【作者】 殷学博；

【导师】 李三忠； 曾志刚；

【作者基本信息】 中国海洋大学 ， 海洋地质， 2013， 博士

【摘要】 海底多金属硫化物是重要的矿产资源，其测试技术一直是一个难题，主要因为其含有常量硫，矿物组成复杂多样，常常难以完全消解，造成了数据结果的精确度与准确度较差，同时像稀土元素、铂族元素含量超微，远低于检出限，增加了准确测试的难度，本论文针对以上问题及大洋矿产战略需求，系统开展了防腐高效溶样罐的研制，微量元素、稀土元素与铂族方法研究，研究海底多金属硫化物样品中元素之间的相互关系及稀土元素配分模式与成因条件的关系，取得了如下成果：（1）设计了防腐高效溶样罐：具有防腐、耐高温高压（合金材质）、密封、操作简单（一秒扣合）、酸不挂壁，不挂顶（提高酸溶效果）、安全（压力极限实验，无爆管现象）、批量消解（可以随意增加、减少使用罐体数量，不影响效果），消解完全等特点，成为目前溶样罐的标志性产品，提高了我国消解容器自主研发的能力。（2）解决了硫化物样品的完全消解难题：提出不同消解法测试不同元素的方法，建立了两种消解方法，一是HNO3消解法测试Ag、Bi等元素，测试结果准确可靠，一是HCl+HF加HNO3消解法，能够有效去除S元素，完全消解硫化物样品，溶液清澈、透亮，实现包括Au、Ba、REE在内的30余种元素的准确测试。（3）海底多金属硫化物中稀土元素的测定方法：优选选取国产732阳离子树脂，先用2mol/L HCl淋洗，去除Cu、Fe、Pb、Zn等二价元素，再用2.5mol/LHNO3淋洗去掉Ba元素，整个流程最优化设计，可获得REE元素高回收率数据，把实验方法应用到黄铁矿（GBW07267）、黄铜矿（GBW07268）、闪锌矿（GBW07270）与WMS‐1a中REE的测试中，采用加标回收验证与参照值对比的方法研究了测试方法的准确性，REE回收率较高，可以实现海底多金属硫化物中REE的准确测试。（4）海底多金属硫化物中铂族元素的测定方法：通过硫镍试金法、阳离子树脂交换法、阴离子树脂交换法实验，发现这些方法都存在着这样或者那样的问题，测试结果不够理想，表现为空白高，干扰大，回收率低或者不稳定等问题，为后续的PGE元素测试方法研究奠定了基础。（5）海底多金属硫化物样品中微量元素的作用关系：测试了东太平洋海隆17A-EPR-TVG1与17A-EPR-TVG2站硫化物样品中Fe2O3、Cu、Zn、Mn等13种元素，属于富Fe型，并对相关性与聚类分析，结果表明TVG1中Cd与Zn及Mo与Zn之间呈现出良好的相关性；而样品TVG2中Cd与Zn及Mo与Zn之间基本上不存在相关性，表明虽然这两块样品虽然采自同一位置的两块样品，其元素富集沉淀机理存在一定的差别，需进一步的工作研究成因与来源。（6）稀土元素的示踪作用：研究了东太平洋海隆、大西洋洋脊、印度洋中脊、西南印度洋洋脊与北斐济海盆区域内7个热液区海底多金属硫化物中的稀土元素特征表现为明显的LREE富集，HREE亏损，其Eu表现出正异常、负异常与无异常等特征，Ce为无异常或者轻微异常特征，Eu异常与海底多金属硫化物的形成温度有直接关系，Eu负异常对应着低温热液矿物，与低温热液活动有关，Eu正异常对应高温热液矿物，与高温热液活动有关。更多还原

【Abstract】 As the important mineral resources at the sea floor, the polymetallic sulphidesare very difficult to be determined because it contains major sulfur and manycomplicated mineral which leads to the poor accuracy and precision of the data, andmeanwhile, the rare earth elements (lanthanide series) and platine group elements(PGE) are in the ultra-trace level that are far less than the detection limits, In regard tothe above problems and the strategic demand for the ocean minerals, this Paperdesigned the anticorrosive efficient digestion vessel, studies on the determinationmethods of trace elements, rare earth elements (REE) and the PGE as well as thestudies on the correlations between elements in the samples of polymetallic sulphidesand the relationship between REE assemblage and the formation conditions, and thefollowing achievements have been obtained:(1)The design of the anticorrosive efficient digestion vessel. The vessel has thefollowing features: it is made of the anti-corrosion alloy material that is resistant tothe high temperature and high pressure, it is airtight and easy to operate (it can beclosed within1second), it retains no acid on the wall or the top, which improves theeffect of acid dissolving, it is safe and free of tube blasting in the test under thepressure limit, it can be used in any quantity without affecting the results so that thepolymetallic sulphides can be cleared up in batches completely. The bomb is thesymbolic product in the manufacturing of the sample-degesting vessel in China thatenhances the capability to develop the sample-digesting containers independently.(2)The solution to problems on clear-up of sulfide samples. This paper puts forward different methods to clear up the different elements and establishes two methods,one is to detect the Ag and Bi elements with HNO3and the results are proven to beaccurate and reliable, and the other is the method of HCl+HF and HNO3, which canefficiently eliminate the S, completely clear up the sulfide samples and make thesolution clear and transparent, and thus achieving the accurate determination for over30elem-ents including Au, Ba, rare earth elements (REE), etc.(3)The method of determining the REE in the polymetallic sulphides at sea floor.Preference is given to the domestically-made732cationic resin that is eluted with2mol/L of HCl to get rid of the divalent elements like Cu, Fe, Pb and Zn, etc. andeliminate the Ba with2.5mol/L of HNO3, the whole process is in the optimal designand obtains the data of high recovery of REE. The method has been used to determine the REE in pyrites (GBW07267), chalcopyrite (GBW07268), sphalerite (GBW07270)and WMS-1a, the accuracy of the determination is proven with the methods ofverifying the recovery results by adding the standard and of contrasting with thereference values, the method can be used to obtain a high recovery of REE, and thusachieving the accurate determination of REE in the polymetallic sulphides.(4)The method of determining the PGE in the polymetallic sulphides at sea floor.Experiments with the nickel sulphide fire assay method, cation resin exchange andanion resin exchange show that all of those methods have problems, which mainlyincludes the poor experimental effect, great interference, low recovery and instability,etc. which plays a important role in the research of determination of PGE in future.（5）The interactive relation of trace elements in the polymetallic sulphides atsea floor. The test has been conducted to determine13elements including Fe2O3, Cu,Zn, Mn in the sulfide samples at Stations of17A-EPR-TVG1and17A-EPR-TVG2atthe rise of the east pacific ocean, all those samples are Fe-concentrated ones, andanalysis was conducted on the correlation and clustering of those elements, and theresults show that there is a good correlation between Cd and Zn, and between Mo andZn in TVG1, while there is no correlation between Cd and Zn, or between Mo and Znin TVG2, which indicates that the two samples, although collected from the sameposition, have difference in the mechanisms of element concentration and deposition,and further work is required to study the causes and sources of the samples.（6）The tracer role of REE. The study has been conducted on the REE in thepolymetallic sulphides at sea floor of7hydrothermal areas at the rise of the eastpacific ocean, Indian Ridge，Mid-Atlantic Ridge，North Fiji Basin, which showsthat those areas are enriched with LREE while lack of HREE, of which, the elementof Eu features the positive anomalies, negative anomalies and no anomalies; Cefeatures no or slight anomalies, the anomalies of Eu has direct relation with thetemperature at which the polymetallic sulphides take shape, the negative anomalies ofEu is corresponding to the hydrothermal minerals at low temperature and it hasrelations with the low temperature hydrothermal activities, while the positiveanomalies of Eu to the hydrothermal minerals at high temperature, and the hightemperature hydrothermal activities.更多还原