EPA-450/4-74-005
I September 1974
(OAQPS No. 1.2-018)
GUIDELINE SERIES
DESIGNATION
OF UNACCEPTABLE
ANALYTICAL METHODS
OF MEASUREMENT
FOR CRITERIA POLLUTANTS
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
-------
EPA-450/4-74-005
(OAQPS No. 1.2-018)
DESIGNATION
OF UNACCEPTABLE
ANALYTICAL METHODS
OF MEASUREMENT
FOR CRITERIA POLLUTANTS
L Froteirjiu:..
Ti-)-.^ TV"?
Monitoring and Data Analysis Division
Office of Air Quality Planning and Standards
and
Quality Assurance and Environmental Monitoring Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina
September 1974
-------
OAQPS GUIDELINE SERIES
The guideline series of reports is being issued by the Office of Air Quality
Planning and Standards (OAQPS) to provide information to state and local
air pollution control agencies; for example, to provide guidance on the
acquisition and processing of air quality data and on the planning and
analysis requisite for the maintenance of air quality. Reports published in
this series will be available - as supplies permit - from the Air Pollution
Technical Information Center, Research Triangle Park, North Carolina
27711; or, for a nominal fee, from the National Technical Information Ser-
vice, 5285 Port Royal Road, Springfield, Virginia 22151.
Publication No. EPA-450/4-74-005
(OAQPS Guideline No. 1.2-018 )
--.^Ci^c^,^
-------
TABLE OF CONTENTS
Page
INTRODUCTION ]
CATEGORIES OF ANALYTICAL METHODS - - 1
REFERENCE AND EQUIVALENCY REGULATIONS - 2
ACCEPTABILITY OF ANALYTICAL METHODS - 3
DISCUSSION OF CRITERIA POLLUTANTS 3
1. Total Suspended Parti culates 3
2. Carbon Monoxide 3
3. Sulfur Dioxide 5
4. Nitrogen Dioxide 5
5. Photochemical Oxidants (Ozone) 5
6. Total Hydrocarbons Corrected for Methane 5
POLLUTANT METHOD CODE — - 6
SUMMARY OF REGIONAL OFFICE RESPONSIBILITIES 6
APPENDIX A. FEDERAL REFERENCE METHODS, UNAPPROVED METHODS,
UNACCEPTABLE METHODS — 25
APPENDIX B. RATIONALE FOR RANKING THE METHODS AS
UNACCEPTABLE- — 39
BIBLIOGRAPHIC DATA SHEET 41
m
-------
Designation of Unacceptable Analytical Methods of Measurement For
Criteria Pollutants
Introduction
It is well known to all who analyze the air to measure criteria
pollutants that some techniques or methods are better than others.
Because important decisions, such as air quality standards achievement
and State Implementation Plan (SIP) revisions, are based on data
derived from these methods, it is imperative that only good quality data
be used. Toward this end, we are designating 14 analytical methods
as unacceptable for continued use for these purposes. Accordingly,
the objective of this guideline is to present the rational for those
methods which are being designated unacceptable, and to provide guidance
on the acceptability of methods for future measurements. This will
enable the Regional Offices and the State agencies to make decisions
concerning implementation of monitoring network requirements, consistent
with the objectives and needs of their monitoring program.
Categories of Analytical Methods
Methods for measuring air pollutants fall into one of three
categories: (1) approved, (2) unacceptable, and (3) those methods
which are neither approved nor unacceptable (unapproved). At present,
the only officially approved methods are the Federal reference methods
described in appendices to 40 CFR Part 50, originally promulgated
on April 30, 1971 (36FR8186) with the National Ambient Air Quality
Standards (NAAQS). This Federal Register also introduced the concept
of an "equivalent method", which is any method which can be demonstrated to
be "equivalent" to the reference method. Thus, unapproved methods may
become approved only by demonstrating equivalence to the reference
method.
-------
Those methods designated as unacceptable are not equivalent to the
reference methods because-they are known to yield measurements of
poor accuracy and reliability. They are considered to be obsolete.
In each case, suitable analytical methods which produce measurements
of greater reliability are available to replace the unacceptable
methods.
Reference and Equivalency Regulations
Regulations governing the procedures and criteria by which unapproved
methods may be determined to be equivalent were proposed in the
Federal Register on October 12, 1973 (38 FR 28438) as a new Part 53.
Pending revision based on comments from interested persons, the new
regulations, when finally promulgated, will require that a method
must be tested according to prescribed procedures and meet certain
prescribed specifications to be approved as an equivalent method. In
essence, manual methods must demonstrate a consistent relationship
to the reference method in side-by-side measurements of ambient air.
Automated methods (automatic air analyzers) must demonstrate such a
consistent relationship as well as meet certain performance specifications,
The new regulations will also cover reference methods which are automated
methods (i.e., CO and oxidants). An analyzer must meet prescribed
performance specifications before it can be determined to be approved
as a reference method.
Unapproved methods must be tested according to the prescribed
procedures and submitted with an application for approval to the
Quality Assurance and Environmental Monitoring Laboratory, NERC, RTP.
Approved methods are to be published in the Federal Register. The
regulations will apply to S02, CO,and oxidants corrected for S02
and N02-
-------
Acceptability of Analytical Methods
Table I lists those analytical methods for which data were
submitted by the States in 1972. We have listed the individual
methods as "approved", "unapproved" and "unacceptable". Use of
methods designated "unacceptable" should be discontinued as soon
as possible. Data derived from those methods will not be accepted
or used by the NADB after September 1974.
For S02, CO, and oxidants corrected for SO? and N02, unapproved
methods may be used until the equivalency regulations are promulgated.
After promulgation of those regulations and additional approved
methods become available, unapproved methods may be used only until
they can be replaced with approved methods, and not later than 5 years
after promulgation after which time only approved methods are to be
used. For NCL and hydrocarbons corrected for methane, guidance for
selecting adequate automated methods may be found in the forthcoming
EPA Environmental Monitoring Series document (EPA-650/4-74-018),
Guidelines for Determining Performance Characteristics of Automated
Methods for Measuring Nitrogen Dioxide and Hydrocarbons Corrected for
Methane in Ambient Air.
Until these regulations and guidelines become available, the
following guidance should be considered:
Discussion of Criteria Pollutants
1. TSP - The high-volume method is the Federal reference method
for total suspended particulates. Since the air quality standard
is defined by the method, the high-volume sampler is the only acceptable
method. No procedures for determining equivalency of alternate methods
have been developed-, so all other methods are to be considered unacceptable,
2. Carbon Monoxide - The non-dispersive infrared (NDIR) is the
Federal reference method for CO. Automated analyzers based on other
principles have not yet been tested with respect to equivalency,
and are therefore unapproved.
-------
Table I. 1972-1973 POLLUTANT-METHOD-STATIONS SUMMARY
Pollutant
TSP 11101
CO 42101
S02 42401
NO. 42602
Photochemical
Ox 44101
(Oxone)
44201
Code
91
11
12
21
11
13
14
15
16
31
33
91
92
93
n
12
13
14
71
72
84
91
94
95
96
11
13
14
15
51
81
82
11
13
Method
Hi-Vol (FRM)a
NDIR (FRM)
Coulometnc
Flame lonization
Colori metric
Conduct! metric
Coulometri c
Autometerc
Fl ame Photometric
Hydrogen Peroxide0
Sequential Conductimetric
West-Gaeke-Sulfamic Acid (FRM)
West-Gaeke Bubbler
Conductimetric Bubbler
Colori metric
Colori metric
Coulometri c
Chemi luminescence
J-H Bubbler (orifice)
Saltzman
Sodium Arsenite (orifice)
J-H Bubbler (frit)
Sodium Arsenite (frit)
TEA
TGS
Alkaline KI Instrumental
Coulometric"
Neut KI Colon metric
Coulometri c
Phenol phthal in
Alkaline KI Bubbler
Ferrous Oxidation
Chemi 1 uminescence (FRM)
Coulometri cd
1972
No. of
Stations
^28 —
223
1
2
~Z2E~
68
80
76
1
12
38
3
1040
45
2
1365
110
15
5
36
11
11
5
816
28
1037
49
10
75
13
5
64
85
62
1
364
1972
Percent
of Total
100
99
0
1
100
5
7
6
0
0
3
0
76
3
0
TOO"
12
1
0
3
1
1
0
79
3
100
13
3
21
4
1
18
23
17
0
100
1973
No. of
Stations
~1B02~
278
2
10
290
89
108
172
1
29
38
6
1510
11
0
T953
136
14
10
8
14
5
26
995
456
1664
10
10
89
22
3
79
91
131
1
436
1973
Percent
of Total
TD'CT
96
0
4
100
5
6
9
0
1
2
0
77
0
0
TTJO~
8
1
1
0
1
0
1
60
28
100
2
2
21
5
1
18
21
30
0
100
Approved Unapproved Unacceptable
X
X
X
xc
X
xc
X
FRM = Federal Reference Method.
See Appendix B for an explanation of why these methods are unacceptable.
Thesa methods should be reported under method code 42401 13.
These methods should be under method code 44101 15.
-------
3. Sulfur Dioxide - The manual West-Gaeke - sulfamic acid (24-hour
bubbler) method is the Federal reference method for S02. The other
manual methods listed are unacceptable. The similarly named "West-Gaeke"
method (SAROAD method code 42401 92) is not equivalent to the
reference method (SAROAD method code 42401 91). Since no continuous
method has yet been tested for equivalency, they are classified as
unapproved.
4. Nitrogen Dioxide - The manual NASN bubbler method is the Federal
reference method for N02- However, in the June 8, 1973,issue of
the Federal Register (38 FR 15174), it was proposed that the NASN
method be withdrawn as the reference method and a new one designated
after testing of proposed candidate methods. Although the method
was not officially withdrawn, the problems with variable collection
efficiency and NO interferences are such that it must be considered
unacceptable. All other methods, both manual and continuous,
have been classified as unapproved.
5. Photochemical Oxidants (Ozone) - The reference method for photochemical
oxidants is a continuous chemiluminescence method based on the gas-phase
reaction of ozone with ethylene. This method is specific for ozone.
All other methods listed in Table I are total oxidant methods. Six
of these methods for total oxidants are being designated unacceptable.
While the remaining automated methods are not being designated
unacceptable, strong consideration should be given to replacing them
with the reference method.
6. Total Hydrocarbons Corrected for Methane - This category is
unique in that, while hydrocarbons corrected for methane is a
criteria pollutant, the ambient air quality standard is only
a guide for achieving the oxidant standard. A gas chromatographic
flame ionization technique is the federal reference method for
hydrocarbons corrected for methane, but this method is difficult and
expensive to use. Other methods are now becoming available and, as
mentioned before, guidance for selection of adequate automated
methods may be obtained in the EPA Environmental Monitoring Series
document (EPA-650/4-74-018), Guidelines for Determining Performance
Characteristics of Automated Methods for Measuring N02 and Hydrocarbons
r.nrrpct.ed for Methane in the Ambient Air.
5
-------
Pollutant Method Code
Correct identification of the pollutant method is of utmost
importance in the reporting of air quality data. It will be of little
help to upgrade the West-Gaeke bubbler procedure (SAROAD method code
42401 92) for example, to the West-Gaeke-Sulfamic Acid method (SAROAD
method code 42401 91) unless the method codes under which the data are
reported to the NADB are also changed. See OAQPS Guideline #1.2-017,
A Description of the Analytical Techniques and Associated SAROAD Method
Codes Used in Storing Data in the National Aerometric Data Bank, for a
description of the analytical technique associated with the SAROAD method
code.
After the equivalency regulations are promulgated, the pollutant
method code will become even more important since there may be a unique
identification code for each method which passes the equivalency testing
and becomes approved as a reference or equivalent method. This new
code may identify not only the method principle but also the instrument
model and manufacturer.
Summary of Regional Office Responsibilities
The Regional Offices should see that those methods designated in
Table 1 as unacceptable are replaced with approved methods as soon as
practical. This will insure adequate data for air quality trend analyses
and compliance with NAAQS after 9/1/74 when data from unacceptable methods
will no longer be used. After promulgation of the equivalency regulations,
EPA Regional Offices should assist in the conversion to the exclusive use
of approved methods for S02> CO and "oxidants corrected for S02 and N0?
and similarly assistance should be provided for selecting adequate methods
for ^ and total hydrocarbons corrected for methane according to the
available guidelines.
To help the Regional Offices identify which states reported data
by which method in 1972, we have included Table II, a printout of
the data from which Table I was prepared. Note that the printout is
by pollutant code and method. Appendix A, which is an extract from OAQPS
Guideline #1.2-017, presents a description of the analytical technique
associated with the SAROAD method code. Lastly, Appendix B, contains a
short paragraph for each method which has been designated unacceptable,
giving the rationale for that designation.
-------
Table II. INVENTORY OF AIR POLLUTANT MONITORING SITES, BY STATE, 1972
STATE
STATE
STATE
STATE
STATE
STATE
STATE"
STATE
STATE
STATE
STATE
STATE
STATF
STATE
STATE
STATE
STATE
STATF
STATE
STATE
STATE
STATE
STATE
STATE
STATE
COUNT
'"COUNT ~
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT ""
COUNT "
COUNT
COUNT
COUNT"
COUNT
COUNT
COUNT"
COUNT
COUNT"
COUNT""
COUNT
"COUNT
POLLUTANT
CODE
uiof
111 01
11 101
11101
11101 "
11101 '
111 01
11101 ""
iii'oT""
mo!
1 1 1 0 1
moi
11101
11101
"ill 01
11101
111 01
11 101
11 101
11101
~ Tiioi
moi"
11101
11101
11101
METH
C'iDE
91
"9l"
91
-------
TABLE II
POLLUTANT MPTH
CODE CDDE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STAT£
STATE
STATE
STATE
STATE
STATE
STATE
COUNT
CUUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
11 101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
11 10 I
11101
11101
11101
11101
11101
11101
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
MISSOURI
MONTANA
NEBRASKA
NEVADA
NEW HAMPSHIRE
NEW JERSEY
NEW MEXICO
NFW YORK
NORTH CAROLINA
NORTH DAKOTA
OHIO
OKLAHOMA
OREGON
PENNSYLVANIA
PUERTO RICO
RHODE ISLAND
SOUTH CAROLINA
SOUTH DAKOTA
TENNESSEE
TEXAS
UTAH
VERMONT
VIRGINIA
WASHINGTON
NUMBER OF
SITES
49
2
36
41
26
79
28
233
199
16
137
95
48
105
5
23
75
2
98
192
8
2
i22
57
-------
TABLE II
STATE
STATE
STATE
STATE
STATE
POLUTCOD
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STAf E
STATE
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT"
COUNT"
COUNT
COUNT
C"OUNT"
COUNT"
COUNT
COUNT"
COUNT "
COUNT
"CO'JNT
COUNT
"COUNT
""con NT"
POLLUTANT
CODE
11101
11101
" 11 101
11101
11101
11 101
42101
""42101
42L01
42101
42101
42ToT
-42TOT--
42101
42101
42101
4?101
42101
42101
4~2~1 01
42101
42TOI
42101
42101 "
42101
MFTH
CODE
91-
91
91
91
91
91
lT~~
11
11
11
11
"" 11
1 1 "
11
11
11
11
11
11
"11
11
11
11
1 1
11
WEST VIRGINIA
WISCONSIN
WYOMING
GUAM
VIRGIN ISLANDS
ALABAMA
ALASKA
ARIZONA
CALIFORNIA
COLORADO
DIST COLUMBIA
FLORIDA
GEORGIA
HAWAII
ILLINOIS
"INDIANA
IOWA
KANSAS
KENTUCKY
LOUISIANA
MARYLAND
MASSACHUSETTS
MICHIGAN
MINNESOTA
NUMBER OF
SITES
38
7
4
11
4
2828
2
1
3
51
1
2
6
2
1
1
3
2
5
7
3
19
5
3
3
-------
TABLE II
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
POLUTCOO
STATE
POLUTCOD
STATE
POLUTCOO
COUNT
COUNT
CO'JNT
COUNT
COUNT
CO'JNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
POLLUTANT
CODE
42101
42101
42101
42101
42101
42101
42101
42101
42101
4?101
42101
42101
42101
42101
42101
42101
42101
42101
42i01
42101
42101
42101
42101
42101
METH
CODE
il
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
12
12
21
21
MISSOURI
NEBRASKA
NEVADA
NEW JERSEY
NtW MEXICO
VFW YORK
NORTH CAROLINA
OHIO
OKLAHOMA
OREGON
PENNSYLVANIA
RHODE ISLAND
TENNESSEE
TEXAS
UTAH
VIRGINIA
WASHINGTON
WEST VIRGINIA
WISCONSIN
OHIO
*•
KENTUCKY
NUMBER OF
SITES
10
1
1
22
1
13
2
13
4
2
2
2
4
1
4
9
10
1
1
223
1
1
2
2
10
-------
TABLE II
POLLUTANT
CODfc
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
POLUTCOD
STATF
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE""""
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
"COUNT
"COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
" COUNT" ""
COUNT
"COUNT
COUNT
COUNT
"COUNT
COUNT
COUNT
"COUNT
COUNT
42401
42401
42401
42401
42401
42401
42401
~4240l
"42401
42401
42401
"~424~6 1
42401
42401
42401
42401
"42401
42401
42401
42401
"""42401""
42401
42401
—42461
~ 42 401
METH
cone
11
Ti
11
11
11
~"H"
11
~TY
11
11
il
11
11
11
11
11
13
13
13
13
13
13
13
13
l"3~"
"ARIZONA
COLORADO
" DELAWARE
DIST COLUMBIA
F'LOR i DA
ILLINOIS
KENTUCKY
MARYLAND
MASSACHUSETTS
MISSOURI
NEW JERSEY
NEW YORK
OHIO
PENNSYLVANIA
WASHINGTON
ARIZONA
CALIFORNIA
COLORADO
CONNECTICUT
DELAWA'RE
DIST COLUMBIA
FLORIDA
"ILL I NCI'S
INDIANA
NUMBER OF
SITES
2
1
6
2
3
1
5
1
4
5
22
7
4
4
1
68
2
18
1
I
7
2
i~
1
8
-------
TABLE II
POLLUTANT
CODE
STATE
STATE
STATE
STATE
STATf
STATED
STATE
STATE
STATE
POLUTCOD
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
JSTATE
J5TATE
STATE
STATE
STATE
COUNT
COUNT
COUNT
„ COUNT
COUNT
_ COUNT
COUNT
COUNT
COUNT
COUNT
_COUNT
_COUNT_
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
42401
42401
42401
4240 1
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
METH
CODE
13
13
U
13
13
13
13
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
14
MARYLAND
MINNESOTA
MISSOURI
NEW YORK
OHIO
OREGON
PENNSYLVANIA
VIRGINIA
WASHINGTON
ALABAMA
ARIZONA
DIST COLUMBIA
FLORIDA
GJORGIA
INDIANA
KANSAS
KENTUCKY
MASSACHUSETTS
MICHIGAN
MINNESOTA
MISSOURI
NEW YORK
NORTH CAROLINA
NUMBER OF
SITES
12
2
2
1
7
2
2
2
9
80
2
8
2
2
2
4
3
6
2
22
4
1
12
1
12
-------
TABLE II
POLLUTANT
CODE
STATE
STATE
STATE
STATE
POLUTCOO
STATE
POLUTCOD
STATE
STATE
POLUTCOD
STATE
POLUTCOD"
STATE
poLuTcob"
STATE
STATE "
STATE
STATE "
STAT6
STATE —
STATE
STATE
- -
$T AT E
-ctAfT
-"e
COUNT
COUNT
COUNT
COUNT
COUNT^
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
"COUNT
"COUNT
"COUNT
COUNT
"COUNT
"COUNT
COUNT
COUNT
COUNT
-COUNT
COUNT
COUNT
--COUNT'
-"COUNT
42401
42401
42401
42401
41401
"42401"
~42401
42401
4240T
42401
42401
"42401
-4240T™
"~42 401
-42401-
42401
~~42401~
42401
"42401
_r
— 42401
METH
CODE
14
14
14
14
14
15
15
16
iV
16
31
31 "
33
"33"
- "gjf-
91
91
"~9i
91
01
91
91
-"" 91
NUMBER OF
SITES
OHIO
PENNSYLVANIA
TENNESSEE
VIRGINIA
"TENNESSEE
MARYLAND
VIRGINIA
NEW YORK
._..
"MI'S SOUR i "
"""
"ALABAMA
ALASKA
ARIZONA
" ARKANSAS
CALIFORNIA
—cOiORADO^
-CONNECTICUT
OEtAVI^E _.
-OiSf-COLOHBlA
"pTtiRToA
^ ._--"'
" ^GEORGIA
1
i
1
2
76
I
1
11
1
12
38
38
3
3
13
1
7
""2
16
4
3
—r~~~
34 "
._-
13
— ' "" "
„_. "••"
-------
TABLE II
— — _ _
STATE COUNT
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
-STATF
STATE
STATE
- TE
STATE
STATE
STATE
_?T4fE
___COUNT
COUNT
. COUNT
COUNT
COUNT
C OUN T
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
- ..COUNT
COUNT
-.COUNT
COUNT
'--'UtyT .
"UN T ,
COUNT
4<
COUNT
PCLLUTAN
CODE
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
,42401
42401
42401
42
—
V4o!
4240 1
'^•y f n
^40j
"> /. A .
t40l
-401
IT METH ~
CODF NUMBER OF
— - SITES
91 HAWAII
12
91 ILLINOIS
- . 38
91 INDIANA
66
91 IOWA
2
91 KANSAS
30
91 KENTUCKY
98
91 LOUISIANA
17
91 ^ A I N £
6
91 MARYLAND
-- _. 49
91 MASSACHUSETTS
91 MICHIGAN
24
91 MINNESOTA
91 MISSISSIPPI
--?-1. MISSOURI
9l- MONTANA 4
NERRASKA
-9L, NEVADA ' _ 4
91
NEW lr-
CWJC»S£y 4
9)
N t~ w
™ r x i r n 8
9|
N6w YORK a
H CARQL r M ^^
92
-------
TABLE II
POLLUTANT
CODE
STATE
STATE
STATF
STATE
STATF
STATE
STATE
STATE
STATE
ST AT E
STATE
STATE
STATE
STATE
STATE
STATE
"POLUTCOD
STATE
STATE
P GLUT COD
STATE
POLUTCOO
STATE
"STATE
"STATE
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
"COUNf
COUNT
COUNT
COUNT" ""
~C~0'JN~T "
COUNT
COUNT
"COUNT
"COUNT
COUNT
"COUNT"
COUNT
42401
42401
42401
42401
42401
42401
42401
42401
42401"
4240 1
42401 "
42401
424QT
4T40I "
424~ol~ ~
~4240~i~
42401
42401
42401
"42401
"424 Ol
42401
42602
"42602" """
42602
METH
CODE
91
91
91
91
91
91
91
91
~~9\
91
91
91
91
-----
91
91
91
92
92
"~92
" 93
93
11
11
11
OREGON
PENNSYLVANIA
PUERTO PICO
RHODfc ISLAND
SOUTH CAROLINA
SOUTH DAKOTA
"TENNESSEE
TEXAS
UTAH
VIRGINIA
"~ WASHINGTON
WEST VIRGINIA
WISCONSIN
WYOMING
GUAM
VIRGIN ISLANDS
"~ '
"FLORIDA
MASSACHUSETTS
"INDIANA
ALABAMA
ARIZONA
CALIFORNIA
NUMBER OF
SITES
1
14
4
18
38
1
37
13
1
49
4
15
3
2
9
3
1040
1
44
45
2
2
2
3
50
15
-------
TABLE II
POLLUTANT METH
STATE
jHTATj;
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
POLUTCOD
STATE
STATE
STATE
STATE
COUNT
__CO'JNT_
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
CODE
42602
.42602
_ 42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
CODE
11
11
11
11
11
11
11
11
11
11
11
11
11
li
11
11
11
11
11
11
12
12
12
12
CONNECTICUT
__PJ_S! COLUMBIA
FLORIDA
GEORGIA
KENTUCKY
MAINE
MARYLAND
MASSACHUSETTS
MINNESOTA
MISSOURI
NEVADA
NEW YORK
NORTH CAROLINA
UHIO
OKLAHOMA
OREGON
PENNSYLVANIA
TENNESSEE
VIRGINIA
COLORADO
DIST COLUMBIA
ILLINOIS
MISSOURI
NUMBER OF
SITES
1
1
4
1
8
1
6
1
1
8
1
13
1
2
1
1
1
1
2
110
1
1
1
1
16
-------
TABLE II
-
STA^E
STATE
STATE
STATE
STATE
POLtlTCOD
STATE
STATE
STATE
STATE
POLUTCOD
STATE
STATE
STATE
STATF
STATE
STATE
STATE
STATE
Sf ATE
STATF
STATE
STATE
STATE
STATE
!
COUNT
COUNT
COUNT
COUNT "
COUNT
COUNT "
COUNT
COUNT"
COUNT
COUNT
"COUNT
COUNT ""
COUNT"
~ccuNf"~
COUNT
COUNT
COUNT
COUNT
COUNT
"COUNT
COUNT
COUNT
COUNT
COUNT""
"COUNT"
3OLLUTANT
CODE
42602 """"
42602
42602
42602
42602
426 0"2
42602
~42~602
42602
42602
42602
"42602
"42602
~42602~"
42602
42602
42602
42602
"42602
""42602
42602
42602
42602
"" 42602
42602"""
METH
CODE
12
12
12
12
12
12
13
13 "
13
- y3
-3~
14
14
14
14
14
14
14
14
14
14
14
14
14
14
--
NEW JERSEY
OHIO
PfcNNSYLVANIA
RHODE ISLAND
VIRGINIA
KANSAS
MINNESOTA
NEVADA
TENNESSEE
ARIZONA
COLOR ADO
CONNECTICUT
DIST COLUMBIA
ILLINOIS
INDIANA
IOWA
KENTUCKY
MARYLAND
MASSACHUSETTS
MINNESOTA
MISSOURI
NEBRASKA
NEW MEXICO
NUMBER OF
SITES
5
1
1
2
2
15
2
1
1
1
5
1
1
1
2
2
1
1
3
1
1
1
2
1
1
17
-------
TABLE II
-
STATE
, STATE,
STATE
STATE
STATED
STATE
POLUTCOO
STATE
POLUTCOD
STATE
POLUTCOO
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
_SJATE
STATE
STATE
P
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
'OLLUTANT
CODE
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
METI
CODI
14
14
14
14
14
14
14
71
71
72
72
91
91
91
91
9i
91
91
91
91
91
91
91
91
-1
NEW" YORK
OHIO
PENNSYLVANIA
TEXAS
UTAH
VIRGINIA
MINNESOTA
INDIANA
ALABAMA
ALASKA
ARIZONA
ARKANSAS
CALIFORNIA
COLORADO
CONNECTICUT
DELAWARE
DIST COLUMBIA
FLORIDA
GEORGIA
HAWAII
ILLINOIS
NUMBER OF
SITES
2
5
5
2
1
2
36
11
11
11
11
13
1
5
2
16
2
4
3
2
22
13
11
4
18
-------
STATE
STATE
STATE"
STATE
STATE
STATE
STAfE~
STATE
STATE "
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
-
"" COUNT"
COUNT
" "COUNT
COUNf
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
POLLUTANT
CODE
42602
42602
" 42602"
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
TABL
METH
CODE
9 r
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
E II
INDIANA
IOWA
""KANSAS
KENTUCKY
LOUISIANA
"MAINE
MARYLAND
MASSACHUSETTS
MICHIGAN
MINNESOTA
MISSISSIPPI
MISSOURI
MONTANA
NEBRASKA
NEW HAMPSHIRE
NEW JERSEY
NEW MEXICO
NEW YORK
NORTH CAROLINA
OHIO
OKLAHOMA
OREGON
PENNSYLVANIA
PUERTO RICO
RHODE ISLAND
- - -
NUMBER OF
SITES
41
2
29
87
4
1
49
54
6
3
. ^ ._
4
1
3
4
8
7
9
~ ~155
67
19
.__ ..._
4
18
19
-------
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STAT E
POLUTCOD
STATE
POLUTCOD
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
COUNT
^COUNT
COUNT
COUNT
COJJNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
POLLUTANT
CODE
42602
_42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
METf
CO Of
91
?1
91
91
91
91
91
91
91
91
91
91
94
94
11
11
11
11
11
11
11
11
11
11
1
SOUTH CAROLINA
SOUTH DAKOTA
TENNESSEE
TEXAS
UTAH
VIRGINIA
WASHINGTON
WEST VIRGINIA
WISCONSIN
WYOMING
GUAM
KENTUCKY
ARIZONA
COLORADO
OIST COLUMBIA
FLORIDA
ILLINOIS
INDIANA
IOWA
KANSAS
MISSOURI
NEW JERSEY
NUMBER OF
SITES
TO
1
41
13
1
7
10
1
3
2
9
816
28
28
1
1
1
2
1
2
1
1
1
4
20
-------
TABLE II
OOLLUTANT MFTH
CODE CODE
STATE
STATE
STATE
ST AT E
STATE
STATE
STATE
STATE
STATE ~
POLUTCOD
STATE
STATE
STATE
STATE
POLUTCOD"
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
"COUNT
COUNT
COUNT
COUNT"
COUNT
COUNT
COUNT
"COUNT"
coWr
COUNT
"44101
"44161
44101
44101
44101
44101
44101
44101
44101
44i01
44101
44101
44101
44101
"44101
"44101
44101
"44101
~44TOF
44101
44101
44101
~~44l6T~
44i01
44101
1 1
ii
11
1 1
if"
if
11
11
11
11
13
13
13
13
~~13
14
14
14
14
14
14
14
14 ~
14
14
NEW YORK
NORTH CAROLINA
OHIO
PENNSYLVANIA
TENNESSEE
TEXAS
VIRGINIA
WASHINGTON
WISCONSIN
KANSAS
NEVADA
NEW MEXICO
WASHINGTON
ALABAMA
ARIZONA
CALIFORNIA
COLORADO
KENTUCKY
MINNESOTA
MISSOURI
OHIO
OREGON
PENNSYLVANIA
NUMBER OF
SITES
12
2
8
1
4
1
4
1
1
49
3
1
1
5
10
1
1
56
1
"1
1
8
2
1
i
21
-------
TABLE II
STATE
STATE
P'lLJTCO',
STATE
STATF
POLUTCOD
STATE
POLUTCOD
STATE
STATF
STATE
STATE
POLUTCOD
STATE
STATE
STATE
POLUTCOD
STATE
STATE
STATE
STATE
STATE
STATE
STATE
COUNT
COUNT
COUNT
C OU N T
CUIJNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
POLLUTANT
CODF
44101
44101
44101
44101
441ui
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44201
44201
44201
44201
44201
44201
44201
'^Th
rnOE
u
14
14
15
i'j
15
51
51
81
81
31
81
81
82
32
82
32
il
11
11
11
11
11
11
1
TciMMiISSF-
VIRGINIA
C/L I FURN IA
VIRGINIA
OKLAHOMA
MINNESOTA
NORTH CAROLINA
OKLAHOMA
SOUTH CAROLINA
KANSAS
KENTUCKY
JHIO
ALABAMA
COLORADO
DIST COLUMBIA
FLORIDA
GEORGIA
HAWAI I
ILLINOIS
NUMBER OF
SITES
1
1
75
12
1
13
5
5
7
7
13
37
64
3
76
6
85
2
1
1
4
1
1
1
22
-------
TABLE II
STATE
STATE
STATF
STATE
STATE
STATE
STATE
STATE
STATF
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
POLUTCOO
STATE
POLUTCOD
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT"
COUNT
COUNT
COUNT""
COUNT
"COUNT
COUNT""
COUNT
POLLUTANT
C 0 0 E
44201
44201
442U1
Xt420i
44201
44201
44201
44201
4420~1
44201
~442T)T
44201
44201
44201
44201
44201
44201
44201
~44~201
44201
'-I t T H
CODE
11
H
11
11
11
11
11
11
11
11
11
11
11
11
il
11
11
ii
13
1~3"~
INDIANA
KANSAS
KENTUCKY
LOJISUNA
MARYLAND
MICHIGAN
MISSOURI
NEBRASKA
NEW YORK
NORTH CAROLINA
OHIO
OKLAHOMA
PENNSYLVANIA
SOUTH CAROLINA
TENNESSEE
TEXAS
VIRGINIA
OREGON
NUMBER OF
SITES
1
2
2
3
6
1
1
3
12
2
7
2
1
1
1
1
5
62
1
1
23
-------
-------
APPENDIX A.*
FEDERAL REFERENCE METHODS
UNAPPROVED METHODS
UNACCEPTABLE METHODS
APPENDIX B.
RATIONALE FOR RANKING THE METHODS
AS UNACCEPTABLE
*Extracted from Guideline Document OAQPS 1.2-017, A Description of the
Analytical Techniques and Associated SAROAD Method Codes Used in StbTing
Data in the National Aerometric Data Bank.
25
-------
Federal Reference Methods
11101 91 SUSPENDED PARTICULATE - HI-VOL - GRAVIMETRIC
Air is drawn at 40 to 60 ft3/min through a glass
fiber filter, by means of a blower, and the sus-
pended particles having a diameter between 100
and 0.1 ym are collected. The suspended particulate
is calculated by dividing the net weight of the
particulate by the total air volume sampled and
reported in density units as yg/m3. Heavy
loading of suspended particulate, oily particulates,
or high humidity can cause reduced air flow
through the filter. Therefore, flow rates should
be measured before and after the sampling period.
1. "Rules and Regulations," Federal Register,
Vol 36, No. 228, U.S. Government Printing Office,
Washington, D.C., (Nov. 25, 1971), p 22388.
2. Intersociety Committee, "Methods of Air
Sampling and Analysis," American Public Health
Association, Washington, D.C., 1972, p 356.
3. "Air Quality Data for 1967, "APTD-0741,
APTIC, Research Triangle Park, North Carolina,
1971, p. 17.
42101 11 CARBON MONOXIDE - INSTRUMENTAL - NON-DISPERSIVE
INFRA-RED
The non-dispersive infrared instrument has a sample
cell, a rererence. cell, and a detector. The detector
is divided by a flexing diaphragm into two equal
cells filled with equal concentrations of CO. The
reference cell is filled with a CO-free air.
When infrared radiation is passed into the sample
cell some of the radiation is absorbed by CO
in this cell in proportion to the concentration
26
-------
of CO and the rest is transmitted to the detector. In the
detector, the radiation causes the CO to expand flexing the
diaphragm in proportion to the transmitted infrared radiation.
Since the reference cell is filled with zero CO air, the
reference cell side of the detector exerts a constant pres-
sure on the diaphragm. When the CO is introduced into the
sample cell, unequal amounts of residual radiation reach
the two compartments of the detector causing an unequal
expansion of the detector gas. This unequal expansion
causes the diaphragm to deflect, creating a change of
electrical capacitance in an external circuit, and ultimate-
ly an amplified signal which is suitable for input to a
servo-type recorder. The detector is calibrated by placing
CO standards in the sample cell and recording the electrical
signals.
1. "Rules and Regulations," Federal Register, Vol. 36,
No. 228, (Nov. 25, 1971), p. 22391.
42401 91 SULFUR DIOXIDE-GAS BUBBLER WEST-GAEKE-SULFAMIC ACID'
Sulfur dioxide is collected in a tetrachloromercurate solution,
forming a stable dichlorosulfitomercurate complex. When acid-
bleached pararosaniline is added to the collected S02 together
with formaldehyde, the amino groups (-NH3) form a red violet
compound called pararosaniline methylsulfonic acid which is
measured spectrophotometrically. The method is described in
the Federal Register. (The NASN procedure, however, uses
1.725 g/1 sulfamic acid rather than 6 g/1 and does not use
EDTA). The sulfamic acid eliminates interference from oxides
of nitrogen.
1. "Rules and Regulations," Federal Register. Vol. 36,
No. 228, U. S. Government Printing Office, Washington, D. C.,
(Nov. 25, 1971), p. 22385.
2. West, P. W. and G C. Gaeke, (1956), "Fixation of Sulfur
Dioxide as Disulfito-Mercurate (II) and Subsequent Colori-
metric Estimation," Anal. Chem. 28, 1819.
27
-------
3. Intersociety Committee, "Methods of Air Sampling and
Analysis," American Public Health Association, Washington, D. C.,
1972, p. 447.
4. "Air Quality Data for 1967, "APTD 0741, APTIC, Research
Triangle Park, N. C., 1971, p. 20.
44201 11 OZONE - INSTRUMENTAL-CHEMILUMINESCENCE
Ambient air to be measured and ethylene are delivered
simultaneously to a mixing cell where ozone reacts with
the ethylene to emit light which is measured by a photomul-
tiplier tube. If the air and ethylene flow rates are constant,
the resulting photomultiplier signal can be related to the input
ozone concentration. Analyzers are calibrated with known
ozone concentration standards.
1. "Rules and Regulations, "Federal Register, Vol. 36,
No. 228, U. S. Government Printing Office, Washington, D.C.,
(Nov. 25, 1971), p. 22392.
2. "A Chemiluminescence Detector for Ozone Measurement,"
Bureau of Mines Report of Investigation RI-7650, United States
Department of the Interior, U. S. Government Printing Office,
Washington, D. C., 1972.
28
-------
Unapproved Methods
42101 21 CARBON MONOXIDE - INSTRUMENTAL - FLAME IONIZATION
Ambient air is passed through two gas chromatographic
columns in series, the first retains most pollutants
but passes CO and CH4, and the second passes only
CO. The CO then flows through a Ni catalyst where
it is converted to CH4 which is measured by a flame
ionization detector. The resulting measured current
is related to the CO concentration of the input
ambient air by dynamic calibration with known CO
concentration standards.
1. Rotterdam, Warsaw, and Bucharest, "The Status
of Instrumentation in Air Pollution Control," Environ-
mental Control Seminar Proceedings, U. S.Department
of Commerce, (May 5-June 4, 1971), p 217.
42401 11 SULFUR DIOXIDE-INSTRUMENTAL-WEST GAEKE-COLORIMETIC
A continuous analyzing system is set up such that
the ambient air flows through a glass beaded absorp-
tion column concurrently with 0.02M sodium tetrachloro-
mercurate. Dichlorosulfitomercurate ion is formed
reacted with acid-bleached pararosaniline and
formaldehyde to produce a red-purple pararosaniline
methylsulfonic acid which is quantitatively measured
colorimetrically. The zero (100%T) baseline is
established with pure reagents for 1 hr and the in-
strument is then dynamically calibrated with known
S02 concentration standards. Air flow rate and
reagent flow rate must be calibrated and maintained
accurately.
42401 13 SULFUR DIOXIDE-INSTRUMENTAL-CONDUCTIMETRIC
Sulfur dioxide is absorbed -in acidic H202 which
oxdizes the S02 to H2S04. The resulting change
in conductivity can be measured, compensated for
29
-------
temperature, and related to the input S02 concentration
by dynamic calibration with known S02 concentration
standards. However, specificity is poor because any
materials that alter the conductivity of the reagent
are potential interfering agents.
1. Beckman Air Quality Acralyzer Operating and
Service Manual, Scientific and Process Inst. Div.,
Fullerton, California, 16TW352, (Aug. 1966).
2. Thomas, M.D., (1932), "Automatic Apparatus for
the Determination of Small Concentrations of Sulfur
Dioxide in Air," Anal. Chem. 5, 253.
3. M. B. Jacobs, "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers, Inc., New York, N.Y., (1960), p 394.
4. Water, Atmospheric Analysis, (1971), "Annual Book
of ASTM Standards," American Society for Testing and
Materials, Philadelphia, Pa., Part 23, p 272.
42401 14 SULFUR DIOXIDE-INSTRUMENTAL-COULOMETRIC
The air to be measured is passed through a cell
containing a neutral buffered iodide or bromide
electrolyte where an electrical current or potential
maintains a constant concentration of free 12 or Br2.
When SO2 in the input air reacts with the I2 or Br2,
the change in electrical current or potential necessary
to restore or maintain the original concentration of
12 or Br2 (coulometric titration) is a quantitative
measure of the S02 input. If the input flow rate is
constant, the S02 concentration can be related to
the electrical signal by dynamic calibration with
known S02 concentration standards.
42401 16 SULFUR DIOXIDE-INSTRUMENTAL-GC FLAME PHOTOMETRIC
Chromatographic columns are used to separate SOo,
H2S, CS2, and CH3SH. Effluent from the columns is
30
-------
burned in a hydrogen-rich flame. A photomultiplier
tube is used to detect the 395 run emission band
characteristic of sulfur. The electrical signal is
related to the input concentration by dynamic cali-
bration with known S02> H2S, CS2/ or CH3SH concen-
tration standards.
1. H. H. Willard, L. L. Merritt, and J. A. Dean,
"Instrumental Methods of Analysis," D. Van Nostrand
Company, Inc., 4th Edition, 1965, p 309.
42401 33 SULFUR DIOXIDE-DAVIS INSTRUMENT-SEQUENTIAL-CONDUCTIMETRIC
Water is deionized by passage through an amberlite
resin column; then its conductivity is measured.
Ambient air, having first passed through a scrubber
of amberlite resin and soda-lime to remove C02/ is
next passed through the deionized water where the S02
is absorbed. The increased conductivity of the water
is a measure of the SC>2 concentration of the air.
1. Thomas, M.D. and J. N. Abersold, (1929), "Automatic
Apparatus for the Determination of Small Concentrations
of Sulfur Dioxide in Air," Anal. Chem. 1, 14.
42602 11 NITROGEN DIOXIDE-INSTRUMENTAL-COLORIMETRIC
The Lyshkow modification of the Griess-Saltzman
reagent is used in various continuous NO2 analyzers.
Users should consult the manufacturer's literature
for details of reagent preparation.
1. "Rules and Regulations" Federal Register, Vol 38,
No. 110, USGPO Wash., D.C., (June 8, 1973), p 15176.
2. Lyshkow, N. A., (1965), "A Rapid Sensitive Colori-
metric Reagent for Nitrogen Dioxide in Air" J. Air
Poll. Control Assoc. 15 (No. 10) 481.
42602 12 NITROGEN DIOXIDE-INSTRUMENTAL-COLORIMETRIC
The original Griess-Saltzman reagent is used in
various continuous N02 analyzers. Users should
31
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consult the manufacturer's literature for details
of reagent preparation.
1. "Rules and Regulation," Federal Register, Vol 38,
No. 110, USGPO, Wash., D.C., (June 8, 1973) p 15176.
2. Saltzman, B. E., (1954) "Colorimetric Micro
Determination of Nitrogen Dioxide in the Atmosphere"
Anal. Chem. 26, 1949.
42602 13 NITROGEN DIOXIDE-INSTRUMENTAL-COULOMETRIC
Air to be measured is passed through a cell containing
neutral buffered iodide-iodine solution causing an
established equilibrium between iodine and iodide
to be unbalanced. The current required to re-
establish the equilibrium (coulometric titration)
is a measure of the input NO? concentration. If
the input flow rate is constant, the N02 concentration
can be related to the electrical signal by dynamic
calibration with known N02 concentration standards.
42602 14 NITROGEN DIOXIDE-INSTRUMENTAL-CHEMILUMINESCENCE
The ambient air to be measured is drawn over a heated
catalytic converter which reduces NO2 to NO. The
NO is then analyzed by method 42601 14, and the
original N02 concentration is obtained by subtracting
the concurrent NO concentration.
1. "Rules and Regulation," Federal Register, Vol 38,
No. 110, USGPO, Wash., D.C., (June 8, 1973) p 15176.
2. NO/NOX/N02 Analyzer Bulletin, Bulletin 4133,
Beckman Instruments, Inc., Fullerton, Calif.
42602 84 NITROGEN DIOXIDE-GAS BUBBLER-NASN SODIUM ARSENITE-
ORIFICE
The method is much like method 42602 71 except for
the absorber (l.Og of NaAs02). Ambient air is in-
troduced into the absorber by means of an orifice
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in the bubbler. The orifice is usually not cali-
brated.
1. "Rules and Regulation," Federal Register, Vol 38,
No. 110, USGPO, Wash., D.C., (June 8, 1973), p 15175.
2. Christie, A. A., R. G. Lidzey, and D. W. F. Radford
(1970), "Field Methods for the Determination of Nitrogen
Dioxide in Air." Analyst 95, 519.
3. Merryman, E. L., et.al., "Effects of NO, C02,
CH4/ H2O and Sodium Arsenite on NO2 Analysis,"
presented at the Second Conference on Natural Gas
Research and Technology. Atlanta, Georgia, June 5, 1972.
42602 94 NITROGEN DIOXIDE-GAS BUBBLER-NASN-SODIUM ARSENITE-
FRIT
This method is identical to method 42602 71 except
that l.Og/1 of NaAs02 is added to the absorbing
solution, and a fritted bubbler is used instead of
an orifice bubbler.
1. Christie, A. A., R. G. Lidzey, and D. W. F. Radford,
(1970), "Field Methods for the Determination of Nitrogen
Dioxide in Air." Analyst 95, 519.
2. Merryman, E. L. et al., "Effects of NO, C02,
CH., H2O and Sodium Arsenite on N02 Analysis,"
presented at the Second Conference on Natural Gas
Research and Technology. Atlanta, Georgia, June 5, 1972,
3. "Selected Method for the Measurement of Air
Pollutants," U.S. Department of Health, Education,
and Welfare 999-AP-ll, Robert A. Taft Sanitary
Engineering Center, Cincinnati, Ohio, May 1965,
p C-4.
44101 11 TOTAL OXIDANT-INSTRUMENTAL-ALKALINE KI
Identical to method 44101 14 except 1 N sodium
hydroxide is used instead of the phosphate buffer
in the absorbing solution.
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44101 14 TOTAL OXIDANT-INSTRUMENTAL-COLORIMETRIC-NEUTRAL KI
Air to be measured is contacted with nuetral
phosphate buffered potassium iodide. Oxidants
convert the KI to 12 or KIg which is measured
spectr©photometrically at 352 nm. If the input
air flowrate is constant, the color density can
be related to the oxidant concentration. Analyzers
are calibrated dynamically with known standard
concentrations of ozone. Sulfur dioxide inter-
ference may be minimized by use of a Cr03 pre-
scrubber, which also causes an NO interference.
1. Intersociety Committee, "Methods of Air
Sampling and Analysis," American Public Health
Association, Wash., B.C., 1972, p 356.
2. Water, Atmospheric Analysis, (1971), "Annual
Book of ASTM Standards," American Society for Testing
and Materials, Philadelphia, Pa., Part 23, p 518.
3. Wartburg, A. F., and B. E. Saltzman, (1965),
"Absorption Tube for Removal of Interfering SO2
in Analysis of Atmospheric Oxidant" Anal. Chem. 37,
779.
44101 15 TOTAL OXIDANT-INSTRUMENTAL-COULOMETRIC-NEUTRAL KI
Air to be measured is passed though a cell containing
potassium iodide and two electrodes. Oxidants
convert iodide ions to I2 which is reduced at the
cathode of the cell causing a current to flow through
an external circuit. If the flow rate is constant,
this electrical signal can be related to the input
concentration of oxidants. Analyzers are calibrated
dynamically with known standard concentrations of
ozone.
34
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Unacceptable Methods
42101 12 CARBON MONOXIDE - INSTRUMENTAL - COULOMETRIC
Atmospheric air is drawn through a heated
column
where I2 is liberated.
The I~ is directed
is measured
into an electrochemical cell where
coulometrically .
1. Beckman Instrumentation, Bulletin 3000 4411-4,
Beckman Instruments, Inc., Fullerton, California.
42401 15 SULFUR DIOXIDE-INSTRUMENTAL-THOMAS AUTOMETER
The Thomas Autometer is a conduc time trie analyzer
developed in 1929. There are later models. The
method is similar to method 42401 13.
42401 31 SULFUR DIOXIDE-DAVIS INSTRUMENT-HYDROGEN PEROXIDE
The Davis instrument is a conductimetric instrument,
and, as such, this method is much like method 42401 13.
42401 92 SULFUR DIOXIDE-GAS BUBBLER-WEST-GAEKE
This method is similar to method 42401 91 except
that the sample absorbing reagent is 0.1M tetra-
chloromercurate*, the starch which is used for
standardization is made with mercuric iodide;
and sulfamic acid is not used except when high con-
centrations of N02 are expected. The sulfamic
acid is added to the sample after collection.
1. "Selected Methods for the Measurement of Air
Pollutants" U.S. Department of Health, Education,
and Welfare 999 AP-11, Robert A. Taft Sanitary
Engineering Center, Cincinnati, Ohio, May 1965,
p A-l.
2. Nauman, R. V., et al. , (1960), Anal Chem. 32,
1307.
35
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3. West, P. W. and F. Ordoveza, (1962), Anal. Chem. 34,
1324.
42401 93 SULFUR DIOXIDE-GAS BUBBLER-CONDUCTIMETRIC
This manual conductimetric method uses the same
principle as the instrumental conductimetric
method. The absorber is a multiple-jet bubbler
system and the sampling is not continuous. The
details are described in the reference.
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health Association,
Washington, D.C., 1972, p 456.
42602 71 NITROGEN DIOXIDE-GAS BUBBLER-JACOBS-HOCHHEISER-
50 ml TUBE + ORIFICE
Ambient air to be measured is bubbled through a.
sodium hydroxide solution where N02 forms a stable
solution of sodium nitrite. The nitrite ion pro-
duced is reacted with phosphoric acid, sulfanilamide,
and N-l naphthylethylenediamine dihydrochloride;
and measured colorimetrically at 540 nm.
42602 72 NITROGEN DIOXIDE-GAS BUBBLER-SALTZMAN (50 ml TUBE +
ORIFICE)
The sample is absorbed in the Griess-Saltzman reagent
and after 15 min the stable pink color is measured
colorimetrically at 550 nm; cannot be used for
sampling period over 30 minutes.
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health Association,
Washington, D.C., 1972, p 329.
2. Saltzman, B. E., (1954), "Colorimetric Micro-
Determination of Nitrogen in the Atmosphere," Anal.
Chem. 26, 1949.
44101 81 TOTAL OXIDANT-GAS BUBBLER-ALKALINE KI
Oxidants in sampled ambient air are absorbed in
an alkaline KI solution in a bubbler. A stable
36
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product is formed which can be stored with little
loss for several days. Analysis is completed
by addition of phosphoric acid-sulfuric acid
reagent/ liberating iodine, which is then determined
spectrophotometrically at 352 nm.
1. Selected Methods for the Measurement of Air
Pollutants U.S. DHEW 999-AP-ll, RATSEC Cincinnati,
Ohio, 1965, p E-l.
2. Water, Atmospheric Analysis, (1971), "Annual
Book of ASTM Standards," American Society for Testing
and Materials, Philadelphia, Pa., Part 23, p 391.
3. M. B. Jacobs, (1960), "The Chemical Analysis of
Air Pollutants," Chemical Analysis, Vol 10, Inter-
science Publishers, Inc., New York, N. Y., p 219.
44101 82 TOTAL OXIDANT-GAS BUBBLER-FERROUS OXIDATION
Air to be measured is filtered through a Whatman
No. 4 paper at 1 ft3/min; then bubbled through two
impingers in series containing acidified ferrous
ammonium sulfate absorbing solution. After sampling
ammonium thiocyanate is added, and the resultant
color is measured with a colorimeter and green filter,
1. M. B. Jacobs, (1960), "The Chemical Analysis of
Air Pollutants," Chemical Analysis, Vol 10, Inter-
science Publishers, Inc., New York, N. Y., p 228.
44201 13 OZONE - INSTRUMENTAL - COULOMETRIC
This method is identical to method 44101 15.
1. Mast, G. M. and H. E. Saunders, (Oct. 1962),
"Research and Development of the Instrumentation of
Ozone Sensing," Instrument Soc. of Amer. Trans.,
!_, 375.
2. Bufalini, J. J., (1968), "Gas Phase Titration of
Atmospheric Ozone," Environ. Sci. Tech. 2, 703.
3. wartburg, A. P., and B. E. Saltzman, (1965),
"Absorption Tube for Removal of Interfering S02 in
Analysis of Atmospheric Oxidant" Anal. Chem. 37, 779,
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42602 91 NITROGEN DIOXIDE-GAS BUBBLER-JACOBS-HOCHHEISER (100
ml TUBE + FRIT)
This method is identical to method 42602 71, except
that a fritted bubbler is used instead of an orifice
bubbler and the volume of the absorbing solution is
doubled.
1. "Selected Methods for the Measurement of Air
Pollutants/1 U.S. Department of Health, Education,
and Welfare 999-AP-ll, Robert A. Taft Sanitary
Engineering Center, Cincinnati, Ohio, May 1965, p C-4.
2. Purdue, L. J., et.al., (1972), "Reinvestigation
of the Jacobs-Hochheiser Procedure for Determining
Nitrogen Dioxide in Ambient Air," Environ. Sci.
and Tech. 6, 152.
44101 13 TOTAL OXIDANTS-INSTRUMENTAL-MAST MODEL 742-2
Identical to method 44101-15.
1. Mast, G. M. and H. E. Saunders, (Oct. 1962), "Research
and Development of the Instrumentation of Ozorui Sensing,"
Instrument Soc. of Amer. Trans., 1, 375.
2. Bufalini, J. J., (1968), "Gas Phase Titration of
Atmospheric Ozone," Environ Sci Technol 2, 703.
3. Wartburg, A. P., and B. E. Saltzman, (1965),
"Absorption Tube for Removal of Interfering SO2 in
Analysis of Atmospheric Oxidant" Anal. Chem. 37, 779,
44101 51 TOTAL OXIDANT-GAS BUBBLER-PHENOLPHTHALIN
Phenolphthalin, in the presence of CuSO/}, is
oxidized to phenolphthalein by ambient air oxidants.
Air is passed through 10 ml of reagent at 800
ml/min for 10 min. The color is read using a
colorimeter and a green filter.
1. M. B. Jacobs, (1960), "The Chemical Analysis
of Air Pollutants," Chemical Analysis, Vol 10,
Interscience Publishers, Inc., New York, N. Y.,
p 226.
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APPENDIX B
Rationale for Ranking the Methods as Unacceptable
CO 42101 12
COULOMETRIC
Interferences with this method include mer-
captans, hydrogen sulfide, olefins, acetylenes,
and water vapor. In addition, the slow response,
need for careful column preparation, and the
need for well controlled temperatures and flow
rates make this an unreliable procedure.
S02 42401 15
THOMAS AUTOMETER
This is a conductimetric analyzer. Data collected
using this analyzer should be reported as 42401-13.
S02 42401 31
DAVIS INSTRUMENT
This is a conductimetric analyzer. Data collected
using this analyzer should be reported as 42401-13.
S02 42401
92 WEST-GAEKE BUBBLER
This method differs only slightly from 42401-91 and
offers no substantial advantages. Method 42401-91
should thus be used for uniformity.
S02 42401
93 CONDUCTIMETRIC BUBBLER
The method lacks specificity; Method 42401-91 should
be used to obtain better measurements.
N02 42602-71 J-H BUBBLER (orifice)
N02 42602 91 J-H BUBBLER (frit)
The objections to these methods have been detailed in
38 FR 15174 (June 8, 1973): The collection
efficiency is a function of N02 concentration and
the presence of NO introduces a positive interference,
39
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N02 42602 72 SALTZMAN
This manual method suffers from interferences
from SO^, ozone, PAN, and prolonged exposure
to light, and cannot be used for periods
over 30 minutes.
TOTAL 0Y 44101 11 ALKALINE KI-INSTRUMENTAL
A
The alkaline KI method produces such variable
results in different hands that data from one
site cannot be compared with data from another.
TOTAL Ov 44101 13 MAST MODEL 742-Z
A
This method is identical to method 44101-15. Data
collected using this analyzer should be reported
as 44101-15.
TOTAL Ox 44101 51 PHENOLPHTHALIN
Results of this method do not agree with those
obtained by other total oxidant methods,.
TOTAL Ov 44101 81 ALKALINE KI BUBBLER
A
The alkaline KI method produces such variable
results in different hands that data from one
site cannot be compared with data from another.
TOTAL Ov 44101 82 FERROUS OXIDATION
A
Results of this method do not agree with those
obtained by other total oxidant methods,,
OZONE 44201 13 COULOMETRIC
This method is identical to method 44101-15.
Data collected using this method should be
reported as 44101-15.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-450/4-74-005
3. RECIPIENT'S ACCESSION
. TITLE AND SUBTITLE
Designation of Unacceptable Analytical Methods
of Measurement for Criteria Pollutants
5. REPORT DATE
September 1974
6. PERFORMING ORGANIZATION CODE
MDAD, OAQPS, QAEML, NERC-
.TP
. AUTHOR(S)
8. PERFORM
PERFORMING ORG \NIZATION NAME AND ADDRESS
Monitoring and Data Analysis Division
Office of Air Quality planning and Standards
Research Triangle Park, N.C. 27711
10. PROGRAM ELEMENT
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Air Quality Planning and Standards
Environmental Protection Agency
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
is. ABSTRACT This report contains a designation of the acceptability of
various analytical measurement methods currently in use. Each monitorinj
method is placed into one of three categories i.e., approved-Federal
Reference Method (FRM) or equivalent; unapproved - not yet determined
to be equivalent to the FRM; and unacceptable - known to yield measure-
ments of poor accuracy and reliability and in most cases obsolete.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Field/Group
Federal Reference Methods
Unapproved Methods
Unacceptable Methods
S02
TSP
CO
N02 and Photochemical Oxidants
18. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report!
None
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
None
22. PRICE
EPA Form 2220-1 (9-73)
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