Advection and removal of Pb and stable Pb isotopes in the oceans: a general circulation model study     

Gideon M. Henderson  Ernst Maier-Reimer 《Geochimica et cosmochimica acta》2002,66(2):257-272

Natural Pb-isotope variability in the oceans encodes information about the sources of continental material to the oceans, about ocean circulation, and about Pb removal. In order to use this information, we must understand the natural cycle of Pb in the oceans, which is overprinted by large anthropogenic input. In this study we use ²¹⁰Pb, which has not been significantly anthropogenically perturbed, to investigate oceanic Pb. GEOSECS ²²⁶Ra and model-derived atmospheric fluxes of ²¹⁰Pb are used to input ²¹⁰Pb into an ocean general circulation model. Irreversible scavenging of this ²¹⁰Pb onto settling biogenic particles and at the seafloor are tuned so that the model replicates the observed pattern of ²¹⁰Pb in the oceans. The best-fit model run provides a map of the variability of residence time for Pb. The global average residence time of Pb in this model is 48 yr, but there is over an order of magnitude variation between areas of high and low productivity. This is expected to enhance provinciality of Pb isotope ratios in the oceans. Because stable Pb isotopes are expected to behave in seawater in a similar fashion to ²¹⁰Pb, the pattern of removal of ²¹⁰Pb derived by the model can be used to investigate the behavior of stable Pb isotopes. We use a simplified input of Pb consisting of five point sources representing major rivers and a disseminated dust input. Although this simplified input scheme does not allow precise reconstruction of Pb concentration and isotopes in the oceans, it allows us to answer some first-order questions about the behavior of Pb as an ocean tracer. With a total Pb input of 6.3 × 10⁷ mol/yr (Chow T. J. and Patterson C. C., “The occurrence and significance of Pb isotopes in pelagic sediments,” Geochim. Cosmochim. Acta26, 263-308, 1962), the model predicts natural seawater Pb concentrations averaging 2.2 pmol/kg. Even in the absence of anthropogenic input, the model ocean exhibits a near-surface maximum in Pb concentration. And the model suggests natural Pb concentrations in the Northern Hemisphere an order of magnitude higher than in the Southern Hemisphere. A point source of Pb is suggested to dominate the seawater Pb inventory close to the source but is reduced to typically less than 10% of the inventory by the time that Pb is advected out of the originating ocean. This length scale of advection for Pb isotope signals confirms their potential as tracers of ocean circulation. Assuming an 8% dissolution of dust, their input to the open ocean are seen to be a significant portion of Pb inventory throughout the oceans and make up >50% of the Pb inventory in the model’s Southern Ocean. Finally, a preliminary investigation of the response of Pb-isotope distributions to changes in boundary conditions between glacial and interglacial times illustrates that significant variation in the Pb isotopes are expected in some regions, even for reasonably small changes in climate conditions.  相似文献   

Isotopic Composition of Non-Methane Hydrocarbons in Emissions from Biomass Burning     

K. v. Czapiewski  E. Czuba  L. Huang  D. Ernst  A.L. Norman  R. Koppmann  J. Rudolph 《Journal of Atmospheric Chemistry》2002,43(1):45-60

The stable carbon isotope ratios of nonmethane hydrocarbons (NMHC) and methyl chloride emitted from biomass burning were determined by analyzing seven whole air samples collected during different phases of the burning process as part of a laboratory study of wood burning. The average of the stable carbon isotope ratios of emitted alkanes, alkenes and aromatic compounds is identical to that of the burnt fuel; more than 50% of the values are within a range of ±1.5 of thecomposition of the burnt fuel wood. Thus for the majority of NMHC emitted from biomass burning stable carbon isotope ratio of the burnt fuel a good first order approximation for the isotopic composition of the emissions. Of the more than twenty compounds we studied, only methyl chloride and ethyne differed in stable carbon isotope ratios by more than a few per mil from the composition of the fuel. Ethyne is enriched in ¹³C by approximately 20–30, and most of the variability can beexplained by a dependence on flame temperature. The ¹³C values decreaseby 0.019 /K (±0.0053/K) with increasing temperature. Methyl chloride is highly depleted in ¹³C, on average by25. However the results cover a wide range of nearly 30. Specifically, in two measurements with wood from Eucalyptus (Eucalyptus delegatensis) as fuel we observed the emission of extremely light methyl chloride (–68.5and–65.5). This coincides with higher than average emission ratiosfor methyl chloride (15.5 × 10^–5 and 18 ×10^–5 mol CH₃Cl/mol CO₂). These high emission ratios are consistent with the highchlorine content of the burnt fuel, although, due to the limited number of measurements, it would be premature to generalize these findings. The limited number of observations also prevents any conclusion on a systematic dependence between chlorine content of the fuel, emission ratios and stable carbon isotope ratio of methyl chloride emissions. However, our results show that a detailed understanding of the emissions of methyl chloride from chloride rich fuels is important for understanding its global budget. It is also evident that the usefulness of stable carbon isotope ratios to constrain the global budget of methyl chloride will be complicated by the very large variability of the stable carbon isotope ratio of biomass burning emissions. Nevertheless, ultimately the large fractionation may provide additional constraints for the contribution of biomass burning emissions to the atmospheric budget of methyl chloride.  相似文献   

Ultrahigh-pressure metamorphism and decompressional P–T paths of eclogites and country rocks from Weihai, eastern China: Reply     

R. Y. Zhang  J. G. Liou  & W. G. Ernst 《Island Arc》1998,7(1-2):250-252

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Experimental studies to 10 kb of the bulk composition tremolite50-tschermakite50+excess H2O     

Cao Rong-Iong  Charles Ross  W. G. Ernst 《Contributions to Mineralogy and Petrology》1986,93(2):160-167

Phase relations for the magnesio-hornblende bulk composition, 2 CaO·4 MgO·Al₂O₃·7 SiO₂+ excess H₂O, have been investigated to 10 kb employing hydrothermal and piston-cylinder techniques. The low-temperature limit of amphibole in this system lies at 519° C, 1,000 bars, 541° C, 2,000 bars, and 718° C, 10 kb. The low-T assemblage consists of an+chl+di+tc(+f), and is related to the adjacent high-T equilibrium assemblage, amph+an+chl+f, by the solid-solid reaction (A): 2 di+tc=tr. Small amounts of aluminum, hypothesized to be preferentially dissolved in the cpx (and in the tc) relative to amph, may account for the broad P-T stability range of the di+tc assemblage in the synthetic work relative to systems involving stoichiometric tr, Ca₂Mg₅Si₈O₂₂(OH)₂, such as are common in natural, Al-poor calc-silicate parageneses. Alternatively, the low-temperature assemblage produced in the experiments may be metastable. For the investigated bulk composition, synthetic tremolitic-cummingtonitic amphibole contains relatively modest amounts of ts, Ca₂Mg₃Al₂ ^IVSi₆-Al₂ ^IVO₂₂(OH)₂; at pressures of 1,000–3,000 bars, solid solution extends from near tremolite only to about cu₁₁tr₆₉ts₂₀, analogous to most analyzed natural magnesio-hornblendic specimens. At 10 kb fluid pressure, the solid solution reaches approximately cu₀₆tr₅₃ts₄₁ for the investigated bulk composition, and appears to be virtually independent of temperature. Amphibole and 14 Å chl react within the amphibole stability field, along curve (B), at about 704° C and 2,000 bars, to produce an, en, fo and f (H=40.9 kcal/ mole); at pressures greater than approximately 7kb, due to the incompatibility of an and fo, the higher temperature assemblage consists of amph, an, en, sp and f. Above P _fluid– T curve (B), the amphibole coexists with an+en+fo+f at low pressures; at higher pressures, the amphibole, which is in equilibrium with an+en+sp+f, is relatively more aluminous. The high-T stability limit of aluminous tr+fo lies approximately 20–25° C below the dehydration curve for stoichiometric tremolite on its own bulk composition. Reaction (C), tr+fo=2 di+5 en+f (H = 39.4 kcal/mole), produces an+di+en+f, the highest temperature subsolidus assemblage investigated for the tr₅₀ts₅₀ bulk composition. Hydrous melt is encountered at temperatures at least as low as 900° C at 10 kb, and at that fluid pressure coexists with amphibole over an interval of more than 60° C. Limited solid solution observed between tr and ts in nature (tr_100-70) is accounted for by the restricted range of amphibole compositions produced in the present study. Such amphiboles, moreover, appear to have both high- and low-temperature stability limits, as demonstrated by the experimental results.Institute of Geophysics and Planetary Physics Publication No. 2811  相似文献   

The heat transfer in the region of the Mauna Kea (Hawaii)—constraints from borehole temperature measurements and coupled thermo-hydraulic modeling     

Grit Büttner  Ernst Huenges 《Tectonophysics》2003,371(1-4):23-40

The objectives of this paper are an understanding of the thermal and hydraulic field because of a negative temperature gradient and cold temperatures in the 1-km-deep borehole of the Hawaiian Scientific Drilling Project (HSDP), located near the coast line. The temperature pattern is attributed to a superposition of thermal and hydraulic processes. In the deeper borehole (HSDP-2, depth 3.1 km) detailed temperature monitoring was performed. Temperature measurements reveal two different thermal regimes. The upper part is characterised by cold temperatures and a negative temperature gradient similar to those observed in the shallow pilot borehole. Below 1100 m, increasing temperatures are observed. Different processes, such as topographically driven groundwater flow, ingress of salt water and conductive heat flow are investigated by numerical modeling. A pure conductive scenario fails to match the temperature measurements, implying that both borehole sections are overprinted by advective conditions. Coupled fluid and heat flow modeling with solute transport yield results that agree with observed temperatures. The results of these simulations suggest that meteoric water flow from the mountain range controls the thermal conditions in the upper part of the borehole. Below this level, the thermal regime is additionally affected by circulation of salt water from the nearby ocean. Each of these flow systems has been observed at other locations: topographically driven fresh water at locations with pronounced topography and ingress of salt water is typical for islands or coastal areas. At Hawaii, they coincide and influence each other, resulting in a salt water interface occurring at greater depth than expected.  相似文献   

A plagioclase-olivine-spinel-magnetite inclusion from Maralinga (CK): evidence for sequential condensation and solid-gas exchange     

Gero Kurat  Ernst ZinnerFranz Brandstätter 《Geochimica et cosmochimica acta》2002,66(16):2959-2979

We report a detailed petrography, mineral chemistry, and trace element study of MaTroc, a large calcium-aluminum-rich inclusion (CAI) (5 × 2.5 mm) of irregular triangular shape. The inclusion has a zonal structure: The core consists of a porous plagioclase-olivine-Ca-rich pyroxene intergrowth with subordinate apatite. Its texture is meta-gabbro-like, similar to other plagioclase-olivine inclusions (POIs). The mantle has variable thickness (0.1-1.5 mm) and consists of a compact symplectitic intergrowth of spinel (hercynite) and plagioclase with abundant dispersed magnetite, subordinate Ca-rich pyroxene, and traces of sulfides. The thin (5-50 μm) discontinuous crust of MaTroc consists mainly of plagioclase with some olivine and magnetite.The Mg-Fe phases of MaTroc are Fe-rich: olivine has Fa33.2 and high NiO content, similar to that in the host rock, Ca-rich pyroxene has much lower TiO₂ and Cr₂O₃ contents than that of the host chondrite, and plagioclase is An55-An74. Magnetites have variable compositions, are poorer in Al₂O₃ and Cr₂O₃ and richer in NiO than those in the host. Spinels have also variable compositions, rich in FeO, NiO, and ZnO.Despite their different mineralogy, both core and mantle have bulk trace element abundances similar to those in average group II CAIs. However, the mantle is richer in Nb and U and poorer in Eu, Be, B, Sr, and Li than the core. All minerals have high trace element contents. Minerals in the core show signs of incomplete equilibration of trace elements within and between them. Mantle minerals are far from equilibrium with each other and the bulk system. Spinel and anorthite carry the trace element signature of their precursor melilite (or hibonite), and magnetite contains large amounts of a heterogeneously distributed remnant extremely rich in trace elements (“obscurite”), possibly of a former perovskite.Inclusion MaTroc has a complex history. The POI core probably formed by reaction of an unknown precursor(s) of condensation origin with a vapor to form olivine, plagioclase, clinopyroxene, apatite, and (an) unknown phase(s) that vanished, leaving abundant void space. The spinel-rich mantle is also a secondary mineral assemblage that formed by breakdown of and solid-vapor reactions with a precursor or precursors, possibly melilite (or hibonite). The abundant magnetite formed by reaction of perovskite with an oxidizing vapor and by precipitation from such a vapor. All phases of the inclusion experienced the metasomatic addition of Fe, Ni, and moderately volatile elements such as V, Be, Li, Cr, and Mn—similar to all other constituents of the Maralinga CK chondrite. Phases in MaTroc and in the host rock are close to equilibrium in the distribution of Fe, Mg, Ni, and Mn but far from equilibrium in the distribution of M⁺³ and M⁺⁴ ions. The minor and trace element abundances in the magnetite of the host rock and of MaTroc preclude an origin by oxidation of a metal precursor.  相似文献   

A percent-of-flow approach for managing reductions of freshwater inflows from unimpounded rivers to Southwest Florida estuaries     

Michael S. Flannery  Ernst B. Peebles  Ralph T. Montgomery 《Estuaries and Coasts》2002,25(6):1318-1332

The Southwest Florida Water Management District has implemented a management approach for unimpounded rivers that limits withdrawals to a percentage of streamflow at the time of withdrawal. The natural flow regime of the contributing river is considered to be the baseline for assessing the effects of withdrawals. Development of the percent-of-flow approach has emphasized the interaction of freshwater inflow with the overlap of stationary and dynamic habitat components in tidal river zones of larger estuarine systems. Since the responses of key estuarine characteristics (e.g., isohaline locations, residence times) to freshwater inflow are frequently nonlinear, the approach is designed to prevent impacts to estuarine resources during sensitive low-inflow periods and to allow water supplies to become gradually more uvailable as inflow increases. A high sensitivity to variation at low inflow extends to many invertebrates and fishes that move upstream and downstream in synchrony with inflow. Total numbers of estuarine-resident and estuarine-dependent organisms have been found to decrease during low-inflow periods, including mysids, grass shrimp, and juveniles of the bay anchovy and sand seatrout. The interaction of freshwater inflow with seasonal processes, such as phytoplankton production and the recruitment of fishes to the tidal-river nursery, indicates that withdrawal percentages during the springtime should be most restrictive. Ongoing efforts are oriented toward refining percentage withdrawal limits among seasons and flow ranges to account for shifts in the responsiveness of estuarine processes to reductions in freshwater inflow.  相似文献   

Mapping of the post-collisional cooling history of the Eastern Alps     

Stefan W. Luth  Ernst Willingshofer 《Swiss Journal of Geoscience》2008,101(1):207-223

We present a database of geochronological data documenting the post-collisional cooling history of the Eastern Alps. This data is presented as (a) georeferenced isochrone maps based on Rb/Sr, K/Ar (biotite) and fission track (apatite, zircon) dating portraying cooling from upper greenschist/amphibolite facies metamorphism (500–600 °C) to 110 °C, and (b) as temperature maps documenting key times (25, 20, 15, 10 Ma) in the cooling history of the Eastern Alps. These cooling maps facilitate detecting of cooling patterns and cooling rates which give insight into the underlying processes governing rock exhumation and cooling on a regional scale.The compilation of available cooling-age data shows that the bulk of the Austroalpine units already cooled below 230 °C before the Paleocene. The onset of cooling of the Tauern Window (TW) was in the Oligocene-Early Miocene and was confined to the Penninic units, while in the Middle- to Late Miocene the surrounding Austroalpine units cooled together with the TW towards near surface conditions.High cooling rates (50 °C/Ma) within the TW are recorded for the temperature interval of 375–230 °C and occurred from Early Miocene in the east to Middle Miocene in the west. Fast cooling post-dates rapid, isothermal exhumation of the TW but was coeval with the climax of lateral extrusion tectonics. The cooling maps also portray the diachronous character of cooling within the TW (earlier in the east by ca. 5 Ma), which is recognized within all isotope systems considered in this study.Cooling in the western TW was controlled by activity along the Brenner normal fault as shown by gradually decreasing ages towards the Brenner Line. Cooling ages also decrease towards the E–W striking structural axis of the TW, indicating a thermal dome geometry. Both cooling trends and the timing of the highest cooling rates reveal a strong interplay between E–W extension and N–S orientated shortening during exhumation of the TW.  相似文献   

Volatiles in a peralkaline system: Abiogenic hydrocarbons and F–Cl–Br systematics in the naujaite of the Ilímaussaq intrusion, South Greenland     

Thomas V. Krumrei  Ernst Pernicka  Melanie Kaliwoda  Gregor Markl 《Lithos》2007,95(3-4):298-314

Agpaitic rocks comprise most of the exposed part of the 1.16 Ga old, 8 × 17 km large and about 1700 m thick Ilímaussaq intrusion in South Greenland. Within these, more than 600 m thick sequence of sodalite-rich “naujaites” (mainly sodalite + arfvedsonite + alkali feldspar + nepheline + eudialyte + aenigmatite) are interpreted as a sodalite flotation cumulate. Sodalites show two to three different zones in cathodoluminescence (CL) and at least two zones in thin sections. The CL zones can be related to chemical differences detectable by electron microprobe, whereas relations with optical zonations are less obvious. Compositional trends in sodalite reflect trends in the evolution of volatile contents in the melt. The sodalite at Ilímaussaq is almost free of Ca and closely corresponds to the pure Na–Cl sodalite endmember with about 7 wt.% of Cl; S contents reach up to 0.9 wt.%. Cl/Br ratios range from 500 to 1700. Raman spectroscopy shows that S is present as [SO₄]²⁻ in sodalite, although sphalerite (ZnS) is a stable phase in naujaites. Peralkalinity and fO₂ conditions allow S²⁻ and [SO₄]²⁻ to be present contemporaneously.

The whole naujaite sequence is divided into two parts, an upper part with low, homogeneous S contents and Cl/Br ratios in the sodalite cores, and a lower part with strongly variable and higher S contents and with Cl/Br ratios, which are decreasing downwards. The details of the S content and the Cl/Br ratio evolution show that sodalite strongly influences the halogen contents of the melt by scavenging Cl and Br.

The naujaites were formed from a highly reduced, halogen-rich magma in equilibrium with magmatic methane at about 800 °C, which, upon ascent, cooling and fractionation, exsolved an aqueous fluid phase. Both fluids were trapped in separate inclusions indicating their immiscibility.

Micrometer-sized aegirine crystals and primary hydrocarbon-bearing inclusions are abundant in the crystal cores. The inclusions were trapped at pressures up to 4 kbar, although the emplacement pressure of the intrusion is about 1 kbar. This indicates growth of the sodalite during melt ascent and a very effective mechanism of trace element scavenging during sodalite growth. Sodalite rims are devoid of aegirine or primary hydrocarbon inclusions and probably reflect the emplacement stage.  相似文献   

Causes of interestuarine variability in bay anchovy (<Emphasis Type="Italic">Anchoa mitchilli</Emphasis>) salinity at capture     

Ernst B. Peebles  Scott E. Burghart  David J. Hollander 《Estuaries and Coasts》2007,30(6):1060-1074

Salinities occupied by different life stages of bay anchovy (Anchoa mitchilli) were compared over annual cycles at 128 stations in 12 Florida estuaries. The comparison included eight stations in an oligotrophic, groundwater-based estuary in which all life stages were rare or absent. At other stations, adults, eggs, and early larvae occurred in intermediate to high salinities (10-30 psu) with no apparent central salinity tendency. The larva-juvenile transition was marked by an upstream shift to lower salinities (0-15 psu), also with no central salinity tendency. Mean salinities of the juvenile catch were strongly dependent on the salinities of the sampling effort. This dependence was strongest in estuaries that had weak horizontal salinity gradients. Weak salinity gradients were either natural or resulted from estuarine dams. After using nonlinear regression to account for the interaction between effort salinity and catch salinity, catch salinities were found to be similar from year to year within estuaries, but widely different among estuaries, with interestuarine differences ranging as high as 10–13 psu. Lower salinities were occupied by juveniles in estuaries that had long freshwater turnover times. Inherent geomorphic and inflow-related effects on the distribution of prey resources, coupled with an ontogenetic diet shift, are proposed as the explanation for both the habitat shift and the strong interestuarine variability in salinity at capture.  相似文献