Geochemical Analysis

Methods
Marshel Emmanuelle Tampah
12113048
Tugas TA3213 Eksplorasi Geokimia dan Analisis Bijih
X-ray Fluorescence (XRF)
X-ray Fluorescence (XRF)
XRF (X-ray fluorescence) is a non-
destructive analytical technique used to
determine the elemental composition of
materials. XRF analyzers determine the
chemistry of a sample by measuring
the fluorescent (or secondary) X-ray
emitted from a sample when it is
excited by a primary X-ray source. Each
of the elements present in a sample
produces a set of characteristic
fluorescent X-rays ("a fingerprint") that
is unique for that specific element,
which is why XRF spectroscopy is an
excellent technology for qualitative and
quantitative analysis of material
composition.
X-ray Fluorescence (XRF)
A solid or a liquid sample is irradiated with high
energy X-rays from a controlled X-ray tube.
When an atom in the sample is struck with an X-
ray of sufficient energy (greater than the atoms
K or L shell binding energy), an electron from one
of the atoms inner orbital shells is dislodged.
The atom regains stability, filling the vacancy left
in the inner orbital shell with an electron from
one of the atoms higher energy orbital shells.
The electron drops to the lower energy state by
releasing a fluorescent X-ray. The energy of this
X-ray is equal to the specific difference in energy
between two quantum states of the electron. The
measurement of this energy is the basis of XRF
analysis.
X-ray Fluorescence (XRF)
X-ray Fluorescence (XRF)
Strengths
X-Ray fluorescence is particularly well-suited for investigations that involve:bulk
chemical analyses of major elements (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P) in rock and
sediment
bulk chemical analyses of trace elements (>1 ppm; Ba, Ce, Co, Cr, Cu, Ga, La, Nb, Ni,
Rb, Sc, Sr, Rh, U, V, Y, Zr, Zn) in rock and sediment
Limitations
In theory the XRF has the ability to detect X-ray emission from virtually all elements,
depending on the wavelength and intensity of incident x-rays. However...In practice,
most commercially available instruments are very limited in their ability to precisely and
accurately measure the abundances of elements with Z<11 in most natural earth
materials.
XRF analyses cannot distinguish variations among isotopes of an element, so these
analyses are routinely done with other instruments (seeTIMSandSIMS).
XRF analyses cannot distinguish ions of the same element in different valence states, so
these analyses of rocks and minerals are done with techniques such as wet chemical
analysis or Mossbauer spectroscopy.
X-ray Powder Diffraction
(XRD)
X-ray Powder Diffraction (XRD)
X-ray powder diffraction
(XRD) is a rapid analytical
technique primarily used
for phase identification of
a crystalline material and
can provide information on
unit cell dimensions. The
analyzed material is finely
ground, homogenized, and
average bulk composition
is determined.
 interference of monochromatic X-rays
and a crystalline sample. These X-rays
X-ray Powder Diffraction (XRD)
are generated by a cathode ray tube,
filtered to produce monochromatic
radiation, collimated to concentrate, and
directed toward the sample.
The interaction of the incident rays with
the sample produces constructive
interference (and a diffracted ray) when
conditions satisfyBragg's Law
(n=2dsin). This law relates the
wavelength of electromagnetic radiation
to the diffraction angle and the lattice
spacing in a crystalline sample.
These diffracted rays are then detected,
processed and counted. By scanning the
sample through a range of 2angles, all
possible diffraction directions of the
lattice should be attained due to the
random orientation of the powdered
material. Conversion of the diffraction
peaks to d-spacings allows identification
of the mineral because each mineral has
a set of unique d-spacings.
X-ray Powder Diffraction (XRD)
X-ray Powder Diffraction (XRD)
X-ray Powder Diffraction (XRD)
Strengths
Powerful and rapid (< 20 min) technique for identification of an unknown mineral
In most cases, it provides an unambiguous mineral determination
Minimal sample preparation is required
XRD units are widely available
Data interpretation is relatively straight forward
Limitations
Homogeneous and single phase material is best for identification of an unknown
Must have access to a standard reference file of inorganic compounds (d-
spacings,hkls)
Requires tenths of a gram of material which must be ground into a powder
For mixed materials, detection limit is ~ 2% of sample
For unit cell determinations, indexing of patterns for non-isometric crystal systems
is complicated
Peak overlay may occur and worsens for high angle 'reflections'
Neutron Activation Analysis
(NAA)
Neutron Activation Analysis (NAA)
Neutron activation analysis (NAA)is
anuclearprocess used for determining the
concentrations ofelementsin a vast amount of
materials. NAA allows discretesamplingof
elements as it disregards the chemical form of a
sample, and focuses solely on its nucleus. The
method is based onneutron activationand
therefore requires a source ofneutrons.
NAA can perform non-destructive analyses on
solids, liquids, suspensions, slurries, and gases
with no or minimal preparation. Due to the
penetrating nature of incident neutrons and
resultant gamma rays, the technique provides a
true bulk analysis. As different radioisotopes have
different half-lives, counting can be delayed to
allow interfering species to decay eliminating
interference. Until the introduction ofICP-AESand
PIXE, NAA was the standard analytical method for
performing multi-element analyses with minimum
detection limits in the sub-ppmrange.
Neutron Activation Analysis (NAA)

The sample is bombarded with neutrons, causing the

elements to form radioactive isotopes.
Theradioactive emissionsand radioactive decay paths for
each element are well known.
Using this information, it is possible to study spectra of the
emissions of the radioactive sample, and determine the
concentrations of the elements within it.
Neutron Activation Analysis (NAA)
Neutron Activation Analysis (NAA)
TheNAAtechniquecan be categorised according to whether gamma rays are measured
during neutron irradiation (PGNAAalso calledPGAA) or at some time after the end of the
irradiation after radioactive decay(s) (DGNAAor justNAA).
ThePGAAtechniqueis generally performed by using a beam of neutrons extracted through a
reactor beam port. Fluxes on samples irradiated in beams are in the order of one million times
lower than on samples inside a reactor but detectors can be placed very close to the sample
compensating for much of the loss in sensitivity due to flux. ThePGAAtechnique is most
applicable to elements with extremely high neutron capture cross-sections (B, Cd, Sm, and Gd);
elements which decay too rapidly to be measured byDGAA; elements that produce only stable
isotopes (e.g. light elements); or elements with weak decay gamma-ray intensities. 2D, 3D-
analysis of (main) elements distribution in the samples can be performed byPGAA.
DGNAA(sometimes called conventionalNAA) is useful for the vast majority of elements that
produce radioactive nuclides. The technique is flexible with respect to time such that the
sensitivity for a long-lived radionuclide that suffers from an interference by a shorter-lived
radionuclide can be improved by waiting for the short-lived radionuclide to decay or quite the
contrary, the sensitivity for short-lived isotopes can be improved by reducing the time
irradiation to minimize the interference of long-lived isotopes. This selectivity is a key
advantage ofDGNAAover other analytical methods.
Neutron Activation Analysis (NAA)
TheNAAtechniquecan also be categorised according to how the analysis is
conducted.
If NAA is conducted directly on irradiated samples it is termedInstrumental
Neutron Activation Analysis(INAA). With the use of automated sample
handling (e.g. using rabbit system), gamma-ray measurement with solid-state
detectors, and computerised data processing it is generally possible to
simultaneously measure more than thirty elements in most sample types without
chemical processing. The application of purely instrumental procedures is
commonly called instrumental neutron activation analysis (INAA) and is one
ofNAA's most important advantages over other analytical techniques, especially
in the multi-element analysis.
If chemical separations are done to samples after irradiation to remove
interferences or to concentrate the radioisotope of interest, the technique is
called Radiochemical Neutron Activation Analysis (RNAA), which is not
frequently performed due to its high labor cost (only done in some cases where
concentration of the radioisotope of interest is needed).
Neutron Activation Analysis (NAA)
Strengths
Can analyze a large number of elements simultaneously
Very low detection limits for many elements
Small sample sizes (1200 mg)
No chemical preparation
Non-destructive. The material is available for other analytical techniques
Limitations
The major limitation is the number of elements that can be analyzed by this
technique. Several elements of geological interest, such as Nb, Y and some
transition metals, are better determined by other analytical methods. For example,
more precise Rb, Sr, Y, Nb, and Zr concentrations can be obtained by x-ray
fluorescence (XRF). In fact, INAA and XRF are complimentary techniques and rock
and mineral chemistries are often determined using both INAA and XRF.
Because there is no chemical pre-separation, the sensitivity of the method is
dependent upon the sample matrix. For example, detection limits for all elements
are lower in tree ring samples than in rock samples.
Fire Assay
Fire Assay
Fire Assay uses a combination of intense heat
(1900F) that is produced by a furnace, dry reagents
called fluxes, and bone ash containers called
crucibles and cupels.
The ability to fire assay a substance relies on a
number of facts. First of all, the samples that contain
gold and silver should be solubility in molten
metallic lead and that gold and silver are insolubility
in slag. Fire assay also relies on the difference
specific gravity between the two liquids, the molten
lead and the slag. This difference in specific gravity
separates the precious metal-bearing alloy from the
slag. The precious metals can be isolated by a
carefully controlled oxidizing fusion, in a porous
container called a cupel. Lastly, fire assay s possible
because of the solubility of silver in nitric acid and
golds insolubility in nitric acid.
Fire Assay Method is centuries old, but it is still one
of the most reliable methods for performing assays
(to determine the metal content of a ore) of ores
that contain precious (noble) metals - Gold, Silver
and Platinum. Ore from the mine, or exploration
sampling program is scientifically sampled using a
statistically accurate method fitting the desired
accuracy, it is then prepared by crushing, splitting
and pulverizing.
This is a process referred to as sample preparation.
Fire Assay

Fire Assay Method can be divided into

five steps
Fluxing and fusion of the sample
Slag separation from the button
Cuppelation
Parting
Weighing/Instrumental Finish
Fire Assay
Atomic Absorption Spectroscopy
(AAS)
Atomic Absorption Spectroscopy
(AAS)
Atomic absorption spectroscopy is a
spectroanalytical procedure for the
quantitative determination of
chemical elements using the
absorption of optical radiation (light)
by free atoms in the gaseous state.
In analytical chemistry the technique
is used for determining the
concentration of a particular element
(the analyte) in a sample to be
analyzed. AAS can be used to
determine over 70 different
elements in solution or directly in
solid samples[citation needed] used
in pharmacology, biophysics and
toxicology research.
Atomic Absorption Spectroscopy
(AAS) The technique makes use of absorption spectrometry to
assess the concentration of an analyte in a sample. It
requires standards with known analyte content to
establish the relation between the measured absorbance
and the analyte concentration and relies therefore on
theBeer-Lambert Law.
In short, the electrons of the atoms in the atomizer can
be promoted to higher orbitals (excited state) for a short
period of time (nanoseconds) by absorbing a defined
quantity of energy (radiation of a givenwavelength).
This amount of energy, i.e., wavelength, is specific to a
particular electron transition in a particular element. In
general, each wavelength corresponds to only one
element, and the width of an absorption line is only of
the order of a few picometers (pm), which gives the
technique its elemental selectivity. Theradiation
fluxwithout a sample and with a sample in the atomizer
is measured using a detector, and the ratio between the
two values (the absorbance) is converted to analyte
concentration or mass using the Beer-Lambert Law.
Flame Atomic Absorption Spectroscopy
(FAAS)
In flame atomic absorption spectrometry, either an air/acetylene or a nitrous
oxide/acetylene flame is used to evaporate the solvent and dissociate the sample into its
component atoms.
When light from a hollow cathode lamp (selected based on the element to be determined)
passes through the cloud of atoms, the atoms of interest absorb the light from the lamp.
This is measured by a detector, and used to calculate the concentration of that element in
the original sample. The use of a flame limits the excitation temperature reached by a
sample to a maximum of approximately 2600C (with the N2O/acetylene flame).
For many elements this is not a problem. Compounds of the alkali metals, for example,
and many of the heavy metals such as lead or cadmium and transition metals like
manganese or nickel are all atomized with good efficiency with either flame type, with
typical FAAS detection limits in the sub-ppm range. However, there are a number of
refractory elements like V, Zr, Mo and B which do not perform well with aflame source.
This is because the maximum temperature reached, even with the N2O/acetylene flame,
is insufficient to break down compounds of these elements. As a result, flame AAS
sensitivity for these elements is not as good as other elemental analysis techniques.
Flame Atomic Absorption Spectroscopy
(FAAS)
Flame Atomic Absorption Spectroscopy
(FAAS)
Strengths
Easy to use
Very fast
Lowest capital cost
Relatively few interferences
Very compact instrument
Good performance
Robust interface
Limitations
Moderate detection limits
Element limitations
1-10 elements per determination
No screening ability
Graphite Furnace Atomic Absorption Spectrometry
(GFAAS)
This technique is essentially the same as flame AA,
except the flame is replaced by a small, electrically
heated graphite tube, or cuvette, which is heated to a
temperature up to 3000C to generate the cloud of
atoms.
The higher atom density and longer residence time in the
tube improve furnace AAS detection limits by a factor of
up to 1000x compared to flame AAS, down to the sub-ppb
range. However, because of the temperature limitation
and the use of graphite cuvettes, refractory element
performance is still somewhat limited.
Graphite Furnace Atomic Absorption Spectrometry
(GFAAS)
Graphite Furnace Atomic Absorption Spectrometry
(GFAAS)
Strengths
Very good detection limits
Small sample size
Moderate price
Very compact instrument
Few spectral interferences
Limitations
Slower analysis time
Chemical interferences
Element limitatins
1-6 elements per determination
No screening ability
Limiter dynamic range
Inductively Coupled Plasma
Emission Spectrometry (ICP-ES)
Inductively Coupled Plasma Emission
Spectrometry (ICP-ES)
An inductively coupled plasma (ICP) is a very
high temperature (7000-8000K) excitation
source that efficiently desolvates, vaporizes,
excites, and ionizes atoms.
Molecular interferences are greatly reduced with
this excitation source but are not eliminated
completely. ICP sources are used to excite atoms
for atomic-emission spectroscopy and to ionize
atoms for mass spectrometry.
 typically Ar.
Inductively Coupled Plasma Emission
The plasma torch consists of concentric
Spectrometry (ICP-ES) quartz tubes, with the inner tube
containing the sample aerosol and Ar
support gas and the outer tube
containing an Ar gas flow to cool the
tubes (see schematic).
A radiofrequency (RF) generator
(typically 1-5 kW @ 27 MHz or 41 MHz)
produces an oscillating current in an
induction coil that wraps around the
tubes.
The induction coil creates an oscillating
magnetic field, which produces an
oscillating magnetic field.
The magnetic field in turn sets up an
oscillating current in the ions and
electrons of the support gas.
These ions and electrons transfer energy
to other atoms in the support gas by
collisions to create a very high
temperature plasma.
Inductively Coupled Plasma Atomic Emission
Spectrometry (ICP-AES)
ICP-AES, is a multi-element analysis technique that uses an
inductively coupled plasma source to dissociate the sample into
its constituent atoms or ions, exciting them to a level where
they emit light of a characteristic wavelength. A detector
measures the intensity of the emitted light, and calculates the
concentration of that particular element in the sample.
When undergoing ICP analysis, the sample experiences
temperatures as high as 10,000C, where even the most
refractory elements are atomized with high efficiency. As a
result, detection limits for these elements can be orders of
magnitude lower with ICP than with FAAS techniques, typically
at the 1-10 parts-per-billion level.
ICP instruments come in two flavors, radial and axial. In the
traditional radial configuration, the plasma source is viewed
from the side, across the narrow emitting central channel of the
plasma. Many newer systems view the emitting channel
horizontally along its length; this is known as the axial method.
Axial viewing increases the path length and reduces the plasma
background signal, resulting in detection limits as much as 5-
10x lower than with the radial configuration.
Simultaneous ICP instruments can screen for up to 60 elements
in a single sample run of less than one minute, with no
compromise of precision or detection limits. Sequential ICPs can
provide analytical results for about five elements per minute.
Inductively Coupled Plasma Atomic Emission
Spectrometry (ICP-AES)
Inductively Coupled Plasma Atomic Emission
Spectrometry (ICP-AES)
Strengths
Easy to use
Multi-element
High productivity
Very economical for many samples and/or elements
Few chemical interferences
Robust interface
Excellent screening abilities
High total dissolved solids
Solid and organic samples
Limitations
Moderate to low detection limits (but often much better than FAAS)
Spectral interferences possible
Some element limitations
Inductively Coupled Plasma Mass Spectrometry (ICP-MS)

ICP-MS is a multi-element technique that also uses

an ICP plasma source to dissociate the sample into
its constituent atoms or ions. However, in this case,
the ions themselves are detected, rather than the
light that they emit.
The ions are extracted from the plasma and passed
into the mass spectrometer, where they are
separated based on their atomic mass-to-charge
ratio by a quadrupole or magnetic sector analyzer.
The high number of ions produced, combined with
very low backgrounds, provides the best detection
limits available for most elements, normally in the
parts-pertrillion range. It is important to remember
that detection limits can be no better than lab
cleanliness allows.
Quadrupole mass spectrometers are most common
in ICP-MS, yet magnetic sector instrumentation
fulfills exacting requirements that demand the
ultimate detectability and isotope ratio
measurement.
Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
Strengths
Excellent detection limits
Multi-element
High productivity
Very economical for many samples and/or elements
Wide dynamic range
Isotopic measurements
Fast semi-quantitative screening
Easily interpreted spectra
Hybrid techniques
Laser Ablation ICP-MS (solids)
Liquid Chromatography ICP-MS (speciation)

Limitations
Some method development skill required
Higher initial capital cost
Some spectral interferences, but well defined
Limited to <0.2% dissolved solids
Methods Comparison
Sources
Rollinson, Hugh R. 1993.Using geochemical data: evaluation, presentation,
interpretation. Harlow, Essex, England: Longman Scientific & Technical.
Speakman, Scott A. Basics of X-Ray Powder Diffraction. From
http://prism.mit.edu/xray/.
Thermo Elemental. 2001. AAS, GFAAS, ICP or ICP-MS? Which technique should I use? An
elementary overview of elemental analysis. Franklin, Massachusetts: Thermo
Elemental.
Tyler, Geoffrey. 1994. ICP-MS, or ICP-AES and AAS?a comparison. Australia: Varian.
https://www.911metallurgist.com/blog/fire-assay/
https://www.911metallurgist.com/fire-assay/
https://en.wikipedia.org/wiki/Atomic_absorption_spectroscopy/
https://en.wikipedia.org/wiki/Inductively_coupled_plasma_atomic_emission_spectroscop
y/
https://en.wikipedia.org/wiki/Inductively_coupled_plasma_mass_spectrometry/
https://en.wikipedia.org/wiki/Metallurgical_assay/
https://en.wikipedia.org/wiki/Neutron_activation_analysis/
https://en.wikipedia.org/wiki/Powder_diffraction/
http://nmi3.eu/neutron-research/techniques-for-/chemical-analysis.html/
http://serc.carleton.edu/research_education/geochemsheets/techniques/INAA.html
http://serc.carleton.edu/research_education/geochemsheets/techniques/XRD.html
http://serc.carleton.edu/research_education/geochemsheets/techniques/XRF.html/
http://www.chemicool.com/definition/inductively_coupled_plasma_excitation.h../