Electronic absorption spectroscopy of natural (Fe2+, Fe3+)-bearing spinels of spinel s.s.-hercynite and gahnite-hercynite solid solutions at different temperatures and high-pressures

Natural Fe²⁺, Fe³⁺-bearing spinel solid solutions from the spinel s.s.-hercynite and gahnite-hercynite series were analyzed and studied by electronic absorption spectroscopy in the spectral range 30000–3500 cm^–1 in the temperature and pressure ranges 77 T_K 600 and 10^–4 P_GPa 11.0. Two crystals were light-violet in color (type I) and six green or bluish-green (type II). The spectra of both types of spinels are dominated by an UV-absorption edge near 28000 to 24000 cm^–1, depending on the iron contents, and a very intense band system in the NIR centered around 5000 cm^–1, which is caused by spin-allowed dd-transition of tetrahedral Fe²⁺, derived from ⁵ E⁵ T₂. The strong band is in all spinels studied, split into four sub-bands, which can only be observed in very thin platelets. Between the UV-edge and the high-energy wing of the NIR-band there occur a number of very weak bands in type I spinels while the green type II spinels show some of these with significantly enhanced intensity. The intensity of the very weak bands is nearly independent from temperature. Such bands are attributed to spin-forbidden electronic transitions of ^IVFe²⁺. Temperature and pressure dependence of the intensity enhanced bands of spinels type II indicate that they are caused by ^IVFe²⁺ and ^VIFe³⁺. They are attributed to spin-forbidden transitions ⁶A_1g⁴A_1g, ⁴E_g, ⁴T_2g and ⁴T_1g of ^VIFe³⁺, the two latter being strongly intensified by exchange-coupling interaction with adjacent ^IVFe²⁺. The pressure dependence of ^IVFe²⁺ dd-band system in the NIR caused by spin-allowed ⁵ E⁵ T₂ transition noticeably differs from that of octahedral Fe²⁺, an effect which is attributed to a dynamic Jahn-Teller effect of ^IVFe²⁺ in the spinel structure.

n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C₁₅, n-C₁₇, n-C₁₉ alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C₂₁, n-C₂₃, n-C₂₅ homologues from aquatic plants, and the n-C₂₉, n-C₃₁ homologues from vascular plants. In contrast, the n-C₂₇ alkane is not categorized in the n-C₂₉ and n-C₃₁ group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ¹³C_org), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ¹³C_org, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ¹³C_org, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.     

Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ¹³C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C₃ plants. The presence of significant amounts of C₄ plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C₃/C₄ vegetation. By approximately 470,000 yr ago, C₃ plants dominated the diets of herbivores studied, suggesting that the abundance of C₄ flora had decreased in the area. For all deer analyzed in this study, the values of δ¹³C and δ¹⁸O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.     

Numerical estimates of mechanical energy transfer from the atmosphere to the Indian ocean

The field of mechanical energy transfer from the atmosphere to the ocean is computed for the first time. The numerical simulation of waves within the Indian Ocean (IO) water area for the period of 1998?C2009 is used. Mechanical energy transfer is described by two integrated parameters calculated per area unit: the speed of complete energy flux from wind to waves, I _E (x, t), and the speed of complete losses in the energy of wind waves, D _E (x, t). In order to solve this problem, the wind field W(x, t) (the NCEP/NOAA data) is used; the I _E (x, t) and D _E (x, t) fields are calculated on the basis of the WAM numerical model containing a modified source function. The results obtained allow us, first, to assess the characteristic spatial distribution of zones ??pumped?? by the wind with mechanical energy for both the wave field and the upper layer of the ocean by seasons, years, and the whole period discussed, second, to determine the extreme and average zonal values of I _E (x, t) and D _E (x, t), the degree of their shift spacing and balance B _E = (I _E + D _E ); and third, to define the characteristic time scales of variations in the wind field and wave field energies, caused by energy transfer from the wind to waves in the zones and within the Indian ocean as a whole. These results significantly specify the climatic estimates obtained earlier.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

Polarized electronic absorption spectra of Cr2SiO4 single crystals

Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000–5000?cm^–1 were obtained for the orthorhombic thenardite-type phase Cr₂SiO₄, unique in its Cr²⁺-allocation suggesting some metal-metal bonding in Cr²⁺Cr²⁺ pairs with Cr-Cr distance 2.75?Å along [001]. The spectra were scanned at 273 and 120?K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6?μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20?μm and 1?nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr₂SiO₄, synthesized at 35?kbar, above 1440?°C from high purity Cr₂O₃, Cr (10% excess) and SiO₂ in chromium capsules. The Cr₂SiO₄-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm^–1, in the absorption spectra of Cr₂SiO₄ single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr²⁺ in a distorted square planar coordination of point symmetry C₂. The crystal field parameter of Cr²⁺ is estimated to be 10?Dq?10700?cm^–1. A relatively intense, sharp band at 18400?cm^–1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr²⁺. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000?cm^–1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr₂ ⁴⁺, whereas the latter alone would be in conflict with the strong polarization of bands I and II parallel [100]. Therefore, it is concluded that the spectra obtained can best be interpreted assuming both dd-transitions of localized d-electrons at Cr²⁺ as well as δ-δ* transitions of Cr₂ ⁴⁺ pairs with metal-metal interaction. To explain this, a dynamic exchange process 2 Cr_loc ²⁺?Cr_{2, cpl} ⁴⁺ is suggested wherein the half life times of the ground states of both exchanging species are significantly longer than those of the respective optically excited states, such that the spectra show both dd- and δ-δ*-transitions.     

辽东湾地区辽中凹陷东营组烃源岩评价

依据烃源岩地球化学实验手段和油气地化理论,对辽东湾地区辽中凹陷东营组东二下段(Ed^2-1)和东三段(Ed³)地层进行了有机地化分析。在实验获取总有机碳(TOC)、生烃潜量(S₁+S₂)、氢指数(I_H)、氢碳比(H/C)、氧碳比(O/C)、最大热解峰温(T_max)、镜质体反射率(Ro)等有机地化参数的基础上,对有机质丰度、类型、成熟度等进行了系统分析,同时对东营组烃源岩进行了综合评价。研究表明,东二下段S₁+S₂集中在0~3 mg/g,TOC集中在0%~1.5%;东三段S₁+S₂集中分布在4~9 mg/g之间,TOC集中分布在1%~1.25%。东二下段有机质类型主要是III型,东三段有机质类型为II₁、II₂型。东二下段Ro < 0.5,东三段Ro > 0.5,并且随着深度的增加东三段烃源岩Ro相应的增加。T_max随着深度的增加呈现出先增加后减少的异常现象,该种异常现象出现的原因与烃源岩有机质类型和有机质丰度之间存在很大关联。     

Hydroxyl in mantle olivine xenocrysts from the Udachnaya kimberlite pipe

The incorporation of hydrogen in mantle olivine xenocrysts from the Udachnaya kimberlite pipe was investigated by Fourier-transform infrared spectroscopy and secondary ion mass spectrometry (SIMS). IR spectra were collected in the OH stretching region on oriented single crystals using a conventional IR source at ambient conditions and in situ at temperatures down to −180°C as well as with IR synchrotron radiation. The IR spectra of the samples are complex containing more than 20 strongly polarized OH bands in the range 3,730–3,330 cm⁻¹. Bands at high energies (3,730–3,670 cm⁻¹) were assigned to inclusions of serpentine, talc and the 10 Å phase. All other bands are believed to be intrinsic to olivine. The corresponding point defects are (a) associated with vacant Si sites (3,607 cm⁻¹ E || a, 3,597 E || a, 3,571 cm⁻¹ E || c, 3,567 E || c, and 3,556 E || b), and (b) with vacant M1 sites (most of the bands polarized parallel to a). From the pleochroic behavior and position of the OH bands associated with the vacant M1 sites, we propose two types of hydrogen—one bonded to O1 and another to O2, so that both OH vectors are strongly aligned parallel to a. The O2–H groups may be responsible for the OH bands at higher wavenumbers than those for the O1–H groups. The multiplicity of the corresponding OH bands in the spectra can be explained by different chemical environments and by slightly different distortions of the M1 sites in these high-pressure olivines. Four samples were investigated by SIMS. The calculated integral molar absorption coefficient using the IR and SIMS results of 37,500±5,000 L mol H₂O cm⁻² is within the uncertainties slightly higher than the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003) (28,450±1,830 L mol H₂O cm⁻²). The reason for the difference is the different distributions of the absorption intensity of the spectra of both studies (mean wavenumber 3,548 vs. 3,570 cm⁻¹). Olivine samples with a mean wavenumber of about 3,548 cm⁻¹ should be quantified with the absorption coefficient as determined in this study; those containing more bands at higher wavenumber (mean wavenumber 3,570 cm⁻¹) should be quantified using the value determined by Bell et al. (J Geophys Res 108(B2):2105–2113, 2003).

Electronic absorption spectra of Cr3+ ions in natural clinopyroxenes

The polarized (E‖a′, E‖b and E‖c) electronic absorption spectra of five natural chromium-containing clinopyroxenes with compositions close to chromdiopside, omphacite, ureyite-jadeite (12.8% Cr₂O₃), jadeite, and spodumene (hiddenite) were studied. The polarization dependence of the intensities of the Cr³⁺ bands in the clinopyroxene spectra cannot be explained by the selection rules for the point groups C ₂ or C _2v but can be accounted for satisfactorily with the help of the higher order pseudosymmetry model, i.e. with selection rules for the point symmetry group C _3v. The trigonal axis of the pseudosymmetry crystal field forms an angle of 20.5° with the crystallographic direction c in the (010) plane. D _q increases from diopside (1542 cm^?1) through omphacite (1552 cm^?1), jadeite (1574 cm^?1) to spodumene (1592 cm^?1). The parameter B which is a measure of covalency for Cr³⁺-O bonds at M1 sites in clinopyroxene depends on the Cr³⁺ concentration and the cations at M2 sites.     

柴达木盆地昆特依地区晚更新世正构烷烃分布特征及其环境变迁

为探讨柴达木盆地晚更新世的环境变迁,同时为青藏高原隆升对气候变化的影响提供基础资料,对柴达木盆地昆特依地区ZK1404钻孔沉积物中的正构烷烃分布特征以及ASM¹⁴C测年数据进行了分析。结果显示,昆特依地区晚更新世沉积物的正构烷烃总体上呈现以高碳数为主的分布特征,多数样品以nC₂₇、nC₂₉为主峰,部分以nC₃₁为主峰,呈现出显著的奇碳优势。少数样品中低于nC₂₁的短链正构烷烃相对丰度较高,主要以nC₁₇、nC₂₀为主峰碳数,无明显的奇偶优势。根据正构烷烃分布特征、AMS¹⁴C测年数据、区域地质调查资料及沉积环境判断,柴达木盆地昆特依地区晚更新世（33600~26370a B.P.）气候环境以温凉干旱与温凉干旱偏湿交替出现为特征,与现代大陆性干旱荒漠气候截然不同。     

Molecular isotopic heterogeneity of fossil organic matter: implications for δCbiomass and δCpalaeoatmosphere proxies

The degree of isotopic variation in fossil organic matter renders bulk δ¹³C signatures strongly influenced by molecular isotopic heterogeneity. For example, in fossil wood the relative abundance of less depleted ¹³C moieties, i.e. preserved ¹³C enriched polysaccharides versus the relatively ¹³C depleted lignin moieties, can be seen to significantly bias δ¹³C_{fossil wood} values. Moreover the variation in δ¹³C values of specific compounds within fossil material are themselves highly variable and reflect the heterogeneity in isotopic values of different carbon atoms within individual compounds. For studies using δ¹³C values of fossil plant material as proxies (e.g., for δ¹³C_{palaeoatmosphere}, δ¹³C_biomass) it is recommended that the biases introduced through molecular heterogeneity, preservation type and taxonomic status of the fossil material are determined initially. Biases inherent in the bulk signature can then be reduced, rendering this value more robust. Alternatively, compound specific stable carbon isotope measurements of individual moieties preserved through geological time might prove to be an alternative proxy for monitoring changes in the bulk δ¹³C value of the plant and might reveal atmospherically induced trends.     

Stable carbon isotope compositions and source rock geochemistry of the giant gas accumulations in the Ordos Basin, China

Ordos Basin, the second largest sedimentary basin in China, contains enormous natural gas resources. Each of the four giant gas fields discovered so far in this basin (i.e., Sulige, Yulin, Wushenqi and Jingbian) has over 100 billion cubic meters (bcm) or 3.53 trillion cubic feet (tcf) of proven gas reserves. This study examines the stable carbon isotope data of 125 gas samples collected from the four giant gas fields in the Ordos Basin. Source rocks in the Upper Paleozoic coal measures are suggested by the generally high δ¹³C values of C₁–C₄ gaseous hydrocarbons in the gases from the Sulige, Yulin and Wushenqi gas fields. While the δ¹³C_iC4 value is higher than that of the δ¹³C_nC4, the dominant ranges for the δ¹³C₁, δ¹³C₂, and δ¹³C₃ values in these Upper Paleozoic reservoired gases are −34 to −32‰, −27 to −23‰, and −25 to −24‰, respectively. The δ¹³C values of methane, benzene and toluene in gases from the Lower Paleozoic reservoirs of the Jingbian field indicate a significant contribution from humic source rocks, as they are similar to those in the Upper Paleozoic reservoirs of the Sulige, Yulin and Wushenqi gas fields. However, the wide variation and reversal in the δ¹³C₁, δ¹³C₂ and δ¹³C₃ values in the Jinbian gases cannot be explained using a single source scenario, thus the gases were likely derived dominantly from the Carboniferous-Permian coal measures with some contribution from the carbonates in the Lower Permian Taiyuan Formation. The gas isotope data and extremely low total organic carbon contents (<0.2% TOC) suggest that the Ordovician Majiagou Formation carbonates are unlikely to be a significant gas source rock, thus almost all of the economic gas accumulations in the Ordos Basin were derived from Upper Paleozoic source rocks.     

Electron paramagnetic resonance study of new paramagnetic centers in microcline-perthites from pegmatites

Four new types of paramagnetic centers — NH⁺ ₃, N^2?, Al-O^?, E ₁ — have been detected in microcline perthites from pegmatites in the Ukrainian Shield. Values are tabulated for their g and A tensors and limits of thermal stability determined. The NH⁺ ₃ center substitutes the K⁺ ion. It occurs naturally in potash feldspars but is intensified by gamma or X-ray irradiation. It is regarded as a radiational development of the more general NH⁺ ₄ ? K⁺ isomorphism. It disappears after heating to temperatures higher than 470 K. The N^2? center is an uncommon example of isomorphous substitution of a bridging oxygen, being located on a O _D(m) site between T ₂(o) and T ₁(m) silicon sites. It is stable to 820 K. The hole center, Al-O^?, has been detected on an O _A(l) oxygen shared by T ₁(o) and T ₁(m) tetrahedra. It is stable to 590 K. The E ₁ center in these alkali feldspars is similar to the E ₁ center in quartz, being an electron trapped in an oxygen vacancy in the O _B (o) position. It is stable to 420 K. The NH⁺ ₃, Al-O^? and E ₁ centers can be restored from temperatures above their stability limits by gamma radiation. Concentration of centers varies from sample to sample depending on conditions of formation and subsequent history of the minerals.     

Formation Laws of Inorganic Gas Pools in the Northern Jiangsu Basin

In the Northern Jiangsu basin there are high pure CO2 gas pools, low condensed oil-containing CO2 gas pools, high condensed oil-containing CO2 gas pools and He-containing natural gas pools, with the δ13Cco2 (PDB) values ranging from -2.87‰ to -6.50‰, 3He/4He 3.71×10-6 to 6.42×10-6, R/Ra 2.64 to 4.5, 40Ar/36Ar 705 to 734, belonging to typical mantle source inorganic gas pools which are related to young magmatic activity. The gas layers occur in two major reservoir-caprock systems, the terrestrial Meso-Cenozoic clastic rock system and the marine Meso-Palaeozoic carbonate rock-clastic rock system. Controlled by the difference in the scale of traps in the two reservoir-caprock systems, large and medium-scale inorganic gas pools are formed in the marine Meso-Palaeozoic Group and only small ones are formed in the terrestrial Meso-Cenozoic strata. Inorganic gas pools in this basin are distributed along the two deep lithospheric faults on the west and south boundaries of the basin. Gas pools are developed     

Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

Composition, lattice parameters, and room temperature elastic constants of natural single crystal xenotime from Novo Horizonte

The composition, lattice parameters, and elastic constants of natural single crystal YPO₄ xenotime from Novo Horizonte (Brazil) were determined using EPMA, XRD, and the pulse-echo technique. The composition indicates a 24% substitution of Y sites with other rare-earth elements. The lattice parameters of the studied crystal deviated only slightly from those reported for synthetic YPO₄ and were in a good agreement with trends obeyed by other orthophosphates with the xenotime structure. The measured elastic constants C ₁₁, C ₃₃, C ₄₄, and C ₆₆ were consistent with synthetic crystals when porosity was accounted for. C ₁₂ and C ₁₃ constants were evaluated based on the comparison with other materials with xenotime structure. The elastic constants could be rationalized using interionic force constants and bond energies.

Single-crystal polarized FTIR spectroscopy and neutron diffraction refinement of cancrinite

We relate a single-crystal FTIR (Fourier transform infrared) and neutron diffraction study of two natural cancrinites. The structural refinements show that the oxygen site of the H₂O molecule lies off the triad axis. The water molecule is almost symmetric and slightly tilted from the (0001) plane. It is involved in bifurcated hydrogen bridges, with Ow···O donor–acceptor distances >2.7 Å. The FTIR spectra show two main absorptions. The first at 3,602 cm^?1 is polarized for E ⊥ c and is assigned to the ν₃ mode. The second, at 3,531 cm^?1, is also polarized for E ⊥ c and is assigned to ν₁ mode. A weak component at 4,108 cm^?1 could possibly indicate the presence of additional OH groups in the structure of cancrinite. Several overlapping bands in the 1,300–1,500 cm^?1 range are strongly polarized for E ⊥ c, and are assigned to the vibrations of the CO₃ group.     

Density functional theory study and kinetic analysis of the formation mechanism of Al30O8(OH)56(H2O)26 (Al30) in aqueous solution

The formation mechanism of Al₃₀O₈(OH)₅₆(H₂O)₂₆¹⁸⁺ (Al₃₀) has been investigated by the density functional theory based on the supermolecule model and kinetic analysis on the ²⁷Al nuclear magnetic resonance (NMR) experimental results in monitoring Al₃₀ synthesis process. The theoretical chemistry calculations on the four possible schemes show that δ-Na-Al₁₃ is the reasonable intermediate followed by the substitution of Na with Al to form δ-Al₁₄, and Na⁺ plays an important role in stabilizing the intermediate (δ-Na-Al₁₃) in the transformation. The kinetic analysis on the ²⁷Al NMR experimental data indicates that ε-Al₁₃ decomposes and isomerizes in the formation of Al₃₀, while Al monomers facilitate the decomposition of ε-Al₁₃ and so the isomerization of ε-isomers to δ-isomers effectively. The favorable formation mechanism of Al₃₀ includes three steps: (1) ε-Al₁₃ decomposes and rearranges into the isomer δ-Al₁₃; (2) Na⁺ reacts with δ-Al₁₃ to stabilize the intermediate δ-Na-Al₁₃, followed by Al monomers replacing Na to form δ-Al₁₄; (3) δ-Al₁₄ reacts with the Al monomers in the solution to finally form Al₃₀. Both Al monomers and Na⁺ are important in the transformation. Al monomers are the basic building units and helpful to the isomerization while Na⁺ can well stabilize the isomer δ-Al₁₃ to yield intermediate δ-Na-Al₁₃. The results also show that other isomers of ε-Al₁₃ (β-Al₁₃ and α-Al₁₃) form in the formation of Al₃₀, and their calculated ²⁷Al NMR tetrahedral resonance shifts are consistent with the experimental ²⁷Al NMR tetrahedral signals in the preparation process of Al₃₀.     

Five new E′ centers and their 29Si hyperfine structures in electron-irradiated α-quartz

Single-crystal electron paramagnetic resonance (EPR) spectra of fast-electron-irradiated quartz, after annealing at 120 and 200°C, reveal five new E′ type centers, herein labeled E ₅^￠ , E ₆^￠ , E ₇^￠ , E ₈^￠ , \textand E ₉^￠ E_{ 5}^{\prime } ,\,E_{ 6}^{\prime } ,\,E_{ 7}^{\prime } ,\,E_{ 8}^{\prime } ,\,{\text{and}}\,E_{ 9}^{\prime } . Centers E ₅^￠ , E ₇^￠ , \textand E ₉^￠ E_{ 5}^{\prime } ,\,E_{ 7}^{\prime } ,\,{\text{and}}\,E_{ 9}^{\prime } are characterized by the orientations of the unique principal g and A(²⁹Si) axes close to a short Si–O bond direction, hence representing new variants of the well-established E ₁^￠ E_{ 1}^{\prime } center. Centers E ₆^￠ E_{ 6}^{\prime } and E ₈^￠ E_{ 8}^{\prime } have the orientations of the unique principal g and A(²⁹Si) axes approximately along a long Si–O bond direction, similar to the E ₂^￠ E_{ 2}^{\prime } centers. Therefore, these new E′ type centers apparently arise from the removal of different oxygen atoms and represent variable local distortions around the oxygen vacancies.     

Stable carbon-isotopic compositions of lipids isolated from the ammonia-oxidizing chemoautotroph Nitrosomonas europaea

For the ammonia-oxidizing bacterium Nitrosomonas europaea, grown autotrophically using semicontinuous culturing, average biomass was depleted in ¹³C relative to CO₂ dissolved in the medium by ca. 20‰ and the total-lipid extract was depleted in ¹³C relative to biomass by 3.7‰. The n-alkyl lipids (weighted average of fatty acids) and isoprenoid lipids (weighted average of hopanoids) were both depleted in ¹³C relative to biomass by about 9‰. The large depletion in the isoprenoid lipids seems to indicate that isotopic fractionations associated with the biosynthesis of methylerythritol phosphate (MEP) affected at least two carbon positions in each isoprene unit. Among the fatty acids, trans-9-hexadecenoic acid was most depleted (13.0‰ relative to biomass), followed by cis-9- hexadecenoic acid (9.6‰) and hexadecanoic acid (6.9‰). Isotopic relationships between the three acids suggest that significant isotope effects were associated with the desaturation and cis to trans isomerization of fatty acids. Given these observations, hopanoids produced by ammonia-oxidizing bacteria growing in natural waters are likely to be depleted in ¹³C by 26–30‰ relative to dissolved CO₂. Since CO₂ at aquatic oxyclines is often depleted in ¹³C, the range of δ values expected for hopanoids is ca. −34‰ to −55‰. The δ values of geohopanoids observed in numerous studies and attributed to unspecified chemoautotrophs fall within this range.