High-temperature hysteresis and other magnetic properties of synthetic monodomain titanomagnetites

A suite of synthetic titanomagnetites of composition Fe_2.4?δAl_δTi_0.6O₄ and Fe_2.6?δAl_δTi_0.4O₄ (δ = 0, 0.1 and 0.2 in both cases) have been prepared by a method of partial self-buffering and pulverized in a ball mill to particle size of about 200–500 Å. Magnetic hysteresis parameters-saturation and remanent magnetizations and coercive force were measured between room temperature and the Curie temperatures and other parameters-X-ray cell edge, initial susceptibility and coercive force of remanence were determined at room temperature. The intrinsic magnetic “hardness” increases with increasing content of Al³⁺ and Ti⁴⁺, both probably corresponding to an increase in the concentration of Fe²⁺ ions on the tetrahedral sites of the spinel structure. The room-temperature hysteresis properties were compared with those resulting from monodomain models for the work done to magnetically saturate an assemblage of grains and the approach to saturation, and the separate contributions from coexisting anisotropies of cubic and uniaxial symmetries (assumed present) inferred. The cubic anisotropy energy constants so derived are larger than those determined from multidomain single crystals. The derived cubic constants are also larger than the derived uniaxial anisotropy constants. The latter, however, dominate the behaviour (e.g., coercive force) because of the lower symmetry. The materials appear to be entirely in the stable monodomain state at room temperature.     

A magnetic study of single-crystal titanomagnetite (Fe2.4Ti0.6O4)

Single crystals of approximate composition Fe_2.4Ti_0.6O₄ were prepared from which spherical samples of diameters 1–2 mm were obtained. The measured values of the Königsberger ratio, the ratio of saturation remanence to saturation magnetization and a Lowrie-Fuller test showed that they were multidomain in character. The temperature variation of the coercive force and saturation magnetization was measured between room temperature and the Curie point. The field dependence of intensity of acquired thermoremanent magnetization (TRM) was determined. The predictions of some of the theoretical models for multidomain TRM, which, of necessity, apply to simplifications of real materials (either natural or synthetic), compare favourably with the results of the present study. The validity of the assumptions made in this comparison is discussed.     

The laboratory simulation of deuteric oxidation of titanomagnetites: effect on magnetic properties and stability of thermoremanence

Synthetic single crystals of titanomagnetite of nominal composition Fe_2.4Ti_0.6O₄ have been oxidized at 1275°C in controlled gas atmospheres, producing multiphase intergrowths to simulate the natural process of deuteric oxidation. The evolution of the intergrowths was monitored using the conventional techniques of petrology: optical and electron microscopy and X-ray and electron microprobe analyses. In addition, the measured magnetic properties — particularly the temperature-dependence of hysteresis properties — provided further information about the composition and concentrations of magnetic phases, and their domain state, as oxidation proceeded. The evolution of a trellis pattern of ilmenite lamellae, characteristic of the “exsolution” stages of deuteric oxidation, was observed in the oxidized crystals. The interlamellar spinel region consisted of two iron-enriched titanomagnetites, one thought to occur along the lamellar boundaries. The magnetic hardness of both phases was found to be greater than the original homogeneous multidomain titanomagnetite crystals, although neither phase achieved monodomain characteristics, and the stability of thermoremanence (TRM) remained quite low (median destructive fields (MDF) of the order of a few thousend A m^?1). The lamellae made little contribution to the total remanence. A sharp rise in magnetic hardness, observed during the post-exsolution stages of oxidation, was due to the presence of fine-grain monodomain magnetite, thought to be distributed within the haemoilmenite matrix, but probably not having been formed by lamellar subdivision. The crystals could now carry an intense and stable TRM with MDFs of many tens of thousands of A m^?1.     

Domain structure of small synthetic titanomagnetite particles and experiments with IRM and TRM

Stoichiometric titanomagnetites Fe_3?xTi_xO₄ with compositions between x = 0 (magnetite) and x = 0.72 (a titanomagnetite having a Curie temperature of 60°C) have been synthesised using the double-sintering technique in controlled atmospheres. The quality of these materials was tested by various mineralogical and magnetic measurements. Isolated small multidomain (MD) and pseudo-single-domain (PSD) particles within pores of the bulk material were investigated with respect to their domain structures, and threshold sizes for the transition from the PSD to the SD stage determined for titanomagnetites of various compositions by extrapolation from the domain state of small MD grains. The threshold size was found to be 0.7 and 0.5 μm, respectively, for TM72 (x = 0.72) and TM62 (x = 0.62). The threshold size decreases slightly for smaller x values; however, the experimental data obtained to date are not sufficiently reliable to yield precise results.Preliminary experiments concerning hysteresis loops and TRM generation are also reported.     

Characteristics of bleaching of sandstone in northeast of Ordos Basin and its relationship with natural gas leakage

Bleaching of sandstone has significant applications to tracing hydrocarbon pathways and evaluating the scale of natural gas seepage. Bleaching of sandstones in the northeast of Ordos Basin is mainly distributed in the Mesozoic Yan’an Formation. Studying on petrology, major elements, REEs and trace elements of bleached sandstones and comparing with adjacent sandstones, combining with geologic-geochemical evidences of gas seepage in the northeast of the basin, the bleached sandstones are formed in the acid environment and reducing fluids. Characteristics of petrology show that the contents of kaolinite are high and the color of margin of ferric oxide minerals is lighter than that of the center. Major elements of sandstone samples show high contents of Al₂O₃ and low ratio of Fe³⁺/Fe²⁺. The TFe₂O₃ content of the bleached sandstone is lower than that of red rock. REE data show that bleached sandstones have low ΣREE contents and Eu-depleted and slightly Ce-enriched. Trace elements show that the bleached sandstones enrich in Co, deplete in Sr, and slightly enrich in Zr and Hf which are close to the values for the green alteration sandstones, and slightly lower than ore-bearing sandstones. Geochemical characteristics of oil-bearing sandstone in the northern basin suggest that the oil-shows are formed by matured Carboniferous-Permian coal bed methane escaping to the surface, and natural gas in field could migrate to the north margin of the basin. The δ ¹³C (PDB) and δ ¹⁸O(PDB) values of calcite cement in the study area range from ?11.729‰ to ?10.210‰ and ?14.104‰ to ?12.481‰, respectively. The δ ¹³C (PDB) values less than ?10‰ imply the carbon sources part from organic carbon. Comprehensive study suggests that the gas leakage has occurred in the northeastern basin, which is responsible for bleaching of the sandstone on top of the Yan’an Formation.     

Pyroxene-garnet solid-solution equilibria in the systems Mg4Si4O12Mg3Al2Si3O12 and Fe4Si4O12Fe3Al2Si3O12 at high pressures and temperatures

Pyroxene-garnet solid-solution equilibria have been studied in the pressure range 41–200 kbar and over the temperature range 850–1,450°C for the system Mg₄Si₄O₁₂Mg₃Al₂Si₃O₁₂, and in the pressure range 30–105 kbar and over the temperature range 1,000–1,300°C for the system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂. At 1,000°C, the solid solubility of enstatite (MgSiO₃) in pyrope (Mg₃Al₂Si₃O₁₂) increases gradually to 140 kbar and then increases suddenly in the pressure range 140–175 kbar, resulting in the formation of a homogeneous garnet with composition Mg₃(Al_0.8Mg_0.6Si_0.6)Si₃O₁₂. In the MgSiO₃-rich field, the three-phase assemblage of β- or γ-Mg₂SiO₄, stishovite and a garnet solid solution is stable at pressures above 175 kbar at 1,000°C. The system Fe₄Si₄O₁₂Fe₃Al₂Si₃O₁₂ shows a similar trend of high-pressure transformations: the maximum solubility of ferrosilite (FeSiO₃) in almandine (Fe₃Al₂Si₃O₁₂) forming a homogeneous garnet solid solution is 40 mol% at 93 kbar and 1,000°C.If a pyrolite mantle is assumed, from the present results, the following transformation scheme is suggested for the pyroxene-garnet assemblage in the mantle. Pyroxenes begin to react with the already present pyrope-rich garnet at depths around 150 km. Although the pyroxene-garnet transformation is spread over more than 400 km in depth, the most effective transition to a complex garnet solid solution takes place at depths between 450 and 540 km. The complex garnet solid solution is expected to be stable at depths between 540 and 590 km. At greater depths, it will decompose to a mixture of modified spinel or spinel, stishovite and garnet solid solutions with smaller amounts of a pyroxene component in solution.     

Low-temperature magnetic hysteresis properties of multidomain single-crystal titanomagnetite

The low-temperature magnetic hysteresis characteristics of multidomain titanomagnetite were fitted by a mixed coercivity model in which magnetocrystalline-controlled and magnetostriction-controlled domain-wall pinning play an important part. The effective contribution of the former was found to decrease systematically with increasing titanium content for compositions in the range Fe_2.48Ti_0.52O₄Fe_2.35Ti_0.65O₄. In agreement with the model, the observed magnetic remanence transitions and the characteristic peaks on the susceptibility vs. temperature curve became less pronounced as the titanium content increased. The problems in using these features as a means of identifying the carriers of natural remanent magnetization are discussed.     

Isotopic evidence for meteoric-hydrothermal alteration of plutonic igneous rocks in the Yakutat Bay and Skagway areas,Alaska

Oxygen and hydrogen isotope ratios were measured on coexisting minerals from quartz diorites and quartz monzonites from a section across the Coast Range batholith in the Skagway area, Alaska, including a variety of outlying plutons west of the batholith in the Yakutat Bay-Mt. St. Elias region (latitudes 59–60°N). The extremely low and variable δ¹⁸Oand δD results indicate widespread meteoric-hydrothermal alternaiton of the Coast Range batholith, and to a lesser extent, of the Yakutat Bay plutons as well. In the Yakutat Bay area, the plutons with K—Ar ages younger than 50 m.y. have widely varying δD values of ?72 to ?148, compared to δD = ?69to?90 for all but one sample in the 50–225 m.y. age grouping (one biotite has δD = ?109). This suggests that the major meteoric-hydrothermal episodes in this area occurred during the Eocene and Miocene. This involved relatively small meteoric water/rock ratios(<0.1), as none of the δ¹⁸O values show any clear-cut evidence of alteration (δ¹⁸O_quartz= 7.4 ?11.8; δ¹⁸O_feldspar= 5.7?10.0). However, in the section across the Coast Range batholith, 85% of the plutonic rocks have very low δD values of ?100 to ?167, and the δ¹⁸O values are extremely variable δ¹⁸O_feldspar= + 10.3to?4.0 and Δ¹⁸O_{quartz-feldspar}= 0.4?10.5. These data indicate that a major portion of the batholith, particularly the quartz monzonite-rich eastern part, but also including many of the quartz diorite plutons as well, interacted with meteoric-hydrothermal convective systems that involved water/rock ratios of about 0.3–1.4. The quart diorite plutons are most depleted in¹⁸O near their northeast contacts against the younger quartz monzonite intrusions. The primary igneous δ¹⁸O values of the quartz diorites were apparently higher than those of the quartz monzonites; they are also unusually high in¹⁸O compared to most other analyzed quartz diorites, suggesting derivation from, exchange with, or assimilation of high-¹⁸O metasediments or altered volcanic rocks. These data and conclusions are very similar to those reached previously on a similar isotopic study of the Coast Range batholith in British Columbia, 700 km to the southeast at latitudes 54–55°N, except that in the Skagway area an even greater proportion of the batholith was apparently depleted in deuterium. This implies that deep (?5km?) circulation of meteoric groundwaters is probably a characteristic of the later stages of emplacement of the Cordilleran batholiths of western North America, suggesting that the eastern sections of these batholiths in particular were emplaced at relatively shallow depths.     

Calorimetric study of the stability of high pressure phases in the systems CoOSiO2 and “FeO”SiO2, and calculation of phase diagrams in MOSiO2 systems

High temperature calorimetric measurements of the enthalpies of solution in molten if2 PbO · B₂O₃ of α- and γ-Fe₂SiO₄ and α-, β-, and γ-Co₂SiO₄ permit the calculation of phase relations at high pressure and temperature. The reported triple point involving α-, β-, and γ-Co₂SiO₄ is confirmed to represent stable equilibrium. The curvature in the α?β phase boundary in Co₂SiO₄ and of an α?γ boundary in Fe₂SiO₄ at high temperature is explained in part by the effects of compressibility and thermal expansion, but better agreement with the observed phase diagram is obtained when one considers the effect of small amounts of cation disorder in the spinel and/or modified spinel phases. The calculated ΔH⁰ and ΔS⁰ values for the α?β, α?γ, and β?γ transitions show that enthalpy and en changes both vary strongly in the series Mg, Fe, Co, and Ni, and are of equal importance in determining the stability relations. The disproportionation of Fe₂SiO₄ and Co₂SiO₄ spinel to rocksalt plus stishovite is calculated to occur in the 170–190 kbar region; cation disorder and/or changes in wüstite stoichiometry can affect the P?T slope. The calorimetric data for CoSiO₃ and FeSiO₃ are in good agreement with the observed phase boundary for pyroxene formation from olivine and quartz. The decomposition of pyroxene to spinel and stishovite at pressures near the coesite-stishovite transition is predicted in both iron and cobalt systems. The use of calorimetric data, obtained from small samples of high pressure phases, is very useful in predicting equilibrium phase diagrams in the 50–300 kbar range.     

Iron-magnesium order-disorder in an orthopyroxene crystal from the Johnstown meteorite

Equilibrium reversals of Fe²⁺Mg distribution between the M1 and M2 sites of an orthopyroxene from the Johnstown meteorite were achieved at several temperatures between 700 and 1000°C. One single crystal was used for the whole thermal treatment and for collecting all the X-ray data after quenching. The intracrystalline ion exchange for the bulk chemical composition: (Mg_1.453Fe_0.441Cr_0.024Ca_0.054Mn_0.015Fe_0.005Ti_0.003Al_0.005)(Si_1.960Al_0.040)O₆ is given by: ln K_D = −3027(±39)/T(K) + 0.872(±0.013)> where K_D is the distribution coefficient for the reaction: Fe_M2²⁺ + Mg_M1 = Mg_M2 + Fe_M1²⁺.A transmission electron microscopy (TEM) study of part of the crystal showed the presence of very thin augite lamellae and Guinier-Preston zones indicating a relatively rapid cooling of the host rock at temperatures close to 1000°C. The new temperature scale yields a relatively high quenching temperature of 379 (±8)°C for the pyroxene which appears consistent with a rapid cooling (estimated few degrees per hundred years) of a magmatic cumulate excavated by an impact on its parental body.     

Titanomagnetites prepared at different oxidation conditions: Hysteresis properties

Atmospheres of different oxidation potentials were used to equilibriate samples at 1300°C starting with a stoichiometric composition xFe₂TiO₄·(1 ? x) Fe₃O₄ where x = 0.3 and 0.6. Samples were selected which appeared homogeneous in polished section and gave only spinel-type X-ray reflections. All specimens were found to have small amounts of included material of higher Curie point than the bulk material. Specimens were made by dispersing grains of known size in a non-magnetic matrix and the hysteresis properties were measured for these speciméns.     

Natural gas geochemistry and its origins in Kuqa depression

According to gas compositional and carbon isotopic measurement of 114 gas samples from the Kuqa depression, accumulation of the natural gases in the depression is dominated by hydrocarbon gases, with high gas dryness (C₁/C_1–4) at the middle and northern parts of the depression and low one towards east and west sides and southern part. The carbon isotopes of methane and its homologues are relatively enriched in ¹³C, and the distributive range of δ ¹³C₁, δ ¹³C₂ and δ ¹³C₃ is ?32‰–?36‰, ?22‰–?24‰ and ?20‰–?22‰, respectively. In general, the carbon isotopes of gaseous alkanes become less negative with the increase of carbon numbers. The δ ¹³ \(C_{CO_2 } \) value is less than ?10‰ in the Kuqa depression, indicating its organogenic origin. The distributive range of ³He/⁴He ratio is within n × 10^?8 and a decrease in ³He/⁴He ratio from north to south in the depression is observed. Based on the geochemical parameters of natural gas above, natural gas in the Kuqa depression is of characteristics of coal-type gas origin. The possible reasons for the partial reversal of stable carbon isotopes of gaseous alkanes involve the mixing of gases from one common source rock with different thermal maturity or from two separated source rock intervals of similar kerogen type, multistages accumulation of natural gas under high-temperature and over-pressure conditions, and sufficiency and diffusion of natural gas.     

The crystal structure and thermal history of orthopyroxene from lunar anorthosite 15415

A single crystal of untwinned orthopyroxene from lunar anorthosite sample 15415, with composition (Mg_1.14Fe_0.80Mn_0.02Ca_0.04)(Si_1.97Al_0.03)O₆, has a unit cell in space groupPbca witha = 18.310(15)Å,b = 8.904(10)Å,c = 5.214(7)Å, containing 2 formula units. A set of 742 counter-measured intensity data made with MoK_α radiation has been used to refine the crystal structure in isotropic thermal mode toR = 0.116. Anisotropic refinement led toR = 0.092, but thermal parameters are distorted by non-random errors resulting from poor crystal texture. The resulting structure is in close agreement with that obtained by Ghose [9] for a hypersthene from Greenland. A parameterq, which gives (Mg_qFe_1?q) for cation siteM(1) and (Mg_1.14?qFe_q?0.18Ca_0.04) for siteM(2), was included in the least-squares analysis, yieldingq = 0.90(1).This orthopyroxene has the high degree of cation order expected of pyroxenes subjected to Apollonian metamorphism at lower than 500–600°C. No evidence exists for a subsequent thermal event of sufficient intensity to disorder the pyroxene. On the basis of previous laboratory studies of argon-release patterns of lunar plagioclase and order-disorder kinetics of terrestrial pyroxenes, we attribute the reported isotopic age (3.9–4.1 AE) to cessation of metamorphism, perhaps caused by impact excavation.     

Chronology and petrogenesis of the Hejiazhuang granitoid pluton and its constraints on the Early Triassic tectonic evolution of the South Qinling Belt

The Hejiazhuang pluton is located in the South Qinling Tectonic Belt(SQTB)in the north side of the Mianxian-Lueyang Suture Zone,and consists dominantly of granodiorites.LA-ICP-MS zircon U-Pb dating and Lu-Hf isotopic analyses reveal that these granodiorites of the Hejiazhaung pluton emplaced at~248 Ma,and show a large variation in zirconεHf(t)values from4.8 to 8.8.These granodiorite samples are attributed to high-K to mid-K calc-alkaline series,and characterized by high SiO2(66.6%–70.0%),Al2O3(15.04%–16.10%)and Na2O(3.74%–4.33%)concentrations,with high Mg#(54.2–61.7).All samples have high Sr(627–751 ppm),Cr(55–373 ppm)and Ni(17.2–182 ppm),but low Y(5.42–8.41 ppm)and Yb(0.59–0.74 ppm)concentrations with high Sr/Y ratios(84.90–120.66).They also display highly fractionated REE patterns with(La/Yb)N ratios of 18.9–34.0 and positive Eu anomalies(δEu=1.10–2.22)in the chondrite-normalized REE patterns.In the primitive mantle normalized spidergrams,these samples exhibit enrichment in LILEs but depletion in Nb,Ta,P and Ti.These geochemical features indicate that the granodioritic magma of the Hejiazhuang pluton was derived from the partial melting of hybrid sources comprising the subducted oceanic slab and sediments,and the melts were polluted by the mantle wedge materials during their ascent.The emplacement ages and petrogenesis of the Hejiazhuang pluton prove that the initial subduction of the Mianlue oceanic crust occurred at~248 Ma ago,and the SQTB was still under subduction tectonic setting in the Early Triassic.     

Mineralogical and geochemical study of a newly discovered mafic granulite, northwest China: Implications for tectonic evolution of the Altay Orogenic Belt

Abstract A mafic granulite body was newly discovered in the Altay Orogenic Belt, northwest China. The rocks comprise a suite of coarse‐grained and fine‐grained granulites. Orthopyroxenes (hypersthenes) in the rocks have high X_Mg and low Al₂O₃ contents, whereas clinopyroxenes have low TiO₂ and Al₂O₃ contents. Amphiboles and biotites have a high Mg/(Mg + Fe²⁺) ratio and low contents of F and Cl. The peak metamorphic pressure–temperature (P–T) conditions are estimated as 750–780°C and 6–7 kbar, and retrograde P–T conditions are in the range of 590–620°C and 2.3–3.7 kbar, indicating significant decompression. Metamorphic reactions and P–T estimates define a clockwise P–T path. Geochemically, the rocks are high in Mg/(Mg + Fe) and Al₂O₃, depleted in U, Th, K and Rb, and characterized by light rare earth element enrichment and a weak positive Eu anomaly. The Altay mafic granulite shows depleted Nb, P and Ti contents in the mid‐oceanic ridge basalt normalized spider diagram. The geochemical characteristics suggest that the protolith of the Altay mafic granulite was calc‐alkaline basalt and andesite with an island‐arc affinity. The rock has a high ¹⁴³Nd/¹⁴⁴Nd ratio with ?Nd(0) > 0, indicating derivation from a mantle‐depleted source. In the present study, a two‐stage model for the evolution of the Altay mafic granulite is proposed: an early stage in which calc‐alkaline basalt and andesite with island‐arc affinity were subducted into a deeper level of the crust and subjected to granulite‐facies metamorphism generating the mafic granulite, followed by the later stage exhumation of the system into the upper crust by the late Paleozoic thrusting.     

An investigation of ulvospinel composition and cation migration during maghemitization in DSDP,Leg 61, titanomagnetites

Titanomagnetites of basalts and diorites from an off-axis volcanic episode in the Pacific Ocean (Leg 61, DSDP) were studied for their ulvospinel composition and for changes in the iron-titanium ratio with progressive low-temperature oxidation. Thermomagnetic analysis and microscopy indicate that these Fe/Ti spinels show relatively little low-temperature oxidation, despite their Cretaceous age. Microprobe investigation shows that the Fe/Ti spinels have a wide range of ulvospinel content directly reflecting the range of parent rock chemistries. This is an important demonstration that ulvospinel contents are not constant but vary within a restricted range of compositions, namely at least x =0.5 to x=0.75 (Fe_2?xTi_xO₄). Recognition of this fact is important in attempting to elucidate changes in cation ratio as a result of progressive low-temperature oxidation.Examination of samples of different oxidation states for cation ratio changes as a result of low-temperature oxidation revealed lower titanium in the more oxidized samples and Ti enrichment in the less oxidized ones. This is probably a reflection of changing x values with progressive crystallization of individual sills, and thus unrelated to cation ratio changes with oxidation.In more than 100 grains analyzed, no evidence was found for a more oxidized shell on the exteriors of grains, suggesting that the oxidation process did not proceed uniformly with respect to grain geometry.     

Magnetic properties of synthetic titanomagnetites

Magnetic properties and crystal structure parameters of synthetic solid solutions Fe₃O₄Fe₃TiO₄, Fe₂O₄MgFe₂O₄ and Fe₃O₄Mg₂TiO₄ have been studied. Basic regularities in the behaviour of saturation magnetisation (I_s), Curie temperature (T_C) and cubic lattice parameter a during the substitution of Ti and Mg ions for Fe ions have been found. As the concentration of Ti ions increases, I_s reduces from 70 Gs·cm³ g^?1 to 0, T_C changes from 580 to 130°C and a from 8.391 to 8.520 Å. Growth of the Mg concentration leads to changes in I_s to 19.8 Gs·cm³, g^?1, T_C, to 440°C and a, to 8.360 Å. The full Fe ions substitution gives $\text{“a”=8.440}\text{A}\text{?}$.Chemical compositions of the samples, in which the valency variation of Fe ions at oxidation leads to an increase in susceptibility and T_C, have been determined.     

Cenozoic evolution of the sulfur cycle: Insight from oxygen isotopes in marine sulfate

We report new data on oxygen isotopes in marine sulfate (δ¹⁸O_SO4), measured in marine barite (BaSO₄), over the Cenozoic. The δ¹⁸O_SO4 varies by 6‰ over the Cenozoic, with major peaks 3, 15, 30 and 55 Ma. The δ¹⁸O_SO4 does not co-vary with the δ³⁴S_SO4, emphasizing that different processes control the oxygen and sulfur isotopic composition of sulfate. This indicates that temporal changes in the δ¹⁸O_SO4 over the Cenozoic must reflect changes in the isotopic fractionation associated with the sulfide reoxidation pathway. This suggests that variations in the aerial extent of different types of organic-rich sediments may have a significant impact on the biogeochemical sulfur cycle and emphasizes that the sulfur cycle is less sensitive to net organic carbon burial than to changes in the conditions of that organic carbon burial. The δ¹⁸O_SO4 also does not co-vary with the δ¹⁸O measured in benthic foraminifera, emphasizing that oxygen isotopes in water and sulfate remain out of equilibrium over the lifetime of sulfate in the ocean. A simple box model was used to explore dynamics of the marine sulfur cycle with respect to both oxygen and sulfur isotopes over the Cenozoic. We interpret variability in the δ¹⁸O_SO4 to reflect changes in the aerial distribution of conditions within organic-rich sediments, from periods with more localized, organic-rich sediments, to periods with more diffuse organic carbon burial. While these changes may not impact the net organic carbon burial, they will greatly affect the way that sulfur is processed within organic-rich sediments, impacting the sulfide reoxidation pathway and thus the δ¹⁸O_SO4. Our qualitative interpretation of the record suggests that sulfate concentrations were probably lower earlier in the Cenozoic.     

Correlation between δ~(18)O,Sr/Ca and Mg/Ca of coral Acropora and seawater temperature from coral culture experiments

To be used as proxies of seawater surface temperature(SST), the δ 18Oc values and Sr/Ca and Mg/Ca ratios of scleractinian coral skeletons must be verified by coral culture experiments in the laboratory. This paper describes a coral culture experiment that was conducted at several seawater temperatures T(21–28°C) using a tandem aquarium system and the new method for depositing coral skeletons grown under controlled conditions. The δ 18Oc values and the Sr/Ca and Mg/Ca ratios of the cultured coral were measured. We concluded that the δ 18Oc values and Sr/Ca and Mg/Ca ratios of the cultured coral are clearly correlated with T. The linear regression curve is δ18Oc(‰)=δ0.1427δT(°C)δ0.1495(n=18, r=0.955, p0.0001), and the slope of δ0.1427‰/°C is at the low end of the range of published values(δ0.13–δ0.29‰/°C). The Sr/Ca ratio decreases with increasing T, whereas the Mg/Ca ratio increases with increasing T, indicating a negative correlation between Sr/Ca and Mg/Ca. Their linear regression curves are Sr/Ca(mmol/mol)=δ0.04156δT+10.59(n=15, r=0.789, p0.005) and Mg/Ca(mmol/mol)= 0.04974δT+2.339(n=17, r=0.457, p0.05), respectively, which demonstrate that when Mg/Ca and Sr/Ca are increased by one unit, T increases by 5.19°C and decreases by 15.62°C, respectively. These variations are significantly lower than published values.     

Multiple sulfur and oxygen isotope compositions in Beijing aerosol

Multiple sulfur isotopes(32S, 33 S, 34 S, 36S) and oxygen isotopes(16O, 18O) in Beijing aerosols were measured with MAT-253 isotope mass spectrometer. The δ34S values of Beijing aerosol samples range from 1.68‰ to 12.57‰ with an average value of 5.86‰, indicating that the major sulfur source is from direct emission during coal combustion. The δ18O values vary from 5.29‰ to 9.02‰ with an average value of 5.17‰, revealing that the sulfate in Beijing aerosols is mainly composed of the secondary sulfate. The main heterogeneous oxidation of SO2 in atmosphere is related to H2O2 in July and August, whereas H2O2 oxidation and Fe3+ catalytic oxidation with SO2 exist simultaneously in September and October. Remarkable sulfur isotope mass-independent fractionation effect is found in Beijing aerosols, which is commonly attributed to the photochemical oxidation of SO2 in the stratosphere. In addition, thermochemical reactions of sulfur-bearing compounds might be also a source of sulfur isotope anomalies based on the correlation between ?33S and CAPE.