Chemicaa Geology I 19 ( B995, ) I- 12

Islam-Planck-bttstirt!s j& Chetnir, Postjach 3060, D-55020 ,Wainz, Cmnan_v

Received 30 January 1994; revision accepted 12 August 1994

A new high-performance liqui cbromatogra~~~ic (HPLC > proc re has been developed and applied to the
determination of Th and U cone trations in geological materials. ck samples are first acid-digested in screw-
cap Savillex@ bcakcrs with HF 104 and I-ICI. Th and U are t isolated from the geological matrix by a
quantitative two-step ion-exchange procedure. Determination of the elements by FIPLC then follows. Th
are separated from one another and residual matrix elements as complexes with a-hydroxyisobutyric acid (
on a reversed-phase column using gradient elution in - 10 min. Detection of Th and U is accomplished by
spectrophotometry after an on-line postcolumn reaction with Arsenazo HI. Detection limits are - 30 and - 100
pg for Th and U (or - 0.75 and - 2.5 ppb using 100-mg rock samples ), respectively.
The HPLC technique has been applied to the analysis of nine international and three well-characterize
standard rocks to eva!uate ana!ytica! erf@r_mance.T?! and U concentrations in the analyzed samples spanned the
range of c 10 ppb to > 10 ppm. The PLC data show excellent agreement with values obtained by spark source-,
inductively coupled plasma- and isotope dilution thermal ionization mass spectrometry. The I sextcrnal precision
of the method is better than I!I2% and + 5% for the determination 3% and U concentrations higher than 50 and 5
ppb, respectively.

and U ab~~da~ces oft

jar subreservoirs form
A detailed knowledge of the geochemistry of . (e.g., Jochum et al., 1983; Taylor and
Th and U is necessary for understanding terres- nan, 1985). Such data also permit a bet-
trial evolution. Models of the thermal history of ter understanding of the physical processes gov-
thz Earth are highly dependent upon assump- erning the fractionation of incompatible trace
tions about the geochemical distribution of Th elements between the silicate reservoirs
and U (e.g., Christensen, 1985; Galer and Gold- Earth (e.g., Galer and O’Nions, 1985).
stein, 199 I ). This is so, because heat production work by White ( 1993) has shown that U-
is solely governed by the abundances of naturally elemental systematics of the mantle may
occurring radioactive elements. Therefore con- similar information. Abundances of T
siderable &x-t has been made to estimate the Th and abundance ratios with other trace elements,
such as Nb, have been used to constrain the mass
INAl

0009~2541/95/$09.50 0 I995 Elsevier Science B.V. All rights reserved

SSDIOOO9-2541(94)00105-7
2 M. Rehkiimper 1 Chemical Geology 119 (1905) i-12

balance of the Earth’s internal differentiation

(e.g., Hofmann et al., 1986).
Th and U are extremely depleted in some geo- 2.1. HPLC system
logical samples (e.g., mid-ocean ridge basalts: Th
-., 150 ppb, U - 60 ppb) and at low concentra- A schematic diagram of the EC apparatus
tion levels in many rock types such as ocean is- is shown in Fig. 1. For eluent delivery a Syk
land basalts (Th - 4 ppm, U - 1 ppm) and or- low-pressure gradient system consisting of an
ogenic andesites (Th - 5 ppm, U - 1.5 pm) 2000 pump with PEEK (polyetheretherketo
(Taylor and McLennan, 1985; Hofmann, 1988; pumpheads, an S 2000 gradient controller and
Sun and McDonough, 1989). Thus, resolution of an S 8110 low-pressure gradient module (with
fine-scale abundance variations requires the use eluent mixer) was used. Two
oftechniques with high analytical sbnsitivity and were employed during this
precision, such as isotope dilution-thermal ion- 125 x 4.6 mm (filled with 3-p
ization mass spectrometry (ID-TIhlS), spark C18 reversed-phase material
source mass spectrometry (SSMS) or induc- 125 x 4 mm with 4-pm Superspher@ ZOORP-18
tively coupled plasma-mass spectrometry (ICP- resin. A metal-free filter with 2-pm polyethylene
MS). The high instrumentation and operating frits (Upchurch Scientific@) was used for col-
costs as weli as limited instrument access are sig- umn protection. Delivery of the postcolumn re-
nificant drawbacks, however. agritt (PCR) waj accomplished Wifh a second
Two HPLC techniques for the determination metal-free PEEK S IO00 pump. The pulse dam-
of trace elements in rock samples have previ- pener behind the PCR pump consisted of a
ously been developed at this institute (Cassidy, 125 x4.6 mm PEEK column (Gram@ ) filled
1988; Rehkgmper, 1994). Long-term experience with 3-pm resin. The PCR mixer, constructed
with one of these methods has shown that HPLC from a PEEK-tee (Upchurch Scientific
can provide reliable trace-element data on a rou- similar to the screen-tee reactor descr
tine basis, while instrumentation and running Cassidy et al. ( 1987). The remaining compo-
costs are relatively low. Several HPLC tech- nents of the HPLC apparatus consisted of an in-
niqucs have been developed in the past for the ert Rheodyne@’9125 injection valve with 500~~1
determination of actinide elements in a variety PEEK sample loop, a Linear Instruments@’ 204
of sample types relevant to the nuclear or min- variable wavelength detector and a Shimadzu*
eral processing industry (e.g., Barkley et al., 1986; C-R6A computing integrator. PEEK capillary
Kerr et al., 1988). These studies demonstrated tubing and fittings were used throughout the
the suitability ofHPLC for precise, routine anal- chromatographic system.
ysis of trace Th and U. Here a new, highly sensi-
tive HPLC technique for the quantitative deter- 2.2. Reagents and materials
mination of Th and U concentrations in
geological samples is presented. HPLC eluents were prepared with deionized
The analytical procedure involves acid-diges- and double-distilled water from a quartz still,
tion of rock samples and the separation of Th and HPLC grade methanol (Merck@’) and a 1 M (x-
U from bulk rock components by ion-exchange hydroxyisobutyric acid (HIBA) stock solution.
chromatography. HPLC analysis then follows. The HIBA stock solution was prepared by disso-
Gradient elution is used to effect a fast separa- lution of purissima grade HIBA ( - 99%, Fluka@ )
tion ( - 10 min) of Th and U from one another in purified water. Insoluble organic residues were
and residual matrix elements on a reversed phase then separated from this solution by filtration
column. With on-line postcolumn addition of using 0.45~pm filters (Millipore@ ). Further pu-
Arsenazo III and spectrophotomctric detection rification was achieved by ion-exchange liltra-
of Th and U, detection limits in the sub-nauti- tion of Zhe solution through a Teflon@ column
gram range are achieved for both elements. filled with - 200 ml of Bio-Rad AG5OWX8@
 Fig. 1. Schematic diagram ofthe

e eluents were p

Cl. After refluxi

Th and U standard solutions ( - 1000 pg ml- ’) heated strongly ( > 140’C ) until completely dry.
HN03 matrix) were obtained from Aldrich@’and A second high-temperature evaporation step was
Alfa@. Concentrated gravimetric ( - 100 pg g- ’, carried 01’~after ad ition of N 1 ml of 6
matrix i M HN03) standard solutions contain- The samples were t en dissolved in 6 m
ing both Th and U were prepared from these and heated overnight in closed beakers to
commercial solutions after their density had been re a complete solution prior to the ion-ex-
determined accurately by repeated weighing of change separation of Th and U.
known volumes. Dilute Th, U standard solu- The dissolution procedure effkiently removes
tions ( - 1 pg g- I9matrix 2 M HN03 ) were pre- HF from the rock solutions following mineral
pared by further dilution of the 100-ppm digestion and thus prevents loss of Th by c
solutions. cipitation with insoluble
4 M. Rehktimper / Chemical Geology 119 (1995) I- 12

rides. Decomposition of samples in $avillex* fraction was collected in a

beakers is convenient and completely adequate evaporated to dryness on a
for the mafic rocks analyzed in this study. High- The second step of the p
pressure bombs, however, must be used for the quantitative separation of
digestion of samples containing resistant min- fraction collected as desc
eral phases (e.g., zircon, baddeleyite ), since these fraction was dissolved in 1
may carry significant amounts of Th and U. then loaded onto a 5-ml b
resin. Table 2 summarizes the column elution se-
2.4. Ion-exchangeseparationof Th and U quence. After the sample had been carefully
washed into the resin (with 3 x 1 ml of
A two-step ion-exchange procedure was used HN03) the column was rinsed with 8 ml of
for the isolation of Th and U from matrix ele- HN03. This eluent achi
ments. The first step, a cation-exchange separa- tiou of most matrix
tion of Th from rock solution, is summarized in amounts of ferric iron and R
Table 1. The sample, dissolved in 6 ml of 6 M column along with U, which
HCl, was added to a 5-ml bed of cation-exchange titatively up to this point. U was completely
resin and carefully rinsed into the column with washed off the resin by addition of 30 ml of 1 M
3x ! ml of 6 M HCl. The bulk sample and U HCl. The U fraction was collected either in the
were then eluted with 30 ml of 6 M HCl. Collec- beaker containing the (dried) Th fraction or in
tion of the eluate up to this point, in a 50-ml Te- a fresh Teflon* beaker and evaporated to
flon@ beaker, assured quantitative recovery of U. dryness.
This bulk rock fraction was dried down on a hot
plate and saved for further processing. 2.5. Preparationof samples and calibration
The column was then washed with 15 ml of 6 standardsfor HPLC analysis
M HCl for further removal of ,the rare-earth ele-
ments (REE) and 10 ml of 3 M HCl to elute re- For quantitative determination of Th and U
sidual Fe3+, which could not be rinsed off effr- by HPLC an external calibration with pure ele-
ciently with 6 M HCl. Th was now stripped from mental standard solutions was carried out. The
the resin with 30 ml of an acid mixture that was HPLC calibration standards were pre
both 6 Min HCl and 1 Min HF (6 XL-Xl-1 M 1 ~+a combined Th, U standard SO-
weighing a di,u.,
HF; this nomenclature is used hereafter). The Th lution into Teflon@ beakers. After evaporation

Table 1
Elution sequence used for the separation of Th from rock solutions
Eluent Volume Kd Eluted
(ml)
Th U(VT)

Rock solution in:

6MHCI -6 60a-b I-2b bulk rock + U

6MHCI @-j&b
33 l-2b bulk rock + U
6MHCI 15 60”eb REE
3MHCI IO 170”-b Fe3+
6MHCl-I MHF 30 -0.Y Th
Column: 5-ml cation-exchange resin AGSUWX12,200-400 mesh. The distribution coeffncients (K,,-values) are compiled from:
‘Strelow and Boshoff ( 1972 ); bNelson et al. ( 1964) [extrapolation of the data by Strelow ( 1960) gives an identical K,-value];
and cMurase et al. ( 1964) and this study.
Table 2

Eluent

-I - 15” - 300”JJ
I-4 -’ 500‘ < Id)
8 M I-IN& 3x 1 -15” - 300aJJ 6uPk rock
8 M WN03 8 - 15” - 300=JJ bulk rock
1 li!fHC~ 30 w I’ < Id u, (Tb)
Column: 5-ml anion-exe ,200-400 mesh. The ~~s~~~u~io~coefficients (&-values) are compiled from: “Faris
andBuchanan (1964); bDanon (1956);’ unneyetal. (1959) and Wish (1959); anddKrausetal. (1956).

dierit atzlysis was m B

2.6. HPLC determination

The determination of Th and U was effected

by gradir.ut
eluent (10.2
were set to 1.5 and 0.5 ml min- I, respectively,
3.1. Separation of7X and U
and the chromatographic system was flushed un-
til fully equilibrated. A reagent absorbance of
w 0.0 1 absorbance units (AU ) vs. the eluent was
obtained1 when the detector was set to the analyt- Initial studies with several ion-exchange an
ical wavelength of 658 nm. reversed-phase chromatograp
After injection of 25-2509.d sample or stan- that it is not possible to separ
dard aliquots, the uent was programmed to 2 5% titatively from rock sample
methanol, 0.2 M IBA (at pH 4.2) over 1 min. for subsequen
Delivery of this eluent followed for a further 4.5 , a two-step proc

min to complete the elution of Th and U. The Section 2.4, was adopted
gradient was then returned to the initial condi- chemical behavior of Th and U during ion-ex-
tions within 0.7 min to re-equilibrate the col- change chemistry was investigated in detail due
6 M, Rehkiinzper / Chemical Geology 119 (I 995) I- 12

to the necessity of obtaining a quantitative maturely in the first IO- 15

chemical yield on a routine basis. from the column. No Tb could be
The high kn-value of Th in 6 M HCl permits fluent fractions collected Curing farther elution.
large-volume sample solutions to be loaded onto Early loss of Th was never detecte
the cation-exchange columns (primary separa- sample size was kept < 115 mg. This su
tion step, Table 1). This is important since ma- view that premature elution of Th
jor-element precipitates may form in more con- cause the capacity of the resin bed is exceeded
centrated sample solutions, possibly scavenging for a limited amount of time during and directly
Th and U. All samples that were analyzed during after sample loading. This explanation is not
this study showed perfectly clear solutions in unique, however. It is also possible that some of
which no precipitate could be detected after the Th forms stable complexes in the sample so-
completion of acid-digestion. lutions (e.g., with trace
Th is efficiently rinsed from the first-step cat- tained by the resin. The
ion column using 6 M HCl-1 A4HF after selec- distribution coefficients
tive elution of major elements and U with 6 A4 graphic; system (Table 2) were otherwise con-
and 3 A4 HCl. Although use of HF in ion-ex- firmed by elution experiments. More than 75 ml
change chemistry is generally not desirable, a of 6 M HCl had to be passed through the column
strong complexing agent, such as fluoride, is nec- before any.
trace Th from rock samples could be
essary to remove Th erfficientlyfrom cation-ex- detected m the cffluzr~.
change resin (Kolarik, 1990). Other possible Quantitative recovery of Th from rock sam-
complexing agents include oxalic and citric acid, ples > 115 mg is nevertheless possible on a rou-
but these are solids and therefore problematic to tine basis. If a large rock sample is loaded on the
purify and difficult to separate from Th follow- cation column, the early-eluting Th will be col-
ing the ion-exchange separation. lected quantitatively together with U in the bulk
U is collected with the bulk rock fraction dur- rock fraction. This fraction is further processed
ing the first-step cation-exchange separation. using anion-exchange chromatography (Table
Even though the distribution coeflicient of U for 2 ) . The second column procedure was designed
the anion-exchange system is not particularly to permit quantitative recovery of U and Th from
high ( - 15, Table 2 ), quantitative recovery of U the bulk rock fractions. The sa 21~sloaded must
( s 99.5%) was routinely achieved, Elution ex- be completely dissolved in 8 M WN03 prior to
periments with rock samples revealed that more column chemistry, however, since any precipi-
than 15 ml of 8 M HN03 had to be passed tate is likely to contain Th. This was generally
through the column before detectable amounts possible, particularly since bulk rock fractions
of U could be found in the emuent. Addition- were found to be more soluble in 8 M nitric acid
ally, potential losses were monitored by the col- than the original rock samples. A comparison of
lection of 8 M HN03 effluent fractions before the the respective distribution coefficients (Table 2)
start of U elution. Very small amounts of U reveals that Th is retained much more strongly
( eO.5016of total) were detected in these frac- than U during elution of the rock matrix. For
tions in some cases. collection, Th can be efficiently rinsed from the
The performance of the first-step cation-ex- anion resin along with the U using 1 MHCl.
change columns was found to be strongly depen- An alternative procedure is also possible. Rock
dent upon sample size, however. Initial analyses samples with sizes > 115 mg are generally only
showed that Th was not quantitatively recovered required for the analysis of U concentrations
in the 6 M HCl- 1 M HF wash if the sample size < 20 ppb (Section 3.2). In such cases, the solu-
was > 125 mg. A detailed investigation of the Th tions can be split prior to column chemistry. The
ehtion pattern was undertaken to investigate this majority ( - 60-80%) of the rock solution ic then
problem. These experiments revealed that fol- used solely for the isolation of U, while Th is sep-
lowing sample loading, some Th was eluted pre- arated from the smaller split, containing < 115
are eluted. The so

Th 0.001 AU

Ii
Ji fined by the repetitive injection of an
solution, was N ?8.5-1.5% (la) for S
containing 1-5 ng of Th and LJ.
I , I I
The calibration curve for quantitative ana
0 2 4 6 8
usually spanned a c entration range of 1-2 or-
Time / min ders of magnitude. owever, the effective ana-
Fig. 2. HPLC chromatogram of Th and U after separation lytical range is far greater than this, because di-
from a basaltic rock. Chromatographic conditions are de- lution factors and injected sample volumes could
scribed in the text (see Section 2.5). The prominent concave be varied and chosen according to needs.
shape of the baseline is caused by the gradient profile. Sam-
ple: 100 ,ul of a 500~~1sample solution obtained by separa-
of
areas are essentially unaffected ( w Eo internal
precision) by variations in sample vc”:a~~~ ~XXD
tion of Th and U from w 90 mg of Hawaii basalt K88-30. The
injected sample contains _ 17 ng Th and _ 5.5 ng U. 25 to 250 ~1. The Th and ‘U concentrations can
S M. Rehkdrnper / Chemical Geology 119 (199s) I- 12

be determined together or independently de- plotted in Fig. 3. Eat individual value for a
pending upon how the ion-exchange separation sample is normalized to
is performed. One advantage in performing the HPLC value in order to h
analyses separately is that the dilution factors can scatter. The data show th
be chosen independently. Due to the lower de- proximately constant for
tection sensitivity of U this may be advanta- tions of > 50 ppb. These results were then use
geous for low concentration samples with high to calculate an overallvalue for the anaIyticaI re-
Th/U ratios. producibility of the technique. This is -- Ir 1.7%
( lo external precision) for samples containin
3.3. Analysisof rock samples Th and U concentrations of > 50 ppb.
cibility is poorer for samples
Nine international geochemical reference ma- Th and U concentrations. A
terials and three well-documented Max-Planck- of + 4.9% ( lcr) for s
Institut fur Chemie (MPI) in-house rock stan- centrations of < 50 ppb is inferred from the an-
dards were analyzed by HPLC for Th and U to alytical results on BIR-2 and JP-1.
evaluate the analytical performance of the new The HPLC results are compared with com-
technique. The highly depleted reference sam- piled literature values and data acquired by mass
ples BIR-I, BTHO and JP-I were used in this spectrometry (ICP-
study to demonstrate the high sensitivity of the and neutron activati
HPLC method. Concentrations varied between der to demonstrate the analytical accuracy of the
0.012 and 19.2 ppm for Th, and 0.008 and 4.76 new method. Agreement is seen, in general, to be
ppm for U in the samples. Ten rock standards good for samples with Th and U concentrations
were analyzed repeatedly using separate disso- of > 50 ppb, with deviations being < 1O”/o in most
lutions to quantify the analytical precision. cases. Excellent agreement is achieved for the
The procedural blank was carefully monitored well-characterizedreference sample BHVG-I and
to avoid an analytical bias on low-concentration the two MPI in-house standarZ
samples. No accurate total blank values could be lZOB previously measured by
determined, however, since the analysis of blank HPLC results for the standard rocks BE-N and
samples consistently revealed no detectable con- W-2 are both very similar to the compilation val-
tent of Th and U. The same result was obtained ues and some mass spectrometric results. Other
on three procedural blanks for U that were pooled literature values for these samples, however, dif-
to increase detection sensitivity. This constrains fer significantly from the results obtained in this
blanks to be < 30 pg for Th and U, thus ruling study. There are no clear systenmaticdifferences
out any significant blank contribution to the between the HPLC and reference data sets for the
measured concentrations. Geological Survey of Japan standard rocks. In
The analytical results obtained on standard general, deviations are smaller if the HPLC val-
rocks are summarized and compared with refer- ues are compared with mass spectrometric data
ence values in Table 3. The standard rocks JA-2, as opposed to the reference values of Govinda-
JB-2, JB-3 and K88-30 were each analyzed 4-6 raju ( 1989). HPLC Th values are generally
times to evaluate the analytical precision. Based higher than ICP-MS and SSMS results for JA-2,
upon separate dissolutions, relative standard de- lower for JB-2 and very similar for JB-3. The
viations ( la) of between + 0.7% and + 3.4% for HPLC U data confirm most mass spectrometric
Th and + 0.9% and + 3.7% for U were obtained results on JA-2 and JB-2 but are significantly
for these particular samples. The analyses of lower for JB-3. This sample, however, was ana-
other samples with fewer repeat measurements, lyzed four times by HPLC and the relatively low
and Th and U concentrations of > 50 ppb ex- U value was confirmed in all analyses. The
hibit a similar precision. The individual anal;+- agreement of HPLC U in DNC-I with the ICP-
cal results for all samples with repeat analyses are MS data of Jenner et. al. ( 1990) is excellent, but
 %-
d
i-1
PI
I ci
10 M. Rehkiinrper/ Chemical Geology I1 9 (1995) I- 12

script. Pormal reviews

(4 mond and C. Roddick resulte
improvements and clarificatio
thanked for editorial handling.
the authors Ph. thesis at the University of
ainz.

B.,,I
0.01 0.1 1 10 100 eferences
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jac, L.A., 1992. Applications of high-performance ion
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.._.__ GO 0
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=
.I -5
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