Geological Materials

Anal. Chem.
1995, 67,71R-85R
Geological and Inorganic Materials

L. L. Jackson,**t P. A. Baedecker,* T. L. Fries$ and P. J. Lamothet
U.S. Geological Survey, P.O. Box 25046, DFC, MS 973, Denver, Colorado 80225, U.S.Geological Survey, National Center,
MS 923, Reston, Virginia 22092, and U.S. Geological Survey, 345 Middlefield Road, MS 938, Menlo Park, Califomia 94025
Review Contents
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Publication Date: June 1, 1995 | doi: 10.1021/ac00108a005
Geostandards
Sample Preparation and Dissolution
Atomic Absorption Spectrometry
Plasmas: ICP-AES and ICPMS
Mass Spectrometry
X-ray Spectrometry
Electron Microbeam Techniques
Particle-Induced X-ray and y-ray Emission
Nuclear Activation Methods
Miscellaneous Spectroscopic Methods
Chromatography Methods
Miscellaneous Methods
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This review surveys the literature on the analysis of geological

and inorganic materials for the two-year period October 1992
through October 1994. The review was conducted in the same
fashion as our previous reviews and with the same focus. A
computerized search of Chemical Abstracts and a manual search
of numerous primary journals were performed. We have continued in our attempt to highlight current trends and identify
geoanalysis methods primarily for the determination of inorganic
species that offer significant changes to research and routine work.
Generally, we have not included applications or techniques for
qualitative identification or elucidation of structural properties of
minerals.
Despite the many incremental changes and important but
relatively minor improvements that we cover in this review, there
is not much that is really new in the analysis of geological
materials. Many geoanalytical laboratories are being asked to
determine more elements in more samples each year and as one
of our colleagues aptly put it, They (ke., geologists and geochemists) are trying to solve the problem with smaller and smaller
samples. This is readily apparent with the increasing interest in
microbeam techniques and in particular with techniques such as
laser ablation inductively coupled plasma mass spectroscopy
(ICPMS). The development and application of ICPMS in the
geosciences is probably the most signifkant advance in geoanalysis in the last decade. Although in other areas of geoanalysis
nothing so striking has occurred, trends that have been ongoing
such as the prolieration and characterization of geostandards,
development of speciation schemes, and a greater push for
standardization, at least by the European community, and an
increasing use of chromatographic techniques have continued
during this review period.
Several noteworthy books appeared during the review period.
Riddle edited a general text, Analysis of Geological Materials, that
covers many aspects of geoanalysis ( A l ) including chapters on
an overview of geochemical research, sampling, sample prepara+
U S . Geological Survey, Denver, CO.
U S . Geological Survey, Reston, VA.
4 US.Geological Survey, Menlo Park, CA.
This article not subject to U.S.Copyright. Published 1995 Am. Chem. SOC
tion, analytical techniques, geostandards, quality assurance/

control programs, and interpretation of geochemical results.
Unfortunately, the examples do not include much emphasis on
the environmental aspects of geochemical analysis. Vander Voet
and Riddle have also prepared a practical guide for analysis of
geological materials (A2) to accompany the Ontario Geological
Surveys manual of methods (A3). Another Canadian effort covers
the sampling and analysis of soils (A4). Manuals on sampling of
contaminated soils (As) and soil testing have been updated (As).
A symposium volume on characterization of soil minerals contains
numerous chapters on analytical techniques (An. Lastly, for
those analysts who are tired of decomposing their samples, there
is a new text-Remote Geochemical Analysis: Elemental and
Mineralogical Composition (AS).
0 EOSTANDARDS
Geostandards Newsletter plays the critical role in the international distribution of information on geostandards. This is no more
apparent than in the latest special issue on the compilation of
working values for 383 geostandards (Bl). In addition to the large
increase in the number of standards included (the previous 1989
edition included 272 standards), there has been a slight increase
in the amount of trace element data reported for individual
standards. One minor problem regarding the ambiguity of the
definition of the nature or form of carbon reported has still not
been clarified. Geostandards information is also available in
computerized databases (B2,B3). Another massive compilation
(B4)has also been published which includes data on about 500
geostandards and has a greater emphasis on ores and refractories
than the Geostandards Newsletter special issue. A compilation of
data on National Institute of Standards and Technology (NISQ
reference materials has been updated (Bs). Data for rare earth
elements (REE) Sc, Y, Zr, and Hf have also been compiled for 26
Geological Survey of Japan reference materials (B6). Abbey has
revised his five-mode method for determining usable values
and evaluated it on new and old data for four Canadian ironformation samples (B7).
The results of several international collaborative studies on the
first GIT-IWG rock reference materials (B8-Bll) and Belgium
sedimentary rocks (BIZ) have been published. Data are beginning to appear on new Russian lake silt and brown coal ash
samples (B13), three new Japanese rocks rich in rare metals
(B14), and 14 South African silicates (B15). S i new Canadian
standards that were intended for certification for Au and platinum
group elements (PGE) (B10)and a NIST refractory gold ore (SRh4
886) have been developed. Independent laboratory data are also
beginning to be published for the three new NIST soils: S M s
2709-2711 (B16,B27). In a very useful departure from the past,
NIST has begun to report leachable element concentrations by
US. EPA method 3050 in addition to the certitied values and
noncertified information values for total element concentrations
Analytical Chemistty, Vol. 67, No. 12, June 15, 1995 71R

for the three soil materials (B18).An insiders perspective on

the use of analytical techniques in the certifying of reference
materials was recently presented (B19).Several routine and
nonroutine analysis procedures used to characterize the US.
Geological Survey organic-rich and sulfur-richshale material, SDO1, have been described (BZO). A new microprobe anorthoclase
standard (B21)and new materials for nitrogen isotope ratio
measurements (BZZ) have been reported. As has been recently
noted (B23), international standards and information on these
latter two types of materials has generally been lacking. Geostandards Newsletter has continued its annual bibliography on
literature related to geostandards (B24, BZ5).
SAMPLE PREPARATION AND DISSOLUTION
In the analysis of geologic and inorganic materials the problem
is often the solution. Whether the solution is the fused glass
disk often used for X-ray fluorescence 0,
the collection button
from fire assay, or the acid digest used for atomic absorption
spectrometry (AAS) , inductively coupled plasma OCP) spectrometry, and various separation techniques, the problems are similar.
Resistant mineral phases, inhomogeneous samples, volatile species, precipitates, and excessive time requirements continue to
generate interest in sample preparation and dissolution.
One of the more recent innovations in this area is the
microwave decomposition technique. Descriptions of microwave
methods with the potential advantages of rapid, controlled heating
are common, and documenting the use of microwave in place of
conventional methods is an important application area. Leaching
of sediments, soils, and sludges, by using closed-vesselmicrowave
methods, has been compared with conventional methods (C1).
Results for the two methods were in good agreement. Total
dissolution methods and automation of microwave procedures
were also discussed. In another area, microwave heating was
compared with conventional procedures in Tessiers extractions
of sediments (CZ). Results for extractions prepared using
microwave heating were similar to those obtained using conventional methods, but the extractions were completed more rapidly
using the microwave approach. Microwave heating has also been
applied to the on-line digestion of various materials, including
sewage sludge, for direct, automated, determination of Cu, Mn,
Pb, and Zn by flame AAS (C3). Digestion was carried out on
slurried samples flowing through a Teflon coil in a microwave
oven. Although Zn results were generally low, data for other
elements were acceptable.
At the other end of the spectrum is fire assay, with origins
dating to the very beginnings of geochemical analysis. This is
still an area of active application developmentwith the recent focus
on nickel sulfide fire assay techniques for PGE. Improved
recovery of PGE was reported using a modified nickel sulfde
method and ICPMS (0).The method simplifies sample handling, reduces waste generation, and eliminates potential loss of
PGE during the recovery phase. Difficulties encountered during
the determination of PGE in kimberlites by using nickel sulfide
fire assay combined with neutron activation analysis (NAA)
resulted in a radiotracer study that detailed problems with
incomplete melting and losses during dissolution (C5). Lower
detection limits than previous NAA analyses were reported, and
results from previous studies of PGE in kimberlites were questioned. Nickel sulfide fire assay, lead fire assay, and leaching by
aqua regia have been compared for the determination of PGE
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Analytical Chemistry, Vol. 67, No. 72, June 15, 1995
using ICPMS (C6). The aqua regia leach generally produced

incomplete recoveries, and nickel sulfde lire assay gave the best
general results. However, it is important to note that lead lire
assay provided better recoveries for Au, Pd, and Pt. An improved
lead fire assay method for the determination of Au, Pt, and Pd
for a wide range of sample types has been described (C7). ICPMS
was used and detection limits lower than those obtained with
traditional methods were reported. Nugget effects were documented, and results were reported for geological reference
materials.
Although many dissolution methods employ extremely vigorous schemes of attack, there are always exceptions. Acceptable
results for the determination of Mn in rocks, ores, and minerals
were reported by using room-temperature decomposition with
hydrofluoric acid and aqua regia (C8). Samples were allowed to
react for 24 h, and Mn was determined by spectrophotometry. In
another application, an ultrasonic bath was used for the digestion
of sediment, sludge, and soil (C9). Aqua regia or an aqua regia/
hydrofluoric acid mixture was used, and Cd, Cr, Cu, Mn, Ni, Pb,
and Zn were determined by AAS. Acceptable results were
obtained for all elements in the sludge sample, for Cd, Cr, and
Cu in the sediment, and for Cd, Cu, and Zn in the soil. In the
field of coal analysis, a very low-temperature ashing method has
been reported (C1O). To decrease the reaction rate, thus
preserving the mineral matter to be extracted, the oxygen used
in ashing was mixed with helium. Conditions were shown to vary
with coal rank.
Precipitates are often cited as potential problems in dissolution
procedures. These precipitates are seldom identified, and the
exact nature of the problem they cause is not often defined. An
exception to this is a study of fluoride precipitates and their effect
on Sm and Nd determination (C11). Three precipitate phases
that fractionate Sm and Nd were identified, and solutions to the
precipitate problem were presented.
Sample preparation and decomposition techniques for specific
methods are found in the appropriate section of this review.
ATOMIC ABSORPTION SPECTROMETRY
The application of atomic absorption spectrometry to the
analysis of geological and inorganic materials continues to
generate a tremendous number of publications. A comprehensive
inventory of the literature can be found in the biennial listings in
Atomic Spectroscopy (01-04,
and exhaustive reviews of AAS
applications in this area are included in the EnvironmentalAnalysis
Updates section of the Journal of Analytical Atomic Spectrometry
(05).In addition to these encyclopedic efforts, a mostly historical
review of the application of AAS to the analysis of geological
materials at the Geological Survey of Canada has been published
(06).
In spite of the substantial number of publications devoted to
geological and inorganic applications of AAS, new applicationsare
relatively rare. This can probably be attributed to the vastness
of the existing literature and to the maturity of the theoretical
and applied aspects of AAS. Most of the current application work
in this area is focused in two general directions.
The first of these is devoted to increasing the throughput of
the method to take advantage of the relative simplicity, low cost,
and high sensitivity of AAS and to make AAS competitive with
multielement techniques such as inductively coupled plasma
atomic emission spectroscopy (ICP-AES) and ICPMS. The
approaches taken include renewed interest in simultaneous,

multielement AAS, applications of solid sampling techniques,

standardless analysis of real samples, and modified pretreatment
programs in electrothermal atomization graphite furnace atomic
absorption spectrometry (ETA-AAS),
The second area is represented by some interesting a g
proaches to isolating various analytes. These include automated
sample preparation steps for separation, concentration, and
introduction. In most cases, these methods could be utilized for
a number of different instrumentaltechniques and are not unique
to AAS. Methods for which the strengths of AAS make it the
obvious detector of choice are included in this section.
The commercial availability of simultaneous multielement
atomic absorption spectrometersmay be a key factor in extending
the useful lifetime of AAS. Such an instrument has been used
for the determination of Ru, Rh, Pt, Ir, Pd, Ag, and Au in rocks,
ores, and other materials by electrothermalatomization (07).The
elements Ru, Rh, Pt, and Ir were determined in one firing and
Ag, Au, and Pd in a second firing. Although higher atomization
temperatures were required to achieve sensitivities comparable
to conventional ETA-AAS, results for reference materials compared
well with accepted values. Simultaneous multielement electrothermal AAS has also been applied to the determination of Sc,
Eu, Dy, Ho, Er, Tm, Yb, Y, Nd, and Sm in rocks (08). After
dissolution and concentrationit was possible to determine Y, Nd,
and Sm in the low microgram per gram range and Sc, Eu, Dy,
Ho, Er, Tm, and Yb in the low nanogram per gram range.
Multiple determinationswere made on single firings, and results
were in general agreement with ICP-AES and ICPMS data.
Direct analysis of solid materials continues to be an area of
active application development. This approach is being used in
both flame and electrothermalatomization AAS with an emphasis
on introducing the sample as a slurry. Slurry sampling coupled
with flow injection has been applied to the flame AAS determination of Fe, Ca, and Mg in silica-based materials (09). A variablevolume chamber allowing on-line dilution of the slurry has been
described, and precision in the 1-5% range was reported for
diatomaceous earth samples. A fast temperature program has
been used in conjunction with slurry sample introduction for ETAAAS determination of Cd, Zn, and Mn in silica-based materials
(010). Aqueous standards and conditions optimized for diatomaceous earth were shown to produce acceptable results for
reference materials. Slurry sampling for ETA-AAS has also been
described for the determination of lead in marine sediments (011).
The effects of various suspension agents and particle sizes were
investigated, and a precision of 5% was reported. Results for
samples prepared by using an acid digestion were not significantly
different from those obtained by using the slurry method. A
method utilizing ~ WHOin Ar demonstrated significant background
reduction in the analysis of soil and sewage sludge by using ETAAAS and slurry sampling (012). This approach resulted in
correctablebackground signals and results for certified reference
materials that were generally acceptable.
Standardless analysis is another approach to making AAS a
universal method. Because improvements in fundamental data
are critical for real-life applications in this area, developments tend
to come in bursts and are often based on the analysis of synthetic
samples. Several investigations of the effects of atomization
temperature on characteristic mass and atomic absorption coefficients, with results for real samples, have been published. These
include studies on the determination of Ag and Cd (013), In
(014,and Cr (015)in sediments and other geological samples.
Results were generally in agreement with published data.

The excellent sensitivity of ETA-AAS for many elements has
made it the method of choice for many types of geological and
inorganic analyses. One weak point of this approach has been
analysis times of 2-3 min per determination. To overcome this
shortcoming, various fast furnace protocols continue to be
investigated. The application of fast furnace methods to the
determination of geologically important elements including As,
Pb, Se, Tl, Cd, Cu, Cr, and V indicated that procedures can be
completed in less than 1min per determination with acceptable
results (016). Although fast furnace programs may seem to be
an easy path to increased throughput, they do not address the
real-world problems of multiple matrices and matrix modifiers.
Fast furnace programs have been compared with traditional ETAAAS methods to demonstrate the application of this approach to
a range of matrices (017). This study included multiple instruments and considered the role of matrix modifiers in fast furnace
programs.
The determination of vapor- or hydride-forming elements has
probably generated more publications than any other subject in
the field of AAS. For the most part, these experiments are
applicable to several different detection methods, but the determination of Se and Hg seem to remain the domain of AAS. A
comparison of fluorometry, hydride generation AAS, hydride
generation ICP-AES, hydride generation ICPMS, and radiochemical neutron activation analysis for the determination of Se indicates
that AAS remains the routine method of choice for all but the
lowest Se levels (018). Cold-vapor AAS also seems to remain
the method of choice for the determination of Hg in a wide variety
of sample types, in spite of interferences in complex matrices. In
one recent example, this method coupled with flow injection has
been applied to the determination of trace Hg in zinc ore (019).
A detection limit of 0.08 pg/g was reported, and results for Hg in
CZN-1 agreed with certified values. In addition to these traditional
gas-phase AAS determinations, a method for the determination
of Cd employing a continuous-flow vapor generation system and
atomic fluorescence spectrometry has been described (020).This
method was successfully applied to the determination of Cd in
sewage sludge and water with a detection limit of 20 ng/L.
Whereas the last application is not an AAS application in the
strictest sense, it is an example of the kind of incremental
development that will allow AAS to retain a role as an important,
modem analytical tool in the field of geological and inorganic
analysis.
PLASMAS ICP=AESAND ICPMS
Because of their high excitation temperatures, plasma sources

(such as inductively coupled, direct current, microwave, and glow
discharge) are popular atomization and excitation devices for the
analysis of geological and inorganic samples. In this section we
will limit our discussions to the two most popular versions of
plasma spectroscopy in use in the field of geoanalysis, namely,
ICP-AES and ICPMS.
Space limitations prevent us from including an exhaustive
review of all work published in this field. Therefore, the ZCP
Information Newsletter (R. M. Barnes, Editor) is a particularly
useful periodical for plasma spectroscopists-it abstracts papers
presented at national and international meetings, presents special
reports, and provides an annual bibliography in the January issue.
Analytical Chemistry, Vol. 67, No. 12,June 15, 1995
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A comprehensive review (El) of the application of atomic

spectroscopy to the field of environmental analysis contains 997
references and has major sections devoted to the analysis of soils,
plants, and geologic materials using various plasma spectrometric
techniques.
It is well-known that the one of the major factors influencing
accuracy in the analysis of geologic materials is the efficiency of
solid sample dissolution. Incomplete digestion of acid-resistant
mineral phases and the loss of volatile species during sample
preparation are two perennial problems that face geoanalysts. One
way of circumventing sample dissolution problems is to volatilize
the elements of interest directly from a solid sample by using a
high-temperature reaction chamber interfaced to an ICP-AES
instrument. Such a device was used, in combination with Freon12 as a halogenation reagent, to determine Cu, Mn, Zn, Al, and
Fe in marine sediment and coal fly ash samples (E2).Another
way of avoiding sample dissolution problems is to introduce the
sample in the form of a slurry. However, it has been found that
slurries (in the absence of dispersing agents) do not behave like
aqueous solutions even when particle sizes are reduced to ~ 1 . 5
pm (E3).Quantitative analyses are possible if correction factors
are determined daily by using matrix-matched reference materials.
Improving the sensitivity of ICP-AES analyses via the generation of volatile species of the element of interest was the subject
of two reports. The first report ( E 4 describes a method for
efficiently generating plumbane (FbH4) using a simultaneous
combination of dichromate and lactic acid to achieve a Pb
detection limit of 1pg/g in sediment samples. The second report
(E5) is an extension of Nakaharas earlier work on the determination of low concentrations of iodine in brine samples. The
method is based upon the generation of volatile iodine by the
oxidation of I- by using NaNOz and sulfuric acid and then
sweeping the vapors into the argon stream of an ICP-AES. The
detection limit of the method was reported to be 0.39 ng of I/mL,
which is 5 times lower than previous achievements utilizing
microwave plasma spectroscopy.
Two new separation and preconcentration methods for ICPAES determinationshave appeared since our last review. A new
chelating resin, containing pyrocatechol violet as a functional
group, has been used for the quantitative separation and determination of Ti, Zr, and Ga in geochemical samples (E@. The
separation of Au from copper concentrates by solvent extraction
permitted the subsequent ICP-AES determination of Au down to
0.1 pg/g (ET).
The field of ICPMS has continued to mature to the point where
it is now in the final stages of receiving EPA approval as SW846
method 6020 for the determination of Ag,Al, As, Ba, Be, Cd, Co,
Cr, Cu, Mn, Ni, Pb, Sb, TI,and Zn in liquid and solid wastes. A
review (ES)on the application of ICPMS to geoanalysis contains
a section on geological applications which includes isotope ratio
measurements, matrix elimination, and speciation studies.
Another popular approach to circumventing problems associated with the dissolution of solid samples is to use laser ablation
as a sampling device for ICPMS measurements. The problem
then becomes one of preparing representative and homogeneous
sample surfaces that will couple with a pulsed laser beam
operating at a wavelength of -lo00 nm. Fusion of a powdered
sample with a lithium tetraborate flux was the subject of a recent
article (E9)which concluded that there is no apparent matrix
effect when this technique is used to prepare samples for laser
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ablation ICPMS determinations of trace elements in silicate

matrices. However, in our experience, matrix independence usiig
fused samples is evident only when laser ablation is performed
with the laser in a Q-switched (high power density) mode.
A popular sample preparation method for laser ablation work
is to mix the powdered sample with a binder and then press a
pellet. This pressed pellet technique was the subject of two
reports (El0,Ell) which investigated the use of both external
calibration and internal standardization for the determination of
REE in soils and silicate rocks. Internal standardization using
43Ca (E12) also has been shown to be an effective way of
determining Sr, Y, Ba, and REE in carbonates using non-matrixmatched standards for calibration. The accurate determination
of light REE (La, Pr) is hampered by the presence of oxychloride
ions, specifically CaC104+,according to Longerich (El3),who
found enhancements in several calcium and magnesium oxychloride ions in HC104 solutions compared to equimolar solutions of
HCl. Furthermore, these interferencescannot be corrected using
blank subtraction strategies because blanks typically do not
contain either Ca or Mg. The attenuation of polyatomic oxide
interferences can also be accomplished by the addition of
hydrogen to the nebulizer gas in ICPMS (E14)-a feat that was
achieved by earlier workers using nitrogen gas addition or spray
chamber cooling procedures.
In the early 1800s, dry chlorination was used to prepare
samples for the determination of PGE. This technique, which
involves subjecting heated samples to a stream of chlorine gas,
has been modified over the last several years by Perry et al. (El$,
who developed a method for handling large samples (250 g) for
the ICPMS determination of PGE in rocks, clays, and sands.
Currently, a widely used method for the determination of PGE is
nickel sulfide fire assay followed by ICPMS. A slightly modified
version of this technique has been reported (El6) to yield
improved recoveries of PGE from geological samples. Of the
PGE, Os is the most d ~ c u l to
t determine because of its low
natural abundance, because of its relatively poor recovery by NiS
(-65%), and because Os04 is highly volatile. A slurry nebulization
method (El 7) has been developed for PGE determinations by
ICPMS which exhibits excellent accuracy for Os. The only
shortcoming of this slurry method is its poor recovery of Pt,which
could be caused by the presence of intermetallic Pt species that
are both refractory and acid resistant. The traditional Pb f i e assay
procedure has been combined with ICPMS (El8)in an attempt
to achieve subnanogramper gram detection limits for Au, Pt, and
Pd. The authors goals were achieved for Pt and Pd (0.1 and 0.5
ng/g detection limits, respectively), but they were only able to
obtain a detection limit of 2 ng/g for Au because of problems
with flux contamination.
The advantages of using flow injection as a sample introduction
system for ICPMS was first demonstrated in 1988for the analysis
of biological fluids. A pair of recent reports (El9,E20) demonstrate that flow injection can be used to minimize matrix effects
in samples containing high total dissolved solids such as brines
and fusion preparations. Detection limits using flow injection are
3-9 times better than those for continuous-flowsample aspiration
of the same matrix.
The topic of chromium speciation analysis is always of great
interest because of C r O toxicity. Chromium speciation analysis
by ICPMS using hydraulic high-pressure nebulization and ion-
pair chromatography to separate and determine both CrgII) and

C r O was reported (E21).
The determination of As and Se by ICPMS is complicated
because both 75Asand 77Sesuffer from isobaric interferences due
to ArCI. One way of overcoming this limitation used selenium
hydride generation in combination with a tubular membrane gas/
liquid separator to minimize entrainment of chloride aerosols
(E22). Another approach that has been used to eliminate chlorine
and sulfur interferences in ICPMS is anion-exchange chromatography (E23). Using this technique, it is possible to simultaneously
determine V, Cr, Cu, Zn, As, and Se in soils and other geological
materials. Group separation of Nb, Ta, W, and Mo from silicate
matrices by using N-benzoyl-N-phenylhyroxlamine in CHCl3 has
made possible the accurate determinations of submicrogram per
gram concentrations of Nb, Ta, and W in HF digests of rock
samples (E24). The solvent extraction using cyclohexane and
ICPMS quantitation of 99Tc is the subject of two reports (E25,
E26) that focus on the minimization of the isobaric interference
from 99Ru.

MASS SPECTROMETRY
Over the past several decades, the technique of thermal

ionization mass spectrometry has been used by geoscientists for
the precise measurement of both radiogenic and stable isotope
abundances in their quest to characterize terrestrial and extraterrestrial samples. Recently, a novel approach to the in situ
determination of oxygen isotopes was published by Sharp (FI),
who described a laser-assisted fluorination technique that was
used to analyze silicate minerals. During the past two years,
several papers have been published (F2-F5) that describe various
modifications to Sharps technique and extend it to the analysis
of sulfur isotopes in sulflde minerals.
One problem with conventional ion-exchange procedures for
the separation of Sr and Rb in rock samples is that if the content
of Rb is high, it is difficult to obtain a Rbfree Sr fraction for isotopic
analysis. An improved sample preparation scheme ( F a for Rb
and Sr uses HPLC in combination with ion exchange to achieve
favorable results for Rb/Sr ratios as high as 3001. A new
generation of extraction chromatographic resins, comprised of
various crown ethers, has been developed by Horwitz et al. These
materials have been applied to the isolation of Pb (F7) and Sr
(FS)from geological samples for subsequent mass spectrometric
isotope determinations. Other workers have used these crown
ether resins to perform efficient Ba/Ra separations for measuring
Ra isotopes in volcanic rocks (F9).
Negative thermal ionization mass spectrometry (NTIMS) is
renowned for its enhanced sensitivity relative to positive thermal
ionization mass spectrometry. Isotopic analysis by NTIMS was
developed by Heumann and co-workers, who recently published
an article (FlO) on the determination of Re isotope ratios using a
V20j-coated Ni filament to reduce the Re blank. With this
technique, they were able to measure 1a5Re/1s7Reratios with a
relative precision of 0.04%. NTIMS was also used for the simple
and precise determination of B isotopes in carbonates and natural
waters (F11) with an uncertainty of 0.07%, which is a 5fold
improvement in analytical precision compared to other negative
ion techniques.
A new Zn reagent method for the quantitative conversion of
HzO to Hz for the hydrogen isotopic analysis of hydrous minerals
and whole rocks has been developed (F12). Analyses by this
method are of an accuracy comparable to those using the

conventional U reagent extraction method, and they are simpler,
faster, and less expensive. The method is also applicable to the
quantitative determination of water in minerals.
A mass spectrometric method for the determination of cosmic
ray-produced 21Nein terrestrial rocks (F13) has implications for
studies involving surface exposure ages, erosion rates, and extent
of glacial cover.
To a great degree, advances in isotope geochemistry have
paralleled advances in the capability of analyzing smaller and
smaller samples. Therefore, techniques suitable for high-resolution microanalysis such as secondary ion mass spectrometry
(SIMS) and accelerator mass spectrometry have become increasingly important in the earth sciences. Because of the lack of
adequate theoretical models, quantitation in SIMS is mainly
empirical, involving comparisons between elemental intensity
ratios in the sample and a standard of similar composition. A
move toward standardless quantitative analysis requires modeling
of ion yield behavior and the ability to predict yields when no
standard is available. Recent advances in the determination of
SIMS relative sensitivity factors for Ru, Rh, Pr, Eu, Tm, Lu, Re,
Os, and Ir have been made (F14) through the successful
implantation of these ions into Si and GaAs.
Particle accelerators interfaced to mass analyzers are capable
of measuring isotopes at very low abundances in small samples.
This technique, commonly labeled accelerator mass spectrometry
(AMs),has been used to study long-lived isotopes such as OBe,
14C,26Al, 36Cl,41Ca,and Iz9I. It has recently been used for the
determination of 59Niin meteorites (F15)and lunar materials
(F16). AMs is the subject of several recent reviews (F17-FZO)
which point out that further developments may allow the measurement of 32Si,53Mn,and 6oTh in geological samples.
The technique of resonance ionization mass spectrometry
(RIMS) uses tuned laser beams to selectively photoionize specitic
species of interest (even isotopes) in a vapor cloud. Recent
progress in the application of RIMS to geochronological studies
is discussed in a review (F21).Laser-induced isotopic effects in
the measurement of Ti isotopes were reported (F22),
and similar
biases were observed in the measurement of Th isotopes (F23).
X=RAYSPECTROMETRY
The application of X-ray spectrometry to the analysis of

geological and inorganic materials encompasses a wide range of
methods and techniques. Applications include various XRF
techniques for quantitative elemental studies and studies of
oxidation states in a wide range of materials using X-ray absorption
spectroscopy (XAS) or X-ray photoelectron spectroscopy (XIS).
X-ray diffraction techniques are also briefly discussed in this
section, although it is not technically a form of X-ray spectrometry.
A wide range of analytical applications was covered in a recent
text on analytical X-ray emission spectrometry (GI). This
comprehensive handbook includes sections on X-ray techniques,
instrumentation, applications for numerous sample types, quantitication procedures, and sample preparation methods. Sample
preparation for energy-dispersiveX-ray fluorescence (EDXRF) in
particular has also been reviewed (G2). Samplingand preparation
of heterogeneous materials such as soils and geologic materials
are emphasized. Methods for preconcentration and separation
of analytes for determination by X-ray spectrometry were also
discussed. A review of microscopic X-ray fluorescence has also
Analytical Chemistry, Vol. 67,No. 12, June 15, 1995
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been completed (G3). Both tube and synchrotron radiation (SR)

X-ray sources are included in the review, with an emphasis on
the analysis of geologic materials.
In a comparison of EDXRF and wavelength-dispersive X-ray
fluorescence spectrometry 0
for the determination of Rb
and Sr in silicate rocks, similar precision was found for the two
methods below 20 pg/g, but WDXRF was found to be more
precise between 50 and 100 pg/g (0.The precision of the
EDXRF determinations could not be improved by longer counting
times because of the low-power source used in this study, and no
benefit was found in the simultaneous determination of Rb and
Sr by using EDXRF.
The method of standard additions for the determination of lead
in sediments by XRF has been shown to overcome matrix and
background problems (GS). Aqueous spikes of a sediment matrix
were used for calibration, and results compared favorably with
data obtained by using EPA methods. Although encouraging
results are also reported for the determination of Zn, Br, and Cd
with this technique, shielding problems make this approach
impractical for most elemental determinations.
A simple approach to the elimination of matrix effects, the use
of a high flux-to-sample ratio (1:10), has been shown to be effective
in the analysis of sulfide and Fe-Mn ores by XRF (G6).
Acceptable results were obtained for reference materials.
XRF has been used to determine trace levels of REE in
geological samples after anion-exchange separation of the REE
and precipitation of the REE as thin films on a membrane filter
(G7). Results were compared to certified values, and data for
inductively coupled plasma optical emission spectrometry was also
presented. The determination of REE by EDXRF using a
fundamental parameters method has also been reported (G8).
Data for 11REE and Th were calculated and precision in the range
of 2-2% was reported. Detection limits that were in the 300 pg/g
range for the heavy REE were 1 order of magnitude higher for
the light REE.
A fundamental parameters method using both EDXRF and
WDXRF information has also been described (G9). Geologic
reference materials were used to test the method, and improved
results for low atomic number elements were reported.
A theoretical approach to background measurement has been
applied to the determination of Ce, La, Ba, and Cs in geologic
samples (G10). A formula defining the continuum as a function
of wavelength was fitted to background measurements on either
side of the peak of interest, and the background under the peak
was calculated. A semiempirical calibration method for XRF
analysis has been applied to various sample types, including
sediment and soil standards (G11).Results were compared to
multiple regression methods for the determination of all elements
in the sample and for the determination of selected elements. A
semiempirical procedure has been used to correct for transparency effects in the determination of Sn by WDXRF (G12). A
detection limit of 4 pg/g was obtained by using a rhodium tube.
A method for determining sample mass thickness and photoelectron cross section, by using incoherent and coherent radiation,
has been applied to the multielement analysis of coal fly ash (G13).
Unweighed samples were prepared as relatively low density
pressed material, and 16 elements were determined from a 1OO@s
count.
In the area of non-SR X-ray microfluorescence 0 ,
elemental mapping continues to be the focus. The application of
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this method to large-area mapping of a rock thin section and a

multiphase alloy sample has been described (G14). Twodimensional X-ray maps as large as 50 mm by 50 mm were
possible, and principal component analysis was used for develop
ing multielement maps. A capillary-basedXRMF system with 3@
pm resolution was used for both microanalysis and mapping of
geologic materials, particles, and glass disks (G15).
Total reflection X-ray fluorescence continues to develop as a
powerful analytical tool. It has been applied to the multielement
analysis of fractions separated from sediments (G16). Application
of this method to various sample types and details of the method,
theory, and instrumentation have also been discussed (G17).
As new synchrotron radiation facilities come on line, X-ray
spectrometry employing this focused, high-intensity source is
applied to more and more analytical problems. Applications of
SR-XRF and X-ray absorption near-edge spectrometry (XANES)
to elemental imaging and oxidation-state studies of meteorites,
art objects, and other sample types have been reviewed (G18). A
variety of SR applications for geologic and other materials have
also been described including the determination of REE by SRWDXRF and the study of Cr oxidation state in soils and minerals
by using XANES (G19).
SR-XRFhas been used for the determination of REE in mineral
grains and synthetic glass samples (G20). The study demonstrates the superiority of the wiggler source for this type of
analysis, and favorable results were reported for comparisons with
data from other analytical techniques. Similar techniques have
been applied to the determination of TI,W, Ta, Nb, and Au in
lepidolites (G21). Excitation conditions and data processing for
the application were also described.
SR-XRFanalysis of individual fluid inclusions in quartz has also
been reported (G22). For synthetic fluid inclusions that were of
known composition, results were normally within 30% of the
nominal ratio.
X-ray photoelectron spectroscopy continues to be developed
as an analytical tool for the surface analysis of geologic materials.
The application of XPS to the study of a variety of problems related
to soil surfaces has been reviewed ((223). Analyses related to
speciation, oxidation states, and exchange sites on various surfaces
were discussed. XPS applications for the study of oxide minerals
and aluminosilicateshave also been reviewed (G24). This review
included a discussion of instrumentation and theory as well as
applications to clay mineralogy.
X-ray diffraction (XRD) is also an important technique for
analysis of geologic and inorganic materials. New applications
continue to be developed in the areas of mineral determination,
quantification, and automated procedures. Quantitative phase
analysis and standardless XRD are among the topics covered in
a recent NIST publication (G25, G26). A variety of XRD applications are presented in a special issue of Analytica Chimica Acta
devoted to the measurement of crystalline silica (G27).
An XRD method for the determination of thickness, composition, and mass absorption of a sample deposited on membrane
filters has been described (G28). Accuracies of 3%, 1%,and 4%
were reported for the determination of mass thickness, mass
absorption, and quantitative mineralogy, respectively.
A number of artificial intelligence or expert systems for XRD
analysis have also been described (G29-G31).

ELECTRON MICROBEAM TECHNIQUES

Electron probe microanalysis (EPMA) has wide usage in the
geosciences. One area that is experiencing a lot of attention is
the characterization of individual particles for various environmental studies. Applications of EPMA and several other microbeam techniques to the analysis of aerosols have been reviewed
(HI, H2).In order to identify particles, numerous multivariate
techniques are used, such as a nonlinear mapping technique that
has been applied to the interpretation of EPMA spectra of mine
dust and lacustrine aerosol samples (H3, H4). EPMA and
automated image analysis have been used to quantitatively
determine iron sulfides in coal ( H a . There is an increasing use
of EPMA to characterize the source of elements and their
bioavailability in soils at residential, industrial, and mine sites.
Because the application of this technique to the evaluation of Pb
in soils is particularly important in health risk assessments, but
standardized methodology does not exist, an interlaboratory
comparison was performed using two mine wastecontaining soils
( H a . Although EPMA results were generally comparable between the four laboratories that participated, more interlaboratory
variability was observed for samples with complex multiplephase
associates. It was also suggested that standard nomenclature for
soil particles and phase associations be adopted.
Numerous problems exist in EPMA analysis, such as movement of elements because of the electron beam. Because this
mobility significantly effects EPMA results, the anisotropic diffusion of F and C1 in apatite has been quantified (H7). The
mounting of EPMA specimens does not always permit subsequent
analyses such as for 40Ar/39Arlaser microprobe dating. Thus, an
alumina ceramic mounting technique was developed for sequential
analysis and dating of minerals (H8).
A new volume in the Reviews in Mineralogy series focuses on
the application of transmission electron microscopy to mineral
studies (H9).
PARTICLE4NDUCED X-RAY AND PRAY EMISSION
Particleinduced X-ray emission (PIXE) is a method capable
of providing data on major, minor, and trace elements in geological
materials. It is used for bulk analysis in either a thin- or a thicktarget mode and, more recently, as a microanalytical technique
01-PIXE). Particle-induced y-ray emission (PIGE) is similar in
practice to PIXE except that photons arising from nuclear
radiations are measured, rather than X-rays. PIGE is used
primarily for the determination of light elements. A laboratory
that does one type of analysis frequently does the other, and
therefore, we have grouped them together in this section. In most
cases, samples are bombarded by protons in an accelerator,
causing ionization and subsequent emission of characteristic
X-rays (PIXE) or nuclear transformation and the emission of
characteristic prays (PIGE). pPIXE, also know as the proton
microprobe, is similar to EPMA except that protons are used
instead of electrons. Although the application of PIXE and PIGE
to geological samples has been growing, the techniques are not
as widely applied to geochemical studies as the other analytical
techniques described here because of the need for an accelerator
facility.
PEE. Two papers have reviewed the application of p-PIXE
to problems in geology and mineralogy (11,12). A third review
treats the application of high-energy (40-60 MeV) proton beams
to the analysis of geological samples by PIXE, PIGE, and charged
particle activation analysis (13). The proceedings of two 1992

conferences on PRE/PIGE have been published: Third International Conference on Nuclear Microprobe Technology and Ap
plications, Sweden (14) and S i International Conference on
P E E and Its Applications, Japan (15). Both proceedings contain
a number of papers on geochemical applications, particularly
applications of the proton microprobe,but are not reviewed here.
,u-PIXE has been applied to the determination of major
elements in mineral specimens by using 75GkeV protons (16)and
major and trace elements in magmatic inclusions (17). The latter
paper describes modifications to the GUPM software for the
analysis of PIXE data. p-PIXE has been applied to the analysis of
silicate reference standards to demonstrate the feasibility of using
the technique to study trace-element zoning and diffusion in
petrogenetic studies of intermediate to silicic igneous rocks (Is).
PME has also been applied to the determination of solid/liquid
partition coefficients for Ni, Cu, Zn, Rb, Sr, Y, Zr, and Nb between
plagioclase and pyroxene phenocrysts and the associated ground
mass in calc-alkaline dacites (19). p-PIXE has been used to study
the partitioning of several trace elements between experimentally
produced amphibole and silicate melts having variable F content
(120). Ionoluminescence has been combined with p-PIXE and
applied to the microcharacterization of geological materials (Ill).
p-PIXE and p-Rutherford backscattering have been used to study
the distribution of trace elements in PGErich mineral grains (122).
Modifications of a proton microprobe facility to aid the analysis
of geological samples have been described (123). A comparative
study of instrumental neutron activation analysis and PIXE for
the determination of heavy metals in estuarine sediments has been
reported (114).
PIGE. PIGE and PIXE have been applied to the analysis of
Nigerian tar sands, PIGE was applied to the determination of Si,
S, N, C, and 0,whereas PIXE was used to determine Si, S, K, Ca,
Ti, Cr, Mn, Fe, Ni, Cu, and Pb (115). B, B isotopes, and Li have
been determined in tourmaline samples by using a proton
microprobe (116).A nuclear microprobe using 1.8MeV deuterons has been applied to the determination of nitrogen in minerals
(117).The detection limit was between 10 and lOOpg/g. LiCO3
has been used as a nonanalyte spike in order to correct for the
relative stopping power of 5MeV protons between samples and
standardsfor the determination of Si in chromite ore samples (118)
and F in phosphate rocks (119). The potential application of
pPIGE for the determination of isotope ratios of Li,B, C, N, 0,
Mg, Si, and S in various mineral phases has been evaluated (120).
NUCLEAR ACTIVATION METHODS
Nuclear activation analytical methods are all based on the
transmutation of stable nuclei into radioactive states, which then
decay emitting characteristic radiation. The goal of most nuclear
activation analysis as applied to geological materials is the
measurement of elemental concentrations, although it is sometimes used for determining isotopic ratios. The scope of this
section includes studies of most geologic materials but excludes
studies relating to the measurement of natural and cosmogenic
radionuclides, or environmental contamination from nuclear explo
sions or by the accidental release of byproducts from the nuclear
power industry. In addition to the computerized abstract search,
the geochemical journals, Geochimica et Cosmochimica Acta,
Chemical Geology, Earth and Planetary Science Letters, Contributions to Mineralogy and Petrology, and Geostandards Newsletter; the
Analytical Chemistry, Vol. 67, No. 12,June 15, 1995
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analytical chemistry journals AnaEytical Chemistry, Talanta, and

Analytica Chimica Acta; and the nuclear analyticaljournalsJournal
of Radioanalytical and Nuclear Chemisty, Nuclear Instruments and
Methods in Physics Research, and Nuclear Geophysicswere searched
manually in preparing this section.
The most common method of nuclear activation involves the
irradiation of the sample by neutrons followed by y- (and
sometimes B-) ray spectrometry to measure the induced activity
(generally called neutron activation analysis, NAA). Most often
the samples are irradiated by thermal neutrons in a reactor
followed by direct counting of the induced y activity (referred to
as instrumental neutron activation analysis, INAA). In some
applications, the samples are irradiated with high-energy neutrons
in order to preferentially activate nuclei with high cross sections
for epithermal neutrons (ENAA) , thereby improving sensitivity
for certain elements, or to take advantage of reactions with fast
neutrons (FNAA) when convenient thermal neutron activation
products do not exist. Detection limits can often be improved
with a chemical purification of the element of interest either before
irradiation (chemical separation, CSNAA) or after irradiation
(radiochemical, RNAA) .
Other nuclear activation methods are also applied in geochemical analysis, although their use is more limited because of the
need for access to an accelerator or an on-site reactor. Th and U
can be determined by counting delayed neutrons (DNAA) after a
short reactor irradiation. Nuclear activation, again followed by
measurement of induced activity, may be accomplished by
irradiating samples with energetic photons (PAA) or charged
particles (CPAA). In some applications, elemental concentrations
are determined by measuring prompt y-rays (photons emitted in
the nuclear reactions) during neutron irradiation (PGNAA) or
during particle bombardment (PIGE).
INAA and ENAA. Instrumental neutron activation analysis
remains an important tool for the routine analysis of geological
samples as indicated by the large number of geochemical papers
in the literature that report INAA trace element data. We estimate
that -40% of the papers that report trace element data in
Geochimica et Cosmochimica Acta, Earth and Planetay Science
Letters, Chemical Geology, and Contributions to Mineralogy and
Petrology report data obtained by neutron activation. It remains
the most commonly used method for trace element analysis,
followed by ICPMS. Elements that are of particular interest in
petrological studies, for which INAA is a preferred analytical
method, include Cs, most of the REE, Hf,Ta, Th, and U. Routine
applications in the recent literature include many studies of
igneous rocks, ores, mantle and crustal xenoliths, meteorites, lunar
rocks, sediments, soils, and coal. The papers referenced in this
review are those papers that gave more than the minimum detail
regarding analytical methodology or that represent an application
to an unusual sample matrix.
INAA has been evaluated for the analysis of soils, and the
quality of the data for various elements was placed in four
categoriesranging from very good to unsatisfactoryVI). The
relative advantages of thermal, epithermal, and Compton suppression counting for the INAA analysis of soils have also been
evaluated VZ). The relative advantages and disadvantages of
INAA and ICPMS for the determination of trace elements in crude
oils, oil fractions, and source rock bitumens have been reported
v3). An INAA method has been developed for the analysis of
large samples of heavy metal concentrates and stream sediment
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Analytical Chemistry, Vol. 67, No. 72,June 75,7995
samples of interest for mineral resource assessment by using a

slow-poke 2 reactor (14). Fission product interferences on the
determination of Zr, Mo, Ba, La, Ce, and Nd have been reevaluated
US,J6) for thermal and epithermal activation. Techniques for
the handling of small samples (40- 100 yg) have been applied to
the analysis of green-glassparticles from lunar soils and breccias
(27).
Recent developments of the k, method have been reviewed
(18), and the application of the method to the measurement of
elements having short-lived indicator radionuclides has been

described v9, 110). The method has been applied to the
determination of 32 elements in sediment reference standards
(111).
A rapid INAA method for the determination of F using the

11.0s activity 20F has been developed (112). Activation with
epithermal neutrons and coincidence spectrometry have been
applied to the determination Ir and Se in sediments at the K-T
boundary v13). A method using separate thermal and epithermal
irradiations and measurement of the 2.25min Al activity has been
applied to the determination of Al and Si in desert aerosols (114).
The use of 252Cfas an irradiation source for borehole cores,
followed by scanning the cores with a Ge(Li) detector, has been
evaluated for the determination of Au (115). An automated system
for the analysis of large (160-300 g) samples of gold ore has been
described with a sensitivity for Au of 0.01 yg/g
The
underestimation of the gold content of ores due to self-shielding
during epithermal neutron irradiation has been measured 7).
A 33% reduction was observed in a sample with particle size in
the range of 150-250 ym. A method has been developed for the
determination of In and Sn in cassiterite which may be of
archaeological interest for potential identification of ore sources
for tin/bronze artifacts V I S ) .
Radiography following neutron activation has been used to
study the distribution of Au, Ag, and other elements in mineral
and ore samples (/IS),as well as for Al, Mn, and Na in rocks
(1.0) .
FNAA. Fast neutron reactions initiated with isotopic neutron

sources (Am-Be or Pu-Be) have been used to measure F
concentrations in drill core samples by measuring the induced
I6N activity (J21) and for the determination of F, Si, and Ba in
fluorites and barites (f22). Cyclic activation analysis with 14MeV
neutrons has been applied to the determination of eight major
and minor elements in four rock standards (123).
DNAA. DNAA is a well-established technique for the nondestructive determination of U and Th that involves counting
delayed neutrons from short-lived (0.2-60-s half-life) fission
products. An automated system (250 samples/day capacity) for
the analysis of large (up to 30 mL) environmental samples has
been described c124).
PGNAA. A pair of recent papers describe the potential
application of the NIST cold neutron source for PGNAA, including
count rate data for 14 elements in the Allende chondrite standard
(/25) and the determination of H at the microgram level in Si
and quartz (126). Another recent paper reviewed elemental
analysis through the measurement of prompt y radiation produced
by inelastic scattering of accelerator-produced neutrons $3).
PGNAA and the related method of monitoring y-rays following
neutron inelastic scattering are finding increased application for
in situ analysis of rocks and coal in bore holes, and in process
control in the coal and minerals industries using neutron sources,

principally using z5zCfas the neutron source. The in situ analysis

of minerals and coal using nuclear methods including PGNAA
with isotopic neutron sources has been reviewed with 86 references cited (128). Several papers that deal with the evaluation of
coal quality through bore-hole logging and the use of on-line
PGNAA methods during coal processing appeared during the
review period (129-133). Additional applications of PGNAA using
isotopic neutron sources include the determination of Fe, Al, Si,
and Ti in rock samples (134),the determination of 23 elements
in hematite and 11 elements in phosphate ore (133, and the
determination of lime, silica, alumina, and FeO in cement raw
materials (136). PGNAA well-logging data have been compared
with laboratory analysis of the core material for nine elements
(137). The impact of statistical uncertainties of elemental concentration on the interpretation of geochemical well logs has been
evaluated (138). Monte Carlo methods have been described for
modeling neutron and photon transport during well logging (139)
and the analysis of neutron capture pray spectra from a spectrum
library (140).
CSNAA. Fire assay preconcentration of the PGE and Au by
using NiS as the collector remains an important tool for the
geochemical determination for those elements (141,142). The
method has been applied to the analysis of kimberlites; alternative
flux compositions were recommended for the analysis of peridotites and high-carbonate samples (142). A separation procedure
that involved the collection of Pd, Ir, Pt, and Au on polyaniline at
low acidities, followed by elution of Pt, Pd, and Au by using
thiourea and Ir with ascorbic acid followed by 10 M HCl, has been
described (143). For the determination of U, a preirradiation
separation procedure into 4-(5nonyl)pyridine/benzene has been
reported (144). Activated charcoal has been used as a collector
for the preirradiation separation of I that is released by heating
from soil samples (145) and as an absorbent for trace elements
released in volcanic emissions (146).
RNAA. As noted in the previous review period, much of the
work on RNAA methods as applied to geochemical studies is
directed toward developing improved methods for the determination of the PGE. An RNAA method has been developed for
the determination of Pd, Pt, Ir, Au, Ag, Se, As, and Sb by
coprecipitation in metallic Te by reduction with SnClz (147).
RNAA methods for the determination of Pt in environmental and
geological samples via I*Au (148) and Au, Ag, Pt, and Pd (149)
have been described. RNAA methods have also been presented
for the determination of Ir (150) and Ir and Os (151) in K-T
boundary sediments. A method for the determination of Re, Os,
and Ir in chondritic meteorites involved the separation of Os by
distillation and Re and Ir by anion-exchange chromatography
(152). A group separation scheme for the determination of 25
elements by using ion-exchange techniques and tetracycline as a
complexing agent for removing interferences (153) has been
described. Iridium was determined by removing the major
activities with AG 50 W x 8 cation resin. Pd, Ir, and Pt have
been determined in ultramafic rocks by extraction with DDTC
and DBDTO (154). In the same work, Cs and Na were determined by recovery with tetraphenyl borate, REE by cation
exchange, and U and Th by TOP0 extraction.
An RNAA method was developed for the determination of the
REE in monazites that involved their separation into three groups
by selective elution from AG 1-X8 resin (155). Microfire assay
methods that used lead, tin, or iron as collectors for the
radiochemical separation of various metals, including the PGE,

have been reviewed (156'). An RNM procedure for the REE by
using multiple precipitations as the fluoride has been developed
and applied to the analysis of the GOG1 gabbro (157). RNAA
methods for the determination of REE (158) and C1, Br, and I
(159) have been applied to the analysis of 15 igneous rock
reference samples prepared by the Geological Survey of Japan.
As, Sb, Se, and Mo have been determined by coprecipitation with
Bi& (160). A method for the determination of 196Hg/202Hg
ratios
in meteorites has been reported in which Hg is released by
stepwise heating (161). A rapid method has been devised for the
determination of In, Zn, and Cu in chondritic meteorites and
standard rocks (162).
CPAA. This technique finds almost no application for routine
geochemical analysis. A method for the determination of Pt in
chromite sulfide ores by a-particle bombardment (163)was noted
during this review period. A microactivation technique for the
determination of 0 in diamonds has been developed using a beam
of 3He2+from a tandem accelerator (164). e+ annihilation radiation
was measured by NaI counting. I*F activity was separated from
other e+ emitters by decay curve analysis.
PAA. PAA also finds few routine applications in geochemical
research. A method has been reported for the determination of
N in silicates (165). A rapid radiochemical separation of the 9.97min N13 activity used prior to NaI y counting of the annihilation
radiation. PAA has also been applied to the determination of up
to 24 elements in Cu-Mo ore samples by using microtron
bremsstrahlung radiation (166).
Miscellaneous Methods. Plastic fission particle track detectors that are packaged along with the analytical sample for neutron
irradiation have been used to measure the U content in bulk
samples of coal and rock following irradiation using both reactor
(167) and isotopic (168) neutron sources.
MISCELLANEOUS SPECTROSCOPIC METHODS
Classical spectrophotometricmethods of analysis continue to
be used routinely in many laboratories and at field sites around
the world. During a two-year period, the reports on spectrophotometric methods for geoanalysis typically number several hundred. However, we have not reviewed them for this article
because they generally focus on applications of new indicators
and/or minor mod~cationsof analysis conditions for specific
sample types. Many other spectroscopictechniques that are not
covered elsewhere in this review are primarily used for mineral
identification and structural studies. Therefore, we only briefly
review recent applications of such techniques as Mossbauer,
Raman, and nuclear magnetic resonance spectroscopy (NMR)
below.
A new book on Mossbauer spectroscopy discusses both theory
and applications of the technique for geochemists (K1).It also
touches on environmental and archeology applications. Although
more costly, the advantages of high-field Mossbauer analysis of
iron-containing phases have been discussed (K2). For garnets
with mixed-valenceiron states, recoil-free fraction ratios have been
obtained leading to a better procedure for the estimation of the
Fe III/II ratio (K3). Ig7AuMossbauer spectroscopy was used to
study Au adsorption on As and Sb sulfides and indicated that
reduced, elemental Au was not formed on the metal sulfide
surfaces (K4).
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Laser Raman microprobe has proved a valuable tool for

studying 5uid inclusions. In an exchange of comments, numerous
points regarding the determination of 5uid compositions have been
discussed and guidelines for documenting Raman analyses have
been proposed (K5, K6). To aid the analysis of 5uid inclusions,
Raman spectral parameters for binary mixtures of CHI and Nz
have been reported for pressures up to 700 bars (K7). h a n
techniques have also been used for mineral identiiication with
Fourier transform spectra of a wide variety of minerals being
reported (K8). A laser Raman microprobe study of 20 sulfide
minerals demonstrated the power of the technique for mineral
identiiication in hand specimens and thin sections with a spatial
resolution of -1 pm (K9). Initial results from a study of the laserexcited 5uorescence of REE in fluorite crystals has shown that
quantitation of individual REE with a spatial resolution of -3 pm
by using a Raman microprobe is possible (KlO).However, the
applicability of the technique to other minerals may be very
problematic. Laser Raman microprobe has been used to characterize carbonaceous material (K11)and the influence of laserinduced sample temperature rise on the Raman characterization
of graphite has been investigated (K12).
Solid-state NMR with magic angle spinning has been used in
numerous mineral studies. The application of 27Al NMR to
investigations of aluminosilicates has been reviewed (K13).zgSi
NMR has been applied to the determination of crystalline silica
in natural iron oxide pigments (K14).Utilizing high fields and
high spinning speeds, the f i s t 25MgNMR spectra for a variety of
mineral classes have been reported (K15).
Infrared methods along with a variety of other sophisticated
spectroscopic techniquesfor use in clay mineral studies have been
reviewed (K16,K17). Applications of near-infrared re5ectance
spectroscopy to a wide variety of materials including geologic and
inorganic materials has also been reviewed (K18).
CHROMATOGRAPHY METHODS
Liquid chromatography (LC) continues to be used in geoanalysis for separation or preconcentration steps. Numerous applications are cited throughout this review. Liquid chromatographic
techniques are also coupled, somewhat more frequently than in
the past, directly to a variety of spectroscopic techniques. The
coupling of chromatography with ICP-AES and ICPMS has been
reviewed, and a few geologic applications were noted (L1).
Generally, these coupled techniques are applied to very limited
types of geoanalysis problems such as the speciation of organ@
metallic compounds in soils and sediments. For example, lead
speciation has been performed by using liquid chromatography
coupled with isotope dilution ICPMS (La.Ion-exchange chromatography has also been used with ICPMS to determine
tributyltin (L3).Gas chromatography (GC) coupled with atomic
spectroscopicdetection methods provides another avenue for the
determination of organometallic compounds. The determination
of organolead compounds by this method has been reviewed (LA),
and the advantages of in situ ethylation of butyltin species prior
to GC-AAS determination have once again been touted (Ls).
Methods for the determination of organotin (L6)and Se species
(L7)have been reviewed. Interferences in a hydride generation
GC-AAS procedure for organotin have been evaluated (Ls). Also,
supercritical fluid extractions have been developed for organotin
species in sediments (L9, L1O).
80R
In the last decade, there has been an increase in the use of

liquid chromatography techniques for the determination of metals,
commonly with either pre- or postcolumn derivatization. The most
active area has been the determination of specific suites of REE
where the chromatographicconditions have been varied to avoid
coelution of elements. For example, La, Ce, Pr, Nd, Er, Tm, Yb,
Lu, and Y have been determined in several Japanese rock
standardsby using ion-interactionchromatography (~511).Yttrlum
was also determined in rare earth ores by a somewhat similar
method (L12).Another group has determined 11REE in various
Japanese, US., and Canadian geologic reference materials (L13,
L14). Based on their observed trends in chondrite-normalized
REE plots compared to previously published data, they suggest
that their chromatography method provides more accurate results
for several of the REE than spectroscopic and nuclear activation
techniques.
Other metals determined by chromatographic techniques
include Th and U in ilmenite, rutile, and zircon mineral sands by
using ion chromatography (L15);Nb over the range of 0.3-100
pg/g in rocks by using reversed-phase high-performance liquid
chromatography (HPLC) (L16);and metal-cyanide complexes
including Au and Ag in ore processing solutions by using capillary
zone electrophoresis (L17)and ion-interaction chromatography
(L18).
Although anions in geologic materials are commonly determined by chromatographicmethods, in many laboratories iodide
is not determined routinely by any method. In order to improve
recovery of iodine from soils, an alkaline ashmg procedure was
developed which was followed by a solvent extraction step and
GC analysis (L19).Iodine concentrationsfrom about 1to 5 pg/g
were determined in several NIST soil and sediment SRMs with
precision on the order of 1-4%.
MISCELLANEOUS METHODS
As noted in our last review, anodic stripping voltammetry has
been used for field testing in Au exploration. Development of
this technique has continued (MI). Based on an aqua regia
decomposition of 10 g of sample followed by an ethyl acetate
extraction, reasonable results were obtained for a variety of
geologic materials by using a portable voltammetry instrument.
The detection limit for the procedure was 10 ng/g. Less
successful results were obtained when cyanide leach solutions
were analyzed. Various stripping techniques have also been used
for field screening of Cd, Cr, Cu, Pb, and Zn in sediments (M2).
Chemically m o d ~ e delectrodes have been used for the voltammetric determination of Au (M3, M4), but their application to
geoanalysis has not been well tested and it is doubtful that they
will see much use in the near hture. This is generally true for
most electrochemical methods other than potentiometry. However, coulometry is used somewhat for the determination of C
and HzO in geologic materials. A coulometric method for total S
in rocks has been recently reported (M5).
The determination of forms of sulfur in geologic materials has
always been problematic. Numerous extraction schemes have
been employed, and frequently the same extraction procedure is
used for materialswith varying age and concentrationsof organic
matter. Ancient sedimentary rocks present particular problems
where it has been found that although mild acid extractions (e.g.,
6 N HCl) recover the majority of acid volatile sulfides (AVS) from
modem sediments,hot 6 N HCl plus stannous chloride is required

for complete recovery of AVS from older materials ( M a . It has

also been found that various commonly used acid and Cr(II)
extractions apparently solubilize more organic S species than
previously believed (M7). Because there is considerable concern
about the association of metals with sedimentary sulfides and their
potential toxicity, the determination of simultaneously extracted
metals along with AVS and disulfides is of renewed interest. A
simplified acid extraction with a colorimetric determination of
evolved H2S has been used for AVS determination in conjunction
with determination of the associated metals (M8). A diffusion
procedure followed by potentiometric determination of the H2S
has also been developed, but 10%more AVS was recovered than
when the more common purge and trap procedures were used
(M9). The trace metals associated with AVS and pyrite can be
overestimated owing to contributions from metals released by
organic matter during the extractions. Heavy liquid separation
of pyrite prior to analysis and several extraction schemes for the
bulk sediment that were designed to remove organic matter but
not pyrite were recently tested (MlO). It was concluded that the
concentration of trace metals associated with pyrite was most
accurately estimated from density-separated pyrite whereas the
total amount of pyrite was best determined by extraction methods.
The determination of reactive iron for interpreting paleoenvironments or iron-limitedsulfide formation has been revisited. One
of the techniques used in the past for iron extraction was a 1 N
HCl leach. This leach was tested on estuarine sediments and
based on Mossbauer results it was found that the Fe oxidation
state was maintained during the extraction ( M l l ) . By using this
leach in conjunction with dc polarography, the extracted Fe(l1I)
and Feu0 were measured and AVS was determined from the
evolved H2S. This same leach was also compared with dithionite
and concentrated HC1 leach procedures to evaluate their ability
to extract iron from pure mineral phases and sediments (Ml2).
It was observed that dithionite and boiling concentrated HCl
extracted all iron oxides that were studied but that cold, dilute
HCl did not. Thus, as a result of this pbservation and other
considerations, it was recommended that these former two
extracts be used to define the degree of pyritization and ironlimited pyrite formation. Techniques for the determination of
reactive silica in sediments have also been evaluated (M13).
Many different speciation or element/phase association schemes
have been developed in the past. Reports on this subject
frequently have several common themes such as examination of
model compounds (Ml4), comparison of sequential and simultaneous techniques ( M I $ , removal of organic matter (Ml6), and
extractions of specific toxic elements such as Cr (M17).Many
of these themes are discussed in a special issue of International
Journal of Environmental Analytical Chemistry, which covers the
proceedings of a European workshop on the sequential extraction
of trace metals from soils and sediments (Ml8). One important
aspect of the work described is the concerted effort of the
European Community Bureau of Reference (BCR) to standardize
extraction procedures (M19). This has resulted in work on testing
the feasibility of developing standards that are certified for
extractable element contents (MZO) and evaluating a BCR
proposed three-stage sequential extraction scheme for sediments
(M21-M23).
The results of standardized extraction schemes may vary
unpredictably from one sample type to another, such as in the
case of a former US.EPA method for the alkaline extraction of
C r O where spike recoveries were unreliable. However, the

method has been found to be satisfactory when restricted to soils
with oxidizing conditions (M24). Measurement of additional soil
parameters may be required to verify whether the sample is
suitable for the method or whether the soil would reduce any
added C r O .
Two different estimators, developed by Gy and by Ingamells,
for the error associated with sampling particulate materials have
been reexamined with a particular focus on Au assay (M25). It
was concluded that the Gy method has more validity in practice.
The Gy estimator was also looked at in regard to the sampling of
cyanide-contaminated soils (M26). A method for estimating the
segregation error was developed.
ACKNOWLEDGMENT
We thank the USGS Library staff in each of the regional centers,
Denver, CO, Menlo Park, CA, and Reston, VA, for their assistance in
the literature search. The use of trade names is for descriptive purposes
only and does not constitute endorsement by the U.S. Geological
Survey. We acknowledge Chemical Abstracts Service for providing
access to STN International to aid in the literature search used in the
preparation of this work.
Larry L. Jackson is a Research Chemist with the U S . Geological
Surve Branch of Geochemisty. He received a B.S. degree in chemisty

ffrom
om
i Colorado
gansas StateStateUniversity
in 1973 and a Ph.D. in analytical chemist
University in 1978. His research interests inch$
the application of electroanalytical techniques to the analysis ofgeological

materials, environmental geochemisty of sul r, element cycling in
wetlands, and the use of biogeochemisty studieskairquality monitoring.
Philip A. Baedecker is a Research Chemist with the U S . Geological

Survey,Branch of Geochemisty. He received his B.S. degree in chemisty
from Ohio University in 1961 and his Ph.D. in inorganac chemisty and
radzochemisty from the Um'verstty of Kentucky an 1967. He has served
as Chzef of the Branch of Anal tzcal Chemistry and as. Ch~azmzanof the
Matenals E ects task group of tie Natzonal Acid Prect itatzon Assessment
Pro ram. %is research interests include the appication of nuclear
anafytical methods to problems in eochemisty, computer methods in y-ray
spectroscopy and actzvation anahis, and the effectsof acidic deposition
on carbonate stone.
Terry L. Fries is a. Research Chemist at the US.Geological Survey,
Branch of Geochemzsty. He received hzs B.S. in chemisty from
California State University, Fresno in 1976 and his M.S. degree in
analytical chemzstyfiom San Jose State University in 1982. His research
znterests are zn the applzcatzon of atomzc spectroscopy to trace element
analysis.
Paul J. Lamothe is a Research Chemist at the U S . Geological Surve
Branch of Geochemisty. He received his B.S. in chemisty from t&
University of San Franczsco in 1968 and his Ph.D. in anal ical chemist
from Marquette University in 1973. Prior to joinin the $SGS in 1 9 7 r
he was a research chemzst wzth the Envzronmentaf Protection T n c y ,
Research Trian le Park, NC. His research interests are in ana ytzcal
spectroscopy a n i trace element analyses.
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been completed (G3). Both tube and synchrotron radiation (SR)

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analytical chemistry journals AnaEytical Chemistry, Talanta, and

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principally using z5zCfas the neutron source. The in situ analysis

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Laser Raman microprobe has proved a valuable tool for

Analytical Chemistry, Vol. 67, No. 12, June 15, 1995

In the last decade, there has been an increase in the use of

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for complete recovery of AVS from older materials ( M a . It has

C r O where spike recoveries were unreliable. However, the

Surve Branch of Geochemisty. He received a B.S. degree in chemisty

the application of electroanalytical techniques to the analysis ofgeological

Philip A. Baedecker is a Research Chemist with the U S . Geological

(AS) Remote .Geoche.mical Anal sis: Elemental and Mineralogical

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(Bl) Govindaraju, K. Geostand. Newsl. 1 9 9 4 , 1 8 (Special Issue, July

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SAMPLE PREPARATION AND DISSOLUTION

(Cl) Kingston, H. M.; Walter, P. J. Spectroscopy 1992, 7, 20, 22,

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ATOMIC ABSORPTION SPECTROMETRY

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