中太平洋M海山富钴结壳稀土元素地球化学

用ICP-AES和重量法测试了中太平洋M海山不同水深范围内(1300~3000 m)25个富钴结壳样品的稀土元素和常量元素。结果显示M海山富钴结壳为水成结壳,稀土元素总量平均为2084.69μg.g-1,LREE/HREE平均为4.84,具有正的Ce异常。ΣREE(不含Ce)随水深增加而增加,而Ce和LREE/HREE比值则以文石溶跃面为界(水深2000 m)呈现不同的变化,稀土元素这些变化除了与海洋背景颗粒的吸附清扫有关外,还与稀土元素在海水中的行为有关。富钴结壳Ce虽随水深变化,但与水深关系不明显,可能反映其通量恒定。富钴结壳中Ce基本全为Ce(Ⅳ),表明氧化富集过程,这一过程受动力学因素控制。     

麦哲伦海山群富钴结壳铈富集的控制因素

利用ICP-OES和ICP-MS,分析了麦哲伦海山群西北端MK海山2170 m水深的MKD23B-3号富钴结壳样品,获得了其剖面上Ce,Co和P2O5含量数据.结果显示,该样品未磷酸盐化壳层的过剩Ce(Cexs)与Co含量之间呈明显的正相关关系,相关系数R2高达0.7893;与生长速率呈负相关关系,相关系数R2高达0.7211,表明壳层生长速率是制约结壳Ce含量的主因,高的Ce含量是低的生长速率造成的.在假设海水pH,Mn2+等条件不变的前提下,结壳生长速率正相关于Fe,Mn的沉积通量,而Fe,Mn的沉积通量正相关于海水中溶解氧含量.因此,在海水pH,Mn2+等条件不变的前提下,Cexs负相关于海水中溶解氧含量,海水溶解氧含量只是制约结壳Ce含量的间接因素,纠正了"结壳高Ce异常指示其形成时海水中高溶解氧含量"的认识.     

电感耦合等离子体质谱测定富钴结壳中的稀土元素

采用封闭压力酸溶(HF+HNO3)消解样品,以Rh为内标,用电感耦合等离子体质谱测定富钴结壳中的稀土元素。用此方法对3个国家一级标准物质富钴结壳标样(GSMC-1,GSMC-2,GSMC-3)进行了多次测定,结果稀土元素的测定值与标准值相符,多次测定结果的相对标准偏差(RSD,n=5)在0.36%～4.0%之间,加标回收率为90%～106%。基于此方法,对6个富钴结壳样品进行了测定,显示富钴结壳样品中稀土元素的配分曲线与标准物质中稀土元素的配分模式一致。方法适用于富钴结壳样品的批量分析。     

多金属结核/结壳中稀土元素的富集特征及其资源效应

多金属结核/结壳是海洋中最重要的固体沉积矿产之一,蕴藏丰富的铁、锰、铜、钴、镍等金属元素,也是稀土元素的富集体.利用等离子质谱仪/光谱仪对太平洋、大西洋、印度洋及南海北部海多金属结核/结壳11个样品25份试样的稀土含量进行了分析,多金属结核/结壳中稀土平均含量为1265 57×10-6,其中结核平均含量为1096.96×10-6,结壳平均含量1623.88×10-6,人人超过地壳和玑积岩的平均含量.稀土元素的富集主要受控于结核/结壳中铁、锰氧化物及粘土矿物对海水和沉积物中稀土元素的吸附作用,Ce元素高度富集,使其成为多金属结核/结壳矿产开发中可能最先利用的稀土元素之一.     

激光剥蚀-电感耦合等离子体质谱研究富钴结壳生长环带的元素分布

建立了以Ti为内标,富钴结壳标准物质GSMC-1为外标,193nmArF准分子激光剥蚀ICP-MS方法研究富钴结壳不同结壳层中元素组成及分布。所建立的定量方法用于GSMC-2和GSMC-3的测定,分析结果的相对标准偏差和相对误差均小于10%;各分析元素的检出限为3.2～191ng/g(除Si外),可以满足富钴结壳原位微区分析的要求。对取自西太平洋麦哲伦海山区富钴结壳样品MDD-42,从核心到最外结壳层以0.5mm的微间距剥蚀并采集140个样品点,不同生长环带的微区分析结果表明,成矿元素和伴生元素在不同结壳层中呈现不同的分布特性,直接反映了结壳形成时期的地质作用和古海洋沉积环境。     

贵州织金寒武纪磷块岩中磷灰石和白云石稀土元素的LA-ICP-MS分析:对沉积环境和成岩过程的指示意义

贵州织金富稀土磷矿是典型的早寒武世肖滩阶海相沉积磷块岩矿床,主要由碳氟磷灰石和白云石组成,其中丰富的小壳动物化石、普遍发育的生物碎屑结构和潮汐层理等特征综合反映了充氧、动荡的潮汐环境,为探讨成磷环境下磷灰石和白云石在沉积成岩过程中稀土元素的地球化学行为提供了理想的制约。通过激光剥蚀-电感耦合等离子体-质谱(LA-ICP-MS)对织金磷块岩钻孔样品中胶状磷灰石、磷酸盐化小壳动物化石和成岩期白云石的稀土及相关主微量元素进行原位分析,根据主微量元素特征分析研究对象中的污染来源,进而提出在成磷环境下使用白云石和磷酸盐矿物稀土元素反映同期海水化学特征的数据筛选指标,最后通过筛选样品的稀土元素特征值讨论当时海水化学特征。结果表明:三种研究对象均具有显著的Ce的负异常(δCe为0.29～0.40)和La正异常(δLa为1.85～2.00)及较高的Y/Ho比值(47.25～56.91),表现出与现代海洋环境相似的氧化特征。磷酸盐矿物表现为一定程度的MREE富集和HREE"右倾"模式,可能与当时浮游生物繁盛并在深部水体中的降解有关,代表了深部富磷洋流的特征;成岩期白云石稀土模式与现代浅海海水相似但HREE为"左倾"模式,代表了同期浅海海水的特征,但白云石与磷酸盐矿物的HREE耦合特征反映了胶磷矿沉积成矿过程中对浅海海水HREE的选择性富集;肖滩阶的浅海海水与深部洋流都具有现代海洋的氧化特征,可能是促使当时小壳动物繁盛的重要因素。     

193nmArF准分子激光剥蚀-等离子体质谱测定富钴结壳中的稀土元素

采用193nm ArF准分子(Excimer)激光剥蚀ICP—MS测定了富钴结壳中痕量稀土元素。比较了^27Al、^49Ti作为内标元素时稀土元素的LA—ICP—MS分析信号的响应行为。结果表明,^27Al与稀土元素具有相似的激光剥蚀行为以及等离子体激发、电离特征;以Al为内标元素,NIST610玻璃标准为外标,可有效抑制基体效应和灵敏度漂移的影响。方法的检出限为1．2～15．8ng／g,用于标准参考物质中稀土元素的测定,测定结果的相对标准偏差(n=5)在2．2％～6．4%,测定值与标准参考值的相对误差小于6．5％。     

宁镇地区燕山期矽卡岩矿床成矿系统稀土元素地球化学研究

通过宁镇地区燕山期矽卡岩矿床成矿系统的稀土元素特征研究,了解了矽卡岩矿床成矿系统的稀土元素地球化学演化规律特征及其制约机制,为矽卡岩型多金属矿床成矿规律及成矿预测研究提供新的地质地球化学信息依据。研究表明,矽卡岩矿床成矿系统稀土演化规律为:矽卡岩期,干矽卡岩阶段到湿矽卡岩阶段稀土组分含量增加;矽卡岩期晚期到热液期早期降低;热液期,汽成热液氧化物阶段到高中温硫化物阶段增加,到中低温硫化物阶段降低。演化规律主要是受自身富集稀土元素的强度、流体含矿性、运移分配及成矿的物理化学条件的影响。矽卡岩矿床成矿系统主要矽卡岩化的发育及其分带性所具有成矿专属性等特点,都为进一步寻找矽卡岩型多金属矿床提供新的地质地球化学信息。     

聚硅氧烷/丙烯酸酯核/壳复合胶乳的粒径分布与成核机理

通过种子乳液法合成出具有高有机硅含量核 壳结构的聚硅氧烷 丙烯酸酯复合粒子 .研究了聚合方法、乳化剂浓度、引发剂浓度、单体滴加速度等工艺条件对复合乳液粒径尺寸、分布与形态的影响 ,并对复合乳液的成核机理进行了探讨 .研究表明 ,乳化剂浓度对乳液粒子的粒径分布和形态、结构有显著影响 ,引发剂浓度增加将使粒子粒径减小 ;相对一次投料法 ,种子乳液法生成的粒子分布窄 ,具有明显核壳结构 ,通过壳层单体滴加速度可以控制粒子的粒径尺寸和分布 ;而壳层丙烯酸酯聚合物主要是在聚硅氧烷种子表面的“过渡层”聚合、富集而成 .     

酸雨胁迫及稀土农用条件下菠菜及其土壤中稀土元素的赋存

利用盆栽实验研究了酸雨胁迫、稀土农用条件下 ,菠菜及其土壤中稀土元素的含量及分布特征。结果表明 :菠菜地上部分的REE含量为 0 .5 2 7～ 0 .696μg·g- 1 之间 ,地下部 2 .668～ 3 .0 0 3 μg·g- 1 。土壤 2 2 9.0 9～ 2 5 0 .3 μg·g- 1 。酸雨明显地影响作物对REE的吸收和利用 ,酸度越大 ,影响越明显。随着酸雨酸度的增大、植株体内、土壤中的REE受淋洗的作用加强而表现出REE的总量随着pH的减小而逐渐减少。施用稀土后 ,植株的地上或地下部分及其土壤中的REE含量均与对照的土壤中的REE分配模式基本相同 ,遵循稀土元素分布丰度的奇偶 (Oddo Harkins)规则、轻稀土富集 ,Eu弱负异常 ,富铈配分型 ,表明稀土元素仍然主要来自土壤并受其影响。     

电感耦合等离子体原子发射光谱法(ICP-AES)测定锰结壳中的多种金属元素

采用硝酸-盐酸-氢氟酸高压封闭消解样品,电感耦合等离子体光谱法测定锰结核GBW07296和富钴结壳GSMC-1标准物质中的18种常、微量元素。实验过程中确定了最佳工作条件,选择了最佳分析谱线。实验结果表明,该方法线性相关系数良好r>0.999 8,方法检出限低,精密度高,RSD小于2.0%(n=6),可同时测定锰结壳中的多种金属元素,方法完全能满足岩石、土壤、海洋沉积物中多个元素的检测需求。     

Random Occupation of Multimetal Sites in Transition Metal-Organic Frameworks for Boosting the Oxygen Evolution Reaction

Developing robust oxygen evolution reaction (OER) electrocatalysts with excellent performance is essential for the conversion of renewable electricity to clean fuel. Herein, we present a facile concept for the synthesis of efficient high-entropy metal-organic frameworks (HEMOFs) as electrocatalysts in a one-step solvothermal synthesis. This strategy allows control of the microstructure and corresponding lattice distortion by tuning the metal ion composition. As a result, the OER activity was improved by optimizing the coordination environment of the metal catalytic center. The optimized Co-rich HEMOFs exhibited a low overpotential of 310 mV at a current density of 10 mA cm⁻², better than a RuO₂ catalyst tested under the same conditions. The finding of lattice distortion of the HEMOFs provides a new strategy for developing high-performance electrocatalysts for energy conversion.     

自贡市城市地质环境分区评价

从自然地理条件、地质条件、环境质量、环境地质问题等方面着手,以地形地貌、区域地壳稳定性、岩（土）体工程地质特征、环境污染、地质灾害为要素开展了自贡市城市地质环境质量评价;采用了权重法、层次分析法等计算方法得出了地质环境综合评价指数,对自贡市进行了地质环境评价分区;为城市的发展规划提供了可靠的地质依据。     

Elemental fractionation of Si, Al, Ti, Fe, Ca, Mn, P, and Ba in five marine sedimentary reference materials: results from sequential extractions

We report on the elemental results from sequential extractions of BCSS-1 (marine sediment), MESS-1 (estuarine sediment), MAG-1 (marine mud), SCo-1 (Cody shale), and NIST-1c (argillaceous limestone) to encourage future comparisons of sequential extraction results within the marine geochemical and paleoceanographic communities. We measured Si, Al, Ti, Fe, Mn, Ca, P, and Ba in sequential de-ionized water (loosely-bound), MgCl₂ (exchangeable), acetic acid (carbonate), hydroxylammonium hydrochloride (oxide), H₂O₂ (organic), Na₂CO₃ (opal), and residual (lithogenic) leaches. The protocol and selected elements were tailored to be most relevant to paleoceanographic geochemical studies instead of to environmental studies. Our results show that the sequential extraction procedure faithfully yields elemental distributions that are consistent with individual SRM lithologies. Our results also show that the procedure is typically reproducible within approximately 15%. However, in almost all cases, the procedure suffers from a systematic under-recovery of material when compared with the certified, bulk chemical analysis, and the under-recovery appears to be related to the lithology of the SRM. Similar under-recovery appears to be typical of sequential extraction procedures as reported by other previous studies. While this is problematic in assessing closure, it does not diminish the potential of inter-lab comparisons and first-order accuracy comparisons. We found that the elemental totals for the sequential extractions of MAG-1 compared best with the certified, bulk totals, and we recommend using this SRM to facilitate future accuracy assessments and inter-lab comparisons.     

Crystals and Life

The record of life's emergence on Earth has been thoroughly obliterated by the remelting and turnover of the crust, soggy and pliable from the water, retained by the planet's gravitational field. Provided that life existed on a smaller body such as Mars with an arrested crustal evolution, a protected sedimentary record there may give clues to the decisive events in the first 500 million years in the history of our solar system. Until such records become available, we have in our guesswork to rely on laboratory constructions that need to satisfy the demands both of chemical feasibility and environmental boundary conditions. The combination leaves few survivors among competing hypotheses. As life entails a decrease in entropy and creation of order, the origin and propagation of crystalline order has become a guiding theoretical concept. Recognizing Jack Dunitz's fundamental contribution to this field of knowledge, I wish to dedicate my modest discourse to this great scientist upon his scoring of the fourth significant time mark on the staff of life.     

离子吸附型稀土高效提取和分离技术进展

离子吸附型稀土资源(或称风化壳淋积型稀土资源)由于中重稀土含量高而得到国内外的广泛重视。对该类资源的开采和分离加工技术以及相关的环境保护问题进行了述评和讨论,包括矿山提取技术、萃取分离技术、沉淀结晶分离技术、材料前躯体制备技术和环境水处理技术。针对矿山开采中的主要问题,提出了该类稀土实现资源与环境保护性开采的环境工程模式及其对应的技术内涵;根据稀土市场和环境保护要求,讨论了离子吸附型稀土开发过程中今后需要开展的研究工作。     

Amorphous Metal–Organic Framework-Dominated Nanocomposites with Both Compositional and Structural Heterogeneity for Oxygen Evolution

Amorphous metal–organic frameworks (aMOFs) are an emerging family of attractive materials with great application potential, however aMOFs are usually prepared under harsh conditions and aMOFs with complex compositions and structures are rarely reported. In this work, an aMOF-dominated nanocomposite (aMOF-NC) with both structural and compositional complexity has been synthesized using a facile approach. A ligand-competition amorphization mechanism is proposed based on experimental and density functional theory calculation results. The aMOF-NC possesses a core–shell nanorod@nanosheet architecture, including a Fe-rich Fe-Co-aMOF core and a Co-rich Fe-Co-aMOF shell in the core–shell structured nanorod, and amorphous Co(OH)₂ nanosheets as the outer layer. Benefiting from the structural and compositional heterogeneity, the aMOF-NC demonstrates an excellent oxygen evolution reaction activity with a low overpotential of 249 mV at 10.0 mA cm⁻² and Tafel slope of 39.5 mV dec⁻¹.     

Evidence for the Formation of Trioctahedral Clay upon Sorption of Co(2+) on Quartz

The sorption mechanism of Co on quartz at room temperature has been investigated by an in-depth analysis of published extended X-ray absorption fine structure (EXAFS) spectroscopy and solution chemistry data. In particular, the 3.5-5 ? mid-range atomic environment of Co has been determined with unprecedented precision by combining ad initio FEFF7.02 calculations and results obtained by polarized EXAFS on the mid-distance structure of sheet silicate minerals. The local atomic environment around sorbed Co atoms is identical to that of Co in trioctahedral clays and substantially different from that in the cobalt hydroxide Co(OH)(2(s)). Neoformation of a trioctahedral clay is consistent with calculated thermodynamic solubilities, which indicate that 2:1 and 1:1 Co-rich hydrous silicates, similar to kerolite and chrysotile, are less soluble than Co(OH)(2(s)). Consequently, precipitation of Co-rich clay is favored over that of Co(OH)(2(s)) at pH values below 9 and for a dissolved Si concentration equal to quartz solubility. New experimental data show that dissolved Si concentrations can approach, and even exceed, that of quartz solubility during the short times of sorption experiments. Based on the available data, it is not possible to conclude unequivocally if the Co layer silicate grew epitaxially on the quartz surface, topotactically in a surface amorphous layer, or independently of the quartz framework structure. The structural and chemical interpretation is supported by recent published studies in which sorption of a hydrolyzable cation leads to the neoformation of a mixed layer phase formed from the sorbate species and the sorbent metal. This surface-induced precipitation mechanism is a general phenomenon that may account for the formation of secondary clays as coatings on silicates. Copyright 1999 Academic Press.     

罗布泊地区环境样品中的放射性检测

随着核能的开发应用,研究环境中铀、钍、钾等长寿命放射性核素的放射性水平,对保护公众安全和生态环境具有重要意义。采用中子活化分析方法,对罗布泊地区环境样品作了放射性检测。根据该样品的比活度以及该样品的元素丰度与中国大陆地壳元素丰度的比较,表明罗布泊地区的地质放射性无明显的放射性异常,并可以作为建筑材料使用,符合GB6566-2001标准。     

Evidence for the Formation of Trioctahedral Clay upon Sorption of Co on Quartz

The sorption mechanism of Co on quartz at room temperature has been investigated by an in-depth analysis of published extended X-ray absorption fine structure (EXAFS) spectroscopy and solution chemistry data. In particular, the 3.5–5 Å mid-range atomic environment of Co has been determined with unprecedented precision by combining ad initio FEFF7.02 calculations and results obtained by polarized EXAFS on the mid-distance structure of sheet silicate minerals. The local atomic environment around sorbed Co atoms is identical to that of Co in trioctahedral clays and substantially different from that in the cobalt hydroxide Co(OH)_2(s). Neoformation of a trioctahedral clay is consistent with calculated thermodynamic solubilities, which indicate that 2:1 and 1:1 Co-rich hydrous silicates, similar to kerolite and chrysotile, are less soluble than Co(OH)_2(s). Consequently, precipitation of Co-rich clay is favored over that of Co(OH)_2(s) at pH values below 9 and for a dissolved Si concentration equal to quartz solubility. New experimental data show that dissolved Si concentrations can approach, and even exceed, that of quartz solubility during the short times of sorption experiments. Based on the available data, it is not possible to conclude unequivocally if the Co layer silicate grew epitaxially on the quartz surface, topotactically in a surface amorphous layer, or independently of the quartz framework structure. The structural and chemical interpretation is supported by recent published studies in which sorption of a hydrolyzable cation leads to the neoformation of a mixed layer phase formed from the sorbate species and the sorbent metal. This surface-induced precipitation mechanism is a general phenomenon that may account for the formation of secondary clays as coatings on silicates.