Flooding a landscape: impact of Holocene transgression on coastal sedimentology and underwater archaeology in Kiladha Bay (Greece)

Franchthi Cave, bordering Kiladha Bay, in Greece, is a key archaeological site, due to its long occupation time, from?~?40,000 to?~?5000 year BP. To date, no clear evidence of Neolithic human dwellings in the cave was found, supporting the assumption that Neolithic people may have built a village where there is now Kiladha Bay. During the Neolithic period/Early Holocene, wide areas of the bay were indeed emerged above sea level. Bathymetric and seismic data identified a terrace incised by a valley in?~?1 to 2 m sediment depth. Eight sediment cores, up to 6.3-m-long, were retrieved and analysed using petrophysical, sedimentological, geochemical, and chronostratigraphic methods. The longest core extends into the exposure surface, consisting of a layer of carbonate rubble in a finer matrix, representing weathering processes. Dated organic remains place this unit at?~?8500 cal year BP. It is overlain by stiff silty mud representing an estuarine environment. This mud is capped by reduced sediments with roots marking an exposure surface. A shell-layer, dated to?~?6300 cal year BP, overlies this terrestrial sequence, reflecting the marine transgression. This layer occurs at 10.8 mbsl, 7.7 m deeper than the global sea level at that time, suggesting tectonic subsidence in the area. It is overlain by finer-grained marine carbonate-rich sediments. The top of the core shows traces of eutrophication, pebbles and marine shells, all likely a result of modern anthropogenic processes. These results are interpreted in the context of human occupation: the exposed surface contains pottery sherds, one dating to the Early to Middle Neolithic period, indicating that Neolithic people were present in this dynamic landscape interacting with a migrating coastline. Even if the artefacts are isolated, future investigations of the submerged landscape off Franchthi Cave might lead to the discovery of a Neolithic village, which eventually became buried under marine sediments.     

High-pressure phase behavior of MnTiO<Subscript>3</Subscript>: decomposition of perovskite into MnO and MnTi<Subscript>2</Subscript>O<Subscript>5</Subscript>

The phase relations and compression behavior of MnTiO₃ perovskite were examined using a laser-heated diamond-anvil cell, X-ray diffraction, and analytical transmission electron microscopy. The results show that MnTiO₃ perovskite becomes unstable and decomposes into MnO and orthorhombic MnTi₂O₅ phases at above 38 GPa and high temperature. This is the first example of ABO₃ perovskite decomposing into AO + AB₂O₅ phases at high pressure. The compression behavior of volume, axes, and the tilting angle of TiO₆ octahedron of MnTiO₃ perovskite are consistent with those of other A²⁺B⁴⁺O₃ perovskites, although no such decomposition was observed in other perovskites. FeTiO₃ is also known to decompose into two phases, instead of transforming into the CaIrO₃-type post-perovskite phase and we argue that one of the reasons for the peculiar behavior of titanate is the weak covalency of the Ti–O chemical bonds.     

Role of Crystal Interlocking on the Strength of Brittle Rocks

Results of an experimental programme on heterogeneous rock-like specimens of dental plaster confirm the pronounced role of tensile microcracks on brittle failure. Microbuckling of very small rock-columns formed amid closely located tensile cracks was observed as the key incident connecting stable phenomenon of tensile cracking to unstable phenomenon of shearing and subsequent macroscopic failure. Using the classical beam and buckling theories and considering geometry of the problem a new failure criterion is proposed. As a novel attempt, this new failure criterion relates the compressive strength of rock to three basic microstructural properties, i.e. degree of crystal interlocking, average Young modulus and average tensile strength of rock forming minerals.     

Hydraulic Conductivity Tests for Evaluating Compatibility of Lateritic Soil—Fly Ash Mixtures with Municipal Waste Leachate

Long term competent performance of liner systems is a critical issue in the design and construction of waste repositories due to adverse interactions associated with leachate generated by wastes. This study was conducted to verify the efficacy of fly ash stabilization in enhancing compatibility between lateritic soil and municipal waste leachate. Applications investigated include soil mixtures containing 0, 5, 10, 15, and 20% fly ash compacted at approximately 2% wet of optimum moisture content with modified proctor energy. Baseline hydraulic conductivity was first established at every level of fly ash content by permeating soil mixtures with tap water before permeation with leachate in a compaction mould permeameter using the falling head test method. Results show that the trend in hydraulic conductivity of specimen containing 0% fly ash was characterized by a gradual but erratic decrease which may suggests partial entry of the leachate cations into the double layer. Conversely, specimens containing fly ash showed a general trend consisting of an initial drop in k (up to an order of magnitude) that was followed by slight decrease sustained until k stabilized and later terminated. Above 10% fly ash content, the relatively high values of k observed was not connected with the reactivity of the soil mixtures with leachate, rather it may be attributed to excessive fly ash content that altered their textural and hydraulic properties. The result of this study is potentially significant in the assessment of fly ash as a compatibility enhancing agent which can be admixed in barrier materials that are susceptible to adverse reactions with the liquid to be contained.     

Helium and argon isotope geochemistry of natural gases in China’s petroliferous basins

The age-accumulation effect of 40Ar in hydrocarbon source rocks was discussed in accordance with the decay law of radioactive elements. In terms of the mean values of 40Ar/36Ar, the old Sinian gas reservoirs (mean values of 40Ar/36Ar: 7009) were definitely distinguished from the Permian gas reservoirs (mean values of 40Ar/36Ar: 1017) in Weiyuan, Sichuan Province, and the gas source of the Permian gas reservoir (mean values of 40Ar/36Ar: 5222) in well Wei-7 with the Weiyuan structure is defined as the Sinian system. Based on the values of 40Ar/36Ar, the coal-type gases (The source rocks are of the C-P system; mean values of 40Ar/36Ar: 1125) are definitely distinguished from the oil-type gases (The source rocks are of the Tertiary system; mean values of 40Ar/36Ar: 590) in the Tertiary reservoirs of the Zhongyuan Oilfield. Besides, 40Ar/36Ar values also have a positive effect on the oil-source correlation of oil reservoirs in ancient hidden mountains. According to the crust-mantle interchange information reflected by 3He/4He values, petroliferous provinces in China can be divided into three major tectonic regions. (1) The eastern active region: The crust-mantle volatile matter exchanges actively, and the 3He/4He values are mainly around 10-6, partly around 10-7. (2) The central stable region: The 3He/4He values are all around 10-8. (3) The western sub-stable region: The 3He/4He values are mainly around 10-8, and around 10-7 on the edges of the basins. Helium contents of some gas wells in China’s eastern petroliferous region reach the industrial abundance (He≈0.05%–0.1%), the 3He/4He values reach 10-6, and the equivalent values for the mantle-source components in helium gas can reach 30%–50%. As viewed from this, a new type of crust-mantle composite helium resources has been proposed. Geneses of some CO2 gas reservoirs in the east of China and some issues concerning mantle-source methane were discussed in the light of the helium and carbon isotopes of CO2 and CH4 in natural gases. In the discussion on helium isotopic characteristics of inclusions in the reservoirs, it was discovered that the 3He/4He values are close to those in natural gases. That is to say, this phenomenon is related to regional tectonism. The 3He/4He, CO2/3He and CH4/3He data were used to discuss the tectonic activities of fault zones in a certain number of regions in China.     

Behaviour of radiogenic Pb in zircon during ultrahigh-temperature metamorphism: an ion imaging and ion tomography case study from the Kerala Khondalite Belt,southern India

Zircon crystals from a locally charnockitized Paleoproterozoic high-K metagranite from the Kerala Khondalite Belt (KKB) of southern India have been investigated by high-spatial resolution secondary ion mass spectrometry analysis of U–Th–Pb and rare earth elements (REE), together with scanning ion imaging and scanning ion tomography (depth-profiled ion imaging). The spot analyses constrain the magmatic crystallization age of the metagranite to ca. 1,850 Ma, with ultrahigh-temperature (UHT) metamorphism occurring at ca. 570 Ma and superimposed charnockite formation at ca. 520–510 Ma, while the ion imaging reveals a patchy distribution of radiogenic Pb throughout the zircon cores. Middle- to heavy-REE depletion in ca. 570 Ma zircon rims suggests that these grew in equilibrium with garnet and therefore date the UHT metamorphism in the KKB. The maximum apparent ²⁰⁷Pb/²⁰⁶Pb age obtained from the unsupported radiogenic Pb concentrations is also consistent with formation of the Pb patches during this event. The superimposed charnockitization event appears to have caused additional Pb-loss in the cores and recrystallization of the rims. The results of depth-profiling of the scanning ion tomography image stack show that the Pb-rich domains range in size from <5 nm to several 10 nm (diameter if assumed to be spherical). The occurrence of such patchy Pb has previously been documented only from UHT metamorphic zircon, where it likely results from annealing of radiation-damaged zircon. The formation of a discrete, heterogeneously distributed and subsequently immobile Pb phase effectively arrests the normal Pb-loss process seen at lower grades of metamorphism.     

Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.     

Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes,Central Kamchatka Depression

The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (²⁰⁸Pb/²⁰⁴Pb = 37.850–37.903, ²⁰⁷Pb/²⁰⁴Pb = 15.468–15.480, and ²⁰⁶Pb/²⁰⁴Pb = 18.249–18.278 at Bezymianny; ²⁰⁸Pb/²⁰⁴Pb = 37.907–37.949, ²⁰⁷Pb/²⁰⁴Pb = 15.478–15.487, and ²⁰⁶Pb/²⁰⁴Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.     

Responses of microorganisms and enzymes to soil contamination with metazachlor

A greenhouse pot experiment was conducted at the University of Warmia and Mazury in Olsztyn, with the aim of describing the influence of metazachlor on counts and biodiversity of soil microorganisms, soil enzymatic activity, physicochemical properties of soil and yield of spring oilseed rape. The first experimental factor was soil contamination with increasing rates of metazachlor: 0 (soil without the herbicide), 0.333 (recommended by the manufacturer), 6.666, 13.332, 26.665, 53.328, 106.656 and 213.312 mg kg^?1 dm of soil, while the second factor comprised two dates of determination: 30 and 60 days after starting the experiment. The tested herbicide had an adverse effect on reproduction of all analyzed microorganisms: oligotrophic bacteria and their endospore forms, Azotobacter spp. bacteria, organotrophic bacteria, actinomycetes and fungi. The values of the colony development and eco-physiological diversity indices decreased under the influence of excessive doses of the herbicide. Also, significant fluctuation in the enzymatic activity of soil was observed in response to the higher doses of metazachlor and depending on the date of determinations. The herbicide had an invariably negative influence on the activity of soil enzymes, causing the inhibition of dehydrogenases, catalase, urease, acid phosphatase, alkaline phosphatase, arylsulfatase and β-glucosidase. The physicochemical status of soil depended significantly on the degree of soil contamination with the herbicide, same as the yield of spring oilseed rape.