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.     

胜利油气区有机包裹体研究及其在油气勘探中的应用

应用显微光度术、显微傅立叶红外光谱（Ｍｉｃｒｏ－ＦＴ．ＩＲ）和飞行时间二次离子质谱（ＴＯＦ－ＳＩＭＳ）等原位微分析技术并结合均一温度测量对胜利油气区下第三系沙河街组沙三段中有机包裹体进行了研究。区分出两类有机包裹体，即原生有机包裹体和次生有机包裹体。结果表明两类有机包裹体特征不同，二者物质组成、有机质成分及化学结构、热演化程度等差别也较大。结合地质分析表明原生有机包裹体是沙三段烃源岩生成烃类运移产物，具“自生自储”特点，而次生有机包裹体是沙四段烃源岩生成的烃类二次运移的产物。沙三段是沙河街组油气运移和聚集的主要层位，因而是寻找油气资源的主要目标层。研究表明，有机包裹体是研究油气生成、运移、聚集和演化等成藏系统最有效的手段之一，在油气勘探中有重要的应用意义。     

Upwelling and river runoff as sources of dissolved nitrous oxide to the Alsea estuary,Oregon

Surface waters of Alsea Bay, an unpolluted estuary on the Oregon coast, were analysed for nitrous oxide, nitrate and nitrite on a weekly or biweekly basis during the summer of 1979. The estuary was found to be a variable source of N₂O to the atmosphere. Large and rapid increases in the concentrations of N₂O, NO₃^?, and NO₂^? occurred at the beginning of the sampling period and are attributed to the influx of nutrient-rich upwelling water into the estuary with the tide. The subsequent decline in concentrations of nitrate, nitrite and nitrous oxide over the remainder of the summer is attributed to a decrease in upwelling intensity, a decline in nitrification rates and to assimilatory nitrate reduction. Measurements of nitrous oxide at six stations along the Alsea River were also made in September and October before and after the onset of the rainy season. Samples taken after flood conditions were established were systematically 50% higher than pre-flood samples. The data suggest that soil runoff results in elevated concentrations of N₂O in rivers.     

On salinity regimes and the vertical structure of residual flows in narrow tidal estuaries

An examination is made of the circulation in narrow estuaries subject to a predominant tidal forcing. Velocity structures are derived separately for residual flow components associated with (a) river flow, (b) wind stress, (c) a well-mixed longitudinal density gradient and (d) a fully stratified saline wedge. Dimensionless parameters are introduced to indicate the magnitude of each component and these parameters are evaluated for 9 major estuaries, thereby revealing their sensitivity to each component.For a channel of constant breadth and depth, formulae are deduced for the length of saline intrusion, L. Comparisons with observed data show that such formulae may be used with confidence to predict changes in L arising from variations in river flow, tidal range or channel depths.The level of stratification is shown to be related to a product of two parameters, one associated with velocity structure and a second involving the square of the ‘flow ratio’ $\text{u}\text{u}\text{?}$ (i.e. residual velocity/amplitude of the tidal velocity). This relationship provides a simple classification system for estuarine stratification which can be used to indicate the sensitivity of any particular estuary to changing conditions.     

A laboratory test of the soil chemical submodels of two models of catchment acidification

Parameters for ion exchange selectivity and aluminium hydroxide dissolution in the soil chemical submodels used in applications of the Birkenes model and of MAGIC are compared and several discrepancies identified for organic soils. A laboratory column simulation of the soil chemical submodels is proposed and applied to soils from the Loch Dee area in Galloway. Experimental results were well predicted by a simplified version of MAGIC, with ion exchange selectivity parameters similar to those used in a previous simulation of one subcatchment of Loch Dee. The aluminium hydroxide dissolution parameter used previously was found to be too low for the organic soil materials, where a value of 106 predicted the experimental results more closely. The model developed also included a simple silicate weathering reaction to release base cations into the system. It is concluded that such simple laboratory simulations are useful for independent calibration of the soil chemical submodel of catchment models.     

The Dependence of Water Exchanges between the Kuroshio Water and Its Surroundings on the Characteristics of the Kuroshio‘s Meanders

Observation of fluid parcel pathways in the Kuroshio Stream revealed a striking crossstream pattern associated with the Kuroshio‘‘ s meanders. In order to understand the observed pattern, a two-dimensional kinematic model of a meandering jet was developed which could be used to examine the relationship between streamfunction patterns and fluid parcel trajectories. The experiments designed to investigate the dependence of the water exchanges between the Kuroshio water and its surroundings on the characteristics of the Kuroshio‘‘s meanders involved the downstream speed,phase speed and the amplitude of other propagating waves. The results suggested that fluid parcels could cross the meandering jet to and fro; and that the water exchanges between the Kuroshio and its surroundings increased with a) increasing meander amplitude, b) decreasing downstream speed, and c) increasing wave phase speed. The results also showed that when the meandering jet was disturbed by other propagating waves, more effective water exchanges could be induced.     

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.     

土壤中氟的形态分析

以宁夏盐池地区高氟土壤为例,采用连续提取法对土壤样品中各形态氟进行提取,离子色谱法测定各形态氟的含量。根据研究目的及土壤特点将氟的形态划分为水溶态、离子交换态、可还原态、可氧化态及残渣态5种形态;对各种形态连续提取过程中使用的提取液进行了选择。采用建立的方法获得提取土壤中F-的检出限为0.76μg/g;方法精密度(RSD,n=7)各形态氟为水溶态氟11.3%,离子交换态氟13.5%,可还原态氟10.7%,可氧化态氟8.9%。     

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.