金属同位素质谱中分析样品处理的基本原则与方法

二十年来,国内外相继建立了多种金属（铁铜锌镁钙锂钼硒汞铬镉矾钡钛等）同位素的分析方法。金属同位素分析中的样品处理包括两个过程：样品的消解和样品中待测元素的分离纯化。为了获得真实、准确的金属同位素数据,样品处理过程必须遵守两个基本原则：①不引入待测元素以及可能会对待测元素同位素分析产生干扰的元素;②待测元素不发生损失。金属同位素分析常用的样品消解方法是酸溶法（包括高压闷罐法和微波消解法）。待测元素的分离纯化主要使用离子交换分离法。相同的树脂可以用于不同元素的化学分离,同一种元素也可以使用不同的树脂进行化学分离。不同类型样品的基质差异较大,需要不同的流程对待测元素进行分离。研究人员可以通过改变前人的分离流程,包括改变树脂的用量、变换淋洗液或用量、增加分离步骤等方法来满足不同样品的分离要求。本文提出了金属同位素样品处理中需要注意的一些细节：①如果消解样品时使用了高氯酸,必须将高氯酸在高温下彻底去除,因为残余的高氯酸具有强氧化性会使后续化学分离中使用的离子交换树脂失效,影响分离效果;②同一体积的树脂放入不同内径的交换柱中,树脂柱越细越长,淋洗液流速越慢、洗脱时间越长,并且待测元素洗脱出来越滞后;③离子交换过程中,每次加入的试剂体积越小,淋洗出来的元素越集中,分离效果越好。     

湄洲湾潮流特性的数值研究

本文运用一个含动边界的二维河口海岸动力模型模拟了湄洲湾潮汐潮流的基本特征，模拟结果与实测数据吻合较好．在此基础上估算了湄洲湾大、小潮过程的纳潮量，并根据湾内保守示踪物的质量（浓度）随涨、落潮流周期性的变化，进一步估算了湄洲湾的水交换周期，其半交换和80％的交换周期分别为5d和15d．同时可以看出，主航道深水区的水交换特性明显强于湾顶浅水区．     

Study of the soil–atmosphere moisture exchanges through convective drying tests in non‐isothermal conditions

This paper deals with the moisture exchanges occurring between soils and the surrounding atmosphere. Convective drying tests are performed on Awans silts at different drying temperatures and air relative humidities in order to reproduce the natural drying conditions. The experiments improve the understanding of the vapour transfers kinetics between the soil samples and the atmosphere. The experimental results are analysed assuming that the transfers take place in a boundary layer existing at the surface of the porous medium. The influence of the thermal conditions on the evaporation is also taken into account. In our model, coupled vapour and energy exchanges are controlled by mass and heat transfer coefficients characterizing the boundary layer. These coefficients are determined from the drying experiments. The modelling of the drying tests in non‐isothermal conditions is performed in order to validate the formulation of the vapour and heat exchanges. The numerical results present a good agreement with the kinetic of the materials desaturation determined during the tests. The analysis of the moisture transport mechanisms into the sample and at the boundary shows that at the beginning of the test, the drying is first achieved by the transport of moisture in its liquid form and its evaporation at the sample outer boundary in contact with the atmosphere. In a second step, vapour diffusion becomes predominant into the sample and it corresponds to the most important decrease of relative humidity. Copyright © 2009 John Wiley & Sons, Ltd.     

Flow regimes and long-term water exchange of the Himmerfjärden estuary

A numerical model of processes determining the water exchange encountered in Baltic coastal archipelagos is calibrated and validated against salinity and temperature field data spanning two decades with approximately bi-weekly resolution assessed in the Himmerfjärden estuary. This area is resolved into 17 basins interconnected by 38 individual straits of varying geometrical properties using GIS-based methods. All formulations of the strait exchange flows are free from parameters that need calibration and permit computations of the flow through a strait contraction with or without a coincident sill under a flow classification scheme, of which the first one (a) consists of two groups of multiple layers including aspirated layers from levels beneath the sill crest. The other regimes are as follows. (b) Pure barotropic flow; (c) rotationally controlled flow and (d) plug-flow, which serves as resort solution for flow situations that cannot be solved with (a) and also for computation of the barotropic part of the total flow. For long canals where friction effects act to reduce the flow, a fifth exchange regime is used. The vertical mixing formulation is based on energy balances between supplied wind energy and its work against buoyancy forces. The values of semi-empirical parameters involved in the mixing scheme have been established by calibration against measured data of the first decade period. A statistical evaluation is performed comparing the model results with the measurements of the second decade.     

Measurement of dissolved oxygen using optodes in a FerryBox system

Optode sensors can provide detailed information on concentrations of dissolved oxygen, which in turn may be used to quantify variations in net primary productivity. Throughout 2005 and 2006 the performance of commercially available oxygen optodes was examined, one in each year. The optode was part of an autonomous measurement system (FerryBox) on a ferry operating between Portsmouth (UK) and Bilbao (Spain). On crossings during which water samples were collected manually, the optode outputs were compared to measurements of dissolved oxygen made by Winkler titrations. The optodes maintained good stability with no evidence of instrumental drift during the course of a year. Over the observed concentration range (230–330 mM m⁻³) the optode data were approximately 2% low in both years. By fitting the optode data to the Winkler data the median difference between the optode and Winkler measurements is reduced to less than 1 mM m⁻³ (0.3%) in both years. The most appropriate calibration factor for 2005 was corrected O₂ = Optode O₂ × 1.018 and for 2006 the corresponding equation is corrected O₂ = Optode O₂ × 0.884 + 36.8. The standard deviation (95%) of the difference between the individual Winkler measurements was 5 mM m⁻³ and 3 mM m⁻³ in 2005 and 2006 respectively.Calculation of the oxygen saturation anomaly is required for calculation of the air sea exchange of oxygen and net biological production. This calculation requires the use of both salinity and temperature data. Salinity is measured to better than 0.1 so the corresponding error in anomaly is less than 0.2 mM m⁻³. Distortion of the temperature data is present due to warming of the water pumped to the optode. In winter this warming at the optode may be as great as 0.4 °C. The difference in the pumped water temperature can be corrected for by reference to other measurements of sea surface temperature reducing the error to less than 1 mM m⁻³.     

Stream temperature dynamics in two hydrogeomorphically distinct reaches

The objective of this study was to analyse stream temperature variability during summer in relation to both surface heat exchanges and reach‐scale hydrology for two hydrogeomorphically distinct reaches. The study focused on a 1·5‐km wildfire‐disturbed reach of Fishtrap Creek located north of Kamloops, British Columbia. Streamflow measurements and longitudinal surveys of electrical conductivity and water chemistry indicated that the upper 750 m of the study reach was dominated by flow losses. A spring discharged into the stream at 750 m below the upper reach boundary. Below the spring, the stream was neutral to losing on three measurement days, but gained flow on a fourth day that followed a rain event. Continuous stream temperature measurements typically revealed a downstream warming along the upper 750 m of the study reach on summer days, followed by a pronounced cooling associated with the spring, with little downstream change below the spring. Modelled surface energy exchanges were similar over the upper and lower sub‐reaches, and thus cannot explain the differences in longitudinal temperature patterns. Application of a Lagrangian stream temperature model provided reasonably accurate predictions for the upper sub‐reach. For the lower sub‐reach, accurate prediction required specification of concurrent flow losses and gains as a hydrological boundary condition. These findings are consistent with differences in the hydrogeomorphology of the upper and lower sub‐reaches. The modelling exercise indicated that substantial errors in predicted stream temperature can occur by representing stream‐surface exchange as a reach‐averaged one‐directional flux computed from differences in streamflow between the upper and lower reach boundaries. Further research should focus on reliable methods for quantifying spatial variations in reach‐scale hydrology. Copyright © 2010 John Wiley & Sons, Ltd.     

Large‐scale modelling of channel flow and floodplain inundation dynamics and its application to the Pantanal (Brazil)

For large‐scale sites, difficulties for applying coupled one‐dimensional (1D)/2D models for simulating floodplain inundation may be encountered related to data scarcity, complexity for establishing channel–floodplain connections, computational cost, long duration of floods and the need to represent precipitation and evapotranspiration processes. This paper presents a hydrologic simulation system, named SIRIPLAN, developed to accomplish this aim. This system is composed by a 1D hydrodynamic model coupled to a 2D raster‐based model, and by two modules to compute the vertical water balance over floodplain and the water exchanges between channel and floodplain. Results are presented for the Upper Paraguay River Basin (UPRB), including the Pantanal, one of the world's largest wetlands. A total of 3965 km of river channels and 140 000 km² of floodplains are simulated for a period of 11 years. Comparison of observed and calculated hydrographs at 15 gauging stations showed that the model was capable to simulate distinct, complex flow regimes along main channels, including channel‐floodplain interactions. The proposed system was also able to reproduce the Pantanal seasonal flood pulse, with estimated inundated areas ranging from 35 000 km² (dry period) to more than 120 000 km² (wet period). Floodplain inundation maps obtained with SIRIPLAN were consistent with previous knowledge of Pantanal dynamics, but comparison with inundation extent provided by a previous satellite‐based study indicates that permanently flooded areas may have been underestimated. The results obtained are promising, and further work will focus on improving vertical processes representation over floodplains and analysing model sensitivity to floodplain parameters, time step and precipitation estimates uncertainty. Copyright © 2010 John Wiley & Sons, Ltd.     

Suspended sediment balance for the mainstem of Changjiang (Yangtze River) in the period 1964–1985

Suspended sediment dynamics during the period 1964–1985 are examined along the mainstem of Changjiang (Yangtze River). The period represents a basin condition prior to major changes in land management policy and dam building on the river's mainstem. The downstream sediment dynamics reflect basin geology and topography and channel morphology. Sediment exchange within the mainstem was calculated by the development of reach sediment balances that reveal complex temporal and spatial patterns. There is relatively little sediment exchange in the upper, bedrock‐controlled reaches, with systematic increases in the downstream alluvial reaches. Degrading, transfer, and aggrading reaches were identified. Relations between input and output in all reaches were significant but no relation was found between sediment exchange and input/output. Comparison between ‘short‐term’ (22 years) and ‘long‐term’ (52 years) records demonstrates the importance of the record length in studying the suspended sediment dynamics in a large fluvial system. The longer record yielded better correlation and different trends than the shorter record. Sediment transfer (output/input ratio) changes downstream: the dominance of the upstream contributing area in sustaining the appearance of net degradation through most of the river system highlights the importance of reach length on characterisation of suspended sediment dynamics in large fluvial systems. Copyright © 2011 John Wiley & Sons, Ltd.     

上海天文台2009年工作总结

总结了2009年度中国科学院上海天文台在科研、国际合作交流、人才培养和引进、佘山科技园区建设、科研管理、精神文明建设等方面取得的成果。     

用于MC-ICP-MS测定环境样品中铜、锌同位素的化学分离方法

对不同离子交换柱、淋洗体积、盐度、分离次数等一系列影响铜、锌纯化分离效果的条件进行了探讨,确定了环境样品(湖泊沉积物、植物和颗粒物)中铜、锌同位素测定时化学分离的最佳条件。采用AGMP-1(100～200目)阴离子交换树脂,以7mol/LHCl+0.001%H2O2、2mol/LHCl+0.001%H2O2、0.5mol/LHNO3作为淋洗液,分别在适当的体积接收淋洗液,可以有效地分离沉积物、植物和悬浮物等样品中的铜和锌。化学分离过程中Cu和Zn的回收率接近100%,同位素分馏在测试误差范围以内。将此方法应用于对红枫湖和阿哈湖水体悬浮物、植物和鱼类等样品中Cu、Zn的分离,经MC-ICP-MS测试后,准确获得了这些样品的Cu、Zn同位素组成。