Atmospheric EnvironmentVol. 27A,No. 15, pp. 2441 2444,1993. 0004-6981/93$6.00+0.

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Printed in Great Britain. © 1993PergamonPress Ltd

TECHNICAL NOTE

AN IMPROVED PROCEDURE FOR ANALYSIS OF PMi0 FILTERS BY X-

RAY POWDER DIFFRACTION

BRIANT L. DAVIS a n d H o N o CHEN

X-ray Diffraction Laboratory, South Dakota School of Mines and Technology, Rapid City,
SD 57701-3995, U.S.A.

(First received 2 February 1993 and in final form 8 June 1993)

Abstract--Speciation results from earlier methods of quantitative analysis of TSP, dichotomous, and PM lo
filters for compounds by XRD were often marginal to unacceptable because of very light loadings and the
interfering effects of substrate fibres in cases of ultrasonic extraction and concentration. A method for
analysis of very lightly loaded PM to filters has been developed, using ultrasonic particle stripping, X-ray
transmission of unloaded blank filters, substrate diffraction X-ray analysis, and mass absorption balance,
along with the usual X-ray diffraction scanning. Analysis of a set of filters having less than 105 #gm crn-2
sample load is used to illustrate the improved procedure.

Key word index: Atmospheric aerosols, X-ray diffraction.

1. INTRODUCTION AND BACKGROUND 2. DESCRIPTION OF THE NEW PROCEDURE

The X-ray reference intensity method (RIM) of X-ray pow-
der diffraction analysis is potentially a powerful procedure
for determination of species of atmospheric pollutants.
Speciation of ambient aerosols, combined with similar quan-
titation of source materials, can be used in source apportion-
ment (Johnson et al., 1984; Gorden et al., 1984; Davis, 1984a)
either alone or in combination with elemental data. The
major drawback of X-ray diffraction analysis is its relative
insensitivity to mass compared to X-ray fluorescence. Never-
theless, compounds are more diagnostic as signature compo-
nents than elements; for example the element calcium may
have many sources but CaSiO 3 has only two sources; a com-
ponent of portland cement, and as a rare mineral component
of metamorphic rocks.
In the Quail Roost study (Stevens and Pace, 1984;
Johnson et al., 1984) XRD analysis proved adequate to
determine the major components of the aerosol, but minor
components were undetected or unquantifiable, and
amorphous components could not be quantified because of
insufficient material for mass absorption analysis. In the
Quail Roost study loads of only 50-200 #g cm-2 were avail-
able on Teflon (PTFE) filters; such load levels are marginal
at best for quantitative XRD analysis.
In recent fugitive dust source apportionment studies (un-
published) of Whatman QMA "Quartz" PM l o filters, speci-
fic load levels of 100-300/~g cm - 2 on the original filter were
increased by ultrasonic extraction in methanol and the sus-
pension concentrated by liquid filtration onto 25-mm VM-1
filters for XRD analysis. The resulting specific masses of the
XRD sample "disk" were found to lie somewhere in the
range of 1000-5000 # g c m - 2, however, a significant
proportion of the sample consisted of glass fibres pulled
down from the filter during extraction. These loads provided
sufficient mass to permit evalution of minor clay components
(very weak diffracting materials), but only by rather inaccur-
ate and very tedious polarizing optical analysis of portions of
the composite sample could the amount of amorphous (car-
bonaceous) component be estimated. Ordinarily routine
XRT and SDIF analysis could not be performed on these
samples because of the glass fibre contamination.
Complete quantitative evaluation of both crystalline and
amorphous components of a filter load may be completed
providing the following conditions exist.
(a) Accurate tare and load weights are available for the
whole filter (assumed to be 8" by 10" [20.34 x 25.4 cm],
although the principle applies to any size filter).
(b) A blank filter is available for direct mass absorption
measurement of the glass material comprising the filter.
If these conditions exist then it is, in principle, possible to
ultrasonically remove the sample, along with contaminating
fibres of the filter substrate, and still be able to both correct
the intensitites for full quantitative analysis and complete
a mass absorption balance to determine the weight fractions
of one or (with additional optical information) two amor-
phous components in this sample.
The details of this procedure (except for the RIM analysis
which is summarized in Davis, 1984b, 1992) are presented here
in order that applications may be readily made to real samples.
Equations required in each step are noted as (A-l), etc., and are
stated in the Appendix. The procedure is accomplished ac-
cording to the following step-by-step instructions:
1. From two to four circles are cut from the blank filter for
either direct-beam transmission (equation (A-l)) or substrate
diffraction analysis (equation (A-2)). This provides the mass
absorption coefficient of the glass material of the filter (#o).
2. The loaded filter is cut into large (we suggest 6-8 cm)
circles and weighed (Mr... M,3 using a sensitive micro-
balance. The total filter area AT to be stripped so that
adequate specific mass can be concentrated onto a 2.5-ern
diameter load area can be estimated from the equation
Ar(cm 2) = 30exp [ --0.0024571] (#g cm- 2)
where AT/is the specific mass of the load over the ambient
fiter.
3. The cut circles are stripped (face down) in methanol for
about 2 rain. Longer stripping brings down more substrate
contamination and should be avoided. It is not necessary to
completely remove all ambient particles from the filter. Turn

2441
 2442 Technical Note

each filter upside down in the methanol for 15 s at the end of
the stripping to remove redeposited particles from the back
side.
4. The methanol suspension is passed through an
aspirator filtration system, with collection onto a 2.5-cm
membrane filter of tare weight Mf (Metricel VM-I is recom-
mended). The loaded filter is dried and weighed (Ms). With
a VM-1 filter area of 4.909 cmz and load coverage of 3.464
cm 2 for our cassette the specific masses ~ f and ~ , ~ (g
cm -z) for blank filter and loaded filter may be computed.
5. The stripped circles are dried and reweighed
(MI°... M°).
6. The reconcentrated VM-I load (with substrate fibre
contamination) is analysed by substrate diffraction to obtain
the composite (sample + glass) mass absorption ~ao) using
(equation {A-3)).
7. The composite sample is scanned in the usual manner
by X-ray diffraction,
8. Quantitative RIM analysis (equation (A-4)) or other
suitable method is applied to determine all crystalline com-
ponent weight fractions (Vii).
9. A mass absorption balance (equation (A-5)) is then
applied to determine the true (uncontaminated) sample mass
absorption coefficient (p.).
I0. From the calculated mass absorption coefficient
#Be obtained from the RIM analysis of crystalline compo-
nents combined with #a from step (9), a second mass absorp-
tion balance (equation (A-6)) is applied to determine the
amount of amorphous material (W.m) present and allow
rcnormalization of the original crystalline weight fraction
W~ to yield the final set W[.
The 10 steps presented above may, of course, be modified
in any manner necessary that will leave the analyst with the
desired end result. For example, X-ray transmission may be
used in place of substrate diffraction to determine #no, pro-
viding that a device to hold small 2.5-cm loaded filters is
available. Our experience in attempting to suspend as
an aerosol the dried methanol suspension stripped from
the original filters is not good; carbonaceous matter
is sufficiently soluble so that self adhesion of particles pre-
cludes use of aerosol suspension as a means for final sample
preparation.
3. EXPERIMENTAL METHODS AND RESULTS FOR A PMto
FILTER SET
Three Whatman QMA "quartz" PMIo filters were
weighed and loaded at an outdoor site in the western U.S.
The original filter and loaded filter data are presented in
Table 1. X-ray diffraction scans were completed with a Phil-
lips Type 1205 generator, high-angle goniometer with scintil-
lation detector, graphite crystal monochromator, automatic
divergence slits, and circular sample spinner. The original
filter circles were stripped with a Branson B-220H ultrasonic
cleaner bath and filters were weighed on a Mettler H51AR
electronic balance readable to 10 #g. Extremely light load-
ings make the measurement of mass absorption by direct-
beam X-ray transmission subject to large experimental
errors. Therefore the above procedure makes use of substrate
diffraction (SDIF) anaysis of the concentrated sample com-
bined with mass absorption balance to determine #,.

1200 EME$0638 .02/4 $/D 20000 IMX

M = MU$COUITF./ILLITE
110o
Q 0 = OLIGOCLI:ISE
I~ = QUARTZ
1000,
C = CRLCITE

900,

800.

¢0
tQ 7 0 0 •

600
0
f ORIGIHRL PH-IO
500
C
H Q HO 0 O
400

.. o IAI DO
300

o HO
200

"'-ENHANCED LORD 01t U!t-1

100 I I I I I i I I I I I
1::] 2b 21 22 23 24 25 26 27 28 29 30 31
l - e n e s 0 6 38, da t 2 Theta

Fig. 1. Diffractometer trace of original PMlo filter and trace of VM-1 filter loaded with concentrated
sample from ultrasonic extraction. Copper Ka radiation scanned at 0.02°C 20 step, and 4 s dwell.
 Technical Note 2443

Table 1. Filter load data for three PM10 samples

Ambient conc. Tare wt Load wt Specific mass

Filter ID (#g m - 3) (g) (g) (/tg c m - 2)

SP1 13.9 4.2798 4.3008 52.3

SP2 18.9 4.3107 4.3405 73.0
SM 1 27.6 4.3318 4.3734 102.9

Table 2. Measured and calculated parameters fr three PMlo samples

Step, parameter SP SP2 SP3

(1),/a C (cm 2 g- 1) 36.26 36.26 36.26

(2), A T (cm 2) 176.7 220.9 220.9
M 1, M 2. . . . M n (g) 0.3616,0.3608 0.3733,0.3706 0.3774,0.3756
0.3703,0.3689 0.3731,0.3732 0.3747,0.3741
0.3728 0.3738
(3,4), Mf~g), ~/f(g cm -2 ) 0.00680,0.001385 0.00685,0.001395 0.00707,0.001440
MB(g), MBG(gcm -z) 0.01845,0.003363 0.02520,0.005297 0.03244,0.007324
(5), M 01, M o2. . . . M°(g) 0.3574,0.3566 0.3668,0.3654 0.3701,0.3676
0.3656, 0.3651 0.3676, 0.3651 0.3677, 0.3666
0.3666 0.3660
(6),/~B~ (cm 2 g- 1) 38.25 37.72 41.81
(7, 8), W~(Wt fraction)
Quartz 0.278 0.214 0.270
Calcite 0.418 0.254 0.384
Oligoclase 0.140 0.153 0.139
M uscovite/illite 0.164 0.200 0.146
Biotite -- 0.054 0.008
Kaolinite -- 0.125 0.052
(9),/~(cm 2 g- 1) 39.9 39. I 45.5
(10), Wbc, #b~(cm 2 g- 1) 0.675, 55.35 0.715, 52.31 0.821, 54.06
w',
Quartz 0.188(0.035) 0.152(0.027) 0.222(0.046)
Calcite 0.282 (0.058) 0.181 (0.047) 0.316(0.075)
Oligoclase 0.095 (0.021 ) 0.109 (0.020) 0.114 (0.024)
M uscovite/illite 0.110(0.028) 0.143 (0.029) 0.120(0.028)
Biotite -- 0.039 (0.016) 0.007 (0.004)
Kaolinite -- 0.090(0.027) 0.042(0.015)
Wa~ = Organic matter 0.325(0.101) 0.285(0.123) 0.179(0.149)

These load levels are generally below even that suitable for
analysis on P T F E membrane filters (Davis and Johnson,
1982). Therefore the stripping/reconcentration procedure
outlined above was used for these analyses. Figure 1 presents
a diffractometer trace of the original unconcentrated filter
sample (cut directly from the filter) and the reloaded VM-1
filter. Only the two strongest component peaks for quartz
and calcite are recognizable for the unconcentrated sample.
After completing the analysis of SP1 the decision was made
to increase the number of 7.5-cm diameter circles stripped
fom 4 to 5. Otherwise the procedure for the analyses is
identical. Table 2 presents the results of the procedure listed
according to the 10 steps enumerated above. The mass
absorption coefficient of the composite sample (/~BG) ob-
tained in step (6) was used along with specific mass data to
correct the integrated intensities needed in steps (7 and 8)
according to our earlier published procedures (Davis and
Johnson, 1982, equation (3)). Steps (7 and 8) provide a "pro-
visional" analysis, using equation (A-4), resulting in the de-
termination of weight fractions of all crystalline components
that could be identified in the concentrated sample. The final
set of weight fractions, which includes values for both cry-
stalline and amorphous components, were obtained from
a second application of equation (A-4) combined with the
mass absorption balance of equation (A-6). The mass ab-
sorption balance results may be verified by applying the raw
data of Tables 1 and 2 to the equations in Appendix A. The
advantage gained by ultrasonic concentration is evident
from Fig. 1 and in the results of Table 2; only the weight
fractions for calcite and quartz could have been determined
from the original filter diffraction trace, and for SPI the
amount of sample was too small with just four stripped
circles for the biotite and kaolinite peaks to be observed.
With five circles and a larger ~/B for SP2 and SM1 a satisfac-
tory quantitative evaluation of all significant components
was achieved. There is no reason to suspect that the various
components are being ultrasonically stripped at different
efficiencies.
It should also be pointed out that X-ray mass absorption
analysis cannot distinguish between "organic" and graphite
carbon; the terms "organic matter" or "carbonaceous mat-
ter" are used here and in other papers to describe any
combination of organically derived or combustion derived
carbon-bearing material; the mass absorption coefficient for
this material is set of 6 cm 2 g-1 for CuK, radiation (the
average value of coal - - pure carbon is 4.2) to reflect a var-
iety of oxygenated and nitrogen-bearing compounds in-
cluded in most forms of carbonaceous matter.
2444 Technical Note
4. MAJORSOURCES OF UNCERTAINTY
The Reference Intensity Method (RIM) of quantitative
analysis has a complete variance error propagation algo-
rithm incorporated into the processing program (Davis,
1981a). These errors are presented for the final weight frac-
tions W~ in parentheses in Table 2. Aside from these para-
meters, additional uncertainty may result from the presence
of more than one amorphous component, or because the
mass absorption coefficient of the amorphous component is
not known accurately. Mixtures of hydrous iron or manga-
nese oxides can create this undesirable situation, but such
occurrences in ambient aerosols would be uncommon. How-
ever, carbonaceous matter and silicious slag glass, fly ash, or
limonite may be present together in many industrial environ-
ments (Davis, 1981b); in these cases additional optical ana-
lysis by polarized light microscopy would be needed to
resolve the amorphous component contributions. The
weight data of Table 2 also provides an indication of the
lateral homogeniety of the PM~o load distribution. The
means and standard deviations of the PMIo specific masses
for the 7.5-cm stripped circles for SPI, SP2, and SM1 are
found to be 96.55 (7.04), 142.32 (25.84), and 170.59 (9.63)
/.tg cm 2, respectively. The homogeniety of SP1 and SM1 are
quite good; the set of stripped circles represent about two-
thirds of the 8 x 10 inch original PMlo filter area.
This complete procedure has been tested only on PMlo
"quartz" filters; however, we have extracted for routine
quantitative analysis particulate matter imbedded in high-
volume filters which were known to consist of borosilicate
glass having mass absorption of about 48-50 cm 2 g-t. The
results of the extraction process, including glass fiber con-
tamination levels, appear to be no different than for "quartz"
microfiber filters. Therefore we believe that this technique
should be applicable to the high-volume filter as well.
REFERENCES
Davis B. L. (1981a) A study of the errors in X-ray quantitat-
ive analysis procedures for aerosols collected on filter
media. Atmospheric Environment 15, 291-296.
Davis B. L. (1981b) Quantitative analysis of crystalline and
amorphous airborne particulates in the Provo-Orem vi-
cinity, Utah. Atmospheric Environment 15, 613-618.
Davis B. L. (1984a) X-ray diffraction analysis and source
apportionment of Denver aerosol. Atmospheric Environ-
merit 18, 2197-2208.
Davis B. L. (1984b) Reference intensity quantitative analysis
using thin-.layer aerosol samples. Adv. X-ray Anal. 27,
339-348.
Davis B. L. (1992) Quantitative phase analysis with reference
intensity ratios. Accuracy in Powder Diffraction II, NIST
Special Publication 846, pp. 7-16.
Davis B. L. and Johnson L. R. (1982) On the use of various
filter substrates for quantitative particulate analysis by
X-ray diffraction. Atmospheric Environment 16, 273-282.
Davis B. L. and Johnson L. R. (1987) The use of mass
absorption in quantitative X-ray diffraction analysis. Adv.
X-ray Anal. 30, 333-342.
Gorden G. E., Pierson W. R., Daisey J. M., Lioy P. J.,
Cooper J. A., Watson J. G. Jr and Cass G. R. (1984)
Considerations for design of source apportionment stud-
ies. Atmospheric Environment 18, 1567-1582.
Johnson D. L., Davis B. L., Dzubay T. G., Hasan H.,
Crutcher E. R., Courtney W. J., Jaklevic J. M., Thompson
A. C. and Hopke P. K. (1984) Chemical and physical
analysis of Houston aerosol for interlaboratory compari-
son of source apportionment procedures. Atmospheric En-
vironment 18, 1539-1533.
Stevens R. K. and Pace T. G. (1984) Overview of the math-
ematical and empirical receptor models workshop (Quail
Roost II). Atmospheric Environment 18, 1499-1506.
APPENDIX A
Analytical equations for mass absorption balance
(From Davis, 1984b; Davis and Johnson, 1987)
1 [- lf-]
(XRT). (A-I)
#t is the mass absorption coefficient of the blank filter (glass),
~/r is the specific mass of the filter, If is the transmitted, direct
X-ray beam flux through the filter, and lo is the unattenuated
direct beam flux.
N s = - 1 ~ Fsin0gn/~ ] (SIDF). (A-2)
2MfL l~d
#fs is the mass absorption coefficient of the blank filter
determined by substrate diffraction (SDIF) where Mt is the
specific mass of the filter, and Ifs and 1~o are intensities
diffracted from the substrate material at angle 20 through the
filter, and without the filter in place, respectively.
1 r l.a , . 'l
#BG=-2---~-~lsinO¢n--+2Mfgfl (SDIF). (A-3)
M.~ L l~o J
#Be is the mass absorption coefficient of the composite
sample plus substrate fibres (glass), MBo is the specific mass
of the composite sample, and l,Gs and l,o are the intensities
diffracted from the substrate material at angle 20 through
the loaded filter, and without the loaded filter in place,
respectively, The filter effect is taken into account in this
equation by the second term within the square brackets.
#t may be replaced by /zts since it is the same quantity
measured by different techniques.
Fk. l.~-]-1
W j - - / ~ x-' l . (A-4)
kl~ k,J
Wi is the weight fraction of the jth component having
reference intensity ratio ki and diffracting intensity lT in
a sample of i components with reference intensity ratios
k~and intensities l~. This equation is self-normalizing so that
all the W~ sum to unity.
/ZBo= W~#f + WB#~ . (A-5)
#Bo is the mass absorption coefficient of the composite
sample and glass fibre contaminant, Wo is the weight frac-
tion of the glass material comprising the filter stripped by
ultrasonic cavitation, and Wa is the weight fraction of pure
sample material in the composite. #B is the quantity to be
determined in this process.
[~B=~,Wi]~i-~Wam#a m . (A-6)
Wi is the weight fraction of crystalline phases in the initial
RIM analysis; the ratios of these weight fractions are correct
regardless of the presence of amorphous or unidentified
other phases in the sample and hence can be used to compute
the true mass absorption coefficient of the crystalline fraction
of the sample,/zBo which is equivalent to the term ~Wdz t in
this equation./h are the mass absorption coefficients of the
crystalline components of the sample which must be meas-
ured or calculated prior to use this equation. W,m is the
weight fraction of amorphous material in the sample (not
including filter matrix material which at this step has been
eliminated from the computations) to be determined, and
#am is its mass absorption coefficient which must be known
beforehand. Wsc (Table 2) is the crystalline weight fraction of
the original sample and is numerically equal t o 1 - W~m.