LITHOS 454-455 (2023) 107274

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LITHOS
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Classification and nomenclature of volcanic rocks using immobile elements:

A novel approach based on big data analysis
Mingde Lang a, Zhaochong Zhang a, *, Zhen Chen b, Zhiguo Cheng a, M. Santosh a, c,
Timothy M. Kusky d
a
State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, China
b
School of Earth Sciences and Resources, China University of Geosciences, Beijing 100083, China
c
Department of Earth Sciences, University of Adelaide, Adelaide, SA 5005, Australia
d
Center for Global Tectonics and State Key Laboratory of Geological Processes and Mineral Resources, School of Earth Sciences, China University of Geosciences, Wuhan
430074, China

A R T I C L E I N F O A B S T R A C T

Keywords: The proper classification and nomenclature of igneous rocks are cornerstones of geology. In contrast to intrusive
Classification and nomenclature rocks, volcanic rocks cannot be named after their mineral assemblages, due to their glassy and dominantly glassy
Volcanic rocks nature. Thus, they are commonly classified based on their major elemental compositions, such as the Total
Immobile elements
Alkali-Silica (TAS) classification. Unfortunately, these major elements (especially K and Na) are commonly
Big data
Machine learning
mobile during metamorphism and alteration, making the use of the TAS diagram problematic for altered or
metamorphosed volcanic rocks. Though it can be replaced by diagrams employing immobile or less mobile el­
ements, the accuracy is relatively low. By compiling data on volcanic rocks from GEOROC dataset, we confirmed
that the classification based on Zr/TiO2-Nb/Y relationship has low accuracy (45.3%), so the results can be
misleading. Although we improve this classification to 68.84% accuracy through refinement based on big data,
the accuracy is still not satisfying. Such a deficiency can be compensated by the application of Machine Learning
methods on a large dataset. Employing the Random Forest algorithm for model training based on 13 immobile
elements, we propose a new classification method where the training accuracy increases to 74% for the verifi­
cation dataset. Our results show that the prediction accuracy of several major rock types, such as basalt and
rhyolite, increase to 89.2% and 97.5%, respectively.

1. Introduction modification during post-magmatic low-temperature alteration and

According to the classification and nomenclature scheme of the In­
ternational Union of Geological Sciences (IUGS), igneous rocks are
mainly grouped according to their mineral associations and relative
modal mineral content (Le Maitre, 1989, 2002). However, because
volcanic rocks are characteristically glassy and dominantly glassy, their
modal mineral content is difficult to determine. Thus, the recommended
classification of volcanic rocks relies on their major element contents
and classification diagrams such as the Total Alkali-Silica (TAS) diagram
that are useful because of the close relationship between the major el­
ements and the percentages of the major rock-forming minerals (Cox
et al., 1979; Le Bas, 2000; Le Bas et al., 1986). However, the TAS clas­
sification scheme is only tentatively applicable to fresh volcanic rocks
because the K2O and Na2O contents are particularly susceptible to
metamorphism (Humphris and Thompson, 1978; Nakamura et al., 2007;
Pandarinath et al., 2007; Patten et al., 2016; Thompson et al., 1985;
Torres-Alvarado et al., 2007; Verma et al., 2017). For altered or meta­
morphosed volcanic rocks, the IUGS does not recommend any classifi­
cation procedure. To account for alteration and metamorphism,
Winchester and Floyd (1977) proposed a classification scheme based on
the immobile elements, Zr/TiO2-Nb/Y diagram, which has been widely
used to identify and classify altered volcanic rocks. However, this
approach has some limitations such as inadequacy of samples (only a
few hundred analyses) and imprecise analytical methods employed in
earlier studies (trace elements by X-ray fluorescence and emission
spectrograph, etc.). As Winchester and Floyd (1977) pointed out, the Zr/
TiO2-Nb/Y diagram is not quite reliable. Having noticed that the
boundary of the diagram was inaccurate, Pearce (1996) redefined the

* Corresponding author.
E-mail address: zczhang@cugb.edu.cn (Z. Zhang).

https://doi.org/10.1016/j.lithos.2023.107274
Received 29 December 2022; Received in revised form 25 June 2023; Accepted 2 July 2023
Available online 6 July 2023
0024-4937/© 2023 Elsevier B.V. All rights reserved.
M. Lang et al. LITHOS 454-455 (2023) 107274

boundary based on a larger dataset of 8000 analyses. However, Pearce’s
diagram omitted some rock types for convenience and only made slight
modifications to the Winchester-Floyd diagram. Similarly, Li et al.
(2015) evaluated the accuracy of trace element discrimination diagrams
for basalts generated in various tectonic environments, and found that
these diagrams were not reliable. They attributed it to the inadequacy of
analyses and diverse tectonic settings.
The greatly increasing high-quality analyses in the past decades
provide a good opportunity to test the reliability of the method (Roll­
inson, 1993). Classification diagrams using immobile trace elements are
preferable but need to be tested and optimized on unaltered rocks (Ross
and Bédard, 2009). Here, we test the classification scheme of volcanic
rocks based on 18,002 high-quality analyses of fresh rocks from works
published after 1980. The results reveal considerable overlap among
different rock types. It is thus clear that the Winchester-Floyd Zr/TiO2-
Nb/Y classification scheme needs to be refined. We approach this
problem through the application of Random Forests (RF) algorithm
composed of multiple decision trees, each decision tree giving a classi­
fication result, with the final result depending on the majority of results
given by all decision trees (Breiman, 2001). The advantage of this
approach is that there is no need to consider the proxy of elements. To
improve the discrimination diagram for slightly altered or meta­
morphosed volcanic rocks, our study developed a new predictive model
including 13 immobile elements based on a machine learning method.
This method effectively enhances the accuracy of graphic classification.
2. Data collection and preprocessing
The data selected in this study are principally from the GEOROC
database (http://georoc.mpch-mainz.gwdg.de/georoc/), with 257,268
volcanic rock analyses (Lehnert et al., 2000). We supplemented the
collection with 4605 analyses from 362 recently published articles
(Cheng et al., 2015; Chernysheva and Kharin, 2007; Lang et al., 2020;
Veter et al., 2017; Zeng et al., 2010). Data published before 1980 were
excluded from our selection. Due to the large volume of data in the
GEOROC database, there may be various problems such as missing data,
inaccurate naming and sample alteration, as well as the outdated
analytical methods. Considerable rigorous data cleaning was thus
required before data processing.
In order to improve the data quality, it is necessary to eliminate
erroneous data through a series cleaning routine. We processed the data
according to the following procedure.

Table 1
Rock names as originally defined in the published works from which data were assembled in this study.
Rock Type (this study) Rock names in the original literature Analyses plotted in Zr/TiO2-Nb/Y Analyses in RF
scheme model

Basalt Basalt, Alkali basalt, Tholeiite, Calc-alkaline basalt, Alkaline basalt, Transitional 5763 2475
basalt
Basaltic andesite Basaltic andesite, Andesite 1587 820
Andesite Andesite, Boninite, Basaltic andesite 1875 740
Dacite Dacite, Rhyodacite 1473 691
Rhyolite Rhyolite, Comendite, Rhyodacite 3521 2064
Trachybasalt / Basaltic Basaltic trachyte, Trachybasalt, Hawaiite, Basaltic trachyandesite, Mugearite, 387 309
trachyandesite Hawaiite, Shoshonite,
Trachyandesite Trachyandesite, Latite, Benmoreite 538 317
Trachyte / Trachydacite Trachyte, Trachydacite, Alkaline Trachyte, Comenditic trachyte 883 545
Comendite Comendite, Rhyolite, Alkaline rhyolite 296 173
Tephrite-Basanite Alkali basalt, Tephrite, Basanite 450 362
Foidite Nephelinite, Foidite 815 296
Phonotephrite / Tephriphonolite Tephritic phonolite, Phonotephrite, Tephriphonolite 135 67
Phonolite Phonolite, Tephritic phonolite, Trachyphonolite 279 121

Fig. 1. Global distribution of the samples from which data were used in this study.

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M. Lang et al.
Fig. 2. Inspection of the rock classification results based on the Zr/TiO2-Nb/Y diagram of Winchester and Floyd (1977). The column headings are rock types based on
TAS and the row headings are diagram fields from Zr/TiO2-Nb/Y diagram. Each value represents the probability.
(1) In order to choose fresh samples, analyses from the Mesozoic and
Cenozoic volcanic rocks were selected in this paper, and analyses
have major elements totals <99.5 wt% or > 100.5 wt% or LOI >
2.0 wt% were rejected.
(2) We excluded analyses with incomplete measurement values of
SiO2, Na2O, K2O, TiO2, Nb, Y, and Zr, or with obvious input er­
rors; Analyses with SiO2 > 80 wt% were deleted as it is almost
impossible for natural fresh volcanic rock samples to achieve such
a high silica content.
(3) All analyses of Fe2O3 and FeO are converted to be total FeOT on
the basis of the formula 0.8998*Fe2O3 + FeO=FeOT.
(4) Because the natural rock series forms a chemical continuum,
there is a large overlap among the different rock types in the
diagram. To ensure the uniformity, we re-plotted the selected
data into the TAS diagram and only kept those falling in the fields
that represent the same rock types as their original ones (Table 1).
Taking andesite as an example, after we plotted the data in the
TAS diagram, only the data falling in the andesite region is
selected and retained.
After the above steps of cleaning and screening, 18,002 sets of high-
quality data were finally selected and they are used in this study to
evaluate the Zr/TiO2-Nb/Y classification scheme. The data after clean­
ing are shown in Appendix A, with 13 rock types classified in TAS (Figs.
A1~A14). Although not exhaustive, the data used in this study represent
a global distribution of previously classified volcanic rocks (Fig. 1).
3. The Zr/TiO2-Nb/Y classification scheme
3.1. Testing the Zr/TiO2-Nb/Y diagram by Winchester and Floyd (1977)
We plotted the cleaned data, according to the steps mentioned in
Section 2, on the Zr/TiO2-Nb/Y diagram, but it is difficult to see the
range of data points visually. Therefore, the density statistics analysis of
the data points distribution in the Zr/TiO2-Nb/Y diagram were carried
out by the ksdensity of matlab (Appendix B), as shown in Figs.B1~B24.
Spatial statistics reveal that the accuracy of this diagram is relatively low
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LITHOS 454-455 (2023) 107274
(Fig. 2), with an overall accuracy of only 45.3%. The highest accuracy is
for andesite at 68%, and tephrite at 62%. The low accuracy includes
comendite at only 25.4%, rhyolite at 31.4%, and phonolite at 31.4%.
The boundaries of these rock divisions are therefore considered to be
inaccurate. In addition, the diagram does not give fields for transitional
rocks such as trachydacite and less common rock types such as trachy­
basalt and basaltic trachyandesite. Therefore, we believe that this dia­
gram has limitations in identifying rocks, and most types of rocks cannot
be accurately identified.
3.2. Testing the boundary between alkaline and sub-alkaline samples
The distinction of the sub-alkaline and alkaline series (Irvine and
Baragar, 1971; Macdonald, 1968; and Rittmann-index; Rittmann, 1957)
in the TAS diagram are all based on the functional relationship between
SiO2 and Na2O + K2O. Indeed, many boundaries have their limitations:
(Na2 O+K2 O)2
the Rittmann-index (δ = SiO2 − 43 ) only applies to intermediate-felsic
rocks and Macdonald (1968)‘s boundaries are too simplistic. Floyd
and Winchester (1975) proposed that alkaline magma displays Nb/Y >
1.0, while sub-alkaline magma usually has Nb/Y < 1.0. For peralkaline
rocks, such as phonolite, the Nb/Y ratio can be >2.0. However,
Winchester and Floyd (1977) believed that Nb/Y = 0.67 could distin­
guish the sub-alkaline series from the alkaline series.
To test if Nb/Y ratio can be used to define the boundary line between
the alkaline and the sub-alkaline series, we selected the boundary pro­
posed by Irvine and Baragar (1971) as the standard, introduced fresh
samples into the TAS diagram for screening and classification, and then
re-plotted them into the Zr/TiO2-Nb/Y diagram (Fig. 3). We could
roughly obtain the respective ranges of alkaline and sub-alkaline sam­
ples and found that they significantly overlap. Obviously, we cannot
draw a line for the boundary between two series using Zr/TiO2-Nb/Y
diagram. Thus, neither Nb/Y = 0.67 nor 1.0 can be used for the
boundary line (Fig. 3 a, b). Especially for felsic rocks, it is difficult to
distinguish the degree of alkalinity simply by Nb/Y.
In addition, we also try to identify peralkaline samples (yellow points
in TAS diagram) based on the Zr/TiO2-Nb/Y diagram, in which the
peralkaline samples are plotted in the high Nb/Y field (Fig. 3 c, d). Thus,
M. Lang et al.
Fig. 3. Alkaline and sub-alkaline samples plotted in (a), (c) TAS and (b), (d) Zr/TiO2-Nb/Y diagrams. TAS diagram screening, boundary I and II, separated by SiO2
and Na2O + K2O content, are from Macdonald (1968) and Irvine and Baragar (1971), respectively.
we give an inclined line {lg(Zr/TiO2) = 5.252 × lg(Nb/Y)-3.187} to
separate peralkaline samples from others. Over 94% of sub-alkaline and
alkaline samples fall in left field, whereas 81.2% of peralkaline samples
fall in right field, suggesting that the line can be considered to be the
boundary between peralkaline rocks and others (including alkaline and
sub-alkaline rocks).
3.3. Redivision of rock boundary in Zr/TiO2-Nb/Y and test of the result
Based on the density contour map, we put the range of 75% indi­
vidual values of each rock type into the Zr/TiO2-Nb/Y diagram, and
fitted new boundary lines according to the test results (Fig. 4). We then
performed spatial statistics on the data points, and found that the overall
accuracy of the new diagram proposed in this study is 68.84% (Fig. 5),
which is a substantial improvement over the classical diagram (45.3%).
Among them, basanite, tephrite, and foidite have the highest accuracy at
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LITHOS 454-455 (2023) 107274
93.27%, 83.33%, 98.28% respectively, but they share one field and
cannot be distinguished, which is not satisfying yet.
3.4. Parameters in volcanic rock classification
Winchester and Floyd (1977) proposed that Zr/TiO2 and Nb/Y can
represent the degree of magma evolution and alkalinity respectively,
like the TAS diagram. Therefore, to explore the reason of low accuracy of
the Zr/TiO2-Nb/Y diagram proposed by Winchester and Floyd (1977),
we should assess the two parameters of Zr/TiO2 and Nb/Y in the
diagram.
3.4.1. Zr/TiO2 ratio
Zr/TiO2 is selected to be a proxy of SiO2 (Govett and Atherden,
1988). The relative immobility of Ti and Zr is substantiated by Dudas
et al. (1983) and Petersen (1983). As shown in Fig. 6a, Zr will
M. Lang et al.
Fig. 4. The distribution range of analyses points and the change of rock name boundaries in Zr/TiO2-Nb/Y diagram (Winchester and Floyd, 1977) (a) before and (b)
after modification. (c) A comparison between the boundaries in the original and improved diagram.
continually be enriched in the residual liquid as crystallization and
crystal fractionation continues (Gisbert and Gimeno, 2017). Moreover,
the Zr/TiO2 ratio increases more noticeably in more alkaline rocks
(Fig. 6b), reflecting the enrichment of Zr in these rocks.
Zirconium may change from incompatible to compatible during
magma evolution if zircon crystallization begins, which, according to
Gisbert and Gimeno (2017), occurs at SiO2 > 70%. However, simulta­
neous TiO2 depletion should overwhelm the minor zircon fractionation,
so Zr/TiO2 can be expected to increase continuously with fractional
crystallization. In addition, in more alkaline magmas, the increased Zr
solubility prevents significant zircon fractionation (Conte and Dolfi,
2002; Watson, 1979; Watson and Harrison, 1983), making Zr/TiO2
particularly useful as a proxy for differentiation in alkaline-peralkaline
rocks, at least until significant zircon fractionation occurs in the more
evolved compositions (Gisbert and Gimeno, 2017). Notice the abrupt
cut-off in increasing SiO2 in Fig. 6a whereas Zr/TiO2 appears to increase.
This can be attributed to silica saturation and quartz fractionation at
high SiO2.
However, this value (Zr/TiO2) may also cause some misjudgments.
For example, Rosa et al. (2004) found that the felsic rocks from Albernoa
(Portugal) were incorrectly classified as andesites in the Zr/TiO2-Nb/Y
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LITHOS 454-455 (2023) 107274
diagram. Some scholars attributed this to the high Ti contents in the
samples, whereas Rosa et al. (2004, 2006) believed that it could be the
result of abnormally low contents of high field strength elements (HFSE,
e.g., Zr). These two factors can lead to decreasing Zr/TiO2.
3.4.2. Nb/Y ratio
The SiO2 content of primitive mafic magmas is a sensitive pressure
indicator and SiO2 decreases as pressure (depth) increases. The Nb/Y
ratio is sensitive to the degree of melting because Nb is much more
incompatible than Y. As the percentage of melting increases during
melting, the Nb/Y ratio plunges. Ignoring variations in the Nb content of
mantle source regions, Nb/Y ratios in oceanic basaltic magmas show a
remarkable correlation with the SiO2 content of primitive mantle
magmas; as SiO2 decreases (pressure increases), the Nb/Y ratios rapid
increase (Fig. 7b). Thus, based on the SiO2 and Nb/Y ratios of oceanic
magmas, it is inferred that as pressure increases, the degree of melting
decreases.
Pearce and Cann (1973) first proposed that Nb/Y could be used as an
indicator of alkalinity in basalts. Winchester and Floyd (1977) also
mentioned the relationship between Nb/Y and Na2O + K2O, but they
constructed the diagram without considering high-K arc volcanic rocks
M. Lang et al. LITHOS 454-455 (2023) 107274

Fig. 5. The accuracy of different types of rocks falling in different fields of the improved diagram.

Fig. 6. Diagrams of Zr/TiO2 vs. (a) SiO2 and (b) Na2O + K2O. based on the 18,002 analyses used in this study. The best least-squares fit and correlation coefficients
are also shown.

(Hastie et al., 2007; Pearce, 1996). As shown in Fig. 7a, although most
points deviate from the trend line and the fitting result is not clear (R2 =
0.2638), a positive correlation can be identified. Moreover, due to the
large number of analyses, the correlation coefficient is highly signifi­
cant. This is because the geochemical behavior of Nb is markedly similar
to that of Na, but not to K. In other words, Nb/Y has a poor correlation
with K2O. Due to the fact that arc volcanics generally have high K2O but
low Nb (Morris, 1988). The Nb/Y ratio is a poor proxy for the alkalinity
of arc volcanic rocks. However, the peralkaline samples can be separated
according to both Nb/Y and Zr/TiO2 values as shown in section 3.2.1.
different bulk distribution coefficients during mantle melting are useful
in identifying rocks. For example, compared with Nb/Y, the Nd/Yb ratio
can avoid the potential impact of subduction-related processes. We note
that the relationship between and Nd/Yb and SiO2 is similar with Nb/Y
and SiO2, with the increase of SiO2, and initial decrease in Nd/Yb fol­
lowed by slight increase (Fig. 8a). However, the correlation between
Nd/Yb ratio and Na2O + K2O is far less than that between Nb/Y and
Na2O + K2O (Fig. 8b). Therefore, this parameter is not very suitable for
sample classification.

3.4.3. Nd/Yb ratio 3.5. Comparison of the old and new Zr/TiO2-Nb/Y diagrams
Except for the Nb/Y, the ratios of elements with dramatically
According to the results (Figs. 2, 5) based on big data, the

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M. Lang et al. LITHOS 454-455 (2023) 107274

Fig. 7. Diagrams of Nb/Y vs. (a) Na2O + K2O and (b) SiO2 based on the 18,002 analyses used in this study. The best least-squares fit and correlation coefficients are
also shown.

Fig. 8. Diagrams of Nd/Yb vs. (a) Na2O + K2O and (b) SiO2 based on the 18,002 analyses used in this study. The best least-squares fit and correlation coefficients are
also shown.

applicability of the new diagram is much better than the Winchester-
Floyd Zr/TiO2-Nb/Y diagram, but the correct naming of samples is
still not satisfying yet.
First of all, the old diagram does not separate the field of basaltic
andesite, and there is a field where andesite and basalt coexist. Specif­
ically, the basaltic andesite mainly falls in this field. Moreover, there is a
considerable overlap among analysis points of these three lithologies
(basalt, basaltic andesite and andesite) in this diagram. Considering this,
we changed the three fields of basalt, basalt or andesite, and andesite
into four fields of basalt, basalt or basaltic andesite, basaltic andesite or
andesite, and andesite in the new diagram. In addition, the large overlap
field of dacite, rhyolite, comendite, trachyandesite, and trachyte is still
seen in the new diagram (Fig. 4), and they cannot be well distinguished.
In the original diagram, only 31.46% of the phonolite samples success­
fully fall within the phonolite field, whereas the accuracy in the new
diagram could reach to 82%.
In the TAS diagram, tephrite and basanite are in the same field, while
foidite is more alkaline, as a “neighbor” field adjacent to tephrite and
basanite. However, in the Winchester-Floyd Zr/TiO2-Nb/Y diagram,
basanite and foidite were plotted in one field, whereas tephrite and
alkali-basalt were placed in one field. Our test based on big data shows
that tephrite, basanite, and foidite fall close together (Figs.B17, B19,
B21), almost completely overlapping, and are difficult to distinguish.
Therefore, in the improved diagram, we put them in one field.
4. The use of immobile elements
Many other immobile elements can be used except for Zr, Ti, Nb, Y
mentioned in the section 3.4. Before we use immobile elements to
classify volcanic rocks, we should discuss which elements are relatively
immobile.

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M. Lang et al.
Fig. 9. Element contents of each rock type. (Abbreviations on horizontal axis represent rock types).
4.1. The mobility of major and trace elements and REEs
The behavior of an element during weathering and hydrothermal
alteration is not only dependent on parent rock composition and the
physicochemical conditions of the environment (pH, salinity, and redox
conditions) (Nesbitt, 1979; Wray, 1995), but also related to its charge/
radius ratio (ionic potential) (Pearce, 1996). In general, elements that
form ions of low ionic potential (<0.03 pm− 1) tend to be preferentially
removed in solution as hydrated cations, whereas elements forming ions
with a high ionic potential (>0.10 pm− 1) tend to be preferentially
removed as hydrated oxyions. Ions of intermediate ionic potential
(0.03– 0.10 pm− 1) tend to be relatively immobile (Hastie et al., 2007).
Thus, large-ion-lithophile elements (LILEs) with low valence states are
commonly mobile in aqueous environments, whereas high-field-
strength elements (HFSE, characterized by small ionic radii and high
valences) have low solubilities and are considered to behave as
8
LITHOS 454-455 (2023) 107274
immobile elements and to preserve source characteristics (e.g., Ti, Y, Nb,
Ta, Zr, Hf, P, Th). Among these elements, Ti, Zr, Y, and Nb have been
widely shown to be immobile, whereas Ta, Hf, P, Th are considered
relatively immobile during alteration and metamorphism (Hastie et al.,
2007).
However, the rare earth elements (REEs), characterized by a uniform
valence of 3+ except for Ce and Eu, show intermediate ionic radii (Hong
et al., 2017). Thus, the mobility of REEs is controversial. An effective
method to test the mobility of an element is proposed by Cann (1970), in
which an immobile element is plotted on the horizontal axis of bivariate
variation diagrams and elements to be evaluated are plotted on the
vertical axis. If the two elements exhibit a good correlation trend, the
element on the vertical axis can be considered to be immobile (Hastie
et al., 2007). Duchesne et al. (2005) studied a set of altered rhyolitic
rocks by using Visé by Cann’s method, and conclude that REEs were
immobile during the alteration processes. This conclusion is also
M. Lang et al. LITHOS 454-455 (2023) 107274

Fig. 10. The result of Discriminant Analysis applied to the three-class classification of volcanic rocks with confusion matrix and polar plot of precision. DP1–1 and
DP1–2 are the calculation formulas for the horizontal and vertical coordinates, respectively.

Fig. 11. The result of Discriminant Analysis applied to the five-class classification of subalkaline volcanic rocks with confusion matrix and polar plot of precision.
DP2–1 and DP2–2 are the calculation formulas for the horizontal and vertical coordinates, respectively.

9
M. Lang et al.
Fig. 12. The result of Discriminant Analysis applied to the four-class classification of transitional volcanic rocks with confusion matrix and polar plot of precision.
DP3–1 and DP3–2 are the calculation formulas for the horizontal and vertical coordinates, respectively.
reinforced by Hastie et al. (2007). However, Ece and Nakagawa (2003)
argued that only MREEs and HREEs (Gd, Dy, Ho, Er, Yb) are relatively
immobile after they studied a set of altered and fresh andesite to rhyolite
rocks. More recently, Anenburg et al. (2020) proposed that REEs are
considered to be immobile in most natural systems, and extensively
soluble only when alkalis were present. Thus, to be on the safe side, we
only consider MREEs and HREEs as immobile elements. Moreover, it is
also necessary to consider phosphorus because as a high field strength
element, it has high ionic potential (π > 3). Although phosphorus is a
mobile element in seawater dominated environment as a nutrient for
life, it shows immobility during metamorphism and alteration in rock
dominated environment (Jenner, 1996). The content of phosphorus in
the crust is estimated as 0.09%. Phosphorus usually occurs in the form of
phosphates, especially in apatite. Apatite remains stable in many
geological environments and is not easily susceptible to metamorphism,
hydrothermal alteration and supergene processes (Ayers and Watson,
1991; Bouzari et al., 2016; Creaser and Gray, 1992). Thus, phosphorus
can be considered as an immobile element. Thus, we choose the thirteen
elements including Dy, Er, Gd, Hf, Nb, Nd, P, Sm, Ta, Ti, Y, Yb, Zr
(generally accepted immobile elements including MREEs and HREEs
with even atomic number) as the parameters below.
4.2. Element contents of each rock type
The ranges of concentrations of these 13 elements in different rock
types are shown in Fig. 9. Among these elements, Ti and P can be used to
classify volcanic rocks according to degree of magma evolution: mafic
rocks have higher average Ti and P content than that of felsic rocks, and
alkaline rocks have a slightly higher average P content than that of sub-
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LITHOS 454-455 (2023) 107274
alkaline rocks. Element contents such as Hf, Nb, Ta, Y, Zr have similar
statistical characteristics: alkaline samples have higher average contents
than the sub-alkaline samples, and felsic rocks have the higher average
contents than the mafic rocks. It is obvious that the content of MREEs
(Nd, Sm, Gd) in alkaline and peralkaline samples is higher than that in
sub-alkaline samples, whereas the average content of HREEs (Dy, Er, Yb)
in these rocks is similar. However, the range of HREEs content in felsic
rocks is larger than that in mafic rocks, so HREEs also play a role in the
classification scheme. Therefore, it can be concluded that these immo­
bile elements can be used to subdivide volcanic rocks into different types
according to alkalinity and the degree of magma differentiation.
5. Two-dimensional diagram: from discriminant analysis
Two-dimensional diagrams are widely used because of their
simplicity, intuitiveness, and visualization. In order to achieve better
classification methods in a two-dimensional diagram, we chose to
reduce the dimensionality of the data and generate discrimination for­
mulas from multi-dimensional data as the horizontal and vertical co­
ordinates of the two-dimensional discrimination diagram. Below are the
detailed steps for implementing this method.
Discriminant analysis (DA) is a multivariate technique that projects
multivariate data into a lower-dimensional space for optimal separation
between user-defined groups (Flury, 1997). It involves supervised
pattern recognition and works by finding linear combinations of selected
variables and can predict new observations to predefined groups using
linear or quadratic functions (Alkarkhi and Alqaraghuli, 2019; Mendlein
et al., 2013). The DA defines the distance of a sample from a class center
and creates new axes to group members closely and separate groups.
M. Lang et al.
Fig. 13. The result of Discriminant Analysis applied to the five-class classification of peralkaline volcanic rocks with confusion matrix and polar plot of precision.
DP4–1 and DP4–2 are the calculation formulas for the horizontal and vertical coordinates, respectively.
These axes are discriminant or canonical variates that are linear com­
binations of original variables. Specifically, the DA calculates a set of
linear discriminant functions that maximize the ratio of the within-
groups (W) to between-groups (B) sum of squares matrices (W/B). The
between-groups matrix is effectively the covariance of the group means
and the within-groups matrix is the weighted covariance matrix for all
the groups. These discriminant functions or projections (DP1, DP2, etc.)
are linear combinations of the original variables (i.e., element concen­
trations) that maximize the differences between the predefined groups,
which allow the samples to be plotted in the discriminant space so that
group separation can be visualized and investigated. The DA also in­
dicates which of the selected variables are most important for deter­
mining maximum group separation based on the size of the structure
coefficient. When predicting unknown samples, the optimal classifica­
tion scheme can be quantitatively determined by calculating the
Mahalanobis distance from a sample to a group centroid. Mahalanobis
distance is based on the means and variances for the variables, and on
the covariances between each pair of variables (Mao et al., 2016). It
should be noted that, DA requires more samples than variables; other­
wise, the calculation fails.
In this study, we selected 17 variables including elements and
element ratios, and performed three classifications to evaluate the reli­
ability of the scheme. Data preprocessing is first performed before
analysis by taking the logarithm of trace elements and trace element
ratios. Figs. 10, 11, 12, 13 and 14 show the projection coefficients,
constants for all of the discriminant functions and classification accu­
racy. Tables 2, 3, 4, 5 and 6 show classification function coefficients that
can be used to calculate the results. When predicting unknown samples,
the data is first preprocessed, then multiplied by the corresponding
11
LITHOS 454-455 (2023) 107274
coefficients under each class and summed to obtain a result. These re­
sults are compared, and the value of which class is the largest indicates
that this sample belongs to this class of rock. The specific discriminant
results are as follows. Discriminant projections or functions DP1–1 vs.
DP1–2 (Fig. 10) can accurately classify most volcanic rocks as
subalkaline-transitional or peralkaline (with an accuracy of 80.3%). In
addition, we performed discriminant analysis on subalkaline series
(basalt, basaltic andesite, andesite, dacite, rhyolite), transitional series
(trachybasalt, basaltic trachyandesite, trachyandesite, trachydacite,
trachyte), and peralkaline series (basanite, tephrite, foidite, tep-
phonolite and pho-tephrite, phonolite) with accuracies of 75.2%,
81.6%, and 79.5%, respectively (Figs. 11, 12, 13). However, for the
classification of all volcanic rocks, the overall accuracy of DA is rela­
tively low (Fig. 14, 58.3%).
Compared to traditional discriminant diagrams, DA has many ad­
vantages. It can obtain an accurate classification result by quantitatively
calculating the Mahalanobis distance, rather than just determining it
based on the field where the points fall in the diagram. However, there
are also obvious disadvantages: 1) the accuracy is not high enough; 2)
transitional type rocks are still difficult to classify; and 3) the inter-class
differences shown on the diagram are not obvious. Given that the ac­
curacy of DA for thirteen-class classifications of volcanic rocks is still not
high, the two-dimensional diagram has significant limitations for the
identification of the various volcanic rocks.
6. A new approach by machine learning: random forests
algorithm
The introduction of big data and machine learning (ML) algorithms
M. Lang et al. LITHOS 454-455 (2023) 107274

Fig. 14. The result of Discriminant Analysis applied to the thirteen-class classification of volcanic rocks with confusion matrix and polar plot of precision. DP5–1 and
DP5–2 are the calculation formulas for the horizontal and vertical coordinates, respectively.

12
M. Lang et al. LITHOS 454-455 (2023) 107274

Table 2 Table 4
Classification function coefficients of volcanic rocks’ three-class classification Classification function coefficients of transitional volcanic rocks’ four-class
scheme. classification scheme.
Subalkaline Transitional Peralkaline Comendite Trachybasalt Basaltic Trachydacite/
Samples Samples Samples Trachyandesite / trachyte
Trachyandesite
log10 Zr/ − 102.32 − 106.191 − 103.723
TiO2 log10 Zr/ − 288.861 − 308.742 − 313.115 − 306.048
log10 Nb/Y − 122.961 − 121.66 − 124.366 TiO2
log10 Nd/Yb − 31.821 − 29.641 − 30.125 log10 − 180.598 − 178.667 − 181.98 − 182.659
TiO2(wt%) − 28.302 − 30.222 − 29.254 Nb/Y
P2O5(wt%) − 27.02 − 24.781 − 18.142 log10 − 16.606 − 2.675 − 16.979 − 21.653
log10 Nb 127.746 127.7 134.566 Nd/Yb
log10 Ta − 5.052 − 5.369 − 6.247 TiO2(wt − 111.108 − 107.62 − 116.299 − 116.09
log10 Zr 137.577 142.963 139.726 %)
log10 Hf − 16.998 − 15.773 − 17.887 P2O5(wt − 0.847 − 2.4 8.354 0.599
log10 Nd 152.038 152.668 152.259 %)
log10 Sm − 133.371 − 130.933 − 135.458 δEu 195.295 207.071 202.526 199.637
log10 Gd − 30.66 − 31.445 − 31.067 log10 Nb − 13.296 − 19.341 − 15.852 − 12.77
log10 Dy 50.59 46.537 49.644 log10 Ta 341.224 347.447 359.182 356.082
log10 Er − 147.611 − 144.013 − 148.707 log10 Zr 0.474 − 5.056 0.827 1.789
δEu − 317.919 − 339.138 − 336.101 log10 Hf 94.877 71.713 86.622 96.26
constant − 102.32 − 106.191 − 103.723 log10 Nd − 139.769 − 133.71 − 137.43 − 138.793
log10 Sm − 45.698 − 36.17 − 40.442 − 41.502
log10 Gd 139.878 119.778 134.002 138.952
log10 Dy − 236.788 − 205.751 − 233.13 − 247.429
Table 3 log10 Er − 673.319 − 723.796 − 747.316 − 729.683
Classification function coefficients of subalkaline volcanic rocks’ five-class constant − 288.861 − 308.742 − 313.115 − 306.048
classification scheme.
Basalt Basaltic Andesite Dacite Rhyolite
Andesite
Table 5
log10 Zr/ − 179.129 − 175.762 − 171.081 − 165.911 − 147.72 Classification function coefficients of peralkaline volcanic rocks’ four-class
TiO2 classification scheme.
TiO2(wt%) − 31.481 − 33.118 − 33.561 − 33.616 − 31.363
P2O5(wt − 16.709 − 16.4 − 16.995 − 22.004 − 29.551 Basanite/ Foidite Tep-phonolite / Pho- Phonolite
%) Tephrite tephrite
δEu 22.066 18.607 17.232 15.94 16.364 log10 Zr/ − 251.739 − 249.683 − 252.062 − 237.023
log10 Nb − 20.96 − 20.513 − 19.311 − 17.501 − 15.554 TiO2
log10 Ta 187.722 185.565 185.295 182.399 166.652 log10 Nb/Y − 99.876 − 101.059 − 101.047 − 104.524
log10 Zr − 33.036 − 28.359 − 24.453 − 21.506 − 17.972 log10 Nd/ − 0.849 1.421 0.32 2.352
log10 Hf 116.063 117.754 119.207 122.336 122.419 Yb
log10 Y 122.073 126.947 128.78 131.803 138.17 TiO2(wt%) − 44.884 − 45.534 − 46.565 − 45.39
log10 Nd − 201.555 − 202.205 − 202.402 − 200.967 − 203.623 P2O5(wt%) − 21.578 − 19.183 − 23.261 − 25.594
log10 Sm − 14.277 − 13.631 − 15.239 − 14.889 − 16.279 δEu 81.667 86.445 77.888 79.37
log10 Gd 114.719 107.158 100.28 95.083 84.641 log10 Nb − 26.865 − 27.765 − 23.655 − 17.182
log10 Dy − 155.701 − 156.409 − 156.018 − 164.198 − 157.864 log10 Ta 360.627 358.145 364.83 351.691
log10 Er 18.161 20.882 21.549 26.513 31.013 log10 Zr − 41.333 − 40.001 − 38.997 − 36.532
log10 Yb − 457.288 − 446.831 − 436.602 − 425.976 − 373.832 log10 Hf 99.226 99.694 106.936 103.258
constant − 179.129 − 175.762 − 171.081 − 165.911 − 147.72 log10 Nd − 50.844 − 52.129 − 50.239 − 54.238
log10 Sm − 33.3 − 31.68 − 33.763 − 37.122
log10 Gd 45.775 48.724 34.497 40.456
has resulted in a great-leap-forward development for geoscience. log10 Dy − 163.548 − 169.509 − 158.672 − 158.185
Essentially, machine learning is the process by which a computer log10 Er − 677.86 − 681.734 − 689.525 − 638.474
automatically learns the characteristics of a sample and models them to constant − 251.739 − 249.683 − 252.062 − 237.023

predict unknown samples. The two primary classes of ML algorithms are

supervised and unsupervised techniques. The methods we use here such
as random forests are supervised learning. In supervised learning, the
algorithms create a map f that relates a data (feature vector x) to a
corresponding label (target vector y): y = f(x), using labeled training
data to optimize the model (Bergen et al., 2019).
Although machine learning (ML) techniques have been widely
applied to various branches of geoscience, particularly in geohazard or
mineral prospecting modeling, their application to geochemical ana­
lyses is relatively recent. For example, Random Forests (RF), have been
used in several studies (Gion et al., 2022; Gregory et al., 2019; Higgins
et al., 2021; Hong et al., 2021). Based on the dataset mentioned in
Section 2, we further eliminate analyses with missing values and thus
8980 analyses were obtained. In the modeling process, the data were
split into two sets, ~90% (8080 analyses; Appendix C) of analyses were
randomly selected for training, and ~ 10% (900 analyses; Appendix D)
withheld for testing. A predictive model identifying rock types were
generated using the training dataset, the accuracy of which was vali­
dated using the validation dataset (Goodfellow et al., 2016; Srivastava
et al., 2014; Wan et al., 2017).
6.1. Random forests algorithm
Decision trees are a supervised method for classification and
regression that learn a piecewise constant function, equivalent to a se­
ries of if-then rules. Random forest (RF) is an ensemble learning algo­
rithm consisting of a combination of independent decision trees, where
the Bootstrap resampling method is used to generate training datasets
for each decision tree by randomly drawing with replacements (Brei­
man, 2001). At each node of the decision tree, features are randomly
selected to search for the best split. The final output of RF is the average
output of all trees (Athey et al., 2019; Choi et al., 2020). Compared with
a single decision tree, RF has the advantage of high predictive accuracy,
fast training speed and strong robustness.
Through this approach, even slight differences between different
rock types can be identified by evaluating the elemental features of the
rock samples which can be regarded as diagnostic ‘fingerprints’ of rocks.

13
M. Lang et al. LITHOS 454-455 (2023) 107274

The method and the Python Code are given in Appendix E.

− 126.054

− 133.599

− 154.531
− 439.032
Phonolite

− 162.45

− 22.472

− 37.346
− 21.738

− 21.447

− 35.095

− 162.45
144.435

196.826

121.974
− 15.6
6.2. Testing results of the scheme using random forest

70.82
We employed a software procedure for rock classification based on
the possible relationships between immobile elements and SiO2, K2O +
Tep-phonolite /

Na2O. In this study, 13 types of rocks were selected according to the

Pho-tephrite

classification results of TAS. Many transition types like rhyodacite are

− 173.768

− 123.333

− 126.362

− 161.309
− 459.544
− 173.768
− 37.389
− 10.899

− 18.976

− 27.172

− 28.946
142.672

199.108

117.909
− 23.27

78.638
not listed in the TAS diagram and therefore are not considered in this
study.
The procedure and its instructions are given in Appendix F. After
− 122.152

− 132.329

− 159.404
− 463.202
testing the modeling using the other 10% of samples, the average ac­
− 173.74

− 14.926

− 36.713

− 21.803

− 25.109

− 173.74
146.802

196.074

102.634
− 30.01

92.203
Foidite

curacy of the predictive model can reach to 74%. The predictive accu­
3.832

racy for rock types with a large number of samples such as basalt and
rhyolite was even higher, 89.2% and 97.5%, respectively (Fig. 15). As
seen in Fig. 15, most of the misclassification cases occur in the
− 176.344

− 120.369

− 127.986

− 176.344
Basanite/

“neighbor” fields (which means most misclassifications produce a rock

− 18.835

− 34.556

− 19.876

− 27.379

− 161.84
− 459.18
Tephrite

142.053

197.875

106.139
− 8.375

− 32.63

92.288
name in some field adjacent to the proper rock name). For example,
most of the trachydacites were recognized as dacites. For those rocks
with high alkalinity like phonolite, the accuracy is as high as 75%.
It is noteworthy that as shown in Fig. 16, Ti, P, La, and Nb are
Trachydacite/

important elements in judging rock types, whereas Sm, Y, and Nd are

− 164.478

− 122.053

− 124.216

− 158.423

− 164.478

relatively the least important. Overall, the accuracy for the classification
− 21.416

− 37.065
− 20.489

− 14.728

− 21.088

− 30.272

− 430.51
133.683

196.133

117.971
trachyte

74.633

results of the RF method is much higher than that of Zr/TiO2-Nb/Y

diagram.

6.3. Advantages and disadvantages of machine learning methods

Basaltic Trachyandesite /

Compared with the traditional discriminant diagram, the machine

Trachyandesite

learning method has more advantages. First, bivariate or ternary

discriminant diagrams can only consider few element characteristics as
− 119.672

− 124.929

− 156.899
− 453.296
− 173.69

− 19.711

− 17.835

− 25.174

− 29.183

− 173.69
134.532

200.459

111.794
− 37.72
− 9.501

parameters (Verma et al., 2013, 2017), whereas machine learning

82.808

classifiers can find subtle differences between different rock types based
on the characteristics of more elements of big data, resulting in more
reliable results. Secondly, bivariate diagrams, while intuitive, do not
Trachybasalt

− 178.562

− 117.926

− 127.584

− 149.485

− 178.562

provide judgment probabilities. Machine learning performs better in this

− 16.875

− 36.187
− 14.295

− 21.107

− 33.739

− 24.739

− 461.43
141.047

197.064

110.259

81.877

aspect. The procedure developed by machine learning has improved the

accuracy of nearly all rock types, demonstrating the utility of the
method by yielding a more accurate and meaningful classification ma­
Comendite

− 152.588

− 121.344

− 129.297

− 151.741
− 394.549
− 152.588
Classification function coefficients of volcanic rocks’ thirteen-class classification scheme.

trix. Thirdly, in the Zr/TiO2-Nb/Y diagram, the data points are plotted in
− 34.846
− 22.925

− 13.345

− 19.841

− 33.624
130.761

186.547

121.274
− 20.66

75.276

considerably scattered fields. However, in RF model the misjudged rock

types are mostly “neighbor” rock types (Fig. 15). Since the rocks
themselves are a chemical continuum, the results can be considered
− 149.923

− 122.559

− 128.746

− 156.882
− 374.752
− 149.923
− 24.829

− 33.663
− 21.746

− 13.492

− 22.944

− 29.325

accurate.
Rhyolite

133.373

179.173

123.806

73.602

This approach has also certain limitations as follows. 1) The RF

cannot give a visual diagram, so the results are not intuitive. 2) An
excessive number of classifications may lead to a decrease in the accu­
− 167.318

− 123.592

− 128.206

− 164.506
− 429.662
− 167.318
− 36.099
− 19.048

− 15.507

− 24.459

− 28.173
134.597

195.863

116.577

racy of discrimination. Therefore, when we utilize this procedure, if the

− 22.97

81.499
Dacite

highest and second highest probabilities in the judgment result are

roughly equal, further distinction is required. 3) Machine learning is
highly dependent on the volume of data. When the data are imbalanced,
− 171.911

− 121.191

− 128.335

− 157.305
− 439.251
− 171.911
− 19.846

− 17.601

− 25.993

− 28.695
Andesite

198.534

109.889
− 36.07
− 16.83
133.88

84.092

the accuracy of discrimination for rock types with less data is signifi­
cantly lower than that of other types. 4) Additionally, variations in
analytical methods, standards, and instruments may cause different data
quality. This may be another reason for the low accuracy.
− 175.972

− 447.855
− 175.972
− 120.15
− 20.426

− 35.765
− 17.071

− 19.069

− 28.298

− 127.88
− 27.611

− 158.29
Andesite

134.554

198.502

108.194
Basaltic

89.84

7. Conclusions

Since Winchester and Floyd (1977) proposed the Zr/TiO2-Nb/Y di­

− 178.776

− 119.254

− 159.548
− 456.904
− 178.776
− 19.295

− 34.199
− 17.881

− 31.444

− 126.63
− 28.154

agram, it has been extensively applied for the classification and

137.536

199.897

102.282
− 19.83

95.827
Basalt

nomenclature of altered volcanic rocks. However, the diagram has some

flaws, including limited rock types, deviations of the fields given by the
diagram from the actual rock fields, and significant overlap of distinct
log10 Nb/Y
log10 Nd/
log10 Zr/

log10 Sm

fields of rocks. The Nb/Y ratio is related to alkalinity but has a weak
log10 Nd
log10 Nb

log10 Gd
log10 Dy

constant
log10 Ta

log10 Hf

log10 Er
log10 Zr
Table 6

TiO2

correlation due to the low value in subduction-related volcanic rocks,

P2O5
Yb
TiO2

δEu

and therefore it cannot distinguish alkaline and subalkaline series

14
M. Lang et al.
Fig. 15. Accuracy of rock type identification by random forest method. The accuracy by RF in the last line is the result of cross-validation of random forest in
training stage.
Fig. 16. The relative importance of the elements given by random forest (RF)
model. Feature importance refers to the average value of feature importance
across all individual trees, which is calculated as the sum of the reduction in
squared loss after splitting based on that feature.
clearly. It is noted that any two elements with dramatically different
bulk distribution coefficients during mantle melting can be employed
successfully. The Nd/Yb ratio avoids the impact from subduction-related
processes, but has a weaker correlation with alkalinity than Nb/Y, and is
therefore not a robust substitute. Additionally, the Zr/TiO2 ratio and Eu
anomaly can be used as substitutes for the SiO2 index, but their corre­
lation is not satisfactory. We evaluate this classification scheme based on
global data and found that the accuracy of the diagram was only 45.3%.
We refined the diagram and increased the accuracy to 68.84%, partic­
ularly for rock types like dacite, rhyolite, and comendite. In addition, we
collected data for four rock types (trachydacite, trachybasalt, basaltic
trachyandesite, and tephrite-phonolite / phonolite-tephrite) which were
not considered in the Zr/ TiO2-Nb/Y diagram, and found that the other
three rock types, with the exception of trachybasalt, have very signifi­
cant overlap with the aforementioned rock fields.
15
LITHOS 454-455 (2023) 107274
As two-dimensional diagrams are relatively simple and easy to
comprehend, we attempted to generate other discrimination diagrams
for volcanic rock classification. Compared to traditional discrimination
diagrams that only consider limited elements, we chose Discriminant
Analysis (DA) to construct discrimination diagrams using more ele­
ments. DA is a supervised learning method that fully considers the dif­
ferences between different groups for modeling. The result is
quantitatively determined by calculating the Mahalanobis distance be­
tween unknown sample and the group centroid, resulting in better
performance for DA. From the results we note that in the three-class
classification (subalkaline-transitional-peralkaline), the accuracy is
relatively high (80.3%), whereas in the thirteen-class classification, the
accuracy of all volcanic rocks was limited to 58.2%, indicating that there
are still limitations in the discrimination process of two-dimensional
diagrams.
The random forest method was also employed for the classification of
volcanic rocks in this study. We selected 13 immobile elements (Dy, Er,
Gd, Hf, Nb, Nd, P, Sm, Ta, Ti, Y, Yb, Zr) as the parameters to train the
model, and verified that the discriminant accuracy can reach 74%, in
which for basalt and rhyolite, the accuracy can be 89.2% and 97.5%
respectively. Hence, our new method is much more reliable than the
conventional Zr/TiO2-Nb/Y diagram for the classification and nomen­
clature of altered volcanic rocks.
Machine learning methods are significantly influenced by the vol­
ume of data. In future studies, high-precision data need to be collected
for achieving more accurate discrimination results. For some rocks with
less data and lower discrimination accuracy, the Discriminant Analysis
can be used for further subdivision. We propose that the combined use of
the two methods can be employed for rock classification with higher
accuracy.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.lithos.2023.107274.
M. Lang et al. LITHOS 454-455 (2023) 107274

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plutons and volcanic sequences. J. Geochem. Explor. 30 (1–3), 223–242. https://doi.
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The authors declare that they have no known competing financial Gregory, D.D., Cracknell, M.J., Large, R.R., McGoldrick, P., Kuhn, S., Maslennikov, V.V.,
interests or personal relationships that could have appeared to influence Baker, M.J., Fox, N., Belousov, I., Figueroa, M.C., Steadman, J.A., Fabris, A.J.,
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Hastie, A.R., Kerr, A.C., Pearce, J.A., Mitchell, S.F., 2007. Classification of Altered
Volcanic Island Arc Rocks using Immobile Trace elements: Development of the
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Foundation of China (42030302, 41772057, 41702064 and 41822301). petrology/egm062.
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