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EPA-340/1-84-001 b
VOC Sampling and
Analysis Workshop
Volume II
Papers and Lecture Notes
U.S. Environmental Protection Agency
EPA LIBRARY SERVICES RTPNC , ^
CnA ,^nM QA rwvih
EPA-340/1-84-UU1D
TECHN.CAL DOCUMENT COLLECT.ON
US ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF AIR QUALITY PLANNING AND STANDARDS
STATIONARY SOURCE COMPLIANCE DIVISION
WASHINGTON, DC 20460
-------
EPA-340/1 -84-001 b
VOC Sampling and Analysis Workshop
Volume II. Papers and Lecture Notes
Prepared by
PEDCo Environmental, Inc.
11499 Chester Road
Post Office Box 46100
Cincinnati, Ohio 45246-0100
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Stationary Source Compliance Division
Washington, D.C. 20460
September 1983
EPA-
-------
INTENDED PURPOSE
This is not an official policy and standards document. The opinions,
findings, and conclusions are those of the authors and not necessarily those
of the Environmental Protection Agency. Every attempt has been made to repre-
sent the present state of the art as well as subject areas still under eval-
uation. Any mention of products or organizations does not constitute endorse-
ment by the Unites States Environmental Protection Agency.
This document is issued by the Stationary Source Compliance Division,
Office of Air Quality Planning and Standards, USEPA. It is for use in work-
shops presented by Agency staff and others receiving contractual or grant
support from the USEPA. It is part of a series of instructional manuals
addressing VOC compliance testing procedures.
Governmental air pollution control agencies establishing training pro-
grams may receive single copies of this document, free of charge, from the
Stationary Source Compliance Division Workshop Coordinator, USEPA, MD-7,
Research Triangle Park, NC 27711. Since the document is specially designed
to be used in conjunction with other training materials and will be updated
and revised as needed periodically, it is not issued as an EPA publication
nor copies maintained for public distribution.
-------
CONTENTS
Page
Summary of Test Methods 1
EPA List of 37 Pollutants 5
Part 60 - Amended 48 FR No. 161 8-18-83 7
Lecture 401—Overview of EPA VOC Emissions Measurement Methods
and Standards A-l
Lecture 402--Review of Organic Chemistry B-l
Lecture 403--App]ication of EPA VOC Reference Methods C-l
Lecture 404--Quality Assurance for VOC Testing
Method 106--Determination of Vinyl Chloride from Stationary
Sources D-l
Supplement A--Determination of Adequate Chromatographic Peak
Resolution D-5
EPA's Quality Assurance Program D-9
Lecture 405--Role of Agency Observer
Observation and Evaluation of Stationary Source Performance
Standards E-l
Lecture 406--Material Balance and Equipment Specifications as
Compliance Evaluation Techniques
Compliance Evaluation Using Material Balance and Equipment
Specifications F-l
Lecture 501--Integrated Bag Sampling and Analysis G-l
Lecture 502--Adsorption Sampling Techniques H-l
Lecture 503--Direct Interface Sampling and Analysis 1-1
Lecture 504--VOC Analysis by Gas Chromatography J-l
Lecture 601--Method 1A - Sample and Velocity Traverses for
Stationary Sources with Small Stacks or Ducts K-l
Lecture 602--Method 2A - Direct Measurement of Gas Volume Through
Pipes and Small Ducts L-l
m
-------
CONTENTS (continued)
Page
Lecture 603--Method 2B - Determination of Exhaust Gas Volume Flow
Rate from Gasoline Vapor Incinerators M-l
Lecture 604--Method 2C - Determination of Stack Gas Velocity and
Volumetric Flow Rate from Small Stacks or Ducts (Standard Pitot
Tube) N-l
Lecture 606--Method 18 - Measurement of Gaseous Organic Compound
Emissions by Gas Chromatography 0-1
Lecture 607--Method 21 - Determination of Volatile Organic Compound
Leaks P-l
Lecture 608--Method 23 - Determination of Halogenated Organics from
Stationary Sources Q-l
Lecture 609--Method 24 - Determination of Volatile Matter Content,
Water Content, Density, Volume Solids, and Weight Solids of Sur-
face Coatings R-l
Lecture 610--Method 24A - Determination of Volatile Matter Content
and Density of Printing Inks and Related Coatings S-l
Lecture 611--Method 25 - Determination of Total Gaseous Nonmethane
Organic Emissions as Carbon T-l
Lecture 612--Method 25A - Determination of Total Gaseous Organic
Concentration Using Flame lonization Analyzer U-l
Lecture 613--Method 25B - Determination of Total Gaseous Organic
Concentration Using a Nondispersive Infrared Analyzer V-l
Lecture 614--Method 27 - Determination of Vapor Tightness of
Gasoline Delivery Tank Using Pressure Vacuum Test W-l
IV
-------
SUMMARY OF TEST METHODS
March 3, 1982/RTS
Method
1-8
1A
1R
2A
2B
2C
3R
4R.5R
5R
5A
5B
5C
6A
6B
7A
6R,7R
9
9A
10
11
12
Reference
42 FR 41754
43 FR 11984
Tentative
Tentative
45 FR 83126
45 FR 83126
Tentative
Tentative
Tentative
45 FR 66752
45 FR 76404
Tentative
Tentative
46 FR 08352
46 FR 08352
Tentative
Tentative
39 FR 39872
46 FR 53144
39 FR 09319
43 FR 01494
47 FR 16564
08/18/77
03/23/78
12/17/80
12/17/80
10/07/80
11/18/80
01/26/81
01/26/81
11/12/74
10/28/81
03/08/78
01/10/78
04/16/82
PP
PP
PP
PP
PP
Description
Velocity, Orsat, PM, S02, NO , etc.
Corr. and amend, to M-l thru 8
Traverse points in small ducts
Revision to reduce number of traverse points
Flow rate in small ducts
Flow rate by stoichiometry
Flow rate in small ducts
Addition of QA/QC
Addition of QA/QC
Filter specification change
PM from asphalt roofing (PP as M-26)
Nonsulfuric acid particulate matter
PM from small ducts
so2/co2
Auto S02/C02
Ion chromatograph NO analysis
Addition of QA/QC
Opacity
Lidar opacity
CO
Pb
Key contact
Roger Shigehara
Gary McAlister
Pete Westlin
Roger Shigehara
Roger Shigehara
Pete Westlin
Pete Westlin
Bill Grimley
Pete Westlin
Pete Westlin
Roger Shigehara
Pete Westlin
Roger Shigehara
Gary McAlister
Pete Westlin
Pete West! in
Pete Westlin
Foston Curtis
Foston Curtis
Pete Westlin
Art Dybdal
Pete Westlin
Foston Curtis
Bill Grimley
Telephone
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
303-234-4658
919-541-2237
919-541-2237
919-541-2237
(continued)
-------
Summary of Test Methods (continued)
Method
13A
13B
14
15
16
16A
17
18
19
19A
20
21
22
23
24
24A
25
25A
25B
27
Reference
45
45
45
45
43
43
43
44
46
43
FR
FR
FR
FR
FR
FR
FR
FR
FR
FR
41852
41852
85016
44202
10866
07568
34784
02578
31904
07568
06/20/80
06/20/80
12/24/80
06/30/80
03/15/78
02/23/78
08/07/78
01/12/79
06/18/81
02/23/78
PP
Tentative
44
44
46
45
45
45
45
45
45
45
45
FR
FR
FR
FR
FR
FR
FR
FR
FR
FR
FR
Other
33580
52792
01160
76404
39766
65956
71538
65956
83126
83126
83126
methods
06/11/79
09/10/79
01/05/81
11/18/80
06/11/80
10/03/80
10/28/80
10/03/80
12/17/80
12/17/80
12/17/80
PP
PP
PP
PP
PP
PP
(continued)
Description
F, colorimetric method
F, SIE method
Corr. to M-13A and 13B
F from roof monitors
TRS from petroleum refineries
TRS from kraft pulp mills
Amendments to M-16, hLS loss after filter
Amendments to M-16, S0? scrubber added
TRS alternative
PM, in-stack
VOC, general GC method
F-factor, coal sampling
NO from gas turbines
X
VOC leaks
Fugitive VE
Halogenated OC
Solvent in surface coatings
Solvent in ink (PP as M-29)
TGNMO
TOC/FID
TOC/NDIR
Tank truck leaks
Ammonium nitrate PM, Urea PM
Key contact
Gary McAlister
Gary McAlister
Bill Grimley
Gary McAlister
Foston Curtis
Gary McAlister
Foston Curtis
Foston Curtis
Roger Shigehara
Bill Grimley
Pete Westlin
Pete Westlin
Pete Westlin
Winton Kelley
John Brown
Bill Grimley
Gary McAlister
Gary McAlister
Gary McAlister
Pete Westlin
Pete Westlin
Winton Kelley
Telephone
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
919-541-
2237
2237
2237
2237
2237
2237
5543
2237
2237
2237
2237
2237
2237
2237
5543
-------
Summary of Test Methods (continued)
oo
Method Reference
101 47 FR 24703 06/08/82
101A 47 FR 24703 06/08/82
102 47 FR 24703 06/08/82
103 38 FR 08820 04/06/73
104 38 FR 08820 04/06/73
105 40 FR 48299 10/14/75
106R 45 FR 76346 11/18/80
107R 45 FR 76346 11/18/80
107A 46 FR 12188 02/12/81
109 Tentative
Other methods
PP
PP
PP
Description
Hg in air streams
Hg in sewage slude incinerators
Hg in H« streams
Be, screening method
Be
Hg in sewage sludge
VC
VC in process streams
VC in process streams
Coke oven VE
As
PS-1R 44 FR 58602 10/10/79 PP Opacity
PS-2R 46 FR 08352 01/26/81 PP SO- and NO
£ A
PS-3R 46 FR 08352 01/26/81 PP C02 and 02
PS-4 Tentative CO
PS-5 46 FR 37287 07/20/81 PP TRS
Key contact
Foston Curtis
(PP as M-lll) Foston Curtis
Foston Curtis
Bill Grimley
Bill Grimley
Foston Curtis
Bill Grimley
Bill Grimley
Bill Grimley
John Brown
Pete Westlin
Pete Westlin
Roger Shigehara
Pete Westlin
Roger Shigehara
Pete Westlin
Foston Curtis
Telephone
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541-2237
919-541
919-541
919-541-
919-541-
919-541-
919-541-
-2237
-2237
2237
2237
2237
2237
-------
EPA LIST OF 37 POLLUTANTS
Acetaldehyde
Acrylonitrile
Benzyl Chloride
Cadmium
Chiorobenzene
Chloroprene
o-,m-,p- Cresol
Dimethyl Nitrosamine
Epichlorohydrin
Ethylene Oxide
Hexachlorocyclopentadiene
Methylene Chloride
(dichloromethane)
Manganese
Nitrobenzene
Perchloroethylene
Phosgene
Propylene Oxide
Trichloroethylene
o-,m-,p- Xylene
Acrolein
Ally! Chloride
Beryllium
Carbon Tetrachloride
Chloroform
Coke Oven Emissions
p-Dichlorobenzene
Dioxin
Ethylene Dichloride
Formaldehyde
Maleic Anhydride
Methyl Chloroform
(1,1,1 trichloroethane)
Nickel
Nitrosomorpholine
Phenol
Polychlorinated Biphenyls
Toluene
Vinylidene Chloride
-------
Federal Register / Vol. 48. No. 161 / Thursday. August 18. 1983 / Rules and Regulations
Dated: August 4.1983.
William D. Ruckelshaus,
Administrator,
PART 60—[AMENDED]
40 CFR Part 60 is amended as follows:
1. By adding a new subpart as follows:
Subpart XX—Standards of Performance for
Bhik GasoHne Terminala
Sec.
60.500 Applicability and designation of
affected facility.
60.501 Definitions.
60.502 Standards for Volatile Organic
Compound (VOC) emissions from bulk
gasoline terminals.
60.503 Test methods and procedures.
60.504 [Reserved.]
60.505 Reporting and recordkeeping.
60,506 Reconstruction.
Authority: Sections 111 and 301(a) of the
Clean Air Act as amended [42 U.S.C. 7411.
7601(a)]. and additional authority as noted
below.
Subpart XX—Standard* of
Performance for Bulk GasoHne
Terminate
560.500 Applicability and designation of
affected facflKy.
(a) The affected facility to which the
provisions of this subpart apply is the
total of all the loading racks at a bulk
gasoline terminal which deliver liquid
product into gasoline tank trucks.
(b) Each facility under paragraph (a)
of this section, the construction or
modification of which is commenced
after December 17,1980, is subject to the
provisions of this subpart
(c) For purposes of this subpart any
replacement of components of an
existing facility, described in paragraph
8 60.500(a). commenced before August
18,1983 in order to comply with any
emission standard adopted by a State or
political subdivision thereof will not be
considered a reconstruction under the
provisions of 40 CFR 60.15.
[Note: The intent of these standards is to
minimi™ the emissions of VOC through the
application of best demonstrated
technologies (BUT). The numerical emission
limits in this standard are expressed in terms
of total organic compounds. This emission
limit reflects the performance of BDT.j
5 60.501 Deflnittona.
The terms used in this subpart are
defined in the Clean Air Act hi 9 60.2 of
this part or in this section as follows:
"Bulk gasoline terminal" means any
gasoline facility which receives gasoline
by pipeline, ship or barge, and has a "
gasoline throughput greater than 75JOO
liters per day. Gasoline throughput shall
be the m."*'"""" calculated design
throughput as may be limited by
compliance with an enforceable
condition under Federal, State or local
law and discoverable by the
Administrator and any other person.
"Continuous vapor processing
system" means a vapor processing
system that treats total organic
compounds vapors collected from
gasoline tank trucks on a demand basis
without intermediate accumulation La a
vapor holder.
"Existing vapor processing system"
means a vapor processing system
[capable of achieving emissions to the
atmosphere no greater than 80
milligram^ of total organic compounds
per liter of gasoline loaded], the
construction or refurbishment of which
was commenced before December 17,
1980, and which was not constructed or
refurbished after that date.
"Gasoline" means any petroleum
distillate or petroleum distillate/alcohol
blend having a Reid vapor pressure of
27.6 kilopascals or greater which is used
as a fuel for internal combustion
- engines.
"Gasoline tank truck" means a
delivery tank truck used at bulk gasoline
terminals which is loading gasoline or
which has loaded gasoline on the
immediately previous load.
"Intermittent vapor processing
system" means a vapor processing
system that employs an intermediate
vapor holder to accumulate total organic
compounds vapors collected from
gasoline tank trucks, and treats the
accumulated vapors only during
automatically controlled cycles.
"Loading rack" means the loading
arms, pumps, meters, shutoff valves,
relief valves, and other piping and
valves necessary to fill delivery tank
trucks.
"Refurbishment" means, with
reference to a vapor processing system,
replacement of components of. or'
addition of components to, the system
within any 2-year period such that the
fixed capital cost of thenew
components required for such
component replacement or addition
exceeds 50 percent of the cost of a
comparable entirely new system.
'Total organic compounds" means
those compounds measured according to
the procedures in 8 60.503.
"Vapor collection system" means any
equipment used for containing total
organic compounds vapors displaced
during the loading of gasoline tank
trucks.
"Vapor processing system" means all
equipment used for recovering or
oxidizing total organic compound*
vapors displaced from the affected
.facility.
"Vapor-tight gasoline tank truck"
means a gasoline tank truck which has
demonstrated within the 12 preceding
months that its product delivery tank
will sustain a pressure change of not
more than 750. pascals (75 mm of water)
within 5 minutes after it is pressurized
to 4,500 pascals (450 mm of water). This
capability is to be demonstrated using
the pressure test procedure specified in
Reference Method 27.
§60.502 Standard for Volatile Organic
Compound (VOC) emtealona from bulk
gasoline terminals. •
"On and after the date on which
§ 60.8(b) requires a performance test to
be completed, the owner or operator of
each bulk gasoline terminal containing
an affected-facility shall comply with
the requirements of this section.-
(a) Each affected facility shall be
equipped with a vapor collection system
designed to collect the total organic
compounds vapors displaced from tank
trucks during product loading.
(b) The emissions to the atmosphere
from the vapor collection system due to
the loading of liquid product into
gaso.line tank trucks are not to exceed 35
milligrams of total organic compounds
per liter of gasoline loaded, except as
noted in paragraph (c) of this section.
(c) For each affected facility equipped
with an existing vapor processing
system, the emissions to the atmosphere
from the vapor collection system due to
the loading of liquid product into
gasoline tank trucks are not to exceed 80
milligrams of total organic compounds
per liter of gasoline loaded.
(d) Each vapor collection system shall
be designed to prevent any total organic
compounds vapors collected at one
loading rack from passing to another
loading rack. '
(e) Loadings of liquid product into
gasoline lank trucks shall be limited to
vapor-tight gasoline tank trucks using
the following procedures:
(1) The owner or operator shall obtain
the vapor tightness documentation
described hi { 60.505(b) for each
gasoline tank truck which is to be
loaded at the affected facility.
(2) The owner or operator shall
require the tank identification number to
be recorded as each gasoline tank truck
is loaded at the affected facility.
(3) The owner or operator shall cross-
check each tank identification number
obtained in (e)(2) of this section with the
file of tank vapor tightness
documentation within 2 weeks after the
corresponding tank is loaded.
(4) The terminal owner or operator
shall notify the owner or operator of
each nonvapefetight gasoline tank truck
loaded at the affected facility within 3
weeks after the loading has occurred
-------
(5) The terminal owner or operator
shall take steps assuring that the
nonvapor-tight gasoline tank truck will
not be reloaded at the affected facility
until vapor tightness documentation for
that tank is obtained.
(6) Alternate procedures to those
described in (e)(l) through (5) of this
section for limiting gasoline tank truck
loadings may be used upon application
to, and approval by, the Administrator.
(f) The owner or operator shall act to
assure that loadings of gasoline tank
trucks at the affected facility are made
only into tanks equipped with vapor
collection equipment that is compatible
with the terminal's vapor collection
system.
(g) The owner or operator shall act to
assure that the terminal's and the tank
truck's vapor collection systems are
connected during each loading of a
gasoline tank truck at the affected
facility. Examples of actions to
accomplish this include training drivers
in the hookup procedures and posting
visible reminder signs at the affected
loading racks.
(h) The vapor collection and liquid
loading equipment shall be designed and
operated to prevent gauge pressure in
the delivery tank from exceeding 4,500
pascals (450 mm of water) during
product loading. This level is not to be
exceeded when measured by the
procedures specified in § 60.503(b).
(i) No pressure-vacuum vent in the
bulk gasoline terminal's vapor collection
system shall begin to open at a system
pressure less than 4.500 pascals (450 mm
of water).
(j) Each calendar month, the vapor
collection system, the vapor processing
system, and each loading rack handling
gasoline shall be inspected during the
loading of gasoline tank trucks for total
organic compounds liquid or vapor
leaks. For purposes of this paragraph,
detection methods incorporating sight,
sound, or smell are acceptable. Each
detection of a leak shall be recorded and
the source of the leak repaired within 15
calendar days after it is detected.
(Approved by the Office of Management and
Budget under control number 2060-0006)
S 60.503 Test methods and procedures.
(a) Section 60.8(f) does not apply to
the performance test procedures
required by this subpart.
(b) For the purpose of determining
compliance with § 60.502(h), the
following procedures shall be used:
(1) Calibrate and install a pressure
measurement device (liquid manometer,
magnehelic gauge, or equivalent
instrument), capable of measuring up to
500 mm of water gauge pressure with
±2.5 mm of water precision.
(2) Connect the pressure measurement
device to a pressure tap in the terminal's
vapor collection system, located as close
as possible to the connection with the
gasoline tank truck.
(3) During the performance test,
record the pressure every 5 minutes
while a gasoline tank truck is being'
loaded, and record the highest
instantaneous pressure that occurs
during each loading. Every loading
position must be tested at least once
during the
(c) For the purpose of determining
compliance with the mass emission
limitations of i 60-502(b) and (c), the
following reference methods shall be
used: I
(1) For the determination of volume at
the exhaust vent:
(i) Method 2B for combustion vapor
processing systems.
(ii) Method 2A for all other vapor
processing systems.
(2) For the determination of total
organic compounds concentration at the
exhaust vent. Method 25A or 25B, The
calibration gas shall be either propane
or butane.
(d) Immediately prior to a
performance test required for
determination of compliance with
§ 60.5Q2(b), {c), and (h), all potential
sources of vapor leakage in the
terminal's vapor collection system
equipment shall be monitored for leaks
using Method 21. The monitoring shall
be conducted only while a-gasoline tank
truck is being loaded. A reading of
10,000 ppmv or greater as methane shall
be considered a leak. All leaks shall be
repaired prior to conducting the
performance test
(e) The test procedure for determining
compliance with § 60.502(b) and (c) is as
follows:
(1) All testing equipment shall be
prepared and installed as specified in
the appropriate test methods.
(2) The time period for a performance
test shall be not less than 6 hours,
during which at least 300,000 liters of
gasoline are loaded. If the throughput
criterion is not met during the initial 6
hours, the test may be either continued
until the throughput criterion is met, or
resumed the next day with another
complete 6 hours of testing. As much as
possible, testing should be conducted
during the 6-hour period in which the
highest throughput normally occurs.
(3) For intermittent vapor processing
systems:
(i) The vapor holder level shall be
recorded at the start of the performance
test. The end of the performance test
shall coincide with a time when the
vapor holder is at its original level.
(ii) At-least two startups and
shutdowns of the vapor processor shall
occur during the performance test. If this
does not occur under automatically
controlled operation, the system shall be
manually controlled.
(4) The volume of gasoline dispensed
during the performance test period at all
loading racks whose vapor emissions
are controlled by the processing system
being tested shall be determined. This
volume may be determined from x
terminal records or from gasoline
dispensing meters at each loading rack.
(5) An emission testing interval shall
consist of each 5-minute period during
the performance test For each interval:
(i) The reading from each
measurement instrument shall be
recorded, and
(ii) The volume exhausted and the
average total organic compounds
concentration in the exhaust vent shall
be determined, as specified in the
appropriate test method. The average
total organic compounds concentration
shall correspond to the volume
measurement by taking into account the
sampling system response time.
(6) The mass emitted during each
testing interval shall be calculated as
follows:
M.,=10-
-------
(f) The owner or operator may adjust
the emission results to exclude the
methare and ethane content in the
exhaust vent by any method approved
by the Administrator.
[Sec. 114 of the Clean Air Act as amended (42
U.S.C. 7414])
(Approved by the Office of Management and
Budget under control number 2060-0006.)
S 64504 [Reserved].
} 60.505 Reporting and racordkecplng.
(a) The tank truck vapor tightness
documentation required under
160.502(e)(l) shall.be kept on file at the
terminal in a permanent form available
for inspection.
(b) The documentation file for each
gasoline tank truck shall be updated at
least once per year to reflect current test
results as determined by Method 27.
This documentation shall include, as a
minimum, the following information:
(1) Test Title: Gasoline Delivery Tank
Pressure Test—EPA Reference Method
27.
(2) Tank Owner and Address.
(3) Tank Identification Number.
(4) Testing Location.
(5) Date of Test.
(6) Tester Name and Signature.
(7) Witnessing Inspector, if any:
Name, Signature, and Affiliation.
(8) Test Results: Actual Pressure
Change in 5 minutes, mm of water
(average for 2 runs).
(c) A record of each monthly leak
inspection required under S 60.502(j)
shall be kept on file at the terminal for
at least 2 years. Inspection records shall
include, as a minimum, the following
information: ^
(1) Date of Inspection.
(2) Findings (may indicate no leaks
discovered; or location, nature, and
severity of each leak).
(3) Leak determination method.
(4) Corrective Action (date each leak
repaired; reasons for any repair interval
in excess of 15 days).
(5) Inspector Name and Signature.
(d) The terminal owner or operator
shall keep documentation of all
notifications required under
S 60.5Q2(e)(4) on file at the terminal foe '
at least 2 years.
fe) [Reserved].
(f) The owner or operator of an
affected facility shall keep records of all
replacements or additions of
components performed on an existing
vapor processing system for at least 3
years.
[Sec. J14 of the Clean Air Act as amended (42
U.S.C. 7414)]
(Approved by the Office of Management and
Budget under control number 2060-0008.)
§ 60.606 Reconstruction.
For purposes of this subpart:
(a) The cost of the following
frequently replaced components of the
affected facility shall not be considered
in calculating either the "fixed capital
cost of the new components" or the
"fixed capital costs that would be
required to construct a comparable
entirely new facility" under § 6045:
pump seals, loading arm gaskets and
swivels, coupler gaskets, overfill sensor
couplers and cables, flexible vapor
hoses, and grounding cables and
connectors.
(b) Under S 60.15, the "fixed capital
cost of the new components" includes
the fixed capital cost of all depreciable
components (except components
specified in § 60.506(a)] which are or
will be replaced pursuant to all
continuous programs of component
replacement which are commenced
within any 2-year period following
December 17,1980. For purposes of this
paragraph, "commenced" means that an
owner or operator has undertaken a
continuous program of component
replacement or that an owner or
operator has entered into a contractual
obligation to undertake and complete,
within a reasonable time, a continuous
program of component replacement
(Sec. 114 of the Clean Air Act as amended (42
'U.S.C. 7414)]
• 2. By adding five new Reference
Methods (Method 2A, Method 2B.
Method 25A. Method 25B, and Method
27) to Appendix A as follows:
Appendix A—Reference Methods
-------
SLIDE 401-1 .
NOTES
voc
VOLATILE ORGANIC
COMPOUNDS
SLIDE 401-2
6O%
All Other
Sources
4O%
Mobile
Vr
VOC Problem — SO million tons
SLIDE 401-3
AM QUALITY
CONTROL HEGKXIS
A-l
-------
SLIDE 401-4 NOTES
lowATTAinMtntT or rtiOTOcncniCAL
OXIDAItTS, AUGUST 1977
| In entire cowMly
| In part of covnty
SLIDE 401-5
EPA issues CTG's
Control Techniques
Guidelines.
SLIDE 401-6
CTG
Working document
Guidance to states
SLIDE 401-7
STATE REGULATIONS AND PERMITS
CAN VARY FROM CTG AND MODEL
REGULATION
A-2
-------
SLIDE 401-8 NOTES
GROUP I
CTG SOURCE CATEGORIES
SURFACE COATING OF:
• Cans • Metal furniture
• Metal coils • Magnet wire
• Paper products • Large appliances
• Automobile and light
trucks
SLIDE 401-9
GROUP I
CTG SOURCE CATEGORIES
(continued)
Fixed roof tanks-storage of liquid petroleum
Bulk terminals-gasoline loading terminals
Stage I vapor control system gasoline stations
Petroleum refineries
Cutback asphalt
Degreasers
SLIDE 401-10
GROUP II
CTG SOURCE CATEGORIES
Leaks from petroleum refineries
Miscellaneous metal parts surface coating
Surface coating of flat wood paneling
Pharmaceutical manufacture
A-3
-------
SLIDE 401-11 NOTES
GROUP II
CTG SOURCE CATEGORIES
(continued)
• Rubber tire manufacture
• External floating roof petroleum tanks
• Graphic arts
• Perchloroethylene dry cleaning
• Gasoline truck leaks and vapor
collection
SLIDE 401-12
GROUP III
CTG SOURCE CATEGORIES
Large petroleum dry cleaners
SOCMI-fugitive
Natural gas/gasoline processing plants
VOC storage vessels
SOCMI-air oxidation
SLIDE 401-13
REGULATIONS AFFECTING
EXISTING SOURCES
EXAMPLES:
• SIP — PACT
• Federal, state, and local permit systems
SLIDE 401-14
RACT
REASONABLY AVAILABLE
CONTROL TECHNOLOGY
• Reasonably available technology
• Considers cost
A-4
-------
SLIDE 401-15 NOTES
REGULATIONS
AFFECTING NEW SOURCE
CONSTRUCTION
NEW SOURCE REVIEW (NSR)
• Process for reviewing new sources
SLIDE 401-16
NSPS
NEW SOURCE
PERFORMANCE STANDARDS
Promulgated for various source categories
Specify emission limitations
Can be found in CFR
SLIDE 401-17
BACT
BEST AVAILABLE
CONTROL TECHNOLOGY
• Best technology available
• Considers cost and energy requirements
SLIDE 401-18
LAER
LOWEST ACHIEVABLE
EMISSION RATE
• Control devices to achieve lowest possible
emission rate
• Required for sources in nonattainment
areas
A-
-------
SLIDE 401-19 NOTES
PSD
PREVENTION OF
SIGNIFICANT DETERIORATION
• EPA policy applied to new sources in
an attainment area
SLIDE 401-20
CONTROLLED TRADING
• Offset policy
• Bubble policy
• Banking emissions
SLIDE 401-21
VOC OFFSET
EXISTING SOURCE NEW SOURCE
420 LBS/HR
t 100 LBS/HR
300LBS/HR
SLIDE 401-22
BUBBLE
POLICY
A-6
-------
SLIDE 401-23 NOTES
SUBPART
• Application and designation of
affected facility
• Definitions
• Standards of pollutants from each
facility
• Test methods and procedures
• Reporting and record keeping
A-7
-------
SLIDE 402-1 NOTES
VOLATILE ORGANIC COMPOUND
Defn.: "A volatile organic compound (VOC) is
any organic compound that, when
released to the atmosphere, can remain
long enough to participate in photochemical
reactions...almost all organics which can
be considered VOC have vapor pressures
>0.1 mm Hg at 20° C and 760 mm Hg."
Note: Some VOCs may have vapor pressures
<0.1 mm Hg.
SLIDE 402-2
HC Hydrocarbon
i*|_|f^ Total
1 "^ Hydrocarbon
MMU/- NonMcthanc
NMHC Hydrocarbon
SLIDE 402-3
HYDROCARBONS
i i
Aliphatic Aromatic
i I I
Alkane* Alkene* Alkyne*
CHjCH3 CH«CH2 HCZCH benzene
ethane ethylenc ethyne
(acetylene)
toluene
B-l
-------
SLIDE 402-4
NOMENCLATURE
NOTES
eth-
prop-
but-
pent-
hex-
hept-
oct-
1 carbon
2 carbon*
3 carbon*
4 carbon*
5 carbon*
6 carbon*
7 carbon*
8 carbon*
CH4
C3H8
C4H10
CIHU
C?H16
methane
ethane
propane
butane
pentane
hexane
heptane
octane
SLIDE 402-5
Alcohols Aldehydes Ketones
O O
R-OH R-C-H R,- C-R2
Esters Acids Ethers
9 9
R-C-O-R R-C-OH R-O-R
SLIDE 402-6
HALOCARBONS
a
a H
a a
perchloroethylene
H
a
a
trichoroethane
(methyl chloroform)
SLIDE 402-7
NITROGEN COMPOUNDS
Nitropnraffin*
9
CHj-CH2-O-N=O
•thvl ottrat*
9
CH3-CHa-N = 0
nttroethane
R-NH2
H
NH2
2-propylamine
B-2
-------
SLIDE 402-8 NOTES
NASTIES
ci o a
PAN
dknln aCDDI pnaucMyl nlmu
SLIDE 402-9
O X'C-H
SLIDE 402-10
RULE 66
high reactive HC's
replaced with
low reactive HC's
SLIDE 402-11
EPA REVIEW OF RULE 66
• little reduction of oxldant levels
• few low reactivity organic*
• many VOC : suspected mutagens,
carcinogens, or teratogens
• ozone layer problems
• low reactivity compounds
have limited applications
B-3
-------
SLIDE 403-1
APPLICATION OF EPA
VOC REFERENCE METHODS
NOTES
SLIDE 403-2
CONSIDER LIMITATIONS OF
PERFORMANCE EVALUATION TECHNIQUES
WHEN REGULATIONS ARE WRITTEN
• Simplicity
• Cost and availability
• Accuracy
• Definition of applicable regulation
SLIDE 403-3
SOURCE PERFORMANCE
EVALUATION TECHNIQUES
1. Stack tests
2. Material balance techniques
3. Equipment design parameters
SLIDE 403-4
KNOWN
MIXTURE
CALIBRATE FOR EACH COMPOUND
AND MEASURE TRUE MASS
• Relatively easy for one or two compounds
• Difficulty increases with number
C-l
-------
SLIDE 403-5
LB/HR
(known)
NOTES
t
SOLVENT
CLEANING
1 COMPONENT
FOR TRUE MASS
FID calibrated with the known
compound
SLIDE 403-6
UNKNOWN
MIXTURE
GENERALLY, CANNOT REASONABLY
MEASURE TRUE MASS
a. For relatively constant mixture — may be
able to get somewhat consistent results
from source to source
Examples: automotive emission, ambient air
b. Can more easily make substitute measure-
ment: total carbon
Example: EPA Method 25
C-2
-------
SLIDE 403-7
^
INCINERATION
.(B) Unknown
compounds
(A) Known compounds, but different mixtures
LB/HR
VOIATILES
n
i
COATING
BAKING
(KNOWN)
(A) FOR TRUE MASS
1. GC/FID with extensive calibration
2. Volatile content of paint (as applicable)
(B) FOR TRUE MASS
1. GC/MS
2. Approximate by Method 25
Note: When open flame is present, the
compounds may change. GC/MS is
very expensive and is truely a labor-
atory instrument.
NOTES
C-3
-------
SLIDE 403-8 NOTES
VOC ANALYZERS RESPONSE
COMPOUND MOLWT. FID M 25
Ql_l is 16 1 carbon
CH3OH 32 ~7 1 carbon
Note: The complexity of obtaining a true mass
increases with the selection of the sampling
technique. Adsorption and desorption efficien-
cies, condensation and reactions must be
eliminated or accounted for.
SLIDE 403-9
NO UNIVERSAL VOC
EVALUATION TECHNIQUE EXISTS
SLIDE 403-10
SUMMARY
1. Determine best method for compliance
determination
• Material balance (record keeping)
• Equipment design parameters
• Pollutant measurement by testing
2. Determine allowable emissions
SLIDE 403-11
(cont)
3. Establish compliance evaluation proto-
col and give definition of emissions
• % efficiency, as
• Ib/hr, as
• ppm, as
• Ib/lb of processed material, as
C-4
-------
METHOD 106
DETERMINATION OF VINYL CHLORIDE FROM STATIONARY SOURCES
(Federal Register, Vol. 47, No. 173, Tuesday, September 7, 1982)
7.3 QUALITY ASSURANCE
7.3.1 Analysis Audit
Immediately after the preparation of the calibration curve and prior to
the sample analyses, perform the analysis audit described in Appendix C, Pro-
cedure 2: "Procedure for Field Auditing GC Analysis."
7.3.2 Bag Leak Checks
Checking of bags for leaks is required after bag use and strongly recom-
mended before bag use. After each use, connect a water manometer and pres-
surize the bag to 5 to 10 cm H20 (2 to 4 in. H20). Allow to stand for 10
min. Any displacement in the water manometer indicates a leak. Also, check
the rigid container for leaks in this manner. (Note: An alternative leak
check method is to pressurize the bag to 5 to 10 cm H^O and allow it to stand
overnight. A deflated bag indicates a leak.) For each sample bag in its
rigid container, place a rotameter in line between the bag and the pump inlet,
Evacuate the bag. Failure of the rotameter to register zero flow when the
bag appears to be empty indicates a leak.
APPENDIX C - QUALITY ASSURANCE PROCEDURES
Procedure 1 - Determination of Adequate Chromatographic Peak Resolution
In this method of dealing with resolution, the extent to which one
Chromatographic peak overlaps another is determined.
For convenience, consider the range of the elution curve of each com-
pound as running from -2a to +2a. This range is used in other resolution
criteria, and it contains 95.45 percent of the area of a normal curve. If
two peaks are separated by a known distance, b, one can determine the frac-
tion of the area of one curve that lies within the range of the other. The
extent to which the elution curve of a contaminant compound overlaps the
D-l
-------
curve of a compound that is under analysis is found by integrating the con-
taminant curve over the limits b-2a to b+2ag, where as is the standard devi-
ation of the sample curve.
This calculation can be simplified in several ways. Overlap can be
determined for curves of unit area; then actual areas can be introduced.
Desired integration can be resolved into two integrals of the normal distri-
bution function for which there are convenient calculation programs and tables.
An example would be in Program 15 in Texas Instruments Program Manual STl,
1975, Texas Instruments, Inc., Dallas, Texas 75222.
In judging the suitability of alternate GC columns or the effects of
altering chromatographic conditions, one can employ the area overlap as the
resolution parameter with a specific maximum permissible value.
The use of Gaussian functions to describe chromatographic elution curves
is widespread. However, some elution curves are highly asymmetric. In cases
where the sample peak is followed by a contaminant that has a leading edge
that rises sharply but the curve then tails off, it may be possible to define
an effective width for t as "twice the distance from the leading edge to a
\f
perpindicular line through the maxim of the contaminant curve, measured along
a perpendicular bisection of that line."
Procedure 2 - Procedure for Field Auditing GC Analysis
Responsibilities of audit supervisor and analyst at the source sampling
site include the following:
A. The audit supervisor verifies that audit cylinders are stored
in a ,safe location both before and after the audit to prevent
vandalism.
B. At the beginning and conclusion of the audit, the analyst
records each cylinder number and pressure. An audit cylinder
is never analyzed when the pressure drops below 200 psi.
C. During the audit, the analyst performs a minimum of two con-
secutive analyses of each audit cylinder gas. The audit
must be conducted to coincide with the analysis of source
test samples, normally immediately after GC calibration and
prior to sample analyses.
D-2
-------
D. At the end of audit analyses, the audit supervisor requests
the calculated concentrations from the analyst and compares
the results with the actual audit concentrations. If each
measured concentration agrees with the respective actual
concentration within +_10 percent, he directs the analyst
to begin analyzing source samples. Audit supervisor judg-
ment and/or supervisory policy determine action when agree-
ment is not within +10 percent. When a consistent bias in
excess of 10 percent is found, it may be possible to proceed
with the sample analysis, with a corrective factor to be
applied to the results at a later time. However, every at-
tempt should be made to locate the cause of the discrepancy,
as it may be misleading. The audit supervisor records each
cylinder number, cylinder pressure (at the end of the audit),
and all calculated concentrations. The individual being
audited must not under any circumstance be told actual audit
concentrations until calculated concentrations have been sub-
mitted to the audit supervisor.
FIELD AUDIT REPORT
Part A
Part A is to be filled out by organization supplying audit cylinders.
1. Organization supplying audit sample(s) and shipping address:
2. Audit supervisor, organization, and phone number:
3. Shipping instructions (name, address, attention)
4. Guaranteed arrival date for cylinders:
5. Planned shipping date for cylinders:
D-3
-------
6. Details on audit cylinders from last analysis
Low cone.
High cone.
Part B
Part B is to be filled out by audit supervisor,
1. Process sampled:
2. Audit location:
3.
4.
5.
Name of indivudal audit:
Audit date:
Audit results:
a. Cylinder number
b. Cylinder pressure before audit,
psi
c. Cylinder pressure after audit,
psi
d. Measured concentration, ppm
Injection #1* Injection #2*
Average
e. Actual audit concentration, ppm
(Part A, 6e)
f. Audit accuracy1
Low Cone. Cylinder
High Cone. Cylinder
Percent' accuracy -
*""-«"
Low cone.
cylinder
-ctual Cone.
High cone.
cylinder
g. Problems detected (if any)
Results of two consecutive injections that meet the sample analy-
sis criteria of the test method.
D-4
-------
SUPPLEMENT A
DETERMINATION OF ADEQUATE CHROMATOGRAPHIC PEAK RESOLUTION
In this method of dealing with resolution, the extent to which
one chromatographic peak overlaps another is determined.
For convenience, consider the range of the elution curve of
each compound as running from -2a to +2a. This range is used in
other resolution criteria, and it contains 95.45 percent of the
area of a normal curve. If two peaks are separated by a known
distance, b, one can determine the fraction of the area of one
curve that lies within the range of the other. The extent to which
the elution curve of a contaminant compounds overlaps the curve
of a compound that is under analysis is found by integrating the
contaminant curve over the limits b-2os to b+2cs, where o is the
standard deviation of the sample curve.
There are several ways this calculation can be simplified.
Overlap can be determined for curves of unit area and then actual
areas can be introduced. The desired integration can be resolved
into two integrals of the normal distribution function for which
there are convenient calculation programs and tables. An example
would be Program 15 in Texas Instruments Program Manual ST1, 1975,
Texas Instruments Inc., Dallas, Texas 75222.
P+2o
b-2o.
2
c dt
x
2
dx.
D-5
-------
The following calculation steps are required:1
2.
3. X] = (b-2as)/ac
4. x.
(b+2as)/ac
5. Q(XI) =-ii
e
Xi
dx
6. Q(xJ =-=
7. I.
£
2
dx
- Q(x2),
- A
9. % overlap = AQ x 100
(Note: In most instances, Q(x2) is very small and may be neglected.)
D-6
-------
Where:
A a The area of the sample peak of Interest determined
by electronic integration, or by the formula A$ » h$t ,
A = The area of the contaminant peak, determined in the
same manner as A$.
b = The distance on the chromatographic chart that
separates the maxima of the two peaks.
h » The peak height of the sample compound of interest,
measured from the average value of the baseline to
the maximum of the curve.
t • The width of the sample peak of interest at 1/2 of
peak height.
t = The width of the contaminant peak at 1/2 of peak
height.
a * The standard deviation of the sample compound of
interest elution curve.
o a The standard deviation of the contaminant elution
c
curve.
Q(x,) 3 The integral of the normal distribution function from
x, to infinity.
Q(x2) = The integral of the normal distribution function from
x2 to infinity.
I * The overlap integral.
o
A = The area overlap fraction
o
D-7
-------
In judging the suitability of alternate gas chromatographic
columns, or the effects of altering chromatographic conditions,
one can employ the area overlap as the resolution parameter with
a specific maximum permissible value.
The use of Gaussian functions to describe chromatographic
elution curves is widespread. However, some elution curves are
highly asymetric. In those cases where the sample peak is
followed by a contaminant that has a leading edge that rises
sharply but the curve then tails off, it may be possible to
define an effective width for tc as "twice the distance from the
leading edge to a perpendicular line through the maxim of the
contaminant curve, measured along a perpendicular bisection of
that line."
D-8
-------
SLIDE 404-1 NOTES
ERA'S QUALITY ASSURANCE PROGRAM
SLIDE 404-2
PERFORMANCE AUDITS ON SOURCE EMISSION
ORGANIC ANALYSIS
BACKGROUND
In 1977, in support of OAQPS, a program was
initiated to audit the GC analysis of source test
samples. Currently, this audit program has been
extended to all EPA, state and local agencies and
their contractors.
SLIDE 404-3
REASON FOR AUDITS OF ORGANIC ANALYSIS
OAQPS conducts source tests in setting new
regulations. In addition, EPA and states require
source owners to test for (1) operating permits
and (2) demonstrate compliance to existing regu-
lations. The accuracy and precision of source
tests must be known.
SLIDE 404-4
THE ROLE OF QUALITY ASSURANCE
IN VOC TESTING
D-9
-------
SLIDE 404-5 NOTES
Defn: PERFORMANCE AUDIT
Performance audits refer to indepen-
dent checks made by supervisor or
auditor to evaluate the quality of data and
are categorized as:
1. Sampling Audits
2. Analysis Audits
3. Data Processing Audits
SLIDE 404-6
Defn: SYSTEM AUDITS
A system audit is an on-site inspection and
review of the quality assurance system used for
the total measurement system. Whereas perfor-
mance audits are a quantitative appraisal, system
audits are normally a qualitative appraisal.
SLIDE 404-7
TECHNICAL APPROACH FOR ORGANIC AUDITS
1. Each audit consists of two gas cylinders:
a) low concentration 5-20 ppm simulates emission standard
b) high concentration 50-700 ppm simulates source emissions
2. Cylinders are analyzed 3 times during the period the source
test samples are analyzed.
3. Audit results are returned to the auditor and accuracy and
precision are calculated and reported to the auditee and
requesting agency.
D-10
-------
SLIDE 404-8
NOTES
TABLE 1. AUDIT MATERIALS CURRENTLY HELD H THE REPOSITORY
Low Concentration Range
High Concentration Range
Conpound No. of
Cylinders
Benzene
Ethylene
Propylcne
Methane/Ethane
Propane
Toluene
Hydrogen Sulf Ide
Meta-Xylene
Methyl Acetate
Chloroform
14
4
4
-
4
2
4
2
2
2
Concentration
Range (ppn)
8-
5-
5-
—
5-
5-
5-
5-
5-
5-
13
20
20
...
20
20
20
20
20
20
Cylinder No. of Concentration Cylinder
Construction* Cylinders Range (ppn) Construction*
S
Al
Al
-
Al
S
Al
S
S
S
17
4
6
4
4
4
2
2
2
2
2
60-
300-
3000-
300-
1000-
200-
300-
300-
300-
300-
300-
300-
400
700
20.000
no
6000(M).
/00(E)
700
700
KO
700
700
TOO
Al.S
Al
Al
Al
Al
Al
S
Al
LS
S
S
SLIDE 404-9
TABLE 2. SUMMARY OF PERFORMANCE AUDIT RESULTS
Audit
No.
1
2
3
4
5
6
7
a
9
Client
A
A
A
A
A
A
B
C
0
Industry
Ethylene oxide
production
Ethylene wide
production
Ethylene oxide
production
Acetone
production
Maleic anhydride
production
Ethylene oxide
production
Maleic anhydride
production
Maleic anhydride
production
Ethyl benzene
styrene
manufacturer
Audit material
Ethylene In N?
Ethylene in l£
Ethane/ethane in N-,
Methane/ethane in l£
Methane/ethane in No
Methane/ethane in f£
Benzene in Np
Benzene in N£
Benzene in No
Benzene In f£
Ethylene in No
Ethylene in f£
Benzene in No
Benzene in N|
Benzene In No
Benzene in (^
Benzene in No
Benzene In Ng
RTI audit
cone, (ppn)
3.239
21.226
1.71QMe/220Et
8.130M3/597Et
1.021Me/315Et
6,207Me/773Et
79.0
374.0
138
300
5.442
18.918
80.0
3S6
101
387
71.0
229
Client audit status of
Xbias(Avg.) audit
-22.5
-20.0
+9.00/-20.0
+9.00/-1.00
+21.5/-4.50
+23.5/-4.50
-19.0
-11.0
-9.40
<4.70
-27.0
-33.0
+2.30
+27.5
+12.9
+14.5
-2.80
-3.90
E
E
E
E
E
E
E
E
E
D-ll
-------
SLIDE 404-10 NOTES
HIGHLIGHTS DURING FY-82
1. Audit repository expanded to 40 compounds
(including halocarbons, hydrocarbons and sulfur
containing organics).
2. Stability studies underway on all organics to
demonstrate utility as audit materials.
3. Complete 20 audits (91 audits completed since
1977).
SLIDE 404-11
EPA PROCEDURE FOR
PROVIDING AUDIT SAMPLES
• Request made to EMSL.
• EPA (RTI) verifies cylinder concentrations.
• High-and-low concentration cylinders ship-
ped with standard letter to contractor by
express carrier or truck.
SLIDE 404-12
(cont.)
Contractor analyzes and reports results to
project officer.
Project officer evaluates results and sends
report to EPA (RTI).
If contractor's results are > ± 10% of that
expected, cylinders are reanalyzed by third
laboratory.
SLIDE 404-13
APPENDIX C
PROCEDURE 1 — Determination of adequate
chromatographic peak resolution
PROCEDURE 2 — Procedure for field
auditing GC analysis
D-12
-------
SLIDE 405-1 NOTES
OBSERVATION AND EVALUATION
OF STATIONARY SOURCE PERFORMANCE TESTS
SLIDE 405-2
DETERMINE APPLICABLE EMISSION
• Allowable pollutant and definition
• Define facility operation
• Define compliance evaluation method
SLIDE 405-3
ESTABLISH COMPLIANCE PROTOCOL
• Facility operational during testing
• Procedures for compliance evaluation method
SLIDE 405-4
OBTAIN AGREEMENT ON PROTOCOL
• Make presite survey
• Designate a contact person from agency, tester
and source
• Clarify protocol procedures and get agreement
E-l
-------
SLIDE 405-5 NOTES
ON SITE OBSERVATION
• Observe facility operation
• Observe compliance evaluation method
• Make screening technique values when possible
SLIDE 405-6
BASELINE CONCEPT
Defn:
The documentation of all pertinent operating
parameters for both process and control equip-
ment operations to provide a narrow band of
operating parameters against which determina-
tions can be made.
SLIDE 405-7
PURPOSES OF DETERMINING
REPRESENTATIVE FACILITY OPERATION
1. Evaluate performance test
2. Establish operation and maintenance programs
3. Issue permit to operate
4. Reference point for future evaluations
SLIDE 405-8
AGREEMENTS ON TESTING PROTOCOL
PROCESS:
• parameters to be monitored and recorded
• acceptable values for each parameter
• process samples to be taken and analyzed
• mode of operation
• instruments to be added and/or calibrated
E-2
-------
SLIDE 405-9 NOTES
(cont.)
CONTROL EQUIPMENT:
• parameters to be monitored and recorded
• acceptable values for each parameter
• control equipment effluent samples to be
taken and analyzed
• mode of operation
• instruments to be added and/or calibrated
SLIDE 405-10
PROCESS OPERATION
• Raw Materials
• Fuel
• Process Rate
• Mode of Operation
SLIDE 405-11
PROCESS MODE OF OPERATION
• Manual or automatic operation
> Cleaning and auxiliary systems
1 Normal period for process cycles
> Diversion or circumvention of pollutants from air
pollution control equipment
1 Operation personnel
E-3
-------
SLIDE 405-12
SAMPLE SITE-*O
EMISSION _
LIMIT -
MEASURED
EMISSIONS
PAINT DRYING
NOTES
E-4
-------
SLIDE 405-13
NOTES
SAMPLE SITE 4*O
DUCT DAMPER
:\
EMISSION . « IK/h
LIMIT - 3 lb/h
MEASURED __
EMISSIONS -
PAINT DRYING
SLIDE 405-14
PRINTING OPERATION TRICKS
• Use most efficient solvent
• Reduce line speed
• Reduce ink coverage
• Reduce number of printing lines
E-5
-------
SLIDE 405-15 NOTES
CONTROL EQUIPMENT
MODE OF OPERATION
• Manual or automatic operation
• Collected pollutant removal cycle
• Cleaning cycle
« Auxiliary or gas conditioning systems
SLIDE 405-16
OBSERVE COMPLIANCE EVALUATION TECHNIQUE
• Performance audit
• System audit
SLIDE 405-17
EXIT INTERVIEW
• Conduct exit interview with plant and
test team.
• Request additional information if needed.
• Critique test program.
SLIDE 405-18
PERFORMANCE TEST REPORT FORMAT
1. Cover
2. Certification
3. Introduction
4. Summary of Results
5. Source Operations
6. Sampling and Analytical Procedures
7. Appendix
E-6
-------
SLIDE 405-19 NOTES
DATA REQUIREMENTS
• Completeness
• Accuracy
SLIDE 405-20
RESULTS OF FACILITY BASELINING
• Performance test can be properly evaluated.
• An operation and maintenance program can be
established.
• Permit to operate can become an effective enforce-
ment tool.
• Future inspections by agency can be more effective
in determining compliance and reasons for non-
compliance.
E-7
-------
SLIDE 406-1 NOTES
COMPLIANCE EVALUATION USING
MATERIAL BALANCE
SLIDE 406-2
VOC SOURCE CATEGORIES THAT USE
MATERIAL BALANCE FOR
COMPLIANCE EVALUATION
• Surface Coating
• Graphic Arts
• Degreasing
SLIDE 406-3
SURFACE COATING
Cans
Metal coils
Paper and fabric products
Automobiles and light trucks
Metal furniture
Magnet wire
Large appliances
Flatwood paneling
Miscellaneous metal parts
F-l
-------
SLIDE 406-4
NOTES
SLIDE 406-5
GRAPHIC ARTS
• Gravure printing presses
• Flexographic printing presses
F-2
-------
SLIDE 406-6
NOTES
SLIDE 406-7
F-3
-------
SLIDE 406-8
DECREASING
• Cold cleaners
• Open-top vapor degreasers
• Conveyorized degreasers
NOTES
SLIDE 406-9
SLIDE 406-10
SURFACE COATING
VOC INPUTS
• Pretreatment
• Coatings
• Dilution solvents
• Clean-up solvents
• Recycled solvents
• Internal
• External
F-4
-------
SLIDE 406-11 N0TES
SURFACE COATING
VOC EMISSION POINTS
• Waste solvent
• Carbon adsorber exhaust
• Carbon adsorber decanter (recycle)
• Fugitive emissions
• Flash-off
• Baking
• Product
• Coating application
SLIDE 406-12
% OF TOTAL EMISSIONS
APPLICATION PRE-DRY CURING
Spray 30-50 10-30 20-40
Flow 30-50 20-40 10-30
Dip 5-20 10-30 50-70
Roller 0-5 10-20 60-80
SLIDE 406-13
SURFACE COATING
VOC EMISSION POINTS
CAN BE QUANTIFIED CANNOT BE QUANTIFIED
• Waste solvent • Fugitive emissions
• Carbon adsorber emissions • Product
• Coating application
• Carbon adsorber decanter
• Baking
F-5
-------
SLIDE 4f)fi-14
NOTES
COMMON TECHNIQUES USED IN THE
COATING OF METAL FURNITURE PIECES
FROM
MACHINE SHOP
CLEANSING AND
PRETREATMENT
FLOW COATING
TOPCOAT OR SINGLE
COAT APPLICATION
SLIDE 406-15
GRAPHIC ARTS
VOC INPUTS
• Inks
• Dilution solvents
• Cleaning solvents
• Recycled solvents
• Internal
• External
F-6
-------
SLIDE 406-16
GRAPHIC ARTS
VOC EMISSION POINTS
• Waste solvent
• Carbon adsorber exhaust
• Carbon adsorber decanter
• Fugitive emissions
• Product
MOTES
SLIDE 406-17
GRAPHIC ARTS
VOC EMISSION POINTS
CAN BE QUANTIFIED CANNOT BE QUANTIFIED
• Waste solvent • Fugitive emissions
Carbon adsorber exhaust
Carbon adsorber decanter
Product
SLIDE 406-18
VOC INPUTS AND EMISSION POINTS
OF A PRINTING OPERATION
FUGITIVE
EMISSIONS
CAPTURE
HOOD
STACK
EMISSIONS
\
PRESS
CLEANUP
SOLVENT
USED
SOLVENT
RETAINED
IN PROD.
•« DISPOSAL
CLEANUP SOLVENT
RECOVERY
RECOVERED
SOLVENT
DISPOSAL
F-7
-------
SLIDE 406-19 NOTES
DECREASING
VOC INPUTS
• Cleaning solvents
• Recycled solvents
• Internal
• External
SLIDE 406-20
DECREASING
VOC EMISSION POINTS
• Waste solvent
• Carbon adsorber exhaust
• Carbon adsorber decanter
• Bath evaporation
• Carry-out
• Lip exhaust
SLIDE 406-21
DECREASING
VOC EMISSION POINTS
CAN BE QUANTIFIED CANNOT BE QUANTIFIED
• Waste solvent • Bath evaporation
• Carbon adsorber exhaust • Carry-out
• Carbon adsorber decanter
• Lip exhaust
F-8
-------
SLIDE 406-22
NOTES
VOC INPUTS AND EMISSION POINTS
OF AN OPEN-TOP VAPOR DEGREASER
BATH EVAPORATION
EMISSIONS
STACK
EMISSIONS
SOLVENT IN
CARBON
ADSORBER
CARRYOUT EMISSIONS
X
WASTE SOLVENT EMISSIONS
SLIDE 406-23
INFORMATION NECESSARY FOR
MATERIAL BALANCE
F-9
-------
SLIDE 406-24 NOTES
SURFACE COATING
Paint inventory at beginning of test period
Paint added during test period
Paint inventory at end of test period
Dilution or clean-up solvent level at begin-
ning of test period
Quantity of dilution or clean-up solvent added
during test period
Dilution or clean-up solvent level at end of
test period
Hours of operation during test period
SLIDE 406-25
GRAPHIC ARTS
Ink inventory at beginning of test period
Ink added during test period
Ink inventory at end of test period
Clean-up solvent at beginning of test period
Clean-up solvent added during test period
Clean-up solvent at end of test period
Dilution solvent at beginning of test period
Dilution solvent added during test period
Dilution solvent at end of test period
Hours of operation during test period
SLIDE 406-26
DECREASING
Degreaser solvent level at beginning of test period.
Quantity of solvent added during test period.
Solvent level at end of test period.
Hours of operation during test period.
F-10
-------
SLIDE 406-27 NOTES
ERRORS IN MATERIAL BALANCE
SURFACE COATING GRAPHIC ARTS
• VOC in coating • VOC in paper
• Fugitive emissions • Fugitive emissions
DECREASING
• Volume of metal chips and other material
remaining in sump
• Volume of oil and grease dissolved in solvent.
• Fugitive emissions.
SLIDE 406-28
MATERIAL BALANCE
ADVANTAGES
• Checks total system
• Simple and inexpensive
• Records of solvent use are
usually available.
DISADVANTAGES
• Time-consuming
SLIDE 406-29
EQUIPMENT SPECIFICATIONS
Equipment specifications are VOC regula-
tions which involve work practices or equip-
ment design for compliance.
F-ll
-------
SLIDE 406-30
NOTES
EQUIPMENT SPECIFICATIONS ARE
USED IN MANY INDUSTRIES
• Pharmaceutical
• Storage tanks
• Vinyl chloride
• Benzene
• Degreasing
• On/cleaning
SLIDE 406-31
PHARMACEUTICAL INDUSTRY
SLIDE 406-32
TYPICAL CHEMICAL SYNTHESIS
PHARMACEUTICAL PROCESS
SOLVENT VENT
HO
SOLVENT
1
r-*-/i rx-~ i
t' ' SOLVENT 5°"
r ' RECEIVER 1
REACTOR
HOLDING
TANK
SOLVENT
DISTILLATION
CRYSTALLIZE
^A-
1
BATCH
CENTRIFUGE
^
!
DRYER
TYPICAL CYCLE 1-24 HOURS
F-12
-------
SLIDE 406-33 NOTES
POTENTIAL EMISSION SOURCES
• Dryers
• Reactors
• Distillation units
• Storage and transfer
SLIDE 406-34
SURFACE CONDENSERS OR EQUIVALENT
CONTROLS ON REACTORS, DISTILLATION
OPERATIONS, CRYSTALLIZERS, CENTRIFUGES,
AND VACUUM DRYERS
SLIDE 406-35
SURFACE CONDENSER REQUIREMENT
CONDENSER OUTLET VOC
GAS TEMPERATURE VAPOR PRESSURE
77° F 0.5TO1.0PSI
50° F 1.0TO2.5PSI
32° F 1.5TO2.9PSI
5°F 2.9TO5.8PSI
-13°F > 5.8 PSI
SLIDE 406-36
STORAGE TANK REQUIREMENTS
Vapor balance or equivalent (> 90% efficiency)
on truck or railcar transfers to storage tanks >
2000 gallons that store VOC with vapor pressure
>4.1 PSI.
Conservation vents set at ± 0.03 PSI on tanks
that store VOC with vapor pressure > 1.5 PSI.
Cover all in-process tanks containing VOC.
F-13
-------
SLIDE 406-37
STORAGE TANKS
NOTES
Fixed Roof Floating Roof Pressure
SLIDE 406-38
RACT
All Tanks > 40.000 gal @ v.p. > 1.5 p$ja
SLIDE 406-39
RACT
(for External Floating Roofs)
• secondary rim-mounted
seal covering the primary
seal
SLIDE 406-40
EXTERNAL FLOATING ROOF TANK
I i -x c *
^ I
F-14
-------
SLIDE 406-41
Pontoon
TYPES OF
EXTERNAL
FLOATING
ROOFS
NOTES
SLIDE 406-42
F-15
-------
SLIDE 4Q6-43
NOTES
SLIDE 406-44
- gap oi»o
F-16
-------
SLIDE 406-45 NOTES
NATIONAL EMISSION STANDARDS
FOR HAZARDOUS AIR POLLUTANTS
(NESHAPS)
• Vinyl Chloride
• Benzene
SLIDE 406-46
FUGITIVE EMISSION SOURCES
• Loading and Unloading lines • Relief Valves
• Slip Gauges • Manual Vents
• Pump Seals • Opening of Equipment
• Compressor Seals • Samples
• Agitator Seals • Inprocess wastewater
SLIDE 406-47
SLIP GAUGES
• Vent any discharged VC through
control device.
F-17
-------
SLIDE 406-48 NOTES
ROTATING PUMPS
• Sealless pumps
• Double Mechanical Seals
1. Maintain pressure so that leak occurs
into pump.
2. Vent emissions through control device.
SLIDE 406-49
RECIPROCATING PUMPS
• Double Outboard Seals
ROTATING COMPRESSORS
• Double Mechanical Seals
RECIPROCATING COMPRESSORS
• Double Outboard Seals
AGITATORS
• Double Mechanical Seals
SLIDE 406-50
RELIEF VALVES
• Install rupture disk between equipment
and relief valve.
• Connect relief valve discharge to process
line or recovery device.
F-18
-------
SLIDE 406-51 NOTES
MANUAL VENTS
Vent through control system.
SLIDE 406-52
BENZENE FUGITIVE EMISSIONS
APPLICABILITY
• Petroleum Refineries
• Organic Chemical Manufacturing Plants
SLIDE 406-53
COMPONENTS IN BENZENE SERVICE
(Fluid That Is > 10% By Weight Benzene)
• Pumps • Safety/Relief Valves
• Compressors • Sampling Systems
• Pipeline Valves • Other Sources
SLIDE 406-54
NEW PUMPS AND COMPRESSORS
A. Dual mechanical seal system with barrier fluid
between seals for new pumps and seal system
with barrier fluid that prevents leaks to atmo-
sphere for new compressors
(Benzene cone. < 10% by volume)
OR
B. Closed vent system to control system
Sensor on each seal system
1. Check Daily
OR
2. Audible Alarm
F-19
-------
SLIDE 406-55 NOTES
(cont.) NEW PUMPS AND COMPRESSORS
• Visually Inspect each pump weekly for liquid leak
• If leak is detected, repair within 15 days (first
attempt at repair within 5 days)
• For each dual mechanical seal system:
1. Operate with barrier fluid pressure > stuffing box
pressure.
or
2. Equip with a barrier fluid degassing reservoir
connected to control system.
or
3. Designed and operated with no benzene emission
when barrier fluid purged.
SLIDE 406-56
SAFETY/RELIEF VALVES IN
GAS/VAPOR SERVICE
• Maintain at < 200 ppm above background.
• After pressure release, return to < 200
ppm within 5 days.
SLIDE 406-57
PIPELINE VALVES, OPEN-ENDED VALVES,
AND EXISTING PUMPS AND COMPRESSORS
• Monitor monthly with portable hydrocarbon
detector.
• If leak > 10,000 ppm, repair within 15 days —
first attempt at repair within 5 days includes.
1. tightening of bonnet bolts
2. replacement of bonnet bolts
3. tightening of packing gland nuts
4. injection of lubrication into lubricated packing
F-20
-------
SLIDE 406-58 ' NOTES
(cont.) PIPELINE VALVES, ETC.
• Quarterly monitoring if leak not detected
for two successive months.
• Equip open-ended valve with cap, blind,
plug, or closed second valve.
• Visually inspect each pump weekly for
liquid leaks.
SLIDE 406-59
DECREASING
SLIDE 406-60
CONTROL OF SOLVENT BATH EMISSIONS
• Covers
• Freeboard height
• Carbon adsorption
• Safety switches
• Refrigerated chillers
SLIDE 406-61
CONTROL OF CARRY-OUT EMISIONS
• Drainage racks
• Drying tunnels
• Rotating baskets
F-21
-------
SLIDE 406-62 NOTES
CONTROL OF BOTH SOLVENT BATH
AND CARRY-OUT EMISSIONS
• Automated cover-conveyor
• Refrigeration condensation
SLIDE 406-63
RACT GUIDELINES
• Separate guidelines for each type of
degreaser
• Each guideline divided into two levels
of control
SLIDE 406-64
CONTROL SYSTEMS
CONTROL SYSTEM A
1. Control equipment
2. Operating requirements
CONTROL SYSTEM B
(Control System A plus)
1. Additional control equipment
2. Additional operating requirements
SLIDE 406-65
OPERATING REQUIREMENTS
Covers
Conveyor speed
Freeboard ratio
Conveyorized degreaser
Refrigeration system
Ventilation rate
Safety switches
F-22
-------
SLIDE 406-66 NOTES
DRYCLEANING
SLIDE 406-67
EMISSION SOURCES
• Washer/Extractor • Still Residue
• Dryer/Reclaimer • Filter Cartridges
• Carbon Adsorber Exhaust • Leaks (Liquid & Vapor)
• Filter Muck
SLIDE 406-68
RACT FOR PERC DRYCLEANERS
Vent dryer exhaust throuch CA or equivalent
Exhaust from control device < 100 ppm perc
Immediately repair liquid leaks
Rlter residue < 25% perc
Still residue < 60% perc
Drain filter cartridges > 24 hours or dry before
disposal
SLIDE 406-69
INSPECTION ITEMS FOR DRYCLEANING
FACILITIES WITH PERC REMOVAL EQUIPMENT
1. Inspect following for vapor leaks
A. Ductwork
B. Improper gasket seating
C. Other
2. Inspect following for liquid perc leaks
A. Hose connections, unions, couplings, and
valves
B. Machine door gaskets and seatings
F-23
-------
SLIDE 406-70 NOTES
(cont.)
C. Filter head gasket and seating
D. Pumps
E. Base tanks and storage containers
F. Water separators
G. Filter sludge recovery
H. Distillation unit
I. Diverter valves
J. Saturated lint from lint basket
K. Cartridge filters
3. Observe location of control system vent
SLIDE 406-71
(cont.)
4. Observe the following equipment to see
where vented
A. Perc removal system
B. Still
C. Muck cooker
D. Separators
E Dry cleaning machine(s)
F. Other sources vented through perc removal
system
SLIDE 406-72
(cont)
5. Inspect perc removal system for lint buildup
and corrosion problems
6. Inspect floor pickup points for pro'per oper-
ation and for lint accumulation
7. Obtain samples of muck cooker and still
bottoms if possible
8. Observe general housekeeping
F-24
-------
SLIDE 501-1 NOTES
INTEGRATED BAG SAMPLING
AND
AND ANALYSIS
SLIDE 501-2
PRINCIPLE
A gas sample is collected in an evacuated
bag by evacuating the rigid air-tight container
holding the bag.
SLIDE 501-3
APPLICABILITY
METHOD IS APPLICABLE:
» In situations where a hydrogen flame
is a hazard.
> To measure halogenated organics.
METHOD IS NOT APPLICABLE:
For sampling polar compounds. -' s"^
For use at sources where organics are
contained in paniculate matter.
High moisture.
G-l
-------
SLIDE 501-4
NOTES
INTEGRATED BAG SAMPLING TRAIN
F.LTFR ffSTACK WALL TEFLON
(GLASS-WOOL) I | fWLE LINE
PROBE t
MALE
U
BALL
CHECKS
QUICK
CONNECTS
FEMALE
TEDLAR OR
ALUMINIZED
MYLAR BAG
RIGID LEAK-PROOF puMP
CONTAINER
FLOW
METER
pi I^VM iJ-
O C6-T
SLIDE 501-5
LEAK CHECK PROCEDURE
Connect a water manometer and pressurize
bag to 5 to 10 cm H2O; allow to stand for 10
min.
ALTERNATIVE LEAK CHECK PROCEDURE
• Pressurize bag to 5 to 10 cm H2O; allow to
stand over night.
• Place a rotameter in line between the bag and
pump inlet and evacuate the bag.
6-2
-------
SLIDE 501-6
NOTES
SLIDE 501-7
6-3
-------
SLIDE 501-8
SAMPLING PROCEDURE
Assemble and leak check sample train.
Connect vacuum line to Teflon sample line
from the probe and purge.
Connect vacuum line to bag and evacuate.
Position sample and vacuum lines for samp-
ling.
Collect sample keeping rate proportional to
stack velocity.
NOTES
(cont.)
SLIDE 501-9
SAMPLING PROCEDURE
At the end of sample period, shut off pump,
and disconnect sample and vacuum lines.
Record source temperature, barometric pres-
sure, ambient temperature, sampling flow rate
and initial and final sampling times.
Protect bag and container from sunlight.
Perform analysis within 2 hours of sample
collection.
SLIDE 501-10
G-4
-------
SLIDE 501-11
NOTES
SLIDE 501-12
G-5
-------
SLIDE 501-13
NOTES
ALTERNATIVE SAMPLING PROCEDURES
(Direct Pump Sampling)
• Place pump and needle valve between the
probe and the bag.
• Leak check the system and purge with stack
gas before connecting to evacuated bag.
SLIDE 501-14
(cont.)
ALTERNATE SAMPLING PROCEDURES
(Explosion Risk Area Sampling)
• Sample bag is enclosed in an airtight steel
drum.
• Sample pump is replaced with an evacuated
steel drum.
SLIDE 501-15
EXPLOSION RISK GAS SAMPLING METHOD
PROBE TEFLON TUBING
*
PINCH
CLAMP
GROMMET
PVC TUBING
FLOWMETERgl
3 t
\ SAMPLED.
i n* M *
AIR TIGHT STEEL DRUM
DIRECTFONAL
LNEEDLE VALVE
(QUICK DISCONNECTORS
EVACUATED STEEL DRUM
G-6
-------
SLIDE 501-16 NOTES
(cont.)
ALTERNATE SAMPLING PROCEDURE
(Modified Procedure When Condensation Is Present)
PROCEDURE I
• Heat box and bag to the source temperature.
• Maintain temperature during transportation
and analysis.
PROCEDURE II
• Pre-fill sampling bag with a known quantity
of inert gas.
• Meter source gas into partially filled bag
through heated sampling lines, flow meter,
and pump.
SLIDE 501-17
ANALYTICAL CHECK
OF BAG SAMPLE
STABILITY:
• Reanalyze bag sample over extended -i^»^/Ji A^ cA^6 ,,&«.-
time period.
CONDENSATION OR ABSORPTION: sL^IJ. 4*
• Empty bag, refill and analyze.
6-7
-------
SLIDE 502-1 MOTES
ADSORPTION SAMPLING TECHNIQUES
SLIDE 502-2
PRINCIPLE
A gas sample is extracted from the stack
and volatile organic vapors are collected on
suitable adsorption media.
APPLICABILITY
This method applies to the determination
of selected organic compounds.
SLIDE 502-3
ADVANTAGES
• Simple method and available equipment.
• Collection efficiency is checked.
• Small sample size.
• Increased storage time with freezer.
H-l
-------
SLIDE 502-4
NOTES
DISADVANTAGES
Not real time data.
Gas temperature must be below 125°F for
good adsorption.
H2O can diminish collection efficiency.
Some gases are not collected and/or may be
replaced by other gases.
Backup tube doubles analysis.
Sample may be lost in the probe.
SLIDE 502-5
ADSORPTION TUBE SAMPLING TRAIN
ADSORPTION
TUBE
FLEXIBLE
TUBING
PROBE
SUPPLEMENTAL
ADSORPTION TUBE
(AS REQUIRED)
ROTAMETER
PUMP
H-2
-------
SLIDE 502-6 NOTES
SAMPLING PROCEDURE
1. Immediately before sampling, break the ends
of tube to provide an opening at least one-
half internal diameter of tube.
2. The small section of charcoal is used as a
back-up and should be positioned nearest
the sampling pump.
3. The charcoal tube should be vertical during
sampling to reduce channeling through the
charcoal.
SLIDE 502-7
(cont.)
SAMPLING PROCEDURE
4. The flow, time, and/or volume must be
measured as accurately as possible. The
sample should be taken at a flow rate of 11pm
or less.
5. The temperature and pressure of the atmos-
phere being sampled should be measured
and recorded.
6. The charcoal tube should be capped with the
supplied plastic caps immediately after samp-
ling. Under no circumstances should rubber
caps be used.
SLIDE 502-8
(cont.)
SAMPLING PROCEDURE
7. One tube should be handled in the same
manner as the sample tube (break seal and
transport), except that no air is sampled
through this tube. This tube should be labeled
as a blank.
8. Capped tubes should be packed tightly before
shipment to minimize tube breakage.
9. Samples of the suspected solvent(s) should
be submitted to the laboratory for qualitative
characterization.
H-3
-------
SLIDE 502-9 NOTES
SAMPLING PARAMETERS ASSOCIATED WITH
VARIOUS ORGANIC COMPOUNDS
Detection limit Sample Volume (liters) Molecular
Organic Solvent (mg/sampte) Minimum Maximum Weight
Do& ^ ' U&
Acetone
Benzene
Carbon tetrachlortde
Trichloroethylene
Toluene
Xylene
—
0.01
0.20
0.05
0.01
0.02
0.5
0.5
10
1
0.5
0.5
7.7
55
60
17
22
31
58.1
78.1
154.0
131
92.1
106
SLIDE 502-10
ROUTINE SAMPLE HANDLING
1. Tightly seal and pack separately from
any process material.
2. Cushion against breakage.
3. Protect from elevated temperature and
low pressure.
4. Store in refrigerator or freezer in the lab-
oratory.
SLIDE 502-11
' for-
SPECIAL HANDLING
1. Some sorbents require shipment in
cooled (4°C) containers.
2. Samples for thermal desorption require
handling with clean, white, nylon gloves
at all times, and individually sealed
containers.
H-4
-------
SLIDE 502-12 NOTE$
COMMON SORBENTS
• Charcoal __
• Tenax® 'A6"~ *~
• Silica Gel
• XAD-2®
• Florisil®
SLIDE 502-13
PRELIMINARY DETERMINATIONS
1. Adsorption Efficiency
2. Desorption Method
3. Desorption Efficiency
4. Capacity
5. Breakthrough Volume
SLIDE 502-14
ADSORPTION EFFICIENCY
1. Sorbent Dependent
2. Analyte Dependent
3. Sampling Rate Dependent ^ '
4. Sampling Conditions (moisture,
temperature, etc.)
SLIDE 502-15
DESORPTION METHOD
1. Solvent Extraction
• displacement
• elution
2. Thermal
H-5
-------
SLIDE 502-16 NOTES
DESORPTION EFFICIENCY
1. Measured in Percent "^ l&"
2. Sorbent Dependent £=" """ u^s
3. Analyte Dependent
4. Solvent Dependent
5. Moisture, etc., may also
have an effect.
SLIDE 502-17
DESORPTION EFFICIENCIES FROM
CHARCOAL WITH CARBON BISULFIDE
SEMI-QUARTILE
ANALYTE MEDIAN (%) RANGE (%)
Benzene 98 95-100
Carbon Tetrachloride 99 97-101
Chloroform 99 97-100
1,2-Dichloroethane 99 97-100
p-Dioxane 94 91-98
Methyl Chloroform 100 98-100
Methylene Chloride 99 96-100
Toluene 98 96-100
Trichloroethylene 99 97-101
o-Xylene 97 94-99
SLIDE 502-18
CAPACITY
1. Measure in mass of analyte/unit weight
of sorbent.
2. Sorbent and analyte dependent.
3. Dependent on amount of other adsorbed
components.
H-6
-------
SLIDE 502-19 NOTES
BREAKTHROUGH VOLUME
1. Measured in same units as sam-
ple volume.
2. Dependent on analyte, sorbent,
temperature.
3. Highly variable with analyte.
SLIDE 502-20
TENAX GC BREAKTHROUGH VOLUMES
(LITERS) FOR TARGET COMPMOUNDS*
b.p. TEMPERATURE (°F)
COMPOUND
Chloroform
Carbon Tetrachloride
1 ,2-Dichloroethane
Methyl Chloroform
Tetrachloroethylene
Trichloroethylene
Chlorobenzene
(°C)
61
77
83
75
121
87
132
50
56
45
71
31
481
120
1989
60
41
36
55
24
356
89
871
70
32
28
41
20
261
67
631
80
24
21
31
16
192
51
459
90
17
17
24
12
141
37
332
100
13
13
19
9
104
28
241
*For a Tenax GC bed of 1.5 x 8.0 cm.
SLIDE 502-21
ANALYSIS
Any gas chromatograph detector de-
pends on analyte and previous know-
ledge of constituents.
Must be calibrated for each compound
to be identified and/or quantified.
Field blanks and reagent blanks must
be analyzed.
H-7
-------
SLIDE 502-22
NOTES
SLIDE 502-23
CALIBRATION
1. Liquid standards are used for calibration
curve for solvent extraction samples.
2. Gas standards are loaded on tubes for
thermally desorbed sample calibration.
H-8
-------
SLIDE 502-24
ADVANTAGES OF
EXTRACTION METHOD
1. Selection of sorbents for different ap-
plication (XAD-2, Florisil, charcoal, Chro-
mosorb 102, etc.)
2. Relatively simple equipment and hand-
ling readily available.
3. Multiple injections are possible from a
single sample. Sample dilutions and,
sometimes, concentration are possible.
NOTES
SLIDE 502-25
ADVANTAGES OF
THERMAL METHOD
1. Extremely sensitive (nanograms/
sample rather than micrograms/
sample).
2. No solvent interferences.
SLIDE 502-26
H-9
-------
SLIDE 502-27 NOTES
DISADVANTAGES OF
EXTRACTION METHOD
1. Requires relatively high concentrations
of large sample volumes.
2. Large solvent peak can mask some
components completely or interfere
with quantification.
3. Blank and/or sorbent preparation (sor-
bent dependent).
SLIDE 502-28
DISADVANTAGES OF
THERMAL METHOD
1. Limited validated sorbents (mainly
Tenax).
2. Special analytical equipment is required
(limited availability).
3. Single shot analysis.
4. Special sorbent preparation and hand-
ling procedures required.
5. High blank levels (especially benzene
and toluene).
6. Storage problems.
H-10
-------
SLIDE 502-29
,"iOTES
H-ll
-------
SLIDE 503-1 NOTES
DIRECT INTERFACE SAMPLING
AND
ANALYSIS
SLIDE 503-2
PRINCIPLE
A gas sample is extracted from the source
using a heated probe and sample line.
The sample is submitted directly to the gas
chromatograph for analysis through a heated
gas sampling valve.
SLIDE 503-3
APPLICABILITY
METHOD IS APPLICABLE AT SOURCES WHERE:
• Moisture content of gas will not interfere with
analytical method.
• Physical requirements of equipment can be
met at the site.
• Source gas concentration is low enough that
detector saturation is not a problem.
1-1
-------
SLIDE 503-4
NOTES
DIRECT INTERFACE SAMPLING SYSTEM
STACK WALL
GLASS
WOOL
NEEDLE
VALVE
HEATED TEFLON
LINE
PUMP
TO 6 C INSTRUMENT
HEATED GAS)
SAMPLING
VALVE IN G C
•-•-CARRIER IN
SLIDE 503-5
SAMPLING PROCEDURE
• Heat probe and heated sample line to a temperature
of 0-3° C above source temperature.
• Inject calibration gas mixture at the gas sampling
valve.
• Flush probe, sample line, and sample loop with
source gas.
• Analyze sample using the same conditions used for
the calibration gas mixture.
SLIDE 503-6
(cont.)
SAMPLING PROCEDURE
• Analyze two additional samples.
• Measure peak area of three samples. If they
do not agree to within 5 percent, analyze
additional samples.
• At end of sampling, analyze a second calibra-
tion gas mixture.
• Analyze audit samples.
• Record all required date on the data sheet.
1-2
-------
SLIDE 503-7
NOTES
DILUTION INTERFACE
SAMPLING PROCEDURE
Heat system to 0-3° C above source temperature or
a temperature high enough to prevent condensation
of water and/or organic compounds.
Verify operation of dilution system.
Analyze source gas samples using the same dilution
settings as used for the standards.
Analyze three separate samples.
Repeat analysis of calibration gas mixtures.
Analyze field audit samples.
SLIDE 503-8
DIAGRAM OF THE HEATED BOX
REQUIRED FOR DILUTION OF SAMPLE GAS
VENT TO CHARCOAL ADSORBERS
;
HEATED LINE
FROM PROBEc
QUICK
CONNECT
SOURCE GAS
PUMP 1.5
1/mln
150
cc/mfn
10:1 100:1
QUICK CONNECTS TO
GAS SAMPLE VALVE
150
3-WAY VALVES
IN 100:1
POSITION
/-S. ISO
I—f- )cc/m1n
CHECK VALVE QUICK
CONNECTS FOR CALIBRATION
FLCUMETERS
(ON OUTSIDE
OF BOX)
FLOW RATE OF
1.350 cc/mln
HEATED BOX AT 120 C OR SOURCE TEMPERATURE
1-3
-------
SLIDE 503-9
NOTES
SLIDE 503-10
1-4
-------
SLIDE 504-1 NOTES
VOC ANALYSIS BY
GAS CHROMATOGRAPHY
SLIDE 504-2
Defn. CHROMATOGRAPHY
Chromatography is a process of
separating mixtures by differential
migration.
SLIDE 504-3
GENERAL REQUIREMENTS
1. Stationary Phase
2. Mobile Phase
3. Defined Migration Path
SLIDE 504-4
SEPARATION PRINCIPLE
As a mixture travels along the defined
path, a component more compatible in or
on the stationary phase is slowed in com-
parison with a component more compatible
in the mobile phase.
J-l
-------
SLIDE 504-5
GAS CHROMATOGRAPHY
In gas chromatography, the mobile phase
is a gas; the stationary phase is a liquid or a
solid, and the mixture is either gaseous or a
liquid which can be vaporized.
NOTES
SLIDE 504-6
COMPONENTS OF A GAS CHROMATOGRAPH
INJECTOR COLUMN
DETECTOR
READOUT
CARRIER
GAS
SLIDE 504-7
COMMON CARRIER GASES
1. Helium
2. Nitrogen
3. Argon
4. Argon/5% Methane
J-2
-------
SLIDE 504-8
INJECTOR SYSTEMS
• Syringe
1. For liquid
2. For gases
• Sample Loops
NOTES
SLIDE 504-9
V, IDF 504 10
J-3
-------
SLIDE 504-11
TYPES OF COLUMNS
• Packed
1. glass
2. metal
• Capillary
1. glass
2. Fused silica
NOTES
SLIDE 504-12
SLIDE 504-13
J-4
-------
SI IDE 504-14
NOTES
SLIDE 504-15
COLUMN OVEN OPERATION
• Isothermal
• Temperature Programmed
SLIDE 504-16
COMMON DETECTORS
• Thermal Conductivity (TCD)
• Flame lonization (FID)
• Electron Capture (ECD)
• Flame Photometric (FPD)
• Mass Spectrometer (MS)
^'' faction
J-5
-------
SI IDE 504-17
NOTES
SLIDE 504-18
J-6
-------
SLIDE 504-19
NOTES
SLIDE 504-20
J-7
-------
SLIDE 504-21
NOTES
SLIDE. 504-22
SLIDE 504-23
READOUTS
• Strip Charts
• Integration
• Microprocessor
• Computer
J-8
-------
SLIDE 504-24
NOTES
SLIDE 504-25
J-9
-------
SLIDE 504-26
NOTES
SLIDE 504-27
SLIDE 504-28
GAS CHROMATOGRAPHIC DATA
• Qualitative (retention time)
• Quantitative (peak area)
J-10
-------
SLIDE 504-29
NOTES
TYPICAL CHROMATOGRAM
START
RUN NO. 38
AREA%
RT
0.25
0.46
2.16
2.78
4.52
5.11
5.54
7.67
8.02
TOTAL AREA = 2.8770E + 07
MUL FACTOR = 1.0000E + 00
AREA
16397
1.8154E + 07
3720200
5931
0
3422400
1296
3449400
871
TYPE
BH
ISHB
TBP
TVP
TPP
TPP
TPP
PB
BP
AR/HT
0.193
0.209
0.220
0.214
0.000
0.106
0.038
0.108
0.097
AREA%
0.057
63.099
12.931
0.021
0.000
11.895
0.005
11.989
0.003
STOP
SLIDE 504-30
UNRESOLVED PEAKS
g
d
01
J-ll
-------
SLIDE 504-31
NOTES
RESOLVED PEAKS
o
g
LU
SLIDE 504-32
QUANTITATION METHODS
• Peak Height
• Peak Area
• Electronic (or Disc) Integration
SLIDE 504-33
PEAK HEIGHT MEASUREMENTS
3.8 6.9
70.4
65.9
START
STOP
J-12
-------
SLIDE 504-34
NOTES
PEAK AREA MEASUREMENTS
SLIDE 504-35
AREA CALCULATION
A = HWi/2
Where:
A = area
H = peak height
-------
SLIDE 504-37
NOTES
CALIBRATION CURVE
E7
co 4
I3
2 2
cc
< 1
0
E-1
0 2 4 6 8 10 12 14 16 18
SLIDE 504-38
PROBLEMS IN
COMPOUND IDENTIFICATION
There are approximately 2,000,000 organic
compounds, of which 15% are volatile. There
are approximately 300,000 possible compounds
which may be found in a chromatogram.
If this number of possibilities is not signifi-
cantly reduced In the source, identification
based on retention time only is impossible.
SLIDE 504-39
PROBLEMS IN
QUANTIFICATION
• Tailing Peaks
• Overlapping Peaks
J-14
-------
SLIDE 504-40
NOTES
TAILING PEAK
START
CO
v to
-------
SLIDE 504-42
ADEQUATE RESOLUTION
EPA Method 625 criterion for adequate
resolution of overlapping compounds with
similar mass spectra:
Baseline to valley height between the
isomers is < 25% of the sum of the two
peak heights.
NOTES
SLIDE 504-43
ADEQUATE RESOLUTION
METHOD 625
12.5
J-16
-------
SLIDE 1A-1 NOTES
METHOD 1A
Sample and Velocity Traverses for
Stationary Sources with Small Stacks or
Ducts
SLIDE 1A-2
APPLICABILITY
For stacks or ducts less than 0.30 m in
diameter, or 0.071 m2 in cross-sectional
area, but > 0.10 m in diameter, or 0.0081
m2 in cross-sectional area.
SLIDE 1A-3
PRINCIPLE
• For representative measurement of pollutant
emissions and/or total volumetric flow rate.
• Select a measurement site where direction of
effluent flow is known.
K-l
-------
SLIDE 1A-4
NOTES
RECOMMENDED SAMPLING ARRANGEMENT
FOR SMALL DUCTS
FLOW
DISTURBANCE
U-2DS
hJ
8 Dc
STANDARD
PITOT TUBE
FLOW
DISTURBANCE
SAMPLING PROBE
SLIDE 1A-5
DETERMINING NUMBER OF TRAVERSE POINTS
• Determine distance between velocity and
sampling sites and to nearest upstream
and downstream disturbances.
• Divide each distance by stack diameter
to determine distances in terms of stack
diameter.
• Determine number of traverse points
corresponding to each of three distances.
K-2
-------
SLIDE 1A-6
NOTES
MINIMUM NUMBER OF TRAVERSE POINTS FOR SMALL DUCTS
NUMBER OF DUCT DIAMETERS BETWEEN VELOCITY MEASUREMENT AND NEAREST DISTURBANCE,
DISTANCE C
0.5 1.0 1.5
32
£
S 24
UJ
to
g 20
<
oe
»-
u. 16
o
I"
8
4
2.0
2.5
I
I
T
I
I
I
J_
"2 3456789 10
NUMBER OF DUCT DIAMETERS BETWEEN SAMPLING SITE AND NEAREST DISTURBANCE,
DISTANCE A
OR
NUMBER OF DUCT DIAMETERS BETWEEN SAMPLING AND VELOCITY MEASUREMENT SITES,
DISTANCE B
SLIDE 1A-7
(cont.)
DETERMINING NUMBER OF TRAVERSE POINTS
• Choose highest of three numbers of traverse
points.
• For circular stacks, number of points must
be a multiple of 4.
• For rectangular ducts, use a matrix layout
from Table 1-1 of Method 1.
K-3
-------
SLIDE 1A-8 NOTES
SELECTION OF MEASUREMENT SITE
• Select a particulate measurement site
located at least 8 stack diameters down-
stream and 10 diameters upstream from
any flow disturbance.
• Locate velocity measurement site 8
equivalent diameters downstream of
particulate measurement site.
SLIDE 1A-9
(cont.)
SELECTION OF MEASUREMENT SITE
• Alternatively, locate particulate measure-
ment site at lease 2 diameters downstream
and 2'/2 diameters upstream from any
flow disturbance.
• Locate velocity measurement site 2
diameters downstream from particulate
measurement site.
K-4
-------
SLIDE 1A-10
NOTES
MINIMUM NUMBER OF TRAVERSE POINTS FOR SMALL DUCTS
(Steady Flow Only)
NUMBER OF DUCT DIAMETERS UPSTREAM FROM NEAREST FLOW DISTURBANCE.
DISTANCE A
2.5
0.5
1.0
1.5
32
« 28
2 24
Ul
VI
3 20
2.0
T
r— 7 FLOW
\ /DISTURBANCE
T
1
B
f
t
L
SAMPLING
h AND
rVELOCITY
SITE
FLOW
I DISTURBANCE
X 1
I
I
I
I
I
23456789 10
NUMBER OF DUCT DIAMETERS DOWNSTREAM FROM NEAREST FLOW DISTURBANCE,
DISTANCE B
K-5
-------
SLIDE 2A-1 NOTES
METHOD 2A
Direct Measurement of Gas Volume Through
Pipes and Small Ducts
SLIDE 2A-2
APPLICABILITY
For measurement of gas flow rates in small
ducts, either in-line or at exhaust positions,
within temperature range of 0° to 50° C.
SLIDE 2A-3
PRINCIPLE
• Gas volume meter is used to directly measure
gas volume.
• Temperature and pressure measurement are
made to correct volume to standard conditions.
L-l
-------
SLIDE 2A-4 NOTES
EQUIPMENT
GAS VOLUME METER
A positive displacement meter, turbine meter,
or other direct volume measuring device
capable of 2% accuracy.
BAROMETER
A mercury, aneroid, or other barometer
capable of measuring atmospheric pressure
to within 2.5 mm Hg.
SLIDE 2A-5
(cont.)
STOPWATCH
A stopwatch capable of measurement to
within 1 second.
SLIDE 2A-6
PROCEDURE
INSTALLATION
Install volume meter in such a manner to
assure leak-tight connections and in a
location to avoid severe vibrations and other
factors that may affect meter calibration.
LEAK TEST
Positive Pressure
Leak-check meter connections using a liquid
leak detector solution containing a surfactant.
1-2
-------
SLIDE 2A-7
NOTES
SLIDE 2A-8
L-3
-------
SLIDE 2A-9
NOTES
I
SLIDE 2A-10
L-4
-------
SLIDE 2A-11 NOTES
(cont.)
LEAK TEST
Negative Pressure
Block flow at inlet of line and observe meter.
Alternatively, visually check all connections
and assure tight seals.
GLIDE 2A-12
VOLUME MEASUREMENT
CONTINUOUS STEADY FLOW
1. Record initial meter volume reading, temper-
ature, and pressure and start stopwatch.
2. Record meter temperature and pressure
throughout test period.
3. At end of test, stop timer and record elapsed
time, final volume reading, meter temperature
and pressure.
SLIDE 2A-13
(cont.)
CONTINUOUS STEADY FLOW
4. Record barometric pressure at beginning
and end of each test run.
NONCONTINUOUS FLOW
1. Record all meter parameters and start and
stop times corresponding to each process
cyclical or noncontinuous event.
L-5
-------
SLIDE 2A-14
NOTES
INITIAL CALIBRATION
VOLUME METER
Calibrate volume meter against standard re-
ference meter prior to initial use in field.
Run calibration over at least 3 different flow
rates.
Difference between maximum and minimum
values at each flow rate should be no greater
than 0.030 and meter coefficient should be
between 0.95 and 1.05.
SLIDE 2A-15
L-6
-------
SLIDE 2A-16
NOTES
SLIDE 2A-17
(cont.)
INITIAL CALIBRATION
BAROMETER
Calibrate barometer against mercury
barometer prior to field test.
SLIDE 2A-18
L-7
-------
SLIDE 2A-19
NOTES
SLIDE 2A-20
POSTTEST CALIBRATION
VOLUME METER
• Check volume meter calibration by per-
forming 3 calibration runs at a single inter-
mediate flow rate with meter pressure set at
average value encountered during field tests.
• Calibration is acceptable if posttest value is
within 5% of pretest value.
L-8
-------
SLIDE 2A-21
NOTES
(cont.)
POSTTEST CALIBRATION
TEMPERATURE GAUGE
Check temperature gauge after each
test series against ASTM mercury-in-
glass reference thermometer, at
ambient temperature.
Temperature gauge should agree
within 2% absolute temperature of
reference thermometer.
SLIDE 2A-22
L-9
-------
SLIDE 2A-23 NOTES
VOLUME METER
(tr + 273) Pb
Y _
(Vm,-Vml) (tm + 273) (Pb + Pg)
Where:
Y_ = test volume meter calibration coefficient, dimensionless
m
3'
m o
V = reference meter volume reading, m
V = test meter volume reading, m
m
t = reference meter average temperature, C.
t = test meter average temperature, °C.
P. = barometric pressure, mm Hg.
P = test meter average static pressure, mm Hg.
f = final reading for run.
i = initial reading for run.
SLIDE 2A-24
VOLUME
V =
ms
0.3853 Ym (Vmf-Vml)
m
Where: 3
V = volume meter reading, m at standard conditions, 20 C and 760 mm Hg.
Y = meter calibration coefficient, dimensionless.
m 3
V ,. = meter volume reading, m at final reading for run.
mf o
V . = meter volume reading, m at initial reading for run.
P. = barometric pressure, mm Hg.
P = average static pressure in volume meter, mm Hg.
o
T = average absolute meter temperature, K.
L-10
-------
SLIDE 2A-25 NOTES
GAS FLOW RATE
w
Qs = ~
Where:
Q = gas flow rate, m /min, standard conditions.
3 o
V = volume meter reading, m at standard conditions, 20 C and 760 mm Hg.
0 = elapsed run time, min.
L-ll
-------
SLIDE 2B-1 NQTES
METHOD 2B
Determination of Exhaust Gas Volume Flow
Rate from Gasoline Vapor Incinerators
SLIDE 28-2
APPLICABILITY
For measurement of exhaust volume flow
rate from incinerators that process gasoline
vapors consisting primarily of alkanes, alkenes,
and/or arenes (aromatic hydrocarbons), assum-
ing amount of auxiliary fuel is negligible.
SLIDE 2B-3
PROCEDURE
INLET INSTALLATION
• Install volume meter in vapor line to
incinerator inlet.
• Install sample probe, sample line and organic
analyzer system at volume meter inlet.
EXHAUST INSTALLATION
• Install sample probe, heated sample line and
sample manifold to incinerator exhaust.
• Install CO2, CO and organic analyzers to
manifold system.
M-l
-------
SLIDE 2B-4
NOTES
SLIDE 2B-5
EXHAUST GAS VOLUME
V = V
ves w
is
K(HC,)
K(HCe) + C02e + CO, - 300
where:
V = exhaust gas volume, m .
3
V. = inlet gas volume, m .
K = calibration gas factor - 2 for ethane calibration gas.
3 for propane calibration gas.
4 for butane calibration gas.
HC = mean organic concentration in system exhaust as defined by the
calibration gas, ppmv.
HC.j = mean organic concentration in system inlet as defined by the
calibration gas, ppmv.
C02e = mean carbon dioxide concentration in system exhaust, ppmv.
CO = mean carbon monoxide concentration in system exhaust, ppmv.
M-2
-------
SLIDE 2B-6 NOTES
(cont.)
PROCEDURE
RECORDING
• Permanently record output of each analyzer
on an analog strip chart, digital recorder or
other recording device.
• Chart speed or number of readings per time
unit must be similar for all analyzers.
• Minimum data recording requirement for
each analyzer is one measurement value per
minute.
SLIDE 2B-7
CALIBRATION
INITIAL
• Prepare and calibrate all equipment and
analyzers according to procedures in re-
spective methods.
• Introduce all calibration gases at the connec-
tion between probe and sample line.
• If manifold system is used for exhaust
analyzers, all analyzers and sample pumps
must be operating when calibrations are
complete.
SLIDE 2B-8
CALIBRATION
INITIAL
• Methane should not be used as an
organic calibration gas.
POSTTEST
• Introduce calibration gases as specified in
respective methods.
• If analyzer output does not meet specifications
of method, invalidate test data for that period.
M-3
-------
SLIDE 2B-9 NOTES
(cont.)
POSTTEST
• Alternatively, calculate volume results using
initial and final calibration data and report
both volumes.
• Calculate results using volume which results
in greatest emission rate or concentration.
SLIDE 2B-10
SAMPLING PROCEDURE
• Record initial parameters for inlet volume
meter.
• Make all recorder strip charts to indicate
start of test.
• Continue recording inlet and exhaust concen-
trations throughout test.
• Note periods of process interruption on strip
charts.
• At end of test, record final parameters for
inlet volume meter and mark end on all strip
charts.
SLIDE 2B-11
EXHAUST GAS VOLUME
V = V,
es is
(See Slide 2B-5 for nomenclature.)
M-4
-------
SLIDE 2B-12 NOTES
EXHAUST GAS VOLUME FLOW RATE
~es 0
Where:
Q = exhaust gas volume flow rate, m /min.
es o
V = exhaust gas volume, m .
9 = sample run time, min.
M-5
-------
SLIDE 2C-1 NOTES
METHOD 2C
Determination of Stack Gas Velocity and
Volumetric Flow Rate from Small Stacks or
Ducts (Standard Pilot Tube)
SLIDE 2C-2
APPLICABILITY
Method applicability is identical to Method
2 except it is limited to stationary source
stacks less than 0.30 m in diameter, or 0.071
m2 in cross-sectional area, but > 0.10 m in
diameter or 0.0081 m2 in cross-sectional
area.
SLIDE 2C-3
PRINCIPLE
Average gas velocity in a stack or duct is
determined from gas density and from measure-
ment of velocity heads with a standard pitot
tube.
SLIDE 2C-4
APPARATUS
STANDARD PITOT TUBE
• One which meets specifications of Method 2.
• Assign coefficient of 0.99 unless it is calibrated
against standard pitot tube with NBS-traceable
coefficient.
N-l
-------
SLIDE 2C-5 NOTES
MODIFIED HEMISPHERICAL-NOSED PITOTTUBE
c
4 STATIC HOLES 3/8 D
IMPACT OPENING 1/2 0
O
10 D
4 D
JL
SLIDE 2C-6
N-2
-------
SLIDE 2C-7 NOTES
(cont.)
ALTERNATIVE PITOT TUBE
• Modified hemispherical-nosed pitot tube
with shortened stem and enlarged impact
and static pressure holes.
• Assign coefficient of 0.99 unless it is
calibrated.
SLIDE 2C-8
VELOCITY PRESSURE VALIDITY TEST
• Measure velocity pressure at final traverse
point.
• Clean out impact and static holes of
standard pitot tube by back-purging with
pressurized air.
• Remeasure velocity pressure at final traverse
point.
• If velocity pressure readings made before
and after air purge are the same (±5*).
traverse is acceptable.
N-3
-------
//.-Oo
3LIDE 18-1 NOTES
METHOD 18
Measurement of Gaseous Organic Compound
Emissions by Gafe Chromatography
SLIDE 18-2
APPLICABILITY
Provides concentration data on approximately
90% of total gaseous organic mass emitted from
an industrial source.
Note: Does not include techniques to
identify and measure trace amounts of
organic compounds, such as those found
in building air and fugitive air emis-
sion sources.
SLIDE 18-3
PRINCIPLE
Based on separating components of a gas
mixture in a gas chromatographic column and
measuring separated components with suitable
detector.
SLIDE 18-4
METHOD CRITERIA
Range — 1 ppm to upper limit of GC
Sensitivity — minimum detection limit or
si'ghal-to-noise ratio 3:1
Precision — ±5% of mean value
Accuracy — ±10% audit sample value
0-1
-------
SLIDE 18-5
NOTES
PRESURVEY SAMPLES
A presurvey shall be performed on each
source to be tested'to obtain all information
necessary to design emission test.
SLIDE 18-6
PRESURVEY DATA
OBTAIN:
• stack temperature and temperature range
• approximate particulate concentration
• static pressure
• water vapor content
SLIDE 18-7
PRESURVEY SAMPLE TRAIN
• 250 ml double-ended glass sampling flask
• Method 7 evacuated flask
• Tedlar or aluminized Mylar flexible bag
• Adsorption tubes
SLIDE 18-8
0-2
-------
SLIDE 18-9 NOTES
PRESURVEY SAMPLE ANALYSIS
• Select GO column
• Select GC conditions for good resolution
• Prepare presurvey samples
• Analyze presurvey samples
SLIDE 18-10
CRITERIA FOR SAMPLE ANALYSIS
1. Prepare calibration standards by
proper technique
2. Determine optimum GC setting
3. Obtain retention times with repeat-
ability of ±0.5 s
4. Use smaller sample loop or dilution
if necessary
5. Identify all peaks >5% of total
SLIDE 18-11
CALIBRATION STANDARDS PREPARATION
• Liquid standard in desorbing solution
• Direct analysis of NBS reference gases or
commercial certified gas mixtures
• Rotameter dilution of high concentration cylinder
gases
• Direct syringe-bag dilution for known quantity
volatile liquid material
• Indirect syringe-bag dilution for known quantity
of less volatile liquid materials
0-3
-------
SLIDE 18-12 NOTES
CALIBRATION OF
DILUTION TECHNIQUE
1. Use rotameter and'micrometer values on high
concentration and diluent gas
2. A positive displacement pump or other meter
devise may be used to provide a fixed flow of
high concentration gas.
SLIDE 18-13
(cpnt.) CALIBRATION OF
DILUTION TECHNIQUE
3. Calibrate rotameter or other metering devices
with a suitably sized bubble meter, spirometer
or wet test meter.
4. Check dilution system by comparing calculated
concentration of diluted high concentration gas
to direct analysis of low concentration gas.
Note: Use single-stage dilutions to prepare
calibration mixtures up to about 1:20 dilution
factor. For greater dilutions, use a double
dilution system and check in similar manner.
0-4
-------
SLIDE 18-14
NOTES
SINGLE-STAGE CALIBRATION
GAS DILUTION SYSTEM
COMPONENT
GAS
CYLINDER
CALIBRATED ROTAMETERS
WITH FLOW CONTROL
VALVES
DILUENT
GAS
CYLINDER
"T" CONNECTOR
TEDLAR BAG
SLIDE 18-15
0-5
-------
SLIDE 18-16
NOTES
TWO-STAGE DILUTION APPARATUS
HIGH
CONCENTRATION
WASTE
ROTAMETERS
XO NEEDLE
I
k
*
io
VA
LVES LOW
•
*A
GAS
PRESSURE REGULATORS ( PR
DILUENT AIR
DILUENT AIR
PURE SUBSTANCE OR
PURE SUBSTANCE/N2 MIXTURE
SLIDE 18-17
DILUTED GAS CONCENTRATION
c -
° "
qd
Where:
C.
"a" in ppm.
X =
concentration of component
mole fraction of component "a" in the calibration gas to be diluted.
= flow rate of component "a" at measured temperature and pressure.
= diluent gas flow at measured temperature and pressure.
0-6
-------
SLIDE 18-18
COMPONENT IN FINAL GAS MIXTURE
CONCENTRATION
c.
Where:
C, = concentration of component "a" in ppm.
a
X, = mole fraction of component "a" in original gas
a
q,i = flow rate of component "a" in stage 1.
a
q,2 = flow rate of component "a" in stage 2.
a
Qji = flow rate of diluent gas in stage 1.
q.2 = flow rate of diluent gas in stage 2.
0-7
-------
SLIDE 18-19
NOTES
DILUTION BY DIRECT SYRINGE
BAG TECHNIQUE
1. Use a 10-liter Tedlar bag that has passed a leak
check.
2. Meter a known volume of about 5 liters with a
0.5 liter per revolution dry gas meter.
3. While filling the bag inlet inject a known quantity
of material through the wall of bag or septum.
4. Withdraw syringe and cover hole with tape.
SLIDE 18-20
0-8
-------
SLIDE 18-21
NOTES
DILUTION BY INDIRECT SYRINGE/
BAG TECHNIQUE
1. Use a 50-liter Tedlar bag that has passed a
leak check.
2. Adjust the flow from the nitrogen tank so It
will pass through the dry gas meter and
impinger on a hot plate with boiling water to
fill bag in approximately 15 mins.
SLIDE 18-22
(cont) DILUTION BY INDIRECT SYRINGE/
BAG TECHNIQUE
3. Fill the liquid syringe with desired liquid volume.
4. Inject liquid to inlet of heated impinger while
bag is filling.
5. Fill bag and record all necessary data.
6. Let sample equilibrate for one hour and analyze.
SLIDE 18-23
APPARATUS FOR PREPARING STANDARD GAS MIXTURES
NITROGEN
CYLINDER
BOILING
WATER BATH
TEDLAR BAG
CAPACITY
50 liters
0-9
-------
SLICE 1C-24 NOTES
STANDARD CONCENTRATION
c 760 (U (e) (273 + Tm)
stdso1 293(M, - M,) (Pbar + Pm)
Where :
Cstd sol = standard solvent concentration, mg/std liter.
I = liquid volume injected, ml.
P = liquid density at room temperature, g/ml .
T = meter temperature, °C.
MfMj = final and initial meter reading, liters.
Pbar = local barometric pressure (absolute), mm Hg.
P = meter pressure (gauge), mm Hg.
SLIDE 18-25
CALIBRATION CURVES PREPARATION
1. Obtain calibration standards such that three
^*
concentrations per attentuator range are available.
2. Establish proper GC conditioning.
3. Flush sampling loop for 30 s at 100 ml/min.
4. Repeat all standard injections until two con-
secutive injections agree within ±5% of average.
SLIDE 18-26
(cont.)
CALIBRATION CURVES PREPARATION
5. Plot concentrations along obscissa and cali-
bration area values along ordinate.
6. Perform a regression analysis and draw a least
squares line.
7. When dilution technique is used, calculated
value should be within ±10% of expected
concentration.
0-10
-------
SLIDE 18-27 NOTES
ADSORPTION AND
DESORPTION EFFICIENCY
ADSORPTION—The backup portion of the sample
must be < 10% of the total sample.
DESORPTION—A minimum desorption efficiency of
50% must be obtained.
SLIDE 18-28
EVALUATION OF CALIBRATION
AND ANALYSIS PROCEDURES
1. Perform audit analysis as described in Part 61
Appendix C, Procedure 2.
2. Audit analysis shall agree within ±10% of audit
concentration
SLIDE 18-29
FINAL SAMPLING AND
ANALYSIS PROCEDURES
CONSIDER:
• Safety
• Source conditions
• Compounds to be measured
0-11
-------
SLIDE 18-30 NOTES
SAFETY
In situations where a hydrogen flame is a
hazard and no intrinsically safe GC is suitable,
use flexible bag collection technique or an
absorption technique.
SLIDE 18-31
SOURCE CONDITIONS
• If source temperature is below 100°C and
organic concentrations are suitable for detector,
use direct interface method.
• If source emissions require dilution, use a
dilution interface and either bag sample or
adsorption tubes.
SLIDE 18-32
COMPOUNDS TO BE MEASURED
If compounds have a stability problem or
polar compounds are to be sampled, use direct
interfacing or dilution direct interfacing.
0-12
-------
SLIDE 21-1 NOTES
METHOD 21
Determination of
Volatile Organic Compound Leaks
SLIDE 21-2
APPLICABILITY
Applies to determination of volatile
organic compound leaks from the
following process equipment:
• flanges and other connections
• pumps and compressors
• pressure relief devices
• process drains
• open-ended valves
• accumulator vessel vents
• pump and compressor seal system
degassing vents
• agitator seals
• access door seals
SLIDE 21-3
PRINCIPLE
Suitable portable instrument is used to detect
VOC leaks from individual sources.
Procedure is intended to locate and classify
leaks only, and is not to be used as a direct
measure of mass emission rates from individual
sources.
P-l
-------
SLIDE 21-4 NOTES
METHOD 21 PERFORMANCE
REQUIREMENTS AND
SPECIFICATIONS
1. The device must respond to those organic
compounds processed at the facility.
2. The analyzer shall be capable of detecting
the leak definition concentration (often 10,000
ppmv) specified in the applicable regulation.
3. The scale of the instrument meter shall be
readable to ± 5 percent of the specified leak
definition concentration.
SLIDE 21-5
(cont.)
4. The instrument shall be equipped with a
pump so that a continuous sample is provided
to the detector. The nominal sample flow rate
shall be 0.5 to 3 liters per minute.
5. The instrument shall be instrinsically safe for
operation in explosive atmospheres as defined
by the National Electrical Code by the National
Fire Prevention Association.
SLIDE 21-6
(cont.)
6. The instrument response factors for the
individual compounds to be measured must
be less than 10 (compared to the reference
compound specified in the applicable reg-
ulation).
7. The instrument response time must be equal
to or less than 30 seconds, using the instru-
ment configuration used during testing.
8. The calibration precision must be equal to or
less than 10 percent of the calibration gas
valve (relative standard deviation of < 10
percent).
P-2
-------
SLIDE 21-7
TYPES OF METHOD 21 ANALYZERS
• Flame ionization
• Photoionization
• Infrared adsorption
• Catalytic combustion
SLIDE 21-8
FLAME IONIZATION DETECTOR (FID)
PRINCIPLE OF OPERATION
The sample stream is introduced into a
hydrogen flame. Upon combustion in the
flame, organic compounds produce ions
which are collected at an electrode. The
resultant current flow is measured with an
electrometer.
SLIDE 21-9
NOTES
°
P-3
-------
SLIDE 21-10
NOTES
DIAGRAM OF A FLAME
IONIZATION DETECTOR (FID)
SAMPLE
OUTLET
COLLECTION
ELECTRODE
BURNER
JET
HYDROGEN
SUPPLY
SAMPLE
INLET
SLIDE 21-11
VOC ANALYZER USING
FID DETECTOR
ELECTROMETER/
AMPLIFIER
EXHAUST—
HYDROGEN
SUPPLY
FLAME
HOUSING
I COLLECTION
ELECTRODE
'IGNITER
PANEL-MOUNTED
OR HAND-HELD
METER
STRIPCHART
RECORDER
(OPTIONAL)
a
ALARM
SAMPLE
INTAKE
SAMPLE
FLOW
METER
PARTICLE
FILTER
P-4
-------
SLIDE 21-12 NOTES
GENERAL GUIDELINES FOR SYSTEM
OPERATION USING A FID ANALYZER
SLIDE 21-13
FID OPERATION
1. Place sample probe at source.
2. Periodically recf\eck zero setting.
3. Avoid monitoring obvious leaks.
4. Periodically check flow rate and fuel supply
and perform maintenance as required.
SLIDE 21-14
FID CALIBRATION
1. Set instrument zero with flame off.
2. Ignite flame and allow to stabilize.
3. Set zero.
4. Introduce known concentration of calibration
compound near leak definition limit and
observe reading.
Note: If necessary, adjust calibration knob to read
known concentration and repeat zero and
calibration determinations until further adjust-
ment is not required.
P-5
-------
SLIDE 21-15 NOTES
FID QUALITY CONTROL/PERFORMANCE
VERIFICATION PROCEDURES
1. Check background (zero) air reading several
times per day and after each high level
measurement.
2. Check calibration daily.
3. Check air flow daily.
4. Leak check air flow system and fuel line daily.
SLIDE 21-16
(cont.)
5. Check instrument response factor.
6. Check calibration precision for three replicate
determinations every three months or after
each use, whichever is longer.
7. Check response time before performing leak
detection measurements and whenever
changes are made in the air flow, detector or
electronic portions of the instruments.
SLIDE 21-17
FID SAFETY CONSIDERATIONS
User should consult manufacturer's literature.
Primary concern is possibility for explosion.
Operator should make sure that flame arrest-
ors are properly installed.
-------
SLIDE 21-18 NOTES
(cont.)
• Refueling, battery charging, or replacement
and similar servicing and maintenance pro-
cedures should not be performed in an area
where high VOC levels might be present.
• Only VOC units which are certified as in-
trinsically safe for the particular facility being
monitored are permitted to be used for
Method 21.
SLIDE 21-19
FID PROBLEMS
• Chlorinated solvents
• Moisture
SLIDE 21-20
PHOTOIONIZATION DETECTOR (PID)
PRINCIPLE OF OPERATION
Ions are produced by an ultraviolet radiation
source rather than a flame. The ions are
collected at an electrode and the resultant
current flow is measured with an electrometer.
P-7
-------
SLIDE 21-21
DIAGRAM OF PHOTOIONIZATION
DETECTOR (PID)
COLLECTION
ELECTRODE C
lONIZATION'
CHAMBER
LAMP
-LAMP HIGH-
VOLTAGE
CONTACT
•LAMP
WINDOW
DETECTOR
EXIT
SAMPLE
INLET
NOTES
P-8
-------
SLIDE 21-22
VOC ANALYZER USING
PID DETECTOR
PID
HOUSING
EXHAUST-
ELECTROMETER/
AMPLIFIER
LAMP
u
SAMPLING
PUMP
COLLECTION
ELECTRODE
INLET
STRIPCHART |
RECORDER
(OPTIONAL)
[ALARM
ANALOG
OR
DIGITAL
DISPLAY
O
SAMPLE
INTAKE
PARTICLE
FILTER
I CHARCOAL
'FILTER
DILUTION
AIR INTAKE
NOTES
P-9
-------
SLIDE 21-23
NOTES
PID PROBLEMS
• 2,000 pprri maximum leak detection.
• No detection of methane and ethane.
• Short-circuits.
SLIDE 21-24
CATALYTIC COMBUSTION DETECTOR
PRINCIPLE OF OPERATION
This system uses a dual "hot-wire" cell in
which one of the wires is coated with a
catalyst to promote oxidation (combustion)
of organic compounds present in the sample
stream. The heat released during the com-
bustion process results in a resistance change
in the coated wire when compared to the
reference wire. This imbalance produces a
signal which is related to the VOC con-
centration.
SLIDE 21-25
P-10
-------
SLIDE 21-26
NOTES
DIAGRAM OF A CATALYTIC
COMBUSTION DETECTOR
SAMPLE INLET
SAMPLE OUTLET
CATALYTIC-COATED
FILAMENT
J'W^
lift
bC^cl
,0'^od
'o^J
°0°?
-REFERENCE CELL
-SAMPLE OUTLET
TO WHEATSTONE
"BRIDGE
SLIDE 21-27
CATALYTIC COMBUSTION DEVICE PROBLEMS
• Slow response time
• Noncornbustible
• Chlorinated solvents
P-ll
-------
SLIDE 21-28
DISPERSIVE INFRARED ADSORPTION (IR)
PRINCIPLE OF OPERATION
A dispersive IR detector involves a direct
adsorbance measurement at a particular
wavelength selected by a filter or grating
monochrometer.
NOTES
SLIDE 21-29
DIAGRAM OF DISPERSIVE
INFRARED (IR) DETECTOR
SERVO-
MOTOR
CIRCULAR
VARIABLE
FILTER
DETECTOR
PREAMPLIFIER
LENS
-PRIMARY MIRROR
P-12
-------
SLIDE 21-30 NOTES
IR DEVICE PROBLEMS
• Specific response
• Calibration gases
SLIDE 21-31
OTHER DETECTION SCHEMES
• Thermal conductivity
• Electron capture
• Enhancement of radiation from
halogens by a spark source
P-13
-------
-a
i
PERFORMANCE COMPARISON OF
FOUR MAJOR VOC ANALYZERS
1. Well detected VOC
classes
2. Poorly detected
VOC Classes
3. Typical calibration
compound
4. Typical detection
range, ppmv
5. Typical calibration
accuracy, %
6. Typical calibration
precision, %
7. Typical response
time, seconds
8. Approximate cost
9. Major advantages
10. Major limitations
L
Aliphatic olefinic, and aromatic
hydrocarbons
Highly oxygenated or halogenated
compounds. Sulfur, nitrogen, phos-
phorus containing compounds also
reduced response
Methane, propane
1-10,000
2-10
2-5
5-10
$2500-5000
a) uniform response for most hydro-
carbons
b) some response obtained for almost
all organic compounds
a) poor response for highly oxyge-
nated or chlorinated compounds
b) external gas supply (hydrogen)
required
PID
Aromatic and olefinic hydrocarbons,
chlorinated compounds
Aliphatic hydrocarbons
Benzene, butadiene
1-2000 or 10-20,000 (with dilution)
5-10
2-5
5-10
$4000-5000
a) detects oxygenated and chlorinated
compounds not detected by FIO
b) no external gas supply required
a) does not respond to aliphatic
hydrocarbons
b) detection of high levels may
require dilution of the sample
stream
Catalytic
Combustion
Similar to FID
Similar to FID
Methane, propane
Several ranges
available from
10 ppm up to low-
er explosion
limit
2-10
2-5
5-20
$300-2000
a) low cost
b) relatively
uniform
response for
most hydro-
carbons
c) no external gas
supply required
a) poor response
for highly oxy-
genated or
chlorinated
compounds
b) not as sensi-
tive as the
other tech-
nique
IR
Hydrocarbons
Highly dependent on IR
absorption spectrum. Water
vapor will interfere with
certain compounds
Compound of interest or very
similar compound
1-10,000 (highly dependent
on specific compound)
2-10
2-5
5-100
$4000-7000
a) qualitative information may
be obtained
b) no external gas supply
required
L
a) water vapor and other
atmospheric constituents
may interfere
b) sensitivity highly dependent
on the specific compound of
interest
c) expensive
L
GO
I—
I—(
o
I
GO
IX)
-------
SLIDE 21-33
COMMERCIALLY AVAILABLE PORTABLE VOC ANALYZERS a
— "
Manufacturer
FID
Analytical Inst.
Development,
Inc.. Avondale,
PA
Foxboro Analy-
tical, S. Nor-
nlk. CT
Health Consult-
ants, Inc..
Stroughton, MA
Survey and
Analysis. Inc.,
(torthboro, MA
P1D
Analytical Inst.
Development,
Avendale, PA
HNU Systems,
Newton, MA
Model
number
712
OVA- 108
Detecto-
Pak II
A-500
S8S
PI-101
Weight,
Ibs
14
12
8
17
8.2
12
Cost,
$
$4.300
$4.200
$2,950
$2.295
$4.200
$4,000
Detection
range,
ppmv
1-2000 or
10-20.000
0-10.000
0-1.000
0-10.000
0-1,000
0-2,000
Sensitivity
ppmv
0.1 (as methane)
0.5 (as methane)
5 (as methane)
2 (as methane)
1 (as benzene)
1 (as benzene)
Calibration
precision.
%
--
+2
--
--
—
--
Calibration
accuracy.
%
--
2
4
20
—
—
Response
time.
seconds
5
2
15
4
2
5
Nominal
sampling
rate. F/mln
1.5
2.0
--
—
0.5
0.5
Comments
Optional GC available
Optional GC available
10.0 and 118 eV lamps
available
9.5. 10.2. 10.9 and
11.7 eV lamps available
SLIDE 21-34
COMMERCIALLY AVAILABLE PORTABLE VOC ANALYZERS (Continued)
1 Model
number
CATALYTIC COMBUSTION
Bacharach Inst.
Co., Santa
Clara, CA
Biomarine
Industries, Inc.
Ha Kern, PA
Gas Tech, Inc.
Mountain View,
CA
Hine Safety
Appliances Co.,
Pittsburgh, PA
Survey and
Analysis, Inc..
Northboro, MA
iNFRAREDJEVICES
Foxboro Analy-
tical, S. Nor-
walk, CT
TLV
Sniffer
922
1177
260
Onmark
Model 5
(OISPERSI
Mlran-
1A
Weight,
Ibs
5
1.5
6
6
5
'11
32
Cost.
$
$900
$500
$500
$800
$300
$7,000
Detection
range,
ppmv
0-10.000
0-100*LELb
0-100%LEL
or 0-500
ppm
0-100JLEL
0-5«LEL
ppm-% level
Sensitivity
ppmv
2 (as methane)
__
__
..
„
1 (highly
dependent on
compound of
Interest)
Calibration
precision,
%
+3
+5
+3
+2
Calibration
accuracy,
%
3
2
3
3-4
Response
time,
seconds
5
4
S
10
Select-
able
1-40
Nominal
sampling
rate,
-------
SLIDE 21-35
PORTABLE VOC
DETECTOR INSTRUMENT CERTIFICATION
Manufacturer
Analytical Instrument Development, Co.,
Avondale, Pennsylvania
Bacharach Instrument Co.,
Santa Barbara , CA
Century Systems,
Arkansas City, Kansas
HNU Systems, Inc.,
Newton Upper Falls, Massachusetts
Mine Safety Appliances Co.,
Pittsburgh, Pennsylvania
Survey and Analysis, Inc.,
Northboro, Massachusetts
Model No.
712
L
TLV Sniffer
OVA-128
OVA- 108
PI-101
40
OnMark
Model 5
Certification
Intrinsically
Intrinsically
Intrinsically
and Class 1,
Intrinsically
Intrinsically
Intrinsically
safe,
Class
safe, Class
safe, Class
Division 2,
safe,
safe,
safe,
Intrinsically safe,
Class 1 , Division 2
Intrinsically
safe,
Class
Class
Class
1
, Division
1, Division
1, Division
Groups A and
1
1
1
Class 1
, Groups
Class
1
, Division
, Division
, Division
, Division
A, B, and
, Division
1,
1,
1,
B
1,
1.
2,
1.
C
1,
Groups
Groups
Groups
Groups
Groups
Groups
Group
Groups
A
C
A
A
A
A
D,
A
, B, C, and D
and D
, B, C, and D,
, B, C, and D
, B, C, and D
, B, C, and D
and
, B, C, and D
NOTES
P-16
-------
SLIDE 21-36
NOTES
SLIDE 21-37
P-17
-------
SLIDE 21-38
SLIDE 21-39
P-18
-------
SLIDE 21-40
NOTES
SLIDE 21-41
INSTRUMENT SUITABILITY
REFINERIES
• FID
• Catalytic combustion
SOCMI
• FID
• PID
• IR
• Catalytic combustion
P-19
-------
SLIDE 21-42 NOTES
FIELD PROBLEMS
• Mqisture
• Calibration gases
• Durability
SLIDES FOR EXTENDED LECTURE
SLIDE 21-43 NOTES
GENERAL GUIDELINES FOR SYSTEM
OPERATION USING A FID ANALYZER
SLIDE 21-44
FID ASSEMBLY/START-UP
1. Install probe.
2. Check fuel supply.
3. Test battery.
4. Turn on electronics and set instrument zero.
5. Check installation of flame arrestors.
P-20
-------
SLIDE 21-45 NOTES
(cont.)
6. Start sampling pump and check probe leakage.
7. Start hydrogen flow, leak check, and ignite
flame.
8. Null meter output and set alarm levels.
9. Calibrate daily.
SLIDE 21-46
FID OPERATION
1. Place sample probe at source.
2. Periodically recrjeck zero setting.
3. Avoid monitoring obvious leaks.
4. Periodically check flow rate and fuel supply
and perform maintenance as required.
SLIDE 21-47
FID SHUTDOWN
1. Close fuel supply valve and tank valve.
2. Shut down electronics except for sample
pump.
3. Wait 10 to 20 seconds and shutdown sampling
pump.
P-21
-------
SLIDE 21-48 NOTES
FID CALIBRATION
1. Set instrument zero with flame off.
2. Ignite flame and allow to stabilize.
3. Set zero.
4. Introduce known concentration of calibration
compound near leak definition limit and
observe reading.
Note: If necessary, adjust calibration knob to read
known concentration and repeat zero and
calibration determinations until further adjust-
ment is not required.
SLIDE 21-49
FID ROUTINE MAINTENANCE
1. Replenish fuel supply.
2. Check/recharge batteries.
3. Replace/clean partfcle filter.
4. Replace charcoal filter.
5. Clean/replace flame arresters.
6. Leak check flow system/gas supply
lines.
SLIDE 21-50
FID QUALITY CONTROL/PERFORMANCE
VERIFICATION PROCEDURES
1. Check background (zero) air reading several
times per day and after each high level
measurement.
2. Check calibration daily.
3. Check air flow daily.
4. Leak check air flow system and fuel line daily.
P-22
-------
SLIDE 21-51 NOTES
(cont.)
5. Check instrument response factor.
— _.._„., •noiiuiiioni icapuiido lauiur.
6. Check calibration precision for three replicate
determinations every three months or after
each use, whichever is longer.
7. Check response time before performing leak
detection measurements and whenever
changes are made in the air flow, detector or
electronic portions of the instruments.
SLIDE 21-52
FID SAFETY CONSIDERATIONS
• User should consult manufacturer's literature.
• Primary concern is possibility for explosion.
• Operator should make sure that flame arrest-
ors are properly installed.
SLIDE 21-53
(cont.)
• Refueling, battery charging, or replacement
and similar servicing and maintenance pro-
cedures should not be performed in an area
where high VOC levels might be present.
• Only VOC units which are certified as in-
trinsically safe for the particular facility being
monitored are permitted to be used for
Method 21.
SLIDE 21-54
FID PROBLEMS
• Chlorinated solvents
• Moisture
P-23
-------
SLIDE 21-55 NOTES
GENERAL GUIDELINES FOR SYSTEM
OPERATION USING A PID ANALYZER
SLID: 21-56
PID ASSEMBLY/START-UP
1. Install probe.
2. Yest battery.
SLIDE 21-57
(cont.)
3. Turn gn electronics and visually
observe lamp.
4. Leak check sample line.
5. Set electronic zero and alarm levels.
6. Set zero.
7. Calibrate.
P-24
-------
SLIDE 21-58 NOTES
PID ROUTINE MAINTENANCE
1. Charge/replace batteries.
2. Replace/clean particle filter.
3. Replace charcoal filter.
4. Replace/clean lamp cell window.
5. Replace lamp.
6. Leak check sample flow system.
SLIDE 21-59
PID QUALITY CONTROL/PERFORMANCE
VERIFICATION PROCEDURES
1. Check background (zero) air reading several
times each day and after each high level
measurement.
2. Check calibration daily.
3. Check air flow periodically.
4. Check instrument response factor.
SLIDE 21-60
(cont.)
5. Check calibration precision for three replicate
determinations every three months or after
each use, whichever is longer.
6. Check response time before performing leak
detection measurements and whenever
changes are made in the air flow, detection,
or electronic portions of the instrument.
P-25
-------
SLIDE 21-61 NOTES
PID OPERATION
1. Place sample probe at source.
2. Periodically recheck zero setting.
3. Avoid direct measurement of obvious leaks to
avoid gross contamination of the instrument.
4. Periodically check battery level and visually
confirm lamp operation.
SLIDE 21-62
PID SHUTDOWN
1. Place instrument in standby
position.
2. Shut off electronics.
SLIDE 21-63
PID CALIBRATION
1. Set electronic zero.
2. Set zero using background air.
3. Introduce known concentration
of calibration compound repre-
senting approximately 80% of
the leak definition.
Note: If necessary, adjust calibration
control to read known concen-
tration. Repeat zero and calibra-
tion measurements until further
adjustment is not necessary.
P-26
-------
SLIDE 21-64 NOTES
PID SAFETY CONSIDERATIONS
• Electrical system has potential to create sparks
which could initiate an explosion.
• Any maintenance or repair work must be
performed away from potential sources of
VOC contamination.
SLIDE 21-65
PID PROBLEMS
• 2,000 ppm maximum leak detection.
• No detection of methane and ethane.
• Short-circuits.
P-27
-------
NOTES
SI.TDC 21-66
GENERAL GUIDELINES FOR SYSTEM
OPERATION USING A CATALYTIC
COMBUSTION ANALYZER
SLTDF 21-67
CCA ASSEMBLY/START-UP
1. Install probe assembly.
2. Test battery.
3. Check installation of flame arresters.
4. Turn on electronics and allow a 5 to 10
minute warm-up period.
5. Null meter output and set alarm levels.
6. Calibrate daily.
SLIDE 21-68
CCA OPERATION
1. Place sample probe at source.
2. Periodically recheck zero setting.
3. Avoid monitoring obvious leaks.
4. Periodically check flow rate and perform
maintenance as required.
P-28
-------
SLIDE 21-69 NOTES
CCA SHUTDOWN
1. Shut down electronics except for sample
pump.
2. Wait 10 to 20 seconds and shutdown sample
pump.
SLIDE 21-70
CCA CALIBRATION
1. Set instrument zero.
2. Set zero using background (charcoal filtered)
or clean air supply.
3. Introduce known concentrations of calibration
compound near (—80% of) leak definition
limit and observe reading.
NOTE: If necessary, adjust calibration knob
to read known concentration and repeat zero
and calibration determinations until further
adjustment is not required.
SLIDE 21-71
CCA ROUTINE MAINTENANCE
1. Replace filaments.
2. Check/recharge batteries.
3. Replace/clean particle filter.
4. Replace charcoal filter.
5. Clean/replace flame arrestor.
6. Leak check sample flow system.
P-29
-------
SLIDE 21-72 NOTES
CCA QUALITY CONTROL/PERFORMANCE
VERIFICATION PROCEDURES
1. Check background (zero) air reading several
times each day and after each high level
measurement.
2. Check calibration daily.
3. Check air flow daily.
4. Leak check air flow system daily.
SLIDE 21-73
(cont.)
5. Check instrument response factor.
6. Check calibration precision for three replicate
determinations every three months or after
each use, whichever is longer.
7. Check response time before performing leak
detection measurements and whenever
changes are made in the air flow, detector or
electronic portions of the instrument.
SLIDE 21-74
CCA SAFETY CONSIDERATIONS
• Possibility for explosion.
• Servicing and maintenance procedures should
not be performed in an area where high VOC
levels might be present.
SLIDE 21-75
CATALYTIC COMBUSTION DEVICE PROBLEMS
• Slow response time
• Noncombustible
• Chlorinated solvents
P-30
-------
SLIDE 21-76 NOTES
GENERAL GUIDELINES FOR SYSTEM
OPERATION USING AN IR DETECTOR
SLIDE 21-77
IR ASSEMBLY/START-UP
1. Install probe.
2. Check battery.
3. Turn on electronics and allow instrument to
warm-up for 10 to 15 minutes. Purge optical
cell with clean, dry air or nitrogen if moisture
condensation is a problem.
SLIDE 21-78
(cent (contjcont)
4. Select analytical and reference wavelengths
for VOC of interest.
5. Leak check sample flow assembly.
6. Check optical system alignment.
7. Determine detector output for background
(zero) air supply.
8. Calibrate daily.
SLIDE 21-79
IR OPERATION
1. Place sample probe at source to be measured.
2. Periodically recheck zero setting.
3. Avoid monitoring obvious leaks to avoid gross
contamination of the instrument.
P-31
-------
SLIDE 21-80 NOTES
(cont.)
4. Periodically check sample flow rate and
perform maintenance as required.
5. Perform measurements at alternate wave-
lengths as appropriate to confirm identity of
the VOC being monitored.
SLIDE 21-81
IR SHUTDOWN
1. Shut down electronics.
SLIDE 21-82
IR CALIBRATION
1. Set zero using background (charcoal filtered)
or zero air supply.
2. Introduce known concentration of calibration
compound near leak definition limit and
observe reading.
3. Repeat process for each analytical wave-
length of interest.
NOTE: If necessary, adjust calibration output
to read known concentration and repeat zero
and calibration determinations until further
adjustment is not required.
P-32
-------
SLIDE 21-83 NOTES
IR ROUTINE MAINTENANCE
1. Flush/clean optical cell.
2. Check/recharge batteries.
3. Replace/clean particle filter.
4. Replace charcoal filter.
5. Leak check sample flow system.
SLIDE 21-84
IR QUALITY CONTROL/PERFORMANCE
VERIFICATION PROCEDURES
1. Check background (zero) air reading several
times each day and after each high level
measurement.
2. Check calibration daily.
3. Check air flow daily.
4. Leak check air flow system daily.
5. Check instrument response factor for regu-
lated compound (relative to reference com-
pound) before performing measurements.
6. Check calibration precision for three replicate
determinations every three months or after
each use, whichever is longer.
7. Check response time before performing leak
detection measurements and whenever chang-
es are made in the air flow, detector, or
electronic portions of the instrument.
SLIDE 21-85
IR DEVICE PROBLEMS
• Specific response
• Calibration gases
P-33
-------
SLIDE 23-1 NOTES
METHOD 23
Determination of Halogenated
Organics from Stationary Sources
SLIDE 23-2
APPLICABILITY
Applies to measurement of halo-
genated organics such as:
• carbon tetrachloride
• ethylene dichloride
• perchloroethylene
• trichloroethylene
• methylene chloride
• 1,1,1-trichloroethane
• trichlorotrifluoroethane
Note: Does not measure halogenated organics
contained in participate matter.
SLIDE 23-3
PRINCIPLE
An integrated bag sample of stack gas
containing one or more halogenated organics Is
subjected to gas chromatographic analysis,
using a flame ionization detector.
Q-l
-------
SLIDE 23-4 NOTES
INTERFERENCES
A suitable gas chromatograph
column must be used to provide
adequate resolution of the halogen-
ated compounds.
SLIDE 23-5
APPARATUS
SAMPLING—Integrated Bag Sampling Train
ANALYSIS—Gas Chromatograph with FID, potentio-
metric strip chart recorder, 1.0 to 2.0 ml
sampling loop, and a stainless steel 3.05
m by 3.2 mm column containing 20%
SP-2100/0.1% Carbowax 1500 on 100/120
Supelcoport.
Note: Adequate peak solution is defined
as an overlap of not more than 10% of the
halogenated organic compound.
SLIDE 23-6
SAMPLING
Use standard integrated bag sampling tech-
nique. The sample must be analyzed within 1
day for:
• Methylene Chloride
• Ethylene Oichloride
• Trichlorotrifluoroethane
within 2 days for:
• Perchloroethylene
• Trichloroethylene
• 1,1,1-Trichloroethane
• Carbon Tetrachloride
Q-2
-------
SLIDE 23-7
NOTES
ANALYSIS
SAMPLE ANALYSIS—Directly from bag to sample loop.
CALIBRATION STANDARDS—Three certified gas cylinders or
prepare standards from 99 Mol.
% halogenated organic
compound.
SLIDE 23-8
INJECTION VALUES FOR PREPARATION OF STANDARDS
Compound
Perchloroethytene,
C2CI«
Trichloroethylene,
1 , 1 ,1 -Trichloroethane,
Methylene Chloride,
CH2CI2
Trichlorotrifluoroethane,
C2CI3F3
Carbon Tetrachloride,
CCI4
Ethylene Dichloride,
C2H4CI2
Molecular
weight,
g/g-mole
165.85
131.40
133.42
84.94
187.38
153.84
98.96
Density
at 293 K,
g/ml
1.6230
1.4649
1.4384
1.3255
1.5790
1.5940
1.2569
/d/50Hter of N2 required
for approximate
concentration of:
200 ppm 100 ppm 50 ppm
42.5
37.3
38.6
26.6
49.3
40.1
32.7
21.2
18.6
19.3
13.3
24.7
20.1
16.4
10.6
9.3
9.6
6.7
12.3
10.0
8.2
SLIDE 23-9
QUALITY ASSURANCE
• Sample bags must pass leak check.
• Analysis audit according to Appendix E,
Supplement B.
Q-3
-------
SLIDE 23-10 NOTES
HALOGENATED ORGANIC
STANDARD CONCENTRATION
c g (24.055 x 10°)
= 6.240 x 104
M Vm Y P,
m • • m
Where:
B = volume of halogenated organic injected, yl.
D = density of compound at 293°K, g/ml.
M = molecular weight of compound, g/g-mole.
V = gas volume measured by dry gas meter, liters.
Y = dry gas meter calibration factor, dimensionless.
P = absolute pressure of dry gas meter, mm Hg.
T = absolute temperature of dry gas meter, °K.
24.055 = ideal gas molal volume at 293°K and 760 mm Hg, liters/g-mole.
3
10 = conversion factor. [(ppm)(ml
Q-4
-------
SLIDE 23-11 NOTES
SAMPLE CONCENTRATIONS
c. =
_ C.PJ.
Where:
C = concentration of the halogenated organic indicated by the gas
chromatograph, ppm.
P = reference pressure, the laboratory pressure recorded during cali-
bration, mm Hg.
T. = sample loop temperature at the time of analysis, °K.
P. = laboratory pressure at time of analysis, mm Hg.
T = reference temperature, the sample loop temperature recorded during
calibration, K.
S . = water vapor content of the bag sample, volume fraction.
Q-5
-------
SLIDE 24-1 NOTES
METHOD 24
Determination of Volatile Matter Content,
Water Content, Density, Volume Solids,
and Weight Solids of Surface Coatings
SLIDE 24-2
APPLICABILITY
For volatile organic content of paints used in
auto, appliance, metal furniture, metal coil coating,
and other industries. Can be used for both
water-borne and solvent-borne coatings.
SLIDE 24-3
ADVANTAGE
Less costly.
DISADVANTAGE
Considerable error may be introduced in
measurement of organic content of water-
borne coatings since this is an indirect
measurement technique.
R-l
-------
SLIDE 24-4 NOTES
NOT APPLICABLE
1. For all kinds of coatings or printing materials.
Method 24A should be used for printing inks.
No method has been specified for glues and
adhesives.
2. For two package (component) coatings, par-
ticularly if the coatings react during curing and
form volatile reaction products.
3. For coatings that require energy other than heat
to initiate curing. May not work on coatings that
require high temperature catalysis for curing.
SLIDE 24-5
SUMMARY OF METHODS
WATER CONTENT
Standard Method of Test for Water in Water-
Reducible Paint by Direct Injection Into a Gas
Chromatograph. ASTM D 3792-79.
OR
ASTM Provisional Method of Test for Water in
Paint or Related Coatings by the Karl Fischer
Titration Method.
CLIDE 24-6
SUMMARY OF METHODS (continued)
VOLATILE MATTER
Provisional Method of Test for Volatile
Content of Paints. ASTM D 2369-81.
DENSITY
Standard Method of Test for Density of
Paint, Lacquer, and Related Products.
ASTM D 1475-60.
R-2
-------
SLIDE 24-7
DATA VALIDATION PROCEDURE
Run duplicate analyses on each sample
tested and compare results with the
within-laboratory precision statements
for each parameter.
NOTES
SLIDE 24-8
ANALYTICAL PRECISION STATEMENTS
PARAMETER WITHIN- BETWEEN-
PAHAMtltH LABORATORY LABORATORY
Volatile Matter Content, Wv 1.5% Wv 4.7% Wv
Water Content. Ww 2.9% Ww 7.5% Ww
Density, Dc 0.001 kg/liter 0.002 kg/liter
R-3
-------
SLIDE 24- 9
CALCULATIONS
NONAQUEOUS VOLATILE MATTER
Solvent-borne Coatings
NOTES
Waterborne Coatings
W = W - W
w
WEIGHT FRACTION SOLIDS
w = 1 - w,
Where:
W = weight fraction nonaqueous volatile matter, g/g.
W = volatile matter content.
v
W = water content.
w
W = weight solids, g/g.
SLIDE 24-10
R-4
-------
SLIDE 24A-1 NOTES
METHOD 24A
Determination of Volatile Matter
Content and Density of Printing Inks
and Related Coatings
SLIDE 24A-2
APPLICABILITY AND PRINCIPLE
Standard methods are used to determine
components of solvent-borne printing inks
or related coatings.
The VOC weight fraction is determined
by measuring the weight loss of a known
quantity which has been heated for a
specified length of time at a specified
temperature.
SLIDE 24A-3
SAMPLING
Obtain a representative sample of
the ink or coating material.
SLIDE 24A-4
ANALYSIS
1. Tare three aluminum foil dishes to the nearest
0.1 mg.
2. Using a 5 ml syringe without needle remove a
sample and weigh to the nearest 0.1 mg.
3. Transfer 1 to 3 g of sample to a tared weighing
dish.
4. Reweigh the syringe to the nearest 0.1 mg.
S-l
-------
SLIDE 24A-5 NOTES
(cont.)
ANALYSIS
5. Heat the weighing dish and sample in a
vacuum oven at an absolute pressure of
510 ± 51 mm Hg and a temperature of 120
±2°C.
6. Alternatively, heat the dish and sample in
a forced draft oven at 120 ± 2° C for 24
hours.
7. After dish has cooled, reweigh to the
nearest 0.1 mg.
8. Repeat this procedue for a total of three
determinations of each sample.
SLIDE 24A-6
(cont.)
ANALYSIS
9. Determine the density of the ink or coating
according to ASTM D 1475-60.
10. Determine the density of the solvent according
ASTM D 1475-60.
11. Calculate the weight fraction volatile organic
content (W ).
S-2
-------
SLIDE 24A-7 NOTES
WEIGHT FRACTION
VOLATILE ORGANIC CONTENT
W = IVix1 "•" IVIcY1 " McY2
o —
"McY2
Where:
W = weight fraction of VOC, g/g.
M , = tare weight of aluminum dish, g.
M Yi = weight of full syringe, g.
M Y2 = weight of syringe after dispensing sample, g.
M 2 = final weight of dish after heating, g.
SLIDE 24A-8
WEIGHT FRACTION
VOLATILE ORGANIC CONTENT
_ MCY1 - MCY2 - (MX2 - MX1)
MCY1 — McY2
(see nomenclature above)
S-3
-------
SLIDE 24A-9 NOTES
VOLUME FRACTION
VOLATILE ORGANIC CONTENT
V =Wo°o
~
Where:
V = volume fraction, ml/ml.
W = weight fraction of VOC, g/g.
D = density of coating.
D = density of solvent.
S-4
-------
SLIDE 25-1 NOTES
METHOD 25
Determination of Total Gaseous
Nonmethane Organic Emissions
as Carbon
SLIDE 25-2
APPLICABILITY
For the measurement of volatile organic
compounds (VOC) as total gaseous nonmethane
organics (TGNMO) as carbon in source e-
missions.
SLIDE 25-3
APPLICABILITY
For measuring control efficiency from coating
operations including auto, appliance, metal
furniture, and metal coil coating.
NOT APPLICABLE
1. For measuring concentations of VOC or mass
emissions of VOC from sources whose con-
centrations are < 50 ppm (as C^.
2. For measuring emissions from sources whose
principle solvents are chlorinated hydrocarbons.
3. Generally, for any situation where a simpler
procedure is more accurate.
T-l
-------
SLIDE 25-4 NOTES
PRINCIPLE
A gas sample is withdrawn from the stack at a
constant rate through a chilled condensate trap
by means of an evacuated sample tank.
TGNMO are determined by combining the
analytical results obtained from independent
analyses of the condensate trap and sample
tank fractions.
SLIDE 25-5
INTERFERENCE
Organic particulate matter will interfere with
the analysis; therefore, an in-stack particulate
filter may be required.
SLIDE 25-6
ADVANTAGES
1. Gives consistent results from source to source
whether sample composition is known or not.
2. Sample train requires no electricity at sample
site (minimizes explosion hazard).
DISADVANTAGES
1. Will not yield true mass emission rate nor
instantaneous results.
2. No real time data (sample must be returned to
lab).
3. High moisture and CO2 together can cause
interferences.
T-2
-------
SLIDE 25-7 NOTES
RM 25-SUMMARY
• Withdraw emission sample from stack
through chilled condensate trap into
evacuated cylinder.
• Analyze contents of trap and cylinder
separately.
• Oxidize organic content of trap to
CO2, reduce to methane, measure
with FID.
• Inject portion of cylinder sample into
GC to separate nonmethane organics,
oxidize NMO to CO2, reduce to
methane, measure with FID.
• Combine results and report as total
gaseous nonmethane organics.
SLIDE 25-8
APPARATUS
SAMPLING SYSTEM:
• Probe
• Condensate Trap
• Flow Control System
• Sample Tank
T-3
-------
SLIDE 25-9
NOTES
PROBE EXTENSION
(IF REQUIRED)
STACK WALL
SAMPLING SYSTEM
FLOW RATE
CONTROLLER
ON/OFF
FLOW
VALVE
PROBE
VACUUM
GAUGE
QUICK
CONNECT
EVACUATED
SAMPLE TANK
CONDENSATE
TRAP
SLIDE 25-10
T-4
-------
SLIDE 25-11
NOTES
ANALYTICAL SYSTEM
• Oxidation system for recovery and
conditioning of condensate trap
contents
1. Heat source
2. Oxidation catalyst
3. Nondispersive infrared analyzer
4. Intermediate collection vessel
• NMO Analyzer
1. GC with backflush capabilities
2. Oxidation catalyst
3. Reduction catalyst
4. FID
SLIDE 25-12
SCHEMATIC OF NONMETHANE ORGANIC (NMO) ANALYZER
CALIBRATION STANDARDS
SAMPLE TANK
INTERMEDIATE COLLECTION VESSEL'
(CONDITIONED TMP «-«»-rtl
CARRIER GAS
te-
SAMPLE
INJECTION
LOOP
SEPARATION COLUMN
CO,CH4,C02
OXIDATION
CATALYST
BACKFLUSH
REDUCTION
CATALYST
DATA RECORDER
FLAME IONIZATION
DETECTOR
-HYDROGEN
-COMBUSTION AIR
T-5
-------
SLIDE 25-13
SAMPLING
• Sample Tank Evacuation and Leak Check
• Sample Train Assembly
• Pretest Leak Check
• Sample Train Operation
• Post Test Leak Check
NOTES
SLIDE 25-14
IDE .25-15
-------
25-16
NOTES
SLIDE 25-17
T-7
-------
SLIDE 25-18
SLIDE 25-19
CONDENSATE TRAP
INLET TUBE, 6mm (1/4 In.) O.D.
PROBE, 3nm (1/8 in.) O.D.
CONNECTOR
EXIT TUBE, 6mn (1/4 in.) O.Dr
CONNECTOR/REDUCER
NO. 40 HOLE ---
(THRU BOTH WALLS).
WELDED JOINTS
CRIMPED AND WELDED GAS-TIGHT SEAL
BARREL 19mn (3/4 in.) O.D.
x 140mm (5-1/2 1n.) LONG,
1.5mm (1/16 in.) WALL
BARREL PACKING.
316 SS WOOL PACKED TIGHTLY AT BOTTOM,
LOOSELY AT TOP
^ -HEAT SINK (NUT,
PRESS-FIT TO BARREL)
"^-WELDED PLUG
MATERIAL: TYPE 316 STAINLESS STEEL
-------
SLIDE 25-20 NOTES
SAMPLE RECOVERY
1. Disconnect condensate trap and
seal both ends.
2. Keep trap in dry ice until returned
to lab for analysis.
3. Remove flow metering system
from sample tank.
4. Attach manometer and record
final tank vacuum.
5. Record tank temperature and
barometric pressure.
6. Disconnect manometer.
7. Properly identify condensate trap
and sample tank(s).
SLIDE 25-21
F '
SLIDE 25-22
ANALYSIS
• Initial Performance Test
• Daily Operations and Calibration
Checks
• Analysis of Recovered Condensate
Sample
• Analysis of Sample Tank
T-9
-------
SLIDE 25-23
NOTES
NONMETHANE ORGANIC (NMO) ANALYZER
NONMETHANE
ORGANIC
(BACKFLUSH)
ZERO
AIR
OR 5%
02/N2
SAMPLE TANK/
CALIBRATION
CYLINDERS
/\ VALVE
CARRIER GAS
SLIDE 25-24
T-10
-------
SLIDE 25-25
INITIAL PERFORMANCE CHECK OF CONDENSATE
RECOVERY AND CONDITIONING APPARATUS
• Carrier Gas and Auxiliary Oxygen
Blank
• Catalyst Efficiency Check
• System Performance Check
NOTES
SLIDE 25-26
CONDENSATE RECOVERY
AND CONDITIONING
• System Blank and Catalyst Efficiency
Check
• Condensate Trap Carbon Dioxide
Purge and Sample Tank Pressurization
• Recovery of Condensate Trap Sample
SLIDE 25-27
CONDENSATE RECOVERY AND
CONDITIONING APPARATUS
(Carbon Dioxide Purge)
VENT
REGULATING
VALVE
(OPEN)
•FOR MONITORING
PROGRESS OF
COMBUSTION ONLV
CONNECT,
SAMPLE
TANK
'•FOR EVACUATING COLLECTION VESSELS
AND SAMPLE TANKS (OPTIONAL)
(CLOSED)
MERCURV VACUUM PUMP**
MAN«ET£R
T-ll
-------
SLIDE 25-28
NOTES
SLIDE 25-29
CONDENSATE RECOVERY AND
CONDITIONING APPARATUS
(Collection of Trap Organics)
(CLOSED)
*FOR EVACUATING COLLECTION VESSELS
AND SAMPLE TANKS (OPTIONAL)
MERCURY VACUUM PUMP*
MANOMETER
T-12
-------
SLIDE 25-30
NOTES
SLIDE 25-31
T-13
-------
SLIDE 25-32
NOTES
SLIDE 25-33
INITIAL NMO
ANALYZER PERFORMANCE TEST
• Oxidation Catalyst Efficiency Check
• Analyzer Linearity Check and NMO
Calibration
• Reduction Catalyst Efficiency Check
and CO2 Calibration.
• NMO System Blank
• System Performance Check
SLIDE 25-34
NMO ANALYZER
DAILY CALIBRATION
• NMO Blank and CO2
• NMO Calibration
T-14
-------
SLIDE 25-35
NOTES
NONMETHANE ORGANIC (NMO) ANALYZER
SEPARATION
COLUMN
NONMETHANE
ORGANIC
(BACKFLUSH)
ZERO
AIR
OR 5*
02/N,
COLUMN
BACKFLUSt
VALVE
CATALYST X
BYPASS VALVE
SAMPLE TANK/
CALIBRATION
CYLINDERS
SAMPLE
INJECT
VALVE
OXIDATION
CATALYST
I HEATED CHAMBER
FLOW
REGULATOR)
CATALYS
BYPASS VALVE
I I REDUCTION
| I CATALYST
HEATED CHAMBER I
I ,_J
FLOW
METER
CARRIER GAS
SLIDE 25-36
T-l
i c
-------
SLIDE 25-37
NOTES
SLIDE 25-38
T-16
-------
SLIDE 25-39 N0TES
ANALYSIS
RECOVERED CONDENSATE SAMPLE:
Inject triplicate samples from the
intermediate collection vessel and
record values obtained for condensible
organics as CO2.
SLIDE 25-40
ANALYSIS (continued)
SAMPLE TANK:
Inject triplicate samples from the
sample tank and record the values
obtained for nonmethane organics.
SLIDE 25-41
SAMPLE TANK AND INTERMEDIATE COLLECTION
VESSEL VOLUME DETERMINATION-
PRIOR TO SERVICE
• Determine volume by weighing empty,
then fill with deionized water, weigh to
nearest 5 gm.
OR
• Measure volume of water used to fill
tank to nearest 5 ml.
T-17
-------
SLIDE 25-42
NOTES
CALCULATIONS
• Sample Volume
• Noncondensible Organics
• Condensible Organics
• Total Gaseous Nonmethane
Organics
• Percent Recovery
• Relative Standard Deviation
SLIDE 25-43
GAS VOLUME SAMPLED
Vs = 0.386
mm Hg
Where:
Vs
0.386
sample volume, ml.
293 K
760 mm Hg
V = sample tank volume, ml.
Pt = gas sample tank pressure after sampling, but prior to
pressurizing, mm Hg absolute.
Tt = gas sample tank temperature after sampling, but prior to
pressurizing, K.
Pt- = sample tank pressure prior to sampling, mm Hg absolute.
Tti- = sample tank temperature prior to sampling, °K.
T-18
-------
SLIDE 25-44 NOTES
SOURCE CONCENTRATION
NONCONDENSIBLE ORGANICS
Ttj
Where:
Ct = calculated noncondensible organic concentration (sample tank) of
effluent, ppm C equivalent.
Ptf = final gas sample tank pressure after pressurizing, mm Hg absolute.
T.f = final gas sample tank temperature after pressurizing, °K.
Ctm = measured concentration (NMO analyzer) for the sample tank, ppm NMO.
SLIDE 25-45
SOURCE CONCENTRATIONS
CONDENSIBLE ORGANICS
Cc = 0.386 * * x C
cm
Where:
C = calculated condensible organic (condensate trap).
\*
Vy = intermediate collection vessel volume, cm.
Pf = final pressure of the intermediate collection vessel, mm Hg
absolute.
V = gas volume sampled, dscm.
Tt = sample tank temperature at completion of sampling, °K.
T-19
-------
SLIDE 25-46 NOTES
TOTAL GASEOUS NONMETHANE
ORGANIC CONCENTRATION
c = c, + cc
Where:
C = total gaseous nonmethane organic concentration of the effluent,
ppm C equivalent.
C = calculated noncondensible organic concentration (sample tank)
of the effluent, ppm C equivalent.
C = calculated condensible organic (condensate trap).
\f
SLIDE 25-47
TOTAL GASEOUS NONMETHANE ORGANIC
MASS CONCENTRATION
IVL = 0.498 C
Where:
Mr = total gaeous nonmethane organic (TGNMO) mass concentration of
ef~"
12
c the effluent.
0.498 -
24.15
C = total gaseous nonmethane organic concentration of the effluent,
ppm C equivalent.
T-20
-------
SLIDE 25-48 MOTES
PERFORMANCE OF CONDENSATE RECOVERY
AND CONDITIONING SYSTEM
PERCENT RECOVERY
% - 1
/O — I. , — ..
L p Tf N
RELATIVE STANDARD DEVIATION
— Y\2
Where:
M = molecular weight of the liquid injected, g/g-mole.
L = volume of liquid injected, micro!iters.
Vy = intermediate collection vessel volume, cm.
p = density of liquid injected, g/cc.
Pf = final pressure of the intermediate collection vessel, mm Hg
absolute.
1^ = final temperature of intermediate collection vessel, °K.
C = measured concentration (NMO analyzer) for the condensate trap
' (intermediate collection vessel), ppm CCL.
N = carbon number of the liquid compound injected (N = 7 for toluene,
N = 6 for hexane).
X.j = individual measurements.
X = mean value.
T-21
-------
SLIDE 25A-1 NOTES
METHOD 25A
Determination of Total Gaseous
Organic Concentration Using
Flame lonization Analyzer
SLIDE 25A-2
APPLICABILITY
For the measurement of total gaseous organic
concentration of vapors consisting of non-
methane alkanes. alkenes and/or arenes (aro-
matic hydrocarbons).
SLIDE 25A-3
PRINCIPLE
A gas sample is extracted from the source
through a heated sample line and glass fiber
filter to a flame ionization analyzer (FIA).
U-l
-------
SLIDE 25A-4 NOTES
ADVANTAGES
1. Yields continuous measurement and real time
results.
2. FIA measurement devices are commercially
available.
DISADVANTAGES
1. Cannot measure true mass and is not consistent
in response from point to point.
2. Requires electricity and gas cylinders at sampling
site.
3. Condensable matter in sample can cause sample
loss in sample lines and instrument unless
adequate precautions are taken.
SLIDE 25A-5
RESULTS
Results are reported as concentration equiv-
alents of the calibration gas organic constituent,
carbon, or other organic compound.
SLIDE 25A-6
METHOD 25A-SUMMARY
Extract samplafrom source through
heated sample line and glass fiber
filter.
Route to flame ionization analyzer.
U-2
-------
SLIDE 25A-7
NOTES
ORGANIC CONCENTRATION MEASUREMENT SYSTEM
PROBE
HEATED
SAMPLE
LINE;
CALIBRATION
VALVE
SAMPLE
PUMP
ORGANIC
ANALYZER
AND
RECORDER
STACK
SLIDE 25A-8
ESSENTIAL COMPONENTS OF
MEASUREMENT SYSTEM
• Organic Concentration Analyzer
• Sample Probe (three-hole rake type)
Sample Line
• Calibration Valve Assembly
• Participate Filter
• Recorder
U-3
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SLIDE 25A-9 NOTES
GASES
CALIBRATION:
Usually consist of propane in air or
nitrogen and are determined in terms
of the span value.
Organic compounds other than propane
can be used by making the appropriate
correction for response factor.
Zero gas — <0.1 ppmv of
organic material or <0.1
percent of span value,
whichever is greater
• Low-level calibration gas —
concentration equivalent to
25 to 35 percent of span value
SLIDE 25A-10
GASES (continued)
CALIBRATION GASES (cont):
• Mid-level calibration gas —
concentration equivalent to
45 to 55 percent; of span value.
• High-level calibration gas —
concentration equivalent to
80 to 90 percent of span value.
FUEL GASES:
40 percent H^GO percent He or 40 percent
Hj/60 percent N2 gas mixture is recommended.
U-4
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SLIDE 25A-11 NOTES
MEASUREMENT SYSTEM
PERFORMANCE SPECIFICATIONS
ZERO DRIFT —<±3% of span value/hr
CALIBRATION DRIFT —<±3% of span value/hr
CALIBRATION ERROR —<±5% of calibration value
(for low and medium standard)
SLIDE 25A-12
PRETEST PREPARATIONS
• Select sampling site
• Install sample probe
• Prepare measurement system
• Conduct calibration error and
response time tests
SLIDE 25A-13
TEST PROCEDURE
• Organic Measurement
1. Begin sampling at start of test.
2. Record time and required
process information.
3. Note process interruption or
cyclic operation.
• Drift Determination
1. At end of test period, reintroduce
zero and mid-level calibration
gases.
2. Record analyzer response.
U-5
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SLIDE 25A-14
ORGANIC CONCENTRATION CALCULATION
• Determine average organic concentration (ppmv)
as propane or other calibration gas
• If concentration required in terms of organic
carbon adjust by:
C = K*C
o meas
K = 2 for ethane
K = 3 for propane
K = 4 for butane
Cg = Carbon observed
C = Carbon measured
U-6
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SLIDE 25B-1 NOTES
METHOD 25B
Determination of Total Gaseous
Organic Concentration Using a
Nondispersive Infrared Analyzer
SLIDE 25B-2
APPLICABILITY
For measurement of total gaseous organic
concentration of vapors consisting primarily of
alkanes. Concentration is expressed in terms of
appropriate organic calibration gas or in terms
of carbon.
SLIDE 25B-3
PRINCIPLE
• Gas sample is extracted from source through a
heated sample line, if necessary, and glass fiber
filter to a nondispersive infrared analyzer.
» Results are reported as volume concentration
equivalents of calibration gas or as a carbon
equivalent.
V-l
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SLIDE 25B-4
NOTES
ORGANIC CONCENTRATION MEASUREMENT SYSTEM
PROBE
HEATED
-SAMPLE
LINE,
CALIBRATION
VALVE
PARTICULATE
FILTER
ORGANIC
ANALYZER
AND
RECORDER
SAMPLE
PUMP
STACK
SLIDE 25B-5
GASES
Calibration
1. Calbration gases usually consist of propane
in air or nitrogen and are determined in terms
of the span value.
2. Organic compounds other than propane can
be used by making the appropriate correction
for response factor.
• Zero gas—< 0.1 ppmv of organic
material or < 0.1% of span value which-
ever is greater.
• Low-level calibration gas—concentra-
tion equivalent to 25 to 35% of span
value.
• Mid-level calibration gas—concentra-
tion equivalent to 45 to 55% of span
value.
• High-level calibration gas—concentr-
ation equivalent to 80 to 90% of span
value.
V-2
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SLIDE 25B-6 NOTES
MEASUREMENT SYSTEM
PERFORMANCE SPECIFICATIONS
ZERO DRIFT —<±3% of span value/hr
CALIBRATION DRIFT —<±3% of span value/hr
CALIBRATION ERROR —<±5% of calibration value
(for low and medium standard)
SLIDE 25B-7
PRETEST PREPARATIONS
Select Sampling Site
Install Sample Probe
Prepare Measurement System
Conduct Calibration Error and
Response Time Tests
SLIDE 25B-8
TEST PROCEDURE
During sampling, record process data and
note process interruption or cyclic operation.
DRIFT DETERMINATION
Determine measurement system drift hourly
during the test and immediately following the
completion of the test period.
V-3
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SLIDE 27-1 NOTES
METHOD 27
Determination of Vapor Tightness
of Gasoline Delivery Tank Using
Pressure Vacuum Test
SLIDE 27-2
APPLICABILITY
For determination of vapor tightness of a
gasoline delivery tank equipped with vapor
collection equipment.
SLIDE 27-3
PRINCIPLE
Pressure and vacuum are applied alternately
to compartments of gasoline delivery tank and
change in pressue or vacuum is recorded after
specified time period.
W-l
-------
SLIDE 27-4
NOT
PRESSURE CHECK
With the use of a pressure source, or by
filling the tank, obtain a stable pressure of 450
mm H2O; shut off valve and observe pressure
for 5 min.
For the arithmetic average of two consecu-
tive runs which agree within ± 12.5 mm H2O,
the change in pressure must be < 75mm H2O.
SLIDE 27-5
VACUUM CHECK
The same procedure should be
used with a vacuum source or alter-
natively by draining the tank.
SLIDE 27-6
w-:
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SLIDE 27-7
NOTES
SLIDE 27-8
W-3
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SLIDF 27-9
NOTES
W-4
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EPA - RIP LIBRARY
-------
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Environmental Protection
Agency
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park NC 27711
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enalty for Private Use
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