the difference between these two average
values.
4.1.4.3 Calculate the deviation of each of the three A-side values of
Cp(s) from Up (side A), and the deviation of each B-side values of Cp(s) from
Cp (side B). Use the following equation:
Deviation = C ~C~(A or B)
P(s) r
Eq. 2-3
4.1.4.4 Calculate a, the average deviation from the mean, for both the A and B
sides of the pitot tube. Use the following equation:
a(side A or B) =
t|Cp(s)
Eq. 2-4
4.1.4.5 Use the Type S pitot tube only if the values of o (side A) and a (side
B) are less than or equal to 0.01 and if the absolute value of the difference
between C~p (A) and Up (B) is 0.01 or less.
4.1.5 Special Considerations.
4.1.5.1 Selection of Calibration Point.
4.1.5.1.1 When an isolated Type S pitot tube is calibrated, select a calibration
point at or near the center of the duct, and follow the procedures outlined in
Sections 4.1.3 and 4.1.4 above. The Type S pitot coefficients so obtained,
i.e., Cp (side A) and (Jj (side B), will be valid, so long as either: (1) the
isolated pitot tube is used; or (2) the pitot tube is used with other components
(nozzle, thermocouple, sample probe) in an arrangement that is free from
aerodynamic interference effects (see Figures 2-6 through 2-8) .
4.1.5.1.2 For Type S pitot tube-thermocouple combinations (without sample
probe), select a calibration point at or near the center of the duct, and follow
the procedures outlined in Sections 4.1.3 and 4.1.4 above. The coefficients so
obtained will be valid so long as the pitot tube-thermocouple combination is used
by itself or with other components in an interference-free arrangement (Figures
2-6 and 2-8).
4.1.5.1.3 For assemblies with sample probes, the calibration point should be
located at or near the center of the duct; however, insertion of a probe sheath"
into a small duct may cause significant cross-sectional area blockage and yield
incorrect coefficient values (Citation 9 in the Bibliography). Therefore, to
minimize the blockage effect, the calibration point may be a few inches off-
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EMTIC TM-002 NSPS TEST METHOD Page 9
center if necessary. The actual blockage effect will be negligible when the
theoretical blockage, as determined by a projected-area model of the probe
sheath, is 2 percent or less of the duct cross-sectional area for assemblies
without external sheaths (Figure 2-lOa), and 3 percent or less for assemblies
with external sheaths (Figure 2-10b).
4.1.5.2 For those probe assemblies in which pitot tube-nozzle interference is
a factor (i.e., those in which the pitot-nozzle separation distance fails to meet
the specification illustrated in Figure 2-6A), the value of Cp(s) depends upon the
amount of free-space between the tube and nozzle, and therefore is a function of
nozzle size. In these instances, separate calibrations shall be performed with
each of the commonly used nozzle sizes in place. Note that the single-velocity
calibration technique is acceptable for this purpose, even though the larger
nozzle sizes (>0.635 cm or 1/4 in.) are not ordinarily used for isokinetic
sampling at velocities around 915 m/min (3,000 ft/min), which is the calibration
velocity; note also that it is not necessary to draw an isokinetic sample during
calibration (see Citation 19 in the Bibliography).
4.1.5.3 For a probe assembly constructed such that its pitot tube is always used
in the same orientation, only one side of the pitot tube need be calibrated (the
side which will face the flow) . The pitot tube must still meet the alignment
specifications of Figure 2-2 or 2-3, however, and must have an average deviation
(o) value of 0.01 or less (see Section 4.1.4.4.)
4.1.6 Field Use and Recalibration.
4.1.6.1 Field Use.
4.1.6.1.1 When a Type S pitot tube (isolated or in an assembly) is used in the
field, the appropriate coefficient value (whether assigned or obtained by
calibration) shall be used to perform velocity calculations. For calibrated Type
S pitot tubes, the A side coefficient shall be used when the A side of the tube
faces the flow, and the B side coefficient shall be used when the B side faces
the flow; alternatively, the arithmetic average of the A and B side coefficient
values may be used, irrespective of which side faces the flow.
4.1.6.1.2 When a probe assembly is used to sample a small duct, 30.5 to 91.4 cm
(12 to 36 in.) in diameter, the probe sheath sometimes blocks a significant part
of the duct cross-section, causing a reduction in the effective value of Cp(,).
Consult Citation 9 in the Bibliography for details. Conventional pitot-sampling
probe assemblies are not recommended for use in ducts having inside diameters
smaller than 30.5 cm (12 in.) (see Citation 16 in the Bibliography).
4.1.6.2 Recalibration.
4.1.6.2.1 Isolated Pitot Tubes. After each field use, the pitot tube shall be
carefully reexamined in top, side, and end views. If the pitot face openings are
still aligned within the specifications illustrated in Figure 2-2 or 2-3, it can
be assumed that the baseline coefficient of the pitot tube has not changed. If,
however, the tube has been damaged to the extent that it no longer meets the
specifications of the Figure 2-2 or 2-3, the damage shall either be repaired to
restore proper alignment of the face openings, or the tube shall be discarded.
4.1.6.2.2 Pitot Tube Assemblies. After each field use, check the face opening
alignment of the pitot tube, as in Section 4.1.6.2.1; also, remeasure the
intercomponent spacings of the assembly. If the intercomponent spacings have not
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EMTIC TM-002 NSPS TEST METHOD Page 10
changed and the face opening alignment is acceptable, it can be assumed that the
coefficient of the assembly has not changed. If the face opening alignment is
no longer within the specifications of Figure 2-2 or 2-3, either repair the
damage or replace the pitot tube (calibrating the new assembly, if necessary).
If the intercomponent spacings have changed, restore the original spacings, or
recalibrate the assembly.
4.2 Standard Pitot Tube (if applicable). If a standard pitot tube is used for
the velocity traverse, the tube shall be constructed according to the criteria
of Section 2.7 and shall be assigned a baseline coefficient value of 0.99. If
the standard pitot tube is used as part of an assembly, the tube shall be in an
interference-free arrangement (subject to the approval of the Administrator) .
4.3 Temperature Gauges. After each field use, calibrate dial thermometers,
liquid-filled bulb thermometers, thermocouple-potentiometer systems, and other
gauges at a temperature within 10 percent of the average absolute stack
temperature. For temperatures up to 405°C (761°F), use an ASTM inercury-in-glass
reference thermometer, or equivalent, as a reference; alternatively, either
a reference thermocouple and potentiometer (calibrated by NBS) or thermometric
fixed points, e.g., ice bath and boiling water (corrected for barometric
pressure) may be used. For temperatures above 405°C (761°F), use an NBS-
calibrated reference 'thermocouple-potentiometer system or an alternative-
reference, subject to the approval of the Administrator.
If, during calibration, the absolute temperature measured with the gauge being
calibrated and the reference gauge agree within 1.5 percent, the temperature data
taken in the field shall be considered valid. Otherwise, the pollutant emission
test shall either be considered invalid or adjustments (if appropriate) of the
test results shall be made, subject to the approval of the Administrator.
4.4 Barometer. Calibrate the barometer used against a mercury barometer.
5. CALCULATIONS
Carry out calculations, retaining at least one extra decimal figure beyond that
of the acquired data. Round off figures after final calculation.
5.1 Nomenclature.
A = Cross-sectional area of stack, m2 (ft2) .
Bws = Water vapor in the gas stream (from Method 5 or Reference
Method 4), proportion by volume.
CP = Pitot tube coefficient, dimensionless.
Kp = Pitot tube constant,
1/2
for the metric system.
34 07 m
sec
(g/g-mole) (mmHg)
(°K) (mmH20)
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EMTIC TM-002
NSPS TEST METHOD
Page 11
85.49
ft
sec
Ib/lb-mole) (in.Hg)
(in.H20)
1/2
for the English system.
M.
Molecular weight of stack gas, dry basis (see Section 3.6),
g/g—mole (Ib/lb-mole).
Molecular weight of stack gas, wet basis, g/g-mole (Ib/lb-
mole) .
= Md(l-Bws) +18.0Bws
PS
Eq. 2-5
Barometric pressure at measurement site, mm Hg (in. Hg)
Stack static pressure, mm Hg (in. Hg).
Absolute stack pressure, mm Hg (in. Hg),
v.
bar
P.t
t.
Eq. 2-6
Standard absolute pressure, 760 mm Hg (29.92 in. Hg) .
Dry volumetric stack gas flow rate corrected to standard
conditions, dsmVhr (dscf/hr).
Stack temperature, °C (°F) .
Absolute stack temperature, °K (°R).
= 273 + t.
for metric.
= 460 + t
Eq. 2-7
for English.
Eq. 2-8
Standard absolute temperature, 293°K (528°R).
Average stack gas velocity, m/sec (ft/sec).
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EMTIC TM-002
NSPS TEST METHOD
Page 12
Ap = Velocity head of stack gas, mm H20 (in. H20).
3,600= Conversion factor, sec/hr.
18.0 = Molecular weight of water, g/g-mole (Ib/lb-mole) .
5.2 Average Stack Gas Velocity.
= KG (,/Sp)
avg
*
s(avg)
5.3 Average Stack Gas Dry Volumetric Flow Rate
T
Qsd = 3,600(l-Bws)vsA
std
T P
s(avg) std
Eq. 2-9
Eq. 2-10
BIBLIOGRAPHY
1.
2.
3.
4.
5.
6.
7.
8.
9.
Mark, L.S. Mechanical Engineers' Handbook. New York. McGraw-Hill Book
Co., Inc. 1951.
Perry. J.H. Chemical Engineers' Handbook. New York. McGraw-Hill Book
Co., Inc. 1960.
Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of Errors in
Stack Sampling Measurements. U.S. Environmental Protection Agency,
Research Triangle Park, N.C. (Presented at the Annual Meeting of the Air
Pollution Control Association, St. Louis, MO., June 14-19, 1970).
Standard Method for Sampling Stacks for Particulate Matter. In: 1971 Book
of ASTM Standards, Part 23. Philadelphia, PA. 1971. ASTM Designation
D 2928-71.
Vennard, J.K. Elementary Fluid Mechanics. New York. John Wiley and Sons,
Inc. 1947.
Fluid Meters - Their Theory and Application.
Mechanical Engineers, New York, N.Y. 1959.
American Society of
ASHRAE Handbook of Fundamentals. 1972. p. 208.
Annual Book of ASTM Standards, Part 26. 1974. p. 648.
Vollaro, R.F. Guidelines for Type S Pitot Tube Calibration. U.S.
Environmental Protection Agency, Research Triangle Park, N.C. (Presented
at 1st Annual Meeting, Source Evaluation Society, Dayton, OH,
September 18, 1975.)
-------
EMTIC TM-002 NSPS TEST METHOD Page 13
10. Vollaro, R.F- A Type S Pitot Tube Calibration Study. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
N.C. July 1974.
11. Vollaro, R.F. The Effects of Impact Opening Misalignment on the Value of
the Type S Pitot Tube Coefficient. U.S. Environmental Protection Agency,
Emission Measurement Branch, Research Triangle Park, NC. October 1976.
12. Vollaro, R.F. Establishment of a Baseline Coefficient Value for Properly
Constructed Type S Pitot Tubes. U.S. Environmental Protection Agency,
Emission Measurement Branch, Research Triangle Park, NC. November 1976.
13. Vollaro, R.F. An Evaluation of Single-Velocity Calibration Technique as a
Means of Determining Type S Pitot Tube Coefficients. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park, NC.
August 1975.
14. Vollaro, R.F. The Use of Type S Pitot Tubes for the Measurement of Low
Velocities. U.S. Environmental Protection Agency, Emission Measurement
Branch, Research Triangle Park, NC. November 1976.
15. Smith, Marvin L. Velocity Calibration of EPA Type Source Sampling Probe.
United Technologies Corporation, Pratt and Whitney Aircraft Division, East
Hartford, CT. 1975.
16. Vollaro, R.F. Recommended Procedure for Sample Traverses in Ducts Smaller
than 12 Inches in Diameter. U.S. Environmental Protection Agency, Emission
Measurement Branch, Research Triangle Park, NC. November 1976.
17. Ower, E. and R.C. Pankhurst. The Measurement of Air Flow, 4th Ed. London,
Pergamon Press. 1966.
18. Vollaro, R.F. A Survey of Commercially Available Instrumentation for the
Measurement of Low-Range Gas Velocities. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, NC.
November 1976. (Unpublished Paper).
19. Gnyp, A.W., C.C. St. Pierre, D.S. Smith, D. Mozzon, and J. Steiner. An
Experimental Investigation of the Effect of Pitot Tube-Sampling Probe
Configurations on the Magnitude of the S Type Pitot Tube Coefficient for
Commercially Available Source Sampling Probes. Prepared by the University
of Windsor for the Ministry of the Environment, Toronto, Canada.
February 1975.
-------
EMTIC TM-002
NSPS TEST METHOD
Page 14
1.90-2.54 cm*
(0.75 -1.0 in.)
I c
7.62 cm (3 in.)'
Temperature Sensor
/ I
TypeS Pilot Tube
* Suggested (Interference Free)
Pilot tube/Thermocouple Spacing
Figure 2-1. Type S pitot tube manometer assembly.
-------
EMTIC TM-002
NSPS TEST METHOD
Page 15
Transverse
Tube Axis
Longitudinal
Tube Axis
Face
Opening
Planes
(a)
A-Side Plane
B-Slde Plane
T
/TOTE
(c)
(a) end view; face opening planes perpendicular
to transverse axis;
(b) lop view; face opening planes parallel to
longrtudna! axis:
(c) side view; both legs of equal length and
oentertines coincident, when viewed from
botfisides. Baseline coeffident values of
0.64 may be assigned to pitot lubes con-
•ductedthitway
Figure 2-2. Properly constructed Type S pitot tube.
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EMTIC TM-002
NSPS TEST METHOD
Page 16
-
Figure 2-3. Types of face-opening misalignment that can result from field use
or improper construction of Type S pitot tubes. These will not affect the
baseline value of Cp(s) so long as a1 and a2 *10°, P1 and (J2 s5°, i <;0.32 cm (1/8
in.) and w *0.08 cm (1/32 in.) (citation 11 in Bibliography).
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EMTIC TM-002
NSPS TEST METHOD
Page 17
Curved or
Mitered Junction
HwnUpnerical
Tip
Figure 2-4. Standard pitot tube design specifications.
-------
EMTIC TM-002 NSPS TEST METHOD Page 18
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EMTIC TM-002
NSPS TEST METHOD
Page 19
PLANT
DATE
RUN NO.
STACK DIA. OR
DIMENSIONS, m (in.) BAROMETRIC PRESS., mm Hg
(in. Hg) CROSS SECTIONAL AREA, m2 (ft2)
OPERATORS
PITOT TUBE I.D. NO.
AVG. COEFFICIENT, Cp
LAST DATE CALIBRATED
SCHEMATIC OF STACK
CROSS SECTION
Traverse
Pt. No.
Vel. Hd., Ap
mm (in. ) H20
Stack Temperature
T.,
°C (°F)
Average
T.,
°K (°R)
Pg
mm Hg
(in.Hg)
Up)1'2
Figure 2-5. Velocity traverse data,
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EMTIC TM-002
NSPS TEST METHOD
Page 20
TypeS Pilot Tube
I »>1.ncn>(KI>i)fcrD lUaiKHta.)
Sampling Nozzle
A. Bottom View; showing minimum pilot tubs-nozzle separation
Sampling
Nozzle
Static Pressure
Opening Plane
Types Nozzle Entry
Pilot Tube
B. Side View; to prevent pilot tube from interfering with gai
flow streamlines approaching the nozzle, the Impact pressure
opening plane of the pilot tube shall be even with or above the
nozzle entry plane.
Figure 2-6. Proper pitot tube-sampling nozzle configuration to
prevent aerodynamic interference; button-hook type nozzle;
centers of nozzle and pitot opening aligned; Dt between 0.48 and
0.95 cm (3/16 and 3/8 in.).
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EMTIC TM-002
NSPS TEST METHOD
Page 21
I w.ja-
Teirperature S«nsor
p. Types Blot Tube
Simple Probe
Temperature Senior
Type S Pilot Tub.
SenpUF
Figure 2-7. Proper thermocouple placement to prevent
interference; Dt between 0.48 and 0.95 cm (3/16 and 3/8 in.).
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EMTIC TM-002
NSPS TEST METHOD
Page 22
TypeS Pilot Tube
Figure 2-8. Minimum pitot-sample probe separation needed to
prevent interference; Dt between 0.48 and 0.95 cm (3/16 and 3/8
in.) .
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EMTIC TM-002
NSPS TEST METHOD
Page 23
PITOT TUBE IDENTIFICATION NUMBER: DATE: CALIBRATED BY:
RUN NO.
1
2
3
RUN NO.
1
2
3
"A" SIDE CALIBRATION
cm H2O
(in H2O)
cm H2O
(in H20)
(SIDE"' A)
CD,.,
"B" SIDE CALIBRATION
cm H2O
(in H20)
ftTT-Q-rarrfi Dpi\H a +- -i nn = n
cm H20
(in H20)
^p, ovg
(SIDE B)
EC - C
. ^p(s) ^p(AorB)
- 1=i _ -Mii«
Deviation
C.,., - CD(A)
Deviation
CD(., - CD(B)
=5t:R^<0 . 01
Cp(SideA)-Cp
-MustBe^O.Ol
Figure 2-9. Pitot tube calibration data.
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EMTIC TM-002
NSPS TEST METHOD
Page 24
t ^^
Figure 2-10
assemblies.
Projected-area models for typical pitot tube
-------
EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
Method 3B - Gas Analysis for the Determination of
Emission Rate Correction Factor or Excess Air
1. APPLICABILITY AND PRINCIPLE
1.1 Applicability.
1.1.1 This method is applicable for determining carbon dioxide (COZ). oxygen (02),
and carbon monoxide (CO) concentrations of a sample from a gas stream of a fossil -
fuel combustion process for excess air or emission rate correction factor
calculations.
1.1.2 Other methods, as well as modifications to the procedure described herein.
are also applicable for all of the above determinations. Examples of specific
methods and modifications include: (1) a multi-point sampling method using an Orsat
analyzer to analyze individual grab samples obtained at each point, and (2) a method
using C02 or 02 and stoichiometric calculations to determine excess air. These
methods and modifications may be used, but are subject to the approval of the
Administrator. U.S. Environmental Protection Agency (EPA).
1.1.3 Note. Mention of trade names or specific products does not constitute
endorsement by EPA.
1.2 Principle. A gas sample is extracted from a stack by one of the following
methods: (1) single-point, grab sampling; (2) single-point, integrated sampling; or
(3) multi-point, integrated sampling. The gas sample is analyzed for percent C02.
percent 02. and. if necessary, percent CO. An Orsat analyzer must be used for excess
air or emission rate correction factor determinations.
2. APPARATUS
The alternative sampling systems are the same as those mentioned in Section 2 of
Method 3.
2.1 Grab Sampling and Integrated Sampling. Same as in Sections 2.1 and 2.2.
respectively, of Method 3.
2.2 Analysis. An Orsat analyzer only. For low C02 (less than 4.0 percent) or high
02 (greater than 15.0 percent) concentrations, the measuring burette of the Orsat
must have at least 0.1 percent subdivisions. For Orsat maintenance and operation
procedures, follow the instructions recommended by the manufacturer, unless
otherwise specified herein.
-------
Prepared by Emission Measurement Branch EMTIC TM-003B
Technical Support Division, OAQPS. EPA May 15. 1990
EMTIC TM-003B EMTIC NSPS TEST METHOD Page 2
3. PROCEDURES
Each of the three procedures below shall be used only when specified in an
applicable subpart of the standards. The use of these procedures for other purposes
must have specific prior approval of the Administrator.
Note: A Fyrite-type combustion gas analyzer is not acceptable for excess air or
emission rate correction factor determinations, unless approved by the
Administrator. If both percent C02 and percent 02 are measured, the analytical
results of any of the three procedures given below may also be used for calculating
the dry molecular weight (see Method 3).
3.1 Single-Point. Grab Sampling and Analytical Procedure.
3.1.1 The sampling point in the duct shall be as described in Section 3.1 of Method
3.
3.1.2 Set up the equipment as shown in Figure 3-1 of Method 3, making sure all
connections ahead of the analyzer are tight. Leak check the Orsat analyzer
according to the procedure described in Section 6 of Method 3. This leak check is
mandatory.
3.1.3 Place the probe in the stack, with the tip of the probe positioned at the
sampling point; purge the sampling line long enough to allow at least five
exchanges. Draw a sample into the analyzer. For emission rate correction factor
determinations, immediately analyze the sample, as outlined in
Sections 3.1.4 and 3.1.5, for percent C02 or percent 02. If excess air is desired.
proceed as follows: (1) immediately analyze the sample, as in Sections 3.1.4 and
3.1.5, for percent C02. 02, and CO; (2) determine the percentage of the gas that is N2
by subtracting the sum of the percent C02, percent 02, and percent CO from 100
percent, and (3) calculate percent excess air as outlined in Section 4.2.
3.1.4 To ensure complete absorption of the C02, 02, or if applicable, CO, make
repeated passes through each absorbing solution until two consecutive readings are
the same. Several passes (three or four) should be made between readings. (If
constant readings cannot be obtained after three consecutive readings, replace the
absorbing solution.) Note: Since this single-point, grab sampling and analytical
procedure is normally conducted in conjunction with a single-point, grab sampling
and analytical procedure for a pollutant, only one analysis is ordinarily conducted.
Therefore, great care must be taken to obtain a valid sample and analysis. Although
in most cases, only C02 or 02 is required, it is recommended that both C02 and 02 be
measured, and that Section 3.4 be used to validate the analytical data. *
3.1.5 After the analysis is completed, leak check (mandatory) the Orsat analyzer
once again, as described in Section 6 of Method 3. For the results of the analysis
-------
to be valid, the Orsat analyzer must pass this leak test before and after the
analysis.
EMTIC TM-003B EMTIC NSPS TEST METHOD Page 3
3.2 Single-Point. Integrated Sampling and Analytical Procedure.
3.2.1 The sampling point in the duct shall be located as specified
• in Section 3.1.1.
3.2.2 Leak check (mandatory) the flexible bag as in Section 2.2.6 of
Method 3. Set up the equipment as shown in Figure 3-2 of Method 3. Just before
sampling, leak check (mandatory) the train as described in Section 4.2 of Method 3.
3.2.3 Sample at a constant rate, or as specified by the Administrator. The
sampling run must be simultaneous with, and for the same total length of time as,
the pollutant emission rate determination. Collect at least 30 liters (1.00 ft3) of
sample gas. Smaller volumes may be collected, subject to approval of the
Administrator.
3.2.4 Obtain-one integrated flue gas sample during each pollutant emission rate
determination. For emission rate correction factor determination, analyze the
sample within 4 hours after it is taken for percent C02 or percent 02 (as outlined in
Sections 3.2.5 through 3.2.7). The Orsat analyzer must be leak checked (see Section
6 of Method 3) before the analysis. If excess air is desired, proceed as follows:
(1) within 4 hours after the sample is taken, analyze it (as in Sections 3.2.5
through 3.2.7) for percent C02, 02. and CO; (2) determine the percentage of the gas
that is N2 by subtracting the sum of the percent C02. percent 02. and percent CO from
100 percent; and (3) calculate percent excess air. as outlined in Section 4.2.
3.2.5 To ensure complete absorption of the C02. 02. or if applicable. CO. follow the
procedure described in Section 3.1.4. Note: Although in most instances only C02 or
02 is required, it is recommended that both C02 and 02 be measured, and that Section
3.4.1 be used to validate the analytical data.
3.2.6 Repeat the analysis until the following criteria are met:
3.2.6.1 For percent C02. repeat the analytical procedure until the results of any
three analyses differ by no more than (a) 0.3 percent by volume when C02 is greater
than 4.0 percent or (b) 0.2 percent by volume when C02 is less than or equal to 4.0
percent. Average three acceptable values of percent C02, and report the results to
the nearest 0.1 percent.
3.2.6.2 For percent 02. repeat the analytical procedure until the results of any
three analyses differ by no more than (a) 0.3 percent by volume when 02 is less than
15.0 percent or (b) 0.2 percent by volume when 02 is greater than or equal to 15.0
percent. Average the three acceptable values of percent 02. and report the results
-------
to the nearest 0.1 percent.
3.2.6.3 For percent CO, repeat the analytical procedure until the results of any
three analyses differ by no more than 0.3 percent. Average the three acceptable
values of percent CO, and report the results to the nearest 0.1 percent.
EMTIC TM-003B EMTIC NSPS TEST METHOD Page 4
3.2.7 After the analysis is completed, leak check (mandatory) the Orsat analyzer
once again, as described in Section 6 of Method 3. For the results
of the analysis to be valid, the Orsat analyzer must pass this leak test before and
after the analysis.
3.3 Multi-Point, Integrated Sampling and Analytical Procedure.
3.3.1 The sampling points shall be determined as specified in Section 5.3 of Method
3.
3.3.2 Follow the procedures outlined in Sections 3.2.2 through 3.2.7, except for
the following: Traverse all sampling points, and sample at each point for an equal
length of time. Record sampling data as shown in Figure 3-3 of Method 3.
3.4 Quality Control Procedures.
3.4.1 Data Validation When Both C02 and 02 Are Measured. Although in most
instances, only C02 or 02 measurement is required, it is recommended that both C02 and
02 be measured to provide a check on the quality of the data. The following quality
control procedure is suggested. Note: Since the method for validating the C02 and 02
analyses is based on combustion of organic and fossil fuels and dilution of the gas
stream with air, this method does not apply to sources that (1) remove C02 or 02
through processes other than combustion, (2) add 02 (e.g., oxygen enrichment) and N2
in proportions different from that of air. (3) add C02 (e.g., cement or lime kilns).
or (4) have no fuel factor. F0. values obtainable (e.g., extremely variable waste
mixtures). This method validates the measured proportions of C02 and 02 for fuel
type, but the method does not detect sample dilution resulting from leaks during or
after sample collection. The method is applicable for samples collected downstream
of most lime or limestone flue-gas desulfurization units as the C02 added or removed
from the gas stream is not significant in relation to the total C02 concentration.
The C02 concentrations from other types of
scrubbers using only water or basic slurry can be significantly affected and would
render the F0 check minimally useful.
3.4.1.1 Calculate a fuel factor, F0, using the following equation:
20.9 - *02
FO Eq. 3B-1
*C02
where:
-------
$02 = Percent 02 by volume, dry basis.
XC02 = Percent C02 by volume, dry basis.
20.9 = Percent 02 by volume in ambient air.
EMTIC TM-003B EMTIC NSPS TEST METHOD Page 5
If CO is present in quantities measurable by this method, adjust the 02 and C02
values before performing the calculation for F0 as follows:
*C02(adj) =
*02(adj) = *02 - 0.5
where:
%CO = Percent CO by volume, dry basis.
3.4.1.2 Compare the calculated F0 factor with the expected F0 values. The following
table may be used in establishing acceptable ranges for the expected F0 if the fuel
being burned is known. When fuels are burned in combinations, calculate the
combined fuel Fd and Fc factors (as defined in Method 19) according to the procedure
in Method 19. Section 5.2.3. Then calculate the F0 factor as follows:
0.209 Fd
F0 Eq. 3B-2
Fuel type F0 range
Coal: Anthracite and lignite 1.016 - 1.130
Bituminous 1.083 - 1.230
Oil: Distillate 1.260 - 1.413
Residual 1.210 - 1.370
Gas: Natural 1.600 - 1.836
Propane 1.434 - 1.586
Butane 1.405 - 1.553
Wood 1.000 - 1.120
Wood bark 1.003 - 1.130
-------
3.4.1.3 Calculated F0 values, beyond the acceptable ranges shown in this table.
should be investigated before accepting the test results. For example, the strength
of the solutions in the gas analyzer and the analyzing technique should be checked
by sampling and analyzing a known concentration, such as air; the fuel factor should
be reviewed and verified. An acceptability range of ±12 percent is appropriate for
the F0 factor of mixed fuels with variable fuel ratios. The level of the emission
rate relative to the compliance level should be considered in determining if a
retest is appropriate, i.e.; if the measured emissions are much lower or much
greater than the compliance limit,
EMTIC TM-003B EMTIC NSPS TEST METHOD Page 6
repetition of the test would not significantly change the compliance status of the
source and would be unnecessarily time consuming and costly.
4. CALCULATIONS
4.1 Nomenclature. Same as Section 5 of Method 3 with the addition of the
following:
Percent excess air.
0.264 = Ratio of 02 to N2 in air. v/v.
4.2 Percent Excess Air. Calculate the percent excess air (if applicable) by
substituting the appropriate values of percent 02. CO. and N2 (obtained from Section
3.1.3 or 3.2.4) into Equation 3B-3.
X02 - 0.5 *CO
*EA - - x 100 Eq. 3B-3
0.264 *N2 - (*02 - 0.5 SCO)
Note: The equation above assumes that ambient air is used as the source of 02 and
that the fuel does not contain appreciable amounts of N2 (as do coke oven or blast
furnace gases). For those cases when appreciable amounts of N2 are present (coal.
oil, and natural gas do not contain appreciable amounts of N2) or when oxygen
enrichment is used, alternative methods, subject to approval of the Administrator.
are required.
5. BIBLIOGRAPHY
Same as Method 3.
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EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
Method 4 - Determination of Moisture Content
in Stack Gases
1. PRINCIPLE AND APPLICABILITY
1.1 Principle. A gas sample is extracted at a constant rate from
the source; moisture is removed from the sample stream and
determined either volumetrically or gravimetrically.
1.2 Applicability. This method is applicable for determining the
moisture content of stack gas.
1.2.1 Two procedures are given. The first is a reference method,
for accurate determinations of moisture content (such as are needed
to calculate emission data). The second is an approximation
method, which provides estimates of percent moisture to aid in
setting isokinetic sampling rates prior to a pollutant emission
measurement run. The approximation method described herein is only
a suggested approach; alternative means for approximating the
moisture content, e.g., drying tubes, wet bulb-dry bulb techniques,
condensation techniques, stoichiometric calculations, previous
experience, etc., are also acceptable.
1.2.2 The reference method is often conducted simultaneously with
a pollutant emission measurement run; when it is, calculation of
percent isokinetic, pollutant emission rate, etc., for the run
shall be based upon the results of the reference method or its
equivalent; these calculations shall not be based upon the results
of the approximation method, unless the approximation method is
shown, to the satisfaction of the Administrator, U.S. Environmental
Protection Agency, to be capable of yielding results within 1
percent H20 of the reference method.
1.2.3 Note: The reference method may yield questionable results
Prepared by Emission Measurement Branch EMTIC TM-004
Technical Support Division, OAQPS, EPA July 11, 1989
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EMISSION MEASUREMENT TECHNICAL INFORMATION CENTER
NSPS TEST METHOD
when applied to saturated gas streams or to streams that contain
water droplets. Therefore, when these conditions exist or are
suspected, a second determination of the moisture content shall be
made simultaneously with the reference method, as follows: Assume
that the gas stream is saturated. Attach a temperature sensor
[capable of measuring to within 1°C (2°F) ] to the reference method
probe. Measure the stack gas temperature at each traverse point
(see Section 2.2.1) during the reference method traverse; calculate
the average stack gas temperature. Next, determine the moisture
percentage, either by: (1) using a psychrometric chart and making
appropriate corrections if stack pressure is different from that of
the chart, or (2) using saturation vapor pressure tables. In cases
where the psychrometric chart or the saturation vapor pressure
tables are not applicable (based on evaluation of the process),
alternative methods, subject to the approval of the Administrator,
shall be used.
2. REFERENCE METHOD
The procedure described in Method 5 for determining moisture
content is acceptable as a reference method.
2.1 Apparatus. A schematic of the sampling train used in this
reference method is shown in Figure 4-1. All components shall be
maintained and calibrated according to the procedures in Method 5.
2.1.1 Probe. Stainless steel or glass tubing, sufficiently heated
to prevent water condensation, and equipped with a filter, either
in-stack (e.g., a plug of glass wool inserted into the end of the
probe) or heated out-stack (e.g., as described in Method 5), to
remove particulate matter. When stack conditions permit, other
metals or plastic tubing may be used for the probe, subject to the
approval of the Administrator.
2.1.2 Condenser. See Method 5, Section 2.1.7, for a description
Prepared by Emission Measurement Branch EMTIC TM-004
Technical Support Division, OAQPS, EPA July 11, 1989
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EMTIC TM-004 EMTIC NSPS TEST METHOD
Page 3
of an acceptable type of condenser and for alternative measurement
systems.
2.1.3 Cooling System. An ice bath container and crushed ice (or
equivalent), to aid in condensing moisture.
2.1.4 Metering System. Same as in Method 5, Section 2.1.8, except
do not use sampling systems designed for flow rates higher than
0.0283 mVmin (1.0 cfm) . Other metering systems, capable of
maintaining a constant sampling rate to within 10 percent and
determining sample gas volume to within 2 percent, may be used,
subject to the approval of the Administrator.
2.1.5 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg. See
NOTE in Method 5, Section 2.1.9.
2.1.6 Graduated Cylinder and/or Balance. To measure condensed
water and moisture caught in the silica gel to within 1 ml or 0.5
g. Graduated cylinders shall have subdivisions no greater than 2
ml. Most laboratory balances are capable of weighing to the
nearest 0.5 g or less. These balances are suitable for use here.
2.2 Procedure. The following procedure is written for a condenser
system (such as the impinger system described in Section 2.1.7 of
Method 5) incorporating volumetric analysis to measure the
condensed moisture, and silica gel and gravimetric analysis to
measure the moisture leaving the condenser.
2.2.1 Unless otherwise specified by the Administrator, a minimum
of eight traverse points shall be used for circular stacks having
diameters less than 0.61 m (24 in.), a minimum of nine points shall
be used for rectangular stacks
having equivalent diameters less than 0.61 m (24 in.), and a
minimum of twelve traverse points shall be used in all other cases.
The traverse points shall be located according to Method 1. The
use of fewer points is subject to the approval of the
Administrator. Select a suitable probe and probe length such that
all traverse points can be sampled. Consider sampling from
opposite sides
of the stack (four total sampling ports) for large stacks, to
permit use of shorter probe lengths. Mark the probe with heat
resistant tape or by some other method to denote the proper
distance into the stack or duct for each sampling point. Place
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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known volumes of water in the first two impingers. Weigh and
record the weight of the silica gel to the nearest 0.5 g, and
transfer the silica gel to the fourth impinger; alternatively, the
silica gel may first be transferred to the impinger, and the weight
of the silica gel plus impinger recorded.
2.2.2 Select a total sampling time such that a minimum total gas
volume of 0.60 scm (21 scf) will be collected, at a rate no greater
than 0.021 mVmin (0.75 cfm) . When both moisture content and
pollutant emission rate are to be determined, the moisture
determination shall be simultaneous with, and for the same total
length of time as, the pollutant emission rate run, unless
otherwise specified in an applicable subpart of the standards.
2.2.3 Set up the sampling train as shown in Figure 4-1. Turn on
the probe heater and (if applicable) the filter heating system to
temperatures of about 120°C (248°F), to prevent water condensation
ahead of the condenser; allow time for the temperatures to
stabilize. Place crushed ice in the ice bath container. It is
recommended, but not required, that a leak check be done, as
follows: Disconnect the probe from the first impinger or (if
applicable) from the filter holder. Plug the inlet to the first
impinger (or filter holder), and pull a 380 mm (15 in.) Hg vacuum;
a lower vacuum may be used, provided that it is not exceeded during
the test. A leakage rate in excess of 4 percent of the average
sampling rate or 0.00057 mVmin (0.02 cfm), whichever is less, is
unacceptable. Following the leak check, reconnect the probe to the
sampling train.
2.2.4 During the sampling run, maintain a sampling rate within 10
percent of constant rate, or as specified by the Administrator.
For each run, record the data required on the example data sheet
shown in Figure 4-2. Be sure to record the dry gas meter reading
at the beginning and end of each sampling time increment and
whenever sampling is halted. Take other appropriate readings at
each sample point, at least once during each time increment.
2.2.5 To begin sampling, position the probe tip at the first
traverse point. Immediately start the pump, and adjust the flow to
the desired rate. Traverse the cross section, sampling at each
traverse point for an equal length of time. Add more ice and, if
necessary, salt to maintain a temperature of less than 20°C (68°F<)
at the silica gel outlet.
2.2.6 After collecting the sample, disconnect the probe from the
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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filter holder (or from the first impinger), and conduct a leak
check (mandatory) as described in Section 2.2.3. Record the leak
rate. If the leakage rate exceeds the allowable rate, the tester
shall either reject the test results or shall correct the sample
volume as in Section 6.3 of Method 5. Next, measure the volume of
the moisture condensed to the nearest ml. Determine the increase
in weight of the silica gel (or silica gel plus impinger) to the
nearest 0.5 g. Record this information (see example data sheet,
Figure 4-3), and calculate the moisture percentage, as described in
2.3 below.
2.2.7 A quality control check of the volume metering system at the
field site is suggested before collecting the sample following the
procedure in Method 5, Section 4.4.
2.3 Calculations. Carry out the following calculations, retaining
at least one extra decimal figure beyond that of the acquired data.
Round off figures after final calculation.
2.3.1 Nomenclature.
Bws = Proportion of water vapor, by volume, in the gas stream.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29o92 in. Hg) .
R = Ideal gas constant, 0.06236 (mm Hg) (m3) / (g-mole) (°K) for
metric units and 21.85 (in. Hg) (ft3) / (Ib-mole) (°R) for
English units.
Tm = Absolute temperature at meter, °K (°R) .
Tstd = Standard absolute temperature, 293°K (528°R) .
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
AVm = Incremental dry gas volume measured by dry gas meter at
each traverse point, dcm (dcf).
= DrY 9as volume measured by the dry gas meter, corrected to
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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standard conditions, dscm (dscf).
vwcistd) = Volume of water vapor condensed, corrected to standard
conditions, scm (scf).
vwsg(std) = Volume of water vapor collected .in silica gel, corrected
to standard conditions, scm (scf) .
Vf = Final volume of condenser water, ml.
Vi = Initial volume, if any, of condenser water, ml.
Wf = Final weight of silica gel or silica gel plus impinger, g.
Wi = Initial weight of silica gel or silica gel plus impinger,
Y = Dry gas meter calibration factor.
pw = Density of water, 0.9982 g/ml (0.002201 Ib/ml).
2.3.2 Volume of Water Vapor Condensed.
v =(v -v )p RTstd
«=(.*., t iJP»PstdMw Eq. 4-1
Where:
K! = 0.001333 mVml for metric units,
= 0.04707 ftVml for English units.
2.3.3 Volume of Water Collected in Silica Gel
RT
v
f - i std
Eq. 4-2
= K2(Wf - W.)
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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Where:
K2 = 0.001335 m3/g for metric units,
= 0.04715 ftVg for English units.
2.3.4 Sample Gas Volume.
(PJ (Tstd)
11 Eq.
V = V Y-
m(std) m
v p
= K Y m m
3
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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Where:
K3 = 0.3858 °K/mm Hg for metric units,
= 17.64 °R/in. Hg for English units.
NOTE: If the post-test leak rate (Section 2.2.6) exceeds the
allowable rate, correct the value of Vra in Equation 4-3, as
described in Section 6.3 of Method 5.
2.3.5 Moisture Content.
3 wc(std) wsg(std) Eq. 4~4
ws V +V +V
wc(std) wsg(std) m(std)
NOTE: In saturated or moisture droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be
made, one using a value based upon the saturated conditions (see
Section 1.2), and another based upon the results of the impinger
analysis. The lower of these two values of Bws shall be considered
correct.
2.3.6 Verification of Constant Sampling Rate. For each time
increment, determine the AVm. Calculate the average. If the value
for any time increment differs from the average by more than 10
percent, reject the results, and repeat the run.
3. APPROXIMATION METHOD
The approximation method described below is presented only as a
suggested method (see Section 1.2).
3.1 Apparatus. See Figure 4-4.
3.1.1 Probe. Stainless steel or glass tubing, sufficiently heated
to prevent water condensation and equipped with a filter (either
in-stack or heated out-stack) to remove particulate matter. A plu*g
of glass wool, inserted into the end of the probe, is a
satisfactory filter.
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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3.1.2 Impingers. Two midget impingers, each with 30-ml capacity,
or equivalent.
3.1.3 Ice Bath. Container and ice, to aid in condensing moisture
in impingers.
3.1.4 Drying Tube. Tube packed with new or regenerated 6- to 16-
mesh indicating-type silica gel (or equivalent desiccant), to dry
the sample gas and to protect the meter and pump.
3.1.5 Valve. Needle valve, to regulate the sample gas flow rate.
3.1.6 Pump. Leak-free, diaphragm type, or equivalent, to pull the
gas sample through the train.
3.1.7 Volume Meter. Dry gas meter, sufficiently accurate to
measure the sample volume to within 2 percent, and calibrated over
the range of flow rates and conditions actually encountered during
sampling.
3.1.8 Rate Meter. Rotameter, to measure the flow range from 0 to
3 liters/min (0 to 0.11 cfm) .
3.1.9 Graduated Cylinder. 25-ml.
3.1.10 Barometer. Mercury, aneroid, or other barometer, as
described in Section 2.1.5 above.
3.1.11 Vacuum Gauge. At least 760-mm (30-in.) Hg gauge, to be
used for the sampling leak check.
3.2 Procedure.
3.2.1 Place exactly 5 ml water in each impinger. Leak check the
sampling train as follows: Temporarily insert a vacuum gauge at or
near the probe inlet; then, plug the probe inlet, and pull a vacuum
of at least 250 mm (10 in.) Hg. Note the time rate of change of
the dry gas meter dial; alternatively, a rotameter (0 to 40 cc/min)
may be temporarily attached to the dry gas meter outlet to
determine the leakage rate. A leak rate not in excess of 2 percent
of the average sampling rate is acceptable. NOTE: Carefully
release the probe inlet plug before turning off the pump.
3.2.2 Connect the probe, insert it into the stack, and sample at
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EMTIC TM-004 EMTIC NSPS TEST METHOD
Page 10
a constant rate of 2 liters/min (0.071 cfm) . Continue sampling
until the dry gas meter registers about 30 liters (1.1 ft3) or
until visible liquid droplets are carried over from the first
impinger to the second. Record temperature, pressure, and dry gas
meter readings as required by Figure 4-5.
3.2.3 After collecting the sample, combine the contents of the two
impingers, and measure the volume to the nearest 0.5 ml.
3.3 Calculations. The calculation method presented is designed to
estimate the moisture in the stack gas; therefore, other data,
which are only necessary for accurate moisture determinations, are
not collected. The following equations adequately estimate the
moisture content, for the purpose of determining isokinetic
sampling rate settings.
3.3.1 Nomenclature.
B^ = Approximate proportion by volume of water vapor in the gas
stream leaving the second impinger, 0.025.
BHS = Water vapor in the gas stream, proportion by volume.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg) .
R = Ideal gas constant, 0.06236 [(mm Hg) (m3) ] / [ (g-mole) (°K) ]
for metric units and 21.85 [(in. Hg) (ft3) ] / [(Ib-mole) (°R)]
for English units.
Tm = Absolute temperature at meter, °K (°R) .
Tstd = Standard absolute temperature, 293°R (528°R) .
Vf = Final volume of impinger contents, ml.
VA = Initial volume of impinger contents, ml. ,
vm = Dry gas volume measured by dry gas meter, dcm (dcf).
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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vm(stdj = DrY gas volume measured by dry gas meter, corrected to
standard conditions, dscm (dscf) .
Y = Dry gas meter calibration factor.
pw = Density of water, 0.9982 g/ml (0.002201 Ib/ml) .
3.3.2 Volume of Water Vapor Collected.
Pstc,Mw Eq. 4-5
Where :
K! = 0.001333 m3/ml for metric units,
= 0.04707 ftVml for English units
3.3.3 Gas Volume.
T
P I I T
Eq. 4-6
Pm M
= K. V -S
2 mm
Where:
K2 = 0.03858 °K/mm Hg for metric units,
= 17.64 °R/in. Hg for English units.
3.3.4 Approximate Moisture Content.
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EMTIC TM-004 EMTIC NSPS TEST METHOD
Page 12
B = +B
ws V +V wm
wcv m(std) Eq. 4-7
wc -+(0.025)
V +V
we m(std)
4. CALIBRATION
4.1 For the reference method, calibrate the metering system,
temperature gauges, and barometer according to Sections 5.3, 5.5,
and 5.7, respectively, of Method 5. The recommended leak check of
the metering system (Section 5.6 of Method 5) also applies to the
reference method. For the approximation method, use the procedures
outlined in Section 5.1.1 of Method 6 to calibrate the metering
system, and the procedure of Method 5, Section 5.7, to calibrate
the barometer.
5. BIBLIOGRAPHY
1. Air Pollution Engineering Manual (Second Edition). Danielson,
J.A. (ed.). U.S. Environmental Protection Agency, Office of Air
Quality Planning and Standards. Research Triangle Park, NC.
Publication No. AP-40. 1973.
2. Devorkin, Howard, et al. Air Pollution Source Testing Manual.
Air Pollution Control District, Los Angeles, CA. November 1963.
3. Methods for Determination of Velocity, Volume, Dust and Mist
Content of Gases. Western Precipitation Division of Joy
Manufacturing Co. Los Angeles, CA. Bulletin WP-50. 1968.
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EMTIC TM-004
EMTIC NSPS TEST METHOD
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Filter
(Either In Stack)
or Out of Stack)
Stack
/ Wall
Condenser-Ice Bath System Including Silica Gel Tube
I
method.
Figure 4-1. Moisture sampling train reference
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EMTIC TM-004 EMTIC NSPS TEST METHOD
Page 14
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Figure 4-2. Field Moisture Determination Reference Method.
Plant
Location.
Operator.
Date
Run No.
Ambient temperature.
Barometric pressure.
Probe Length
SCHEMATIC OF STACK CROSS SECTION
Traverse
Pt. No.
Sampling
Time
(9) , min
Stack
Temperature
°C (°F)
Average
Pressure
differential across
orifice meter AH
mm (in.) H20
Meter
Reading gas
sample
volume
m3 (ft3)
AVn
m3
(ft3)
Gas sample
temperature at
dry gas meter
Inlet
Tmln
°C(°F)
Outlet
Tnw
°C(°F)
Temperature
of gas
leaving
condenser or
last
impinger
°C(°F)
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EMTIC TM-004 EMTIC NSPS TEST METHOD
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Figure 4-3. Analytical data - reference method.
Impinger Silica gel
volume. ml weight, o
Final
Initial
Difference
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EMTIC NSPS TEST METHOD
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Figure 4-4,, Moisture Samping Train - Approximation Method.
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EMTIC TM-004
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Figure 4-5. Field Moisture Determination - Approximation Method.
Location.
Test
Date
Operator
Barometric pressure.
Comments:
Clock Time
Gas volume
through
meter, (VB) ,
m3 (ft3)
Rate meter
setting mVmin
(ftVmin)
Meter
temperature
0 C (° F)
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APPENDIX A TO PART 63--TEST METHODS
* * * * *
METHOD 315 - DETERMINATION OF PARTICULATE AND METHYLENE CHLORIDE
EXTRACTABLE MATTER (MCEM) FROM SELECTED SOURCES
AT PRIMARY ALUMINUM PRODUCTION FACILITIES
NOTE: This method does not include all of the specifications (e.g., equipment and supplies) and
procedures (e.g., sampling and analytical) essential to its performance. Some material is incorporated by
reference from other methods in this part. Therefore, to obtain reliable results, persons using this method
should have a thorough knowledge of at least the following additional test methods: Method 1, Method
2, Method 3, and Method 5 of 40 CFR part 60, appendix A.
1.0 Scope and Application.
1.1 Analytes. Particulate matter (PM). No CAS number assigned. Methylene chloride
extractable matter (MCEM). No CAS number assigned.
1.2 Applicability. This method is applicable for the simultaneous determination of PM and
MCEM when specified in an applicable regulation. This method was developed by consensus with the
Aluminum Association and the U.S. Environmental Protection Agency (EPA) and has limited precision
estimates for MCEM; it should have similar precision to Method 5 for PM in 40 CFR part 60, appendix
A since the procedures are similar for PM.
1.3 Data quality objectives. Adherence to the requirements of this method will enhance the
quality of the data obtained from air pollutant sampling methods.
2.0 Summary of Method.
Particulate matter and MCEM are withdrawn isokinetically from the source. PM is collected on
a glass fiber filter maintained at a temperature in the range of 120 ± 14°C (248 ± 25°F) or such other
temperature as specified by an applicable subpart of the standards or approved by the Administrator for a
particular application. The PM mass, which includes any material that condenses on the probe and is
subsequently removed in an acetone rinse or on the filter at or above the filtration temperature, is
determined gravimetrically after removal of uncombined water. MCEM is then determined by adding a
methylene chloride rinse of the probe and filter holder, extracting the condensable hydrocarbons
collected in the impinger water, adding an acetone rinse followed by a methylene chloride rinse of the
sampling train components after the filter and before the silica gel impinger, and determining residue
gravimetrically after evaporating the solvents.
1Q_ Definitions. [Reserved]
4.0 Interferences. [Reserved]
10 Safety.
This method may involve hazardous materials, operations, and equipment. This method does not
purport to address all of the safety problems associated with its use. It is the responsibility of the user of
this method to establish appropriate safety and health practices and determine the applicability of
regulatory limitations prior to performing this test method.
6.0 Equipment and Supplies.
NOTE: Mention of trade names or specific products does not constitute endorsement by the
EPA.
6.1 Sample collection. The following items are required for sample collection:
6.1.1 Sampling train. A schematic of the sampling train used in this method is shown in Figure
5-1, Method 5,40 CFR part 60, appendix A. Complete construction details are given in APTD-0581
(Reference 2 in section 17.0 of this method); commercial models of this train are also available. For
changes from APTD-0581 and for allowable modifications of the train shown in Figure 5-1, Method 5,40
CFR part 60, appendix, A see the following subsections.
NOTE: The operating and maintenance procedures for the sampling train are described in
APTD-0576 (Reference 3 in section 17.0 of this method). Since correct usage is important in obtaining
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valid results, all users should read APTD-0576 and adopt the operating and maintenance procedures
outlined in it, unless otherwise specified herein. The use of grease for sealing sampling train components
is not recommended because many greases are soluble in methylene chloride. The sampling train
consists of the following components:
6.1.1.1 Probe nozzle. Glass or glass lined with sharp, tapered leading edge. The angle of taper
shall be <30°, and the taper shall be on the outside to preserve a constant internal diameter. The probe
nozzle shall be of the button-hook or elbow design, unless otherwise specified by the Administrator.
Other materials of construction may be used, subject to the approval of the Administrator. A range of
nozzle sizes suitable for isokinetic sampling should be available. Typical nozzle sizes range from 0.32 to
1.27 cm (1/8 to 1/2 in.) inside diameter (ID) in increments of 0.16 cm (1/16 in.). Larger nozzle sizes are
also available if higher volume sampling trains are used. Each nozzle shall be calibrated according to the
procedures outlined in section 10.0 of this method.
6.1.1.2 Probe liner. Borosilicate or quartz glass tubing with a heating system capable of
maintaining a probe gas temperature at the exit end during sampling of 120 ± 14°C (248 ± 25°F), or such
other temperature as specified by an applicable subpart of the standards or approved by the
Administrator for a particular application. Because the actual temperature at the outlet of the probe is
not usually monitored during sampling, probes constructed according to APTD-0581 and using the
calibration curves of APTD-0576 (or calibrated according to the procedure outlined in APTD-0576) will
be considered acceptable. Either borosilicate or quartz glass probe liners may be used for stack
temperatures up to about 480°C (900°F); quartz liners shall be used for temperatures between 480 and
900°C (900 and 1,650°F). Both types of liners may be used at higher temperatures than specified for
short periods of time, subject to the approval of the Administrator. The softening temperature for
borosilicate glass is 820°C (1,500°F) and for quartz glass it is 1,500°C (2,700°F).
6.1.1.3 Pitot tube. Type S, as described in section 6.1 of Method 2, 40 CFR part 60, appendix A,
or other device approved by the Administrator. The pitot tube shall be attached to the probe (as shown in
Figure 5-1 of Method 5, 40 CFR part 60, appendix A) to allow constant monitoring of the stack gas
velocity. The impact (high pressure) opening plane of the pitot tube shall be even with or above the
nozzle entry plane (see Method 2, Figure 2-6b, 40 CFR part 60, appendix A) during sampling. The Type
S pitot tube assembly shall have a known coefficient, determined as outlined in section 10.0 of Method 2,
40 CFR part 60, appendix A.
6.1.1.4 Differential pressure gauge. Inclined manometer or equivalent device (two), as described
in section 6.2 of Method 2, 40 CFR part 60, appendix A. One manometer shall be used for velocity head
(Dp) readings, and the other, for orifice differential pressure readings.
6.1.1.5 Filter holder. Borosilicate glass, with a glass frit filter support and a silicone rubber
gasket. The holder design shall provide a positive seal against leakage from the outside or around the
filter. The holder shall be attached immediately at the outlet of the probe (or cyclone, if used).
6.1.1.6 Filter heating system. Any heating system capable of maintaining a temperature around
the filter holder of 120 ± 14°C (248 ± 25°F) during sampling, or such other temperature as specified by an
applicable subpart of the standards or approved by the Administrator for a particular application.
Alternatively, the tester may opt to operate the equipment at a temperature lower than that specified. A
temperature gauge capable of measuring temperature to within 3°C (5.4°F) shall be installed so that the
temperature around the filter holder can be regulated and monitored during sampling. Heating systems
other than the one shown in APTD-0581 may be used.
6.1.1.7 Temperature sensor. A temperature sensor capable of measuring temperature to within
±3°C (5.4°F) shall be installed so that the sensing tip of the temperature sensor is in direct contact with
the sample gas, and the temperature around the filter holder can be regulated and monitored during
sampling. *
6.1.1.8 Condenser. The following system shall be used to determine the stack gas moisture
content: four glass impingers connected in series with leak-free ground glass fittings. The first, third,
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and fourth impingers shall be of the Greenburg-Smith design, modified by replacing the tip with a 1.3 cm
(1/2 in.) ID glass tube extending to about 1.3 cm (1/2 in.) from the bottom of the flask. The second
impinger shall be of the Greenburg-Smith design with the standard tip. The first and second impingers
shall contain known quantities of water (section 8.3.1 of this method), the third shall be empty, and the
fourth shall contain a known weight of silica gel or equivalent desiccant. A temperature sensor capable
of measuring temperature to within 1°C (2°F) shall be placed at the outlet of the fourth impinger for
monitoring.
6.1.1.9 Metering system. Vacuum gauge, leak-free pump, temperature sensors capable of
measuring temperature to within 3°C (5.4°F), dry gas meter (DGM) capable of measuring volume to
within 2 percent, and related equipment, as shown in Figure 5-1 of Method 5, 40 CFR part 60, appendix
A. Other metering systems capable of maintaining sampling rates within 10 percent of isokinetic and of
determining sample volumes to within 2 percent may be used, subject to the approval of the
Administrator. When the metering system is used in conjunction with a pitot tube, the system shall allow
periodic checks of isokinetic rates.
6.1.1.10 Sampling trains using metering systems designed for higher flow rates than that
described in APTD-0581 or APTD-0576 may be used provided that the specifications of this method are
met.
6.1.2 Barometer. Mercury, aneroid, or other barometer capable of measuring atmospheric
pressure to within 2.5 mm (0.1 in.) Hg.
NOTE: The barometric reading may be obtained from a nearby National Weather Service
station. In this case, the station value (which is the absolute barometric pressure) shall be requested and
an adjustment for elevation differences between the weather station and sampling point shall be made at
a rate of minus 2.5 mm (0.1 in) Hg per 30 m (100 ft) elevation increase or plus 2.5 mm (0.1 in) Hg per 30
m (100 ft) elevation decrease.
6.1.3 Gas density determination equipment. Temperature sensor and pressure gauge, as
described in sections 6.3 and 6.4 of Method 2, 40 CFR part 60, appendix A, and gas analyzer, if
necessary, as described in Method 3,40 CFR part 60, appendix A. The temperature sensor shall,
preferably, be permanently attached to the pitot tube or sampling probe in a fixed configuration, such that
the tip of the sensor extends beyond the leading edge of the probe sheath and does not touch any metal.
Alternatively, the sensor may be attached just prior to use in the field. Note, however, that if the
temperature sensor is attached in the field, the sensor must be placed in an interference-free arrangement
with respect to the Type S pitot tube openings (see Method 2, Figure 2-4,40 CFR part 60, appendix A).
As a second alternative, if a difference of not more than 1 percent in the average velocity measurement is
to be introduced, the temperature sensor need not be attached to the probe or pitot tube. (This alternative
is subject to the approval of the Administrator.)
6.2 Sample recovery. The following items are required for sample recovery:
6.2.1 Probe-liner and probe-nozzle brushes. Nylon or Teflon® bristle brushes with stainless
steel wire handles. The probe brush shall have extensions (at least as long as the probe) constructed of
stainless steel, nylon, Teflon®, or similarly inert material. The brushes shall be properly sized and
shaped to brush out the probe liner and nozzle.
6.2.2 Wash bottles. Glass wash bottles are recommended. Polyethylene or tetrafluoroethylene
(TFE) wash bottles may be used, but they may introduce a positive bias due to contamination from the
bottle. It is recommended that acetone not be stored in polyethylene or TFE bottles for longer than a
month.
6.2.3 Glass sample storage containers. Chemically resistant, borosilicate glass bottles, for
acetone and methylene chloride washes and impinger water, 500 ml or 1,000 ml. Screw-cap liners shall
either be rubber-backed Teflon® or shall be constructed so as to be leak-free and resistant to chemical
attack by acetone or methylene chloride. (Narrow-mouth glass bottles have been found to be less prone
to leakage.) Alternatively, polyethylene bottles may be used.
6.2.4 Petri dishes. For filter samples, glass, unless otherwise specified by the Administrator.
6.2.5 Graduated cylinder and/or balance. To measure condensed water, acetone wash and
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methylene chloride wash used during field recovery of the samples, to within 1 ml or 1 g. Graduated
cylinders shall have subdivisions no greater than 2 ml. Most laboratory balances are capable of weighing
to the nearest 0.5 g or less. Any such balance is suitable for use here and in section 6.3.4 of this method.
6.2.6 Plastic storage containers. Air-tight containers to store silica gel.
6.2.7 Funnel and rubber policeman. To aid in transfer of silica gel to container; not necessary if
silica gel is weighed in the field.
6.2.8 Funnel. Glass or polyethylene, to aid in sample recovery.
6.3 Sample analysis. The following equipment is required for sample analysis:
6.3.1 Glass or Teflon® weighing dishes.
6.3.2 Desiccator. It is recommended that fresh desiccant be used to minimize the chance for
positive bias due to absorption of organic material during drying.
6.3.3 Analytical balance. To measure to within 0.1 mg.
6.3.4 Balance. To measure to within 0.5 g.
6.3.5 Beakers. 250ml.
6.3.6 Hygrometer. To measure the relative humidity of the laboratory environment.
6.3.7 Temperature sensor. To measure the temperature of the laboratory environment.
6.3.8 Buchner fritted funnel. 30 ml size, fine (<50 micron)-porosity fritted glass.
6.3.9 Pressure filtration apparatus.
6.3.10 Aluminum dish. Flat bottom, smooth sides, and flanged top, 18 mm deep and with an
inside diameter of approximately 60 mm.
7.0 Reagents and Standards.
7.1 Sample collection. The following reagents are required for sample collection:
7.1.1 Filters. Glass fiber filters, without organic binder, exhibiting at least 99.95 percent
efficiency (<0.05 percent penetration) on 0.3 micron dioctyl phthalate smoke particles. The filter
efficiency test shall be conducted in accordance with ASTM Method D 2986-95A (incorporated by
reference in § 63.841 of this part). Test data from the supplier's quality control program are sufficient for
this purpose. In sources containing S02 or S03, the filter material must be of a type that is unreactive to
S02 or S03. Reference 10 in section 17.0 of this method may be used to select the appropriate filter.
7.1.2 Silica gel. Indicating type, 6 to 16 mesh. If previously used, dryatl75°C(350°F)for2
hours. New silica gel may be used as received. Alternatively, other types of desiccants (equivalent or
better) may be used, subject to the approval of the Administrator.
7.1.3 Water. When analysis of the material caught in the impingers is required, deionized
distilled water shall be used. Run blanks prior to field use to eliminate a high blank on test samples.
7.1.4 Crushed ice.
7.1.5 Stopcock grease. Acetone-insoluble, heat-stable silicone grease. This is not necessary if
screw-on connectors with Teflon® sleeves, or similar, are used. Alternatively, other types of stopcock
grease may be used, subject to the approval of the Administrator. [Caution: Many stopcock greases are
methylene chloride-soluble. Use sparingly and carefully remove prior to recovery to prevent
contamination of the MCEM analysis.]
7.2 Sample recovery. The following reagents are required for sample recovery:
7.2.1 Acetone. Acetone with blank values < 1 ppm, by weight residue, is required. Acetone
blanks may be run prior to field use, and only acetone with low blank values may be used. In no case
shall a blank value of greater than 1E-06 of the weight of acetone used be subtracted from the sample
weight.
NOTE: This is more restrictive than Method 5,40 CFR part 60, appendix A. At least one
vendor (Supelco Incorporated located in Bellefonte, Pennsylvania) lists <1 mg/1 as residue for its
Environmental Analysis Solvents.
7.2.2 Methylene chloride. Methylene chloride with a blank value <1.5 ppm, by weight, residue.
Methylene chloride blanks may be run prior to field use, and only methylene chloride with low blank *
values may be used. In no case shall a blank value of greater than 1.6E-06 of the weight of methylene
chloride used be subtracted from the sample weight.
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NOTE: A least one vendor quotes <1 mg/1 for Environmental Analysis Solvents-grade
methylene chloride.
7.3 Sample analysis. The following reagents are required for sample analysis:
7.3.1 Acetone. Same as in section 7.2.1 of this method.
7.3.2 Desiccant. Anhydrous calcium sulfate, indicating type. Alternatively, other types of
desiccants may be used, subject to the approval of the Administrator.
7.3.3 Methylene chloride. Same as in section 7.2.2 of this method.
8.0 Sample Collection. Preservation. Storage, and Transport.
NOTE: The complexity of this method is such that, in order to obtain reliable results, testers
should be trained and experienced with the test procedures.
8.1 Pretest preparation. It is suggested that sampling equipment be maintained according to the
procedures described in APTD-0576.
8.1.1 Weigh several 200 g to 300 g portions of silica gel in airtight containers to the nearest 0.5
g. Record on each container the total weight of the silica gel plus container. As an alternative, the silica
gel need not be preweighed but may be weighed directly in its impinger or sampling holder just prior to
train assembly.
8.1.2 A batch of glass fiber filters, no more than 50 at a time, should placed in a soxhlet
extraction apparatus and extracted using methylene chloride for at least 16 hours. After extraction, check
filters visually against light for irregularities, flaws, or pinhole leaks. Label the shipping containers
(glass or plastic petri dishes), and keep the filters in these containers at all times except during sampling
and weighing.
8.1.3 Desiccate the filters at 20 ± 5.6°C (68 ± 10°F) and ambient pressure for at least 24 hours
and weigh at intervals of at least 6 hours to a constant weight, i.e., <0.5 mg change from previous
weighing; record results to the nearest 0.1 mg. During each weighing the filter must not be exposed to
the laboratory atmosphere for longer than 2 minutes and a relative humidity above 50 percent.
Alternatively (unless otherwise specified by the Administrator), the filters may be oven-dried at 104°C
(220°F) for 2 to 3 hours, desiccated for 2 hours, and weighed. Procedures other than those described,
which account for relative humidity effects, may be used, subject to the approval of the Administrator.
8.2 Preliminary determinations.
8.2.1 Select the sampling site and the minimum number of sampling points according to Method
1,40 CFR part 60, appendix A or as specified by the Administrator. Determine the stack pressure,
temperature, and the range of velocity heads using Method 2,40 CFR part 60, appendix A; it is
recommended that a leak check of the pitot lines (see section 8.1 of Method 2,40 CFR part 60, appendix
A) be performed. Determine the moisture content using Approximation Method 4 (section 1.2 of
Method 4, 40 CFR part 60, appendix A) or its alternatives to make isokinetic sampling rate settings.
Determine the stack gas dry molecular weight, as described in section 8.6 of Method 2,40 CFR part 60,
appendix A; if integrated Method 3 sampling is used for molecular weight determination, the integrated
bag sample shall be taken simultaneously with, and for the same total length of time as, the particulate
sample run.
8.2.2 Select a nozzle size based on the range of velocity heads such that it is not necessary to
change the nozzle size in order to maintain isokinetic sampling rates. During the run, do not change the
nozzle size. Ensure that the proper differential pressure gauge is chosen for the range of velocity heads
encountered (see section 8.2 of Method 2, 40 CFR part 60, appendix A).
8.2.3 Select a suitable probe liner and probe length such that all traverse points can be sampled.
For large stacks, consider sampling from opposite sides of the stack to reduce the required probe length.
8.2.4 Select a total sampling time greater than or equal to the minimum total sampling time
specified in the test procedures for the-specific industry such that: (1) The sampling time per point is not
less than 2 minutes (or some greater time interval as specified by the Administrator); and (2) the sample
volume taken (corrected to standard conditions) will exceed the required minimum total gas sample
volume. The latter is based on an approximate average sampling rate.
8.2.5 The sampling time at each point shall be the same. It is recommended that the number of
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minutes sampled at each point be an integer or an integer plus one-half minute, in order to eliminate
timekeeping errors.
8.2.6 In some circumstances (e.g., batch cycles), it may be necessary to sample for shorter times
at the traverse points and to obtain smaller gas sample volumes. In these cases, the Administrator's
approval must first be obtained.
8.3 Preparation of sampling train.
8.3.1 During preparation and assembly of the sampling train, keep all openings where
contamination can occur covered until just prior to assembly or until sampling is about to begin. Place
100 ml of water in each of the first two impingers, leave the third impinger empty, and transfer
approximately 200 to 300 g of preweighed silica gel from its container to the fourth impinger. More
silica gel may be used, but care should be taken to ensure that it is not entrained and carried out from the
impinger during sampling. Place the container in a clean place for later use in the sample recovery.
Alternatively, the weight of the silica gel plus impinger may be determined to the nearest 0.5 g and
recorded.
8.3.2 Using a tweezer or clean disposable surgical gloves, place a labeled (identified) and
weighed filter in the filter holder. Be sure that the filter is properly centered and the gasket properly
placed so as to prevent the sample gas stream from circumventing the filter. Check the filter for tears
after assembly is completed.
8.3.3 When glass liners are used, install the selected nozzle using a Viton A 0-ring when stack
temperatures are less than 260°C (500°F) and an asbestos string gasket when temperatures are higher.
See APTD-0576 for details. Mark the probe with heat-resistant tape or by some other method to denote
the proper distance into the stack or duct for each sampling point.
8.3.4 Set up the train as in Figure 5-1 of Method 5,40 CFR part 60, appendix A, using (if
necessary) a very light coat of silicone grease on all ground glass joints, greasing only the outer portion
(see APTD-0576) to avoid possibility of contamination by the silicone grease. Subject to the approval of
the Administrator, a glass cyclone may be used between the probe and filter holder when the total
particulate catch is expected to exceed 100 mg or when water droplets are present in the stack gas.
8.3.5 Place crushed ice around the impingers.
8.4 Leak-check procedures.
8.4.1 Leak check of metering system shown in
Figure 5-1 of Method 5,40 CFR part 60, appendix A. That portion of the sampling train from the pump
to the orifice meter should be leak-checked prior to initial use and after each shipment. Leakage after the
pump will result in less volume being recorded than is actually sampled. The following procedure is
suggested (see Figure 5-2 of Method 5, 40 CFR part 60, appendix A): Close the main valve on the meter
box. Insert a one-hole rubber stopper with rubber tubing attached into the orifice exhaust pipe.
Disconnect and vent the low side of the orifice manometer. Close off the low side orifice tap. Pressurize
the system to 13 to 18 cm (5 to 7 in.) water column by blowing into the rubber tubing. Pinch off the
tubing, and observe the manometer for 1 minute. A loss of pressure on the manometer indicates a leak in
the meter box; leaks, if present, must be corrected.
8.4.2 Pretest leak check. A pretest leak-check is recommended but not required. If the pretest
leak-check is conducted, the following procedure should be used.
8.4.2.1 After the sampling train has been assembled, turn on and set the filter and probe heating
systems to the desired operating temperatures. Allow time for the temperatures to stabilize. If a Viton A
0-ring or other leak-free connection is used in assembling the probe nozzle to the probe liner, leak-check
the train at the sampling site by plugging the nozzle and pulling a 380 mm (15 in.) Hg vacuum.
NOTE: A lower vacuum may be used, provided that it is not exceeded during the test.
8.4.2.2 If an asbestos string is used, do not connect the probe to the train during the leak check.
Instead, leak-check the train by first plugging the inlet to the filter holder (cyclone, if applicable) and
pulling a 380 mm (15 in.) Hg vacuum. (See NOTE in section 8.4.2.1 of this method). Then connect th*e
probe to the train and perform the leak check at approximately 25 mm (1 in.) Hg vacuum; alternatively,
the probe may be leak-checked with the rest of the sampling train, in one step, at 380 mm (15 in.) Hg
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vacuum. Leakage rates in excess of 4 percent of the average sampling rate or 0.00057 mVmin (0.02
cfm), whichever is less, are unacceptable.
8.4.2.3 The following leak check instructions for the sampling train described in APTD-0576
and APTD-058I may be helpful. Start the pump with the bypass valve fully open and the coarse adjust
valve completely closed. Partially open the coarse adjust valve and slowly close the bypass valve until
the desired vacuum is reached. Do not reverse the direction of the bypass valve, as this will cause water
to back up into the filter holder. If the desired vacuum is exceeded, either leak-check at this higher
vacuum or end the leak check as shown below and start over.
8.4.2.4 When the leak check is completed, first slowly remove the plug from the inlet to the
probe, filter holder, or cyclone (if applicable) and immediately turn off the vacuum pump. This prevents
the water in the impingers from being forced backward into the filter holder and the silica gel from being
entrained backward into the third impinger.
8.4.3 Leak checks during sample run. If, during the sampling run, a component (e.g., filter
assembly or impinger) change becomes necessary, a leak check shall be conducted immediately before
the change is made. The leak check shall be done according to the procedure outlined in section 8.4.2 of
this method, except that it shall be done at a vacuum equal to or greater than the maximum value
recorded up to that point in the test. If the leakage rate is found to be no greater than 0.00057 mVmin
(0.02 cfm) or 4 percent of the average sampling rate (whichever is less), the results are acceptable, and
no correction will need to be applied to the total volume of dry gas metered; if, however, a higher
leakage rate is obtained, either record the leakage rate and plan to correct the sample volume as shown in
section 12.3 of this method or void the sample run.
NOTE: Immediately after component changes, leak checks are optional; if such leak checks are
done, the procedure outlined in section 8.4.2 of this method should be used.
8.4.4 Post-test leak check. A leak check is mandatory at the conclusion of each sampling run.
The leak check shall be performed in accordance with the procedures outlined in section 8.4.2 of this
method, except that it shall be conducted at a vacuum equal to or greater than the maximum value
reached during the sampling run. If the leakage rate is found to be no greater than 0.00057 mVmin
(0.02 cfm) or 4 percent of the average sampling rate (whichever is less), the results are acceptable, and
no correction need be applied to the total volume of dry gas metered. If, however, a higher leakage rate
is obtained, either record the leakage rate and correct the sample volume, as shown in section 12.4 of this
method, or void the sampling run.
8.5 Sampling train operation. During the sampling run, maintain an isokinetic sampling rate
(within 10 percent of true isokinetic unless otherwise specified by the Administrator) and a temperature
around the filter of 120 ± 14°C (248 ± 25°F), or such other temperature as specified by an applicable
subpart of the standards or approved by the Administrator.
8.5.1 For each run, record the data required on a data sheet such as the one shown in Figure 5-2
of Method 5, 40 CFR part 60, appendix A. Be sure to record the initial reading. Record the DGM
readings at the beginning and end of each sampling time increment, when changes in flow rates are
made, before and after each leak-check, and when sampling is halted. Take other readings indicated by
Figure 5-2 of Method 5, 40 CFR part 60, appendix A at least once at each sample point during each time
increment and additional readings when significant changes (20 percent variation in velocity head
readings) necessitate additional adjustments in flow rate. Level and zero the manometer. Because the
manometer level and zero may drift due to vibrations and temperature changes, make periodic checks
during the traverse.
8.5.2 Clean the portholes prior to the test run to minimize the chance of sampling deposited
material. To begin sampling, remove the nozzle cap and verify that the filter and probe heating systems
are up to temperature and that the pitot tube and probe are properly positioned. Position the nozzle at the
first traverse point with the tip pointing directly into the gas stream. Immediately start the pump and
adjust the flow to isokinetic conditions. Nomographs are available, which aid in the rapid adjustment of
the isokinetic sampling rate without excessive computations. These nomographs are designed for use
when the Type S pitot tube coefficient (Cp) is 0.85 ± 0.02 and the stack gas equivalent density (dry
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molecular weight) is 29 ± 4. APTD-0576 details the procedure for using the nomographs. If Cp and Md
are outside the above-stated ranges, do not use the nomographs unless appropriate steps (see Reference 7
in section 17.0 of this method) are taken to compensate for the deviations.
8.5.3 When the stack is under significant negative pressure (height of impinger stem), close the
coarse adjust valve before inserting the probe into the stack to prevent water from backing into the filter
holder. If necessary, the pump may be turned on with the coarse adjust valve closed.
8.5.4 When the probe is in position, block off the openings around the probe and porthole to
prevent unrepresentative dilution of the gas stream.
8.5.5 Traverse the stack cross-section, as required by Method 1,40 CFR part 60, appendix A or
as specified by the Administrator, being careful not to bump the probe nozzle into the stack walls when
sampling near the walls or when removing or inserting the probe through the portholes; this minimizes
the chance of extracting deposited material.
8.5.6 During the test run, make periodic adjustments to keep the temperature around the filter
holder at the proper level; add more ice and, if necessary, salt to maintain a temperature of less than 20°C
(68°F) at the condenser/silica gel outlet. Also, periodically check the level and zero of the manometer.
8.5.7 If the pressure drop across the filter becomes too high, making isokinetic sampling
difficult to maintain, the filter may be replaced in the midst of the sample run. It is recommended that
another complete filter assembly be used rather than attempting to change the filter itself. Before a new
filter assembly is installed, conduct a leak check (see section 8.4.3 of this method). The total PM weight
shall include the summation of the filter assembly catches.
8.5.8 A single train shall be used for the entire sample run, except in cases where simultaneous
sampling is required in two or more separate ducts or at two or more different locations within the same
duct, or in cases where equipment failure necessitates a change of trains. In all other situations, the use
of two or more trains will be subject to the approval of the Administrator.
NOTE: When two or more trains are used, separate analyses of the front-half and (if applicable)
impinger catches from each train shall be performed, unless identical nozzle sizes were used in all trains,
in which case the front-half catches from the individual trains may be combined (as may the impinger
catches) and one analysis of the front-half catch and one analysis of the impinger catch may be
performed.
8.5.9 At the end of the sample run, turn off the coarse adjust valve, remove the probe and nozzle
from the stack, turn off the pump, record the final DGM reading, and then conduct a post-test leak check,
as outlined in section 8.4.4 of this method. Also leak-check the pitot lines as described in section 8.1 of
Method 2,40 CFR part 60, appendix A. The lines must pass this leak check in order to validate the
velocity head data.
8.6 Calculation of percent isokinetic. Calculate percent isokinetic (see Calculations, section
12.12 of this method) to determine whether a run was valid or another test run should be made. If there
was difficulty in maintaining isokinetic rates because of source conditions, consult the Administrator for
possible variance on the isokinetic rates.
8.7 Sample recovery.
8.7.1 Proper cleanup procedure begins as soon as the probe is removed from the stack at the end
of the sampling period. Allow the probe to cool.
8.7.2 When the probe can be safely handled, wipe off all external PM near the tip of the probe
nozzle and place a cap over it to prevent losing or gaining PM. Do not cap off the probe tip tightly while
the sampling train is cooling down. This would create a vacuum in the filter holder, thus drawing water
from the impingers into the filter holder.
8.7.3 Before moving the sample train to the cleanup site, remove the probe from the sample
train, wipe off the silicone grease, and cap the open outlet of the probe. Be careful not to lose any
condensate that might be present. Wipe off the silicone grease from the filter inlet where the probe was
fastened and cap it. Remove the umbilical cord from the last impinger and cap the impinger. If a
flexible line is used between the first impinger or condenser and the filter holder, disconnect the line at
the filter holder and let any condensed water or liquid drain into the impingers or condenser. After
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wiping off the silicone grease, cap off the filter holder outlet and impinger inlet. Ground-glass stoppers,
plastic caps, or serum caps may be used to close these openings.
8.7.4 Transfer the probe and filter-impinger assembly to the cleanup area. This area should be
clean and protected from the wind so that the chances of contaminating or losing the sample will be
minimized.
8.7.5 Save a portion of the acetone and methylene chloride used for cleanup as blanks. Take
200 ml of each solvent directly from the wash bottle being used and place it in glass sample containers
labeled "acetone blank" and "methylene chloride blank," respectively.
8.7.6 Inspect the train prior to and during disassembly and note any abnormal conditions. Treat
the samples as follows:
8.7.6.1 Container No. 1. Carefully remove the filter from the filter holder, and place it in its
identified petri dish container. Use a pair of tweezers and/or clean disposable surgical gloves to handle
the filter. If it is necessary to fold the filter, do so such that the PM cake is inside the fold. Using a dry
nylon bristle brush and/or a sharp-edged blade, carefully transfer to the petri dish any PM and/or filter
fibers that adhere to the filter holder gasket. Seal the container.
8.7.6.2 Container No. 2. Taking care to see that dust on the outside of the probe or other
exterior surfaces does not get into the sample, quantitatively recover PM or any condensate from the
probe nozzle, probe fitting, probe liner, and front half of the filter holder by washing these components
with acetone and placing the wash in a glass container. Perform the acetone rinse as follows:
8.7.6.2.1 Carefully remove the probe nozzle and clean the inside surface by rinsing with acetone
from a wash bottle and brushing with a nylon bristle brush. Brush until the acetone rinse shows no
visible particles, after which make a final rinse of the inside surface with acetone.
8.7.6.2.2 Brush and rinse the inside parts of the Swagelok fitting with acetone in a similar way
until no visible particles remain.
8.7.6.2.3 Rinse the probe liner with acetone by tilting and rotating the probe while squirting
acetone into its upper end so that all inside surfaces are wetted with acetone. Let the acetone drain from
the lower end into the sample container. A funnel (glass or polyethylene) may be used to aid in
transferring liquid washes to the container. Follow the acetone rinse with a probe brush. Hold the probe
in an inclined position, squirt acetone into the upper end as the probe brush is being pushed with a
twisting action through the probe, hold a sample container under the lower end of the probe, and catch
any acetone and PM that is brushed from the probe. Run the brush through the probe three times or more
until no visible PM is carried out with the acetone or until none remains in the probe liner on visual
inspection. With stainless steel or other metal probes, run the brush through in the above-described
manner at least six times, since metal probes have small crevices in which PM can be entrapped. Rinse
the brush with acetone and quantitatively collect these washings in the sample container. After the
brushing, make a final acetone rinse of the probe as described above.
8.7.6.2.4 It is recommended that two people clean the probe to minimize sample losses.
Between sampling runs, keep brushes clean and protected from contamination.
8.7.6.2.5 After ensuring that all joints have been wiped clean of silicone grease, clean the inside
of the front half of the filter holder by rubbing the surfaces with a nylon bristle brush and rinsing with
acetone. Rinse each surface three times or more if needed to remove visible particulate. Make a final
rinse of the brush and filter holder. Carefully rinse out the glass cyclone also (if applicable).
8.7.6.2.6 After rinsing the nozzle, probe, and front half of the filter holder with acetone, repeat
the entire procedure with methylene chloride and save in a separate No. 2M container.
8.7.6.2.7 After acetone and methylene chloride washings and PM have been collected in the
proper sample containers, tighten the lid on the sample containers so that acetone and methylene chloride
will not leak out when it is shipped to the laboratory. Mark the height of the fluid level to determine
whether leakage occurs during transport. Label each container to identify clearly its contents.
8.7.6.3 Container No. 3. Note the color of the indicating silica gel to determine whether it has
been completely spent, and make a notation of its condition. Transfer the silica gel from the fourth
impinger to its original container and seal the container. A funnel may make it easier to pour the silica
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gel without spilling. A rubber policeman may be used as an aid in removing the silica gel from the
impinger. It is not necessary to remove the small amount of dust particles that may adhere to the
impinger wall and are difficult to remove. Since the gain in weight is to be used for moisture
calculations, do not use any water or other liquids to transfer the silica gel. If a balance is available in
the field, follow the procedure for Container No. 3 in section 1 1 .2.3 of this method.
8.7.6.4 Impinger water. Treat the impingers as follows:
8.7.6.4.1 Make a notation of any color or film in the liquid catch. Measure the liquid that is in
the first three impingers to within 1 ml by using a graduated cylinder or by weighing it to within 0.5 g by
using a balance (if one is available). Record the volume or weight of liquid present. This information is
required to calculate the moisture content of the effluent gas.
8.7.6.4.2 Following the determination of the volume of liquid present, rinse the back half of the
train with water, add it to the impinger catch, and store it in a container labeled 3W (water).
8.7.6.4.3 Following the water rinse, rinse the back half of the train with acetone to remove the
excess water to enhance subsequent organic recovery with methylene chloride and quantitatively recover
to a container labeled 3 S (solvent) followed by at least three sequential rinsings with aliquots of
methylene chloride. Quantitatively recover to the same container labeled 3S. Record separately the
amount of both acetone and methylene chloride used to the nearest 1 ml or 0.5g.
NOTE: Because the subsequent analytical finish is gravimetric, it is okay to recover both
solvents to the same container. This would not be recommended if other analytical finishes were
required.
8.8 Sample transport. Whenever possible, containers should be shipped in such a way that they
remain upright at all times.
9.0 Quality Control.
9.1 Miscellaneous quality control measures.
Section Quality Control Measure Effect
8.4, Sampling and equipment Ensure accurate
10.1-10.6 leak check and calibration measurement of
stack gas flow rate,
_ sample volume __
9.2 Volume metering system checks. The following quality control procedures are suggested to
check the volume metering system calibration values at the field test site prior to sample collection.
These procedures are optional.
9.2. 1 Meter orifice check. Using the calibration data obtained during the calibration procedure
described in section 10.3 of this method, determine the AH@ for the metering system orifice. The AH@ is
the orifice pressure differential in units of in. H20 that correlates to 0.75 cfm of air at 528°R and 29.92 in.
Hg. The AH@ is calculated as follows:
= 0.0319 AH
@ P v2 v2
rbar T vm
where
0.0319 = (0.0567 in. Hg/°R)(0.75 cfm)2;
AH = Average pressure differential across the orifice meter, in. H20;
Tm =. Absolute average DGM temperature, °R;
0 = Total sampling time, min;
Pb« = Barometric pressure, in. Hg;
-------
Y = DGM calibration factor, dimensionless;
Vm = Volume of gas sample as measured by DGM, dcf.
9.2.1.1 Before beginning the field test (a set of three runs usually constitutes a field test),
operate the metering system (i.e., pump, volume meter, and orifice) at the AH@ pressure differential for
10 minutes. Record the volume collected, the DGM temperature, and the barometric pressure. Calculate
a DGM calibration check value, Yc, as follows:
Ye"
10
0.0319 T
m
bar
where
Yc = DGM calibration check value, dimensionless;
10 = Run time, m in.
9.2.1.2 Compare the Yc value with the dry gas meter calibration factor Y to determine that: 0.97
Y < Yc < 1.03Y. If the Yc value is not within this range, the volume metering system should be
investigated before beginning the test.
9.2.2 Calibrated critical orifice. A calibrated critical orifice, calibrated against a wet test meter
or spirometer and designed to be inserted at the inlet of the sampling meter box, may be used as a quality
control check by following the procedure of section 16.2 of this method.
10.0 Calibration and Standardization.
NOTE: Maintain a laboratory log of all calibrations.
10.1 Probe nozzle. Probe nozzles shall be calibrated before their initial use in the field. Using a
micrometer, measure the ID of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time, and obtain the average of the measurements. The
difference between the high and low numbers shall not exceed 0.1 mm (0.004 in.). When nozzles
become nicked, dented, or corroded, they shall be reshaped, sharpened, and recalibrated before use.
Each nozzle shall be permanently and uniquely identified.
10.2 Pitot tube assembly. The Type S pitot tube assembly shall be calibrated according to the
procedure outlined in section 10.1 of Method 2, 40 CFR part 60, appendix A.
10.3 Metering system.
10.3.1 Calibration prior to use. Before its initial use in the field, the metering system shall be
calibrated as follows: Connect the metering system inlet to the outlet of a wet test meter that is accurate
to within 1 percent. Refer to Figure 5-5 of Method 5, 40 CFR part 60, appendix A. The wet test meter
should have a capacity of 30 liters/revolution (1 ffYrev). A spirometer of 400 liters (14 ft3) or more
capacity, or equivalent, may be used for this calibration, although a wet test meter is usually more
practical. The wet test meter should be periodically calibrated with a spirometer or a liquid displacement
meter to ensure the accuracy of the wet test meter. Spirometers or wet test meters of other sizes may be
used, provided that the specified accuracies of the procedure are maintained. Run the metering system
pump for about 15 minutes with the orifice manometer indicating a median reading, as expected in field
use, to allow the pump to warm up and to permit the interior surface of the wet test meter to be
thoroughly wetted. Then, at each of a minimum of three orifice manometer settings, pass an exact
quantity of gas through the wet test meter and note the gas volume indicated by the DGM. Also note the
barometric pressure and the temperatures of the wet test meter, the inlet of the DGM, and the outlet of
the DGM. Select the highest and lowest orifice settings to bracket the expected field operating range of
the orifice. Use a minimum volume of 0.15 m3 (5 cf) at all orifice settings. Record all the data on a form
similar to Figure 5-6 of Method 5,40 CFR part 60, appendix A, and calculate Y (the DGM calibration
factor) and AH@ (the orifice calibration factor) at each orifice setting, as shown on Figure 5-6 of Method
5, 40 CFR part 60, appendix A. Allowable tolerances for individual Y and AH@ values are given in
-------
Figure 5-6 of Method 5,40 CFR part 60, appendix A. Use the average of the Y values in the calculations
in section 12 of this method.
10.3.1.1. Before calibrating the metering system, it is suggested that a leak check be conducted.
For metering systems having diaphragm pumps, the normal leak check procedure will not detect
leakages within the pump. For these cases the following leak check procedure is suggested: make a 10-
minute calibration run at 0.00057 mVmin (0.02 cfm); at the end of the run, take the difference of the
measured wet test meter and DGM volumes; divide the difference by 10 to get the leak rate. The leak
rate should not exceed 0.00057 mVmin (0.02 cfm).
10.3.2 Calibration after use. After each field use, the calibration of the metering system shall be
checked by performing three calibration runs at a single, intermediate orifice setting (based on the
previous field test) with the vacuum set at the maximum value reached during the test series. To adjust
the vacuum, insert a valve between the wet test meter and the inlet of the metering system. Calculate the
average value of the DGM calibration factor. If the value has changed by more than 5 percent,
recalibrate the meter over the full range of orifice settings, as previously detailed.
NOTE: Alternative procedures, e.g., rechecking the orifice meter coefficient, may be used,
subject to the approval of the Administrator.
10.3.3 Acceptable variation in calibration. If the DGM coefficient values obtained before and
after a test series differ by more than 5 percent, either the test series shall be voided or calculations for
the test series shall be performed using whichever meter coefficient value (i.e., before or after) gives the
lower value of total sample volume.
10.4 Probe heater calibration. Use a heat source to generate air heated to selected temperatures
that approximate those expected to occur in the sources to be sampled. Pass this air through the probe at
a typical sample flow rate while measuring the probe inlet and outlet temperatures at various probe
heater settings. For each air temperature generated, construct a graph of probe heating system setting
versus probe outlet temperature. The procedure outlined in APTD-0576 can also be used. Probes
constructed according to APTD-0581 need not be calibrated if the calibration curves in APTD-0576 are
used. Also, probes with outlet temperature monitoring capabilities do not require calibration.
NOTE: The probe heating system shall be calibrated before its initial use in the field.
10.5 Temperature sensors. Use the procedure in section 10.3 of Method 2, 40 CFR part 60,
appendix A to calibrate in-stack temperature sensors. Dial thermometers, such as are used for the DGM
and condenser outlet, shall be calibrated against mercury-in-glass thermometers.
10.6 Barometer. Calibrate against a mercury barometer.
11.0 Analytical Procedure.
11.1 Record the data required on a sheet such as the one shown in Figure 315-1 of this method.
11.2 Handle each sample container as follows:
11.2.1 Container No. 1.
11.2.1.1 PM analysis. Leave the contents in the shipping container or transfer the filter and any
loose PM from the sample container to a tared glass weighing dish. Desiccate for 24 hours in a
desiccator containing anhydrous calcium sulfate. Weigh to a constant weight and report the results to the
nearest 0.1 mg. For purposes of this section, the term "constant weight" means a difference of no more
than 0.5 mg or 1 percent of total weight less tare weight, whichever is greater, between two consecutive
weighings, with no less than 6 hours of desiccation time between weighings (overnight desiccation is a
common practice). If a third weighing is required and it agrees within ±0.5 mg, then the results of the
second weighing should be used. For quality assurance purposes, record and report each individual
weighing; if more than three weighings are required, note this in the results for the subsequent MCEM
results.
11.2.1.2 MCEM analysis. Transfer the filter and contents quantitatively into a beaker. Add 100
ml of methylene chloride and cover with aluminum foil. Sonicate for 3 minutes then allow to stand for
20 minutes. Set up the filtration apparatus. Decant the solution into a clean Buchner fritted funnel. *
Immediately pressure filter the solution through the tube into another clean, dry beaker. Continue
decanting and pressure filtration until all the solvent is transferred. Rinse the beaker and filter with 10 to
-------
20 ml methylene chloride, decant into the Buchner fritted funnel and pressure filter. Place the beaker on
a low-temperature hot plate (maximum 40°C) and slowly evaporate almost to dryness. Transfer the
remaining last few milliliters of solution quantitatively from the beaker (using at least three aliquots of
methylene chloride rinse) to a tared clean dry aluminum dish and evaporate to complete dryness.
Remove from heat once solvent is evaporated. Reweigh the dish after a 30-minute equilibrium in the
balance room and determine the weight to the nearest 0.1 mg. Conduct a methylene chloride blank run
in an identical fashion.
11.2.2 Container No. 2.
11.2.2.1 PM analysis. Note the level of liquid in the container, and confirm on the analysis
sheet whether leakage occurred during transport. If a noticeable amount of leakage has occurred, either
void the sample or use methods, subject to the approval of the Administrator, to correct the final results.
Measure the liquid in this container either volumetrically to ±1 ml or gravimetrically to ±0.5 g. Transfer
the contents to a tared 250 ml beaker and evaporate to dryness at ambient temperature and pressure.
Desiccate for 24 hours, and weigh to a constant weight. Report the results to the nearest 0.1 mg.
11.2.2.2 MCEM analysis. Add 25 ml methylene chloride to the beaker and cover with
aluminum foil. Sonicate for 3 minutes then allow to stand for 20 minutes; combine with contents of
Container No. 2M and pressure filter and evaporate as described for Container 1 in section 11.2.1.2 of
this method.
NOTES FOR MCEM ANALYSIS:
1. Light finger pressure only is necessary on 24/40 adaptor. A Chemplast adapter #15055-240
has been found satisfactory.
2. Avoid aluminum dishes made with fluted sides, as these may promote solvent "creep,"
resulting in possible sample loss.
3. If multiple samples are being run, rinse the Buchner fritted funnel twice between samples
with 5 ml solvent using pressure filtration. After the second rinse, continue the flow of air until the glass
frit is completely dry. Clean the Buchner fritted funnels thoroughly after filtering five or six samples.
11.2.3 Container No. 3. Weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5
g using a balance. This step may be conducted in the field.
11.2.4 Container 3W (impinger water).
11.2.4.1 MCEM analysis. Transfer the solution into a 1,000 ml separatory funnel quantitatively
with methylene chloride washes. Add enough solvent to total approximately 50 ml, if necessary. Shake
the funnel for 1 minute, allow the phases to separate, and drain the solvent layer into a 250 ml beaker.
Repeat the extraction twice. Evaporate with low heat (less than 40°C) until near dryness. Transfer the
remaining few milliliters of solvent quantitatively with small solvent washes into a clean, dry, tared
aluminum dish and evaporate to dryness. Remove from heat once solvent is evaporated. Reweigh the
dish after a 30-minute equilibration in the balance room and determine the weight to the nearest 0.1 mg.
11.2.5 Container 3S (solvent).
11.2.5.1 MCEM analysis. Transfer the mixed solvent to 250 ml beaker(s). Evaporate and weigh
following the procedures detailed for container 3W in section 11.2.4 of this method.
11.2.6 Blank containers. Measure the distilled water, acetone, or methylene chloride in each
container either volumetrically or gravimetrically. Transfer the "solvent" to a tared 250 ml beaker, and
evaporate to dryness at ambient temperature and pressure. (Conduct a solvent blank on the distilled
deionized water blank in an identical fashion to that described in section 11.2.4.1 of this method.)
Desiccate for 24 hours, and weigh to a constant weight. Report the results to the nearest 0.1 mg.
NOTE: The contents of Containers No. 2,3W, and 3M as well as the blank containers may be
evaporated at temperatures higher than ambient. If evaporation is done at an elevated temperature, the
temperature must be below the boiling point of the solvent; also, to prevent "bumping," the evaporation
process must be closely supervised, and the contents of the beaker must be swirled occasionally to
maintain an even temperature. Use extreme care, as acetone and methylene chloride are highly
flammable and have a low flash point.
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12.0 Data Analysis and Calculations.
12.1 Carry out calculations, retaining at least one extra decimal figure beyond that of the
acquired data. Round off figures after the final calculation. Other forms of the equations may be used as
long as they give equivalent results.
12.2 Nomenclature.
A,, = Cross-sectional area of nozzle, m3 (ft3).
Bws = Water vapor in the gas stream, proportion by volume.
C. = Acetone blank residue concentration, mg/g.
Cs = Concentration of particulate matter in stack gas, dry basis, corrected to standard
conditions, g/dscm (g/dscf).
I = Percent of isokinetic sampling.
L, = Maximum acceptable leakage rate for either a pretest leak check or for a leak check
following a component change; equal to 0.00057 mVmin (0.02 cfm) or 4 percent of the
average sampling rate, whichever is less.
L, = Individual leakage rate observed during the leak check conducted prior to the "i"1"
component change (I = 1,2,3...n), mVmin (cfm).
Lp = Leakage rate observed during the post-test leak check, mVmin (cfm).
ma = Mass of residue of acetone after evaporation, mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Psld = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg)(m3)]/[(°K)
(g-mole)] {21.85 [(in. Hg)(ft3)]/[(°R)(lb-mole)]}.
Tm = Absolute average dry gas meter (DGM) temperature (see Figure 5-2 of Method 5,40
CFR part 60, appendix A), °K (°R).
Ts = Absolute average stack gas temperature (see Figure 5-2 of Method 5, 40 CFR part 60,
appendix A), °K(°R).
Tstd = Standard absolute temperature, 293 °K (528°R).
V. = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
V, = Volume of methylene chloride blank, ml.
Vw = Volume of methylene chloride used in wash, ml.
Vlc = Total volume liquid collected in impingers and silica gel (see Figure 5-3 of Method 5,
40 CFR part 60, appendix A), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm(dcf).
= Volume of gas sample measured by the dry gas meter, corrected to standard conditions,
dscm (dscf).
= Volume of water vapor in the gas sample, corrected to standard conditions, scm (scf).
Vs = Stack gas velocity, calculated by Equation 2-9 in Method 2,40 CFR part 60, appendix
A, using data obtained from Method 5,40 CFR part 60, appendix A, m/sec (ft/sec).
Wa = Weight of residue in acetone wash, mg.
Y = Dry gas meter calibration factor.
AH = Average pressure differential across the orifice meter (see Figure 5-2 of Method 5,40
CFR part 60, appendix A), mm H20 (in H20).
P, = Density of acetone, 785.1 mg/ml (or see label on bottle).
pw = Density of water, 0.9982 g/ml (0.002201 Ib/ml).
Pi = Density of methylene chloride, 1316.8 mg/ml (or see label on bottle).
0 = Total sampling time, min.
®i = Sampling time interval, from the beginning of a run until the first component change,
-------
mm.
©i = Sampling time interval, between two successive component changes, beginning with the
interval between the first and second changes, min.
0p = Sampling time interval, from the final (n*) component change until the end of the
sampling run, min.
13.6 = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.
12.3 Average dry gas meter temperature and average orifice pressure drop. See data sheet
(Figure 5-2 of Method 5, 40 CFR part 60, appendix A).
12.4 Dry gas volume. Correct the sample volume measured by the dry gas meter to standard
conditions (20°C, 760 mm Hg or 68°F, 29.92 in Hg) by using Equation 315-1.
T (p
1 std rbar
V - V Y v 13'6^ Ea. 315-1
T PM
m sto
=V = K,VmY
where
K, = 0.3858 °K/mm Hg for metric units,
= 17.64 °R/in Hg for English units.
NOTE: Equation 315-1 can be used as written unless the leakage rate observed during any of the
mandatory leak checks (i.e., the post-test leak check or leak checks conducted prior to component
changes) exceeds L,. If Lp or Li exceeds La, Equation 315-1 must be modified as follows:
(a) Case I. No component changes made during sampling run. In this case, replace V,,, in Equation
315-1 with the expression:
[Vm-(Lp-LJ0]
(b) Case II. One or more component changes made during the sampling run. In this case, replace
Vm in Equation
315-1 by the expression:
[V,, - (L, - L.) 6, - (L,. - /..) 0,. - (Lf - /.,) 0p]
/=2
and substitute only for those leakage rates (L; or Lp) which exceed Lt.
12.5 Volume of water vapor condensed.
-------
where
K2 = 0.001333 mVml for metric units;
= 0.04706 ftVml for English units.
12.6 Moisture content.
B- Vw(std) - _._ _
- - Eq. 315-3
wa V + V
vm(std) vw(std)
NOTE: In saturated or water droplet-laden gas streams, two calculations of the moisture content
of the stack gas shall be made, one from the impinger analysis (Equation 315-3), and a second from the
assumption of saturated conditions. The lower of the two values of Bws shall be considered correct. The
procedure for determining the moisture content based upon assumption of saturated conditions is given
in section 4.0 of Method 4, 40 CFR part 60, appendix A. For the purposes of this method, the average
stack gas temperature from Figure 5-2 of Method 5, 40 CFR part 60, appendix A may be used to make
this determination, provided that the accuracy of the in-stack temperature sensor is ±1°C (2°F).
12.7 Acetone blank concentration.
M
c -
,
a a
12.8 Acetone wash blank.
W. = C.Vawp. Eq.315-5
12.9 Total particulate weight. Determine the total PM catch from the sum of the weights
obtained from Containers 1 and 2 less the acetone blank associated with these two containers (see Figure
315-1).
NOTE: Refer to section 8.5.8 of this method to assist in calculation of results involving two or
more filter assemblies or two or more sampling trains.
12.10 Particulate concentration.
cs = K3mAra(s«d) Eq.315-6
where
K = 0.001 g/mg for metric units;
= 0.0154 gr/mg for English units.
12.11 Conversion factors.
From
ft3
gr
gr/ft3
mg
gr
12.12
Io
m3
mg
mg/m3
g
Ib
Isokinetic variation.
Multiply by
0.02832
64.80004
2288.4
0.001
1.429X10-4
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12.12.1 Calculation from raw data.
ioo r
/ = —
m • i i « .AH
s " '" ' Tm J I •" 13.6; Ea. 315-7
60 0 vs Ps An
where
K4 = 0.003454 [(mm Hg)(m3)]/[(ml)(°K)] for metric units;
= 0.002669 [(in HgXft3)]/[(mlX°R)] for English units.
12.12.2 Calculation from intermediate values.
TV P 100
/ = s ms 2 Eg. 315-8
7.« ^s © >A, Ps 60 (1 -Bws)
' s
where
K5 = 4.320 for metric units;
= 0.09450 for English units.
12.12.3 Acceptable results. If 90 percent <• I <; 110 percent, the results are acceptable. If the
PM or MCEM results are low in comparison to the standard, and "I" is over 110 percent or less than 90
percent, the Administrator may opt to accept the results. Reference 4 in the Bibliography may be used to
make acceptability judgments. If "I" is judged to be unacceptable, reject the results, and repeat the test.
12.13 Stack gas velocity and volumetric flow rate. Calculate the average stack gas velocity and
volumetric flow rate, if needed, using data obtained in this method and the equations in sections 5.2 and
5.3 of Method 2,40 CFR part 60, appendix A.
12.14 MCEM results. Determine the MCEM concentration from the results from Containers 1,
2,2M, 3W, and 3S less the acetone, methylene chloride, and filter blanks value as determined in the
following equation:
mmcem = Zmtoto/ ~ WB ~ Wt ' ft>
13.0 Method Performance. [Reserved]
.1.4,0 Pollution Prevention. [Reserved]
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15.0 Waste Management. [Reserved]
16.0 Alternative Procedures.
16.1 Dry gas meter as a calibration standard. A DGM may be used as a calibration standard for
volume measurements in place of the wet test meter specified in section 16.1 of this method, provided
that it is calibrated initially and recalibrated periodically as follows:
16.1.1 Standard dry gas meter calibration.
16.1.1.1. The DGM to be calibrated and used as a secondary reference meter should be of high
quality and have an appropriately sized capacity, e.g., 3 liters/rev (0.1 ftVrev). A spirometer (400 liters
or more capacity), or equivalent, may be used for this calibration, although a wet test meter is usually
more practical. The wet test meter should have a capacity of 30 liters/rev (1 ftVrev) and be capable of
measuring volume to within 1.0 percent; wet test meters should be checked against a spirometer or a
liquid displacement meter to ensure the accuracy of the wet test meter. Spirometers or wet test meters of
other sizes may be used, provided that the specified accuracies of the procedure are maintained.
16.1.1.2 Set up the components as shown in Figure 5-7 of Method 5, 40 CFR part 60, appendix
A. A spirometer, or equivalent, may be used in place of the wet test meter in the system. Run the pump
for at least 5 minutes at a flow rate of about 10 liters/min (0.35 cfm) to condition the interior surface of
the wet test meter. The pressure drop indicated by the manometer at the inlet side of the DGM should be
minimized (no greater than 100 mm H2O [4 in. H2O] at a flow rate of 30 liters/min [1 cfin]). This can be
accomplished by using large- diameter tubing connections and straight pipe fittings.
16.1.1.3 Collect the data as shown in the example data sheet (see Figure 5-8 of Method 5,40
CFR part 60, appendix A). Make triplicate runs at each of the flow rates and at no less than five different
flow rates. The range of flow rates should be between 10 and 34 liters/min (0.35 and 1.2 cfm) or over
the expected operating range.
16.1.1.4 Calculate flow rate, Q, for each run using the wet test meter volume, Vw, and the run
time, q. Calculate the DGM coefficient, Y^, for each run. These calculations are as follows:
P V
Qis bar w
= K. — Eg. 315-9
Yd Vw (Tds + Tstd) Pbar
Vds (Tw + Tstd)(Pbar + -^) Eg. 315-10
1 o.b
where
K, = 0.3858 for international system of units (SI);
17.64 for English units;
Pbar = Barometric pressure, mm Hg (in Hg);
Vw = Wet test meter volume, liter (ft3);
tw = Average wet test meter temperature, °C (°F);
tsld = 273°C for SI units; 460°F for English units;
0 = Run time, min;
tds = Average dry gas meter temperature, °C (°F);
Vds = Dry gas meter volume, liter (ft3);
Ap = Dry gas meter inlet differential pressure, mm H2O (in H2O).
16.1.1.5 Compare the three Y^ values at each of the flow rates and determine the maximum an4
minimum values. The difference between the maximum and minimum values at each flow rate should
be no greater than 0.030. Extra sets of triplicate runs may be made in order to complete this requirement.
In addition, the meter coefficients should be between 0.95 and 1.05. If these specifications cannot be
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met in three sets of successive triplicate runs, the meter is not suitable as a calibration standard and
should not be used as such. If these specifications are met, average the three Y^ values at each flow rate
resulting in five average meter coefficients, Y^.
16.1.1.6 Prepare a curve of meter coefficient, Y^, versus flow rate, Q, for the DGM. This curve
shall be used as a reference when the meter is used to calibrate other DGMs and to determine whether
recalibration is required.
16.1.2 Standard dry gas meter recalibration.
16.1.2,1 Recalibrate the standard DGM against a wet test meter or spirometer annually or after
every 200 hours of operation, whichever comes first. This requirement is valid provided the standard
DGM is kept in a laboratory and, if transported, cared for as any other laboratory instrument. Abuse to
the standard meter may cause a change in the calibration and will require more frequent recalibrations.
16.1.2.2 As an alternative to full recalibration, a two-point calibration check may be made.
Follow the same procedure and equipment arrangement as for a full recalibration, but run the meter at
only two flow rates (suggested rates are 14 and 28 liters/min [0.5 and 1.0 cfm]). Calculate the meter
coefficients for these two points, and compare the values with the meter calibration curve. If the two
coefficients are within 1.5 percent of the calibration curve values at the same flow rates, the meter need
not be recalibrated until the next date for a recalibration check.
16.2 Critical orifices as calibration standards. Critical orifices may be used as calibration
standards in place of the wet test meter specified in section 10.3 of this method, provided that they are
selected, calibrated, and used as follows:
16.2.1 Selection of critical orifices.
16.2.1.1 The procedure that follows describes the use of hypodermic needles or stainless steel
needle tubing that has been found suitable for use as critical orifices. Other materials and critical orifice
designs may be used provided the orifices act as true critical orifices; i.e., a critical vacuum can be
obtained, as described in section 7.2.2.2.3 of Method 5,40 CFR part 60, appendix A. Select five critical
orifices that are appropriately sized to cover the range of flow rates between 10 and 34 liters/min or the
expected operating range. Two of the critical orifices should bracket the expected operating range. A
minimum of three critical orifices will be needed to calibrate a Method 5 DGM; the other two critical
orifices can serve as spares and provide better selection for bracketing the range of operating flow rates.
The needle sizes and tubing lengths shown in Table 315-1 give the approximate flow rates indicated in
the table.
16.2.1.2 These needles can be adapted to a Method 5 type sampling train as follows: Insert a
serum bottle stopper, 13 x 20 mm sleeve type, into a 0.5 in Swagelok quick connect. Insert the needle
into the stopper as shown in Figure 5-9 of Method 5,40 CFR part 60, appendix A.
16.2.2 Critical orifice calibration. The procedure described in this section uses the Method 5
meter box configuration with a DGM as described in section 6.1.1.9 of this method to calibrate the
critical orifices. Other schemes may be used, subject to the approval of the Administrator.
16.2.2.1 Calibration of meter box. The critical orifices must be calibrated in the same
configuration as they will be used; i.e., there should be no connections to the inlet of the orifice.
16.2.2.1.1 Before calibrating the meter box, leak-check the system as follows: Fully open the
coarse adjust valve and completely close the bypass valve. Plug the inlet. Then turn on the pump and
determine whether there is any leakage. The leakage rate shall be zero; i.e., no detectable movement of
the DGM dial shall be seen for 1 minute.
16.2.2.1.2 Check also for leakages in that portion of the sampling train between the pump and
the orifice meter. See section 5.6 of Method 5,40 CFR part 60, appendix A for the procedure; make any
corrections, if necessary. If leakage is detected, check for cracked gaskets, loose fittings, worn 0-rings,
etc. and make the necessary repairs.
16.2.2.1.3 After determining that the meter box is leakless, calibrate the meter box according to
the procedure given in section 5.3 of Method 5,40 CFR part 60, appendix A. Make sure that the wet test
meter meets the requirements stated in section 7.1.1.1 of Method 5,40 CFR part 60, appendix A. Check
the water level in the wet test meter. Record the DGM calibration factor, Y.
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16.2.2.2 Calibration of critical orifices. Set up the apparatus as shown in Figure 5-10 of Method
5, 40 CFR part 60, appendix A.
16.2.2.2.1 Allow a warm-up time of 15 minutes. This step is important to equilibrate the
temperature conditions through the DGM.
16.2.2.2.2 Leak-check the system as in section 7.2.2.1.1 of Method 5, 40 CFR part 60, appendix
A. The leakage rate shall be zero.
16.2.2.2.3 Before calibrating the critical orifice, determine its suitability and the appropriate
operating vacuum as follows: turn on the pump, fully open the coarse adjust valve, and adjust the bypass
valve to give a vacuum reading corresponding to about half of atmospheric pressure. Observe the meter
box orifice manometer reading, DH. Slowly increase the vacuum reading until a stable reading is
obtained on the meter box orifice manometer. Record the critical vacuum for each orifice. Orifices that
do not reach a critical value shall not be used.
16.2.2.2.4 Obtain the barometric pressure using a barometer as described in section 6.1.2 of this
method. Record the barometric pressure, Pbar, in mm Hg (in. Hg).
1 6.2.2.2.5 Conduct duplicate runs at a vacuum of 25 to 50 mm Hg (1 to 2 in. Hg) above the
critical vacuum. The runs shall be at least 5 minutes each. The DGM volume readings shall be in
increments of complete revolutions of the DGM. As a guideline, the times should not differ by more
than 3.0 seconds (this includes allowance for changes in the DGM temperatures) to achieve ±0.5 percent
in K'. Record the information listed in Figure 5-1 1 of Method 5, 40 CFR part 60, appendix A.
1 6.2.2.2.6 Calculate K1 using Equation 315-11.
, _
_
E. 315-11
where
K1 = Critical orifice coefficient, [mJX0K)*]/
[(mm Hg)(min)] {[(ft3)(°R)'^)]/[(in. Hg)(min)]};
Tarib = Absolute ambient temperature, °K (°R).
16.2.2.2.7 Average the K1 values. The individual K1 values should not differ by more than ±0.5
percent from the average.
16.2.3 Using the critical orifices as calibration standards.
16.2.3.1 Record the barometric pressure.
16.2.3.2 Calibrate the metering system according to the procedure outlined in sections 7.2.2.2.1
to 7.2.2.2.5 of Method 5, 40 CFR part 60, appendix A. Record the information listed in Figure 5-12 of
Method 5, 40 CFR part 60, appendix A.
16.2.3.3 Calculate the standard volumes of air passed through the DGM and the critical orifices,
and calculate the DGM calibration factor, Y, using the equations below:
Vm(sld) = K, Vm [?„„ + (AH/i3.6)]/T. Eg. 315-12
Vcl
-------
factors obtained from two adjacent orifices each time a DGM is calibrated; for example, when checking
orifice 13/2.5, use orifices 12/10.2 and 13/5.1. If any critical orifice yields a DGM Y factor differing by
more than 2 percent from the others, recalibrate the critical orifice according to section 7.2.2.2 of Method
5,40 CFR part 60, appendix A.
17.0 References.
1. Addendum to Specifications for Incinerator Testing at Federal Facilities. PHS, NCAPC.
December 6,1967.
2. Martin, Robert M. Construction Details of Isokinetic Source-Sampling Equipment.
Environmental Protection Agency. Research Triangle Park, NC. APTD-0581. April 1971.
3. Rom, Jerome J. Maintenance, Calibration, and Operation of Isokinetic Source Sampling
Equipment. Environmental Protection Agency. Research Triangle Park, NC. APTD-0576. March 1972.
4. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of Interpreting Stack Sampling Data.
Paper Presented at the 63rd Annual Meeting of the Air Pollution Control Association, St. Louis, MO.
June 14-19,1970.
5. Smith, W.S., et al. Stack Gas Sampling Improved and Simplified With New Equipment.
APCA Paper No. 67-119. 1967.
6. Specifications for Incinerator Testing at Federal Facilities. PHS, NCAPC. 1967.
7. Shigehara, R.T. Adjustment in the EPA Nomograph for Different Pitot Tube Coefficients and
Dry Molecular Weights. Stack Sampling News 2:4-11. October 1974.
8. Vollaro, R.F. A Survey of Commercially Available Instrumentation for the Measurement of
Low-Range Gas Velocities. U.S. Environmental Protection Agency, Emission Measurement Branch.
Research Triangle Park, NC. November 1976 (unpublished paper).
9. Annual Book of ASTM Standards. Part 26. Gaseous Fuels; Coal and Coke; Atmospheric
Analysis. American Society for Testing and Materials. Philadelphia, PA. 1974. pp. 617-622.
10. Felix, L.G., G.I. Clinard, G.E. Lacy, and J.D. McCain. Inertial Cascade Impactor Substrate
Media for Flue Gas Sampling. U.S. Environmental Protection Agency. Research Triangle Park, NC
27711. Publication No. EPA-600/7-77-060. June 1977. 83 p.
11. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating and Using Dry Gas Volume
Meters as Calibration Standards. Source Evaluation Society Newsletter. 3_(I):17-30. February 1978.
12. Lodge, J.P., Jr., J.B. Pate, B.E. Ammons, and G.A. Swanson. The Use of Hypodermic
Needles as Critical Orifices in Air Sampling. J. Air Pollution Control Association. 1&197-200. 1966.
18.0 Tables. Diagrams. Flowcharts, and Validation Data
TABLE 315-1. Flow Rates for Various Needle Sizes and Tube Lengths.
Gauge/length
(cm)
12/7.6
12/10.2
13/2.5
13/5.1
13/7.6
13/10.2
Flow rate
(liters/min)
32.56
30.02
25.77
23.50
22.37
20.67
Gauge/length
(cm)
14/2.5
14/5.1
14/7.6
15/3.2
15/7.6
15/10.2
Flow rate
(liters/min)
19.54
17.27
16.14
14.16
11.61
10.48
-------
Particulate analysis
Plant
Date
Run No.
Filter No.
Amount liquid lost during
transport
Acetone blank volume (ml)
Acetone blank concentration (Eq.315-4) (mg/mg)
Acetone wash blank (Eq.3 1 5-5) (mg)
Container
No. 1
Container
No. 2
Final weight
(mg)
,
Tare weight (mg)
Total
Less Acetone blank
Weight of particulate matter
Weight gain (mg)
Moisture analysis
Impingers
Silica gel
Final volume
(mg)
Note 1
Initial volume (mg)
Notel
Total
Liquid collected (mg)
FIGURE 315-1. Particulate and MCEM Analyses
Note 1: Convert volume of water to weight by multiplying by the density of water (1 g/ml).
-------
MCEM analysis
Container No.
Final
weight
(mg)
Tare of
aluminum
dish (mg)
Weight
gain
Acetone
wash volume
(ml)
Metflrjfanfe
wash
volume
(ml)
2+2M
3W
3S
Total
m
total
Less acetone wash blank (mg)
(not to exceed 1 mg/1 of
acetone used)
Wa = Ca Pa E Ve»
Less methylene chloride wash
blank (mg) (not to exceed
1.5 mg/1 of methylene
chloride used)
w
t = c A E
tw
Less filter blank (mg)
(not to exceed....
(mg/filter)
MCEM weight (mg)
mMCEOM ~ 2^ m total Wa Wt 'b
FIGURE 315-1 CContinuedt. Particulate And MCEM Analyses
-------
State of California
California Environmental Protection Agency
Air Resources Board
Method 429
Determination of Poly cyclic Aromatic Hydrocarbon (PAH)
Emissions from Stationary Sources
Adopted: September 12, 1989
Amended: [insert date of amendment]
-------
TABLE OF CONTENTS
1 INTRODUCTION 1
1.1 APPLICABILITY 1
1.2 PRINCIPLE 1
1.3 DEFINITIONS AND ABBREVIATIONS 1
2 THE PRE-TEST PROTOCOL 4
2.1 RESPONSIBILITIES OF THE END USER, TESTER, AND ANALYST 4
2.2 PRE-TEST REQUIREMENTS 5
2.3 REQUIRED PRELIMINARY ANALYTICAL DATA 6
2.4 EXPECTED RANGE IN TARGET PAH CONCENTRATIONS
OF INDIVIDUAL PAHs 7
2.5 SAMPLING RUNS, TIME, AND VOLUME 7
3 INTERFERENCES . . 10
4 SAMPLING APPARATUS, MATERIALS, AND REAGENTS 11
4.1 SAMPLING APPARATUS 11
4.2 SAMPLING MATERIALS AND REAGENTS . . . 14
4.3 PRE-TEST PREPARATION 18
4.4 SAMPLE COLLECTION 21
4.5 CALCULATIONS 26
4.6 ISOKINETIC CRITERIA . 30
5 SAMPLE RECOVERY 31
5.1 SAMPLE RECOVERY APPARATUS 31
5.2 SAMPLE RECOVERY REAGENTS 32
5.3 SAMPLE RECOVERY PROCEDURE 32
5.4 SAMPLE PRESERVATION AND HANDLING 34
6 ANALYTICAL PREPARATION . 34
6.1 SAFETY 34
6.2 CLEANING OF LABORATORY GLASSWARE 35
August 9, 1996 Proposed M-429 Page i
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6.3 APPARATUS 35
6.4 SAMPLE PREPARATION: REAGENTS 36
6.5 SAMPLE EXTRACTION 37
6.6 COLUMN CLEANUP 40
7 GC/MS ANALYSIS 42
7.1 APPARATUS 42
7.2 REAGENTS 43
7.3 INITIAL CALIBRATION 45
7.4 CONTINUING CALIBRATION 48
7.5 GC/MS ANALYSIS 49
7.6 QUALITATIVE ANALYSIS 50
7.7 QUANTITATIVE ANALYSIS 51
8 QUALITY ASSURANCE/QUALITY CONTROL 52
8.1 QA SAMPLES 52
8.2 ACCEPTANCE CRITERIA 54
8.3 ESTIMATION OF THE METHOD DETECTION LIMIT (MDL)
AND PRACTICAL QUANTITATION LIMIT IPQL) 56
8.4 LABORATORY PERFORMANCE T . . 57
9. CALCULATIONS 57
9.1 ANALYST'S CALCULATIONS 57
9.2 TESTER'S CALCULATIONS 61
10 REPORTING REQUIREMENTS 64
10.1 SOURCE TEST PROTOCOL 64
10.2 LABORATORY REPORT 65
10.3 EMISSIONS TEST REPORT 68
11 BIBLIOGRAPHY 70
August 9, 1996 Proposed M-429 Page ii
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TABLES
1 Method 429 Target Analytes ................. 71
2 Practical Quantitation Limits for Target PAHs 72
3 PAH Analysis by HRMS of Different Lots
of Cleaned Resin 73
4 Composition of the Sample Spiking Solutions 74
4A Composition of Alternative Sample Spiking Solutions 75
5 Concentrations of PAHs in Working GC/MS Calibration
Standard Solutions for Low Resolution Mass Spectrometry , 76
6 Concentrations of PAHs in Working GC/MS Calibration
Standard Solutions for High Resolution Mass Spectrometry . 78
6A Concentrations of PAHs in Alternative Working GC/MS Calibration
Standard Solutions for High Resolution Mass Spectrometry 80
7 Spike Levels for Labelled Standards 82
7A Spike Levels for Labelled Standards for Alternative
HRMS Spiking Scheme 83
8 Target Concentrations for Labelled Standards in Sample Extract 84
8A Target Concentrations f9r Labelled Standards in Sample Extract
Obtained with Alternative HRMS Spiking Scheme 85
9 Concentrations of Compounds in Laboratory Control Spike Sample 86
10 Recommended Gas Chromatographic Operating Conditions
for PAH Analysis 87
11 Assignments of Internal Standards for Calculation of RRFs
and Quantitation of Target PAHs and Surrogate Standards . 88
11A Assignments of Internal Standards for Calculation of RRFs
and Quantitation of Target PAHs and Surrogate
Standards Using Alternative HRMS Spiking Scheme ............... 89
12 Assignments of Recovery Standards for Determination of Percent
Recoveries of Internal Standards and the Alternate Standard . 90
12A Assignments of Recovery Standards for Determination of
Percent Recoveries of Internal Standards and the Alternate Standard
Using Alternative HRMS Spiking Scheme 91
13 Quantitation and Confirmation Ions for Selected
Ion Monitoring of PAHs by HRGC/LRMS 92
14 Mass Descriptors Used for Selected Ion Monitoring
of PAHs by HRGC/HRMS 94
August 9, 1996 Proposed M-429 Page iii
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FIGURES
1 Method 429 Flowchart 96
2 PAH Sampling Train 97
3 Condenser and Sorbent Trap for Collection of Gaseous PAH 98
4 XAD-2 Fluidized Bed Drying Apparatus 99
5 Method 429 Field Data Record 100
6 Recovery of PAH Sampling Train 101
7 Flowchart for Sampling, Extraction and Cleanup for 102
Determination of PAH in a Split Sample
8 Flowchart for Sampling, Extraction and Cleanup for
Determination PAH in a Composite Sample 103
9 Example of Pre-Test Calculations for PAH Emissions Test 104
10 CARB Method 429 (PAHs) Sampling Train Setup Record 105
11 CARB Method 429 (PAHs) Sampling Train Recovery Record 106
12 Chain of Custody Sample Record 107
13 Chain of Custody Log Record 108
14A Example of GC/MS Summary Report (HRMS) for
Initial Calibration Solution #1 109
14B Example of Initial Calibration (ICAL) RRF Summary 110
14C Example of Continuing Calibration Summary . 111
15A Example of Summary Report of LCS Results 112
15B LCS Recoveries for Benzo(a)pyrene 113
16A Example GC/MS Summary Report (HRMS) for Sample Run #32 114
16B Example Laboratory Report of PAH Results for Sample Run #32 115
17A Example of Tester's Summary of Laboratory Reports . 116
17B Field Data Summary for PAH Emissions Test 117
17C Example of Emissions Test Report 118
APPENDIX A
Determination of the Method Detection Limit 119
August 9, 1996 Proposed M-429 Page iv
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Method 429
Determination of Polycyclic Aromatic Hydrocarbon (PAH)
Emissions From Stationary Sources
1. INTRODUCTION
1.1 APPLICABILITY
This method applies to the determination of nineteen polycyclic aromatic
hydrocarbons (PAH) in emissions from stationary sources. These are listed in
Table 1. The sensitivity which can ultimately be achieved for a given sample will
depend upon the types and concentrations of other chemical compounds in the
sample as well as the original sample size and instrument sensitivity.
Any modification of this method beyond those expressly permitted shall be
considered a major modification subject to approval by the Executive Officer of
the California Air Resources Board or his or her authorized representative.
1.2 PRINCIPLE
Particulate and gaseous phase PAH are extracted isokinetically from the stack
and collected on XAD-2 resin, in impingers, or in upstream sampling train
components (filter, probe, nozzle). Only the total amounts of each PAH in the
stack emissions can be determined with this method. It has not been
demonstrated that the partitioning in the different parts of the sampling train is
representative of the partitioning in the stack gas sample for paniculate and
gaseous PAH.
The required analytical method is isotope dilution mass spectrometry combined
with high resolution gas chromatography. This entails the addition of internal
standards to all samples in known quantities, matrix-specific extraction of the
sample with appropriate organic solvents, preliminary fractionation and cleanup
of extracts and analysis of the processed extract for PAH using high-resolution
capillary column gas chromatography coupled with either low resolution mass
spectrometry (HRGC/LRMS), or high resolution mass spectrometry
(HRGC/HRMS). To ensure comparable results, the same MS method must be
used for samples collected at all tested locations at those sources where more
than one location is tested.
Minimum performance criteria are specified herein which must be satisfied to
ensure the quality of the sampling and analytical data.
1.3 DEFINITIONS AND ABBREVIATIONS
1.3.1 Internal Standard
An internal standard is a 2H-labelled PAH which is added to all field samples,
blanks and other quality control samples before extraction. It is also present
in the calibration solutions. Internal standards are used to measure the
August 9, 1996 Proposed M-429 Page 1
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concentration of the analyte and surrogate compounds. There is one internal
standard assigned to each of the target analytes and surrogates.
1.3.2 Surrogate Standard
A surrogate standard is a labelled compound added in a known amount to the
XAD-2 resin of the sampling train, and allowed to equilibrate with the matrix
before the gaseous emissions are sampled. The surrogate standard has to be
a component that can be completely resolved, is not present in the sample,
and does not have any interference effects. Its measured concentration in
the extract is an indication of the how effectively the sampling train retains
PAH collected on the XAD-2 resin. The recovery of the surrogate standards
in the field blanks can be used to determine whether there are 'any matrix
effects caused by time or conditions under which the sample is transported
and stored prior to analysis.
1.3.3 Alternate Standard
An alternate standard is a 2H-labelled PAH compound which is added to the
impinger contents prior to extraction to estimate the extraction efficiency for
PAHs in the impinger sample.
1.3.4 Recovery Standard
A recovery standard is a 2H-labelled PAH compound which is added to the
extracts of all field samples, blanks, and quality control samples before
HRGC/MS analysis. It is also present in the calibration solution. The
response of the internal standards relative to the recovery standard is used to
estimate the recovery of the internal standards. The internal standard
recovery is an indicator of the overall performance of the analysis.
1.3.5 Relative Response Factor
The relative response factor is the response of the mass spectrometer to a
known amount of an analyte or labelled compound (internal standard or
surrogate standard) relative to a known amount of an internal standard or
another labelled compound (recovery standard or internal standard).
1.3.6 Performance Standard
A performance standard is a mixture of known amounts of selected standard
compounds. It is used to demonstrate continued acceptable performance of
the GC/MS system. These checks include system performance checks,
calibration checks, quality checks, matrix recovery, and surrogate recoveries.
1.3.7 Performance Evaluation Sample
A performance evaluation sample is one prepared by EPA or othsr
laboratories that contains known concentrations of method analytes, and has-
been analyzed by multiple laboratories to determine statistically the accuracy
and precision that can be expected when a method is performed by a
August 9, 1996 Proposed M-429 Page 2
-------
competent analyst. Concentrations must be in the same range as typical
field samples. Analyte concentrations are not known by the analyst.
1.3.8 Laboratory Control Sample
A laboratory control sample is one that contains known concentrations of
method analytes that is analyzed by a laboratory to demonstrate that it can
obtain acceptable identifications and measurements with procedures to be
used to analyze field samples containing the same analytes. Analyte
concentrations are known by the analyst. The laboratory must prepare the
control sample from stock standards prepared independently from those used
for calibration.
1.3.9 End User
The regulating agency shall be considered the end user if this test method is
conducted for regulatory purposes, or the regulating agency shall designate
the end user for the purposes of this method. Otherwise the end user shall
be the party who defrays the cost of performing this test method. In any
case, the pre-test protocol (Section 2) must identify the end user.
1.3.10 Tester
Usually the tester is a contract engineering firm that performs the sampling
procedures and delegates responsibility for specific analytical procedures to
an analytical group (usually part of a subcontracting laboratory firm). In
some cases, the tester may be part of the regulating agency. The tester shall
be the party ultimately responsible for the performance of this test method
whether directly or indirectly through the co-ordination of the efforts of the
analytical group and the efforts of the sampling group.
1.3.11 Analyst
This term refers to the analytical group that performs the analytical
procedures to generate the required analytical data.
1.3.12 Source Target Concentration
This is the target concentration for each emitted PAH of interest specified by
the end user of the test results. The target concentration shall be expressed
in units of mass of target substance per volume of emissions; typical units
are nanograms per dry standard cubic meter or micrograms per dry standard
cubic meter (ng/dscm or /;g/dscm)
1.3.13 The Method Detection Limit
The method detection limit (MDL) is based on the precision of detection of
the analyte concentration near the detection limit. It is the product of the
standard deviation of seven replicate analyses of resin samples spiked with
low concentrations of the analyte and Student's t value for 6 degrees of
freedom at a confidence level of 99 %.
August 9, 1996 Proposed M-429 Page 3
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1.3.14 The Practical Quantitation Limit
The practical quantitation limit (PQL) is a limit for each compound at or below
which data must not be reported. It is the minimum sample mass that must
be collected in the sampling train to allow detection during routine laboratory
operation within the precision limits established by the MDL determination.
The PQLs will be estimated at 5 times the MDL for those PAH that are not
contaminants of the resin. The PQL for the remainder will be estimated at 5
times the blank XAD-2 resin level.
2. THE SOURCE TEST PROTOCOL
Every performance of this test method shall have an identified operator of the
source to be tested, an identified end user of the test method results, and an
identified tester who performs this test method. Figure 1 is a summary of the
responsibilities of the parties involved in the coordination and performance of the
source test. The protocol for the entire test procedure should be understood and
agreed upon by the responsible parties prior to the start of the test.
2.1 RESPONSIBILITIES OF THE END USER AND THE TESTER
2.1.1 The End User
Before testing may begin, the end user of the test results (1.3.9) shall specify
a source target concentration for each of the PAH to be determined by this
method using the guidelines of Section 2.2.1.
The end user shall approve the source test protocol only after reviewing the
document and determining that the minimum pre-test requirements (Sections
2.2 to 2.5 ) have been met.
2.1.2 The Tester
The tester (1.3.10) shall have the primary responsibility for the performance
of the test method, and shall co-ordinate the efforts of the analytical group
and the efforts of the sampling group.
The tester shall be responsible for the selection of an analyst with
documented experience in the satisfactory performance of the method. The
tester shall obtain from the analyst all of the analytical data (Section 2.3)
that are required for pre-test calculations of sampling parameters.
Before performing the rest of this method, the tester shall develop and write
a source test protocol (Section 2.2) to help ensure that useful test method
results are obtained. The tester shall plan the test based on the information
provided by the end user, the results of pre-test survsys of the source, and
the tester's calculations of target source testing parameters (Section 2,2).
The tester shall be responsible for ensuring that all of the sampling and
analytical reporting requirements (Section 10) are met.
August 9, 1996 Proposed M-429 Page 4
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2.1.3 The Analyst
The analyst shall be responsible for performing all of the required analytical
procedures described in this test method and reporting the results as required
by Sections 2.3, 4.2.1, 4.2.2, 10.1.1, 10.1.2, 10.1.3, and 10.2).
2.2 PRE-TEST REQUIREMENTS
The source test protocol shall specify the test performance criteria of the end
user and all assumptions, required data and calculated targets for the following
testing parameters:
(1) source target concentration of each emitted PAH of interest (2.2.1),
(2) preliminary analytical data (2.3) for each target PAH, and
(3) planned sampling parameters (2.5.4, 2.5.5, and 2.5.6).
The protocol must demonstrate that the testing parameters calculated by the
tester will meet the needs of the end user. The source test protocol shall
describe the procedures for all aspects of the source test including information
on supplies, logistics, personnel and other resources necessary for an efficient
and coordinated test.
The source test protocol shall identify the end user of the results, the tester, the
analytical group, and the sampling group, and the protocol shall be signed by the
end user of the results and the tester.
The tester shall not proceed with the performance of the remainder of this
method unless the source test protocol is signed by the tester and tha end user.
2.2,1 Source Target Concentration (STC)
The tester shall not proceed with the test unless a target concentration has
been chosen. This will be the primary reporting objective of the emissions
test. The end user shall select a basis for determining each target
concentration from: a) regulatory limits, b) environmental risk assessments,
and (c) the interests of the end user, the tester, and the stationary source.
2.2.1.1 Regulatory Limits
The regulatory limit shall be the basis for determining a target
concentration for stationary source emissions in those cases where the
purpose of the emissions test is to demonstrate compliance with the
established regulatory limit.
2.2.1.2 Environmental Risk Assessments
In some cases testing is conducted for an environmental risk
assessment. A pre-test estimate of the permissible risk shall then be
used to determine the target concentration for stationary source
emissions.
August 9, 1996 Proposed M-429 Page 5
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Note that some risk assessment methodologies will assume that a PAH
is present at the detection limit or one half of the detection limit even
when the compound is not detected. This is inappropriate for planning
for the performance of the test method because by definition a
substance cannot be detected at one half of its detection limit. In such
cases, the target sampling parameter must be the maximum practical
sample volume.
2.2.1.3 Interests of the End User, the Tester and the Stationary Source
In cases where the emissions test is not being performed to demonstrate
compliance with a regulation, nor is it required for a risk assessment,
the end user may use emissions results from previous tests of the
facility or from similar facilities.
If estimates of the emissions are not availble, the tester must conduct a
preliminary test at each emissions point of interest. This target
concentration is necessary for the calculation of the target sampling
parameters required by Section 2.5. Therefore, the emissions measured
during the preliminary test must be representative of source operation.
The tester must document operating conditions, and know from
historical data, the extent to which the results of this preliminary run are
representative of emissions from the source. This will require
documentation of operating conditions during the preliminary test, and a
knowledge of the potential variability in emissions with differences in
source operation.
As an alternative to conducting a preliminary test, the end user may
specify, as a sampling target, the longest practical sampling time so as
to obtain the lowest practically achievable source reporting limit
(Section 2.5.6).
2.3 REQUIRED PRELIMINARY ANALYTICAL DATA
2.3.1 Results of Blank Contamination Checks
The tester must obtain from the analyst the results of the PAH contamination
checks. The analytical report must satisfy the reporting requirements of
Sections 10 and 10.1.
The analyst shall use the procedures described in Sections 4.2.1 and 4.2,2 to
clean the sampling media (filters and XAD-2 resin) and check for PAH
contamination.
Table 3 shows the results of analyses of different lots of re-cleaned XAD-2
resin. The purpose of this table is to show typical variability. Actual results
may vary from one test to another.
August 9,1996 Proposed M-429 Page 6
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2.3.2 The Method Detection Limit
The method detection limit (MDL) must be determined by the same analyst
(1.3.11) that will perform the analyses subsequent to sampling. Before
estimating the method detection limit ( MDL), the analyst shall identify those
PAH that are contaminants of the XAD-2 resin using the procedures
described in Sections 4.2.2.1 to 4.2.2.4. The analyst shall determine the
MDL as described in Section 8.3 and Appendix A.
2.3.3 The Practical Quantitation Limit
The analyst shall calculate the practical quantitation limits (PQLs) for the
target PAH. This value will be 5 times the MDL or 5 times the XAD-2
background level for those compounds that have been identified by the
analyst as contaminants.
Table 2 lists practical quantitation limits obtained during ARB's development
of this method. The values for the PQLs will vary with the performance of
individual laboratories. Therefore, the tester must obtain PQL values for all of
the target analytes from the analyst.
2.4 EXPECTED RANGE IN TARGET CONCENTRATIONS OF INDIVIDUAL PAHs
The PAH compounds in a source test sample can show large differences in
concentrations. A sample that might provide sufficient analyte for the detection
and quantitation of the lowest concentration PAH could contain levels of other
PAHs that exceed the upper limit of the method.
In some cases the solution is two GC/MS injections - first with the undiluted
extract, and then again after appropriate dilution of the extract. At other times
the required minimum dilution might be so large as to result in the reduction of
the internal standard response below the minimum required by the method. With
prior notification of expected levels of the target analytes, the analyst can modify
the preparation of the samples so that useful results might be obtained. All
major modifications must be approved by the Executive Officer.
2.5 SAMPLING RUNS, TIME, AND VOLUME
2.5.1 Sampling Runs
A test shall include at least three sampling runs in series and a blank
sampling train.
2.5.2 Minimum Sample Volume (MSV)
This is the minimum sample volume that must be collected in the sampling
train to provide the minimum reportable mass of PAH for quantitation. It
must be based on a) the practical quantitation limit (2.3.3), b) the source
target concentration (2.2.1), and c) sampling limitations. Use Equation
429-1 to calculate the target MSV for each PAH analyte.
August 9, 1996 Proposed M-429 Page 7
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< 429-1
MSV(dscm) =PQL x _I_
O I W
Where:
PQL = The practical quantitation limit, ng/sample (Section 2.3.3)
STC = The source target concentration, ng/dscm (Section 2.2.1)
2.5.3 Minimum Sampling Time (MST)
This is the minimum time required to collect the minimum sample volume at
the expected average volumetric sampling rate (VSR). Use Equation 429-2
to calculate the minimum sampling time (MST) required to collect the
minimum sample volume calculated in Section 2.5.2. The tester must use an
average volumetric sampling rate (VSR) appropriate for the source to be
tested.
Where:
VSR = Expected average volumetric sampling rate, dscfm
60 = Factor to convert minutes to hours
0.028317 = Factor to convert dscf to dscm
The end user must decide whether the MSTs are all practically feasible and
whether they can be increased to allow for any deviation from the sampling
and analytical conditions assumed by the test plan. Based on this decision,
the tester must use either Section 2.5.4 (a) or 2.5.4 (b) to calculate a
planned sample volume (PSV).
2.5.4 Planned Sample Volume (PSV)
This is the volume of emissions that must be sampled to provide the target
analytes at levels between the PQL and the limit of linearity. The planned
sample volume is the primary sampling target whenever practically feasible.
The PSV is calculated according to either 2.5.4 (a) or 2.5.4 (b).
(a) If the end user has decided that the MSTs can be increased, the
tester must use Equation 429-3 to calculate the PSV using the largest
of the 19 MSV values calculated in Section 2.5.2. and the largest
value for F that will give a practically achievable sample volume that
provides the target analytes at levels between the PQL and the limit
of linearity. Use this PSV to calculate the planned sampling time
(Section 2.5.5 a) and Equation 429-6.
(b) If the MSTs are not all practically achievable, the tester and the end
user must agree on a maximum practical sampling time
(Section 2.5.5b). This value must then be used for the PST in
Equation 429-4 to calculate the PSV. The tester must identify in the
August 9, 1996 Proposed M-429 Page 8
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source test protocol the target analytes for which the PSV is lower
than the MSV. The primary reporting objective of the test cannot be
achieved for those analytes. If the primary reporting objective cannot
be achieved for all of the target analytes, it must be discussed in the
protocol and the alternative reporting objective (Section 2.5.6) must
be approved by the end user of the results.
The volume of sample that is actually collected will be determined by
practical sampling limitations, the intended use of the data and the
level of uncertainty that the end user can tolerate in the measurement
of the target concentrations. This uncertainty will decrease as the
value of F (Equation 429-5) increases.
429-3
PSV(dscm) =MSV x F
429-4
PSV(dscm) = PST x VSR
PSV 429"5
"MSV
Where:
PST = Planned sampling time from Section 2.5.5
F = A safety factor (>1) that allows for deviation from ideal sampling
and analytical conditions
2.5.5 Planned Sampling Time (PST)
Two options are available for calculating the planned sampling time
depending on whether the primary objective can be achieved for all of the
target analytes.
(a) The planned sampling time (PST) shall be long enough to 1) collect
the planned sample volume with reportable levels of the target
analytes and 2) sample representative operating conditions of the
source. If the average sampling rate (VSR) used to estimate the
planned sampling time cannot be achieved in the field
(Section 4.4.4.1), the sampling time must be recalculated using the
actual VSR and the target PSV in equation 429-6.
(b) The planned sampling time shall be a practical maximum approved by
the end user and it shall be long enough to sample representative
operating conditions of the source.
1 1 429-6
002131
August 9, 1996 Proposed M-429 Page 9
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2.5.6 Preliminary Estimate of Source Reporting Limit (SRL)
Before the test proceeds, the end user and the tester shall agree on a
preliminary estimate of the source reporting limit for each target PAH. The
SRL shall be calculated using Equation 429-7. The planned sample volume
will contain reportable levels of a given analyte if that analyte is present in
the emissions at a concentration that is equal to or greater than the
calculated SRL.
429'7
SRL(ng/dscm)
Where:
SRL = Preliminary estimate of source reporting limit, ng/dscm
PQL = Practical quantitation limit, ng
PSV = Planned sample volume, dscm
2.5.7 Example Calculations
Figure 9 B is an example of the minimum required calculations of sampling
parameters for the source test protocol.
3. INTERFERENCES
Interferences may be caused by contaminants in solvents, reagents, sorbents,
glassware, and other sample processing hardware that lead to discrete artifacts
and/or elevated backgrounds at the ions monitored. All of these materials must
be routinely demonstrated to be free from interferences under the conditions of
the analysis by running laboratory reagent blanks as described in Section 6.1.1.
The use of high purity reagents and solvents helps to minimize interference
problems. Purification of solvents by distillation in all-glass systems may be
required.
Transformation of PAH and the formation of artifacts can occur in the sampling
train. PAH degradation and transformation on sampling train filters have been
demonstrated. Certain reactive PAH such as benzolalpyrene,
benzo[a]anthracene, and fluoranthene when trapped on filters can readily react
with stack gases. These PAH are transformed by reaction with low levels of
nitric acid and higher levels of nitrogen oxides, ozone, and sulfur oxides.
PAH degradation may be of even greater concern when they are trapped in the
impingers. When stack gases such as sulfur oxides and nitrogen oxides come in
contact with the impinger water they are converted into sulfuric acid and nitric
acid respectively. There is evidence that under such conditions certain PAH will
be degraded. It is recommended that the PAH levels in the impingers be used as
a qualitative tool to determine if breakthrough has occurred in the resin.
August 9, 1996 Proposed M-429 Page 10
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4. SAMPLING APPARATUS, MATERIALS AND REAGENTS
4.1 SAMPLING APPARATUS
The sampling train components listed below are required. The tester may use an
alternative to the required sampling apparatus only if, after review by the
Executive Officer, it is deemed equivalent for the purposes of this test method.
Mention of trade names or specific products does not constitute endorsement by
the California Air Resources Board. In all cases, equivalent items from other
suppliers may be used.
A schematic of the sampling train is shown in Figure 2. The train consists of
nozzle, probe, heated particulate filter, condenser, and sorbent module followed
by three impingers and a silica gel drying cartridge. An in-stack filter may not be
used because at the in-stack temperatures the filter material must be of a
material other than the Teflon required by the method. A cyclone or similar
device in the heated filter box may be used for sources emitting a large amount
of particulate matter.
For sources with a high moisture content, a water trap may be placed between
the heated filter and the sorbent module. Additional impingers may also be
placed after the sorbent module. If any of these options are used, details must
be provided in the test report. The train may be constructed by adaptation of an
ARB Method 5 train. Descriptions of the train components are contained in the
following sections.
4.1.1 Probe Nozzle
Quartz, or borosilicate glass with sharp, tapered leading edge. The angle of
taper shall be 30° and the taper shall be on the outside to preserve a
constant internal diameter. The probe nozzle shall be of the button-hook or
elbow design, unless otherwise approved by the Executive Officer.
A range of sizes suitable for isokinetic sampling should be available, e.g.,
0.32 to 1.27 cm (1/8 to 1/2 in.) - or larger if higher volume sampling trains
are used - inside diameter (ID) nozzles in increments of 0.16 cm (1/16 in.).
Each nozzle shall be calibrated according to the procedures outlined in
Section 5.1 of ARB method 5.
4.1.2 Probe
The probe should be lined or made of Teflon, quartz, or borosilicate glass.
The liner or probe is to provide an inert surface for the PAH in the stack gas.
The liner or probe extends past the retaining nut into the stack. A
temperature-controlled jacket provides protection of the liner or probe. The
liner shall be equipped with a connecting fitting that is capable of forming a
leak-free, vacuum tight connection without the use of sealing greases.
August 9, 1996 Proposed M-429 Page 11
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4.1.3 Preseparator
A cyclone, a high capacity impactor or other device-may be used if
necessary to remove the majority of the particles before the gas stream is
filtered. This catch must be used for any subsequent analysis. The device
shall be constructed of quartz or borosilicate glass. Other materials may be
used subject to approval by the Executive Officer.
4.1.4 Filter Holder
The filter holder shall be constructed of borosilicate glass, with a Teflon frit
or Teflon coated wire support and glass-to-glass seal or Teflon gasket. The
holder design shall provide a positive seal against leakage from the outside or
around the filter. The holder shall be attached immediately at the outlet of
the probe, cyclone, or nozzle depending on the configuration used. Other
holder and gasket materials may be used subject to approval by the Executive
Officer.
4.1.5 Sample Transfer Line
The sample transfer line shall be Teflon (1/4 in. O.D. x 1/32 in. wall) with
connecting fittings that are capable of forming leak-free, vacuum tight
connections without using sealing greases. The line should be as short as
possible.
4.1.6 Condenser
The condenser shall be constructed of borosilicate glass and shall be
designed to allow the cooling of the gas stream to at least 20°C before it
enters the sorbent module. Design for the normal range of stack gas
conditions is shown in Figure 3.
4.1.7 Sorbent Module
The sorbent module shall be made of glass with connecting fittings that are
able to form leak-free, vacuum tight seals without the use of sealant greases
(Figure 3). The vertical resin trap is preceded by a coil-type condenser, also
oriented vertically, with circulating cold water. Gas entering the sorbent
module must have been cooled to 20 °C (68°F) or less. The gas temperature
shall be monitored by a thermocouple placed either at the inlet or exit of the
sorbent trap. The sorbent bed must be firmly packed and secured in place to
prevent settling or channeling during sample collection. Ground glass caps
(or equivalent) must be provided to seal the sorbent-filled trap both prior to
and following sampling. All sorbent modules must be maintained in the
vertical position during sampling.
4.1.8 Impinger Train
Connect three or more impingers in series with ground glass fittings able to •
form leak-free, vacuum tight seals without sealant greases. All impingers
shall be of the Greenburg-Smith design modified by replacing the tip with a
August 9, 1996 Proposed M-429 Page 12
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1.3 cm (1/2 in.) I.D. glass tube extending to 1.3 cm (1/2 in.Jfrom the bottom
of the flask.
The first impinger may be oversized for sampling high moisture streams. The
first and second impingers shall contain 100 ml of 3 mM sodium bicarbonate
(NaHC03) and 2.4 mM sodium carbonate Na2C03) (Section 4.2.5). This is
intended to neutralize any acids that might form in the impingers. The third
impinger shall be empty. Silica gel shall be added to the fourth impinger.
A thermometer which measures temperatures to within 1°C (2°F), shall be
placed at the outlet of the third impinger.
4.1.9 Silica Gel Cartridge
This may be used instead of a fourth impinger. It shall be sized to hold 200
to 300 gm of silica gel.
4.1.10 PitotTube
Type S, as described in Section 2.1 of ARB Method 2 or other devices
approved by the Executive Officer. The pilot tube shall be attached to the
probe extension to allow constant monitoring of the stack gas velocity as
required by Section 2.1.3 of ARB Method 5. When the pitot tube occurs
with other sampling components as part of an assembly, the arrangements
must meet the specifications required by Section 4.1.1 of ARB Method 2.
Interference-free arrangements are illustrated in Figures 2-6 through 2-8 of
ARB Method 2 for Type S pitot tubes having external tubing diameters
between 0.48 and 0.95 cm (3/1 6 and 3/8 in.).
Source-sampling assemblies that do not meet these minimum spacing
requirements (or the equivalent of these requirements) may be used only if
the pitot tube coefficients of such assemblies have been determined by
calibration procedures approved by the Executive Officer.
4.1.11 Differential Pressure Gauge
Two inclined manometers or equivalent devices, as described in Section 2.2
of ARB Method 2. One manometer shall be used for velocity head (AP)
readings and the other for orifice differential pressure readings.
4.1.12 Metering System
Vacuum gauge, leak-free pump, thermometers accurate to within 3°C
(5.4°F), dry gas meter capable of measuring volume to within 2 percent, and
related equipment, as shown in Figure 2. Other metering systems must meet
the requirements stated in Section 2.1.8 of ARB Method 5.
4.1.13 Barometer
Mercury, aneroid, or other barometer capable of measuring atmospheric
pressure to within 2.5 mm Hg (0.1 in. Hg). In many cases, the barometric
reading may be obtained from a nearby national weather service station, in
which case the station value (which is the absolute barometric pressure) shall
August 9, 1996 Proposed M-429 Page 13
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be requested and an adjustment for elevation differences between the
weather station and sampling point shall be applied at a rate of minus 2.5
mm Hg (0.1 in. Hg) per 30 m (100 ft) elevation increase or vice versa for
elevation decrease.
4.1.14 Gas Density Determination Equipment
Temperature sensor and pressure gauge, as described in Section 2.3 and 2.4
of Method 2, and gas analyzer, if necessary, as described in Method 3. The
preferred configuration and alternative arrangements of the temperature
sensor shall be the same as those described in Section 2.1.10 of ARE
Method 5.
4.1.15 Filter Heating System
The heating system must be capable of maintaining a temperature around the
filter holder during sampling of (120 ± 14°C) (248 ± 25°F). A temperature
gauge capable of measuring temperature to within 3°C (5.4°F) shall be
installed so that the temperature around the filter holder can be regulated and
monitored during sampling.
4.1.16 Balance
To weigh the impingers and silica gel cartridge to within 0.5 g.
4.2 SAMPLING MATERIALS AND REAGENTS
4.2.1 Filters
The filters shall be Teflon coated glass fiber filters without organic binders, or
Teflon membrane filters, and shall exhibit at least 99.95 percent efficiency
(0.05 percent penetration) on 0.3 micron dioctyl phthalate smoke particles.
The filter efficiency test shall be conducted in accordance with ASTM
standard Method D 2986-71. Test data from the supplier's quality control
program are sufficient for this purpose. Record the manufacturer's lot
number.
4.2.1.1 Contamination Check of Filter
The tester must have the filters cleaned by the analyst and checked for
contamination prior to use in the field. The contamination check must
confirm that there are no PAH contaminants present that will interfere
with the analysis of the sample PAHs of interest at the target reporting
limits. The analyst must record the date the filter was cleaned.
The filters shall be cleaned in batches not to exceed 50 filters. To clean
the filters, shake for one hour in methylene chloride in a glass dish that
has been cleaned according to Section 6.2. After extraction, remove
the filters and dry them under a clean N2 stream. Analyze one filter
using the same extraction, clean-up and analysis procedures to be used
for the field samples (Sections 6.5.1.2, 6.6, and 7.5).
August 9, 1996 Proposed M-429 Page 14
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Blank value _ Total mass (ng) of analyte 429-8
per filter NO. filters extracted
The acceptance criteria for filter cleanliness depends on 1) the method
reporting limit, 2) the expected field sample volume and 3) the desired
reporting limit for the sampled emissions stream. Filters with PAH
levels equal to or greater than the target reporting limit for the analyte(s)
of concern shall be rejected for field use.
If the filter does not pass the contamination check, re-extract the batch
and analyze a clean filter from the re-extracted batch. Repeat the re-
extraction and analysis until an acceptably low background level is
achieved. Store the remainder tightly wrapped in clean hexane-rinsed
aluminum foil as described in Section 4.3.3.
Record the date of the last cleaning of the filters and the date of the
PAH analysis, and prepare a laboratory report of the analytical results
that includes all of the information required by Section 10.2.
The tester shall obtain this laboratory report with the date of cleaning of
the filters, and the date of the filter contamination check from the
analyst, and report them in the source test protocol and the test report
as required by Sections 10.1 and 10.3.
4.2.2 Amberlite XAD-2 Resin
The XAD-2 resin must be purchased precleaned and then cleaned again as
described below before use in the sampling train.
4.2.2.1 Cleaning XAD-2 Resin
This procedure must be carried out in a giant Soxhlet extractor which
will hold enough XAD-2 for several sorbent traps, method blanks and QC
samples. Use an all glass thimble containing an extra coarse frit for
extraction of the XAD-2. The frit is recessed 10 to 15 mm above a
crenelated ring at the bottom of the thimble to facilitate drainage. The
resin must be carefully retained in the extractor cup with a glass wool
plug and stainless steel screen to prevent floating on the methylene
chloride.
Clean the resin by two sequential 24 hour Soxhlet extractions with
methylene chloride. Replace with fresh methylene chloride after the first
24 hour period.
4.2.2.2 Drying Cleaned XAD-2 Resin
The adsorbent must be dried with clean inert gas. Liquid nitrogen from a
standard commercial liquid nitrogen cylinder has proven to be a reliable
source of large volumes of gas free from organic contaminants. A
10.2 cm ID Pyrex pipe 0.6 m long with suitable retainers as shown in
Figure 4 will serve as a satisfactory column. Connect the liquid nitrogen
August 9, 1996 Proposed M-429 Page 15
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cylinder to the column by a length of cleaned 0.95 cm ID copper tubing,
coiled to pass through a heat source. A convenient heat source is a
water bath heated from a steam line. The final nitrogen temperature
should only be warm to the touch and not over 40 °C.
Continue the flow of nitrogen through the adsorbent until all the residual
solvent is removed. The rate of flow should be high enough that the
particles are gently agitated but not so high as to cause the particles to
break up.
4.2.2.3 Residual Methylene Chloride Check.
Extraction: Weigh a 1.0 g sample of dried resin into a small vial, add 3
rnL of hexane, cap the vial and shake it well.
Analysis: Inject a 2 ^L sample of the extract into a gas chromatograph
operated under the following conditions:
Column: 6 ft x 1/8 in stainless steel containing 10% OV-101
on 100/120 Supelcoport.
Carrier Gas: Helium at a rate of 30 mL/min.
Detector: Flame ionization detector operated at a sensitivity of 4
X 1Q-11 A/mV.
Injection Port
Temperature: 250 °C.
Detector
Temperature: 305 °C.
Oven
Temperature: 30 °C for 4 min; programmed to rise at 40 °C per min
until it reaches 250 °C; return to 30 °C after 1000
seconds.
Compare the results of the analysis to the results from a reference
solution prepared by adding 2.5 //L of methylene chloride into 100 mL of
hexane. This corresponds to 100 ;/g of methylene chloride per g of
adsorbent. The maximum acceptable concentration is 1000/yg/g of
adsorbent. If the methylene chloride in the adsorbent exceeds this level,
drying must be continued until the excess methylene chloride is
removed.
4.2.2.4 Contamination Check of XAD-2 Resin
The cleaned, dried XAD-2 resin must be checked for PAH contamination.
Analyze a sample of the resin equivalent in size to the amount required
to charge one sorbent cartridge for a sampling train. The extraction,
concentration, cleanup and GC/MS analytical procedures shall be the
August 9, 1996 Proposed M-429 Page 16
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same for this sample as for the field samples (Sections 6.5.1.2, 6.6, and
7.5).
The acceptance limit will depend on the PQL, the expected
concentration in the sampled gas stream, and the planned sample
volume. The contamination level must be less than the PQL or no more
than 20 percent of the expected sample level.
If the cleaned resin yields a value for a target analyte which is not
acceptable for the end user's intended application of the test results,
repeat the extraction unless the analyst has historical data that
demonstrate that re-extraction cannot reasonably be expected to further
reduce the contamination levels. The tester must obtain these data from
the analyst and include them in both the source test protocol and the
emissions test report.
The contamination check shall be repeated if the analyst does not have
such historical data. The analyst shall reclean and dry the resin
(4.2.2.1, 4.2.2.2, and 4.2.2.3) and repeat the PAH analysis of the re-
cleaned resin. If the repeat analysis yields a similar result to the first,
record the contamination level for both the initial cleaning and the re-
cleaning.
The analyst shall record the dates of the cleaning and extraction of the
resin, and prepare a laboratory report of the analytical results that
includes all of the information required by Section 10.2.
The tester shall obtain the dates of cleaning and the laboratory report of
the results of the contamination check from the analyst, and report them
in both the source test protocol and the emissions test report as required
by Sections 10.1 and 10.3.
The tester shall identify the analytes for which the PQLs wiil be based
on a blank contamination value, and calculate the PQLs as required by
Section 2.3.3.
4.2.2.5 Storage of XAD-2 Resin
After cleaning, the resin may be stored in a wide mouth amber glass
container with a Teflon-lined cap, or placed in one of the glass adsorbent
modules wrapped in aluminum foil and capped or tightly sealed with
Teflon film at each end. The containers and modules shall then be
stored away from light at temperatures 4 °C or lower until the resin is
used in the sampling train.
The adsorbent must be used within twenty one (21) days of cleaning. If
the adsorbent is not used within 21 days, it must be re-checked for
contamination before use.
August 9, 1996 Proposed M-429 Page 17
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4.2.3 Silica Gel
Indicating type, 6 to 16 mesh. If previously used, dry at 175°C (350°F) for 2
hours. New silica gel may be used as received. Alternatively, other
desiccants (equivalent or better) may be used, subject to approval by the
Executive Officer.
4.2.4 Reagent Water
Deionized, then glass-distilled, and stored in hexane- and methylene chloride-
rinsed glass containers with TFE-lined screw caps.
4.2.5 Impinger Solution
Sodium bicarbonate 3 mM, and sodium carbonate 2.4 mM. Dissolve
1.0081 g sodium bicarbonate (NaHC03) and 1.0176 g of sodium carbonate
(Na2C03) in reagent water (4.2.4), and dilute to 4 liters.
4.2.6 Crushed Ice
Place crushed ice in the water bath around the impingers.
4.2.7 Glass Wool
Cleaned by sequential rinsing in three aliquots of hexane, dried in a 110 °C
oven, and stored in a hexane-washed glass jar with TFE-lined screw cap.
4.2.8 Chromic Acid Cleaning Solution
Dissolve 200 g of sodium dichromate in 15 ml of reagent water, and then
carefully add 400 ml of concentrated sulfuric acid.
4.3 PRE-TEST PREPARATION
The positive identification and quantitation of PAH in an emissions test of
stationary sources are strongly dependent on the integrity of the samples
' received and the precision and accuracy of all analytical procedures employed.
The QA procedures described in Sections 4.3.7 and 8 are to be used to monitor
the performance of the sampling methods, identify problems, and take corrective
action.
4.3.1 Calibration
All sampling train components shall be maintained and calibrated according to
the procedure described in APTD-0576 (Section 11.7), unless otherwise
specified herein. The tester shall maintain a record of all calibration data.
4.3.1.1 Probe Nozzle
Probe nozzles shall be calibrated according to the procedure described in
ARB Method 5.
August 9, 1996 Proposed M-429 Page 18
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4.3.1.2 PitotTube
Calibrate the Type S pitot tube assembly according to the procedure
described in Section 4 of ARB Method 2.
4.3.1.3 Metering System
Calibrate the metering system before and after use according to the
requirements of Section 5.3 of ARB Method 5.
4.3.1.4 Temperature Gauges
Use the procedure in Section 4.3 of ARB Method 2 to calibrate in-stack
temperature gauges. Dial thermometers, such as those used for the dry gas
meter and condenser outlet, shall be calibrated against mercury-in-glass
thermometers.
4.3.1.5 Leak Check of Metering System Shown in Figure 1
The tester shall use the procedure described in Section 5.6 of ARB Method 5
4.3.1.6 Barometer
Calibrate against a mercury barometer.
4.3.2 Cleaning Glassware for Sampling and Recovery
All glass parts of the train upstream of and including the sorbent module and
the first impingers shall be cleaned as described in Section 3A of the 1974
issue of Manual of Analytical Methods for Analysis of Pesticide Residues in
Human and Environmental Samples (Reference 11.4). Take special care to
remove residual silicone grease sealants on ground glass connections of used
glassware. These greasy residues shall be removed by soaking several hours
in a chromic acid cleaning solution (4.2.8) prior to routine cleaning as
described above. Other cleaning procedures may be used as long as
acceptable blanks are obtained. Acceptance criteria for blanks are stated in
Section 8.2.
Rinse all glassware with acetone, hexane, and methylene chloride prior to use
in the PAH sampling train.
Glassware used in sample recovery procedures must be rinsed as soon as
possible after use with the last solvent used in it. This must be followed by
detergent washing with hot water, and rinses with tap water, deionized
water, acetone, hexane, and methylene chloride. Other cleaning procedures
may be used as long as acceptable blanks are obtained. Acceptance criteria
for blanks are stated in Section 8.2.
4.3.3 Preparation of Filter
The clean dry filter (4.2.1) must be kept tightly wrapped in hexane-rinsed
aluminum foil and stored at 0 to 4°C in a container away from light until
August 9, 1996 Proposed M-429 Page 19
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sampling. Before inserting the filter in the sampling train, check visually
against light for irregularities and flaws or pinhole leaks.
4.3.4 Preparation of Sorbent Cartridge, Method Blank, and
Laboratory Control Samples
Sorbent Cartridge
Use a sufficient amount (at least 30 gms or 5 gms/m3 of stack gas to be
sampled) of cleaned resin to completely fill the glass sorbent cartridge which
has been thoroughly cleaned as prescribed (4.2.2).
Add the required surrogate standards (Table 7) to the sorbent cartridges for
all of the sampling and blank trains for each series of test runs. Follow the
resin with hexane-rinsed glass wool, cap both ends, and wrap the cartridge in
aluminum foil. Store the prepared cartridges as required by Section 4.3.5.
The sorbent cartridges must be loaded, and the surrogate standards must be
added to the resin in a clean area in the laboratory. There must be no
turnaround of a used cartridge in the field.
The analyst shall record the date that the surrogate standards were added to
the resin and the amount of each compound. The tester shall obtain these
data from the analyst and report them in the source test protocol and the
test report.
The appropriate levels for the surrogate standards are given in Table 7 which
shows the spiking plan for surrogate standards, internal standards, alternate
standards, and recovery standards. All of these required compounds are
generally available. Additional labelled PAH may also be used if available.
The labelled compounds used as surrogate standards must be different from
the internal standards used for quantitation, and from the alternate and
recovery standards. If the spiking scheme (Table 7) is modified, the tester
must demonstrate that the proposed modification will generate data of
satisfactory quality. Table 7A shows an approved modification that has been
used in ARB's method development. All modifications must be approved by
the Executive Officer before the emissions test is performed.
Laboratory Method Blank
Take a sample of XAD-2 resin from the same batch used to prepare the
sampling cartridge. This will serve as the laboratory method blank
(Section 8.1.1). The mass of this sample must be the same as that used in
the sampling train. Spike with the same surrogate standards at the same
levels used in the sampling cartridges.
Laboratory Control Sample
Set aside two samples of XAD-2 resin from the same batch used to prepare
the sampling cartridge. These will serve as the laboratory control samples.
(Section 8.1.3). The mass of each sample must be the same as that used in
the sampling train.
August 9, 1996 Proposed M-429 Page 20
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4.3.5 Storage of Prepared Cartridges. Method Blank and Laboratory Control Sample
Store the aluminum foil wrapped sorbent cartridges away from light at 4 °C
or lower until they are fitted into the sampling trains. Do not remove the
caps before the setup of the sampling train.
The maximum storage time from cleaning of the resin to sampling with the
spiked resin cartridge must not exceed 21 days (4.2.2.5).
Store the laboratory method blank and laboratory control samples in amber
glass jars with Teflon lined lids at temperatures no higher than 4 °C.
4.4 SAMPLE COLLECTION
Because of the complexity of this method, testers must be experienced with the
test procedures in order to ensure reliable results.
4.4.1 Preliminary Field Determinations
Select the sampling site and the minimum number of sampling points
according to ARB Method 1 or as specified by the Executive Officer.
Determine the stack pressure, temperature, and the range of velocity heads
using ARB Method 2. Conduct a leak-check of the pitot lines according to
ARB Method 2, Section 3.1.
Determine the moisture content using ARB Method 4 or its alternatives for
the purpose of making isokinetic sampling rate settings.
Determine the stack gas dry molecular weight, as described in ARB
Method 2, Section 3.6. If integrated sampling (ARB Method 3) is used for
molecular weight determination, the integrated bag sample shall be taken
simultaneously with, and for the same total length of time as, the sample
run.
Select a nozzle size based on the range of velocity heads, such that it is not
necessary to change the nozzle size in order to maintain isokinetic sampling
rates. Do not change the nozzle size during the run. Ensure that the proper
differential pressure gauge is chosen for the range of velocity heads
encountered (see Section 2.2 of ARB Method 2).
Select a probe extension length such that all traverse points can be sampled.
For large stacks, consider sampling from opposite sides of the stack to
reduce the length of probes.
The target sample volume and sampling time must already have been
calculated for the source test protocol and approved by the end user as
required by Sections 2.2 and 2.5. The total sampling time must be such that
(1) the sampling time per point is not less than 2 minutes (or some greater
time interval as specified by the Executive Officer), and (2) the total gas
sample volume collected (corrected to standard conditions) will not be less
than the target value calculated for the source test protocol (Section 2.5.5).
August 9, 1996 Proposed M-429 Page 21
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To avoid timekeeping errors, the number of minutes sampled at each point
should be an integer or an integer plus one-half minute.
4.4.2 Preparation of Collection Train
Keep all openings where contamination can occur covered until just prior to
assembly or until sampling is about to begin.
Caution: Do not use sealant greases in assembling the sampling train.
Record the performance of the setup procedures for the sampling train.
Figure 10 is an example of a form for recording the sampling train setup data.
The tester must record all of the routine information indicated on this form as
well as any additional data which are necessary for documenting the quality
of any reported results.
Place 100 ml of the impinger solution (4.2.5) in the first impinger and weigh.
Record the total weight. Repeat the procedure for the second impinger.
Leave the third impinger empty. Weigh the empty third impinger and record
the weight.
Weigh 200 to 300 g of silica gel to the nearest 0.5 g directly into a tared
impinger or silica gel cartridge just prior to assembly of the sampling train.
The tester may optionally measure .and record in advance of test time the
weights of several portions of silica gel in air-tight containers. One portion of
the preweighed silica gel must then be transferred from its container to the
silica gel cartridge or fourth impinger. Place the container in a clean place for
later use in the sample recovery.
Using tweezers or clean disposable surgical gloves, place a filter in the filter
holder. Be sure that the filter is properly centered and the gasket properly
placed so as to prevent the sample gas stream from circumventing the filter.
Check the filter for tears after assembly of the filter holder is completed.
Mark the probe extension with heat resistant tape or by some other method
to denote the proper distance into the stack or duct for each sampling point.
Assemble the train as in Figure 2. Place crushed ice around the impingers.
4.4.3 Leak Check Procedures
4.4.3.1 Pretest Leak Check
After the sampling train has been assembled, turn on and set the filter
and probe heating systems at the desired operating temperatures. Allow
time for the temperature to stabilize. Leak-check the train at the
sampling site by plugging the nozzle with a TFE plug and pulling a
vacuum of at least 380 mm Hg (15 in. Hg).
Note: A lower vacuum may be used, provided that it is not
exceeded during the test.
August 9, 1996 Proposed M-429 Page 22
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The following leak-check instructions for the sampling train are
described in Section 4.1.4.1 of ARE Method 5. Start the pump with by-
pass valve fully open and coarse adjust valve completely closed.
Partially open the coarse adjust valve and slowly close the by-pass valve
until the desired vacuum is reached. Do not reverse the direction of the
by-pass valve. This will cause water to back up into the filter holder. If
the desired vacuum is exceeded, either leak-check at this higher vacuum
or end the leak-check as described below and start over.
Determine the leakage rate. A leakage rate in excess of 4 percent of the
average sampling rate or 0.00057 m3 per min. (0.02 cfm), whichever is
less, is unacceptable. Repeat the leak check procedure until an
acceptable leakage rate is obtained. Record the leakage rate on the field
data sheet (Figure 5).
When the leak-check is completed, first slowly remove the plug from the
inlet to the probe nozzle and immediately turn off the vacuum pump.
This prevents water from being forced backward and keeps silica gel
from being entrained backward.
4.4.3.2 Leak Checks During Sample Run
If, during the sampling run, it becomes necessary to change a
component (e.g., filter assembly or impinger), a leak check shall be
conducted immediately before the change is made. The leak-check
shall be done according to the procedure described in Section 4.4.3.1
above, except that it shall be done at a vacuum equal to or greater than
the maximum value recorded up to that point in the test. If the leakage
rate is found to be no greater than 0.00057 m3/min (0.02 cfm) or 4
percent of the average sampling rate (whichever is less), the results are
acceptable, and no correction will need to be applied to the total volume
of dry gas metered. If, however, a higher leakage rate is obtained, the
tester shall either (1) record the leakage rate and correct the volume of
gas sampled since the last leak check as shown in Section 4.4.3.4
below, or (2) void the sampling run. Record the leakage rate.
Immediately after component changes, leak-checks must be conducted
according to the procedure outlined in Section 4.4.3.1 above. Record
the leakage rate on the field data sheet (Figure 5).
4.4.3.3 Post Test Leak Check
A leak-check is mandatory at the conclusion of each sampling run. The
leak-check shall be done in accordance with the procedures outlined in
Section 4.4.3.1 except that it shall be conducted at a vacuum equal to
or greater than the maximum value recorded during the sampling run.
Record the leakage rate on the field data sheet (Figure 5). If the leakage
rate is found to be no greater than 0.00057 m3/min (0.02 cfm) or 4
percent of the average sampling rate (whichever is less), the results are
acceptable, and no correction need be applied to the total volume of dry
gas metered. If, however, a higher leakage rate is obtained, the tester
August 9, 1996 Proposed M-429 Page 23
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shall either, (1) record the leakage rate and correct the sample volume as
shown in Section 4.4.3.4 below, or (2) void the sampling run.
4.4.3.4 Correcting for Excessive Leakage Rates
If the leakage rate observed during any leak-check after the start of a
test exceeds the maximum leakage rate La (see definition below).
replace Vm in Equation 429-9 with the following expression.
Vm -(L, -La)6| - (Lp -La}6
429-9
Where:
Vm = Volume of gas sampled as measured by the dry gas meter
(dscf).
La = Maximum acceptable leakage rate equal to 0.00057 m3/min
(0.02 ft3/min) or 4% of the average sampling rate, whichever is
smaller.
Lp = Leakage rate observed during the post-test leak-check, m3/m?n
(ft3/min).
Lj = Leakage rate observed during the leak-check performed prior to
the "ith" leakcheck (i = 1,2,3...n), m3/min (ft3/min).
9, = Sampling time interval between two successive leak-checks
beginning with the interval between the first and second leak-
checks, min.
6p = Sampling time interval between the last (nth) leak-check and the
end of the test, min.
Substitute only for those leakage rates (Lj or Lp) which exceed La.
4.4.4 Train Operation
4.4.4.1 Sampling Train
During the sampling run maintain a sampling rate within 10 percent of true
isokinetic, unless otherwise specified or approved by the Executive Officer.
The actual sampling rate must be at or above the VSR (Equation 429-4) to
collect the target sample mass in the estimated sampling time. If the target
sampling rate cannot be achieved, adjust the planned sampling time to
achieve the target sample volume (PSV).
For each run, record the data required on the sample data sheet shown in
Figure 5. The operator must record the dry gas meter reading at the
beginning of the test, at the beginning and end of each sampling time
August 9, 1996 Proposed M-429 Page 24
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increment, when changes in flow rates are made, before and after each leak
check, and when sampling is halted.
Record other readings required by Figure 5 at least once at each sample point
during each time increment and additional readings when significant changes
(20 percent variation in velocity head readings) necessitate additional
adjustments in flow rate.
Level and zero the manometer. Because the manometer level and zero may
drift due to vibrations and temperature changes, make periodic checks during
the traverse.
Clean the portholes prior to the test run to minimize the chance of sampling
the deposited material. To begin sampling, remove the nozzle cap and verify
that the pitot tube and probe extension are properly positioned. Position the
nozzle at the first traverse point with the tip pointing directly into the gas
stream.
Immediately start the pump and adjust the flow to isokinetic conditions.
Nomographs are available, which aid in the rapid adjustment of the isokinetic
sampling rate without excessive computations. These nomographs are
designed for use when the Type S pitot tube coefficient (Cp) is 0.85 ±0.02,
and the stack gas equivalent density (dry molecular weight) (Md) is equal to
29 ±4. APTD-0576 (Reference 11.7) details the procedure for using the
nomographs. If Cp and Md are outside the above stated ranges, do not use
the nomographs unless appropriate steps (see Reference 11.8) are taken to
compensate for the deviations.
When the stack is under significant negative pressure (height of impinger
stem), take care to close the coarse adjust valve before inserting the probe
extension assembly into the stack to prevent water from being forced
backward. If necessary, the pump may be turned on with the coarse adjust
valve closed.
When the probe is in position, block off the openings around the probe and
porthole to prevent unrepresentative dilution of the gas stream.
Turn on the recirculating pump for the adsorbent module and the condenser,
and begin monitoring the temperature of the gas entering the adsorbent trap.
Ensure that the temperature of the gas is 20 °C or lower before sampling is
started.
Traverse the stack cross section, as required by ARB Method 1 or as
specified by the Executive Officer, being careful not to bump the probe
nozzle into the stack walls when sampling near the walls or when removing
or inserting the probe extension through the portholes. This minimizes the
chance of extracting deposited material.
During the test run, take appropriate steps (e.g., adding crushed ice to the
impinger ice bath) to maintain the temperature at the condenser outlet below
20°C (68°F). Also, periodically check the level and zero of the manometer.
August 9, 1996 Proposed M-429 Page 25
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If the pressure drop across the filter becomes too high, making isokinetic
sampling difficult to maintain, the filter may be replaced during a sample run.
Another complete filter assembly must be used rather than changing the filter
itself. Before a new filter assembly is installed, conduct a leak-check as
outlined-in Section 4.4.3.2. The total PAH analysis shall include the
combined catches of all filter assemblies.
A single train shall be used for the entire sample run, except in cases where
simultaneous sampling is required in two or more separate ducts or at two or
more different locations within the same duct, or, in cases where equipment
failure necessitates a change of trains. In all other situations, the use of two
or more trains will be subject to approval by the Executive Officer.
Note that when two or more trains are used, a separate analysis of each train
shall be performed, unless identical nozzle sizes were used on all trains, in
which case the catches from the individual trains may be combined and a
single analysis performed.
At the end of the sample run, turn off the pump, remove the probe extension
assembly from the stack, and record the final dry gas meter reading. Perform
a leak-check, as outlined in Section 4.4.3.3. Also, leak-check the pitot lines
as described in ARB Method 2; the lines must pass this leak-check, in order
to validate the velocity head data. Record leakage rates.
Record any unusual events during the sampling period.
4.4.4.2 Blank Train
There shall be at least one blank train for each series of three or fewer test
runs. For those sources at which emissions are sampled at more than one
sampling location, there shall be at least one blank train assembled at each
location for each set of three or fewer runs.
Prepare and set up the blank train in a manner identical to that described
above for the sampling trains. The blank train shall be taken through all of
the sampling train preparation steps including the leak check without actual
sampling of the gas stream. Recover the blank train as described in
Section 5.3. Follow all subsequent steps specified for the sampling train
including extraction, analysis, and data reporting.
4.4.5 Calculation of Percent Isokinetic
Calculate percent isokinetic (Section 4.5.7) to determine whether the run
should be repeated. If there was difficulty in maintaining isokinetic rates
because of source conditions,, consult with the Executive Officer for possible
variance on the isokinetic rates.
4.5 CALCULATIONS
«
Carry out calculations retaining at least one extra decimal figure beyond that of
the acquired data. Round off figures after the final calculation.
August 9, 1996 Proposed M-429 Page 26
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4.5.1 Nomenclature
A = Cross-sectional area of stack, ft2.
An = Cross-sectional area of nozzle, ft2.
BWS = Water vapor in the gas stream, proportion by volume.
Cs = Concentration of PAH in stack gas, ng/dscm, corrected to standard
conditions of 20°C, 760 mm Hg (68°F. 29.92 in. Hg) on dry basis.
Gs = Total mass of PAH in stack gas sample, ng.
AH = Average pressure differential across the orifice meter, mm H20 (in.
H20).
I = Percent isokinetic sampling.
La = Maximum acceptable leakage rate for either a pretest leak-check or
for a leak check following a component change; equal to 0.00057
m3/min (0.02 cfm) or 4 percent of the average sampling rate,
whichever is less.
Lj = Individual leakage rate observed during the leak-check conducted
prior to the "ith" component change (i = 1, 2, 3, ...n), m^/min
(cfm).
4*
I. = Leakage rate observed during the post-test leak check, rrr/min
(cfm).
Md = Molecular weight of stack gas, dry basis, Ib/lb-mole (g/g-mole).
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 Ib/lb-mole).
Ms = Molecular weight of stack gas, wet basis, Ib/lb-mole (g/g-mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in. Hg).
Ps = Absolute stack gas pressure, mm Hg (in Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qj^ = Dry volumetric stack gas flow rate corrected to standard conditions,
dscf/min (dscm/min).
pw = Density of water, 0.9982 g/mL (0.002201 Ib/mL).
R = Ideal gas constant 0.06236 mm Hg-m3/°K-g-mole (21.85 in Hg-
ft3/R-lb-mole).
August 9, 1996 Proposed M-429 Page 27
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Tm = Absolute average dry gas meter temperature. °K (°R).
Ts = Absolute average stack gas temperature °K (°R).
Tstd = Standard absolute temperature, 293°K (528°R).
V1c = Total volume of liquid collected in impingers and silica gel, m!_.
Vm = Volume of gas sample as measured by dry gas meter, dcm (dcf).
vm(std) = Volume of gas sample measured by the dry gas meter, corrected to
standard conditions, dscm (dscf).
vw(std) = Volume of water vapor in the gas sample, corrected to standard
conditions, dscm {dscf).
vs = Stack gas velocity, calculated by ARB Method 2, Equation 2-9,
ft/sec (m/sec).
Y = Dry gas meter calibration factor.
0 = Total sampling time, min.
61 = Sampling time interval, from the beginning of a run until the first
component change, min.
8j = Sampling time interval between two successive component
changes, beginning with the interval between the first and second
changes, min.
6p = Sampling time interval, from the final (nth) component change until
the end of the sampling run, min.
cpw = Sampling time interval, from the final (nth) component change until
13.6 = Specific gravity of mercury.
60 = Conversion factor, sec/min.
100 = Conversion to percent.
4.5.2 Average Dry Gas Meter Temperature and Average Orifice Pressure Drop
See sampling run record (Figure 5).
4.5.3 Dry Gas Volume
Use Equation 429-10 to correct the sample volume measured by the dry gas
meter to standard conditions (20°C, 760 mm Hg or 68°F, 29.92 in Hg).
August 9. 1996 Proposed M-429 Page 28
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4. AH ] /p, 4. Ah 1 429-10
T ^ I1 oar i-a fi bar iQ c ^zs IU
= x/ v I std \ 13.b/ - K w Y ] 13.r
m(std) vm Y -^ 5 ~ N1 vm Y ^
1 m 'std ' m
Where:
Tstd
K! = = 0.3858 °K/mm Hg for metric units
= 17.65 °R/in Hg for English units
Pstd
NOTE: Equation 429-10 may be used as written unless the leakage rate
observed during any of the mandatory leak-checks (i.e., the post-test leak-
check or leak-checks conducted prior to component changes) exceeds La. If
Lp or LJ exceeds La, Vm in Equation 429-10 must be modified as described in
Section 4.4.3.4.
4.5.4 Average Stack Gas Velocity
Calculate the average stack gas velocity, vs/ as specified in ARB Method 2,
Section 5.2.
4.5.5 Volume of Water Vapor
Calculate the volume of water vapor using Equation 429-1 1 and the weight
of the liquid collected during sampling (Sections 5.3.6 and 5.3.8).
v _ w Pw RTstd _ K v
Vw(std) - Vlc - -_- - K2 Vlc
Where:
K2 = 0.001333 m3/mL for metric units, or
= 0.04707 ft3/mL for English units.
4.5.6 Moisture Content
Calculate the moisture content of the gas, Bws.
Vw,std> 429-12
B
ws
vm(std) +Vw(std)
NOTE: In saturated or water-droplet laden streams, the procedure for
determining the moisture content is given in the note to Section 1.2 of
Method 4. For the purpose of this method, the average stack-gas
temperature from Figure 5 may be used for this determination, provided
that the accuracy of the in-stack temperature sensor is ± 1°C (2°F)
Augusts, 1996 Proposed M-429 Page 29
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4.5.7 Isokinetic Variation
4.5.7.1 Calculation from Raw Data
100TS[K3V1C + (Pbar + -* 429-13
60 9 vs Ps An
Where:
K3 = 0.003454 mm Hg-m3/mL-°K for metric units
= 0.002669 in Hg-ft3/mL-°R for English units
4.5.7.2 Calculation from Intermediate Values
Vm(std)
Tstd vs 6 An Ps 60 (1 - Bws) 429-14
= K4
Ts Vm(std)
PSVS6 An(1 -Bws)
Where:
K4 = 4.320 for metric units.
= 0.09450 for English units.
4.5.8 Average stack gas dry volumetric flow rate
Use Equation 429-1 5 to calculate the average dry volumetric flow rate of the
gas.
=60K, (1 -B^) vs
429-15
Where:
Tstd
K! = = 0.3858 °K/mm Hg for metric units
pstd
= 17.65 °R/in Hg for English units
4.6 ISOKIIMETIC CRITERIA
If 90 percent < I < 110 percent, the isokinetic results are acceptable. If there
is a bias to the results because I < 90 percent or I > 110 percent, then the
results must be rejected and the test repeated, unless the test results are
accepted by the Executive Officer.
August 9, 1996 Proposed M.42g Rage
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5 SAMPLE RECOVERY
5.1 SAMPLE RECOVERY APPARATUS
5.1.1 Probe Nozzle Brush
Inert bristle brush with stainless steel wire handle. The brush shall be
properly sized and shaped to brush out the probe nozzle.
5.1.2 Wash Bottles
Teflon wash bottles are required; Teflon FEP*.
5.1.3 Glass Sample Storage Containers
Precleaned narrow mouth amber glass bottles, 500 ml or 1000 mL. Screw
cap liners shall be Teflon.
5.1.4 Filter Storage Containers
Sealed filter holder or precleaned, wide-mouth amber glass containers with
Teflon lined screw caps.
5.1.5 Balance
To measure condensed water to within 0.5 g.
5.1.6 Silica Gel Storage Containers
Air tight metal containers to store silica gel.
5.1.7 Funnel and Rubber Policeman
To aid in transfer of silica gel to container; not necessary if silica gel is
weighed in the field.
5.1.8 Funnel
To aid in sample recovery. Glass or Teflon* must be used.
5.1.9 Ground Glass Caps or Hexane Rinsed Aluminum Foil
To cap off adsorbent tube and the other sample-exposed portions of the
aluminum foil.
5.1.10 Aluminum Foil
Heavy-duty, precleaned with methylene chloride.
Augusts, 1996 Proposed M-429 Page 31
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5.2 SAMPLE RECOVERY REAGENTS
5.2.1 Reagent Water
Deionized (Dl), then glass distilled, and stored in hexane and methylene
chloride-rinsed glass containers with TFE-lined screw caps.
5.2.2 Acetone
Nanograde quality. "Distilled in Glass" or equivalent, stored in original
containers. A blank must be screened by the analytical detection method.
5.2.3 Hexane
Nanograde quality. "Distilled in Glass" or equivalent, stored in original
containers. A blank must be screened by the analytical detection method.
5.2.4 Methylene Chloride
Nanograde quality or equivalent. A blank must be screened by the analytical
detection method.
5.3 SAMPLE RECOVERY PROCEDURE
Proper cleanup procedure begins as soon as the probe is removed from the stack
at the end of the sampling period and a post test leak check has been performed
(4.4.3.3). Allow the probe to cool.
When the probe can be safely handled, wipe off all external participate matter
near the tip of the probe nozzle. Conduct the post test leak check as described
in Section 4.4.3.3. Remove the probe from the train and close off both ends of
the probe with precleaned aluminum foil (5.1.10). Seal off the inlet to the train
with a ground glass cup or precleaned aluminum foil.
Transfer the probe and impinger assembly to the cleanup area. This area must
be clean, and enclosed so that the chances of contaminating the sample will be
minimized.
No smoking is allowed.
Inspect the train prior to and during disassembly and note any abnormal
conditions, broken filters, color of the impinger liquid, etc. Figure 6 summarizes
the recovery procedure described in Sections 5.3.1 to 5.3.8.
Figure 11 is an example of a form for recording the performance of the sample
recovery procedure. The tester must record all of the routine information
indicated on this form as well as any additional data which are necessary for
documenting the quality of any reported results.
August 9, 1996 Proposed M-429 Page 32
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5.3.1 Sample Container No. 1 (front half rinses)
Quantitatively recover materialdeposited in the nozzle, probe, the front half
of the filter holder, and the cyclone, if used, first by brushing and then by
sequentially rinsing with acetone, hexane, and methylene chloride three times
each. Place all these rinses in Container No. 1. Mark the liquid level.
5.3.2 Cyclone Catch
If the optional cyclone is used, quantitatively recover the particulate matter
by sequentially rinsing the cyclone with acetone, hexane, and methylene
chloride. Store in a clean sample container and cap.
5.3.3 Sample Container No. 2 (filter)
Carefully remove the filter from the filter holder and place it in its identified
container. Use a pair of precleaned tweezers to handle the filter. Do not
wrap the filter in aluminum foil. If it is necessary to fold the filter, make sure
that the particulate cake is inside the fold. Carefully transfer to the container
any particulate matter and/or filter fibers which adhere to the filter holder
gasket by using a dry inert bristle brush and/or a sharp-edged blade. Seal the
container.
5.3.4 Sorbent Module
Remove the sorbent module from the train and cap it.
5.3.5 Sample Container No. 3 (back half rinses)
Rinse the back half of the filter holder, the transfer line between the filter and
the condenser, and the condenser (if using the separate condenser-sorbent
trap) three times each with acetone, hexane and methylene chloride, and
collect all rinses in Container Mo. 3. If using the combined condenser/sorbent
trap, the rinse of the condenser shall be performed in the laboratory after
removal of the XAD-2 portion. If the optional water knockout trap has been
employed, the contents and rinses shall be placed in Container No. 3. Rinse
it three times each with acetone, hexane, and methylene chloride. Mark the
liquid level.
The back half rinses may also be combined in a single container with the
front half rinses (Section 5.3.1).
5.3.6 Sample Container No. 4 (Impinger contents)
Wipe off the outside of each of the first three impingers to remove excess
water and other material. Weigh the impingers and contents to the nearest
±0.5 g using a balance. Record the weight. Calculate and then record the
weight of liquid collected during sampling. Use this weight and the weight of
liquid collected in the silica gel (Section 5.3.8) to calculate the moisture
content of the effluent gas (Sections 4.5.5 and 4.5.6). Pour the impinger
catch directly into Container No. 4. Mark the liquid level.
August 9, 1996 Proposed M-429 Page 33
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5.3.7 Sample Container No. 5 (Impinger rinses)
Rinse each impinger sequentially three times with acetone, hexane, and
methylene chloride and pour rinses into Container No. 5. Mark the liquid
level. These rinses may be combined with the previously weighed impinger
contents in Container No. 4.
5.3.8 Weighing Silica Gel
Weigh the spent silica gel to the nearest 0.5 g using a balance. Record the
weight. Calculate and then record the weight of liquid collected during
sampling. Use this weight and the weight of liquid collected in the impingers
(Section 5.3.6) to calculate the moisture content of the effluent gas
(Sections 4.5.5 and 4.5.6). .
5.4 SAMPLE PRESERVATION AND HANDLING
From the time of collection to extraction, maintain all samples (Sections 5.3.1 to
5.3.7) at 4°C or lower and protect from light. All samples must be extracted as
soon as practically feasible, but within 21 days of collection; and all extracts
must be analyzed as soon as practically feasible, but within 40 days of
extraction. Success in meeting the holding time requirement will depend on pre-
test planning by the tester and the laboratory.
6 ANALYTICAL PREPARATION
This method is restricted to use only by or under the supervision of analysts
experienced in the use of capillary column gas chromatography/mass
spectrometry and skilled in the interpretation of mass spectra. Each analyst
must demonstrate the ability to generate acceptable results with this method
using the procedures described in Sections 7.3, 8.2.6, and 8.3.1.
6.1 SAFETY
The toxicity or carcinogenicity of each reagent used in this method has not been
precisely defined. Nevertheless, each chemical compound should be treated as a
potential health hazard and exposure to these chemicals must be reduced to the
lowest possible level by whatever means available. The laboratory is responsible
for maintaining a current file of OSHA regulations regarding the safe handling of
the chemicals specified in this method. A reference file of material data handling
sheets should also be made available to all personnel involved in the chemical
analysis. Reference 11.9 describes procedures for handling hazardous chemicals
in laboratories.
The following method analytes have been classified as known or suspected
human or mammalian carcinogens: benzo(a)anthracene and dibenzo-
(a,h,)anthracene. A guideline for the safe handling of carcinogens can be found
in Section 5209 of Title 8 of the California Administrative Code.
August 9, 1996 Proposed M-429 Page 34
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6.2 CLEANING OF LABORATORY GLASSWARE
Glassware used in the analytical procedures (including the Soxhlet apparatus and
disposable bottles) must be cleaned as soon as possible after use by rinsing with
the last solvent used in it. This must be followed by detergent washing with hot
water, and rinses with tap water, deionized water, acetone, hexane, and
methylene chloride. Other cleaning procedures may be used as long as
acceptable blanks are obtained. Acceptance criteria for blanks are given in
Section 8.2.
Clean aluminum foil with acetone followed by hexane and methylene chloride.
6.3 APPARATUS
6.3.1 Grab Sample Bottle
Amber glass, 125-mL and 250-mL, fitted with screw caps lined with Teflon.
The bottle and cap liner must be acid washed and solvent rinsed with
acetone and methylene chloride, and dried before use.
6.3.2 Concentrator Tube, Kuderna-Danish
10-mL, graduated (Kontes-K-570050-1025 or equivalent). Calibration must
be checked at the volumes employed in the test. A ground glass stopper
must be used to prevent evaporation of extracts.
6.3.3 Evaporation Flask, Kuderna-Danish
500-mL (Kontes K-570001-0500 or equivalent). (Attached to concentrator
tube with springs).
6.3.4 Snyder Column, Kuderna-Danish
Three-ball macro {Kontes K-569001-0121 or equivalent).
6.3.5 Snyder Column, Kuderna-Danish
Two-ball micro (Kontes K-569001-0219 or equivalent).
6.3.6 Minivials
1.0 ml vials; cone-shaped to facilitate removal of very small samples; heavy
wall borosilicate glass; with Teflon-faced rubber septa and screw caps.
6.3.7 Soxhlet Apparatus
1 liter receiver, 1 heating mantle, condenser, Soxhlet extractor.
6.3.8 Rotary Evaporator
Rotovap R (or equivalent), Brinkmann Instruments, Westbury, NY.
Augusts, 1996 Proposed M-429 Page 35
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6.3.9 Nitrogen Slowdown Apparatus
N-Evap Analytical Evaporator Model 111 (or equivalent), Organomation
Associates Inc., Northborough, MA.
6.3.10 Analytical Balance
Analytical. Capable of accurately weighing to the nearest 0.0001 g.
6.3.11 Disposable Pipet
5 3/4 inch x 7.0 mm OD.,
6.4 SAMPLE PREPARATION REAGENTS
6.4.1 Reagent water
Same as 5.2.1.
6.4.2 Acetone
Same as 5.2.2.
6.4.3 Hexane
Same as 5.2.3.
6.4.4 Methylene Chloride
Same as 5.2.4.
6.4.5 Sulfuric Acid
ACS. Reagent grade. Concentrated, sp. gr. 1.84.
6.4.6 Sodium Sulfate
ACS. Reagent grade. Granular, anhydrous. Purify prior to use by extracting
with methylene chloride and oven drying for 4 or more hours in a shallow
tray. Place the cleaned material in a glass container with a Teflon lined screw
cap, and store in a desiccator.
6.4.7 Silica Gel
For column chromatography, type 60, EM reagent, 100-200 mesh, or
equivalent. Soxhlet extract with methylene chloride, and activate by heating
in a foil covered glass container for longer than 16 hours at 130 °C, then
store in a desiccator. The storage period shall not exceed two days.
NOTE: The performance of silica gel in the column cleanup procedure varies
with manufacturers and with the method of storage. The analyst shall
establish a procedure that satisfies the performance criteria of Section 6.6.1.
August 9, 1996 Proposed M-429 Page 36
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6.4.8 Alumina: Acidic
Soxhlet extract with methylene chloride, and activate in a foil covered glass
container for 24 hours at 190 °C.
NOTE: The performance of alumina in the column cleanup procedure varies
with manufacturers and with the method of storage. The analyst shall
establish a procedure that meets the performance criteria of Section 6.6.1.
6.4.9 Nitrogen
Obtained from bleed from liquid nitrogen tank.
6.5 SAMPLE EXTRACTION
WARNING: Stack sampling will yield both liquid and solid samples for PAH
analysis. Samples must not be split prior to extraction even when they appear
homogeneous as in the case of single liquid phase samples. Solid samples such
as the resin are not homogeneous and particulate matter may not be uniformly
distributed on the filter. In addition, filter samples are generally so small that the
desired detection limit might not be achieved if the sample were split.
The recovered samples may be combined as follows:
1) Particulate filter and particulate matter collected on the filter (Section 5.3.3),
cyclone catch (Section 5.3.2) and sample container No. 1 (Section 5.3.1).
2) Sample container No. 3 (Section 5.3.5), resin (Section 5.3.4) and rinse of
resin cartridge.
3) Sample container No.4 (Section 5.3.6) and sample container No.5 (Section
5.3.7)
Two schemes for sample preparation are described in Sections 6.5.1 and 6.5.2
below. One of these must be used.
Section 6.5.1 describes sample preparation procedures for separate GC/MS
analyses of impingers and the remainder of the sampling train. Figure 7 is a
flowchart of the extraction and cleanup procedures.
Section 6.5.2 describes sample preparation procedures for GC/MS analysis of a
single composite extract from each sampling train. The recovered samples are
combined as shown in Figure 8.
6.5.1 Separate Analysis of Impingers
A separate analysis of the impingers can be used to determine whether there
has been breakthrough of PAHs past the resin.
Augusts, 1996 Proposed M-429 Page 37
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6.5.1.1 Extraction of Liquid Samples
A. Sample Container No. 1 (Front half rinses)
Concentrate the contents of sample container No. 1 (Section 5.3.1)
to a volume of about 1-5 mL using the nitrogen blowdown
apparatus. Rinse the sample container three times with small
amounts of methylene chloride and add these rinses to the
concentrated solution. Concentrate further to about 1-5 mL. This
residue will likely contain particulate matter which was removed in
the rinses of the probe and nozzle. Transfer the residue (along with
three rinses of the final sample vessel) to the Soxhlet apparatus with
the filter and particulate catch and proceed as described under
Section 6.5.1.2 below.
B. Sample Container No. 3 (Back half rinses)
Concentrate the contents of sample container No. 3 (Section 5.3.5)
to a volume of about 1-5 mL using the nitrogen blowdown
apparatus. Rinse the sample container three times with small
amounts of methylene chloride and add these rinses to the
concentrated solution. Concentrate further to about 1-5 mL.
Combine this residue (along with three rinses of the finaP sample
vessel) in the Soxhlet apparatus with the resin sample, and proceed
as described under Section 6.5.1.2 below.
C. Containers No. 4 and No. 5 (Impinger contents and rinses)
Place the contents of Sample Containers No. 4 and No. 5 (Sections
5.4.6 and 5.4.7) in a separatory funnel. Add the appropriate
amount of 2H-labelled alternate standard solution (Section 7 and
Table 7 or 7A) to achieve the final extract concentrations indicated
in Table 8 or 8A. The amounts required by Section 7.2.4 are based
on a final volume of 500 //L for analysis (450 fjL of sample extract
and 50 jjL of recovery standard solution). Extract the sample three
times with 60 mL aliquots of methylene chloride. Combine the
organic fractions. Divide the extract in two - one half to be
archived, and the other for cleanup and GC/MS analysis. Store the
archive sample at 4°C away from light.
Pour the remaining extract through Na2S04 'nto a round bottom
flask. Add 60 to 100 mL hexane and evaporate to about 10 mL.
Repeat three times or less if the methylene chloride can be removed
with less hexane. Add the appropriate amount of alternate standard
(Section 7.2.7) to achieve the final extract concentrations shown in
Table 6 or 6A. This standard must be used to monitor the efficiency
of the cleanup procedure.
Concentrate the remaining sample to 2 mL with a Kuderna-Danish
concentrator or rotary evaporator, then transfer the extract to a 8-
mL test tube with hexane. Proceed with sample cleanup procedures
below (Section 6.6).
August 9, 1996 Proposed M-429 Page 38
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6.5.1.2 Extraction of Solid Samples
Filter, Paniculate matter, and Resin
The Soxhlet apparatus must be large enough to allow extraction of
the sample in a single batch. Clean the Soxhlet apparatus by a 4 to
8-hr Soxhlet with methylene chloride at a cycling rate of 3 cycles
per hour. Discard the solvent. Add 20 g Na2S04 to the thimble.
Combine the filter, resin, glass wool, and concentrated front and
back half rinses (6.5.1.1A and 6.5.1.1B) and place on top of the
Na2S04. Add the appropriate amount of internal standard (Section
7.2.4 and Table 7) to achieve the final extract concentrations
indicated in Table 8.
Place the thimble in the Soxhlet apparatus, and add about 700 ml
of methylene chloride to the receiver. Assemble the Soxhlet, turn
on the heating controls and cooling water, and allow to reflux for 16
hours at a rate of 3 cycles per hour. After extraction, allow the
Soxhlet to cool. Divide the sample in two - one half to be archived,
and the other for cleanup and GC/MS analysis. Store the archive
sample at 4°C away from light.
Exchange the remaining extract to hexane. Add 60 to 100 ml
hexane and evaporate to about 10 mL. Repeat three times or as
necessary to remove the methylene chloride. Add the appropriate
amount of alternate standard (Section 7.2.7 and Table 7 or 7A) to
achieve the final extract concentrations shown in Table 8 or 8A.
This alternate standard must be used to monitor the efficiency of
the cleanup procedure when the impingers are analyzed separately
from the remainder of the sampling train.
Concentrate the remaining sample to about 2 ml with a Kuderna-
Danish concentrator or rotoevaporator, then transfer the extract to a
8-mL test tube with hexane. Proceed with sample cleanup
procedures below (Section 6.6).
6.5.2 Single Composite Extract For Analysis
6.5.2.1 Extraction of Aqueous Samples
Containers No. 4 and No. 5 (Impinger contents and rinses)
Pour the contents of Sample Containers No. 4 and No. 5 (Sections
5.3.6 and 5.3.7) into an appropriate size separatory funnel. Do not
add internal standards. Instead, add the appropriate amount of
alternate standard spiking solution (Section 7 and Table 7 or 7A) to
achieve the final extract concentrations indicated in Table 8 or 8A.
Extract the sample three times with 60 ml aliquots of methylene
chloride. Combine the organic fractions with the solid samples and
concentrated rinses (6.5.2.2) in a Soxhlet extractor.
August 9, 1996 Proposed M-429 Page 39
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6.5.2.2 Extraction of Solid Samples
Concentrate the front and back half rinses as described in Sections
6.5.1.1 A and 6.5.1.1B. Clean the Soxhlet apparatus as in Section
6.5.1.2. Place the filter and resin in the Soxhlet apparatus along with
the concentrated front and back half rinses and the impinger extract.
Add the internal standards, extract the sample, and concentrate the
extract as described in Section 6.5.1.2. Divide the extract into two
equal portions. Store one of these, the archive sample, at 4 °C away
from light. The remaining extract must be exchanged to hexane as
described in Section 6.5.1.2. Do not add the alternate standard to this
composite extract. It has already been added to the impinger sample
(6.5.2.1).
Concentrate the extract to 2 ml with a Kuderna-Danish concentrator or
rotary evaporator, then transfer to a 8-mL test tube with hexane or
equivalent non-polar solvent such as isooctane. Proceed with sample
cleanup procedures below (Section 6.6)
6.6 COLUMN CLEANUP
Several column chromatographic cleanup options are available. Either of the two
described below may be sufficient. Before using a procedure for the cleanup of
sample extracts, the analyst must demonstrate that the requirements of Sections
8.1.3.1 and 8.2.6 can be met using the cleanup procedure. Acceptable
alternative cleanup procedures may also be used provided that the analyst can
demonstrate that the performance requirements of Sections 8.1.3.1 and 8.2.6
can be met. Compliance with the requirements of Sections 8.1.1.1 and 8.2.6
must also be demonstrated whenever there is a change in the column cleanup
procedure used for the initial demonstration.
The sample extract obtained as described in Sections 6.5.1C and 6.5.1.2 or
6.5.2.2 is concentrated to a volume of about 1 ml using the nitrogen blowdown
apparatus, and this is transferred quantitatively with hexane rinsings to at least
one of the columns described below.
6.6.1 Column Preparation
A. Silica Gel Column
Pack a glass gravity column (250 mm x 10 mm) in the following
manner:
Insert a clean glass wool plug (Section 4.2.7) into the bottom of the
column and add 10 grams of activated silica gel (Section 6.4.7) in
methylene chloride. Tap the column to settle the silica gel, and then add
a 1 cm layer of anhydrous sodium sulfate (Section 6.4.6)
Variations among batches of silica gel may affect the elution volume of
the various PAH. Therefore, the volume of solvent required to
completely elute all of the PAH must be verified by the analyst. The
weight of the silica gel can then be adjusted accordingly. Satisfactory
August 9, 1996 Proposed M-429 Page 40
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recovery (as defined in Section 6.6) of each native PAH in the LCS
(8.1.3) must be demonstrated whenever there is a change in the method
of preparing the silica gel columns.
B. Acid Alumina Column
Pack a 250 mm x 10 mm glass gravity column as follows:
Insert a clean glass wool plug (Section 4.2.7) into the bottom of the
column. Add 6 g of acid alumina prepared as described in
Section 6.4.8. Tap the column gently to settle the alumina, and add 1
cm of anhydrous sodium sulfate to the top.
Satisfactory recovery (as defined in Section 6.6) of each native PAH in
the LCS (8.1.3) must be demonstrated whenever there is a change in
the method of preparing the acid alumina columns.
6.6.2 Column Chromatography Procedure
A. Silica Gel Column
Elute the column with 40 mL of hexane. The rate for all elutions should
be about 2 mL/min. Discard the eluate and just prior to exposure of the
sodium sulfate layer to the air, transfer the 1 ml sample extract onto the
column using two additional 2 mL rinses of hexane to complete the
transfer. Just prior to exposure of the sodium sulfate layer to the air,
begin elution of the column with 25 mL of hexane followed by 25 mL of
methylene chloride/hexane (2:3)(v/v). Collect the entire eluate.
Concentrate the collected fraction to about 5 mL using the K-D
apparatus or a rotary evaporator. Do not allow the extract to go to
dryness.
Transfer to a minivial using a hexane rinse and concentrate to 450 /jL
using a gentle stream of nitrogen. Store the extracts in a refrigerator at
4 °C or lower away from light until GC/MS analysis (Section 7).
Bo Alumina Column
Elute the column with 50 mL of hexane. Let the solvent flow through
the column until the head of the liquid in the column is just above the
sodium sulfate layer. Close the stopcock to stop solvent flow.
Transfer 1 mL of the sample extract onto the column. Rinse out extract
vial with two 1 mL rinses of hexane and add it to the top of the column
immediately. To avoid overloading the column, it is suggested that no
more than 300 mg of extractable organics be placed on the column.
Just prior to exposure of the sodium sulfate to the air, elute the column
with a total of 15 mL of hexane. If the extract is in 1 mL of hexane,
and if 2 mL of hexane was used as a rinse, then 12 mL of additional
hexane should be used. Collect the effluent and concentrate to about 2
mL using the K-D apparatus or a rotary evaporator.
August 9, 1996 Proposed M-429 Page 41
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Transfer to a minivial using a hexane rinse and concentrate to 450//L
using a gentle stream-of nitrogen. Store the extracts at 4°C or lower
away from light until GC/MS analysis.
7 GC/MS ANALYSIS
7.1 APPARATUS
7.1.1 Gas Chromatograph
An analytical system complete with a temperature programmable gas
chromatograph and all required accessories'including syringes, analytical
columns, and gases. The GC injection port must be designed for capillary
columns. Splitless injection is recommended.
7.1.2 Column
Fused silica columns are required.
A. 30 M long x 0.32 mm ID fused silica capillary column coated with a
crosslinked phenyl methyl silicone such as DB-5.
B. Any column equivalent to the DB-5 column may be used as long as it
has the same separation capabilities as the DB-5.
7.1.3 Mass Spectrometer
7.1.3.1 Low Resolution
A low resolution mass spectrometer (LRMS) equipped with a 70 eV
(nominal) ion source operated in the electron impact ionization mode,
and capable of monitoring all of the ions in each Selected Ion Monitoring
(SIM) group (Table 13) with a total cycle time of 1 second or less.
7.1.3.2 High Resolution
The high resolution mass spectrometer (HRMS) must be capable of
operation in the SIM mode at a resolving power of 8,000. Electron
impact ionization must be used. The mass spectrometer must be
capable of monitoring all of the ions listed in each of the three SIM
descriptors (Table 14) with a total cycle time of 1 second or less.
7.1.4 GC/MS Interface
Any gas chromatograph to mass spectrometer interface may be used as long
as it gives acceptable calibration response for each analyte of interest at the
desired concentration and achieves the required tuning performance criteria
(Sections 7.3.5 and 7.3.6). All components of the interface must be glass
or glass-lined materials. To achieve maximum sensitivity, the exit end of the
capillary column should be placed in the mass spectrometer ion source
without being exposed to the ionizing electron beam.
August9, 1996 Proposed M-429 Page 42
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7.1.5 Data Acquisition System
A computer system must be interfaced to the mass spectrometer. The
system must allow the continuous acquisition and storage on machine-
readable media of all data obtained throughout the duration of the
chromatographic program. The computer must have software that can
search any GC/MS data file for ions of a specific mass and plot a Selected
Ion Current Profile or SICP (a plot of the abundances of the selected ions
versus time or scan number). Software must also be able to integrate, in any
SICP, the abundance between specified time or scan-number limits.
The data system must provide hard copies of individual ion chromatograms
for selected gas chromatographic time intervals.
The data system must also be able to provide hard copies of a summary
report of the results of the GC/MS runs. Figures 14A to 14C show the
minimum data that the system must be available to provide.
7.2 REAGENTS
7.2.1 Stock Standard Solution (1.00 //g///L)
Standard solutions can be prepared from pure standard materials or
purchased as certified solutions.
7.2.2 Preparation of Stock Solutions
A. Calibration standards. Prepare stock calibration standard solutions of
each of the PAH analytes by accurately weighing the required amount of
pure material. Dissolve the material in isooctane and dilute to volume.
When compound purity is assayed to be 96% or'greater, the weight may
be used without correction to calculate the concentration of the stock
standard.
Commercially prepared stock standards may be used at any
concentration if they are certified by the manufacturer or by an
independent source.
B. Internal standards. Prepare stock solutions in isooctane of the fourteen
internal standards listed in Table 4 or 4A at concentrations of 1000
ng//;L.
C. Recovery standards. Prepare stock solutions in isooctane of the three
recovery standards listed in Table 4 or 4XA at concentrations of
1000ng///L.
D. Alternate standard. Prepare a stock solution in isooctane of the
alternate standard listed in Table 4 or 4A at a concentration of
1000 ng///L.
August 9, 1996 Proposed M-429 Page 43
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E. Surrogate standards. Prepare stock solutions in isooctane of the
surrogate standards listed in Table 4 or 4A at a concentration of
1000 ng//;L.
Store stock standard solutions in Teflon'-sealed screw-cap bottles at 4°C and
protect from light. Stock standard solutions must be checked frequently for
signs of degradation or evaporation, especially just before using them to
prepare calibration standard solutions or spiking solutions.
*«•
Replace stock standard solutions every 12 months or more frequently if
comparison with quality control check samples according to Section 7.4.1
indicates a problem.
7.2.3 Calibration Standards
Prepare calibration standards at a minimum of five concentration levels. One
of the calibration standards should be at a concentration near, but above, the
method detection limit. The others should include the range of
concentrations found in real samples but should not exceed the linear range
of the GC/MS system.
Prepare calibration working standard solutions by combining appropriate
volumes of individual or mixed calibration standards with internal standard,
recovery standards, and alternate standard spiking solution and making up to
volume with hexane to obtain the solution concentrations given in Tables 5,
6, and 6A. The suggested ranges are 0.25 ng//;L to 5.0 ng//y|_ for LRMS and
10 pg//;L to 500 pg///L for HRMS.
All standards must be stored at 4°C or lower and mustjDe freshly prepared if
the check according to Section 7.4.1 indicates a problem.
7.2.4 Internal Standard (IS) Spiking Solution
The concentration of internal standard in the IS spiking solution must be such
that the amount of solution added to the calibration standard solution and the
sample is at least 2 ml.
Prepare the internal standard spiking solution by using appropriate volumes of
stock solutions of Section 7.2.2B to give the concentrations shown in
Table 4 or 4A. A volume of 2 ml of either the LRMS or HRMS spiking
solution will provide the amount of the internal standards that must be
added to the sample (Table 7 or 7A) before extraction to achieve, in a final
volume of 500 ;/L, the sample extract concentrations shown in Table 8 for
LRMS and Table 8 or 8A for HRMS analysis. The target concentrations in
Tables 8 and 8A are based on a final volume of 500 //L and 100 percent
recovery of the internal standards added to the sample.
7.2.5 Recovery Standard Spiking Solution
The concentration of recovery standard in this spiking solution must be such
that the amount of solution added to the concentrated sample extract is
50 //L to give a final extract volume of 500 //L.
August 9, 1996 Proposed M-429 Page 44
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Use an appropriate volume of stock solution of Section 7.2.2C to prepare a
recovery standard spiking solution with the concentrations shown in
Table 4or 4A. Store at 4 °C or lower.
A volume of 50 //L of the recovery standard spiking solution shown in
Table 4 or 4A will provide the amount of each recovery standard required by
Table 7 or 7A to achieve the target sample concentration of Table 8 or 8A.
Final volumes, may be adjusted depending on the target detection limit.
7.2.6 Surrogate Standard Spiking Solution
The concentration of surrogate standard in this spiking solution must be such
that the amount of solution added to the calibration standard solution and the
sorbent module is at least 2 ml.
Prepare the surrogate standard spiking solution by using the appropriate
volume of stock solution of Section 7.2.2E to give the concentration shown
in Table 4 or 4A. A volume of 2 ml of either the LRMS or HRMS spiking
solution will provide the amount of the surrogate standards that must be
added to the sample (Table 7 or 7A) before sampling to achieve the sample
extract concentrations shown in Table 8 or 8A in a final sample volume of
500 pL.
7.2.7 Alternate Standard Spiking Solution
The concentration of alternate standard in this spiking solution must be such
that the amount of solution added to the calibration standard solution and the
sample extracts is at least 2 ml.
Prepare the alternate standard spiking solution by using the appropriate
volume of stock solution of Section 7.2.2D to give the concentration shown
in Table 4 or 4A. A volume of 2 ml of either the LRMS or HRMS spiking
solution will provide the amount of the alternate standard that must be
added to the sample (Table 7 or 7A) before extraction to achieve the sample
extract concentrations shown in Table 8 or 8A in a final sample volume of
500/yL.
7.2.8 Calibration Check Standard
The calibration check standard shall be used for column performance checks,
and for continuing calibration checks. Solution #3 from Table 5 shall be the
calibration check standard for LRMS, while Solution #3 from Table 6 or 6A
shall be the calibration check standard for HRMS.
7.3 INITIAL CALIBRATION
An acceptable initial calibration (7.3.8) is required before any samples are
analyzed, and then intermittently throughout sample analyses as dictated by
results of the continuing calibration procedures described in Section 7.4. The
GC/MS system must be properly calibrated and the performance documented
during the initial calibration.
August 9, 1996 Proposed M-429 Page 45
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7.3.1 Retention Time Windows
Before sample analysis, determine the retention time windows during which
the selected ions will be monitored. Determine Relative Retention Time
(RRTs) for each analyte by using the corresponding 2H - labelled standard.
7.3.2 GC Operating Conditions
The GC column performance (Section 7.3.5) must be documented during the
initial calibration. Table 10 summarizes GC operating conditions known to
produce acceptable results with the column listed. The GC conditions must
be established by each analyst for the particular instrumentation by injecting
aliquots of the calibration check standard (7.2.8). It may be necessary to
adjust the operating conditions slightly based on observations from analysis
of these solutions. Other columns and/or conditions may be used as long as
column performance criteria of Section 7.3.5 are satisfied.
Thereafter the calibration check standard must be analyzed daily to verify the
performance of the system (Section 7.4).
7.3.3 GC/MS Tuning Criteria
A. Low Resolution Mass Spectrometry
Use a compound such perfluorotributylamine (PFTBA) to verify that the
intensity of the peaks is acceptable. If PFTBA is used, mass spectral
peak profiles for m/z 69, 219 and 264 must be recorded, plotted, and
reported. The scan should include a minimum of +/- two peaks (i.e, m/z
67-71 for the m/z 69 profile).
B. High Resolution Mass Spectrometry
Tune the instrument to meet the minimum required resolving power of
8,000 at 192.9888 or any other PFK reference signal close to 128.0626
(naphthalene). Use peak matching and the chosen PFK reference peak
to verify that the exact mass of m/z 242.9856 is within 5 ppm of the
required value. The selection of the low and high mass ions must be
such that they provide the largest voltage jump performed in any of the
three mass descriptors.
7.3.4 MS Operating Conditions
A. Low Resolution Mass Spectrometry
Analyze standards and samples with the mass spectrometer operating in
the Selected Ion Monitoring (SIM) mode with a total cycle time of 1
second or less.
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B. High Resolution Mass Spectrometry
Analyze standards and samples with the mass spectrometer operating in
the SIM mode with a total cycle time (including the voltage reset time)
of one second or less.
A reference compound such as Perfluorokerosene (PFK) must be used to
calibrate the SIM mass range. One PFK ion per mass descriptor is used
as a lock-mass ion to correct for mass drifts that occur during the
analysis. In addition to the lock-mass ion, several ions characteristic of
PFK are monitored as QC check ions (Table 13).
7.3.5 GC Column Performance Criteria
A. The height of the valley between anthracene and phenanthrene at m/z
178 or the 2H-analogs at m/z 188 shall not exceed 50 percent of the
taller of the two peaks.
B. The height of the valley between benzo(b)fluoranthene and
benzo(k)fluoranthene shall not exceed 60 percent of the taller of the two
peaks.
If these criteria are not met and normal column maintenance procedures are
not successful, the column must be replaced and the initial calibration
repeated.
7.3.6 Mass Spectrometer Performance
A. Low Resolution Mass Spectrometry
Verify acceptable sensitivity during initial calibration. Demonstrate that
the instrument will achieve a minimum signal-to-noise ratio of 10:1 for
the quantitation and confirmation ions when the calibration standard
with the lowest concentration is injected into the GC/MS system.
B. High Resolution Mass Spectrometry
Record the peak profile of the high mass reference signal (m/z
242.9856) obtained during peak matching by using the low-mass PFK
ion at m/z 192.9888 (or lower in mass) as a reference. The minimum
resolving power of 8,000 must be demonstrated on the high-mass ion
while it is transmitted at a lower accelerating voltage than the low-mass
reference ion, which is transmitted at full sensitivity.
The format of the peak profile representation must allow manual
determination of the resolution, that is, the horizontal axis must be a
calibrated mass scale (amu or ppm per division).
The peak width of the high mass ion at 5 percent of the peak height
must not exceed 125 ppm in mass.
August 9, 1996 Proposed M-429 Page 47
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7.3.7 Calibration Procedure
Using stock standards, prepare at least five calibration standard solutions,
using the same solvent that was used in the final sample extract. Keep the
recovery standards and the internal standards at fixed concentrations. Adjust
the concentrations recommended in Tables 5 and 6, if necessary, to ensure
that the sample analyte concentration falls within the calibration range. The
calibration curve must be described within the linear range of the method.
Calibrate the mass spectrometer response using a 2 /;L aliquot of each
calibration solution. Analyze each solution once.
Calculate:
A. the relative response factors (RRFs) for each analyte as described in
Sections 7.7.1.1, 7.7.1.2, and 7.7.1.3.
B. the mean RRFs as required by Section 7.7.1.4.
C. the standard deviation (SD) and relative standard deviation (RSD) as
required by Section 7.7.2.
Report all results as required by Section 10.2.
7.3.8 Criteria for Acceptable Initial Calibration
An acceptable initial calibration must satisfy the following performance
criteria:
A. The requirements of Sections 7.3.5 and 7.4.6 must be met.
B. The signal to noise ratio (S/N) for the GC signals present in every
selected ion current profile (SICP) must be > 10:1 for the labelled
standards and unlabelled analytes.
C. The percent relative standard deviation for the mean relative response
factors must be no greater than 30 percent for both the unlabelled
analytes and internal standards (Section 7.7.2). Otherwise, take
corrective action as required by Section 7.7.2.
7.4 CONTINUING CALIBRATION
The continuing calibration consists of an analysis of the calibration check
standard (Section 7.2.8) once during each 12-hour shift as described in Section
7.4.1.
The criteria for acceptable continuing calibration are given in Section 7.4.2.
These must be satisfied or else corrective action must be taken as required by
Section 7.4.2.
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7.4.1 Calibration Check
The calibration check standard (Section 7.2.8) must be analyzed at the
beginning and end of each analysis period, or at the beginning of every 1 2-
hour shift if the laboratory operates during consecutive 12 hour shifts.
Inject a 2-//L aliquot of the calibration check standard (Section 7.2.8) into the
GC/MS. Use the same data acquisition parameters as those used during the
initial calibration.
Check the retention time windows for each of the compounds. They must
satisfy the criterion of Section 7.4.2C
Check for GC resolution and peak shape. Document acceptable column
performance as described in Section 7.3.5. If these criteria are not met, and
normal column maintenance procedures are unsuccessful, the column must
be replaced and the calibration repeated.
Calculate the continuing RRF and ARRF, the relative percent difference (RPD)
between the daily RRF and the initial calibration mean RRF as described in
Section 7.7.1.5.
Report the results as required by Section 10.2.
7.4.2 Continuing Calibration Performance Criteria
An acceptable continuing calibration must satisfy the following performance
criteria:
A. The signal to noise ratio (S/N) for the GC signals present in the selected
ion current profile (SICP) for all labelled and unlabelled standards must
be > 10:1.
B. The measured RRFs of all analytes (labelled and unlabelled} must be
within 30 percent of the mean values established during the initial
calibration. If this criterion is not satisfied, a new initial calibration curve
must be established before sample extracts can be analyzed.
C. The retention time for any internal standard must not change by more
than 30 seconds from the most recent calibration check. Otherwise,
inspect the chromatographic system for malfunctions and make the
necessary corrections. Document acceptable performance with a new
initial calibration curve.
7.5 GC/MS ANALYSIS
The laboratory may proceed with the analysis of samples and blanks only after
demonstrating acceptable performance as specified in Sections 7.3 and 7.4.
Analyze standards, field samples and QA samples (Section 8.1) with the gas
chromatograph and mass spectrometer operating under the conditions
recommended in Sections 7.3.2 and 7.3.4.
August 9, 1996 Proposed M-429 Page 49
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Approximately I hr before HRGC/LRMS or HRGC/HRMS analysis, adjust the
sample extract volume to approximately 500 /;L This is done by adding 50 fjL of
the recovery standard spike solution (Section 7.2.5, and Table 4 or 4A) to the
450 ^L final volume (Section 6.6.2) of the concentrated sample extract give the
sample extract concentration required by Table 8 or 8A. If the sample volume
must be changed to achieve a desired detection limit, the recovery spike solution
concentration must be adjusted accordingly to achieve the target concentrations
of Table 8 or 8A.
Inject a2fjl aliquot of the sample extract (Section 6.6.2) on to the DB-5
column. Use the same volume as that used during calibration. Recommended
GC/MS operating conditions are described in Section 7.3.
The presence of a given PAH is qualitatively confirmed if the criteria of Section
7.6.1 are satisfied.
The response for any quantitation or confirmation ion in the sample extract must
not exceed the response of the highest concentration calibration standard.
Collect, record, and store the data for the calculations required by Sections
9.1.7, 9.1.8, 9.1.9, and 9.1.10. Report the results as required by Section 10.2.
7.6 QUALITATIVE ANALYSIS
7.6.1 Identification Criteria
7.6.1.1 Ion Criteria
For LRMS analysis, all quantitation and confirmation ions (Table 13)
must be present.
7.6.1.2 Relative Retention Time (RRT) Criteria
The relative retention time (RRT) of the analyte compared to the RRT for
the 2H-standards must be within ±0.008 RRT units of the relative
retention times obtained from the continuing calibration (or initial
calibration if this applies).
7.6.1.3 Signal to Noise Ratio
The signal to mean noise ratio must be 10:1 for the internal standards.
This ratio for the unlabelled compounds must be greater than 2.5 to 1
for the quantitation ions for HRMS and for both quantitation and
confirmation ions for LRMS.
If broad background interference restricts the sensitivity of the GC/MS
analysis, the analyst must employ additional cleanup on the archive
sample and reanalyze.
August 9, 1996 Proposed M-429 Page 50
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7.7 QUANTITATIVE ANALYSIS
7.7.1 Relative Response Factors (RRFs)
7.7.1.1 RRF for Unlabelled PAH and Surrogate Standards
from Initial Calibration Data
Use the results of the calibration and Equation 429-13 to calculate the
relative response factors (RRFs) for each calibration compound and
surrogate standard in each calibration solution (Tables 5 or 5A). Table
11 shows the assignments of the internal standards for calculation of
the RRFs for the calibration solution shown in Table 5. Table 11A
shows the assignments of the internal standards for calculation of the
RRFs for the calibration solution shown in Table 5A. Report the results
as required by Section 10.2.
7.7.1.2 RRF for Determining Internal Standard Recovery
Use the results of the calibration in Equation 429-18 to calculate the
relative response factor for each internal standard relative to an
appropriate recovery standard. Table 11 shows the assignments of the
recovery standards for calculating internal standard recoveries for the
calibration solution shown in Table 5. Table 11A shows the
assignments of the recovery standards for calculating internal standard
recoveries for the calibration solution shown in Table 5A. Report the
results as required by Section 10.2.
7.7.1.3 RRF for Determining Alternate Standard Recovery
Use the calibration results and Equation 429-19 to calculate the
response factor for the alternate standard relative to the appropriate
recovery standard. Table 11 shows the assignment of the recovery
standards for calculating alternate standard recovery for the calibration
solution shown in Table 5. for the calibration solution shown in Table 5.
Report the results as required by Section 10.2.
7.7.1.4 Mean Relative Response Factor
Use Equation 429-20 to calculate the mean RRF for each compound
(unlabelled calibration standards, surrogate standards, internal standards
and alternate standard). This is the average of the five RRFs calculated
for each compound (one RRF calculated for each calibration solution).
The mean RRF may be used if the linearity criterion of Section 7.7.2 is
satisfied.
Report the results as required by Section 10.2.
7.7.1.5 RRF from Continuing Calibration Data
Analyze one or more calibration standards (one must be the medium
level standard) on each work shift of 12 hours or less. Use Equations
429-1 7, 429-18, and 429-19 to calculate the RRFs for each analyte.
Use Equation 429-22 to calculate ARRF, the relative percent difference
August 9, 1996 Proposed M-429 Page 51
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between the daily RRF and the mean RRF calculated during initial
calibration. Check whether the performance criterion of Section 7.4.2B
is satisfied. Report the results as required by Section 10.2.
7.7.2 Relative Standard Deviation of Relative Response Factors
For each analyte, calculate the sample standard deviation (SD) of the RRFs
used to calculate the mean RRF. Use Equation 429-21 to calculate the
percent relative standard deviation (%RSD) for each analyte. The analyst
may use the mean RRF if the percent relative standard deviation of the RRFs
is 30% or less. If the RSD requirement is not satisfied, analyze additional
aliquots of appropriate calibration solutions to obtain an acceptable RSD of
RRFs over the entire concentration range, or take action to improve GC/MS
performance. Otherwise, use the complete five point calibration curve for
that compound.
8 QUALITY ASSURANCE/QUALITY CONTROL
Each laboratory that uses this method is required to operate a formal quality
control program. The minimum quality control requirements of this program
consists of an initial demonstration of laboratory capability (according to
Sections 7.3 and 8.1.3.1), and periodic analysis of blanks and spiked samples as
required in Sections 8.1.1 and 8.1.3.2 as a continuing check on performance.
The laboratory must maintain performance records to document the quality of
data that are generated. The results of the data quality checks must be
compared with the method performance criteria to determine if the analytical
results meet the performance requirements of the method. The laboratory must.
generate accuracy statements as described in Section 8.4.1.
8.1 QA SAMPLES
8.1.1 Laboratory Method Blank
The analyst must run a laboratory method bfank with each set of 15 or fewer
samples. The method blank must be a resin sample from the same batch
used to prepare the sampling cartridge and the laboratory control samples.
The method blank must be prepared and stored as described in
Sections 4.3.4 and 4.3.5.
The analyst shall perform all of the same procedures on the method blank as
are performed on the solid samples (Section 6.5.2.1) from the beginning of
sample extraction through to the end of the GC/MS analytical procedures.
8.1.2 Performance Evaluation Samples
The laboratory should analyze performance evaluation samples quarterly
when these samples become available. These samples must be prepared and
analyzed by the same methods used for the field samples. Performance for
the most recent quarter should be reported with the results of the sample
analysis.
August 9, 1996 Proposed M-429 Page 52
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8.1.3 Laboratory Control Sample (LCS)
8.1.3.1 Initial Demonstration of Laboratory Capability
Before performing sample analyses for the first time, the analyst shall
demonstrate the ability to generate results of acceptable precision and
accuracy by using the following procedures.
Prepare spiking solutions from stock standards prepared independently
from those used for calibration. Spike at least four resin samples
cleaned as described in Section 4.2.2 with each of the target unlabelled
analytes as indicated in Table 9. Blank resin contamination levels must
be no greater than 10 percent of the levels of the spiked analytes. Add
the amounts of internal standards required by Table 7 or 7A. Add the
alternate standard to the extract to monitor the efficiency of the cleanup
procedure.
The LCS spikes shall undergo all of the same procedures as are
performed on the solid samples (Section 6.5.1.2) from the beginning of
sample extraction through to the end of the GC/MS analytical
procedures.
Calculate:
(A) percent recoveries for the internal standards and alternate standard,
(B) the mass of each target analyte in //g/sample or ng/sample,
(C) the average of the results for the four analyses in ^g/sample or
ng/sample,
(D) the average recovery (R) as a percentage of the amount added, and
(E) the relative standard deviation SR.
Report the results as required by Section 10.2.4.
If all the acceptance criteria of Section 8.2.6 are satisfied for all of the
target PAH, the analyst may begin analysis of blanks and samples.
Otherwise, corrective action must be taken as required by Section 8.2.6.
8.1.3.2 Ongoing Analysis of LCS
The analyst must run two laboratory control samples with each set of
15 or fewer samples. The resin for the LCS must be taken from the
same batch used to prepare the sampling cartridge and the laboratory
method blank. The LCS resin must be prepared and stored as described
in Sections 4.3.4 and 4.3.5.
Prepare spiking solutions from stock standards prepared independently
from those used for calibration. Spike each resin sample with each of
the target unlabelled analytes as indicated in Table 9. Blank resin
contamination levels must be no greater than 10 percent of the levels of
the spiked analytes. Add the amounts of internal standards required by
Table 7 or 7A. Add the alternate standard to the extract to monitor the
efficiency of the cleanup procedure.
August 9, 1996 Proposed M-429 Page 53
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The LCS spikes shall undergo all of the same procedures as are
performed on the solid samples (Section 6.5.1.2) from the beginning of
sample extraction through to the end of the GC/MS analytical
procedures.
Calculate:
(A) percent recoveries for the internal standards and alternate standard.
(B) the mass of each target analyte in /;g/sample or ng/sample,
(C) the average of the results for the two analyses in //g/sample or
ng/sample,
(D) the average recovery as a percentage of the amount added, and
(E) the relative percent difference for the two analyses.
Report the results as required by Section 10.2.
Add the results which satisfy the performance requirements of Section 8.2.6
to the results of the initial LCS analyses (8.1.3.1) and previous ongoing data
for each compound in the LCS sample.
Update the charts as described in Section 8.4.1.
8.2 ACCEPTANCE CRITERIA
8.2.1 Blank Trains
The levels of any unlabelled analyte quantified in the blank train must not
exceed 20 percent of the level of that analyte in the sampling train. If this
criterion cannot be met, calculate a reporting limit that is five times the
blank value (Equations 429-32 and 429-33). Do not subtract the blank value
from the sample value.
8.2.2 Surrogate Standard Recovery
Acceptable surrogate (field spike) recoveries should range from 50 to 150
percent. If field spike recoveries are not within the acceptable range, this
must be clearly indicated in the laboratory report. The affected sampling run
must be identified in the report of the calculated emissions data.
8.2.3 Internal Standard Recovery
Recoveries for each of the internal standards must be greater than 50
percent and less than 150 percent of the known value.
If internal standard recoveries are outside of the acceptable limits, the signal
to noise ratio of the internal standard must be greater than 10. Otherwise
the analytical procedure must be repeated on the stored portion of the
extract.
-*
NOTE: This criterion is used to assess method performance. As this is an
isotope dilution technique, it is, when properly applied, independent
of internal standard recovery. Lower recoveries do not necessarily
August 9, 1996 Proposed M-429 Page 54
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invalidate the analytical results for PAH, but they may result in
higher detection limits than are desired.
If low internal standard recoveries result in detection limits that are
unacceptable, the cleanup and GC/MS analysis must be repeated with the
stored portion of the extract. If the analysis of the archive sample gives low
recoveries and high detection limits, the results of both analyses must be
reported.
8.2.4 Laboratory Method Blank
The laboratory method blank must not contain any of the target analytes
listed in Table 1 at levels exceeding the PQL or 5 percent of the analyte
concentration in the field sample.
If the method blank is contaminated, check solvents, reagents, standard
solutions apparatus and glassware to locate and eliminate the source of
contamination before any more samples are analyzed. Table 3 shows those
compounds that commonly occur as contaminants in the method blank, and
the ranges of concentrations that have been reported.
If field samples were processed with a laboratory method blank that showed
PAH levels greater than 5 percent of the field sample, they must be re-
analyzed using the archived portion of the sample extract.
Recoveries of the internal standards must satisfy the requirements of 8.2.3.
If the internal standard recoveries are less than 50%, the S/N ratio must be
greater than 10 for the internal standard.
8.2.5 Performance Evaluation Sample
The following will be a requirement when performance evaluation samples
become available, and performance criteria have been established:
Performance for the most recent quarter must be reported with the results of
the sample analysis. If the performance criteria (to be established) are not
achieved, corrective action must be taken and acceptable performance
demonstrated before sample analysis can be resumed.
8.2.6 Laboratory Control Samples
8.2.6.1 Initial and Ongoing Analysis
The signal of each analyte in the initial and ongoing laboratory control
samples must be at least 10 times that of the background.
Acceptable accuracy is a percent recovery between 50 and 150 percent.
Acceptable precision for the initial LCS samples is a relative standard
deviation (RSD) of 30 percent or less.
Acceptable precision for the ongoing analysis of duplicate samples is a
relative percent difference of 50 percent or less.
August 9, 1996 Proposed M-429 Page 55
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If the RSD for the initial demonstration exceeds the precision limit, or any
calculated recovery falls outside the range for accuracy, the laboratory
performance for that analyte is unacceptable.
If the RPD for any ongoing duplicate analyses exceeds the precision limit, or
any calculated recovery falls outside the range for accuracy, the laboratory
performance for that analyte is unacceptable.
Beginning with Section 8.1 .3.1 , repeat the test for those analytes that failed
to meet the performance criteria. Repeated failure, however, will confirm a
general problem with the measurement system. If this occurs, locate and
correct the source of the problem and repeat the test for all compounds of
interest beginning with Section 8.1.3.1 for the initial analysis and
Section 8.3.1.2 for the ongoing analysis.
8.3 ESTIMATION OF THE METHOD DETECTION LIMIT (MDL) AND PRACTICAL
QUANTITATION LIMIT (POL)
8.3.1 Initial Estimate of MDL and PQL
The analyst shall prepare a batch of XAD-2 resin as described in Sections
4.2.2. 1 to 4.2.2.3, then check for contamination as required by Section 4.2.2.4.
Identify those PAH analytes present at background levels that are too high for
the MDL determination. Use the procedure of Appendix A to calculate MDLs for
the remaining target PAH compounds. A suggested initial spike level for the
MDL determination is 5 times a theoretical method quantitation limit (TMQL)
estimated according to Equation 429-16.
TMQL = Cxx100x2 429-16
Where:
C = the concentration of the PAH in the lowest concentration calibration
standard used in the initial calibration, (ng///L)
V = the final extract volume, (//L)
P = the assumed percent recovery (50%) of the internal standard
2 = a factor to account for the fact that the final extract volume (V) contains
one half of the analyte in the sample. The other half is archived.
8.3.2 Ongoing Estimation of MDL and PQL
Once every quarter in which this method is used, the analytical laboratory must
analyze one spiked resin sample as described in Appendix A. Include all initial
and quarterly results in the calculation of the standard deviation and MDL for
each analyte that has not been identified as a common contaminant of the
XAD-2 resin.
August 9, 1996 Proposed M-429 Page 56
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If the MDL for any analyte exceeds the MDL established during the initial
determination, take corrective action as necessary, and repeat the monthly
analysis. If any MDL still exceeds the initial MDL, then the initial standard
deviation estimation procedure (Appendix A) must be repeated.
8.4 LABORATORY PERFORMANCE
The analyst must have documented standard operating procedures (SOPs) that
contain specific stepwise instructions for carrying out this method. The SOPs
must be readily available and followed by all personnel conducting the work. The
SOP must be made available for review upon request by the Executive Officer,
the tester or reviewer of the analytical results. The analyst may impose
restrictions on the dissemination of the information in the SOP.
The analyst must have documented precision and accuracy statements
(Section 8.4.1) readily available.
The analyst must have results of the initial and ongoing estimates of the MDL
(Sections 8.3.1 and 8.3.2) readily available.
8.4.1 Precision and Accuracy Statement
The precision and accuracy statements for the analytical procedure shall, be
based on the results of the initial and ongoing LCS analyses. The frequency of
analysis is stated in Section 8.1.3.
Prepare a table of the recoveries and the relative percent difference for each
ongoing analysis of the LCS and LCS duplicate. Figure 15A is an example of
such a table. This must be included in the analytical data package submitted for
each set of sample analyses.
Prepare a quality control chart for each target analyte that provides a graphic
representation of continued laboratory performance for that target analyte.
Figure 15B is an example QC chart for benzo(a)pyrene.
9. CALCULATIONS
Carry out calculations retaining at least one extra decimal figure beyond that of
the acquired data. Round off figures after the final calculation.
9.1 ANALYST'S CALCULATIONS
The analyst shall carry out the calculations described in Sections 9.1.1 to
9.1.11.
August 9, 1996 Proposed M-429 Page 57
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9.1.1 Relative Response Factors (RRF) for Unlabelled PAH and Surrogate Standards
Calculate the RRF for each target unlabelled PAH analyte and surrogate standard
in each calibration solution . Use Equation 429-17 and the data obtained during
initial calibration (7.3.7) or continuing calibration (7.4.1).
RRF . *.«
Where:
As = Area of the response for characteristic ions of the unlabelled analyte
or surrogate standard (Tables 11 or 1 1A, 13, and 14).
Ajs = Area of the response for characteristic ions of the appropriate internal
standard (Tables 1 1 or 1 1 A, 13, and 14).
Qs = Amount of the unlabelled PAH calibration analyte or surrogate
standard injected on to GC column, ng.
Qis = Amount of the appropriate internal standard injected on to GC column, ng.
9.1 .2 RRF for Determination of Internal Standard Recovery
Calculate RRFJS according to Equation 429-18, using data obtained from the
analysis of the calibration standards.
RRF,s A x Q 429-18
Ars * Qis
Where:
Ars = Area of the response for characteristic ions of the appropriate
recovery standard (Tables 11 or 11 A, 13, and 14).
Qrs = Amount of the appropriate recovery standard injected on to GC
column, ng.
9.1.3 RRF for Determination of Alternate Standard Recovery
Calculate RRFas according to Equation 429-19, using data obtained from the
analysis of the calibration standards.
A°* X Q" 429'19
Ars * Qas
Where:
Aas = Area of tne response for characteristic ions of the alternate standard
(Tables 13 and 14).
Qas = Amount of alternate standard injected on to the GC column, ng.
August 9, 1996 Proposed M-429 Page 58
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9.1.4 Mean Relative Response Factors (RRF)
Calculate the mean RRF for each target unlabelled PAH, surrogate standard,
internal standard and alternate standard using Equation 429-20 and the RRFs
calculated according to Sections 9.1.1, 9.1.2, and 9.1.3.
1 n 429-20
HKF = 1 £ (RRF)j
n pf
Where:
RRFj = RRF calculated for calibration solution "i" using one of Equations
429-17,429-18 or 429-19.
n = The number of data points derived from the calibration. The
minimum requirement is a five-point calibration (Section 7.2.3,
Tables 5 and 6 or 6A)
9.1.5 Percent Relative Standard Deviation (%RSD) of Relative Response Factors
Use Equation 429-21 to calculate the relative standard deviation of the Relative
Response Factors for each analyte.
%RSD = -S-H x 100% 429-21
Where:
RRF = Mean relative response factor of a given analyte as defined in
Sections 7.7.1 .4 and 9.1 .4.
SD = The sample standard deviation of the relative response factors used
to calculate the mean RRF.
9.1.6 Continuing Calibration ARRF
Use Equation 429-22 to calculate ARRF, the relative percent difference (RPD)
between the daily RRF and the mean RRF calculated during initial calibration.
„ ,00% «9-22
HRF
Where:
RRFC = The RRF of a given analyte obtained from the continuing calibration
{Section 7.4).
August 9, 1996 Proposed M-429 Page 59
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9.1.7 Percent Recovery of Internal Standard, Ris
Calculate the percent recovery, Ris for each internal standard in the sample
extract, using Equation 429-23.
js . * " _ x 100%
Ars x FTFTF^ x Qjs
Where:
RRTis = Mean relative response factor for internal standard (Equations 429-18
and 429-20).
9.1.8 Percent Recovery of Surrogate Standard, R
S3
Calculate the percent recovery, Rss for each surrogate standard in the sample
extract, using Equation 429-24.
Rss . _ * i* _ x 100%
Ais x HRF; x QSS
Where:
Ass = Area of the response for characteristic ions of the surrogate standard
(Tables 13 and 14).
Qss = Amount of the surrogate standard added to resin cartridge before
sampling, ng.
RRFS = Mean relative response factor for surrogate standard (Equations
429-17 and 429-20).
9.1 .9 Percent Recovery of Alternate Standard, R^
Calculate the percent recovery, Ras for the alternate standard in the sample
extract, using Equation 429-25.
Ras - Aas X °" _ - x 100% 429'25
Ars x fTRF^ x Qas
Where:
RRFas = Mean relative response factor for alternate standard (Equations 429-
19 and 429-20).
August 9, 1996 Proposed M-429 Page 60
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9.1.10 Mass of the Target Analytes and Surrogate Standards in
Emissions Sample or Blank Train
Use Equation 429-26 to determine the total mass of each PAH compound or
surrogate standard in the sample:
Report the PQL (9.1.11) for those analytes that were not present at levels
higher than the PQL provided to the tester prior to testing (2.3.3).
M . QJS x As 429-26
AJS x RRF
Where:
M = Mass (ng) of surrogate standard (Ms) or target analyte (Mt) detected
in the sample.
Qjs = Amount of internal standard or surrogate standard added to each
sample.
As = Area of the response for characteristic ions of the unlabelled analyte
or surrogate standard (Tables 13 and 14).
Ais = Area of the response for characteristic ions of the appropriate
internal standard (Tables 13, and 14).
RRP = Mean relative response factor of a given analyte calculated as
required by Sections 7.7.1.4 and 9.1.4.
9.1.11 Analytical Reporting Limit
The analyst shall report the PQL (Section 2.3.3) for those analytes that were
not present in the emissions sample or blank train at levels higher than the
pre-test estimate of the PQL.
9.2 TESTER'S CALCULATIONS
9.2.1 Sample/Blank Train PAH Mass Ratio
Use Equation 429-27 to calculate the sample/blank train mass ratio for each PAH
detected at levels above the MOL in both the field sample and the blank train.
RAT,0 . * 429'27
MBT
Where:
Mt = Mass of target PAH analyte detected in the sampling train
(Equation 429-26).
MBT = Mass of the same PAH analyte detected in the blank train.
August 9, 1996 Proposed M-429 Page 61
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If the sample to blank train PAH mass ratio is less than five, calculate the
reporting limit for the tested source as required by Section 9.2.4.2. Do not
calculate Mc (Section 9.2.2} or Me (Section 9.2.3) for the emissions report.
9.2.2 PAH Concentration in Emissions
Use Equation 429-28 to calculate the concentration in the emissions of 1) the
PAH analytes detected in the sampling train but not in the blank train, and 2) the
PAH analytes that satisfy the minimum sample to blank train mass ratio required
by Section 9.2.1.
429-28
9.2.3
M,
Mt
1
V,
m(std)
0.028317
Where:
M
m(std)
= Concentration of PAH in the gas, ng/dscm, corrected to standard
conditions of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on dry
basis.
= Mass of PAH compound in gas sample, ng (Equation 429-26)
= Volume of gas sample measured by the dry gas meter, corrected
to standard conditions, dscf (Equation 429-10)
0.028317 = Factor for converting dscf to dscm.
PAH Mass Emission Rate
Use Equation 429-29 to calculate the mass emission rate for each PAH
compound that satisfies the minimum sample/blank train PAH mass ratio
(Section 9.2.1).
Mf
V,
m(std)
"std
~60~
429-29
Where:
'std
60
= Mass emission rate for PAH analyte, ng/second
= Mass of PAH compound in the gas sample, ng (Equation 429-26)
= Average stack gas dry volumetric flow rate corrected to standard
conditions, dscf/min.
= Factor for converting minutes to seconds
August 9, 1996
Proposed M-429 Page 62
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9.2.4 Source Reporting Limit
9.2.4.1 PAH Not Detected in Either Sampling or Blank Train
Use Equation 429-30 or 429-31 to calculate the reporting limit for those analytes
that were not detected at levels above the PQL in either the sampling or blank
train.
RL - PQL y 1 429-30
CS " 0.028317
Where:
RL
PQL
es
V
m(std)
Qstd
"60"
429-31
RLCS = Reporting limit for the tested source, (ng/dscm), corrected to
standard conditions of 20°C, 760 mm Hg (68°F, 29-92 in. Hg) on
dry basis.
RLes = Reporting limit for the tested source, (ng/sec.).
0.028317 = Factor for converting dscf to dscm.
60 = Factor for converting minutes to seconds.
9.2.4.2 PAH Detected in Blank Train and Sample/Blank Train Ratio < 5
If the sample to blank train PAH mass ratio is less than five, then Equation
429-32 or 429-33 shall be used to calculate the reporting limit for that PAH.
Where:
RL
eb
M
BT
5 x MBT
vm(std)
1
RLeb
5 x MBT
V
m(std)
0.028317
-60-
429-32
429-33
Reporting limit for the tested source, (ng/dscm), corrected to
standard conditions of 20°C, 760 mm Hg (68°F, 29-92 in. Hg) on
dry basis.
Reporting limit for the tested source, (ng/sec.).
The total mass of that PAH analyte in the field blank train.
August 9, 1996
Proposed M-429 Page 63
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10. REPORTING REQUIREMENTS
The source test protocol must contain all the sampling and analytical data
required by Sections 2.2 to 2.5, 4.2.1.1, and 4.2.2.4, as well as the information
listed in Sections 10.1 and 10.2 that pertain to identification and quantitation of
the samples.
The emissions test report must contain all of the sampling and analytical data
necessary to calculate emissions values for the target analytes or to demonstrate
satisfactory performance of the method.
The end user or reviewer should be able to obtain from the source test report all
information necessary to recalculate all reported test method results or to verify
that all required procedures were performed.
Any deviations from the procedures described in this method must be
documented in the analytical and sampling report.
10.1 SOURCE TEST PROTOCOL
At a minimum, the source test protocol must include all of the data required by
Section 2.2 and the information listed in Sections 10.1.1 through 10.1.4.
10.1.1 Preparation of Filters
A. Manufacturer's lot number for the batch of filters to be used in the test.
B. Contamination check of filter (Section 4.2.1.1)
(i) Date of cleaning.
(ii) Date of PAH analysis.
(iii) Table of results of PAH analysis required by Section 4.2.1. The
analytical report must include all of the data listed in Section 10.2.
C. Storage conditions prior to the test (4.3.3)
10.1.2 Preparation of XAD-2 resin
A. ID for the batch to be used in the test. The same batch must be used
for the sampling train and the laboratory QC samples.
B. Contamination check of resin (Sections 4.2.2.1 to 4.2.2.4)
(i) Date of cleaning.
(ii) Date of PAH analysis.
(iii) Table of results of PAH analysis required by Secton 4.2.2.4. The
analytical report must include all of the data listed in Section 10.2.
C. Addition of surrogate standards to the resin cartridge.
(i) Amount of each compound.
(ii) Date of spiking.
August 9,1996 Proposed M.42g Pagfl 64
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D. Storage conditions prior to the test (Section 4.3.3)
10.1.3 Method Detection Limits and Practical Quantitation Limits
The MDL and PQL for each target analyte determined as required by Sections
2.3.2 and 2.3.3.
10.1.4 Target Sampling Parameters
A. Source target concentration of each emitted PAH of interest.
B. Results of calculations required by Sections 2.5.2 to 2.5.5.
Figure 9 shows the minimum required calculations of target sampling
parameters.
10.2 LABORATORY REPORT
The analyst must generate a laboratory report for each pre-test analysis of the
sampling media (Sections 2.3, 4.2.2.1, and 4.2.2.4) and each post-test analysis
of the sampling trains and laboratory QC samples.
A minimum of 7 post-test analyses are required to determine the emissions from
the source and to document the quality of the emissions data. These are the
analyses of three sampling runs, one blank train, one laboratory method blank
and two laboratory control samples.
At a minimum, any report (data package) from the analyst to the tester shall
contain the information listed in Sections 10.2.1 to 10.2.6 pertaining to
identification and PAH quantitation of all samples.
10.2.1 Five-point Initial Calibration
The report of the results of the initial five-point calibration must include the
data listed in A, B, and C below:
A. Mass chromatograms for each initial calibration solution that show at a
minimum:
(i) Instrument ID,
(ii) laboratory sample ID on each chromatogram.
(iii) date and time of GC/MS analysis,
(iv) mass of monitored ions for each compound in the calibration solution -
unlabelled PAH, internal standard, surrogate standard, alternate
standard and recovery standard,
(v) retention time for each compound in the calibration solution, and
(vi) either peak height or area of the signals observed for the monitored ion
masses.
August 9, 1996 Proposed M-429 Page 65
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B. A summary table of the data obtained for each initial calibration
solution that shows at a minimum:
(i) Instrument ID,
(ii) laboratory sample ID,
(iii) date and time of GC/MS analysis,
(iv) retention time for each compound - unlabelled PAH, internal standard.
surrogate standard, alternate standard and recovery standard,
(v) relative retention time for each unlabelled PAH,
(vi) either peak height or area of the signals observed for the monitored ion
masses,
(vii) the relative response factors for each unlabelled PAH, internal standard,
surrogate standard, and alternate standard, and
(viii) analyst's signature
Figure 14A is an example of a summary table that contains the minimum
required information for the analysis of a single calibration solution.
C. A summary table that shows at a minimum:
(i) Instrument ID,
(ii) the date and time of the GC/MS analysis,
(iii) the relative response factor (RRF) calculated for each unlabelled PAH,
internal standard, surrogate standard, and alternate standard in each
calibration solution,
(iv) the average relative response factor (RRF) calculated for the five point
calibration,
(v) the relative standard deviation of the relative response factors, and
(vi) the recovery of each internal standard in percent.
Figure 14B is an example of a report that contains the minimum required
information for a five point calibration summary.
10.2.2 Continuing Calibration
The report of the results of a continuing calibration must include the data
listed in 10.2.2 A, B, and C below:
A. Mass chromatogram that shows at a minimum the information listed in
10.2.1 A.
B. A summary table of the raw data obtained for the continuing calibration
that shows at a minimum, the information listed in 10.2.1 B.
C. A summary table that shows at a minimum:
(i) the relative response factor (RRF) for each unlabelled PAH, internal
standard, surrogate standard, and alternate standard in the continuing
calibration solution,
(ii) the average relative response factor (RFTF) for each compound
calculated for the five point calibration,
August 9, 1996 Proposed M-429 Page 66
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(iii) ARRF for each unlabelled PAH, internal standard, surrogate standard.
and alternate standard in the continuing calibration solution,
(iv) the recovery of each internal standard in percent.
Figure 14C is an example of a summary report that contains the minimum
information required by Section 10.2.2C for the analysis of the continuing
calibration solution.
10.2.3 Laboratory Method Blank
The laboratory report of the results of the analysis of the method blank must
include at a minimum the data listed in 10.2.3 A, B, and C below:
A. Mass chromatograms that show at a minimum the information listed in
10.2.1 A.
B. A summary table of the data obtained for each method blank that
shows at a minimum, the information listed in 10.2.5 B.
C. A summary table that reports the same data as listed in 10.2.5 C
below.
10.2.4 Laboratory Control Samples
The report of the results of the analysis of the LCS samples must include at
a minimum the data listed in 10.2.4 A, B, and C below:
A. Mass chromatograms that show at a minimum the information listed in
10.2.1 A.
B. A summary table of the raw data for each sample that shows at a
minimum, the information listed in 10.2.1 B, and in addition:
(i) Client's sample ID
(ii) mass of each analyte,
(iii) the recovery of each internal standard, and alternate standard.
Figure 16A is an example of a summary table that contains the minimum
information required by 10.2.4 B.
C. A summary table that reports for the two LCS analyses:
(i) client's sample ID,
(ii) sample matrix description,
{iii) date of cleaning of the XAD-2 resin,
(iv) lot number for the resin (resin for all field samples and QA samples
must come from the same lot),
(v) date of extraction of LCS samples,
Figure 15A is an example of a summary table that contains the minimum
information required by 10.2.4 C.
Augusts, 1996 Proposed M-429 Page 67
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10.2.5 Emissions Samples
The report of the results of the analyses of the three sampling trains and the
blabk train must include the data listed in 10.2.5 A, B, and C below:
A. Mass chromatograms that show at a minimum the information listed in
10.2.1 A, and in addition,
(i) client's sample ID
B. A summary table of the data for the analysis of each sample that
shows at a minimum, the information listed in 10.2.1 B, and in
addition,
(i) client's sample ID
(ii) Date of five point initial calibration (ICAL)
(iii) ICAL ID,
(iv) mass of each analyte,
(v) the recovery of each internal standard, alternate standard and surrogate
standards in percent.
Figure 16A is an example of a summary table that contains the minimum-
information required by 10.2.5 B.
C. A summary table that reports:
(i) client's sample ID (from a chain of custody record submitted by the
tester),
(ii) sample matrix description,
(iii) date of cleaning of the XAD-2 resin,
(iv) lot number for the resin (resin for all field samples and QA samples
must come from the same lot),
(ii) date of submittal of the tester's samples
(v) date of extraction of samples,
(vi) Initial calibration Run ID,
(vii) Continuing calibration ID
Figure 16B is an example of a summary table that contains the minimum
information required by 10.2.5C.
10.2.6 Data Flags
The laboratory report must include an explanation of any qualifiers that are
used to indicate specific qualities of the data.
10.3 EMISSIONS TEST REPORT
The emissions test report should include narrative that describes how the test
was done. The tester's report must also include all the appropriate sections used
in a report from a Method 5 test such as a description of the plant process,
sampling port locations, control equipment, fuel being used, general plant load
August 9, 1996 Proposed M-429 Page 68
-------
conditions during the test (description of plant production equipment problems,
etc.), and anything else necessary to characterize the condition being tested.
The tester's report must also include all of the information listed in Sections
10.3.1 to 10.3.4.
10.3.1 Tester's Summary of Analytical Results
The tester must summarize the results of the minimum seven analyses
required for each source test. At a minimum, the summary must contain the
information listed in Figure 17A including all data flags.
The tester must obtain the detailed analytical results (Section 10.2) from the
laboratory and include them in the appendices as required below.
10.3.2 Field Data Summary
The report from the tester to the end user must contain a field data
summary. This summary must include at a minimum a table of the results of
the calculations required by Section 4.5. as well as the values which were
used to calculate the reported results. Figure 17B is an example of a field
data summary that contains the minimum required information.
10.3.3 PAH Emissions Results
Figure 17C show the calculations of the concentrations and mass emission
rates of the target PAH. The reviewer should be able to use the data in
Figures 17A and 17B to check the calculations in Figure 17C. The reviewer
should also be able to check the appendix to the report to determine the
accuracy and the quality of the data summarized by the tester in Figures
17Aand 17B.
10.3.4 Appendix to the Emissions Test Report
At a minimum, the following raw data or signed copies must be included in
an appendix to the emissions test report.
A. Record of data for sample site selection and minimum number of
traverse points.
B. Moisture determination for isokinetic settings.
C. Velocity traverse data.
D. Gas analysis for determination of molecular weight.
E. Calibration records.
F. Method 429 sampling run sheets.
G. PAH laboratory reports listed in Section 10.2
August9, 1996 Proposed M-429 Page 69
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The information listed above is to be considered as the minimum that should be
included to characterize a given operating condition. The end user or the
executive officer may require additional information for any given project.
11. BIBLIOGRAPHY
11.1 U.S. Environmental Protection Agency/Office of Water Engineering and
Analysis Division (4303), Washington D.C., Method 1613. Tetra-through
Octa-Chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS.
EPA821-B-94-005. (1994).
11.2 U.S. Environmental Protection Agency/Office of Solid Waste, Washington
D.C., Method 3611 A. Alumina Column Cleanup and Separation of Petroleum
Wastes. In "Test Methods for Evaluating Solid Waste-Physical/Chemical
Methods" SW-846 (1986).
11.3 U.S. Environmental Protection Agency/Office of Solid Waste, Washington
D.C., Method 3630B. Silica Gel Cleanup. In "Test Methods for Evaluating
Solid Waste-Physical/Chemical Methods" SW-846 (1986).
11.4 Thomason, J.R., ed., Cleaning of Laboratory Glassware. Section 3, A, pp 1-7
in "Analysis of Pesticide Residues in Human and Environmental Samples",
Environmental Protection Agency, Research Triangle Park, N.C. (1974).
11.5 ARB Method 428. Determination of Polychlorinated Dibenzo-p-dioxin (PCDD)
and Polychlorinated Dibenzofuran (PCDF) Emissions From Stationary Sources.
September, 1990.
11.6 U. S. Environmental Protection Agency, Method 1625 Revision B -
Semivolatile Organic Compounds by Isotope Dilution. 40 CFR Ch.1 (7-1-95
Edition) Pt. 136, App. A.
11.7 Rom, Jerome J., Maintenance, Calibration, and Operation of Isokinetic Source
Sampling Equipment. Environmental Protection Agency. Research Triangle
Park,NC. APTD-0576. March, 1972.
11.8 Shigehara, R.T., Adjustments in the EPA Nomograph for Different Pitot Tube
Coefficients and Dry Molecular Weights. Stack Sampling News, 2: 4-11.
October, 1974
11.9 "Prudent Practices in the Laboratory. Handling and Disposal of Chemicals,"
National Academy Press. Washington D.C. 1995.
August 9, 1996 Proposed M-429 Page 70
-------
TABLE 1
METHOD 429 TARGET ANALYTES
Naphthalene
2-Methylnaphthalene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Ben2o(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Augusts, 1996 Proposed M-429 Page 71
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TABLE 2
PRACTICAL QUANTITATION LIMITS FOR TARGET PAHs
Naphthalene
2-MethylnaphthaIene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fiuoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
lndeno{ 1 ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
LRMS
(/yg/sample)
/. ao
244
1.25
0.210
0.104
0.207
0.85
0.146
0.346
0.191
0.167
0.272
1.119
0.738
0.146
0.191
0.143
0.798
0.465
0.305
HRMS
(ng/sample)
480
66
5.0
5.0
16.5
22
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
370
19
5.0
5.0
5.5
14
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
August 9, 1996
Proposed M-429 Page 72
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TABLE 3
PAH ANALYSIS BY HRMS OF DIFFERENT LOTS OF CLEANED RESIN
PAH ANALYTES
Naphthalene
CONCENTRATION (ng/sample)
SAMPLE
A,
480
2-Methylnaphthalene j 65
Acenaphthylene
Acenaphthene
< 5.0
< 5.0
Fluorene j 16.5
Phenanthrene
Anthracene
22
< 5.0
A2
220
32
A3
198
38
< 5.0 < 5.0
< 5.0
n ».»«•*•*»•.
9.8
16
< 5.0
< 5.0
A4
120
15.6
< 5.0
< 5.0
A5
350
32
< 5.0
< 5.0
13 j < 5.0 | 5.7
A6
340
15.6
< 5.0
< 5.0
— •
32 j<12.5" I 14 j 14.8
i j : :
< 5.0 j < 5.0
Fluoranthene | < 5.0 j < 5.0 < 5.0
Pyrene j < 5.0 | < 5.0 j < 5.0
Benzo(a)anthracene ! < 5.0 ! < 5.0 < 5.0
i i
Chrysene
Benzo(b)fluoranthene
< 5.0
< 5.0
Benzo(k)fluoranthene j < 5.0
Benzo(e)pyrene j < 5.0
Benzo(a)pyrene
Pery'ene
lndeno{1.2,3-cd)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
< 5.0
:
j < 5.0
| < 5.0
| .
j < 5.0
:
| < 5.0
! < 5.0
< 5.0 | < 5.0
< 5.0 | < 5.0
! < 5.0
i .
<5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
! < 5.0
< 5.0
| < 5.0 j < 5.0
| < 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0 j < 5.0
:
IDENTIFICATION
A7 | A8 | A9
320
32
< 5.0
360 I 370
!
26 ! 19
A10 JA11 |A12 |A13
380 340 520 220
45 15 32 48
< 5.0 | < 5.0 I < 5.0 < 5.0 < 5.0 < 5.0
< 5.0 i < 5.0 | < 5.0
7.4
16
< 5.0 < 5.0 < 5.0 < 5.0
5.8 I 5.5 I 10 5.5 6.8 5.0
i :
12 | 14
24 13 <13.0' 14
< 5.0 ! < 5.0 ! < 5.0 < 5.0 j < 5.0 I < 5.0 < 5.0 < 5.0 < 5.0
! i i : i
< 5.6 < 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
-------
TABLE 4
COMPOSITION OF THE SAMPLE SPIKING SOLUTIONS
Spiking
Solutions
Analytes
Concentration
LRMS
HRMS
1. Surrogate Standards
d10-Fluorene
d14-Terphenvl
2. Internal Standards
d8-Naphthalene
d10-2-Methylnaphthalene
dg-Acenaphthylene
d10-Phenanthrene
d10-Fluoranthene
d 12-Benzo(a)anthracene
d12-Chrysene
d 12-Benzo(b)f luoranthene
d 12-Benzo(k)f luoranthene
d12-Benzo(a)pyrene
d12-Perylene
d12-lndeno(1,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d12-Benzo(ghi)perylene
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
250
250
100
100
100
100
100
100
100
200
200
200
200
200
200
200
3. Alternate Standard
d10-Anthracene
4. Recovery Standards
d10-Acenaphthene
d10-Pyrene
d 1 2-benzo(e)pyrene
1.0
20.0
20.0
20.0
100
2000
2000
2000
August 9, 1996
Proposed M-429 Page 74
-------
TABLE 4A
COMPOSITION OF ALTERNATIVE SAMPLE SPIKING SOLUTIONS
Spiking
Solutions
Analytes
Concentration
P9///I
HRMS
1A.
2A.
Surrogate Standards
-------
TABLE 5
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR LOW RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (ng///L)
Solutions
Calibration Standards
Naphthalene
2-Methyl naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Internal Standards
d8-Naphthalene
d10-2-Methylnaphthalene
d8-Acenaphthylene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d T 2-Benzo(b)f luoranthene
d ! 2-Benzo{k)f luoranthene
d12-Benzo(a)pyrene
d12-Perylene
d12-lndeno(1 ,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d T 2-Benzo(ghi)perylene
1
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
2
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
3
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
4
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
5
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
August 9, 1996
Proposed M-429 Page 76
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TABLE 5 (CONT)
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR LOW RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (ng///L)
Solutions
Surrogate Standards
d10-Fluorene
dm-Terphenyl
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Alternate Standard
d10-Anthracene
Recovery Standards
d10-Acenaphthene
d10-Pyrene
d12-benzo(e)pyrene
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
August 9, 1996
Proposed M-429 Page 77
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TABLE 6
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (pg/j/L)
Solutions
Calibration Standards
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Internal Standards
d8-Naphthalene
dgMethylnaphthalene
dg-Acenaphthylene
d ^-Phenanthrene
diQ-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d ! 2-Benzo(b)f luoranthene
d12-Benzo(k)fluoranthene
d 1 2-Benzo(a)pyrene
d12-Perylene
d12-lndeno(1 ,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d 1 2-Benzo(ghi)perylene
1
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
100
100
100
100
100
100
100
200
200
200
200
200
200
:200
2
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
100
100
100
100
100
200
200
200
200
200
200
200
3
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
200
200
200
200
200
200
4
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
100
100
100
100
100
100
100
200
200
200
200
200
200
200
5
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
100
100
100
100
100
100
100
200
200
200
200
200
200
200
Augusts, 1996
Proposed M-429 Page 78
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TABLE 6 (CONT)
CONCENTRATIONS OF PAHS IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (pg/^L)
Solutions
Surrogate Standards
d10-Fluorene
du-Terphenyl
100
100
100
100
100
100
100
100
100
100
Alternate Standard
d10-Anthracene 100 100 100 100 100
Recovery Standards
d10-Acenaphthene 200 200 200 200 200
d10-Pyrene 200 200 200 200 200
d12-benzo(e)pyrene 200 200 200 200 200
August 9, 1996 Proposed M-429 Page 79
-------
TABLE 6A
CONCENTRATIONS OF PAHs IN ALTERNATIVE WORKING GC/MS CALIBRATION
STANDARD SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (pg/^L)
Solutions
Calibration Standards
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Internal Standards
da-Naphthalene
d8-Acenaphthylene
d10-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d 1 2-Benzo(b)f luoranthene
d 1 2-Benzo(k)f luoranthene
d12-Benzo(a)pyrene
d12-lndeno(1 ,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d12-Benzo(ghi)perylene
1
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
100
100
100
100
100
100
100
100
200
200
200
200
200
200
2
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
100
100
100
100
100
100
100
100
200
200
200
200
200
200
3
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
200
200
200
200
200
4
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
100
100
100
100
100
100
100
100
200
200
200
200
200
200
5
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
500
100
100
100
100
100
100
100
100
200
200
200
200
200
200
August 9, 1996
Proposed M-429 Page 80
-------
TABLE 6A (CONT)
CONCENTRATIONS OF PAHs IN ALTERNATIVE WORKING GC/MS CALIBRATION
STANDARD SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (pg//yL)
Solutions
Surrogate Standards
d12-benzo(e)pyrene 100 100 -100 100 100
du-Terphenyl 100 100 100 100 100
Alternate Standard
d10-Anthracene 100 100 100 100 100
Recovery Standards
d10-2-Methylnaphthalene 200 200 200 200 200
d10-Pyrene 200 200 200 200 200
d12-Perylene 200 200 200 200 200
August 9,1996 Proposed M-429 Page 81
-------
TABLE 7
SPIKE LEVELS FOR LABELLED STANDARDS
Time of
Addition
Before
sampling
Before
extraction
Before
extraction
Before
GC/MS
Analyte
Surrogate Standards
d10-Fluorene
d14-Terphenyl
Internal Standards
dg-Naphthalene
d10-2-Methylnaphthalene
d8-Acenaphthylene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d i 2-Benzo(b)f luoranthene
d 1 2-Benzo(d)f luoranthene
d12-Benzo(a)pyrene
d12-Perylene
d12-lndeno(1 ,2,3,c-d)pyrene
d-,4-Dibenz(a,h)anthracene
d 1 2-Benzo(ghi)perylene
Alternate Standard
d10-Anthracene
Recovery Standards
d10-Acenaphthene
d10-Pyrene
d12-benzo(e)pyrene
LRMS
(pg/sample)
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.0
1.0
1.0
HRMS
(ng/sample)
500
500
200
200
200
200
200
200
200
400
400
400
400
400
400
400
200
100
100
100
August 9. 1996
Proposed M-429 Page 82
-------
TABLE 7A
SPIKE LEVELS FOR LABELLED STANDARDS FOR ALTERNATIVE HRMS SPIKING SCHEME
Time of
Addition
Analyte
HRMS
(ng/sample)
Before
sampling
Before
extraction
Before
extraction
Before
GC/MS
Surrogate Standards
d12-benzo(e)pyrene
d14-Terphenyl
Internal Standards
d8-Naphthalene
d8-Acenaphthylene
d10-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d 12-Benzo(b)f luoranthene
d 12-Benzo(d)f luoranthene
d! 2-Benzo(a)pyrene
d12-lndeno(1,2,3,c-d)pyrene
du-Dibenz(a,h)anthracene
d! 2-Benzo(ghi)perylene
Alternate Standard
d10-Anthracene
Recovery Standards
d 10-2-Methylnaphthalene
d10-Pyrene
d12-Perylene
500
500
200
200
200
200
200
200
200
200
400
400
400
400
400
400
200
100
100
100
Augusts, 1996
Proposed M-429 Page 83
-------
TABLE 8
TARGET CONCENTRATIONS FOR LABELLED STANDARDS IN SAMPLE EXTRACT1
LRMS
P9///I
HRMS
Surrogate Standards
d10-Fluorene
du-Terphenyl
Internal Standards
d8-Naphthalene
d10-2-Methylnaphthalene
d8-Acenaphthylene
d10-Phenanthrene
d10-Fluoranthene
d -| 2-Benzo(a)anthracene
d12-Chrysene
d 12-Benzo(b)f luoranthene
d 12-Benzo(k)f luoranthene
d12-Benzo(a)pyrene
d12-Perylene
d ! 2-lndeno( 1,2,3,c-d)pyrene
d 14-Dibenz(a,h)anthracene
d T 2-Benzo(ghi)perylene
Alternate Standard
d10-Anthracene
Recovery Standards
d10-Acenaphthene
d10-Pyrene
d12-benzo(e)pyrene
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1.0
1.0
1.0
1.0
500
500
200
200
200
200
200
200
200
400
400
400
400
400
400
400
200
200
200
200
1 Assuming 100 percent recovery.
August 9, 1996
Proposed M-429 Page 84
-------
TABLE 8A
TARGET CONCENTRATIONS FOR LABELLED STANDARDS IN SAMPLE EXTRACT
OBTAINED WITH ALTERNATIVE HRMS SPIKING SCHEME1
P9///I
HRMS
Surrogate Standards
d12-benzo(e)pyrene 500
du-Terphenyl 500
Internal Standards
d8-Naphthalene 200
d8-Acenaphthylene 200
d10-Acenaphthene 200
d10-Fluorene 200
d10-Phenanthrene 200
d10-Fluoranthene 200
d12-Benzo(a)anthracene 200
d12-Chrysene 200
d12-Benzo(b)fluoranthene 400
d12-Benzo(k)fluoranthene 400
d12-Benzo(a)pyrene 400
d12-lndeno(1,2,3,c-d)pyrene 400
d14-Dibenz(a,h)anthracene 400
d12-Benzo(ghi)perylene 400
Alternate Standard
d10-Anthracene 200
Recovery Standards
d10-2-Methylnaphthalene 200
d10-Pyrene 200
d12-Perylene 200
1 Assuming 100 percent recovery.
August 9. 1996 Proposed M-429 Page 85
-------
TABLE 9
CONCENTRATIONS OF COMPOUNDS IN LABORATORY CONTROL SPIKE SAMPLE
ng/sample
LRMS
HRMS
Unlabelled Compounds
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo{a)pyrene
Perylene
IndenoCI ,2,3,c-d)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Alternate Standard
d10-Anthracene
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
1000
200
200
200
200
500
200
200
200
200
200
200
200
200
200
200
200
200
200
2.0
200
August 9, 1996
Proposed M-429 Page 86
-------
TABLE 10
RECOMMENDED GAS CHROMATOGRAPHIC OPERATING
CONDITIONS FOR PAH ANALYSIS
Column Type
Length (m)
ID (mm)
Film Thickness (//m)
Helium Linear Velocity (cm/sec)
Injection mode
Splitless Time (sec)
Initial Temperature (°C)
Initial Time (min)
Program Rate (°C/min)
Final Temperature (°C)
Final Hold Time
Injector Temperature (°C)
DB-5
30
0.25
0.32
30
Splitless
30
45
4
8
300
until benzo(ghi)
perylene has eluted
320
August 9, 1996
Proposed M-429 Page 87
-------
TABLE 11
ASSIGNMENTS OF INTERNAL STANDARDS FOR CALCULATION OF RRFs
AND QUANTITATION OF TARGET PAHs AND SURROGATE STANDARDS
Analyte
Internal Standards
Unlabeled PAH
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Surrogate Standards
d10-Fluorene
d-|4-Terphenyl
d8-Naphthalene
d-iQ-2-Methylnaphthalene
dg-Acenaphthylene
da-Acenaphthylene
d10-Phenanthrene
d10-Phenanthrene
d10-Phenanthrene
d-iQ-Fluoranthene
d10-Fluoranthene
d } 2-Benzo(a)anthracene
d12-Chrysene
d T 2-Benzo(b)f luoranthene
di 2-Benzo(k)f luoranthene
d12-Benzo(a)pyrene
di 2-Benzo(a)pyrene
d12-Perylene
d12-lndeno(1,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d T 2-Benzo(ghi)perylene
d10-Phenanthrene
d10-Fluoranthene
August 9. 1996
Proposed M-429 Page 88
-------
TABLE 11A
ASSIGNMENTS OF INTERNAL STANDARDS FOR CALCULATION OF RRFs
AND QUANTITATION OF TARGET PAHs AND SURROGATE STANDARDS
USING ALTERNATIVE HRMS SPIKING SCHEME
Analyte
Internal Standards
Unlabeled PAH
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)f luoranthene'
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
IndenoCI ,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
Surrogate Standards
d14-Terphenyl
d12-Benzo(e)pyrene
dg-Naphthalene
d10-Acenaphthene
dg-Acenaphthylene
d! g-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Phenanthrene
d10-Fluoranthene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d12-Benzo(b)fluoranthene
d 12-Benzo(k)f luoranthene
d12-Benzo(a)pyrene
d12-Benzo(a)pyrene
d12-Benzo(a)pyrene
d12-lndeno(1,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d12-Benzo{ghi)perylene
d10-Fluoranthene
d 12-Benzo(a)pyrene
August9, 1996
Proposed M-429 Page 89
-------
TABLE 12
ASSIGNMENTS OF RECOVERY STANDARDS FOR DETERMINATION
OF PERCENT RECOVERIES OF INTERNAL STANDARDS AND
THE ALTERNATE STANDARD
Analyte
Recovery Standard
Internal Standards
dg-Naphthalene
d10 -2-Methylnaphthalene
d8-Acenaphthylene
d-|0-Phenanthrene
d-jQ-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d ! 2-Benzo(b)f luoranthene
d 12-Benzo(k)f luoranthene
d12-Benzo(a)pyrene
d12-Perylene
d12-lndeno{1,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
dj 2-Benzo(ghi) perylene
Alternate Standard
d10-Anthracene
d10-Acenaphthene
d-iQ-Acenaphthene
d10-Acenaphthene
d10-Pyrene
d10-Pyrene
d10-Pyrene
d10-Pyrene
di2-Benzo(e)pyrene
d 12-Benzo(e)pyrene
d12-Benzo(e)pyrene
d 12-Benzo(e)pyrene
d12-Benzo(e)pyrene
d12-Benzo(e)pyrene
d12-Benzo(e)pyrene
d10-Pyrene
August 9, 1996
Proposed M-429 Page 90
-------
TABLE 12A
ASSIGNMENTS OF RECOVERY STANDARDS FOR DETERMINATION OF
PERCENT RECOVERIES OF INTERNAL STANDARDS AND THE ALTERNATE
STANDARD USING ALTERNATIVE HRMS SPIKING SCHEME
Analyte
Recovery Standard
Internal Standards
dg-Naphthalene
d10 -2-Methylnaphthalene
dg-Acenaphthylene
d10-Phenanthrene
djQ-Fluoranthene
d 12-Benzo(a)anthracene
d12-Chrysene
d12-Benzo(b)fluoranthene
d12-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
d12-Perylene
d12-lndeno(1,2,3,c-d)pyrene
d14-Dibenz(a,h)anthracene
d12-Benzo{ghi)perylene
Alternate Standard
d10-Anthracene
d, 0-2-Methylnaphthalene
d 10-2-Methylnaphthalene
d10-2-Methylnaphthalene
d10-Pyrene
d10-Pyrene
d10-Pyrene
d10-Pyrene
d12-Perylene
d12-Perylene
d12-Perylene
d12-Perylene
d12-Perylene
d12-Perylene
d12-Perylene
d10-Pyrene
August 9, 1996
Proposed M-429 Page 91
-------
TABLE 13
QUANTITATION AND CONFIRMATION IONS FOR SELECTED
ION MONITORING OF PAHs BY HRGC/LRMS
Analyte
Naphthalene
d8-Naphthalene
2-Methylnaphthalene
d10-2-Methylnaphthalene
Acenaphthylene
da-Acenaphthylene
Acenaphthene
d10-Acenaphthene
Fluorene
d10-Fluorene
Phenanthrene
d10-Phenanthrene
Anthracene
d10-Anthracene
Fluoranthene
d10-Fluoranthene
Pyrene
d^-Pyrene
Benzo(a)anthracene
d12-Benzo(a)anthracene
Chrysene
d12-Chrysene
d14-Terphenyl
Quant.
Ion
128
136
142
152
152
160
154
164
166
176
178
188
178
188
202
212
202
212
228
240
228
240
244
Confirm.
Ion
127
68
141
153
153
165
176
94
176
94
101
106 '
101
106
114
120
114
120
122
% Relative
Abundance of
Confirm. Ion
10
80
80
15
86
80
15
15
15
15
15
15
15
August 9, 1996
Proposed M-429 Page 92
-------
TABLE 13(CONT)
QUANTITATION AND CONFIRMATION IONS FOR SELECTED
ION MONITORING OF PAHs BY HRGC/LRMS
Analyte
Benzo(b)fluoranthene
d12-Benzo(b)fluoranthene
Benzo(k)fluoranthene
d 1 2-Benzo(k)f luorantbene
Benzo(e)pyrene
d12-Benzo(e)pyrene
Benzo(a)pyrene
d12-Benzo(a)pyrene
Perylene
d12-Perylene
Indenod ,2,3-cd)pyrene
d12-lndeno{1 ,2,3-cd)pyrene
Dibenz(ah)anthracene
d 1 4-Di benz(ah)anthracene
Benzo(ghi)perylene
d T 2-Benzo(ghi) perylene
Quant.
Ion
252
264
252
264
252
264
252
264
252
264
276
288
278
292
276
288
Confirm.
Ion
126
132
126
132
126
132
126
132
126
132
138
139
138
% Relative
Abundance of
Confirm. Ion
25
25
25
25
26
28
24
37
August 9, 1996
Proposed M-429 Page 93
-------
TABLE 14
MASS DESCRIPTORS USED FOR SELECTED ION MONITORING FOR HRGC/HRMS
Descriptor Analyte
No.
1
2
IS
SS
AS
RS
LOCK
QC
Naphthalene
PFK
da-Naphthalene
2-Methyl naphthalene
d ! g-2-Methylna phthalene
Acenaphthylene
d8-Acenaphthylene
Acenaphthene
d10-Acenaphthene
PFK
Fluorene
d10-Fluorene
Phenanthrene
d10-Phenanthrene
Anthracene
d10-Anthracene
Fluoranthene
d^-Fluoranthene
Pyrene
PFK
d10-Pyrene
Benzo(a)anthracene
d T 2-Benzo-a-Anthracene
Chrysene
d12-Chrysene
PFK
d14-Terphenyl
= Internal Standard
= Surrogate Standard
= Alternate Standard
= Recovery Standard
= Lock-Mass Ion
= Quality Control Check Ion
Ion
Type
M
LOCK
IS
M
IS
M
IS
M
RS
QC
M
SS
M
IS
M
AS
M
IS
M
QC
RS
M
IS
M
IS
LOCK
SS
Accurate
m/z
128.0626
130.9920
136.1128
142.0782
152.1410
152.0626
160.1128
154.0782
164.1410
169.9888
165.0782
176.1410
178.0782
188.1410
178.0782
188.1410
202.0782
212.1410
202.0782
2C4.9888
212.1410
228.0939
240.1692
228.0939
240.1692
230.9856
244.1974
August 9, 1996
Proposed M-429 Page 94
-------
TABLE 14(CONT)
MASS DESCRIPTORS USED FOR SELECTED ION MONITORING FOR HRGC/HRMS
Descriptor Analyte
No.
The
H «
IS
SS
AS
RS
3 Perylene
d12-Perylene
PFK
Benzo(b)fluoranthene
d T 2-Benzo(b)f luoranthene
Benzo(k)fiuoranthene
d 1 2-Benzo-k-f luoranthene
Benzo(e)pyrene
d12-Benzo(e)pyrene
Benzo(a)pyrene
d12-Benzo(a)pyrene
Benzo(ghi)perylene
d12-Benzo(ghi)perylene
Indenod ,2,3-cd)pyrene
d12-lndeno(1 ,2,3-cd)pyrene
Dibenzo(ah)anthracene
PFK
d14-Dibenzo(ah)anthracene
following nuclidic masses were used:
1.007825 2H = 2.014102
= Internal Standard
= Surrogate Standard
= Alternate Standard
= Recovery Standard
Ion
Type
M
IS
QC
M
IS
M
IS
M
RS
M
IS
M
IS
M
IS
M
LOCK
IS
C = 12.000000
Accurate
m/z
252.0939
264.1692
268.9824
252.0939
264.1692
252.0939
264.1692
252.0939
264.1692
252.0939
264.1692
276.0939
288.1692
276.0939
288.1692
278.1096
280.9824
292.1974
LOCK = Lock-Mass Ion
QC
= Quality Control Check Ion
August 9, 1996
Proposed M-429 Page 95
-------
FIGURE 1
METHOD 429 FLOWCHART
7
§1.3.9 The end user is identified
51.3.10 The tester is designated
The end user chooses:
§2.1.1 • source target concentration
§2.1.2 The tester selects analyst with documented
§8.4 experience in satisfactory performance of analytical
§8.4.1 procedures
Tester and laboratory coordinate:
§4.3.2 • pre-test cleaning of glassware
§4.2 • pre-test cleaning, contamination checks, and
§4.3.3 storage of sampling materials and reagents
§4.3.4 • preparation of filter, sorbent cartridges, method
blanks, and LCS
§10.1
§10.1
§10.1
Tester requests pre-test analytical results from
laboratory:
1 • contamination check of filters
.2 • contamination check of XAD-2 resin
.3 • Method detection limits (MDLs) and
Practical quantitation limits (PQLs)
6
§2.5
Tester calculates and plans:
• S3 sampling runs and £1 blank sarnpSing train
• sample volume
• sampling time
• source reporting limit
• chain of custody
S4.3.1
Tester performs:
• calibration of equipment
8
§2.2
Tester writes:
• pre-test protocol
9
§4.4.1
§4.4.2
§4.4.3
§4.4.4
§5
Tester performs:
• preliminary field sampling determinations
• sampling train preparation
• leak checks
• sampling procedure
• £3 sampling runs
• £1 blank sampling train
• recovery of all runs and blank sampling train
10
§5.3
§5.4
Tester delivers:
• recovered sampling runs and blank train(s)
• chain of custody record
77
§6
§7
§8
§9
§10.2
Laboratory performs:
• extraction of field samples
• analyses
• QA/QC procedures
• chain of custody
• reporting requirements
12
§4.3.1
§9.2
§10.3
Tester performs:
• post-test calibrations
• calculations
• data recording and chain of custody
• reporting requirements
August 9, 1996
Proposed M-429 Page 96
-------
Heated Probe,
S-type Pilot
&Temp. Sensor
Stack
Wall
Temp. L
Readout
Pilot
Manometer
Orifice
Orifice
Manometer
Thermocouple
Dry Gas
Meter
Oven
Cyclone (Optional)
Filter Assembly
— Transfer Line
Condenser
(watercooled)
Sorbent Module
(watercooled)
ImpingersinlceBath:
Buffer Solution in/1 &12
/3 Empty
Silica Gel in #4
Bypass
Valve
Main
Valve
Pump
Check
Valve
Figure 2
PAH Sampling Train
August 9, 1996
Proposed M-429 Page 97
-------
c
(O
c
(O
(O
CD
O)
H To Suith
8 mm Glass
Cooling Coil
1—Water Jacket—'
XAD-2
Glass Sintered
Disk
Condenser
Sorbent Trap
O
TJ
O
0)
(0
Q.
(D
TJ
Q)
(Q
O
(O
00
Figure 3
Condenser and Sorbent Trap for Collection
of Gaseous PAHs
-------
Liquid Take Off
Liquid Nitrogen
Cylinder
(150L)
Loo.se Weave Nylon
Fabric Cover
10.2 cm (41)
Pyrex Pipe
0.95 cm (3/8')
/ Tubing
Heat Source
Rne Screen
Figure 4
XAD-2 Fluidized Bed Drying Apparatus
August 9, 1996
Proposed M-429 Page 99
-------
FIGURE 5
METHOD 429 FIELD DATA RECORD
Run No.
Location
Date
Operator
Meter Box No.
Local Time
Start/Stop _
AH@
Pitot Tube Factor
Probe Tip Dia, in.
Probe Length
Sampling Train Leak Test
Before in. Hg _
After
in. Hg
Stack Diameter
Meter Box Calibration
Factor (Y)
Leak Check Volume
Pitot Tube Leak Check
Before After
Leak Rate
cu.ft/min
cu.ft/min
cu. ft.
Project No.
Plant Name
Ambient Temp °F
Meter Temp °F _
Bar. Press, "Hg _
Stack Press,
'H2O
Assumed Moisture, % _
Heater Box Setting, °F _
Probe Heater Setting, °F
Assumed M.W. (wet%)
Assumed M.W. (dry%)
Sampling
Point
Start
Clock
Time
Dry Gas
Meter, cu, ft.
Pitot AP
in. H2O
Orifice AH
"H20
Desired
Actual
Temperature (°F)
Impinger
Filter box
Stack
Pump
Vacuum
in. Hg
August 9, 1996
Proposed M-429 Page 100
-------
c
CO
c
CD
CO
CO
O)
Figure 6
Recovery of PAH Sampling Train
Rinse with known volume:
1. acetone
2. methylene chloride
3.hexane
Container
o
•a
o
CO
CD
a
ro
CO
0)
ca
(D
Mark liquid level,
Store at 4v or lower
away from lioht
Transfer
Filter
« Container \\
No 2 ))
Store at 4'C
or lower away
from light
Rinse with known volume:
1. acetone
2. methylene chloride
3. hexane
/
\
Filter support,
Back hall
filter holder
Transfer | Condenser |
Mark liqu d level,
Store at 4 C or lower
away from light
Cap
C
Resin
cartridge
Store at 4°C or lower
away from light
A. Tare weigh Container /4
B. Decant contents of
Impingers into tared
Container /4
I
C. Weigh Container /4
D. Mark liquid level.
Store at 4°C or lower
away from light
Rinse with known volume:
1. acetone
2. methylene chloride
3. hexane
Mark liquid level,
Store at 4°C or lower
away from light
A. Tare weigh
cartrtridge with
silica gel
B. Weigh after
sampling
Recycle
-------
Figure 7
Flow Chart for Sampling, Extraction and Cleanup for
Determination of PAH in a Split Sample
Surrogate Standards
Added to XAD-2 Resin
Sampling
[G.C7 Mass Spec.]
G.C7 Mass Spec.)
11 Containers No. land No. 3
Augusts, 1996
Proposed M-429 Page 102
-------
Figure 8
Flow Chart for Sampling, Extraction and Cleanup for
Determination of PAH in a Composite Sample
Surrogate Standards
Added to XAO-2 Resin
MeCI2
Soxhlet Extraction
Recovery Standards
Containers No. 1 and No. 3
G.C./ Mass Spec.
August 9, 1996
Proposed M-429 Page 103
-------
FIGURE 9
EXAMPLE OF PRE-TEST CALCULATIONS FOR PAH EMISSIONS TEST
Naphthalene
2-Methylnaphthalene
PQL
(ng/sample)
STC
(ng/dscm)
2400 < 1 500
330
Acenaphthylene j 5.0
Acenaphthene
Fluorene1
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
BenzoikTfluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
5.0
83
110
5.0
5.0
~""5To'""'
5.0
5.0
_._
5.6
. ... ^
5.0
5.0
5.0
5.6
5.0
5.0
NA
180
6
<6
120
<6
' 46
46
<6
42
„„
50
NA
MSV
(dscf)
>56.5
NA
0.98
29.4
>489
32.4
>29.4
3.8
3.8
... ^_._™....._
... 4_
"" 3.5
3.5
NA
<6 I >29.4
NA
<6
<6
<6"
NA
>29.4
>29.4
>29.4
MST
(hours)
>1.89
NA
0.03
0.98
>16.3
1.08
>0.98
0.13^
""6.13""
>_f
0.14
0.12
0.12
...__
>0.98
NA
......>0:9L
>0.98
>0.98
PST = 6 hours
PSV = 180 dscf
F
NA
NA
183
6
NA
6
NA
47
47
NA
43
51
51
NA
NA
NA
NA
NA
NA
SRL
(ng/dscm}
471
64.7
0.98
0.98
16.3
21.6
0.98
0.98
6798
0.98
0.98
0.98
"__~
0.98
0.98
0.98
0.98
0.98
0.98
Average Volumetric Sampling Rate (VSR) = 0.5 dscfm = 30 dscf/hr
PQL = Practical quantitation limit for analyte (based on pre-test analysis of XAD-2 resin)
STC = Source target concentration for analyte. (From previous emissions test. Samples
were analyzed by HRGC/LRMS).
MSV = Minimum sample volume required to collect detectable levels of target analyte.
(MSV = PQL •»• STC) Equation 429-1
MST = Minimum sample time required to collect detectable levels of target analyte at VSR.
(MST - MSV -f- VSR) Equation 429-2
PST = Planned sampling time (6 hours chosen as the longest practical sampling
time for the planned emissions test)
PSV = Planned sample volume (PSV = PST x VSR) Equation 429-4
F = Safety factor (> 1) that allows for deviation from ideal sampling and analytical
conditions. (F = PSV - MSV) Equation 429-5
SRL = Source reporting limit if the target analyte cannot be detected with the planned test
parameters. (SRL = PQL * PSV) Equation 429-7
NA This calculation is not applicable either because there is no STC value available or the
STC is a detection limit.
1 PSV is lower than the MSV. Therefore, the analyte is not expected to be detected if it
is present at the target concentrations. It will only be detected if the actual
concentration is lower than the indicated SRL.
August 9, 1996
Proposed M-429 Page 104
-------
RUN NO.
PLANT NAME
SET-UP DATE
RECEIVED BY
FIGURE 10
CARB METHOD 429 (PAHs) SAMPLING TRAIN SET-UP RECORD
PROJECT NO.
PLANT LOCATION
SET-UP BY
DATE/TIME
1.
2.
3.
4.
COMPONENTS
NOZZLE
PROBE
FILTER HOLDER
5. TRANSFER LINE
AND CONDENSER
6.
Fittings
XAD-2 RESIN
CARTRIDGE
7. IMPINGERS: No. 1
U-Connector
No. 2
U-Connector
No. 3
U-Connector
8.
SILCA GEL
CARTRIDGE
COMPONENT ID
FILTER Lot*
OTHER INFORMATION
Material
Diameter
Liner material
Length
Before set-up, all
openings sealed with
Filter support type
Filter Type
Size
Contamination check?
Transfer line material
Both ends sealed in
lab prior to set-up
Fittings
Contamination check?
Spiked?
Charge with 100 mL
impinger solution and weigh
Charge with 100 mL
impinger solution and weigh
Weigh empty
Tare weight
Appearance
August 9, 1996
Proposed M-429 Page 105
-------
FIGURE 11
CARB METHOD 429 (PAHs) SAMPLING TRAIN RECOVERY RECORD
RUN NO. PROJECT NO.
PLANT NAME PLANT LOCATION
RECOVERY DATE RECOVERED BY
1. CHECK whether openings were covered. RINSE 3x each with Acetone. MeCI2, Hexane.
MARK liquid level and STORE containers at temp. <4°C away from light.
Openings Rinse volume (mL) Storage
Component covered? Acetone MeCU Hexane Container(s) IDs
Nozzle ,
Probe liner
Filter holder front
2. STORE filterls) at temp. <4°C away from light. RECORD ALL sample storage information.
Storage Storage
Component Appearance after sampling (Temperature & light) Container(s) ID
Filter
Filter
Filter
3. CHECK whether openings were covered. RINSE 3x each with Acetone, MeCI2, Hexane.
MARK liquid level and STORE containers at temp. <4°C away from light.
Openings Rinse volume (mL) Storage Storage
Component covered? Acetone MeCU Hexane Temp. & lisht Container ID
Filter support and
filter holder back
Transfer line ,
Condenser
4. STORE Resin cartridges at temp. <4°C away from light. RECORD ALL storage information.
ID Appearance after sampling Storage temperature & light conditions
5. WEIGH impinger contents and silica gel cartridge.
MARK liquid level and STORE impinger contents at temp. <4°C away from light.
Additional impingers Silica gel
Weight No. 1 No. 2 No. 3 No. 4 No. 5 cartridge
Final (g) . _
Before sampling (g)
Gain (g) (A) (B) (C) (D) (E) (F).
Total condensate (A) + (B) + (C) + (D) + (E) + (F) _____ (g)
STORAGE CONTAINER ID(s)
6. RINSE impingers 3x each with Acetone, MeCI2, Hexane.
MARK liquid level and STORE impinger rinses at temp. <4°C away from light.
Rinse volumes (mL) Acetone
MeCI2
Hexane
STORAGE CONTAINER ID(s)
August 9, 1996 Proposed M-429 Page 106
-------
Project #
FIGURE 12
CHAIN OF CUSTODY SAMPLE RECORD
Date:
Source name:
Sampling location:
Chain of Custody Log Record # (s)
SAMPLE STORAGE INFORMATION
Start:
Stop:
Sample/Run #
Sample type: _
Operator:
SAMPLE PRESERVATION
Ice/Dry ice?
Comments
CHAIN OF CUSTODY
ACTION
DATE
TIME
GIVEN BY
TAKEN BY
RELATED
IDs
FR
F
BR
C
I
IR
DESCRIPTION/COMMENTS
Front rinse (nozzle, probe, filter holder front)
Filter in sealed storage container
Back rinse (filter support, filter holder, sample line &
condenser
Resin cartridge
Impinger contents
Impinger rinses
Log #s
August 9, 1996
Proposed M-429 Page 107
-------
FIGURE 13
CHAIN OF CUSTODY LOG RECORD
PROJECT NO.
Page
of
Log #
Sample
ID
Date
Time
Comments
Given
by
Taken by
Sample Identifier
FR
F
BR
IR
Sample Description
Rinses of probe and front half of filter holder
Filter in sealed storage container
Rinses of filter support, back half of filter holder, sample transfer line and
condenser
Aluminum foil wrapped, capped resin cartridge
Impinger contents
Impinger rinses
August 9, 1996
Proposed M-429 Page 108
-------
FIGURE 14A
EXAMPLE GC/MS SUMMARY REPORT (HRMS) FOR INITIAL CALIBRATION SOLUTION #1
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
INSTRUMENT: W
OPERATOR: MPA
RRF
0.75
1.30
1.44
0.94
1.05
1.15
1.02
1.26
1.31
1.13
1.13
1.69
1.24
1.20
1.07
0.70
2.19
1.66
2.23
4.22
1.29
1.32
0.93
0.82
1.03
0.75
0.82
1.35
1.95
1.91
0.92
0.87
0.80
0.52
0.37
0.69
ICALID: ST1120A1
RUN #: PAHCS1
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzofalanthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzolalpyrene
Perylene
lndeno(1,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
dg-Naphthalene
dg-Acenaphthylene
d10- Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d 1 2-Benzo(b) f luoranthene
d12-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
d12-lndeno(1,2,3-c,d)pyrene
du-Dibenzo(a,h)anthracene
d 5 2-Benzo(g,h,i)perylene
d14-Terphenyl
d12-Benzo(e)pyrene
d10- Anthracene
d , 0-2-Methylnaphthalene
d10-Pyrene
d12-Perylene
ACQUIRED: 12/3/94 16:23::
PROCESSED: 12/3/94
RT
8:20
9:42
11:04
11:20
12:06
13:20
13:23
14:38
14:55
16:34
16:39
18:54
18:58
19:42
19:51
20:06
23:60
24:01
25:15
8:17
11:02
11:17
12:04
13:18
14:37
16:32
16:36
18:50
18:54
19:47
23:52
23:52
25:07
14:59
19:37
13:22
9:38
14:54
20:01
RRT
1.006
1.007
1.003
1.004
1.003
1.003
1.001
1.001
1.001
1.002
1.003
1.004
1.004
1.004
1.003
1.004
1.006
1.006
1.005
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
Area
6.66 E + 07
1.44 E + 07
1.57 E + 07
1.05 E + 07
8.15 E + 06
1.99 E + 07
7.07 E + 06
3.18 E + 07
3.31 E + 07
2.08 E + 07
2.26 E + 07
2.35 E + 07
2.50 E + 07
2.41 E + 07
2.11 E + 07
1.38 E + 07
2.07 E + 07
1.49 E + 07
1.84 E + 07
3.54E + 08
1.09 E + 08
1.11 E + 08
7. 78 E + 07
6.92 E + 07
2.53 E + 08
1.83 E + 08
2.00 E + 08
2.77 E + 08
4.03 E + 08
3.93 E+08
1.89 E+08
1.80 E + 08
1.65 E+08
2.65 E + 08
1.44 E + 08
5.82 E + 07
8.40 E + 07
2.45 E + 08
1.03 E + 08
August 9, 1996
Proposed M-429 Page 109
-------
FIGURE 148
EXAMPLE OF INITIAL CALIBRATION (ICAL) RRF SUMMARY
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
ICAL ID:
RUN #:
ST1120
NA
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzolalanthracene
Chrysene
Benzofbjfluoranthene
Benzo(k)fluoranthene
Benzolelpyrene
Benzo(a)pyrene
Perylene
Indenol 1,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
d8-Naphthalene
d8-Acenaphthylene
d10-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d T 2-Benzo(b)f luoranthene
d12-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
dl2-lndeno(1,2,3-c,d)pyrene
d14-Dibenzo(a,h)anthracene
d12-Benzo(g,h,i)perylene
d14-Terphenyl
d12-Benzo(e)pyrene
d10-Anthracene
d, 0-2-Methylnaphthalene
d10-Pyrene
d12-Perylene
ACQUIRED: 3-DEC-94
PROCESSED: 3-DEC-94
RRF #1
0.75
1.30
1.44
0.94
1.05
1.15
1.02
.26
.31
.13
.13
.69
.24
.20
1.07
0.70
2.19
1.66
2.23
4.22
1.29
1.32
0.93
0.82
1.03
0.75
0.82
1.35
1.95
1.91
0.92
0.87
0.80
0.52
0.37
RRF #2
0.66
1.15
1.27
0.84
0.94
1.06
1.00
1.15
1.27
1.05
1.02
1.45
1.25
1.12
0.99
0.63
2.01
1.60
2.05
4.15
1.29
1.34
0.95
0.82
1.00
0.70
0.79
1.39
1.95
1.96
0.88
0.84
0.76
0.52
0.37
RRF #3
0.61
1.10
1.24
0.80
0.88
1.01
0.98
1.08
1.13
1.05
0.97
1.46
1.14
1.06
0.96
0.58
1.92
1.56
1.96
4.16
1.28
1.32
0.94
0.82
1.07
0.70
0.81
1.46
2.14
2.11
0.98
0.91
0.83
0.49
0.37
RRF #4
0.64
1.12
1.28
0.83
0.92
1.05
0.95
1.13
1.15
1.04
0.98
1.42
1.18
1.06
0.96
0.60
1.99
1.61
2.00
4.18
1.27
1.30
0.95
0.86
1.07
0.72
0.83
1.27
1.84
1.82
0.85
0.78
0.73
0.48
0.36
RRF #5
0.71
1.26
1.43
0.94
1.07
1.23
1.14
1.28
1.41
1.23
1.11
1.86
1.26
1.19
1.14
0.70
2.26
1.87
2.32
4.10
1.30
1.32
0.95
0.88
0.99
0.70
0.84
1.32
2.11
1.99
0.98
0.89
0.80
0.51
0.36
INSTRUMENT: W
OPERATOR: MPA
Mean
RRF
0.67
1.19
1.33
0.87
0.97
1.10
1.02
1.18
1.25
1.10
1.04
1.58
1.21
1.12
1.02
0.64
2.07
1.66
2.11
4.16
1.29
1.32
0.94
0.81
1.03
0.71
0.82
1.36 '
2.00
1.96
0.92
0.86
0.78
0.51
0.36
SD
0.056
0.089
0.096
0.067
0.082
0.088
0.074
0.085
0.115
0.082
0.073
0.194
0.052
0.066
0.080
0.059
0.143
0.122
0.154
0.044
0.012
0.013
0.011
0.026
0.038
0.022
0.021
0.072
0.124
0.107
0.059
0.049
0.042
0.018
0.005
%RSD
8.29%
7.47%
7.19%
7.72%
8.43%
8.00%
7.25%
7.21%
9.22%
7.43%
7.00%
12.33%
4.32%
5.89%
7.81%
9.12%
6.90%
7.35%
7.28%
1.05%
0.91%
1.00%
1.21%
3.09%
3.71%
3.09%
2.56%
5.32%
6.23%
5.46%
6.40%
5.71%
5.36%
3.59%
1.50%
0.69
0.73
0.74
0.80
0.90
0.77
0.080 10.40%
August 9, 1996
Proposed M-429 Page 110
-------
FIGURE 14C
EXAMPLE OF CONTINUING CALIBRATION (CONCAL) SUMMARY
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
CONCAL ID:
CONCAL DATE:
CC1202 ICALID: ST1120
12/3/94 ICALDATE: 3-DEC-94
RRF ICAL RRF ARRF
RPD
INSTRUMENT: W
OPERATOR: MPA
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzolelpyrene
Benzolalpyrene
Perylene
Indenod ,2, 3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzofg, h,i)perylene
dg-Naphthalene
d8-Acenaphthylene
d10- Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d 1 2-Benzo(a)anthracene
d12-Chrysene
d12-Benzo(b)fluoranthene
d12-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
d12-lndeno(1 ,2,3-c,d)pyrene
d14-Dibenzo(a,h)anthracene
d , 2-Benzo(o,h,i)perylene
d14-Terphenyl
d12-Benzo(e)pyrene
0.68
1.42
1.42
0.91
0.98
1.10
0.98
1.12
1.18
1.08
1.04
1.46
1.12
1.04
0.95
0.62
2.04
1.61
2.11
4.78
1.20
1.25
0.85
0.79
1,05
0.69
0.82
1.24
1.91
1.87
0.84
0.80
0.76
0.50
0.37
0.67
1.19
1.33
0.87
0.97
1.10
1.02
1.18
1.25
1.10
1.04
1.58
1.21
1.12
1.02
0.64
2.07
1.66
2.11
1.16
1.29
1.32
0.94
0.81
1.03
0.71
0.82
1.36
2.00
1.96
0.92
0.86
0.78
0.51
0.36
0.01
0.23
0.09
0.04
0.01
0.00
-0.04
-0.06
-0.07
•0.02
0.00
-0.12
-0.09
-0.08
-0.07
-0.02
-0.03
-0.05
0.00
0.68
-0.09
-0.07
-0.09
-0.02
0.02
-0.02
0.00
-0.12
-0.09
-0.09
-0.08
-0.06
-0.02
-0.01
0.01
1.5
17.6
6.6
4.5
1.0
0.0
4.0
5.2
5.8
1.8
0.0
7.9
7.7
7.4
7.1
3.2
1.5
3.1
0.0
15.3
7.2
5.5
10.1
2.5
1.9
2.9
0.0
9.2
4.6
4.7
9.1
7.2
2.6
2.0
2.7
d10-Anthracene
d10-2-Methylnaphthalene
d10-Pyrene
d12-Perylene
0.71
0.77
1.000
1.000
-0.06
8.1
August 9, 1996
Proposed M-429 Page 111
-------
FIGURE 15A.
EXAMPLE OF SUMMARY REPORT OF LCS RESULTS
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
Client ID CARB
Lab ID: 14129/LCS1/LCS2
Instrument: _W
Operator: .
Reviewer:
MPA
JCM
COMPOUND:
Sample Matrix: XAD-2
Date Received: NA
Date Extracted: 11/30/94
Date Analyzed:
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
lndeno(1,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzolg,h,i)perylene
Internal Standards (%R)
d8-Naphthalene
d8-Acenaphthylene
d10-Acenaphthene
d10-Fluorene
di0'Phenanthrene
d10-Fluoranthene
d 12-Benzo(a)anthracene
d12-Chrysene
d 12-Benzo(b)f luoranthene
d12-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
d12-lndeno(1,2,3-c,d)pyrene
d14-Dibenzo(a,h)anthracene
d, 2-Benzo(g,h,i)perylene
Alternate Standard (%R)
d10-Anthracene
d: 12/3/94
nt: Sample
LCS1
%R
100
96
95
92
94
93
91
90
87
87
83
92
92
97
89
89
87
88
89
67
73
76
79
88
84
96
96
88
85
92
104
96
102
CONC
Units
LCS2
%R
103
95
97
94
96
94
89
92
89
86
89
93
95
99
92
89
90
90
91
64
70
75
81
93
80
98
91
85
84
90
105
96
103
ICALID: ST1120
ICAL DATE:
CONCAL ID:
CONCALDATE: NA
NA
12/3/94
NA
RPD
3.0
1.0
2.1
2.2
2.1
1.1
2.2
2.2
2.3
1.2
7.0
1.1
3.2
2.0
3.3
0.0
3.4
2.2
1.2
Resin Lot #: LC1130M
LCS IDs: NA
LCS DATE: NA
83
85
August 9, 1996
Proposed M-429 Page 112
-------
-------
FIGURE 16A
EXAMPLE GC/MS SUMMARY REPORT (HRMS) FOR SAMPLE RUN #32
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
Lab ID: 14129-02
Acquired: 12/3/94 16:23:40
Client ID: M429-32
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzolalanthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzofalpyrene
Perylene
Indenof 1,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzolg.h.ilperylene
d8-Naphthalene
de-AcenaphthyIene
d10- Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d T 2-Benzo{a)anthracene
d12-Chrysene
d12-Benzo(b)fluoranthene
d 12-Benzo(k)fluoranthene
d 12-Benzo(a)pyrene
d12-lndeno(1,2,3-c,d)pyrene
d14-Dibenzo(a,h)anthracene
d12-Benzo(g,h,i)perylene
du-Terphenyl
d,2-Benzo(e)pyrene
d10-Anthracene
d10-2-Methylnaphthalene
d10-Pyrene
d,2-Perylene
ICALID: 12/3/94 16:23:40
ICALDATE: 12/3/94
Instrument: W
Operator: MPA
Reviewer: JCM
RT
RRT
Area
RRF Amt. (ng)
%REC
8:21
9:41
11:03
11:19
12:05
13:17
13:21
14:36
14:52
16:32
16:32
18:49
Not found
19:36
19:46
20:01
23:54
23:56
25:09
8:18
11:01
11:16
12:02
13:16
14:34
16:28
16:31
18:45
18:50
19:41
23:46
23:45
24:60
14:55
19:32
13:20
9:38
14:51
19:56
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.053 E+10
1.790 E + 08
9.371 E + 08
7.649 E + 06
2.417 E + 07
8.402 E + 08
2.905 E + 07
5.932 E + 08
7.611 E + 08
3. 120 E + 06
9.620 E + 06
1.030 E + 06
0.0
1.646 E + 07
4.936 E + 06
1.823 E + 06
5.728 E + 06
5.875 E + 05
1.584 E + 07
4.794 E + 08
1.972 E+08
2.142 E + 08
1.658 E + 08
1.652 E + 07
3.955 E + 08
2.835 E + 08
2.987 E + 08
3.439 E + 08
4.304 E + 08
4.895 E + 08
2.529 E + 08
2.400 E + 08
2.006 E + 08
7.988 E + 08
3.011 E + 08
6.795 E + 07
1.844 E + 07
6.576 E + 08
3.057 E + 08
0.67
1.19
1.33
0.87
0.97
1.10
1.02
1.18
1.25
1.10
1.04
1.58
1.21
1.12
1.02
0.64
2.07
1.66
2.11
1.16
1.29
1.32
0.94
0.81
1.03
0.71
0.82
1.36
2.00
1.96
0.92
0.86
0.78
0.51
0.36
0.77
...
...
—
10,478.37
140.98
712.59
8.21
30.02
925.53
34.54
254.36
307.62
1.9
6.2
7.6
13.61
3.95
2.32
4.37
0.59
14.95
124.92
166.07
176.19
190.71
213.39
116.22
121.18
1 1 1 .08
165.79
141.02
163.67
179.71
182.65
167.24
523
676.33
95.29
100
100
100
62.5
83.0
88.1
95.4
106.7
58.1
60.6
55.5
41.4
35.3
40.9
44.9
45.7
41.8
105
135.3
47.6
August 9, 1996
Proposed M-429 Page 114
-------
FIGURE 16B
EXAMPLE LABORATORY REPORT OF PAH RESULTS FOR SAMPLE RUN #32
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
Client ID M429-32
Lab ID: 14129-02
Instrument: W
Operator: MPA
Reviewer: JCM
COMPOUND:
Sample Matrix: M429
Date Received: 11/18/94
Date Extracted: 11 /30/94
Date Analyzed: 12/3/94
Sample amount: Sample
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo (a)anthracene
Chrysene
Benzolblfluoranthene
Benzo(k) f luoranthene
Benzo(e)pyrene
Benzolalpyrene
Perylene
Indenod ,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Internal Standards (%R)
d8-Naphthalene
d8-Acenaphthylene
d10-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d! 2-Benzo(b)f luoranthene
d 12-Benzo(k)fluoranthene
d 12-Benzo!a)pyrene
d12-lndeno(1,2,3-c,d)pyrene
du-Dibenzo(a,h)anthracene
d12-Benzo(g,h,i)perylene
Alternate Standard (%R)
d10-Anthracene
Surrogate Standard (%R)
d14-Terphenyl
d12-Benzo(e)pyrene
Cone.
10478
141
712
8.2
30
930
35
254
307
ND
6.2
7.6
ND
14
ND
ND
ND
ND
15
62
83
88
95
107
58
61
56
41
35
41
45
46
42
48
105
135
ICAL ID: ST1120
ICAL DATE:
CONCAL ID:
CONCALDATE: N>
Units: no/sample
12/3/94
NA
R.L
1600
94
5.0
5.0
27
80
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
Resin Lot #: LC1130M
LCS IDs: 14129-LCS1/LCS2
LCS DATE: 12/3/94
Flags
H
H
H
H
H
H
Augusts, 1996
Proposed M-429 Page 115
-------
FIGURE 17A
EXAMPLE OF TESTER'S SUMMARY OF LABORATORY REPORTS
Run »:
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenol 1 ,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
Internal Standards (%R)
d8-Naphthalene
d8-Acenaphthylene
d 10-Acenaphthene
d10-Fluorene
d10-Phenanthrene
d10-Fluoranthene
d12-Benzo(a)anthracene
d12-Chrysene
d12-Benzo(b)fiuoranthene
31
32
33
Field
Blank
Method
Blank
ng/sampla
4300
< 94
140
9.2
27
310
26
83
iio
< 5.0
< 5.6
< 5.0
< 5.6
35
< 5.0
< 5.0
< 5.6
< 5.0
< 85
66
82
85
91
106
79
100
91
69
d12-Benzo(k)fiuoranthene j 62
d12-Benzo(a)pyrene j 70
d12-indeno(i,2,3-c,d)pyrene 82
d14-bibenzo(a,h)anthracene 72
d12-Benzo(g,n,i)perylene 84
Surrooate Standards (%R)
d14-Terphenyl
d12-Benzo(e)pyrene
Alternate Standard (%R)
d,0-Anthracene
Test Date
125
72
67
11/15/94 .
10000 J460000 *
140
710
8.2
30
930
35
250
310
< 5.0
6.2
7.6
< 5.0
< 35
< 5.0
< 5.0
< 5.0
< 5.0
< 85
62
83
6400 •
8 5666 •
500
180
43666" •
24o6
1606"6 •
26666 *
170
300
340
89
530
240
110
ib'o
6.4
440
57 •
85 •
88 80 *
95 102
107 79 *
58 75 •
61 108
56 99
41 H 60
35"H 50
41 H 58
45 H 58
42 H 58
46 H 58
'.';•; ': .
105
135
48 H
90
112 1
115
11/16/94 J11/17/94
<1600
< 94
9.1
< 5.6
< 27
< 80
5.3
16
19
< 5.0
< 5.0
< 5.0
< 5.0
6.9
< 5.0
< 5.0
< 5.0
< 5.0
. ..„.._.
53
73
81
90
107
83
114
__ -.
85
78
86
<1700
<78
< 5.0
< 5.0
< 27
< 74
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
< 5.0
55
69
75
82
93
80~
93
88
84
84
89
106' 106
92 92
107
123
103
116
11/16/94
LCS #1
LCS tt2
percent recovery
100
96
95
92
94
93
91
90
87
87
83
92
92
97
89
89
87
103
95
97
94
96
94
89
92
89
86
89
93
95
99
92
89
90
88 j 90
89
67
73
76
79
88
84
96
96
88
85
92
104
96
104 j 102
130
112
101
83
91
" ' .... 'H. *!s
- i '• i '. | -. -,
64
70
75
81
93
80
98
91
85
84
90
105
""""96
103
' ••ri'iv.V"
85
NA ;NA |NA
Date received by lab. 11/18/94" i'l/18/94 |TT/ 18/94 11/18/94 ;NA jNA jNA
Date extracted 11/3"6794 |li730"/94 11/30/94 11/30/94 j 11/30/94 |11/30/94|1 1/30/94
Date analyzed 12/3/94 J12/3/94 12/3/94 12/3/94 1 1273/94 j 12/3/94 112/3/94
• < • denotes that the compound was not detected at levels above the indicated reporting limit.
•H" indicates internal Standard Recovery Results below 50%, but signal-to-noise greater than 10:1.
••• indicates compounds reanalyzed at 1:50 dilution due to saturation.
August 9, 1996
Proposed M-429 Page 116
-------
FIGURE 17B
FIELD DATA SUMMARY FOR PAH EMISSIONS TEST
RUN ID
DATE
START/STOP TIME
LOCATION
STACK DIAMETER
NOZZLE DIAMETER
METER BOX ID
STANDARD DRY GAS VOLUME Vm(.tdl
m
P.,.,
Tm
K,
Y
PERCENT MOISTURE Bw,
Impinger + tare
Final wt.
Net imp. catch
Silica gel tare
Post sampling wt.
Moisture gain
Total moisture (V1
^w(itd)
Vm|ttd|
K2
MOLECULAR WEIGHT Md
M.
°2
CO
C02
N2
"wi
GAS VELOCITY v.
Ap
T.
P.
P.
M.
K.
CP
VOLUMETRIC FLOW RATE Q,1d
BW«
v.
A
sec/min
Ki
ISOKINETIC RATIO 1
T,
''mlitd)
P.
e"
R
WI
K4
31
11-15-95
1015/1435
STACK
35.5 in.
0.3106
6419
146.19
132.65
29.78
1.15
60.0
17.64
1.08
12.9
2183.3
2609.8
426.5
1561.8
1 590.0
28.2
c) 464.7
21.43
145.19
O.O471
29.93
28.40
11.25
0.00
9.25
79.50
12.86
38.4
0.530
420
-0.27
29.76
28.40
86.49
0.83
8241
12.86
38.38
6.8736
60
17.64
96
420
145.19
29.76
38.38
240
12.86
0.00063
0.09460
32
11-16-95
1020/1645
STACK
35.6 in.
0.31 3 in.
6419
235.67
213.67
29.98
1.36
60.0
17.64
1.08
16.0
2092.3
2934.9
842.6
1788.8
1826.9
38.1
880.7
41.50
235.57
0.0471
29.95
28.16
10.76
0.00
9.50
79.75
14.98
40.88
0.66
428
-6.27
29.96
28.16
85.49
0.83
8631
14.98
40.88
6.8736
60
17.64
99
428
236.57
29.96
40.88
360
14.98
0.00063
0.09450
33
11-17-95
0855/1525
STACK
36.5 in.
0.3125 in.
5419
250.76 DSCF(68° F)
228.10 cubic ft
29.88 inches Hg
1.56 inches H2O
60.0 e F
17.64
1.08
18.4 percent
2063 grams
3210.2 grams
1 147.2 grams
1585.7 grams
1 536.2 grams
49.5 grams
1196.7 grams
66.39 DSCF(68° F)
250.76 DSCF(68° F)
0.0471
30.08 Ib/lbmole
27.86 Ib/lbmole
1 0.00 percent
0.00 percent
10.50 percent
79.50 percent
18.36 percent
43.2 feet/second
0.59 inches H,O
427 °F
-0.27 inches H2O
29.86 inches Hg
27.86 Ib/lbmole
85.49
0.83
8641 DSCF(68° F)
1 8.36 percent
43.23 feet/second
6.8736 sq. feet
60
17.64
1 04 percent
427 e F
250.76 DSCFM(68° F)
29.86 inches Hg
43.23 feet/second
360 minutes
18.36 percent
0.00053 sq. feet
0.09450
August 9, 1996
Proposed M-429 Page 117
-------
FIGURE 17C
EXAMPLE OF EMISSIONS TEST REPORT
(ng/dscm)
Naphthalene
2-MetnyinapFthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indenod ,2,3-c,d)pyrene
Dibenzo(a,h)anthracene
Benzo(g,h,i)perylene
/ r (ng/sec)
Naphthalene
2-Methylnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo{b7fTuoranfhene
Benzolkifiuoranthene
Benzolejpyrene
Benzo(a]pyrene
Perylene
]ndeno(1 .i.S-c.dTpyrene
Dibenzofa,h)anthracene
Benzolg.hjlperyiene
Run #31
1046
<23
34
2.2
6.6
75
<6.3
20
27
<1.2
<1.2
<1.2
<1.2
..„.„<*•*
<1.2
<1.2
<1.2
<1.2
<21
4068
<89
132
8.7
26
293
<25
79
104
<4.7
<4.7
<4.7
<4.7
<33
<4.7
<4.7
<4.7
<4.7
<80
Run #32
1499
21.6
106
1.2
4.5
139
o
::"38
47
<0.75
6.92
1.1
<0.75
<5.3
<0.75
<0.75
<0.75
<0.75
"~"
-------
METHOD 429 - APPENDIX A
DETERMINATION OF THE METHOD DETECTION LIMIT
This procedure is based on the approach adopted by the EPA and included as Appendix B
to Title 40, Part 136 of the Code of Federal Regulations (40 CFR 136). The samples shall
be subjected to the same extraction, concentration, cleanup, and analytical procedures as
those required for the field samples.
A1 Procedure
A1.1 Make an estimate of the detection limit (MDL) of each target compound
using one of the following:
(a) The concentration value that corresponds to an instrument
signal/noise ratio in the range of 2.5 to 5.
(b) The concentration equivalent of three times the standard deviation
of replicate instrumental measurements of the analyte in reagent
methylene chloride.
(c) That region of the standard curve where there is a significant
change in sensitivity, i.e., a break in the slope of the standard curve.
(d) Instrumental limitations.
(e) The concentration equivalent to five times the theoretical
quantitation limit (Section 8.3.1 of the test method)
The experience of the analyst is important to this process, but one of the
above considerations must be included in the initial estimate of the detection
limit.
A1.2 Prepare according to the procedures described in Sections 4.2.2.1 to
4.2.2.4 enough XAD-2 resin to provide, at a minimum, eight aliquots
each with mass equal to that required to pack a Method 429 sorbent
cartridge. A contamination check must be conducted to identify those
PAH for which a MDL cannot be determined by this method.
A1.3 To each of seven (7) aliquots of the clean resin, add an amount of each
target analyte equal to the estimated detection limit. The mass of each
resin aliquot must be known, and should be approximately 40 grams, the
amount required to pack a Method 429 sorbent cartridge. The eighth
aliquot shall be a blank.
A1.4 Process each of the eight samples through the entire PAH analytical
method. All quality criteria requirements of the analytical method must
be satisfied.
August 9, 1996 Proposed M-429 Page 119
-------
A1 .5 Report the analytical results. The laboratory report must satisfy all of the
reporting requirements of Section 10 of the test method.
A1 .6 It may be economically and technically desirable to evaluate the
estimated method detection limit before proceeding with step A1.3. This
will: (1) prevent repeating this entire procedure and (2) insure that the
procedure is being conducted at the correct concentration. It is quite
possible that an inflated MDL will be calculated from data obtained at
many times the real MDL even though the level of analyte is less than
• five times the calculated method detection limit. To insure a good
estimate of the method detection, it is necessary to determine that a
lower concentration of analyte will not result in a significantly lower
method detection limit. Take two aliquots of the sample to be used to
calculate the method detection limit and process each through the entire
method, including blank measurements as described above in step A1.3.
Evaluate these data:
(1 ) If the sample levels are in a desirable range for determination of the
MDL, take five additional aliquots and proceed. Use all seven
measurements for calculation of the MDL according to Section A2.
(2) If these measurements indicate the selected analyte level is not in
correct range, reestimate the MDL with a new sample as in A1 .2
and repeat steps A1 .3 to A1 .5.
A2 Calculation
A2.1 Calculate the variance (S2) and standard deviation (S) of the replicate
measurements, as follows:
S2 =J_
n-1 LR
429-(A)-(34)
Where:
i = 1 to n, are the analytical results in the final method reporting units
obtained from the n sample aliqouts and I refers to the sum of the X
values from i = 1 to n.
Au9USt9'1"6 Proposed M-429 Page 120
-------
A2.2 (a) Compute the MDL as follows:
MDL = t(n.1( ,_. .o.99) x (S) 429(A)-(35)
Where:
MDL = the method detection limit
t(n-i, 1-a = 0.99) = Students' t-value appropriate for a 99%
confidence level and a standard deviation estimate with n-1 degrees
of freedom. See Table 429(A)-1.
S = standard deviation of the replicate analyses.
(b) The 95% confidence interval estimates for the MDL derived in
A2.2(a) are computed according to the following equations derived
from percentiles of the chi square over degrees of freedom
distribution (x2/df).
LCL = 0.64 MDL
UCL = 2.20 MDL
where: LCL and UCL are the lower and upper 95% confidence
limits respectively based on seven aliquots.
A3 Optional Iterative Procedure
A3.1 This is to verify the reasonableness of the estimate of the MDL and.
subsequent MDL determinations.
(a) If this is the initial attempt to compute MDL based on the estimate
of MDL formulated in Step A1.1, take the MDL as calculated in Step
A2.2, spike the matrix at this calculated MDL and repeat the
procedure starting with Step A1.3.
(b) If this is the second or later iteration of the MDL calculation, use S2
from the current MDL calculation and S2 from the previous MDL
calculation to compute the F-ratio. The F-ratio is calculated by
substituting the larger S2 into the numerator S2A and the other into
the denominator S B. The computed F-ratio is then compared with
the F-ratio found in the table which is 3.05 as follows: if
S2A/S2B<3.05, then compute the pooled standard deviation by the
following equation:
429(A)-(36)
oa » -t- oar.
Spooled =
12
August 9, 1996 Proposed M-429 Page 121
-------
if S2A/S2B>3.05, respika at the most recent calculated MDL and process
the samples through the procedure starting with Step A1.3. If the most
recent calculated MDL does not permit qualitative identification when
samples are spiked at that level, report the MDL as a concentration
between the current and previous MDL which permits qualitative
identification.
(c) Use the Spooled as calculated in Equation 429(A)-3 to compute the
final MDL according to the following equation:
MDL = 2.681 (Spooled) 4291AM37).
Where: 2.681 is equal to t(12( ^ = .99)-
(d) The 95% confidence limits for MDL calculated using Equation
429(A)-4 are computed according to the following equations derived
from percentiles of the chi squared over degrees of freedom
distribution.
LCL = 0.72 MDL
UCL = 1.65 MDL
where LCL and UCL are the lower and upper 95% confidence limits
respectively based on 14 aliquots.
TABLE 429(A)-1
SELECTED STUDENT'S t VALUES AT THE 99 PERCENT CONFIDENCE LEVEL
v
Number of
Replicates
7
8
9
10
11
16
21
26
31
61
Degrees
of Freedom
(n-1)
6
7
8
9
10
15
20
25
30
60
Vl, .99}
3.143
2.998
2.896
2.821
2.764
2.602
2.528
2.485
2.457
2.390
August 9, 1996 Proposed M-429 Page 122
-------
FORMULA: Table 1
M.W.: Table 1
POLYNUCLEAR AROMATIC HYDROCARBONS
~~~~METHOD: 5506
ISSUED: 5/15/85
OSHA: proposed for B[a]P: 0.2 vg/m3
ACGIH: suspect carcinogen (B[a]P)
PROPERTIES: Table 1
COMPOUNDS: acenaphthene
acenaphthylene
anthracene
benz[a]anthracene
benzo[b]fluoranthene
benzoCk]f1uoranthene
benzo[ghi]perylene
benzo[a]pyrene
benzo[e]pyrene
chrysene
dibenz[a,h]anthracene
fluoranthene
fluorene
i ndenoC1,2,3-cd]pyrene
naphthalene
phenanthrene
pyrene
SYNONYMS: PAH: PNA: also see Table 2.
SAMPLING
MEASUREMENT
SAMPLER: FILTER + SORBENT
(2->im, 37-ron PTFE + washed XAD-2,
100 mg/50 mg)
FLOW RATE: 2 L/min
VOL-MIN: 200 L
-MAX: 1000 L
SHIPMENT: transfer filters to culture tubes;
wrap sorbent and culture tubes in
Al foil; ship @ 0 °C
SAMPLE STABILITY: unknown; protect from
heat and UV radiation
FIELD BLANKS: 101 (>3) of samples
MEDIA BLANKS: 6 to 10
AREA SAMPLES: 8 replicates on preweighed
filters for solvent selection
ACCURACY
RANGE STUDIED, BIAS, AND OVERALL
PRECISION (sr) : not measured
i
1METHOO: HPLC, FLUORESCENCE/UV DETECTION
i
IANALYTE: compounds above
i
'.EXTRACTION: 5 mL organic solvent appropriate to
! sample matrix (step 7)
i
! COLUMN: 15 cm x 4,6 mm, reverse phase, 5-iirn CJQ
i
! INJECTION VOLUME: 10 to 50 )iL
i
1MOBILE PHASE: HgO/C^CN gradient 9 ambient
! temperature
t
!FLOW RATE: 1.0 mL/min
i
! DETECTORS: UV @ 254 nm; fluorescence @ 340 nm
! (excitation), 425 nm (emission)
i
JCALIBRATION: external standards in O^CN
i
iRANGE, LOD AND PRECISION (sr) : EVALUATION OF
! METHOD
i
i
i
i
i
APPLICABILITY: The working range for B[a]P is 1 to 50 vg/m3 for a 400-L air sample.
Specific sample sets may require modification in filter extraction solvent, choice of
measurement method, and measurement conditions (see EVALUATION OF METHOD).
INTERFERENCES: Any compound which elutes at the same HPLC retention time may interfere. Heat,
ozone, N02, or UV light may cause sample degradation.
OTHER METHODS: This revises P&CAH 206 and 251 [1]. The spectrophotometric methods, P&CAM 184
*nr± 186 [13. have not been revised. Also see Method 5515 (GC).
5/15/85 5506-1
-------
POLYNUCLEAR AROHATIC HYDROCARBONS
METHOD; 5506
REAGENTS:
1. Filter extraction solvent:
benzene,* cyclohexane, methylene
chloride, or other appropriate
solvents, pesticide grade
grade (step 7).
2. Water, distilled, deionized,
degassed.
3. Acetonitrile, HPLC grade, degassed.
4. PAH reference standards,*
appropriate to the PAH-containing
matrix sampled.
5. Calibration stock solution,
0.25 mg/ml.* Check purity of each
PAH reference standard by GC/FID,
HPLC/fluorescence and/or melting
point. Purify, if necessary, by
recrystallization. Weigh 25 mg
of each PAH into a 100-ml volumetric
flask; dilute to volume with
acetonitrile. Stable six months
if refrigerated and protected
from light.
*See SPECIAL PRECAUTIONS.
EQUIPMENT:
1. Sampler:
a. Filter. PTFE-laminated membrane filter, 2-ym
pore size, 37-mn diameter (ZEFLOUR, Hembrana,
Pleasanton, CA or equivalent), backed by a
gasket (37-mn 00, 32-flro ID) cut from a cellulose
support pad, in cassette filter holder.
NOTE 1: If sampling is to be done in bright
sunlight, use opaque or foil-wrapped
cassettes to prevent sample degradation.
NOTE 2: Take filters to be preweighed from the
filter package and allow to equilibrate
24 hrs with laboratory atmosphere before
taring.
b. Sorbent tube, connected to filter with minimum
length PVC tubing. Plastic caps are required
after sampling. Washed XAD-2 resin (front =
100 mg; back = 50 mg) (Supelco ORBO 43 or
equivalent). Pressure drop at 2 L/min airflow
1.6 to 2 kPa (15 to 20 cm H^).
2. Personal sampling pump capable of operating for
8 hrs at 2 L/min, with flexible connecting tubing.
3. Aluminum foil.
4. Vial, scintillation, 20-mL, glass, PTFE-lined cap.
5. Refrigerant, bagged.
6. Culture tubes, PTFE-lined screw cap, 13-mm x
100-mn.
7. Forceps.
8. Filters, 0.45-pm, PTFE or nylon (for filtering
sample solutions).
9. Pipet, 5-mL.
10. Syringe or micropipets, 1- to 100-yL.
11. Ultrasonic bath.
12. HPLC, with gradient capability, fluorescence
(excitation 9 240 nm, emission 9 425 nm) and UV
(254 nm) detectors in series, electronic
integrator, and column [HC-OOS-SILX (Perkin-Elmer
Corp.), Vydac 201TP (The Separations Group) or
equivalent; see page 5506-1].
13. Volumetric flasks, 10- and 100-mL.
14. Lighting in laboratory: incandescent or
UV-shielded fluorescent.
15. Kuderna-Danish extractor.
SPECIAL PRECAUTIONS: Treat benzene and all polynuclear aromatic hydrocarbons as carcinogens
Neat compounds should be weighed in a glove box. Spent samples and unused standards aretoxic
waste. Regularly check counter tops and equipment with "black light" for fluorescence as an
indicator of contamination by PAH.
5/15/85
5506-2
-------
METHOD; 5506 POLYNUCLEAR AROMATIC HYDROCARBONS
SAMPLING:
1. Calibrate each personal sampling pump with a representative sampler in line.
2. Take personal samples at 2 L/min for a total sample size of 200 to 1000 L. Take a
concurrent set of eight replicate area samples at 2 to 4 L/min on preweighed, 2-um PTFE
filters in an area of highest expected PAH concentration.
NOTE: The area samples are needed for solvent selection (step 7).
3. Immediately after sampling, transfer the filter carefully with forceps to a scintillation
vial. Hold filter at edge to avoid disturbing the deposit. Cap the scintillation vial and
wrap it in aluminum foil.
NOTE: This step is necessary to avoid loss of analytes due to sublimation and degradation
by light.
4. Cap the sorbent tube and wrap it in aluminum foil.
5. Ship to laboratory in insulated container with bagged refrigerant.
SAMPLE PREPARATION:
NOTE: UV light may degrade PAH. Use yellow, UV-absorbing shields for fluorescent lights or use
incandescent lighting,
6. Refrigerate samples upon receipt at laboratory.
7. Determine optimum extraction solvent.
a. Allow the preweighed area filter samples to equilibrate 24 hrs with the laboratory
atmosphere.
b. Weigh the area filters. Determine total weight collected on each.
c. Extract the first pair of area filters with acetonitrile, the second with benzene, the
third with cyclohexane, and the fourth with methylene chloride, according to step 8.
NOTE: Use alternate solvents, if appropriate. PAH of interest may be entrained within,
and adsorbed by, particulate matter collected on the filter. It is necessary to
determine the solvent which maximizes recovery of the PAH from each sample
matrix. For example, methylene chloride [2,3] and benzene:ethanol (4:1 v/v) [4]
have been recommended for extraction of PAH from diesel exhaust particulate.
d. Analyze the extracts for the PAH of interest (steps 10 through 18). Normalize the total
mass of PAH found to the mass of sample collected.
e. Choose the solvent which gives the highest recovery of PAH of interest. Use the solvent
chosen to extract the personal filter samples.
8. Extract filters.
a. Add 5.0 mL of the solvent chosen in step 7 to each scintillation vial containing a
filter. Start media and reagent blanks at this step.
b. Cap and let sit 15 to 20 min in an ultrasonic bath.
NOTE 1: Soxhlet extraction may be required when large amounts of highly adsorptive
particulate matter (e.g., fly ash or diesel soot) are present.
NOTE 2: The sample must be dissolved in acetonitrile for chromatography. If needed,
perform solvent exchange as follows:
CAUTION: To avoid loss of volatile components, do not allow the sample to go to
dryness at any time.
(1) After filtration (step 10), take the sample to near dryness in a
Kuderna-Danish extractor.
(2) Add ca. 1 mL acetonitrile, take to near dryness, and adjust final volume to
1.0 mL with acetonitrile and filter again.
9. Desorb PAH from sorbent.
a. Score each sorbent tube with a file in front of the front (larger) sorbent section.
Break tube at score line.
5/15/85 5506-3
-------
POLYNUCLEAR AROHATIC HYDROCARBONS METHOD: 5506
b. Transfer glass wool plug and front sorbent section to a culture tube. Discard the foam
plug. Transfer back sorbent section to a second culture tube.
c. Add 5.0 mL acetonitrile to each culture tube. Cap the culture tubes.
d. Allow samples to sit for 30 min. Swirl occasionally.
10. Filter all sample extracts through an 0.45-ym membrane filter.
CALIBRATION AND QUALITY CONTROL:
11. Calibrate daily with at least five working standards.
a. Dilute aliquots of calibration stock solution with acetonitrile in 10-mL volumetric
flasks (e.g., to 2.5, 0.5, 0.1, 0.02, and 0.002 ug/mL).
b. Intersperse working standards and samples in the measurements.
c. Prepare calibration graphs (peak area vs. ug of each PAH per sample).
12. Recovery and desorption efficiency.
a. Determine recovery (R) from filters and desorption efficiency (DE) from sorbent tubes at
least once for each lot of filters and sorbent tubes used in the range of interest.
(1) Filters. Using a microliter syringe or micropipette, spike four filters at each of
five concentration levels with a mixture of the analytes. Allow the filters to dry
in the dark overnight. Analyze the filters (steps 8, 10, and 14 through 16.
Prepare graphs of R vs. amounts found.
NOTE: This step may not be used for some highly adsorptive particulate matrices for
which calibration by the method of standard additions may be more accurate.
(2) Sorbent tubes. Transfer an unused front sorbent section to a culture tube. Prepare
a total of 24 culture tubes in order to measure DE at five concentration levels plus
blanks in quadruplicate. Using a microliter syringe or micropipette, add
calibration stock solution directly to sorbent. Cap culture tubes and allow to
stand overnight. Analyze (steps 9, 10, and 14 through 16). Prepare graphs of DE
vs. amounts found.
b. Check R and DE at two levels for each sample set, in duplicate. Repeat determination of
R and DE graphs if checks do not agree to within +51 of DE graph.
13. Analyze at least three field blanks for each sample medium.
MEASUREMENT:
14. Set HPLC according to manufacturer's recommendations and to conditions on page 5506-1.
Equilibrate column at 601 CH3CN/401 H20 at 1.0 mL/min for 15 min before injecting first
sample.
15. Inject sample aliquot. Start mobile phase gradient:
a. Linear gradient 601 CHsCN to 1001 O^CN, 20 min.
b. Hold at 1001 CH^CH for 20 min.
NOTE: Hold longer if necessary to prevent carryover of background, e.g., from coal dust.
c. Linear gradient to initial condition, 5 min.
16. Measure peak areas.
NOTE 1: Approximate retention times appear in Table 3.
NOTE 2: If peak area is above the calibration range, dilute with appropriate solvent,
reanalyze, and apply dilution factor in calculations.
NOTE 3: If sample has many interferences, additional sample cleanup may be necessary. Many
cleanup procedures have been published. Liquid-liquid partitioning between
cyclohexane and nitrcmethane [5,6] is widely used, but other techniques may be more
appropriate for specific samples.
5/15/85 5506-4
-------
METHOD: 5506 POLYNUCLEAR AROHATIC HYDROCARBONS
CALCULATIONS:
17. Read the mass, pg (corrected for R or DE) of each analyte found on the filter (W) and
front sorbent (Wf) and back sorbent (HO) sections, and on the average media blank
filter (B) and front sorbent (Bf) and back sorbent (65) sections from the calibration
graphs.
18. Calculate concentration, C (yg/m3), in air as the sum of the particulate concentration
and the vapor concentration using the actual air volume sampled, V (L).
C = (W-B.Wf.Wb-Bf-Bb).lQ3i
V
NOTE: Uf and W^ include analyte originally collected on the filter as particulate, then
volatilized during sampling. This can be a significant fraction for many PAH (e.g.,
fluoranthane, naphthalene, fluorene, anthracene, phenanthrene).
EVALUATION OF METHOD:
The fluorescence detector used in this method is both sensitive and selective. The detector
can "see" as little as 50 pg of many PAH injected on the column. LODs for the 17 analytes
range from 50 to 350 ng per sample. It does not respond to non-fluorescent molecules such as
aliphatics. The method is, therefore, most amenable to determination of trace amounts of PAH
in mixtures of aliphatic compounds. Successful applications include: aluminum reduction
facilities, asphalt fume, coal gasification plants, coal liquefaction plants, coal tar pitch,
coke oven emissions, creosote treatment facilities, diesel exhaust, graphite electrode
manufacturing, petroleum pitch, and roofing tearoff operations.
This method has been evaluated by analyzing spiked filters, spiked sorbent tubes, and complete
spiked sampling trains through which were drawn 500 L of air [7]. Each of the three groups was
spiked with each analyte at two concentration levels in sextuplicate. Particular note should
be made that the effect of particulate matter has not been evaluated, and every sampling matrix
is unique. The data on the following page were obtained on spiked samplers stored refrigerated
in the dark for three months followed by measurement with HPLC.
5/15/85 5506-5
-------
CALIBRATION RANGE (
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
COMPOUND
ACENAPHTHENE
ACENAPHTHYLENE
ANTHRACENE
BENZ[a]ANTHRACENE
BENZO[b]FLUORANTHENE
BENZO[k IFLUORANTHENE
BENZO[ghi]PERYLENE
BENZO[a]PYRENE
BENZO[e]PYRENE
CHRYSENE
DIBENZta , h ]ANTHRACENE
FLUORANTHENE
FLUORENE
INDENO[ 1 ,2 ,3-cd]PYRENE
NAPHTHALENE
PHENANTHRENE
PYRENE
(ug per sample)
2.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0 -
0 -
4 -
4 -
4 -
4 -
5 -
4 -
5 -
4 -
0.5 -
0.
0.
0.
0.
4 -
7 -
5 -
6 -
0.4 -
0.5 -
13
100
13
13
12
13
25
14
13
12
25
13
13
12
13
13
13
LOO
ug per
sample)
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.8
.35
.05
.15
.1
.15
.2
.2
.2
.15
.2
.15
.25
.2
.25
.1
.2
MEASUREMENT PRECISION
SPIKED +
t_
SPIKED9
.058
.032
.039
.032
.027
.025
.031
.027
(O
.039
.026
.026
.031
.044
.041
.036
(C)
S
S
S
F
F
F
F
F
AIR°
.093
.075
.037
.064
.028
.027
.029
.029
(50)
(100)
(5)
(5)
(10)
(1)
(10)
(5)
(0
F
F
S
S
F
S
S
.024
.029
.050
.090
.032
.125
.070
(5)
(10)
(10)
(10)
(10)
(50)
(2)
(C)
aRSD for filter (F) where volatilization is nil or for sorbent (S) where substantial
volatilization may occur during sampling.
bRSD determined at the pg level shown in parenthesis for a spiked filter followed by a
sorbent tube. After spiking, laboratory air was drawn through the sampling train at 2 L/min
for 4 hrs.
cNot determined.
REFERENCES:
[1] NIOSH Manual of Analytical Methods, 2nd ed., Vol. 1, U.S. Department of Health, Education.
and Welfare, Publ. (NIOSH) 77-157-A (1977).
[2] Breuer, G. M. Anal. Lett.. V7(A11). 1293-1306 (1984).
[3] Zweidinger, R. B., S. B. Tejada, D. Dropkins, 0. Huisingh, and L. Claxton. "Characteriza-
tion of Extractable Organics in Diesel Exhaust Particulate," paper presented at Symposium
on Diesel Particulate Emissions Measurement Characterization, Ann Arbor, MI (1978).
[4] Swarin, S. J. and R. L. Williams. "Liquid Chromatographic Determination of Benzo[a]pyrene
in Diesel Exhaust Particulate: Verification of the Collection and Analytical Methods,"
Polynuclear Aromatic Hydrocarbons: Physical and Biological Effects. Bjorseth, A. and
Dennis, Eds., Battelle Press, 771-790 (1980).
[5] Wise, S. A., et al_. "Analytical Methods for the Determination of Polycyclic Aromatic
Hydrocarbons on Air Particulate Matter," Polynuclear Aromatic Hydrocarbons: Physical and
Biological Chemistry. Cooke, Dennis and Fisher, Eds., Battelle Press, 919-929 (1982).
[6] Novotny, M., H. L. Lee and K. D. Bartle. 0. Chroma tog. Sci.. J2, 606-612 (1974).
[7] Backup Data Report for Method 5506, Analytical Report for NIOSH Sequence 4170 (NIOSH
unpublished, March 16, 1984). '
[8] Studt., P., Liebigs Ann. Chem.. 528 (1978).
[9] Clar, E. Polycyclic Hydrocarbons. Academic Press (1964).
[10] Handbook of Chemistry and Physics, 62nd ed., CRC Press (1982).
METHOD REVISED BY: B. R. Bel inky and E. J. Slick, NIOSH/DPSE.
5/15/85 5506-6
-------
HETHOO: 5506
Table 1. Formulae and physical properties.
COMPOUND (bv H.W.)
1. NAPHTHALENE
2. ACENAPHTHYLENE
3. ACENAPHTHENE
4. FLUORENE
5. ANTHRACENE
6. PHENANTHRENE
7. FLUORANTHENE
8. PYRENE
9. BENZ[a]ANTHRACENE
10. CHRYSENE
11. BENZO[b]FLUORANTHENE
12. BENZO[k]FLUORANTH£NE
13. BENZO[a]PYRENE
14. BENZO[e]PYRENE
15. BENZO[ghi]P£RYLENE
16. INDENO[l,2,3-cd]PYRENE
17. DIBENZ[a,h]ANTHRACENE
EMPIRICAL
FORMULA
ClQHs
C12H8
C12H10
Cl3"lO
C14H10
C14H10
Cl6»10
C16H10
C18H12
C18H12
C20H12
C20H12
C20H12
C20H12
C22H12
C22H12
C22H14
MOLECULAR
WEIGHT
128.17
152.20
154.21
166.22
178.23
178.23
202.26
202.26
228.29
228.29
252.32
252.32
252.32
252.32
276.34
276.34
278.35
DETECTOR
UV
UV
UV
UV
UV
UV
FL
FL
FL
UV
FL
FL
FL
FL
FL
FL
FL
MELTING
POINT
(OQ)
80
92-93
96.2
116
218
100
110
156
158-159
255-256
168
217
177
178-179
273
161.5-163
262
BOILING
POINT
(°Q*
218
265-275
279
293-295
340
340
—
399
—
—
—
480
—
—
—
—
—
REF.
[9]
[10]
[10]
[9]
[9]
[9]
[9]
[9]
[9]
[9]
[9]
[10]
[9]
[9]
[9]
[8]
[9]
*Many of these compounds will sublime.
Table 2. Synonyms.
COMPOUND (alphabetically)
1. ACENAPHTHENE
2. ACENAPHTHYLENE
3. ANTHRACENE
4. BENZ[a]ANTHRACENE
5. BENZO[b]FLUORANTHENE
6. BENZO[k]FLUORANTHENE
7. BENZO[ghi]PERYLENE
8. BENZO[a]PYRENE
9. BENZO[e]PYRENE
10. CHRYSENE
11. OIBENZ[a,h]ANTHRACENE
12. FLUORANTHENE
13. FLUORENE
14. INDEMOn.2.3-cd]PYRENE
15 NAPHTHALENE
16. PHENANTHRENE
17. PYRENE
SYNONYMS
CAS* 83-32-9
CAS* 208-96-8
CAS* 120-12-7
1,2-benzanthracene; benzo[b]phenanthrene; 2B3-benzophenanthrene;
tetraphene; CAS* 56-55-3
3,4-benzofluoranthene; 2,3-benzofluoranthene;
benz[e]acephenanthrylene; B[b]F; CAS* 205-99-2
11,12-benzofluoranthene; CAS* 207-08-9
1,12-benzoperylene; CAS* 191-24-2
3,4-benzopyrene; 6,7-benzopyrene;'B[a]P; BP; CAS* 50-32-8
1,2-benzopyrene; 4.5-benzopyrene; B[e]P; CAS* 192-97-2
1,2-benzophenanthrene; benzo[a]phenanthrene; CAS* 218-01-9
1,2,5,6-dibenzanthracene; CAS* 53-70-3
benzo[jk]fluorene; CAS* 206-44-0
CAS* 86-73-7
2,3-phenylenepyrene; CAS* 193-39-5
naphthene; CAS* 91-20-3
CAS* 85-01-8
benzo[def]phenanthrene; CAS*129-00-0
5715/85
5506-7
-------
POLYNUCLEAR AROHATIC HYDROCARBONS
METHOD: 5506
Table 3. Approximate PAH retention times.
COMPOUND
1. NAPHTHALENE
2. ACENAPHTHAIENE
3. ACENAPHTHENE
4. FLUORENE
5. PHENANTHRENE
6. ANTHRACENE
7. FLUORANTHENE
8. PYRENE
9. BENZ[a]ANTHRACENE
10. CHRYSENE
11. BENZO[e]PYRENE
12. BENZO[b]FLUORANTHENE
13. BENZO[k]FLUORANTHENE
14. BENZO[a]PYRENE
15. OIBENZ[a,h]ANTHRACENE
16. BENZO[ghi]PERYLENE
17. INOENO[l,2,3-cd]PYRENE
RETENTION TIME (min)*
2.4
2.8
3.6
3.9
4.7
5.8
6.8
7.7
11.2
12.1
14.0
14.8
16.5
17.3
20.0
20.0
21.2
*NOTE: Determined with a Perkin-Elmer HC-ODS-SILX column. Actual retention times will vary
with individual columns and column age.
5/15/85
5506-8
-------
METHOD: 5506
POLYNUCLEAR AROMATIC HYDROCARBONS
ACENAPHTHENE
ACENAPHTHYLENE
ANTHRACENE
BENZQcOANTHRACENE BENZOCWFLUORANTHENE BENZOOQFLUORANTHENE
BENZOC9 h HPERYLENE BENZOCeOPYRENE
CHRYSENE
DIBENZCa.h} ANTHRACENE
INDENOCl,2,3-c d^PYRENE
PHENANTHRENE PYRENE
Figure 1. Structures of PAH.
BENZOQOPYRENE
FLUORANTHENE
NAPHTHALENE
5/15/85
5506-9
-------
TECHNICAL REPORT DATA
Please read instructions on the reverse before completing
1. REPORT NO.
EPA^t54/R-99-002c
2.
4. TITLE AND SUBTITLE
Final Report - Emissions Testing of Combustion Stack and Pushing Operations at Coke
Battery No. 5/6 at ABC Coke in Birmingham, Alabama
Volume III of III
7. AUTHOR(S)
Franklin Meadows
Daniel F. Scheffel
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Pacific Environmental Services, Inc.
Post Office Box 12077
Research Triangle Park, North Carolina 27709-2077
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Office of Air Quality Planning and Standards
Emissions, Monitoring and Analysis Division
Research Triangle Park, North Carolina 2771 1
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
February 1999
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-D-98-004
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
The United States Environmental Protection Agency (EPA) is investigating the coke making industry to characterize hazardous air pollutants (HAPs)
emitted from coke pushing operations and combustion (underfire) stacks. This test report addresses pushing emissions from a coke oven, and emissions
from the combustion (underfire) stack that serves Coke Battery No. 5/6 at ABC Coke in Birmingham, Alabama. The purpose of this test program was to
quantify emissions from the inlet and outlet of the baghouse controlling emissions from the coke pushing operation and to quantify emissions from the
combustion outlet stack. The data may be used by the EPA in the future to support a residual risk assessment for coke oven facilities.
The testing was performed to quantify uncontrolled and controlled air emissions of filterable particulate matter (PM), methylene chloride extractable
matter (MCEM) and 19 polycyclic aromatic hydrocarbons (PAHs) including acenaphthene, acenaphthylene, anthracene, benzo(a)anthracene,
benzo(a)pyrene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(k)fluoranthene, benzo(ghi)perylene, chrysene, dibenzo(a,h)anthracene, fluoranthene,
fluorene, indeno(l,2,3-cd)pyrene, 2-methylnapthalene, napthalene, perylene, phenanthrene, and pyrene. In addition, following the PM and MCEM
analyses, the samples were analyzed to screen for the presence of 17 trace metals. Baghouse dust samples were also collected and analyzed for 16 trace
metals. Simultaneous testing was performed at the inlet and outlet of the baghouse controlling emissions from the coke pushing operation. Sampling
was also performed on the combustion outlet stack. In addition to pollutant testing, oxygen (O2) and carbon dioxide (COJ were measured at each
location. During the sampling program, Research Triangle Institute (RTI), another EPA contractor, monitored and recorded process and emission
control system operating parameters.
This volume (Volume HI) is comprised of 379 pages and consists of Appendices: E (Calculations), F (QA/QC Data), G (Participants), and
H (Sampling and Analytical Procedures).
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTIONS
Baghouse
Coke Ovens
Emission Measurements
Hazardous Air Pollutants
Metals
Methylene Chloride Extractable
Matter
Particulate Matter
Polycyclic Aromatic Hydrocarbons
18. DISTRIBUTION STATEMENT
Unlimited
b. IDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (This Report)
Unclassified
20. SECURITY CLASS (This page)
Unclassified
c. COASTI Field/Group
21. NO. OF PAGES
1647
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION IS OBSOLETE
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