1. B. J. Scheiner, R. E. Lindstrom, D. E. Shanks, and T. A.

Henrie, U. S. Bur. Mines Tech. Prog. Rep. 26 June (1970).

2. W. W. Whitton, Calif. J. Tech. 4, 35 (1904).
3. C. M. Bouton and L. H. Duschak, U. S. Bur. Mines Tech.
Paper 227, 5 (1920).
4. Lemaire Instruments Brochure, type SI mercury detector,
1965, Lemaire Instruments, 3800 N. Virginia St., Reno, Nev.
5. W. W. Vaughn, Geol. Survey Circ. 540, U. S. Geological
Survey (1967).
6. R. Hatch and W. T. Ott, Anal. Chem. 4, 2085 (1968).
7. O. T. Joensuu, Appl. Spectrosc. 25, 526 (1971).
8. Reference to specific maker or models of equipment is made
for identification only and does not imply endorsement by
the Bureau of Mines.

9. H. A. Liebhafsky, H. G. Pfeiffer, E. H. Winslow, and P. D.

Zemany, X-Ray Absorption and Emission in Analytical
Chemistry (Wiley, New York, 1960), Chaps. 6-8.
10. F. W. Lytle, K. R. Stever, and H. H. Heady, "X-Ray
Spectroscopy of Rare Earth Elements," Proc. Intern. Conf.
Peaceful Uses At. Energy 2nd, Geneva, 1958 (1958), p. 2
and Fig. 1.
11. D. C. Manning, At. Absorp. Newslett. 9, 97 (1970).
12. W. W. Vaughn and J. H. McCarthy, Jr., Geol. Survey
Professional Paper 501-D, U. S. Geol. Survey Res., D123
(1964).
13. R. Kenneston, Mineral Infor. Service, Calif. Div. Mines
Geol. 22, 179 (1969).

X-Ray Fluorescence Determination of Chlorine

in Standard Silicate Rocks::'
Brent P. Fabbi and Laureano F. Espos
U. S. Geological Survey, Menlo Park, California 94025
(Received 23 September 1971; revision received 4 November 1971)

Chlorine has been determined in seventeen international silicate rock standards by x-ray fluorescence analysis, yielding values which compare well with published values. The detection limit for
the method is about 10 ppm. Sources of chlorine contamination are considered.
INDEX HEADINGS: X-ray fluorescence; Analytical method; Determination of chlorine in silicate
rocks.

INTRODUCTION
The relative abundance of chlorine in silicate rocks
is useful in correlating geochemical changes in geologic
sequences. Several chemical methods have been successfully employed in determining chlorine in geological samples. Some methods were restricted to
limited concentration ranges. The gravimetric procedure of precipitating chlorine as AgC1 was not
reliable for trace amounts of chlorine ( < 0 . 0 5 % ) . 1,~
A turbidmetric titration method detected traces, but
could only be used for up to 0.20% chlorine. 1,8 A
modified spectrophotometric m e t h o d has been used
by the U. S. Geological Survey to determine the low
levels of chlorine normally found in silicate rocks;
however, the technique is lengthy and tedious. 4
The work presented herein demonstrates the applicability of x-ray fluorescence ( X R F ) to determining
minor and trace levels of chlorine in silicate rocks.
X R F has been used for multielement analysis by
m a n y investigators once a pellet of the sample has
been prepared. The ubiquity of chlorine, especially
its presence in the atmosphere, 1 restricted the continuous use of standard pellets in the X R F chlorine
determination. An accurate X R F method has been
used to determine chlorine in seventeen international
silicate standards. Seven U. S. Geological S u r v e y
* Publication authorized by the Director, U. S. GeologicalSurvey.
Volume 26, Number 2, 1972

standards and two analyzed samples were used to

calibrate the method. Since more chlorine values were
needed for other reference standards, chlorine was
determined in six Centre de Recherche Petrographique
et G6ochimique standards, one U. S. Geological
Survey standard, one Canadian Association of Applied
Spectroscopy standard, one Leningrad State University standard, and one Geological Survey of
Tanzania standard.
I. E X P E R I M E N T A L

METHOD

A. Apporotus
A P E T analyzing crystal, a goniometer 20 setting of
65.42 , flow proportional counter at 1400 V, and a
5-mil collimator were used in conjunction with a
General Electric X R D - 6 spectrograph under v a c u u m
conditions. X - r a y s were generated at 50 kV and 50 m A
on the Cr side of a C r - W dual target tube. Interference of second order K s chromium radiation from
the target was effectively discriminated against by
setting the baseline and window of the pulse height
selector at 0.70 and 1.00 V, respectively.

B. Procedure
The direct dilution (1 : 1) method of sample preparation and the m e t h o d of making durable pellets have
APPLIED SPECTROSCOPY

293

been described in earlier papers. 5,6 All samples were

thoroughly mixed. One-half g of sample was ground
for 10 rain in a mixer-mill, the ground powder was
poured into a mortar, 0.5 g of chromatographic
cellulose (Whatman CF11) was added, and the
cellulose and sample were hand ground until well
mixed. The mixture was returned to the vial and reground for 5 min; the finely ground powder (95%
minus 400 mesh) was then pressed into a pellet at
30 000 psi, and the pellets were irradiated for 200 sec
and intensities recorded. U. S. Geological Survey
standards W-l, G-2, GSP-1, AGV-1, PCC-1, DTS-1,
and BCR-1, and analyzed samples H3683 and I4085
established a calibration curve, counts per second vs
concentration, using a least squares regression.
Analyzed samples H3683 and I4085, reported to the
nearest 100 ppm, extended the range of the calibration
curve above 300 ppm.

II. ANALYTICAL RESULTS AND DISCUSSION

A. Chlorine Contamination
Glass lenses, against which the powdered samples
were pressed to make reproducibily smooth pellet
surfaces, were a source of chlorine contamination.
A dilute HN03 solution (5%) was used to remove
alkalis from the lenses in this work, instead of the
dilute HC1 reported in an earlier paper. ~ The protective rim of the pellets aided in reducing chlorine contamination from handling.
Standard pellets prepared by the direct dilution
method have been used in the calibration and determination of many elements for three years without
noticeable deterioration, loss of intensity, or contamination. Adsorption of chlorine from the atmosphere 1
onto the pellet surfaces restricted the repeated use of
prepared standards in the chlorine determination.
This adsorption was due to regassing of the pellets
with air after outgassing under vacuum conditions in
the x-ray spectrograph. A nonuniform increase in
count rate for duplicate standard pellets was observed.
A freshly prepared standard pellet was placed under
vacuum and then allowed to regas each hour for two
days to check for chlorine adsorption. An 8.5% increase in count rate occurred the first day and 11%
the second day. Fresh standard pellets should be
prepared and run with each new lot of samples. The
standard pellets can, of course, be repeatedly used
for the calibration and standardization of other
elements after they have been used in the chlorine
determination.
Standard pellets were stored in desiccated cabinets,
as were all samples prior to analysis. Barium oxide
desiccant is preferred to magnesium perchlorate, as
magnesium perchlorate can also be a source of
chlorine contamination.
Chlorine is present in the double acid-washed
chromatographic cellulose binder. Replicate pellets
of the same standard prepared with the same batch
of cellulose gave a maximum deviation of 10 ppm

294

Volume 26, Number 2, 1972

Table I. XRF chlorine content of standard rocks.

Standard rock

XRF
( p p m C1)

G r a n i t e G-1
Diabase W-1
Granite G-2
Granodiorite GSP-1
Andesite AGV-1
Peridotite PCC-1
Dunite DTS-1
Basalt BCR-1
S y e n i t e S-1
Granite GR
Granite GA
Granite GH
Basalt BR
Diorite DR-N
Serpentine UB-N
Nepheline syenite USSR
Tonalite T-1
Glass shard H3683
Scapolite concentrate I4085

75 ::t:4
219 8
54 8
3055
1088
59 3
11 1 0
645
1743
415 4
213 3
721
385 12
40023
90012
5203
1597
8 8 0 12
312030

NAA*
( p p m C1)

Range
( p p m C1)

19-130 ~
206
25-270~
53
53-192 b
311
311-365 b
115
115-,319 b
66
65-100 b
9.4
9.4-33 b
58
58-120 b
...
220

100-315 d
--242-30@
...
58-503 a

287-400 d
. . . . . . .
. . . . . .
o
...
180-600 f
. . . . . .
g
1000 h
3100 h

* NAA =neutron activation analyses.

a M. Fleischer, Geochim. Cosmochim. Aeta 33, 65 (1969).
b F. J. Flanagan, Geoehim. Cosmoehim. Aeta 33, 81 (1969).
N. M. Sine, W. O. Taylor, G. R. Webber, and C. R. Lewis, Geochim. Cosmoehim. Acta 33, 121 (1969).
d M. Roubault, H. de la Roche, and K. Govindaraju, Sci. Terre 13, 379
(1968).
e H. de la Roche and K. Govindaraju, Rept. Natl. Assc. Tech. Res. France
(1969).
A. A. Kukharenko st al., Vses. Mineralog. Obshehest. Zapiski 97, 133
(1968).
Geol. Surv. Tanzania, Dar es Salaam, Msusule Tonalite Suppl. No. 1
(1963).
h Analyses by chemical methods, U. S. Geological Survey Analytical Labs.,
under the direction of L. C. Peck.

chlorine, indicating homogeneity of the cellulose with

regard to chlorine contamination. Duplicate fresh
standards have been prepared and run with several
lots of duplicate samples, and the error of the chlorine
determination for both standards and samples was
observed to be within this deviation. Chlorine must
be determined on each new batch of cellulose so that
homogeneity of chlorine in the cellulose can be
assessed. Chlorine was determined on duplicate 1-g
blanks from five different 500-g batches in the writers'
laboratory. A range of chlorine from 35=i=5 to 100=t=10
ppm was found in the five batches of cellulose.
The lower limit of detection could not be determined using the normal measured background intensity at 67.0 20 because of blank contamination.
Spec-pure quartz was mixed with cellulose (1:1) and
duplicate pellets were counted at the chlorine peak
to obtain true "background" counting rate. Standard,
nepheline syenite USSR, was also counted to determine the peak counting rate. The lower limit of detection, using the equation of Jenkins and deVries, ~ was
found to be 8 ppm at the 2z confidence level.

B. Accuracy of the Method

There is good agreement between the X R F values
and neutron activation analysis values s for the seven
U. S. Geological Survey standards and chemical values
for the two analyzed samples used to calibrate this
method (Table I). The X R F values generally fall
within the range of values reported elsewhere in the
literature for six other reference standards. The X R F
value of 415 ppm chlorine is outside the range of

published values for granite GR. I t does agree with the

unpublished chemical value of 400 p p m found b y L. C.
P e c k of the U. S. Geological Survey Analytical
Laboratories (private communication, 1971). X - r a y
fluorescence chlorine values are presented for four
other standards for which a range of values are not
reported elsewhere. Matrix effects tend to be compensatory in the X R F chlorine determination. No
corrections were made for matrix effects in this work.
Precision of this m e t h o d for duplicate determinations
was found to average ~ 7 p p m and includes all combined X R F errors such as instrument stability,
counting, pellet placement, homogeneity, mineralogical effects, etc.

III. CONCLUSIONS
The accuracy of this X R F method of chlorine
analysis can be no better t h a n t h a t of the methods

used in calibration, as it is a secondary m e t h o d of

analysis. Once calibrated, m a n y silicate rock samples
can be analyzed rapidly and routinely for minor and
trace concentrations of chlorine. Care must be exercised in the preparation, use, and storage of prepared
pellets to avoid adverse chlorine contamination.
1. J. A. Maxwell, Rock and Mineral Analysis (Interscience, New
York 1968), pp. 244-248.
2. A. V. Volborth, Elemental Analysis in Geochemistry. A. Major
Elements (Elsevier, New York, 1969), pp. 138-141.
3. L. C. Peck and E. J. Tomasi, Anal. Chem. 31, 2024 (1959).
4. D. F. Boltz, Colorimetric Determination of Nonmetals (WileyInterscience, New York, 1958), pp. 161-180.
5. B. P. Fabbi and W. J. Moore, Appl. Spectrosc. 24, 426 (1970).
6. B. P. Fabbi, in "Geological Survey Research 1970," U. S.
Geol. Survey Prof. Paper 700-B, B187 (1970).
7. R. Jenkins and J. L. deVries, Analyst 94, 447 (1969).
8. O. Johansen and E. Steinnes, Geochim. Cosmochim. Acta 31,
1107 (1969).

APPLIED SPECTROSCOPY

295