ANALYTICAL TECHNIQUES IN GEOLOGY

OBJECTIVE

• Understanding the geochemistry

• Understanding the isotopic variation
• Understanding the crystal structures
• Understanding the mineral zonation.
• Interpretation of geochemical data.
• Understanding the petrogenesis
• Understanding the Plate Tectonics

IMPORTANT TECHNIQUES
• XRD Spectroscopy
• Neutron Activation Analyses
• ICP-MS Spectroscopy
• Mass Spectroscopy
• RNNA
• ASS
• Electron Microprobe
• Ion Microprobe
• Scanning Electron Microprobe

PRECISION OF DATA

Refers to the repeatability of a measurement. (Till 1974).

Precision = Coefficient of Variation

100 x Standard Deviation

Means

DETECTION LIMIT

Lowest Concentration that can be detected by particular method

e.g.

XRF Spectroscopy cannot detect elements lighter than Na ( 11)

AAS Can not detect “P”, Be, Li

X RAY DIFFERACTION SPECTROSCOPY (XRD)

• Most widely used for major and trace element analyses.

• Can analyze 80 elements with 100 % concentration.
 • Detection Limit- Na (11)

Principle of XRD:
• A primary X Ray beam excites the sample.
The primary beam excites the secondary beam ( X Ray fluorescence) .
• The secondary wavelength is characteristics of each element.
• The intensity of the secondary wavelength is used to determine the concentration of elements
present by reference of the calibration standards.

Preparation of Samples for XRD Analyses

For major element analyses

FUSED GLASS DISC/BEAD

Fused with Lithium Metaborate and Tetraborate ( Norish & Hutton, 1969)

For Trace Element analyses

PRESSED POWDERED PELLETS/ DISCS

Process Outline

Types of Detectors in XRD

1) Gas flow proportional counters

2) Sealed gas detectors
3) Scintillation counters
4) Semiconductor detectors

INSTRUMENTAL NEUTRON ACTIVATION ANALYSES (INNA)

Process Outline

SampleNeutron FluxShort Lived Radiogenic IsotopesGamma Radiation Gamma Ray Spectroscopy

Preparation of Sample for INNA

• Powdered sample is placed in a neutron flux, together with the standard.

• They are irradiated for 30 hours
•
RADIOCHEMICAL NEUTRON ACTIVATION ANALYSES (RNNA)

Importance

• Useful for Chemical separation of selected Elements when element concentration is very low viz.
• > 2ppm ( less than two parts per millions)
INDUCED COUPLED PLAZMA MASS SPECTROSCOPY (ICP MS)

Developed by Thomson & Walsh (1983)

Importance

• Capable of measuring most elements in the periodic table with very low detection limit.
• It is a flame technique with the flame temperature range of 600 -1000o K.
Process

• The sample solution is passed in an “aerosol “from a nebulizer into an “Argon” plasma.
• The induced coupled plasma is a stream of Argon atoms, heated by the induced heating of a radio frequency coil
• Ignited by a high frequency Tesla Spark.
• large number of atomic and ionic spectrums are excited.
• The spectral lines are determined by a range of photo multipliers and they are compared with calibration lines
• Finally, the intensities are converted into concentrations.
Usage
• Geology: Soil Water and Mineral Analyses.
• Medical and forensic field, specifically, toxicology.
• A physician may order a metal assay for a number of reasons, such as
• suspicion of heavy metal poisoning,
• metabolic concerns, and even hepatological issues.
• samples collected for analysis can range from whole blood, urine, plasma, serum, to even packed red blood cells.
• Environmental field. Such applications include water testing for municipalities or private individuals all the way to soil,
water and other material analysis for industrial purposes.

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Principle

• Based upon the observation that the atoms of an element can absorb electromagnetic radiation.
 • The wavelength of the light absorbed is specific to each element.

Units
• Atomizing Device
• Light Source
• Detector

Limitation
• Sample must be prepared as solution.
• Only one sample can be analyzed at a time.
• ( It can be overcome with multiple lamp holder)
• Cannot detect “P”, Be, Li
• It is slow as compared to the XRF and ICP MS

ISOTOPE DILUTION MASS SPECTROSCOPY (IDMS)

• Most accurate and most sensitive of all trace element analytical techniques.
• Developed by Henderson and Pankthrust,1984)
• Very useful to determine the trace elements and REE at very low concentrations

Applications

The minerals grains may preserve chemical information adopted during their formation and subsequent alteration.

1. Crystallization,
2. Lithification,
3. Volcanism
4. Metamorphism,
5. Organic events (mountain building)
6. Plate tectonics.

In Mineralogy
• The change in elemental composition from the center (also known as core) to the edge (or rim) of a mineral can yield
information about the history of the crystal's formation, including the temperature, pressure, and chemistry of the
surrounding medium.
• Quartz crystals, for example, incorporate a small, but measurable amount of titanium into their structure as a function
of temperature, pressure, and the amount of titanium available in their environment. Changes in these parameters are
recorded by titanium as the crystal grows.

In Palaeontology
 • In exceptionally preserved fossils, such as those of the Burgess shale, soft parts of organisms may be preserved. Since
these fossils are often compressed into a 2D film, it can be difficult to deduce what features were what:
• Triangular extensions in Opabinia, which were interpreted as either legs or extensions of the gut. Elemental mapping
showed that they had a similar composition to the gut, favouring the second interpretation.
• Because of the thin nature of the carbon films, only low voltages (5-15V) can be used in such specimens.

ION MICROPROBE
Significance
• It has the analytical accuracy of Mass Spectroscopy.
• It has spatial resolution of “Electron Microprobe”.
• Widely used in the field of Geochemistry.

Principles
• A finely focused beam of oxygen ions bombard on specific area of the sample (20 µ -30 µ in diameter.)
• Secondary ion is excited.
• The secondary ionization (sputtering) drills a small hole in the surface of sample.
• The secondary ion mass spectrum (SIMS) is analyzed for concentration.

Application
• Trace Element Analyses
• Stable Isotope Analyses
• Element Diffusion Studies

SCANNING ELECTRON MICROSCOPY

Significance

• It is a type of electron microscope that images a sample by scanning it with a beam of electrons in a raster scan pattern.
• The electrons interact with the atoms that make up the sample producing signals that contain information about the
sample's surface topography, composition, and other properties such as electrical conductivity.
• The types of signals produced by a SEM include secondary electrons, back-scattered electrons (BSE), characteristic X-
rays, light (cathodoluminescence), specimen current and transmitted electrons

Sample Preparation:
• All samples must also be of an appropriate size to fit in the specimen chamber.
• Sample is generally mounted rigidly on a specimen holder called a specimen stub.
• Several models of SEM can examine any part of a 6-inch (15 cm) semiconductor wafer, and some can tilt an object of
that size to 45°.
• For conventional imaging in the SEM, specimens must be electrically conductive, at least at the surface, and electrically
grounded to prevent the accumulation of electrostatic charge at the surface.

Magnification:
 • Magnification in a SEM can be controlled over a range of up to 6 orders of magnitude from about 10 to 500,000 times.
• 3D data can be measured in the SEM
SELECTION OF APPROPRIATE TECHNIQUE

The selection of appropriate technique for analyses depends upon the nature of Problem

Major & Trace Element Analyses

– XRF/ICP MS (Best options)

Trace Element Analyses

– XRF/ICP MS/INNA/RNAA (Best options)

Experimental Petrology

– Electron/Ion Microprobe

Orogenesis/Metamorphism/Plate Tectonics

– Electron/Ion Microprobe

Paleontology

Electron Microprobe