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.     

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     

Drought and institutional adaptation in the Great Plains of Alberta and Saskatchewan, 1914–1939

Agriculture in the southern Great Plains of Canada has been particularly vulnerable to prolonged episodes of drought. Using climate data and a precipitation minus potential evapotranspiration index, the extent of the region’s exposure to drought is examined. Between 1914 and 1917, the Dry Belt was particularly vulnerable to drought, whereas after 1928, a much larger region known as the Palliser Triangle covering most of southern Alberta and Saskatchewan was much more exposed to drought. These droughts provoked major institutional adaptation, in particular the establishment of the Special Areas Board by the Government of Alberta, and the creation of the Prairie Farm Rehabilitation Administration by the Government of Canada. Both organizations have proved to be relatively permanent public adaptations to the natural hazard of drought in the region. Moreover, these earlier experiences with prolonged drought as well as institution-building may be of value in helping the residents of the Palliser Triangle adapt to predicted climate changes in the future as well as anticipate some of the barriers to effective institutional adaptation.     

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。     

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     

北太平洋亚热带环流区表层水中226Ra和228Ra的分布与变化

对1999年9～10月采自北太平洋亚热带环流区的19份表层海水样品的Ra同位素分析表明。研究海域表层水中的^226Ra、^228Ra放射性比度分别介于0．67～0．92、0．08～0．30Bq／m^3之间，平均值分别为0．74、0．11Bq/m^3．^226Ra/^228Ra)A．R．活度比的变化范围为0．11～0．44，平均值为0．19．上述数值明显低于近岸海域水体的相应值，表现为典型的开阔大洋水的特征．从空间分布的特征看，研究海域Ra同位素含量与^226Ra/^228Ra)A.R.值均呈均匀分布态势．将本研究结果与历史数据进行对比后发现，本研究获得的^226Ra、^228Ra放射性比度比20世纪60～80年代得到的数据来得低，可能与水体层化作用加强导致的Ra补充量的减少以及生物生产力升高导致的Ra迁出量的增加有关．北太平洋亚热带环流区表层水中Ra同位素的时间变化与文献报道的该海域叶绿素a、硅酸盐、磷酸盐含量与初级生产力的历史变化趋势相吻合．     

Determination of phospholipid fatty acid structures and stable carbon isotope compositions of deep-sea sediments of the Northwest Pacific, ODP site 1179

Sediment samples ranging from 0.05 to 278 m below sea floor (mbsf) at a Northwest Pacific deep-water (5564 mbsl) site (ODP Leg 191, Site 1179) were analyzed for phospholipid fatty acids (PLFAs). Total PLFA concentrations decreased by a factor of three over the first meter of sediment and then decreased at a slower rate to approximately 30 mbsf. The sharp decrease over the first meter corresponds to the depth of nitrate and Mn(IV) reduction as indicated by pore water chemistry. PLFA-based cell numbers at site 1179 had a similar depth profile as that for Acridine orange direct cell counts previously made on ODP site 1149 sediments which have a similar water depth and lithology. The mole percentage of straight chain saturated PLFAs increases with depth, with a large shift between the 0.95 and 3.95 mbsf samples. PLFA stable carbon isotope ratios were determined for sediments from 0.05 to 4.53 mbsf and showed a general trend toward more depleted δ¹³C values with depth. Both of these observations may indicate a shift in the bacterial community with depth across the different redox zones inferred from pore water chemistry data. The PLFA 10me16:0, which has been attributed to the bacterial genera Desulfobacter in many marine sediments, showed the greatest isotopic depletion, decreasing from − 20 to − 35‰ over the first meter of sediment. Pore water chemistry suggested that sulfate reduction was absent or minimal over this same sediment interval. However, 10me16:0 has been shown to be produced by recently discovered anaerobic ammonium oxidizing (anammox) bacteria which are known chemoautotrophs. The increasing depletion in δ¹³C of 10me16:0 with the unusually lower concentration of ammonium and linear decrease of nitrate concentration is consistent with a scenario of anammox bacteria mediating the oxidation of ammonium via nitrite, an intermediate of nitrate reduction.