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1.
We have performed a detailed Mössbauer study of synthetic annites on the (OH, F)-join. Recently developed data treatment and spectral analysis methods were used to extract true intrinsic Fe2+ quadrupole splitting distributions (QSDs) that represent the most information that can be resolved from the spectra. The overall room temperature (RT) QSDs can be consistently interpreted in terms of four QSD contributions (or populations) centered at: QSHH2.55 mm/s for Fe2+O4(OH)2 octahedra (cis and trans not resolved), QSHF 2.35 mm/s for Fe2+O4(OH)F octahedra (cis and trans not resolved), QScFF2.15 mm/s for cis-Fe2+O4F2 octahedra, and QStFF 1.5 mm/s for trans-Fe2+O4F2 octahedra. Each such contribution has a width ( 0.2 mm/s) caused by distortions of the octahedra. Minor contributions due to Fe2+O5(OH) and Fe2+O5F octahedra probably also contribute to the overall Fe2+ QSDs. The ferric iron spectral components were also characterized. Here, two distinct types of octahedral Fe3+ contributions are seen and interpreted as being due mainly to Fe3+O5OH and Fe3+O5F octahedra, respectively. Tetrahedral Fe3+ is seen only in the OH-annite end-member and the total Fe3+ content drops significantly on addition of F. On leave from: Department of Materials Physics, University of Science and Technology Beijing, 100083 Beijing, China  相似文献   

2.
An electron probe and chemical study of bulk phosphorite samples and separated constituents from various Negev deposits was carried out together with XRD, FTIR spectroscopy and textural analysis. The results allow a better understanding of the distribution of fluorine in these Upper Cretaceous phosphorite sequences and shed light on variations in the composition of the carbonate fluorapatite (CFA) phase during phosphogenesis. Two facies are recognized: (1) a pristine, microbially generated phosphorite facies; (2) a recycled, peloidal and biodetrital facies. Fluorine distribution in the Negev phosphorites is facies controlled: F/P2O5 is much lower in the pristine facies (0·090–0·107) than in the recycled facies (0·107–0·120). In addition, F/P2O5 varies considerably between the various constituents of the phosphate fraction; F‐poor francolites (F/P2O5 as low as 0·080) co‐exist with F‐rich francolites (F/P2O5 as high as 0·135) in the same phosphorite bulk sample. A lower F/P2O5 in francolite is associated with higher Cd and Zn concentrations in the phosphorite, an increase in Fe‐rich smectites in the clay fraction and the presence of structural OH in the francolite. The lower F/P2O5 ratios in the pristine facies are attributed to high organic deposition rates during the formation of these matted sediments, leading to rapid burial of the in situ‐forming CFA. This is possibly coupled with diffusion of F from sea water into bottom sediments being hampered by microbial mat coatings. These conditions resulted in O2‐depleted porefluids, inducing the precipitation of Cd‐rich Zn sulphides and the formation of Fe‐rich smectites. F‐enrichment probably takes place when the earlier formed F‐poor ‘primary’ CFA is relocated close to the sea floor and bathed with interstitial sea water solutions of higher F concentrations. Oxidation and removal of the sulphide‐bound Cd and Zn apparently occurred together with enrichment in F of the francolite. Combining chemical data with XRD and FTIR results suggests a multistage growth for the Negev phosphate constituents in shifting formational sites and porefluids of varying F concentrations. This multiphase growth is reflected in the patchy distribution of F in the Negev constituents and might explain the inverse correlation between mean CO2/F and F/P2O5 ratios of the analysed phosphorites in the two facies. It also suggests that CFA (or an amorphous precursor) initially formed with some OH groups in the apatite structure, which were subsequently substituted by F ions in recycled francolite through re‐equilibration with porefluids of higher F concentrations.  相似文献   

3.
226Ra, 228Ra and Ba distributions as well as 228Ra/226Ra and 226Ra/Ba ratios were measured in seawater, suspended and sinking particles at the DYFAMED station in the Western Mediterranean Sea at different seasons of year 2003 in order to track the build-up and fate of barite through time. The study of the 228Raex/226Raex ratios (Raex = Ra activities corrected for the lithogenic Ra) of suspended particles suggests that Baex (Baex = Ba concentrations corrected for the lithogenic Ba, mostly barite) formation takes place not only in the upper 500 m of the water column but also deeper (i.e. throughout the mesopelagic layer). Temporal changes in the 228Raex/226Raex ratios of sinking particles collected at 1000 m depth likely reflect changes in the relative proportion of barite originating from the upper water column (with a high 228Ra/226Ra ratio) and formed in the mesopelagic layer (with a low 228Ra/226Ra ratio). 228Raex/226Raex ratios measured in sinking particles collected in the 1000 m-trap in April and May suggest that barite predominantly formed in the upper water column during that period, while barite found outside the phytoplankton bloom period (February and June) appears to form deeper in the water column. Combining ratios of both the suspended and sinking particles provides information on aggregation/disaggregation processes. High 226Raex/Baex ratios were also found in suspended particles collected in the upper 500 m of the water column. Because celestite is expected to be enriched in Ra [Bernstein R. E., Byrne R. H. and Schijf J. (1998) Acantharians: a missing link in the oceanic biogeochemistry of barium. Deep-Sea Res. II45, 491-505], acantharian skeletons may contribute to these high ratios in shallow waters. The formation of both acantharian skeletons and barite enriched in 226Ra may thus contribute to the decrease in the dissolved 226Ra activity and 226Ra/Ba ratios of surface waters observed between February and June 2003 at the DYFAMED station.  相似文献   

4.
The attachment energies, the slice energies and the specific surface energies can be calculated in an electrostatic point charge model using the formula derived by Madelung for the potential introduced by an infinite row of equally spaced point charges. Power series are given for the Hankel function iH (0) (1) (iy) and (x)=d ln x!/dx. The logarithmic expression in the Madelung formula converges rapidly when applying a power series, which combines equally charged cations and anions. Besides the specific surface energy ( hkl), the slice energy (E s hkl ) and the attachment energy (E a hkl ) can be considered as special categories of surface energies as they depend on surface configurations as well. The specific surface energy is the energy per unit area of surface needed to split the crystal parallel to a face (hkl). The attachment energy (E a) is the energy released per mole, when a new slice of thickness d hkl crystallizes on an already existing crystal face (hkl). The growth rate of the crystal face (hkl) is a function of its attachment energy. The slice energy (E s) is the energy released per mole, when a new slice d hkl is formed from the vapour neglecting the influence of edge energies. The lattice energy (E c) which is the energy released per mole of a crystal crystallizing from the vapour, is given by the following relation: E c=E a+E s.  相似文献   

5.
The western Awulale metallogenic belt in northwestern China hosts a number of small‐ to medium‐sized porphyry Cu deposits that are associated with albite porphyry. The common presence of plagioclase (albite) as phenocrysts and the absence of hydrous minerals (amphibole and biotite) indicate that the water content of albite porphyry is low. Trace‐element compositions of whole rocks and zircon grains from these ore‐bearing porphyries were measured. Zircon grains from albite porphyries exhibit Ce4+/Ce3+ ratios ranging from 7.75 to 95.1, which indicate that these porphyries have a low oxygen fugacity. Trace element compositions of ore‐bearing porphyries exhibit (La/Yb)N ratios ranging from 1.09 to 11.1 and Eu/Eu* ratios ranging from 0.10 to 0.66. These ore‐bearing porphyries have Zr values ranging from 171 to 707 ppm and Hf values ranging from 8.30 to 18.9 ppm. Combining these porphyries with other ore‐bearing porphyries that formed in the Central Asian Orogenic Belt (CAOB) and the Pacific Rim metallogenic belt, we found that the (La/Yb)N and Eu/Eu* ratios of ore‐bearing porphyries in western Awulale are low, while the Zr and Hf values are high. Specifically, REEs can be used to evaluate the degree of differentiation and degree of partial melting, and Zr and Hf can be used to evaluate the redox conditions and water content of magmatic rocks. Our findings indicate that ore‐bearing porphyries in western Awulale have a lower oxygen fugacity, degree of differentiation, and water content than do others in the CAOB and the Pacific Rim metallogenic belt. Compared to those of ore‐bearing porphyries with lower zircon Ce4+/Ce3+ ratios, the (La/Yb)N ratios of ore‐bearing porphyries in our study are low, and the Zr and Hf values are high. This finding indicates that, under reducing conditions, the degree of evolution and water content may have an important influence on the metal abundance in magmas. There is also a clear relationship between (La/Yb)N, Eu/Eu*, Zr, Hf, and the size of the deposits. Large‐ (>4 Mt Cu) and intermediate (1.5–4 Mt Cu)‐sized porphyry Cu deposits are associated with granitic intrusions that have higher (La/Yb)N and Eu/Eu* ratios and lower Zr and Hf values. This finding indicates that, in addition to oxygen fugacity, the degree of evolution and water content are controlling parameters for metal abundance in magmas, especially in low oxygen fugacity porphyry Cu deposits. Such a conclusion may be useful in the exploration for other concealed porphyry Cu deposits.  相似文献   

6.
Francolite in unaltered Tertiary phosphorites is highly substituted with about 1.2% Na, 0.25% Sr, 0.36% Mg and 2.7% SO4 within the structure in substitution for Ca and PO4. These substitutions reflect the composition of the solution from which francolite forms and are not influenced by the mechanism, rate or redox conditions of formation. The remarkably constant composition for a wide range of samples reflects the relative constant composition of sea water, during Tertiary times. Francolite in sulphate-reducing sediments forms in an uppermost zone where bioturbation maintains the concentrations of Na, Sr, Mg and SO4 at sea water concentrations. The structura-CO2 content of unaltered francolites vary from 1.4% to 6.3%, in response to variations in pH. The maximum level of carbonate substitution is limited by the disruption of the francolite structure at levels above 6.3% CO2. For the samples considered here F/P2O5 ratios vary with X-ray CO2 contents showing that PO43? is replaced by (CO32? + F?) and not by CO32? alone. In Phosphoria Formation francolite the Na/P2O5 ratios and X-ray CO2 contents show areal trends related to burial depth and thermal metamorphism. These two processes together with weathering and fresh water diageneses explain all observed variation in francolite composition.  相似文献   

7.
Summary Potassium-fluor-richterite is reported from wollastonite-rimmed metachert bands embedded in marbles of the Bufa del Diente aureole, NE-Mexico. K-F-richterites were generated via reaction of previously formed contact-metamorphic diopside with infiltrated hypersaline brines of magmatic origin that used the metachert bands as metamorphic aquifers. Their formation occurred at peak metamorphic conditions of 500 to 600 °C at 1 kbar according to the generalised reaction 10 CaMgSi2O6 + 8 SiO2 + 2 KClaq + 6 NaClaaq + 4 H2O + 4 HF diopside + quartz = 2 KNaCaMg5Si8O22(F)2 + 4 Ca2NaH(SiO3)3 + 8 HClaq K-F-richterite + pectolite Compositional ranges in two samples are K-Ri58–69Ri16–25Tri12–21 and K-Ri58–66Ri32–40Tr0–5. Mg/(Mg + Fe2+) ranges from 0.81 to 0.95, F/(F + OH) from 0.55 to 0.85, and the K-F-richterites are Cl-free.Microthermometrically determined K/(K + Na)-ratios of hypersaline brines trapped at 500°C to 600°C range from 0.50 to 0.64, resulting in distribution coefficients K DK-Na Amph-F1 = X K(in A) Amph /X N(in A) Amph · X Na F1 /X K F1 of 0.85 to 1.3 for the Na-K amphibole-fluid exchange reaction. Very low Ca-contents in bulk fluid leachates indicate that Cacontaining fluids cannot coexist with richterite and that Ca is incorporated into amphibole as a tremolite component. Amphibole compositions in Al-free systems can predict Na-K-Ca-ratios of metasomatic brines that equilibrated with them. Despite the hypersaline nature of the brines, Cl is not incorporated into the Mg-rich K-F-richterites because of the Mg-Cl and Fe-F avoidance rules in amphiboles.
Kalium-Fluor-Richterit in kontaktmetamorphem Quarziten der Bufa del Diente Aureole, NO-México
Zusammenfassung In die Marmore der Kontaktaureole des Bufa del Diente-Alkalisyenits sind 5-15 cm mächtige Quarzitbänder eingeschaltet, die mehrere cm-dicke Wollastonitsäume aufweisen. Die Metaquarzite enthalten Kalium- und Fluor-reiche Richterite. Die K-FRichterite bildeten sich durch Reaktion von zuvor gebildetem, kontaktmetamorphem Diopsid mit infiltrierenden hochsalinaren Fluiden magmatischen Ursprungs. Die Metaquarzite dienten als metamorphe Aquifere für diese Fluide.Die K-F-Richterite wurden bei den Maximaltemperaturen der Kontaktmetamorphose von 500-600°C bei 1 kbar nach der folgenden schematischen Reaktion gebildet: 10 CaM9Si2O6 + 8 SiO2 + 2 KClaq + 6 NaClaq + 4 H2O + 4 HF Diopsid + Quarz = 2 KNaCaMg5Si8O22(F)2 + 4 Ca2NaH(SiO3)3 + 8 HClaq K-F-Richterit + Pektolit Der Zusammensetzungsbereich von zwei Proben aus unterschiedlichen Metaquarzitbändern liegt bei K-Ri58–69Ri16–25Tr12–21 und K-Ri58–66Ri32–40Tr0–5. K-FRichterite in beiden Proben haben F/(F + OH)-Verhältnisse von 0.55 bis 0.85 und enthalten kein Cl.Mikrothermometrisch bestimmte K/(K + Na)-Verhältnisse der bei 500°-600°C in Flüssigkeitseinschlüssen okkludierten, hochsalinaren Fluide betragen 0.50–0.64. Daraus lassen sich Verteilungskoeffizienten K DK-Na Amph-Fi = X K(in A) Amph /X N(in A) Amph · X Na F1 /X K F1 von 0.85-1.3 für die Amphibol-Fluid Austauschreaktion in tremolitfreien Amphibolen ableiten. Wässrige Extrakte der Gesamtfluidpopulationen enthalten sehr geringe Ca-Konzentrationen im Vergleich zu K und Na. Dies zeigt, daß Fluide mit signifikanten Ca-Konzentrationen nicht mit Richteriten koexistieren können und Ca bevorzugt als Tremolitkomponente eingebaut wird. Amphibolzusammensetzungen in Al-freien Systemen eignen sich als Indikatoren für K-Na-Ca-Verhältnisse von koexistierenden metasomatischen Fluiden. Die K-F-Richterite sind Cl-frei, obwohl sie mit hochsalinaren Fluiden koexistiert haben. Mg-reiche Amphibole können kein CI einbauen und Fe-reiche Amphibole kein F.

With 4 Figures  相似文献   

8.
We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO2/H2S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H2S flux of 6 to 9 t · d−1 for the summit crater. For Mt. Etna and Stromboli, we found SO2/H2S molar ratios of ≈20 and ≈15, respectively, which combined with SO2 flux measurements, suggest H2S emission rates of 50 to 113 t · d−1 and 4 to 8 t · d−1, respectively. We observe that “source” and plume SO2/H2S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H2S emission.  相似文献   

9.
Several hydraulic techniques were used to estimate the flow depth (0.3 m) associated with the deposition of a tabular set (micro-delta) of cross-stratified sand in the Brampton esker. The competency of the flow, deduced from both the grain size and structural characteristics of the set, gave a value of approximately 0.65 m/sec for the palaeo-velocity of the flow. Estimates of palaeo-depth and velocity facilitated calculation of the Froude and Reynolds numbers, about 0.38 and 1.24 · 105, respectively. Extrapolation of other parameters included bed shear stress τ0 (4.50 N/m2), shear velocity U* (0.067 m/sec), dimensionless Chezy coefficient C/√g (9.7), slope of the energy gradient S(0.00153), Darcy-Weisbach friction factor f(0.085), Manning roughness coefficient n(0.027) and discharge of bed-material load (19 metric tons/day/m). The figures cited are reasonable estimates only. The occurrence of regressive ripples in the bottomset of the micro-delta aided in the hydraulic interpretation. These flow characteristics are only representative of the final stages of deposition at one location on the flank of the esker. The core of the esker was probably deposited under different hydraulic conditions.  相似文献   

10.
This study examines the links between 31P solidstate NMR studies of aluminum phosphate minerals and their crystallographic structures. We found that 31P isotropic chemical shift values, iso, carry little information about mineral structures. There seems to be no relation between the chemical shift anisotropy, =33–11 (33>22> 11), and indicies of phosphate-tetrahedra distortion. 31P1H heteronuclear magnetic dipole interactions, on the other hand, carry important information about hydrous phosphate mineral structures, information that should prove to be quite valuable in studies of phosphate adsorbed on mineral surfaces. This interaction can be measured through a variety of qualitative and quantitative experiments. It appears that spin diffusion is so rapid that subtle differences in hydrogen-bonding environments cannot be resolved.  相似文献   

11.
The co-treatment of landfill leachate (LFL) with municipal wastewater (MWW) using shortcut sequencing batch reactor combined with coagulation–settling process (SBR + CS) was investigated. Four ratios of LFL to MWW volume (v/v) were used during experiments including the ratios 1:9, 2:8, 3:7 and 5:5. The average quality of the LFL was chemical oxygen demand (COD) of 20,800 mg L?1 and NH4-N of 2,645 mg L?1. The SBR-treating LFL in six series where mixing aeration and settling phases were varied from 4 to 14 h was combined with coagulation (FeCl3, Al2(SO4)3) with an interval of 2 h. It was found that ratio (1:9) of leachate to MWW under aeration and mixing phase of 4 h with settling time of 1.5 h exhibited the highest ability to remove both COD and NH 4 + -N, 99% and 85%, respectively. The short-time sequential batch reactor was tested for the treatment of raw LFL, and only 47% and 23% removal of COD and NH 4 + -N, respectively, could be achieved.  相似文献   

12.
D/H ratios of leaf waxes (δDwax) derived from terrestrial plants and preserved in lake sediments can provide important information on past continental hydrology. Ideally, δDwax can be used to reconstruct precipitation D/H ratios (δDP) which is a well-established paleoclimate proxy. However, many other factors, such as vegetation and relative humidity (RH), also affect δDwax variation. How the combination of these factors affects sedimentary δDwax is unclear. Here, we use a transect of 32 lake surface sediments across large gradients of precipitation, relative humidity, and vegetation composition in the southwestern United States to study the natural factors affecting sedimentary δDwax. δD values of C28n-alkanoic acids show significant correlation with δDP values (R2 = 0.76) with an apparent isotopic enrichment of ∼99 ± 8‰, indicating that sedimentary δDwax values track overall δDP variation along the entire transect. Leaf waxes produced by plants grown under controlled conditions (RH = 80%, 60%, 40%) show a small increase in D/H ratios as RH decreases, consistent with prediction from the Craig-Gordon model. However, the isotopic effect of RH on δDwax along the natural transect is partially countered by the opposing influence of vegetation changes. The correlation between δDwax and δDP values is significantly higher (R2 = 0.84) in the drier portions of the transect than in the wetter regions (R2 = 0.64). This study suggests that D/H ratios of sedimentary leaf waxes can be used as a proxy for precipitation δD variations, with particularly high fidelity in dry regions, although more studies in other regions will be important to further test this proxy.  相似文献   

13.
Grandite garnet-rich calcsilicate rocks from the Lower Calcsilicate Unit of the regionally metamorphosed Reynolds Range Group (central Australia) crop out along a strike-parallel section in which a transition zone from M22 amphibolite to granulite facies rocks is exposed. Across this transition the grandite-rich layers do not show systematic changes in mineral assemblages, compositions and modes, or stable isotope compositions. These layers are deformed by F22 folds that are associated with the peak of regional low-pressure/high-temperature metamorphism. Therefore, the grandite-rich layers appear to pre-date regional metamorphism and to have acted as closed chemical systems during prograde M22 metamorphism. Mineral assemblages in the grandite-rich layers are consistent with their formation through the infiltration of oxidized, water-rich fluids (Xco2 < 0.1–0.3; log fo2 -16 to -14). The stable isotope values of calcite (Δ13C=-4.2 to -0.8%0 PDB; Δ18O = 10.5–14.0%0 V-SMOW) and bulk-silicate fractions (Δ18O = 6.1 to 10.8%) of the grandite-rich layers are most consistent with the infiltrating fluid being from a magmatic source. It is most likely that fluid infiltration occurred during the pre-M22 contact metamorphism (M21) that affected much of the Reynolds Range Group. The preservation of these assemblages is probably due to their high variance and little pervasive fluid-rock interaction having occurred during M22. The clinopyroxene- and feldspar-rich calcsilicate rocks that host the grandite-rich layers contain poikiloblastic grandite garnet that formed during prograde M22 metamorphism. Thin marbles that locally occur with the grandite-rich layers contain a third garnet generation that is post- or late M22. This grossular-rich garnet occurs in coronas around calcite, plagioclase, clinopyroxene, wollastonite and scapolite. These coronas are consistent with cooling and/or compression. However, because the marble assemblages are themselves overprinted by M21 grandite-rich layers the development of coronal garnet does not reflect a continuous P-T-t path. Rather, it more probably reflects the partial re-equilibration of M21 contact metamorphic assemblages to post-M22 conditions.  相似文献   

14.
Kern(1982)和 Kern 与 Richter(1981)介绍了他们通过高温高压实验测定的、多种岩石在不同温度和压力条件下模拟地震 P 波和 S 波的波速 Vp 和 Vs,这些资料对于探索地壳内的岩石矿物组成和各种物理性质是十分宝贵的。我们知道,Vp 和 Vs 既依赖于温度,也依赖于压力。  相似文献   

15.
Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca5(PO4)3F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean Ksp values were calculated by using PHREEQC for HAP of 10− 53.28 (10− 53.02–10− 53.51) and for FAP of 10− 55.71 (10− 55.18–10− 56.13) at 25 °C, the free energies of formation ΔGfo[HAP] and ΔGfo[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.  相似文献   

16.
The influence of vorticity and rheology of matrix material on the development of shape-preferred orientation (SPO) of populations of rigid objects was experimentally studied. Experiments in plane strain monoclinic flow were performed to model the fabric development of two populations of rectangular rigid objects with object aspect ratios (Rob) 2 and 3. The density of the rigid object populations was 14% of the total area. Objects were dispersed in a Newtonian and a non-Newtonian, power law matrix material with a power law exponent n of 1.2. The kinematic vorticity number (Wn) of the plane strain monoclinic flow was 1, 0.8 and 0.6 with finite simple shear strain of 4.6, 3.0 and 0.9, respectively. In experiments with Rob=3, the SPO is strongly influenced by Wn and the material properties of the matrix. Deformation of a power law matrix material and low Wn resulted in a stronger SPO than deformation of a linear viscous matrix and high Wn. Strain localization coupled with particle interaction plays a significant role in the development of a shape-preferred orientation. High strain simple shear zones separate trains of rigid objects that are surrounded by low strain zones with Wn lower than the bulk Wn. In fabrics involving populations of objects with Rob=2, rheology of the matrix materials does not systematically influence the intensity of the SPO.  相似文献   

17.
We measured 228Raex/226Raex and 226Raex/Baex ratios in suspended and sinking particles collected at the Oceanic Flux Program (OFP) time-series site in the western Sargasso Sea and compared them to seawater ratios to provide information on the origin and transport of barite (BaSO4) in the water column. The 228Raex/226Raex ratios of the suspended particles down to 2000 m are nearly identical to those of seawater at the same water depth. These ratios are much lower than expected if suspended barite was produced in surface waters and indicate that barite is produced throughout the mesopelagic layer. The 228Raex/226Raex activity ratios of sinking particles collected at 1500 and 3200 m varied mostly between 0.1 and 0.2, which is intermediate between the seawater ratio at these depths (<0.03) and the seawater ratios found in the upper 250 m (0.31-0.42). This suggests that excess Ba (i.e., Baex = Batotal − Balithogenic), considered to be mainly barite, present in the sinking flux is a mixture of crystals formed recently in the upper water column, formed several years earlier in the upper water column, or formed recently in deeper waters. We observe a sizeable temporal variability in the 228Raex/226Raex ratios of sinking particles, which indicates temporal variability in the relative proportion of barite crystals originating from surface (with a high 228Raex/226Raex ratio) and mesopelagic (with a low 228Raex/226Raex ratio) sources. However, we could not discern a clear pattern that would elucidate the factors that control this variability. The 226Ra/Ba ratios measured in seawater are consistent with the value reported from the GEOSECS expeditions (2.3 dpm μmol−1) below 500 m depth, but are significantly lower in the upper 500 m. High 226Raex/Baex ratios and elevated Sr concentrations in suspended particles from the upper water column suggest preferential uptake of 226Ra over Ba during formation of SrSO4 skeletons by acantharians, which must contribute to barite formation in shallow waters. Deeper in the water column the 226Raex/Baex ratios of suspended particles are lower than those of seawater. Since 228Raex/226Raex ratios demonstrate that suspended barite at these depths has been produced recently and in situ, their low 226Raex/Baex ratios indicate preferential uptake of Ba over Ra in barite formed in mesopelagic water.  相似文献   

18.
Biotite dissolution experiments were carried out to better understand the dissolution kinetics and Fe behavior under low O2 conditions, and to give an insight into the Precambrian weathering. Mineral dissolution with a continuous flow-through reactor was employed at 25 °C for up to 65 days varying partial pressure of atmospheric oxygen (PO2), pH (6.86 and 3.01) and Fe content in mineral (1.06 and 0.11 mol of Fe per O10(OH,F)2 for biotite and phlogopite, respectively) independently for the examination of their effects on biotite dissolution. Low PO2 conditions were achieved in a newly developed glove box (PO2 ? 6 × 10−4 atm; referred to as anoxic conditions), which was compared to the present, ambient air conditions (0.2 atm of PO2; oxic conditions). The biotite dissolution rate was slightly faster under anoxic conditions at pH 6.86 while it was not affected by PO2 at pH 3.01. There was no direct effect of Fe content on dissolution rate at pH 6.86 while there was a small difference in dissolution rate between biotite and phlogopite at pH 3.01. The 1.5 order-of-magnitude faster release rate of Fe under anoxic conditions for biotite dissolution at pH 6.86 resulted from the difference in ratio of Fe3+ precipitates remaining in the reactor to Fe dissolved (about 60% and 100% under anoxic and oxic conditions, respectively), which is caused mainly by the difference in PO2. The results infer that the Fe2+ and Fe3+ contents in the Paleoproterozoic paleosols, fossil weathering profiles, are reflected by atmospheric oxygen levels at the time of weathering.  相似文献   

19.
Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise 206Pb/204Pb and 207Pb/204Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The 207Pb-206Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (Tc) for Pb diffusion in rutile that is less than the Tc of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the Tc for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher Tc than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current Tc estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.  相似文献   

20.
A laboratory experiment has been performed to study the effect of ventilation on the rate of evaporation of the millimeter sized charged and uncharged water drops suspended in a vertical wind tunnel. The linear relationship,f u = 0.907 + 0.282X, observed between the mean ventilation coefficient, fu, and a non-dimensional parameterX, (X =N Sc,v 1/3 N Re 1/2 whereN Sc,uis Schmidt number andN Reis Reynold’s number) is in agreement with the results of earlier investigations for uncharged water drops. However, in case of charged drops carrying 10-10C of charge, this relationship gets modified tof u = 0.4877 + 0.149X. Thus, the rate of evaporation of charged drops is slower than that of uncharged drops of the same size. Oscillations of the drop and the change in airflow around drops are suggested to contribute to lowering of the ventilation coefficients for charged drops. Applicability of the results to a small fraction of highly charged raindrops falling through the sub-cloud layer below thunderstorm is discussed. The relaxation time required for a ventilated drop to reach its equilibrium temperature increases with the drop size and is higher for the charged than for the uncharged drops. It is concluded that in a given distance, charged drops will evaporate less than that of uncharged drops.  相似文献   

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