天山东部冰川雪坑离子浓度特征的对比研究

对2004年获取的天山奎屯河哈希勒根51号冰川1个雪坑和哈密庙尔沟平顶冰川4个雪坑的离子浓度特征进行了研究,结果表明：Ca²⁺、NO^-3和SO₄^2-是哈密庙尔沟平顶冰川雪坑雪层和积累区雪坑底部冰中的主要离子（尤其是Ca²⁺ ）,其雪层中的主要阳离子关系可在底部冰中得以较好的反映,但雪层中各离子浓度与海拔的相关性不明显,可能与海拔的跨度较小和挖取的雪坑较疏有关;雪坑底部冰中的离子浓度与海拔间明显的相关性说明淋融作用随着海拔升高、气温降低而逐渐减弱。SO₄^2-和Ca²⁺是奎屯河哈希勒根51号冰川雪坑中的主要离子（尤其是SO₄^2-）,其雪坑离子化学特征与哈密庙尔沟平顶冰川差别较大,可能与哈密庙尔沟平顶冰川处于塔克拉玛干沙漠、古尔班通古特沙漠和鄯善沙漠的下风向相关,还可能与雪层内淋融作用的强弱和沉积通量的高程效应有关。哈密庙尔沟平顶冰川积累区雪坑中NH₄⁺、NO₃^-和K⁺的Cs/Ci较Ca²⁺、Mg²⁺和Na⁺要大,奎屯河哈希勒根51号冰川Na⁺和NH4⁺的“雪冰比”较Cl-、SO₄^2-、Mg²⁺和Ca²⁺要大,说明这两条冰川雪坑中的Ca²⁺和Mg²⁺信号较其它离子可能更易于在冰芯记录中保存下来,为冰芯研究和古气候记录的恢复提供了保障。     

Behaviour of Fe-oxides relevant to contaminant uptake in the environment

The behaviour of Fe-oxides was investigated during precipitation and co-precipitation, phase transformation and dissolution, while their ability to adsorb and incorporate trace components was examined. Some samples were synthesised and studied under controlled laboratory conditions and other samples were taken from experiments designed to test the effectiveness of waste treatment strategies using iron. Surface-sensitive and high-resolution techniques were used to complement information gathered from classical, macroscopic methods.

Adsorption isotherms for Ni²⁺ uptake on synthetic ferrihydrite (Fe₅HO₈·4H₂O, often written simply Fe(OH)₃), goethite (-FeOOH), hematite (-Fe₂O₃) and magnetite (Fe₃O₄) were all similar, increasing as expected at higher pH. Desorption behaviour was also similar, but one third or more of the Ni²⁺ failed to return to solution. In the past, “irreversible sorption” has been blamed on uptake into micro-fractures or pores, but during examination (using Atomic force microscopy, AFM) of hundreds of Fe-oxide particles, no evidence for such features could be found, leading to the conclusion that Ni²⁺ must become incorporated onto or into the solids. When solutions of Fe(II) are oxidised in controlled laboratory conditions or during treatment of ash from municipal waste incinerators, two-line ferrihydrite forms rapidly and on never-dried samples, AFM shows abundant individual particles with diameter ranging from 0.5 to several tens of nanometers. Aging in solution at 70°C promotes growth of the particles into hematite and goethite and their identification (by X-ray powder diffraction, XRPD, with Rietveld refinement) becomes possible at the same aging stage as mineral morphology becomes recognisable by AFM. In other experiments that were designed to mimic natural attack by organic acids, colloidal lepidocrocite (γ-FeOOH) was observed in situ by AFM, while reductive dissolution removed material on specific crystal faces. Lath ends are eroded fastest while basal planes are more stable.

In order to help elucidate mechanisms of contaminant immobilisation by Fe-oxides, we examined samples from a reactive barrier made with 90% quartz sand, 5% bentonite and 5% zero-valent iron filings that had reacted with a solution typical of leachate from coal-burning fly ash using time-of-flight secondary ion mass spectroscopy (TOF-SIMS). Fe(0) oxidised to Fe(III), while soluble and toxic Cr(VI) was reduced to insoluble Cr(III). Chemical maps show Fe-oxide coatings on bentonite; Cr is associated with Fe-oxides to some extent but its association with Ca in a previously undescribed phase is much stronger. Other samples taken from municipal waste incinerator ash that had been treated by aeration in Fe(II) solutions were examined with transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS). Pb and some Zn are seen to be dispersed throughout two-line ferrihydrite aggregates, whereas Sn and some Zn are incorporated simply as a result of entrainment of individual ZnSn-oxide crystallites.

Geochemical speciation models that fail to account for contaminant uptake in solid solutions within major phases or as thin coatings or entrained crystals of uncommon phases such as those described here risk to underestimate contaminant retardation or immobilisation.     

汉诺坝幔源单斜辉石巨晶氢同位素组成的离子探针分析:微尺度不均一性

运用离子探针技术测定了河北汉诺坝新生代玄武岩中3个单斜辉石巨晶的氢同位素组成,结果显示同一颗粒内部表现出微尺度的不均一性,2mm范围内δD的变化达到60‰。δD和氢含量之间不存在同步的变化,巨晶内部的化学成分均一,因此我们认为巨晶的氢同位素不均一性继承自母岩浆。母岩浆的氢同位素变化可能是去气过程中气相与熔体之间的分馏引起的。单斜辉石巨晶形成后很短的时间内即被寄主岩浆带至地表并经历了快速淬火。