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.     

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.     

Distinct climate change synchronous with Heinrich event one, recorded by stable oxygen and carbon isotopic compositions in stalagmites from China

Uranium-series dating of oxygen and carbon isotope records for stalagmite SJ3 collected in Songjia Cave, central China, shows significant variation in past climate and environment during the period 20-10 ka. Stalagmite SJ3 is located more than 1000 km inland of the coastal Hulu Cave in East China and more than 700 km north of the Dongge Cave in Southwest China and, despite minor differences, displays a clear first-order similarity with the Hulu and Dongge records. The coldest climatic phase since the Last Glacial Maximum, which is associated with the Heinrich Event 1 in the North Atlantic region, was clearly recorded in SJ3 between 17.6 and 14.5 ka, in good agreement in timing, duration and extent with the records from Hulu and Dongge caves and the Greenland ice core. The results indicate that there have been synchronous and significant climatic changes across monsoonal China and strong teleconnections between the North Atlantic and East Asia regions during the period 20-10 ka. This is much different from the Holocene Optimum which shows a time shift of more than several thousands years from southeast coastal to inland China. It is likely that temperature change at northern high latitudes during glacial periods exerts stronger influence on the Asian summer monsoon relative to insolation and appears to be capable of perturbing large-scale atmospheric/oceanic circulation patterns in the Northern Hemisphere and thus monsoonal rainfall and paleovegetation in East Asia. Climatic signals in the North Atlantic region propagate rapidly to East Asia during glacial periods by influencing the winter land-sea temperature contrast in the East Asian monsoon region.     

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     

低风速下海面附近气温场对海气动量通量的影响

实用测的海上和层平均风剖面数据和温度剖面数据，通过数据回归和迭代方法计算出了在不同大气稳定情况下的海面阻力系数。得到了与前人理论计算一致的结论：海面阻力系数随海面大气稳定度的增加而减小，另外，我们还发现：在海面风速小于１３ｍ／ｓ时，不能认为气温剖面外推到海面的值与海面水温的是一致的。这样若用海气温差作为衡量海面上方大气的稳定程度，难于得到上面给出了理结论。这一点同前人的理论计算结果是不相同的。     

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。     

Methyl halide production and loss rates in sea water from field incubation experiments

Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl⁻ varied from < 1 to 18% day^− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH₃I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates.     

九龙江河口区水体中的226Ra和228Ra

用ＭｎＯ２－纤维富集大体积水样中的Ｒａ同位素，并用直接射气法测定２２６Ｒａ和２２８Ａｃ的β计数法测定２２８Ｒａ的方法，研究了九龙江河口区２２６Ｒａ，２２８Ｒａ的行为，结果表明：在该河口区２２６Ｒａ，２２８Ｒａ均呈非保守行为，２２６Ｒａ，２２８Ｒａ的最高值分别在盐度为１９和９处测得。２２８Ｒａ／２２６Ｒａ）Ａ．Ｒ．值在盐度小于１９的区域约为３左右。与世界其他河口区相比，九龙江河口区的２２６Ｒａ，２２