Übungen zur Analtytischen Geochemie

Analytical Geochemistry Practical

Dr Ambre LUGUET

Outline of the Lecture

Theory => Basic principles

=> Sampling and sample preparations
=> Analytical methods
=> Data evaluation
Analytical Geochemistry
Practical

1. Basic Principles
What is a geochemical analysis?

Measurement that provides information on the chemical composition of a sample

- Concentrations of elements or compounds

- Relative abundance of isotopes of a given element
- Proportion of a chemical form of an element

Why do we perform geochemical analysis?

To solve a problem, to test a theory

- Characterise the composition of a sample

- Determine the sample history -> P-T-t, origin
- Understand a geological process-> behaviour of elements
- Study spatial distribution of elements -> track pollution/contamination/mixing
Type of geochemical analysis?

Qualitative => identification of chemical elements present in a sample

Quantitative=> determination of concentrations

Major constituents => concentrations >1 wt.%

Minor constituents => concentrations =0.1-1 wt.%
Trace constituents => concentrations <0.1 wt.%

Ore deposits: ~ 30 wt.% S => Major element

Fresh basalt:~ 0.08-0.1 wt.% S => Trace element

60 wt.% Cr2O3=> Major component

0.5 wt.% Cr2O3=> Minor component

Type of geochemical analysis?

• Concentration

• Isotopic Composition
Accurate and precise determination of the ratio of two or more isotopes of a
given element
Both Stable isotopes (18O/16O) or radiogenic isotopes (143Nd/144Nd)
Carry information about age (chronometers) or source (tracers)

Bulk Analysis => overall composition

Spatially-resolved analysis=> Analysis of specific constituents (mineral separates,
part of a mineral (zonation))
Type of geochemical analysis?

Chemical Form-Speciation
Oxidation state
S may exist as sulfides => S2-
S may exist as sulfates => S2+
Same for elements which exhibit multiple oxidation state in nature (e.g. Fe, C)

Spectroscopic Analysis
Measure slight differences in spectral wavelength
Information on chemical bonding
Of interest for mineralogist or structural chemist
Units of concentration

Concentration : amount of a particular chemical component (in mass or molar

units) present in a unit of volume of the substance being analysed
- mol.l-1
- g.l-1

In geochemistry=> amount of chemical component per unit mass of sample

1g per 1g = 1g/g = 100%

0.01 g per 1g = 0.01g/g = 1%

1mg (10-3g) per 1g = 0.1% = 1000 ppm

1µg (10-6g) per 1g = 1 ppm => 1 part per million
1ng (10-9g) per 1g = 1 ppb => 1 part per billion
1pg (10-12g) per 1g = 1 ppt => 1 part per trillion
1fg (10-15g) per 1g = 1 ppq => 1 part per quadrillion
Units of concentration-Exercise

Ex: 0.3% Ni => 3 mg Ni per 1 g sample (3mg/g)=> 3000 µg/g => 3000 ppm
3000 ppm=> 3000µg/g=> 0.3%Ni

Calculate 1200 ng/g

0.2 ng/g
1500 pg/g
500 pg/mg
2100 µg/g
200 ppt
0.5 ppm
1700 ppb
500 ppq
Units of concentration-Exercice

Ex: 0.3% Ni => 3 mg Ni per 1 g sample (3mg/g)=> 3000 µg/g => 3000 ppm
3000 ppm=> 3000µg/g=> 0.3%Ni

Calculate 1200 ng/g 1200 ppb = 1.2 ppm

0.2 ng/g 0.2 ppb = 200 ppt
1500 pg/g 1500 ppt = 1.5 ppb
500 pg/mg 500 ppb = 0.5 ppm
2100 µg/g 2100 ppm = 0.21%
200 ppt 200 pg/g = 0.2 ng/g
0.5 ppm 0.5 µg/g = 500 ng/g
1700 ppb 1700 ng/g = 1.7 µg/g
500 ppq 500 fg/g = 0.5 pg/g
 Analytical Geochemistry
Practical

2. Sampling and sample preparations

Geochemical Investigation

THINKING 1. Decide on geochemical objectives (i.e. pb to be solved)

SAMPLING 2. Collect Samples

ANALYSIS 3. Prepare samples for analysis

4. Decompose samples => solution (if necessary)
5. Analyse samples

INTERPRETATION 6. Assess quality of analysis

7. Geochemical Interpretation

CONCLUSIONS 8. Draw Conclusion

Sampling

•Size of the samples required

=>Many materials are heterogeneous mixtures. Individual grains are representative of one
component of the mixture but not the mixture as a whole.
=>Sample large enough for the influence of individual grains on sample composition to be
insignificant
=>Grain size of sample is an important factor=> the larger the grain size, the large the mass
of sample needed to be representative

Basalt Granite
Sampling

•Number of samples required

=> several samples per site (10-20 samples/site).
Not too many => Quality better than quantity
=> several sites from an outcrop => heterogeneity? (i.e. km-size massif)

1m

Harzburgite-Lherzolite layers
Sampling

•Spatial distribution of the sample sites (i.e. sampling density)

=> systematic sampling across a layer/vein (step=fº(layer thickness))

Dunite-harzburgite layering (Troodos ophiolite-Cyprus)

=> systematic sampling along a river from pollution imput => every 10 m or
every 500 m

•Quality of the samples (i.e. alteration rims, veins…)

•Sample Identification + Location (description + GPS)

Sample Preparation

•Remove unwanted contaminants (suspended organic matters from waters, secondary crusts,
alteration rims, crosscutting veinlets)

5 cm

•Converts into suitable form for analysis => solution

•Eventually separate or concentrate a particular constituent

Preparation

Minimal Complex & multi-step

Water sample with no Separate Minerals

suspended organic matter from silicate rocks
Preparation of Bulk Inorganic Sample (rock, sediment & soil)
1-Removal of weathered or contaminated surface (licken & mineral coating, reactions rims, alteration surface,
veins)
-Sawing, Leaching with MQ or acid

2-Crushing from gravel to small chips 2-High Quality thin sections

- Steel Crusher

3-Powdering-Coarse Powder or Fine Powder

- Crusher, agate mill (negligible metal content-very suitable for trace element and radiogenic isotopic
studies) or W carbide mill ( potential Ti, Co and Ta contamination)

Mineral separation Whole-Rock

- Gravity & magnetic

susceptibility

4-Chemical Processing
Mineral Separation-Heavy Liquids

Low density mineral

Hi h density mineral

Funnel + Filter

Quartz 2.65 g/cc

Plagioclase 2.69 g/cc
Enstatite 3.19 g/cc
Diopside 3.27 g/cc
Olivine 3.32 g/cc
Spinel 3.64 g/cc
Mineral Separation-Heavy Liquids

Low density mineral

Hi h density mineral

Funnel + Filter
Bromoform is used as heavy liquid (π=2.87 g/cc)

Quartz 2.65 g/cc

Plagioclase 2.69 g/cc
Enstatite 3.19 g/cc
Diopside 3.27 g/cc
Olivine 3.32 g/cc
Spinel 3.64 g/cc
Mineral Separation-Heavy Liquids

Low density mineral

Hi h density mineral

Funnel + Filter
Bromoform is used as heavy liquid (π=2.87 g/cc)

Quartz 2.65 g/cc

Plagioclase 2.69 g/cc
Enstatite 3.19 g/cc
Diopside 3.27 g/cc
Olivine 3.32 g/cc
Spinel 3.64 g/cc
Mineral Separation-Heavy Liquids

Low density mineral

Hi h density mineral

Funnel + Filter
Methylene Iodide is used as heavy liquid (π=3.32 g/cc)

Quartz 2.65 g/cc

Plagioclase 2.69 g/cc
Enstatite 3.19 g/cc
Diopside 3.27 g/cc
Olivine 3.32 g/cc
Spinel 3.64 g/cc
Mineral Separation-Heavy Liquids

Low density mineral

Hi h density mineral

Funnel + Filter
Methylene Iodide is used as heavy liquid (π=3.32 g/cc)

Quartz 2.65 g/cc

Plagioclase 2.69 g/cc
Enstatite 3.19 g/cc
Diopside 3.27 g/cc
Olivine 3.32 g/cc
Spinel 3.64 g/cc
Mineral Separation-Magnetic susceptibility
Separation using a Frantz magnetic barrier separator based on the magnetic
properties of minerals
Dissolution Procedures for solution analysis (AAS, ICP-AES & ICP-MS)
Sample digestion required for sample to be analysed as solution
Acid Attacks

Silicates are chemically resistant => powerful reagents are needed to attack them
HCl-HNO3 => Aqua Regia or König Wasser => Metals (Base metals: Cu, Cd, Mn,
Pb) and Phosphates

HF- HNO3 => HF attacks the silicate matrix

=> might fail to dissolve refractory minerals (spinel, zircon, rutile)
HF-HClO4 => any silicate
HF-H2SO4 => Cr-bearing silicate
HNO3/H2O2 => Organic matter-bearing material

Attacks for 1-3 days at 100-

300 ºC and atm P to 120
bars
Dissolution Procedures for solution analysis (AAS, ICP-AES & ICP-MS)

Sample digestion required for sample to be analysed as solution

Fusions
Fusion of a silicate sample with an appropriate flux is the most complete and
rigorous method for sample digestion
Flux
-Li metaborate (LiBO3) will attack most of the major and accessory minerals (Flux/Sample=3)
-Li tetraborate (Li2B4O7) => fused mixture slower to dissolve
-Sodium carbonate (Na2CO3) => incomplete attack of refractory minerals (Flux/Sample=6)
-Sodium Peroxide (Na2O2)=>low temperature (600ºC) (Flux/Sample=4)
-Sodium Hydroxide (NaOH) (Flux/Sample=10)

Fusions at >900ºC in a muffle furnace

=> Introduction of significant amount of reagents= Blank

Issues?
Preconcentration Procedures for solution analysis

Low abundance component may have original concentrations close to the detection limit of the
analytical methods

Separation of matrix => less interferences + preconcentration = lower detection limits

1. Fire assay
- some elemens have a strong affinity for metal=> so when silicate melt in contact
with molten metal or sulfide (Pb, Sn, S-Ni), those elements partition strongly into the
metal

Silicate melt +
lithophile elements

Metal + siderophile elements

Sulfide + chalcophile elements
Preconcentration Procedures for solution analysis

2. Solvent extraction
- elements forming stable complex that partition strongly into an organic phase
- aqueous solution and organic phase put in contact => organic phase enriched in
the complex
- discard the denser aqueous solution

Example: solvent extraction of Os in CCl4

Aqua regia
HSE Os HBr
Os+HSE Os
Os CCl4
Preconcentration Procedures for solution analysis

3. Ion Exchange Separation

- slow percolation downward of the sample solution through ion resin
- different solute ion species attracted to varying degrees by the active sites of the
resin and migrate at different rates as carrier solution is passed through the column
Analytical Geochemistry
Practical

3. Analytical Methods
 Preparation
Preparation of Bulk
of Bulk Inorganic
Inorganic Sample
Sample (rock,(rock, sediment
sediment & soil)& soil)
1-Removal of weathered or contaminated surface (licken & mineral coating, reactions rims, alteration surface,
veins)
-Sawing, Leaching with MQ or acid

2-Crushing from gravel to small chips 2-High Quality thin sections

- Steel Crusher

3-Powdering-Coarse Powder or Fine Powder

- Crusher, agate mill (negligible metal content-very suitable for trace element and radiogenic isotopic
studies) or W carbide mill ( potential Ti, Co and Ta contamination)

Mineral separation Whole-Rock

- Gravity & magnetic

susceptibility

4-Chemical Processing

5-Analytical Method
 Analytical
Analytical Methods-
Methods- Spatially
Spatially resolved
resolved Analysis
Analysis

=> In-situ Analysis

Wt.% ppm ppb ppt

Major Minor Trace Ultra-trace

Electron Microprobe
- well-focused electron beam => micro-scale analysis
- quantitative analysis

Non-destructive
Ion Microprobe
- well-focused ion beam => micro-scale analysis
- ion beams (O-, O2-, O2+, Cs+)
- quantitative analysis
- isotopic analysis=> U-Pb ages of zircons

Laser-ablation ICP-MS
- well-focused laser beam => micro-scale analysis Destructive
- quantitative analysis
- isotopic analysis
Electron Microprobe:
Electron Mineral
Microprobe: composition
Mineral analysisanalysis
composition

Silicate Mineral analysis

Amphibole
Mass % oxide Cations per 24 Site occupancy
oxygens
Si 57.73 7.786
Al 12.04 Tet 0.214 Z=8.000
Oct 1.700
Fe (3) 1.16 0.118
Fe (2) 5.41 0.610
Mn 0.10 0.011
Mg 13.02 2.617 Y=5.056
Ca 1.04 0.150
Na 6.98 1.825 X=1.975
K 0.68 0.117 A=0.117
H 2.27 2.042 OH=2.042
Total 100.4

Amphibole => Silicate, so analysis expressed as oxide

Quality of analysis checked by calculating the mineral formula
Formula of Amphibole = AX2Y5Z8O22(OH)2
 Electron
Electron Microprobe:
Microprobe: Elemental
Elemental distribution
distribution maps maps

Elemental distribution maps of

transition metals in a sulfide
grain
=> Reconstruction of sulfide
mode and determination of
spatial distribution of the
different sulfides
Analytical Methods- Spatially resolved Analysis

=> In-situ Analysis

Wt.% ppm ppb ppt

Major Minor Trace Ultra-trace

Electron Microprobe
- well-focused electron beam => micro-scale analysis
- quantitative analysis

Non-destructive
Ion Microprobe
- well-focused ion beam => micro-scale analysis
- ion beams (O-, O2-, O2+, Cs+)
- quantitative analysis
- isotopic analysis=> U-Pb ages of zircons

Laser-ablation ICP-MS
- well-focused laser beam => micro-scale analysis Destructive
- quantitative analysis
- isotopic analysis
Laser Ablation ICP-MS: Age and Isotopic compositions of Zircons

Microscale heteroge eity of age

and isotopic signature
Laser Ablation ICP-MS: Composition and mineralogy of HSE in sulfides

Different ablation patterns depending on material

Information on occurrence of elements wihin
minerals (nugget)

200 µm LAM-ICPMS ablation run

Analysis

Counts

Luguet et al., 2003 Time (sec)

Analytical Methods- Buk Analysis

=> Whole-rock and Mineral (single or separate fraction) Analysis

Wt.% ppm ppb ppt

Major Minor Trace Ultra-trace

X-ray fluorescence (XRF)

- primary X-rays radiation=> emission of secondary X-Rays
- X-ray peaks characteristic of the major and trace elements of the sample
- height of X-ray peaks relates to concentration of the given element

Atomic absorption/emission Spectrometry (AAS/AES)

- absorbtion of energy from a light beam at specific wavelength of the element present
- re-emission of excited atoms at the same wavelength but in random direction=> attenuation of light
proportional to the amount of ground-state element atoms=> provide concentration

Quadrupole ICP-Mass Spectrometer

- positive ions generated in an inductively coupled plasma
- quadrupole (separation only by electric field) allows ONLY ions with a given
m/z through to the detector (electron multiplier)
- low mass resolution=> difficulty in resolving interference from polyatomic ions
X-ray fluorescence analysis

Dolerite (oxide •Most rocks consist mainly of silicate minerals, in which

mass the metals and metalloids are considered bonded to O =>
%) so analysis expressed as oxides
Major elements
( id %)
SiO2 48.3
TiO2 2.591 •Trace of H2O lost when rock powder is heated up to
110ºC=> H2O- => atmospheric water adsorbed on powder
Al2O3 13.03 particles.
Fe2O3 6.84
FeO 7.72 •Many rock-forming minerals contain OH- ions within the
MnO 0.23 crystal structure=> at T~1200ºC dissociation as H2O
vapor=> H2O+
MgO 5.46
CaO 10.91
Na2O 2.34
•Carbonates will decompose => CO2
K2O 0.51
P2O5 0.26 •High quality rock analysis => total: 99.5-100.5 %
H2O+ 1.41
CO2 0.49 • Analysis over 100.5% => erroneous analysis or
assumption. For example, if all iron assumed as Fe3O2
Total 100.1 when also FeO is present, too much O for a mole of Fe.
Speciation of Iron

•In terrestrial rocks, iron occurs as Fe2+ (ferrous) and Fe3+ (ferric)
•Different charges and ionic radii=> occupy different sites in silicate crystals

•Fe2+ in the digested rock solution may be determined by titration against an

oxidising agent (KMnO4)=>REDOX TITRATION
•Fe3+ determined by subtraction from the total iron concentration

Direct titration

•Sample digestion H2S04+HF in a crucible

•The dissolved Fe2+ is titrated against potassium permanganate used as indicator

Analytical Methods- Bulk Analysis

=> Whole-rock and Mineral (single or separate fraction) Analysis

Wt.% ppm ppb ppt

Major Minor Trace Ultra-trace

X-ray fluorescence (XRF)

- primary X-rays radiation=> emission of secondary X-Rays
- X-ray peaks characteristic of the major and trace elements of the sample
- height of X-ray peaks relates to concentration of the given element

Atomic absorption/emission Spectrometry (AAS/AES)

- absorbtion of energy from a light beam at specific wavelength of the element present
- re-emission of excited atoms at the same wavelength but in random direction=> attenuation of light
proportional to the amount of ground-state element atoms=> provide concentration

Quadrupole ICP-Mass Spectrometer

- positive ions generated in an inductively coupled plasma
- quadrupole (separation only by electric fields) allows ONLY ions with only a
given m/z through to the detector (electron multiplier)
- low mass resolution=> difficulty in resolving interference from polyatomic ions
Atomic absorbtion spectrometry

•Measure of concentrations of metals such as for example Fe, Cu, Al, Pb, Ca,
Zn and Cd

•Typical concentration range =>low ppb

•Method of choice between 1960 and 1980

•Single element analysis

•Applicable to a wide range of samples

- Rock, Soil, Sediment, Plant, Water

•Dissolution of samples via fusion with Li borate or acid digestion with HF or

aqua regia

•Relatively free from interferences

Atomic absorbtion spectrometry

The flame causes atoms to undergo a transition from ground state to the first excited state
during this transition, atoms absorb a specific wavelength of light
For example Ca absorbs light with a wavelength of 433.7 nm and Fe at 248.3 nm
=> attenuation of light proportional to the amount of excited atoms=> provide concentration

Light Source
Flame

Atomisation

Atomic Detector
cell
Sample
Atomic absorbtion spectrometry

Atomic Absorption spectrum

Atomic absorbtion spectrometry

Light Beam => Generated by a lamp that is specific for a target metal

Cathode Lamp for Aluminium

Atomic absorbtion spectrometry

Flame => Sample aspirated into a flame using a nebuliser

Atomic absorbtion spectrometry

Graphite Furnace => Flameless : Uses a graphite tube with a strong electric current to heat the sample
Atomic absorbtion spectrometry

ICP-AAS
Atomic absorbtion spectrometry

Detector=> photon multiplier

Photon multiplier can detect the amount of reduction of the light intensity due to
absorbtion by analyte=> can be directly related to the amount of element in the sample
Atomic absorbtion spectrometry => Calibration

Standard Curve Stated by the Beer’s law : absorbance of an

absorbing analyte is proportional to its
concentration

A = ln I0 = KxCxD
I

A = Absorption
K = Coefficient of Absorption
D = Wavelength of light through medium
C = Concentration of element
I0 = Intensity of the incident beam
I = Intensity of the emerging beam

•Deviation from linearity occur when concentration of metallic analyte increases due to
unabsorbed radiations or disproportionate decomposition of molecules at high concentrations
•Deviation minimised but difficult to avoid
Atomic absorbtion spectrometry => Calibration

Rule of thumbs : minimum 5 standards and a blank to have sufficient information

to fit the standard curve appropriately
Analytical Methods- Bulk Analysis

=> Whole-rock and Mineral (single or separate fraction) Analysis

Wt.% ppm ppb ppt

Major Minor Trace Ultra-trace

Quadrupole ICP-Mass Spectrometer (MS)

- positive ions generated in an inductively coupled plasma
Concentration - quadrupole (separation only by electric fields) allows ONLY ions
with only a given m/z through to the detector ( 1 electron multiplier)
- low mass resolution=> difficulty in resolving interference from
Coupled
polyatomic ions
with LA
Multi-collector ICP-Mass Spectrometer (MC-ICP-MS)
-separation only by electric and magnetic fields => allows ONLY ions
with only a given m/z through to the detectors
- multiple detectors => SEM, Faraday Cups (9), MIC
Concentration
-Resolution of interference from polyatomic ions
Isotopic composition
Thermo Ionisation Mass Spectrometer (TIMS)
-Ionisation by heating/evaporation
MC-ICPMS

•Sample ionised in a plasma

•Combination of electrostatic and magnetic field to separate ions following their mass/charge
ratio
Determination of concentrations

•External Standard Calibration

-Use of 3 (at least) solutions containing the elements to be analysed to calibrate a signal
vs. concentration curve
-Concentrations of the solutions are known and covered the expected range of
concentrations of the samples

concentration

signal
Sol 1 Sol 2 Sol 3
Determination of concentrations

•External Standard Calibration

-Use of 3 (at least) solutions containing the elements to be analysed to calibrate a signal
vs. concentration curve
-Concentrations of the solutions are known and covered the expected range of
concentrations of the samples

concentration

signal
Sol 1 Sol 2 Sol 3
 Determination of concentrations

•External Standard Calibration

-Use of 3 (at least) solutions containing the elements to be analysed to calibrate a signal
vs. concentration curve
-Concentrations of the solutions are known and covered the expected range of
concentrations of the samples

concentration

Concentration sample 2

Concentration sample 1

signal
Sample 1 Sample 2
Determination of concentrations

•Internal Standard Addition

- Addition of a known quantity of an element (e.g. In, Rh, Re)

20 ppb In => 4 V on 115In

X ppb Nd <= 8 mV on 144Nd

Calculate X Considering that 115In=95.7 % of In and 144Nd=23.8% of Nd

4V on 115In=>20*95.7%=19.14 ppb 115In

8 mV 144Nd=>(0.008*19.14/4)=0.03828 ppb 144 Nd => 0.03828/23.80%=0.160 ppb Nd

The answer is 0.160 ppb Nd or 160 ppt Nd

Determination of concentrations

•Isotopic Dilution
- addition of spike (solution enriched in one specific isotope) to the sample

85Rb
Mole 85Rb
sample + Mole 85Rb spike
=
87Rb Mole 87Rb Mole 87Rb
sample+ spike