GUIDELINE SERIES
OAQPS NO. 1.2-ois
DESIGNATION OF UNACCEPTABLE
ANALYTICAL METHODS OF MEASUREMENT
FOR CRITERIA POLLUTANTS
This document supersedes OAQPS 1.2-018
dated 2-8-74 entitled "Designation of Criteria
Pollutant Analytical Methods as Acceptable/Not
Acceptable for Purposes of Data Analysis"
~^ ~~ in nn
~ri inn
US. ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina
-------
DESIGNATION OF UNACCEPTABLE ANALYTICAL METHODS
OF MEASUREMENT FOR CRITERIA POLLUTANTS
May 1974
OAQPS Number 1.2-018
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
-------
TABLE OF CONTENTS
Page
INTRODUCTION 1
CATEGORIES OF ANALYTICAL METHODS 1
REFERENCE AND EQUIVALENCY REGULATIONS 2
ACCEPTABILITY OF ANALYTICAL METHODS 3
'DISCUSSION OF CRITERIA POLLUTANTS 3
1. Total Suspended Parti dilates 3
2. Carbon Monoxide 3
3. Sulfur Dioxide --^- .- 4
4. Nitrogen Dioxide '4
5. Photochemical Oxldants (Ozone) ?--- 4
6. Total Hydrocarbons Corrected for Methane ..... 4
POLLUTANT METHOD CODE -« --- 5
SUMMARY OF REGIONAL OFFICES RESPONSIBILITIES - 5
APPENDIX A
APPENDIX B
-------
Designation of Unacceptable Analytical Methods of Measurement For
Criteria Pollutants
.Introduction
'ItTTsf we'll known tt> a3J ultt>janrtlyze.t*+.*ir to measure criteria
pollutants that some techniques trr'n«thaii!»~dre better than others.
Because important decisions, such as air quality standards achievement
and State Implementation Plan (SIP) revisions are based on data
t
derived from these methods, 1t 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, consistant
with the objectives and needs of their monitoring program.
Categories of Analytical Methods
Methods for measuring ate 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 (NAAQSJ. 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 t
Regulations governing the procedures and criteria by which unapproveJ
methods may be determined to be equivalent have been 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 neJPregulations 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 QAEML,
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
-------
- 3 -
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 "apprpved", "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 S02 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 N02 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), 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 hi-vol method is the federal reference method
for total suspended particulates. Since the air quality standard
is defined by the method, the hi-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 4
principles have not yet been tested with respect to equivalency,
and are therefore unapproved.
-------
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-Gaek-e"
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. 1n the Oune 8, 1973 issue of
the Federal Register (38 "FR T5T74), it xas .proposed that the NASN
method be withdrawn as the reference TnethruJ jmd a new one designated
after testing of proposed candidate methods. Although the method
wa,s 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 photochemica
oxidants is a continuous chemiluminescent method based on the gas-phase
reaction of ozone with ethylene. This method is specific for ozone.
t f
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), Guidelines for Determining Performance
Characteristics of Automated Methods for Measuring N0£ and Hydrocarbons_
for Methane in the Ambient Air.
-------
- r-
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 (SAROA'O method code
42401 92) for example, to. the West-Gaeke-Sulfamic Add 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, 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 principal 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,
the Regional Offices should assist in the conversion to the exclusive use
of approved methods for S02, CO and Oxidants corrected for S02 and N02
and similarly assistance should be provided for selecting adequate methods
for N02 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 Guide!ine #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 thie rational
for that designation.
-------
TADLE 1
IfTl Pollut.iiii-vetho
18
23
' 17
0
100
z
X
X
X
X
X
X
X
X
X
X
X
X
X
z
'x
p.M » federal Reference :
-------
P'JLLUTA.'iT
CODE
YFTH
NUMBER OF
SITES
STATt CU'J'NT ' iliOl ill
STATE (fnu.N'fTIlOl
-------
TABLE II
-r-
PCLLMTANT "rTH
CO')E CTO'i
NUMBER OF
SITES I
t "'N. ^
STATF
STATF
STATE
STATE
STATE
STATE
STATE_
STATE
STATE
STATE
STATE
STATF
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
ST.TF.
STATF
STATF
COUNT _
_ CUU NT
COUNT
COUNT
COUNT _
---COUNT-- -
COUNT
COUNT _
COUNT
COUNT
COU NT-
COUNT
COUNT
COUNT
COUNT
COUNT
, CO' INT
COUNT
COUNT
COUNT
CC'JNT
COUNT
COUNT
C'JUNT
.Ui°>_
uioi -..;_
11101
11101
11101 _
11101
11101
1_1 10_1 _____
11101
11101
1110.1
11101
11101
11101
11101
11101
11101
11101
11101
11101
11101
1 1 1 0 1
11101
11101
91
91
91
91
91
91
91
.jti.
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
91
MISSCJRI _
' ^MONTANA ' ' _
NEBRASKA
NEVADA
iMEW HAHPSHMf".. .
NEW JrPSlY
NEW MEXICO
NFW__Y_ORK ;
NORTH CAROLINA
NORTH OAKCTA
__OHIO _ :
OKLAHOMA
OREGON
PENNSYLVANIA
PUERTO PICO
RHODE ISLAND
SOUTH CAROLINA
SOUTH DAKOTA
TENNESSEE
TEXAS
UTAH
._-,;V£**fnT
VIRGINIA
WASHINGTON
-^ -
2;-..
36
41
_26
79
' 28
233
199
16
J137__
95
48
105
5
23
75
2
98
192
8
2
122
57
-------
TABLE II <}-
POLLUTANT '^rTH
CPOt CODE
STATF
ST. AT:
V
STATF
STATF
STATE
P GLUT COD
^ .
STATE
STATE
STATE
"STATE
STATE
STATE
STATE
"STATE "*
STATE"
"STATE r"
STATE
STATE
STATE
'STATE
STATE
STATE
STATE
STATE
STATE
"CUNT
-.ru'-iT ""'
CUiJNT :
COUNT
C O'JN T
CC'JNT
^i*" ""*
COUNT
COUNT
COUNT
COUNT*
COUNT
COUNT
COUNT
"COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
ccjirT" ".'
TCUNT"~
COJMT
CG'I,\T
illOl
iiibi
~ n 101
11101
"""liioi
11101
42101
42l6i
42101
42101
42101
42101
42101
"~42T6T
42101
42101
42101
42101
42101
42101
42101
"zlbi
"42101
42101
42101
91
~'*T
' '. V9l' "
9l"
9V
91
11
-_._..__._.
11
11
11
11
11
11
11
11
11
11
11
11
11
' ~ "ll
u
11
11
NUMBER OF
SITES
WEST VIPG1MA
. .JISC3MSIN """"."" '
* '
"WYOMING
GUAM "
VIRGIN ISLANDS
ALAdAMA
ALASKA
ARIZONA
CALIFORNIA
"COLORADO *
DIST COLUMBIA
FLORIDA
GEORGIA
HAWAII
ILLINOIS
INDIANA
IOWA
KANSAS
KENTUCKY
LOUISIANA
MARYLAND ~.~
MASS\CH!JSETrS
MICHIGAN
MINNESOTA
33
7
" 4
11
4 '.."
"2828
2
7 x ~
3
"" '51
1
2
6
2
1
1
3
2
5
7
3
"19"" ~. ~~~
"' ' 5
3
-------
L'AULE 11
-lo-
POLL'JTAilT Nf:TH
CC.)E COOE
STATE
STATE-
STATE
STATE
STATE
1I^T * ^.
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
POLUTCDD
STATE
PHLUTCOD
STATE
PCLUTCGD
COUNT
Cp'.ST
CO'I,\'T
COUNT
CO'JM
~£Sm
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
_COU\T
COUNT
COUNT
COUNT
COUNT
COUNT
COJ'JT
COUNT
42101
42101
42101
421J1
__^101
:^^?^1
42101
42101
42101
42101
_42101
42101
42101
42101
42101
_ 42101
42101
42101
42101
42101
42101
42101
42101
42101
il
11
11
11
11
11
11
11
11
11
11
11
11
U
11
H_
11
11
11
11
12
12
21
21
NUMBER OF
SITES '
MISS::USI
NEV&UA
NEW JERSEY
NcW MEXICO
NEW YORK
NORTH CAROLINA
OHIO
OKLAHOMA
OREGON
PENNSYLVANIA
RHODE ISLAND
TENNESSEE
TEXAS
UTAH
VIRGINIA
WASHINGTON
WEST VIRGINIA
WISCONSIN
OHIO
.
KENTUCKY
.
10
.____ I .
I
22
1
13
2
Jl3
4
2
2
2
4
__l
4
9
10
1
1
223
1
I
2
2
-------
TABLE II
V
POLLUTANT
COOh
NUMBER OF
SITES I
STATE
STATE
"STATE"""
"STATE
STATE
"STATE
"STATE
"STATE
"STATE
"STATE
"STATE ~
STATE
"STATE"
STATE
"POLUTCOD
"STATE
STATE
'STATE ........
"STATE
STATE
» , ^
"STATE "
STATE
STATE
STATE
COUNT
~rPJNT
COUNT
COUNT
COUNT
COUNT
" C OUN T
"COUNT"
"COUNT
COUNT
"CO'JN T
COUNT
COUN T
C OUNT"
COUNT
COUNT
Cbl'JN'f
COUNT
COUN" t
COU'NT
COUNT
COUNT
COUNT
'COUNT
CCl.'NT
42401
' 42401
42401
42401
42401
"42401
~:4 2 401
42~4o7
42401
4246T
"424J 1
424
42~40~i
42401
42401
424b"l
4240T
424JI
"4240r
4240 1
42"40"l
42401
42401
42401
424J1
11
Vi
11
^
ll
i
ll
i'i
ir
"11
ll
11
1 1
1 1
ll
11
IT
13
13
f3 '
13
13
13'
13
13
ARIZONA
COLORADO"
DELAWARE'" ......
DI$T CUUJMBIA
FLORIDA"""""
llLINOIS "" ~ '
K E NT UC KY
MAR YL AND "" ........ "
~MASSACHUSETTS
MI SSOUk'l 7
NEW~ JERSEY
NEW" YORK "
~OH 10 ...........
PEWSYLV ANt A
WASHINGTON
........... ~ ...... """"
ARIZONA
CALIFORNIA
"COLORADO
CONNECT I CUT
2
1
6
2
3
1
5
22
OIST COLUMBIA
»
FLCIIDA
ILLINOIS
INDIANA
4-
1
68
~2
18
..... i
T
7
2
1
1
8
-------
TABLE II
-IA -
POLLUTANT MfcTH
cnnn
NUMBER OP
SITES
STATE _
STATE
STAT?
STATE
STATE
5TATE _
STATE
STATE
POL'iJTCGO
.STATE
STATE_
STATE __
STATE
STATE
STATE '
STATE
ST AT E
STATE _
STATE
STATE
STATE
STATE
STATE
COUNT
CCUNT
CC'JNT
COUNT
COUNT
CO'JNT
COUNT.
COUNT
COUNT
_C_CUNT
C pUN T
_CO_JNT_
COUNT
COUNT
COUNT_
CO'JNT
COUNT
COUNT
COUNT
COUNT
CCO NT
COUNT
COUNT
A2401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
4240.1
42401
42401
13
13
13
I3
13
13
13_
13
13
13
14
14
14
14
14
14
14
14
14
14
14
14
14
14
MAPYLAND
MtN.Nfc.SOTA-
MISSO'JPI
NEW YORK
OH IJ3
OREGON
PENNSYLVANIA
VI KGINIA
WASHINGTON
ALABAMA
ARIZONA__
D 1ST COLUMBIA
FLORIDA . '_
GEORGIA '
T" .-.--. - . -.-.- ,.^.-.
INDIANA
KANSAS
KENTUCKY
MASSACHUSETTS
MICHIGAN
MINNESOTA
MISSOURI
NEW YORK
NO^.TH CAROLINA
12
2
2
I
7
2
2
' 2
9
80
2;
8
2
2
. 4
3
6
2
22
4
1
12
1
-------
TABLE II
PfiLLUTAUT MFTH NUMBER OF
""" C"Dr . CQDE ' ' ~ SITES
STATE
.STATE
STATE" '
STATE"
POLUTCCD
STATE.
POLUTCOO"
"STATE
STATE
POLUTCOO
"STA'TE"
>dLAJTCOb"
STATE
POLUTCOO
STATE
"STATE' "
"STATE
STATE
'STATE, ~
STATE
1
STATE "
t '
STATE
ST/TE'
STATE '
STATE """'"
COUNT
COUNT"
COUNT
CCUNT
COUNT
COUNT
"COUNT
"COUNT
CCUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
.COUN'f
"COUNT ~~
"COUNT
COUNT"
CHUNT "~
-rc-rit;--1-
"COUNT
42401 "
42401
42401
42401
42401
424"0l ~
4240T
42401
42401
42401
42401
42401
42401
42401
42401
42401
42-401" '
42401 "
42401""
42401" >
42401
42401"
14
14
T4
14
14
l"5"
15
~16~
16-
16
31
31
3?
33
91
91
91
91
_
91
"91
91
91
91
91
UH I - J
PENNSYLVANIA
"'"T'ENN'ESSPE
VIRGINIA
"" TEfWfcSScE
MARYLAND ~
VIRGINIA
NEW YORK
" MISSOURi
ALABAMA
ALASKA
ARIZONA
ARKANSAS
CALIFORNIA
COLORADO "
"-"CONNECTICUT" "~
"DELAWARE" ." "'"
"bisf COLUMBIA
"FLoRIOA
"GEORGIA'"
i
"7 " "i ~
2
76
i
1
"""." 11 "
*
_.. .. ..
12
38
"38
'" 3"" """ '"
" 3 '" "
I
7 :;. ;
16
2' -
4 ' '
- -v> -''..
34
:;,-.vi-3" " ; ' ' :
-------
STATE
>T*ye
STATE
STATE"
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
Ctlim
COUNT
v COUNT
""COUNT
Jrx-^:.-^i=^.._
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
'COUNT
COUNT
_ COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
PCLL'JTA'
CODE
42401
42401
"*""" * * ' t
42401
42401
T-~-"'C^ -
A' ^ A-f^^-i
42401
42401
_4240l
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
42401
424J1
* T J ^ T LJ
Y i T 7 * n
CC!?e
91 .
..-.. -'1,-
91
91
91
91
91
91
91
91
91
91
91
__.___?l_.
91
91
91
91
91
91
91
91
91
.
HAWAII
_,_ ILLINOIS
INDIANA
IOWA
KANSAS
KET1TITCKY
LOUISIANA
KAIN6
MAPYLANO
MASSACHUSETTS
MICHIGAN
MINNESOTA
MISSISSIPPI
MISSOURI
MONTANA
NEBRASKA
NEVADA
NEW HAMPSHIRE
NEW JERSEY .
NEW MEXICO
NEW YOrfK
NiOrtTH CAROLINA
OHIO
. OKLAHOMA
NUMBER OP
SITES
12 .
..- .a«._._,.
66
2
30
98
17
* *
49
53
24
18
2
^
1
4
3
4
8
_ 8
34
156
67
27
-------
TABLE II
STATE
'ST/.TE
.STATF ~
STATE
STATF
STATUE
STATE
"STATF. "
STATE
STATE
"STATE
"STATE
STATE
STATE "
STATE
STALE
"POLUTC
STATE
STATE
POLUTC
STATE"
POLUTC
STATE
STATF
t
STAT
COUNT
COUNT
""COUNT
~ COUNT
"COUNT
COUNT
"COUNT
COUNT
COUNT
*
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
6~D~ COU.NT
"""COUNT
COUNT
00 COUNT
(TOUNT
00 COUNT
C'?')NT
COUNT
CO'IM
POLL UT AN
CODfc
2_ 42401
42401
42401
42401
42401"
42401"
42401
424~bT
42401
42401
~424"bT
42401
42401
42401
42401
42401
4240r
42407
42401
42401
42401
424"ai~
42602
42602
42602
T MPTH ' . NUMBER OF
CODE
"g'l"
*.l
91
--91-
_._...
91 ""
91
91
91
___
91
91
91
91
91
-_.._..
92
92
92
93
93
11
" li
" U
1
. OREGON
PENNSYLVANIA
PUERTO PICU
RHODE ISLAND
SOUTH CAROLINA
"SOUTH "DAKOTA
TENNESSEE
"TEXAS '""
UTAH
VIRGINIA
"'WASHINGTON
WEST" VIRGIN I A7""
WISCONSIN
WYOMING
GUAM
VIRGIN ISLANDS
««.*..... _ ._.«- - «...*. . _ . .....
"FLORIDA " ~
MASSACHUSETTS
INDIANA
*"«*- "- - ... - . - i .. v. w. ..»
ALABAMA
ARUJNA ~"~ .
CALIFORVIA
SITES
14
4
18
-- 38
1
37
""'13- "
1
49
" ""15 '
3
2
'9
3
"1040
1 "" "
44
45
2
'"'" ' 2
2
-' - 3 ; ' -
50
*, f.
-------
TABLE II
STATE
STATF
STATF
STATF
STATE
STATF
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
i
STATE
STATE
STATE
STATE
POLUTC
STATE
STATF
STATE
STATF
COUNT
COUNT
COUNT
COUNT
COUNT
"" COUNT"'
COUNT
COUNT
COUNT.
CPUNT
COUNT
*
COUNT
COUNT
COUNT
COUNT
i
COUNT
COUNT
COUNT
COUNT
OD COUNT
COUNT
COUNT
COUNT
COUNT
P-ULMTA
CODE
42C02
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
_42602
42602
42602
42602
42602
42602
JT '-1CTH
'CODfc
11
11
11
11
.11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
11
I'd
12
12
12
NUMBER OF
SITES
CONNECTICUT
oisr COLUMBIA"
FLORIDA
GFCRGIA
KENTUCKY
MAINE
MARYLAND
4
MASSACHUSETT S
MINNESOTA ;
MISSOURI
NEVADA
.
NEW YORK
NORTH CAROLINA
UHIO
OKLAHOMA
OREGON
PENNSYLVANIA
TENNESSEE
VIRGINIA
i
COLORADO
DISt COLUM3TA
ILLINOIS
MISSHUM
1
1
4
1
8
1
6
1
1
8
1
13
1
2
1
1
1
,1 _..
2
10
I
1
1
I
-------
POLLUTANT Mf-TM
STAT±
.STATF.
'** '
STATE ~~
POLJTCOO
STATE
STATE
STATE
STATE
POLUTCOD
STATUE.
* _ & .
S T A !,,£>'
STATE
STATF
STATE
STATE
STATE
STATE
STAfE
STATF
STATE
STATt ?f
STATE
STATF
C'^JNT
COUNT
COUNT
COUNT
"CtKftT ':?-
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
"COUNT
COUNT
'COUNT"
COUNT
COUNT"""
COUNT ""'
COUNT
cc'.m
COOF
42.0,
42602
42602
42602
-42^02
"42602"
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602"
42602
426~J2~
426:02"
42602
42602
42602
42602"
CODE
12
12
~ 12 ~"
12
12"
13
13
13
13
13
14
14
14
14
14
14
"-
14
_._
_._._.
14
j^ "'
14
14" '
NUMBER OF
'
Nf .%' JfcP.SfcY
OHIO
PbNNSYLVANIA
AHODE ISLAND
-VIRGINIA
KANSAS
MINNESOTA
NEV/VDA
TENNESSEE
ARIZONA
COL OP ADO
CONNECTICUT
OIST COLUMBIA
ILLINOIS
INDIANA
"IOWA" ~
KENTUCKY
""MARYLAND" " ~"
KAS'SACHUSETTS "
"MINNESOTA ~
^ .*"... .. . . . . _
NEBRASKA ~
Nflw MEXICO
SITES
1
1
""""2
2
15
2
' ~ -~l
1
1
5
1
1
i -
2
2
1
" i'"
'3
I "
1
1
2
1
1
-------
TABLE II ~/S-
PGLLUTA'.
CTJE
_ STATE
STATE
STATf
STATE
StATE
STATE ._...
POLUTCOO
STATE
POLUTCOD
STATE
PDLUTCO^
STATE
STATE
STATE
STATF
STATE '
STATE
STATE
STATE
. STATt
STATE
STME.
STATE
COUNT
COUNT
COUNT _
COUNT
COUNT
COUNT..., ---
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT _
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
CT-'UNT '
COUNT
COUNT
42A02
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
.CODE
14
,1"* '
14
14 _
14
14
71
71
72
72
91 _
91
91
91
91
91
91
91
91
91
91
91
91
NUMBER OF
SITES
NRW VrWK
OH i n .
PENNSYLVANIA _.. _'_
TEXAS
UTAH
VIRGINIA
MINNESOTA _
INDIANA
ALABAMA
ALASKA
ARIZONA
ARKANSAS
CALIFORNIA
COLORADO
CONNECTICUT
DELAWARE
01 ST COLUMBIA
FLCiKIDA
.GEORGIA '
HAWAII
ILLINOIS
2
5
5
2
1
2
36
11
11
11
11
13
1
5
2
16
2
4
3
2
22
13
11
4
-------
-/f-
-- .
STA^t
-^
"STATE
STATE
STATE
STATE
"POtJTCOO
'STATE
STAf|
STATE
STATE
POLUTCOD
STATE
STATE
STATE
STATE
STATE
STATE
' STATp
STATE
STATE
STATE
STATE
STATt ""
STATE
STATF
-
C '>-) NT
COUNT"
COUNT .
COUNT
COUNT
COUNT
cnuNT ~
COUNT
COUNT
COMNT
COUNT
COUNT"
COUNT
COUNT
COUNT
COUNT
COUNT
c'o'ifNT"
cnuNf""
COUNT"
COUNT
CO'JNT""
COUNT""
cau\f ~
ccVpu""
PDLLUTA
CODE
426002
~~42602
42602
42602
42602
' 42"602
426~02
42602
42602
42602
42602
42602
~ 4260 2
~ 4 26 02
42602
42602
" 42602
"42602
"42602
42602
\'T ME-TH _.. NUMBER OF
CODE SITES
12
12
12
12
-"12-
12
13
, 13
13
13
13
iV
14
14
14
14
14
14
14'
"14
14
J4
J -IV
14"
14
NF.V JfcP.SbY
OHIO
""" VbMNSYLVANlA "
RHODE ISLAND
'vi^OI-NlA
KANSAS
MINNESOTA
NEVADA
TENNESSEE
"""ARfZONA ~~
COLORADO
CONNECTICUT
DIST COLUMBIA
ILLINOIS
INDIANA
"IOWA"
KENTUCKY " ~
MASYLAND
MASSACHUSETTS
"MINNESOTA"""
^Missojrti" " ~" "
NEBRASKA ~
NC'X MEXICO'
5
1
i
" 2
'"" 2
15
2
1
*
1
1
5
1
""" i"
i
2
2
1
' " 1"
'3
""" 1
1
I
2
1
1
-------
TABL.E II
POLLUTANT *PTH
root CODE"
STATE
STATE"
STATE
STATE
"STATE"...
"STATE"
STATE
STATE
STATE"
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE
STATE"
STATE
STATE "
STATE
CCU.MT
COMNT
" "COUMT .
COUNT"
COUMT
COUNT
""COUNT"
COUNT
COUNT
COUMT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
" "COUNT
COUNT
COUNT
COMNT ~
COUNT
cru.'JT
42602
426U2
42602
42602
42602
52602
' 42602"
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
42602
'42602'
42602"
42602
42~602
42602
42602
42602
91
91
SI
«1
91
91
91
91
91
91
91
91
91
91
91
91
91
..
INDIANA
IO..A
KANSAS
KENTUCKY
LOUISIANA
MAINE
MASSACHUSETTS
MICHIGAN
MINNESOTA
MISSISSIPPI
MISSOURI
MONTANA
NEBRASKA. '
N₯W "HAMPSHIRE
NEW JERSEY
NEW MEXICO
NFW YORK
NORTH CAROL I NA~
OHIO
OKLAHOMA "'
JREGUN
PENNSYLVANIA
PUFRTO RICO
3HCOE "ISLAND
NUMBER OF
SITES
41
2
87
4
" 1
49 "
.54
6
3
2
4
1
3
4
8
7
9
""""155
67 ~
19
1
14
" " '4
-------
TABLE II -JV-.
\
STATE-
STAT C
STATE "
STATE
STATE
STATE
STATE
STATE
STATE
STATE
POLUTCOO
STATE
POLUTCOO
STATE
STATE
STATE
STATE
STATE
STATE
STATf
STATF
'TAT?
MtTE
-
CCJU.MT
COUMT
COUNT
CO'JNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT.
COUNT
COUMT
COUMT
CO'JNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
CO'JNT
COUNT
COUNT
COUNT
POLLUTANT
42602
_ 42602
42602
42602
42602
42602
42602
42602
_42602
42602
42602
42602
42602
42602
44101
44101
4410i_
44101
44101
44101
44101
44101
44101
44101
CODE
91
91
91
91
91
91
91
91
91
91
91
91
S4
94
11_
11
11
11
11
11
11
11
11
11
SOUTH CAROLINA
SOUTH DAKOTA
TENNESSEE
TEXAS
UTAH
VIRGINIA
WASHINGTON
WEST VIRGINIA
WISCONSIN
WYOMING
GUAM
'. '
K-ENTUCKY
ARIZONA
COLORADO
01 ST_ COLUMBIA
FLORIDA
ILLINOIS
INDIANA
IOWA
KANSAS
MISSOURI
NEW JERSFY
NUMBER OF
SITES
38
; 1 ' .
41
13
1...
_ _ 7
10
4
_. 1
3
2
9
816
2B
28
1
1
1 ______
2
1
2
*
1
1
4
-------
\
STATE
ST>.TC
STATf
STATFT
STATE
S» * ^ C
i M i r
STATF
STATP
STATE
POL'-JTCCD
STATE
STATE
STATE
STATE
POLUTCnO
STATF .
STATE
STATF
STATE
STATE
STATF
ST/.TF
STATC
STATC
STATc
CO' INT
Cl'TJT
cn-.riT
COUNT
COUNT
CnUNT
CCUMT
COUNT
COUNT
COUNT "
\
COUNT
.COUNT
COUNT
COUNT
COUNT
COUNT
" COUNT""
COUNT
COUNT
COUNT
COUNT
COUNT'"
cnjMT
CC'JM
/co .INT
1
POLLUTANT
COPE
441)1
4'tlUi
44101
44101
44101
441 01
44 1 0 1
44101
44101
44101
44101
44101
44101
44101
44101
44101
~44fOi
44101
44101
44101
44101
44101
44101
44101
44101
[ABLE
MPTH
cone
11
11
u
~ii
u
u
11
11
11
13
13
13
13
13
14
~ T4 ""
14
14
14
14
14
14
14
14
II -JJ_
--- -
NEW YUHK
NO'TH CAROLINA
* » '
OHIO
PENNSYLVANIA
TENNESSEE
"TEXAS
VIPGINIA
WASHINGTON
WISCONSIN
KANSAS
NEVADA
NEW MEXICO
WASHINGTON
ALASAMA
ARIZONA
CALIFORNIA
COLORADO
KENTUCKY
MINNESOTA
MISSOURI"
i
OHIO ~
ORUGLN
PF.TiNSYLVANIA
NUMBER OF
SITES
12
2
"' 8
" " " 1
4
I
4
,1
I
49
3
1
1
5
10
1
._ ._.
56
1
1
1
8
2
I
I
-------
-AC-
TABLE II
POLLUTANT '4^TH
.STATE
STATE
POLJTCOO
STATE
STATF
POLUTCCU-
J5TATE
_Pp_LUTCqO
_STATE ___
STATF
STATE
STATE
POLUTCOO
STATE
STATE
STATE
POLUTCOD
STATE
STAT E
STATE
STATE
STATP
STATF
STATF
COUNT
COUNT
COUNT
COUNT
COUNT _
COUNT"
COUNT
COUNT_
COUNT
C.O'JNT
COUNT__
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
CC'J NT
C3JMT
COUNT
CODE
44101
44'lOi
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44101
44201
44201
44201
44201
44201
4't20i
44201
NUMBER OF
CODE - S1ITES
14
I* .
14
15
15.
15
51
51
81
81
31
81
81
32
32
82
*2
11
11
11
11
11
11
11
TENNESSEE
'VIRGINIA
CALIFORNIA
VIRGINIA
OKLAHOMA
MINNESOTA
NORTH CAROLINA
OKLAHOMA
SOUTH_ CAROLINA
KANSAS
KENTUCKY
OHIO
ALABAMA
COLORADO
DIST COLUMBIA
FLORIDA'
"GEd9.GI A.
HAWAI I
ILLINOIS
1
' i
75
12
1
13
5
5
..7. '
7
13
37 _
64
76
6
85
2 ____
1
1
4
1
1
1
-------
- -av-
, -'>
TATF
,T£TE
.TATF
x
,T4TE
,TATE -.-.
TATE "
-TATE
TATF
TATF
TATE
TATE
TATE
TATE
TATE
TATE
TATE
TATE
OLUTCOO
TATE
ciLUTcon
COUNT
CCtHT
CO'. 'NT
*
COUNT""
C.ojJ.'.!J......
COUNT""
COUNT
COUNT
COUNT
COUNT"
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
COUNT
CDJ NT
POLLUTANT
CCSi)*:
44201
'»4201
~~442U1
~ 44201
44201
~ ^V2ol~^
44201
44201
44201
44201
44201
44201
44201
44201
44201
44201
44201
44201
44201
44201
-1ETH
cone
11
11 .
~~ii
.__ ..^_ ..._.
u
T ii
11
11
11
11 ~"~
11
11
11
11
il
11
U
il
13
13
-
I. 'JO I ANA
*ANSAS'
KENTUCKY
LOUISIANA
MARYLAND
xiciYicAM
MISSOURI
NEBRASKA
NEW YORK
NORTH CAROLINA
OHIO
OKLAHOMA
PENNSYLVANIA
SOUTH CAROLINA
TENNESSFE
TEXAS
VIRGINIA
OREGON
NUMBER OF
SITES
1
2
" 2" '
3 '
6
1
I
3
4
12
2
7
2
1
'"" ~~1" "" ' " " ' '
1
1
5
62
1
1
-------
A DESCRIPTION OF THE ANALYTICAL TECHNIQUES
AND ASSOCIATED SAROAD METHOD CODES USuD IN
STORING DATA IN THE NATIONAL AEROMETRIC DATA BANK
APPENDIX A
EXTRACT FROM GUIDELINE DOCUMENT OAQPS 1.2-017
January 1974
-------
Federal Reference Methods
11101 91 SUSPENDED .PARTICULATE - HI-VOL - GRAVIMETRIC
Air is drawn at 40 to 60 ft.3/rain through a glass
fiber filter, by means of a blower, and the sus-
pended particles having a diameter between 100
and 0.1 pra 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 ug/m3. Heavy
loading of suspE3Kteu:'-;part'iwiiloLer'oily particulates,
or high humidity can cause xeduced 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," EPA-APTD-0741, v
Office of Technical Information and Publications,
Research Triangle Park, Nprth Carolina, 1971,
P 17.
42101 11 CARBON MONOXIDE - INSTRUMENTAL - NON-DISPERSIVE
INFRA-RED
' The non-disperive infrared instrument has a sample
'cell, a reference, cell, and a detector. The detector
is divided by a flexing diaphragm into two equal
cells filled with equal concentrations of CO. The
i
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
-------
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 pressure on the
diaphragm; -When the CO is introducedinto the sample
cell, unequal amounts of residual radiation re'aches
the two compartment 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
ultimately an amplified signal which is suitable for
input to a servo-type recorder. The detector is calibrat
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 dichlorosulfitoraercurate
complex. When acid bleached pararosaniline is added
to the collected S02 together with formaldehyde,
the amino groups (-Nflt) form a red violet compound
called pararosaniline methylsulfonic acid which is
measured spectrophotometrically. The method is des-
cribed 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 sulfaraic acid
eliminates interference from oxides of nitrogen.
1. "Rules and Regulations," Federal Register, Vol 36,
No. 228, U.S. Government Printing Office, Washington, D.
(Nov. 25, 1971), p 22385.
2. West, P. W. and G. C. Gaeke, (1956), "Fixation
of Sulfur Dioxide as Disulfito-Mercurate (II) and
Subsequent Colorimetric Estimation," Anal. Chem. 28,
1819. .
3. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health .Association,
Washington, D.C., 1972, p 447.
-------
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 CH$, 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 Proceeding/ 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 setup 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 h and the in-
strument is then dynamically calibrated with known
SO2 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 H2O2 which
oxdizes the S02 to H2S04, The resulting charge
in conductivity can be measured, compensated for
-------
temperature, and related to the input S(>2 concentration
by dynamic calibration with known SO2 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, 16TW3'52, (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, *Thfi Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Imterscience
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 ah electrical current or potential
maintains a constant concentration of free 12 or Br2.
When S02 in the input air reacts with the 12 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 SO2 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 S02,
H2S, CS2, and CH3SH. Effluent from the columns is
-------
burned in a hydrogen-rich flame. A phptomultiplier
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 SO2/ ^S, CS2/ or CH^SH 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-CONDUCTIMETR]
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 SO, 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 N02 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 NO2 analyzers. Users should
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consult this 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, 194.9.. . . .
'
42.602 13 NITROGEN DIOXIDE-INSTRUMENTAL-COULOMETRIC
^Air to.be measured is passed through a cell containing
neutral buffered ix>d^t--o;x>7:iiv»c'iiolut.ion 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 NO2 concentration
can be related to the electrical signal by dynamic
calibration with known NO, 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 NO^ concentration is obtained by subtracting1
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/NOV/NO0 Analyzer Bulletin, Bulletin 4133,
A f, \
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. Nitroger
Dioxide in Air." Analyst 95, 519.
3. Merryman, E. L., et.al., "Effects of NO, CO2,
CHL, HjO and Sodium Arsenite on NCU Analysis,"
presented at the Second Conference on Natural Gas
Research and Technology. Atlanta, Georgia, June 5, 1972
42602 94 NITROGEN DIOXIDE-GAS BUBBLER-TfJASN- SODIUM ARSENITE-
FRIT
This method is identical to method 42602 71 except
that l.Og/1 of NaAsO, 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 Nitroger.
Dioxide in Air." Analyst 95, .519.
2. Merryman, E. L., et.al., "Effects of NO, COj.,
CH4, HjO and Sodium Arsenite on NO, 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-normal sodium
hydroxide is used instead of the phosphate buffer
in the absorbing solution.
-------
v
44101 14 TOTAL UXIDANT-INSTRUMENTAL-COLGRIHETRIC-NEUTRAL KI
Air to be"measured is contacted with nuetral
phosphate buffered potassium iodide. Oxidants
convert the KI to I2 °r KI3 which is measured
spectrophotomotrically at 352 run. If the input
air flowrate is constant, the color density can
be related to the pxidant concentration. Analyzers
. ,
are calibrated dynamically with known standard
concentrations of ozone. Sulfur dioxide inter-
ference may be minimized by use of a CrO-j pre-
scrubber, which also causes an NO interference.
1. Intersociety Committee, "Methods of Air
Sampling and Analysis," American Public Health
Association/ Wash., D.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.
I
44101 15 TOTAL OXIDANT-INSTRUMENTAL-COULOMETRIC-NEUTRAL KI
4
Air to be Measured is passed through a cell containing
potassium iodide and two electrodes. Oxidants(
convert iodide ions to I- which is reduced at the
z i
cathode of the cell causing a current to flow thru
an external circuit. If the flow rate is constant,
this electrical signal can be related to the input
concentration of oxidants. Analyzers are calibrated
dynamicajl^rf^w;ith known standard .concentrations of
ozone.;,*-- . ~"\'-.
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Unacceptable Methods
42101 12 CARBON MONIXIDE - INSTRUMENTAL - COULOMETRIC
Atmospheric air is drawn through a heated 12^5 column
where I2 is liberated. The I2 is directed
into an electrochemical cell where I~ is measured
«
coulometrically.
1. Beckman Instrumention, Bulletin 3000 4411-4,
Beckman Instruments, Inc., Fullerton, California.
42401 15 SULFUR DIOXIDE-INSTRUMENTAL-THOMAS AUTOMETER
The Thomas Autometer is a conductimetric analyzer
developed in 1929. There are later models. The
t
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, it 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 O.lM TCM,
the starch which is used for standardization is
made without mercuric iodide, and sulfamic acid
is not used except when high concentration of NOj
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.. Nauraan, R. V., et.al., (1960), Anal Chem. 32,
1307.
-------
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-HGCHHEISER-
50 Ml TUBE + ORIFICE
Ambient air to be measured is bubbled through a
sodium hydroxide solution where NO2 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 nmf 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.
-------
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.
o
1. "Selected Methods 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.
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) , "Researc
and Development of the Instrumentation of Oxone Sensing,
Instrument'Soc. of Amer. Trans., 1,_ 375.
"' " " ' "II" I-BI'MH I ' ^^MHWMMHMIMn - I I ! MIIIB ! ll I . I I II |I- ^
2. Bufalini, J. J., (1968), "Gas Phase Titration of
AVjnospheric Oxone," Environ Sci Technol 2, 703.
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 51 TOTAL OXIDANT-GAS BUBBLER-PHENOLPHTHALIN
Phenolphthalin, in the presence of CuS04 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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- -M.7-: .
44101. 81 TOTAL OXIDANT-GAS BUBBLER-ALKALINE
Oxidants in sampled ambient air are absorbed in
an alkaline KI solution in a bubbler. A stable
product is formed which can be stored with little
loss for several days. Analysis is completed
by addition of phorphoric 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 cfm then bubbled through two
impingers in series containing acidified ferrons
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.,
1, 375.
2. Bufalini, J. J., (1968), "Gas Phase Titration of
Atmospheric Ozone," Environ. Sci. Tech. 2, 703.
3. Wartburg, A. F., 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," U.S» Department of Health, Education,
and Welfare 999^-P-K.l-i ; .Pcvbert 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
j
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), "Resear
and Development of the Instrumentation of Oxone Sensing,
Instrument Soc. of Amer. Trans., 1, 375.
2. Bufalini,jJ. J., (1968), "Gas Phase Titration of
AVjnospheric Oxone," Environ Sci Techno! 2, 703.
3. Wartburg, JA. P., and B. E. Saltzman, (1965),
"Absorption Tube for Removal of Interfering SO2 in
Analysis of Atmospheric Oxidant" Anal. Chem. 37, 779.
i
44101'51 TOTAL OXIDANT-GAS BUBBLER-PHENOLPHTHALIN
Phenolphthalin, in the presence of CuS04 is
oxidized to phenolphthalein by ambient air oxidants.
Air is passed/through 10 ml of reagent at 800
ml/rain 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,
Interscienqe 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' . c
\ v '
v Interferences with this method Include mer-
captans, hydrogen sulfide, oleflns, 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 1s 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
v- 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 iJ-H.BUBBLER;(|r|t|v:y
^i^he objections to'iihiese'methods have been;detailed in
;.38" FR ,15174 .(Junef 8, 1973^: The collection
efficiency is a function of N02 concentration and
the presence of NO introduces a positive interference.
-------
N02 42602 72 SALTZMAN
This manual method suffers from interferences
from SOg, ozone, PAN, AND prolonged exposure
to light, and cannot be used for periods
* . . , ,
over 30 minutes.
TOTAL Ox 44101 11 ALKALINE KI-INSTRUMENTAL '
...Jhe-alkaline KI jnp.thod.frMurp«:...s,urh variable
.results in different /hands, tirat aata from one
site cannot be compared with data from another.
TOTAL Ox 44101 13 MAST MODEL 742-Z
This method is identical to method 44101-15. Data
collected using this analyzer should be reported
as 44101-15.
TOTAL 0 44101 51 PHENOLPHTHALIN
A
Results of this method do not agree with those
obtained by other total oxidant methods.
TOTAL 0₯ 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 Ox 44101 82 FERROUS OXIDATION
Results of this method do not agree with those
obtained by other total oxidant methods.
OZONE 44201 13 COULOMETRIC ,
TMs method is identical to method 44101-15.
Data collected using .this method should be
reported as 44101-15.
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