Earth Sciences 4502/6211 Introduction To Geochemistry, Geochemical Nomenclature, Sampling, Analytical Methods, and QA/QC

Earth Sciences 4502/6211
Introduction to Geochemistry, Geochemical

Nomenclature, Sampling, Analytical
Methods, and QA/QC
Stephen J. Piercey, PhD, PGeo*

Memorial University of Newfoundland
St.John’s,NL, Canada
A1B 3X5
spiercey@mun.ca
Thursday, 6 September, 12
Outline
• Geochemical element classification
• Major, minor, trace elements.
• Field strength, trace element nomenclature.
• Sampling, Analytical Methods (Brief)
• Philosophy regarding sampling. Sampling for

purpose.
• Analytical instrumentation - what instrument gives

you what data.
• Quality Control and Quality Assurance (Brief)
• Precision and accuracy - basic concepts in QA/QC.
• QA/QC protocols for lithogeochemical surveys.
• Testing QA/QC - Scatterplots, Thompson-Howarth

plots, reference materials.
• Summary
Geochemistry
• Using the geochemistry (e.g., major, trace, rare-earth elements,
isotopes, etc) of rocks, minerals, soils, tills, and other media to
understand Earth processes.
• In many cases we are interested in geochemical dispersion in

surficial media (traditional exploration geochemistry) and
lithogeochemistry (e.g., alteration dispersion of elements).
• Other processes of interest may include:
• Crystal-liquid fractionation.
• Hydrothermal alteration.
• Sedimentary rock provenance.
• Geochronology.
• Fluid and metal source tracing.
Geochemistry
• Lithogeochemistry - using rock geochemistry to understand Earth
processes, mostly past processes (e.g., igneous processes,
sedimentary processes, fluid-rock interaction, tectonic
environment discrimination etc.).
• Surficial geochemistry - using geochemistry of surface materials

(soils, till, water, stream sediments, lake sediments) to understand
various surficial processes (e.g., exploration geochemistry, acid
rock drainage, environmental).
• Biogeochemistry - using biological materials to understand

various biological processes (e.g., metal uptake, exploration
geochemistry).
• Isotope Geochemistry - using isotopes to understand Earth

processes.
• Assay Geochemistry - multi-element methods of rocks/surficial

materials/etc. often aimed at an exploration/development problem
(e.g., exploration geochemistry, baseline data, mineral resources).
• What elements we choose, what methods we choose, and our

sampling is dependent on the discipline of interest above.
Geochemical Nomenclature
• Major Elements
• Essential components of rocks and minerals
• >0.1 wt%
• given wt% oxides (e.g., SiO2, MgO, etc).
• Minor Elements
• Minor components of rocks and minerals
• 0.01-0.1 wt%
• Given at wt% oxides (e.g., MnO, P2O5, etc)
• Trace Elements -
• Trace components of rocks and minerals
• <0.01wt% (1000 ppm)
• Given in ppm, ppb, etc. and in elemental form (e.g., Th, Nb)
• Compatible Elements: elements that favour solid phases

(crystals) during melting or crystallization (e.g., Ni, Cr,
Co).
• Incompatible Elements: elements that favour the liquid

phases (melt) during melting or fractional crystallization
(e.g., Nb, Ta, Th).
LITHOPHILE
Magma Cr Ni
Ni
Ni Cu
Cr
Cr, Ni, Cu = compatible

Lithophile = incompatible
Cumulate
• Low Field Strength Elements (LFSE): cations with large ionic radii to
ionic charge (ir/ic>0.2): Cs, Rb, K, Ba, Sr, Th, U, and Pb (generally
highly incompatible, sometimes called Large-Ion Lithophile Elements
or LILE)
• High Field Strength Elements (HFSE): cations with very small ionic
radii to ionic charge (ir/ic<0.2): Zr, Hf, Nb, Ta, Y, ±Sc, Ti, P (generally
highly incompatible).
• Rare Earth Elements (REE): largely trivalent (+3) cations which are
part of the lanthanide series of periodic table. Like HFSE in most
cases, includes: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
Often divided into groups, including: light REE (LREE = La, Ce, Pr,
Nd), middle REE (MREE = Sm, Eu, Gd, Tb, Dy, Ho), and heavy REE
(HREE – Er, Tm, Yb, Lu) (generally incompatible).
• Transition Elements (TE): these are metals that lie in the middle of the
periodic table and include: Cr, Ni, Sc, V, Co, Cu, Zn ± Ti, Fe, Mn
(moderately compatible).
• Noble Metals: these are the platinum group elements (PGE) and other
precious metals: Pt, Pd, Ir, Os, Ru, Rh, Au, Ag, Re (highly compatible).
• Base Metals: metals that commonly form most ore deposits: Cu, Zn,
Pb (highly compatible).
• Volatile Elements: great pathfinder elements that are often

transported by volatiles during magmatism or hydrothermal fluids,
includes: Cd, In, Sn, Sb, As, Hg, Tl, Bi (incompatible????).
Modified from
Rollinson (1993)
LFSE
LFSE Transition
TE Base Metals
Base Metals
H HFSE
HFSE NobleMetals
Noble Metals He
Li Be B C N O F Ne
REE
REE Volatile
Vol. Elem.
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U
Sampling
Sample Prep
Analytical
Methods
QA/QC
Using Lithogeochemical Data: Why?
Assay: Provides, as accurately as possible, the mean concentration of one

or several elements in a representative sample
Hypothesis test (lithogeochemistry): Provides a multi-element data set for

a specifically chosen group of samples to test a user-defined hypothesis
(D)
1 AlkRhyolite
Phonolite
Rhyolite/Dacite Trachyte
Tephri-phonolite
.1
Zr/TiO 2
TrachyAnd
Andesite/Basalt
Foidite
.01
Subalkaline
Alkaline
Basalt AlkBasalt
.01 .1 1 10
Nb/Y
1000
50
Y/Ho = 44 (seawater) 100
Rock / Primitive Mantle

40
Y/Ho 10
30
1
Y/Ho = 27 (chondritic)
20 .1
0 20 40 60 80 Th Nb La Ce Pr Nd Sm Zr Hf Eu Ti Gd Tb Dy Y Er Yb Lu Al V Sc
La
Assay Sampling
• Assay data may eventually become the backbone of a
decision whether a deposit is economic or not
• Such data are often subject to external scrutiny and

independent audits
• Observe legal requirements and professional guidelines

(e.g., NI-43-101, JORC, IMMM)
• Attempt to stick to a rigorous protocol without

compromise
• Ensure that different exploration teams are interpreting

protocol in identical fashion
Hypothesis Driven Sampling
• The best hypothesis is when both negative and positive

outcomes add value to exploration
• Hypotheses should be tested initially with the most

‘typical’, best exposed or drilled set of rocks, using the
highest quality data available
• No amount of effort should be spared to obtain the

freshest, most comparable rocks (minerals) for an initial
test of hypothesis
• The geologist who developed the hypothesis should play a

major role in testing it
Avoiding Murky Water
• Most geochemical patterns, fingerprints, gradients, etc.
mimic lithological, mineralogical and textural features of
rocks
• They may, however, be more subtle or highly magnified

and extend beyond optically visible attributes of rocks
• Without any indications from field, stratigraphy,

mineralogy, aspect, texture, etc. geochemistry is unlikely
to reveal a pattern - FIELD CONSTRAINT
• If there is no real question, there won’t be a real answer
Getting the Best Samples
• Representative.
• Depends on problem to be solved (e.g., petrology,

provenance, alteration).
• Fresh samples are imperative.
• Must be stratigraphically controlled as best as possible.

Chemistry is not a substitute for stratigraphy - MUST
HAVE FIELD CONTROL.
• Depending on problem you may need spatial distribution

as well (e.g., alteration studies - more later).
Assay Sampling
• Statistical approach (i.e., every five meters regardless of
geological features).
• Geostatistical approach (i.e., every five meters or change

in lithology/mineralization/alteration - takes into account
geological features).
• Random.
• Often dependent the type and stage of project.
• Hereon all things will be concentrating on hypothesis-

driven sampling for lithogeochemistry.
Getting the Right Samples in the
Field
• Depends on project.
• Representative samples.
• Unweathered material.
• Use sledge hammer or mallet (geological hammers are

insufficient!).
• Remove weathered edges with hammer.
• Goal is to get fresh sample equivalent in size to two fists.
Sampling to Understand Primary
Processes
• Primary processes - not related to alteration (e.g., tectonic
setting, provenance, petrology, etc.).
• Samples must be free of veins, filled amygdules,

weathering rinds, and hydrothermal/metamorphic
minerals, if possible. You do the best you can.
• If required, use saws, drills, explosives to get best

samples - don’t let conditions dictate quality of sample.
• Time and physical effort often the key!
• Take multiple samples from an outcrop.
• Field control is essential.
Sampling to Understand Alteration
• Must get fresh samples (unless weathering is important to
your study, e.g., laterites).
• Sample spatially from fresh (or least altered) to most

altered with samples of various alteration types and in
varying intensities.
• If required, use saws, drills, explosives to get best

samples - don’t let conditions dictate quality of sample.
• Time and physical effort often the key!
• Take multiple samples from an outcrop or drill core.
• Field control is essential.
Trimming Samples
• Following field sample must prepare by trimming with
saws.
• Use block for thin section and crushing/grinding/

pulverizing.
• Avoid discoloured samples, those with veins, filled

amygdules, etc. - cut these parts of the sample out unless
they are representative of alteration type.
• Only need a little sample so make sure it’s representative.
• Wash and dry cut slabs (e.g., wash in water or alcohol).
Sawing
• What to look out for when using a saw:
• Oil-cooled saws recycle coolant and have horrible

memory effects from previous samples. Only ever use
water-cooled saws
• Saw blades may be contaminated from earlier samples

(including your own)
• Arrange samples in logical order (e.g. first cut all

unmineralized samples, then the rest)
• Clean and sharpen blade with fast cut into brick
• Pre-contaminate blade with a separate cut through an

unwanted part of the sample
For Ultra Clean Preparation
• Remove saw marks on steel grinding wheel
• Crush sawn slabs in plastic bags
• Pick chips from crush, avoiding areas of saw marks and

other unwanted surfaces
• Clean chips in deionized water in an ultrasonic bath
• Dry chips at 110ºC
Crushing, Grinding, Pulverization
• To analyze a sample we must convert to a powder via

crushing, grinding, and pulverization - this homogenizes
samples.
• For fine grained samples need around fist of rock for

representative homogenization.
• For coarser samples (e.g., intrusives) need two to four

times this, depends on how coarse. Coarser it is the
larger the sample should be done.
• Crushing done with steel jaw crusher. Grinding done with

grinder. Pulverizing with puck mill or ball mill assembly.
http://www.esslabshop.co.uk/
acatalog/
Retsch_Disc_Mill_DM200.html http://www.ga.gov.au/image_cache/
GA4015.jpg
http://www.xrf.ethz.ch/xrf_instr_grinding.html
Homogenization
• Pay for good pulverization - adequate time with the right

pulverizer.
• Pulverizers: agate, ceramic, tungsten-carbide, mild

(hardened carbon) steel.
• For lithogeochemistry avoid tungsten-carbide and oxide-

based pulverizers at all costs due to contamination.
• Arrange similar samples together. Separate mineralized

from unmineralized samples.
Homogenization
• Clean pulverizer with alcohol and quartz in between

samples.
• Pre-contaminate pulverizer with your own sample.
• Dump powder onto clean piece of paper for each sample

(avoid spoons, spatula, etc.)
• Put in plastic, screwtop jars.
Submitting Samples
• Submit samples in batches to laboratory. Arrange in

groups according to rock type, mineralized versus
unmineralized etc.
• Include field duplicates and sample preparation

duplicates.
• Include reference materials to be run (e.g., every 20

samples). For QA/QC.
Analytical Methods
• Lithogeochemistry
• Solid Source: XRF, INAA
• Solution Methods: ICP-ES, ICP-MS
• Mineral Chemistry
• In Situ Analyses: SEM, EPMA, LA-ICP-MS, LA-MC-ICP-

MS
• Isotopic Methods
• TIMS, MC-ICP-MS, GC-MS
Solid Source Methods
• XRF
• Major elements - fused discs.
• Trace elements - pressed pellets (e.g., Zr, Nb, Y, Ti, Sc,

V, Ni).
• INAA
• Incomplete suite of REE
• Many traces.
• PGE
Analysis by X-ray Fluorescence
• Principle of X-ray induced fluorescence
From Potts (1978)
From Potts (1978)
From Potts (1978)
• Sample preparation is either as ‘pressed’ pellet;
• Or Li-borate fluxed, quenched melt disc
XRF
• Workhorse for major elements and loss on ignition.
• Fused discs - major and some minor elements (SiO2,

Al2O3, TiO2, Na2O, K2O, CaO, Fe2O3, MgO, MnO, P2O5, LOI).
• Pressed pellets - many trace elements of interest at good

levels (e.g., Zr, Nb, Y, Ni, Sc, V, Ga).
• Vintage trace elements often by XRF. Often used to test

digestions by ICP methods.
Instrumental Neutron Activation
Analysis (INAA)
• Principle is that irradiation of sample in nuclear reactor
leads to neutron capture.
• Neutron capture transforms a stable isotope into a

radioactive isotope.
• The gamma rays from the decay of these isotopes have

characteristic energies that are quantified with a detector
From Potts (1978)

Instrumental Neutron Activation
Analysis (INAA)
• Advantages:
• Minimal sample preparation
• No problems with digesting refractory phases
• Very sensitive for certain trace elements (earliest ppb

range data)
• Disadvantages:
• Slow (cool off period) and expensive
• Incomplete data sets
Solution Methods
• Involves dissolving sample. Numerous “digestions” or
“extractions” are available:
• Aqua regia - partially dissolves sample; dissolves

sulphides.
• HF-HNO3 - strong dissolution, but some zircon, barite,

etc. might remain.
• Fusions then HF-HNO3 - fuses sample to bead then

dissolve, ensures heavy minerals are dissolved.
• Bomb dissolution - dissolves samples in acid under

pressure - ensures heavy minerals are dissolved.
• MMI and Enzyme Leach.
• Upon dissolving to a solution we analyze solutions on an

instrument to get chemical and isotopic data (e.g., ICP-
MS, ICP-ES).
Partial Extractions and Selective
Leaches
• Partial extractions result in a sample having

part of it extracted.
• Selective leach will attack a “selective” part of

the sample.
• Partial extractions and selective leaches result

in “incomplete” dissolution of the sample.
• Strength of extraction determines what

elements are extracted.
Partial Extractions and Selective Leaches
• Aqua regia - partially dissolves sample; dissolves sulphides,
arsenide, tellurides. Will not dissolve barite, chromite, spinel, zircon,
garnet, monazite, etc..
• “Four-acid”, HF-HClO4-HNO3-HCl, ‘nearly total’: Most silicates

dissolve but minerals above still may be partial. Often not total for
REEs, Al, Ba, Ta, Nb, Hf, Sn, Cr, W, Fe.Si volatilises as do Cr, As, Sb,
Au sometimes. (dependent on conditions)
• For weakly held metals and elements:
• Enzyme LeachSM (manganese oxides)
• Hydroxylamine-HCL (iron oxides)
• Sodium pyrophosphate (organic material)
• MMI® (mobile component of sorbed metals)
• Ammonium acetate
• Partial extractions and selective leaches are often targeted to specific

metals and loosely bound materials. Commonly used in surficial
samples and for sulfide-rich materials.
Complete and Near-Complete
Dissolution
• Complete to near-complete dissolutions are commonly
used in whole rock and mineral chemistry to completely
dissolve a sample and then analyze it.
• Common complete dissolutions:
• HF-HNO3 - strong dissolution, but some zircon, barite,

etc. might remain.
• Sodium-Peroxide Sinter - mix samples with flux to

dissolve. Leads to contamination and some loss of
volatiles. Dirt on instrumentation.
• Fusions then HF-HNO3 - fuses sample to bead then

dissolve, ensures heavy minerals are dissolved.
• Bomb dissolution - dissolves samples in acid under

pressure - ensures heavy minerals are dissolved.
Testing for Complete Dissolution of
Samples
• This is easily done by comparing a solid-
source method with one that is a dissolution
technique (i.e., same elements on the same
samples are analyzed by two techniques - THIS
IS VERY COMMON).
• Solid source methods like XRF and INAA do not

require dissolution of material, hence, values of
elements are absolute values.
• The values from solid source are then

compared to a solution method via X-Y plots to
test if dissolutions were complete.
• For whole rock methods we want a COMPLETE

DISSOLUTION.
• Choose an appropriate method for whole rock!

Testing for Complete Dissolution
30000
n
l u tio
o
ss
t Di
fe c
r
Pe
=
RF)
(X
20000
Zr (ICP-MS)
Zr
) =
MS
P-
(IC
Zr
1=
=
m
10000 m<1 = Zr (ICP-MS) < Zr (XRF) =

Incomplete Dissolution
0
0 10000 20000 30000
Zr (XRF)
Photo from M.Burnham Fusing a sample
Photo from M.Burnham Photo from M.Burnham
XRF Powder Pellet XRF Fused Disc
Teflon Parr Bomb

Sample Preparation: Fire Assay
• Au, Ag, and PGE (Pt, Pd, Ir, Os, Ru, Rh) are at
such low concentrations in most Earth materials
that they must be pre-concentrated.
• Sample + flux + reagents (i.e., NiS or PbS).
• Flux reduces melting point of rocks, causes

them to melt, then we form a NiS or PbS bead
and slag.
• Au, Ag, and PGE are compatible in NiS and PbS

bead and are pre-concentrated in this bead.
• Bead is then dissolved in acid and solution

analyzed for Au, Ag, and/or PGE.
• Fire assay does not necessarily mean the same

as “assay” as described previously. It’s a
specific preparation method.
Sample Preparation: Fire Assay
From Potts (1987) and Marcus Burnham
Solution Sample Preparation:
Summary
• Partial or full digestions.
• For whole rock lithogeochemistry we want

FULL DIGESTIONS
• Fusions (e.g., lithium metaborate)
• Bomb dissolution.
• For Au, Ag, and PGE we may use fire assay pre-
preparation then dissolve in acids.
Solution Analytical Methods
• ICP-ES - Inductively Coupled Plasma Emission
Spectrometer (aka ICP-OES - optical emission
spectometer)
• Major elements, (wt% to ppm) medium level trace

elements (ppm)
• ICP-MS - Inductively Coupled Plasma Mass Spectrometer
• Trace elements to ultra-low levels (down to ppt and

ppq levels).
• REE, HFSE, LFSE.
ICP-ES
• Used for mid-level trace elements, some majors and minor

elements.
• Involves sample introduction into a machine which is then

converted into a plasma via an inductive coupling.
• Energizes atoms which then give off specific light spectra

that is detected.
• Concentration is proportional to intensity, etc.
The ICP
From Hall (2007)

From Gunther&Hattendorf (2005)
The ICP
From Hall (2007)

ICP-ES
From Potts (1978)
ICP-ES
• Advantages:
• Rapid analysis for large number of elements.
• In geological material best for major elements.
• Excellent for certain elements in water.
• Disadvantages:
• Because solution properties affect plasma condition, this

technique is matrix sensitive.
• Requires close matching of calibration standards with

geological samples.
• Incomplete trace element data sets.
ICP-MS
• Unparalleled instrument for ultra-low level values of most

trace elements (>40) including rare earth elements (REE),
high field strength elements (HFSE), low field strength
elements (LFSE), volatile metals (e.g., Tl, Sb, As), and
other trace metals (e.g., V, Co, Cr, Ni, Sc, Ti).
• Involves introduction of a sample solution and conversion

into a plasma.
• This plasma creates ions for specific elements which are

then detected by a quadrapole mass spectrometer based
on atomic mass.
ICP-MS
LA-ICPMS: Schematic setup
ICP-MS
• Advantages:
• Rapid analysis for large number of elements.
• If blanks are controlled, low ppb detection limits.
• At high dilution factor, very little matrix effect.
• Disadvantages:
• Digestion of refractory minerals (see above).
• Potential problems with memory (for Au, PGE).
• This is a relative method.
Thermal Ionization Mass
Spectrometry (TIMS)
• Ionization of sample using voltage.
• Ionizes material and then measured via a

magnetic sector mass spectrometer.
• Ultra-precise and the benchmark for many

radiogenic isotopes, including U-Pb
geochronology.
• Great for: Sr, Nd, U-Th-Pb isotopes.
• N-TIMS (negative-TIMS) used for Os isotopes.
• Isotope dilution elemental measurements.
http://www.eos.ubc.ca/research/pcigr/Instrumentation.htm#TIMS
TIMS: Thermal Ionization Mass Spectrometry

http://www.eos.ubc.ca/research/pcigr/Instrumentation.htm#TIMS
TIMS: Thermal Ionization Mass Spectrometry

Multi-Collector ICP-MS
• Major technological advancement and uses a

front end like the ICP-MS, but a hind-end like a
TIMS with a magnetic sector mass
spectrometer.
• Outstanding resolution and has revolutionized

many fields including:
• Lu-Hf isotopes
• Heavy metal stable isotopes (e.g., Zn, Cu,

Mo, Fe).
• In addition to above, it allows one to obtain

radiogenic and stable isotopes on a variety of
isotopes, including radiogenic isotopes (U-Th-
Pb, Sr, Nd, W, Os) and stable isotopes (Li, B,
Mg, Ca, Ge, and Tl).
MC-ICP-MS
From Rehkämper et al. (2007)

MC-ICP-MS (Picture)
http://www.nu-ins.com/index.php/plasma-source/the-nu-plasma-1700#
In-Situ Methods for Minerals
• SEM - Scanning Electron Microscope
• Mostly for imaging, semi-quantitative data
• EPMA - Electron Microprobe Microanalysis (Probe)
• Mostly for major elements, some traces at >100 ppm

levels.
• LA-ICP-MS - Laser Ablation ICP-MS
• Ultra-low level, in-situ trace element analyses.
• These tools are extremely important in diamond indicator

mineral work and will likely become more commonplace in
industry within the next decade.
• VERY IMPORTANT in metallurgy, grade control, etc.
SEM
• Primarily an imaging tool and mineral identification tool

for minerals.
• Provides semi-quantitative major element data.
• Important tool in mineral benefication and metallurgy, i.e.,

GeoMetallurgy and Mineral Liberation Analysis (MLA).
SEM
Three lens probe-forming

column
Condensing lens:
Provide control of
beam current and
crossover spot
size
Objective lens:
= probe-forming
lens;
controls focus,
working distance,
depth-of-field.
From McDonald
(2006)
SEM
Secondary
electron images
(SEI): Brightness
Electron-solid Events of image
components a
Cathodoluminesc function of depth
ent images (CLI): relative to
Brightness of detector
image
components α Back-scattered
specific trace- electron
element contents images (BSEI):
Brightness of
image
components α
average
atomic #
Secondary
electron image
of SIMS
ablation pit in
pyrite.
CL images of zircons, Topsails Complex (D. Courage, MSc, MUN)
 General notes and hypothesis of Au-‐rich VMS Slide from Stefanie Brueckner
 Ming Mine (geology, stratigraphy, Mineralogy)
Coff+Hem
Bran+Hem
Zrc+Hem
Gold liberated? Gold locked
Legend for sample 7917
%
Legend for sample 7917
%
Electron Probe Microanalysis (EPMA)
• Mainly for quantitative major element and minor trace

element concentrations of minerals.
• Important for understanding residence of major elements

and some traces.
• Mineral chemical work.
• Useful for indicator mineral studies.
• Metallurgy and mineral benefication.
Electron Probe Microanalysis (EPMA)
Laser Ablation ICP-MS
• Laser attachment on ICP-MS.
• Rather than introducing the sample via solution we

introduce by “ablating” the sample with a laser (either UV,
Nd:YAG, etc.).
• Ablated material is then transferred to ICP-MS for analysis

of trace elements.
• Provides ultra low-level trace element concentration in

samples.
• Useful for low resolution U-Pb geochronology (e.g., first

pass and detrital zircon). Very larger errors and NOT a
substitute for TIMS U-Pb.
Laser
Attachment
for
ICP-MS
LA-ICPMS: Schematic setup
Merensky Reef, composite sulfide
(po-ccp-pnt)
From Ulrich et al. (2009)
Other Analytical Methods
• IR-MS - Isotope ratio mass spectrometry - primarily for

stable isotopes of C-O-H-S-Ar.
• SIMS - secondary ion mass spectrometry - used for in-situ

analysis of U, O, S - often for U-Pb geochronology.
• SHRIMP - Sensitive High Resolution Ion MIcroprobe - used

for in situ analysis of U, O, S - often for U-Pb
geochronology.
• More on the above methods in different sections of the

course.
Bulk Rock Elemental Analyses
Concentration: ppt-ppb ppm wt%
XRF, ICP-ES
ICP-MS, INAA
Mineral Chemical Elemental Analyses
SEM: imaging EPMA

LA-ICP-MS
Isotopic Methods
TIMS - radiogenic isotopes
MC-ICP-MS - radiogenic isotopes
LA-MC-ICP-MS - in situ radiogenic isotopes
LA-ICP-MS - in situ radiogenic isotopes
IRMS - stable isotopes
QA/QC: Why Should We Care?
• When interpreting geochemical data we want to make
sure that elemental variations are due geochemical
processes and not due to sampling or instrumentation
(i.e., remove all other effects except geochemical
processes).
• We wish to know the limitations of our data (e.g., if 2σ

error is 5ppm then can separate anomalies only if they
are outside error range).
• NI-43-101
• Increase confidence in the quality of your data for

peers (e.g, reviewers, stock exchange, etc.).
Background Theory
• Precision: measure of reproducibility (i.e., how many

times we can replicate a result)
• Accuracy: measure of how close we are to a known, or

accepted, value (i.e., how close is our result to a true
value).
• Drift: this is the systematic shift in measured values with

time.
Instrument Drift
Testing Precision
• Precision: measure of reproducibility (i.e., how many times we can
replicate a result)
• When we talk about testing precision we are testing:
• Sampling Precision – how good are we at sampling?
• Laboratory preparation and instrumentation precision – how

good is our laboratory?
• Testing sampling precision involves duplicate sampling (i.e., every 20

samples we take a duplicate sample) – this also to test sample
homogeneity.
• Testing laboratory precision can be done by having random analytical

duplicates (i.e., every 20 samples or so), and using standard
reference materials (SRMs; or internal reference materials – IRMs;
analyzing SRM every 20 samples or so).
Testing Precision
• But where do we go from here?
• How do we assess the quality of our duplicate data?
• How do we assess the quality of our SRM or IRM data?
Testing Precision
• Over time SRM (or IRMs) are analyzed multiple times and
we end up with mass of data.
• Using said data we measure the precision using the

Percent Relative Standard Deviation (%RSD) on this
dataset using:
• Where:
• µi = mean value of element i over a series of analytical

runs
• si = standard deviation of the mean from the series of

analytical runs for element i
Al2O3 CaO Fe2O3 K2O MgO MnO Na2O P2O5 SiO2 TiO2 LOI
wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt%
LOD 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
LOQ 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03
GSD-11 10.70 0.50 4.34 3.43 0.62 0.34 0.44 0.06 76.28 0.36 3.36
GSD-11 10.69 0.49 4.34 3.43 0.62 0.34 0.35 0.06 76.35 0.36 3.36
GSD-11 10.69 0.52 4.34 3.43 0.60 0.34 0.42 0.06 76.32 0.36 3.36
GSD-11 10.69 0.51 4.34 3.44 0.60 0.33 0.45 0.06 76.35 0.36 3.36
GSD-11 10.70 0.49 4.34 3.43 0.61 0.34 0.48 0.06 76.30 0.36 3.36
GSD-11 10.71 0.48 4.34 3.43 0.61 0.33 0.41 0.06 76.22 0.36 3.36
GSD-11 10.70 0.49 4.34 3.43 0.60 0.34 0.37 0.06 76.27 0.36 3.36
GSD-11 10.68 0.48 4.34 3.43 0.60 0.34 0.32 0.06 76.21 0.36 3.36
GSD-11 10.69 0.48 4.34 3.43 0.60 0.33 0.42 0.07 76.31 0.36 3.36
GSD-11 10.67 0.50 4.34 3.44 0.63 0.34 0.44 0.07 76.29 0.37 3.36
GSD-11 10.68 0.50 4.34 3.43 0.61 0.34 0.48 0.07 76.31 0.36 3.36
GSD-11 10.71 0.49 4.34 3.43 0.61 0.34 0.37 0.06 76.26 0.36 3.36
GSD-11 10.71 0.49 4.34 3.44 0.62 0.33 0.41 0.06 76.27 0.36 3.36
GSD-11 10.69 0.48 4.35 3.44 0.61 0.33 0.37 0.06 76.29 0.37 3.36
GSD-11 10.73 0.49 4.33 3.43 0.60 0.33 0.38 0.06 76.50 0.36 3.36
GSD-11 10.70 0.49 4.34 3.44 0.62 0.34 0.35 0.07 76.30 0.36 3.36
GSD-11 10.71 0.50 4.34 3.44 0.62 0.34 0.35 0.07 76.27 0.37 3.36
GSD-11 10.73 0.56 4.35 3.41 0.65 0.34 0.48 0.06 76.26 0.36 3.36
µi 10.70 0.50 4.34 3.43 0.61 0.34 0.41 0.06 76.30 0.36 3.36
si 0.02 0.02 0.00 0.01 0.01 0.00 0.05 0.00 0.06 0.00 0.00
%RSD 0.15 3.85 0.10 0.21 2.15 1.44 12.34 7.34 0.08 1.06 0.00
2σ 0.01 0.01 0.00 0.00 0.01 0.00 0.02 0.00 0.03 0.00 0.00
Known 10.37 0.47 n/a 3.28 0.62 0.32 0.46 0.06 76.25 0.35 n/a
%RD 3.17 5.67 - 4.64 -1.16 5.21 -11.96 6.40 0.06 3.33 -
What does it mean?
• General rules (Jenner, 1996):
• %RSD = 0-3%= EXCELLENT PRECISION
• %RSD = 3-7%= VERY GOOD PRECISION
• %RSD = 7-10% = GOOD PRECISION
• %RSD >10% = POOR PRECISION
Standard Error
• From SRMs or IRMs we can also get standard error of the

mean for an element. This is critical for separating what is
real variation versus variation within error.
• Standard error at the 95% confidence level for element i

(2σi) is:
• Where:
• si = standard deviation of element i over number of

analytical determinations
• n = number of analytical determinations
Some Other Considerations
• Typically we run a range of SRMs or IRMs proportional to

the materials that we are using (MATRIX MATCHING – i.e.,
don’t use a soil standard if you are doing
lithogeochemistry; if doing ore reserves use ore
standards, etc.)
• SRMs or IRMs should be inserted in with regular samples

at a regular interval (i.e., every 20 samples, 25 samples,
etc.) – tests precision with drift.
• Dependent on cost, size of analytical program, etc.
Advantages/Disadvantages of SRM or IRM
• Advantage: well known values (more important for
accuracy).
• Advantage: history of being analyzed in labs around

world, or multiple times by a given organization.
• Advantage: often very well established values for certain

elements.
• Disadvantage: often expensive to purchase.
• Disadvantage: cost of analysis, have many more analyses

to be undertaken.
• Disadvantage: limited range of values for a given element,

or group of elements.
• Disadvantage: fixed matrix (i.e., not variable matrices of

material).
Testing Precision with Duplicate
Samples
• Involves the analysis of random analytical duplicates or
random field duplicates throughout an analytical program.
• Sample duplicates involve taking random duplicate

samples in the field – it is aimed at precision of sampling,
sample homogeneity, duplication of sampling – also tests
sample preparation process.
• Analytical duplicates are random duplicates (every 20-25

samples or so), aimed at testing the analytical method.
Sample Nb Nb Zr Zr Y Y Sr Sr
00RAY267A 3 3 71 72 29 29 123 121
00RAY084B 3 3 20 21 5 4 424 424
01RAY245A2 7 7 84 85 n.d. n.d. 1190 1188
01GGA155A1 7 6 184 184 33 34 269 268
01DM295 27.8 28 411.5 410.9 31.2 30.5 73.8 73.2
01DM94 20.1 20.6 195.5 195.8 39.5 39.3 269.3 269.9
01MC-072 14.9 15 138.5 137.4 15.7 14.6 128.8 128.7
01MC-160 3.7 2.9 27.7 28.2 13.7 13.2 24.4 24.4
02RAYP82A1 8 8 101 102 15 15 757 755
02RAY52A1 7 7 89 88 (1) (1) 1151 1152
02RAYP103B1 5 5 81 82 33 32 203 203
Now what do we do?
• We can employ two main methods to test precision from

duplicate samples:
• Precision Scatterplots
• Thompson-Howarth Plots
Duplicate Data: Precision
Scatterplots
• Precision scatterplots are logarithmic plots of the original
analyses (X1) plotted on the X-axis against the duplicate
analyses (X2) on the Y-axis.
• On this diagram we have a 1:1 control line where samples

should lie if X1=X2.
• The latter situation isn’t realistic and we are willing to

accept a level of variation within a given precision.
• Thus, we have a set of control lines set at a given

precision (i.e., you set precision – level is dependent on
the problem –FIT FOR PURPOSE).
Sr by XRF, 10% precision
X2 (duplicate) 1000
100
10% control lines
1:1 control line
10
10 100 1000
X1 (original)
Plotting the Control Lines
• Plot of X1 and X2 raw data is straightforward in Excel, etc.
• To create 1:1 line plot X2 = X1 (i.e., Y=X) for a series of X1

values that are dependent on the range of concentrations
in your dataset (i.e., 0.1, 1, 100, etc.).
• To plot the precision control lines we have two lines:
• X2 = X1+ X1*(%precision) [this is the upper limit of

precision]
• X2 = X1- X1*(%precision) [this is the lower limit of

precision]
Interpreting the Graphs
• If data lies between lines at a given precision, than they
are precise to that level of precision.
• If they are outside of the lines at that precision or highly

scattered, than they are not precise to that level of
precision.
• But what if we have a mixture?
Nb via XRF - 5% Precision
X2 (duplicate) 100
10
1
1 10 100
X1 (original)
Cd via ICP-ES, 10% Precision
X1 (original)
1 10 100
100
X2 (duplicate)
10
Hf via ICP-MS at 5%
Hf via ICP-MS at 15%
Precise Moderate Precision
No Bias
precision precision
X2 (duplicate)
X2 (duplicate)
control control
lines lines
1:1 control line 1:1 control line
X1 (original) X1 (original)
Imprecise Rotational
Bias
precision precision
X2 (duplicate)
X2 (duplicate)
control control
lines lines
Translational Decreased Precision
Bias at Low Concentrations
(appoaching detection
limit)
precision precision
X2 (duplicate)
X2 (duplicate)
control control
lines lines
Thompson-Howarth Plots
• Created in the 1970s by Thomson and Howarth (1978 - Journal of
Geochemical Exploration, 9: 23-30) for duplicate analyses.
• It consists of plotting the (X1+X2)/2 (estimate of mean value) on the

X-axis and |X1-X2| (estimate of standard deviation) on the Y-axis,
where X1 and X2 are the original and duplicate analyses,
respectively.
• With Thompson-Howarth there are two types of graphs:
• One for <50 pairs of duplicates (Short Method – good for small
datasets)
• One for >50 pairs of duplicates (Long Method – good for larger
datasets)
Thompson-Howarth Plots: Short Method
• In short method we have (X1+X2)/2 (estimate of mean)
versus |X1-X2| (estimate of std. dev.)
• We also plot a “control line” which is a line that is

prescribed at a defined precision (i.e., user-defined
precision).
• Control line is the major challenge to making this short-

method diagram. [Hand-out describes how to make the
control line.]
• Now it’s interpreting the plot……..
TiO2 at 5% precision via XRF
Control Line
All below, precise

to 5% via XRF.
W at 5% precision via ICP-ES
All above, not precise

to 10% via ICP-ES.
Nb at 3% precision via ICP-MS
But what about this?
N = 15 (total pairs of duplicates)

M = 1 (how many above control line)
N M=1 M=2 M=3
1 0.100000 Since there is a 79% chance
2 0.190000 that point is random it’s likely
0.010000
3 0.271000 0.028000
Nb is precise to 3%.
0.001000
4 0.343900 0.052300 0.003700
5 0.409510 0.081460 0.008560
6 0.468559 0.114265 0.015850
7 0.521703 0.149694 0.025692
8 0.569533 0.186895 0.038092
9 0.612580 0.225159 0.052972
10 0.651322 0.263901 0.070191
11 0.686189 0.302643 0.089562
12 0.717570 0.340998 0.110870
13 0.745813 0.378655 0.133883
14 0.771232 0.415371 0.158360
15 0.794109 0.450957 0.184061
Cs at 3% precision via ICP-MS
But what about this?
N = 15 (total pairs of
duplicates)
M = 5 (how many
above control line)
N M=1 M=2 M=3 M=4 M=5 M=6
1 0.100000
Since there is a 1.2% chance
2 0.190000 0.010000 that these points are random.
3 0.271000 0.028000 0.001000 Cs is unlikely precise to 3%
4 0.343900 0.052300 0.003700
(i.e., worse than 3%).
0.000100
5 0.409510 0.081460 0.008560 0.000460 0.000010
6 0.468559 0.114265 0.015850 0.001270 0.000055 0.000001
7 0.521703 0.149694 0.025692 0.002728 0.000177 0.000006
8 0.569533 0.186895 0.038092 0.005024 0.000432 0.000023
9 0.612580 0.225159 0.052972 0.008331 0.000891 0.000064
10 0.651322 0.263901 0.070191 0.012795 0.001635 0.000147
11 0.686189 0.302643 0.089562 0.018535 0.002751 0.000296
12 0.717570 0.340998 0.110870 0.025637 0.004329 0.000541
13 0.745813 0.378655 0.133883 0.034161 0.006460 0.000920
14 0.771232 0.415371 0.158360 0.044133 0.009230 0.001474
15 0.794109 0.450957 0.184061 0.055556 0.01272 0.002250
Thursday, 6 September, 0.814698

12 0.485272 0.210751 0.068406 0.017004 0.003297
Thompson-Howarth Plots: Long
Method (Fletcher, 1986)
• In long method we have (X1+X2)/2 (estimate of mean) versus |
X1-X2| (estimate of std. dev.) as well.
• In a spreadsheet we rank the pairs of duplicates in order of

increasing concentration means (i.e., increasing (X1+X2)/2)
• From the first 11 results obtain the mean concentration

[(X1+X2)/2 ] and median difference [|X1-X2|].
• Repeat this for each successive group of 11 ignoring any

remainders <11.
Thompson-Howarth Plots: Short
Method (Fletcher, 1986)
• Calculate or obtain graphically the linear regression of the
median difference of the means (i.e., a linear regression of
the plot)
• Since |X1-X2| is an estimate of the standard deviation (s) and

(X1+X2)/2 is an estimate of the mean concentration (X) this
linear regression yields an equation of the form:
• where
• m is the slope of the regression and
• c is the y-intercept
Thompson-Howarth Plots: Short
Method
• Using the values of s determined in the previous equation we
can input different concentrations to obtain pre
concentration using:
• Where Pc is the precision at the 95% confidence level.
Ba Ba (X1+X2)/2 |X1-X2|
01DM-106-1 0 0 0.043840933 0.192112144
O1DM-F1 31 31 31 0
01DM-295 43 42 42.5 1
03-BHA-0229A 53 53 53 0
03-BHA-0358 98 100 99 2
01DM-106-2 115 117 116 2
03-BHA-0450A 132 137 134.5 5
03-BHA-0261 137 132 134.5 5
03GGA420A2 145 142 143.5 3
03-BHA-0099 153 162 157.5 9
03RAY316A3 174 167 170.5 7 98.3676219 2
03-BHA-0187 210 212 211 2
PER-1 220 213 216.5 7
03GGA089A1 224 232 228 8
02RAYR001A1 248 248 248 0
03RAYP027A1 263 259 261 4
02RAYP27A1 283 295 289 12
03ASP0094.1.1 359 339 349 20
03-BHA-0125A 401 410 405.5 9
03SJP031-1-1 452 447 449.5 5
03-PJM-132n 479 451 465 28
03ASP0003.1.1 493 491 492 2 328.5909091 7
Typical Thompson-Howarth
Long Method Plot
Cr via ICP-ES
Duplicates: Average Coefficient of
Variation
• The above methods are useful if the data are
normally distributed; however, this is not always
the case, particularly for samples that exhibit a
nugget effect (e.g., Au, Pt, Pd).
• Use average coefficient of variation:
$ a −b 2'
2 & ( i i) )
N
CVavg (%) = 100 × ∑ & 2)!
N i=1 % ( ai + bi ) (
• where
• CVavg = avg coefficient of variation;

€ • ai,bi = original and duplicate for the i pairs;
• N = number of duplicate pairs.
Duplicates: Average Coefficient of
Variation
• The average coefficient of variation method is

the best and most robust method of measuring
precision using duplicate data as it is
independent of the nature of the distribution of
errors (e.g., normal versus non-normal) and is
equally applicable to elements that exhibit and
do not exhibit the nugget effect.
Advantages/Disadvantages of Duplicates
• Advantage: not restricted by concentration. Typically
duplicates have a wide range of concentrations, unlike
SRMs or IRMs, therefore have ability to test precision as a
function of concentration.
• Advantage: independent gauge of precision of sampling

and analytical method – random samples make it a more
independent measure of precision.
• Advantage: matrix can be variable (i.e., in litho can be a

variety of rock types) and can test precision as a function
of variable matrixes. SRMs and IRMs often have restricted
matrixes.
• Disadvantage: cost of duplicate samples - still, this is the

cost of doing business - NI-43-101 expects this to be done
(i.e., poor QA/QC = untrustworthy data).
• Best bet: use combination of both SRM/IRMs and

duplicates to measure precision.
Testing Accuracy
• Accuracy: measure of how close our results are to a

known or accepted value
• Test accuracy with SRMs or IRMs
• Run SRMs or IRMs during analytical program. Obtain

mass of data, then test accuracy.
Testing Accuracy
• When we test for accuracy we use the percent relative difference
(%RD):
• where
• µi = mean value of element i in the standard over a number of

analytical runs.
• STDi = “known” or “certified” value of element i in the standard or

reference material
Testing Accuracy
• General rules (Jenner, 1996):
• %RSD = ±0-3%= EXCELLENT ACCURACY
• %RSD = ±3-7%= VERY GOOD ACCURACY
• %RSD = ±7-10% = GOOD ACCURACY
• %RSD = ±>10% = POOR ACCURACY
Al2O3 CaO Fe2O3 K2O MgO MnO Na2O P2O5 SiO2 TiO2 LOI
wt% wt% wt% wt% wt% wt% wt% wt% wt% wt% wt%
LOD 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
LOQ 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03
GSD-11 10.70 0.50 4.34 3.43 0.62 0.34 0.44 0.06 76.28 0.36 3.36
GSD-11 10.69 0.49 4.34 3.43 0.62 0.34 0.35 0.06 76.35 0.36 3.36
GSD-11 10.69 0.52 4.34 3.43 0.60 0.34 0.42 0.06 76.32 0.36 3.36
GSD-11 10.69 0.51 4.34 3.44 0.60 0.33 0.45 0.06 76.35 0.36 3.36
GSD-11 10.70 0.49 4.34 3.43 0.61 0.34 0.48 0.06 76.30 0.36 3.36
…….
…….. …….. …….. …….. …….. …….. …….. …….. …….. …….. ……..
.
GSD-11 10.73 0.56 4.35 3.41 0.65 0.34 0.48 0.06 76.26 0.36 3.36
μi 10.70 0.50 4.34 3.43 0.61 0.34 0.41 0.06 76.30 0.36 3.36
si 0.02 0.02 0.00 0.01 0.01 0.00 0.05 0.00 0.06 0.00 0.00
%RSD 0.15 3.85 0.10 0.21 2.15 1.44 12.34 7.34 0.08 1.06 0.00
2s 0.01 0.01 0.00 0.00 0.01 0.00 0.02 0.00 0.03 0.00 0.00
Expected 10.37 0.47 n/a 3.28 0.62 0.32 0.46 0.06 76.25 0.35 n/a
%RD 3.17 5.67 - 4.64 -1.16 5.21 -11.96 6.40 0.06 3.33 -
Testing Accuracy: Shewart Control
Charts
• X-axis - Involves plotting the samples on a diagram as a
function of analytical order (e.g., the order in which they
were analyzed in the lab in between the normal samples).
• Y-axis - concentration obtained for a given element in the

standard.
• There are also control points with the mean value for the
standard and the upper and lower confidence limits at the
95% confidence level (e.g., 2SE).
• Samples that lie inside bounds suggest lab is doing well.
• Samples outside suggest that batch of samples containing

the outlier point should be re-run or there is a problem with
analytical method.
• You can test outliers with Grubb test (see below).
Pb Standard Replicate Analysis
6000
5500
5000
Concentration
Data
+2s
4500
-2s
Mean
4000
3500
3000
0 10 20 30 40 50 60
Sample
Zn Standard Replicate Analysis
20000
19500
19000
18500
Concentration
Data
+2s
18000
-2s
Mean
17500
17000
16500
16000
0 10 20 30 40 50 60
Sample
Zr Standard Replicate Analysis
195
190
185
Concentration
Series1
Series2
180
Series3
Series4
175
170
165
0 5 10 15 20 25 30 35 40 45
Standard Analytical Position
Nb Standard Replicate Analysis
15
14.5
14
Concentration
Series1
Series2
Series3
Series4
13.5
13
12.5
0 5 10 15 20 25 30 35 40 45
Standard Analytical Position
Schewart Control Charts
Accurate Minor Outliers
(transcription errors)
+2SD +2SD
Concentration
Concentration
certified certified
mean mean
-2SD -2SD
Order of Standard Analysis Order of Standard Analysis

Analytical Bias Data Tampering
(poor equipment or Tampering During
calibration) Handling
+2SD +2SD
Concentration
Concentration
certified certified
mean mean
-2SD -2SD
Order of Standard Analysis Order of Standard Analysis
Schewart Control Charts
Drift During Program

or Degredation of Standard
+2SD
Concentration certified
mean
-2SD
Order of Standard Analysis
Grubb Test for Outliers
• This is useful in testing outliers in your standard or blank
data.
• Based on calculating a Grubb statistic (G) for a given

outlier using the following equation:
• where
• Yi is the outlier point,
• Ybar is the mean value of element i in a standard or the

average value of element i in the blank; and
• s = is the standard deviation of element i in a standard or

the long average value of element i in the blank.
Grubb Test for Outliers
• We then compare our Grubb statistic to the test statistic

using the t distribution:
• where
• t2 α/(2n),N-2 = critical value of the t-distribution with N − 2 degrees of

freedom and a significance level of α/(2N). For the one-sided tests,
replace α/(2N) with α/N
• N = number of datapoints in the dataset from which the

value is taken (e.g., total number of analysis of standard
or the total number of values in the blank dataset).
Grubb Test: Example
Sample # Zn Standard Values
Sample # Zn Standard Values
12 17700 Zn 17390
12 17700 Zn 17390
13 17900 2s 460
13 17900 2s 460
14 14 17500 17500 N N 18 18
15 15 17500 17500 N-2 =N-2
DF = DF 16 16
16 16 16600 16600
17 17 17600 17600
18 18 17700 17700
19 19 17700 17700
20 20 17900 17900
21 21 16900 16900
22 22 16900 16900
23 23 16200 16200
24 24 16400 16400
25 25 17300 17300
26 26 17800 17800
27 17400
27 17400
28 17300
28 17300
29 11800
29 11800 Is this point an outlier?
Grubb Test: Example
DF α = 0.05
1 12.706
Zn outlier − µZn s tan dard 11800 −17390
2 4.303
G= = = 24.3
sZn s tan ard 230
3 3.182
4 2.776
5 2.571
N −1 tα2 /( 2N ),N − 2 18 −1 2.12
6 2.447 = = 1.56
2
7 2.365 N N − 2 + tα /( 2N ),N − 2 18 18 − 2 + 2.12
8 2.306
€ 9 2.262 Since Grubb statistic is greater
10 2.228 than the critical statistic then the
11
€ 2.201 point is an outlier.
12 2.179
13 2.16
14 2.145
15 2.131
16 2.12
17 2.11
18 2.101
Matrix Matching with Reference
Materials
• Matrix refers to the nature of the sample one is analyzing.
For example, a sulphide ore is a different type of matrix
than a silicate rock, versus a water sample, versus soils,
etc.
• When choosing SRMs or IRMs choose those that are most

representative of the medium in the study (i.e., water,
sediment, rock, ore, etc.).
• Even within a certain medium (e.g., silicate rocks) try to

choose SRM/IRMs in the range of matricies (and elemental
concentrations) proportional to those in the study.
• For example, if you are looking at volcanic rocks that

range from komatiite through rhyolite, have SRMs or IRMs
that represent this range of matrix and elemental
concentrations.
Other Considerations: Precision and
Accuracy as a F(Concentration)
• When considering precision and accuracy we must also
consider the concentration and the limits of
instrumentation.
• Limit of Detection (LOD): this is the lowest concentration

an instrument can detect (i.e., the point above which a
signal can be recognized from background).
• Limit of Quantification (LOQ): this is the point above

which the concentration can be trusted (i.e., a clear signal
is recognizable).
• Upper Limit of Detection (ULD): this is the point above

which values cannot be determined (i.e., in your tables
you may see >10000 ppm, etc., 10000ppm would be ULD)
• Precision and accuracy decrease dramatically as one

approaches the detection limits for an element!
Think of a radio dial!
Relationship of Precision to Concentration
Cr via ICP-ES
Relationship of Precision to Concentration
200.00
180.00
160.00
140.00
120.00
%RSD
100.00
80.00
60.00
40.00
20.00
0.00
1 10 100 1000 10000
Mean/LOD
Relationship of Accuracy to Concentration
Relationship of Accuracy to Concentration
250
200
150
100
%RSD
50
0
1 10 100 1000 10000
-50
-100
Mean/LOD
Creating Your Own Reference
Materials (Smee, 2007)
• You can create your own standards.
• Done to create a standard that has an acceptable mean

and standard deviation for the element or suite of
elements you are interested and with the matrix that is
similar to the one in question (see below).
• You often undertake a “round robin” period of data

collection for a standard to get the accepted mean and
standard deviation.
• Round robin involves a minimum of 60 analyses at 5

different labs.
Blanks and Contamination
• Blanks are samples that are generally free of the

elements you are interested in. Should be
relatively homogeneous.
• They are inserted during the analytical program

to monitor contamination at various stages (e.g.,
field, crushing, grinding, pulverizing).
• You should submit a sample that is similar to the

media you are submitted (e.g., rock, soil, water).
• You can plot blanks as a function of time (e.g.,

X-axis is time, Y is blank composition for
element “i”) and use a Shewart Control Chart.
Shewart Control Chart: Zn Blank
180
160
140
120
Blank Concentration
100
Data
u
80
u+2s
u-2s
60
40
20
0
0 10 20 30 40 50 60
-20
Order of Analysis
Blanks: Grubb Test for Outliers
• In the last plot we notice that there is a very wide

average and standard deviation for the blank for Zn.
• This should not be, but is a function of the

inclusion of outlier points in the data causing the
average and standard deviation to the quite large.
• We must remove outliers, revised the mean and

standard deviation, but which ones are outliers?
• Use a Grubb test. Remove outliers, revise limits

and then see which elements are true outliers and
have to be re-run.
• Always be careful for nuggety data - e.g., Au, PGE.
Blank Zn
1 33
Zn outlier − µZn 42 − 43.5
2 36
G= = = 1.55
3 39
sZn 35.6
4 42
5 26 N −1 tα2 /( 2N ),N − 2 13 −1 2.16
6 25 2
= = 1.64
7 24
N N − 2 + tα /( 2N ),N − 2 13 13 − 2 + 2.16
8 34
9 70 Since Grubb statistic is less than the critical statistic
10 € 51 then the point is not an outlier.
11 € 164
12 30
Zn outlier − µZn 164 − 43.5
G= = = 3.38
13 30 sZn 35.6
14 27
15 21
Since Grubb statistic is greater than the critical statistic
Mean 43.5 then the point is an outlier and must be removed.
STDev 35.6
N 15
DF (N-2) 13
tstat 2.16
€
α = 0.05
Shewart Control Chart: Zn Blank Before Culling Outliers
180
160
140
120
Blank Concentration
100
Data
u
80
u+2s
u-2s
60
40
20
0
0 10 20 30 40 50 60
-20
Order of Analysis
Shewart Control Chart: Zn Blank After Culling
Outliers
180
160
140
120
Blank Concentration
100 Data
u
u+2s
80 u-2s
60
40
20
0
0 10 20 30 40 50 60
Order of Analysis
Memory Effects or Contamination
• Contamination: element contamination via crushing material,

sampling process, laboratory contaminants, etc.
• Memory Effects: when elements stick to machinery and they are

transmitted into later samples (e.g., Au on ICP-MS)
Shewart Control Chart: Zn Blanks
180
160
140
120
Blank Concentration
100 Data
u
u+2s
80 u-2s
60
40
20
0
0 10 20 30 40 50 60
Order of Analysis
Choosing the Right Lab for You
• The lab and instrumentation you choose is a function of

the problem you are trying to solve.
• It is typically a function of:
• Problem (e.g., scientific, exploration, ore reserves,

etc.).
• Matrix (e.g., soils, ore, rocks, minerals)
• Elements required (e.g., metals, REE, isotopes, etc.)
• Turn-around time
• Cost
• Some labs are better for different things:
• e.g., commercial labs are great for assays,

exploration-based analyses.
• e.g., most research laboratories are best at providing

data for research problems (e.g., ultra-low level REE,
isotopes, geochronology, etc.)
• e.g., commercial labs are typically best at

developments related to industry (e.g., MMI, Enzyme
Leach, Soil Gas)
• Time
• e.g., lithogeochemistry from commercial lab can give

great turn around time, typically at lower precision/
accuracy, however – reflects client base.
• e.g., academic labs often are too slow for commercial

clients but often provide superior precision/accuracy.
• FIT FOR PURPOSE (Bettenay and Stanley, 2001)
• Choose the lab for the problem you are trying to solve.
Summary
• Geochemical nomenclature
• Sampling
• Analytical methods
• Why should we care about QA/QC?
• Testing Precision
• Accuracy
• Matrix matching
• Importance of LOD and LOQ of instrumentation and

relationship to precision and accuracy.
• Memory effects and contamination
• Other issues – Choosing the right lab for you.

Earth Sciences 4502/6211 Introduction To Geochemistry, Geochemical Nomenclature, Sampling, Analytical Methods, and QA/QC

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Earth Sciences 4502/6211 Introduction To Geochemistry, Geochemical Nomenclature, Sampling, Analytical Methods, and QA/QC

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Earth Sciences 4502/6211

Introduction to Geochemistry, Geochemical

Stephen J. Piercey, PhD, PGeo*

• Major, minor, trace elements.

• Field strength, trace element nomenclature.

• Sampling, Analytical Methods (Brief)

• Philosophy regarding sampling. Sampling for

• Analytical instrumentation - what instrument gives

• Quality Control and Quality Assurance (Brief)

• Precision and accuracy - basic concepts in QA/QC.

• QA/QC protocols for lithogeochemical surveys.

• Testing QA/QC - Scatterplots, Thompson-Howarth

• In many cases we are interested in geochemical dispersion in

• Other processes of interest may include:

• Sedimentary rock provenance.

• Fluid and metal source tracing.

• Surficial geochemistry - using geochemistry of surface materials

• Biogeochemistry - using biological materials to understand

• Isotope Geochemistry - using isotopes to understand Earth

• Assay Geochemistry - multi-element methods of rocks/surficial

• What elements we choose, what methods we choose, and our

• Compatible Elements: elements that favour solid phases

• Incompatible Elements: elements that favour the liquid

Cr, Ni, Cu = compatible

• Volatile Elements: great pathfinder elements that are often

Assay: Provides, as accurately as possible, the mean concentration of one

Hypothesis test (lithogeochemistry): Provides a multi-element data set for

Y/Ho = 44 (seawater) 100

Rock / Primitive Mantle

• Such data are often subject to external scrutiny and

• Observe legal requirements and professional guidelines

• Attempt to stick to a rigorous protocol without

• Ensure that different exploration teams are interpreting

• The best hypothesis is when both negative and positive

• Hypotheses should be tested initially with the most

• No amount of effort should be spared to obtain the

• The geologist who developed the hypothesis should play a

• They may, however, be more subtle or highly magnified

• Without any indications from field, stratigraphy,

• If there is no real question, there won’t be a real answer

• Depends on problem to be solved (e.g., petrology,

• Fresh samples are imperative.

• Must be stratigraphically controlled as best as possible.

• Depending on problem you may need spatial distribution

• Geostatistical approach (i.e., every five meters or change

• Often dependent the type and stage of project.

• Hereon all things will be concentrating on hypothesis-

• Use sledge hammer or mallet (geological hammers are

• Remove weathered edges with hammer.

• Goal is to get fresh sample equivalent in size to two fists.

• Samples must be free of veins, filled amygdules,

• If required, use saws, drills, explosives to get best

• Time and physical effort often the key!

• Take multiple samples from an outcrop.

• Field control is essential.

• Sample spatially from fresh (or least altered) to most

• If required, use saws, drills, explosives to get best

• Time and physical effort often the key!

• Take multiple samples from an outcrop or drill core.

• Field control is essential.

• Use block for thin section and crushing/grinding/

• Avoid discoloured samples, those with veins, filled

• Only need a little sample so make sure it’s representative.