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.     

Origin and mechanisms of K–Si-metasomatism of ca. 3.4–3.3 Ga volcaniclastic deposits and implications for Archean seawater evolution: Examples from cherts of Kittys Gap (Pilbara craton, Australia) and Msauli (Barberton Greenstone Belt, South Africa)

The effects of K–Si-metasomatism during the formation of Early Archean replacement cherts have been quantified in this study by the investigation of two well-known stratigraphic sections: the Msauli chert (MC, Barberton greenstone belt, South Africa) and the Kittys Gap chert (KGC, Pilbara craton, Western Australia). The KGCs have a dacitic precursor similar to Duffer Formation dacites (Pilbara craton), while the MCs are derived from Al-depleted komatiites similar to those from the Weltevreden Formation (Barberton greenstone belt). Mass balance calculations reveal that the volcaniclastic deposits had initial porosities of up to 85 vol.% for the KGC and of 65 vol.% for the MC. Secondary porosities (27 vol.%: MC, 8 vol.%: KGC) produced during K-metasomatism are proportional to the dissolution of Fe, Ca, Mg-rich glass and precursor minerals. Komatiites have a higher chemical exchange potential than dacites, each gram releasing 1.2 mmol Fe²⁺, 2.8 mmol Mg²⁺, 1.4 mmol Ca²⁺ and 1.1 mmol Na⁺ to seawater, together with 4.4 mmol O²⁻. K-metasomatism of 1 g of komatiite further implies an uptake of 0.67 mmol of K⁺ and 2.7 mmol of H⁺. The highest silica uptake is achieved for the KGC (82 mmol/g of precursor). This silica enrichment most likely operated in the water column and at the sediment–water interface by sorption mechanisms on the surface of detrital particles and particulate organic matter, as a result of seawater silica-saturation. Acidic conditions (pH 5.5–6.5) and hot temperatures (>70 °C) favored the formation of K-rich phyllosilicates by interaction with seawater during the early diagenetic alteration of the volcaniclastic particles. The widespread occurrence of K–Si-metasomatism in volcanic and sedimentary rocks can be regarded as a general alteration process of the Early Archean seafloor, with a major influence on seawater composition. The highly K-selective metasomatism confirms previous studies suggesting that the Archean ocean was acidic and probably in equilibrium with a CO₂-rich atmosphere.     

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。     

顶空气相色谱法测定海水二甲基硫和浮游植物细胞二甲基硫丙酸的研究

建立了顶空ＧＣ／ＦＰＤ测定海水中二甲基硫（ＤＭＳ）和浮游植物细胞中二甲基硫丙酸（ＤＭＳＰ）的方法，并研究盐度、温度、气液相比ＤＭＳ诸因素对ＤＭＳ顶空灵敏度的影响。该法对ＤＭＳ测定的相对标准偏差均小于６％，平均回收率为１０６％，最低检出限为２０ｎｇ／Ｌ。细胞ＤＭＳＰ先经碱作用转化为ＤＭＳ，在５０℃下作用时间不少于６ｈ，峰高与浓度的双对数线性相关系数大于０．９９。对１９９４年冬、１９９５年夏采自胶州湾     

污水-海水混合过程中磷转移的动力学

模拟研究厦门市污水排海时污水-海水混合过程中磷含量和形态的变化,及其在海水-颗粒物界面交换的动力学过程;提供转移模式,确定转移速率,进行磷的容量校正,为厦门西海域环境容量估算和水质控制提供定量参数和理论依据。     

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