y
GUIDELINE SERIES
OAQPS NO. 1.2-017
A DESCRIPTION OF THE ANALYTICAL TECHNIQUES
AND ASSOCIATED SAROAD METHOD CODES USED IN
STORING DATA IN THE NATIONAL AEROMETRIC
DATA BANK
US. ENVIRONMENTAL PROTECTION AGENCY
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina
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A DESCRIPTION OF THE ANALYTICAL TECHNIQUES AND
ASSOCIATED SAROAD METHOD CODES USED IN
STORING DATA IN THE NATIONAL AEROMETRIC DATA BANK
OAQPS 1.2-017
March 1974
Monitoring and Reports Branch
Office of Air Quality Planning and Standards
and
Quality Assurance and Environmental Monitoring Laboratory
Office of Research and Development
National Environmental Research Center
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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TABLE OF CONTENTS.
Page
Introduction . ' 1
Suspended Particulates 3
Benzene Soluble Organic 3
Soiling Index 4
Light Scatter 4
Radioactivity 4
Metals, by Hi-Vol, AA, Emission Spectra 6
Arsenic 9
Mercury 9
Water Soluble Particulates 10
Benzo(A)Pyrene 15
Dustfall Procedures 16
Carbon Monoxide 23
Sulfur Dioxide 24
Hydrogen Sulfide 27
Sulfation Rate Procedures ' 28
Fluoride Ion 31
Nitrogen Oxides 32
Ammonium 36
Hydrocarbons 38
Aldehyde 39
Oxidants 40
Ozone 43
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The purpose of this document is to bring together for
the first time a $AROAD code number with a description of
the analytical technique used in gathering data stored in the
National Aerometric Data Bank CNADB). It has long been
needed. The SAROAD code numbers and methods in this
compilation are only those for which data have been sub-
mitted since 1969. The titles of the methods (in capital
letters following the code number) are those which were
assigned in the past and which appear in the computer
printout of Common Parameters and Methods (the "Farm File"),
similar to Code Table 4 of the SAROAD Users Manual.
It is to be emphasized that we do not endorse all of
the procedures described herein. Some are known to yield
erroneous or misleading data. Nor do we endorse a par-
ticular manufacturer's instrument even though the name is
referred to in a title. The rule governing the compilation
was: every method used since 1969 together with its Farm
File title is to be included for the purposes of completeness.
Beneath each SAROAD number and title there is a brief
description of the sampling and analysis principles followed
by references which the reader should consult for details.
Whenever possible, we have given references to those pub-
lications which we think should be readily available to
field workers. In no case have we included enough details
for a worker to start an analysis program which will produce
valid data. The references must be consulted.
Instrumental techniques have not been thoroughly re-
ferenced and the instrument user should consult the pro-
cedure prepared by the manufacturer.
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Through this publication we hope to achieve some degree
of uniformity in reporting data to. the NADB. If, for example,
data have been submitted to the Bank under a given code number,
but the description of that method as found in this compilation
is different from the method which was actually used to obtain
the data, then the reporter must do one of three things:
a. he must begin submitting data under the proper
code number which agrees with the method actually
used; (data previously reported must be re-reported
under the correct code);
b. the reporter must change his methodology to agree
with the method described and data then submitted
using that code number; or
c.. a new code number must be applied for.
We encourage the persons who submit data to the NADB
to verify with the laboratory personnel that the SAROAD codes
used agree with the analytical procedures described herein.
If there are problems or questions, we urge you to call the
chief of the data processing section, NADB, Durham, N.C.
(FTS 919/688-8247); or your SAROAD contact or quality control
coordinator in the Regional Office. Also, we will welcome
your pointing out any errors and/or omissions in the text.
There are a few blanks which we have not been able to fill
in.
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11101 91 SUSPENDED PARTICULATE - HI-VOL GRAVIMETRIC
Air is drawn at 40 to 60 ft. /rain through a glass
fiber filter by means of a blower, and the suspended
particles having a diameter greater than 0.1 ym are
collected. The flow rate of air drawn through the
filter is measured by means of a rotameter which should
be calibrated frequently. The suspended particulate
is reported in density units, yg/m . Oily particulates
or high humidity can cause reduced air flow through the
filter. Therefore, flow rates shoiald be measured before
and after the sampling period.
1. Inter society Committee, "Methods of Air Sampling
and Analysis," American Public Health Association, •
Washington, D.C., 1972, p 365.
2. "Rules and Regulations," Federal Register, Vol 36,
No. 228, U.S. Government Printing Office, Washington, D.C.,
(Nov. 25, 1971) , p 22388.
3. "Air Quality Data for 1967," EPA APTD-0741, Office of
Technical Information and Publications, Research Triangle
Park, North Carolina, 1971, p 17.
11103 91 BENZENE SOLUBLE ORGANICS - HI-VOL BENZENE EXTRACTION
An 8% aliquot of the filter is placed in a soxhlet
extractor and extracted with 75 ml of benzene for 6 h.
The benzene is evaporated and the residue is weighed and
reported in aerometric units; yg/m . Errors may result
from non-volatile material in the benzene used for
extraction.
1. Stanley, T. W. , J. E. Meeker and M. J. Morgan, (1967),
Environ. Sci. and Tech. '1, (11), 927.
. 2. "Air Quality. Data for 1967," EPA APTD-0741, Office
of Technical Information and Publications, Research
Triangle Park, North Carolina, 1971, pp 17-18.
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11201 81 SOILING INDEX (COH) - TAPE SAMPLER TRANSMITTANCE
Air is drawn through a 1 in. diameter spot on a 'con-
tinuous strip of filter paper. The measurement is based
on light transmission through the spot having the col-
lected matter on it, and reported in COH's (coefficient
of haze) per 1000 linear foot of sampled air. The
standard is a clear spot on the paper. The inlet air
funnel must be kept upside down, and sampling lines
must be kept short.
1. Water, Atmospheric Analysis, (1971) , "Annual Book
of ASTM Standards," American Society for Testing and
Materials, Philadelphia, Pa., Part 23, p 420.
2. "Air Quality Data for 1967," EPA APTD-0741, Office
of Technical Information and Publication, Research
Triangle Park, North Carolina, 1971, p 20.
11202 91 SOILING INDEX (RUD) - TAPE SAMPLER - REFLECTANCE
The sampling procedure is similar to that of 11201 81.
Measurement of the soiling is based on light reflectance
from the spot and is reported in RUD's (reflectance
unit density).
1. Water, Atmospheric Analysis, (1971), "Annual Book
of ASTM Standards," American Society for Testing and
Materials, Philadelphia, Pa., Part 23, p 420.
11203 11 LIGHT SCATTER NEPHELOMETER
Air enters an optically black metal tube at 5 cfm. Light
of 410 nm is scattered from particles in the air stream.
The amount of light scattered at 90° from the main beam
is measured by a photomultiplier tube.
11302 91 RADIOACTIVE-GROSS-BETA-HI-VOL PROPORTIONAL COUNTER
The radioactive matter on a filter paper is counted with
a beta sensitive detector to establish the gross concen-
tration of beta emitters in the sampled ambient air. The
daughter products of natural radon and thoron in the at-
mosphere can be minimized by waiting three days until they
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have decayed. A self-absorption correction must be made
if inert matter on the filter interferes.
1. Intersociety Committee, "Methods of Air Sampling and -
Analysis," American Public Health Association, Wash., D.C.,
1972, p 379.
2. Settler, L. R. and G. I. Coats, (1964), "The Determi-
nation of Airborne Radioactivity," Airier'.' TridV Hygiene
Assoc., J. 22, 64.
3. Schulte, H. F., Monitoring Airborne Radioactivity,
"Air Pollution," Vol II, 2nd Ed.f A. C. Stern, Ed.,
Academic Press, New York, N. Y., 1968, p 393.
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12101-12185 ATOMIC ABSORPTION (AA)
Aliquots of samples from the low temperature ashing
procedure are sprayed into a reducing flame by an
atomizer, where metal ions, are reduced to the atomic
state. The atoms absorb monochromatic light pro-
duced by a lamp having a cathode made of the element
to be measured. The light absorbed by the atoms in
the flame is a measure of their concentration. The
influence of one element on the excitation potential of
another does not interfere. The analysis of Al, Sb,
As, Be, Bi, Ba, Cd, Ca, Cr, Co, Cu, Fe, Pb, Mn, Mo,
Ni, Hg, Sn, Ti, V, and Zn is done by AA. The AA
is more sensitive than emission spectra for most
metals.
1. W. Slavin, "Atomic Absorption Spectroscopy,"
Interscience Publishers, New York, 1968, pp 69-74.
2. Perkin Elmer Corp., Methods Manual-Analytical
Methods for Atomic Absorption Spectrophotometry,
The Perkin Elmer Corp., 1968.
3. F. J. Welcher, Standard Methods of Chemical Analysis,
D. Van Nostrand Company, Inc., Princeton, New Jersey,
1966, p 105.
4. Thompson, R. J., G. B. Morgan, and L. J. Purdue,
(1970), "Analysis of Selected Elements in Atmospheric
Particulate Matter by Atomic Absorption," Atomic
Absorption Newsletter 9, (No. 3), 55.
12102-12185 EMISSION SPECTRA '
A solution containing metallic ions is placed between
two electrodes and subjected to 13-15 kilovolts AC
discharge. The spark so created generates enough
heat to atomize the ions and the high voltage excites
many electrons per atom. Spectra characteristic of
each element are formed when the electrons return to
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their normal energy levels. Internal standards are
used to reference a known spectral line so that other
lines can be located. NASN uses indium and yttrium
as internal standards. Metals as Sb, Be, Bi, Ba,
Cd, Cr, Co, Cu, Fe, Pb, Mn, Mo, Ni7 Sn, Ti, Sm, V,
and Zn are analyzed by emission spectra.
1. H. H. Willard, L. L. Merritt, J. A. Dean, "In-
strumental Methods of Analysis," D. Van Nostrand
Company, Inc. 4th Edition, 1965, p 280.
2. F. J. Welcher,"Standard Methods of Chemical Analysis,"
D. Van Nostrand Company, Inc., Princeton, New Jersey,
1966, p 141.
3. "Air Quality Data for 1967," EPA-APTD 0741, (1971),
Office of Technical Information and Publication, Research
Triangle Park, N.C., 1971, p 19. •
12102-12185 LOW TEMPERATURE ASHING PROCEDURE
Particulates are ashed to remove organic matter. A 1 or
2 in. by 7 in. strip of the exposed glass filter (or a
composite of 5-8 strips) is heated at 150°C for 1 h. at
1 torr with an 02 flow of 3000 ml/h. The ashed filter
is fluxed for 3 h. with 8 ml of 20% HC1 and 32 ml of
40% HNO^. The acid extract is concentrated to 1 or 2
ml by evaporation, centrifuged, and the residue is
washed three times with dilute HC1. Samples from non-
urban air are then diluted with distilled H-O to 3 ml/2
in. strip and samples from urban air are diluted to 4.4
2
ml/9 in. of filter taken. Samples so prepared are
ready for emission spectra analysis, but must be diluted
10 fold .for AA analysis.
1. Thompson, R. J., G. B. Morgan and L. J. Purdue,
(1970) "Analysis of Selected Elements in Atmospheric
Particulate Matter by Atomic Absorption," Atomic
Absorption Newsletter 9, 54.
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12102-12185 MUFFLE FURNACE PROCEDURE
Prior to the invention of the low temperature asher,
organic material was removed by heating samples to
500°C for 1 h. in a muffle furnace. Samples are then
extracted twice for 1 h. with 40 ml of 1:1 redistilled
HNO-, at a temperature just below boiling. The solution
is filtered, evaporated to 4 ml and diluted to 10.4
ml with H-O. The samples are then analyzed by the
emission spectrograph. Metals as Sb, As, Be, Bi, Cd,
Cr, Co, Cu, Fe, Pb, Mn, Mo, Ni, Sn, Ti, V, and Zn are
measured by this procedure. This procedure may volatilize
some portion of some of the metals and thus result in
an unknown fraction recovered.
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12103-93 ARSENIC - HI-VOL NASN-ARSINE-COLORIMETRIC
The arsenates and oxides of arsenic are extracted from a
2 in. square exposed filter by digestion for 1 hr with
30 ml of 6 N HC1 at 90 °C, and then reduced to the trivalent
state with KI and SnCl2- Arsine is then generated by Zn
and HC1 Gutzeit procedure. The evolved arsine passes
through a HLS scrubber and into an absorber containing silver
diethyldithiocarbamate. The resulting red complex is
measured spectrophotometrically at 535 run. Antimony like-
wise forms stibine which also complexes with the carbamate
but at low concentrations does not interfere with arsenic
determination. High concentrations of Mi, Cu, Cr, and
Co interfere with arsine formation. Many interferences
can be minimized by using an internal standard of added
arsenic.
1. Intersociety Committee, "Methods of Air Sampling and
Analysis," American Piiblic Health Association, Wash., D.C., •
1972, p 289.
12142 92 MERCURY - ACID IC1 ATOMIC ABSORPTION
This is a flameless AA technique. The total mercury is
collected through a glass impinger in 30 ml of 0.1N
acidic iodine monochloride at a flow-rate of 200 ml/min.
Hglj is reduced to elemental mercury by hydroxylamine
hydrochloride in basic solution which is aerated to
vaporize the mercury. The vapor is passed into a quartz
absorption cell where it absorbs light at 253.7 nm. This
method is not applicable to atmosphere containing less than
50 ng Hg/m of air due to high and erratic blanks.
1. Hatch, R. W. and W." L. Ott, (1968), "Determination
. of Sub-Microgram Quantities of Mercury by Atomic Absorption
Spectrophotometry," Anal. Chem. 40, p 2085.
2. Lynch, A. L., R. F. Stalzer, and D. T. Lefferts, (1968),
"Methyl and Ethyl Mercury Compounds — Recovery from Air
and Analysis," Am. TndV Hygiene Assoc. J., 79.
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12202 91 FLUORIDE-HI-VOL WILLARD-WINTER/SPECIFIC ION ELECTRODE
The Willard-Winter distillation is carried out to remove
interfering ions. Two 1 3/4 in. diameter circles of the "
filter are placed in a platinum dish, covered with 10 ml of
Ca(OH)2 suspension (2.5% Ca by weight), and evaporated to
dryness over a steam bath. The residue is heated for
30 min. in an oven at 150°C, and ignited in a muffle
furnace at 550°C for 5-6 h. The ash is mixed with
Ig AgCl04 and steam distilled using 10 ml of 60% HC104
at 135°C. A total of 190 ml of distillate is collected.
The fluoride ion concentration is then measured with a
specific ion electrode. See 42513 91.
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers, Inc., New York, N.Y., p 200.
12203 91 CHLORIDE-HI-VOL-THIOCYANATE
Chloride in the aqueous extract of the hi-vol particulate
sample forms mercuric chloride and liberates SCN ion
from mercuric thiocyanate. The SCN~" ion forms a colored
complex with Fe+++ ion from ferric ammonium sulfate. The
complex is measured colorimetrically at 416 nm.
1. R. B. Fisher, "Quantitative Chemical Analysis,"
W. B. Saunders Co., Philadelphia, Pa. 1957, p 238.
2. Morgan, G. B., E. C. Tabor, C. Golden, and H. Clements,
Automated Laboratory Procedure for the Analysis of Air
Pollutants 66-p 108B, Technicon Industrial Systems,
Tarrytown, N.Y., p 536.
12301 91 AMMONIUM - HI-VOL NES'SLER
Ammonium ion is .removed from an 8% aliquot of the filter by
fluxing the filter in 50 ml of H^O for 30 min, then placed
in a Nessler tube with 4 ml of Nessler reagent. Should
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the solution become cloudy, Rochelle salt solution (lOg of
KNaC4H4Og,4H20 in 200 ml of .01N NaOH) is added dropwise
with shaking. The absorption is read using a No. 54 filter
with a 50 ml glass cell, using a reagent blank as reference.
(Rochelle salt prevents Ca and Mg precipitation at the high
pH of the Nessler reagent).
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers, Inc., New York, p 216.
2. G. B. Morgan, E. C. Tabor, C. Golden, and H. Clements
Automated Laboratory Procedures for the Analysis of Air
Pollutants 66-p 108B, Technicon Industrial Systems,
Tarrytown, N. Y., p 536.
12301 92 AMMONIUM-HI-VOL SODIUI1 PHENOLATE
Ammonium ions are extracted from a 3/4 in. by 8 in. strip
of the exposed filter by fluxing with 25 ml of H20. The
filtrate is diluted to 50 ml and sodium phenolate and
sodium hypochlorite are added producing a blue complex when
pH is above 7.0. The absorbance is read spectrophotometrically
at 626 nm.
1. Russell, J. A., (1944), "The Colorimetric Estimation
of Small Amounts of Ammonia by the Phenol-Hypochlorite
Reaction," J. Biol. Chem. 156, 457.
2. Morgan, G. B., E. C. Tabor, C. Golden, and H. Clements,
Automated Laboratory Procedure for the Analysis of Air
Pollutants 66-p 108B, Technicon Industrial Systems,
Tarrytown, N. Y., p 536.
3. "Air Quality Data for 1967," EPA-APTD 0741,
Office of Technical Information and Publication, Research
. Triangle Park, N.C., 1971, p 18.
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12306 91 NITRATE-HI-VOL 2,4 XYLENOL
Nitrate nitrates 2,4-xylenol, The nitrated 2,4-xylenol
is separated from other water soluble colored substances
by NaOH and toluene. A 3/4 in. strip of the filter is
fluxed in 25 ml of H20, filtered (Whatman No. 1), and washed
until 50 ml of filtrate is obtained. A 5 ml sample and
15 ml of 85% H2SO are mixed, cooled, and 1 ml of 1% xylenol
is added. The solution is heated at 60°C for 0.5 h and
diluted to 80 ml. Then, 10 ml of toluene is added and the
mixture is shaken for 2 min. in a separatory funnel. The
lower layer is discarded, 10 ml of 0.4N NaOH added, and
the funnel again shaken for 5 min. The lower aqueous layer
is drawn through cotton into a cuvette. The absorbance
is measured at 435 nm.
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 1-1.
2. Pate, J. B., E. C. Tabor, (1962), "Analytical Aspects
of Glass Fiber Filters," Am. Ind. Hyg. Assoc. J. 23.
3. Barnes, H., (1950), "A Modified 2,4-Xylenol Method for
Nitrate Estimation," Analyst 75, 388.
12306 92 NITRATE-HI-VOL REDUCTION-DIAZO COUPLING
The nitrate is reduced to nitrite by alkaline hydrazine,
converted to HN02 which diazotizes sufanilamide, and coupled
with N (Irnaphthyl)-ethylenediamine dihydrochloride which
absorbs light at 535 nm.
1. Morgan, G. B., E. C. Tabor, C. Golden and H. Clements,
Automated Laboratory Procedure for the Analysis of Air .
Pollutants 66, p 108B, Technicon Industrial System, .
Tarrytown, N. Y., p 536.
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2. "Air Quality Data for 1967," EPA-APTD 0741,
Office of Technical Information and Publication, Research
' Triangle Park, N.C., 1971, p 18. .
12306 93 NITRATE-HI-VOL SPECIFIC ION ELECTRODE
The aqueous extract of a hi-vol glass fiber filter-is
analyzed for nitrate ion by means of a specific ion
electrode.
12345 91 PHOSPHATE - HI-VOL-MOLYBDATE • STANNOUS CHLORIDE
Phosphate ions in the water extract of the filter are
precipitated as ammonium molybdophosphate in an acid
medium, which is then reduced to a molybdenum blue com-
plex with stannous chloride. The absorbance is read at
650 nm.
1. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 23, pp 41-49.
2. Lundell, G. E. and J. I. Hoffman, (1923), "Notes on
the Determination of Phosphate," Ind. and Eng. Chem. Anal.
Ed. 15, 71.
12403 91 SULFATE - HI-VOL COLORIMETRIC
Water soluble sulfate is reacted with excess reagent con-
taining equivalent amounts of methylthymol blue and BaCl2.
Ba++ and SOT ions form BaS04 leaving a [SO^] equivalent
of free methylthymol blue. If the pH is changed from 2.8
to 12.4 by KOH, Ba++ ion forms a chelate with the free dye.
The unchelated dye is yellow and absorbs light at 460 nm.
1. Morgan, G. B., E. C. Tabor, C. Golden and H. Clements
Automated Laboratory Procedure for the Analysis of Air
Pollutants 66, p 108B, Technicon Industrial Systems-
Ta'rrytown, N. Y., p 538.
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14
2. A. L. Lazrus, K. C. Hill and J. P. Lodge, "A New
Coloriraetric Microdetermination of Sulfate Ion in Rainwater,"
personal communication, Division o'f Atmospheric Sur-
veillance, Research Triangle Park, N.C., 1965.
3. "Air Quality Data for 1967," EPA-APTD 0741,
Office of Technical Information and Publication, Research
Triangle Park, N.C., 1971, p 19.
12403 92 SULFATE-HI-VOL TURBIDIMKTRIC
The water soluble sulfate extract of the filter forms BaSO^
in a Bad,, solution. Suspended BaSO, particles scatter
^ ~x
light, and the diminished intensity of a light beam is
measured by a turbidimeter.
An aliquot of the filter extract is chosen so that the
sample contains the equivalent of 1 to 20 yg/m of SOT.
To the sample diluted to 20 ml, 1 ml of ION HC1 is added,
followed by 4 ml of a glycerol/absolute ethanol solution
(l:2v/v). After mixing, the absorbance is measured at
500 nm and compared with H~0. Then 0.25g of BaCl^ crystals
are added and shaken to dissolve the crystals. After
standing for 40 min. at 20°C, the absorbance is measured
again.
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 1-1.
2. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 23, pp 50-53.
12602 91 HYDROGEN ION CONCENTRATION - HI-VOL pH METER
The water soluble extract of the filter is tested by a
pH meter and the hydrogen ion is calculated from the pH
value.
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17242 91 BENZOCAJPYRENE - HI-VOL THIN LAYER CHH01JZVTOGRAFHY
This is a technique whereby the benzene soluble organics
are separated by means of thin layer chromatography. The
isolated benzo(A)pyrene as indicated by comparison with a
standard is removed from the thin layer plate and excited
with radiant energy of 470 run. The fluorescence is measured
at 540 run.
1. Intersociety Committee, "Methods of Air Sampling and
Analysis," American Public Health Association, Wash., D.C.,
1972, p 159.
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21101 51 TOTAL DUSTFALL - BUCKET GRAVIMETRIC
A 1 gallon container having a mouth diameter of 4.4 in.
is placed in a copper can (5 in. high and 5 in. diameter) on a
stand,C4 ft. above a roof and four stories from the ground).
Five hundred to 1500 ml of antifreeze-treated water is placed
in the container. The collected sample is filtered using
Whatman No. 41H paper which is then dried and weighed.
The filtrate is evaporated at 105°C, the residue weighed,
and both weights added for total dustfall.
1. M. B. Jacobs, "The Chemical Analysis of Air Pollutants,"
Chemical Analysis, Vol 10, Interscience Publishers, Inc.,
New York, N.Y., (1960), p 37.
21101 71 TOTAL DUSTFALL - BUCKET - GRAVIMETRIC (APCA)
The dust falls into a glass or stainless steel container,
5 in. in diameter and 10-15 in. high. The top of the con-
tainer is maintained at from 8 to 50 ft. above the ground
and 4 ft. above any surface. Neighboring roof surfaces
must subtend an angle of 30° or less from the horizontal.
Distilled water should be maintained in the container and
a quaternary ammonium salt is added (1 to 2 mg/1) to suppress
algal growth. Isopropyl alcohol may be added as antifreeze.
The 30 day sample is filtered through a 20 mesh screen to
remove extraneous material and treated as method 21101 51
except that samples having antifreeze are evaporated to
dryness at 105°C, 300 ml distilled water is added, and the
sample again evaporated to dryness.
1. "Recommended Standard Method for Containing Dustfall
Survey (APMI-a)," (Nov. 1955), APCA Journal 5. (No. 3),
p 176.
21101 81 DUSTFALL - BUCKET GRAVIMETRIC (ASTM)
A 6 in. diameter/ 12-18 in. high, glass, plastic/ or
stainless steel cylinder, mounted with a bird ring, is
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17
use to collect the dustfall. The analysis is the same as
method 21101 71.
1. Water, Atmospheric. Analysis, C1971), "Annual Book of
ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 23, p 425.
2. Nader, J. S., (1958), "Dust Retention Efficiencies
of Dustfall Collector," APCA Journal 8, p 35.
21102 81 ORGANIC FRACTION - BUCKET GRAVIMETRIC (ASTM)
The water insoluble residue and the filter from method
21101 81 are dried, weighed, placed in a soxhlet apparatus,
and extracted for 2 h using 50 ml of benzene. Benzene
should remain in the flask at all times. The remaining
residue and paper are dried at 105°C and weighed to
report the v/eight loss as organic fraction, BSO (benzene
soluble organics).
1. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 23, p 427.
21113 71 INORGANIC FRACTION •- BUCKET GRAVIMETRIC (APCA)
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21113 81 INORGANIC FRACTION - BUCKET GRAVIMETRIC (ASTM)
The combined weight of water insolubles and soluble
matter corrected for any solid present in a distilled water
blank.
1. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards," American Society for Testing and Material,
Philadelphia, Pa., Part 23, p 428.
21114 71 WATER SOLUBLE WEIGHT - BUCKET GRAVIMETRIC (APCA)
The sample is filtered through a 20 mesh screen to remove
extraneous material and if antifreeze'was used, the filtrate
is evaporated to dryness over a steam bath or in an oven
at 105°C. Thirty ml of distilled H-O is added, heated to
boil, and the sample filtered through an alundum crucible.
If no antifreeze was used, the sample is adjusted to 300
ml and filtered through the crucible. The filtrate is
evaporated to a small volume. The filtrate is placed in
a weighed platinum crucible (if fluoride is present) or
else a borosilicate dish and evaporated to 25 ml. It is
evaporated slowly to dryness on a steam bath or in an oven
at 105°C. Dryings are repeated for 3 h periods until
constant weight is obtained.
1. "Recommended Standard Method for Continuing Dustfall
Survey, (APMI-a)," (Nov. 1955), APCA Journal 5 (No. 3), 177.
21114 81 WATER SOLUBLE WEIGHT - BUCKET GRAVIMETRIC (ASTM)
The soluble material, described as the water soluble weight
in method 21101 81,is evaporated in a tared platinum dish if
fluoride or caustic materials are present or else a boro-
silicate dish. The dish is heated slowly until 25 ml
remain. Then a steam bath or a thermoregulated hot plate
is used to evaporate to dryness at a temperature of 99°C.
Drying is continued in an oven at 105°C until a constant
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weight is obtained. The water soluble weight is the
difference between this constant weight and tare.
• 1. Water, Atmospheric Analysis, (1971), "Annual Book
of ASTM Standards," American Society for Testing and
Materials, Philadelphia, Pa., Part 23, p 427.
21115 51 WATER INSOLUBLE WEIGHT - BUCKET JACOBS METHOD
The collected sample is filtered through a 20 mesh sieve,
and the coarse material discarded. The insoluble material
in the sample is collected on a 9 cm Whatman No. 41 H
filter. Alternatively, a tared gooch crucible equipped with
a light asbestos mat or an alundum crucible could be used.
The v/eight of the dry solid is reported as water in;-
soluble weight.
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience Publishers
Inc., New York, N.Y., p 38.
21115 71 WATER INSOLUBLE WEIGHT - BUCKET GRAVIMETRIC (APCA)
The water soluble weight was obtained to report the total
dustfall, method 21101 71. The sample is filtered
through a 20 mesh screen, the volume made to 300 ml, boiled,
and filtered through a weighed 35 ml alundum filter crucible.
The crucible is dried in an oven at 105°C for 3 h, cooled,
and the drying is repeated to constant weight. The increased
weight of the crucible is reported as water insoluble weight.
1. "Recommended Standard Method for Continuing Dustfall
Survey (APMI-a), (Nov. 1955), APCA Journal 5 (No. 3), 176.
21115 81 WATER INSOLUBLE WEIGHT - BUCKET GRAVIMETRIC (ASTM)
The material collected on a dried and weighed filter from
method 21101 81, is dried in a weighing bottle overnight
at 105°C. The net weight less the weight of the filter
paper and weighing bottle is the water insoluble weight.
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20
1. Water, Atmospheric Analysis, (.1971) , "Annual Book
of ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 213, p 427.
21116 71 TOTAL WEIGHT ASH - BUCKET GRAVIMETRIC (APCA)
The water insolubles and the water solubles are ignited
in a dish at red heat for 20 to 30 min, cooled in a
desiccator, reheated and cooled until a constant weight
is obtained. The dish must have been pretreated in the
same manner. The excess weight is the total weight ash.
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers Inc., New York, N.Y., p 47.
21116 81 TOTAL WEIGHT ASH - BUCKET GRAVIMETRIC (ASTM)
The total weight ash is the weight of the insoluble and
soluble materials after the removal of BSO and the com-
bustible materials.
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21
22114 92, 22126 92, 22132 92, and 22136 92
COPPER, IRON, MANGANESE, NICKEL - BUCKET ATOMIC ABSORPTION
Thirty ml of HN03/H20 (1/1) is added to the dustfall
in a beaker, heated below boiling for 1 h, and concentrated
to remove excess HNO.,. The solids are removed by
centrifuging. The solution is analyzed by AA.
1. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards/" American Society for Testing and Materials,
Philadelphia, Pa., Part 23, p 678.
22403 81 SULFATES - BUCKET TURBIDIHETRIC (ASTM)
Turbid samples are filtered and the temperature adjusted
to between 15 and 30°C. Ten ml glycerin solution (glycerin/
H20, 1/1), and 5 ml of NaCl solution (240g of NaCl and 20 ml
cone. HCl/liter) are added to 50 ml of the sample. A 40 mm
cell filled with the treated sample is used as the blank
sample by setting the colorimeter to zero absorbance at 380-
400 nm. The cell sample is combined with the remaining
treated sample, 0.3g of BaCl2.2H20 crystals added, and the
mixture stirred for 1 min. After standing for 4 min the
mixture is stirred again for 15 sec. The cell is then
filled with the turbid solution and absorbance measured
again at the same wavelength as the blank sample.
1. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 23, p 51.
22602 81 pH (DUSTFALL) - BUCKET pH METER
Total acidity of the water soluble portion of the total dust-
fall is obtained by using a pH meter, or less accurately
by use of pH test paper.
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience Publishers,
Inc., New York, N.Y., p 40.
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22
25101 81 DUSTFALL COMBUSTIBLE-BUCKET GRAVIMETRIC - 500-DEG.
C. LOSS (ASTH)
After the BSO has been remove from the water insoluble
material, the material and the filter paper are ashed at
500°C in a tared crucible and the weight loss is reported as,
"Combustibles and volatile particulates oi,ier than benzene
soluble."
1. Water, Atmospheric Analysis, (1971), "Annual Book of
ASTM Standards," American Society for Testing and Materials,
Philadelphia, Pa., Part 23, p 428.
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23
42101 11 CARBON MONOXIDE - INSTRUMENTAL NON-DISPERSIVE INFRA-RED
The principle is described in Vol,3G.. No. 228 of the
Federal Register. The major interference is H20 vapor
which can be minimized by drying the air sample before
it enters the cell. Calibrated gases and a narrowband
optical filter are essential. Variations in temperature
and pressure affect the instrument response and should
be controlled. Filters of 2-10 ym porosity should be
used in the entering air stream to remove fine particulates
1. "Rules and Regulations," Federal Register, Vol 36,
No. 228, (Nov. 25, 1971), p 22391.
42101 12 CARBON MONOXIDE - INSTRUMENTAL COULOMETRIC
Atmospheric air is drawn through a heated 1205 tube
and 12 is liberated. The gas containing ^ is directed
into an electrochemical cell where I2 is reduced to
iodide coulometrically.
1. Beckman Instrumention, Bulletin 3000 4411-4,
Beckman Instruments, Inc., Fullerton, California.
42101 21 CARBON MONOXIDE - INSTRUMENTAL FLAME IONIZATION
Ambient air is introduced into two gas chromatographic
columns in series, the first of which retains most
pollutants except CO and CH4, and the second of which
passes only CO. The CO is then led over a Ni catalyst
where it is converted to CH4. The CH4 is passed into
a flame ionization detector, where the resulting measured
current can be related to the initial CO concentration
of the ambient air. See also.43102 11 and 43201 11.
1. "Rules and Regulations," Federal Register, Vol 36,
No. 228, (Nov. 25, 1S71), p 22391.
42102 .11 CARBON DIOXIDE-INSTRUMENTAL INFRARED ABSORPTION
This procedure is similar to the NDIR procedure for carbon
monoxide, 42101 11, except that water does not have to
be removed from the air stream.
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42401 11 SULFUR DIOXIDE-INSTRUMENTAL WEST-GAEKE COLORIMETER
A continuous analyzing system is set up so that the
ambient air flows through a glass spiral absorption column
concurrently with 0.02M sodium tetrachloromercurate.
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 95%
baseline is established with pure reagents for 1 h and
the instrument is then calibrated. Air flow rate and
reagent flow rate must be calibrated and maintained
accurately.
1. Yunghans, R. S. and W. A. Monroe, Technicon Symposium
on Automation in Analytical Chem., 1965, p 279.
2. "Technicon Air Pollution Detection System," In-
struction Manuals T 67-105, Technicon Corp.
42401 13 SULFUR DIOXIDE-INSTRUMENTAL CONDUCTIMETRIC
Sulfur dioxide is absorbed in acidic H-O- which oxidizes
it to II-SO,. The method is a measure of all materials
that increase conductivity. Thus, any materials that
alter the conductivity of the reagent are potential in-
terfering 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. 4, 253.
3. M. B. Jacobs, (I960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience Publishers
Inc., New York, N.Y., 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
Coulometric analyzers measure the current necessary to
maintain a halogen concentration (Br2 or 12) constant in
the sample cell. The magnitude of this current is pro-
portional to the amount of absorbed SO?. There are several
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25
versions of instruments using this principle.
1. J. F. Welcher, "Standard Methods of Chemical Analysis,"
D. Van Nostrand Company, Inc. Princeton, N.J., 1966,
P 377.
42401 15 SULFUR DIOXIDE-INSTRUMENTAL : THOMAS AUTOMETER
The Thomas Autometer is a conductimetric analyzer de-
veloped in 1929.
42401 16 SULFUR DIOXIDE-INSTRUMENTAL FLAME PHOTOMETRIC
Chromatographic columns are used to separate S02, H2S,
CS,,, and CH..SH. Effluent from the columns is burned in
a hydrogen-rich flame where a 395 nm emission band
characteristic of sulfur is created. A photomultiplier
tube is used to detect the luminescence. Response is linear
on a log-log scale.
1. H. H. Willard, L. L. Merritt, and J. A. Dean, "In-
strumental Methods of Analysis," D. Van Nostrand Company,
Inc., 4th Edition, 1965, p 309.
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. There are
several models in use.
42401 33 SULFUR DIOXIDE-DAVIS INSTRUMENT SEQUENTIAL-CONDUCTIMETRIC
Water is deionized by passage through an amberliet resin
column, then its conductivity is measured. Ambient air,
having first passed through a scrubber of amberlite re-
sin and soda-lime to remove C02, is next passed through
. . '. the deionized water where the S02 is absorbed. The in-
creased conductivity of the water is a measure of the
S02 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.
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26
42401 91 SULFUR DIOXIDE-GAS BUBBLER WEST-GAEKE SULFAMIC ACID
The method is described in Vol 36, No. 228 of 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. Sulfur dioxide is collected in a tetra-
chlororaercurate solution, forming a stable dichlorosulfito-
mercurate complex. When acid-bleached pararosaniline
is added to the collected S02 together with formaldehyde,
the amino groups (-NH,) form a red-violet compound called
pararosaniline methylsulfonic acid which is measured spec-
trophotometrically.
1. West, P. W. and G. C. Gaeke, (1956), "Fixation of
Sulfur Dioxide as Disulfito-Mercurate (II) and Subsequent
Colorimetric Estimation," Anal. Chem. 28, 1819.
2. "Rules and Regulations," Federal Register, Vol 36,
No. 228, U.S. Government Printing Office, Washington, D.C.,
(Nov. 25, 1971), p 22385.
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," EPA-APTD 0741, Office of
Technical Information and Publication, Research Triangle
Park, N.C., 1971, p 20.
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 TCM, the starch which is
used for standardization is made without mercuric iodide,
and sulfamic acid is not used except when high concen-
• trations of N07 are expected. The sulfamic acid is added
to the sample after collection.
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27
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.
3. West, P.W. and F. .Ordoveza, (1962), Anal. Chem. 34,
1324.
42401 93 SULFUR DIOXIDE-GAS BUBBLER CONDUCTIMETRIC
Manual conducttmetric methods use the same principles as
instrumental conductimetric except the absorber is a
multiple jet bubbler system and the sampling is not con-
tinuous. 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.
42402 71 HYDROGEN SULFIDE-TAPE SAMPLER AISI LEAD ACETATE PAPER
Filter paper (Whatman, No. 1) is cut into 2 by 4 in. strips,
impregnated with Pb(C2H302) (10g/100 ml H2O plus 5 ml
CE-COOH) .and dried in H2S free air. Air is pumped over the
strips. A concentration of 0.025 mg/1 of H~S gives a
positive test for H2S. The stain on the paper is com-
pared with a color chart for H2S concentration.
1. M. B. Jacobs, (1960), "The Analytical Chemistry of Indus
trial Poisons, Hazards, and Solvents," Chemical Analysis,
Vol 1, Interscience Publishers, Inc., New York, N.Y.,
P 108.
42402 91 HYDROGEN SULFIDE-GAS BUBBLER
(100 ml tube + orifice)
METHYLENE BLUE
Air is bubbled through a Cd(OH)2 solution in a large im-
pinger at 1 cfm for 30 min. Ferric chloride solution and
p-aminodimethylaniline test solution are added to the im-
pinger and agitated. The sample is diluted and allowed to
stand for 30 min. The sulfide ion forms a methylene blue
complex. The absorbance of the sample is compared with a
standard which consists of 45 ml of the Cd(OH)2 solution,
amine test solution, and the ferric chloride.
-------
1. Inter society Committee, "Methods of Air Sampling
and Analysis," American Public Health Association,
Washington, D.C., 1972, p 426.
2. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers, Inc, New York, N.Y., p 185.
3. Lodge, J. P., et al., (1966), "The Use of Hypodermic
Needles as Critical Orifice," J. Air Poll. Control Assoc.
X6, 197.
4. Scaringelli, F. P., S. A. Frey, B. E. Saltzman, (1967),
"Evaluation of Teflon Permeation Tubes for use with
Sulfur Dioxide," Am. Ind. Hyg. Assoc. J. 28, 260.
42-410 71 SULFATION RATE-LEAD PLATE GRAVIMETRIC (HUEY)
The Pb02 is converted to PbSO, by the SO2 in the ambient
air and the SOT is removed by Ma-CO., and boiling H20.
Barium chloride is used to precipitate the SOT as BaSO,.
The dried BaSO, is weighed and the SO- equivalence is
reported.
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29
42410 72 SULFATION RATE-LEAD PLATE COLORLMETRIC (HUEY)
42410 73 SULFATION RATE-LEAD PLATE TURBIDIMETRIC (HUEY)
Sulfur dioxide reacts with lead peroxide to form lead
sulfate. The amount of SOT formation per unit time is
the sulfation rate. The SOT is removed from the plate
by boiling Na-CO., solution and the pH is adjusted between'
2.5 and 4.0 so that sulfaspend or sulfaver precipitates
the SOT. The absorbance of the stirred precipitate is
read at 450 nm, turbidimetrically.
1. Intersociety Committee, "Methods of Air Sampling and
Analysis," American Public Health Association, Wash., D.C.,
1972, p 442.
2. Huey, N. A., M. A. Wallar, and C. D. Robson,
(June 1969) "Field Evaluation of an Improved Sulfation
Measurement System." Paper No. 69-133, Air Pollution
Control Association Annual Meeting.
3. Hickey, H. R., and E. R. Hendrickson, (1965), "A
Design Basis for Lead Dioxide Cylinder," J. Air Poll.
Control Assoc. 15, 409.
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30
42410 74 SULFATION RATE-LEAD PLATE POTASSIUM CARBONATE (HUEY)
This method is similar to method 42410 73 except K2C03
is used instead of Na
42410 81 SULFATION RATE-RAC CANDLE GRAVIMETRIC
42410 "91 SULFATION RATE-LEAD CANDLE GRAVIMETRIC (MASN)
The lead candle functions on the same principle as the
lead plate. Sulfation is reported as mg of S03/100 sq.
cm/day as determined by gravimetric precipitation of
BaSO,. The procedure is spelled out in the report by
Keagy, et.al.
1. Thomas, F. W. and C. M. Davidson, "Monitoring Sulfur
Dioxide with Lead Peroxide Cylinders" presented at the
53rd Meeting of APCA, Cincinnati, Ohio, May 22-26, 1960.
2. Keagy, D. M., et.al., "Sampling Stations and Time
Required for Urban Air Pollution Surveys, Part I: Lead
Peroxide and Dustfall Collectors," Presented at the
53rd Meeting of APCA, Cincinnati, Ohio, May 22-26, 1960.
42410 93 SULFATION RATE-LEAD CANDLE TITRIMETRIC (NASN)
This method is similar to method 42410 91 except that
excess BaCl^ is added when the pll is 3 and the excess
titrated with EDTA using Eriochrome Black T as indicator.
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31
1. Wilsdon, B. H. and F. J. McConnel, C1934), "The
Measurement of Atmospheric Sulfur Pollution by Means
of Lead Peroxide, JV SocV Chem. TridV 53, 385,
2. Kainzer, A., (1957), Zemeht-Kalk-Gyis 10, 281.
3. "Standard Methods for the Examination of Water and
Waste-water," 12th Ed., American Public Health Assoc.,
Inc., Nev/ York, N. Y., 1965, p 147-151.
42410 94 SULFATION.RATE-LEAD CANDLE POTASSIUM CARBONATE (NASN)
This method substitutes K-CO., for Na2C03 in method
42410 91.
42410 95 SULFATION RATE-LEAD CANDLE TURBIDIMETRIC
Gaseous and particulate fluoride in ambient air are
collected by filtration and chemisorption on filter
paper impregnated with sodium formate. Water soluble
fluorides are extracted from the filter, made basic
with Na-CO.,, and complexed with citrate ion to reduce
the iron and aluminum interference. The fluoride ion
concentration is measured with a specific ion electrode.
1. Thompson, R. J., T. B. McMullen and G. B. Morgan,
(1971), "Fluoride Concentrations in the Ambient Air,"
J. Air Poll. Control Assoc. 21, 484.
42513 91 FLUORIDE HI-VOL SPECIFIC ION ELECTRODE
The concentration of fluoride in an aqueous sample is
measured by means of the fluoride-specific ion electrode.
1. Elfers, L. A. and Decker, C. E., (1968), Anal. Chem.,
Vol. 40, p 1658.
2. Frant, M. S. and J. W. Ross, Jr., (1966), "Electrode for
Sensing Fluoride Ion Activity in Solution," Science 154,
1553.
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32
42601-11 NITRIC OXIDE-INSTRUMENTAL COLORIMETRIC
NO is converted to N02 by passing the ambient air through
an aqueous KMnO. solution. The resulting N0? is measured-
colorimetrically. An independent measurement of the ambient
N02 concentration is required. This value, subtracted
from the first, gives a value for the NO concentration. See
Methods 42602 11 and 42602 12 for HO measurement procedure.
1. Water, Atmospheric Analysis, (1971), "Annual Book
of ASTM Standards," American Society for Testing and
Materials," Philadelphia, Pa., Part 23, p 523.
2. Rogers, L. M. , (1958), "Nitric Oxide and Nitrogen
Dioxide in the Los Angeles Atmosphere," J. of Air Poll.
Control Assoc. 8, 124.
3. Saltzman, B. E. , (1954), "Colorimetric Micro-Determination
of Nitrogen Oxide in the Atmosphere, Anal. Chem. ,26, 1949.
4. Thomas, M. D., et.al., (1956), Automatic Apparatus
for Determination of Nitric Oxide and Nitrogen Dioxide
in the Atmosphere, Anal. Chem. 28, 1810.
42601 14 NITRIC OXIDE-INSTRUMENTAL
When 0., reacts with NO to form N02,
CHEMILUMINESCENCE
some of the liberated
energy appears in the form of light of 600-875 nm. The
reaction is extremely rapid. The instrument generates
an excess of 03 such that the quantity of light emitted
from the reaction and measured by the instrument, is a
direct measure of the NO concentration in the sampled
air. See also 42602 14.
1. Fontijn, A., A. J. Sabadell and J. R. Ronco, (1970),
Anal. Chem. 42, 575.
2. Stevens, R. K., et.al., "Field Performance Characteristics
of Advanced Monitors for Oxides of Nitrogen, Ozone, Sulfur
Dioxide, Carbon Monoxide, Methane, and Nonmethane Hydro-
carbons," Environmental Protection Agency, Research Triangle
Park, N.C., presented at the APCA Meeting, June 1972.
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33
42601 91 NITRIC OXIDE-GAS BUBBLER SALTZMAN (.100 Ml TUBE + ORIFICD
Nitrogen oxide is oxidized to NO- by KMnO. and the
Method 42602 72 is followed.
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health.Association,
Wash., D.C., 1972, p 329.
42602 11 NITROGEN DIOXIDE-INSTRUMENTAL COLORIMETRIC
The Lyshkow modification of the Criess-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 Coloriinetric
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 NO~ analyzers. Users should consult the
manufacturer's literature for details of reagent pre-
paration.
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. 25,
1949.
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42602 13 NITROGEN DIOXIDE-INSTRUMENTAL COULOMETRIC
Nitrogen dioxide is absorbed in a buffered iodide-iodine
solution causing the equilibrium between iodine and iodide
to be unbalanced. The current required to re-establish
the equilibrium is a measure of the N02 concentration.
42602 14 NITROGEN DIOXIDE-INSTRUMENTAL CHEMILUMINESCENCE
The nitrogen dioxide is drawn over a gold catalytic con-
verter which reduces N02 to NO. The NO is then analyzed
by method 42601 14.
1. NO/NOX/N02 Analyzer Bulletin, Bulletin 4133, Beckman
Instruments, Inc., Fullerton, Calif.
42602 71
42602 72
NITROGEN DIOXIDE-GAS BUBBLER'
TUBE + ORIFICE
JACOBS-HOCHHJ3ISSR-50 Ml
The method is that described in the Federal Register.
The N02 is converted to NO" in NaOH solution. The
collection efficiency is a function of the N02 con-
centration and high concentrations of NO interfere.
1. "Rules and Regulations," Federal Register, Vol 36,
No. 228, U.S. Government Printing Office, Washington, D.C.
(Nov. 25, 1971), p 22396.
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.
1. Intercocisty 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. 2G, 1949.
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42602 91 NITROGEN DIOXIDE-GAS BUBBLER JACOBS-HOCHHEISER (106
Ml TUBE + FRIT)
A fritted bubbler and 100 ml tube, instead of a glass
tube orifice and 50 ml tube, makes this method different
from method 42602 71. The disadvantages of the method
still apply.
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 C-4.
2. Purdue, L. J., et.al., (1972), "Reinvestigation
of the Jacobs-Hochheiser Procedure for Determining
Nitrogen Dioxide in Ambient Air,;i Environ. Sci. and Tech. 6 ,
152.
42602 94 NITROGEN DIOXIDE-GAS BUBBLER NASM-SODIUM ARSEHITE-FRIT
The method is much like method 42602 91 except for the
absorber (l.Og of NaAs02 and 4.Og of NaOH diluted to one
liter with distilled H20). The NaAs02 increases the N02
collection efficiency, but NO still interferes.
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, CH4, H20
and Sodium Arsenite on NO- Analysis," presented at the
Second Conference on Natural Gas Research and Technology.
Atlanta, Georgia, June 5, 1972.
3. "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 C-4. " . ...
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u
42603 11 OXIDES OF NITROGEN-INSTRUMENTAL COLORIMETRIC
The total oxides of nitrogen (NO + N0~) are measured
"
by the methods 42601 11 and 42602 12. The instrument
reports the total as NO (total oxides of nitrogen).
^* ' *-
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health Association,
Wash., D.C., 1972, p 325.
42604 91 AMMONIA-GAS BUBBLER' NESSLER REAGENT-50 Ml TUBS + ORIFICE
Ammonia reacts with the alkaline HgI2.2KI solution
(Nessler reagent) to produce an orange colored complex
that is measured colorimetrically at 400 to 425 nm. The
absorbing solution (3.27N H-SO.) is returned to the
laboratory after the sampling period and Nessler reagent
added, (lOOg of Hgl^, 70g of KI dissolved in minimum
of H20, 160g of NaOH/500 ml, mixed when cooled and
diluted to one liter). Rochelle salt (0.5g of
KNaC4H4Og.4H20/ml) is added to prevent Ca and Mg pre-
cipitation.
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers, Inc., New York, N. Y. , p 216.
2. Morgan, G. B., E. C. Tabor, C. Golden, and H. Clements
Automated, Laboratory Procedure for the Analysis of Air
I
Pollutants 66-p 108B, Technicon Industrial System,
Tarrytown, N. Y., p 538.
3. Water, Atmospheric Analysis, (1971), "Annual
Book of ASTM Standards," American Society for Testing
and Materials, Philadelphia, Pa., Part 23, p 236-331.
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37
42604 92 AMMONIA-GAS BUBBLER-SODIUM PHENOLATE
The chemical principle used is the same as method
12301 92. Ammonia is collected in 0.0504 N H~S04 as
(NH.)?S04 producing a blue complex with sodium
phenolate and sodium hypqchlorite.
1. Russell, J. A., (1944), "The Colorimetric Estimation
of Small Amounts of Ammonia by the Phenol-Hypochlorite
Reaction," J. Biol. Chem., 156, 457.
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43101' 11 TOTAL HYDROCARBONS-INSTRUMENTAL FLAMF.
Ambient air is passed into the, instrument where, the
organic compounds present are burned in a hydrogen-rich
flame. A sensitive electrometer coupled with a
recorder measures the current resulting from the
ions produced in the flame. The response is
approximately proportional to the number of carbon
atoms in the sample. The analyzer is calibrated using
methane and the results are reported as methane
equivalents.
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health Association,
Wash., B.C., 1972, p 184.
2. "Rules and Regulations," Federal Register,
Vol 36, No. 228, U.S. Government Printing Office,
Wash., D.C., (Nov. 25, 1971), p 22394.
43102 11 NONMETHANE HYDROCARBONS-INSTRUMENTAL FLAME IONIZATION
Measured volumes of air are delivered semicontinuously
(4-12 times per hour) to a hydrogen flame ionization
detector to measure its total hydrocarbon (THC) content.
An aliquot of the same air sample is introduced into
a stripper column which removes H?0, CO- and hydro-
carbons other than CH.. CH, and CO are passed
to a gas chromatographic column where
they are separated. The CH4 is eluted first, and
is measured by the flame ionization detector. This
value subtracted from that for THC results in a
measure of the non-methane hydrocarbon (NMHC) concen-
tration of the sampled air. See also 42101 21.
• 1. "Rules and Regulations," Federal Register, Vol 36,
No. 228, (.Nov. 25, 1971}, p 22394.
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43201 11 METHANE-INSTRUMENTAL- FLAME IONIZATION
A stripper chroroatographic column (charcoal) is used to
remove BUO, C02f and hydrocarbons other than CH..
Methane and CO are then separated by a gas chromato-
graphic column and the CH. measured by a hydrogen
flame ionization detector.
1. Water, Atmospheric Analysis, (1971), "Annual Book
of ASTM Standards," American Society for Testing
and Materials, Philadelphia, Pa., Part 23, p 783.
2. "Rules and Regulations," Federal Register, Vol 36,
No. 228, U.S. Government Printing Office, Wash., D.C.,
(Nov. 25, 1971), p 22394.
3. Ortman, G. C., (1966), Anal. Chem. 36, 644.
43501 11 ALDEHYDE-INSTRUMENTAL COLORIIIETRIC
This method is an automated MBTH technique. See 43501 91.
43501 91 ALDEHYDE-GAS BUBBLER MBTH
Water soluble aliphatic aldehydes (measured as formalydehyde,
HCHO) in the ambient air are measured using an aqueous
3- methyl - 2- benzothiazolone hydrazone hydrochloride
(MBTH) which forms an azine. The excess MBTH is
oxidized with ferric chloride and reacts with the azine
to form a blue cationic dye in acidic media, measurable
at 628 nm, colorimetrically.
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 F-l.
2. Sawicki, E., et.al., (1951), Anal. Chem. 33, p 93.
3. Hauser, T. R. and R. L. Cummins, (1964) ibid., 36, 679.
4. "Air Quality Data for 1967," EPA-APTD-0741, Office
of Technical Information and Publication, Research Triangle
Park, N.C., 1971, p 20.
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40
44101 11 TOTAL OXIDANT-INSTRUMENTAL-ALKALINE KI
Oxidants in ambient air are absorbed in an alkaline
KI solution. On acidification, iodine is liberated
and measured colorimetrically.
44101 13 TOTAL OXIDANTS-INSTRUMENTAL - MAST MODEL 742-2
Air is drawn over electrodes at a controlled rate to-
gether with a continuous stream of fresh electrolyte.
Hydrogen is maintained on the working electrode by a
polarizing voltage. Oxidants convert I to I2 which
reacts with the H9 ,* thus depolarizing the electrode.
c* \
The current required to repolarize the electrode is a
measure of the oxidant concentration of the sample.
1. Mast, G. M. and H0 E. Saunders,(Oct. 1962), "Research
and Development of the Instrumentation of Ozone Sensing,"
Instrume'rtt Soc.' of 'Amer. Trann., 1, 375.
2. Bufalini, J. J. , (1968), "Gas Phase Titration of
Atmospheric Ozone," Environ Sci Technol 2, 703.
3. Wartburg, A. F., and B. E. Saltzman, (1965),
"Absorption Tube for Removal of Interfering SO.-, in Analysis
^
of Atmospheric Oxidant" Anal. Chem. 37, 779.
44101 14 TOTAL OXIDANT-INSTRUMENTAL COLORIMETRIC-ITEUTRAL T
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I i.
41
44101 15
removed by using a. Cr03 scrubber.
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 SO- in
£
Analysis of Atmospheric C;:idant" Anal. Chem. 37, 779
TOTAL OXIDANT-INSTRUMENTAL COULOMETRIC-NEUTRAL KI
This method is based on the same principle as 44101 13,
The electrolyte flov;s between two electrodes which are
used to measure the current needed to re-establish the
halogen-halide balance. Nitrogen dioxide interference
has to be subtracted. Sulfur dioxide interference is
reduced by a CrCU scrubber.
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American'Public Health Association,
Wash., D.C., 1972, p 341.
44101 51 TOTAL OXIDANT-GAS BUBBLER PHENOLPHTHALIN
Phenolphthalin in the presence of CuSO^ can be 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 green filter and a
colorimeter.
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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42
44101 81 TOTAL OXIDANT-GAS BUBBLER ALKALINE KI
Oxidants in 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 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. DIIEW 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 Material;
Philadelphia, Pa., Part 23, p 391.
3. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers, Inc., New York, N. Y., p 219.
44101 82 TOTAL OXIDANT-GAS BUBBLER FERROUS OXIDATION
Air is filtered through a Whatman No. 4 paper at 1 cfm
then bubbled through two impingers in series containing
the absorbing reagent. The absorbance is determined
with a blue filter and a colorimeter. The standard is
made by oxidizing the absorbing reagent with known
amounts of H^O- and reading the absorbance.
1. M. B. Jacobs, (1960), "The Chemical Analysis of Air
Pollutants," Chemical Analysis, Vol 10, Interscience
Publishers Inc., New York, N. Y., p 228.
44101 83 TOTAL OXIDANT-GAS BUBBLER NEUTRAL BUFFERED KI
This is the reference method for standardization and
calibration of total oxidant and ozone measuring
techniques. Maximum sampling time is 30 minutes.
Sulfur dioxide interferes.
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43
1. Intersociety Committee, "Methods of Air Sampling
and Analysis," American Public Health Association,
Wash., D.C., 1972, p 351.
2. "Rules and Regulations" Federal Register, Vol 36,
No. 228, U.S. Government Printing Office, Wash., D.C.,
(Nov. 25, 1971) , p 22392.
3. "Selected Methods for the [Measurement of Air Pollutants,"
U.S. DREW, 999-AP-ll, R. A. Taft Sanitary Engineering
Center, Cincinnati, Ohio, May 1965, p D-l.
44103 11 INSTRUMENTAL - TOTAL OXIDANT - 0.2(NO +
44201 11 OZONE - INSTRUHENTAL-CHEMILUMINESCENCE
The Federal Register describes this method. Ozone
.ozonizes ethylene and the excited molecule emits a
spectrum peaking at 450 nm. A photomultiplier tube is
used to measure the cheiniluminescence.
1. "A Chemiluininescence Detector for Ozone Measurement,"
Bureau of Mines Report of Investigation RI-7650,
United States Department of the Interior, U.S. Government
Printing Office, Wash., D.C., 1972.
2; "Rules and Regulations," Federal Register Vol 36, No. 228,
U.S. Government Printing Office, Wash., D.C., (Nov. 25, 1971),
p 22392.
44201 13 OZONE - INSTRUMENTAL - COULOMETRIC
This method is similar to method 44101 13.
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