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High Precision and High Sensitivity Measurements of Osmium in Seawater

机译:海水中O的高精度和高灵敏度测量

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We present improved chemical separation and mass spectrometric procedures that permit precise and accurate determination of Os concentration and isotopic composition in seawater samples. Water samples (50 mL) with added ~(190)Os tracer are heated to 300 deg C at 128 bar in quartz carius tubes with Cr~(VI)O_(3). This allows tracer-sample equilibration via complete oxidation of all Os species to OsO_(4), which is then separated and purified using distillation. Samples are measured using negative thermal ionization mass spectrometry. A new loading technique using face-to-face double-filament geometry is developed that reduces organic interference and improves effective ionization efficiency, which is about 5percent for 200 fg of Os (1 fg of Os velence 3 X 10~(6) atoms). The total yield of the chemical procedure is approx90percent, and the total procedural blank is 3.6 fg. We applied the new procedure on seawater depth profiles from the Atlantic, Pacific, and Southern Oceans and found that (1) the improved procedure results in an increase in Os concentration of 25-35percent over previous methods, (2) Os in seawater does not appear to behave conservatively, and (3) surface seawater has lower ~(187)Os/~(188)Os values than deep waters.
机译:我们提出了改进的化学分离和质谱分析程序,可以精确,准确地测定海水样品中的Os浓度和同位素组成。将添加了〜(190)Os示踪剂的水样品(50 mL)在带有Cr〜(VI)O_(3)的石英玻璃试管中在128 bar下加热到300摄氏度。这样可以通过将所有Os物种完全氧化为OsO_(4)来实现示踪剂样品平衡,然后通过蒸馏将其分离和纯化。使用负热电离质谱法测量样品。开发了一种使用面对面双丝几何结构的新加载技术,该技术可减少有机干扰并提高有效电离效率,对于200 fg的Os(1 fg的os velence 3 X 10〜(6)原子)约为5%。 。化学程序的总产率约为90%,程序空白总量为3.6 fg。我们对大西洋,太平洋和南部海洋的海水深度剖面应用了新程序,发现(1)改进的程序导致Os浓度比以前的方法增加了25-35%,(2)海水中的Os没有(3)地表海水的〜(187)Os /〜(188)Os值低于深水。

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