Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

The pillars of cosmology: a short history and assessment

Is the big bang model of the universe ascendant and unshakable, or declining and outdated? This paper cursorily explores the state of cosmology today.     

Small-Amplitude Disturbances in a Radiating and Scattering Grey MediumIII. Gravitational Effects on the Solutions of Given Real Wave Number k

We study the fundamental modes of radiation hydrodynamic linear waves that arise from one-dimensional small-amplitude initial fluctuations with wave number k in a radiating and scattering grey medium by taking into account the gravitational effects. The equation of radiative acoustics is derived from three hydrodynamic equations, Poisson’s equation, and two moment equations of radiation, by assuming a spherical symmetry for the matter and radiation and by using the Eddington approximation. We solve the dispersion relation as a quintic function of angular frequency ω, the wave number k being a real parameter. Numerical results reveal that wave patterns of five solutions are distinguished into three types: the radiation-dominated, type 1, and type 2 matter-dominated cases. In the case of no gravitaional effects (Kaneko et al., 2005), the following wave modes appear: radiation wave, conservative radiation wave, entropy wave, Newtonian-cooling wave, opacity-damped and cooling-damped waves, constant-volume and constant-pressure diffusions, adiabatic sound wave, cooling-damped and drag-force-damped isothermal sound waves, isentropic radiation-acoustic wave, and gap mode. Meanwhile, the gravitaional effects being taken into account, the growing gravo-diffusion mode newly arises from the constant-pressure diffusion at the point that k agrees with Jeans’ wave number specified by the isothermal sound speed. This mode changes to the growing radiation-acoustic gravity mode near the point that k becomes Jeans’ wave number specified by the isentropic radiation-acoustic speed. In step with a transition between them, the isentropic radiation-acoustic wave splits into the damping radiation-acoustic gravity mode and constant-volume diffusion. The constant-volume diffusion emerges twice if the gravitational effects are taken into account. Since analytic solutions are derived for all wave modes, we discuss their physical significance. The critical conditions are given which distinguish between radiation-dominated and type 1 matter-dominated cases, and between type 1 and type 2 matter-dominated cases. Waves in a self-gravitating scattering grey medium are also analyzed, which provides us some hints for the effects of energy and momentum exchange between matter and radiation.     

Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

Natural radioactivity in sediment of Wei River,China

The concentrations of natural radionuclides in sediment of Wei River of China were measured using γ-ray spectrometry with the aim of estimating the radiation hazard as establishing a database for radioactivity levels of river sediment of China. The activity concentrations of ²²⁶Ra, ²³²Th and ⁴⁰K in sediment samples ranged from 10.4 to 39.9 Bq kg⁻¹, 15.3 to 54.8 Bq kg⁻¹ and 514.8 to 1,175.5 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil and Shaanxi soil. Radium equivalent activity (Ra_eq), external hazard index (H _ex) and representative level index (I _γr) were calculated for the samples to assess the radiation hazards arising due to the use of these sediment samples in the construction of dwellings. All the sediment samples have Ra_eq lower than the limit of 370 Bq kg⁻¹, H _ex less than unity and I _γr close to 1 Bq kg⁻¹. The overall mean outdoor terrestrial gamma dose rate is 64.8 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.079 mSv. None of the studied location is considered a radiological risk and sediment can be safely used in construction.     

<Superscript>226</Superscript>Ra, <Superscript>232</Superscript>Th and <Superscript>40</Superscript>K activities in soils of Cuihua Mountain National Geological Park,China

Gamma activity from the naturally occurring radionuclides namely, ²²⁶Ra, ²³²Th, the primordial radionuclide ⁴⁰K was measured in the soil of Cuihua Mountain National Geological Park, China using γ-ray spectrometry technique. The mean activity of ²²⁶Ra, ²³²Th and ⁴⁰K were found to be 27.2 ± 6.5, 43.9 ± 6.2 and 653.1 ± 127.6 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil. The radium equivalent activity, the air absorbed dose rate, the annual effective dose rate, and the external hazard index were evaluated and compared with the internationally approved values. All the soil samples have Ra_eq lower than the limit of 370 Bq kg⁻¹ and H _ex less than unity. The overall mean outdoor terrestrial gamma dose rate is 66.3 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.081 mSv.     

Trace elements in groundwater as indicators of anthropogenic impact

The distribution of several minor and trace elements mainly in fresh (dominating TDS 160–400 mg/l) groundwater of Latvia have been investigated by the Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) technique. An evaluation of results of about 700 analyses leads to the conclusion that concentrations of these elements is influenced by: pH–Eh conditions, groundwater residence time and diffuse contamination, whereas the role of water-bearing sediments is of secondary importance. Most trace elements are characterised by low mobility under alkaline and reducing conditions; concentrations in confined aquifers are much smaller than the Maximum Permissible Values for drinking water. The strongest anomalies of REE, Al and P were found in shallow groundwater around the former agrochemical storehouses.     

Magma Ascent and Crustal Accretion at Ultraslow-Spreading Ridges: Constraints from Plagioclase Ultraphyric Basalts from the Arctic Mid-Ocean Ridge

Plagioclase ultraphyric basalts (PUBs) with up to 54% plagioclasephenocrysts were dredged in the rift valley and adjacent flanksof the ultraslow-spreading Mohns and Knipovich ridges. The PUBsshow large variations in crystal morphologies and zoning. Thelarge variations suggest that single basalt samples containa mixture of plagioclase crystals that aggregated at differentlevels in the magma conduits. Resorbed crystals and repeatedreverse zones suggest that the magma reservoirs were replenishedand heated several times. Thin concentric zones with melt inclusions,and sharp reductions in the anorthite content of 3–7%,are common between the reverse zones. These zones, and skeletalcrystals with distinctly lower anorthite contents than massivecrystals, are interpreted to be the result of rapid crystalliztionduring strong undercooling. The changes between short periodsof cooling and longer periods with reheating are explained bymultiple advances of crystal-rich magma into cool regions followedby longer periods of gradual magma inflow and temperature increase.The porphyritic basalts are characterizd by more depleted andmore fractionated compositions than the aphyric basalts, withlower (La/Sm)_N, K₂O and Mg-numbers. This relationship, and theobservation that PUBs are sampled only close to segment centresalong these ridges, suggests that the PUBs formed by higherdegrees of melting and evolved in more long-lived magma reservoirs.We propose that the zoning patterns of plagioclase crystalsand crystal morphologies of these PUBs reflect the developmentand flow of magma through a stacked sill complex-like conduitsystem, whereas the aphyric equivalents represent later flowof magma through the conduit. The formation of voluminous higher-degreemelts may trigger the development of the magma conduits andexplain the generally depleted compositions of PUB magmas. KEY WORDS: basalt; mineral chemistry; MORB; magma mixing; magma chamber; major element     

海水中234Th的超低水平液闪谱仪测定

本文提出了利用超低水平液闪谱仪测定海水中234Th的方法.海水经氢氧化铁吸附共沉淀富集后,接着用阴离子交换和TBP/煤油萃取进行Th同位素的分离与纯化.对一系列测定条件进行了详细的研究,提出了测定海水中234Th的适宜程序,即在含有234Th和产额示踪剂230Th的纯化后的5mol/dm3HNO3溶液中加入TBP/煤油进行萃取,然后用0.1mol/dm3HNO3反萃取,后者是先用契伦柯夫计数法测量234Th(通过234mPa),后加入闪烁液Hisafe 3用α/β模式测量α放射体230Th.对于α和β放射体液闪谱仪的计数效率分别为100%和55.7%±2.7%.234Th的化学回收率和总探测效率分别为70%～80%和30%～45%.该法测定海水中的234Th快速、简便和高效.     

厦门海域鱼体稀土元素的生态化学特征

于1995—1996年在厦门海域采集了28种鱼类样品，用ICP—MS法测定了15种稀土元素(REE)的含量，研究了鱼体稀土元素的组成和分布模式及与海水环境之间的关系。结果表明，厦门海域鱼体REE总量介于12．4—596．5ng／g，平均为(77．5l2．8)岭g。鱼体明显官集轻稀土，同时轻、重稀土之间则存在较大的分馏作用，说明轻稀土的生物学效应比重稀土更为显著。鱼类稀土元素分布模式总体上与海水REE分布模式接近，并且鱼类REE含量与近岸陆架海水REE含量之间有很好的相关性，说明海洋鱼类对稀土元素的利用遵从丰度规律。鱼类对稀土元素的富集系数在103以上。稀土元素沿厦门海域食物链的迁移传递没有表现出明显的生物放大作用。