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1.
Miron  Assaf  Tadmor  Rafael  Pinkert  Shmulik 《Acta Geotechnica》2023,18(1):95-104
Acta Geotechnica - This paper presents a novel conceptual approach for evaluating the mechanical effect of pore liquids on the overall geotechnical behavior. The approach is based on empiric...  相似文献   

2.
Determination of xenobiotics in samples of airport runoff water is both a complex and indispensable task due to an increasing threat resulting from the activities of numerous airports. The aim of this study was to develop, optimize, and validate a procedure based on liquid–liquid extraction (LLE) coupled with gas chromatography–mass spectrometry (GC–MS) for the determination of polycyclic aromatic hydrocarbons (PAHs). So far, no procedure was available that would ensure reliable data about concentration levels of these toxic pollutants in a new type of environmental samples, such as airport stormwater. The most difficult step in the analytical procedure used for the determination of fuel combustion products in airport stormwater samples is sample preparation. In this work, eight different protocols of sample preparation were tested. The evaluation of the LLE demonstrated that the best extraction conditions were as follows: dichloromethane (extraction solvent), solvent volume of 15 mL and sample volume of 250 mL. The percent recovery values ranged from 66 to 106 %, which shows that the LLE technique is a powerful method for extracting PAHs from airport runoff water samples with a complex matrix composition. Moreover, the developed procedure was characterized by satisfactory selectivity and a relatively low LOQ (0.17–0.52 μg/L). The procedure has been successfully applied to the analysis of stormwater samples collected from different sites at international airport in Poland. The procedure can thus be used as a tool for tracking the environmental fate of these compounds and for assessing the environmental effect of airports.  相似文献   

3.
Clinopyroxene + liquid equilibria to 100 kbar and 2450 K   总被引：5，自引：1，他引：4  
One of the most active issues in igneous petrology is the investigation of mantle melting, and subsequent differentiation. To evaluate alternative hypotheses for melting and differentiation it is essential to accurately predict clinopyroxene compositions in natural systems. Expressions have thus been derived that describe clinopyroxene-melt equilibria, and allow equilibrium clinopyroxene compositions to be calculated. These equations were constructed from least-squares regression analysis of experimental clinopyroxene-liquid pairs. The calibration database included clinopyroxenes synthesized from both natural and synthetic basalt compositions; experimental conditions ranged from 0 to 100 kbar and 1350 to 2450 K. Regression equations were based on thermodynamic functions. Empirical expressions were also derived, since such models yield more precise estimates of clinopyroxene compositions, and may be easily incorporated into existing liquid line-of-descent models. Such equations may be useful for calculation of high pressure liquid fractionation, or for constraining P-T conditions for basalts produced by partial melting of a pyroxene-bearing source. Models of mantle melting often rely on expressions involving simple element ratios. Partition coefficients (K d cpx/liq ) for the minor elements, Na and Ti, were thus also calibrated as a function of P, T and composition. K Ti cpx/liq , while sensitive to composition was relatively insensitive to P and T. In contrast, K Na cpx/liq increases substantially with increasing P, and exceeded 1 in some experiments. Since oceanic basalts show variations in Na/Ti ratios, the potential exists for partial melting depths to be inferred from K Na cpx/liq . Received: 28 May 1997 / Accepted: 20 November 1998  相似文献   

4.
We consider two-component (typically, water and hydrogen) compressible liquid–gas porous media flows including mass exchange between phases possibly leading to gas-phase (dis)appearance, as motivated by hydrogen production in underground repositories of radioactive waste. Following recent work by Bourgeat, Jurak, and Smaï, we formulate the governing equations in terms of liquid pressure and dissolved hydrogen density as main unknowns, leading mathematically to a nonlinear elliptic–parabolic system of partial differential equations, in which the equations degenerate when the gas phase disappears. We develop a discontinuous Galerkin method for space discretization, combined with a backward Euler scheme for time discretization and an incomplete Newton method for linearization. Numerical examples deal with gas-phase (dis)appearance, ill-prepared initial conditions, and heterogeneous problem with different rock types.  相似文献   

5.
We present new thermometers and barometers based on clinopyroxene–liquid equilibria specific to alkaline differentiated magmas. The new models were calibrated through the regression analyses of experimental datasets obtained by merging phase equilibria experiments from the literature with new experiments performed by using trachytic and phonolitic starting compositions. The regression strategy was twofold: (1) we have tested previous thermometric and barometric equations and recalibrated these models using the new datasets; (2) we have calibrated a new thermometer and a new barometer including only regression parameters that closely describe the compositional variability of the datasets. The new models yield more precise estimates than previous thermometers and barometers when used to predict temperatures and pressures of alkaline differentiated magmas. We have tested the reliability of the new equations by using clinopyroxene–liquid pairs from trachytes and phonolites erupted during major explosive eruptions at the Phlegrean Fields and Mt. Vesuvius (central Italy). The test yielded crystallization conditions comparable to those determined by means of melt and fluid inclusion analyses and phase equilibria studies; this validates the use of the proposed models for precise estimates of crystallization temperatures and pressures in differentiated alkaline magmas. Because these magmas feed some of the most voluminous, explosive, and threatening volcanic eruptions in the world, a better understanding of the environmental conditions of their reservoirs is mandatory and this is now possible with the new models provided here.  相似文献   

6.
The density of liquid Fe–S was measured at 4 GPa and 1,923 K using a sink/float method with a composite density marker. The density marker consisted of a Pt rod core and an Al2O3 tube surrounding. The uncertainty in the density of the composite marker is much smaller than that of the composite sphere, which had been used in previous density measurements. The density of liquid Fe–S decreases nonlinearly with increasing sulfur content at 4 GPa and 1,923 K. This tendency is consistent with the results measured at ambient pressure. The molar volume of FeS calculated from the measured density gradually increases with sulfur content. The excess molar volume from ideal mixing of Fe and S at 4 GPa was negative value. The new method proposed here is applicable to the density measurement of other Fe alloys at high pressure. The tendency of the molar volume and the excess molar volume with sulfur content at ambient pressure is consistent with these at high pressure at least up to 4 GPa. The excess molar volume at high pressure is essential for estimating the amount of light elements in the outer core.  相似文献   

7.
Glycerol ether lipid distributions have been developed as proxies for reconstructing past environmental change or, in their intact polar form, for fingerprinting the viable microbial community composition. However, due to their structural complexity, full characterization of glycerol ether lipids requires separate protocols for the analysis of the polar head groups and the alkyl chain moieties in core ether lipids. As a consequence, the valuable relationship between core ether lipid composition and specific polar head groups is often lost; this limits understanding of the diversity of ether lipids and their utility as biogeochemical proxies. Here, we report a novel reversed phase liquid chromatography–electrospray ionization-mass spectrometry (RP-ESI-MS) protocol that enables the simultaneous analysis of polar head groups (e.g. phosphocholine, phosphoglycerol, phosphoinositol, hexose and dihexose) and alkyl moieties (e.g. alkyl moieties modified with different numbers of cycloalkyl moieties, hydroxyl and alkyl groups and double bonds) in crude lipid extracts without further preparation. The protocol greatly enhances detection of archaeal intact polar lipids (IPLs) and core lipids (CLs) with double bond- and hydroxyl group-bearing alkyl moieties. With these improvements, widely used ratios that describe relative distributions of the core lipids, such as TEX86 and ring index, can now be directly determined in specific intact polar lipids (IPL-specific TEX86 and ring index). Since IPLs are the putative precursors of the environmentally persistent core lipids, their detailed examination using this protocol can potentially provide new insights into diagenetic and biological mechanisms inherent to these proxies. In a series of 12 samples from diverse settings, core and IPL-specific TEX86 values followed the order: 2G-GDGTs > core GDGTs > 1G-GDGTs > 1G-GDGT-PI and the ring indices followed: 1G-GDGTs ≈ core GDGTs > 2G-GDGTs > 1G-GDGT-P1G > 2G-OH-GDGTs ≈ 1G-OH-GDGTs (1G, monoglycosyl; 2G, diglycosyl; P1G, phosphomonoglycosyl; GDGT, glycerol dialkyl glycerol tetraether).  相似文献   

8.
To evaluate the applicability of P2O5 concentration in potassic alkali feldspar as a monitor of P2O5 in melt for undercooled systems, crystal–melt partitioning for P was evaluated via feldspar growth experiments in P-bearing ((3 wt% P2O5), water-saturated haplogranitic liquids at 200 MPa, with liquidus undercoolings (ΔT) of 25, 50, 100, 200, and 300°C. Increasing undercooling in the range ΔT=25–200°C shows an evolution of crystal morphologies, from euhedral and well-filled individuals at ΔT=25–50°C to radial clusters with increasingly skeletal habit at greater undercooling. Experiments at ΔT=100–200°C also document the development of P- (up to (9 wt% P2O5) and Si-enriched, more alkaline boundary layers adjacent to crystals. Experiments at ΔT=300°C show an additional change in crystallization fabric in which spherulites of skeletal crystals form in open (vapor) space created by the dissolution of bulk silicate, and compositional boundary layers are not observed. We interpret the changes in reaction products at ΔT=300°C to indicate conditions below a glass transition; hence, partition coefficients were not determined for this undercooling. Values of K d(P)Kfs/melt from experiments at ΔT=25–200°C, calculated from pairs of crystal and immediately adjacent liquid compositions (including boundary layers at higher undercooling), are mostly in the range of 0.25–0.55 and show no effective change with increased undercooling. Essentially no change in K d(P)Kfs/melt with undercooling apparently stems from an interplay between boundary layer composition and a change in the substitution mechanism for P in feldspar from AlPSi−2, common in peraluminous to metaluminous liquids near equilibrium, to increasing proportions of ([ ],P)(M+,Si)−1 with increased undercooling. Bulk glass and liquid beyond boundary layers in experiments with significant percentages of crystallization are homogeneous, and show pronounced fractionation primarily due to the removal of an orthoclase component. Because crystallization was still in progress in experiments with ΔT≤200°C, compositional homogeneity in the bulk liquid requires extremely rapid diffusion of most haplogranite components (Na, K, and Al), apparently resulting from chemical potential gradients stemming from the removal of components from the liquid by crystal growth. Similar homogeneity and bulk fractionation in experiments with ΔT=300°C requires rapid diffusive equilibration for the alkalis even at temperatures below an apparent glass transition. Unlike the haplogranite components, P is only concentrated in liquid boundary layers (ΔT≤200°C) or low-density aqueous vapor (ΔT=300°C) adjacent to crystals. Hence, the P2O5 contents of melt inclusions likely are not representative of bulk melt concentrations in significantly undercooled systems (ΔT≤50–100°C).  相似文献   

9.
The compositional dependence on the density of liquid Fe alloys under high pressure is important for estimating the amount of light elements in the Earth’s outer core. Here, we report on the density of liquid Fe–Si at 4 GPa and 1,923 K measured using the sink–float method and our investigation on the effect of the Si content on the density of the liquid. Our experiments show that the density of liquid Fe–Si decreases from 7.43 to 2.71 g/cm3 non-linearly with increasing Si content (0–100 at%). The molar volume of liquid Fe–Si calculated from the measured density gradually decreases in the compositional range 0–50 at% Si, and increases in the range 50–100 at% Si. It should be noted that the estimated molar volume of the alloys shows a negative volume of mixing between Fe and Si. This behaviour is similar to Fe–S liquid (Nishida et al. in Phys Chem Miner 35:417–423, 2008). However, the excess molar volume of mixing for the liquid Fe–Si is smaller than that of liquid Fe–S. The light element contents in the outer core estimated previously may be an underestimation if we take into account the possible negative value of the excess mixing volume of iron–light element alloys in the outer core.  相似文献   

10.
《Comptes Rendus Geoscience》2019,351(2-3):154-162
We present a comprehensive analysis of electrical resistivity for liquid Fe–Si, Fe–S, and Fe–O alloys from first principles computations, covering the pressure/temperature conditions and major light element candidates inside the cores of terrestrial planets. By fitting optical conductivity with the Drude formula, we explicitly calculate the effective electron mean free path, and show that it becomes comparable to the interatomic distance for high densities and Si/S concentrations (Ioffe–Regel criterion). In approaching the Ioffe–Regel criterion, the temperature coefficient of resistivity decreases with compression for all compositions, eventually vanishes (Fe–Si), or even changes sign (Fe–S). Differences in resistivity and the degree of saturation between the iron alloys studied are explained in terms of iron–light element coordination numbers and their density dependence. Due to competing temperature and pressure effects, resistivity profiles along proposed core adiabats exhibit a small negative pressure gradient.  相似文献   

11.
In this paper, a local non-equilibrium diffuse interface model is introduced for describing solid–liquid dissolution problems. The model is developed based on the analysis of Golfier et al. (J Fluid Mech 457:213–254, 2002) upon the dissolution of a porous domain, with the additional requirement that density variations with the mass fraction are taken into account. The control equations are generated by the upscaling of the balance equations for a solid–liquid dissolution using a volume averaging theory. This results into a diffuse interface model (DIM) that does not require an explicit treatment of the dissolving interface, e.g., the use of arbitrary Lagrangian–Eulerian (ALE) methods, for instance. Test cases were performed to study the features and influences of the effective coefficients inside the DIM. In particular, an optimum expression for the solid–liquid exchange coefficient is obtained from a comparison with the referenced solution by ALE simulations. Finally, a Ra–Pe diagram illustrates the interaction of natural convection and forced convection in the dissolution problem.  相似文献   

12.
This research presents the individual amino acid δ13C values in bone collagen of humans (n = 9) and animals (n = 27) from two prehistoric shell midden sites in Korea. We obtained complete baseline separation of 16 of the 18 amino acids found in bone collagen by using liquid chromatography-isotope ratio mass spectrometry (LC-IRMS). The isotopic results reveal that the humans and animals in the two sites had similar patterns in essential amino acids (EAAs) and non-essential amino acids (NEAAs). The EAA and NEAA δ13C values in humans are intermediate between those in marine and terrestrial animals. However, the threonine δ13C values in humans and animals measured in this study are more highly enriched than those of other amino acids. At both sites, all amino acids in marine animals are 13C-enriched relative to those of the terrestrial animals. The isotopic evidence suggests that the Tongsamdong human had EAAs and NEAAs from marine food resources, while the Nukdo humans mainly had EAAs from terrestrial food resources but obtained NEAAs from both terrestrial and marine resources. The δ13C isotopic differences in amino acids between marine and terrestrial animals were the largest for glycine (NEAA) and histidine (EAA) and the smallest for tyrosine (NEAA) and phenylalanine (EAA). In addition, threonine among the EAAs also had a large difference (∼8‰) in δ13C values between marine and terrestrial animals, and has the potential to be used as an isotopic marker in palaeodietary studies. Threonine δ13C values were used in conjunction with the established Δ13CGlycine-phenylalanine values and produced three distinct dietary groups (terrestrial, omnivorous, and marine). In addition, threonine δ13C values and Δ13CSerine-phenylalanine values were discovered to separate between two dietary groups (terrestrial vs. marine), and these δ13C values may provide a potential new indicator for investigating the distinction between marine and terrestrial protein sources in human diets.  相似文献   

13.
The metasomatism observed in the oceanic and continental lithosphere is generally interpreted to represent a continuous differentiation process forming anhydrous and hydrous veins plus a cryptic enrichment in the surrounding peridotite. In order to constrain the mechanisms of vein formation and potentially clarify the nature and origin of the initial metasomatic agent, we performed a series of high-pressure experiments simulating the liquid line of descent of a basanitic magma differentiating within continental or mature oceanic lithosphere. This series of experiments has been conducted in an end-loaded piston cylinder apparatus starting from an initial hydrous ne-normative basanite at 1.5 GPa and temperature varying between 1,250 and 980°C. Near-pure fractional crystallization process was achieved in a stepwise manner in 30°C temperature steps and starting compositions corresponding to the liquid composition of the previous, higher-temperature glass composition. Liquids evolve progressively from basanite to peralkaline, aluminum-rich compositions without significant SiO2 variation. The resulting cumulates are characterized by an anhydrous clinopyroxene + olivine assemblage at high temperature (1,250–1,160°C), while at lower temperature (1,130–980°C), hydrous cumulates with dominantly amphibole + minor clinopyroxene, spinel, ilmenite, titanomagnetite and apatite (1,130–980°C) are formed. This new data set supports the interpretation that anhydrous and hydrous metasomatic veins could be produced during continuous differentiation processes of primary, hydrous alkaline magmas at high pressure. However, the comparison between the cumulates generated by the fractional crystallization from an initial ne-normative liquid or from hy-normative initial compositions (hawaiite or picrobasalt) indicates that for all hydrous liquids, the different phases formed upon differentiation are mostly similar even though the proportions of hydrous versus anhydrous minerals could vary significantly. This suggests that the formation of amphibole-bearing metasomatic veins observed in the lithospheric mantle could be linked to the differentiation of initial liquids ranging from ne-normative to hy-normative in composition. The present study does not resolve the question whether the metasomatism observed in lithospheric mantle is a precursor or a consequence of alkaline magmatism; however, it confirms that the percolation and differentiation of a liquid produced by a low degree of partial melting of a source similar or slightly more enriched than depleted MORB mantle could generate hydrous metasomatic veins interpreted as a potential source for alkaline magmatism by various authors.  相似文献   

14.
The monitoring of sulfur species in crater lakes has proven to be useful for forecasting episodes of volcanic unrest in certain active volcanoes, including Poás, Costa Rica; Kusatsu-Shirane, Japan; and Mt. Ruapehu, New Zealand. In this study, we have improved the current geochemical monitoring of El Chichón volcano through the setting of optimal high-performance liquid chromatography conditions (HPLC) for the analysis of S2−, SO32−, S2O32−, S4O62− and SO42− using a common chromatographic system. The procedure was applied to the analysis of lake samples taken in March, July and October of 2014 and April of 2015. The results were promising, since nearly all species were detected (with the exception of S2O32−) in measurable amounts, including S2− (<0.85–5.05 mg/L), SO32− (<2.77–26.1 mg/L), S4O62− (108.27–303.82 mg/L) and SO42− (489.58–676.26 mg/L). The spatial distribution of these species along the lakeshore showed zones of increased concentrations to the east and southeast of the lake, which provides information on the distribution of faults or cracks that feed hydrothermal fluids to the lake. This method thus provides additional information linked to the volcanic and hydrothermal activity of the volcano.  相似文献   

15.
As there are many correlations linking the liquid limit directly or indirectly with various engineering properties of the soil, the accurate determination of the liquid limit is quite essential. Generally, two methods, i.e. Casagrande’s and fall cone are adopted to determine the liquid limit of soil. Research was carried out to study the influence of the properties of bentonite and the presence of the salt solution on the liquid limit values of soil-bentonite mixtures determined by the Casagrande’s and fall cone methods. The results showed that irrespective of the presence of the type of bentonite or salt solution, a higher value of the liquid limit was obtained by the Casagrande’s method as compared to the fall cone method. However, the difference between the two methods decreased with the decrease in the liquid limit, clay fraction, specific surface area and free swelling capacity of the bentonite present in the mixture. Similarly, the difference in the liquid limit values obtained by both these methods is reduced with an increase in the salt concentration.  相似文献   

16.
Trace element partition coefficients between clinopyroxenes and associated glassy matrix (Cpx/L D) have been determined for 13 REE, HFSE4+,5+, U, Th, Sr, Pb, Sc and V from combined LA-ICP-MS/EMP analyses in selected trachytes and trachyphonolites from Campi Flegrei. Composition of clinopyroxene and glass is pretty homogeneous in the trachyphonolites, pointing to an overall attainment of the equilibrium conditions. In trachytes, conversely, phases show some compositional heterogeneity (due to the presence of clinopyroxene xenocrysts) that requested a more careful petrographic and geochemical inspection of the samples to assess the equilibrium clinopyroxene composition. In the trachyte clinopyroxenes, REE are compatible from Nd to Lu (Cpx/L D up to 2.9), like Y, Ti, Sc and V. The Cpx/L D for Eu is lower than those of the adjacent REE, highlighting Eu2+ contribution. High D values are also shown by U, Th, Pb, Zr, Hf, Nb and Ta relatively to basaltic and andesitic systems, whereas the D Sr is roughly similar to that found for less evolved magmas. Trachyphonolites are characterized by an overall decrease of the Cpx/L D for highly-charged cations (with the exception of V), and by a slight increase of D Sr. REE are still compatible from Nd to Lu (Cpx/L D up to 2.1), like Ti, Y, Sc and V. This variation is also predicted for REE and Y by models based on the elastic strain theory, being consistent with the slightly lower polymerization degree estimated for the trachyphonolites. However, the observed Cpx/L D (REE,Y) are matched by the modelled ones only considering very low T (≤825°C), which are believed unlikely. This mismatch cannot be attributed to effects induced by the water-rich composition of the trachyte–trachyphonolite suite, since they would lower the observed Cpx/L D (REE,Y). Moreover, the anomalous inflections of measured Cpx/L D for HREE suggests some crystal-chemical control, such as the entrance of these elements in a site distinct from M2. It is concluded that the large Cpx/L D determined for trachytes and trachyphonolites are likely induced by hitherto unconstrained changes of the Z3+ activities related to the composition of melt and/or solid. All these considerations strongly highlight the importance of a direct characterization of trace element partitioning in natural samples from magmatic systems poorly characterized by experimental studies. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

17.
正1 Introduction Salt lakes are widely distributed in the western of China,especially in the area of Qinghai-Xizang(Tibet)Plateau.A series of salt lakes in the Qaidam Basin,located in Qinghai Province,China,is famous for their abundance of lithium,potassium and boron resources(Zheng et al,1988;Deng et al,2012).It is well known that the  相似文献   

18.
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19.
Melt inclusions in clinopyroxenes of olivine foidite bombs from Serra di Constantinopoli pyroclastic flows of the Vulture volcano (Southern Italy) were studied in detail. The rocks contain abundant zoned phenocrysts and xenocrysts of clinopyroxene, scarce grains of olivine, leucite, haüyne, glass with microlites of plagioclase and K-feldspar. The composition of clinopyroxene in xenocrysts (Cpx I), cores (Cpx II), and in rims (Cpx III) of phenocrysts differs in the content of Mg, Fe, Ti, and Al. All clinopyroxenes contain two types of primary inclusion-pure silicate and of silicate-carbonate-salt composition. This fact suggests that the phenomena of silicate-carbonate immiscibility took place prior to crystallization of clinopyroxene. Homogenization of pure silicate inclusions proceeded at 1 225 – 1 190°C. The composition of conserved melts corresponded to that of olivine foidite in Cpx I, to tephrite-phonolite in Cpx II, and phonolite-nepheline trachyte in Cpx III. The amount of water in them was no more than 0.9 wt.%. Silicate-carbonate inclusions decrepitated on heating. Salt globules contained salts of alkali-sulphate, alkali-carbonate, and Ca-carbonate composition somewhat enriched in Ba and Sr. This composition is typical of carbonatite melts when decomposed into immiscible fractions. The formation of sodalite-haüyne rocks from Vulture is related to the presence of carbonate-salt melts in magma chamber. The melts conserved in clinopyroxenes were enriched in incompatible elements, especially in Cpx III. High ratios of La, Nb, and Ta in melts on crystallization of Cpx I and Cpx II suggest the influence of a carbonatite melt as carbonatites have extremely high La/Nb and Nb/Ta and this is confirmed by the appearance of carbonatite melts in magma chamber. Some anomalies in the concentrations and relatives values of Eu and especially Ga seems typical of Italian carbonatite related melts. The mantle source for initial melts was, most likely, rather uniform, undepleted and was characterized by a low degree of melting and probable presence of garnet in restite.  相似文献   

20.
We consider the correlation between seismicity, variations in the length of day, and geomagnetic jerks. We found that the jerks precede with in-phase variations in the number of strong earthquakes with М > 6.5 and the rate of the length of day in the range of periods of 5–8 years.  相似文献   

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