GR Focus ReviewChalcophile element (Cu, Zn, Pb) and Ga distribution patterns in ancient and modern oceanic crust and their sources: Petrogenetic modelling and a global synthesis
Graphical abstract
Introduction
The occurrence and distribution of chalcophile elements in the rock record have been both scientifically and societally important because of their unique properties, which played an important role in the development of human civilizations. Transition metals Cu, Zn, Pb and Ga have been mined extensively in the upper crustal lithologies of many Phanerozoic ophiolites and Precambrian greenstone belts throughout history (e.g., Galley and Koski, 1999). Copper (Cu), in particular, is one of the most significant metals in the society, and its stable face–centered cubic crystal structure, which does not change with varying temperatures and its properties of a high electrical and thermal conductivity make cupper most attractive for a wide spectrum of applications in human lives (Copper: An Ancient Metal, https://sites.dartmouth.edu/toxmetal/more-metals/copper-an-ancient-metal/). It was one of the first metals utilized by humans, and the eventual discovery of bronze as an alloy of cupper and tin ushered in the beginning of the Bronze Age around 3000BCE (Cartwright, 2017).
Zinc was commonly used to make brass around 1400 to 1000BCE in today’s Palestine, and the Romans smelted cadmia (zinc oxide) with copper to create brass. The people of India produced zinc metal by burning organic materials with zinc carbonate (smithsonite) in the 1200 s (Alam, 2020). Zinc is a highly flexible metal, and therefore it has been used widely in architecture and construction, and for prototyping products and building small components in electronics. When combined with other metals, zinc alloys strengthen and harden them, an extremely valuable treat in construction (Habashi, 2013).
Lead was one of the first metals extracted from natural ore bodies > 8,000 years ago and had many uses in ancient civilizations because of its soft and easy nature with which the artisans and construction people could work easily (de Keersmaecker et al., 2018). Because lead melts at a relatively low temperature and resists corrosion over time, many civilizations used this common metal for making pipes, cosmetics, coins, and paints. The Romans, in particular, used lead widely in building the first municipal plumbing systems such that this common practice gave the name “plumbum” to lead for its chemical symbol, Pb (de Keersmaecker et al., 2018). In the 15th century Europe, lead was used for creating the first moveable printing press and stained glass windows held together by lead frames in medieval churches.
Gallium (Ga) was discovered in sphalerite (a zinc-sulfide mineral) by Paul-Émile Lecoq de Boisbaudran who introduced its name and description to the French Academy of Sciences in Paris in 1875 (Brennan, 2014). The name was derived from the Latin name for France (Gaul), Gallia. Although until then gallium was not known, its existence and properties were predicted by Dmitri Mendeleev in 1871 because his periodic table showed a gap below aluminum that was yet to be occupied. Elemental gallium is not found in nature and does not exist as a free element in the Earth's crust, but it occurs in bauxite and zinc ores. It is produced as a byproduct during the processing of the ores of other metals, and is widely used in the semiconductor industry, particularly in the production of smartphones and solar cells (Sahlström et al., 2017).
The main sources of chalcophile Cu, Zn and Pb are related to metal enrichment and ore mineralisation processes in hydrothermal systems along seafloor spreading centers in former ocean basins (e.g., Alt, 1995, Alt et al., 2010, Pirajno et al., 2020) or within island arc – forearc settings of supra-subduction zone tectonic environments (e.g., Hein and Mizell, 2013, Varnavas and Papavasiliou, 2020). Gallium, although sensu stricto lithophile (Goldschmidt, 1937), commonly demonstrates chalcophile behaviour and is associated with sulphides, in particular sphalerite (ZnS) (Paradis, 2015, Sahlström et al., 2017).
Chalcophile ore deposits may form at and near the surface of submarine volcanoes, or in the upper stratigraphic and structural levels of submarine magmatic complexes, known as volcanogenic massive sulphide deposits (VMS) (e.g., Koski et al., 1984, Large, 1992, Hannington et al., 1995; summarized in Galley et al., 2007). In addition to their economic importance, chalcophile elements, particularly Cu and Pb, are commonly used as geochemical tracers in the melt evolution of mafic magmas in oceanic environments (e.g., Jenner et al., 2015, Wang and Becker, 2015). Some of the best examples of ophiolite–hosted metallic ore deposits of copper, zinc, lead, silver and gold include the Troodos ophiolite in Cyprus (Dilek and Eddy, 1992, Eddy et al., 1998, Hannington et al., 1998, Antivachis, 2015), the Semail ophiolite in Oman (Mahfoud and Beck, 1997), the Khoy ophiolite in Iran (Aftabi et al., 2006), the Mirdita ophiolite in Albania (Dilek et al., 2005, Phillips-Lander and Dilek, 2008, Milushi, 2015), the Løkken (McQueen, 1990) and Karmøy (Grønlie and Logn, 1978) ophiolites in the Norwegian Caledonides, and the Palaeoproterozoic ophiolites in the North Karelia Schist Belt in Finland (Saalmann and Laine, 2014).
One significant question pertaining to the occurrence of chalcophile elements in the mafic rocks (dikes and lavas) of ophiolites is what parameters and processes control their distribution in ophiolites with different magmatic and tectonic origins. In this study, we have examined and analyzed published data on Cu, Zn, Pb and Ga distributions in basaltic lithologies of dike complexes and lava sequences of Phanerozoic and Proterozoic ophiolites, and Archean greenstone belts that are interpreted as ophiolites with varying ages, internal structures, and tectonic origins, as well as their upper mantle peridotite sources. Here, we compare and discuss the distribution of these elements in the investigated ophiolites exposed in different orogenic belts within the framework of our recent ophiolite classification (Dilek and Furnes, 2011, Dilek and Furnes, 2014, Furnes et al., 2014, Furnes et al., 2020). We have sub-grouped and examined compositionally identified ophiolitic subunits with discrete geochemical affinities (i.e., alkali basalts, mid-ocean-ridge basalts, island arc tholeiites and boninites) in terms of their elemental patterns (in histogram distribution), and then we have modelled partial melting and fractional crystallization trends of their magmas.
The chalcophile element behaviour in ophiolitic rocks is not a new topic. However, two aspects of our approach in this paper are new and fundamentally important: (1) this is the first comprehensive synthesis of the extant data on the chalcophile element distribution patterns in upper crustal rocks of the global ophiolite inventory; and (2) these emerging patterns tell us more about the petrogenesis, particularly the mantle melt sources and melt evolution trends of different ophiolite types in comparison to those of the modern oceanic crust. These two aspects of our paper provide global–scale perspectives, which should be appealing to petrologists, geochemists and geophysicists working not only on ophiolites, but also on modern oceanic crust and mantle evolution through time. We consider these aspects of our paper a major contribution to the ophiolite concept. In order to understand how the distribution of chalcophile elements in ophiolites compares with rock sequences of comparable geochemical affinities in in-situ oceanic environments, we have done petrogenetic modelling to decipher the mode of their occurrences in both ancient and modern oceanic lithosphere. Therefore, our results also provide significant insights about how different tectonic settings of oceanic crust formation and the related petrological and geochemical processes potentially affect chalcophile element distribution patterns and hence mineralization and ore forming processes in oceanic crust.
Section snippets
Ophiolite types and their upper crustal lithologies
Ophiolites represent archives in the history of the evolution of oceanic lithosphere through time and provide important information regarding the evolution of ancient ocean basins and orogenic belts (e.g., Maruyama et al., 1996, Dilek et al., 1999, Dilek, 2006, Furnes et al., 2015, Dilek and Furnes, 2019). The initial ophiolite concept was restricted to the comparison of the lithological makeup of the Troodos ophiolite in Cyprus to that of modern oceanic crust developed at mid – ocean ridges
Ophiolite types and mineralization
Volcanogenic Massive Sulphide (VMS) deposits are common in both ophiolites and modern oceanic crust. They are known to have developed in hydrothermal systems (e.g., Oudin and Constantinou, 1984, Hannington et al., 1998) along active seafloor spreading centers of the mid-ocean ridges (e.g., Barrie and Hannington, 1999, Shanks, 2012, German et al., 2016, Murton et al., 2019) and backarc basins (e.g., Anderson et al., 2017). Modern oceanic hydrothermal systems involve convective circulation of
Data collection and analytical procedures
The geochemical data for this paper has been collected from 329 published articles. Some appropriate information on the general geology, the reports of Cu, Zn, Pb and Ga, reference to each paper, and analytical methods applied, are given in the Supplementary Data Tables 1–3. The full reference information to the papers listed in each of the Supplementary Data Tables 1–3, is provided in Supplementary Information referred to as References to Supplementary Data Tables 1–3.
The geochemical data used
Elemental patterns of different ophiolite types
One of the main goals in our processing of the collected data is to illustrate the characteristic Cu, Zn, Pb and Ga patterns of the various ophiolite types, as well as of their individual rock types. For characterisation of elemental patterns as presented in Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6, we use histograms, based on the geochemical data of basaltic rocks (lavas and dikes, and locally isotropic gabbro). Given the appropriate scaling (bins), histograms provide a good way to
Elemental patterns of different rock types in the ophiolites
Mafic lithological units, i.e., dike complexes and lava sequences, in most ophiolites are compositionally made of a variety of basaltic rocks, i.e., alkaline to subalkaline basalts (mid-ocean ridge basalts - MORB, and island arc tholeiites - IAT) and basalts with boninite affinities (Dilek et al., 2008, Dilek and Thy, 2009, Dilek and Furnes, 2011, Dilek and Furnes, 2014, Furnes et al., 2014, Furnes et al., 2015, Furnes et al., 2020, Saccani et al., 2018, Sarıfakıoglu et al., 2017, Belgrano and
Elemental patterns of upper mantle sources
The patterns defined by the Cu, Zn, Pb and Ga histograms (Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5), based on the contents of these elements in the basalts (lavas and dikes) of the examined ophiolites, define a large scatter. This scatter is caused by many parameters, as will be discussed below, and one important factor must be the mantle source material. Therefore, we have examined a variety of mantle material for the purpose of visualizing the compositional range in the contents of the elements
Alteration and element mobility
Most of the ophiolites examined in this study underwent seafloor alteration and lower greenschist facies metamorphism prior to their emplacement into continental margins (e.g., McGulloch et al., 1981, Harper et al., 1988, Bickle and Teagle, 1992, Gillis and Banerjee, 2000, Fonneland-Jørgensen et al., 2005, Parendo et al., 2017, Furnes and Safonova, 2019, Furnes et al., 2020). During seafloor alteration and low-grade metamorphism of basaltic rocks in ophiolites, most major oxides (e.g., FeO,
Discussion
Fig. 1, Fig. 2, Fig. 3, Fig. 4 demonstrate the histogram patterns of different ophiolite types in the subduction-unrelated and subduction-related categories, with respect to the elemental behaviour of Cu, Zn, Pb and Ga. This compilation shows that Cu and Pb patterns differ significantly among different ophiolite types, whereas Zn and Ga patterns hardly display any differences. However, even though these histograms are well suited for demonstrating differences in elemental distribution among
Effects of primary versus secondary factors and concluding remarks
We have described and discussed above various parameters that may have controlled the behavior and hence the distribution patterns of Cu, Zn, Pb and Ga in basaltic and boninitic lavas and dikes of Phanerozoic through Precambrian ophiolites. The primary factors include: the mantle material from which melts were generated, the degree of partial melting, and the extent of subsequent fractional crystallization processes.
The secondary factors that may have changed the original composition are
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
We thank Vasiliy Belyaev, Weiliang Liu, Franco Pirajno, Reimar Seltmann, Elham Bahramnejad for help in providing the relevant literature on mineralised ophiolites. We have interacted with and had numerous discussions with many colleagues in the international ophiolite community during our fieldwork and research in different orogenic belts and in Precambrian greenstone belts around the globe over the years; it is impossible to name all of them here, but we gratefully acknowledge all those
Harald Furnes became a full professor at the Department of Earth Science, University of Bergen, Norway in 1985, a position that he held until retirement at the end of 2013; he is currently emeritus professor at the same institute. He received his D.Phil. from Oxford University, UK, in 1978. His main research interests involve the physical volcanology, geochemistry, and petrology of volcanic rocks in ophiolites and island arc systems. He has also worked on Precambrian greenstones, in particular
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Cited by (1)
Harald Furnes became a full professor at the Department of Earth Science, University of Bergen, Norway in 1985, a position that he held until retirement at the end of 2013; he is currently emeritus professor at the same institute. He received his D.Phil. from Oxford University, UK, in 1978. His main research interests involve the physical volcanology, geochemistry, and petrology of volcanic rocks in ophiolites and island arc systems. He has also worked on Precambrian greenstones, in particular the Paleoarchean Barberton Greenstone Belt in South Africa. His research on the alteration of modern and ancient volcanic glass led him to a long-term study on the interactions between submarine basaltic volcanic rocks and micro-organisms, and to the quest for traces of early life in the Archean rock record. On all these topics he has published many refereed papers in international journals together with numerous collaborators.
Yildirim Dilek is a University Distinguished Professor and a Professor of Tectonics and Chemical Geodynamics at Miami University, USA. He received his PhD at the University of California, and he has been a visiting professor at the University of Bergen (Norway), Tohoku University (Sendai, Japan), Tsukuba University (Tsukuba, Japan), Ecole Normale Supérieure (Paris, France), and China University of Geosciences (Beijing, China). He has worked extensively on the Tethyan and Cordilleran ophiolites and has published over 300 peer-reviewed papers on related topics. His other research interests include extensional tectonics and magmatism in young orogenic belts, notably in Anatolia, Aegean region, Tibetan Plateau, and eastern China. His most recent projects focus on the Rodinian tectonics of the Tarim Block (China) and the seismotectonics and Cenozoic magmatism in central Iran. He served as the Vice President of the International Union of Geological Sciences (IUGS) and the Editor of the Geological Society of America Bulletin.
Ekaterina S. (Kate) Kiseeva completed her PhD in experimental petrology at the Australian National University (Canberra, Australia) in 2012. Between 2012 and 2015 she worked as a postdoctoral researcher, followed by a NERC Independent Research Fellow in the University of Oxford, U.K. Since 2018, Kate has been a Lecturer at the University College Cork, Ireland. Her research focuses on the behaviour of chalcophile elements in mantle processes and during the Earth’s accretion and differentiation in deep time. Her broader scientific interests also include the oxidation state of the Earth’s mantle, high-pressure phase transitions, mantle metasomatism, and upper- and lower-mantle inclusions in diamonds. In her current research project she is working on reconstruction of the Earth’s transition zone composition.