"ni7!T>AT>ni
it Hi!Ultl
A STUDY OF THE NATURE OF THE CHEMICAL
CHARACTERISTICS OF PARTICIPATES
, ' COLLECTED'FROM AMBIEhTC>IR'''
FINAL REPORT
Covering the Period
June 30, 1969, to August 15, 1970
Contract CPA 22-69-153
. j
I.iljLiL.lii
ii
COLUMBUS LABORATORIES
-------
MANAGEMENT SUMMARY
Contract CPA 22-69-? S3
"A Study of the Nature of the Chemical Characteristics of Particulates Collected From Ambient
Air".
Objective of Research
This program was designed to produce a complete elemental chemical analysis of the air par-
ticulates in selected urban environments.
Significance of Research Results to Date
With only a few exceptions, every element in the periodic chart has been sought in the particulates
collected in six cities. These data, summarized in two tables in this report and in more detail in sixteen
tables in the Appendix, are expected to be of interest to health physicists, pollution control administra-
tors, and others involved with air quality. The data provide a base for future and current studies in
related research topics.
Application of Research Results
The tabulated and pictorial data can be used directly, for example, to describe the levels of specific
elements in urban air. They can also be used in studies directed toward describing the compounds and
materials that comprise the particulates.
Goals for Next Period
No further work is scheduled under the present contract. A new contract, CPA 70-159, calls for
the identification of species as mentioned above.
-------
FOREWORD
The work described in this report was performed under the professional and administrative
supervision of Mr. William M. Henry, with Mr. E. R. Blosser assisting. It is a pleasure to acknowledge the
contributions of others of the Battelle staff, including D. L. Chase, R. L. Foltz, R. E. Heffelfinger, R. B.
Iden, D. K. Landstrom, C. W. Melton, and D. C. Walters. Their efforts, and those of their assistants,
made possible the compilation of data and figures included in this report.
-------
ABSTRACT
The elemental composition of paniculate material collected from the ambient urban air in six
locations is presented. Both major and minor constituents were determined by utilizing several tech-
niques and analytical instruments. In a broad sense the compositions for each city were similar; but
certain distinct differences, especially in the less abundant elements, are apparent. Some work has been
begun to identify compounds and elemental associations. This work is presently under way in a
continuing program.
-------
A STUDY OF THE NATURE OF THE CHEMICAL CHARACTERISTICS OF
PARTiCULATES COLLECTED FROM AMBIENT AIR
by
E. R. Blosser
INTRODUCTION
The data collected on air particulate samples of ambient urban air pulled during the Winter and
Spring of 1969-1970 in Cincinnati, St^^Loyis, Washjggtpjg D.C.^Dejjver, Ph^jidelpliia^and Chicago_are
presented in this report. These data are the first comprehensive listings of specific elements to be found
in the literature, and as such are a significant addition to the large body of knowledge that has been
accumulated concerning the air in typical American cities.
Gaseous pollutants (NOX, S02, CO, hydrocarbons) have been monitored for some time. Serious
efforts in studying these compounds were begun in the 1940's, especially in problem areas such as Los
Angeles. Elemental monitoring of key elements, lead being a prime example, began about the same time
because it was becoming evident that many pollutants were caused by the leaded gasoline consumed by
automobiles. More recently,.the impact upon our environment by other sources industries, individuals,
utilities, agriculture has received widespread publicity. For this reason, as a step in taking corrective
action to reduce the paniculate pollution of our air, the National Air Pollution Control Administration
(NAPCA) decided to make a complete inventory of the elements present in urban air. Some of these
undoubtedly arise from natural sources such as wind erosion of soil. Others originate from fuel
combustion, and still others from industrial operations. In this report no attempt is made to pinpoint
the specific sources of elements. Rather, the intent of this study is to provide base-line data upon which
future studies of point sources, long-term trends, abatement effects, and other studies can be based.
EXPERIMENTAL WORK
Sample Collection and Preparation
Air participate samples were collected on glass and cellulose estejutiltos,* in six cities by NAPCA.
The sampling stations are part of the Continuous Air Monitoring Program (CAMP) and employ "Hi-Vol"
samplers. These use a series-wound motor ("vacuum sweeper") pulling air down through the filter which
is supported on a wire grid. The units have roofs to protect the filter from gross falling contamination.
Each filter represents 1 to 2 weeks of sampling, had from 0.8 to 4 grams of particulate deposited, and
passed from 6,000 to 13,000 cubic meters of air. The details of the sampling dates, volumes, and
weights are given in the Appendix.
Each filter was processed in several ways. The analytical samples were prepared by a^hjag (cellulose
ester filters), by ultrasoiucaUy shaking the particulate from both glass and cellulose filters in benzene, by
acidjeaching, and by grinding the filter with the sample (glass filters). Each method has its advantages,
b~ut ingeneral it is desirable to separate the sample from the filter matrix. When this is not done, as in
the case when the glass filter is ground with the sample, blank contamination and matrix contributions
become significant in some techniques. On the other hand, the less chemical or thermal treatment that is
performed on a sample, the less the chance of IgsjJQg, certain elements such as mercurYjmd selenium.
*Glass filters were supplied by Gelman, cellulose ester filters by Millipore.
-------
2
Analytical Techniques
The specific analytical techniques that were employed, and the information they are best suited to
provide are described below.
Spark-Source Mass Spectrography (SSMS)
This technique gives complete elemental coverage with (as used in this laboratory) semiquantitative
accuracy. It is most useful /or elements present at tnic? levels and for elements difficult to determine by
other means.
Optical Emission Spectrography (OES)
Major to moderately low trace metals are determined by this technique. The data are at least
semiquantitative, and spectral interferences from organic compounds (either particulate or from the filter
itself) are nil.
Wet (Classical) Chemistry (Chem)
Specific elements are determined by various methods, including combustion, titration, atomic
absorption, colorimetry, and distillation. These methods are generally accepted as relatively accurate
provided the possible interferences are known and allowed for.
X-Ray Fluorescence (XRF)
Once standardized, this technique provides accurate, rapid analyses of elements heavier than
sodium. In the present work, ashed samples were used, but on a routine basis it should be possible to
analyze the cellulose ester filters directly if corrections for the carbon absorption are made.
» JSprical (Light) Microscopy (OM)
Although difficult to quantify, this step is very useful in describing the morphology of particles
larger than about 0.5 M- Discrete entities such as soot, flyash, minerals, insect parts, etc., can be
identified.
^Electron Microscopy (EM)
Particles down to the angstrom range can be identified, and some small but important species such
as asbestos fibers were found in several samples. As in the case of optical microscopy, quantification is
difficult.
(/El
Electron Microprobe (EMP)
This technique is most useful when determining the distribution of elements in a sample, and when
elemental associations in individual particles are desired. The basic gram detcctability of this instrument
is better than that of any other technique commercially available today.
-------
Gas Mass Spcciroiiiciiy (GMS)
The adsorbed gases on air participates were analyzed using this technique. It is capable of good
accuracy and extreme detectability for specific compounds. For paniculate analysis, either thermal or
chemical means must be employed to obtain a sample in the gas phase.
High-Resolution Mass Spectrometry (HRMS)
Because every combination of atoms has a slightly different mass because of elemental mass
defects, HRMS can, in many cases, give the elemental formula for compounds. In the present work it
was employed to search for organometallic compounds in the benzene-soluble phase of air particulates.
X-Ray Diffraction (XRD)
Crystalline materials can be identified by this technique. A computer program is used to compare
the measured lines on the diffraction film with the library of known reference compounds. Some care
must be taken in interpreting the data because X-ray lines of several compounds may overlap at any
given measured distance.
RESULTS
The elemental data obtained are summarized in Table 1. The range found for each element in the
six cities, together with a typical value, is presented. The latter is more or less a combination of an
arithmetical average and a median value, with some subjective weighting, depending on the individual
results. Specific data for each city, and other data generated in this work, are included in the Appendix.
When evaluating these data from a health standpoint, one can assume that over a 70-year lifetime, a
person will breathe about 3 x 10^ cubic meters. Thus, if an element is present at the 3000-nanogram
level, approximately 1 gram will be inhaled during a lifetime. Fortunately, much of the inhaled
particulate is exhaled or is trapped before entering the lungs.
Elemental Analysis
As a first approximation, the a\[ PfjiMiliUSS TJ^VJiufc t-^aiLJ^^^J^IIli!:'^ J^1"* 's to sav>
carbon, silicon, calc^m, aluminum, sodium,Qron^ sulfur, anoQ^aJ) predominate. Looking at the data in
the Typical column in Table 1 (and at the data in Tables A-14 and A-16), it is seen that roughly
g-half of the parjkujglte^jT]^texj£^nzejic^lubleLj^r Q^garjiCujP3^ othe^half is mainly_jjjjca^ with
major amounts of other materialsincluding minerals and TTlyash. "These facts were established by XRD,
OMj_and EM. See Table 2 for elemental analysis of the particulates collected in these cities. It should be
noted that these are, in most cases, values obtained on more than 1 filter and by more than 1 method.
Beyond this broad observation, however, are significant differences. For example, of the six cities
sampled, Chicago had the highest carbon and hydrogen content, and Washington and Cincinnati the
least. Washington, Chicago, and PhJM^lj^uaaJpj^vgr. had thefaj&j^^ajpjjd^uaai^y^ of
IjQj Chlorine ranged from very low values in Philadelphia to high in Chicago and Denver. Lead JsJiifili
and_fjjrly_jjniforrn^ in all six cities, probably reflecting the density of automobile traffic in any urban
area. The rare earths are not. as rare as sometimes thought; about' one-half of these elements were
detected in all cities. Some very toxic elements Se, Te. Tl^Hp gwer^dthej^jTpj^_dejte^cd_ or were
XQJiJid^only^tr::gLuitelQW,.Ie.V-Cils.-There is some uncertainty about mercury, because if it is present as Ifie
-------
element it would not be caught on filters but would pass through as a 535. Other elements may be
present as gases, such as H2S, H2Se, etc. The use of silver filters to form an amalgam or compound
might solve this problem.
Organometallic Compounds
Since the normal procedure for analyzing air paniculate involves a preliminary benzene extraction
to remove the organic phase, the pj£Sjrjc£j}|U)r4>amBaeJalii£=^^
insoluble phase. Even in this present work, when no extraction was made in most cases, ashing or even
'TBoTrV-ternperature evaporation might volatilize some Organometallic compounds. Therefore, the benzene-
soluble phase from one glass filter from each city was examined by HRMS. No identifiable Organo-
metallic compounds were found. If present, they should have been seen as peaks having negative mass
defects, as compared with hydrocarbons which have positive mass defects. The benzene was also
evaporated at room temperature and the residue remaining was examined by SSMS. Most of the
elements present in significant amounts in the overall sample were also found in the extract residue, but
in quantities (in terms of nanograms/M^) very much lower than in the bulk sample. Two exceptions
were noted: bromine and iodine/These two elements are extracted almost quantitatively.
Adsorbed Gases
Some S02. N^XjJH2JJH^^nd__CQ2_were found Jg_^de^rbjd£roniJhe,partlcuIate matter on
glass filters. Tn*e"arnou'nt was small, and~amourTty~foraboTrt" alelTflvpercenFoT the total sample weight.
Some correlation was noted between the amount of carbon and the amount of desorbed gas, as might
be expected if the carbon ("soot") could be considered a form of activated charcoal.
Optical and Electron Microscopy
^ .(fj~-. ^-.- ---; - ^7- -.- ,-XSS
The usual particles that have been identified previously were found in these samples. These include
flyash, sop^*, fibers, asbestos, and^njinerals. Color pictures of typical material from each city are
included in the Appendix. Electron microscopy revealed many fine particles below optical visibility.
Many were opaque amorpho^s^articles (probably soot from combustion) that had not been reported
previously.rAj few asbestos fibenpwore also found, emphasizing the importance of monitoring this
pollutant. Tru's pollutant is cur^^ijtJtimg^sto.clied~in_anolher program at Battellg^lujmhus»-jujd_has
been found to run as high asJu^g/ml^ojLjJoint sourgg!), and more
ambient urban air.
Compound Identification
Work on this aspect of particulate analysis is just getting under way as the second year begins.
However, a start was made during the last quarter of this present program. X-ray diffraction techniques
were used to identify Si02 (cv-quartz) and other classes of compounds. Electron microprobe studies were
made to establish elemental associations in particles and.areas.
*Flyash and soot may be defined as "a particulate effluent from a combustion operation" (Walter C.
McCrone, The Particle Atlas).
-------
TABLE 1. RANGE AND TYPICAL VALUES FOR ELEMENTS IN PARTICULATES COLLECTED FROM AMBIENT URBAN AIR
(Nanograms/cubic meter)
(a)
Element
H total
"Inorganic" (b>
He
Li
J3e .
'B
C total .
, "Inorganic" W
N total
"Inorganic" C°)
F
Ke
Na
Mg
Ai
Si
P
S total
"Inorganic"(b'
Cl
Ar
K
Ca
Sc
Ti
V
Ci-
Mr>
Fe
Co
Ni
Cu
Zn
Ga
Ge
Low
3,000
1,600
2
0
3
28,000
15,000
2,400
2,100
20
500
1,000
1,000
4 , 000
50
3,000
1,700
<4
600
2,000
1
150
1
3
30
1.500
3
2
100
200
3
<0
High
11,600.
4,700.
. i .
20.
.01 0.6
30.
110,000.
50,100.
9,700.
7,300.
~no t Q6 te rmlned
900.
4~ , . f .
12,000.
5; 000.
10,000.
45,000.
. . 600.
11,000.
8,700.
13,000.
. . *>Ui *-
10,000.
20,000.
10.
600.
300.
50.
200.
9,000.
10.
100.
3,000.
3,000.
8.
.4 10.
Typical
5,000.
3,000.
4.
0.2
3 .
50,000.
25,000.
4,000.
3,000.
5.0.
2,000.
2,000.
3,000.
10,000.
100.
5,000.
4,000.
1,000.
1,000.
6,000.
1.
200.
30.
20. "
100.
4,000.
5.
20.
500.
500.
5.
2.
Ele-
ment
As
~Se "
"Br '
Kr
Rb
Sr
Y
Zr
Nb
Mo
TV
i C
Ru
Rh
Pd
Ag
Cd
In
Sti
Sb
Te
I
Xe
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Low
2.
2.
" 10'.'
not
10.
20.
1.
2.
0.3
0.5
_ _ no t
<0.01
<0.01
<0.2
0.5
<0.3
-0.5
6.
2.
<0. 1
£0.01
hot
0.3
10.
2.
3.
1.
1.
0.4
0.1
, 0.3
0.05
<0.2
0.03
-------
.6
TABLE 2. APPROXIMATE ELEMENTAL.CONCENTRATIONS FOUND IN PARTICULATES
COLLECTED FROM AMBIENT URBAN AIR
(Nanograms/M )
Ele-
ment
H
Li
Be
^
C
N
F
Na
Mg
Al
Si
P
S
Cl
K
Ca
Sc
Ti
V
Cr
Mn
Fe
, Co
Nl
Cu
Zn
Ga
Ge
As
Se
Br
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
CcL
Cincinnati
3,000.
5.
0.2
10.
30,000.
3,000.
40.
4,000.
1,000.
2,000.
5,000.
100.
4,000.
1,000.
1,000.
6,000.
<1.
200.
10.
20.
100.
5,000.
5.
. .20.
300.
1,000.
5.
5.
20.
4.
' ' 50.
10.
10.
3.
4.
0.4
2.
<0.04
<0.04
£0.2
<1.
1-
De.nver
5,000.
20.
0.04
20.
40,000.
2,000.
400.
10,000.
1,000.
7,000.
40,000.
300.
3,000.
5,000.
10,000.
6,000.
2.
400.
20.
20.
100.
5,000.
5.
30.
500.
200.
4.
3.
5.
2.
200.
100.
100.
4.
20.
2.
5.
<0.06
<0.2
<1.
1.
1. .
\
St. Louis
7,000.
10.
0.4
30. :
60,000.
6,000.
200.
10,000.
2,000.
3,000.
6,000.
200.
8,000.
1,000.
2,000.
20,000.
1.
300.
20.
20.
50.
5,000.
3.
20.
3,OCO.
3,000.
10.
5.
50.
10.
300.
20.
50.
2.
10.
1.
3.
<0.04
<0.1
<0.4
20.
___ , r~-~t=Z*=£- -,
Washington
3,000.
3.
oa
-10,
30,000.
2,000.
100.
1,000.
1,000.
2,000.
5,000.
30.
4,000.
300.
1,000.
3,000.
1.
200.
100.
10.
50.
2,000.
5.
50.
400.
400.
5.
4.
20.
5.
200.
5.
10.
1.
4.
0.3
2.
<0.01
<0.03
<0. 1
0.6
0.3
Chicago
10,000.
2.
<0.1
5.
100,000.
10,000.
30.
5,000.
5,000.
2,000.
6,000.
60.
3,000.
10,000.
2,000.
10,000.
3.
300.
100.
20.
100.
4,000.
10.
40.
400.
500.
6.
7.
60.
2.
100.
20.
40.
1.
4.
0.5
3.
<1.
<0.06
<0.3
2.
3.
Philadelphia
4,000.
2.
0.05
5.
30,000.
5,000.
20.
1,000.
5,000.
3,000.
10,000.
50.
3,000.
4.
1,000.
8,000.
10.
400.
200.
40.
200.
4,000.
20.
100.
200.
500.
6.
<0.4
10.
2.
20.
20.
40.
2.
10.
0.3
2.
<0.03
<0.01
<0.3
0.6
1.
-------
TABLE 2. APPROXIMATE ELEMENTAL CONCENTRATIONS FOUND IN PARTICULATES
COLLECTED FROM AMBIENT URBAN AIR (Continued)
Ele-
ment
In
Sn
Sb
Te
I
Cs -
Ba_7
La
Ce j '
Pr '..
\
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
. W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
Th
U
Cincinnati
<2.
100.
8.
20.2
0.5
0.4
*)0.
2.
3.
1.
3.
0.4
<0.2
<0.6
-------
8
SUMMARY
The data given in this report and the attached Appendix show the amounts of almost every natural
element as found in ambient air participates collected in six cities. Some significant differences were
found in both major and trace elements. The morphology of the particulates is shown in optical and
electron micrographs in the Appendix. Examples of the XRD and HRMS data output are also shown.
FUTURE WORK
No further work is planned under the present contract. A new contract has been negotiated, CPA
70-159. Under the new contract a detailed study of ions, molecules, and compounds is beginning. The
new work, combined with the present report, should give a comprehensive view of the inorganic air
particulates.
RATE OF EFFORT
Through June 30, 1970, the total expenses were $35,829.37 and $390 is committed for the nylon
filters, leaving $9,980.63. About 1600 man-hours have been expended, exclusive of the effort to prepare
this Final Report. It is expected that most of the remaining funds will be required for the preparation
and reproduction of the Final Report.
-------
APPENDIX
SUPPLEMENTARY DETAILS AND DATA
-------
A-l
APPENDIX
r.JP?LEMENTARY DETAILS AND DATA
Adsorbed Gases in Participates
10 rrtwr
will: be /
cereal \ '
trap. 0';
were .;y.-
ttet 1% :;-:
no* j.1-. :.?.-.::'
the KV-C:'
grarai or £'
not ICJS-TJ.-.V
any C2V:
"htmi^r
spark- *:.
Second ;
Mack p.-.-.
accow.pl ;
ths? GOH'.
identify ..
.ample container with appropriate valves, flanges, etc., was attached to
.j-sensitivity Aero Vac mass spectrometer. The entire system was baked,
"i the same manner as subsequently used for the sample analyses. This
.-..sckground.
to liberate at least some of the gases adsorbed on and absorbed in the
_ on the filter itself). An extraction temperature of 130 C was chosen
.;- particulates. Almost no inorganic compounds likely to be in the air
jerature, and past research has shown that natural products such as
.gnificantly below about 150 C.
(area) was cut from the filter and was placed in the stainless steel
:ged with helium purified by passing through a liquid-nitrogen-cooled
ithout a sample or blank in the container and no significant impurities
; the container was isolated and cooled with a liquid-nitrogen-filled
; was pumped from the system. This step also would remove H2, CO,
boiling-point gases. The container was warmed to 130 C and held at
he amount of gas released was measured and analyzed.
"ier was isolated and cooled to -80 C, using a Dry Ice-acetone bath, to
and most of the hydrocarbon present. This method confirmed the
H2S by showing that the hydrocarbon fragmentation patterns were
at the mass-to-charge positions used to calculate the concentrations of
able A-l. They are reported as standard cc atmospheres rather than as
irst, the samples have been exposed to various atmospheres since their
has been lost or picked up during that time is unknown. Second, it is
; be determined, how efficient the gas-evolution technique really is. In
on a comparative basis. For example, the results show somewhat less
the other areas. This correlates with two other observations. First, the
spectra of the Denver samples (as physically removed from the
v the organic phase) showed evidence of fewer organic compounds.
,=d by light and electron microscopy, had less soot and other carbon
?.$ from the other three cities. These components can be considered as
/cry active adsorbers.
ed from all the filters, including the blank, was water. It would
.I the off gas. The breakdown of the individual nitrogen oxides is
: s surprising to see such a large proportion present as NO.
not include all the hydrocarbon present, but were included to indicate
\ydrocarbons having a major mass at m/e 43. No attempt was made to
".ermine the total amount present.
-------
A-2
TABLE A-l. EVOLVED GAS FROM PARTICULATE MATTER
Location
Filter number
i 2
Sample size, cm
Net weight sample,
Washington
0006989
69
0.12
St. Louis
0006986
69
0.29
Cincinnati
0006997
66
0.14
Denver
0006982
69
0.59
Blank
_
69
-
g
Total evolved gas,
cc-atm (STP)
5.10
9.55
8.49
14.8
0.86
Compound
so2
CO,.
2
NO
x
NO
N02
N.O
H0S
2
HC1
m/e 43
cc Atmospheres Per Gram Particulate Total cc Atmospheres
0.081
' 0.16
0.54
0.30
0.04
0.20
0.009
0.0005
0.032
j-\v+ t- S\rl 4- j-» f* V* o**r%0 T-^>
0.007
0.27
0.31
0.28
0.02
0.01
0.007
0.0003
0.062
0.003
0.47
0.70
0.44
0.10
0.16
0.016
0.0008
0.036
r* T-»f» 4-1^ f\ fa
0.035
0.16
0.23
0.20
0.01
0.02
0.003
0.0003
0.019
molecular
2 x 10"5
4 x 10"5
2 x 10"4
-.
-
-
1 x 10"4
-5
1 x 10
1 x 10"4
weight
VjO.J.1 L/C *-WHVCJLl-C«U UU g,JL 0.1110 L^^ 1UUO. UJ.pJ.yj,Hg L/^ L.11C i-CLV^ L.WJ. O O/
^C ^f IK
For example 0.54 cc atm NO^ in Washington is equivalent to about 0,08 percent
of the total sample. X
Note: Water and air components (02, N2, and Ar) were not calculated.
-------
A-3
Those values reported for hydrogen chloride should be considered the maximum values possible,
since some hydrocarbon-fragment interference is possible and since they are approaching the blank level.
Elemental Analysis of Participates
Procedure
Optical Emission Spectrographic. For both Millipore and glass filters the sample was removed from
the filter by ultrasonic agitation in benzene. The filters were examined by optical microscopy after this
treatment. Some particles remained on or in the glass filters, but essentially all were removed from the
Millipore. The suspension was dried and then ashed at 500 C. Almost no elements detectable by this
technique would be lost in this process. (Mercury would probably be volatilized, however; therefore,
special analyses were made for that element.) The ignited residues were mixed with germanium and
carbon in the ratio 1:9:10 (sample:Ge:C) and arced in graphite electrodes. Synthetic standards were run
on each film as references.
The last group of filters (Chicago and Philadelphia) were examined by a slightly modified
technique. The Millipore filter was ashed directly rather than performing the extraction step, avoiding
any possibility of incomplete, sample removal. The Millipore blank introduces no detectable error.
Mercury was determined directly on Millipore filters using a "boiler cap" technique. Samples were
run from Cincinnati, St. Louis, Denver, and Washington. These "boiler cap" data are included in the
OES results in Tables A-2 through A-5.
Spark-Source Mass Spectrographic. Three sample preparation techniques were employed. In each
case the sample was briquetted with graphite.
(1) The sample was removed from Millipore and glass filters by ultrasonic agitation in
benzene, then dried but not ashed. This is referred to as "C6H6 Wash" in the following
tables.
(2) Millipore filters were ashed at 500 C. This is referred to as "Ash".
(3) The glass filters were ground in an agate (Si02) mortar.
In no case was a benzene extraction per se made. In other words, any trace metals in the organic
(benzene soluble) phase would be detected. The organic compounds did cause some spectral
interferences. On the other hand, in the ground-glass filter there is no possibility of loss of volatile
components except those lost at room temperature in vacuum, such as metallic mercury.
The samples were briquetted isostatically with graphite in polyethylene dies. They were sparked for
a series of exposures of varying intensities. The resulting photoplates were read visually. Elemental
concentrations were estimated by noting in which exposure a given isotopic line was just detectable.
X-Ray Fluorescence. Samples were prepared by ashing the Millipore filters with the particulates. A
fixed weight of sample ash was mixed with Li2B407-5H20 and briquetted in round aluminum dies.
Synthetic standards were prepared to duplicate closely the range of impurities in the samples.
-------
TABLE A-2. ANALYSIS OF AIR PARTICULATES ON MILLIPORE - CINNCINNATI
(Nanograms/lO
Sample Declination
le-
fint SSKS
lie 0.4
F 80.
P 100.
!, 4000.
Cl 2000.
Ga 3.
As 10.
Se 4.
Be 80.
Te SO. 2
I 0.04 '
lia <0.03
71 SO. 02
?:> 1000.
3i 0.6
M 000 417
(Ash)
OES
0.3
<0.05
500.
--
Chem
3750.
--
XRF
550
6400.
800.
--
M 000 4]
(C,H, Was
SSMS
0.1
30.
50.
600.
2000.
8.
10.
4.
80.
SO. 3
0.5
SO. 4
<0.2
600.
0.6
L7
.h)
SSKS
0.2
30.
50.
2000.
300.
3.
4.
2.
10.
SO.l
SO. 01
<0.03
SO. 03
1000.
0.4
M 428
(Ash)
OES
0.4
<0.4
Chem
XRF
M 41
\C£H- V
6 §Sl
o.:
60.
600. 50.
3300. 2000.
15. 300.
3.
7.
4.
100.
SI.
!8
iash)
IS
L
SSMS
M 000 416 M 000 416
(Ash) (C.H. Wash)
OES Chem XRF SSHS
0.5 0.3 0.5
30. -- T- 60.
50. -- 475. 50.
2000. 5800. 2000.
300. -- 10. 300.
5. 5.
10. ' 30.
3. -- 5.
6. 30.
sO.l -- <0.2
<0.01 1.
<0.03 <0.7 ' <0.3
<1. <0.02 <0.2.
1400.
--
3200.
2300,
--
1500.
<4.
200.
0.5
360. 2600. 2100. 300.
0.5
M 000 405 M 000 405
(Ash) (C.H. Wash)
SSMS
0.3
50.
50.
1000.
300.
3.
10.
2.
10. ~ -'
SO.l
so. 01
<0.04
SO. 02
1000.
1.
OES
0.2
<0.4
1000.
"
Chem XRF SSHS
0.6
200.
50.
40. 1000.
4200. 300.
20.
5.
60. .
2.
2.
S2.
3120. 3000. 1500.
3.
Sample Designation
-ie-
,ent SSMS
Li 4.
B 10.
!ia 4000.
I!g 2000.
Al 1000.
Si 4000.
K 8000.
Ca 8000.
S; . SI.
Ti 300.
V 15.
Cr 40.
Mn 400.
Fc 4000.
Co 15.
Ni 30. W
Cu 300.
Zn 400.
Ge 6.
Rb 15.
Sr 40.
Y 2.
Zr 4.
Nb 0.4
Mo 2.
Ru <0.04
Rh <0.04
Pd SO. 2
Ag 1.
Cd 0.6
M 000 4
(Ash)
OES
5.
1500.
1500.
2500.
5000.
1000.
5000.
150.
5.
20.
150.
2500.
5.
15.
150.
500.
5.
2.
--
1.
"
17
Chem
--
--
6400.
1500.
950.
6000.
5700.
__
450.
1950.
--
--
"
XRF
--
2500.
7000.
1500.
7000.
250.
20.
7300.
__
350.
1500.
--
--
Ele-
ment
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Cd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Th
U
M 000 417
(Ash)
SSMS OES
<2.
500. 100.
10.
0.3
100. (a> 25.
4.
10.
1.
4.
0.4
<0.2
<0.6
<0.1
<0.3
<0.1
<0.3
<0.06
<0.2
<0.1
<0.04
<0. 1
0.2
<0.02
<0.02
<0.02
<0.03
<0.1
0.1
0.2
XRF
150.
--
--
--
--
Ele-
ment
Na
Mg
Al
Si
K
Ca
Tl
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Zr
Mo
Ag
Sn
Ba
OES
500.
1500.
3300.
9200.
1000.
7000.
200.
1.3
3.
25.
2500.
7.
2.
150.
1000.
1.
7.
1.
7.
7.
M 428
Chem
750.
1750.
.-
__
950.
6450.
--
7700.
250.
2200.
--
XRF
--
2500.
7500.
1400.
8100.
170.
12.
9200.
125.
1600.
13.
OES
980.
1300.
2000.
4300.
1300.
4220.
200.
4.
20.
130.
1950.
7.
15.
200.
200.
7.
2.
0.7
20.
20.
M 000 416
Chem XRF
3770.
1170.
3000.
7200.
1040. 1500.
4420. 5500.
200.
20.
4750. 6100.
650. 600.
1000.
45.
OES
260.
1540.
2700.
7600.
1540.
5100.
180.
0.5
20.
135.
1500.
4.
1.
88.
440.
10.
45.
0.5
25.
25.
M 000 405
(Ash)
Chem
780.
1500.
340.
6000.
3870.
308.
1450.
--
--
--
XRF -^
1
--
2,800.
8,000.
1,300.
17,300.
220.
20.
4,500.
--
160.
1,250.
--
--
120.
«
HI, 15; Cu, 150; Sn, 100; Ba, 40.
-------
A-4
Wet Chemistry. Atomic absoipikm was employed to determine Na, K, Ca, Mg, Fe, Cu, Pb, and Zn.
Millipore filters were ashed, and the residue was dissolved in acid. Appropriate aliquots were then
analyzed and compared with synthetic standards.
Chlorine was determined by a colorimetric method or, an acid leach from glass filters, and fluorine
by a distillation technique from glass filters. Unfortunately the fluorine blank of the glass filters is quite
high. Nitrogen, carbon, and hydrogen were determined using a CHN analyzer (based on the Dumas-
Pregel method) to burn the glass filters. Sulfur was determined by a combustion technique using glass
filters.
It is recognized that ashing may cause the loss of certain elements such as Pb, Hg, Cd, and Se.
However, a comparison of the data for nonashed samples with ashed samples shows no loss of volatile
elements within the expected accuracy of the procedures. The exceptions to that statement are the
elements bromine and iodine, which do appear to be lost by ashing in several instances. In any case, the
reduction of spectral interferences by ashing is a sufficient advantage over nonashed or acid-leached
samples to outweigh the disadvantage of losses. Those elements possibly lost can be determined on
nonashed samples.
Oxygen. This is the one area where complete failure must be reported. Had it been possible to
collect samples on silver as originally planned, it is virtually certain that oxygen could have been
determined by vacuum fusion. But both glass and Millipore obviously contain large amounts of oxygen
and therefore could not be analyzed directly. All attempts to separate the sample from its filter failed.
Ultrasonic agitation removed small amounts of the filter, either glass or Millipore. Dissolving the
Millipore in acetone and filtering on silver failed because the silver plugged almost immediately. In the
future, if oxygen must be determined, it is imperative that another sampling approach be found.
Tabulated Data
The city-by-city elemental analyses of Millipore filters are given in Tables A-2 through A-7, with
cross check data shown where available. Similar data are given for glass filters in Tables A-8 through
A-13. Owing to the large number of data in some of the tables it was necessary to reduce them for
reproduction. Also, abbreviations were used to conserve space and these are as follows:
M-3 Cubic meter
Ash Ash from Millipore plus particulate
^6^6 Wash Dried (not ignited) residue from ultrasonic removal of
particles in benzene
SSMS Spark-source mass spectrography
OES Optical emission spectrography
Chem Wet (classical chemistry including atomic absorption,
combustion, etc.)
XRF X-ray fluorescence
The analyses for H, C, and N are given in a separate table (Table A-14) to save space in the other
tables.
-------
TABLE A-2. ANALYSIS OF AIR PARTICUIATES ON MILLIPORE - CINNCHWATI
(Nanograms/M )
Sanwle Desienation
Ele-
nent SSMS
Be 0.4
F 80.
P 100.
S 4000.
Cl 2000.
Ga 8.
As 10.
Se 4.
3r 80.
Te SO. 2
I 0.04
Hg <0.03
TI SO. 02
Pb 1000.
Bi 0.6
M 000 417
(Ash)
OES
0.3
<0.05
500.
--
Chem
-
3750.
-
XRF
550
6400.
800.
M 000 417
(C.H, Wash)
§SHS
0.1
30.
50.
600.
2000.
8.
10.
4.
80.
SO. 3
0.5
SO. 4
<0.2
600.
0.6
M 428
(A oh)
SSMS
0.2
30.
50.
2000.
300.
3.
4.
2.
10.
SO.l
SO. 01
<0.03
SO. 03
1000.
0.4
OES
0.4
<0.4
Chem XRF
600
3300
15
M 4
- (c'H!s
0.
60.
50.
. 2000.
300.
3.
7.
4.
100.
si.
28
Wash)
MS
1
M 000 416 M 000 416
(Ash) (C.H. Wash)
SSMS
OES
0.5 0.3
30.
50.
2000.
300.
5.
10.
3.
5.
SO. 1
<0.01
<0.03 <0.7
.
-------
A-6
TABLE A-2. ANALYSIS OF AIR PARTICIPATES ON HILLIPORE - DENVER
(Nanograms/M )
Sample Designation
Ele-
ment
Be
F
P
S
Cl
Ca
As
Se
Br
Te
I
Hg
Tl
Pb
Bi
Ele-
ment
Li
B
Na
Mg
Al
Si
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Nl
Cu
Zn
Gc
Rb
Sr
Y
Zr
Kb
Mo
Ru
Rh
Pd
Ag
Cd
SSMS
0.1
600.
200.
2,000.
10,000.
5.
5.
2.
200.
<0.2
0.1
<0. 1
0.1
1,000.
1.
SSMS
20.
20.
7,000.
2,000.
5,000.
High
10,000.
10,000.
2.
500.
30.
20.
100.
5,000.
10.
50.
500.
30.
<2.
100.
200.
5.
10.
1.
2.
<0.06
<0.2
<1.
2.
0.6
M 000 412
(Ash)
OES Chem
0.04
0.4
XRF
250.
3,700.
5,000.
M 000 412
0.1
600.
400.
3,000.
3,000.
10.
5.
3.
200.
<0.4
2.
<0.3
0.2
1,600. 6,
--
M 000 412
(Ash)
OES
30.
4,000. 12
1,200. 1
10,000.
44,000.
10,000. 1
7,000. 5
400.
20.
24.
120.
4,400. 8
8.
20.
400.
240.
--
24.
.
B.
--
0.4
--
240.
""
Chem
..
,500.
,400.
,800.
,200.
--
,000.
590.
390.
--
-.
--
..
--
--
700.
XRF
7,000.
44,000.
9,500.
6,500.
--
170.
30.
--
8,400.
--
400.
210.
--
-.
-.
..
--
2,000.
1.
Ele-
ment
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sra
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Th
U
Sample
SSMS
<3
6.
5.
2.
500.
20.
20.
5.
10.
1.
0.5
1.
0.1
1.
0.1
0.5
<0.2
<1.
0.3
<0.6
<0.3
2.
<0.05
<0.1
<0.05
<0. 1
<0. 1
0.6
0.3
Designation
M 000 412
(Ash)
OES Chem XRF
20.
240.
..
',-
-.
-.
--
M 000 413
(Ash)
SSMS
0.01
300.
200.
1,000.
300.
5.
5.
£1.
100.
£0.2
<0.02
o!i
2.000.
0.5
Ele-
ment
Ha
«8
Al
Si
K
Ca
Tl
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Zr
Mo
Ag
Sn
Ba
OES
Chem
0.06
<0.6
1,800.
--
OES
1,00.
900.
9,070
27,800.
9,000.
9,000.
360.
18.
18.
120.
5,400.
6.
18.
600.
180.
35.
60.
1.
'30.
360.
--
5,820.
--
M 000 413
(Ash)
Chem
4,020.
1,560.
--
1,860.
6,900.
--
--
.-
8,820.
..
--
600.
420.
--
-.
M 000 413
(C,H, Wash)
XRF SSMS
0.01
300.
210. 200.
3,300. 2,000.
30. 400.
5.
5.
£1.
200.
£0.4
4.
<0.3
<0.4
4,700. 1,000.
0.5
XRF
..
..
8,500.
33,500.
6,600.
7,200.
260.
25.
8,500.
-.
480.
300.
.-
<6.
-------
A-7
TABLE A-4. ANALYSIS OF AIR PARTICULATES ON MILLIPORE - ST. LOUIS
(Nanograms/M )
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
Tl
Pb
Bl
SSMS
0.6
200.
200.
5,000.
1,500.
5.
100.
10.
100.
10.
SO. 04
<0.06
<0.03
2,000.
2.
M 000 408
(Ash)
OES Chem.
0.3
.-
16
..
<1.6
600. 10,000. 2
--
Sample
M 000 408
(C.I!. Wash)
XRF SSMS
0.4
200.
185. 200.
,000. 5,000.
60. 1,500.
20.
300.
30.
300.
5.
1.
<2.
S0.3
,600. 3,000.
3.
Designation
M
SSMS OES
0.6 0.
3CC.
200.
5,000.
5,000.
3.
20.
3.
700.
SO. 3
£0.1
<0.1 <0.
<0.03
1,000. 2,400.
0.2
000 409
(Ash)
Chem
3
'
--
'
8
5,430
--
M 000 409
(C,H, Wash)
XRF °S§MS
11,
7,
1,
0.3
300.
125. 300.
000. 15,000.
200. 3,000.
10.
30.
6.
1,500.
si.
3-
<2.
1.
200 3,000.
1.
Sample Designation
Ele-
ment
Li
B
Na
Mg
Al
Si
K
Ca ,
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ge
Rb
Sr
V
Zr
Nb
Mo
Ru
Rh
Pd
Ag
Cd
SSMS
20.
20.
5,000.
' 2,000.
2,000.
6,000.
4,000.
, 10,000.
1.
600.
40.
60.
100.
5,000.
10.
50.
2,000.
1,000.
10.
40.
100.
2.
6.
2.
10.
<0.04
<0. 1
<0.4
20.
10.
M 000 408
(Ash)
OES Chem
30.
1,200. 12,500.
1,500. 1,920.
3,000.
6,000.
1,500. 1,920,
40,000. 16,600.
.-
300.
12.
15. -- .
60.
1,500. 6,900.
3.
15.
300. 3,200.
600. 3,840.
--
12.
.-
3.
30.
-
Ele-
.XRF ment
In
Sn
Sb
Cs
3,200. Ba
10,200. La
2,300. Ce
17,000. Pr
Nd
320. Sm
50. Eu
Gd
Tb
8,200. Dy
Ho
Er
3,100. Tra
3,800. Yb
Lu
H£
Ta
-- . W
Re
Os
Ir
Pt
Au
Th
U
M 000 408
(Ash)
SSMS OES
S2.
500. 30. (fl)
10.
2.
200. 50.
2.
5.
1.
3.
0.6
<0.4
<1.
<0.2 '
<0.6
<0.2
<0.6
<0.1
<0.4
<0.2
<0.2
<0.3
0.6
<0.06
<0.06
<0.03
<0.1
<0.03
1.
2.
Ele-
ment OES
Na 2
Mg 3
Al
Si 2
K 3
Ca 17
Ti
.V
Cr
Mn
Fe 5
Co
Ni
Cu
Zn
Zr
Mo
Ag
Sn
Ba
,430.
,240.
570.
,200.
,240.
,100.
400.
25.
32.
80.
,670.
16.
32.
320.
570.
6.
40.
0.9
32.
80.
M 000 409
(Ash)
Chem XRF
15,900.
2,350.
2,000.
13,500.
1,460. 2,300.
16,200. 18,500.
485.
45.
-.
7,940. 8,100.
--
810. 530.
1,050. 640.
-.
70.
XRF result: 60.
-------
A-8
TABLE A-5. ANALYSIS OF AIR PARTICULATES ON MILLIPOR£ - WASHINGTON
(Nanograms/M )
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
TI
Pb
Bi
SSMS
0.1
20.
30.
1,000.
50.
3.
10.
3.
10.
0.2
S0.01
<0.02
0.02
1,500. 1
0.2
M 000 406
(Ash)
OES
.0.02
--
--
._
<0.5
-------
A-9
TABLE A-6. ANALYSIS OF AIR PARTICULATES ON MILLIPORE - CHICAGO
(Nanagrams/M )
Sample Designation
Ele-
ment
Be
F
P
S
Cl
Ca
As
Se
Br
Te
I
Kg
11
Pb
Bl
Ele-
ment
Li
B
Na
Mg
Al
SI
K
Ca
Sc
Tl
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
Cd
SSMS
<0.1
30.
60.
1,000.
2,000.
6.
60.
2.
100.
SO. 2
SO. 7
<0.04
SO. 01
1,500.
1.
SSMS
2.
3.
3,000.
4,000.
1,500.
5,000.
3,000.
10,000.
3.
300.
200.
20.
100.
2,000.
10.
20.
300.
70.
7.
20.
40.
1.
4.
0.5
3.
<1.
<0.06
<0.3
2.
3.
M 000 414
(Ash)
OES Chem
<3.
..
3,000. 4,570
-_ --
H 000 414
(Ash)
OES
^_
10.
3,000.
5,200.
3,000.
15,000.
1,000.
10,000.
300.
100.
20.
100.
5,200.
60.
300.
300.
<10.
--
<3.
--
--
--
XRF
5
10
3
Chem
,_
8,600
5,290
--
--
590
10,420
--
--
--
3,520
400
560
--
--
--
--
--
60.
,400.
,000.
--
,600.
-
XRF
..
.
Cs
1,850.
5,500.
1,200.
12,000.
-.
S2.
40.
--
4,500.
430.
500.
--
--
--
Si
Ele-
ment
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Th
U
M 000 415
(Ash)
SSMS
0.3
150.
100.
2,000.
400.
10.
60.
6.
200.
SO. 2
<0.6
<0.1
0.04
3,000.
3.
OES
<6.
--
4,200.
--
Chem
--
10,040.
--
XRF
300.
15,500.
3,600.
--
5,500.
--
imple Designation
SSMS
<1.
40.
8.
0.7
60.
5.
7.
2.
5.
2.
0.3
2.
SO.l
0.3
0.1
SO. 2
sO.l
SO. 5
<0.1
<0.3
SO.l
1.
<0.05
<0.04
<0.02
<0.04
<0.1
0.4
0.2
M 000 414
(Ash)
OES Chem XRF
20. -- 10.
--
30.
--
.-.
._
--
--
--
--
..
..
--
--
..
-- .
--
--
--
--
-.
--
..
Ele-
ment
Na
Mg
Al
Si
K
Ca
Ti
V
Cr
Tl
V
Cr
Mn
Fe
Ni
Cu
Zn
Zr
Mo
Sn
Ba
OES
2,100.
10,500.
6,000.
30,000.
1,500.
21,000.
600.
60.
40.
600.
60.
40.
200.
10,500.
120.
600.
600.
<20.
<6.
40.
60.
M 000 415
(Ash)
Chem
6,430.
13,520.
--
--
1,260.
25,900.
--
-.
-_
--
8,050.
--
960.
1,080.
--
--
XRF
--
5,400.
18,500.
3,400.
30.000.
200.
30.
--
200.
30.
-.
10,300.
900.
800.
--
..
2.
--
-------
A-10
TABLE A-7. ANALYSIS OF AIR PARTICULATES ON MILLIPORE - PHILADELPHIA
(Nanograms/M )
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
HS
Tl
Pb
Bl
SE
imple Designation
M 000 419
(Ash)
SSMS
0.1
40.
60.
1.000.
4.
6.
10.
2.
20.
S0.1
0.01
<0.03
0.04
1,500.
0.6
OES
Chem
XRF
<4.
50.
3,400.
<4.
2,000. 2,060. 2,000.
M
SSMS OES
Sample Designation
M 000 419
Ele-
ment
LI
B
Na
Mg
Al
Si
K
Ca
Sc
Tl
V
Cr
Mn
Fe
Co
NI
Cu
Zn
Ge
Rb
Sr
y
Zr
Nb
Ho
Ru
Rh
Pd
Ag
Cd
(Ash)
SSMS
2.
2.
1,000.
5,000.
2,000.
10,000.
1,000.
5,000.
10.
600.
250.
60.
200.
6,000.
20.
100.
200.
500.
<0.4
20.
40.
2.
10.
0.3
2.
<0.03
<0.01
<0.3
0.6
1.
OES
__
8.
480.
4,000.
4,800.
19,000.
1,000.
6,800.
480.
280.
35.
160.
4,000.
80.
80.
280.
..
20.
<4.
--
--
Chem
__
820.
5,240.
--
620.
9,620.
--
--
3,800.
160.
820.
--
--
XRF
_
--
2,500.
9,000.
1,600.
8,000.
--
250.
200.
--
4,050.
350.
500.
--
..
--
--
Ele-
ment
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Th
U
M 000 419
(Ash)
SSMS OES Chem XRF
<1.
70.
60.
0.
30.
20.
20.
4.
7.
1.
0.
0.
0.
0.
0.
0.
0.
0.
SO.
0.
£0.
1.
<0.
<0.
<0.
<0.
<0.
0.
0.
40. 30.
--
4
40.
..
--
2
6
2
6
1
3
06
3
04
2
2
..
02
03
06
03
06
2
2
0
10
60
600
10
4,
2
2,
5,
fiO
SO
<0.
0
2,000,
1,
000 418
(Ash)
Chem XRF
.04 <4.
330.
3,100.
10.
.1
.01
.02
,04
1,900. 2,380. 2,400
M 000 418
Ele-
ment
Na
Mg
Al
Si
K
Ca
Ti
V
Cr
Mn
Fe
Ni
Cu
Zn
Zr
Mo
Sn
Ba
OES
630.
3,100.
3,100.
12,500.
630.
4,200.
330.
210.
25.
130.
3,100.
80.
130.
210.
12.
<4.
25.
35.
(Ash)
Chem
920.
3,250.
--
500.
6,000.
--
--
2,830.
--
170.
830.
--
XRF
..
--
1,900.
5,800.
1,000.
5,400.
170.
17.
2,900.
-.
590.
550.
20.
-------
TABLE A-8. ANALYSIS OF AIR PARTICULATES ON GLASS - CINCINNATI
(Nnnograms/M )
Sample Designation
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
Tl
Pb
CfiHfi
SSMS
0.2
50.
50.
3000.
5000.
5.
20.
7.
200.
SO. 6
2.
<1.
<0.4
300.
G 000
Wash
OES
0.2
--
--
--
--
900.
Sample
G 000 6978
Ele-
ment
Li
B
Na
Mg
Al
Si
K
Ca
Sc
Tl
V
Cr
Mn
Fe
Co
Si
Cu
Zn
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
Cd
C6Hfi
SSMS
5.
30.
2000.
800.
2500.
3000.
1000.
2000.
1.
100.
3.
2.
100. .
1000.
2.
25.
150.
300.
4.
4.
2.
4.
si.
0.5
3.
<0.6
<0.6
<1.
<1.
6.
Wash
OES
30.
1400.
1400.
2500.
7000.
1200.
4000.
200.
2.
4.
40.
900.
2.
6.
60.
400.
4.
0.6
6978
Crushed
SSMS Chera
(a)
(a) <400. (b)
(a)
3000. 4400. (b)
5000. 5330. (b)
5.
20.
7 .
200.
SO. 6
2.
<1.
<0.4
300.
Designation
G 000
G 000 6977
CfiHA Wash Crushed
SSMS OES SSMS
0.1 0.2 (a)
20. - (a)
300. -- (a)
7000. -- 7000.
3000. -- 3000.
10. 10.
40. -- 20.
15. -- 10.
200. 200.
<0.6 -- S2.
2. -- 2.
<0.4 -- <3.
I
(a) Too high in blank to make estimate.
(b) On residue after CjHj extraction.
(c) SSMS results on crushed: Th, 0.2; U, 0.2.
-------
A-12
TABLE A-9. ANALYSIS OF AIR PARTICULATES ON GLASS - DENVER
(Nanograms/M )
Sample Designation
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
Tl
Pb
Bi
Ele-
ment
Li
B
Na
Mg
Al
Si
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ge
Rb
G 000
Cpflf, Wash
SSMS
0.3
200.
100.
1,000.
2,000.
5.
10.
SI.
200.
£0.3
2.
<1.
<0.6
1,000.
1.
G 000
OES
0.04
--
--
--
--
--
--
--
--
--
1,500.
--
6981
C6H6 Wash
SSMS
10.
30.
high
1,500.
5,000.
high
4,000.
7,000.
3.
500.
20.
15.
30.
5,000.
5.
50.
500.
100.
5.
70.
OES
-_
40.
3,000.
760.
7,200.
--
5,700.
4,200.
--
380.
8.
15.
80.
3,000.
1.
15.
380.
150.
--
--
6981
Crushed C
SSMS
(a)
(a)
(a)
1,000.
2,000.
£3.
£5.
si.
200.
<0.3
1.
<1.
<0.3
400.
1.
Sample
Ele-
ment
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sm
Chem
__
<400.(b)
--
1,700. (k)
9,030.(b)
--
--
--
--
--
--
--
Designation
G 000 6981
CfiHfi Wash
SSMS OES
70.
3.
10. 15.
3.
4. 8.
<0.5
<0.2
<2.
<1. 1.
2.
<10.
10. 8.
4.
1.
700. 380.
10.
15.
3.
10.
2.
SSMS
<0.
700.
200.
2,500.
1,500.
<3.
10.
£10.
600.
si.
5.
<5.
<2.
5,000.
--
Ele-
ment
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Th
U
G 000 6982
!fiHp,Wash Crushed
OES SSMS Chem
1 0.04 (a)
(a)
(a)
2,000. 6,980.(b)
2,000. 6,400.(b)
3.
10.
10.
600.
£1.
5.
<2 .
<1.
4,000. 2,000.
-- _ ~ -.-
G 000 6981
CfiHf, Wash
SSMS
<2.
<3_
<1.
<3.
<0.6
<0.5
<0.2
<1.
<0.6
<1.
<0.6
2.
<0.6
<1.
<0.6
<1.
<0.4
<0.2
<1.
(a) Too high in blank to make estimate.
(b) On residue after C.H, extraction.
o b
-------
A-13
TABLE A-10. ANALYSIS OF AIR PARTICULATE ON GLASS - ST. LOUIS
(Nanograms/M^)
G 000 6985
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te .
I
Hg
Tl
Pb
Bi
Ele-
ment
Li
B
F
Na
Mg
Al
Si
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni '
Cu
Zn
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
C^HA Wash
SSMS
0.2
200.
200.
6,000.
1,500.
3.
50.
10.
200.
6.
3.
<1.
<2.
100.
3.
G 000
OES
0.1
-- i
;
Sample Designation
G 000 6986
Crushed CfiHfi Wash Crushed
SSMS
(a)
(a)
(a)
6,000.
Chem SSMS OES SSMS Chem
0.3 0.1 (a)
<400.(b) 200. -- (a)
- 100. - (a)
8,700.(b> 500. -- 500. 6,.290.(b)
1,500. 13,200. (b) 500. -- 500. 15, 300. (b)
--
--
--
--
--
--
--
--
560.
--
Sample
6985
C6H6 Wash
SSMS
5.
30.
200.
3,000.
400.
3,000.
5,000.
3,000.
10.000.
1.
200.
3.
30.
100.
2,000.
3.
30.
1,000.
600.
3.
5.
10.
2.
5.
0.3
3.
<0.2
<0.2
<1.
6.
OES
_
30.
t
800.
560.
1,400.
4,000.
800.
4,000.
--
140.
3.
14.
30.
800.
1.
14.
300.
560.
--
--
--
--
--
.._
1.
--
--
--
2.
£3.
50.
5.
200.
6.
3.
<0.4
<0.2
400.
1.
Designation
Ele-
ment
Cd
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
4 Ir
Pt
Au
Th
U
1. 1.
5. 5.
2. 2.
100. -- 100.
so. 3 -- SO. 3
1. -- 1.
<2. -- <1.
SO. 5 -- SO. 5
500. 600. 300.
-- -_ ^ - _ __ __
G 000 6985
CfiHfi Wash
SSMS OES
3.
<2.
60. 20.
5.
1.
100. 50.
2.
2.
0.7
2.
<0.6
<2.
<0.3
<0.1
<0.5
<1.
<0.1
<0.1
<0.5
<0.1
<0.3
<2.
SO. 3
<0.2
<0.3
<0.4
<0.2
<0.2
<1.
<0.5
(a;Too hign in bTank to make estimate.
(b) On residue after C(,H(, extraction.
-------
A-14
TABLE A-11. ANALYSIS OF AIR PARTICIPATE ON GLASS - WASHINGTON
(Nanograms/M )
Sample Designation
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
Tl
Pb
Bi
Ele-
ment
Li
B
Na
Mg
Al
Si
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ge
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
CfiHfi
SSMS
0.1
500.
100.
7000.
1000.
3.
50.
10.
300.
so. 6
10.
<1.
<2.
2000.
5.
G 000
G 000
Wash
OES
0.2
--
--
--
--
--
--
--
--
--
1200.
--
Sample
6990
C^HA Wash .
SSMS
4.
10.
5000.
2000.
1000.
6000.
4000.
4000.
<2.
200.
200.
20.
100.
2000.
4.
100.
400.
500.
5.
4.
4.
1.
4.
<0.6
2.
<4.
<0.6
<3.
<1.
OES
25.
900.
900.
2000.
8000.
1400.
2000.
--
200.
200.
14.
45.
900.
9.
100.
360.
360.
--
--
-_
9.
--
2.
--
--
--
1.
6990
SSMS
__
(a)
(a)
7000.
300.
S3.
20.
10.
100.
=£0.
4.
<1.
<0.
200.
1.
Crushed
Chem
...
--
--
6760. (b)
1670. (b)
--
--
6
--
5
--
--
G 000 6989
CgHg Wash Crushed
SSMS OES SSMS Chem
0.01 0.04
100. -- (a) <400.(b)
100. - (a) -
2000. -- 2000. 4400. (b>
300. -- 300. 270. (b)
1. 1.
10. -- 10.
£2, 5.
200. -- 300.
SO. 6 -- SQ. 6
3. -- 3.
S2. <0.5
<0.5 -- <0.2
100. 1500. 1000.
--
Designation
Ele-
ment
Cd
In
Sn
Sb
Cs
Ba
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Th
U
G 000 6990
C^HA Wash
SSMS OES
-- _ _
<1.
30. 10.
4.
<0.1
200. 90.
4.
6.
0.6
<2.
si.
<1.
<1.
<0.2
<0.6
<1.
<0.3
<0.3
<0.3
<0.2
<0.5
<1.
<1.
<0.5
<1.
<0.5
<1.
<1.
<4.
<4.
(a) Too high in blank to make estimate.
(b) On residue after CgHg extraction.
-------
A-15
TABLE A-12. ANALYSIS OF AIR PARTICULATE ON GLASS - CHICAGO
3
(Nanograms/M )
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
Tl
Pb
Bi
G 000 6979
SSMS Chem
(b) -- ' ^
(b) <400.(c)
100.
3,000.
3,000. 10,690.(c)
10.
100.
£5. -- .
700.
£0.2
5.
<1.
<0.6
5,000.
1.
(a)
Sample Designation
G 906 280
SSMS Chem
(b)
(b) 940. (c)
100.
3,000. 7,000.(c)
500. 9,870.(c)
20.
100.
£10.
500.
£0.6
4.
£0.5
£0.5
4,000.
4.
G
SSMS
(b)
(b)
300.
1,000.
2,000.
(a)
70.
£3.
300.
<0.
1.
<1.
<0.
2,000.
0.
686 900
Chem
<400.
__
__
7,930.
--
--
--
--
6
--
--
3
__
6
(c)
(c)
(a) Samples were crushed.
(b) Too in blank to make estimate.
(c)
On residue after C,H, extraction.
b fa
-------
A-16
TABLE A-13.
ANALYSIS OF AIR PARTICULATE ON
GLASS - PHILADELPHIA
3
(Nanograms/M )
(a)
Sample Designation
Ele-
ment
Be
F
P
S
Cl
Ga
As
Se
Br
Te
I
Hg
Tl
Pb
Bi
G 000 6967
SSMS Chem
(b)
(b) <400.(c)
100.
1500.
150. 680. (c)
(a)
(a)
£10.
500.
<1.
5.
<2.
£l.
3000.
4.
G
SSMS
(b)
(b)
30.
2500.
150.
(a)
10.
^5.
150.
<0.3
1.
<0.5
<0.3
1000.
0.2
000 6968
Chem
<
<400.
__
5200.
190.
--
--
--
--
--
--
--
--
--
(c)
(c)
(c)
(a) Samples were crushed.
(b) Too high in blank to make estimate.
(c) On residue after C,H, extraction.
b o
-------
TABLE A-14. ANALYSIS OF AIR PARTICULES ON GLASS FOR HYDROGEN, CARBON, AND NITROGEN
(Nanograms/M )
Sample
Designation
G 000 6978
G 000 6985
G 000 6989
G 000 6968
G 000 6981
G 906 280
City
Cincinnati
St. Louis
Washington
Philadelphia
Denver
Chicago
Hydrogen
3,100.
7,370.
2,950.
4,110.
4,910.
11,600.
As Received
Carbon
30,200.
62,000.
27,800.
30,500.
44,000.
111,000.
Nitrogen
2,760.
6,020.
2,390.
4,540.
2,490.
9,730.
Benzene
Hydrogen
1,610.
3,320.
1,820.
2,190.
2,780.
4,710.
Insoluble
Carbon
16,900.
28,400.
17,300.
15,300.
30,500.
50,100.
Phase
Nitrogen
2,430.
4,620.
2,120.
3,050.
2,850.
7,830.
>
I
-------
A-18
Discussion of Data. The data in the tables should be Self-explanatory. There are no ready
explanations for the wide variations in some of the values by the various techniques. Synthetic standards
were made and run for each method except the mass spcctrographic. Where spreads occurred the original
data were rcexamined for obvious errors, and a few errors were spotted and corrected. On the positive
side, a large number of the values agree better than the estimated accuracy of the method. This
probably means that the stated accuracies for the techniques are conservative. High concentration
elements are not easily determined by mass spectrography because the isotopic lines, especially for
monoisotopic elements, are too heavy to read accurately. Therefore, in those instances where the SSMS
data do not agree with other values, the SSMS results should be ignored.
On the basis of experience and intuition, the expected ranking of accuracy for each technique and
method is roughly in this or'der:
Chemical and XRF
Optical emission on Millipore
Mass spectrography on ashed Millipore
Mass spectrography on C6Hg Wash of Millipore
Mass spectrography on C^H^ Wash of glass
Optical emission on glass
Mass spectrography on crushed (ground) glass.
If these data are to be published later as an HEW document, it might be best to pick a single value
for each element in each filter rather than to give cross-check data. The thrust of such a publication
should be the presentation of values, not a comparison of techniques.
Light (Optical) and Electron Microscopy
Specimen Preparation
Light Microscopy. In the case of light microscopy, benzene extraction was carried out in a series of
petri dishes containing copper screen platforms supported by bent glass rods. The level of benzene in
each dish was adjusted so that the holes in the screen were filled with benzene. A piece of lens tissue
was numbered with the sample number and a piece of membrane filter bearing the collected particles
was placed particle-side-up on the lens tissue and together they were placed on the screen platform in
the petri dish, covered, and allowed to remain 2 hours. Extraction was carried out for 2 hours in each
of three petri dishes.
One of the specimens for light microscopy was prepared by scraping particles off the membrane
filters onto microscope slides and dispersing the particles in balsam beneath a coverslip. The particles
were too heavily deposited on the filter to examine directly. Even in these diluted preparations, the
relative abundance of particles too small to be resolved by light microscopy was so high that many of
the larger particles were not clearly visible. To avoid thin masking by the smaller particles, centrifugation
was employed to separate and concentrate the larger particles to make specimen preparations for
photomicrography. All the photomicrographs in this report were made of these coarse particle fractions.
Electron Microscopy. Benzene extraction of the samples prior to electron microscopy was done in a
manner different from that for light microscopy, primarily because specimen preparation for electron
microscopy involved suspending the collected particles in a liquid and redepositing them on another
Millipore filter. The redeposition was done to obtain a more thinly dispersed preparation which could be
examined electron microscopically. The liquid chosen to suspend the particles was benzene since
benzene-extraction was desired and benzene does not attack the Millipore filter. The following steps
were involved in specimen preparation for electron microscopy:
-------
A-19
(1) Glassware (beakers, filtering apparatus, etc.) was cleaned with aqua regia, rinsed with
deionized water, dried, and finally rinsed with ben/cne.
(2) The collection filter was cut into a square 0.5 x 0.5 cm which was then cut in half to
result in an area of 0.125 cm2.
(3) This filter area was placed in 20 ml of benzene and treated ullrasonically to remove
particles from the filter and to suspend them in benzene.
(4) While the particles were kept in suspension by ultrasonification, the benzene was
aspirated from the container and filtered through a Millipore filter area 17 mm in
diameter.
(5) After the filter was dry, carbon was vapor deposited over the particles and the Millipore
filter was dissolved to leave a carbon film holding the particles.
(6) The carbon film and particles were picked up on an electron-microscope support grid and
examined in the electron microscope.
The ^electron micrographs shown in this report were made from the preceding type of preparation.
In addition to the images of the air-pollution particles, the electron micrographs show the replica of the
Millipore filter structure in the background.
Results of Microscopy
eraltherj:jir_e^ ^ollectedJn^ajl -six. cities (Washington,
Denver, CmcTnnaufcnTcagoVPhiladelphia, and St. Louis). These materials are: ilyasli, carbon,, black,
^^^^^S ^-f "Y~ ~~~~~* f _ j"^if~ -* f*i
quartz, and iron.rust. «tasft (particlAS-Cje^tedJauMfflfcu^UoiQj^
compositions, ranging from carbonaceous to^jiliceous, and to be the most
^ofJltfed sampte1f^lfF^iarMtW==oTTlyash particles ranges from approximately 15.0 ydown^to
submicron jriz,esj<0.2 JK. In addition, electron microscopy revealed particles down to 250A^rTrs~clcarly
demonstrates the effectiveness of 3-n pore-size membrane (Millipore) filters in trapping much smaller
particles than does the nominal pore size.
$b"of or~ carbon blacK is alsci. very__prevalentas a particulate product of combustion ^a
the deKmt"ioTfToT~Ttyash; however, it isTeTOh^nh'e^iain'e'dzstfuclure^haTapfwisGb'of'finely divided
carT5oTrT>lacTr"plIceT if in a unique category. It is found" in' large quantities in all samples and, because of
various origins and large surface area, may carry very valuable chemical information a^J.o_ajr_pplliitants,
gaseous as well as particulat^imj^e^othe collection
"
Quartz is not nearly as prevalent in air samples as are flyash and soot, but does comprise a
significant fraction which is markedly greater in the Denver sample; consequently, the ratio of quartz to
carbon black is also greater. The observed absolute quantity of carbon black per cubic meter is less in
the Denver samples, but the elemental carbon analysis is quite high. There are other crystalline
particulates, in addition to quartz, present in all samples. It is anticipated that some of these will be
identified with the aid of X-ray diffraction and the electron microprobe during the new contract period.
Very few insect or plant fragments were found in any of the samples studied. This is probably
because the samples were collected during the winter.
Electron and light micrographs are included in this report. The electron micrographs are presented
in Figures 1 through 12, and the light micrographs are shown in Figures 13 through 24.
-------
A-32
Future Work
During the past contract period, little emphasis was placed on the identification of the various
species of airborne particulates; however, in the new contract period, particle identification will
constitute a major effort. It is planned to identify particles not only through recognition of
characteristic morphology observed by means of the light and electron microscopes, but also from
electron-probe and X-ray and electron diffraction data. The analyses will be performed on specially
prepared specimen, designed to facilitate the correlation of data from all possible sources in an effort to
generate more complete information on each particulate species. This may aid in singling out the
contributing sources to air pollution within a particular area.
In general there are two planned approaches to specimen preparation; one involves the analysis of
single particles, and the other involves the analysis of separated particle fractions. Single-particle analyses
will be made on specimen preparations suited to locating the same particle for analysis by microscopy,
electron diffraction, and the electron probe. Also attempts will be made to devise and employ
procedures to separate particle collections into fractions according to species and to subject portions of
each fraction to various analytical techniques to yield more detailed analytical data. .
Electron Microprobe
This technique logically follows elemental analysis and precedes structure identification techniques.
Knowledge of which elements to seek saves probe time; the probe data on elemental associations help,
for example, in XRD identification of compounds.
In the present work, the probe was used to examine Millipore filters as received. They were
sufficiently conductive so as not to require coating. Figures 25 through 80 show the results obtained by
examining areas of the filter for selected elements including Pb, Br, Zn, Cu, Fe, Cl, S, and P. In the
Denver sample lanthanum and cerium were also sought because these elements had been found in fairly
high amounts by SSMS. One area of lanthanum and cerium was located. It is observed that the lead is
present not as the chloride or bromide but as the sulfate, in some cities. In St. Louis there seems to be
some association of bromine with lead. Note also the areas of vanadium in the Washington sample.
Benzene Extraction
Benzene extractions of Millipore filters were accomplished as described under Specimen Preparation
in the section on Light and Electron Microscopy. The benzene-soluble phase was examined to determine
what, if any, elements other than C, H, 0, and N are being overlooked in the procedure of benzene
extraction prior to the elemental analysis. Two techniques were employed.
First, high-resolution mass spectra were obtained of the benzene extracts from Chicago, St. Louis,
Denver, and Washington. Low-resolution mass spectra were obtained of these samples and of those from
Cincinnati and Philadelphia.
The benzene extracts were introduced into the mass spectrometer via the heated-inlet system. A
sufficient amount of sample was used to produce a source pressure of 1 x 1(>6 ton. None of the
samples showed evidence of organometallic compounds of volatility similar to the solvent, although the
methods employed do not exclude the presence of trace compounds less volatile than benzene.
A computer analysis of one of the high-resolution spectra is shown in Figure 81. The many "NO
SATISFACTORY FIT" messages appearing on the leading edge of the m/e77 peak resulted from a
multiplier cascade occurring, and do not represent actual species present in the spectrum.
-------
A-47
BMTtLLE MEMORIAL INSTITUTE
MASS iPECTRQ«£Ih!y L490«*TO»Y
VCRSIU* 3 0»/t>e/7U COM*"J
SAMPLE MflOOM* C«(C*liO. mALTtR
06/12//0* RU*J N(J. j
SOUBCt te*P6»*TU8E- 300 C. "ULIJPLtErf SGTTIN^-O.O '
SAMPLt JNTfiOn.KEl1 VJ* itMt'U INLEtt TK«.DfcRfiTUfIE 209 C,
IONI.UNG vOLTtGt- 70 V- *CCtLCMAM«G VOtMGs- 8 fU.
NOMINAL qcSOLVlNG Pl)«ta 10 X
BACKGROUND HAS NOT Hf.tN $lMTW*CTEu F«*OH til5 SPECTRUM
CALCULATION
COMPUTE* JOS U
MONiru* CURHCNT-* 58. MAXIMUM MONITOR CU«R£KT-« 60
IRR'JR N 0 F
15. g
MEASURED PEL. INTENSITY
C(I3)
13.0023 0*
IS. 0200
IB. 0092
18.0106
25.0096
26.0167 1
27.02*7 1
27.9955
20.0320
36.0007
37.5129
3B.0170 3
38.5198
J9.0I3S
39.5266
0.02B3
0.0320
2.0*71
t 6.9931
a. 0005
50.0059
SO. 0157 11
SI.OOSl
SI. 0233 1*
SI. 0377
S2.0I4*
52.0316 18
33.03*7
S5.055Z
59.9985
61.006*
62.0161
11
OH
n*
50 .03
25 .03
13
G4
23
9*
50 .12
35
05
?3
23
II
G6
0*
20
1*
42 .52
06 '
70 .65
06
06
3* .Hi
«4 .10
09
05
35
*2
CL e«
CAUCULAlCO
lri.0106
25.00'e
26.0156
27.0235
27*49*9
2*. 0313
36.0000
75.0?33
3M.OIS6
77.0397
Ix.0265
74.0512
10.05**:
0.03I3
*2.0«69
8.0000
50.0156
SI.023S
52,0167
52.0313
53.03*7
55.05*11
60.0000
61.0078
62.0156
! 5
ERROR
(PPM)
.0
69.3
2.3
««.2
19.3
25.4
20.8
3*. 6
'
17.6
*S
10.6
.4
2.5
13.6
6.2
1.6
7.3
24.7
23. a
7.0
f SI i>
FORMULA
HZ 0
C2 H
C2 M2
C2 H3
C U
C2 H*
C3
C3 H
(OUUWLY ICNIZgul
C3-H2
IOOUULY IONIZED)
(OOUtiLY 10N1ZE01
C3 M3
(OOUtiLY IONIZED)
[UUUeiY IONI2EU)
C3 n*
C3 H6
C4
C* H2
C* H3
C3 H2 N
C* H*
C3 CI13) Ht
C* «7
CS
C5 M
C5 H2
ClUl MAIIM
6«
NO SAIISFACIOHY FIT
NU SATISFACTORY FIT
NO SATISFACTORY Fll
NU SATISFACTORY FIT
NO SATISFACTORY FIT
NO SATISFACTORY FIT
63.
64.
»e.
68.
V68.
72.
7*.
T5.
76.
76.
76.
T6.
76.
J6.
f76.
'76.
76.
76.
76.
76.
76.
76.
76,
76.
76.
76.
77.
*,:
77.
77.
77.
78.
78,
78.
78,
78.
78.
78.
79.
'
80.
VI.
O119.
127.
128.
131.
131.
01*2.
181.
»1V«.
«21«.
«!|8.
0233
0251
0617
95H1
4765
0006
0159
0233
OOS2
01*5
OIB7
0316
0*68
0629
094*
1265
150*
1673
1749
1D96
339D
557
518S
6683
794*
9*62
0084
0230
ni97
0602
0691
7037
GOS6
0130
0179
0265
0467
0902
1161
0311
0512
OS42
0576
9928
0343
0620
024\
0096
9945
0167
9972
9992
9266
2.25
.15
.05
04
.23
21
4.32
1.75
. 13
.04
.04
4.40
.34
.09
.10
.06
.07
06
.06
. 3
0626
0000
.0156
.0235
0061
01U7
.0313
.0637
0391
07|5
0106
.0106
0469
.0296
.0503
.0541
0626
.015*
0007
2.0
27,4
34.*
13.8
8.2
3.6
2.5
27.1
.6
3.5
9.5
7.*
30.4
2*. 6
31.6
2.7
19,2
11.3
1.3
5.0
i.a
7,1
cs
c«
H*
C5
C6
C6
C6
C*
C5
C6
C?-
C6
C2
CS
CS
C6
C*
C5
Cll
CIO
Cll
C14
H3
CI13I H3
N2 U2
HH
H2
M3
N2
H2 N
H*
MB Hi 0
M5
«9 N2 0
HZ 0
HZ 0
H6
H3 N2
CII3I H6
31 H7 N2 02
HB
H3 N OJ
H X 02
NO
NkJ
NO
NU
NU
NO
NO
NU
NO
NO
NO
NO
NO
NU
NO
NU
NO
NO
NO
NU
NO
Nli
NO
NO
NO
NO
NU
NU
NU
NO
NU
NU
*A'l5FACIOUr
SATISFACTORY
SATISFACTORY
SAUSFACTOHV
SATIS ACIOMY
SATIS ACTOHY
SATIS ACTOKY
SATIS ACTOHY
SATIS ACTOHY
SATIS ACfOftY
SATIS ACTOKY
SATIS AC10MV
SATIS AClOuv
SA11S ACTORV
SATIS ACTORY
SATIS ACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATISFACTORY
SATlSFACTOHT
SATISFACTORY
FIT
FIT
FIT
FIT
FlTI
Fll
IT
IT
T
I
T
T
T
IT
IT
IT
IT
III
FIT
FIT
FIT
Fit
FIT
FIT
FIT
FIT
Fll
FIT
FIT
Fll
FIT
rii
CMiltipK.rcA6u.lA,
ach».l
FIGURE 81.
-------
A-48
Second, the extract was slowly evaporated at room temperature on graphite. The mixture was
briquetted and sparked as a normal sample. The data obtained are shown in Table A-15.
With the exception of bromine and iodine, it is clear that the amounts of the elements found in
the extracted fraction are quite small compared with the total amounts in the samples. The presence of
bromine and iodine, on the other hand, suggests that these elements should be sought in the benzene
phase when a complete analysis is desired. If this work is repeated under the new contract, the benzene
extract should be concentrated by careful drying and analyzed again, using the high-resolution mass
spectrometer. The computer program should be set to accept bromine and iodine in its computations
this can be done very easily.
The amounts of benzene-soluble material on the glass filters are shown in Table A-16. If one
compares these data with those in Table A-14 (C, H, and N in as-received and in extracted samples), the
amount extracted (Table A-16) agrees quite well with the difference in carbon and hydrogen values in
Table A-14. (Unfortunately, owing to poor coordination, different filters were run for Denver, Chicago,
and St. Louis.)
X-Ray Diffraction
Although this effort is a part of the new contract, some preliminary XRD work was performed
under the present contract. The major emphasis was on the Denver air sample (M 000 412).
Considerable hand searching of the XRD files was done in order to positively identify the major
compounds present. In addition, computer searches of the data have produced tables of possible
compounds which could now be manually compared in order to provide positive identifications. An
example of the computer search is shown in Figure 82.
The hand searching of the data files for the Denver air sample has identified the major X-ray
diffractor to be SiC"2 (a-quartz). A probable minor constituent is^muscovite mica. The probable
compounds that have been selected by the computer search constitute many categories of similar
structures. Among these, the sulfates, silicates, alumino-silicates, carbonates, borates, and phosphates of
the metals found at 500 nanograms per cubic meter or higher predominate. No attempt was made to
search for each compound manually in order to prove its existence in the sample, since it appears that a
general indication of the types of structures present would be most useful at this time.
Only a partial manual search was performed on the Washington, D.C., sample (M 000 406). Again,
as in the Denver sample, the compound with the highest diffracting power was Si02 (ct-quartz). Since
the subtraction of the SiC>2 pattern from the diffraction data left only weak lines to work with, no
other work was done on this sample.
These preliminary results show that good sample-handling techniques combined with separations of
the material by several methods will give samples which can be identified and that many more
compounds will be found. This work will continue throughout the coming year.
Filters Examined
The filters, with the sample weights, air volumes, and sampling dates are listed in Table A-17. When
the volume was not known it was assumed to be 10,000 M^ for glass. It is not necessary to know
sample weights because the data are generated as weight of element per square centimeter and then
converted by the factor total area per total volume.
-------
A-49
TABLE A-15. ANALYSIS OF BENZENE-SOLUBLE FRACTION OF AIR PARTICIPATES
EXTRACTED FROM MILLIFORE FILTERS - SSMS DATA
3
(Nanograms/M )
Ele-
ment
Li
Be
Na
Mg
Al
Si
P
S
Cl
K
Ca
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
As
Br
Rb
Sr
Sn
I
Ba
Pb
Cincinnati
M 000 428
0.01
--
--
--
5.
7.
1.
3.
7.
5.
10.
0.2
0.3
3.
4.
0.6
--
3.
2.
0.2
10.
--
--
--
--
--
2.
St. Louis
M 000 408
0.02
0.006
20.
7.
10.
15.
1.
5.
15.
10.
20.
--
--
0.7
30.
--
--
3.
10.
4.
15.
0.5
1.
2.
2.
30.
10.
Sample Designation
Washington Denver
M 000 407 M 000 413
0.05
0.005
10.
__
7.
1. 0.7
3.
3.
5.
5.
20.
3.
__
__
30.
__
--
0
__
0.5
100. 3.
__
__
__
i -~
i.
1.
20.
Philadelphia
M 000 419
0.02
0.01
6.
--
10.
5.
1.
5.
7.
4.
50.
2.
--
--
0.7
--
0.7
5.
3.
0.5
15.
--
--
--
1.
--
6.
Chicago
M 000 414
0.004
--
2.
--
0.2
--
0.4
1.
3.
3.
--
__
--
__
0.2
__
--
0.2
0.2
0.2
10.
--
_..
--
0.2
--
1.
-------
A-50
TABLE A-16.
BENZENE-SOLUBLE PORTION EXTRACTED
FROM GLASS FILTERS
Sample
Designation
G 001
G 002
G 000 6966
G 000 6977
G 000 6978
G 000 6989
G 000 6990
G 000 6985
G 000 6986
G 000 6982
G 000 6979
G 000 6967
City
Cincinnati
Cincinnati
Cincinnati
Cincinnati
Cincinnati
Washington
Washington
St. Louis
St. Louis
Denver
Chicago
Philadelphia
C,H, Extract,
,,O D /,,J
Nanograms/M
17,500.
17,200.
32,700.
14,000.
14,000.
13,600.
17,700.
24,600.
13,900.
19,100.
14,400.
15,600.
-------
A-52
TABLE A-17. FILTER SAMPLES ANALYZED
G-0006977
G-0006978
G-001
G-002
G -0006966
M-000417
M-000416
M- 0004 05
M-428
G-0006981
G-0006982
M-000412
M-000413
G -0006 985
G-0006986
M-000408
M -000409
G-0006989
G-000699C
M-000407
M-000406
G-0006979
G-906280
G-686900
M-000418
M-000419
G-0006967
G-0006968
Philadelphia
G = Glass, M
------- |