较低稀释比熔片制样X射线荧光光谱法测定磷矿石中12种主次痕量组分

当前应用X射线荧光光谱熔片制样技术分析测定较低含量、低荧光产额氟组分时,准确度较低,精密度较差、检出限较高。本文运用5:1较低稀释比熔样制片技术,采用波长色散X射线荧光光谱法测定磷矿石中12个主次量组分(F、Na₂O、MgO、Al₂O₃、SiO₂、P₂O₅、K₂O、CaO、TiO₂、MnO、TFe₂O₃和痕量SrO)。采用磷矿石、岩石国家一级标准物质、磷矿石管理样品和人工配制标准样品校准,经验系数法进行基体校正,结果表明12个组分分析方法的精密度和准确度较好,检出限较低,未知样品的分析结果比较满意;氟的精密度、准确度和检出限均好于文献中10:1熔样稀释比得出的结果。该方法解决了压片制样测定氟组分,熔片制样测定其他主次量组分的技术问题,同时也降低了熔片制样技术测定氟的检出限。     

河北临漳曹村窑址青釉器物工艺特征研究

河北地区古代瓷窑产品的理化测试工作多集中于隋唐、宋金时期的器物,北朝等早期产品的分析数据则少有报道。本文运用X射线荧光光谱、X射线衍射、岩相、吸水率测试和烧成温度测定等分析方法,对曹村窑址出土青釉样品的工艺特征开展研究。结果表明,2件样品釉层氧化钙含量分别为17.86%和14.1%,烧成温度分别达到1150.1℃和1185.2℃,证明这2件样品属于青瓷,从而证实了曹村窑是已发现的我国北方早期烧制青瓷的窑口之一;其余样品釉层氧化铅含量大于42%,部分样品吸水率低于5%,X射线衍射结果显示胎体中出现莫来石相,证明曹村窑可以生产出瓷胎铅釉陶。结合样品烧成温度均在1000℃以上,远高于铅釉成熟温度,推断曹村窑的瓷胎铅釉陶在北朝时期已经使用了二次烧成工艺。这一复杂工艺的产生,有可能为唐三彩的出现作了技术铺垫。     

酸消解-车载偏振能量色散X射线荧光法现场测定祁曼塔格多金属矿中高品位铜铅锌

能量色散X射线荧光光谱法(ED-XRF)是勘查与找矿现场常用的分析手段.对于高矿化度样品或矿石样品,由于存在严重的基体效应,难以找到与基体匹配的校准样品,分析数据的准确度会受到严重影响,乃至给出错误的结果,成为制约现场分析高矿化度地质样品的主要难题.本文针对XRF现场分析高矿化样品存在的问题,研制了两种具有双层薄膜结构的液体样品盒,以强酸性溶液进样,应用车载台式偏振激发能量色散X射线荧光光谱(PE-EDXRF)技术,采用标准溶液进行含量校准,二级靶钼Kα谱线的康普顿散射峰作为内标校正基体效应,实现了现场准确分析青海祁曼塔格高原矿区铜铅锌多金属矿石中的铜、铅、锌三种元素.为制备适合PE-EDXRF分析的溶液,在祁曼塔格矿区现场对实验室管理样及未知样品试验了水浴加热与电热板加热两种样品处理方式.采用电热板加热方式,分析2件矿区样品的方法精密度(RSD,n=10)均优于2％;分析4件管理样的方法准确度均优于5％(当含量＞5‰时);13件矿区未知样品PE-EDXRF与原子吸收分光光度法(AAS)分析结果的平均相对偏差为:Cu 2.87％(含量范围在0.75％～8.57％),Pb 2.82％(含量范围在0.78％ ～29.1％),Zn 6.84％(含量范围在0.11％ ～2.51％),两种方法的分析结果具有很好的一致性.而采用水浴加热方式消解样品,由于在海拔四千多米地区水的沸点仅约为88℃C,样品消解不够完全,导致测定结果系统偏低.现场实验和结果表明,在高原低气压环境下,采用电热板加热方式消解样品,结合使用双层膜液体样品盒建立的PE-EDXRF分析方法,可以解决高矿化度样品及矿石样品的较高精度现场分析问题.本文建立的溶液制样方法可以解决基体匹配的难题,结合使用研制的双层膜溶液样品盒保护了仪器,是对粉末制样法PE-EDXRF现场分析技术的一个补充和完善.     

长江口及其邻近海域溶解硒的地球化学控制过程研究

Dissolved selenium in the Changjiang(Yangtze) Estuary and its adjacent waters was determined by hydride generation atomic fluorescence spectrometry to elucidate the source, behavior in estuary, adsorption-desorption process and biological role. In surface water, Se(IV) concentration ranged 0.05–1.14 nmol/L and Se(VI) concentration varied 0.01–1.20 nmol/L, with the means of 0.76 and 0.49 nmol/L, respectively. In bottom water, Se(IV) content varied 0.03–0.27 nmol/L and Se(VI) content ranged 0.04–0.85 nmol/L, with the averages of 0.10 and 0.40 nmol/L, respectively. High level of Se(IV) was observed near the shore with a significant decrease towards the open sea, suggesting the continental input from the adjacent rivers. Large value of Se(VI) was found in bottom water, reflecting the release from suspended sediment. Besides, high value appeared in the same latitude of the Changjiang Estuary and Hangzhou Bay illustrated the effect of lateral mixing and the long-distance transport of selenium. Se(VI), more soluble, occupied higher percentage in aqueous environment. The presence of Se(IV) resulted from the degradation of residue and the reduction of Se(VI) under anaerobic condition. The positive relationship to suspended particulate material(SPM) and negative correlation to depth indicated that Se(IV) tended to be released from the high density particulate matter. Instead, Se(VI) content did not significantly relate to SPM since it generally formed inner-sphere complex to iron hydroxide. Se(IV) content negatively varied to salinity and largely depended on the freshwater dilution and physical mixing. While, Se(VI) level deviated from the dilution line due to the in situ biogeochemical process such as removal via phytoplankton uptake and inputs via organic matter regeneration. As the essential element, Se(IV) was confirmed more bioavailable to phytoplankton growth than Se(VI), and moreover, seemed to be more related to phosphorus than to nitrogen.     

Occurrence and distribution of dissolved tellurium in Changjiang River estuary

With the implementation of the GEOTRACES program, the biogeochemical cycle and distribution of tellurium （Te） in marine environments are becoming increasing environmental concerns. In this study, the concentration of dissolved Te in the Changjiang （Yangtze） River estuary and nearby waters was determined in May 2009 by hydride-generation atomic fluorescence spectrometry to elucidate the abundance, dominant species, distribution, and relationship with environmental factors. Results show that： （1） dissolved Te was low owing to its low abundance in the Earth＇s crust, high insolubility in water, and strong affinity to particulate matter; （2） Te（IV） and Te（VI） predominated in surface water. Te（VI） was the dominant species in bottom water, and Te（IV） was the minor species; （3） Horizontally, resulting from low phytoplankton metabolism and the weak reduction from Te（VI） to Te（IV） in the shore, Te（IV） was concentrated in the central zone instead of the coastal region. However, Te（VI） was abundant near the mouth of the Changjiang River where the Changjiang water is diluted and in the area to the south where the Taiwan Warm Current invaded. In the adsorption-desorption process, Te（IV） was negatively related to suspended paniculate matter （SPM）, indicating that it was adsorbed by particulate matter. While for Te（VI）, the positive correlation with SPM suggested that it was desorbed from the solid phase. In the estuary, dissolved Te had a negative correlation to salinity. However, it deviated from the dilution line in high-salinity regions due to the invasion of the Taiwan Warm Current and the mineralization of organic matter. The relationship between Te（IV） and SPM nutrients indicated that it was more bioavailable and more related to phosphorus than to nitrogen. Progress in the field is slow and more research is needed to quantify the input of Te to the estuary and evaluate the biochemical role of organisms.     

反射定标板污染对典型月球矿物定量分析影响的研究

悬浮月尘存在污染月表就位光谱仪反射定标板的可能。文中工作模拟并分析了近红外光谱仪反射定标板在无污染、受轻度和重度污染情况下对模拟月壤矿物混合物光谱指纹特征及定量分析模型预测精确度的影响。结果表明：以受污定标板为参比的月壤矿物混合物反射光谱在反射率和指纹特征上均异于无污染样品,且污染越重差异越大;用无污染光谱数据建立的偏最小二乘(PLS)定量分析模型,预测受污样品时其预测精确度显著降低;采用受污后光谱数据重建PLS模型会在一定程度上能提高受污样品的预测准确度。该研究和获得的结论,在星表光学载荷的设计、数据校正以及定量分析模型预测能力评估等方面具有一定的指导意义。     

熔融玻璃片制样-X射线荧光光谱测定页岩中主量元素

熔融片法制样,用X射线荧光光谱法测定页岩样品中硅、铝、铁、钙、钾、镁、钠7个主量元素,以页岩、岩石、水系沉积物、土壤国家一级标准物质作为校准样品,使用理论α系数和经验系数相结合的方法校正基体效应。方法精密度(RSD,n=12)≤1.50%。分析结果与化学法进行对照基本一致。     

原子荧光光谱法测定土壤和水系沉积物国家标准物质中砷

用王水浸提法和硝酸-高氯酸-氢氟酸混合酸消解法处理样品,原子荧光光度光谱法测定土壤和水系沉积物国家标准物质样品中的砷。方法检出限为0.02 mg/kg。两种前处理方法砷的测定值与标准值相符,均可以满足土壤和水系沉积物样品中砷含量的测定要求。单纯测定样品中砷含量时,王水浸提法更好;如果在测定砷同时还要测定其他元素,则可以选用混合酸消解法。     

氢化物发生-原子荧光光谱法测定三氧化二锑中锡

500℃时在锌粉、氯化铵存在下,锑以三氯化锑形式被挥发除去,锡与锌形成锌-锡合金留在残渣中,从而消除锑对锡的干扰。在10%(体积分数)的盐酸介质中,硼氢化钾将锡(Ⅱ)还原成四氢化锡,用氢化物发生-原子荧光光谱法测定锡的荧光强度。方法检出限为0.20 mg/kg,精密度(RSD,n=7)为3.73%,回收率为91.0%~104.5%。