Geochemical Analyses For Mapping Geological Processes

WEBINAR – Geochemical Analyses for Mapping Geological Processes – Scott Halley
Comparison of assay methods
How “complete” is a 4 acid digest?
What are the advantages and disadvantages of a 4 acid digest

compared with a Li-borate fusion?
1
Scott Halley
Consulting Geochemist,
Mineral Mapping Pty Ltd,
Hawley Beach, Tasmania, 7307.
Email: minmap@westnet.com.au
Web: www.scotthalley.com.au
Quartz-topaz-andalusite-fluorite breccia, Akulla, Sweden
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Digest Methods
Aqua regia
Mixture of nitric acid and hydrochloric acid in a molar ratio of 1:3.
Aqua regia readily dissolves many sulfide, oxide and carbonate minerals, and chlorite, as well as
retaining mercury, a particularly volatile element.
Four acid digest 2

HNO3, HClO4, HF, HCl. Quantitatively dissolve nearly all minerals.
Li Borate Fusion
Flux for melting the sample into a glass which is then acid soluble. Strongest fusion technique in order
to fully digest zircons, barite, rare earth oxides, and tin, tungsten, niobium and tantalum minerals.
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What is a 4A digestion?
Acids used are nitric HNO3, perchloric HClO4, hydrofluoric HF, and hydrochloric HCl
Sample is digested in nitric and perchloric first and heated.
HF is added, solution is heated and evaporated to some extent.
Max temperature over 150°C

3
Lastly, HCl is added.
No two lab companies perform their sample decomposition methods exactly the same way.
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4A Digestion: Compromises
Not fully dissolved: Not fully retained:

• Zircon! • Si is fumed off as SiF6
• Monazite, sphene • All Hg is lost due to the temperature
• Cassiterite, rutile, xenotime, barite, of digestion
corundum, chromite • Semi-volatiles (As, Se, Sb, Tl, Ge,
• Scheelite etc.) may be lost depending on
• Columbite-tantalite exact methodology 4
• Massive/refractory sulfides • Some elements may re-precipitate
as insoluble salts depending on
exact methodology
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“Research Quality Assays”
By combining several methods into one package, a

complete sample characterization is obtained. These
packages combine whole rock analysis, trace
elements by fusion, aqua regia digestion for the
volatile trace elements, carbon and sulfur by
combustion analysis, and several detection limit
options for the base metals.
Costs are typically around $100/sample 5

This assay package is not routinely used because of
the high unit cost.
ALS Schedule of Services and Fees, Australia 2019
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Exploration Assays
In exploration it is common to use a 4 acid
digest and a combination of ICP-AES and MS
assay methods. This gives a broad suite of
major elements, trace elements and metals,
with exceptionally low detection limits
Costs are typically around $42/sample;

cheap enough to be used routinely.
Resource Definition Assays

In a resource drill out where the very low 6
detection limits are not important, it is
common to use a 4 acid digest with just ICP-
AES assays.
Costs are typically around $22/sample.
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Comparison of Methods
The following presentation compares 4 acid digest ICP results with LiBorate fusion
assays,
These plots compare standard immobile trace element scatterplots that are used to
categorise rock compositions and plots that are used to track magmatic
fractionation.
7
Also presented are plots of 4 acid digest results versus Complete Characterization
results for elements that might be volatilised during digestion, or elements that are
difficult to dissolve.
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Comparison of Methods 4 acid digest ICP-MS

These data are from calc-alkaline volcanics in a VMS province. The rocks include organic-rich black shale, siltstone, pumice breccia and a
porphyry unit. These plots show a classification of the assay data from plots of Sc vs Th, Ti, V, Zr, Nb and Cr. Note these do not form distinct
populations because of the heterogeneous nature of the rocks. These assays are from a 4 acid digest ICP-MS method. The same samples
were also assayed with a LiBorate fusion ICP-MS. The same plots are presented in the next slide:
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SH1
Comparison of Methods “Complete Characterization”
These are immobile trace element plots from LiBorate fusion ICP-MS. These assays are more accurate than the 4 acid digest since it is a
more complete digestion process, but the precision of the analyses is poorer.
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There are some specific plots we can use to track fractional crystallization of particular minerals. In this suite of samples, the pumice
breccias show evidence of fractional crystallization of plagioclase, magnetite and eventually biotite and zircon.
V/Sc vs Sc is a plot designed to show the degree of fractional crystallization of magnetite; decreasing V/Sc with decreasing Sc (increasing
SiO2).
This is very obvious in the 4 acid digest data, and not at all obvious on the Li Borate data.
4 acid digest ICP-MS Complete Characterization
Organometallic V
10
Magnetite fractionation
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There are some specific plots we can use to track fractional crystallization of particular minerals. In this suite of samples, the pumice
breccias show evidence of fractional crystallization of plagioclase, magnetite and eventually biotite and zircon.
Ta/Nb vs Ti is a plot designed to show the degree of fractional crystallization of biotite; Increasing Ta/Nb with decreasing Ti.
This is very obvious in the 4 acid digest data, and scattered from the Li Borate data.
4 acid digest ICP-MS Complete Characterization
Biotite fractionation
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Comparison of Methods; Aluminium

Li-borate fusion produces more accurate analyses of the major elements.
4-acid digest produces higher precision analyses of the trace elements because it results in lower inference effects during analysis.
Choose a method that is fit for purpose!
Can you accept lower accuracy on the major elements in order to get greater information from the trace elements?
If too much liquid is retained during the HF/heating stage, Al is precipitated as a fluoride complex.
Al_pct
4 acid digest
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Al2O3_pct_LiBorate fusion
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Comparison of Methods; Potassium

Test how “complete” the 4 acid digest is by plotting 4acid vs Li Borate results from the same samples.
With a 4 acid digest, some K may reprecipitate as potassium perchlorate.
K_pct
4 acid digest
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K2O_pct_LiBorate fusion
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Comparison of Methods; Titanium

Ti is a real test of the efficiency of the 4 acid digestion. Zr will usually underreport quite significantly even with the best 4 acid procedure.
If a 4 acid digest is done well, >90% of the Ti will dissolve. Ti is more difficult to dissolve in samples that have had advanced argillic alteration.
If Al under-reports, then it is likely there will be significant under-reporting of Ti.
Ti_pct
4 acid digest
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TiO2_pct_LiBorate fusion
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Comparison of Methods; Arsenic

Arsenic under-reporting at higher values; volatilization during digest?
As_ppm
4 acid digest
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As_ppm_aqua regia ICP-MS
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Comparison of Methods; Antimony

It is common for antimony to be incompletely dissolved in aqua-regia.
Sb_ppm
4 acid digest
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Sb_ppm_aqua regia ICP-MS
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Conclusions
• Good quality 4 acid digest ICP-MS trace element data has significant
advantages over Li Borate fusion “research quality” assays.
• With the exception of Zr, in most data sets the digestion is very close to
total.
• The major elements are measured with less accuracy than a Li Borate fusion,
but the results are good enough for quantitative mineralogy calculations. 17
• The calculated mineralogy estimates are significantly improved by adding
SiO2 analyses by portable XRF to the assay suite.
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ALS has developed a proprietary ICP-MS method with a modified sample introduction method and a collision/reaction
cell. This method has an order of magnitude reduction in detection limits and increase in precision due to fewer oxide
and polyatomic interferences, and low carry over effects. The difference between this and the standard ICP-MS is as
great as the difference between ICP-MS and LiBorate fusion ICP-MS.
ALS is now working to introduce the same proprietary method for LiBorate samples, which will give complete digest
AND high precision.
Costs are typically around $50/sample.
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Sample fractional crystallization diagrams from
ME-MS61L with ultra-low detection limit 4 acid
digest ICP-AES/MS. The effect of the higher
precision in these assays is obvious.
Hf versus Zr, ME-MS61L Hf versus Zr, Li-borate fusion
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BUT,….
Not all 4 acid digests are the same!!
Each assay company has different procedures for the digestion process.
• The following discussion compares data sets from ALS and laboratory X
• Both were analysed twice, by Li-borate fusion ICP-AES, and 4 acid digest
ICP-AES/MS. 20
• This demonstrates that some laboratories DO get close to a complete
dissolution with a 4 acid digest, but some DO NOT.
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Potassium
ALS 4 acid digest ICP-AES vs Li-borate fusion Lab X 4 acid digest ICP-AES vs Li-borate fusion
K_pct 4 acid digest

K_pct 4 acid digest
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K2O_pct_LiBorate fusion K2O_pct_LiBorate fusion
ALS has good repeatability of K to 6% and above. Lab X has very significant under-reporting of K at 3% and above.
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Aluminium
ALS 4 acid digest ICP-AES vs Li-borate fusion Lab X 4 acid digest ICP-AES vs Li-borate fusion
Al_pct 4 acid digest

Al_pct 4 acid digest
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Al2O3_pct_LiBorate fusion Al2O3_pct_LiBorate fusion
ALS has repeatable Al analyses but with modest precision. Lab X has huge under-reporting of Al. This is a very common outcome where acid digests leave too
much water during the heating process before addition of HCl. Al is retained as an insoluble fluoride.
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Conclusions
• Whether or not 4 acid digest ICP-AES/MS analyses are fit for purpose
depends on which laboratory provided the data. In my experience, there are
2 global assay chains that are satisfactory, and the rest are not.
• In a 4 acid digest ICP-AES/MS package, the major elements are assayed by
ICP-AES. Therefore ICP-AES assays from a reputable lab will be sufficient for
the calculated mineralogy estimates (at about 20% of the cost of complete
characterization assays). SiO2 by pXRF can be added for around $3.50 23
sample to significantly improve the estimations.
• If/when the Li Borate fusion ultra-low detection limit method is available it
will provide superior quality results than the current research quality assay
at about half the unit cost.
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Multielement Geochemistry
data validation
Just because your data passes the validation tests in Acquire or Datashed
doesn’t mean it is correct!
Try these simple tools as an extra check on your data quality.

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Scott Halley
Native Sulfur in advanced argillic alteration, Puren Sur, La Coipa
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Check the Elements and units in your database.

ioGAS has useful data validation tools. Set the element name and units (ppb, ppm, %) for all data columns.
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Check the Elements and units in your database.

Does your data base have a mixture of ppb, ppm and pct values?
It is very easy to make a series of scatter plots or cumulative frequency plots. It is obvious when the wrong
units are in a table, or when elements have been imported to the wrong columns.
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Have some idea of what ranges to expect.

When you are using multielement data, you should have an idea about what ranges of analytical
results are reasonable, and which are not.
Typical Ranges Basalt Rhyolite

Sc 30 - 50 2 - 10
Th 0.5 - 3 10 - 20
Ti 5000 - 10000 1000 - 3000
V 200 - 300 10 - 40
Zr 40 - 80 150 - 250 27
Nb 4-8 10 - 15
La 4-8 20 - 40
Ce 10 - 20 60 - 80
Cr 100 - 300 5 - 10
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ALWAYS check that you have the correct locations in your database
First thing; always plot a map of your data. Are the locations correct?
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Check for data type

Many software systems will have tools that identify non-numeric (text), >, <, - in data tables. Fix these before
you start interpreting data. Make sure that below detection results are properly flagged.
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Check the digestion method.

A 4 acid digest will dissolve almost everything. Most, but not all of the zircons will dissolve, especially in younger rocks. Aqua
regia will dissolve carbonates, sulfides, Fe oxide and chlorite, but it will not dissolve quartz, feldspar, illite or most accessory
minerals. Volcanic rocks will always have around 6 to 9% Al. However with aqua regia, the Al results will be around 1 to 3%. A
scatterplot of Al versus Zr shows 2 very distinct populations. This clearly separates 4 acid digest from aqua regia data.
30
4 acid digest
Aqua regia digest
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Check the assay method; ICP-AES or ICP-MS?

Many historic data sets will contain a compilation of data from different assay methods. To check whether the ICP data is
AES or MS, make a probability plot of a pathfinder like Te for example, which has a low natural abundance. The detection
limit by MS is 0.01ppm. The detection limit by AES is usually 5ppm. If there are AES results mixed with MS, it will be
obvious!
ICP-AES results with a 5ppm DL
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Note; for assay results that are below detection, store these results as the negative value of the detection limit.
That way, everybody will know that the result was below detection, and they will know what the detection limit
was, without any ambiguity.
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Check for batch errors.

Plot maps of elements. Check to see if there are mis-matches between batches of data or level shifts from sample line
to sample line. Note the higher background levels in the data on the western side. These types of errors are most
obvious when you look at elements that have low crustal abundances (it is unusual to see an error like this in arsenic!).
This data will still pass database import validation rules, but something is clearly wrong.
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Check for contamination.

Quartz-rich samples (veins) often produce around 100ppm Cr contamination from Cr-steel in an LM5 mill. This section shows drill
holes with high Cr that look out of place. Zoom in. Every second sample has high Cr. 2 different ring mills with different grades of
steel!
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Check for calibration errors.

There are some pairs of elements which are VERY highly correlated in nature, eg La versus Ce
Low precision High precision, but…..
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There are some pairs of elements which are VERY highly correlated in nature, eg Hf versus Zr
Low precision High precision
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There are some pairs of elements which are VERY highly correlated in nature, eg Ta versus Nb
Low precision High precision, but a few Ta values are clearly wrong
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Check for out of range values.

Make a K/Al versus Na/Al molar ratio plot. It is highly improbable that any valid assays plot above the albite-orthoclase tie-line.
This is a common outcome in samples where the 4 acid digest was not taken to incipient dryness. Al remains in the test tube
as an insoluble fluoride complex; samples plot with impossibly high (K+Na)/Al ratios.
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Database management
• Set up your database to export ICP-MS data in a format that is ready to use without the need to
manipulate data in excel.
• Just one column per element; export the data as ppm of the element to avoid any ambiguity.
o Even where results are reported by the lab as % or oxides, convert to ppm of the element
for the export.
• Below detection results should be exported as the negative of the detection limit value. That
way, the user knows explicitly that the result was below detection, and what the DL value was.
• Each row should also include a field for the Assay Lab name and a field for the lab assay method
(code, eg ME-MS61). That way we can check the digest and assay method.
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• Ideally, the export should also include a field for the logged lithology and logged alteration from
that interval. This is a nice to have, but not a have to have, since these can very easily be
merged using Leapfrog. X,Y,Z coordinates are also nice to have for downhole data, but these
similarly can be added in Leapfrog.
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Making the most of multi-

element geochemistry
A work-flow for interpreting ICP assays
39
Scott Halley
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Advantages of 4 acid digest ICP

Exploration
• Better identification of rock compositions,

including magmatic fertility.
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• Better characterization of alteration.
• Map the full extent of pathfinder footprints and

metal zonation patterns.
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Advantages of 4 acid digest ICP

Resource Drilling
• Consistent logging of lithology and alteration mineralogy.

• Better geological model
• Map the variability in ore types;
• improved metallurgical test work sample selection. 41
• Proxies for rock hardness domains
• Clay mineralogy distribution
• map sulfide mineralogy and abundance.
• Map deleterious elements
• Impact on concentrate quality and environmental
management
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Trace elements; Compatible versus Incompatible

Incompatible element; size and/or charge of the cation is unsuitable for inclusion in the crystallizing mineral phases.
Partition coefficient between rock-forming minerals and melt much smaller than 1
Two groups of incompatible elements;

• LILE, or large-ion lithophile elements have large ionic radius, such as rubidium, caesium, strontium, barium;
• HFSE, or high-field-strength elements have large ionic valences (or high charges), such as zirconium, niobium,
hafnium, rare-earth elements (REE), thorium, uranium and tantalum.
42
Equilibrium Constant KD = Xisolid/Xiliquid
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Compatible elements have decreasing abundance with increasing SiO2

Example: Ti is a compatible element.
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Compatible elements have increasing abundance with increasing SiO2

Example: Th is an incompatible element.
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Accessory mineral phases control HFSE distribution patterns

Example; zircon crystallization begins at around 800oC; Zr changes from incompatible to compatible behavior at
around 70% SiO2
Onset of zircon crystallization
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Recommended references
R.R. Loucks (2014) Distinctive composition of copper-ore-forming arc magmas, Australian Journal of Earth
Sciences: An International Geoscience Journal of the Geological Society of Australia, 61:1, 5-16
Richards, J.P., 2011. High Sr/Y arc magmas and porphyry Cu±Mo±Au deposits: just add water. Economic
Geology, 106(7), pp.1075-1081.
Olson, N.H., Dilles, J.H., Kent, A.J. and Lang, J.R., 2017. Geochemistry of the Cretaceous Kaskanak batholith
and genesis of the Pebble porphyry Cu-Au-Mo deposit, southwest Alaska. American Mineralogist: Journal of
Earth and Planetary Materials, 102(8), pp.1597-1621.
46
Escolme, A., Berry, R.F., Hunt, J., Halley, S. and Potma, W., 2019. Predictive Models of Mineralogy from Whole-
Rock Assay Data: Case Study from the Productora Cu-Au-Mo Deposit, Chile. Economic Geology, 114(8),
pp.1513-1542.
Halley, S., 2020. Mapping Magmatic and Hydrothermal Processes from Routine Exploration Geochemical
Analyses. Economic Geology, 115(3), pp.489-503.
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Procedure for Rock Compositions
Scandium; Immobile, Substitutes for Fe in silicate minerals.

Plot Sc vs Ti, Th, V, Zr, P, Nb, Al, Cr
Titanium; Immobile, Occurs in Fe-Ti oxides + biotite, amphibole.
Plot Ti vs Sc, Th, V, Zr, P, Nb, Al, Cr
Individual plots to pick specific signatures;
• V/Sc vs Sc; to pick signatures of high pressure melting of an amphibole-bearing source, or

fractional crystallization of magnetite 47
• Ti vs Nb; to characterize opaque oxide mineralogy
• Ta vs Nb; to pick fractional crystallization of biotite
• Hf vs Zr; to pick fractional crystallization of zircon
• Sr/Y vs Y; to pick high P melting of plagioclase in hydrous environment
• Sc vs Ni; to pick sulfur saturated magmas
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Classifying rock compositions from 4 acid digest ICP-MS analyses

4 acid digest ICP-OES/MS reports all the major elements except SiO2.
Without SiO2, plot immobile trace elements against 2 different immobile compatible elements;
Sc substitutes for Fe in silicates.
Ti is an immobile compatible element; mostly in opaque oxide minerals.
As a guide;
• Basalt 30 to 50ppm Sc
• Andesite 20 to 30ppm
• Dacite 10 to 20 ppm
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• Rhyolite <10ppm Sc
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Rock Compositions
Plot Sc vs Al, Nb, P, Th, Ti, V,

Zr, Cr. Look for clusters in the
data. Assign each cluster to a
category.
Chemistry does not
differentiate rock type, ie an
intrusive, extrusive,
volcaniclastic or epiclastic. 49
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Rock Compositions
Take the same suite of

elements and plot Ti first; ie
Ti vs Sc, Al, Nb, P, Th, V. This
shows patterns related to the
accessory mineral phases in
each magmatic event, eg
magnetite, rutile, titanite,
apatite, monazite etc. 50
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Classifying rock compositions from 4 acid digest ICP-MS analyses; Case study
In this particular case study, some of the clearest distinctions between different eruptive products are shown by a plot of
Sc vs Th.
Chemical Classification
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Magmatic Fractionation
Pine Hill Granite (Sn)
• Trace element pairs indicate;
▪ Which mineral is fractionating
▪ Extent of fractionation
▪ Sulfur saturation
▪ Infer redox
▪ Infer Temp
▪ Infer H2O.
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• This is nothing new, BUT modern
analytical methods have broader suite
of elements and precision 2 orders of
magnitude better than 1990’s data
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Redox sensitive elements

Consider Sc and V; both are compatible elements. Sc substitutes for Fe in silicate minerals (behaves like the
silicate-hosted component of Fe). V3+ behaves the same way as Sc. V4+ behaves more like Ti.
Sc and V have the same trajectories in reduced magma, but different trajectories in oxidized melts.
53
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Compare and contrast typical crustal melts with porphyry Cu magma

Mount Read Volcanics vs Southern Peru, Eocene porphyries
• Magnetite Fractionation; V depleted more rapidly than Sc
• Hornblende (Cpx) Fractionation V/Sc starts at higher values, Sc depleted more rapidly than V, especially in
more oxidized systems.
• Reduced magmas; V/Sc constant with fractionation.
Mount Read Volcanics, VMS district Tintaya, Porphyry Cu district
Fe-silicate fractionation
54
Ilmenite fractionation
Magnetite fractionation
Cyril Chelle-Michou, 2013
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Porphyry Cu fertility
Without SiO2 analysis, plot V/Sc versus Sc
Fertile porphyry Cu field
Fractional crystallization of Cpx Hbl
55
Ilmenite
Fractional crystallization of magnetite
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Sulfide Saturation
Most magmas have Ni/Sc
between 1 and 2, Cu/Sc
around 2.5
Magmas that fractionate

magnetite become S-
saturated.
56
Immiscible ISS first (Fe-
Ni-Co-S),
MSS second (Fe-Cu-Au-S)
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In-situ fractionation in the Golden Mile Dolerite
Top of sill
• Golden Mile Dolerite

• Same bulk chemistry
as the Lunnon Basalt
• Same as 90% of
Archean Basalt
• Fractionates to Magnetite
magnetite instead of Zone
ilmentite.
• Sulfur saturated at 57
the onset of
magnetite
crystallization.
Base of sill
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Fractional Crystallization of Zircons

Commonly observed in magmatic hydrothermal orebodies, eg Sn granite, Intrusion-related Au deposits.
Reduced total Zr content, but high Hf/Zr ratio.
58
Zircon fractionation
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Ti vs Nb; to characterize opaque oxide mineralogy

Contrast magnetite versus titanite fractionation
Mount Read Volcanics, VMS district Tintaya, Porphyry Cu district
59
Increasing SiO2
Increasing SiO2
Cyril Chelle-Michou, 2013
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Fractional Crystallization of Biotite
Commonly observed in
fractionated granites.
Strongly depleted Ti but

increasing Ta/Nb ratio. 60
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Classifying rock compositions from 4 acid digest ICP-MS analyses; Case study
All of these melts plot on a spectrum from high Sr-low Y to low Sr – high Y. This maps a transition from hydrous melting
at high pressure where garnet is stable in the source region and all the plagioclase melts, to low pressure melting where
plagioclase is fractionating.
High pressure melting of HBL-bearing source
61
Field of porphyry Cu magmas
Mid-crustal melting
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Fractional Crystallization of Plagioclase

REE’s have 3+ valency. Eu can be 2+; Ce can be 4+. In reduced to moderately oxidized melts, Ce2+ substitutes for
Ca2+. Plagioclase fractionation removes Eu from a melt relative to other REE’s.
Plagioclase fractionation 62
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Example; Lithology model from assays
63
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Conclusions
It is difficult to consistently log lithology, especially in very altered rocks.
Immobile trace element chemistry provides quantitative data that can significantly
improve the accuracy and consistence of logging; note, this is an aid to logging, it does
not replace logging.
Consistent logging will lead to better geological interpretations, more reliable resource
models, and better classification of ore-types. 64
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Alteration Mineralogy from Assays
A work-flow for interpreting ICP assays
65
• Scott Halley
• Consulting Geochemist,
• Mineral Mapping Pty Ltd,
• Hawley Beach, Tasmania, 7307.
• Email: minmap@westnet.com.au
• Web: www.scotthalley.com.au
______________________________________________________________________________________________________________________
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Alteration Mineralogy from Assays

CODES (University of Tasmania) AMIRA copperbelt project data;
A suite of samples from across the Central African Copperbelt in Zambia and DRC
66
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Common alteration minerals include;

This process can be captured as a standard workflow.
• K/Al vs Na/Al molar ratio plot to map sericite alteration
• Al-K-Mg ternary plot to map relative proportions of sericite
vs chlorite
• Ca vs Mg to map calcite vs dolomite
• Ca-Fe-Mg ternary plot to pick carbonate compositions
• Ca-K-Na to map feldspar compositions
• Fe vs S to map the degree of sulfidation
• Ca-Fe-S ternary plot to map anhydrite
67
• Rb vs K to map alunite
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Carbonate; Ca vs Mg
Plot Ca versus Mg to identify samples that might have a high abundance of calcite or dolomite.
68
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Ca versus C
This data set contains Carbon analyses. There are a few Ca-rich samples plotting near the Calcite line, but most of the data
points are dolomite bearing. Note the samples with high Mg and low Ca.
69
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Sericite; K/Al vs Na/Al molar ratio plot

Note the proportion of samples that are strongly depleted in Na.
Na-depleted samples could contain dominantly K feldspar, sericite, kaolinite or chlorite
70
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Chlorite; Al-K-Mg ternary plot

Samples on the K-rich side of the muscovite-chlorite tie line are mixtures of sericite, K feldspar and chlorite.
Samples on the K-poor side of the muscovite-chlorite tie line are mixtures of sericite, chlorite and albite.
71
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Chlorite; Al-Fe-Mg ternary plot

This plot shows that the chlorite present in particularly the Congolese deposits is particularly Mg-rich.
72
Mg5Al2Si3O10(OH)8
Fe2.5Mg2.5Al2Si3O10(OH)8
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Barite; Ba versus K
Where Ba is substituting for K in potassium silicates, there is a relatively linear correlation between Ba and K. Samples that
plot above this trendline have barite, even where it is present in quantities that are difficult to log.
73
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V versus Sc; Organometallic suite

These rocks typically have a V/Sc ratio of 7:1. Where organic carbon is (was) present in the rock it acts as a collector for V,
Mo, U, +/- Cr, Ni, As etc. The relative proportions of the organometallic metals varies from one blavk shale to the next.
Vanadium with organics
74
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V versus Sc; Organometallic suite

These rocks typically have a V/Sc ratio of 7:1. Where organic carbon is (was) present in the rock it acts as a collector for V,
Mo, U, +/- Cr, Ni, As etc. The relative proportions of the organometallic metals varies from one black shale to the next.
75
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Ca-Fe-S ternary plot

Samples that plot on the S-rich side of the tieline from the Ca apex to the projected position of pyrite contain anhydrite.
Anhydrite
76
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Metamorphism or alteration
Deposits in the Domes region of Zambia commonly contain phlogopite, kyanite, quartz muscovite. Is this a hydrothermal
assemblage, or is it metamorphism of a quartz-sericite-dolomite protolith?
77
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Metamorphism or alteration
Deposits in the Domes region of Zambia commonly contain phlogopite, kyanite, quartz muscovite. Is this a hydrothermal
assemblage, or is it metamorphism of a quartz-sericite-dolomite protolith?
Quartz-muscovite-phlogopite-pyrite schist.
Kyanite-phlogopite schist.
78
Phlogopite-Mg chlorite-talc schist.
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Classification of Mineralogy from Assays

3D slice of the classified silicate mineralogy from a Zambian Cu deposit.
79
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Conclusions
It is REALLY difficult to consistently log alteration.
Much of the alteration mineralogy can be guesstimated and quantified from major
element geochemistry. Identification of the clay mineralogy is vastly improved if SWIR
data is collected along with the assay information.
Consistent logging will lead to better geological interpretations, more reliable resource
models, and better classification of ore-types. 80
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Pathfinder chemistry
Plot pathfinder elements as a factor of average crustal abundance levels for

each element. A coherent footprint (multi-point anomaly) of >10 x average
crustal abundance is a significant anomaly!
81
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Pathfinder Zoning
Many pathfinder elements are hosted in the lattice of pyrite.
Consistent temperature controlled zoning pattern; Mo => Sn => Bi => Te => As => Sb => Hg
Tl>2ppm
Sb>5ppm
As>50ppm
Bi, Te>1ppm
Sn>5ppm
Mo>5ppm
Porphyry Cu
82
mineralization
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Pathfinder chemistry; importance of detection limits

Bismuth assays by ICP-MS, detection limit 0.01ppm Bismuth assays by ICP-AES, detection limit 5ppm
Blind Porphyry Cu deposits Outcropping Porphyry Cu deposit
300m below surface
83
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Calculated Mineralogy from Assays
Calculation of weight% gangue minerals from 4 acid digest

ICP analyses + SWIR
84
• Scott Halley
• Consulting Geochemist,
• Mineral Mapping Pty Ltd,
• Hawley Beach, Tasmania, 7307.
• Email: minmap@westnet.com.au
• Web: www.scotthalley.com.au
______________________________________________________________________________________________________________________
______________________________________________________________________________________________________________________
______________________________________________________________________________________________________________________
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Quantitative Mineral estimates from chemistry alone are non-unique;

there are always more variables than
Or
constraints.
For example, a point here It could be a mixture
could be a mixture of orthoclase-muscovite-
of orthoclase-muscovite- biotite
chlorite
85
We could use extra information from qXRD, QEMSCAN or CoreScan to provide extra constraints,
Or we can use thermodynamics to predict the permissible mineral assemblage.
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Calculated Mineralogy
Anhydrite
86
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Feldspar Muscovite
87
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Mineral percentages can be calculated from ICP analyses and treated like assay fields.
This will change the way we model orebodies.
88
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Summary. Rock Compositions

To classify compositional groups,
Plot Sc vs Ti, Th, V, Zr, P, Nb, Al, Cr

Plot Ti vs Sc, Th, V, Zr, P, Nb, Al, Cr
Individual plots to pick specific signatures;

• V/Sc vs Sc; to pick signatures of high pressure melting of an amphibole-bearing 89
source, or fractional crystallization of magnetite
• Ti vs Nb; to characterize opaque oxide mineralogy
• Ta vs Nb; to pick fractional crystallization of biotite
• Hf vs Zr; to pick fractional crystallization of zircon
• Sr/Y vs Y; to pick high P melting of plagioclase in hydrous environment
• Sc vs Ni; to pick sulfide saturated magmas
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Summary. Alteration categories

• K/Al vs Na/Al molar ratio plot to map sericite alteration
• Al-K-Mg ternary plot to map relative proportions of sericite
vs chlorite
• Ca vs Mg to map calcite vs dolomite
• Ca-Fe-Mg ternary plot to pick carbonate compositions
• Ca-K-Na to map feldspar compositions
• Fe vs S to map the degree of sulfidation
• Ca-Fe-S ternary plot to map anhydrite
90
• Rb vs K to map alunite
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91
92

Geochemical Analyses For Mapping Geological Processes

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WEBINAR – Geochemical Analyses for Mapping Geological Processes – Scott Halley

Comparison of assay methods

How “complete” is a 4 acid digest?

What are the advantages and disadvantages of a 4 acid digest

Quartz-topaz-andalusite-fluorite breccia, Akulla, Sweden

Four acid digest 2

Sample is digested in nitric and perchloric first and heated.

HF is added, solution is heated and evaporated to some extent.

Max temperature over 150°C

Lastly, HCl is added.

Not fully dissolved: Not fully retained:

“Research Quality Assays”

By combining several methods into one package, a

Costs are typically around $100/sample 5

ALS Schedule of Services and Fees, Australia 2019

Costs are typically around $42/sample;

Resource Definition Assays

Costs are typically around $22/sample.

ALS Schedule of Services and Fees, Australia 2019

Comparison of Methods 4 acid digest ICP-MS

4 acid digest ICP-MS Complete Characterization

4 acid digest ICP-MS Complete Characterization

Comparison of Methods; Aluminium

Comparison of Methods; Potassium

Comparison of Methods; Titanium

Comparison of Methods; Arsenic

As_ppm_aqua regia ICP-MS

Comparison of Methods; Antimony

Sb_ppm_aqua regia ICP-MS

Costs are typically around $50/sample.

ALS Schedule of Services and Fees, Australia 2019

Hf versus Zr, ME-MS61L Hf versus Zr, Li-borate fusion

K_pct 4 acid digest

K2O_pct_LiBorate fusion K2O_pct_LiBorate fusion

Al_pct 4 acid digest

Al2O3_pct_LiBorate fusion Al2O3_pct_LiBorate fusion

Try these simple tools as an extra check on your data quality.

Native Sulfur in advanced argillic alteration, Puren Sur, La Coipa

Check the Elements and units in your database.

Check the Elements and units in your database.

Have some idea of what ranges to expect.

Typical Ranges Basalt Rhyolite

Check for data type

Check the digestion method.

Check the assay method; ICP-AES or ICP-MS?

ICP-AES results with a 5ppm DL

Check for batch errors.

Check for contamination.

Check for calibration errors.

Low precision High precision, but…..

Check for calibration errors.

Low precision High precision

Check for calibration errors.

Check for out of range values.

Making the most of multi-

Advantages of 4 acid digest ICP

• Better identification of rock compositions,

• Map the full extent of pathfinder footprints and

Advantages of 4 acid digest ICP

• Consistent logging of lithology and alteration mineralogy.

Trace elements; Compatible versus Incompatible

Two groups of incompatible elements;