Lithogeochemical Classifications of whole rock

geochemistry using the ioGAS software based on an

example using the OGS MRD274 database.
A “teach-yourself” guide book.

Scott Halley
November 2012

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Introduction ................................................................................................................................... 3
Digest and Assay Methods ............................................................................................................. 4
Litho-geochemical classifications ................................................................................................... 8
Getting Started ............................................................................................................................. 10
Ultramafic Rocks........................................................................................................................... 11
Basalts .......................................................................................................................................... 14
Felsic to Intermediate Compositions ............................................................................................ 16
Other Plot Types ........................................................................................................................... 20
Creating Maps .............................................................................................................................. 22
Alteration Classifications .............................................................................................................. 23
Carbonate Index ........................................................................................................................... 34

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Introduction
This is a teach-yourself guide to lithogeochemistry interpretation. By operating the ioGAS
software program with the dataset provided, the user can follow the interpretation procedures
set out in this document to gain an insight into some of the information that can be extracted
from a geochemical data set. This data is from the Ontario Geological Survey MRD274 project. It
includes over 1000 analyses from across the Kirkland Lake – Timmins district.

The interpretation of a multielement data set can be considered in three stages;

 subdivision into litho-geochemical classifications, ie., making a geological-style map
based on the chemistry.
 geochemically fingerprinting alteration.
 looking at the distribution of metals and pathfinder elements within the context of a
geochemical/geological and alteration background.

To do this requires some knowledge of geochemistry and mineralogy, but it is mostly a matter of
pattern recognition. There is no right or wrong way to go about interpreting a dataset. To some
extent it is a trial and error process. The following discussion contains a brief background to help
with geochemical classification.

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Digest and Assay Methods
This discussion and the assay schemes displayed are based on the ALS schedule of Services.
However, all major assay labs offer equivalent packages.

There is a broad choice of digest and assay methods available for multielement geochemical
analyses. Careful thought needs to be given to what it is that you want to achieve from the
geochemical survey before the digest and assay methods are selected, the benefits of the
different methods, and the cost. An aqua regia digest will dissolve carbonates, sulphides, some
oxides and clay minerals, but it will not dissolve most silicates and accessory minerals. It is most
commonly used for soil geochem where it is pathfinder element patterns that are of greatest
interest.

Although some base metals may dissolve quantitatively, in the majority of geological matrices,
data reported from an aqua regia leach should be considered as representing only the leachable
portion of the particular analyte. The recovery percentages for many analytes from more
resistive minerals can be very low, but the acid leachable portion can also be an excellent
exploration tool.

In most cases, the 4 acid digest procedure quantitatively dissolves nearly all elements for the
majority of geological materials. The most common problem is incomplete dissolution of zircon.
It seems that in Archean rocks, the zircons dissolve quite well, but are only partly dissolved in
younger rocks. This is likely to be a function of the amount of radiation damage. In order to get
fully quantitative results, it may sometimes be necessary to use even stronger dissolution
techniques such as fusions. In order to report the widest possible concentration range, this
method uses both the ICP-MS and ICP-AES techniques.

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A lithium borate fusion of the sample prior to acid dissolution and ICP-MS analysis provides the
most quantitative analysis for a broad suite of elements. This technique solubilises most mineral
species, including those that are highly refractory. Options for adding the whole rock elements
from an ICP-AES analysis of the fusion or base metals from a separate four acid digestion are
available. The downside of using a Li-borate fusion is that the detection limits for many of the
really useful pathfinder elements are much poorer when this method is applied.

By combining a number of methods into one cost effective package, a complete sample
characterisation can be obtained. This package uses the whole rock package ME-ICP06 plus
carbon and sulfur by combustion furnace (ME-IR08) to quantify the major elements in the
sample. Trace elements including the full rare earth element suites are reported from three
digestions with either ICP-AES or ICP-MS finish: a lithium borate fusion for the resistive elements
(ME-MS81), a four acid digestion for the base metals (ME-4ACD81) and an aqua regia digestion
for the volatile gold related trace elements (ME-MS42).

The MRD274 data is a complete characterization package of this type. The major elements and
trace elements are excellent quality data, but the pathfinder elements do not have the low

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detection limits attainable from the AR or 4 acid digest methods. The 4 acid digest method is a
very good compromise between cost, quality of data, and broad applicability. A significant short
coming of the 4 acid ICP-MS/AES method is that it does not give SiO2, but in this exercise, the
full data package will be tested to demonstrate how to get around not having SiO2.

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Immobile Elements
Subdividing a data set into geochemical groupings is best achieved by looking at the distribution
of immobile elements. Igneous rocks are usually subdivided on a classification scheme that
reflects the silica content, eg basalt, andesite, rhyolite. Changes in silica content will be coupled
with changes in Mg, Fe, Ca, Na, K etc. In the petrology literature there are dozens of
classification systems to describe this that make use of the immobile elements. The classical
discrimination systems are based on suites of elements that could be analysed precisely with
early analytical systems like XRF. However, with the recent development of ICP techniques, half
of the periodic table can be analysed very quickly and cheaply, with extraordinary detection
limits. Much more useful and discriminating classification schemes can be constructed using the
trace elements, rather than majors.

As a generalization, cations that have a 1+ or 2+ valancy are soluble as complexes with ligands
like chloride; elements that are stable with a 5+ or 6+ valancy are relatively soluble as oxyanions;
elements with a 3+ or 4+ valancy are usually the least soluble.

From the standard suite of elements, the most immobile elements are Ti, Zr, Hf, Nb, Ta, Cr, Th,
Sc, V, Al, Ce and La. These elements are primarily hosted in resistate heavy minerals like
ilmenite, rutile, zircon, apatite, spinels, etc. These are minerals that generally survive through
intense weathering and alteration (which is why the elements are called immobile).

Incompatible element is a term used in petrology and geochemistry.

During the fractional crystallization of magma, and magma generation by the partial melting of
the Earth's mantle and crust, elements that have difficulty in entering cation sites of the
minerals are concentrated in the melt phase of magma (liquid phase). An incompatible element
is an element that is unsuitable in size and/or charge to the cation sites of the minerals, and is
defined by the partition coefficient between rock-forming minerals and melt being much smaller
than 1.

Two groups of incompatible elements that have difficulty entering the solid phase are known by
acronyms. One group includes elements having large ionic radius, such as potassium, rubidium,
caesium, strontium, barium (called LILE, or large-ion lithophile elements), and the other group
includes elements of large ionic valences (or high charges), such as zirconium, niobium, hafnium,
rare earth elements (REE), thorium, uranium and tantalum (called HFSE, or high field strength
elements). Another way to classify incompatible elements is by mass: light rare earth elements
are La - Sm, and heavy rare earth elements (HREE) are Eu - Lu.

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Litho-geochemical classifications
A typical lithogeochemical classification of rocks from an assay file would begin by plotting major
elements against silica. In this data set, we do have silica reported, but in an ICP-MS/AES suite, silica is not
included. In the absence of Si, one of the most useful elements from picking broad compositional groups
is scandium.

This plot shows scandium plotted against SiO2, with the points coloured by the logged rock
types. Scandium is a particularly useful immobile element because it substitutes for Fe into
common silicate minerals such as hornblende, pyroxene, chlorite, etc. Sc can be considered as a
proxy for the Fe content, but it is much less mobile than Fe during alteration and weathering. As
a rule of thumb, basalts will have 30 to 50 ppm Sc, andesites 20 to 30ppm, dacites 10 to 20, and
rhyolites less than 10ppm. (There are some unusual low Sc mafic rocks in this data set).

In unaltered rocks, most of the first row transition metals are very strongly correlated. This is
especially so when those metals are contained within silicates. However the behaviour of the
metals diverges when oxide minerals are present. Sc will normally be highly correlated with Fe,

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V, Ti, Cu and Zn. In the case of Cu and Zn, departure from the linear trend will map areas of Cu
and Zn enrichment or depletion.

The immobile elements discussed above can be thought of as comprising 3 suites

a mafic suite (correlating with Fe); Ti, Sc, V
a felsic suite (correlating with Si); Zr, Hf, Th, La, Ce, P, Nb, Ta
an ultramafic suite (correlating with Mg) Cr, Ni

A useful methodology for distinguishing rock types is to;

1. Start by plotting Sc against all the other immobile elements and classifying the broad
compositional groups within the data.
2. Plot Ti against all the other immobile elements. Most of the immobile elements are
hosted with accessory minerals.
When Ti is plotted against Zr, Th, La, and P, for example, what this shows is the behaviour of
early crystallizing Ti oxides relative to late crystallizing zircon and phosphate minerals. Scandium
shows us about the broad compositions, but the other elements show differentiation between
basalts or andesites or different porphyry phases.

To geochemically classify the rock types in a lithogeochemical data set, we want generate a
series of plots that will allow us to recognize discrete populations within the data. The best way
to do this is to plot elements that have high concentrations in one type of rock against elements
that have high concentrations in another rock type. Building on the concept of mafic, ultramafic
and felsic suites listed above, we could for example plot Ti against Zr. By plotting elements of
opposing character, it causes the data points to spread across the whole area of the plot. Basalts
will be high in Ti but low in Zr, so they will tend to plot towards the top left. Rhyolites will be
high in Zr but low in Ti, so they will tend to plot towards the bottom right. Ultramafics will be
relatively low in each, so they will plot closer to the origin. By generating lots of these plots, we
will eventually be able to see all of the separate populations in the data.

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Getting Started
Start up the ioGAS program and open the MRD274_Geochem.xls file. Make sure the field types
are properly assigned for each column in the table. In this file, set North to be “North” and set
East to be “East”. It is advisable to set the projection of the data. This allows images created
from the data to be exported as Geotiffs. This data is NAD83 UTM Zone17.

Click on the Guess Aliases button. This prompts the software to assign the element name and
units for each field. Scroll down the table to check that the correct element names and units
were auto-assigned. Assigning these allows us to make use of some of the features built into
ioGAS, particularly using pre-programmed rock classification and alteration diagrams. Then click
OK. We are ready to start interpreting data.

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Ultramafic Rocks
In an Archaen data set, the first thing to do is identify the komatiites (Ultramafics) and basaltic
komatiites (High Mg Basalts). Magnesium can be a highly mobile element during alteration and
weathering. Therefore it is more reliable to select the ultramafic rocks based on the Cr content.

From the “Display Select Variables Dialogue” button, scroll down the list of variables and double
click on Sc, Cr, Mg, Al and Zr to select these elements for plotting.

From the selected list of elements, Yx plots can be generated.

There are two scatterplot symbols on the upper tool bar. The one on the left will take the first
element on the selected list and plot it on the X-axis, with each sequential element on the Y-
axis. The second scatterplot symbol does the same thing, except it plots the first element on the
Y-Axis.

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The Ultramafics and high Mg basalts will be selected from the Sc vs Cr plot, but at the same time
we will be able to see how this compares to the Mg, Al and Zr content. In the Attribute
Manager, add a new colour group. Double click on the name, and change the name of the new
group to “Ultramafic”. Click on the colour button and change it to purple.

Within the Attribute Manager, make sure the Ultramafic group is highlighted. Now click on the
Attribute Polygon button on second from the top on the right hand side tool bar. Click to create
a polygon around all the points with greater than 0.1% Cr2O3, then double click to complete the
polygon. All the points inside the polygon will now be coloured purple. The ultramafic rocks
have high Cr, but also low Al (high olivine content, but low plagioclase content, hence low Al),

12
and low Zr content. It will be noted that some of the high Cr samples also have high Al and Hf
(these are not ultramafic, so change them back to the default black group.

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Basalts
In the Attribute Manager, turn off the tick in the visible box next to the Ultramfic group. The
purple points are no longer displayed on the scatter plots.

Select Sc, TiO2, Zr, Th, Nb, P2O5, and La as the plotting variables.

Click the Display Yx scatterplot button.

There are some very high values for La, P and Th that compress the scale of the plots. On the
right hand side tool bar there is a zoom button that can be used to re-scale the plots. There is
also a point density contour overlay function (on the right hand side tool bar) that makes the
clusters in the data much more obvious.

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The basalts have around 25 to 45ppm Sc. They are relatively low in Zr, Nb, Th and La. In the
Attribute Manager, make a new colour group. Name it as Basalt, and give it a green colour.

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Felsic to Intermediate Compositions

With the mafic group turned off, and point density contours overlaid, a spectrum of
compositions is evident, but there are 4 clusters of points within this. The high Nb group
probably has a syenitic association.

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 A useful check on the classifications is to try a different series of plots and see if the colour
groupings are still consistent. As indicated previously, it is very useful to plot Ti against this same
suite of elements.

Note how TiO2 vs Zr and TiO2 vs Nb plot as a series of linear trends that project back towards
the origin. There are a few orange and yellow points that look like they belong with the green
group. There are some yellow and pink points that may belong with the red group. With more
data points, we would probably see that there were two or perhaps three different populations
within the pink group. Another unusual feature in this data is that rather than plotting as a very
tight population as would normally be the case, the mafic rocks show a scatter to higher Zr, Nb,
P, Th and LREE values. A group of the basalts are variably enriched in incompatible elements.

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A dark green group was selected based on very low vanadium values relative to the scandium
content and/or high phosphorous values. Note that these samples also have high TiO2 and
relatively high zircon.

The same enrichment factors are evident when these elements are plotted against TiO2. There
is a very interesting feature with regards to the low vanadium contents in the enriched basaltic
rocks. ). The vanadium depletion is a result of magnetite fractionation. For most of the
crystallization history of the tholeiites, ilmenite is the main Ti-oxide that crystallizes. As the
water content in the melt increases, it will form magnetite rather than ilmenite. Vanadium
substitutes into the lattice of magnetite with a very strong partition coefficient. Therefore the
magnetite-bearing rocks are initially vanadium enriched, until the melt becomes V-depleted.
The late crystallizing melts have very low V relative to the Ti and Sc contents. Not only are these
melts fractionating magnetite, but at the same time they are becoming enriched in Zr, P, LREE,
Th etc. This has to be a result of fractionation, and yet there enriched rocks are pillow lavas. The
fractionation must have occurred in a much deeper environment. The variations in basalt

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chemistry are still consistent with fractionation of the magmas within the mantle prior to
eruption.

Rocks with a low feldspar content will obviously have low Al2O3 contents. This is apparent in the
plot above. The olivine-rich rocks form a trend back towards the origin; with increasing olivine
content, the Al levels trend back towards zero. The black points (were pink) have low Al and high
Fe2O3. These are chemical sediments (chert/BIF).

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Other Plot Types

The classification of the data points based on immobile trace elements can be compared with a
major element classification. In this case, we are going to compare with a Jensen Cation plot. On
the top tool bar, go to Diagrams => Provided => Rock Classification => Major Elements => Jensen
Cation Plot.

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The correlation is not too bad, but in altered rocks, the Mg numbers should not be trusted. The
“enriched basalts” plot in the High-Fe tholeiite field.

Some of the other pre-programmed plots include REE spider plots. Go to the top tool bar and
click on Spider => Chondrite => REE C1 Chondrite (Sun and McDonough, 1995).

This shows that the red group has fractionated feldspar (and may be a crustal melt). The orange,
yellow and pink groups all have the typical REE patterns of Archean TTG melts. The enriched
basalt group is strongly LREE enriched and weakly HREE enriched; there is a hint of hornblende
fractionation here as well as magnetite fractionation. The Bif’s show a positive Eu anomaly,
which is typical of chemical sediments with a hydrothermal input.

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Creating Maps

There are a variety of map plotting options in ioGAS. Now that the assay points have been
classified into compositional groups, click on the Attribute Map button.

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Alteration Classifications
The classification of the assay points can be saved as a new column in the spreadsheet. Go to
Data => Make Variable From Colour.
Save the Colour group name as a new variable called Classification.

The classification of the rock types can be saved as a new field called Composition.

Now that the lithogeochemical signature of each sample has been defined, the changes in bulk
chemistry can be investigated. Consider a rock that is totally sericitised. 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
sericitised rock is 1:3. K has an atomic weight of 39 and Al has an atomic weight of 27. The 1:3
ratio on a weight percent basis is 39:81. Similarly, a totally KSpar (KAlSi 3O8) altered rock will have
a K:Al ratio of 1:1, or 39:27 on a weight percent basis (figure 4). In the same way, albitisation can
also be tracked. Albite is NaAlSi3O8: Na:Al =1:1, or 23:27 on a weight percent basis.

The best way to track sericitisation or albitisation is to plot K/Al aginst Na/Al. The ioGAS
software has some “one click” options for generating plots like these.

Go to Diagram => Alteration Vectoring => PER=GER diagrams => Feldspar GER => Feldspar Na-K
Control Diagram.

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This diagram shows the composition of the rocks relative to the projected compositions of albite
and muscovite. It is possible to add the projected compositions of selected minerals and typical
rock compositions to this diagram.

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On the right hand tool bar, the Show/Hide Mineral Compositions button adds projected mineral
compositions to the plot. The Change Selected Mineral Groups can be used to add minerals or
typical rock compositions to the plot; different species can be toggled on or off.

Instead of using colours to represent the lithological groups, we can add new shape attributes,
and change lithological classifications from a colour attribute to a new shape attribute. In the
Attribute Manager, click on the shape tab, click on the attribute field and set this to
“Composition Text”, then click on “auto attribute”. This process will add that the names that
were created from the immobile trace element chemistry and assign each of the points to a new
shape group based on those classification names. Now we can use colour groups to represent
alteration types rather than rock types. Go back to the colour tab in the Attribute Manager and
delete all of the colour groups.

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Each rock type will have its own starting point on one of these molar ratio plots, and the
composition of the least altered version of each lithology needs to be defined as a starting point
in order to track the changes in the bulk mineralogy as the alteration reactions proceed. This is
the reason for grouping rocks of similar bulk chemistry together and defining them with a shape
attribute. The approximate projection of unaltered rock compositions is shown on the figure
below.

For each compositional group that was defined on the basis of the immobile element
distribution, the simplest way to define the starting point on the molar ratio projection is to plot
K/Al vs Na/Al, and superimpose the point density overlay. In a large scale data set, it is likely that
the majority of samples will be unaltered or weakly altered. The reaction path can be traced
(towards albite or muscovite) for those samples that deviate from the main population.

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Go to the colour attribute tab, and make up a new set of colour classes that look like this.

Go to the shape attribute tab and turn off all the shape groups except Basalt and Enriched
Basalt. Now return to the colour tab. on the K/Al vs Na/Al molar ratio plot, only the basalt
samples will be displayed.

The following plot shows an alteration index scheme for the basaltic samples, relative to the
interpreted composition of unaltered basalts.

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28
Next, turn off the shape attribute group for basalts, and turn on the dacite group. By going
through a similar process, the alteration classification for the dacitic rocks should look
something like this.

Repeat this process for all the compositional groups. Now, we can display all of the
compositional groups and look at the distribution of albite and sericite alteration, normalized
against rock type, in a plan view.

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An alternative to the molar ratio plot is a ternary Al-K-Na plot. This essentially does exactly the
same thing as the K/Al vs Na/Al molar ratio plot. This shows the alteration index for all
compositional groups. Ternary plots can be found on the top tool bar of ioGAS.

The other alteration diagram worth knowing about is the Chlorite-Muscovite-Feldspar diagram.
Go to Diagram => Alteration Vectoring => PER=GER diagrams => Feldspar GER => Chl-Mus-K
Feldspar Control Diagram. This however, is not so applicable in orogenic gold systems.

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Now go to Data => Make Variable From Colour. Save this new colour classification as a field
called Alteration.

One of the limiting factors of this alteration classification scheme is that it really only works in
lower to middle greenschist conditions. Under these conditions, feldspars are altered to sericite,
and pyroxenes are altered to chlorite. In upper greenschist conditions, feldspars are not altered,
and pyroxenes are altered to biotite, but the overall change in alkali element contents is
minimal!

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Pathfinders vs Alteration

Probability plots provide a very useful way to examine the distribution of different metals with
respect to the silicate mineral assemblage. In probability plots, the assay value is plotted against
the N score for that sample. The N score is defined as:
N = (X - mean)/ standard deviation.
In these plots, each silicate mineral group is plotted by the same colour scheme as previously
defined, and each group plots as its own line on the probability plot. Examining the data in this
fashion permits a rapid assessment of where each metal is preferably located in terms of the
silicate mineral assemblage. In the latest version of ioGAS, probability plots can be plotted either
against N-score values, or as cumulative frequency plots. These plots show that arsenic,
antimony and sulfur are most abundant in strongly sericitised rocks. These are also the samples
with the highest LOI, which will reflect carbonate, and to a lesser extent chlorite.

Interestingly, gold and tungsten are more commonly associated with the albite and alkali-
feldspar alteration styles. A common pattern in these gold systems is that the mineralization
occurs at a transition from alkaline to acid fluid chemistry, to the gold is associated with feldspar
rich alteration, but the spent fluid makes a sericite-rich plume with anomalous As-Sb-pyrite.

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33
Carbonate Index
Orogenic gold systems very typically show a zonation pattern from ferroan dolomite to ankerite
to calcite.

This plot shows CaO plotted against C, and it includes the projected compositions of pure
ankerite and calcite. There are two linear trends of points, one heading towards ankerite and
one heading towards calcite. The next plot is a zoom to show this more clearly.

For the points that plot on the ankerite trend, all of the available Ca in those samples is
contained within ankerite. For the points that fall on the calcite trend, all of the available Ca is in
calcite. Some of the samples are weakly carbonated, and a large cluster has no carbonate. From
this we can make a carbonate index.

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Note the scale of the carbonate alteration cells! This is perhaps the best broad-scale
geochemical reconnaissance indicator for gold systems in Archean rocks.

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