Bioreduction of natural specular hematite under flow conditions

Dissimilatory reduction of Fe(III) by Shewanella oneidensis MR-1 was evaluated using natural specular hematite as sole electron acceptor in an open system under dynamic flow conditions to obtain a better understanding of biologic Fe(III) reduction in the natural environment. During initial exposure to hematite under advective flow conditions, cells exhibited a transient association with the mineral characterized by a rapid rate of attachment followed by a comparable rate of detachment before entering a phase of surface colonization that was slower but steadier than that observed initially. Accumulation of cells on the hematite surface was accompanied by the release of soluble Fe(II) into the aqueous phase when no precautions were taken to remove amorphous Fe(III) from the mineral surface before colonization. During the period of surface colonization following the detachment phase, cell yield was estimated at 1.5-4 × 10⁷ cells/μmol Fe(II) produced, which is similar to that reported in studies conducted in closed systems. This yield does not take into account those cells that detached during this phase or the Fe(II) that remained associated with the hematite surface. Hematite reduction by the bacterium led to localized surface pitting and localized discrete areas where Fe (II) precipitation occurred. The cleavage plane of hematite left behind after bacterial reduction, as revealed by our results, strongly suggests, that heterogeneous energetics of the mineral surface play a strong role in this bioprocess. AQDS, an electron shuttle shown to stimulate bioreduction of Fe(III) in other studies, inhibited reduction of hematite by this bacterium under the dynamic flow conditions employed in the current study.     

He incorporation and diffusion pathways in pure and defective zircon ZrSiO4: A density functional theory study

In this paper, we report a detailed study of helium (He) incorporation and diffusion pathways in the perfect and defective zircon lattice. Ab initio methods based on Density Functional Theory (DFT) were used to calculate the structural features, the solution energies in interstitial sites in the perfect zircon and in vacancy sites of the defective lattice and He diffusion pathways in these systems. We show that the mode of He incorporation in the perfect zircon is influenced mainly by the topological features of the lattice, promoting site preference of He towards accommodation in the interstitial sites present in the middle of c cylinder channels. The presence of defect species in the form of lattice vacancies and interstitials has a significant effect on He solubility and diffusivity in the lattice, where the ability of lattice vacancies to act as physical traps or repulsive sites depends greatly on the electronic nature of the vacancy, which can enhance solubility of He in the lattice and affect the kinetics of He mobility in zircon mineral.     

Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar/Ar dating

(U-Th)/He chronometry of zircon has a wide range of potential applications including thermochronometry, provided the temperature sensitivity (e.g., closure temperature) of the system be accurately constrained. We have examined the characteristics of He loss from zircon in a series of step-heating diffusion experiments, and compared zircon (U-Th)/He ages with other thermochronometric constraints from plutonic rocks. Diffusion experiments on zircons with varying ages and U-Th contents yield Arrhenius relationships which, after about 5% He release, indicate E_a = 163-173 kJ/mol (39-41 kcal/mol), and D₀ = 0.09-1.5 cm²/s, with an average E_a of 169 ± 3.8 kJ/mol (40.4 ± 0.9 kcal/mol) and average D₀ of 0.46^+0.87_−0.30 cm²/s. The experiments also suggest a correspondence between diffusion domain size and grain size. For effective grain radius of 60 μm and cooling rate of 10°C/myr, the diffusion data yield closure temperatures, T_c, of 171-196°C, with an average of 183°C. The early stages of step heating experiments show complications in the form of decreasing apparent diffusivity with successive heating steps, but these are essentially absent in later stages, after about 5-10% He release. These effects are independent of radiation dosage and are also unlikely to be due to intracrystalline He zonation. Regardless of the physical origin, this non-Arrhenius behavior is similar to predictions based on degassing of multiple diffusion domains, with only a small proportion (<2-4%) of gas residing in domains with a lower diffusivity than the bulk zircon crystal. Thus the features of zircon responsible for these non-Arrhenius trends in the early stages of diffusion experiments would have a negligible effect on the bulk thermal sensitivity and closure temperature of a zircon crystal.We have also measured single-grain zircon (U-Th)/He ages and obtained ⁴⁰Ar/³⁹Ar ages for several minerals, including K-feldspar, for a suite of slowly cooled samples with other thermochronologic constraints. Zircon He ages from most samples have 1 σ reproducibilities of about 1-5%, and agree well with K-feldspar ⁴⁰Ar/³⁹Ar multidomain cooling models for sample-specific closure temperatures (170-189°C). One sample has a relatively poor reproducibility of ∼24%, however, and a mean that falls to older ages than predicted by the K-feldspar model. Microimaging shows that trace element zonation of a variety of styles is most pronounced in this sample, which probably leads to poor reproducibility via inaccurate α-ejection corrections. We present preliminary results of a new method for characterizing U-Th zonation in dated grains by laser-ablation, which significantly improves zircon He age accuracy.In summary, the zircon (U-Th)/He thermochronometer has a closure temperature of 170-190°C for typical plutonic cooling rates and crystal sizes, it is not significantly affected by radiation damage except in relatively rare cases of high radiation dosage with long-term low-temperature histories, and most ages agree well with constraints provided by K-spar ⁴⁰Ar/³⁹Ar cooling models. In some cases, intracrystalline U-Th zonation can result in inaccurate ages, but depth-profiling characterization of zonation in dated grains can significantly improve accuracy and precision of single-grain ages.     

He diffusion systematics in minerals: Evidence from synthetic monazite and zircon structure phosphates

Helium diffusivity was measured in synthetic rare-earth-element orthophosphates with systematically varying properties to evaluate potential controls on He transport in minerals. In the zircon structure phosphates (in this study, the phosphates of Tb, Dy, Ho, Er, Tm, Yb, and Lu as well as synthetic xenotime, YPO₄), He diffusion is strongly anisotropic. Transport apparently proceeds preferentially through channels aligned with the c-axis. The activation energy for diffusion is almost the same (122 ± 6 kJ/mol) in all members of this family, but there is a monotonic decrease in D_o with atomic number from TbPO₄ (∼10⁵ cm²/s) to LuPO₄ (∼10 cm²/s). The c-parallel channels become increasingly constricted in the same sequence, likely accounting for the systematically decreasing diffusivity. The He closure temperature (r = 1 cm, dT/dt = 10 °C/Myr) increases with atomic number from 44 °C for TbPO₄ to 88 °C for LuPO₄. Diffusion of radiogenic helium from natural zircon and xenotime is much slower than these synthetic analogs predict, suggesting that coupled substitution of REE and P for Zr and Si and/or radiation damage profoundly modify the energetics of interstitial He diffusion. In particular, α-recoil may play a key role by damaging the continuity and integrity of the channels.Monazite structure phosphates (here La, Ce, Pr, Nd, Sm, and Gd phosphate) are far more He retentive than those of the zircon structure. Activation energies increase smoothly with atomic number from LaPO₄ (183 kJ/mol) to NdPO₄ (224 kJ/mol) then decrease again to GdPO₄ (198 kJ/mol). D_o values mimic this pattern, spanning a range from ∼10⁻¹ cm²/s (GdPO₄) to 10⁴ cm²/s (NdPO₄). Nevertheless, He closure temperatures increase monotonically with atomic number, from 300 °C in LaPO₄ to 410 °C in GdPO₄. No evidence was obtained bearing on diffusion anisotropy, but the monazite structure lacks through-going channels so it is not expected. Diffusion parameters for radiogenic helium in natural monazite are similar to those obtained on the synthetic analogs.Ionic porosity is not the primary control on He diffusion in the orthophosphates. Within a given structure and with limited elemental substitution, ionic porosity and He closure temperature are negatively correlated, as predicted. However, differences between crystal structures are far more important than ion packing density: at comparable ionic porosity the monazite structure phosphates have He closure temperatures ∼300 °C higher than the xenotime structure phosphates. Modifications to the structures by radiation damage likely play a similarly significant role in controlling He diffusion.     

A computer simulation study of the accommodation and diffusion of He in uranium- and plutonium-doped zircon (ZrSiO4)

We report the results of an atomistic computational study of He accommodation and diffusion in the Pu⁴⁺- and U⁴⁺-doped zircon (ZrSiO₄). The He-cation potentials derived for this work give results of comparable accuracy to DFT calculations. We have calculated the structural features of doped lattices as well as He solution energies in interstitial sites in the perfect and doped zircon and its diffusion in these lattices. The mode of He accommodation in the perfect zircon is influenced mainly by the topological features of the lattice, promoting site preference of He towards accommodation in the interstitial sites present in the middle of c cylinder channels, whereas the presence of Pu⁴⁺ and U⁴⁺ dopants in the zircon lattice significantly affects the energetics of He accommodation and diffusion in the lattice. Doping causes strong local structural distortions, extending to next nearest-neighbour atoms of the dopants to a radius of up to ∼4 Å, in agreement with experimental results. The presence of dopants in the vicinity of He enhances the solubility of He in the lattice compared to the perfect lattice. The mechanism of diffusion is also affected, where the dopants can create a He trap along the most energetically favourable pathway in the (0 0 1) direction, which may slow down the movement of He along the c direction. The dopants also lower the energy barriers by ∼50% in the octahedral sites.     

^3He／^4He Ratios and Heat Flow in the Continental Rift—valley,Eastern China

Heat flow and the origin of helium in natural gases from fault basins of the continental rift-valley in eastern China are discussed in terms of helium isotope geochemistry.³He/⁴He ratios in natural gases from the rift-valley range from 2.23 × 10⁻⁷ to 7.21 × 10⁻⁶, which are directly proportional to the concentration of helium and ΣNHC/ΣHC ratio in natural gases. Geological and isotope geochemical data suggest that helium in natural gases consists predominantly of crustal radio-genic and upper mantle-derived helium. In a simple mixing pattern between crustal He and mantle-derived He, mantle-derived helium in natural gases would account for 10–60%. Calculated values for heat flow (Q) range from 59.7 to 82.4mWm⁻², of which about 60 percent in the rift-valley is derived from the upper mantle. Natural helium reservoirs would be found in the areas where the upper mantle uplifted greatly and heat flow is large in the continental rift-valley. The project is financially supported by the National Natural Science Foundation of China.     

4He同位素含量测试技术研究

4He同位素含量的准确测定是(U-Th)/He同位素定年方法的关键,因为4He同位素是气体,所以其含量测定难度是比较大的,国内其他实验室还没有建立4He同位素含量的测定方法.本文详细介绍了国外(U-Th)/He同位素定年实验室4He同位素含量的测试技术和本实验室基于现有仪器条件建立的4He同位索含量的测试方法.笔者等利...     

~3He/~4He比值质谱计的研制与应用

本文介绍了本课题组研制的国内第一台用于地学气体样品测定的NG 10 0 0型3 He/ 4He比值质谱计。该质谱计具有小的静态容积 ,分辨率和灵敏度高及重现性等良好的分析性能。利用该质谱计测定了我国一些地区气体样品中的3 He/ 4He、4He/ 2 0 Ne比值。所分析的3 He/ 4He结果与VG 5 40 0型、MM 5 40 0型质谱计外检结果相符。     

Controls on pore-fluid concentration of 4He and 222Rn and the calculation of 4He/222Rn ages

Controls governing the production of ⁴He and ²²²Rn in the solid phase as well as parameters and processes contributing to their transport into the pore fluid are discussed. ²²²Rn activity is used to quantify the uranium sources for ⁴He and the result is a simplified pore-fluid age equation which is virtually independent of the porosity, the water/rock ratio, the rock density and the uranium concentration, but does require a Th/U estimate. The crucial parameter is the ratio of the release factors for the two species, /GL_Rn//GL_He, which is discussed in terms of three possible release mechanisms: (1) recoil; (2) recoil followed by diffusion; and (3) weathering release of accumulated ⁴He. It was found that /GL_Rn//GL_He can vary over several orders of magnitude, but can be expressed in terms of the effective grain size r, and the diffusive half-length for ²²²Rn decay, r_e.⁴He measurements are used to “date” gases from known gas fields and the agreement with the assumed source-rock age is good. Application of ⁴He/ ²²²Rn measurements to continental freshwater springs indicates that the weathering release of accumulated ⁴He dominates the input and results in a large overestimate of groundwater age. Measurement in the Lardarello geothermal field indicates that the ⁴He/²²²Rn method can indicate relative transport direction. Other possible applications in various geochemical fields are suggested.     

Spatial variations in 3He/4He ratios along a high strain rate zone,central Japan

A linear zone with high strain rates along the Japan Sea coast, the Niigata-Kobe Tectonic Zone (NKTZ), is considered to be associated with rheological heterogeneities in the lower crust and/or upper mantle. Helium isotope variations along the NKTZ reveal a close association with the geophysical evidence for rheological heterogeneities in the crust and mantle. In the southern NKTZ, the ³He/⁴He ratios lower than 3.4 Ra (Ra denotes the atmospheric ³He/⁴He ratio of 1.4 × 10⁻⁶) could be interpreted as a two-component mixture of helium stored in aqueous fluids driven off the subducting oceanic crust and radiogenic crustal helium. Higher ³He/⁴He ratios are observed in the central NKTZ where Quaternary volcanoes and high-temperature hot springs are concentrated, suggesting that the ³He emanation manifest in the central NKTZ results from the effective transfer of mantle helium by intrusion and degassing of mantle-derived magma in the crust. In the northern NKTZ where two large inland earthquakes occurred recently, there appears to be many samples with ³He/⁴He ratios significantly higher than those observed in the fore-arc side of northeast Japan. A plausible source of mantle helium could be attributed to upward mobilization of aqueous fluids generated by dehydration of the subducting Pacific Plate slab.     

Low-temperature anisotropic diffusion of helium in zircon: Implications for zircon (U-Th)/He thermochronometry

In the last decade the zircon (U-Th)/He (ZHe) thermochronometer has been applied to a variety of geologic problems. Although bulk diffusion coefficients for He in zircon are available from laboratory step-heating experiments, little is known about the diffusion mechanism(s) and their dependence on the crystallographic structure of zircon. Here, we investigate the diffusion of He in perfectly crystalline zircon using atomistic simulation methods that provide insights into the structural pathways of He migration in zircon. Empirical force fields and quantum-mechanical calculations reveal that the energy barriers for He diffusion are strongly dependent on structure. The most favorable pathway for He diffusion is the [0 0 1] direction through the open channels parallel to the c-axis (, activation energy for tracer diffusion of a He atom along [0 0 1]). In contrast, energy barriers are higher in other directions where narrower channels for He diffusion are identified, such as [1 0 0], [1 0 1], and [1 1 0] (ΔE^∗ of 44.8, 101.7, and 421.3 kJ mol⁻¹, respectively). Molecular dynamics simulations are in agreement with these results and provide additional insight in the diffusion mechanisms along different crystallographic directions, as well as the temperature dependence. Below the closure temperature of He in zircon [T_c ∼ 180 °C, Reiners P. W., Spell T. L., Nicolescu S., and Zanetti K. A. (2004) Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar-40/Ar-39 dating. Geochim. Cosmochim. Acta68, 1857-1887], diffusion is anisotropic as He moves preferentially along the [0 0 1] direction, and calculated tracer diffusivities along the two most favorable directions differ by approximately five orders of magnitude (D_[001]/D_[100] ∼ 10⁵, at T = 25 °C). Above this temperature, He atoms start to hop between adjacent [0 0 1] channels, along [1 0 0] and [0 1 0] directions (perpendicular to the c-axis). The diffusion along [1 0 0] and [0 1 0] is thermally activated, such that at higher temperatures, He diffusion in zircon becomes nearly isotropic (D_[001]/D_[100] ∼ 10, at T = 580 °C). These results suggest that the anisotropic nature of He diffusion at temperatures near the closure temperature should be considered in future diffusivity experiments. Furthermore, care should be taken when making geologic interpretations (e.g., exhumation rates, timing of cooling, etc.) from this thermochronometer until the effects of anisotropic diffusion on bulk ages and closure temperature estimates are better quantified.     

Fish Canyon Tuff 榍石 He 扩散及(U-Th)/He年代学研究

榍石富含U和Th,是(U-Th)/He定年的理想矿物之一。本文以Fish Canyon Tuff榍石为例,开展了榍石He扩散行为和榍石(U-Th)/He定年实验方法研究。榍石分步加热扩散实验结果表明He扩散系数ln(D/a²)与温度倒数呈负相关,与期望的热活化扩散过程一致。测试Fish Canyon Tuff榍石(U-Th)/He年龄分布在28.3～24.6 Ma之间,平均值为26.7±1.2 Ma (1σ),Th/U分布在4.6～5.5之间,平均值为5.2±0.2,在误差范围内与国际上已出版数据一致,表明建立的榍石(U-Th)/He定年实验方法可靠。本次测试15粒榍石碎片外表层(～20μm)存在不同程度的磨蚀(即不完整晶体),且榍石表层磨蚀厚度随着等效半径的增加而增大。榍石碎片(U-Th)/He年龄介于完整晶体(U-Th)/He年龄和真实(U-Th)/He年龄之间,且随着榍石等效半径及表层磨蚀厚度(<20μm)的增大,(U-Th)/He年龄更接近真实年龄,这表明榍石(U-Th)/He年龄不确定度与等效半径大小和表层磨蚀厚度有关。     

Low-energy 3He and 4He ions in interplanetary space during quiet periods of the 23rd solar cycle

Data from the ULEIS instrument aboard the ACE spacecraft are used to study the energy spectra of ³He and ⁴He ions produced during periods of the quiet Sun in the 23rd solar cycle in the energy range ～0.08–2 MeV/nucleon. Differences in the spectra and ³He/⁴He relative abundances for three groups of quiet periods dominated by different sources of ions are demonstrated: weak impulsive solar flares, particles of the solar corona, and solar wind particles accelerated to energies of several MeV/nucleon.     

He diffusion and (U–Th)/He thermochronometry of zircon: initial results from Fish Canyon Tuff and Gold Butte

To evaluate the potential of (U–Th)/He geochronometry and thermochronometry of zircon, we measured He diffusion characteristics in zircons from a range of quickly and slowly cooled samples, (U–Th)/He ages of zircons from the quickly cooled Fish Canyon Tuff, and age-paleodepth relationships for samples from 15 to 18 km thick crustal section of the Gold Butte block, Nevada. (U–Th)/He ages of zircons from the Fish Canyon Tuff are consistent with accepted ages for this tuff, indicating that the method can provide accurate ages for quickly cooled samples. Temperature-dependent He release from zircon is not consistent with thermally activated volume diffusion from a single domain. Instead, in most samples apparent He diffusivity decreases and activation energy (E_a) increases as cycled step-heating experiments proceed. This pattern may indicate a range of diffusion domains with distinct sizes and possibly other characteristics. Alternatively, it may be the result of ongoing annealing of radiation damage during the experiment. From these data, we tentatively suggest that the minimum E_a for He diffusion in zircon is about 44 kcal/mol, and the minimum closure temperature (T_c, for a cooling rate of 10 °C/myr) is about 190 °C. Age–paleodepth relationships from the Gold Butte block suggest that the base of the zircon He partial retention zone is at pre-exhumation depths of about 9.5–11 km. Together with constraints from other thermochronometers and a geothermal gradient derived from them in this location, the age–depth profile suggests a He T_c of about 200 °C for zircon, in reasonable agreement with our interpretation of the laboratory measurements. A major unresolved question is how and when radiation damage effects become significant for He loss from this mineral.     

辽河盆地黄沙坨油田原油中氦同位素的来源及其地质意义

辽河盆地黄沙坨油田原油样品中氦、氖和氩稀有气体同位素值的测试研究结果显示:①黄沙坨油田原油中稀有气体3He/4He(Rc)分布于2.61×10-6~3.50×10-6,平均3.06×10-6,具有幔源氦混入的特征,幔源氦的侵入份额为20.13%~30.24%,表明该区具有切割至上地幔的深大断裂;②据3He/4He计算,辽河盆地黄沙坨油田大地热流值分布于75.3~77.3 mWm-2之间,平均76.4mWm-2,与我国中部、西部盆地相比该地区具有较高的大地热流值,对有机质的成熟与成烃较有利;③上述研究结果表明原油氦同位素的研究与天然气中氦同位素的研究相似,可为大地构造背景、大地热流、油气来源和演化判识等方面的研究提供有益的科学信息.     

Twin formation in hematite during dehydration of goethite

Twin formation in hematite during dehydration was investigated using X-ray diffraction, electron diffraction, and high-resolution transmission electron microscopy (TEM). When synthetic goethite was heated at different temperatures between 100 and 800 °C, a phase transformation occurred at temperatures above 250 °C. The electron diffraction patterns showed that the single-crystalline goethite with a growth direction of [001]_G was transformed into hematite with a growth direction of [100]_H. Two non-equivalent structures emerged in hematite after dehydration, with twin boundaries at the interface between the two variants. As the temperature was increased, crystal growth occurred. At 800 °C, the majority of the twin boundaries disappeared; however, some hematite particles remained in the twinned variant. The electron diffraction patterns and high-resolution TEM observations indicated that the twin boundaries consisted of crystallographically equivalent prismatic (100) (010), and (1\(\bar{1}\)0) planes. According to the total energy calculations based on spin-polarized density functional theory, the twin boundary of prismatic (100) screw had small interfacial energy (0.24 J/m²). Owing to this low interfacial energy, the prismatic (100) screw interface remained after higher-temperature treatment at 800 °C.     

Glide systems of hematite single crystals in deformation experiments

The critical resolved shear stresses (CRSSs) of hematite crystals were determined in compression tests for r-twinning, c-twinning and {a}<m>-slip in the temperature range 25 °C to 400 °C, at 400 MPa confining pressure, and a strain rate of 10^− 5 s^− 1 by Hennig-Michaeli, Ch., Siemes, H., 1982. Experimental deformation of hematile crstals betwen 25 °C and 400 °C at 400 MPa confining pressure. In: Schreyer, W. (Ed.) High Pressure Research in Geoscience, Schweizerbart'sche Verlagsbuchhandlung, Stuttgart, p. 133–150. In the present contribution newly performed experiments on hematite single crystals at temperatures up to 800 °C at strain rates of 10^− 5 s^− 1 and 300 MPa confining pressure extends the knowledge about the CRSS of twin and slip modes. Optical observations, neutron diffraction goniometry, SEM forescatter electron images and electron backscatter diffraction are applied in order to identify the glide modes. Both twinning systems and {a}<m>-slip were confirmed by these methods. Besides the known glide systems the existence of the (c)<a>-slip system could be stated. Mechanical data establish that the CRSS of r-twinning decreases from 140 MPa at 25 °C to  5 MPa at 800 °C and for {a}<m>-slip from > 560 MPa at 25 °C to  40 MPa at 700 °C. At room temperature the CRSS for c-twinning is around 90 MPa and at 600 °C  60 MPa. The data indicate that the CRSSs above 200 °C seem to be between the values for r-twinning and {a}<m>-slip. For (c)<a>-slip only the CRSS at 600 °C could be evaluated to  60 MPa. Exact values are difficult to determine because other glide systems are always simultaneously activated.     

红色花岗岩中的赤铁矿及岩石中赤铁矿的人工合成

通过对红色花岗岩的研究,发现红色花岗岩的成色矿物为赤铁矿。赤铁矿主要赋存在长石等矿物的解理缝及其显微缝隙中,赤铁矿的含量越多,颜色越红。本文对赤铁矿的成因作了简要分析,认为红色花岗岩中的赤铁矿大多为高氧逸度条件下的产物。由此设计了在花岗岩中人工合成赤铁矿的技术方法,对重要技术参数做了说明。通过在花岗岩中人工合成赤铁矿,可使普通浅色（灰白、浅肉红色）花岗岩改变为红色,对提高普通花岗岩的利用率有一定意     

Nonlocal bacterial electron transfer to hematite surfaces

Mechanisms by which dissimilatory iron-reducing bacteria utilize iron and manganese oxide minerals as terminal electron acceptors for respiration are poorly understood. In the absence of exogenous electron shuttle compounds, extracellular electron transfer is generally thought to occur through the interfacial contact area between mineral surfaces and attached cells. Possible alternative reduction pathways have been proposed based on the discovery of a link between an excreted quinone and dissimilatory reduction. In this study, we utilize a novel experimental approach to demonstrate that Shewanella putrefaciens reduces the surface of crystalline iron oxides at spatial locations that are distinct from points of attachment.