Elemental Distribution Behavior of Sulfonic Acid Cation-Exchange Resins and Applications to High-precision Isotope Analysis
-
摘要:
不同元素在离子交换树脂的分配系数是元素纯化和分离的基础，不同酸中各元素分配系数差异可用于设计高效的元素提纯流程，从而被广泛应用于现代高精度同位素分析。本文以AG®50W-X8阳离子树脂为研究对象，以分配系数(Kd)作为量化指标，通过系统实验研究不同元素在该树脂中的分配行为。在前人研究基础上，本实验增加了元素数量和酸的种类，涵盖了金属、类金属、非金属和稀土元素。结果表明：在盐酸和硝酸介质中，几乎所有元素的Kd都与酸度呈负相关，当酸度达到6mol/L时，除Th和Ca以外的所有元素都会被酸洗脱。稀土元素(REEs)和高场强元素在0.1～0.5mol/L稀硝酸和稀盐酸中强烈吸附在树脂上；而一些过渡金属、类金属和非金属元素(如Mo、W、Re、Ir、Sb、Ge、As、Se、Te等)在酸溶液中会形成含氧阴离子，不与阳离子树脂发生吸附。Al、Fe、Se、Pd、Cd、In等元素在盐酸中易与氯离子形成配位化合物或离子团，导致这些离子在盐酸中的分配系数显著降低。在硝酸和盐酸与氢氟酸的混合酸中，除稀土元素外，绝大部分元素随酸度增加Kd迅速降低。稀土元素在盐酸-氢氟酸混合介质中，随着盐酸的浓度增加(从0.1mol/L盐酸-0.2mol/L氢氟酸至6mol/L盐酸-0.2mol/L氢氟酸)，稀土元素分配系数（KdREE）具有先增加后降低的趋势。氢氟酸的加入可显著降低Be、Al、Sc、Fe、Sn、Th、U、Ti、Zr、Hf等元素在稀盐酸和稀硝酸中的分配系数，使这些元素几乎不与树脂发生吸附。本研究揭示了不同酸介质中各类元素在阳离子交换树脂上的分配行为存在差异，尤其是氢氟酸的加入可显著改变高场强元素、部分过渡金属和稀土元素的分配系数，为应用该树脂开发和优化适用于高精度金属稳定同位素分析的元素提纯流程(如Li、Mg、K、Sr、Ce、U等)提供了数据支撑，并可有效地减少后续实验设计的工作量。
-
关键词:
- BioRad AG®50W-X8阳离子树脂 /
- 元素提纯 /
- 高精度同位素分析 /
- 分配系数 /
- 离子交换柱
要点(1)应用6mol/L硝酸再生AG®50W-X8树脂的清洗效果较好，但Th会在树脂中残留累积。
(2)氢氟酸可显著降低高场强元素和部分过渡金属在AG®50W-X8树脂上的分配系数。
(3)在盐酸-氢氟酸中，随酸度增加，稀土元素分配系数呈现先增后降的趋势。
HIGHLIGHTS(1) The cleaning effect of 6mol/L nitric acid in regenerating AG50W-X8 resin is good, but Th remains in the resin.
(2) Hydrofluoric acid can significantly change the distribution behavior of high field strength elements, some transition metals and rare earth elements in AG50W-X8 cations.
(3) In the mixture of HCl-HF acid, with the increase of HCl concentration, the distribution coefficient of rare earth elements has a trend of first increasing and then decreasing.
Abstract:The distribution coefficient (Kd) of elements in ion exchange resin is the basis of element purification and separation, which is the premise for high-precision isotope analysis. However, systematic comparison of the Kd in different types of acid is lacking, which has hindered the development of efficient separation procedures for emerging isotope system. In this research, the Kd of 60 elements in AG®50W-X8 cationic resin with different concentrations and types of acid was studied. Our results show that, in acid solutions, the Kd of almost all elements is negatively related to acidity. Compared to nitric acid, a significant decrease in the Kd for Al, Fe, Se, Pd, Cd, and In is observed in hydrochloric acid. The addition of hydrofluoric acid can significantly reduce the Kd of Be, Al, Sc, Fe, Sn, Th, U, Ti, Zr, and Hf in dilute hydrochloric and nitric acid, so that they can be quantitively eluted from the resin. In the mixed hydrofluoric acid solutions, KdREE shows an initial increasing and then decreasing trend as the concentration of HCl increases. The present study provides data support for the development and optimization of element purification processes that are suitable for high-precision metal stable isotope analysis. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202309260154.
BRIEF REPORTSignificance: With the development of analytical instruments, significant breakthroughs on high-precision isotope studies have been made in recent years. The dissolution of geological samples leads to solutions with complex matrices that jeopardize the accuracy and precision of the data, i.e. the so called “matrix effect”. Chemical purification of the elements of interest from the sample matrices can suppress and minimize matrix effects, and therefore provides an improved analytical precision for various isotopes on instruments such as, multiple collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). Ion exchange resins have been widely used for the separation and purification of target elements, in which cationic resins are widely used in the development of metal stable isotopes. Distribution coefficients (Kd) are essential for ion exchange chromatography because they provide information on elements distributed between the solution and resin for particular acids; hence enabling the choice of acid and strength that are suitable for effective separation of certain elements in solution. However, previous studies of the Kd on typical cationic exchange resins is incomplete, some alkali metals and transition metals have not been included in previous studies. Also, direct comparison of the distribution coefficients for various elements in different acids is lacking.
Methods: Two sets of experiments were performed, one was an equilibrium time test, and the other was to determine Kd in different molarity (0.1mol/L to 6mol/L) of HCl and HNO3 and their mixtures with 0.2mol/L HF.
For the equilibrium time test, 400 mg of Bio-Rad AG® 50W-X8 200-400 mesh cation resin was accurately weighed into 30mL PFA beaker and 10mL 0.5mol/L HNO3 added. Then, 200μL of 10mg/L multi-element standards was added into the beaker. The initial concentration of analytes added was ~200ng/g so that they could be precisely analysed by ICP-MS before and after the partitioning. Small aliquots of the solutions were collected in PFA beakers at 0.5, 1, 5, 10, 30min and 1, 2, 4, 8, 24h. The solutions were then dried and reflux with 2% HNO3 added, and finally analyszed on ICP-MS. After the concentrations of each analyte were determined, precise Kd were calculated using the equation of Kd=Csolid/Csolution=(CB−CA)×V/(CA×w), where CB and CA are the elemental concentrations in μg/mL of solution before and after equilibration, V is the total volume of solutions in mL, and w is the weight in gram of dry resin.
For Kd dertermination, experiments were performed at room temperature (23℃) using the batch method. First, 400mg of Bio-Rad AG® 50W-X8 200-400 mesh cation resin was accurately weighed into 30mL PFA beakers and 10mL solutions of HNO3, HCl, a mixture of HNO3-HF and HCl-HF of varying strengths from 0.1mol/L to 6mol/L were added. Then, 200μL of 10mg/L multi-element standards in different type of acid were added into the corresponding beakers. The mixtures were shaken for 5 to 10min every 2h and left to for 24h to achieve equilibrium. The solutions were collected in pre cleaned PFA beakers by filtering the resin mixture through empty 10mL Bio-Rad polypropylene columns. Afterwards, the solutions were evaporated to dryness on a hotplate at 60℃ and refluxed with 10mL 2% HNO3 for ~5h with the cap sealed at 60℃. Finally, the solutions were transferred to 7mL PP tubes and were analysed by ICP-MS and precise distribution coefficients were calculated for each element in each solution. Blank samples were prepared using the same procedure, without adding any multi-element standards. The blank solutions were used to determine the background of reagents, resin and containers.
Data and Results: The distribution coefficients of almost all elements on AG®50W-X8 cation exchange resin in hydrochloric acid and nitric acid were negatively correlated with the molarity (0.1mol/L to 6mol/L). For most elements, the calculated Kd in 6mol/L HNO3 were slightly lower than in 6mol/L HCl, suggesting that using 6mol/L nitric acid to regenerate AG®50W-X8 cation exchange resin was slightly better than 6mol/L hydrochloric acid. Significantly lower Kd for high field strength elements (HFSE) such as Zr and Hf was observed in hydrofluoric acid, and may be due to the strong ligand capacity of Cl-. Some transition metals, metalloids, and non-metallic elements, such as Mo, W, Re, Ir, Sb, Ge, As, Se, Te, etc., would form oxygen-containing anions in acid solutions, and hence not adsorb in cation exchange resins with low Kd.
In the mixed acid of HNO3-HF and HCl-HF, the partition coefficient of most elements in the mixed acid also decreased rapidly with the increase of acidity. The addition of hydrofluoric acid can significantly reduce the distribution coefficients of some elements in dilute hydrochloric acid and nitric acid, including Be, Al, Sc, Fe, Sn, Th, U and HFSE (Ti, Zr, Hf). The distribution coefficient of rare earth elements (REEs) in HNO3-HF mixed acid was similar to that in nitric acid, but in HCl-HF mixed acid, as the concentration of hydrochloric acid increased (from 0.1mol/L HCl-0.2mol/L HF to 6mol/L HCl-0.2mol/L HF), KdREE showed a trend of first increasing and then decreasing. This trend of change indicates that in a mixture of hydrochloric acid and 0.2mol/L hydrofluoric acid, an increase in hydrochloric acid concentration will reduce the coordination ability of hydrofluoric acid to rare earth elements, and the proportion of complex compounds formed by rare earth elements will decrease. This leads to a rapid increase in KdREE as the concentration of hydrochloric acid in the mixed acid increases in the 0.1-0.5mol/L HCl-0.2mol/L HF mixture. Subsequently, as the concentration of hydrochloric acid further increased, [H3O]+ rapidly increased to the dominant position in the mixed acid solution, leading to a rapid decrease in KdREE, ultimately resulting in an arched distribution coefficient curve of rare earth elements in HCl-HF mixed acid.
-
得益于海相页岩层系油气资源的钻完井和压裂技术革新，美国成为世界上最早实现页岩气商业化开采的国家, 其页岩气资源主要来自海相或海陆过渡相地层[1]。美国页岩气的成功商业化为中国页岩油气勘探开发关键技术探索提供了一定经验和借鉴[2]。我国广泛发育有海相、陆相和海陆过渡相三类富有机质页岩[3]，页岩气可采资源量排名世界第二，其中陆相页岩气可采资源潜力为7.9×1012m3[4]。然而，与海相富有机质页岩相较，陆相页岩在沉积环境、干酪根类型、有机质成熟度和矿物组分等方面存在较大差异[5-7]。当前，我国海相页岩气储量评估方法与压裂技术基本达成共识，然而关于陆相页岩气(油)的研究在广度与深度上远远不足。鄂尔多斯盆地作为我国中新生代大型内陆坳陷沉积盆地，发育有石炭系、二叠系和三叠系等系列页岩沉积。其中三叠系延长组7段(C7)烃源岩埋藏浅，有机质丰度高，热演化程度低，具有良好的页岩气(油)成藏条件[8-9]，有必要对其展开深入研究。
页岩孔隙结构是决定储层储集与运移能力的关键，对构建页岩气渗流模型[10]、完善压裂技术[11]具有重要意义。Loucks等[12]研究表明页岩中孔隙类型丰富，包括粒间孔、粒内孔、微裂缝和有机孔等，不同类型孔隙结构成因不同，对页岩气储集能力的贡献亦不相同。Wang等[13]证实页岩矿物基质与有机质分布模式在一定程度上控制和反映页岩的孔隙结构特征。王跃鹏等[14]提出延长组页岩中普遍发育的纹理结构会形成平行层理的孔缝结构，严重时造成井壁坍塌。前人工作表明，研究页岩孔隙结构有必要同时考虑有机质与矿物基质的空间分布特征。研究者围绕鄂尔多斯C7页岩孔隙结构已开展了大量研究工作，但是受测试方法的限制，对其微观结构的认识仍较为薄弱。吴银辉等[15]、杨维磊等[16]、庞铭等[7]、Jiang等[17]通过气体吸附实验、高压压汞实验和核磁共振实验对C7页岩孔隙结构特征展开研究，结果表明C7页岩中3~30nm的孔隙对总孔隙度贡献最大，为构建页岩孔隙模型提供了重要数据参考，但是上述成果对闭孔表征不足且缺乏对孔隙空间结构特征的直观认识。徐红卫等[18]采用扫描电镜对C7页岩孔隙结构特征展开研究，其研究成果表明C7页岩中主要发育纳米级狭缝型黏土矿物层间孔，然而其采用机械抛光制样对页岩表面孔隙结构造成了一定破坏，同时缺乏对页岩不同组分三维空间分布特征的认识。
目前，油气领域多采用氩离子抛光-扫描电镜方法对页岩孔隙结构进行直观观测[13, 19-20]。该方法有助于快速认识页岩孔隙类型、分布模式及孔径范围等，然而不足以提供精确数据用以构建页岩气三维渗流模型。对页岩三维结构的认识主要是利用微米X射线显微镜(micro X-ray microscope)[13, 21]、纳米X射线显微镜(nano-transmission X-ray microscope, TXM)[21-24]与聚焦离子束-扫描电子显微镜(focused ion beam-scanning electron microscope, FIB-SEM)[25-27]。与TXM和FIB-SEM方法相较，微米X射线显微镜方法的扫描范围大且成本较低，是研究陆相页岩纹理结构特征的重要技术手段。基于此，本文选取鄂尔多斯盆地南缘代表性C7页岩，采用氩离子抛光-扫描电镜与同步辐射微米X射线显微镜方法，对C7页岩的孔隙结构特征进行详细表征，探究陆相页岩孔隙结构特征影响因素，以期为完善陆相页岩气产能评估与压裂技术提供参考。
1. 实验部分
1.1 实验样品
C7页岩实验样品采自鄂尔多斯盆地遥科一(YK1)井。YK1井位于陕西省铜川市，构造位置属于鄂尔多斯盆地南缘渭北隆起构造单元(图 1)。长7油层组位于延长组中下部，代表湖盆最大扩张期。该时期随着盆地强烈沉陷，湖盆从长8期开始至长7期达到鼎盛时期，环绕湖盆退积型三角洲广泛发育并在开阔的浅湖-深湖区形成延长组的最主要的生油岩系[16]。岩心观测发现，C7页岩以黑色油页岩、凝灰岩与含油砂岩为主，夹杂碳酸盐岩薄层，如图 2所示。
![]()
图 1 鄂尔多斯盆地遥科1井构造位置示意图1—逆冲推覆带；2—古板块碰撞对接带；3—河流。Figure 1. Geotectonic position of Yaoke-1 Well, Ordos Basin![]()
图 2 遥科1井延长组7段岩性柱状图与岩心样品Figure 2. Lithological column and core sample of Member 7, Yanchang Formation shale from Yaoke-1 WellX射线粉晶衍射测试表明，C7页岩样品中的石英与长石平均含量较高(分别为32%和24%)，碳酸盐岩和黄铁矿含量相对较低，分别为9%和3%。脆性矿物平均含量大于50%，有利于天然裂隙和人工诱导裂缝的发育。黏土矿物含量为33%，几乎全部由伊蒙混层组成。伊蒙混层中伊利石含量为80%，主要为有序混层矿物(R=1型)，表明延长组7段页岩处于成岩阶段中期[28]。实验样品有机碳平均含量为4.79%，属于富有机质页岩，其平均镜质体反射率为0.72%，对应有机质未成熟或低成熟阶段。
1.2 样品测试和数据分析方法
1.2.1 扫描电镜测试
选取新鲜页岩样品薄片(~1cm2)，对其进行初步机械抛光后(2400目)，放入离子减薄仪(LJB-1A，沈阳华业公司)，利用氩离子束轰击预抛光的表面，得到品质较高的平面进行扫描电镜观察。制样过程中，氩离子减薄仪的工作电压为5kV，电流为100μA，抛光时间为10~12h[19, 25]。扫描电镜观测利用Merlin Compact LE0 1530 VP电镜(卡尔·蔡司公司)完成，矿物元素组成定性定量分析使用AZtec X-Max能谱仪(牛津仪器)进行。实验时扫描电镜加速电压为5kV，工作距离为4~6mm；能谱仪的工作电压为15kV，工作距离为8~10mm。
1.2.2 同步辐射X射线显微镜测试
利用砂纸将C7页岩样品打磨成圆柱形，直径大约5mm。微米X射线显微镜扫描实验在上海同步辐射装置X射线成像及生物医学应用光束线(BL13W1)[29]开展。X射线在磁场强度1.9T、磁周期14cm的十六极摆动器中激发，通过Si(111)双晶单色器进行单色化后穿过样品，然后被带有闪烁体的电荷耦合元件系统接收[11]。本文实验像素尺寸为3.25μm，能量为25keV, 样品到探头的距离为10cm。扫描过程中将样品的一端固定在旋转样品台上。整个实验中样品台共旋转180°，每隔0.2°采集一张投影图像。通过样品台的旋转，采集不同视角的投影图像，利用PITRE (phase-sensitive X-ray image processing and tomography recons-truction)软件进行图像重构[30]。首先，利用5张暗场图像与20张明场图像进行背景强度校正；其次，将采集的投影图像转换成正弦图像并进行归一化处理；最后，利用滤波反投影方法对正弦化图像进行重构[31]。
1.2.3 数据分析方法
微米X射线显微镜重构数据利用Avizo软件进行分析。首先，选择页岩代表性体积块1625μm × 1625μm × 1625μm，利用非局部均值滤波算法对所选CT图像进行平滑。其次，依据孔隙、有机质、碳酸盐岩和硅酸盐岩等对X射线的吸收系数差异, 采用阈值分割方法进行图像分割，实现延长7段页岩三维结构的重建与可视化。
2. 结果与讨论
2.1 孔隙二维结构特征
本文在参考Loucks等[12]页岩孔隙分类方案基础上，依据孔隙成因与其赋存特征将C7页岩气储集空间划分为无机孔、有机孔和微裂缝三类，如表 1所示。
表 1 遥科1井延长7段页岩孔隙类型及其特征Table 1. Pore types and characteristics of C7 Member shale from Yaoke-1 Well孔隙类型 孔隙示意图 孔隙形态 孔径范围 分布特征 无机孔 粒间孔 
三角形或狭缝形 30nm~1μm 发育在脆性矿物周缘及粉砂级黏土矿物碎屑之间，普遍发育，连通性较好 黏土矿物层间孔 
平直狭缝状 长1~3μm，孔宽数十纳米 分布于黏土矿物层间，不甚发育 溶蚀孔 
凹坑状 50~300nm 多见于石英、长石等矿物内部，彼此孤立 晶内孔、生物孔、晶间孔等 
圆形、椭圆形或方形等 百纳米~数十微米 与矿物相关，如生物遗体被黄铁矿充填，彼此孤立; 或形成于矿物晶间 有机质与有机孔 致密有机质 
连续且不规则状 N/A 有机质最主要的赋存方式，即粒间孔被有机质完全充填，且有机质内部无孔隙发育 
集合体形式 N/A 与黄铁矿呈现出包裹关系，与微晶之间残余少许孔缝 
有机质分散状，发育锯齿状孔隙 数百纳米至数微米 致密有机质与基质矿物接触面之间发育孔隙，较为普遍 有机孔 
狭缝状、三角状 50~300nm 受控于黏土矿物层间孔结构，有机孔最主要的存在形式 
凹坑状或椭圆状 30~200nm 受生烃作用控制，发育较少 微裂缝 
狭缝状 长数微米，宽几百纳米 发育于脆性矿物的边缘或机械不稳定部位，较平直，延伸长 注：N/A表示not applicable(不适用)。 2.1.1 无机孔和微裂缝结构特征
C7页岩中无机孔广泛发育，包括粒间孔、黏土矿物层间孔和溶蚀孔等。粒间孔主要发育在脆性矿物周缘和黏土碎屑之间。脆性矿物周缘孔以狭缝形为主，孔长约1μm，孔宽约100nm (图 3a)，在C7页岩中普遍发育；粉砂级黏土岩屑彼此连接，形成原生粒间孔，是C7页岩中发育最多的孔隙类型，以三角形为主，孔径集中于30~250nm，连通性较好(图 3b)。黏土矿物层间孔发育在黏土矿物层间，以平直狭缝状为主，孔长1~3μm，孔宽数十纳米(图 3c)，发育较少。溶蚀孔是烃源岩生烃过程中产生大量有机酸将矿物溶解所形成的次生孔隙。C7页岩中溶蚀孔数量较少且孤立存在，以凹坑状为主，孔径50~300nm(图 3d)。
![]()
C7页岩中同时发育黄铁矿晶内孔和锐钛矿晶间孔等特殊的孔隙类型。黄铁矿晶内孔见图 3e。能谱图(图 3f)表明图 3e中十字标记区域元素组成主要为Fe、S、O、Si。该类孔隙基本呈圆形，黄铁矿质孔隙壁厚3~5μm，孔径数十微米，孔隙部分或全部被矿物碎屑或有机质充填，彼此之间并无连通性。锐钛矿晶间孔如图 3h和图 3i所示，孔径集中于数百纳米，连通性较好。此前在海相沉积威远九老洞组页岩[19]、辽河凹陷沙河街组页岩[32]中均观测到该类型孔隙，表明锐钛矿晶间孔的主要形成机理并非受控于沉积环境。C7页岩中亦发育少许生物孔，如图 3g所示，孔径30~50nm，推测为生物遗体被矿物质充填所形成。
微裂缝在C7页岩中较为发育，以构造裂缝为主。构造裂缝一般沿机械不稳定面发育，如脆性矿物与片状黏土矿物的外部或颗粒之间(图 3j，3k)，或沿黏土矿物层理发育(图 3l)，较平直，延伸尺度较大，长数微米，宽度几百纳米。普遍发育的微裂缝是沟通各类微观孔隙的桥梁，为页岩气运移提供了重要的渗流通道。
2.1.2 有机质与有机孔发育特征
C7页岩中有机孔发育较少，依据发育形态和成因可分成两类。第一类有机孔发育在离散状有机质内部，其形成受控于有机质生烃作用，发育极少，呈椭圆状或凹坑状(图 4a)等，孔径30~200nm。另外一类有机孔与有机黏土矿物共生，是C7页岩中有机孔最主要的存在形式。该类有机孔具有继承性结构，受黏土矿物层间孔的形貌控制，以狭缝状或层状为主，如图 4b和4c所示。黏土矿物强烈的吸附能力促使有机质在烃源岩中富集，与黏土矿物以结合态存在。在有机质生烃过程中，黏土矿物降低了生烃反应活化能，同时为其提供了电子(OH-)和质子(H+)来源。类似结构在四川盆地页岩气勘探有利储层龙马溪组海相页岩中发现较多[6]，不仅佐证了黏土矿物的催化生烃作用，而且说明陆相页岩有机孔的形成机理与海相页岩具有一定相似性。
![]()
图 4 遥科1井延长7段页岩中有机孔和有机质的赋存特征a, b, c—有机孔, 主要发育在有机质之间; d, e, f, g, h, i—有机质赋存特征。Figure 4. Organic pores and organic matter in C7 Member shale from Yaoke-1 WellC7页岩中存在大量致密有机质，大小数百纳米至数微米，形态复杂，主要受控于无机孔缝的形状。图 4d中有机质彼此连接，填充于不规则状矿物碎屑粒间孔中，与粒间孔边缘完全接触；图 4e中条带状有机质充填于粒间孔中，彼此孤立存在，单个有机质长达数十微米；图 4f中条带状有机质则充填于黏土矿物层间，取向与黏土矿物一致，宽50~200nm。部分有机质与黄铁矿共生，表现为包裹关系，如图 4g所示，黄铁矿晶间孔几乎完全被有机质充填，仅在有机质与微晶之间残余少许孔缝。致密有机质与矿物基质接触面之间发育部分孔隙，该类孔隙往往与有机质取向一致，呈锯齿状、平直状和三角状等，孔径集中于数微米，如图 4h和图 4i所示。
2.2 页岩三维结构特征
C7页岩微米X射线重构图像如图 5a所示。图像中灰度值由白(255)到黑(0)代表物质的密度由大到小。结合扫描电镜数据判断，白色部分主要为黄铁矿，灰白色部分主要是钙质或铝铁质矿物；黑色部分代表低密度物质，理论上包括微孔隙、微裂缝和有机质。以下将低密度物质界定为有机质，主要原因如下：扫描电镜观测证实C7页岩中主要发育纳米孔，本文微米X射线扫描实验(分辨率3.25μm)不足以识别；从重构图像中可以看出，低密度物质大小集中于亚微米至微米，主要呈带状或星点状等，与扫描电镜下有机质的形貌大小一致；剖面线(图 5b)经过低密度物质时，灰度值均在90左右(孔隙灰度值接近0)。
![]()
图 5 基于X射线重构图像的物质识别a—页岩微米X射线重构图像:有机质(黑色)，黄铁矿(白色)；b—L1、L2为a图中剖面线所示物质的灰度值剖面图。纵坐标:灰度值。Figure 5. Segmentations based on X-ray microscopy images经过物相分割，通过三维数值模拟得到C7页岩三维结构，如图 6所示。有机质、钙质(包括铝铁质)矿物和黄铁矿分别以红色，绿色以及黄色标记，空白区域代表硅铝质矿物(石英和长石等)。图 6表明C7页岩中，有机质与钙质、铝铁质矿物排列有序，在微米尺度上具有明显的纹层结构，黄铁矿则以无序状分散在矿物基质中。
图 6b展示了C7页岩有机质三维空间分布特征。有机质体积含量为3.4%，整体呈纹层结构。大部分有机质体积较小，均匀地分散于矿物基质中；少数有机质体积较大，取向与纹层一致，如图 7a所示。图 7a是图 6b中部分有机质的放大图，从图中能够看出该有机质颗粒长约700μm，宽约80μm，呈不完全连续分布。钙质和铝铁质矿物的三维空间结构如图 6c所示，其体积百分数达7.5%，同样具有纹层结构，取向与有机质分布模式一致。与有机质的均匀分布不同，钙质与铝铁质矿物在某些纹层内出现富集。此外，少量铝铁质矿物呈球状，体积较大, 如图 7b所示，随机分布于矿物基质中。黄铁矿体积含量较低，约0.7%，在三维空间中随机分布，如图 6d所示。黄铁矿颗粒大小集中于10~20μm，相对均匀地分散于矿物基质中；少数黄铁矿聚集在一起，形成团块儿状集合体。部分黄铁矿可能充填于生物遗体中，其三维结构放大图如图 7c所示。从图中可以看出，该类孔呈不封闭的球状，孔径约45μm。
![]()
图 7 延长7段页岩中不同物相三维结构的放大图a—有机质; b—铝铁质矿物; c—黄铁矿晶内孔。Figure 7. Enlarged images showing three dimensional structures of different phases in C7 Member shale2.3 孔隙结构特征与其控制因素
扫描电镜观测结果表明C7页岩中无机孔和微裂缝最为发育。无机孔以发育在黏土碎屑颗粒之间的原生粒间孔为主，黏土矿物层间孔和脆性矿物周缘孔等海相页岩中普遍发育的孔隙类型发现较少。一方面，页岩中大量存在的碎屑状黏土矿物为孔隙发育提供了物质基础，是控制主要孔隙类型发育的重要因素之一；另一方面受成岩作用控制，原生层间孔和脆性矿物周缘孔难以保存[33]。与四川盆地广泛发育的海相页岩相较，C7页岩中有机孔鲜有发育[5-7]。有机孔的形成、形貌及大小主要与有机质含量、类型和热成熟度密切相关。鄂尔多斯盆地三叠系C7页岩热演化程度较低，大部分处于低成熟阶段，因此不具备大量发育有机孔的条件。有机质主要呈致密态，不均匀地充填于无机孔与微裂缝中，在一定程度上进一步降低了孔隙度。
扫描电镜测试表明C7页岩中介孔数量占绝对优势，对孔隙体积贡献最大，提供了主要的储集空间。黏土矿物颗粒细小，分选好，是介孔大量发育的关键因素。鄂尔多斯盆地长7期深湖细粒沉积背景导致原始的粒间孔隙相对较小[34-35]；强烈的压实作用使颗粒间紧密接触，同时胶结作用使大的粒间孔隙消失，残留了小尺度的粒间孔隙[36]。C7页岩中亦发育少量宏孔，孔径主体数百纳米，主要以粒间孔和微裂缝形态存在。脆性矿物含量较高是宏孔发育的重要原因。但是细粒黏土矿物与有机质的充填作用，在一定程度上导致宏孔数量降低。
2.4 对页岩气运移和压裂的启示
本文利用微米X射线显微镜证实C7页岩在微米尺度上具有明显的纹层结构，有机质纹层发育且连续性强，表明C7页岩具有较强塑性。李丽慧等[37]通过三轴压裂实验证实该类结构中，压裂缝以沿纹层扩展为主且易再次闭合，从而降低了储层的可压裂性。不过，随着有机质成熟度的增加，该结构沿层理方向易于形成相互连接的孔隙网络，从而有利于页岩气的横向运移[38]。扫描电镜测试表明各纹层中的微米级微构造裂缝发育较多，王跃鹏等[14]认为该类裂缝可能是由于水进入页岩内部发生水化作用，导致黏土矿物沉淀而形成的。该结构意味着水力压裂开采技术容易破坏C7页岩结构的完整性，引发井壁坍塌等严重问题。
3. 结论
本文利用氩离子抛光-扫描电镜和微米X射线显微镜方法，对鄂尔多斯陆相延长7段页岩孔隙结构特征进行研究。测试结果表明：①受黏土碎屑和成岩作用控制，延长7段页岩中主要发育纳米级粒间孔与微米级微裂缝，是页岩气的主要储运空间。有机质主要呈致密状，有机孔发育较少，一般与有机黏土矿物共存。②延长7段页岩在微米尺度上具有明显的纹层结构，有机质纹层发育且连续性强，不利于储层压裂。同时，大量存在的黏土矿物与微裂缝在水力压裂时容易引发井壁坍塌等严重问题。
微米X射线显微镜技术是深入研究陆相页岩纹层三维结构特征的有效方法，与氩离子抛光-扫描电镜技术结合，有利于实现页岩孔隙结构特征的多尺度多维度综合表征。本文研究成果可为后期页岩气水平井结构设计、提高井壁稳定性提供改进思路。
-
![]()
图 1 AG®50W-X8阳离子树脂在0.5mol/L和6mol/L硝酸介质中各元素Kd的重现性，除Th、Hf和Te元素外，两组平行实验获取的各元素的分配系数均靠近1∶1拟合线
Figure 1. Distribution coefficients (Kd) for duplicate samples in 0.5 and 6mol/L nitric acid using AG® 50W-X8 resin, the distribution coefficients of the element in two parallel experiments are close to the 1∶1 fitting line, except for Th, Hf and Te.
![]()
图 2 代表性元素在AG®50W-X8阳离子树脂和0.5mol/L硝酸间Kd随交换平衡时间的变化曲线，大部分元素在10min前即达到平衡，而Al和V元素的平衡时间较长，分别需2h和8h
Figure 2. Time of element exchange equilibrium between AG®50W-X8 cation exchange resin and 0.5mol/L nitric acid. Most elements reached equilibrium before 10min, while Al and V needed longer time to reach equilibrium, which were 2h and 8h, respectively.
![]()
图 3 AG®50W-X8阳离子交换树脂在(a) 0.1～6mol/L硝酸介质和(b) 0.1～6mol/L盐酸介质中的元素分配系数(纵坐标为对数坐标，图中虚线代表在树脂中不吸附的元素)
Figure 3. Element partition coefficients on AG®50W-X8 cation exchange resin in (a) 0.1-6mol/L nitric acid medium and (b) 0.1-6mol/L hydrochloric acid medium (The ordinate is logarithmic, where the dashed lines represent elements that do not adsorb in the resin)
![]()
图 4 AG®50W-X8阳离子交换树脂在(a) 0.1～6mol/L硝酸-0.2mol/L氢氟酸介质；(b) 0.1～6mol/L盐酸-0.2mol/L氢氟酸介质中的元素分配系数
Figure 4. Element distribution coefficients of AG®50W-X8 cation exchange resin in (a) 0.1-6mol/L nitric acid and 0.2mol/L hydrofluoric acid medium; and in (b) 0.1-6mol /L hydrochloric acid and 0.2mol/L hydrofluoric acid medium
表 1 ICP-MS仪器工作参数
Table 1 Working parameters of ICP-MS instrument
灵敏度 低质量数：Li(7)≥55×106cps/(μg/g)
中质量数：Y(89)≥320×106cps/(μg/g)
高质量数：U(238)≥350×106cps/(μg/g)检测限[3σ，ng/g] Be(9)≤0.2ng/g
In(115)≤0.05ng/g
Bi(209)≤0.08ng/g氧化物产率(Ce2+/Ce+) ≤1.5% 二价离子产率(Ce2+/Ce+) ≤3.0% 短期稳定性(RSD) ≤2% (20min) 长期稳定性(RSD) ≤3% (2h/s) 同位素精度 107Ag/109Ag＜0.1% 
下载: 导出CSV
-
[1] Lin J, Yang A, Lin R, et al. Review on in situ isotopic analysis by LA-MC-ICP-MS[J]. Journal of Earth Science, 2023, 34(6): 1663−1691. doi: 10.1007/s12583-023-2002-4
[2] 郭冬发, 李金英, 李伯平, 等. 电感耦合等离子体质谱分析方法的重要进展(2005~2016年)[J]. 质谱学报, 2017, 38(5): 599−610. Guo D F, Li J Y, Li B P, et al. Major advances in inductively coupled plasma mass spectrometry (2005—2006)[J]. Journal of Chinese Mass Spectrometry Society, 2017, 38(5): 599−610.
[3] 蒋少涌, 陈唯, 赵葵东, 等. 基于LA-(MC)-ICP-MS的矿物原位微区同位素分析技术及其应用[J]. 质谱学报, 2021, 42(5): 623−640. Jiang S Y, Chen W, Zhao K D, et al. In situ micro-analysis of isotopic compositions of solid minerals using LA-(MC)-ICP-MS methods and their applications[J]. Journal of Chinese Mass Spectrometry Society, 2021, 42(5): 623−640.
[4] 杜媛媛, 朱振利, 郑洪涛, 等. 色谱与MC-ICP-MS联用在线同位素分析的研究进展[J]. 分析测试学报, 2022, 41(1): 32−42. Du Y Y, Zhu Z L, Zheng H T, et al. On-line isotopic analysis by chromatography coupled to MC-ICP-MS[J]. Journal of Instrumental Analysis, 2022, 41(1): 32−42.
[5] Makishima A, Nakamura E J G N. Suppression of matrix effects in ICP‐MS by high power operation of ICP: Application to precise determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g−1 levels in milligram silicate samples[J]. Geostandards Newsletter, 1997, 21(2): 307−319. doi: 10.1111/j.1751-908X.1997.tb00678.x
[6] Horwitz E P, Dietz M L, Chiarizia R, et al. Separation and preconcentration of uranium from acidic media by extraction chromatography[J]. Analytica Chimica Acta, 1992, 266(1): 25−37. doi: 10.1016/0003-2670(92)85276-C
[7] le Fèvre B, Pin C J A C A. A straightforward separation scheme for concomitant Lu-Hf and Sm-Nd isotope ratio and isotope dilution analysis[J]. Analytica Chimica Acta, 2005, 543(1-2): 209−221. doi: 10.1016/j.aca.2005.04.044
[8] Strelow F W, Rethemeyer R, Bothma C J A C. Ion exchange selectivity scales for cations in nitric acid and sulfuric acid media with a sulfonated polystyrene resin[J]. Analytical Chemistry, 1965, 37(1): 106−111. doi: 10.1021/ac60220a027
[9] 李津, 唐索寒, 马健雄, 等. 金属同位素质谱分析中样品处理的基本原则与方法[J]. 岩矿测试, 2021, 40(5): 627−636. Li J, Tang S H, Ma J X, et al. Principles and treatment methods for metal isotopes analysis[J]. Rock and Mineral Analysis, 2021, 40(5): 627−636.
[10] Blichert-Toft J, Chauvel C, Albarède F J C T M, et al. Separation of Hf and Lu for high-precision isotope analysis of rock samples by magnetic sector-multiple collector ICP-MS[J]. Contributions to Mineralogy and Petrology, 1997, 127(3): 248−260. doi: 10.1007/s004100050278
[11] Chen H, Tian Z, Tuller-Ross B, et al. High-precision potassium isotopic analysis by MC-ICP-MS: An inter-laboratory comparison and refined K atomic weight[J]. Journal of Analytical Atomic Spectrometry, 2019, 34(1): 160−171. doi: 10.1039/C8JA00303C
[12] 周春山. 化学分离富集方法及应用[M]. 长沙: 中南工业大学出版社, 1996: 279-284. Zhou C S. Method and application of chemical separation and preconcentration[M]. Changsha: Central South University of Technology Press, 1996: 279-284.
[13] 刘文刚, 刘卉, 李国占, 等. 离子交换树脂在地质样品Sr-Nd同位素测定中的应用[J]. 地质学报, 2017, 91(11): 2584−2592. Liu W G, Liu H, Li G Z, et al. The application of ion exchange resins in Sr-Nd isotopic in geological samples[J]. Acta Geologica Sinica, 2017, 91(11): 2584−2592.
[14] 闫斌, 朱祥坤, 陈岳龙. 样品量的大小对铜锌同位素测定值的影响[J]. 岩矿测试, 2011, 30(4): 400−405. Yan B, Zhu X K, Chen Y L. Effects of sample size on Cu and Zn isotope ratio measurement[J]. Rock and Mineral Analysis, 2011, 30(4): 400−405.
[15] 尹鹏, 何倩, 何会军, 等. 离子交换树脂法分离沉积物中锶和钕的影响因素研究[J]. 岩矿测试, 2018, 37(4): 379−387. Yin P, He Q, He H J, et al. Study on the factors influencing the separation of Sr and Nd in sediments by ion exchange resin[J]. Rock and Mineral Analysis, 2018, 37(4): 379−387.
[16] 李世珍, 马健雄, 朱祥坤, 等. 离子交换分离过程中铅同位素分馏评估及针对MC-ICPMS铅同位素测定的分离纯化方法的修正[J]. 岩石矿物学杂志, 2015, 34(5): 785−792. Li S Z, Ma J X, Zhu X K, et al. Pb isotopic fractionation during the ion exchange process and the modification of purification methods for isotope determination by MC-ICPMS[J]. Acta Petrologica et Mineralogica, 2015, 34(5): 785−792.
[17] Gu H O, Sun H, Wang F Y, et al. A new practical isobaric interference correction model for the in situ Hf isotopic analysis using laser ablation-multi-collector-ICP-mass spectrometry of zircons with high Yb/Hf ratios[J]. Journal of Analytical Atomic Spectrometry, 2019, 34(6): 1223−1232. doi: 10.1039/C9JA00024K
[18] 漆亮, 黄小文. 地质样品铂族元素及Re-Os同位素分析进展[J]. 矿物岩石地球化学通报, 2013, 32(2): 171−189. Qi L, Huang X W. A review on platinum-group elements and Re-Os isotopic analyses of geological samples[J]. Bulletin of Mineralogy, Petrology and Geochemistry, 2013, 32(2): 171−189.
[19] 冯林秀, 李正辉, 曹秋香, 等. 硼同位素分析测试技术研究进展[J]. 岩矿测试, 2023, 42(1): 16−38. Feng L X, Li Z H, Cao Q X, et al. A review on the development of boron isotope analytical techniques[J]. Rock and Mineral Analysis, 2023, 42(1): 16−38.
[20] 苟龙飞, 金章东, 邓丽, 等. 高效分离Li及其同位素的MC-ICP-MS精确测定[J]. 地球化学, 2017, 46(6): 528−537. Gou L F, Jin Z D, Deng L, et al. Efficient for Li and high-precision and accuracy determination of Li isotopic compositions by MC-ICP-MS[J]. Geochimica, 2017, 46(6): 528−537.
[21] 李子夏, 贺茂勇, 逯海, 等. 多接收等离子质谱高精度测定现代人齿中Mg同位素[J]. 分析化学, 2016, 44(5): 787−791. Li Z X, He M Y, Lu H, et al. Separation and isotopic measurement of Mg isotope ratios in tooth samples using multiple collector-inductively coupled plasma-mass spectrometry[J]. Chinese Journal of Analytical Chemistry, 2016, 44(5): 787−791.
[22] 陈雅祺, 孙贺, 顾海欧, 等. 基于MC-ICP-MS的地质样品的高精度钾同位素分析方法[J]. 地质学报, 2023, 97(4): 1360−1370. Chen Y Q, Sun H, Gu H O, et al. High precision potassium isotope analysis of geological samples using MC-ICP-MS[J]. Acta Geologica Sinica, 2023, 97(4): 1360−1370.
[23] 刘峪菲, 祝红丽, 刘芳, 等. 钙同位素化学分离方法研究[J]. 地球化学, 2015, 44(5): 469−476. Liu Y F, Zhu H L, Liu F, et al. Methodological study of chemical separation of calcium for TIMS measurements[J]. Geochimica, 2015, 44(5): 469−476.
[24] 田兰兰, 于慧敏, 南晓云, 等. Ba同位素分析方法综述[J]. 高校地质学报, 2021, 27(3): 289−305. Tian L L, Yu H M, Nan X Y, et al. A review of barium isotope analytical methods[J]. Geological Journal of China Universities, 2021, 27(3): 289−305.
[25] 霍金晶, 韩延兵. 利用MC-ICP-MS测定铁同位素方法综述[J]. 西北地质, 2021, 54(4): 280−289. Huo J J, Han Y B. A review of MC-ICP-MS Fe isotope analytical methods[J]. Northwestern Geology, 2021, 54(4): 280−289.
[26] 史凯, 朱建明, 吴广亮, 等. 地质样品中高精度铬同位素分析纯化技术研究进展[J]. 岩矿测试, 2019, 38(3): 341−353. Shi K, Zhu J M, Wu G L, et al. A review on the progress of purification techniques for high precision determination of Cr isotopes in geological samples[J]. Rock and Mineral Analysis, 2019, 38(3): 341−353.
[27] 陈栩琦, 曾振, 于慧敏, 等. 高精度稳定锶同位素分析方法综述[J]. 高校地质学报, 2021, 27(3): 264−274. Chen X Q, Zeng Z, Yu H M, et al. High precision analytical method for stable strontium isotopes[J]. Geological Journal of China Universities, 2021, 27(3): 264−274.
[28] 万丹, 陈玖斌, 张婷, 等. 镉同位素分馏及其在示踪土壤镉来源和迁移转化过程中的应用进展[J]. 岩矿测试, 2022, 41(3): 341-352. Wan D, Chen J B, Zhang T, Cadmium isotope fractionation and its applications in tracing the source and fate of cadmium in the oil: A review[J]. Rock and Mineral Analysis, 2022, 41(3): 341-352.
[29] 张卓盈, 马金龙, 张乐, 等. 铷同位素分析方法及研究进展[J]. 地学前缘, 2020, 27(3): 123−132. Zhang Z Y, Ma J L, Zhang L, et al. Advances in rubidium isotope analysis method and applications in geological studies[J]. Earth Science Frontiers, 2020, 27(3): 123−132.
[30] 杨林, 石震, 于慧敏, 等. 多接收电感耦合等离子体质谱法测定岩石和土壤等国家标准物质的硅同位素组成[J]. 岩矿测试, 2023, 42(1): 136−145. Yang L, Shi Z, Yu H M, et al. Determination of silicon isotopic compositions of rock and soil reference materials by MC-ICP-MS[J]. Rock and Mineral Analysis, 2023, 42(1): 136−145.
[31] Nielsen S G, Prytulak J, Halliday A N J G, et al. Determination of precise and accurate 51V/50V isotope ratios by MC‐ICP‐MS. Part 1: Chemical separation of vanadium and mass spectrometric protocols[J]. Geostandards and Geoanalytical Research, 2011, 35(3): 293−306. doi: 10.1111/j.1751-908X.2011.00106.x
[32] Prytulak J, Nielsen S G, Halliday A N J G, et al. Determination of precise and accurate 51V/50V isotope ratios by multi‐collector ICP‐MS. Part 2: Isotopic composition of six reference materials plus the allende chondrite and verification tests[J]. Geostandards and Geoanalytical Research, 2011, 35(3): 307−318. doi: 10.1111/j.1751-908X.2011.00105.x
[33] 赵博, 朱建明, 秦海波, 等. 锑同位素测试方法及其应用研究[J]. 矿物岩石地球化学通报, 2018, 37(6): 1181−1189. Zhao B, Zhu J M, Qin H B, et al. Research progress in measurement and application of antimony isotope[J]. Bulletin of Mineralogy, Petrology and Geochemistry, 2018, 37(6): 1181−1189.
[34] 陈娟, 唐红峰, 王宁, 等. W同位素分析方法进展及全岩样品的消解研究[J]. 矿物岩石, 2013, 33(3): 86−92. Chen J, Tang H F, Wang N, et al. Progress in analytical methods of tungsten isotope and experimental research on digestion of whole rock samples[J]. Mineralogy and Petrology, 2013, 33(3): 86−92.
[35] 辛晓莹, 张天睿, 颜妍. 基于MC-ICP-MS测定水中铀同位素比值的富集方式对比研究[J]. 铀矿地质, 2022, 38(3): 537−544. Xin X Y, Zhang T R, Yan Y. Comparative study on enrichment methods for the determination of uranium isotope ratio in water by MC-ICP-MS[J]. Uranium Geology, 2022, 38(3): 537−544.
[36] 韦刚健, 黄方, 马金龙, 等. 近十年我国非传统稳定同位素地球化学研究进展[J]. 矿物岩石地球化学通报, 2022, 41(1): 1−44, 223. Wei G J, Huang F, Ma J L, et al. Progress of non-traditional stable isotope geochemistry of the past decade in China[J]. Bulletin of Mineralogy, Petrology and Geochemistry, 2022, 41(1): 1−44, 223.
[37] Zhang Z, Ma J, Zhang L, et al. Rubidium purification via a single chemical column and its isotope measurement on geological standard materials by MC-ICP-MS[J]. Journal of Analytical Atomic Spectrometry, 2018, 33(2): 322−328. doi: 10.1039/C7JA00406K
[38] Zhu H L, Zhang Z F, Wang G Q, et al. Calcium isotopic fractionation during ion-exchange column chemistry and thermal ionisation mass spectrometry (TIMS) determination[J]. Geostandards and Geoanalytical Research, 2016, 40(2): 185−194. doi: 10.1111/j.1751-908X.2015.00360.x
[39] Davies C. Determination of distribution coefficients for cation exchange resin and optimisation of ion exchange chromatography for chromium separation for geological materials[D]. Manchester: The University of Manchester, 2012: 20-43.
[40] Li H, Tissot F L H, Lee S G, et al. Distribution coefficients of the REEs, Sr, Y, Ba, Th, and U between α-HIBA and AG50W-X8 resin[J]. ACS Earth and Space Chemistry, 2020, 5(1): 55−65.
[41] Pourmand A, Dauphas N J T. Distribution coefficients of 60 elements on TODGA resin: Application to Ca, Lu, Hf, U and Th isotope geochemistry[J]. Talanta, 2010, 81(3): 741−753. doi: 10.1016/j.talanta.2010.01.008
[42] Rouxel O J, Luais B. Germanium isotope geochemistry[J]. Reviews in Mineralogy and Geochemistry, 2017, 82(1): 601−656. doi: 10.2138/rmg.2017.82.14
[43] Dellinger M, Hilton R G, Nowell G M. Measurements of rhenium isotopic composition in low-abundance samples[J]. Journal of Analytical Atomic Spectrometry, 2020, 35(2): 377−387. doi: 10.1039/C9JA00288J
[44] Miller C A, Peucker-Ehrenbrink B, Ball L. Precise determination of rhenium isotope composition by multi-collector inductively-coupled plasma mass spectrometry[J]. Journal of Analytical Atomic Spectrometry, 2009, 24(8): 1069−1078. doi: 10.1039/b818631f
[45] Liu J, Chen J, Zhang T, et al. Chromatographic purification of antimony for accurate isotope analysis by MC-ICP-MS[J]. Journal of Analytical Atomic Spectrometry, 2020, 35(7): 1360−1367. doi: 10.1039/D0JA00136H
[46] Hu X, Nan X Y, Yu H M, et al. High precision Rb isotope measurements by MC-ICP-MS[J]. Journal of Analytical Atomic Spectrometry, 2021, 36(12): 2744−2755. doi: 10.1039/D1JA00315A
[47] Huang C, Gu H O, Sun H, et al. High-precision determination of stable potassium and magnesium isotopes utilizing single column separation and multicollector inductively coupled plasma mass spectrometry[J]. Spectrochimica Acta Part B: Atomic Spectroscopy, 2021, 181: 106232. doi: 10.1016/j.sab.2021.106232
-
期刊类型引用(8)
1. 王小花，黄韡，顾培良，李静，周佳. 基于自动顶空-固相微萃取-气相色谱质谱检测葡萄酒中的9种木塞污染物. 食品科技. 2024(08): 322-328 . 
百度学术
2. 吴悦，赖永忠，陆国永，林晓昇，梁树生，许文帅. 顶空/气相色谱-质谱法同时测定印染废水中吡啶、苯胺和硝基苯. 岩矿测试. 2023(04): 781-792 . 本站查看
3. 陶慧，黄理金，欧阳磊，帅琴. 氨基化共价有机骨架固相微萃取涂层用于水体中酚类的高效萃取. 岩矿测试. 2022(06): 1040-1049 . 本站查看
4. 黄百祺，沈丹妮，王如意，李双林，林焕怡，李咏梅. 不同萃取头分析大高良姜挥发性成分效果比较. 中成药. 2021(06): 1656-1662 . 百度学术
5. 赵佳平，王俊霞，刘婷婷，张占恩. 含铁二氧化硅涂层固相微萃取-GC/MS法测定水中的有机磷阻燃剂. 现代化工. 2021(09): 235-240 . 百度学术
6. 梁淼，杨艳，石嘉悦，汪兴平，郑福平，余爱农. 酶/酸水解毛叶木姜子中键合态香味成分的比较. 精细化工. 2020(05): 989-996 . 百度学术
7. 孙书堂，严倩，黎宁，黄理金，帅琴. 铁丝原位自转化-固相微萃取新涂层应用于萃取环境水样中多环芳烃的性能研究. 岩矿测试. 2020(03): 408-416 . 本站查看
8. 杨洪早，李锦宇，王东升，张世栋，董书伟，闫宝琪，那立冬，吴春丽，邓俊，吴冠连，陈新丽，赵留涛，朱凯，梁永喜，严作廷. GC法测定马香苓口服液中百秋李醇含量研究. 中国畜牧兽医. 2020(07): 2264-2276 . 百度学术
其他类型引用(3)
计量
- 文章访问数: 135
- HTML全文浏览量: 58
- PDF下载量: 33
- 被引次数: 11
京公网安备 11010202008159号