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An electron microprobe study was carried out on olivine, clinopyroxene, and oxy-spinel occurring in basalts and dunite xenoliths from the archipelagos of the Azores, the Canary Islands, and Cape Verde. By comparing our results with previously published data from the volcanic islands of Macaronesia, we confirmed the validity of the compositions of olivine, clinopyroxene, and oxy-spinel as geochemical tracers. The origin of olivine, i.e., crystallized in the lithospheric mantle or in volcanic rocks, was successfully discriminated. Olivine from Lanzarote dunite xenoliths, which represent fragments of the mantle transported to the surface by host magmas, exhibited higher Fo% values (Fo91.02 to Fo91.94) and a different distribution of minor elements Ca, Ni, and Mn (CaO up to 0.42 wt%, NiO 0.07–0.41 wt%, MnO 0.06–0.3 wt%) when compared with olivine occurring as phenocrysts in basaltic lavas from the Macaronesian islands. The highly variable forsterite contents (Fo75.1 to Fo94.4) in olivine from gabbro and peridotite xenoliths found across the islands of Macaronesia were attributed to fractional crystallization that started in a deep magma reservoir, suggesting that these xenoliths represent cumulate rocks and not mantle fragments. Alternatively, these xenoliths may have been affected by the interaction with metasomatic fluids. The composition of clinopyroxene phenocrysts was used to decipher formation conditions under extensional tectonics. Their composition suggests that the host lavas have an alkaline to calc-alkaline signature. Furthermore, clinopyroxene euhedral shapes and compositions suggest an origin by fractional crystallization in a closed magmatic system. The composition alone of oxy-spinel from Macaronesian basalts and xenoliths was not sufficient to draw conclusions about the geodynamic environment where they were formed. Nevertheless, the relationship between oxy-spinel and olivine crystallized in equilibrium was successfully used as oxybarometers and geothermometers. The oxy-spinel–olivine pairs show evidence that the basaltic lavas were crystallized from melts with higher oxygen fugacity and different cooling histories than those of the mantle xenoliths, as the latter crystallized and re-equilibrated much slower than the basalts.

Corundum primary deposits in Greece occur in four locations: Paranesti in Drama and Gorgona in Xanthi, both belonging to the wider Rhodope Massif, as well as, Ikaria island and Kinidaros in Naxos island, both belonging to Attic-Cycladic Massif. Eight samples were examined with spectroscopic methods (FTIR, UV-Vis, EDXRF) in order to better characterize these four primary deposits: two pink sapphires from Paranesti, a pink and a blue sapphire from Gorgona, two blue sapphires from Ikaria and three blue sapphires from Kinidaros. Under the microscope, all samples present characteristics linked to post-crystallization deformation, decreasing their gem quality. The FTIR absorption spectra of all samples present in different relative intensities, bands of boehmite, diaspore, goethite, mica and/or chlorite inclusions and CO2 in fluid inclusions. Boehmite and diaspore inclusions are most likely epigenetic. In the UV-Vis spectra, the pink color of the samples is linked with Cr3+ absorptions and the blue color with absorptions due to Fe2+-Ti4+ intervalence charge transfer. EDXRF analyses in the studied samples show relatively high titanium and iron concentrations that are related with mineral inclusions. Gallium is slightly variable in samples from different regions; also, different colored samples from Gorgona present diverse gallium content.

The Vathi porphyry Cu-Au ± Mo mineralization is located in the Serbo-Macedonian metallogenic province of the Western Tethyan Metallogenic Belt. It is mainly hosted by a latite and is genetically associated with a quartz monzonite intrusion, which intruded the basement rocks of the Vertiskos Unit and the latite, 18 to 17 Ma ago. A phreatic breccia crosscuts the latite. The quartz monzonite was affected by potassic alteration, whereas the latite was subjected to local propylitic alteration. Both styles of alteration were subsequently overprinted by intense sericitic alteration. M-type and A-type veins are spatially associated with potassic alteration, whereas D-type veins are related to the sericitic alteration. Three ore assemblages are associated with the porphyry stage: (1) pyrite + chalcopyrite + bornite + molybdenite + magnetite associated with potassic alteration; (2) pyrite + chalcopyrite related to propylitic alteration; and (3) pyrite + chalcopyrite + native gold ± tetradymite associated with sericitic alteration. A fourth assemblage consisting of sphalerite + galena + arsenopyrite + pyrrhotite + pyrite ± stibnite ± tennantite is related to an epithermal overprint. Fluid inclusion data indicate that the A-type veins and related porphyry-style mineralization formed at 390–540 °C and pressures of up to 646 bars (

The Lavrion area corresponds to the western part of the Attic-Cycladic metamorphic belt, in the back-arc region of the active Hellenic subduction zone. Between the Eocene and the Miocene, metamorphic rocks (mainly marbles and schists) underwent several stages of metamorphism and deformation due to collision and collapse of the Cycladic belt. Exhumation during the Miocene was accommodated by the movement of a large-scale detachment fault system, which also enhanced emplacement of magmatic rocks, leading to the formation of the famous Lavrion silver deposits. The area around the mines shows the stacking of nappes, with ore deposition mainly localized within the marbles, at marble-schist contacts, below, within, or above the detachment. The Lavrion deposit comprises five genetically-related but different styles of mineralization, a feature never observed in another ore deposit elsewhere, containing the highest number of different elements of any known mining district. The local geology, tectonic, and magmatic activity were fundamental factors in determining how and when the mineralization formed. Other key factors, such as the rise and the fall of sea level, which resulted from climate change over the last million years, were also of major importance for the subsequent surface oxidation at Lavrion that created an unmatched diversity of secondary minerals. As a result, the Lavrion deposit contains 638 minerals of which Lavrion is type-locality for 23 of them, which is nearly 12% of all known species. Apart from being famous for its silver exploitation, this mining district contains more minerals than any other district on Earth. The unique geological, mineralogical, and educational (mining, archaeological, and environmental) features suggest that it is highly suitable to be developed as a future UNESCO Global Geopark.

The Konos Hill and Pagoni Rachi porphyry-epithermal prospects in northeastern Greece are characterized by abundant pyrite that displays important textural and geochemical variations between the various ore stages. It is commonly fine-grained and anhedral in the porphyry-related mineralization (M- and D-type veins), while it forms idiomorphic, medium- to coarse-grained crystals in the late, epithermal style veins (E-type). Porphyry-style pyrite from both prospects is characterized by an enrichment in Co, Se, Cu, and minor Zn, and a depletion in other trace elements, like Bi, Mo, Ag, etc. Pyrite in epithermal-style mineralization is mostly characterized by the presence of As, Bi, Pb, Ni, and Se. Gold in pyrite from all mineralization stages occurs as a non-stoichiometric substituting element, and its abundance correlates with As content. Arsenic in pyrite from Konos Hill records an increase from the porphyry stage to the epithermal stage (along with gold); however, at Pagoni Rachi, the highest Au and As contents are recorded in D-type pyrite and in the epithermal stage. The composition of the studied pyrite marks changes in the physico-chemical conditions of the ore-forming fluids and generally follows the geochemical trends from other porphyry-epithermal systems elsewhere. However, a notable enrichment of Se in the porphyry-style pyrite here is a prominent feature compared to other deposits and can be considered as an exploration tool towards Au-enriched mineralized areas.

The Maronia Cu-Mo ± Re ± Au deposit is spatially related to a microgranite porphyry that intruded an Oligocene monzonite along the Mesozoic Circum-Rhodope belt in Thrace, NE Greece. The magmatic rocks and associated metallic mineralization show plastic and cataclastic features at the south-eastern margin of the deposit that implies emplacement at the ductile-brittle transition, adjacent to a shear zone at the footwall of the Maronia detachment fault. The conversion from ductile to brittle deformation caused a rapid upward magmatic fluid flow and increased the volume of water that interacted with the host rocks through high permeable zones, which produced extensive zones of potassic and sodic-calcic alteration. Potassic alteration is characterized by secondary biotite + K-feldspar (orthoclase) + magnetite + rutile + quartz ± apatite and commonly contains sulfides (pyrite, chalcopyrite, pyrrhotite). Sodic-calcic alteration consists of actinolite + sodic-calcic plagioclase (albite/oligoclase/andesine) + titanite + magnetite + chlorite + quartz ± calcite ± epidote-allanite. The high-oxidation state of the magmas and the hydrothermal fluid circulation were responsible for the metal and sulfur enrichments of the aqueous fluid phase, an increase in O2 gas content, the breakdown of the magmatic silicates and the production of the extensive potassic and sodic-calcic alterations. Brittle deformation also promoted the rapid upward fluid flow and caused interactions with the surrounding host rocks along the high temperature M-, EB-, A- and B-type veins.

In the Hellenides Orogen, minerals of various gem quality occur in various rock types from mainly four tectono-metamorphic units, the Rhodope, Pelagonian, and the Attico-Cycladic massifs, and the Phyllites-Quartzites unit of Crete Island. In crystalline rocks, gemstones are related to both regional metamorphic-metasomatic processes (e.g., gem corundums, Mn-andalusite, thulite/clinothulite, spessartine, titanite, jadeite), and to the formation of late alpine-type fissures, such as, for example, quartz, albite, adularia and titanite. The Tertiary (and Mesozoic) magmatic-hydrothermal environments provide gem-quality sapphire, beryl, garnet, vesuvianite, epidote, fluorite, and SiO2 varieties. The supergene oxidation zone of the Lavrion deposit hosts gem-quality smithsonite and azurite. Coloration in the studied material is either due to various chromophore trace elements present in the crystal structure, or due to inclusions of other mineral phases. Future modern exploration methods combined with gemological investigations (such as treatment and faceting of selected stones), are necessary in order to obtain a better knowledge of the gemstone potential of Greece for its possible exploitation.

The Trikorfo area (Thassos Island, Rhodope massif, Northern Greece) represents a unique mineralogical locality with Mn-rich minerals including kyanite, andalusite, garnet and epidote. Their vivid colors and large crystal size make them good indicators of gem-quality materials, although crystals found up to now are too fractured to be considered as marketable gems. The dominant lithology is represented by a garnet−kyanite−biotite−hematite−plagioclase ± staurolite ± sillimanite paragneiss. Thermodynamic Perple_X modeling indicates conditions of ca. 630−710 °C and 7.8−10.4 kbars. Post-metamorphic metasomatic silicate and calc-silicate (Mn-rich)-minerals are found within (i) green-red horizons with a mineralogical zonation from diopside, hornblende, epidote and grossular, (ii) mica schists containing spessartine, kyanite, andalusite and piemontite, and (iii) weakly deformed quartz-feldspar coarse-grained veins with kyanite at the interface with the metamorphic gneiss. The transition towards brittle conditions is shown by Alpine-type tension gashes, including spessartine−epidote−clinochlore−hornblende-quartz veins, cross-cutting the metamorphic foliation. Kyanite is of particular interest because it is present in the metamorphic paragenesis and locally in metasomatic assemblages with a large variety of colors (zoned blue to green/yellow-transparent and orange). Element analyses and UV-near infrared spectroscopy analyses indicate that the variation in color is due to a combination of Ti4+−Fe2+, Fe3+ and Mn3+ substitutions with Al3+. Structural and mineralogical observations point to a two-stage evolution of the Trikorfo area, where post-metamorphic hydrothermal fluid circulation lead locally to metasomatic reactions from ductile to brittle conditions during Miocene exhumation of the high-grade host-rocks. The large variety of mineral compositions and assemblages points to a local control of the mineralogy and fO2 conditions during metasomatic reactions and interactions between hydrothermal active fluids and surrounding rocks.

Greece contains several gem corundum deposits set within diverse geological settings, mostly within the Rhodope (Xanthi and Drama areas) and Attico-Cycladic (Naxos and Ikaria islands) tectono-metamorphic units. In the Xanthi area, the sapphire (pink, blue to purple) deposits are stratiform, occurring within marble layers alternating with amphibolites. Deep red rubies in the Paranesti-Drama area are restricted to boudinaged lenses of Al-rich metapyroxenites alternating with amphibolites and gneisses. Both occurrences are oriented parallel to the ultra-high pressure/high pressure (UHP/HP) Nestos suture zone. On central Naxos Island, colored sapphires are associated with desilicated granite pegmatites intruding ultramafic lithologies (plumasites), occurring either within the pegmatites themselves or associated metasomatic reaction zones. In contrast, on southern Naxos and Ikaria Islands, blue sapphires occur in extensional fissures within Mesozoic metabauxites hosted in marbles. Mineral inclusions in corundums are in equilibrium and/or postdate corundum crystallization and comprise: spinel and pargasite (Paranesti), spinel, zircon (Xanthi), margarite, zircon, apatite, diaspore, phlogopite and chlorite (Naxos) and chloritoid, ilmenite, hematite, ulvospinel, rutile and zircon (Ikaria). The main chromophore elements within the Greek corundums show a wide range in concentration: the Fe contents vary from (average values) 1099 ppm in the blue sapphires of Xanthi, 424 ppm in the pink sapphires of Xanthi, 2654 ppm for Paranesti rubies, 4326 ppm for the Ikaria sapphires, 3706 for southern Naxos blue sapphires, 4777 for purple and 3301 for pink sapphire from Naxos plumasite, and finally 4677 to 1532 for blue to colorless sapphires from Naxos plumasites, respectively. The Ti concentrations (average values) are very low in rubies from Paranesti (41 ppm), with values of 2871 ppm and 509 in the blue and pink sapphires of Xanthi, respectively, of 1263 ppm for the Ikaria blue sapphires, and 520 ppm, 181 ppm in Naxos purple, pink sapphires, respectively. The blue to colorless sapphires from Naxos plumasites contain 1944 to 264 ppm Ti, respectively. The very high Ti contents of the Xanthi blue sapphires may reflect submicroscopic rutile inclusions. The Cr (average values) ranges from 4 to 691 ppm in the blue, purple and pink colored corundums from Naxos plumasite, is quite fixed (222 ppm) for Ikaria sapphires, ranges from 90 to 297 ppm in the blue and pink sapphires from Xanthi, reaches 9142 ppm in the corundums of Paranesti, with highest values of 15,347 ppm in deep red colored varieties. Each occurrence has both unique mineral assemblage and trace element chemistry (with variable Fe/Mg, Ga/Mg, Ga/Cr and Fe/Ti ratios). Additionally, oxygen isotope compositions confirm their geological typology, i.e., with, respectively δ18O of 4.9 ± 0.2‰ for sapphire in plumasite, 20.5‰ for sapphire in marble and 1‰ for ruby in mafics. The fluid inclusions study evidenced water free CO2 dominant fluids with traces of CH4 or N2, and low CO2 densities (0.46 and 0.67 g/cm3), which were probably trapped after the metamorphic peak. The Paranesti, Xanthi and central Naxos corundum deposits can be classified as metamorphic sensu stricto (s.s.) and metasomatic, respectively, those from southern Naxos and Ikaria display atypical magmatic signature indicating a hydrothermal origin. Greek corundums are characterized by wide color variation, homogeneity of the color hues, and transparency, and can be considered as potential gemstones.

Vein-type Pb-Ni-Bi-Au-Ag mineralization at the Clemence deposit in the Kamariza and “km3„ in the Lavrion area, was synchronous with the intrusion of a Miocene granodiorite body and related felsic and mafic dikes and sills within marbles and schists in the footwall of (and within) the Western Cycladic detachment system. In the Serpieri deposit (Kamariza area), a porphyry-style pyrrhotite-arsenopyrite mineralized microgranitic dike is genetically related to a garnet-wollastonite bearing skarn characterized by a similar base metal and Ni (up to 219 ppm) enrichment. The Ni⁻Bi⁻Au association in the Clemence deposit consists of initial deposition of pyrite and arsenopyrite followed by an intergrowth of native gold-bismuthinite and oscillatory zoned gersdorffite. The zoning is related to variable As, Ni, and Fe contents, indicating fluctuations of arsenic and sulfur fugacity in the hydrothermal fluid. A late evolution towards higher sulfur fugacity in the mineralization is evident by the deposition of chalcopyrite, tennantite, enargite, and galena rimming gersdorffite. At the “km3„ locality, Ni sulfides and sulfarsenides, vaesite, millerite, ullmannite, and polydymite, are enclosed in gersdorffite and/or galena. The gersdorffite is homogenous and contains less Fe (up to 2 wt.%) than that from the Clemence deposit (up to 9 wt.%). Bulk ore analyses of the Clemence ore reveal Au and Ag grades both exceeding 100 g/t, Pb and Zn > 1 wt.%, Ni up to 9700 ppm, Co up to 118 ppm, Sn > 100 ppm, and Bi > 2000 ppm. The “km3„ mineralization is enriched in Mo (up to 36 ppm), Ni (>1 wt.%), and Co (up to 1290 ppm). Our data further support a magmatic contribution to the ore-forming fluids, although remobilization and leaching of metals from previous mineralization and/or host rocks, through the late involvement of non-magmatic fluid in the ore system, cannot be excluded.

A new porphyry Mo prospect has been discovered in the Aisymi-Leptokarya area, along the southern margin of the Byala Reka⁻Kechros metamorphic dome, south-eastern (SE) Rhodope metallogenic zone. The study area is dominated by an Oligocene felsic dike complex, which hosts the porphyry Mo mineralization and intrudes into upper Eocene sandstones-marls and the Leptokarya monzodiorite pluton. The Aisymi-Leptokarya felsic dike complex displays a rhyodacitic to dacitic composition with post-collisional affinities. The porphyry Mo mineralization occurs in the form of porphyry-style quartz stockworks in the felsic dike complex associated with potassic alteration characterized by hydrothermal K-feldspar. The ore minerals consist mainly of pyrite, molybdenite, kesterite, bismuthinite and galena within both the stockwork and the rock matrix. Bulk ore analyses indicate enrichment in Mo (up to 215 ppm), Se (up to 29 ppm), Bi (up to 8 ppm) and Sn (up to 14 ppm) in the porphyry quartz veins. Late-stage, north-east (NE-) and north-west (NW-)trending milky quartz intermediate-sulfidation epithermal veins with base metals, crosscut previous vein generations and are characterized by Ag, Sn and Te anomalies. The Aisymi-Leptokarya porphyry Mo prospect is set in a back-arc geotectonic regime and shares similarities to other post-subduction porphyry molybdenum deposits elsewhere.

The color of quartz and other minerals can be either caused by defects in the crystal structure or by finely dispersed inclusions of other minerals within the crystals. In order to investigate the mineral chemistry and genesis of the famous prase (green quartz) and amethyst association from Serifos Island, Greece, we used electron microprobe analyses and oxygen isotope measurements of quartz. We show that the color of these green quartz crystals is caused by small and acicular amphibole inclusions. Our data also shows that there are two generations of amphibole inclusions within the green quartz crystals, which indicate that the fluid, from which both amphiboles and quartz have crystallized, must have had a change in its chemical composition during the crystallization process. The electron microprobe data also suggests that traces of iron may be responsible for the amethyst coloration. Both quartz varieties are characterized by isotopic compositions that suggest mixing of magmatic and meteoric/marine fluids. The contribution of meteoric fluid is more significant in the final stages and reflects amethyst precipitation under more oxidizing conditions.

The Konos Hill prospect in NE Greece represents a telescoped Mo⁻Cu⁻Re⁻Au porphyry occurrence overprinted by deep-level high-sulfidation mineralization. Porphyry-style mineralization is exposed in the deeper parts of the system and comprises quartz stockwork veins hosted in subvolcanic intrusions of granodioritic composition. Ore minerals include pyrite, molybdenite, chalcopyrite, and rheniite. In the upper part of the system, intense hydrothermal alteration resulted in the formation of a silicified zone and the development of various advanced argillic alteration assemblages, which are spatially related to N⁻S, NNW⁻SSE, and E⁻W trending faults. More distal and downwards, advanced argillic alteration gradually evolves into phyllic assemblages dominated by quartz and sericite. Zunyite, along with various amounts of quartz, alunite, aluminum phosphate⁻sulfate minerals (APS), diaspore, kaolinite, and minor pyrophyllite, are the main minerals in the advanced argillic alteration. Mineral-chemical analyses reveal significant variance in the SiO2, F, and Cl content of zunyite. Alunite supergroup minerals display a wide compositional range corresponding to members of the alunite, beudantite, and plumbogummite subgroups. Diaspore displays an almost stoichiometric composition. Mineralization in the lithocap consists of pyrite, enargite, tetrahedrite/tennantite, and colusite. Bulk ore analyses of mineralized samples show a relative enrichment in elements such as Se, Mo, and Bi, which supports a genetic link between the studied lithocap and the underlying Konos Hill porphyry-style mineralization. The occurrence of advanced argillic alteration assemblages along the N⁻S, NNW⁻SSE, and E⁻W trending faults suggests that highly acidic hydrothermal fluids were ascending into the lithocap environment. Zunyite, along with diaspore, pyrophyllite, and Sr- and Rare Earth Elements-bearing APS minerals, mark the proximity of the hypogene advanced argillic alteration zone to the porphyry environment.

Native iron has been identified in an active thermogenic travertine deposit, located at Ilia area (Euboea Island, Greece). The deposit is forming around a hot spring, which is part of a large active metallogenetic hydrothermal system depositing ore-bearing travertines. The native iron occurs in two shapes: nodules with diameter 0.4 and 0.45 cm, and angular grains with length up to tens of μm. The travertine laminae around the spherical/ovoid nodules grow smoothly, and the angular grains are trapped inside the pores of the travertine. Their mineral-chemistry is ultra-pure, containing, other than Fe, only Mn (0.34–0.38 wt.%) and Ni (≤0.05 wt.%). After evaluating all the possible environments where native iron has been reported up until today and taking under consideration all the available data concerning the study area, we propose two possible scenarios: (i) Ilia’s native iron has a magmatic/hydrothermal origin i.e., it is a deep product near the magmatic chamber or a peripheral cooling igneous body that was transferred during the early stages of the geothermal field evolution, from high temperature, reduced gas-rich fluids and deposited along with other metals in permeable structural zones, at shallow levels. Later on, it was remobilized and mechanically transferred and precipitated at the Ilia’s thermogenic travertine by the active lower temperatures geothermal fluids; (ii) the native iron at Ilia is remobilized from deep seated ophiolitic rocks, originated initially from reduced fluids during serpentinization processes; however, its mechanical transport seems less probable. The native iron mineral-chemistry, morphology and the presence of the other mineral phases in the same thermogenic travertine support both hypotheses.

Epithermally altered volcanic rocks in Greece host amethyst-bearing veins in association with various silicates, carbonates, oxides and sulfides. Host rocks are Oligocene to Pleistocene calc-alkaline to shoshonitic lavas and pyroclastics of intermediate to acidic composition. The veins are integral parts of high to intermediate sulfidation epithermal mineralized centers in northern Greece (e.g., Kassiteres–Sapes, Kirki, Kornofolia/Soufli, Lesvos Island) and on Milos Island. Colloform–crustiform banding with alternations of amethyst, chalcedony and/or carbonates is a common characteristic of the studied amethyst-bearing veins. Hydrothermal alteration around the quartz veins includes sericitic, K-feldspar (adularia), propylitic and zeolitic types. Precipitation of amethyst took place from near-neutral to alkaline fluids, as indicated by the presence of various amounts of gangue adularia, calcite, zeolites, chlorite and smectite. Fluid inclusion data suggest that the studied amethyst was formed by hydrothermal fluids with relatively low temperatures (~200–250 °C) and low to moderate salinity (1–8 wt % NaCl equiv). A fluid cooling gradually from the external to the inner parts of the veins, possibly with subsequent boiling in an open system, is considered for the amethysts of Silver Hill in Sapes and Kassiteres. Amethysts from Kornofolia, Megala Therma, Kalogries and Chondro Vouno were formed by mixing of moderately saline hydrothermal fluids with low-salinity fluids at relatively lower temperatures indicating the presence of dilution processes and probably boiling in an open system. Stable isotope data point to mixing between magmatic and marine (and/or meteoric) waters and are consistent with the oxidizing conditions required for amethyst formation.

The quantitative characterisation of the degree of randomness and aggregation of surface micro‐ and nanostructures is critical to evaluate their effects on targeted functionalities. To this end, the methods of point pattern analysis (PPA), largely used in ecology and medical imaging, seem to provide a powerful toolset. However, the application of these techniques requires the extraction of the point pattern of nanostructures from their microscope images. In this work, we address the issue of the impact that Scanning Electron Microscope (SEM) image processing may have on the fundamental metric of PPA, that is, the Nearest Neighbour Index (NNI). Using typical SEM images of polymer micro‐ and nanostructures taken from secondary and backscattered electrons, we report the effects of the (a) noise filtering and (b) binarisation threshold on the value of NNI as well as the impact of the image finite size effects. Based on these results, we draw conclusions for the safe choice of SEM settings to provide accurate measurement of nanostructure randomness through NNI estimation. [ABSTRACT FROM AUTHOR]