Effect of Laser Energy Density on Data Quality during LA-ICP-MS Measurement
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摘要: LA-ICP-MS分析矿物元素含量时激光能量密度会影响样品的剥蚀速率，从而影响测试过程的信号强度。激光能量密度变化对测试数据精确度的影响，以及不同天然矿物对激光能量密度的响应尚需进一步明确。本文测定了不同莫氏硬度天然矿物可稳定剥蚀的最小激光能量密度，评估了193nm ArF准分子激光系统中能量密度对地质标准样品（NIST SRM614、USGS BCR-2G、USGS GSC-1G）和天然矿物测试数据质量的影响。研究结果表明：①稳定剥蚀石英和萤石所需的最小激光能量密度为4~5J/cm2，低于前人的报道值（10J/cm2），而稳定剥蚀其他矿物（如滑石、磷灰石、刚玉等）所需的最小能量密度一般在1~2J/cm2；②不同激光能量密度剥蚀条件下，标准样品中大部分微量元素测试结果与推荐值的相对误差小于20%，相对标准偏差（RSD）小于10%，而天然矿物中含量>1μg/g的大部分微量元素测试数据的RSD小于20%；③在一定范围内，激光能量密度越大，数据平均相对误差越小，整体质量更好。要点
(1) 测试了LA-ICP-MS稳定剥蚀不同莫氏硬度矿物的最小激光能量密度值。
(2) 分析了不同激光能量密度对标准样品和天然矿物测试数据质量的影响。
(3) 研究结果显示一定范围内激光能量密度越大，数据平均相对误差越小。
HIGHLIGHTS(1) The minimum laser energy density for stable denudating minerals of different Mohs hardness was determined during LA-ICP-MS measurement.
(2) The effects of various laser energy densities on the data quality for standard samples and natural minerals were evaluated.
(3) The greater the laser energy density in the appropriate range, the smaller the average relative error of the data.
Abstract:BACKGROUNDLaser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a frequent instrument for the analysis of trace element content. When LA-ICP-MS is used to analyze the element content of minerals, the laser energy density will affect the denudation rate of the sample and thus affect the signal intensity during the analysis.OBJECTIVESTo further clarify the impact of laser energy density changes on the quality of test data and the response of different natural minerals to laser energy density.METHODSThe element content data of standard samples and nature minerals with different Mohs hardness under different laser energy densities were determined using LA-ICP-MS. Then authors analyzed the relative error (RE) between the test data and the reference values of the standard samples, average of the relative error of elements with RE within the limits of -20%-10% in the same standard sample, and the relative standard deviation of the standard samples and nature minerals test results to evaluate the effect of laser energy density on the test results.RESULTSThe minimum laser energy density required to stabilize ablated quartz and fluorite was 4-5J/cm2, which was lower than the previously reported value (10J/cm2), whereas stable denudation of other minerals such as talc, apatite, and corundum require the minimum energy density of generally 1-2J/cm2. Under the different condition of laser energy density, the relative error of most trace elements in standard samples between analytical results and recommended values was less than 20% and the relative standard deviation was less than 10%. The relative standard deviation of most trace element test data was less than 20% for natural minerals with most element contents >1μg/g. Within a certain range, the greater the laser energy density, the smaller the average relative error of the data, and the better the overall quality.CONCLUSIONSQuartz and fluorite require higher laser energy density for stable ablation than other minerals. Within the appropriate range, laser energy density has little effect on the quality of the individual element data, but it affects the overall quality of the data.-
Keywords:
- LA-ICP-MS /
- laser energy density /
- standard samples /
- natural minerals /
- data quality
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油井岩心是发现油气层和研究地层结构的重要资料，其中汞的富集和扩散是岩心分析的一个重要指标[1]。在原油加工过程中，砷会影响催化剂的活性[2]。在地质找矿中，汞和砷也是重要指示元素[3]。石油钻探往往达到几千米的深度，需要投入巨大的人力和物力，测定油井岩心中汞和砷的含量，能够同时为石油钻探和地质找矿提供技术服务，达到节约高效的目标。
汞和砷的测定方法有滴定法[4]、液相色谱法[5-6]、气相色谱法[7]、电感耦合等离子体发射光谱法[8]、分光光度法[9]、原子吸收光谱法[10-11]、电感耦合等离子体质谱法[12-13]、便携式仪器测定法[14-15]等。王水溶矿-原子荧光光度检测方法因其检出限低、灵敏度高、稳定性好、样品前处理简单而被广泛应用，如苏明跃等[16]采用王水消解-原子荧光光谱法测定矿石中的汞和砷，相对标准偏差在0.93%~8.1%之间；倪润祥等[17]采用湿法消解-原子荧光光谱法测定煤中的硒和砷，砷的相对标准偏差在5.6%~6.0%之间。但是，当采用王水溶解含油岩心时，由于原油的疏水性会造成许多样品漂浮在液面上，或者在溶液中的样品也由于表面原油的包裹与酸接触不充分[18]，样品中的部分汞和砷无法被溶解出来，导致检测结果偏低。对于这种样品，传统方法主要通过高温烧制和强酸氧化将有机物分解后再进行溶矿测试。例如，罗荣根[19]利用高温分解载金碳中的汞，结果显示高温会造成汞的损失，导致结果偏低。杨常青等[20]用硝酸-硫酸-氢氟酸分解无烟煤中的汞，由于反应温度较高，敞口溶解造成结果偏低。
索氏提取法是一种可以通过有机溶剂将原油从固体物质中提取分离出来的方法，该方法对原油的提取分离彻底，提取温度低不易造成汞和砷的损失，是对含油岩心中原油进行提取分离的理想选择。本文拟建立一种通过索氏提取法将岩心中的原油提取分离，用50%王水溶解剩余样品中的汞和砷元素，用原子荧光光谱仪测定汞和砷含量的方法。
1. 实验部分
1.1 仪器与工作条件
AFS-9561原子荧光光谱仪(北京海光仪器有限公司)；汞、砷空心阴极灯(北京有色金属研究院)。测汞的工作条件为：灯电流30mA，辅助阴极电流0mA(汞灯没有辅助阴极)，负高压300mV，载气流量300mL/min，原子化器高度8cm，读数时间12s，读数延迟时间3s，进样量1000μL，还原剂用量1834μL/min。测砷的工作条件为：灯电流30mA，辅助阴极电流15mA，负高压270mV，载气流量300mL/min，原子化器高度10cm，读数时间12s，读数延迟时间3s，进样量500μL，还原剂用量1000μL/min。
索氏提取器(100mL，沈阳市昌昊玻璃仪器有限公司)；RE-52A旋转蒸发仪(上海亚荣生化仪器厂)。
1.2 标准溶液和主要试剂
砷、汞标准储备液(中国计量科学研究院，100μg/mL)。
汞标准系列溶液(0、0.05、0.20、0.50、1.50、3.00、5.00μg/L)：由汞标准储备液用含重铬酸钾(0.5g/L)的10%硝酸逐级稀释至所需浓度[21]。
砷标准系列溶液(0、0.5、2、5、15、50、100.00μg/L)：由砷标准储备液用10%盐酸逐级稀释至所需浓度。
氯仿；硝酸；盐酸；氢氧化钠；硼氢化钾；抗坏血酸；硫脲；抗坏血酸-硫脲混合溶液(抗坏血酸浓度50g/L，硫脲浓度50g/L)；还原剂溶液(硼氢化钾浓度20g/L，氢氧化钠浓度5g/L)；载流溶液(5%盐酸)。以上试剂均为分析纯，水为超纯水。
1.3 实验方法
1.3.1 样品的前处理
选取油井含油层原油含量差异明显的4个岩心样品作为实验对象，编号为SY-1、SY-2、SY-3和SY-4。称取样品5g(粒径≤75μm)于滤纸筒中，将滤纸筒包好，放入索氏提取器中，向底瓶加入氯仿100mL，在75℃下提取8h，冷却，将提取液浓缩至5mL，转移至称量瓶中，室温挥发至干，称取抽提物质量。取出纸筒中岩心样品，晾干，待测[22]。
称取提取过的样品0.2500g于25mL比色管中，用水润湿，加入50%王水10mL，摇匀，在沸水浴中加热2h，中间摇匀2次[23]，取出，冷却，定容至刻度，摇匀，放置过夜，待测。同时进行空白实验。
1.3.2 样品测定
移取上层清液10mL于样品管中，对汞进行测定。移取上层清液2.5mL于25mL比色管中，加入盐酸5mL，加入抗坏血酸-硫脲混合溶液5mL，摇匀，静置反应1h以上，对砷进行测定。
2. 结果与讨论
2.1 样品中原油含量的影响
称取含油岩心平行样品SY-1两份，一份经过索氏提取，一份未经过索氏提取，同时用50%王水加热分解，定容，两种处理所得的溶液如图 1所示，两种溶液中汞和砷测定结果见表 1。由图 1可见，对于未经过提取的样品溶液，由于原油的疏水性，许多样品漂浮在液面上，与酸接触不充分。与经过提取的样品溶液相比，未经过提取的样品溶液颜色明显偏淡，这主要是因为原油在溶矿过程中被氧化而消耗部分王水[24]，导致王水中的氯化亚硝酰减少，氧化性变弱。由表 1检测结果对比可得，未经过提取的样品由于与酸接触不充分以及王水溶液氧化性变弱，导致汞和砷检测结果偏低。通过索氏提取法用氯仿对样品中的原油进行提取后，样品完全浸入王水溶液中，溶液颜色也显示为强氧化性的黄色，汞和砷检测结果明显增大。
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图 1 经过提取和未经过提取的溶样效果对比1—未经过索氏提取的样品SY-1溶液，2—经过索氏提取的样品SY-1溶液。Figure 1. Comparison of sample dissolution effect between the extracted and unextracted samples表 1 经过提取和未经过提取的汞和砷的测定结果对比Table 1. Comparison of analytical results of Hg and As in the extracted and unextracted samples样品编号 氯仿沥青含量(%) Hg测定值(mg/kg) As测定值(mg/kg) 未经过提取 经过提取 未经过提取 经过提取 SY-1 0.078 0.065 0.105 19.3 24.4 SY-2 0.134 0.044 0.114 16.4 26.5 SY-3 0.033 0.076 0.108 18.3 22.4 SY-4 0.254 0.049 0.128 12.3 31.5 2.2 提取条件的选择
2.2.1 提取溶剂
在常用有机溶剂中，对原油具有高溶解度的主要有甲苯、石油醚、正己烷、氯仿、二硫化碳、二氯甲烷、辛烷、庚烷等[25-26]。通过毒性和溶解性的筛查，以石油醚、正己烷和氯仿作为提取的备选溶剂进行实验。由表 2测定结果可得，氯仿的提取能力最强，石油醚次之，正己烷最弱，所以选择氯仿作为提取剂。
表 2 不同溶剂提取原油的结果对比Table 2. Comparison of crude oil extracted by different solvents样品编号 氯仿
(g)相对提取率
(%)石油醚
(g)相对提取率
(%)正己烷
(g)相对提取率
(%)SY-1 0.0777 100 0.0748 96.3 0.0722 92.9 SY-2 0.1336 100 0.1242 93.0 0.1205 90.2 SY-3 0.0328 100 0.0302 92.1 0.0284 86.6 SY-4 0.2536 100 0.2311 91.1 0.2206 87.0 2.2.2 提取温度
索氏提取法是一种利用虹吸效应对固体物质中的有机物进行多次提取的方法。提取温度越高，在一定时间内提取的次数越多，提取效率越高，但是溶剂的损失也越严重[27]，对于本研究也会引起汞和砷的损失，进而导致测得浓度值偏低。综合考虑，将提取速度控制在3次/h，对应的水浴温度为75℃。
2.2.3 提取时间
索氏提取的基本原理是连续多次萃取，这就决定了萃取物含量越高的样品往往需要更长的萃取时间[28-29]，因此选择原油含量最高的SY-4样品作为萃取时间实验的对象。将提取温度设置为75℃，分别测定提取时间为1、2、3、4、5、6、7、8、9和10h时样品中汞和砷的含量。由图 2测定结果得知，随着提取时间的延长，汞和砷的测定值越来越大。这主要是因为随着样品中原油越来越多地被溶剂提取分离，其中的汞和砷更多地被王水溶解。但是，当提取时间大于8h时，汞的测定值有明显下降的趋势，这是因为长时间的高温回流造成了汞的挥发损失[30]，所以将提取时间设置为8h。
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图 2 不同提取时间汞和砷的测定结果Figure 2. Analytical results of Hg and As at different extraction time2.3 方法技术指标
2.3.1 检出限和线性范围
对一个汞和砷含量都很低的沉积物标准物质GBW07121(砷认定值0.25mg/kg，汞认定值0.0040mg/kg)进行7次平行实验，测得汞含量分别为0.0043、0.0038、0.0068、0.0053、0.0061、0.0044、0.0046mg/kg，计算汞的方法检出限为0.003mg/kg，测得砷含量分别为0.25、0.20、0.34、0.26、0.29、0.24、0.27mg/kg，计算砷的方法检出限为0.10mg/kg。
通过标准系列溶液的测定可得本方法在汞含量为0.010~0.50mg/kg具有良好的线性，相关系数为0.9998；在砷含量为0.25~50mg/kg具有良好的线性，相关系数为0.9998。
2.3.2 精密度和回收率
对未经过提取分离、经过高氯酸处理和经过提取分离的样品SY-1分别进行7次平行实验，测得结果见表 3。对比可知，未经过提取分离的测定精密度很差，这主要是因为对于未提取的样品，在溶矿过程中，由于原油的疏水性导致许多样品漂浮在液面上方[31]，随着王水的沸腾，部分样品被随机浸入溶液中，其中的汞和砷不定量地溶解出来。对于经过高氯酸处理的样品，由于部分原油组分不能被高氯酸完全碳化[32]，在溶矿过程中仍有小部分样品漂浮在液面上，造成测定结果精密度较差。而经过有机溶剂的提取后，由于原油被完全分离提取，样品沉入王水底部，其中的汞和砷被王水完全溶解，方法精密度有了很大提高。
表 3 精密度实验结果Table 3. Precision tests of the method样品处理 元素 分次测定值(mg/kg) RSD(%) 未经提取的SY-1 Hg 0.065 0.038 0.044 0.07
30.061 0.086 0.03533.0 As 15.3 11.4 14.2 18.7
17.0 20.1 9.6725.0 高氯酸处理的SY-1 Hg 0.089 0.082 0.068 0.073
0.089 0.094 0.07115.0 As 22.1 21.6 18.7 20.7
22.2 23.6 18.59.0 经过提取的SY-1 Hg 0.105 0.098 0.102 0.112
0.104 0.092 0.1147.3 As 24.4 26.5 23.2 23.5
25.6 24.1 25.95.1 对样品SY-1进行三种浓度的加标实验，测得结果见表 4。在三种不同加标浓度下，加标回收率均在92.5%以上。这说明提取过程造成汞和砷的损失较小，样品溶解完全，该方法具有良好的准确度。
表 4 加标回收实验结果Table 4. Spiked recovery tests of the method实验序号 元素 样品浓度
(mg/kg)加标浓度
(mg/kg)测得浓度
(mg/kg)回收率
(%)1 Hg 0.105 0.200 0.296 95.5 As 24.4 50.0 72.4 96.0 2 Hg 0.105 0.100 0.199 94.0 As 24.4 25.0 48.1 94.8 3 Hg 0.105 0.040 0.142 92.5 As 24.4 10.0 33.8 94.0 3. 结论
本文建立了用索氏提取法低温提取分离含油岩心中的原油，用50%王水溶解剩余样品，再采用原子荧光光谱测定汞和砷含量的方法。本方法避免了由于原油的疏水性造成样品与王水接触不充分、分解不完全和反应温度过高造成汞元素损失的问题，与传统方法相比较，具有精密度好、准确度高的优点，可为含油岩心中其他元素的检测提供借鉴。
致谢: 感谢合肥工业大学陈天虎教授提供的天然矿物样品。感谢审稿老师对本文提出的重要修改意见。 -
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图 1 不同矿物的最小稳定激光能量密度与莫氏硬度的相关性
Figure 1. Correlation of minimum stable laser energy density and Mohs hardness for different minerals
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图 2 不同能量密度下天然矿物中部分主微量元素测试数据的相对标准偏差(RSD)与该元素含量的趋势图(主量元素的含量大于0.01%，微量元素的含量大于0.1μg/g)
Figure 2. Trend chart of relative standard deviation (RSD) and the content of some major and trace elements in natural minerals under different energy densities (major elements content is greater than 0.01%, and trace elements content of is greater than 0.1μg/g)
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图 3 不同激光能量密度下标准样品中主微量元素测试数据相对误差分布图(从左至右元素含量依次增大)
Figure 3. Relative error (RE) distribution maps of experimental data of main and trace elements in standard samples under different laser energy densities (the elements content increases from left to right)
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图 5 不同激光能量密度下标准样品中部分主微量元素测试数据相对标准偏差(RSD)分布图(主量元素的含量大于0.01%，微量元素的含量大于0.1μg/g)
Figure 5. Relative standard deviation (RSD) distribution maps of experimental data of some main and trace elements in standard samples under different laser energy densities (major elements content is greater than 0.01%, and trace elements content is greater than 0.1μg/g)
表 1 LA-ICP-MS微量元素分析工作参数
Table 1 Equipment parameters for LA-ICP-MS trace elemental analysis
ICP-MS工作参数 设定值 激光工作参数 设定值 射频功率 1350W 波长 193nm 等离子体流量 15L/min 能量密度 以实测为准 辅助气流量 0.92L/min 载气 He 检测器 Dual(脉冲和模拟计数) 剥蚀方式 点剥蚀 扫描模式 跳峰 剥蚀束斑大小 60μm 单位质量扫描时间 8ms 剥蚀频率 8Hz 获取模式 时间分辨率分析 脉冲数 320 
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表 2 不同莫氏硬度矿物可稳定剥蚀的最小激光能量密度
Table 2 Minimum laser energy density for stable ablation of different Mohs hardness minerals
矿物 莫氏硬度 可产生稳定信号的最小激光能量密度(J/cm2) 石英 7 5 萤石 4 4 刚玉 9 2 黄玉 8 2 钠长石 6 2 钠铁闪石 5.5~6 2 透闪石 5~6 2 磷灰石 5 2 白云母 2.5~4 2 方解石 3 1 石膏 2 1 滑石 1 1
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