Direct analysis of copper-base alloys using laser ablation techniques is an increasingly common procedure in cultural heritage studies. However, main discussions remain focused on the possibility of using non-matrix m...Direct analysis of copper-base alloys using laser ablation techniques is an increasingly common procedure in cultural heritage studies. However, main discussions remain focused on the possibility of using non-matrix matched external reference materials. To evaluate the occurrence of matrix effects during in situ microanalysis of copper-base materials, using near infrared femtosecond laser ablation techniques (NIR fs-LA-ICP-MS), two bronzes, i.e., (Sn-Zn)-ternary and (Sn)-binary copper-matrix reference materials, as well as a reference synthetic glass (NIST-SRM-610) have been analyzed. The results have been compared to data obtained on a sulfide-matrix reference material. Similar values in relative sensitivity averages of 63Cu, 118Sn and 66Zn, as well as in 118Sn/63Cu and 66Zn/63Cu ratios were obtained, for all analyzed matrix types, i.e., copper-base-, silicate-, and sulfide-reference materials. Consequently, it is possible to determinate major and minor element concentrations in copper alloys, i.e., Cu, Sn and Zn, using silicate and sulfide reference materials as external calibrators, without any matrix effect and over a wide range of concentrations (from wt.% to ppm). Equally, Cu, Sn and Zn concentrations can be precisely determined in sulfides using homogeneous alloys (reference) materials as an external calibrator. Thus, it is possible to determine Cu, Sn and Zn in copper-base materials and their ore minerals, mostly sulfides, in a single analytical session, without requiring specific external calibrators for each matrix type. In contrast, immiscible elements in copper matrix, such as Pb and Fe show notable differences in their relative sensitivity values and ratios for different matrix-materials analyzed, implying that matrix-matched external calibrations remain to be applied for their trace quantification.展开更多
An innovative application of laser ablation inductively coupled plasma mass spectrometry （LA-ICP-MS） technique in illustrating elemental distributions on stainless steel sheets was presented. The technique proved to...An innovative application of laser ablation inductively coupled plasma mass spectrometry （LA-ICP-MS） technique in illustrating elemental distributions on stainless steel sheets was presented. The technique proved to be a systematic and accurate ap- proach in producing visual images or maps of elemental distributions at cross-sectional surface of a stainless steel sheet. Two stain- less steel sheets served as research objects： 3 mm×l 300 mm hot-rolled stainless steel plate and 1 mm×l 260 mm cold-rolled plate. The cross-sectional surfaces of the two samples at 1/4 position along the width direction were scanned （raster area -44 mm2 and 11 mm2） with a focused laser beam （wavelength 213 nm, diameter of laser crater 100 μm, and laser power 1.6 mJ） in a laser abla- tion chamber. The laser ablation system was coupled to a quadrupole ICP-MS, which made the detection of ion intensities of 27A1＋, 44Ca＋, 47Ti-, 55Mn＋ and 56Fe＋ within an area of interest possible. One-dimensional （ID） content line distribution maps and two- dimensional （2D） contour maps for specific positions or areas were plotted to indicate the element distribution of a target area with high accuracy. Statistic method was used to analyze the acquired data by calculating median contents, maximum segregation, sta- tistic segregation and content-frequency distribution.展开更多
建立一种准确测定铀矿中铼和钪含量的方法,为铀矿中伴生元素的分析与研究提供数据支持,对探勘铼钪矿实现战略资源合理利用化有着重大意义。采用氢氟酸-硝酸-盐酸-高氯酸四酸作溶剂、密闭聚四氟乙烯坩埚-电热板加热方式溶解样品,利用电...建立一种准确测定铀矿中铼和钪含量的方法,为铀矿中伴生元素的分析与研究提供数据支持,对探勘铼钪矿实现战略资源合理利用化有着重大意义。采用氢氟酸-硝酸-盐酸-高氯酸四酸作溶剂、密闭聚四氟乙烯坩埚-电热板加热方式溶解样品,利用电感耦合等离子体质谱(ICP-MS)法测定铀矿中铼和钪。通过探讨分解方法、称样量、酸用量、溶样温度及时间、基体干扰、内标选择的影响。结果表明,酸溶分解结果准确性高于碱熔分解,3 mL HF、4 mL HNO3、2 mL HCl和1 mL HClO4为最佳消解体系,0.05~0.10 g、10~12 mL为最佳称样量和酸用量,闭盖160℃、开盖190℃18 h为最佳溶样条件,选择碰撞气流速为3.0 mL/min,稀释气流速为0.8 L/min降低基体干扰,In作为内标能够达到测试要求。方法操作简单,其中铼和钪的检出限分别为0.002和0.122 mg/kg;铼准确度在92.9%~98.4%,相对标准偏差在2.4%~5.7%;钪准确度在93.5%~98.2%,相对标准偏差在1.6%~6.2%;铼加标回收率为87.2%~93.8%,钪加标回收率为90.7%~92.3%,检出限低,精密度良好,满足铀矿中铼和钪的分析要求。展开更多
Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in ...Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in the Haima cold seeps at a water depth of 1381 m.Based on the scanning electron microscope(SEM)analyses,the prismatic layer and nacreous layer were identified,which are characterized by prismatic structure and stratified structure,respectively.In addition,the profile can be subdivided into two parts:altered and unaltered zones.Laser inductively coupled plasma mass spectrometry(LA-ICP-MS)mapping shows that the element concentrations of the altered zones were influenced by the authigenic carbonate rocks,whereas the element concentrations of unaltered zones remain stable.In-situ X-ray diffraction(XRD)analyses show that the mineral constituent of the prismatic layer is mainly composed of aragonite.Along with the growth profile,Mg/Ca ratios of unaltered zones have minor variations,ranging 0.72-0.97 mmol/mol(mean=0.87 mmol/mol),with estimated temperatures of 3.8-4.1℃,indicating that the temperature of the surrounding seawater remains constant and agree with the measured data of 3.9℃which was conducted by a conductivity-temperature-depth system(CTD).The minor variations of Ba/Ca ratios(0.01-0.06 mmol/mol;mean=0.04 mmol/mol)indicate a relatively stabilized salinity of the surrounding seawater.S/Ca ratios show large variations of 0.04-4.15 mmol/mol(mean=1.37 mmol/mol).S/Ca ratios have regular variations which generally correspond to the variations of the Mg/Ca ratios,highlighting that the S/Ca ratios of bivalve shells show the potential to reflect the growth rate of the Gigantides.However,further studies should be carried out on the understanding of the links between the S/Ca ratios and seepage intensity of cold-seep fluids.展开更多
文摘Direct analysis of copper-base alloys using laser ablation techniques is an increasingly common procedure in cultural heritage studies. However, main discussions remain focused on the possibility of using non-matrix matched external reference materials. To evaluate the occurrence of matrix effects during in situ microanalysis of copper-base materials, using near infrared femtosecond laser ablation techniques (NIR fs-LA-ICP-MS), two bronzes, i.e., (Sn-Zn)-ternary and (Sn)-binary copper-matrix reference materials, as well as a reference synthetic glass (NIST-SRM-610) have been analyzed. The results have been compared to data obtained on a sulfide-matrix reference material. Similar values in relative sensitivity averages of 63Cu, 118Sn and 66Zn, as well as in 118Sn/63Cu and 66Zn/63Cu ratios were obtained, for all analyzed matrix types, i.e., copper-base-, silicate-, and sulfide-reference materials. Consequently, it is possible to determinate major and minor element concentrations in copper alloys, i.e., Cu, Sn and Zn, using silicate and sulfide reference materials as external calibrators, without any matrix effect and over a wide range of concentrations (from wt.% to ppm). Equally, Cu, Sn and Zn concentrations can be precisely determined in sulfides using homogeneous alloys (reference) materials as an external calibrator. Thus, it is possible to determine Cu, Sn and Zn in copper-base materials and their ore minerals, mostly sulfides, in a single analytical session, without requiring specific external calibrators for each matrix type. In contrast, immiscible elements in copper matrix, such as Pb and Fe show notable differences in their relative sensitivity values and ratios for different matrix-materials analyzed, implying that matrix-matched external calibrations remain to be applied for their trace quantification.
基金Sponsored by National Major Instrument and Equipment Development Special Project of China(2011YQ14014710)
文摘An innovative application of laser ablation inductively coupled plasma mass spectrometry （LA-ICP-MS） technique in illustrating elemental distributions on stainless steel sheets was presented. The technique proved to be a systematic and accurate ap- proach in producing visual images or maps of elemental distributions at cross-sectional surface of a stainless steel sheet. Two stain- less steel sheets served as research objects： 3 mm×l 300 mm hot-rolled stainless steel plate and 1 mm×l 260 mm cold-rolled plate. The cross-sectional surfaces of the two samples at 1/4 position along the width direction were scanned （raster area -44 mm2 and 11 mm2） with a focused laser beam （wavelength 213 nm, diameter of laser crater 100 μm, and laser power 1.6 mJ） in a laser abla- tion chamber. The laser ablation system was coupled to a quadrupole ICP-MS, which made the detection of ion intensities of 27A1＋, 44Ca＋, 47Ti-, 55Mn＋ and 56Fe＋ within an area of interest possible. One-dimensional （ID） content line distribution maps and two- dimensional （2D） contour maps for specific positions or areas were plotted to indicate the element distribution of a target area with high accuracy. Statistic method was used to analyze the acquired data by calculating median contents, maximum segregation, sta- tistic segregation and content-frequency distribution.
文摘建立一种准确测定铀矿中铼和钪含量的方法,为铀矿中伴生元素的分析与研究提供数据支持,对探勘铼钪矿实现战略资源合理利用化有着重大意义。采用氢氟酸-硝酸-盐酸-高氯酸四酸作溶剂、密闭聚四氟乙烯坩埚-电热板加热方式溶解样品,利用电感耦合等离子体质谱(ICP-MS)法测定铀矿中铼和钪。通过探讨分解方法、称样量、酸用量、溶样温度及时间、基体干扰、内标选择的影响。结果表明,酸溶分解结果准确性高于碱熔分解,3 mL HF、4 mL HNO3、2 mL HCl和1 mL HClO4为最佳消解体系,0.05~0.10 g、10~12 mL为最佳称样量和酸用量,闭盖160℃、开盖190℃18 h为最佳溶样条件,选择碰撞气流速为3.0 mL/min,稀释气流速为0.8 L/min降低基体干扰,In作为内标能够达到测试要求。方法操作简单,其中铼和钪的检出限分别为0.002和0.122 mg/kg;铼准确度在92.9%~98.4%,相对标准偏差在2.4%~5.7%;钪准确度在93.5%~98.2%,相对标准偏差在1.6%~6.2%;铼加标回收率为87.2%~93.8%,钪加标回收率为90.7%~92.3%,检出限低,精密度良好,满足铀矿中铼和钪的分析要求。
基金Supported by the Key Research and Development Project of Guangdong Province(No.2020B1111510001)the National Natural Science Foundation of China(No.U2244224)+1 种基金the PI Project of Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(No.GML2020GD0802)the Guangdong Special Support Team Program(No.2019BT02H594)。
文摘Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in the Haima cold seeps at a water depth of 1381 m.Based on the scanning electron microscope(SEM)analyses,the prismatic layer and nacreous layer were identified,which are characterized by prismatic structure and stratified structure,respectively.In addition,the profile can be subdivided into two parts:altered and unaltered zones.Laser inductively coupled plasma mass spectrometry(LA-ICP-MS)mapping shows that the element concentrations of the altered zones were influenced by the authigenic carbonate rocks,whereas the element concentrations of unaltered zones remain stable.In-situ X-ray diffraction(XRD)analyses show that the mineral constituent of the prismatic layer is mainly composed of aragonite.Along with the growth profile,Mg/Ca ratios of unaltered zones have minor variations,ranging 0.72-0.97 mmol/mol(mean=0.87 mmol/mol),with estimated temperatures of 3.8-4.1℃,indicating that the temperature of the surrounding seawater remains constant and agree with the measured data of 3.9℃which was conducted by a conductivity-temperature-depth system(CTD).The minor variations of Ba/Ca ratios(0.01-0.06 mmol/mol;mean=0.04 mmol/mol)indicate a relatively stabilized salinity of the surrounding seawater.S/Ca ratios show large variations of 0.04-4.15 mmol/mol(mean=1.37 mmol/mol).S/Ca ratios have regular variations which generally correspond to the variations of the Mg/Ca ratios,highlighting that the S/Ca ratios of bivalve shells show the potential to reflect the growth rate of the Gigantides.However,further studies should be carried out on the understanding of the links between the S/Ca ratios and seepage intensity of cold-seep fluids.
