贵州中医药大学 药用矿物研究中心,贵阳 550025
卓鱼周,博士,讲师,从事地球化学方法在矿物药资源开发与利用中的研究,E-mail:zhuoyuzhou163@163.com
收稿:2024-07-02,
录用:2024-09-11,
网络出版:2024-09-04,
纸质出版:2025-04-05
移动端阅览
卓鱼周.矿物药南寒水石微区微量元素及氧同位素组成的均一性分析[J].中国实验方剂学杂志,2025,31(07):163-171.
ZHUO Yuzhou.Homogeneity Analysis of Trace Elements and Oxygen Isotope Composition in Micro-region of Mineral Medicine Calcitum[J].Chinese Journal of Experimental Traditional Medical Formulae,2025,31(07):163-171.
卓鱼周.矿物药南寒水石微区微量元素及氧同位素组成的均一性分析[J].中国实验方剂学杂志,2025,31(07):163-171. DOI: 10.13422/j.cnki.syfjx.20250464.
ZHUO Yuzhou.Homogeneity Analysis of Trace Elements and Oxygen Isotope Composition in Micro-region of Mineral Medicine Calcitum[J].Chinese Journal of Experimental Traditional Medical Formulae,2025,31(07):163-171. DOI: 10.13422/j.cnki.syfjx.20250464.
目的
2
通过矿物原位微区分析方法探究矿物药南寒水石的微量元素及氧同位素组成的均一性问题。
方法
2
收集贵州省贞丰县烂泥沟(LNG-1、LNG-2)、兴仁市太平洞(TPD)和紫木凼(ZMD)、安龙县戈塘(GT),广西壮族自治区田林县高龙(GL)和八渡(BD)、兴仁市凌云县明山(MS)的南寒水石样品。采用X射线能谱面扫描法(EDS)对TPD样品的光薄片进行原位微区的钙(Ca)、锰(Mn)、铁(Fe)元素面扫描分析;采用阴极发光法(CL)对各南寒水石样品的光薄片进行发光性分析;采用激光剥蚀电感耦合等离子体质谱法(LA-ICP-MS)分析LNG-1、TPD、GL、BD样品光薄片的原位微区Mn、Fe、稀土元素的含量及分布均匀性,以及LNG-2、ZMD、GT、MS样品光薄片的原位微区
δ
18
O及分布均匀性。
结果
2
不同产地的南寒水石的元素及氧同位素组成均存在差异性。EDS分析结果显示,南寒水石中的Fe、Mn元素具有明显的环带结构。CL及LA-ICP-MS分析结果显示,南寒水石不同区域阴极光呈红色且明暗不一,其中Mn、Fe及稀土元素的含量为南寒水石阴极光明暗的重要影响因素。Fe元素含量高而Mn元素含量低的区域阴极光颜色较暗,Fe元素含量低而Mn元素含量高的区域阴极光颜色较亮,当稀土元素总含量
>
10 μg·g
-1
时,将对阴极光的明亮度产生影响,其总含量越高的区域阴极发光颜色也越明亮。在不同产地样品中,MS地区所测试的南寒水石具有最大的
δ
18
O不均一性,且形成了微米级的
δ
18
O差异性环带,同时,阴极光较暗的区域
δ
18
O含量较低,阴极光较亮的区域
δ
18
O含量较高。
结论
2
南寒水石的Fe、Mn、稀土元素及
δ
18
O组成不均一且具有明显的化学成分环带,其中烂泥沟地区的南寒水石因化学成分相对均一,具有较高的Fe、Mn元素含量而具有良好的品质。该研究可为南寒水石质量标准的制定提供实验依据。
Objective
2
To investigate the homogeneity of trace elements and oxygen isotope composition of the calcitum by
in situ
micro-region analysis.
Methods
2
Samples of calcitum were collected from Lannigou in Zhenfeng county, Guizhou province(LNG-1, LNG-2), Taipingdong(TPD) and Zimudang(ZMD) in Xingren county, Guizhou province, Getang in Anlong county, Guizhou province(GT), Gaolong(GL) and Badu(BD) in Tianlin county, Guangxi province, and Mingshan in Lingyun county, Guangxi province(MS). The surface scanning of Ca, Mn and Fe elements in the microregions of TPD samples was analyzed by X-ray energy spectrum surface scanning method(EDS). Cathodoluminescence method(CL) was used to analyze the luminescence properties of the thin slices of calcitum samples. The content and distribution uniformity of Mn, Fe and rare earth elements in the
in situ
microregions of LNG-1, TPD, GL and BD samples, and the
δ
18
O and the distribution uniformity in the in situ microregions of the thin slices of LNG-2, ZMD, GT and MS samples were analyzed by laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS).
Results
2
The composition of elements and oxygen isotopes of calcitum from d
ifferent origins were different. EDS analysis results showed that the Fe and Mn elements in calcitum had obvious girdle structure. The results of CL and LA-ICP-MS analysis showed that the cathode light in different regions of calcitum was red and varied in brightness, and the contents of Mn, Fe and rare earth elements were important factors affecting the brightness of the cathode light of calcitum. Regions with high content of Fe and low content of Mn had darker cathode light color, while regions with low content of Fe and high content of Mn had brighter cathode light color. When the total content of rare earth elements was
>
10 μg·g
-1
, the brightness of the cathode light would be affected, and the higher the total content of the region, the brighter the cathode light color would be. Among the samples from different origins, the calcitum tested in MS area had the largest
δ
18
O heterogeneity, and the
δ
18
O difference ring band with micron level was formed. Meanwhile, the
δ
18
O content was lower in the region with darker cathode light, on the contrary, the content was higher.
Conclusion
2
The composition of Fe, Mn, rare earth elements and
δ
18
O of calcitum is uneven and has obvious chemical compositional ring bands, among which the calcitum in Lannigou area has good quality because of its relatively uniform chemical composition and high content of Fe and Mn elements. This study can provide experimental basis for the formulation of quality standard of calcitum.
卓鱼周 , 刘晓琴 , 王贤书 , 等 . 朱砂及其不同炮制品的显微结构及主微量元素含量差异性研究 [J]. 中国药学杂志 , 2023 , 58 ( 21 ): 1922 - 1930 .
ZHUO Y Z , LIU X Q , WANG X S , et al . Microstructure and content difference of main and trace elements in cinnabaris and its different processed products [J]. Chin Pharm J , 2023 , 58 ( 21 ): 1922 - 1930 .
陈琴芳 . 芒硝外敷联合生长抑素在急性胰腺炎患者护理中的应用效果 [J]. 沈阳药科大学学报 , 2021 , 38 ( S1 ): 101 .
CHEN Q F . Application effect of glauberite external application combined with somatostatin in nursing of patients with acute pancreatitis [J]. J Shenyang Pharm Univ , 2021 , 38 ( S1 ): 101 .
陆景坤 , 陈朝军 , 周昊菲 , 等 . 不同产地北寒水石炮制前后药效学研究 [J]. 中华中医药杂志 , 2011 , 26 ( 11 ): 2547 - 2550 .
LU J K , CHEN C J , ZHOU H F , et al . Comparative study on pharmacodynamic activity in vivo of north Calcitum from different origins before and after processing [J]. China J Tradit Chin Med Pharm , 2011 , 26 ( 11 ): 2547 - 2550 .
陈榆 . 寒水石的本草考释 [J]. 中国中药杂志 , 1989 , 14 ( 12 ): 7 - 10 .
CHEN Y . Herbal commentary on calcitum [J]. China J Chin Mater Med , 1989 , 14 ( 12 ): 7 - 10 .
胡密霞 , 周昊霏 , 王美玲 , 等 . 蒙药寒水石的研究进展 [J]. 中国民族医药杂志 , 2014 , 20 ( 9 ): 34 - 36 .
HU M X , ZHOU H F , WANG M L , et al . Recent development of study on mongolian medicine Gypsum Fibrosum [J]. J Med Pharm Chin Minorities , 2014 , 20 ( 9 ): 34 - 36 .
卓鱼周 , 刘晓琴 , 李涛 , 等 . ICP-MS分析不同产地南寒水石原生矿石微量元素含量 [J]. 中国现代应用药学 , 2022 , 39 ( 19 ): 2521 - 2527 .
ZHUO Y Z , LIU X Q , LI T , et al . Analysis of trace elements in calcite raw ore from different areas by ICP-MS [J]. Chin J Mod Appl Pharm , 2022 , 39 ( 19 ): 2521 - 2527 .
ZHUO Y H , HU R Z , XIAO J F , et al . Trace elements and C-O isotopes of calcite from Carlin-type gold deposits in the Youjiang Basin,SW China:Constraints on ore-forming fluid compositions and sources [J]. Ore Geol Rev , 2019 , 113 : 103067 .
张彩虹 , 曹赟 , 古锐 , 等 . 南寒水石的生药学研究 [J]. 中国实验方剂学杂志 , 2015 , 21 ( 24 ): 65 - 68 .
ZHANG C H , CAO Y , GU R . Pharmacognosy analysis of Calcitum [J]. Chin J Exp Tradit Med Form , 2015 , 21 ( 24 ): 65 - 68 .
朱林燕 , 谢建锋 , 孔子铭 , 等 . 藏药奶制南寒水石X-射线衍射指纹图谱及其在微波炮制中的应用 [J]. 中国中药杂志 , 2015 , 40 ( 10 ): 1948 - 1952 .
ZHU L Y , XIE J F , KONG Z M , et al . Fingerprint of X-ray diffraction of Tibetan medicine dairy Nanhanshuishi and its application in processing by microwave [J]. China J Chin Mater Med , 2015 , 40 ( 10 ): 1948 - 1952 .
卓鱼周 , 刘晓琴 , 张文会 , 等 . 基于微量元素-硫同位素示踪技术的朱砂产地差异性分析 [J]. 中国实验方剂学杂志 , 2022 , 28 ( 23 ): 182 - 188 .
ZHUO Y Z , LIU X Q , ZHANG W H , et al . Origin difference analysis of Cinnabaris based on trace element-sulfur isotope tracing technique [J]. Chin J Exp Tradit Med Form , 2022 , 28 ( 23 ): 182 - 188 .
魏健雄 , 袁明洋 , 崔红娇 , 等 . 花蕊石的本草考证及物相分析 [J]. 中国实验方剂学杂志 , 2024 , 30 ( 21 ): 185 - 193 .
WEI J X , YUAN M Y , CUI H J , et al . Herbal textual research,quality evaluation and phase analysis of Ophicalcitum [J]. Chin J Exp Tradit Med Form , 2024 , 30 ( 21 ): 185 - 193 .
魏健雄 , 孙媛 , 陈代红 , 等 . 钟乳石品质评价的本草考证及物相分析 [J]. 中国实验方剂学杂志 , 2024 , 30 ( 21 ): 203 - 211 .
WEI J X , SUN Y , CHEN D H , et al . Herbal textual research,quality evaluation and phase analysis of Stalactitum [J]. Chin J Exp Tradit Med Form , 2024 , 30 ( 21 ): 203 - 211 .
王晓飞 , 王友邵 , 陈代红 , 等 . 赤石脂品质评价的本草考证及物相分析 [J]. 中国实验方剂学杂志 , 2024 , 30 ( 21 ): 176 - 184 .
WANG X F , WANG Y S , CHEN D H , et al . Herbal textual research,quality evaluation and phase analysis of Halloysitum Rubrum [J]. Chin J Exp Tradit Med Form , 2024 , 30 ( 21 ): 176 - 184 .
陈朝军 , 陆景坤 , 高甜 , 等 . 南寒水石炮制工艺及药效学初探 [J]. 中国实验方剂学杂志 , 2013 , 19 ( 1 ): 191 - 194 .
CHEN C J , LU J K , GAO T , et al . Processing technology and pharmacodynamics of Hanshuishi [J]. Chin J Exp Tradit Med Form , 2013 , 19 ( 1 ): 191 - 194 .
LI J W , HU R Z , XIAO J F , et al . Genesis of gold and antimony deposits in the Youjiang metallogenic province, SW China:Evidence from in situ oxygen isotopic and trace element compositions of quartz [J]. Ore Geol Rev , 2020 , 116 ( 11 ): 103257 .
YANG P , WU G H , NURIEL P , et al . In situ LA-ICPMS U-Pb dating and geochemical characterization of fault-zone calcite in the central Tarim Basin,northwest China:Implications for fluid circulation and fault reactivation [J]. Chem Geol , 2021 , 568 : 120125 .
LEI Z C , XU H M , JIANG T W , et al . In-situ major and rare earth elements constraint on the growth mechanism of calcite cement in shallow marine sandstone:An example from the Donghe sandstones,Tabei uplift,Tarim Basin,NW China [J]. Mar Pet Geol , 2021 , 134 ( 8 ): 105325 .
员媛娇 , 范成龙 , 吕喜平 , 等 . 电子探针和LA-ICP-MS技术研究内蒙古浩尧尔忽洞金矿床毒砂矿物学特征 [J]. 岩矿测试 , 2022 , 41 ( 2 ): 211 - 225 .
YUAN Y J , FAN C L , LV X P , et al . Application of EPMA and LA-ICP-MS to study mineralogy of Arsenopyrite from the Haoyaoerhudong gold deposit,Inner Mongolia,China [J]. Rock Min Anal , 2022 , 41 ( 2 ): 211 - 225 .
王辉 , 汪方跃 , 关炳庭 , 等 . 激光能量密度对LA-ICP-MS分析数据质量的影响研究 [J]. 岩矿测试 , 2019 , 38 ( 6 ): 609 - 619 .
WANG H , WANG F Y , GUAN B T , et al . Effect of laser energy density on data quality during LA-ICP-MS measurement [J]. Rock Min Anal , 2019 , 38 ( 6 ): 609 - 619 .
LIANG Q , JING H , GREGOIRE D C . Determination of trace elements in granites by inductively coupled plasma mass spectrometry [J]. Talanta , 2000 , 51 ( 3 ): 507 - 513 .
LIU Y H , TANG G Q , LING X X , et al . Speleothem annual layers revealed by seasonal SIMS δ 18 O measurements [J]. Sci China Earth Sci , 2015 , 58 ( 10 ): 174101747 .
XU L , XIE J F , ZHANG S K , et al . Fossil turtle eggs from the upper cretaceous Gaogou formation, Xiaguan-Gaoqiu Basin,Neixiang county,Henan province,China:Interpretation of the transformation from aragonite to calcite in fossil turtle eggshell [J]. Cretaceous Res , 2022 , 134 : 105166 .
CLAES H , DE MIRANDA T S , FALCÃO T , et al . Model for calcite spherulite formation in organic,clay-rich,lacustrine carbonate shales (Barbalha Formation,Aptian,Araripe Basin,NE Brazil) [J]. Mar Pet Geol , 2021 , 128 : 104988 .
GABITOV R I , WATSON E B , SADEKOV A Y , et al . Oxygen isotope fractionation between calcite and fluid as a function of growth rate and temperature:An in situ study [J]. Chem Geol , 2012 , 306-307 ( 10 ): 92 - 102 .
卓鱼周 . 右江盆地卡林型金矿-汞矿矿床成因机制对比研究 [D]. 北京 : 中国科学院大学 , 2019 .
ZHUO Y Z . Comparative study on genetic mechanism of Carlin-type gold and mercury deposits in Youjiang Basin [D]. Beijing , University of Chinese Academy of Sciences , 2019 .
刘杰 , 熊亮 , 周勤梅 , 等 . 中药道地性研究新技术应用进展 [J]. 中医药学报 , 2021 , 49 ( 8 ): 110 - 115 .
LIU J , XIONG L , ZHOU Q M , et al . Progress in application of new technologies for geo-herbalism of genuine medicinal materials [J]. Acta Chin Med Pharmacol , 2021 , 49 ( 8 ): 110 - 115 .
张明华 , 封亮 , 胡绍英 , 等 . 药材道地性的物质基础本质:组分结构的独特性 [J]. 中国中药杂志 , 2013 , 38 ( 1 ): 136 - 140 .
ZHANG M H , FENG L , HU S Y , et al . Essence of material base in geoherbs:Specificality of constituent structure [J]. China J Chin Mater Med , 2013 , 38 ( 1 ): 136 - 140 .
ZHUO Y Z , ZHANG W H , LI Y N , et al . Calming effect of traditional Chinese medicine cinnabar based on neurotransmitter content and metal elements concentration in PCPA-induced insomnia rats [J]. Pharmacol Res Mod Chin Med , 2024 , 11 : 100431 .
马彦平 , 石磊 , 何源 . 微量元素铁、锰、硼、锌、铜、钼营养与人体健康 [J]. 肥料与健康 , 2020 , 47 ( 5 ): 12 - 17 .
MA Y P , SHI L , HE Y , et al . Trace elements iron,manganese,boron,zinc,copper,molybdenum and human health [J]. Fertil Health , 2020 , 47 ( 5 ): 12 - 17 .
O'DELL B L , SUNDE R A . Handbook of nutritionally essential mineral elements [M]. NewYork : Chemical & Rubber Company , 1997 : 335 - 356 .
邓蒙蒙 , 高慧 , 刘建新 , 等 . 稀土元素的生物学功能及其在动物生产中的应用 [J]. 动物营养学报 , 2024 , 36 ( 2 ): 789 - 797 .
DENG M M , GAO H , LIU J X , et al . Biological functions of rare earth elements and Th applications in animal production [J]. Chin J Anim Nut , 2024 , 36 ( 2 ): 789 - 797 .
秦俊法 , 陈祥友 , 李增禧 . 稀土的生物学效应 [J]. 广东微量元素科学 , 2002 , 9 ( 3 ): 1 - 16 .
QING J F , CHEN X Y , LI ZENG X . Biological effect of rare earth element [J]. Guangdong Trace Elem Sci , 2002 , 9 ( 3 ): 1 - 16 .
吴卫东 , 秦孝发 , 江泉观 , 等 . 稀土化合物对温石棉表面产生羟基自由基的抑制作用 [J]. 卫生毒理学杂志 , 1994 , 8 ( 3 ): 201 - 202 .
WU W D , QIN X F , JIANG Q G , et al . Inhibition of hydroxyl radical on chrysotile surface by rare earth compounds [J]. J Toxicol , 1994 , 8 ( 3 ): 201 - 202 .
孟祥才 , 李晓颖 , 姚杰 , 等 . 生态胁迫促进道地药材质量形成机制与质量评价思路 [J]. 中草药 , 2022 , 53 ( 5 ): 1587 - 1594 .
MENG X C , LI X Y , YAO J , et al . Mechanism of ecological stress enhancing quality of genuine medicinal materials and its quality evaluation idea [J]. Chin Tradit Herb Drugs , 2022 , 53 ( 5 ): 1587 - 1594 .
席少阳 , 曹后康 , 郭延秀 , 等 . 地理空间视角下的甘肃道地药材当归酚酸类成分总含量分异特征及驱动因子定量分析 [J]. 中国中药杂志 , 2021 , 46 ( 22 ): 5781 - 5791 .
XI S Y , CAO H K , GUO T X , et al . Quantitative analysis of total content differentiation and driving factors of phenolic acids in Angelicae Sinensis Radix of Gansu Dao-di herbs from perspective of geographical space [J]. China J Chin Mater Med , 2021 , 46 ( 22 ): 5781 - 5791 .
0
浏览量
224
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010802024621
