Bull. Kitakyushu Mus. Nat. Hist. Hum. Hist., Ser.

A, 3: 1-12, March 31, 2005

X-ray fluorescence analysis of major and trace elements in

silicate rocks using 1:5 dilution glass beads
Yasushi Mori1 and Hidehisa Mashima2*

1Kitakyushu Museum of Natural History and Human History, 2-4-1, Higashida,

Yahatahigashi-ku, Kitakyushu 805-0071, Japan
2Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami,
Kumamoto 860-8555, Japan
*Present address: Japan Nuclear Cycle Development Institute Tono Geoscience Center,
959-31, Jorinji, lzumi-cho, Toki 509-5102, Japan.

(Received September 9, 2004; accepted December 21, 2004)

ABSTRACT—This report describes analytical techniques for major and trace elements in silicate rocks
by X-ray fluorescence (XRF) spectrometry. The analyzed elements are SiOz, Ti02, A1203, total
Fe203, MnO, MgO, CaO, Na20, K20, P2Os, Sc, V, Cr, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Nd
and Pb. All of these elements were determined on a single glass bead made from mixtures of 1 g of
sample powder, 5 g of Li2B407 flux and about 50 mg of Lil releasing agent. A series of synthetic
standard samples were prepared from pure chemical reagents to calibrate an XRF spectrometer.
Matrix and line overlap corrections using a fundamental parameter approach yields reliable calibration
lines with wide optimal ranges of composition. Analytical results of GSJ geochemical reference
samples are in good agreement with their recommended values and exhibit sufficient precision and
sensitivity for both major and trace elements.

INTRODUCTION
X-ray fluorescence (XRF) spectrometry is widely
used for major and trace element analyses of geological
materials. For the analysis of silicate rocks, samples are
generally fused with a flux into glass beads to reduce
matrix effects and eliminate mineralogical and particle
size effects. Many authors have examined the fusion
techniques involving various samples to flux ratios such as
1:10 (e.g., Hattori, 1971; Ohmori & Ohmori, 1976; Goto
& Tatsumi, 1991), 1:5 {e.g., Sugisaki et al., 1977;
Matsumoto & Urabe, 1980; Nakada, 1985; Nakada et
al., 1985) and 1:2 (e.g., Kimura & Yamada, 1996;
Yamada et al., 1995; Goto et al., 2002). The 1:10
dilution glass beads are suitable for major element analy
sis, but such a high dilution causes low fluorescent X-ray
intensity and consequent difficulty in trace element analy
sis. The 1:5 and 1:2 dilution glass beads are available for
both major and trace element analyses. There is little
difference in analytical precisions between them (Yajima
et al., 2001).
The aim of this study is XRF analysis of major (SiOz,
Ti02, A1203, total Fe203, MnO, MgO, CaO, Na20, K20
and P205) and trace elements (Sc, V, Cr, Ni, Cu, Zn, Rb,
Sr, Y, Zr, Nb, Ba, La, Ce, Nd and Pb) in silicate rocks
with ultramafic, basic, felsic, calcic and alkalic composi
tions. This study plans to analyze both the major and
trace elements on single glass beads. For this purpose,
we employed the 1:5 dilution glass beads, which is avail
able to wide ranges of compositions and can be prepared
more easily than the 1:2 dilution glass beads. We also
applied a fundamental parameter approach to matrix and
line overlap corrections. Analytical precision and accu
racy of this method will be evaluated and reported.
ANALYTICAL TECHNIQUES
Sample preparation
The samples used in this study were GSJ geochemical
reference samples provided by National Institute of
Advanced Industrial Science and Technology: JA-I an-
desite, JB-1, JB-lb and JB-2 basalts, JG-la and JG-3
granodiorites, JGb-l gabbro, JH-1 hornblendite, JP-1
peridotite, JR-I and JR-2 rhyolites and JSy-1 syenite.
The flux and releasing agent used were Li2B407 (Merck
Spectromelt A 10) and Lil (Strem Chemicals, assay> 99.9
%), respectively. Prior to be fused, the sample powders
and flux were dried at 110 °C for over 6 hours in a drying
 Yasushi Mori and Hidehisa Mashima

oven. The releasing agent was dissolved into water to
make a 50 wt.% Lil solution (Mashima, 2002; Mashima
et al., 2002).
After cooling in a desiccator, 1 g of each sample
powder and 5 g of the flux were accurately weighed and
mixed. About 100 mg of the Lil solution, which corre
sponds to about 50 mg of anhydrous Lil, was added to the
mixture. The mixture was homogenized with an agate
mortar, and then put into an Au-Pt alloy crucible com
bined with a mold of glass beads. A Tokyo Kagaku
TK-4200 automated high frequency bead sampler was
used to fuse the mixture. The mixture was heated to 1100
°C for 5 minutes until totally melted. It was automati
cally agitated by a spin with tilt of the crucible for a
further 4 minutes keeping the temperature of 1100°C, and
then cooled and cast into a glass bead within the crucible.
In most cases, the glass beads were easily released
from the crucible. If the glass bead stuck to the crucible,
the Lil solution was added to the glass bead, and the
melting process was carried out again. To check the
evaporation of light elements, the change in fluorescent
X-ray intensity of Na was monitored during five times
1.05
re-melting of a single glass bead (Fig. la). The change
was within the analytical error, suggesting that there is
little evaporation of Na during the re-melting. Further
more, the change in fluorescent X-ray intensity of Fe was
simultaneously monitored to check the evaporation of the
flux (Fig. lb). If the flux evaporates, enrichment of
heavy elements such as Fe, and consequent increase of the
X-ray fluorescent intensities takes place. The measured
intensity was almost constant, suggesting that Fe was not
enriched in the glass bead during the re-melting. There
fore, the re-melting of the glass beads had no influence on
the results of XRF analysis.
Standard samples
A series of synthetic standard samples were prepared
from pure chemical reagents to calibrate an XRF
spectrometer. The reagents used are listed in Table 1.
They were typically dried in a muffle furnace and drying
oven. The heating temperatures and durations are shown
in Table 1. The heated reagents were cooled in a desic
cator just before preparation. MnOz, NH4V03 and Cu
were dried at room temperature in a desiccator.
The procedure for preparing the standard samples
mainly followed that of Nakada (1985) and Nakada et

Table I. Reagents used for standard samples.

Drying conditions
Reagent Assay (%) Manufacture
^ (°C) (hours)
1.00 Major elements
^ SiOz 99 W 1000 10 (min)
TiOj. 99.9 W 600 0.5
ai2o3 99 S 1000 10 (min)
Fe203 99.9 W 600 0.5
Mn02 99.5 W RT >24
MgO 99.9 W 400 1
0.95
CaC03 99.99 W 400 1
Na2C03 99.999 M 400 1
1.05 K2C03 99.9 W 400 1.5
(b)Fe KH2P04 99 W 400 1.5
Trace elements
Sc203 99.9 w 110 >6
-
NH4V03 99 w RT >24
Cr 99.5 w RT >24
^ NiO 99.9 w 110 >6
1.00 • • • • •
^ Cu
ZnO
99.9
99.9
w
w
110
110
>6
>6
-
Rb2SO< 99 w 110 >6
SrC03 99.99 w 110 >6
Y203 99.9 w 110 >6
Zr02 99 w 110 >6
055 1 • 1 1 Nb205 99.9 w no >6
BaC03 99.99 w 110 >6
La203 99.99 w no >6
Number of re-melting {n) CeOz 99.9 w no >6

Fig. 1. Changes in fluorescent X-ray intensities of Na and Fe during Nd203 99.9 w no >6
re-melting of a single glass bead. The sample used was JG-3. PbO 99.9 w no >6

The I„/l0 indicates the net intensity after n times re-melting Abbreviations: W = Wako Pure Chemical, S = Strem Chemicals, M =
normalized to the original value. Merck, RT=room temperature.
 XRF analysis of silicate rocks

Table 2. Calculated chemical compositions of standard samples.

N201 N202 N203 N204 N205 N206 N207 N208 N209 N210 N2II N212

(wt.%)
Si02 52.38 45.25 39.36 56.20 75.86 28.71 42.49 32.45 68.42 0.00 36.44 0.00
Ti02 1.35 0.32 2.48 2.00 0.11 1.00 6.91 0.69 2.95 9.91 0.84 0.50
Al203 14.85 7.21 9.79 16.39 12.88 29.69 3.96 5.39 9.85 34.65 21.67 0.00
Fe^ 9.17 11.92 2.95 4.98 0.88 3.47 2.47 16.66 1.78 13.86 0.69 29.78
MnO 0.16 0.00 9.85 2.49 0.06 0.98 0.78 0.00 0.59 1.98 1.23 2.98
MgO 7.86 25.71 14.81 5.98 0.12 3.96 29.64 0.00 1.97 10.90 34.47 9.43
CaO 9.46 7.47 1.48 5.47 0.98 24.73 0.10 29.39 3.45 1.98 0.30 39.70
Na20 2.84 0.69 4.95 3.68 4.03 1.78 0.25 4.90 5.91 15.84 2.36 12.90
K20 1.47 0.10 9.90 1.80 4.44 3.66 11.86 6.27 2.75 7.92 0.69 2.28
p2o5 0.26 0.00 2.97 0.50 0.02 0.99 0.35 2.45 0.79 1.98 0.59 1.69
(ppm)
Sc 100 20 50 0 995 497 796 30 597 0 100 995
V 99 49 1086 494 198 395 395 247 296 0 691 20
Cr 101 4036 2523 50 0 2019 2018 5047 3027 505 1009 303
Ni 104 4047 2528 52 0 2023 2022 5061 3033 510 1011 313
Cu 105 5 II 808 0 102 152 28 706 1014 31 64
Zn 102 21 51 0 1009 507 807 33 605 0 101 1012
Rb 100 398 601 21 2 11 14 600 51 999 200 200
Sr 101 51 1087 495 198 401 395 254 297 0 692 29
Y 101 20 50 0 1008 504 807 30 605 0 101 1008
Zr 101 399 599 21 1 12 II 599 51 999 201 199
Nb 99 398 597 20 0 10 10 597 50 994 199 199
Ba 99 49 1087 494 198 395 395 247 296 0 692 20
La 104 21 52 0 1037 518 829 31 622 0 104 1037
Ce 100 0 10 800 0 100 150 20 700 1000 30 50
Nd 100 399 598 20 0 10 10 598 50 997 200 199
Pb 100 0 10 802 0 100 150 20 702 1003 30 50

Table 2. -Extended.
N2I3 N2I4 N215 N216 N2I7 N218 N2I9 N220 N22I N222 N223

(wt.%)
Si02 5.75 64.15 15.87 0.49 59.35 0.79 9.93 23.65 80.30 0.00 47.32
Ti02 4.96 0.00 1.15 2.48 1.78 3.94 4.97 4.44 0.00 3.47 1.53
Al203 11.39 0.39 18.14 39.70 1.09 19.69 8.45 0.19 0.00 0.00 2.21
Fe203 39.64 27.63 0.00 0.00 15.33 19.70 34.79 0.39 5.95 22.79 6.90
MnO 1.59 4.93 7.93 3.97 0.00 5.91 0.45 2.27 0.00 9.91 0.30
MgO 4.95 0.34 0.75 14.90 0.10 0.98 19.87 54.21 12.90 0.00 39.19
CaO 18.33 0.00 44.63 11.91 21.27 34.46 14.91 2.66 0.00 49.53 0.00
Na20 1.19 0.15 0.89 7.94 0.00 10.83 0.54 8.87 0.00 0.00 0.44
K20 9.91 0.66 8.93 14.89 0.00 0.98 5.36 1.18 0.00 13.37 0.49
P205 1.39 0.42 0.89 2.98 0.00 1.18 0.10 0.69 0.00 0.00 0.20
(ppm)
Sc 696 50 597 199 299 398 199 0 10 150 70

V 49 1975 790 691 1186 1482 889 0 889 1975 99

Cr 1514 1009 101 303 202 0 50 5045 20 0 3028
Ni 1529 1020 101 303 207 6 62 5054 22 7 3035
Cu 320 63 202 605 1015 613 418 0 204 161 305
Zn 708 51 609 203 305 407 203 0 10 156 71
Rb 24 399 153 105 50 997 2 150 797 5 797
Sr 54 1976 801 694 1191 1490 893 1 889 1987 99
Y 706 51 605 202 303 403 202 0 10 152 71
Zr 22 399 151 104 50 998 1 150 797 1 797
Nb 20 398 149 99 50 994 0 149 796 0 796
Ba 49 1976 790 692 1186 1482 889 0 889 1976 99
La 726 52 622 207 311 415 207 0 10 156 73
Ce 300 50 200 600 1000 600 400 0 200 150 300
Nd 20 399 150 100 50 997 0 150 798 0 798
Pb 301 50 201 602 1003 602 401 0 201 151 301
 Yasushi Mori and Hidehisa Mashima

Table 3. Instrumental operating conditions of XRF spectrometer

X-ray tube Collimator Analyzing Angle ("20) Countinj! time (sec) PHD
Element Line Detector
(kV) (ImA) (/*m) crystal Peak BG 1 BG 2 Peak BG LL UL

Si02 Si Ka 32 125 700 PE002 FPC 109.21 105.71 112.71 10 10X2 24 78

Ti02 Ti Ka 40 100 150 LiF200 FPC 86.18 84.98 87.38 20 10X2 29 71
Al203 Al Ka 32 125 700 PE002 FPC 145.06 141.16 147.96 10 10X2 22 78
Fe203 * Fe Ka 60 66 150 LiF200 DU 57.52 56.02 59.02 10 10X2 34 66
MnO Mn Ka 60 66 150 LiF200 DU 62.98 61.98 63.98 10 10X2 35 65
MgO Mg Ka 32 125 700 PX-I FPC 22.71 -
25.01 40 40X1 19 78
CaO Ca Ka 32 125 150 LiF200 FPC 113.13 111.33 114.93 10 10X2 30 70
Na20 Na Ka 32 125 700 PX-I FPC 27.44 25.64 29.54 80 40X2 22 78
K20 K Ka 32 125 150 LiF200 FPC 136.70 134.10 139.20 20 10X2 31 69
P205 P Ka 32 125 700 Gel II FPC 141.08 137.58 144.08 40 20X2 25 75
Sc Sc Ka 32 125 150 LiF200 FPC 97.73 96.93 98.73 400 200X2 35 65
V V Ka 50 80 150 LiF200 DU 76.96 75.46 77.96 80 40X2 31 69
Cr Cr Ka 50 80 150 LiF200 DU 69.37 68.17 70.57 80 40X2 33 67
Ni Ni Ka 60 66 150 LiF200 DU 48.66 47.86 49.66 20 10X2 37 63
Cu Cu Ka 60 66 150 LiF200 DU 45.01 44.36 45.66 20 10X2 38 62
Zn Zn Ka 60 66 150 LiF200 SC 41.77 41.17 42.37 40 20X2 15 75
Rb Rb Ka 60 66 150 LiF200 SC 26.58 26.08 27.08 80 40X2 22 78
Sr Sr Ka 60 66 150 LiF200 SC 25.11 24.46 25.76 20 10X2 22 78
Y Y Ka 60 66 150 LiF200 SC 23.75 23.15 24.35 20 10X2 23 77
Zr Zr Ka 60 66 150 LiF200 SC 22.51 22.01 23.01 20 10X2 24 78
Nb Nb Ka 60 66 150 LiF200 SC 21.36 20.81 21.81 40 20X2 24 78
Ba Ba La 40 100 150 LiF200 SC 87.19 -
88.19 400 400X1 33 62
La La La 50 80 150 LiF200 SC 82.94 81.94 83.94 800 400X2 30 70
Ce Ce La 50 80 150 LiF200 DU 79.03 78.33 80.03 800 400X2 15 75
Nd Nd La 50 80 150 LiF200 DU 72.15 70.95 73.15 400 200X2 32 68
Pb Pb Lfl 60 66 150 LiF200 SC 28.22 27.62 29.17 200 100X2 21 69

Common settings: anode=Rh,, filter = none, chamber = vacuum., sample spiimerlon, PR gas flow rate== 1.1 1/hr.
Abbreviat ions: BG = backgrou nd, PHD = pulse height distribut ion, LL = lower limit, UL = upper limit, F-PC ==gas flow
proportional detector, SC = scintillation detector, DU = duplex detector (F-PC + Xe-sealed detectors in tandem).
*Total iron as Fe203.

al. (1985). First, the reagents of major elements were
weighed and mixed based on the planned standard compo
sitions. Each mixture was about 20 g in weight. It was
homogenized for 2 hours with an agate mortar, and then
dried at room temperature for over 24 hours in a desic
cator. Next, the reagents of trace elements were diluted
with the flux (Li2B407) to obtain the 10000 ppm mixtures
of (1) Sc, Zn, Y and La, (2) V, Sr and Ba, (3) Cr and Ni,
(4) Cu, Ce and Pb, and (5) Nb, Zr, Rb and Nd. The
reagents were combined so that no spectral interference of
analysis lines occurs in each group. The 10000 ppm
mixtures were successively diluted with the flux to make
the 1000 ppm, 100 ppm and 10 ppm mixtures. These
mixtures, about 20 g each, were homogenized for 2 hours
with an agate mortar, and then dried at room temperature
for over 24 hours in a desiccator. Finally, the mixtures of
major elements and the mixtures of trace elements (with
the flux) were blended at appropriate mixing ratios. The
mixing ratios were determined so that the total amounts of
major and trace element oxides (i.e., standard samples)
might be set to 1 g in a single blend. The samples to flux
ratios were adjusted to 1:5 by adding the flux to the blend.
After adding about 100 mg of the Lil solution, the blend
was fused into a glass bead by the melting process de
scribed above. Calculated chemical compositions of the
standard samples are shown in Table 2.
Instrumental conditions
The instrument used was a PANalytical MagiX PRO
wave length dispersive XRF spectrometer at Kitakyushu
Museum of Natural History and Human History. The
operating conditions are shown in Table 3. The
spectrometer was equipped with a Philips 4 kW Rh anode
Super Sharp X-ray Tube (PW2592/45). The acceleration
voltage and tube current ranged from 60 kV and 66 mA to
32 kV and 125 mA, respectively. Four analyzing crystals
(PE002, LiF200, Gel II and PX-1) and three types of
detectors (gas flow proportional, scintillation and duplex)
were used for the analysis. The analysis was fully
automated using a Philips PW2540/00 VRC sample chan
ger and SuperQ software package attached with the
spectrometer.
Calibration lines
In order to set up calibration lines, theoretical matrix
corrections were applied to all the analyzed elements.
The matrix correction model used was that of de Jongh
(1973). A term of spectral line overlap corrections was
•oznpo!ZN-<w^ n n z O r (S z N - < w n n z o < 5? t» ^ z > H 55
ff a " B B cr ^ or 3 c —
D<S?,'°.?:?022 •n > H S£>. a* Z
r? 0. 3 c — -1
0 2 2
" ~ O O 5l oo £ 0 p
Po»o5r6Sbb O O "Q o o o o

KJOOOO — — r-JhJI-J — Uiu>00 — o — o — oooooo — O p p p p p p 00000000 — — OOO

U 06 - - - -j w w ecnO©nO©00©00sIOnnOn©v© © 'o \&
_ \0
_ ^5
_ \£>
_ \& \©
Id Id Id On n© s l — ON ON — _
s l. ON -
W "
ON sj O in - OO i i Id NO 00 si ON 4> 82
A VO
_ .M- vj- _
Ui - ". - - lsj
L/l. _ — ~
_ 4*
. — ._ .
.. _ 9« O * Ji On NO s l Id W L/i U U - 4n 06 4n
NOIdL/iNOL/islOOONWON — s 1 O n 4 ^ 0 0 s 1 n © \ © 4 » . s 1 ie w ui o ov -u NONOUlNONOId — Id — Ul NO NO

Uppp-NljOUtdUW ©O — — — © — © O p © — — WW — — — s*Js*Js*>WOJs*Js*Js*>s#J— O o o <*» u> o —

w bo "no 'no < t « Kl U ^ be no — © —- si —• >c on U io b • OWOQOslboNO^NOOQsl^4^oLA4^4^wL'iW4^tyi4^04^
- - - _ - _ J Ui * Ul O «N)^Uilv)pN|k>J^UiOO«tC siooOQouiO>ONvioeo^oc-iOsi-oeooio>ooouiOsi-
O * - JS.ON00 — Id — — o o — Osls0O0000s/lNO00*ksl'45sl0Nsl004^ — «Ui«4iU004n-
^-uigt-ooo^uouiooui sIVltdONWNO — 00>OldOWWl — OslOOUl — O U IO 06 A <0 ON

4>. © — — — W .U 4*. * <i wo - — — — — o — — © © — — — OOOOOOOOOOOOOOOOOOOOOOOOOO

OnnOO© — bo — L/i ON — — — O P Id — Id 4^ Id P sl On © id — NONOvONOOOOOOOOONONOONONONO>OOOslOOIdOOIdNO <C Id 00 si
Id On S sl On — 00 «i WvCO04^O0Onn©Onn©0000© — — Id — 0 < 0 4 ^ s | \ 0 0 — 4 > W W I d — 004^Ul — ONWId W s i NO 4^
K J C h S O O J ^ — On _ O004*.L/i©«©slslW si — l d t > i s l s l O U > l d — ©"OslWsl — ON«45>OOslsl
____ 0<-^NOId
NO Id W W 00 Id NO O L/lL/iNOONOONOsl|dtd4^ 4iONoe — 06«siuiwo> s/ild4^slWt^iWslsltdWsl00ONW

sl -J p — — Id Id Id — Id O Id O Id Id O Id O slOOOOONONslslslONONONOOOOOOOO — — OOO
— W *AlnON--vO>JvJO ibiu^ONNoLnuiUiU — O^lnCN On l/i s/> <-n On oc O O O O0 Si ON <-H s/1 ON On On s/i On
00 On — WAOO'vOJiUivlvO Owi«M-w-otoe-jusioe- Ul 00 Id ON 00 l^i W L/l si <_/! si si UJ s/l —
L/i W ^MIJON|J9UtOUi O W 00 s/i 4^ s i — NO 00 s/l si
»»suoN^-0->c>coevi^»: W4^ldONONONOW — nOs/i On O Id 4^ O

L/i Id Id Id Id 4i 00 00 O0 ON — — — Id Id Id Id Id © Id © Id Id © Id © si — OOOOnOnsIsIsIOnOnOn — OOOOOOO — — OOO

vOO>0>0>--IU\0«UiUOJi--Jvl OOOnIWOOA^UUiOOCn — W On s/i L/i « OO-OOONUAWUlUlUiUiUlUislOOViUilA
OWsl«\O-J0CUi O — Id L/l -J X fc * - — l/i Id O 4^ 4^ O NO On 00 NO - 4l.slOONOOO — s!sInOnOU»nOV/iOOPOns100
4i-CN«0e00-»J4i«IJ _ U> — OOUiOOXk — WiW — 06 Id W 00 L/i L/1 NO Id W Onl/isInOL»jO — 00V»\O00OnU»sIOnsIO —
OtdOCs/i4^0CW — 4w W V/i O td Id si Id Id O ON — 00 — <J> <J\ — O

H
ONtdtdldWNONONOslON — — tdWWWOWOW©ldld©WO OOOOOOOOOOOOOOOOOOOOOOOOOO
_ __
o NO NO NO o NO sl ON 4* 4* sl o o o OO o W o *• sl ON L/l OOOOOOOOOOslslsl si — slldOOOOONOO
ON w sl 00 NO -b. sl w W L/l ON sl ON *. ON L/l si o -J 00 L/l sl L/l 4>. Id Id Id — — L/l si NO _ _OCNONOIdW4^NO —
-J 00 w Id o ON oo sl si sl sl 00 o sl l/i 00 00 00 o u On — si — s l 4v L/l On 00 sIONU-WUI/iUi^UiAOO-UiUi
o Id o w Id •u ON 00 ON o Id ON o 4* Id — si 4* *. Id W Id 4^nOOLn»^OsI — L>jsOONW4^sl|d — — ONLoL/islONO

© w w w w © © si si © — t d w w w w p w p w o w w o w © L^WL^U)WLOO/0/L>/U/L>JL~IWLOWWpppp W W p W O
4^ id id id LO Lo id ^ O NO NO id !t. OJ L> 4^. NO Id 4i U> 4^ — b Ul * >i bo w w w id on si bo bo bo si on on 4^ w id w L/i w no !u L/i w id w
NO Lrt sl 00 00 NO — NO 06 si — ©ONL/iONWWslpONOOOOOOtd — 4nv04n-«M|J-u4n U«AMONUONUAO>AslWUi«Ul
UMslKIJlOOM^MUMaiAUiOeiCONMIO-' W — Id L/i s] IdOOLnOOtd — — N04^sl >0W4NNO--00WlNe00UiN0>0>
0!>lldWyislUi(6iN-W-OMlft\005sJ>JUiN05ViONslW On — O — — L j O O O n O O n W0OL>J— 0 0 O O O s l U l l d t d L A 4 ^ N O 4 ^

O W W W W — 00sl©OtdldldWWWOW©W©WWOW© p p p p p p p p p p p p p p p p ppppPPPP 3
4nO\ONONvI-U|1C>OUiUSN06>1sJv100Ui4nONUi W Ui si si slslslslslON "ONONslslslslslslslslbNON — slONslslONslON
Ov — ldldtdL/i>©NO©©ONWO0 — — slOOOOtdOO© 00 v© ON Id — Id Id Id Id ON slNOO — WUlWIdld — IdNOLftOldtdWIdldtd
-U>IOOOOONI^>l^9>"CNUOOtO-UiOOvl4N- -J ON NO Id 00 L/l Id — O O nOnOOnWOOsIOnONWOn — 0<*>4^0nnO — t>JO —
W W ON * - U^^W>OO00UlOM90N- 00 Kl U sl © sl — -U Ul si W — si s)W4^4tONvOWOOOOOOslOL/lOOOOL/lOOON — si

— W W W Id O — — — — OOO pNWId — — O — © 00 NO — Id — WWWWWWWWWWWWWWWWOOOWOWWOW

41. Id — © no NO Id l/i L/i L/i 00 On itw L/i id w id si on no be L/i no o bo — siwidtdW4^LrtbNbNsibNLrtL«wid — w b o w o w w 4 i » w i d w
OnL/i — N>OnnOOOL/is1s14>wO O O O U i O M t > l < J \ C O W si C* A O O L / i l d O s l s l s I N O — |J si u to O A — NOOOOOslW — O —
L/i — L/iOn©W — NOW — P O s ] U»-JvO-~4— S o o s1WW004*OnOOOOOnO — N0l*J0N000NNOOsJO0000ld — O0 4n
00NO00ON — 00 si u u - Id sl — 00O0N4^td0N4^ON NOslONWOL/lOONOL/lOOOOOOOL/lL/lONNOOL/lNOOOIdL/lJi.sl

Kl U U W M - — Id jd |d — — — W Ul W - — © — O NO O — Id — — — p — p — p — — O — P
— 4> id — no On nO id id id l/> W O d 4* id id si On no no © L/i — •-> — O o o o o o © © lu *© id © id — — id o w
ONL/lL/l4^L/lL/lL/l£tONONtdOOOIdO©tdL/lONL/l — — VO — slON Lft NO sl sl ON ON NO Id w 4^ sl sl ON Q 004itp©L/itds] — wnOOnW
4i A Ui U - 0000v04kWtd00ON0 — OOOUUOOIJOOOMAWsl *. w 00 o w ON ON ON sl sl sl £k Id © WLnWWN04^0NONIdN04^ —
OOOOONOtdOOONUi — — s l s l — 0 0 O t d O 0 N 0 N O O N O 4 ^ 0 N 0 N W ON w L/l — 4^ Id o o NO 4* W O nO © 4 ^ O N 0 0 © s l L f t O N O N s l O N s l

WWWUWWtJUUUIJW-WUIIJ PWP NO — Id — Ui J> 4v 4i - L/iL/iL/lL/iL/iL/lL/lL/l *. — p p p P p t A y > 0 « p

O La w — booNNoidid — idOsiboLdiduibcsiobouisi — si id ON \o 00 00 w w ON ON <
bNiu^uwNooowIckl/iw'siw© — wsi4^
si NO Ul O 4^ Id Id — — NO sl Id sl Id Id Id © — Ul O — L/l © NO ON L/l UiUUl--WslW4i ONsl©ldslslNO — nOOO — nOOnlunOsIO
CNOtNUsl-lA00UMIvl«OOsl\09>00O0NUlUiMt0slM Wsl^ld-Uislslsl WL/ild4^4^00sO©0000£tWWIdslNOW
W W - s l \ O O N O N O O O U l W O « 9 > W O - O l d — N© Id — O n O s I WONIdWONNOL/iONW AOUlWOOtOsllOUOUU- NOOOtdsl

4n U Ul U M A 4N4NUUUUWIO--plOp;bp0-|yl- si — — — — ©nOnsIsIsIsIOnOn — — OOOOOOONONO- O

l/i si u> 0 bo — sjsicNW-'os-wjilosi-bo-ln-Uu WOONOJiONOOO- — © SNUiUi4nOA4nUi^4n4n
NO 00 © — L/i — 4i-ON*-Wsl-UiWiWW6NUi-iOO>>e ©NOLftWOOONslslWOOOO sl O sl 00 Id 00 W NO Id NO
_ _ O — Id NO Id — ONslldld — — 04> — Id W L/l Id sl 06 Id U l * O > * - 0 0 W U i—- 4> On W O ON
On On On 4^ 00 sl — 00
ON Id ON W 00 L/l 00 06 A O ON - ldL/iNOStdWONsl4l.L/l — W s | Ui A 4n - O0 O w 5 4* — — w — L/l Id sl ON — Id ON

— W W Id Id Id
uyiUiuiwwpuiyi4»yiuiuiyii/iUi-4NOf»OuiUiOUiO OO — — — psIslOOpopOslslsltJ- © pop O O Id sl © O ©
id on L/i 4^ '41 bo on id — bovoNobosioNwo — L/ibooNsibosil/iNO J ON - CN ON L/i On L/>
UUl|OUiUUll/lsl-4,00KJ0N00-|k06s|iNslUisl0000Q|O _>l 4i L/l L/l 00 8± 00 Ln
Ui4nO0«ON4»00- sl0\***0N«W00004»>OAJl00UOO L/lL/iNOOOL/iOO — ON — ONNO sl — OO— UislWW
ONUsIUisIsIUi^iSNU(>JONVOAOOU4nOO- — © 00 L/l ON L/i U>4^ — — LdL>JWWLANOslO sl — 0C Id sl NO NO — O
 Yasushi Mori and Hidehisa Mashima

Table 5. Line overlap correction coefficients.

La Li; JU Li, Li, Li, Li,s; Li,
Ti02
Fe^ 0.00066
MgO 0.00093 -0.00002
Na20 -0.00072
PaOs
Sc 0.00009
V 0.00190
Cr
Ni 0.00004
Cu 0.00004
Zn 0.00000
Rb 0.00000
Sr
Y
Zr
Nb
Ba 0.00111 0.04921
La 0.00002
Ce
Nd
Pb

Table 5. -Extended.
Lit L« La Li, L..zr Li, Li, Li,
Ti02 -0.01489
Fe203
MgO
Na20
P2Os 0.01644
Sc
V -0.00948
Cr 0.00889
Ni 0.00014
Cu
Zn
Rb -0.00069 0.00072
Sr 0.00230 -0.00132
Y 0.03384 0.00101
Zr 0.01205 0.00144
Nb 0.00063
Ba
La
Ce 0.03596
Nd -0.00865
Pb 0.00106

additionally introduced into the model. The equation of beads. The intercept and slope of the calibration lines
the calibration lines is written as: were calculated likewise. The SuperQ software package
Wi=(Di+EiIi)(l+'EaulVj)'2LijlVJ was used for the calculations. The results are summar
j j

where W{ is a concentration of element /, Dt and Et are an ized in Tables 4, 5 and 6.

intercept and a slope of the calibration line, respectively,
/, is a fluorescent X-ray intensity of element /, and atJ and
Lu are matrix correction coefficients and line overlap
correction coefficients for element i, respectively. The
matrix and line overlap correction coefficients were calcu
lated using a fundamental parameter approach and fluo
rescent X-ray intensities measured on the standard glass
The matrix and line overlap corrections yield reliable
calibration lines. Figure 2 shows examples of the cali
bration lines. By these corrections, the accuracy of the
calibration line for Fe203 was improved from 2.67 wt.% to
0.09 wt.%. That for Sc was improved from 112 ppm to 5
ppm, and the calibration line came to pass through the
vicinity of the origin. These findings suggest that the
 XRF analysis of silicate rocks

Table 6. Calculated results of calibration lines. 5000

Intercept A Slope Ei Accuracy'

Si02 -0.02995 0.15230 0.30(wt.%) 0.044
TiOz 0.00044 0.06430 0.05 0.025
A1203 0.00046 0.14252 0.15 0.038
Fe203* 0.00096 0.01066 0.09 0.026
MnO O.OOI53 0.01456 0.06 0.022
MgO -0.03111 0.09691 0.20 0.043
CaO -0.00113 0.08002 0.13 0.029
Na20 -0.02096 0.24589 0.08 0.038
K20 -0.02457 0.08803 0.06 0.032
p2o5 0.00473 0.04146 0.02 0.018
Sc -0.00006 0.05336 5(ppm) 0.001 20 30 50
V 0.00009 0.02404 11 0.003
Cr -0.00136 0.01508 13 0.002
Fe203 (wt.%)
Ni -0.00299 0.00412 34 0.005
Cu -0.00429 0.00372 13 0.003
Zn -0.00234 0.00220 5 0.001
Rb -0.00154 0.00068 8 0.002
Sr 0.00047 0.00063 25 0.005
Y 0.00068 0.00057 10 0.003
Zr 0.00091 0.00053 5 0.001
Nb 0.00048 0.00049 8 0.002 u,
Ba -0.00160 0.12652 23 0.005 •(—>

C
La 0.00015 0.11315 8 0.002 3
O
Ce -0.00001 0.07554 18 0.005
U
Nd -0.00018 0.05567 10 0.003
Pb 0.00089 0.00236 5 0.001

*Total iron as Fe203. 500 1000 1500

fAccuracy =y „- ^ 2/Crhcm ~ Qalc)2 Sc (ppm)

-p_,j V, (Qhcm
*K factor-.,
v n
_
K l—i cchem t
,Qalc)
c0 Fig. 2. Calibration lines for Fe203 and Sc. The open and solid
where n is number of samples, k is number of correction coefficients, circles indicate the data before and after the matrix and line
Cchum is original concentration, Ccalc is calculated concentration, and overlap corrections, respectively.
C0 is weighting constant.

matrix and line overlap corrections were successfully Sample = N214

achieved in both the major and trace elements. As Crystal = LiF200
shown in Table 6, accuracies of the calibration lines were
sufficient for the wide ranges of composition. The K
factors indicating the reliability are less than 0.05 and
0.006 for the major and trace elements, respectively.
Thus the calibration lines have sufficient quality for
quantitative analysis of silicate rocks.
Mashima et al. (2002) have pointed out the problem
of the line overlap of I L& (269 = 86.17° for LiF200) on Ti
Ka. They have experimentally corrected the line overlap
using the intensity relationship between I L#> and I La.
In this study, no peak of I L&2 was detected on the TiKa
BaLa
fluorescent X-ray spectra for Ti-free samples (Fig. 3). ILp2
Furthermore, the line overlap correction using I La inten
sity deteriorated the accuracy of the calibration line for
Ti02. For these reasons, this study did not apply such a
85 86 87 88
line overlap correction for TiOz analysis.
Angle (° 20)
RESULTS AND DISCUSSION Fig. 3. An example of fluorescent X-ray spectra for Ti-free
samples. The lines on the scale indicate positions of Ti
Analytical results of the GSJ samples are shown in Ka. I L& and Ba La.
8 Yasushi Mori and Hidehisa Mashima

Table 7. The compositions are an average of three times
measurements. The relative standard deviations indicate
\a of the measurements. The errors derived from instru
mental drift have been corrected using synthetic monitor
samples (N205, N2I0, N220 and N223 in Table 2) run
every 24 hours of analysis time.
For major elements of > 0.1 wt.%, the analyzed
compositions are very close to their recommended values.
The differences between them are below 15 % (typically
below 5 %) relative to the recommended values. Si02
contents tend to be slightly higher than the recommended
values. The cause of this phenomenon is not clear. The
differences are below 2 % relative to the recommended
values, so that they may not have influence on petrologic
and geochemical discussion. Ti02 contents are very
close to the recommended values. The relative standard
deviations of the analyzed values are smaller than 1.6 %.
For trace elements of > 10 ppm, the analyzed compo
sitions are typically close to the recommended values.
The differences between them are below 20 % for Sc, V,
Cu, Zn, Sr, Zr, La, Ce, Nd and Pb relative to the recom
mended values. The Cr, Ni, Rb, Y, Nb and Ba contents
show somewhat large differences (below 36 % relative to
the recommended values) for some low-concentration
samples.
Figure 4 shows relationships between the relative
standard deviation and average concentration of the trace
elements. As indicated by the regression lines (y = axb),
the standard deviation increases with approaching the
zero concentration. It reaches 10 % at 2 ppm for Zn and
Zr, 5 ppm for Rb, Sr, Y and Nb, 10 ppm for Sc, V, Cr, Ni,
Cu and Pb, 15 ppm for Ba, La, Ce and Nd.
In summary, the analytical results are in good agree
ment with their recommended values as a whole. They
also exhibit sufficient precision and sensitivity for both
major and trace elements. The use of a fundamental
parameter approach yielded reliable calibration lines with
wide optimal ranges of composition from ultramafic to
felsic (e.g., 0-80 wt.% of Si02, 0-39 wt.% of total Fe203 and
0-54 wt.% of MgO, see Table 2). The calibration lines
also cover calcic (<49 wt.% of CaO) and alkalic composi
tions (< 12 wt.% of K20 and < 15 wt.% of Na20). They
enable the XRF analysis of various types of silicate rocks
including metasomatic rocks such as skarn and jadeitite.

Table 7. Analytical results of GSJ geochemical reference samples.

JA-1 JB-I JB-lb JB-2

RV XRF RSTD RV XRF RSTD RV3 XRF RSTD RV XRF RSTD

(wt.%)
Si02 63.97 64.56 0.07 52.37 53.13 0.0 51.11 52.03 0.1 53.25 53.71 0.1
Ti02 0.85 0.83 0.15 1.32 1.31 0.3 1.26 1.24 0.2 1.19 1.17 0.2
Al203 15.22 15.08 0.10 14.53 14.53 0.1 14.38 14.25 0.1 14.64 14.63 0.2
Fe203* 7.07 6.85 0.05 8.99 8.84 0.0 9.02 8.89 0.1 14.25 14.16 0.2
MnO 0.16 0.16 0.29 0.15 0.16 0.3 0.15 0.15 0.3 0.22 0.23 0.4
MgO 1.57 1.55 0.08 7.71 7.87 0.1 8.14 8.56 0.0 4.62 4.68 0.1

CaO 5.70 5.57 0.09 9.25 9.19 0.1 9.60 9.46 0.1 9.82 9.65 0.2
Na20 3.84 3.87 0.11 2.77 2.77 0.1 2.63 2.64 0.2 2.04 2.04 0.2
K20 0.77 0.76 0.11 1.43 1.44 0.3 1.32 1.29 0.1 0.42 0.40 0.3
p2o5 0.17 0.17 0.28 0.26 0.27 0.4 0.26 0.26 0.0 0.10 0.10 0.5
Total 99.32 99.39 98.78 99.50 97.87 98.78 100.55 100.77
(ppm)
Sc 29 29 2.0 28 29 1.2 30 3.1 54 56 2.2
V 105 107 1.5 211 211 0.8 214 213 0.7 575 599 0.6
Cr 8 0 425 471 0.4 439 454 0.5 28. 21 10.8

Ni 3 3 133 140 0.9 148 149 1.3 17 12 3.3

Cu 43 35 5.0 55 54 2.4 56 57 3.3 225 210 0.5
Zn 91 91 0.6 85 86 0.9 80 77 0.8 108 111 0.4
Rb 12 10 0.5 41 38 1.0 39 32 0.5 7 5
Sr 263 257 0.1 444 445 0.2 439 442 0.1 178 181 0.2

Y 31 30 1.1 24 24 1.7 23 2.7 25 25 2.7

Zr 88 84 1.1 141 138 0.4 130 0.2 51 52 2.5

Nb 2 3 33 33 1.0 26 1.5 2 2

Ba 311 303 0.4 493 504 0.5 509 0.4 222 227 1.6

La 5 1 39 37 2.1 37 6.6 2 n.d.

Ce 13 11 15.6 68 70 2.6 71 1.5 7 4

Nd 11 16 12.7 27 31 4.3 33 3.2 7 8

Pb 7 9 10 9 7.9 7 5 5 8

RV = recommended or preferable values after 'Imai et al. (1995), 2Terashima et al. (1998) and 3Imai et al. (1999), XRF = analytical
results, RSTD = relative standard deviations (Iff in %), n.d. = not detected.
*Total iron as Fe203.
 XRF analysis of silicate rocks

Table 7. -Extended.

JG-la JG-3 JGb-1 JH-I

RV XRF RSTD RV XRF RSTD RV XRF RSTD RV2 XRF RSTD

(wt.%)
Si02 72.30 72.94 0.0 67.29 67.80 0.0 43.66 44.07 0.1 48.18 48.77 0.1
Ti02 0.25 0.24 0.7 0.48 0.46 0.6 1.60 1.60 0.2 0.67 0.68 0.7
Al203 14.30 14.10 0.1 15.48 15.41 0.0 17.49 17.55 0.1 5.66 5.70 0.1
Fe203* 2.00 1.96 0.2 3.69 3.60 0.1 15.06 15.01 0.1 10.27 10.19 0.1
MnO 0.06 0.06 0.07 0.07 0.19 0.20 0.4 0.19 0.19 0.2
MgO 0.69 0.70 0.3 1.79 1.79 0.1 7.85 8.01 0.1 16.73 17.10 0.1
CaO 2.13 2.11 0.1 3.69 3.68 0.2 11.90 11.67 0.2 15.02 14.70 0.2
Na20 3.39 3.41 0.1 3.96 4.08 0.2 1.20 1.23 0.2 0.71 0.70 0.4
K20 3.96 4.08 0.1 2.64 2.66 0.1 0.24 0.21 0.5 0.53 0.52 0.7
P205 0.08 0.09 0.12 0.13 0.0 0.06 0.06 0.10 0.10 0.5
Total 99.16 99.69 99.21 99.67 99.25 99.60 98.06 98.64
(ppm)
Sc 6 6 9 10 36 35 3.2 78 79 1.3
V 23 23 9.3 70 69 0.7 635 672 0.2 228 234 0.8
Cr 18 12 6.3 22 15 10.2 58 51 1.3 616 629 0.5
Ni 7 7 14 11 15.3 25 25 8.6 58 56 0.7
Cu 2 2 7 9 86 81 0.6 9 13
Zn 37 38 1.2 47 43 1.3 109 100 0.8 62 60 1.6
Rb 178 170 0.4 67 64 0.4 7 6 14 12 2.5
Sr 187 181 0.3 379 360 0.2 327 328 0.5 153 160 0.9
Y 32 32 2.8 17 18 2.3 10 11 5.6 14 16 4.7
Zr 118 122 0.5 144 151 0.4 33 35 0.7 48 52 0.8
Nb 11 10 7.7 6 6 3 4 4 5
Ba 470 471 0.2 466 461 0.5 64 73 3.9 106 115 3.3
La 21 23 9.2 21 19 4.7 4 n.d. 8 7
Ce 45 47 4.1 40 41 1.3 8 13 18 14 1.8
Nd 20 26 5.4 17 22 5.5 5 8 12 14 10.7
Pb 26 23 2.8 12 9 4.4 2 0 3 1

Table 7. -Extended.

JP-I JR-I JR-2 Jsy-I

RV XRF RSTD RV XRF RSTD RV XRF RSTD RV2 XRF RSTD
(wt.%)
Si02 42.38 43.40 0.1 75.45 75.28 0.1 75.69 75.98 0.1 60.02 60.63 0.1
Ti02 0.01 0.01 0.11 0.11 0.4 0.07 0.06 0.00 0.01
A1203 0.66 0.68 0.5 12.83 12.64 0.1 12.72 12.56 0.0 23.17 23.25 0.1
Fe203* 8.37 8.22 0.1 0.89 0.87 0.1 0.77 0.74 0.2 0.08 0.08
MnO 0.12 0.12 0.4 0.10 0.10 0.9 0.11 0.12 0.4 0.00 0.00
MgO 44.60 45.86 0.1 0.12 0.13 1.0 0.04 0.05 0.02 0.01
CaO 0.55 0.53 0.2 0.67 0.68 0.2 0.50 0.50 0.2 0.25 0.25 0.2
Na20 0.02 '0.00 4.02 3.97 0.2 3.99 3.99 0.1 10.74 10.84 0.1
K20 0.00 n.d. 4.41 4.51 0.2 4.45 4.56 0.1 4.82 4.87 0.1
P2Os 0.00 0.01 0.02 0.02 0.01 0.01 0.01 0.01
Total 96.71 98.82 98.62 98.31 98.35 98.56 99.11 99.96
(ppm)
Sc 7 7 5 7 6 5 n.d.
V 28 24 5.8 7 6 3 2 2 n.d.
Cr 2807 2937 0.1 3 n.d. 3 n.d. 2 n.d.
Ni 2460 2460 0.1 2 n.d. 2 3 1 n.d.
Cu 7 4 3 1 1 2 1 n.d.
Zn 42 43 1.5 31 28 1.0 28 27 2.8 3 n.d.
Rb 1 n.d. 257 237 0.3 303 281 0.2 66 59 0.6
Sr 3 5 29 33 1.9 8 14 19 23 1.7
Y 2 5 45 43 0.1 51 47 0.8 3 7
Zr 6 12 100 94 0.4 96 90 0.3 70 71 0.5
Nb 1 2 15 12 6.2 19 15 3.1 1 3
Ba 20 20 5.0 50 53 6.8 40 36 1.8 16 20 8.4
La 0 n.d. 20 17 10.3 16 12 2.3 1 n.d.
Ce 0 n.d. 47 42 5.4 39 36 5.8 3 n.d.
Nd 0 5 23 26 8.2 20 23 6.3 1 4
Pb 0 n.d. 19 48 0.6 22 57 1.8 5 4
10 Yasushi Mori and Hidehisa Mashima

50

40 y =5236x0-9008 40 y =86.589x0-8993
§ 30 30

Q
H
00
PC
20

10

0
^ N~ —£*--
50
* •
100
20 |fc

10

0 IW^.TT
0 100 200 300 400 500 600
• • • »
700

Sc (ppm) V (ppm)

y = 36.094x 0.6108

I i i i »t:
0 100 200 300 400 500 600 700 50 100 150 200 250

Cr (ppm) Ni (ppm)

50 50 p
40 I- y=111.64x 1J0544
40 - y = 5.744*-0.4747
$ 30 - 30 -

H 20 20
oo

* 10 10

0 =*=t ^ i • • i 0 S »l|i • •'»•»•

50 100 150 200 250 0 50 100 150

Cu (ppm) Zn (ppm)
50
50 |-
y=143.73x 1.4059
40
y = 21.470x •0.7760
40 -

30
30 -

20 20
oo

10 10

0 * • — i i i i +1 i i i i i g i 0
I
\fm i n|i i n __
i i nni i i |i i
0 50 100 150 200 250 ° 100 200 300 400 500

Rb (ppm) Sr (ppm)

Fig. 4. Relationships between the relative standard deviation (RSTD) and the average concentration of trace elements.
 XRF analysis of silicate rocks 11

DU DU

40 y=16.428x-0*291 40 y =2.1347x-02559
£ 30 30
Q
H 20 20 -

00

* 10 10
•
*F~^-« —E— 1 • i • » i n-1—
0 0

10 20 30 40 50 0 50 100 150

Y (ppm) Zr (ppm)

50 r

y =59.919x-11806 40 I- y=10332x •0.8710

T • w 1 1 0

10 20 30 40 50 0 100 200 300 400 500

Nb (ppm) Ba (ppm)

50 r 50 r
1.0787
y=182.47x

20 30

La (ppm)

DU

40 y=193.37x"11423 y = 85356x 1XJ787

£ 30 _

Q •\
H 20 ^ •
00
QC
* 10
*V^^^ •
n . •
10 20 30 40 50 0 10 20 30 40 50

Nd (ppm) Pb (ppm)

Fig. 4. -Extended
12 Yasushi Mori and Hidehisa Mashima
Thus the techniques described in this report are available
for petrologic and geochemical studies.
CONCLUSIONS
1. Analytical techniques for silicate rocks by XRF
spectrometry were examined. The use of 1:5 dilution
glass beads and a fundamental parameter approach
yields reliable calibration lines with wide optimal
ranges of composition. This method enabled the
major and trace element analyses of silicate rocks with
ultramafic, basic, felsic, calcic and alkalic compositions
using a single glass bead.
2. Analytical results of GSJ geochemical reference sam
ples are in good agreement with their recommended
values. They also exhibit sufficient precision and sen
sitivity for both major and trace elements. Thus the
techniques described in this report are available to
petrologic and geochemical studies of various types of
silicate rocks including metasomatic rocks.
ACKNOWLEDGEMENTS
The authors are grateful to Dr. T. Nishiyama and an
anonymous reviewer for their critical reading and com
ments of the manuscript. We thank Drs. T. Yanagi and
T. Miyamoto who gave us GSJ geochemical reference
samples (JB-1 and JR-2). This study was partly support
ed by the Ministry of Education, Science, Sports and
Culture, Grant-in-Aid for Young Scientists (B), No.
16740303 (Y. Mori) for 2004-2006.
REFERENCES
de Jongh, W. K., 1973. X-ray fluorescence analysis applying theoreti
cal matrix corrections-Stainless steel. X-Ray Spectrometry, 2:
151-158.
Goto, A., Horie, T., Ohba, T. & Fujimaki, H., 2002. XRF analysis
of major and trace elements for wide compositional ranges from
silicate rocks to carbonate rocks using low dilution glass beads.
Japanese Magazine of Mineralogicai and Petrological Sciences, 33:
162-173 (in Japanese with English abstract).
Goto, A. & Tatsumi, Y., 1991. Quantitative analysis of rock samples
by an X-ray fluorescence spectrometer (I). Rigaku-Denki Journal,
22: 28-44 (in Japanese with English abstract).
Hattori, H., 1971. Preparation of glass disc sample of rock for light
element analysis by X-ray spectrometry. Bulletin of the Geological
Survey of Japan, 22: 103-116 (in Japanese with English abstract).
Imai, N., Terashima, S., Itoii, S. & Ando, A., 1995. 1994 compila
tion of Analytical Data for Minor and Trace Elements in Seventeen
GSJ Geochemical Reference Samples, "Igneous Rock Series".
Geostandards Newsletter, 19: 135-213.
Imai, N., Terashima, S., Itoh, S. & Ando, A., 1999. 1998 compila
tion of analytical data for five GSJ geochemical reference samples:
The "instrumental analysis series". Geostandards Newsletter, 23:
223-250.
Kimura, J. & Yamada, Y., 1996. Evaluation of major and trace
element XRF analyses using a flux to sample ratio of two to one
glass beads. Journal of Mineralogy, Petrology and Economic
Geology, 91: 62-72.
Mashima, H., 2002. Improvement of XRF analysis for trace elements
in silicate rock samples using the flux fused disk method. Science
Reports, Department of Earth and Planetary Sciences, Kyushu
University, 21: 37-48 (in Japanese with English abstract).
Mashima, H., Maeda, S., Takahashi, Y., Sato, N. & Ide, T., 2002.
Re-examination of XRF analyses for major element compositions of
silicate rock samples. Science Reports, Department of Earth and
Planetary Sciences, Kyushu University, 21: 27-35 (in Japanese with
English abstract).
Matsumoto, R. & Urabe, T., 1980. An automatic analysis of major
elements in silicate rocks with X-ray fluorescence spectrometer using
fused disc samples. Journal of Mineralogy, Petrology and Eco
nomic Geology, 75: 272-278 (in Japanese with English abstract).
Nakada, S., 1985. X-ray fluorescence analysis of trace elements in
silicate rocks using fused disk samples. Science Reports, Depart
ment of Geology, Kyushu University, 14: 117-127 (in Japanese with
English abstract).
Nakada, S., Yanagi, T., Maeda, S., Fang, D. & Yamaguchi, M.,
1985. X-ray fluorescence analysis of major elements in silicate
rocks. Science Reports, Department of Geology, Kyushu Univer
sity, 14: 103-115 (in Japanese with English abstract).
Ohmori, T. & Ohmori, E., 1976. X-ray fluorescence analysis of major
elements in rocks and minerals, part 1, preparation of glass disc
samples. Bulletin of the Geological Survey of Japan, 27: 95-211
(in Japanese with English abstract).
Sugisaki, R., Shomomura, T. & Ando, K., 1977. An automatic X-ray
fluorescence method for the analysis of silicate rocks. Journal of
the Geological Society of Japan, 83: 725-733 (in Japanese with
English abstract).
Terashima, S., Taniguchi, M.. Mikoshiba, M. & Imai, N., 1999.
Preparation of two new GSJ geochemical reference materials: Basalt
JB-lb and coal fly ash JCFA-I. Geostandards Newsletter, 22:
113-117.
Yajima, K.., Ono, M. & Fujimaki, H., 2001. Analytical accuracy and
precision of major and trace elements for bulk rocks using a 1:5
dilution glass bead by XRF. Japanese Magazine of Mineralogicai
and Petrological Sciences, 30: 28-32 (in Japanese with English
abstract).
Yamada, Y., Koiino, H. & Murata, M., 1995. A low dilution fusion
method for major and trace clement analysis of geological samples.
Advance in X-ray Chemical Analysis Japan, 26: 33-44 (in Japanese
with English abstract)