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.     

Response of groundwater chemistry to water deliveries in the lower reaches of Tarim River,Northwest China

In this paper, we analysed the monitored data from nine groundwater-monitoring transects in the lower reaches of Tarim River during the five times of stream water deliveries to the river transect where the stream flow ceased. The results showed that the groundwater depth in the lower reaches of Tarim River rose from −9.30 m before the conveyances to −8.17 and −6.50 m after the first and second conveyances, −5.81 and −6.00 m after the third and fourth the conveyance, and −4.73 m after the fifth. The horizontal extent of groundwater recharge was gradually enlarged along both sides of the channel of conveyance, i.e., from 250 m in width after the first conveyance to 1,050 m away from the channel after the fourth delivery. With the rising groundwater level, the concentrations of major anions Cl⁻, SO₄²⁻ and cations Ca²⁺, Mg²⁺, Na⁺, as well as total dissolved solids (TDS) in groundwater underwent a significant change. The spatial variations in groundwater chemistry indicated that the groundwater chemistry at the transect near Daxihaizi Reservoir changed earlier than that farther from it. In the same transect, the chemical variations were earlier in the monitoring well close to watercourse than that farther away from the stream. In general, the concentration of the major ions and TDS at each monitoring well increased remarkably when the water delivery started, and decreased with the continued water delivery, and then increased once again at the end of the study period. Hence, the whole study period may be divided into three stages: the initial stage, the intermediate stage and the later stage. According to the three stages of groundwater chemistry reaction to water delivery and the relationships between groundwater chemical properties and groundwater depths, we educe that under the situation of water delivery, the optimum groundwater depth in the lower reaches of the Tarim River should be −5 m.     

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     

Global Correlations of Ocean Ridge Basalt Chemistry with Axial Depth: a New Perspective

The petrological parameters Na₈ and Fe₈, which are Na₂O andFeO contents in mid-ocean ridge basalt (MORB) melts correctedfor fractionation effects to MgO = 8 wt%, have been widely usedas indicators of the extent and pressure of mantle melting beneathocean ridges. We find that these parameters are unreliable.Fe₈ is used to compute the mantle solidus depth (P_o) and temperature(T_o), and it is the values and range of Fe₈ that have led tothe notion that mantle potential temperature variation of T_P= 250 K is required to explain the global ocean ridge systematics.This interpreted T_P = 250 K range applies to ocean ridges awayfrom ‘hotspots’. We find no convincing evidencethat calculated values for P_o, T_o, and T_P using Fe₈ have anysignificance. We correct for fractionation effect to Mg^# = 0·72,which reveals mostly signals of mantle processes because meltswith Mg^# = 0·72 are in equilibrium with mantle olivineof Fo_89·6 (vs evolved olivine of Fo_{88·1–79·6}in equilibrium with melts of Fe₈). To reveal first-order MORBchemical systematics as a function of ridge axial depth, weaverage out possible effects of spreading rate variation, local-scalemantle source heterogeneity, melting region geometry variation,and dynamic topography on regional and segment scales by usingactual sample depths, regardless of geographical location, withineach of 22 ridge depth intervals of 250 m on a global scale.These depth-interval averages give Fe₇₂ = 7·5–8·5,which would give T_P = 41 K (vs 250 K based on Fe₈) beneathglobal ocean ridges. The lack of Fe₇₂–Si₇₂ and Si₇₂–ridgedepth correlations provides no evidence that MORB melts preservepressure signatures as a function of ridge axial depth. We thusfind no convincing evidence for T_P > 50 K beneath globalocean ridges. The averages have also revealed significantcorrelations of MORB chemistry (e.g. Ti₇₂, Al₇₂, Fe₇₂,Mg₇₂, Ca₇₂, Na₇₂ and Ca₇₂/Al₇₂) with ridge axial depth. Thechemistry–depth correlation points to an intrinsic linkbetween the two. That is, the 5 km global ridge axial reliefand MORB chemistry both result from a common cause: subsolidusmantle compositional variation (vs T_P), which determines themineralogy, lithology and density variations that (1) isostaticallycompensate the 5 km ocean ridge relief and (2) determine thefirst-order MORB compositional variation on a global scale.A progressively more enriched (or less depleted) fertileperidotite source (i.e. high Al₂O₃ and Na₂O, and low CaO/Al₂O₃)beneath deep ridges ensures a greater amount of modal garnet(high Al₂O₃) and higher jadeite/diopside ratios in clinopyroxene(high Na₂O and Al₂O₃, and lower CaO), making a denser mantle,and thus deeper ridges. The dense fertile mantle beneath deepridges retards the rate and restricts the amplitude of the upwelling,reduces the rate and extent of decompression melting, givesway to conductive cooling to a deep level, forces melting tostop at such a deep level, leads to a short melting column,and thus produces less melt and probably a thin magmatic crustrelative to the less dense (more refractory) fertile mantlebeneath shallow ridges. Compositions of primitive MORB meltsresult from the combination of two different, but geneticallyrelated processes: (1) mantle source inheritance and (2) meltingprocess enhancement. The subsolidus mantle compositional variationneeded to explain MORB chemistry and ridge axial depth variationrequires a deep isostatic compensation depth, probably in thetransition zone. Therefore, although ocean ridges are of shalloworigin, their working is largely controlled by deep processesas well as the effect of plate spreading rate variation at shallowlevels. KEY WORDS: mid-ocean ridges; mantle melting; magma differentiation; petrogenesis; MORB chemistry variation; ridge depth variation; global correlations; mantle compositional variation; mantle source density variation; mantle potential temperature variation; isostatic compensation     

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。     

Budgets of Mn,Cd and Cu in the macrotidal Gironde estuary (SW France)

The behavior and budget of Mn, Cd and Cu in the Gironde estuary were investigated through data from both the water column (WC) and sediment depth profiles. In the estuarine freshwater reaches, Mn and Cd removal from and Cu addition to the dissolved phase occurs with a magnitude equivalent to 10%, 30% and 25% of their respective annual fluvial gross dissolved input, respectively. In the saline estuary, diffusive benthic outflow is the main source of dissolved Mn (74% of the total gross dissolved input within the estuary) to the WC. In contrast, Cd (96%) and Cu (89%) are mainly released into the dissolved phase of the WC from fluvial, estuarine and dredging-related particles through complexation (Cd) and organic carbon mineralization (Cu). Anthropogenic activities (sediment dredging) induce pore water inputs, particulate sulfide oxidation and sediment resuspension, significantly contributing to the metal budget of the WC. The related amounts of metals released could be equivalent to 20–50% (Cd) and up to 70% (Cu) of their respective net dissolved addition. Mass balances suggest that a large part of the metals previously released into the dissolved phase from processes within the estuary are removed by suspended particles due to (co-)precipitation of Fe/Mn (oxy)hydroxides and scavenging on autochthonous organic matter. On an annual basis, the Gironde estuary acts as a net sink of dissolved Mn, removing 60% of the dissolved fluvial inputs, and as a net source of dissolved Cd and Cu, contributing ∼ 85% and 20–45% to the dissolved Cd and Cu fluxes to the ocean.     

Estuary/ocean exchange and tidal mixing in a Gulf of Maine Estuary: A Lagrangian modeling study

A Lagrangian particle method embedded within a 2-D finite element code, is used to study the transport and ocean–estuary exchange processes in the well-mixed Great Bay Estuarine System in New Hampshire, USA. The 2-D finite element model, driven by residual, semi-diurnal and diurnal tidal constituents, includes the effects of wetting and drying of estuarine mud flats through the use of a porous medium transport module. The particle method includes tidal advection, plus a random walk model in the horizontal that simulates sub-grid scale turbulent transport processes. Our approach involves instantaneous, massive [O(500,000)] particle releases that enable the quantification of ocean–estuary and inter-bay exchanges in a Markovian framework. The effects of the release time, spring–neap cycle, riverine discharge and diffusion strength on the intra-estuary and estuary–ocean exchange are also investigated.The results show a rather dynamic interaction between the ocean and the estuary with a fraction of the exiting particles being caught up in the Gulf of Maine Coastal Current and swept away. Three somewhat different estimates of estuarine residence time are calculated to provide complementary views of estuary flushing. Maps of residence time versus release location uncover a strong spatial dependency of residence time within the estuary that has very important ramifications for local water quality. Simulations with and without the turbulent random walk show that the combined effect of advective shear and turbulent diffusion is very effective at spreading particles throughout the estuary relatively quickly, even at low (1 m²/s) diffusivity. The results presented here show that a first-order Markov Chain approach has applicability and a high potential for improving our understanding of the mixing processes in estuaries.