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81.
Marine-evaporitic brines frequently display Na, Cl and Br concentrations that significantly deviate from seawater evaporation paths, yielding markedly conflicting degrees of evaporation calculated for a specific brine. Here we present 493 new and 33 previously reported analyses of Ca-chloridic waters of Neogene age from the Dead Sea Rift (DSR) valley to explain such offsets. The DSR brines plot along an almost perfect mixing line (R2 = 0.990) on a Br/Cl-Na/Cl diagram, extending between two end members A and B. Points A and B are located at Na/Cl = 0.804 and Br/Cl = 0.00193, and at Na/Cl = 0.00773 and Br/Cl = 0.0155, respectively, within the halite and bischofite stability fields.Brines A and B originated in a dual-mode evaporation basin. Brine A formed under the classic lagoon scenario (mode A), with seawater inflow and brine outflow at steady state. Occasional drops in water level, imposed by climatic or tectonic causes, resulted in outflow cutoff and in rapid concentration buildup. The second mode (B) initiated upon equilibration of the activity of water in the brine with the overlying relative humidity, resulting in composition and salinity approaching that of brine B, sustaining it until the next reversal to mode A.Thick evaporite deposits inhibited infiltration of brines A and B into the subsurface terrain, a process that was enabled only when the brine reached the permeable carbonate rock rim and border faults of the basin. Hence, brines that formed during the relatively short shifts from mode A to mode B could not penetrate into the deep subsurface, and bittern minerals that were formed during the frequent mode shifts were dissolved and flushed out into the sea upon the next resumption of outflow.The proposed model accounts for the deviations of brines from the marine evaporitic evolution curve by brine mixing, rather than due to a change in ocean chemistry. It also explains the absence of bittern minerals in the thick halite and gypsum/anhydrite succession, and the compositional gap between the widely different end member hypersaline fluids. This model applies directly to the studied DSR brines and evaporites, but it may be relevant to other inland evaporitic basins.  相似文献   
82.
The biogeochemical cycle of iron and associated elements in Lake Kinneret   总被引:2,自引:0,他引:2  
Iron biogeochemical cycling and distribution between particulate, reactive (colloidal + dissolved, oxine-labile, Fe(II)) fractions were studied in the seasonally stratified, mesotrophic Lake Kinneret. This article presents various aspects of the Fe budget in the lake and relates them to the chemical reactivity of various physicochemical forms of Fe.The budget of Fe in Lake Kinneret is dominated by fluvial Fe load, rather than by internal recycling of Fe from the sediment, as shown by the fact that 75 to 94% of the variance in Fe concentrations in the lake can be explained by the fluctuation in the water discharge of the Jordan River. Iron associated with phytoplankton accounts for 9-16% of the bulk particulate Fe in the lake. However, within patches of the dominate algae, the dinoflagellate Peridinium gatunense, algal Fe accounts for more than 70% of the lake’s particulate Fe. The algal Fe is predominantly intracellular, and the Fe: chlorophyll a ratios were within the range of published values for dinoflagellates and cyanobacteria. Iron associated with particles larger than 0.025 μm (20-300 nM) accounts for 80-95% of total Fe in the epilimnion of Lake Kinneret throughout the year. In contrast, this fraction of Fe is dominant in the hypolimnion only during the period of lake mixing. Iron concentration of different size fractions (<0.025 μm, <0.2 μm and >0.025 μm) in the surface water covaried throughout the research period. These covariations suggest dynamic transformations of Fe between different size fractions, either due to partial dissolution/precipitation or desorption/adsorption. Oxine-labile Fe concentrations, the Fe fraction considered chemically labile and available for phytoplankton, ranged from 15 to 75 nM. In wintertime, the oxine-labile Fe accounts for only 10-20% of the total Fe, while in other seasons most of the Fe is oxine-labile. Oxine-labile Fe concentrations always exceed the 0.025 μm-filtered Fe, implying that some of the larger particles contain oxine labile-Fe, and therefore are reactive. The fraction of reactive particles in Lake Kinneret (10-80%) is high relative to that of the marine environments, and can most likely be attributed to its fluvial source, which contains a significant proportion of reactive Fe oxide and hydrous oxide particles.The annual variability in the epilimnetic concentrations of other trace elements and nutrients, such as Al, Mn, Cd, Zn, Pb, and P were studied and grouped according to their resemblance with river water discharge, redox processes, or biological uptake and scavenging. Distribution patterns of Al, Pb and Cd resembled that of Fe, suggesting that similar processes control the concentrations of these metals, namely significant contribution from the watershed, high affinity to particulate matter and little control of biota on their fate in the lake. Other elements such as Zn and P are more affected by biological uptake, while Mn is more affected by redox cycling within the lake.  相似文献   
83.
We investigated the effects of diagenetic alteration (dissolution, secondary aragonite precipitation and pore filling) on the distribution of U in live and Holocene coral skeletons. For this, we drilled into large Porites lutea coral-heads growing in the Nature Reserve Reef (NRR), northern Gulf of Aqaba, a site close to the Marine Biology Laboratory, Elat, Israel, and sampled the core material and porewater from the drill-hole. In addition, we sampled Holocene corals and beachrock aragonite cements from a pit opened in a reef buried under the laboratory grounds. We measured the concentration and isotopic composition of U in the coral skeletal aragonite, aragonite cements, coral porewater and open NRR and Gulf of Aqaba waters.Uranium concentration in secondary aragonite filling the skeletal pores is significantly higher than in primary biogenic aragonite (17.3 ± 0.6 compared to 11.9 ± 0.3 nmol · g−1, respectively). This concentration difference reflects the closed system incorporation of uranyl tri-carbonate into biogenic aragonite with a U/Ca bulk distribution coefficient (KD) of unity, versus the open system incorporation into secondary aragonite with KD of 2.4. The implication of this result is that continuous precipitation of secondary aragonite over ∼1000 yr of reef submergence would reduce the coral porosity by 5% and can produce an apparent lowering of the calculated U/Ca - SST by ∼1°C and apparent age rejuvenation effect of 7%, with no measurable effect on the calculated initial U isotopic composition.All modern and some Holocene corals (with and without aragonite cement) from Elat yielded uniform δ234U = 144 ± 5, similar to the Gulf of Aqaba and modern ocean values. Elevated δ234U values of ∼180 were measured only in mid-Holocene corals (∼5000 yr) from the buried reef. The values can reflect the interaction of the coral skeleton with 234U-enriched ground-seawater that washes the adjacent granitic basement rocks.We conclude that pore filling by secondary aragonite during reef submergence can produce small but measurable effects on the U/Ca thermometry and the U-Th ages. This emphasizes the critical importance of using pristine corals where the original mineralogy and porosity are preserved in paleooceanographic tracing and dating.  相似文献   
84.
In this study, we explored the spatial and temporal relations between boulders and their original in-situ locations on sandstone bedrock cliffs. This was accomplished by combining field observations with dating methods using cosmogenic isotopes (10Be and 14C) and optically stimulated luminescence (OSL). Our conclusions bear both on the landscape evolution and cliff retreat process in the hyperarid region of Timna and on the methodology of estimating exposure ages using cosmogenic isotopes.

We recognize three discrete rock fall events, at 31 ka, 15 ka, and 4 ka. In this hyperarid region, the most plausible triggering mechanism for rock fall events is strong ground acceleration caused by earthquakes generated by the nearby Dead Sea fault (DSF). Our record, however, under represents the regional earthquake record implying that ongoing development of detachment cracks prior to the triggering event might be slower than the earthquake cycle.

Cliff retreat rates calculated using the timing of rock fall events and estimated thickness of rock removed in each event range between 0.14 m ky− 1 and 2 m ky− 1. When only full cycles are considered, we derive a more realistic range of 0.4 m ky− 1 to 0.7 m ky− 1. These rates are an order of magnitude faster than the calculated rate of surface lowering in the area. We conclude that sandstone cliffs at Timna retreat through episodic rock fall events that preserve the sharp, imposing, landscape characteristic to this region and that ongoing weathering of the cliff faces is minor.

A 10%–20% difference in the 10Be concentrations in samples from matching boulder and cliff faces that have identical exposure histories and are located only a few meters apart indicates that cosmogenic nuclide production rates are sensitive to shielding and vary spatially over short distances. However, uncertainties associated with age calculations yielded boulder and matching cliff face ages that are similar within 1 σ . The use of external constraints in the form of field relations and OSL dating helped to establish each pair's age. The agreement between calculated 14C and 10Be ages indicates that the accumulation of 10Be at depth by the capture of slow deep-penetrating muons was properly accounted for in the study.  相似文献   

85.
Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H2S(gas). Up to 70% of this organic sulfur is released as H2S(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in 34S during thermal maturation compared with the initial δ34S values. The δ34S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most 34S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H2S is a result of the system not being in equilibrium. As partial pressure of H2S(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ34S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ34S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H2S-pyrite correlations. In particular, the use of pyrite-kerogen δ34S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ34S of each phase including the H2S(gas). H2S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.  相似文献   
86.
87.
Bubble growth in rhyolitic melts: experimental and numerical investigation   总被引:2,自引:0,他引:2  
 Bubble growth controlled by mass transfer of water from hydrated rhyolitic melts at high pressures and temperatures was studied experimentally and simulated numerically. Rhyolitic melts were hydrated at 150 MPa, 780–850  °C to uniform water content of 5.5–5.3 wt%. The pressure was then dropped and held constant at 15–145 MPa. Upon the drop bubbles nucleated and were allowed to grow for various periods of time before final, rapid quenching of the samples. The size and number density of bubbles in the quenched glasses were recorded. Where number densities were low and run duration short, bubble sizes were in accord with the growth model of Scriven (1959) for solitary bubbles. However, most results did not fit this simple model because of interaction between neighboring bubbles. Hence, the growth model of Proussevitch et al. (1993), which accounts for finite separation between bubbles, was further developed and used to simulate bubble growth. The good agreement between experimental data, numerical simulation, and analytical solutions enables accurate and reliable examination of bubble growth from a limited volume of supersaturated melt. At modest supersaturations bubble growth in hydrated silicic melts (3–6 wt% water, viscosity 104–106 Pa·s) is diffusion controlled. Water diffusion is fast enough to maintain steady-state concentration gradient in the melt. Viscous resistance is important only at the very early stage of growth (t<1 s). Under the above conditions growth is nearly parabolic, R2=2Dtρm(C0–Cf)/ρg until the bubble approaches its final size. In melts with low water content, viscosity is higher and maintains pressure gradients in the melt. Growth may be delayed for longer times, comparable to time scales of melt ascent during eruptions. At high levels of supersaturation, advection of hydrated melt towards the growing bubble becomes significant. Our results indicate that equilibrium degassing is a good approximation for modeling vesiculation in melts with high water concentrations (C0>3 wt%) in the region above the nucleation level. When the melt accelerates and water content decreases, equilibrium can no longer be maintained between bubbles and melt. Supersaturation develops in melt pockets away from bubbles and new bubbles may nucleate. Further acceleration and increase in viscosity cause buildup of internal pressure in the bubbles and may eventually lead to fragmentation of the melt. Received: 19 June 1995 / Accepted: 27 December 1995  相似文献   
88.
Sr, O, and D/H isotopic compositions have been analyzed in Miocene metaluminous to slightly peraluminous (I-type) granitoids of the central Aegean. Individual plutonic complexes display significant variations in their 18O and initial87Sr/86Sr compositions.D and 18O compositions of minerals and whole-rocks are mostly in the magmatic range. Some samples from Naxos and Mykonos/Delos show low D and 18O values characteristic of meteoric-water-hydrothermal interaction, but as a whole the changes in 18O and Sr isotopic compositions as a result of hydrothermal alteration were slight, even in instances where marked alteration is petrographically observable. Consequently, the bulk-rock variations of 18O from 8.1 to 12.0 and of87Sr/86Sr from 0.70438 to 0.71450 may be regarded as primary and indicative of the conditions of their evolution. Heterogeneous isotopic compositions observed in the individual plutons of Serifos, Ikaria, Samos and Kos may be caused by the multiple intrusion of chemically and isotopically distinct magma pulses, with high viscosities and relatively rapid consolidation in most cases preventing complete homogenization. The granitoids of Serifos, Ikaria and Kos display weak correlations between the initial87Sr/86Sr and 18O and 1/Sr. The granitoid province shows a positive correlation between87Sr/86Sr and 18O and a non-linear relationship between87Sr/86Sr and 1/Sr, whereby 1/Sr increases more rapidly than the isotopic ratio as the degree of fractionation of the rocks increases. It is argued that assimilation of older continental material by mantle-derived arc magmas with combined fractionation (AFC) is the most plausible model to explain the chemical and isotopic characteristics of the granitoids and the geological situation in which rock-types trend from granodiorites in the (south)west, near the inferred Oligocene-Miocene suture, to granites in the center and monzonites in the (north)east of the province.  相似文献   
89.
The kinetics and mechanisms of the dehydration reactions of zoisite have been studied at 635°–792° C, 1–2 kbar. The equilibrium reaction does not occur and is replaced by metastable reactions involving the formation of gehlenite and a calcium tri-octahedral mica, instead of corundum: zoisite anorthite+grossular+gehlenite +calcium 3T mica+H2O.The experimental data can be interpreted by zero-order equations dX An/dt=k (X An=fractional extent of reaction, t=time, k=zero-order rate constant). These relations hold for variations in P, T, A initial(the initial surface area of zoisite) and also in the presence of seed crystals, which enhance the reaction rate. No induction period is evident and only at advanced stages of reaction are sharp decreases observed in the rate, which are attributed to physical affects (shrinking particles, armouring). SEM studies show that dissolution of zoisite is anisotropic, occurring preferentially parallel to the crystallographic b-axis, with the result that a characteristic sawtooth etch structure develops. Garnet grows as euhedral crystals located in cavities or on teeth of dissolving zoisite, whereas anorthite forms as clusters of coalescing grains which spread over and enclose the zoisite. In seeded runs, garnet growth initiates on both seeds and on zoisite surfaces whereas anorthite growth is more closely tied to the seeds, resulting in the development of clusters of smaller grains.The experimental evidence favours dissolution and nucleation-controlled growth as rate-determining processes. The preservation of zero-order kinetics in the face of shrinking particles is attributed to the anisotropic dissolution mechanism, which effectively preserves a constant reaction interface. The rate effects of nucleation appear to accord with the classic model in which growth of crystal layers is initiated by the formation of coherent nuclei.The temperature dependence of rate constants reflects both thermally activated Arrhenius-type behaviour and the rate-depressing influences of approach to equilibrium. Similarly pressure affects on reaction rate can be interpreted in terms of competition between rate enhancement due to pressure increase and rate-depression accompanying the approach to equilibrium. Although the equilibrium-approach effects accord with current treatments of reaction kinetics, a problem exists in deriving an exact relation coupling dissolution and nucleation rate control. Consequently an overall-reaction rate equation, such as that of Fisher and Lasaga (1981), is only partially successful in interpreting the temperature dependence of rates. The data suggest that the surface reaction equation of Wood and Walther (1983) only applies when nuclei are present.  相似文献   
90.
Crystallization of anatectic melts in high-temperature metamorphic terrains releases volatile-rich magmas that can be transported into adjacent lithologies. This study addresses the variations in the oxygen, boron and hydrogen isotopic composition of aplite-pegmatite dikes that formed during the crystallization of anatectic melts in regional high-temperature metamorphism on the island of Naxos, Greece, and propagated upward into the overlying sequences of metamorphic schist. The transport distance of these dikes was increased through a significant horizontal component of travel that was imposed by contemporaneous low-angle extensional shearing. Laser fluorination oxygen isotope analyses of quartz, tourmaline, garnet, and biotite mineral separates from the aplite-pegmatite dikes show a progressive rise in δ18O values with increasing distance from the core. Oxygen isotope fractionations among quartz, tourmaline, and garnet show temperature variations from > 700°C down to ∼400°C. This range is considered to reflect isotopic fractionation beginning with crystallization at high temperatures in water-undersaturated conditions and then evolving through lower temperature crystallization and retrograde sub-solidus exchange. Two processes are examined for the cause of the progressive increase in δ18O values: (1) heterogeneous δ18O sources and (2) fluid-rock exchange between the aplite/pegmatite magmas and their host rock. Although the former process cannot be ruled out, there is as yet no evidence in the exposed sequences on Naxos for the presence of a suitable high δ18O magma source. In contrast, a tendency for the δ18O of quartz in the aplite/pegmatite dikes to approach that of the quartz in the metamorphic rock suggests that fluid-rock exchange with the host rock may potentially be an important process. Advection of fluid into the magma is examined based on Darcian fluid flow into an initially water-undersaturated buoyantly propagating aplitic dike magma. It is shown that such advective flow could only account for part of the 18O-enrichment, unless it were amplified by repeated injection of magma pulses, fluid recycling, and deformation-assisted post-crystallization exchange. The mechanism is, however, adequate to account for hydrogen isotope equilibration between dike and host rock. In contrast, variations in the δ11B values of tourmalines suggest that 11B/10B fractionation during crystallization and/or magma degassing was the major control of boron geochemistry rather than fluid-rock interaction and that the boron isotopic system was decoupled from that of oxygen.  相似文献   
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