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31.
Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ34SSO4 and δ18OSO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ18OH2O and initial δ18OSO4, all strains show 34S enrichment, whereas only six strains show significant 18O enrichment. The remaining six show no (or minimal) change in δ18OSO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO32−), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.  相似文献   
32.
Anthropogenic activities are a disturbance factor of coastal systems and can be widely recognized as a major threat to the health of coastal systems. However, natural events cannot be disregarded from management issues because of their significant influence on the communities living in these areas. Based on long-term subtidal data from the Mondego Estuary (Portugal), the effects of natural events (e.g., floods and droughts) on macrobenthic communities were compared with the anthropogenic events. Sampling stations were grouped into characteristic zones (mouth, north arm, south arm) so the community dynamics of each of these estuarine areas could be followed over time. Environmental assessment was performed for stations using the Benthic Assessment Tool (BAT), and compared with the existing pressures. Human impacts persist over a number of years and gradually reduce ecosystem health, as discussed in the European Water Framework Directive. Paradoxically, natural events cause stronger impacts but are of a shorter duration, which allows for a faster recovery of macrobenthic communities. The study showed that caution should be taken when developing and implementing water policies so as not to disregard the importance of the different events (natural and human-caused) on the ecosystem health (e.g., community degradation and water quality and ecological quality status assessment).  相似文献   
33.
Amphibole is widely employed to calculate crystallization temperature and pressure, although its potential as a geobarometer has always been debated. Recently, Ridolfi et al. (Contrib Mineral Petrol 160:45–66, 2010) and Ridolfi and Renzulli (Contrib Mineral Petrol 163:877–895, 2012) have presented calibrations for calculating temperature, pressure, fO2, melt H2O, and melt major and minor oxide composition from amphibole with a large compositional range. Using their calibrations, we have (i) calculated crystallization conditions for amphibole from eleven published experimental studies to examine the problems and the potential of the new calibrations; and (ii) calculated crystallization conditions for amphibole from basaltic–andesitic pyroclasts erupted during the paroxysmal 2010 eruption of Mount Merapi in Java, Indonesia, to infer pre-eruptive conditions. Our comparison of experimental and calculated values shows that calculated crystallization temperatures are reasonable estimates. Calculated fO2 and melt SiO2 content yields potentially useful estimates at moderately reduced to moderately oxidized conditions and intermediate to felsic melt compositions. However, calculated crystallization pressure and melt H2O content are untenable estimates that largely reflect compositional variation in the crystallizing magmas and crystallization temperature and not the calculated parameters. Amphibole from Merapi’s pyroclasts yields calculated conditions of ~200–800 MPa, ~900–1,050 °C, ~NNO + 0.3–NNO + 1.1, ~3.7–7.2 wt% melt H2O, and ~58–71 wt% melt SiO2. We interpret the variations in calculated temperature, fO2, and melt SiO2 content as reasonable estimates, but conclude that the large calculated pressure variation for amphibole from Merapi and many other arc volcanoes is evidence for thorough mixing of mafic to felsic magmas and not necessarily evidence for crystallization over a large depth range. In contrast, bimodal pressure estimates obtained for other arc magmas reflect amphibole crystallization from mafic and more evolved magmas, respectively, and should not necessarily be taken as evidence for crystallization in two reservoirs at variable depth.  相似文献   
34.
35.
Four samples (TL5b, TL11h, TL11i, and TL11v) from the pristine collection of the Tagish Lake meteorite, an ungrouped C2 chondrite, were studied to characterize and understand its alteration history using EPMA, XRD, and TEM. We determined that samples TL11h and TL11i have a relatively smaller proportion of amorphous silicate material than sample TL5b, which experienced low‐temperature hydrous parent‐body alteration conditions to preserve this indigenous material. The data suggest that lithic fragments of TL11i experienced higher degrees of aqueous alteration than the rest of the matrix, based on its low porosity and high abundance of coarse‐ and fine‐grained sheet silicates, suggesting that TL11i was present in an area of the parent body where alteration and brecciation were more extensive. We identified a coronal, “flower”‐like, microstructure consisting of a fine‐grained serpentine core and coarse‐grained saponite‐serpentine radial arrays, suggesting varied fluid chemistry and crystallization time scales. We also observed pentlandite with different morphologies: an exsolved morphology formed under nebular conditions; a nonexsolved pentlandite along grain boundaries; a “bulls‐eye” sulfide morphology and rims around highly altered chondrules that probably formed by multiple precipitation episodes during low‐temperature aqueous alteration (≥100 °C) on the parent body. On the basis of petrologic and mineralogic observations, we conclude that the Tagish Lake parent body initially contained a heterogeneous mixture of anhydrous precursor minerals of nebular and presolar origin. These materials were subjected to secondary, nonpervasive parent‐body alteration, and the samples studied herein represent different stages of that hydrous alteration, i.e., TL5b (the least altered) < TL11h < TL11i (the most altered). Sample TL11v encompasses the petrologic characteristics of the other three specimens.  相似文献   
36.
Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO2 gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO2 gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO2 gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C292H288O12(c) to produce a mature (oxidized) kerogen represented by C128H68O7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C8.8H16.9 (C8.8H16.9(l)) and CO2 gas (CO2(g)) can be described by writing
(A)  相似文献   
37.
This study establishes for the first time the chronology and limnological history of Lake Amora (Dead Sea basin, Israel), whose deposits (the Amora Formation) comprise one of the longest exposed lacustrine records of the Pleistocene time. The Amora Formation consists of sequences of laminated primary aragonite and silty-detritus, Ca-sulfate minerals, halite and clastic units. This sedimentary sequence was uplifted and tilted by the rising Sedom salt diapir, exposing ∼320 m of sediments on the eastern flanks of Mt. Sedom (the Arubotaim Cave (AC) section).The chronology of the AC section is based on U-disequilibrium dating (230Th-234U and 234U-238U ages) combined with floating δ18O stratigraphy and paleomagnetic constraints. The determination of the 230Th-234U ages required significant corrections to account for detrital Th and U. These corrections were performed on individual samples and on suites of samples from several stratigraphic horizons. The most reliable corrected ages were used to construct an age-elevation model that was further tuned to the oxygen isotope record of east Mediterranean foraminifers (based on the long-term similarity between the sea and lake oxygen isotope archives).The combined U-series-δ18O age-elevation model indicates that the (exposed) Amora sequence was deposited between ∼740 and 70 ka, covering seven glacial-interglacial cycles (Marine Isotope Stages (MIS) 18 to 5).Taking the last glacial Lake Lisan and the Holocene Dead Sea lacustrine systems as analogs of the depositional-limnological environment of Lake Amora, the latter oscillated between wet (glacial) and more arid (interglacial) conditions, represented by sequences of primary evaporites (aragonite and gypsum that require enhanced supply of freshwater to the lakes) and clastic sediments, respectively. The lake evolved from a stage of rapid shifts between high and low-stand conditions during ∼740 to 550 ka to a sabkha-like environment that existed (at the AC site) between 550 and 420 ka. This stage was terminated by a dry spell represented by massive halite deposition at 420 ka (MIS12-11). During MIS10-6 the lake fluctuated between lower and higher stands reaching its highest stand conditions at the late glacial MIS6, after which a significant lake level decline corresponds to the transition to the last interglacial (MIS5) low-stand lake, represented by the uppermost part of the Formation.δ18O values in the primary aragonite range between 6.0 and −1.3, shifting cyclically between glacial and interglacial intervals. The lowest δ18O values are observed during interglacial stages and may reflect short and intense humid episodes that intermittently interrupted the overall arid conditions. These humid episodes, expressed also by enhanced deposition of travertines and speleothems, seem to characterize the Negev Desert, and in contrast to the overall dominance of the Atlantic-Mediterranean system of rain patterns in the Dead Sea basin, some humid episodes during interglacials may be traced to southern sources.  相似文献   
38.
Carbonate sediments in non‐vegetated habitats on the north‐east Adriatic shelf are dominated by shells of molluscs. However, the rate of carbonate molluscan production prior to the 20th century eutrophication and overfishing on this and other shelves remains unknown because: (i) monitoring of ecosystems prior to the 20th century was scarce; and (ii) ecosystem history inferred from cores is masked by condensation and mixing. Here, based on geochronological dating of four bivalve species, carbonate production during the Holocene is assessed in the Gulf of Trieste, where algal and seagrass habitats underwent a major decline during the 20th century. Assemblages of sand‐dwelling Gouldia minima and opportunistic Corbula gibba are time‐averaged to >1000 years and Corbula gibba shells are older by >2000 years than shells of co‐occurring Gouldia minima. This age difference is driven by temporally disjunct production of two species coupled with decimetre‐scale mixing. Stratigraphic unmixing shows that Corbula gibba declined in abundance during the highstand phase and increased again during the 20th century. In contrast, one of the major contributors to carbonate sands – Gouldia minima – increased in abundance during the highstand phase, but declined to almost zero abundance over the past two centuries. Gouldia minima and herbivorous gastropods associated with macroalgae or seagrasses are abundant in the top‐core increments but are rarely alive. Although Gouldia minima is not limited to vegetated habitats, it is abundant in such habitats elsewhere in the Mediterranean Sea. This live–dead mismatch reflects the difference between highstand baseline communities (with soft‐bottom vegetated zones and hard‐bottom Arca beds) and present‐day oligophotic communities with organic‐loving species. Therefore, the decline in light penetration and the loss of vegetated habitats with high molluscan production traces back to the 19th century. More than 50% of the shells on the sea floor in the Gulf of Trieste reflect inactive production that was sourced by heterozoan carbonate factory in algal or seagrass habitats.  相似文献   
39.
Mathematical Geosciences - EURO-CORDEX is an international initiative which provides regional climate projections based on multiple dynamical and empirical–statistical downscaling models. The...  相似文献   
40.
ABSTRACT

Movement patterns of the Southern Rock Lobster Jasus edwardsii in Victoria, Australia were investigated from 8,533 tag-recapture events across a 20-year period (1992–2012). In total, 83% of lobsters were recaptured within 1?km of their tagging site and 93% within 5?km. While largely resident, elevated movements were observed within specific regions, with the overall direction of movement being from inshore to offshore areas. Movement was not impacted by lobster sex, size, or reproductive stage. The fishery for Southern Rock Lobster within Victoria is currently managed into two zones with separate total allowable commercial catches in each area. Given the high levels of site fidelity, our findings suggest that management of the resource at this spatial scale is appropriate and that consideration of significant movement between zones is not warranted in fishery stock assessment models.  相似文献   
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