Interpreting Multielement

Geochemical data
Scott Halley
July 2015
ALS ME-MS61
4 acid digest uses a combination of HCl (hydrochloric acid), HNO3 (nitric acid), HF
(hydrofluoric acid) and HClO4 (perchloric acid). Because hydrofluoric acid dissolves
silicate minerals, these digestions are often referred to as 'near-total digestions'.

48 elements by ICP-MS and ICP-AES analysis.

ALS ME-ICP61
4 acid digest uses a combination of HCl (hydrochloric acid), HNO3 (nitric acid), HF
(hydrofluoric acid) and HClO4 (perchloric acid). Because hydrofluoric acid dissolves
silicate minerals, these digestions are often referred to as 'near-total digestions'.

These packages can be used as an economical alternative to analysing low grade ore
or samples with known mineralisation. The method precision is intermediate between
exploration geochemistry and an assay procedure.

33 elements by ICP-AES analysis.

Applied Lithogeochemistry

3 objectives

Identify Rock types

Immobile trace elements
Sc, Ti, V, Zr, Hf, Nb, Th, La, Ce
Quantify Alteration
Major elements
Al, K, Na, Ca, Fe, Mg, (Ba, Rb, Cs, Sr)
Pathfinder patterns
As, Sb, W, Mo, Bi, Te, Tl, Ag, Au
Consider the importance of ;

Digest Method
Assay Method
Detection Limit
Mineralogical Controls

What is background?
Importance of Detection Limits

Bismuth assays by ICP-MS, detection limit 0.01ppm

Blind Porphyry Cu deposits

300m below surface
Outcropping Porphyry Cu
deposit
Importance of Detection Limits

Bismuth assays by ICP-AES, detection limit 5ppm

Blind Porphyry Cu deposits

300m below surface
Outcropping Porphyry Cu
deposit

Must use ICP-MS to get useful detection limits for most elements
Accuracy versus Precision
Accuracy versus Precision
Comparison of Scandium assays from 4 acid digest versus Li-borate fusion. Sc is hosted
in Fe-silicates; easily dissolved in mixed acid.
Li-borate analyses might have better ACCURACY, but the 4 acid digest provides better
PRECISION. This is true for many of the immobile trace elements.
Lithium Borate Fusion

4 acid digest

This is a data set from a rhyolite-hosted VMS system; samples have been assayed twice; once with a lithium borate fusion AND
once with a 4 acid digest.
 Tungsten
Comparison of assays from 4 acid digest versus aqua regia digest. Is W
insoluble as H2WO4 or is it in silicates?
Aqua Regia digest

4 acid digest

This is a data is from soil geochem over porphyry Cu project; samples have been assayed twice; once with an aqua regia digest
AND once with a 4 acid digest.
Mineralogical Controls
What are the host minerals for each element?

Are these sparsely distributed accessory minerals, or

ubiquitous, homogeneously distributed alteration
minerals?

This has a big impact on assay variance.

Pathfinders hosted in homogenously distributed minerals

allow a small sample size and a very broad sampling
pattern; important when designing sampling programs.
Pathfinder Chemistry Average crustal Abundance
Hellyer, Tasmania
Pathfinder chemistry from exploration holes surrounding the massive
sulfide; Cu-Pb-Zn confined to small veinlets, but pyrite is pervasive.
Trace elements from pyrite give a much more consistent near-miss
signal!

Zinc; blue<50ppm, red>500ppm Antimony; blue<1ppm, red>10ppm

Pathfinder Ranges

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!
ALS ME-MS61; Immobile trace elements to map Lithology.
From the ME-MS61 package, the following elements are considered to be the most
immobile. Use these to classify rock compositions. Note that the immobile trace
elements have an ionic charge of +3 or +4.
ALS ME-MS61; Major elements to map Alteration.
Major elements track changes in the abundance of rock-forming minerals and alteration
minerals.
Lithogeochemistry Workflow; Rock types
1. xY plots Sc vs Cr, Mg, Al, Zr (to pick ultramafic rocks)
2. xY plots Sc vs Ti, Th, V, Zr, Nb, P
3. xY plots Ti vs Sc, Th, V, Zr, Nb, P
4. Check Sc vs Cr, Al, La, Ce
5. Plot Sc vs V to check for magnetite fractionation
6. Plot Zr vs Hf to check for zircon fractionation

Lithogeochemistry Workflow; Alteration

1. K/Al (molar) vs Na/Al (molar) to pick sericite and advanced argillic alteration
2. Ca-K-Na ternary plot to pick hydrothermal feldspars
3. Al-K-Mg ternary plot to pick Mg metasomatism
4. Fe vs S to pick sulfidation
5. Cu-Fe-S ternary to pick Cu-sulfide mineralogy
6. Ca vs Mg to pick carbonate mineralogy
Lithogeochemistry Workflow; Alteration2
1. Plot Xy plot of Sc vs Cu, Zn, Mn, Co, Ni, In to look for evidence of enrichment
or depletion of divalent transition element metals
2. Plot K vs Tl (thallium) to look for low temp Tl-bearing pyrite
3. Plot K vs Cs to look for low temp, disordered illite
4. Plot K vs Ba to look for evidence of barite
5. Plot Sc vs V to look for evidence of organic carbon (in black rocks) or extreme
oxidation (in red rocks)
6. Plot V vs Mo, U, Cr, As to look for evidence of organic carbon

Lithogeochemistry Workflow; Pathfinders

1. Split cumulative frequency plots, coloured by mineralogy to look fro correlations
between pathfinders and alteration; Au, Cu, Mo, Sn, W, Se, Bi, Te, As, Sb, Tl, etc
Common Hydrothermal minerals

Mineral Composition Cations Ratio

Illite KAl3Si3O10(OH)2 K/Al 1/3
Orthoclase KAlSi3O8 K/Al 1/1
Albite NaAlSi3O8 Na/Al 1/1
Montmorillonite (Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2nH2O
Kaolinite Al2Si2O5(OH)4
Pyrophyllite Al2Si4O10(OH)2
Dickite Al2Si2O5(OH)4
Calcite CaCO3
Dolomite CaMg(CO3)2
Biotite K(Mg,Fe)3AlSi3O10(OH)2 K/Al 1/1
Chlorite (Fe,Mg)5Al2Si3O10(OH)8 (Fe+Mg)/Al 5/2
Examples of recommended scatterplots; selecting Ultramafic rocks
Start by plotting Sc versus Cr, Mg, Al and Zr. It is not always reliable picking ultramafic rocks from the Mg content since Mg
can be mobile during alteration and it is easily stripped during weathering. Ultramafic rocks have >1000ppm Cr. They will
have a low Al content (since they have abundant olivine, but low plagioclase, and they will have low Zr. We are looking for
those samples that meet all of these criteria.
Examples of recommended scatterplots; mafic rocks
xY plots Sc vs Ti, Th, V, Zr, Nb, P; This is an example that shows sequential lava flows (eruptions) from a fractionating magma
chamber. The ultramafics were picked from the previous Sc-Cr plot. Point density contour overlays were used here to
highlight the compositional clusters in the data. The mafic rocks typically have 30 to 50ppm Sc.
Examples of recommended scatterplots; mafic rocks
xY plots Sc vs Ti, Th, V, Zr, Nb, P; This is the same plot as the previous slide with the point density contours removed. The red
arrows show fractionation pathways. Ti and V are fractionation indicators for titanomagnetite. V and Sc substitute for Fe in
silicate minerals. However, V can substitute into oxides, but Sc does not. When these melts start to crystallize significant
amounts of titanomagnetite, the Ti and V contents increase, until the melt becomes depleted in V (pink group). All the time,
the HFSE elements (eg Zr, Nb, Th, REE) are increasing during fractionation.
Examples of recommended scatterplots; mafic rocks
xY plots Ti vs Sc, Th, V, Zr, Nb, P; Plotting Sc first is useful to pick broad compositional groups eg, mafic, intermediate, felsic.
Plotting Ti first is useful for picking fractionation sequences.
Examples of recommended scatterplots.
Plot Ti versus Nb. There are a couple of scattered andesitic populations in purple and mauve.
Note the pale blue group; these are sample that are quartz-rich; Quartz-rich to the extent that all the other components are
diluted! Mantle melts plot with a high Ti/Nb ratio. Crustal melts and fractionated magmas plot with a low Ti/Nb ratio.
Examples of recommended scatterplots; magnetite fractionation
Plot Sc versus V.
Most magmas have a Sc to V ratio of around 1:7. Both Sc and V substitute for Fe in amphibole and pyroxene, and they tend
to have very linear correlations. However, V can substitute into oxides, but Sc does not. There is a very high partition
coefficient of V into titanomagnetite. Calc-alkaline rocks begin fractional crystallization of magnetite early in the cooling
history. As the melts fractionate, V is depleted. These rocks show a very clear sequence of magnetite fractional
crystallization, indicated by the array of arrows.
Project X Regional Lithogeochemistry, Zircon Fractionation
Hf and Zr always plot with a near perfect straight line correlation; Hf can only substitute into the lattice of zircon crystals.
However, as zircon crystallizes, the melt very gradually evolves to higher Hf/Zr ratios. Zircons tend not to nucleate as new
crystals, rather they just form overgrowing rims, so the final Hf/Zr ratio remains constant. However, where there is
fractional crystallization of zircons, early formed zircons are left behind in a restite phase, and the separated melt has a
lower zircon content but a higher Hf/Zr ratio.
Project X Regional Lithogeochemistry, Fractionation plots
Usually these trends are easily recognised with resorting to ratios or log plots, but here is an example where it works really
well; log Hf/Zr versus log Ti/Nb

Fractional Crystallization of zircons

Crustal melts Mantle melts

Project X Regional Lithogeochemistry, Fractionation plots
Usually these trends are easily recognised with resorting to ratios or log plots, but here is an example where it works really
well; log Sc/V versus log Ti/Nb

Fractional Crystallization of magnetite

Crustal melts Mantle melts

Increasing V/Sc with fractionation is a key magmatic indicator of fertility in porphyry Cu-(Au)
systems.

Strongly oxidized magma; high water

content, increasing V/Sc with fractionation

Reduced magma; constant V/Sc ~ 7:1

Moderately oxidized magma; low water

content, fractional crystallization of
magnetite, declining V/Sc
Fractionation plot

Increasing
fractionation

Increasing fractionation
Alteration Classification
With a 4 acid digest method, the changes in whole rock chemistry due to hydrothermal alteration reactions can be
investigated. Consider a rock that is totally sericitized. The mineralogy of the rock might be muscovite-quartz-carbonate-
pyrite. All of the K and Al in that rock will be within sericite. Muscovite has a composition of KAl3Si3O10(OH)2. Therefore the
ratio of K:Al in the sericitized rock is 1:3. Similarly, a totally K feldspar (KAlSi3O8) altered rock will have a K:Al ratio of 1:1. In
the same way, albitisation can also be tracked. Albite is NaAlSi3O8: Na:Al =1:1.
Alteration Classification
Ca:K:Na ternary plot with point density contour overlay; useful for mapping hydrothermal feldspar compositions.

Ca
Anorthite

Sodic-Calcic Alteration
(Oligoclase)

Albite Alteration

Albite
K Kspar, Muscovite Na
3
7
Alteration Classification
Al-K-Mg ternary plot to pick Mg metasomatism.
Alteration Classification
Al-K-Mg ternary plot to pick Mg metasomatism.
Alteration Classification; Extent of sulfidation
Plot Fe versus S. On this plot, the pyrite line shows Fe to S ratios that match the stoichiometry of pyrite, ie, Fe:S (molar) =
1:2
In the vast majority of hydrothermal systems, pyrite precipitation is just a sulfidation process; the reaction just utilizes Fe
that is already present in the rock. The trend of increasing Fe and S up the pyrite line maps samples that contain additional
pyrite in veins. Points that plot of the Sulfur-rich side of the pyrite line contain sulfates.

sulfidation
Alteration Classification
Plot Ca versus Mg to map carbonate mineralogy.
For example, this plot shows a limestone (40 wt% Ca) being partially replaced by dolomite.
Sulfide Mineralogy
Plot Cu-Fe-S ternary to map sulfide mineralogy.
Alteration Classification
Plot Xy plot of Sc vs Cu, Zn, Mn, Co, Ni, In to look for evidence of enrichment or depletion of divalent transition element
metals. This plot shows that samples with relatively acid alteration mineralogy have depleted levels of Zn, Mn, Ni and Co
relative to less-altered samples of the same lithology. This also provides the basis for identifying samples with enrichment
of these metals relative to background.
Alteration Classification
Plot K vs Tl (thallium) to look for low temp Tl-bearing pyrite. Thallium is a most unusual element as it can reside in either
silicates of sulfides. In the vast majority of cases, Tl substitutes for K in silicate minerals. This produces a linear trend on a K
vs Tl plot. At low temperatures, Tl can substitute into the lattice of pyrite. These points plot on the Tl-rich side of the silicate
trend.

Thallium in sulfides