Extraction condition and determination of exopolysaccharides from various biofilm species
\\n\\n
Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\\n\\nSeeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\\n\\nOver these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\\n\\nWe are excited about the present, and we look forward to sharing many more successes in the future.
\\n\\nThank you all for being part of the journey. 5,000 times thank you!
\\n\\nNow with 5,000 titles available Open Access, which one will you read next?
\\n\\nRead, share and download for free: https://www.intechopen.com/books
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Preparation of Space Experiments edited by international leading expert Dr. Vladimir Pletser, Director of Space Training Operations at Blue Abyss is the 5,000th Open Access book published by IntechOpen and our milestone publication!
\n\n"This book presents some of the current trends in space microgravity research. The eleven chapters introduce various facets of space research in physical sciences, human physiology and technology developed using the microgravity environment not only to improve our fundamental understanding in these domains but also to adapt this new knowledge for application on earth." says the editor. Listen what else Dr. Pletser has to say...
\n\n\n\nDr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\n\nSeeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\n\nOver these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\n\nWe are excited about the present, and we look forward to sharing many more successes in the future.
\n\nThank you all for being part of the journey. 5,000 times thank you!
\n\nNow with 5,000 titles available Open Access, which one will you read next?
\n\nRead, share and download for free: https://www.intechopen.com/books
\n\n\n\n
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\r\n\tHumans have always managed their environments, but modern environmental management is based on the development of models that reflect our understanding about how humans relate to nature. Environmental management is a constantly changing decision-making process that is driven by our capacities to identify problems and rectify the problems based upon data that inform our perspectives. Professional environmental managers employ an array of technologies to measure, monitor, and manage the components of our environments to achieve the goals that businesses, organizations, and agencies deem important.
\r\n\r\n\tThis volume will include studies of the many facets of environmental management that scholars offer from all disciplinary perspectives, about all types of environmental management, occurring anywhere in the world. The desire is to produce a text that offers a diversity of experiences and highlights many perspectives about environmental management of the past, present, and future.
\r\n\r\n\tThe chapters can feature studies: in which people must be managed to improve environmental quality; where nature must be managed to fit human environmental needs and desires; when environments must be monitored to maintain and guide environmental management; when modeling provides key insights to predict and respond to environmental issues; where environments or systems must be restored before environmental management can proceed to maintain desired conditions; or where the processes of environmental management have failed, broken down, or generated other management problems. Virtually any topic related to environmental management is likely to fit within the conversations promoted in this book.
\r\n\t
Microbial biofilm development is observed on virtually all submerged surfaces in natural and industrial environments. Biofilms are also observed at interfaces as pellicles, or in the bulk of aquatic environments as flocs or granules [1, 2]. A biofilm is a complex structure made of aggregates of microbial cells within a matrix of extracellular polymeric substances (EPS) (Figure 1). The matrix structure constitutes the elastic part of the biofilm. Interstitial voids and channels separating the microcolonies contain a liquid phase, mainly constituted by water. This liquid phase is the viscous part of the biofilm. The EPS matrix provides the biofilm with mechanical stability through these viscoelastic properties [3].
All major classes of macromolecule, i.e., polysaccharides, proteins, nucleic acids, peptidoglycan, and lipids can be present in a biofilm. Although extracellular polysaccharides are considered as the major structural components of the biofilm matrix, extracellular DNA plays an important role in the establishment of biofilm structure [4]. Moreover, nucleases can be regulators of biofilm formation [5]. To get a better understanding of the role of extracellular polysaccharides in the biofilm architecture and mechanical properties, it is necessary to take a look at the properties of a limited number of components, which can be isolated. Most microbial exopolysaccharides are highly soluble in water or dilute salt solutions, and capsule-forming polysaccharides are attached to the cells surface through covalent bonds to other surface polymers. Many of the extracellular polysaccharides produced in biofilms are insoluble and not easily separated from the cells, complicating the precise determination of their chemical structures and physical properties. Jahn et al. extracted a mixture of polymers from
Biofilms in differing environments can be exposed to a very wide range of hydrodynamic conditions, which greatly affect the matrix and the biofilm structure [8]. The shear rate determines the rate of erosion of cells and regions of the matrix from the biofilm. Polysaccharides of the matrix exhibit flow and elastic recovery; because of the flexibility of the matrix its shape can change in response to an applied force. The shear stress to which a biofilm is exposed also affects the physical morphology and dynamic behaviour. Biofilms grown under higher shear are more strongly adhered and have a stronger EPS matrix than those grown under lower shear [9]. Biofilm density can be influenced by the fluid shear during growth [10].
In this chapter, after the presentation of exopolysaccharides extraction and purification from the biofilm matrix, the structural and physical properties of bacterial alginates, cellulose and other exopoysaccharides related to biofilm formation are discussed. An illustration of the complexity of the biofilm matrix architecture and the role of exopolysaccharides in the properties of the matrix is given through biofilms formation at the surface of nanofiltration membranes used for drinking water production.
This section focuses on specific extraction methods targeting exopolysaccharides. General extraction methods for exopolysaccharides are first presented, followed by a presentation of the corresponding exopolysaccharides properties and carbohydrate contents.
Exopolysaccharides constitute the main EPS in many biofilms. They form the backbone of a network where other EPS components can be included. The stability of the biofilm matrix is dominated by entanglement of EPS and weak physicochemical interactions between molecules. These interactions correspond to various binding forces such as electrostatic attractive forces, repulsive forces (preventing collapsing), hydrogen bonds, van der Waals interactions and ionic attractive forces [13].
Schematic representation of a mature biofilm. In the centre, overall diagram of the structure of a biofilm to an interface solid / liquid: bacteria are attached to the solid surface and included in a self-induced polymer matrix. In the area of contact between bacteria and surface, the microbial cells can interact with the surface via several protein and polysaccharide appendages (pili, flagella, LPS, capsular polysaccharides) depending on the type of bacteria. On the basis of the biofilm, bacterial cells are embedded in a matrix containing high eDNA concentrations, in addition to proteins and polysaccharides. The eDNA plays a major role in early biofilm formation. In the core of the biofilm, channels of water carrying ions and nutrients cross the biofilm matrix containing high concentrations of exopolymeric substances. All these exocellular compounds form a protective gel around the microorganisms. In the biofilm detachment area, microbial enzymes destroy the exopolymeric matrix and release the cells that regain mobility, to be able to colonize new surfaces.
The exopolysaccharides recovery from the biofilm matrix in order to get a better understanding of their nature, requires to break down the interactions between EPS and selectivity separate them from other EPS and from matrix cells without cell lysis. The evaluation of cell lysis can be performed by measuring activity of the intracellular marker enzyme glucose-6-phosphate dehydrogenase (G6PDH; EC 1.1.1.49). Thus, substantial cell lysis occurring during the EPS extraction is commonly observed [14]. Regarding extraction methods, publications dealing with selective extraction of exopolysaccharides are missing, as already reviewed by Denkaus
Physical and/or chemical methods are used to extract EPS from biofilms. Some EPS are tightly associated to the biofilm structure, sometimes through covalent bounds to the cells surface and are not directly extracted. Others free EPS are directly released. The easily released EPS can be separated using physical methods such as high-speed centrifugation and ultrasonication. Indeed, centrifugation is often used to separate soluble EPS from bacterial cells from pure cultures. Firmly cells-associated EPS require chemical methods of extractions. EPS cross-linked by divalent cations can be released from the biofilm matrix by complexing agents such as ethylenediamine tetraacetic acid (EDTA), by cation-exchange resins such as Dowex or by a formaldehyde treatment with or without sodium hydroxide [14, 16].
Various methods used to extract EPS can be applied to the extraction of exopolysaccharides as illustrated on Figure 2.
Pathways of exopolysaccharides extraction methods from biofilms
EPS extraction can be done from pure cultures of from complex microbial communities. For example, EPS material can be removed from
Extraction condition and determination of exopolysaccharides from various biofilm species
The content of the EPS extracts is done by chemical analyses. The exopolysaccharide content of EPS can be determined by the phenol-sulphuric acid method described by Dubois
As mentioned by several authors, yields of EPS extracted from biofilms depend on the extraction method used. Pan
The ability to synthesize exopolysaccharides is widespread among microorganisms, and microbial exopolysaccharides play important roles in biofilm formation, pathogen persistence, and have several applications in the food and medical industries. Exopolysaccharides are considered to be important components of the biofilms matrix [27]. However, some studies suggest that exopolysaccharides may not always be essential for biofilm formation [28]. Most of the matrix exopolysaccharides are very long with a molecular weight of 500-2000 kDa. They can be homo-polymers such as cellulose, curdlan or dextran, or hetero-polymers like alginate, emulsan, gellan or xanthan. Exopolysaccharide chains can be linear or branched. They are generally constituted by monosaccharides and some non-carbohydrate substituents such as acetate, pyruvate, succinate, and phosphate [29]. Various examples of exopolysaccharides encountered in bacterial biofilm are presented in Table 2.
Composition as well as conformation of sugar monomers may modify the properties of the exopolysaccharides and thus of the biofilm matrix. Mono-carbohydrate constituted exopolysaccharides are often D-glucose, D-galactose, D-mannose, L-fucose, L-rhamnose, L-arabinose, N-acetyl- D-glucose amine and N-acetyl-D-galactose amine as well as the uronic acids D-glucuronic acid, D-galacturonic acid, D-manuronic acid and L-guluronic acid. Other sugar monomers less frequently occurring are D-ribose, D-xylose, 3-keto-deoxy-D-mannooctulosonic acid and several hexoseamineuronic acids [29]. Some examples of carbohydrate content in biofilm are presented in Table 3.
In conclusion of this section, it is clear that the extraction of exopolysaccharides from biofilms usually require a multi-method protocol. Furthermore, there is no standard extraction procedure established, making difficult the meaning, comparison and interpretation of published results. However, recent studies tend to evaluate whether molecular diversity of EPS are potential markers for biofilm macro-scale characteristics [40].
Examples of exopolysaccharides of bacterial biofilms
Carbohydrate content of various biofilms
The most famous exopolysaccharides present inside biofilms are alginate, cellulose and poly-N-acetyl glucosamine. This section focuses on their structures and their function inside biofilms.
Alginate, a polysaccharide which occurs in brown algae and in different bacteria like
Structure of alginate
Generally, the monomers form a block copolymer with homopolymeric regions of poly-β-D-mannuronate (M-blocks) and poly-α-L-guluronate (G-blocks) as well as heteropolymeric regions (MG-blocks). The absence of G-blocks differentiates alginates produced by
There are 24 genes located on the bacterial chromosome, involved in the production and secretion of alginate in
Alginates can form a gel in the presence of chelating divalent cations. This structure formed is called a Grant “egg-box” [47]. The alginate gel is formed by ionic bonds between the G-rich blocks and divalent cations. The mechanical properties of alginate gels can vary depending on the amounts of guluronic acid present in the polymer. Moreover, alginate gels can be formed in vitro in the presence of proteins such as gelatin [48].
Biosynthesis of bacterial alginate
Cellulose is the most abundant sugar polymer found on the surface of the planet. It is found throughout the living world: in plants, animals, fungi and in bacteria such as
Cellulose has a crystalline structure. Each crystal of cellulose contains numerous glycan chains in parallel orientation. The reducing ends are at one terminus while the non-reducing ends are at the opposite terminus. The structure is not uniform and amorphous regions cohabit with highly crystalline regions.
Structure of cellulose
Genes involved in the production of cellulose in
Cellulose biosynthesis
Cellulose can form a gel at adequate temperatures. Cellulose solutions are liquid at room temperature. Gels can form in a cellulose solution at either high temperature (above 50 °C) or low temperature (less than 10 °C). After gelification, cellulose solutions remain more or less stable in the gel state at room temperature [51, 52]. The gel structure of cellulose may explain the mechanical properties of biofilms formed by bacterial species producing this polymer.
The polysaccharide intercellular adhesin (PIA) or the related poly-N-acetyl glucosamine (PNAG) polymer is required for bacterial adherence and biofilm formation of some bacterial species. This polysaccharide family was first described in
Structure of PNAG
The genes involved in the biosynthesis of PIA are named
PNAG forms a protective matrix around bacterial cells that is also involved in cell-to-cell interactions [53, 54]. PNAG can also interact with eDNA, reinforcing the biofilm matrix structure [58].
Individual strains or one strain put in different environmental conditions, are able to produce several different extracellular polysaccharides. In mucoid strains of
Other polymers are present in the matrix of the biofilm of
PNAG biosynthesis
Structure of teichoic acid
In
Structure of colanic acid
It must be remembered that although different strains can apparently synthesize the same EPS, there can be differences in physical properties especially with respect to viscosity and gel formation. Several biofilm studies have used colanic acid-producing
We and others have previously studied very complex biofilms formed on nanofiltration (NF) membranes during surface water filtration in drinking water production processes [63, 64]. After several years of filtration, the foulant consists in a brown viscous layer covering the entire surface of the membrane [65] (Figure 11).
Visual examination of a fouled NF membrane
Dry weight of the foulant is about 2 g/m2. The NF biofilms harbours mainly exopolysaccharides and proteins, as shown by characteristic ATR-FTIR signals near 1650 cm-1 (amide I), 1550 cm-1 (amide II), 1450 cm-1 (due in part to C-H deformation), 1400 cm-1 (due in part to symetric stretch for the carboxylate ion), 1250 cm-1 (P=O and C-O-C stretching and/or amide III), and in a broad complex region from 1250 to 900 cm-1 (due in part to C-O-C, C-O, ring-stretching vibrations of polysaccharides and the P=O stretch of phosphodiesters) (Figure 12).
ATR-FTIR spectra of a virgin membrane (plain line) and of a fouled membrane (dotted line)
Fluorescence microscopy observations after nucleic acid staining with DAPI and polysaccharides staining with lectins labelled with fluorescein isothiocyanate or tetramethylrhodamine isothiocyanate indicate a high spatial heterogeneity inside the foulant matter with a mean thickness of 32.5 ± 17.7 μm [66] (Figure 13). Examples of lectins that can be used for such polysaccharides staining experiments are peanut agglutinin (PNA) targeting β-gal(1->3)galNAc residues, wheat germ agglutinin (WGA) targeting (glcNAc)2 and NeuNAc residues,
CLSM visualization of the heterogeneity of a NF biofilm after staining with DAPI, TRITC and TITC-labelled lectins. Magnification x630
The microbial cells, mainly composed of bacteria, are localized in the superficial layer of the fouling material and are organized as microcolonies interspersed at the membrane surface. Some algae are also present, as shown by autofluorescence properties. The presence of a dense and wide polysaccharide matrix harbouring few microbial cells at the NF membrane surface has been associated with differences in the efficiency of cleaning procedures against different foulants categories [65, 67]. Polysaccharide residues are found in areas where microcolonies are present and in areas devoid of microbial cells. This polysaccharide organization has been previously observed with environmental biofilms grown in vitro with river water as the sole source of carbon and nutrients [68]. High staining with PNA and BS-1, respectively reveals high occurrence of galactosides residues in the polysaccharide components of the foulants. The BS-1 lectin staining pattern indicates a high degree of spatial organisation with the observation of long and entangled fibers. WGA staining shows short fibers and cloud stained areas. PNA and ConA lectin staining are more interspersed. The polysaccharide composition of the fouling layer changes quantitatively and qualitatively during spring and summer [64]. Lectin staining increases from March to September for all the lectins used. Staining with BS-1 increases constantly in March, June and September. A high increase of binding with PNA, and ConA is observed between March and June, but the binding of these two lectins does not change between June and September. Staining with the WGA is weak in March and June and is higher in September. The lectin-binding changes with time may be linked to an increase of the biomass attached at the membrane surface and to changes among the populations of attached cells. Nutrients, oxygen level and the concentration of metals can influence the exopolymer abundance of environmental model biofilms grown in vitro with river water as the sole source of carbon and nutrients [69]. The modification of these parameters leads to a shift in the glycoconjugate makeup of the biofilms.
Biofilms may be considered to be highly porous polymer gels [70] and diffusion studies demonstrate gel-like characteristics [71]. Previous work has suggested that laboratory-grown and some natural biofilms are viscoelastic in nature [3, 8, 72]. During rotation analysis, a rheofluidification behaviour is observed for NF biofilms [66]. Different mechanisms can explain shear thinning of a biofilm. Break down of links between polymers in the biofilm matrix or deflocculation of particles corresponding to an irreversible modification of the biofilm structure can occur. Such irreversible modifications are unlikely in the experimental conditions published because of the reversibility of viscosity changes with shear rate [66]. Shear thinning of NF biofilms may be related to the polymeric composition of the biofilm matrix. With shear acceleration, polymers may follow the direction of the flow leading to viscosity decrease. This has been previously observed with purified polysaccharides like cellulose [73]. Moreover, bending of biofilm structures in the shear direction during the application of shear stress has been mentioned to explain the viscoelastic response of a mixed culture biofilm [72]. NF biofilms have been submitted to oscillation analysis with a cone-plate rheometer [66]. In such experiments, a sinusoidal oscillation of defined maximum strain and oscillatory frequency is applied to a sample and the storage (
The time-dependent strain response observed in the creep curves clearly indicated that NF biofilms exhibited viscoelastic behaviour. Viscoelasticity is thought to be a general mechanical property of biofilms. A very wide range of elasticity and viscosity values has been previously observed for a wide sample of biofilms formed artificially in laboratory experiments or coming from natural aquatic environments [4, 72, 76]. Thus, it wasn\'t surprising to observe that the rheological properties of NF biofilms are different from the ones of natural biofilms from different aquatic environments like Nymph Creek (Yellowstone National Park) and Chico Hot springs (Montana) algal biofilms [4]. These differences in viscosity and elasticity between biofilms can be related to different exopolysaccharide contents and to different shearing strains. Bacterial and algal alginates are known to have different monomeric composition leading to a stronger binding of cations for bacteria, a property involved in the formation of a stable gel in the presence of ambient Ca2+ cations [77].
The specificity of NF biofilms may be the necessity to resist shear forces applied to the membrane during the filtration process. In the Méry-sur-Oise plant, NF membranes are operated at feed pressure of approximately 10 bars [78]. The high membrane feed pressures may influence the rheological properties of NF biofilms by increasing cohesive forces in the biofilm bulk, increasing forces, which keep the exopolymers to the membrane surface, and thus strengthening the mechanical stability of the biofilm. This may explain at least in part the NF biofilms resistance to industrial cleaning [65].
Shaw et al. have previously shown that the elastic relaxation time varied much less between biofilms of different origins. λ was estimated to be the time required for viscous creep length to equal elastic deformation length (so that memory of initial conditions is lost), i.e., λ ≈
The elastic relaxation time of about 30 minutes lies within the range previously determined for various biofilms [4]. The universality of the viscoelastic transition of biofilms has been suspected to have critical survival impact [4]. The ability of biofilms to deform in response to mechanical stress may be a conserved strategy of defence to enable persistence on surfaces in different flow conditions.
Extracellular polysaccharides are considered as the major structural components of the biofilm matrix. A large variety of polysaccharides required for bacterial adherence and biofilm formation have been described. Polysaccharide molecules can interact with themselves or with ions and proteins. These interactions result from electrostatic attractive forces, repulsive forces, hydrogen bonds, van der Waals interactions and ionic attractive forces. All these forces influence the structure and the stability of the biofilm matrix and the way EPS and polysaccharides can be extracted from the biofilm bulk. A universal protocol for extracellular polysaccharide extraction from the biofilm matrix does not exist. Each study may adapt usual extraction procedures to biofilm specificities and to the nature of the polysaccharide studied. The viscoelasticity nature of biofilms is universal but biofilms in differing environments exposed to different hydrodynamic conditions will encounter changes in the structure, composition and then physical properties of their matrix. Biofilm science is highly exciting since it is a mixture of biology, biophysic, chemistry and much more.
One of the pressing problems of collision zones of the study is to elucidate the evolution of magmatism occurring within them. Display magmatic associations, their petrochemical characteristics reflect the specificity of their manifestations, as well as the development of magmatism from magma generation to the evolution of magmatic melt in the Earth’s crust. Materials on the distribution of rare and rare earth elements in different rock types, as well as other of their geochemical and petrological characteristics allow using the well-known models [1, 2, 3, 4, 5, 6, 7, 8] to analyze some aspects of the processes of birth, evolution, and crystallization of deep magmatic melts.
\nIn this sense, the study of the geochemical characteristics of mantle and crystal sources of magmatism that have come out in a collision like the continent – the continent is quite topical. Therefore, the study late collision volcanism of the Lesser Caucasus is a theoretical and practical interest.
\nSuch, more than 10 geodynamic models have been proposed on the genesis of Cenozoic collision volcanism including the Eastern Anatolian-Caucasian zone. The most popular models are: (1) lateral upper mantle flow of plume material from the East African rifts [3, 6]; (2) break-off of a subduction slab at the early collision (inversion) stage and, as a result, formation of an asthenospheric uplift under the growing collision orogen directly below the Moho boundary [2, 4, 5, 6, 9, 10]; (3) collision magmatism with a leading role of oxidation of deep fluids [1]; (4) Paleogene collision-riftogenic volcanoplutonic magmatism, which occurred from lateral compression of the lithosphere and uplift of a less compacted mantle substrate [11]; (5) relationship of late collision volcanism with longitudinal and latitudinal extension structures, which formed in the suture-collision zone during activation of an area along the junction zone [12]; and (6) collision-riftogenic origin of late collision volcanism with mantle metasomatosis playing a leading role [13].
\nSome of these models do not contradict each other and, as noted by Koronovskii and Demina [1], differ in the heat sources necessary for melting and mechanisms by which sources of late collision volcanism melt. On the basis of seismic tomographic, geological-petrochemical, and geophysical data, we have developed a geodynamic model that relates the geodynamic processes and magmatism at the late collision stage of the evolution of the Lesser Caucasus. We also used seismic and seismic tomographic data for the Lesser Caucasus and adjacent collision regions (Eastern Anatolia, northwestern Iran). Having developed the model and analyzed previous models, we tried to assess the role of lithospheric mantle and asthenosphere in the Late Cenozoic collision volcanism of the Lesser Caucasus.
\nLate Cenozoic geodynamics of the Alpine-Himalayan belt is defined sector of the Mediterranean collision of Eurasian and the Afro-Arabian megaplate [1]. According to modern concepts, folded structures of the Caucasus emerged as a result of their convergence. According to Koronovsky and Demina [1] in the Caucasian segment of the Alpine-Himalayan orogen Late Cenozoic volcanism manifested itself in an atmosphere of NS compression in the region, led to an accelerated movement towards the north of the Arabian plate due to disclosure in the Late Miocene (about 11–10 million years ago) the Red Sea [1]. This collision stage is divided into the stage of mild collisions (late Middle Eocene – Middle Miocene) and the stage of hard collisions (with the Late Miocene to present). This fragmentation of rigid crust was accompanied by volcanism; mark the sites of local stretching of the lithosphere.
\nWithin the Lesser Caucasus Late Cenozoic volcanism covers part of the Transcaucasian transverse uplift (Akhalkalaki volcanic region, Kechut, Aragats volcano-structural sub-zones) and the eastern volcanic zone (Gegham, Vardenis, Syunik, Kaphan – in Armenia, Karabakh, Kelbajar, Nakhchivan in Azerbaijan) (Figure 1).
\nThe distribution of Neogene-Quaternary volcanoes in Eastern Anatolia, the Caucasus, North-West Iran.
Since the Middle Miocene, in these zones formed a high volcanic terrain, located on 2–3 km above sea level. Their association corresponds to the Caucasian age of folding, when the intense collision of the Arabian and Eurasian plates. Due to volcanic activity, there were formed many relatively large volcano-tectonic structures, such as Aragats, Ishygly, and others, erupting volcanoes of the central, central-type fracture (Figure 1).
\nProducts of the Late Cenozoic volcanism in the Azerbaijan distributions upper river Terter and Akera are characterized by lava flows and pyroclastics varied composition.
\nNeogene volcanism in the Lesser Caucasus is mainly manifested itself, starting from the upper Sarmatian, Meotis-Ponte to the Upper Pliocene. However, Rustamov in the south-western part of Lesser Caucasus to carry a Molasse basin (Nakhchivan, Karadag) trachyandesite-teschenite and analcite alkaline basalt-trachyandesite, with the absolute age of 14–15 million years, volcanic fissure and concludes that the Neogene stage of volcanism in the region did not begin in the upper Sarmatians and in the Middle Miocene (based on determining the age of rocks with the K-Ar method, and by the stratigraphic position of the studied rocks) [11].
\nIn the central part of the Lesser Caucasus upper-volcanogenic complex with a capacity of 200 m in the literature described as Agdzhagyz suite and submitted dacite, rhyolite, pyroclastic rhyodacites and their derivatives – dacite and rhyolite tuffs. The layers of fine-sedimentary rocks – carbonaceous shales, lignites are present between the volcanic rocks.
\nVolcanic complex with a thickness of 1150 m Meotis-Pont age first isolated as Basarkechar suite [14] and submitted dacite-trachydasite, andesite and trachyandesite, and latites (Figure 2). This complex with the angular and azimuthally unconformity lies at Agdzhagyz suite and places, Eocene and Cretaceous sediments. They overlap with an angular unconformity Upper Pliocene and Quaternary volcanic rocks in the volcanic highlands (Figure 2).
\nGeological map of Late Cenozoic volcanic associations in the central part of the Lesser Caucasus (Azerbaijan), scale 1:100,000. Compiled by Imamverdiyev [
These volcanic complexes are distinguished in the differentiated andesite-dacite-rhyolite association [13]. Based on geological data, the age of association is defined as the Late Miocene-Low Pliocene. Volcanics of close age are also known in other regions of the Lesser Caucasus. For example, an Early Pliocene andesite-dacite association is developed within the Miskhan-Zangezur and Yerevan-Ordubad zones. Similar rocks are found within the Gegham and Vardenis highlands in Armenia.
\nLate Pliocene-quaternary acidic volcanic associations as independent volcanism are widely developed within the Caucasian segment of the Mediterranean belt. Within Azerbaijan, they are confined Kelbajar and Karabakh uplands and form a dome-shaped volcanoes, and a number of small extrusive domes (Kechaldag, Devegezy) with their lava flows composed of rhyolite, rhyodacites their subalkaline varieties, as well as obsidian and perlite (Figure 2).
\nThe age of acidic volcanic rocks of the Lesser Caucasus in the studied region based on their stratigraphic position was considered late Pliocene-Akchagyl-Absheron [15]. This is confirmed by the absolute age. Thus, according to [16] age of rhyolite volcanic rocks Devegezy identified 0.61 million years, Kechaldagh 0.7 million years. Based on these data, the age of acidic volcanic rocks can be considered Quaternary.
\n\n
This chapter used data from the Neogene-Quaternary volcanism of the Azerbaijan part of Lesser Caucasus based on the authors. Chemical analysis of rocks was determined by the Institute of Geology of Azerbaijan Academy of Sciences X-ray fluorescence method. Rare and rare-earth elements are in Geological and Geochemical Bronitsk expeditions in Russia. Microprobe analysis of mineral composition written in Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences, Moscow and Russian Geological Research Institute (VSEGEI), St. Petersburg. Measuring the isotopic composition of He performed in Geochemistry Institute of Academy of Sciences Russia, also used the data Sr and Nd [17, 18] performed on the material of Armenia and Georgia.
\nThe rocks of the
Photomicrographs of the thin sections of rocks of the andesite-dacite-rhyolite association. Plagioclase and hornblende phenocrysts in andesites and trachyandesites, ×80, with an analyzer; zoned-plagioclase and quartz phenocrysts in dacites, ×80, with an analyzer.
The compositions of plagioclase in the rocks have
Component | \n1 | \n2 | \n3 | \n4 | \n5 | \n6 | \n7 | \n8 | \n9 | \n10 | \n|||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
SiO2\n | \n53.51 | \n50.60 | \n52.28 | \n49.54 | \n48.93 | \n39.57 | \n42.97 | \n42.17 | \n39.32 | \n40.71 | \n|||
TiO2\n | \n0.54 | \n0.27 | \n0.64 | \n0.69 | \n1.52 | \n0.08 | \n2.94 | \n3.00 | \n\n | 2.91 | \n4.09 | \n||
Al2O3\n | \n3.92 | \n2.34 | \n5.00 | \n4.10 | \n6.98 | \n— | \n11.56 | \n10.79 | \n13.55 | \n13.87 | \n|||
FeO* | \n8.46 | \n12.12 | \n7.63 | \n7.53 | \n7.96 | \n14.94 | \n12.08 | \n14.29 | \n12.77 | \n11.51 | \n|||
MnO | \n0.22 | \n0.25 | \n0.13 | \n0.18 | \n0.13 | \n0.28 | \n0.14 | \n0.25 | \n\n | 0.16 | \n0.10 | \n||
MgO | \n14.63 | \n12.81 | \n15.09 | \n15.46 | \n13.72 | \n44.86 | \n13.11 | \n13.06 | \n12.91 | \n14.44 | \n|||
CaO | \n18.50 | \n20.43 | \n18.65 | \n19.94 | \n19.97 | \n0.22 | \n9.94 | \n10.68 | \n12.06 | \n11.70 | \n|||
Na2O | \n0.52 | \n0.47 | \n0.56 | \n0.64 | \n0.53 | \n— | \n2.48 | \n2.76 | \n\n | 2.88 | \n2.63 | \n||
K2O | \n— | \n— | \n— | \n0.04 | \n0.04 | \n— | \n0.92 | \n0.92 | \n\n | 1.42 | \n1.49 | \n||
Total | \n100.27 | \n99.65 | \n100.0 | \n98.11 | \n99.58 | \n99.95 | \n96.14 | \n97.92 | \n97.99 | \n100.54 | \n|||
SiO2\n | \n58.47 | \n64.59 | \n\n | 62.87 | \n57.06 | \n52.52 | \n\n | 51.39 | \n|||||
Al2O3\n | \n25.23 | \n19.48 | \n\n | 24.02 | \n26.82 | \n28.94 | \n\n | 30.62 | \n|||||
FeO* | \n0.42 | \n0.09 | \n\n | 0.22 | \n0.36 | \n0.43 | \n\n | 0.75 | \n|||||
CaO | \n7.16 | \n0.17 | \n\n | 5.55 | \n8.68 | \n13.17 | \n\n | 12.99 | \n|||||
Na2O | \n7.61 | \n4.12 | \n\n | 6.96 | \n6.14 | \n4.39 | \n\n | 3.79 | \n|||||
K2O | \n0.63 | \n11.22 | \n\n | 1.02 | \n0.87 | \n0.12 | \n\n | 0.23 | \n|||||
Total | \n99.52 | \n99.66 | \n100.63 | \n99.93 | \n99.52 | \n99.77 | \n|||||||
TiO2\n | \n1.10 | \n4.14 | \n\n | 5.49 | \n6.10 | \n5.41 | \n\n | 11.10 | \n|||||
Al2O3\n | \n0.60 | \n2.71 | \n\n | 3.04 | \n4.55 | \n4.23 | \n\n | 5.10 | \n|||||
Fe2O3\n | \n— | \n\n | 65.89 | \n\n | 53.62 | \n53.08 | \n60.33 | \n\n | 43.22 | \n||||
FeO | \n91.0 | \n\n | 14.02 | \n\n | 28.39 | \n19.60 | \n15.68 | \n\n | 17.76 | \n||||
MgO | \n4.0 | \n\n | 2.95 | \n\n | 1.99 | \n5.97 | \n7.69 | \n\n | 4.06 | \n||||
Total | \n96.70 | \n89.71 | \n82.53 | \n89.30 | \n93.34 | \n81.24 | \n
Chemical composition (wt %) of (1–5) clinopyroxene, (6) olivine, (7–10) amphibole, (11–16) plagioclase, and (17–22) magnetite from the late Cenozoic volcanic rocks [13, 19].
Note: Rocks:
Analyses of rock-forming minerals were carried out at the analytical laboratories of the Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences, Moscow State University; Moscow and Russian Geological Research Institute (VSEGEI), St. Petersburg on a Camebax microprobe. Magnetite was analyzed by conventional chemical techniques at Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Analysts A.I. Tsepin, V.K. Garanin, and V.S. Pavshukov.
\nThe rocks of the
The rocks of the
Photomicrographs of the thin sections of rocks of the trachybasalt-trachyandesite association. Trachyandesite (one can see a glomeroporphyritic cluster of clinopyroxenes and opacitized hornblende, plagioclase, and clinopyroxene phenocrysts), ×80, with an analyzer; moderately alkaline olivine basalt with olivine, clinopyroxene, and plagioclase phenocsrysts, ×80, with an analyzer; crushed olivine in trachybasalt, ×80, with an analyzer; trachydolerite, ×80, with an analyzer.
Clinopyroxene rock associations more calcium and composition correspond to augite and salite. Plagioclases have relatively basic composition
The rocks occur as idiomorphic porphyritic crystals of apatite precipitates; the number of which reaches 0.5–1.25%, and fluoro-apatite. Often present as inclusions in phenocrysts of clinopyroxene and hornblende, indicating that the earlier crystallization.
\nIn the rocks of andesite-dacite-rhyolite and trachybasalt-trachyandesites associations there are two types of inclusions: 1-inclusion, representing cumulates parent rocks, (pyroxenites, gabbro, hornblendites, etc.), 2-crustal inclusion - xenoliths of country rocks, trapped melts of crustal rocks (gabbro-amphibolites, quartz-diorite, quartz-feldspar rocks, etc.). Typical mantle inclusions in rocks associations are absent. Along with the rocks in the rocks of these associations are marked megacrystes sanidine, clinopyroxene, amphibole, phlogopite.
\nThe association rocks form a continuous series from andesites to rhyolites by SiO2 contents (SiO2 > 60%) (Table 2), and the ratio (Na2O + K2O)-SiO2 [21] are the rocks of normal alkalinity (Figure 5) (some rocks – mid alkaline) in the diagram K2O-SiO2 [22] most of the samples falls within the high K calc-alkaline series, the diagram FeO */ MgO-SiO2 composition points are located in the field calc-alkaline series.
\n\n | 1 | \n2 | \n3 | \n4 | \n5 | \n6 | \n7 | \n8 | \n9 | \n10 | \n11 | \n12 | \n13 | \n14 | \n15 | \n16 | \n|
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Elements | \n40 | \n8 | \n15 | \n100 | \n190 | \n194 | \n106 | \n74 | \n96 | \n12/13 | \n6/174 | \nOA 409 | \nMA 19 | \n105 | \n129 | \n132 | \n|
SiO2\n | \n61.09 | \n62.1 | \n62.32 | \n62.99 | \n63.75 | \n63.89 | \n64.81 | \n65.99 | \n68.19 | \n73.99 | \n75.51 | \n76.75 | \n77.01 | \n51.23 | \n48.35 | \n48.88 | \n|
TiO2\n | \n0.59 | \n0.49 | \n0.58 | \n0.6 | \n0.81 | \n0.75 | \n0.6 | \n0.52 | \n0.27 | \n0.01 | \n0.01 | \n0.08 | \n0.09 | \n1.39 | \n1.2 | \n1.57 | \n|
Al2O3\n | \n15.7 | \n15.41 | \n16.9 | \n16.6 | \n14.81 | \n17.15 | \n17.03 | \n16.41 | \n15.77 | \n13.48 | \n13.79 | \n12.85 | \n12.67 | \n16.49 | \n15.77 | \n15.86 | \n|
Fe2O3\n | \n3.47 | \n2.5 | \n3.91 | \n3.28 | \n3.91 | \n4.94 | \n3.38 | \n3.59 | \n1.69 | \n1.2 | \n0.55 | \nn.d. | \nn.d. | \n7.74 | \n6.38 | \n5.61 | \n|
FeO | \n1.29 | \n0.94 | \n1.01 | \n1.29 | \n2.46 | \n0.43 | \n0.73 | \n0.28 | \n0.43 | \n1.78 | \n0.71 | \n0.66 | \n0.71 | \n0.86 | \n2.16 | \n2.73 | \n|
MnO | \n0.06 | \n0.06 | \n0.04 | \n0.09 | \n0.1 | \n0.09 | \n0.03 | \n0.09 | \n0.04 | \n0.01 | \n0.01 | \n0.08 | \n0.06 | \n0.13 | \n0.15 | \n0.14 | \n|
MgO | \n1.85 | \n1.77 | \n1.95 | \n1.9 | \n3.18 | \n1.86 | \n1.43 | \n1.31 | \n0.05 | \n0.14 | \n0.36 | \n0.11 | \n0.05 | \n6.04 | \n6.74 | \n6.29 | \n|
CaO | \n4.85 | \n5.34 | \n4.24 | \n4.32 | \n6.13 | \n5.25 | \n3.97 | \n3.19 | \n1.32 | \n0.53 | \n1.9 | \n0.44 | \n0.47 | \n8.33 | \n9.8 | \n9.09 | \n|
Na2O | \n4.19 | \n3.93 | \n4.07 | \n4.08 | \n3.37 | \n3.3 | \n4.27 | \n4.05 | \n4.57 | \n3.27 | \n2.92 | \n4.44 | \n4.06 | \n4.22 | \n3.61 | \n4 | \n|
K2O | \n3.54 | \n2.73 | \n2.95 | \n3.08 | \n2.37 | \n1.87 | \n3.47 | \n2.55 | \n4.14 | \n4.87 | \n3.96 | \n4.59 | \n4.86 | \n1.42 | \n1.96 | \n1.92 | \n|
P2O5\n | \n0.41 | \n0.38 | \n0.28 | \n0.3 | \n0.28 | \n0.35 | \n0.33 | \n0.23 | \n0.06 | \n0.01 | \n0.01 | \nn.d. | \n0.01 | \n0.65 | \n1.03 | \n1.18 | \n|
LOI | \n0.81 | \n1.96 | \n0.54 | \n0.46 | \n0.13 | \n0.83 | \n0.47 | \n0.96 | \n0.27 | \n0.38 | \n0.54 | \nn.d. | \nn.d. | \n0.7 | \n1.5 | \n0.93 | \n|
Total | \n98.63 | \n99.31 | \n99.08 | \n98.1 | \n98.3 | \n99.21 | \n100.72 | \n98.15 | \n99.23 | \n99.67 | \n100.27 | \n100 | \n99.99 | \n99.2 | \n98.65 | \n98.1 | \n|
Rb | \n83 | \n66 | \n63 | \n74 | \n42 | \n51 | \n86 | \n72 | \n97 | \n160 | \n180 | \n209 | \n174 | \n23 | \n34 | \n32 | \n|
Li | \n20 | \n14 | \n19 | \n19 | \n19 | \n8 | \n12 | \n14 | \n13 | \n67 | \n70 | \nn.d. | \nn.d. | \n9 | \n9 | \n9 | \n|
Sr | \n1105 | \n935 | \n935 | \n850 | \n520 | \n860 | \n935 | \n833 | \n420 | \n150 | \n100 | \n10 | \n16 | \n1190 | \n1700 | \n1700 | \n|
Ba | \n1250 | \n640 | \n650 | \n690 | \n400 | \n850 | \n690 | \n760 | \n830 | \n100 | \n100 | \n10 | \n26 | \n748 | \n780 | \n1060 | \n|
Cr | \n120 | \n180 | \n180 | \n180 | \nn.d. | \nn.d. | \n180 | \n100 | \nn.d. | \n30 | \nn.d. | \n3.13 | \n2.75 | \n346 | \n412 | \n270 | \n|
V | \n170 | \n40 | \n60 | \n60 | \n150 | \n110 | \n40 | \n100 | \n40 | \nn.d. | \n20 | \nn.d. | \nn.d. | \n170 | \n170 | \n210 | \n|
Ni | \n24 | \n22 | \n30 | \n31 | \n69 | \n25 | \n32 | \n25 | \n15 | \n20 | \n3 | \nn.d. | \nn.d. | \n115 | \n113 | \n110 | \n|
Co | \n20 | \n30 | \n35 | \n16 | \n34 | \n24 | \n3 | \n15 | \n9 | \n5 | \n3 | \n0.1 | \n0.2 | \n31 | \n29 | \n50 | \n|
Zr | \n178 | \n150 | \n160 | \n150 | \n130 | \n160 | \n170 | \n150 | \n240 | \n100 | \n80 | \n83 | \n86 | \nn.d. | \n230 | \n240 | \n|
Nb | \n12 | \n10 | \n11 | \n10 | \n8 | \n11 | \n14 | \n14 | \n17 | \n15 | \n10 | \n37 | \n34 | \nn.d. | \n20 | \n18 | \n|
Ta | \n0.84 | \n0.82 | \n0.72 | \n0.94 | \n0.46 | \n0.77 | \n1.4 | \n1.1 | \n1.2 | \nn.d. | \nn.d. | \n3.11 | \n2.71 | \n0.85 | \n0.92 | \n0.92 | \n|
Hf | \n4.8 | \n4 | \n3.6 | \n3.3 | \n3.8 | \n4.3 | \n4.7 | \n4.2 | \n6 | \nn.d. | \nn.d. | \n3.87 | \n3.51 | \n4.7 | \n4.6 | \n5.2 | \n|
Th | \n11 | \n11 | \n9.3 | \n10 | \nn.d. | \n10 | \n18 | \n16 | \n5.2 | \n25 | \n31 | \n37.3 | \n34.5 | \n3.2 | \n2.6 | \n2.6 | \n|
U | \n2.7 | \n4.7 | \n5.7 | \n4.4 | \n4 | \n4 | \n5.4 | \n3.3 | \n14 | \n9.3 | \n12 | \n12.1 | \n10.2 | \n4 | \n4 | \n4 | \n|
La | \n45 | \n37 | \n43 | \n36 | \n23 | \n47 | \n47 | \n38 | \n47 | \n33.5 | \n36 | \n23.5 | \n30.7 | \n40 | \n65 | \n63 | \n|
Ce | \n88 | \n73 | \n77 | \n76 | \n57 | \n91 | \n87 | \n74 | \n78 | \n60 | \n59 | \n41.4 | \n53 | \n81 | \n130 | \n130 | \n|
Sm | \n4.2 | \n3.6 | \n3.9 | \n4.2 | \n7.5 | \n5.1 | \n3.6 | \n4.4 | \n5 | \n3 | \n2.8 | \n2.42 | \n2.51 | \n5.3 | \n9.5 | \n9.8 | \n|
Eu | \n1.2 | \n1 | \n1.2 | \n1 | \n1.6 | \n1.6 | \n1.1 | \n0.95 | \n0.79 | \n0.2 | \n0.65 | \n0.1 | \n0.16 | \n1.7 | \n2.5 | \n2.5 | \n|
Tb | \n0.67 | \n0.43 | \n0.56 | \n0.58 | \n1.1 | \n0.9 | \n0.44 | \n0.42 | \n0.57 | \n0.6 | \n0.68 | \n0.15 | \n0.13 | \n0.88 | \n1.5 | \n1.3 | \n|
Yb | \n1.2 | \n1.3 | \n1.4 | \n1.5 | \n3.6 | \n1.8 | \n1.3 | \n1.3 | \n1.4 | \n2.3 | \n2.3 | \n1.3 | \n1.32 | \n2.4 | \n2.7 | \n2.4 | \n|
Lu | \n0.19 | \n0.18 | \n0.2 | \n0.2 | \n0.69 | \n0.23 | \n0.17 | \n0.17 | \n0.18 | \n0.32 | \n0.42 | \n0.24 | \n0.22 | \n0.42 | \n0.39 | \n0.33 | \n|
Y | \n36 | \n16 | \n11 | \n10 | \n11 | \n16 | \nn.d. | \n11 | \n29 | \n10 | \n10 | \n11 | \n11 | \n31 | \n30 | \n34 | \n
\n | 17 | \n18 | \n19 | \n20 | \n21 | \n22 | \n23 | \n24 | \n25 | \n26 | \n27 | \n28 | \n29 | \n30 | \n31 | \n32 | \n33 | \n
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Elements | \n134 | \n21 | \n57 | \n208 | \n53 | \n87 | \n109 | \n120 | \n167 | \n174 | \n13 | \n25 | \n33 | \n143 | \n160 | \n185 | \n73/P | \n
SiO2\n | \n48.05 | \n51.84 | \n49.42 | \n52.97 | \n53.32 | \n53.05 | \n54.92 | \n55.67 | \n54.31 | \n54.01 | \n57.66 | \n58.52 | \n59.85 | \n57.08 | \n59.28 | \n57.85 | \n67.8 | \n
TiO2\n | \n1.45 | \n1.36 | \n1.44 | \n1.3 | \n0.97 | \n1.14 | \n1.14 | \n1.08 | \n1.18 | \n1.5 | \n0.79 | \n0.82 | \n0.8 | \n1.24 | \n1.24 | \n0.75 | \n0.48 | \n
Al2O3\n | \n15.53 | \n16.64 | \n16.27 | \n16.46 | \n17.39 | \n17.46 | \n16.38 | \n17.13 | \n16.82 | \n17.49 | \n16.41 | \n16.23 | \n16.57 | \n17.25 | \n16.55 | \n17.7 | \n15.7 | \n
Fe2O3\n | \n3.55 | \n6.11 | \n7.16 | \n7.04 | \n6.11 | \n5.66 | \n4.54 | \n6.59 | \n5.02 | \n5.79 | \n4.09 | \n4.8 | \n4.88 | \n4.62 | \n4.95 | \n3.79 | \nn.d. | \n
FeO | \n4.46 | \n1.01 | \n0.72 | \n0.3 | \n0.57 | \n1.65 | \n2.59 | \n0.43 | \n2.17 | \n2.46 | \n1.87 | \n0.87 | \n0.5 | \n3.09 | \n1.3 | \n1.88 | \n3 | \n
MnO | \n0.13 | \n0.11 | \n0.12 | \n0.12 | \n0.1 | \n0.13 | \n0.1 | \n0.12 | \n0.12 | \n0.12 | \n0.05 | \n0.09 | \n0.11 | \n0.11 | \n0.1 | \n0.13 | \n0.05 | \n
MgO | \n6.81 | \n4.42 | \n5.27 | \n3.65 | \n3.81 | \n4.12 | \n3.76 | \n4.66 | \n3.84 | \n3.37 | \n3.18 | \n3.23 | \n2.67 | \n2.29 | \n2.79 | \n2.77 | \n1.1 | \n
CaO | \n9.19 | \n8.58 | \n9.1 | \n7 | \n7.17 | \n6.71 | \n6.88 | \n6.24 | \n6.66 | \n6.8 | \n6.25 | \n6.24 | \n5.61 | \n6.09 | \n5.82 | \n6.12 | \n2.2 | \n
Na2O | \n4.18 | \n4.14 | \n3.22 | \n4.39 | \n5.03 | \n4.27 | \n0.7 | \n4.22 | \n4.78 | \n4.53 | \n3.85 | \n4 | \n4.38 | \n4.53 | \n4.65 | \n4.53 | \n5.5 | \n
K2O | \n1.73 | \n2.92 | \n2.48 | \n3.16 | \n2.8 | \n2.77 | \n2.17 | \n2.6 | \n2.96 | \n3.25 | \n3.01 | \n2.8 | \n3.11 | \n2.87 | \n3.46 | \n2.89 | \n4 | \n
P2O5\n | \n1.13 | \n1.31 | \n1.04 | \n0.93 | \n0.82 | \n0.83 | \n0.94 | \n0.58 | \n0.75 | \n0.94 | \n0.57 | \n0.68 | \n0.79 | \n0.68 | \n0.76 | \n0.44 | \n0.35 | \n
LOI | \n1.79 | \n0.61 | \n1.9 | \n1.1 | \n0.14 | \n0.35 | \n0.85 | \n0.41 | \n0.19 | \n0.44 | \n0.64 | \n0.4 | \n0.35 | \n0.27 | \n0.2 | \n1.15 | \n0.01 | \n
Total | \n98 | \n99.05 | \n98.14 | \n98.42 | \n98.23 | \n98.14 | \n98.47 | \n99.07 | \n98.8 | \n100.7 | \n98.32 | \n98.68 | \n99.72 | \n100.12 | \n101.1 | \n100 | \n100.19 | \n
Rb | \n34 | \n60 | \n31 | \n60 | \n37 | \n36 | \n42 | \n54 | \n70 | \n43 | \n55 | \n49 | \n66 | \n40 | \n56 | \n48 | \n70 | \n
Li | \n9 | \n14 | \n9 | \n13 | \n12 | \n12 | \n13 | \n14 | \n14 | \n13 | \n10 | \n12 | \n16 | \n14 | \n17 | \n15 | \n20 | \n
Sr | \n1700 | \n2635 | \n2550 | \n1900 | \n1615 | \n1615 | \n1445 | \n1020 | \n1275 | \n1785 | \n1360 | \n1275 | \n1615 | \n1647 | \n1360 | \n790 | \n1356 | \n
Ba | \n990 | \n1300 | \n1170 | \n1170 | \n1140 | \n1000 | \n1080 | \n680 | \n1100 | \n1770 | \n830 | \n1060 | \n900 | \n900 | \n1016 | \n930 | \n1100 | \n
Cr | \n450 | \n170 | \n220 | \nn.d. | \n157 | \n200 | \n224 | \n280 | \nn.d. | \nn.d. | \n160 | \n188 | \n100 | \nn.d. | \nn.d. | \nn.d. | \n140 | \n
V | \n260 | \n140 | \n200 | \n150 | \n200 | \n200 | \n150 | \n170 | \n240 | \n150 | \n80 | \n130 | \n100 | \n140 | \n140 | \n110 | \n70 | \n
Ni | \n100 | \n43 | \n64 | \n45 | \n46 | \n48 | \n34 | \n65 | \n40 | \n39 | \n50 | \n54 | \n50 | \n33 | \n29 | \n31 | \n13.5 | \n
Co | \n24 | \n26 | \n50 | \n45 | \n19 | \n50 | \n22 | \n45 | \n55 | \n35 | \n45 | \n16 | \n20 | \n40 | \n19 | \n13 | \n11 | \n
Zr | \n250 | \n200 | \n220 | \n250 | \n180 | \n210 | \n250 | \n190 | \n250 | \n250 | \n190 | \n180 | \n220 | \n207 | \n200 | \n160 | \n303 | \n
Nb | \n20 | \n28 | \n27 | \n23 | \n10 | \n21 | \n18 | \n19 | \n23 | \n22 | \n18 | \n13 | \n18 | \n21 | \n23 | \n15 | \n33 | \n
Ta | \n0.96 | \n1.2 | \n1.7 | \n1.5 | \n0.8 | \n0.99 | \nn.d. | \n1 | \n1.4 | \n1.3 | \n0.81 | \n0.87 | \n1 | \n0.98 | \n1.4 | \n0.88 | \n1.43 | \n
Hf | \n5.1 | \n4.5 | \n4.6 | \n5.2 | \n4.2 | \n4.7 | \nn.d. | \n4.4 | \n4.8 | \n5 | \n4.8 | \n4.5 | \n5.3 | \n4.7 | \n4.7 | \n4.3 | \n6.6 | \n
Th | \n4.9 | \n5.2 | \n7.4 | \n8.1 | \n6.1 | \n5.3 | \nn.d. | \n5.6 | \n6.4 | \n6.5 | \n6.3 | \n6.5 | \n8.8 | \n5.6 | \n9.5 | \n9.7 | \n3.2 | \n
U | \n4 | \n4 | \n4 | \n3 | \n4 | \n4 | \nn.d. | \n4 | \n3 | \n4 | \n3.6 | \n6.3 | \n4 | \n4 | \n4 | \n4 | \n12.2 | \n
La | \n62 | \n76 | \n77 | \n77 | \n59 | \n66 | \n69 | \n52 | \n96 | \n80 | \n60 | \n60 | \n70 | \n59 | \n67 | \n48 | \n72 | \n
Ce | \n120 | \n150 | \n160 | \n160 | \n120 | \n130 | \n130 | \n98 | \n120 | \n160 | \n120 | \n120 | \n120 | \n120 | \n140 | \n88 | \n115 | \n
Sm | \n9.1 | \n10 | \n11 | \n9.5 | \n6.3 | \n7.4 | \n7.4 | \n5.9 | \n7.4 | \n9.8 | \n5.7 | \n5.3 | \n5.8 | \n7.2 | \n8.6 | \n5.7 | \n6 | \n
Eu | \n2.4 | \n2.5 | \n2.8 | \n2.5 | \n1.6 | \n1.8 | \n2 | \n1.7 | \n2.2 | \n2.7 | \n1.6 | \n1.7 | \n1.7 | \n2 | \n2 | \n1.4 | \n1.5 | \n
Tb | \n1.1 | \n1 | \n1.3 | \n1.3 | \n1 | \n1.4 | \n1.1 | \n0.9 | \n1.1 | \n0.95 | \n1.1 | \n0.94 | \n0.85 | \n1.8 | \n1.2 | \n0.59 | \n1.12 | \n
Yb | \n2.2 | \n1.8 | \n1.9 | \n2.3 | \n1.8 | \n2.1 | \n2 | \n2 | \n2.2 | \n2 | \n1.8 | \n1.9 | \n2 | \n2.2 | \n2.1 | \n1.3 | \n2.1 | \n
Lu | \n0.31 | \n0.22 | \n0.34 | \n0.34 | \n0.25 | \n0.28 | \n0.22 | \n0.39 | \n0.31 | \n0.27 | \n0.31 | \n0.3 | \n0.26 | \n0.25 | \n0.24 | \n0.24 | \n0.25 | \n
Y | \n29 | \n16 | \n23 | \n23 | \n20 | \n24 | \n21 | \n19 | \n27 | \n25 | \n14 | \n15 | \n19 | \n16 | \n19 | \n15 | \n10 | \n
Major (wt %) and trace-element (ppm) composition of a representative rocks of the Late Cenozoic associations in the Lesser Caucasus (Azerbaijan).
1–9 – andesite-dacite-rhyolite; 10–14 – rhyolitic association; 15–33 – trachybasalt-trachyandesite associations.
Total alkali vs. -SiO2 (TAS) classification diagrams [
The rocks of this association are characterized by different contents of major elements. In volcanic rocks with increasing SiO2 content decreases TiO2, Al2O3, Fe2O3, MgO, CaO, and P2O5, due to fractionation of titanomagnetite, clinopyroxene, plagioclase, and possibly apatite. Weak rates increased content of K2O. Na2O is distributed evenly, but also an increase in the number of its slower rate. The reason for this pattern may be a potassium feldspar in the more acidic varieties of rocks.
\nRocks associations, in contrast to the previous rock associations, are characterized by ultra-structure and high alkalinity. There is approximately equal ratio of Na2O and K2O and low contents of CaO, MgO, and FeO (Table 2). In the normative composition of the rocks are calculated high content of salic components of quartz, feldspar, and corundum.
\nFor silica rock associations form a continuous series from basalts to andesites (Table 2) and belong to the mildly alkaline series (Figure 5). In the diagram K2O-SiO2 composition points fall in the region high-K calc-alkaline and shoshonite series. In rock associations in the range of “trachybasalt-basaltic trachyandesite” with increasing silica content of TiO2, MgO, Fe2O3, CaO, and P2O5 is reduced to a large extent, the contents of the same Al2O3, Na2O decreases the slow pace. In the transition to trachyandesites content of these elements varies in a narrow range. The maximum content of MgO is observed in trachybasalts and alkaline olivine basalts and varies from 3.97 to 6.81% (Table 2), and the coefficient of Mg≠ (M) from 56 to 71. In subsequent decrease differentiates the content of MgO and “M.”
\nIn the normative part of some mildly alkali olivine basalts and trachybasalts calculated normative nepheline and olivine, and in more acidic differentiates calculated hypersthene and quartz. Normative and mineral composition reflects the characteristic feature of the association: transition nepheline-normative, olivine containing mildly alkaline rocks to hypersthene-normative, and sometimes quartz-bearing alkaline rocks.
\nThe concentrations of rare and rare earth elements are in rocks of andesite-dacite-rhyolite association as a whole regularly changing. Thus, the concentration of lithophile elements increases from andesite to rhyolites (Rb from 44 to 128 ppm, Th 6 to 24 ppm) (Table 2). From the coherent elements in increasing the acidity of rocks in general, the content of V, Cr, Co, and Ni decreases. These elements are the same Sr form of silica negative dependence. Positive, but more vague correlation with silica form the content of Y and highly charged elements (HFSE – Nb, Zr, Hf). The above features show the leading role of crystallization differentiation in the association of rocks. As shown Dilek et al. [2] comparison of impurity elements rocks andesite-dacite-rhyolite association and the primitive mantle [23] shows the reduced content of Nb and Ta and elevated levels of lung large ionic lithophile elements (Rb, Ba, Th, La, Ce, and Sr) (LILE). Thus, in relation to the primitive mantle, there is a maximum Rb, Ba, Th, La, Ce, Sr, and negative Ta-Nb anomalies (Figure 6).
\nNormalized to the primitive mantle [
It is conceivable that this feature brings these rocks with subduction volcanic associations. From the same type of rocks of andesite-dacite-rhyolite association rocks rhyolite associations differ depleted femic components, a lower content of iron group elements, highly charged elements, and enrichment of ore elements in the earth crust, as well as lithophile elements (Pb, Th, U). The distribution of trace elements normalized to primitive mantle for the rhyolite showed that, like the rock of the previous association, rhyolite is enriched in LILE and depleted in highly charged elements. However, the nature of the schedule of rhyolites differs from the schedule of rocks of the previous association and is similar to the composition of the rocks of the earth’s crust, which indicates a different genesis of the rocks of this association. In the rocks, trachybasalt-trachyandesite association occurs in about the same pattern as in the rocks of andesite-dacite-rhyolite association, but more clearly. Rocks of this association are inherent to the high content of Rb, Ba, La, Sr, as well as high values of La/Yb, La/Sm relations. Compared with the composition of primitive mantle [23], alkaline basalts are enriched in most LILE and some highly charged elements: Rb, Ba, Th, La, Ce, Sr, Zr (Figure 7).
\nNormalized to the primitive mantle [
Geochemical data for this association show that the diversity of species association is due mainly to fractional crystallization. This is evidenced by: (1) with increasing SiO2 content decreases compatible elements (Cr, Ni) and increasing concentrations of incompatible elements (Rb, Th, U) due to fractionation of olivine and clinopyroxene, and (2) revealed clear positive correlation connection LREE with phosphorus, calcium and fluoride, due to the concentration of light rare earth elements in apatite (the distribution coefficients of REE for apatite is 10–100). These data indicate that fractional crystallization is particularly important for trachybasalts and basaltic trachyandesites. In the process of differentiation of the content of trace elements naturally varies depending on the composition of the melt, its temperature, as well as the composition and crystal-chemical properties of rock-forming minerals. Content and types of spectra of these elements of the rock trachybasalt-trachyandesite associations of the Lesser Caucasus are close to the rocks of oceanic islands and the rift zones formed from the enriched mantle source. Similarity of plots, the distribution of elements on the primitive mantle may indicate comagmatic members of the association.
\nFor the Neogene-Quaternary rocks of the Lesser Caucasus, we have obtained for the seven samples of volcanic rocks and their nodules isotopic compositions of He (Table 2). The highest ratio of 3He/4He (3He/4He = 0.93 × 10−5) is characteristic for alkali olivine basalts, which brings them to the mantle derivatives. Approximately, the same value is obtained for amphibole megacrysts from trachyandesite approaching the isotope ratios of primary helium mantle reservoirs (1–5 × 10−5) [24] and to the gases carbon sources, the most active areas associated with manifestations of modern volcanism of the Lesser Caucasus (3He/4He = 10−5) [24]. A fractional difference between the rocks of trachybasalt-trachyandesite association, their nodules, as well as andesite of andesite-dacite-rhyolite association has lower values of helium isotopes (Table 3). These data indicate that differentiate the first association, incorporation, and andesite second association crystallized in the earth crust.
\nNo samples | \nRocks and minerals | \n\n3He/4He·10−6\n | \n\n4He·10−6\n | \n
---|---|---|---|
132 | \nAlkaline olivine basalte | \n9.29 (±1.46) | \n0.604 (±0.006) | \n
21 | \nTrachybasalte | \n1.76 (±0.27) | \n2.70 (±0.03) | \n
13 | \nTrachyandesite | \n1.05 (±0.18) | \n1.54 (±0.02) | \n
15 | \nAndesite | \n0.924 (±0.162) | \n2.36 (±0.02) | \n
Nodules | \n\n | \n | |
25-b | \nPyroxsenites | \n3.33 (±0.49) | \n3.43 (±0.03) | \n
13-m | \nMegacryste amphybole | \n9.39 (±1.42) | \n2.90 (±0.03) | \n
Isotopic composition He in Late Cenozoic rocks of the Lesser Caucasus.
Unfortunately, Sr and Nd isotope data for Late Cenozoic volcanics in the Azerbaijani part of the Lesser Caucasus are absent. There is anecdotal evidence about the Armenian and Georgian part of the Lesser Caucasus. Chernyshev and his co-workers [17, 18] determined the absolute age of alkali basalts Javakheti Plateau; they proposed a new version of the geochronological scale of the Neogene-Quaternary magmatism of the Caucasus. Dan precises absolute age of rhyolite volcanism for different volcanic highlands of the Lesser Caucasus [16]. Data above authors argue that the dominant role in the petrogenesis of lavas played by processes of fractional crystallization and contamination of the parent melts geochemically distinct from them, crustal matter [17]. A sour rhyolite volcanism developed in the context of tectonic and thermal activity of mantle lesions and relationship with the processes of local anatexis in the lower crust zones of metamorphism [16]. Our petrology and geochemistry data confirm these findings.
\nThis section discusses the nature of the mantle substrate region under study as well as the origin of each of volcanic associations.
\nThese isotopic compositions of Sr and Nd for late Cenozoic volcanic rocks of the Lesser Caucasus show that the primary melts to produce a mantle sources. Acid rock has mostly crustal origin. There have been offset mantle and crustal magmas. In general, this assumption is acceptable for the Azerbaijan part of the region.
\nA common feature for most of the Neogene-Quaternary volcanic rocks of the Lesser Caucasus is a relative enrichment in light REE and large lithophile elements (Rb, Ba), and weak depletion for heavy rare earth elements, as well as Nb, Ta, Hf [1, 2, 3, 7, 8, 13, 18, 25, 26, 27, 28, 29, 30, 31, 32, 33]. These geochemical data confirm the presence of restite of garnet in the magmatic source for the andesite-dacite-rhyolite and trachybasalt-trachyandesite associations. In addition, we believe in the petrogenesis of Late Cenozoic collision basaltoids important role played mantle substance metasomatically processed by previous subduction processes, as evidenced by the relatively high oxidized rocks associations.
\n\nFigure 8 (Ce/Yb)MN – Yb MN shows the calculated line of equilibrium partial melting of garnet peridotite with different contents of garnet. Calculated trends melting portions of garnet peridotite, containing 2.5, and 4% garnet, borrowed from [34]. As seen from Figure 8, composition points of rocks of andesite-dacite-rhyolite associations are in the range of values with a relatively high degree of melting (3–10%) mantle source containing 4% garnet. Lineups alkali basaltoids trachybasalt-trachyandesite association on this chart are in the range of values with a low degree of melting (1–2.5%) garnet peridotite and, apparently, mantle source was more metasomatized [13]. It can be assumed that a lower degree of melting of the mantle of the substrate led to the association of basaltic melt at high alkalinity and a significant enrichment of the melt K, P, F, Ba, LREE due priority to the melting of phlogopite, apatite, amphibole, which are the main carriers of these elements.
\nNormalized to primitive mantle [
At present, the association of these volcanic rocks is often associated with the association of subduction “windows” (slab-window) and sees the result of decompression melting of asthenospheric diapir. These volcanics differ from typical subduction magma and have geochemical characteristics of OIB sources. They are described for the active continental margin of North America, Philippines, Kamchatka, East Sikhote-Alin [35, 36]. For collision volcanics, this idea is developed [3, 4, 5, 6, 7, 8, 9, 10, 25, 26, 30, 31, 32, 33, 37]. Such rocks are called adakites. They are characterized by high ratio LREE/HREE and are formed by melting of garnet containing material (eclogite) oceanic plate.
\nNote that we also do not deny the delamination subduction lithospheric slab in the association of Late Cenozoic volcanic rocks of the Lesser Caucasus [2, 7, 8, 30, 31]. This is evidenced Seismic and some of petrology and geochemistry data. Part of Late Cenozoic andesite and dacite of the Lesser Caucasus can be considered derivatives adakites melts. They (La/Yb)n vary from 17.5 to 26.4, the concentration of Y from 6 to 13 ppm, Yb from 1.2 to 1.8 ppm. Figure Sr/Y-Y majority of species fall into the field adakites [38] (Figure 9).
\nSr/Y vs. Y in the Neogene andesite-dacite-rhyolite association. The range of adakite and arc magmatic rocks is after [
Thus, it is found that the rocks of the Neogene andesite-dacite-rhyolite and Upper Pliocene-Quaternary trachybasalt-trachyandesite association smelt garnet sources at a depth of not less than 60–80 km [8, 33]. Not be excluded on the association of andesite melting subduction oceanic crust [39]. As Upper Pliocene-Quaternary acidic volcanic rocks, as shown by the full range of studies and published isotopic data for the region, the source of rhyolite-dacite magmas could serve as a rock granite-metamorphic layer, metamorphosed to amphibolite, and granulite facies metamorphism. The high concentrations of K, Li, Rb, Cs, U, Th, Rb and low Sr, Ba, Zr, Ti and light lanthanides, the presence of a deep negative Eu – anomalies may indicate relatively low levels of fusion substrate, in which a significant portion of plagioclase and accessories remained in the restite. The eastern part of the Lesser Caucasus (Vardenis and Syunik uplands) (Figure 1) 87Sr/86Sr are 0,70,444–0,70,811 [18].
\nPetrochemical data show that the association of andesite-dacite-rhyolite and trachybasalt-trachyandesite association of fractional crystallization occurred. Thus, in the rocks of andesite-dacite-rhyolite association with increasing silica content decreases femic rock-forming oxides, increasing the content of incompatible elements due to fractionation of dark-colored minerals and feldspars. However, fuzzy trends show the influence of processes of assimilation and crustal contamination on the association of these rocks. Thus, an attempt to get out of andesitic dacites and from dacitic rhyolites by fractionation of clinopyroxene, amphibole, biotite, magnetite, and feldspar failed [31, 32, 33]. Therefore, as will be shown below, apparently, the formation of these rocks is dominated by a single process of AFC, that is, assimilation and fractional crystallization.
\nWe believe that fractional crystallization played a leading role in the association of rocks trachybasalt-trachyandesite association [13, 32, 33]. This is evidenced by the behavior of a number of rock-forming trace elements. For example, a change in slope of trends MgO-SiO2, TiO2-SiO2, and Ni-SiO2 in the field trachyandesite explained by fractionation of olivine, clinopyroxene, and magnetite.
\nPast balance calculations on a computer showed that the evolution of the melt occurred as a result of changes in the composition and quantity of rock-forming minerals. The results of balance calculation of fractional crystallization of alkaline olivine basalt-trachybasalts showed that the latter is obtained by fractionation of 19.8% Cpx, 57.6% Pl (An65), 15.0% Ol (Fo 84) and 7.6% Mt. As seen from Table 4, the absolute and calculated values for major and trace elements in the whole match (ΔR2 = 0.507). The degree of fractionation at the same time is about 61%.
\n\n | \n | SiO2\n | \nTiO2\n | \nAl2O3\n | \nFeO* | \nMgO | \nCaO | \nNa2O | \nK2O | \nP2O5\n | \n
---|---|---|---|---|---|---|---|---|---|---|
Parental magma | \n1 | \n51.36 | \n1.05 | \n16.77 | \n7.76 | \n6.29 | \n10.48 | \n3.14 | \n2.10 | \n1.05 | \n
Calculated parental magma | \n2 | \n51.76 | \n0.84 | \n16.68 | \n7.80 | \n6.31 | \n10.46 | \n3.36 | \n1.61 | \n1.14 | \n
Daughter magma | \n3 | \n54.60 | \n1.07 | \n17.13 | \n6.85 | \n4.28 | \n8.57 | \n4.28 | \n2.14 | \n1.07 | \n
\n | Rb | \nBa | \nSr | \nV | \nCr | \nNi | \nZr | \nSc | \nCu | \nLa | \nCe | \nSm | \nEu | \nYb | \nY | \n
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | \n35 | \n943 | \n1871 | \n105 | \n315 | \n105 | \n240 | \n11 | \n73 | \n63 | \n130 | \n9.8 | \n2.5 | \n2.4 | \n19 | \n
2 | \n44 | \n953 | \n1956 | \n2119 | \n575 | \n56 | \n151 | \n22 | \n73 | \n158 | \n112 | \n7.5 | \n1.5 | \n0.8 | \n12 | \n
3 | \n64 | \n1392 | \n2821 | \n150 | \n182 | \n46 | \n214 | \n21 | \n101 | \n81 | \n161 | \n10.7 | \n2.1 | \n1.1 | \n17 | \n
D | \n0.01 | \n0.01 | \n0.04 | \n1.99 | \n4.02 | \n1.53 | \n0.08 | \n1.12 | \n0.16 | \n0.03 | \n0.05 | \n0.08 | \n0.09 | \n0.11 | \n0.11 | \n
Fractionation of the above minerals and amphibole leads to further differentiates associations and the result is a continuous differential series – trachybasalt-basaltic trachyandesite-trachyandesite. Possible further differentiation of the melt to the trachytes, trahyriodasites, that is, for example, in a large polygenic volcano Ishygly.
\nAlthough, FC simulation of least squares using the basic rock-forming oxides and some trace elements gives good results, the majority of trace elements do not conform to this model. Thus, the content of LREE and HREE for different types of rocks vary in narrow limits. At Harker diagrams micronutrients – SiO2, where not all elements give a clear linear dependence. This suggests their association by other mechanisms, too.
\nBy Imamverdiyev previously shown that the role of crustal contamination in the genesis of Late Cenozoic volcanic rocks of the Lesser Caucasus is negligible [13]. In other works [12, 18, 39] speculation is about a significant transassociation of the primary magmas of crustal processes. We obtained the last petrogeochemical data suggest involvement in petrogenesis Late Cenozoic volcanic enriched mantle source (lithospheric mantle) and a significant contribution to processes of crustal contamination. The calculations show AFC – a model of crustal material required for the appropriate changes to the source mantle composition of rocks trachybasalt-trachyandesite association can be achieved during the fractionation of basalts (degree of fractionation of F = 0.5–0.6) with the absorption of a large number of acid melt (the ratio of assimilation rock and cumulates r = 0.3–0.5) (Table 5). A similar pattern is observed for rocks of andesite-dacite-rhyolite association, but this shift is achieved with a high degree of fractionation (F = 0.7–0.9) and with a large number of acidic substances (r = 0.6). Obviously, with such volumes of assimilation acidic substances are not stored petrochemical characteristics of the primary rocks (andesites and basalts). Therefore, Harkers figures are not observed clear trends.
\nElements | \n1 | \n2 | \n3 | \n4 | \n5 | \n6 | \n7 | \n8 | \n
---|---|---|---|---|---|---|---|---|
SiO2\n | \n52.46 | \n79.17 | \n64.73 | \n64.94 | \n55.74 | \n79.17 | \n58.76 | \n58.90 | \n
TiO2\n | \n1.09 | \n0.00 | \n0.00 | \n0.10 | \n1.09 | \n0.00 | \n0.00 | \n0.61 | \n
Al2O3\n | \n16.39 | \n13.54 | \n17.86 | \n17.87 | \n16.39 | \n13.54 | \n18.16 | \n17.89 | \n
FeO* | \n7.10 | \n0.00 | \n4.02 | \n4.04 | \n6.01 | \n0.00 | \n5.98 | \n5.99 | \n
MgO | \n6.56 | \n0.00 | \n2.23 | \n2.24 | \n4.37 | \n0.00 | \n3.21 | \n2.96 | \n
CaO | \n9.84 | \n0.00 | \n5.58 | \n5.55 | \n8.74 | \n0.00 | \n7.48 | \n7.51 | \n
Na2O | \n4.37 | \n4.17 | \n3.35 | \n3.34 | \n4.37 | \n4.17 | \n4.27 | \n3.95 | \n
K2O | \n1.09 | \n3.13 | \n2.23 | \n1.87 | \n2.19 | \n3.13 | \n2.14 | \n1.75 | \n
P2O5\n | \n1.09 | \n0.00 | \n0.00 | \n0.04 | \n1.09 | \n0.00 | \n0.00 | \n0.47 | \n
Rb | \n32 | \n180 | \n59 | \n68 | \n37 | \n174 | \n35 | \n58 | \n
Sr | \n1700 | \n100 | \n1819 | \n1918 | \n2635 | \n16 | \n1543 | \n1306 | \n
Ba | \n1060 | \n100 | \n815 | \n524 | \n1300 | \n26 | \n662 | \n666 | \n
Zr | \n240 | \n80 | \n223 | \n125 | \n250 | \n86 | \n205 | \n152 | \n
Ni | \n110 | \n3 | \n45 | \n28 | \n43 | \n3 | \n43 | \n56 | \n
Cr | \n270 | \n30 | \n180 | \n174 | \n170 | \n3 | \n214 | \n166 | \n
V | \n110 | \n20 | \n78 | \n790 | \n140 | \n20 | \n128 | \n142 | \n
∑R2 = 0.154 r = 0.53 F = 0.57 | \n\n | \n | \n | \n | \n | \n | \n | ∑R2 = 0.93 r = 0.25 F = 0.68 | \n
Results AFC – modeling for rocks trachybasalt-trachyandesite association.
1 – alkaline olivine basalts (initial melt), 2 – rhyolite (assimilation rock), 3 – trachyandesite (hybrid), 4 – calculated composition of trachyandesites, 5 – trachybasalt (initial melt), 6 – rhyolite (assimilation rock), 7 – basaltic trachyandesite (hybrid), 8 – calculated composition (all analyses have been converted to 100%).
Below are the results of AFC – modeling for rocks trachybasalt-trachyandesite association.
\nAs seen from Table 4, the intermingling rhyolite and basic rocks (alkaline olivine basalts and trachybasalt) may be formed basaltic trachyandesite and trachyandesite.
\nSummarizing the above data, the association of Late Cenozoic volcanic series of the Lesser Caucasus can be represented as follows.
\nWithin the Lesser Caucasus in the late Cenozoic volcanism expressed high-K calc-alkaline, mildly alkaline, and partly alkaline associations. In Neogene time (Upper Miocene-Lower Pliocene), with decompression occurs anatexis metasomatized mantle and lower strata of basalt layer at a sufficiently large depth, which determines the enrichment of these melts with alkali, alkaline earth, and light rare earth elements.
\nThis process resulted in association of basaltic melts, enriched in alkalis. Perhaps such a melt was formed at low degrees of partial melting (3–10%) of garnet peridotite or eclogite. We can assume that it corresponds subduction oceanic crust. In the future, as a result of growing tension mantle melts penetrated the upper layers of the earth crust, where it mixes basic and acid magma, with the association of hybrid andesite, andesite-dacite lavas (Figure 10). Progressive cooling of the deep source magma origin may be the cause of education dike fields in the region studied and possibly fractured outpouring mildly alkaline volcanism observed in the other parts of the Lesser Caucasus. Due to additional heating and the flow of volatiles formed fairly large volcanoes of calc-alkaline composition of Neogene age. Then Upper Pliocene-Quaternary formed bimodal volcanism. Thus, the temporal spatial conjugation of crustal and mantle magmatism led to the introduction of mantle melts, under conditions of tension in the lower crust, which resulted in its melting and the association of acidic volcanic rocks rich in radiogenic Sr and Nd (rhyolite association). Simultaneously, in this situation, a change of scenery compression and tensile contributed to the development rifts depressions, arching and exercise slow differentiated and undifferentiated volcanic (trachybasalt-basaltic trachyandesite-trachyandesite and basanite-tefrite series). Thus, the evolution of the melt in the earth crust is dominated by a single process of AFC (assimilation and fractional crystallization). As the fractionation rare elements, intermediate rocks can be formed by mixing trachybasaltic and rhyolite melts.
\nScheme of tectonic development and volcanism of the areas of matium magma formation at the Late Cenozoic stage of development of the Lesser Caucasus [
A distinctive feature of the investigated Late Miocene-Early Pliocene rocks of the Lesser Caucasus is that they are generally medium and acid. Volcanite composition meets mainly andesites and trachyandesites, dacites and trachydacites and also rhyolites. The volcanism was very powerful in relation to the attic tectonic activity of Late Miocene-Early Pliocene. During this period, there occurs Pre-Mesozoic base uplift and volcanism is mainly manifested in the central parts of the anticlinal zones of the Lesser Caucasus. The andesites and andesidacites with acid pyroclasts dominate in the products’ composition at the beginning of the volcanic phase and at its end – andesite lavas. Magmatism of the main composition of high alkalinity has locally been manifested in the extreme parts of the anticlinal zones. Subvolcanic appearings of formation invaded after volcanogenic strata (Basarkechar suite) formation and have more acid composition. After active effusive-explosive activity of Meotian-Pontian-Early Pliocene volcanoes, more acid and viscous magma, cooling at a depth, rising along fractures at shallow depths hardened in the form of dikes and other subvolcanic bodies.
\nOn the basis of nine petrogenic elements oxides (SiO2, TiO2, Al2O3, FeO*, MgO, CaO, Na2O, K2O, P2O5) such independent groups as andesite-trachyandesite-quartz latites, dacite-trachydatsites and rhyodacite-rhyolites have been defined for andesite-dacite-rhyolite formation using factorial diagram.
\nIt has been shown that with increasing SiO2 content in the rocks composition, the content of TiO2, Al2O3, FeO*, MgO, CaO, P2O5 decreases due to fractionation of titanomagnetite, clinopyroxene, plagioclase, amphibole, and apatite. The calc-alkaline trend of andesite-dacite-rhyolite series is controlled not only by magnetite fractionation but also by the hornblende crystallization, having a high Fe/Mg ratio and by SiO2 under saturation. First, it has been proved that the early hornblende crystallization in the Neogene magmatism evolution is the principal factor in the calc-alkaline series formation. This regularity is especially obvious during change of SiO2 content between 60 and 64%. The slow increase of K2O and Na2O content in the rocks formation is explained by potassium feldspar crystallization.
\nIn formation’s volcanites with increasing SiO2 content from andesites to rhyolites and with decreasing MgO quantity the coherent (compatible) elements as macroelements give a linear and sometimes expressed broken dependence. The figurative points of the homogenous inclusions are at the beginning of these dependence trends. These elements distribution in the rocks of formation is controlled by fractionation of rock-forming minerals and accumulative (homogenous) crystallization of the inclusions. The incompatible elements content (Rb, Th, Nb, Zr, Hf, LREE, etc.) is minimal in the deep-seated inclusions.
\nIn rocks of formation the light lanthanoids prevail in relation to heavy, and therefore La/Sm, La/Yb relations are high. In medium rocks (quartz latites and andesites), it is defined approaching Eu/Eu* relation to unit (Eu/Eu* = 0.94–1.05) and in more acid rocks – Eu-minimum (Eu/Eu* = 0.58–0.63) that indicates on plagioclase fractionation. It has been established that the content of Ba and Ba/Y, Rb/Y, Th/Yb relations are rapidly increased in the formation’s rocks. The formation’s rocks enrichment with lithophylous and rare-earth elements caused by relatively high degree of fusion melting that enriched by fluids.
\nBased on the modeling, it was determined that as a result of high fractionation of the initial melt (F = 0.96) during mixing of 32.4% andesite and 63.4% rhyodacite; it is possible to obtain dacite of hybrid origin. The leading role of single process of Assimilation and Fractional Crystallization (AFC) is responsible for forming the igneous rocks of formation.
\nIt has been shown that the enrichment of formation’s rock with light rare-earth elements and many incompatible elements indicates on sufficiently important role of the enriched mantle matter in their formation. The high-alumina basalts can be considered as the parental magma for formation’s rocks. Their formation is connected with fractionation in the environment of high water pressure from the initial high-magnesian melt of the olivine-clinopyroxene association.
\nSo, the Neogene volcanic series formation of the Lesser Caucasus can be represented as follows.
\nAt the beginning of the Late Cenozoic, the mantle metasomatism occurred as a result of regional compression in the lifting diapir. In the Late Miocene-Early Pliocene anatexis of the metasomatized mantle and lower parts of the basalt layer occurs due to decompression at sufficiently great depth that determines these melts enrichment with alkali, alkaline-earth, light rare-earth elements. As a result of this process, there is formed basalt melts enriched by alkalines. Further evolution of these melts occurs in conditions of continental Earth crust where medium-acidic rocks as steeply dipping dikes and volcanic edifices of the central, central-fractured type are formed due to melts differentiation (Figure 10).
\nThe primary magma evolution was accompanied by fractionation of olivine-clinopyroxenic mineral associations and the appearance of high-alumina residual magma in the deep-seated foci. The last ones outcropping are accompanied by a stop at the intermediate foci, fractionation of plagioclase, clinopyroxene, amphibole, surrounding rock melting, crustal material contamination, and by hybrid magma formation.
\nThe works area can be considered metallogenetically perspective in relation to new Au, Ag, Hg, As, Sb, Cu-Mo with Au, Pb-Zn, Cu-Pb-Zn fields and ore occurrences. The investigated area is also rich by non-metallic raw materials – tuffs, scorias, pumices, etc.
\nTherefore, for andesite-dacite-rhyolite formation, developed in the central part of Lesser Caucasus, rocks formation of high-potassium calc-alkaline series is specific unlike the rocks of calc-alkaline series of normal alkalinity. Rocks formation of andesite-dacite-rhyolite formation is caused by fractionation of the rock-forming minerals in the intermediate foci and later due to contamination of the differentiated basaltic melt by the surrounding rocks. Single process of crystallization and assimilation caused the rocks buildup of the formation.
\nTwo volcanic formations of the Late Pliocene-Quaternary age are separated at the end of the collision stage of development of the Azerbaijan part of the Lesser Caucasus, forming a bimodal association: 1 – rhyolite; 2 – trachybasalt-trachyandesite.
\nIn the mafic volcanics of the behavior of major elements indicate their origin by fractionation of olivine, clinopyroxene, hornblende, basic plagioclase, apatite, magnetite. Acidic volcanic rocks associated with the formation of “dry” high temperature of the melt in the intermediate chambers are not of fractional crystallization.
\nThe distribution of rare earth elements in rocks trachybasalt-trachyandesite formation indicates that the source was the metasomatic alteration of volcanic rocks containing garnet mantle. In the studied volcanics, (Tb/Yb)n = 1.7–3.0 indicates the presence of garnet in the source of the primary magma.
\nIn the rocks of rhyolite formation contents of rare earth elements is low (REE = 66–116 ppm), there is a pronounced low ratio of europium, which indicates that early removal of the molten plagioclase and alkali feldspar.
\nTrace element composition of the rocks trachybasalt-trachyandesite formation and their relationships complicate the model and determine the fractional crystallization of the magma mantle interaction with the substrate of the crust. In this substrate can be rhyolites, geochemical, and isotopic composition similar to the Earth’s crust and forming a spatio-temporal association with the rocks contrast trachybasalt-trachyandesite formation.
\nThe simulation revealed that the evolution of moderately alkaline olivine basalts (considered a primary mantle melt the rocks trachybasalt-trachyandesite formation) occurs due to changes in the composition of the main rock-forming and accessory minerals. Average rock formations formed by the assimilation of poorly differentiated primary magma acidic melt. Geochemical features of moderately alkaline olivine basalts indicate that the source of magma is metasomaticized, phlogopite-garnet-rutile containing lithospheric mantle. It is very possible that the melting of such a source is rutile to a restaurant, and magma is depleted Nb and Ta.
\nThe calculations have shown that the proportion of melting rhyolitic melt separated from andesite substrate close to 15%. After removal of the remaining melt restite entirely consistent with the composition of the lower crust. The typical ratio of rare earth elements is to confirm this.
\nThese fact sheets, model calculations indicate various sources of education salic and mafic melts. Thus, the generation of mafic melt (moderately alkaline olivine basalt composition) came from a differentiated mantle protolith formation of a salic melt occurs during lifting mafic magma by melting of crustal substrate. On the other hand, the salic is going to melt in the top of the magma reservoir and prevents lifting heavier mafic magma, and in a short time in the melt is subjected to intermediate focuses differentiated. During subsequent evolution differentiated mafic melt reacts with rhyolitic melt, which entails the formation of secondary rocks.
\nThus, the formation of bimodal volcanism in contrast, the central part of the Lesser Caucasus in the Late Pliocene-Quaternary period is as follows.
\nTemporary space conjugate crust and mantle magmatism led to the introduction of mantle melts under tension in the lower crust, which led to its melting and the formation of acidic volcanic rocks enriched in radiogenic
Thus, in the petrogenesis of the majority of Caucasian young volcanic rocks has played a significant role lower mantle source material which is close to the tank “Common” with characteristic isotopic 87Sr/86Sr = 0.7041 ± 0.0001, ∋Nd = +4.1 ± 0.2; 147Sm/144Nd = 0.105–0.114 and named “Caucasus” [17, 18]. The primary melt composition corresponds to K-Na moderately alkaline olivine basalts. The magma formed by the plume of the Caucasus in the atmosphere of Earth’s crust formed the ever-increasing mantle diapir; he’s at the very beginning of its process uplift served the development of large volumes of mantle fluids. Due to the hot magma mantle diapir melts the material of Earth’s crust, magma is formed, which corresponds to the isotopic composition of the Earth’s crust, and subsequently, to varying degrees due to contamination of the mantle and crustal magma formed hybrid rocks.
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