辽宁赛马碱性岩体异性石化学成分特征及其蚀变组合对碱性岩浆-热液演化的指示意义

辽宁赛马碱性岩体早年因产铀矿而闻名,该岩体主要由响岩、霞石正长岩和异霞正长岩组成,其中铀、锆和稀土等元素矿化主要集中于异霞正长岩岩浆阶段。异性石是异霞正长岩中特征的锆-稀土矿物,主要分为两期,晚期异性石表现出更加富集Nb、REE等高场强元素的特点。早期异性石经历了一系列的热液蚀变,根据蚀变强弱程度,蚀变矿物组合可分为:(1)异性石+钠锆石+霓石±钠沸石;(2)异性石+钠锆石+锆石+钠沸石±霓石;(3)异性石假晶,假晶主要由残余异性石+钠锆石+锆石+钠沸石+霓石+钾长石+铈硅磷灰石组成。相比于岩浆锆石,蚀变组合中次生锆石具有富Ca、Al、Fe的特点,与异性石本身化学成分和流体性质密切相关。通过对异性石及其蚀变组合的精细矿物学研究,我们得知假晶的形成可能是异性石"溶解-再沉淀"的结果,致使假晶形成的流体至少包括:(1)占主导的富Na(±K)、Al、F的自交代流体;(2)少量晚期富Ca流体。假晶中次生锆石和铈硅磷灰石的结晶说明了Zr和REE等高场强元素的热液活动性,自交代碱性流体和富Ca流体在此过程中起到"搬运"和"提纯"的作用,这对认识碱性岩稀有、稀土成矿机制具有重要的指示意义。     

湘江下游河床沉积物元素地球化学背景值估算

本研究对湘江下游河床沉积物进行了元素地球化学分析,在认识沉积物元素地球化学特征、甄别人为源与自然源重金属的基础上,估算了沉积物的元素地球化学背景值。结果表明:SiO2、TiO2、Al2O3、Fe2O3、K2O等主量元素及V、Co、Cr、Ba、Sc、U、Sr、Ga、Ge、Rb、Nb、Y、REE等微量元素在沉积物中含量变化相对稳定(Cv<0.2),分布相对均匀,且富集不明显(EF<2.0,Sr明显亏损)。而MnO、MgO、CaO、Na2O、P2O5等主量元素,及Cd、Mn、Cu、Pb、Zn等重金属在沉积物中含量变化大(Cv>0.25),分布极不均匀,且沉积物中重金属明显富集(EF>2.0)。主成分及Pearson线性相关性分析显示,沉积物中不明显富集的微量元素主要赋存于难溶硅酸盐矿物相中,为自然源元素。而沉积物中显著富集的重金属主要赋存于铁—锰氧化物等矿物相中,为有人为源叠加的元素。故针对不同来源特征的元素用不同的方法进行了背景值计算,求得沉积物中47个元素的背景值。再利用元素比值等方法对所得背景值进行检验。结果表明,本文得到的湘江沉积物元素背景值合理,可用作流域沉积物重金属污染评价参考。     

Pyroxenite xenoliths and clinopyroxene megacrysts from the Cenozoic Jbel Saghro Volcanic Field (Anti-Atlas,Morocco): Petrography,mineral chemistry and equilibration conditions

A suite of mafic pyroxenite xenoliths and clinopyroxene megacrysts was brought to the surface by Cenozoic nephelinites of the Jbel Saghro Volcanic Field (Anti-Atlas, Morocco). The large population of samples was subdivided into five groups: (i) clinopyroxenites sensu stricto; (ii) olivine clinopyroxenites; (iii) mica-bearing clinopyroxenites; (iv) kaersutite-bearing clinopyroxenites; (v) clinopyroxene megacrysts. These xenoliths display a cumulate texture (adcumulate, heteradcumulate with poikilitic clinopyroxene including olivine). The clinopyroxenes have the composition of augite and show an appreciable variation of MgO (7.02–14.80 wt.%), TiO₂ (0.58–5.76 wt.%) and Al₂O₃ (2.81–12.38 wt.%) contents in grains. The clinopyroxenes are characterized by convex upward chondrite-normalized REE patterns, they display very similar trace element compositions with low contents of incompatible elements such as Rb (0−0.9 ppm), Ba (0.1–8.3 ppm), Th (0.1−0.3 ppm), U (0.01−0.04 ppm) and Nb (1.3–3.2 ppm). REE contents of the calculated melts in equilibrium with the clinopyroxene megacrysts and clinopyroxene from pyroxenite xenoliths are similar to those of the nephelinites exposed in Jbel Saghro. Crystallization temperatures of pyroxenite xenoliths and clinopyroxene megacrysts range from 950 °C to 1150 °C. Clinopyroxene barometry yielded pressure of crystallization ranging from 0.4 to 0.8 GPa for pyroxenite xenoliths and 0.3 to 0.7 GPa for clinopyroxene megacrysts. This pressure range is in agreement with pyroxenite xenoliths and clinopyroxene megacrysts being crystallized from their parental melts at the lower and upper crust.     

Geochemical constraints on the distribution of trace elements and volatiles in fluorapatite from the Panasqueira tin-tungsten deposit (Portugal)

A large, euhedral crystal of fluorapatite (ca. 19.5 × 20.0 mm) from the Panasqueira tin-tungsten deposit (Portugal) was investigated in terms of the distribution of trace elements by using several microanalytical techniques. The studied material represents almost pure fluorapatite with minor amounts of other cations (mainly Sr, Mn, REE and Fe), OH and Cl. Particular interest was given to the distribution of rare earth elements with respect to the crystallographic orientation. A broad range of analytical techniques were used, including optical microscopy coupled with cathodoluminescence imaging, electron probe microanalysis (EPMA), laser ablation – inductively coupled plasma mass spectrometry (LA-ICPMS), Raman microspectroscopy, and simultaneous thermal analysis coupled with mass spectrometry. The investigated crystal consists of the main crystal with a distinct core and rim (Ap_2core and Ap_2rim, respectively), which grew on a previous, euhedral crystal (Ap₁). The fluorapatite demonstrates various types of zoning: regular oscillatory, irregular, and internal sectoring, which is also reflected in trace elements concentrations. The rim Ap_2rim has lower concentrations of Mn, Sr and Fe, and significantly higher concentrations of REE compared to the core Ap_2core and older crystal Ap₁. Furthermore, the rim Ap_2rim is strongly depleted in Th, U and Pb. The entire crystal shows elevated Eu contents, expressed as a strong positive anomaly in chondrite-normalized REE patterns. With regards to the volatiles, F concentrations are constant in Ap₁, Ap_2core and Ap_2rim, whereas Cl is below the EPMA detection limit. The Ap_2rim was the only part of the investigated material containing OH and CO₃, which were observed in the Raman spectra. Furthermore, part of the crystal Ap_2core is extensively altered, likely due to fluid-induced metasomatic processes. LA-ICPMS U-Pb dating yielded highly discordant dates due to common Pb content. A lower intercept age of 297 ± 13 Ma (MSWD = 0.13) indicates the age of the fluorapatite crystallization. The overall analytical data constrain growth and post-growth processes, including crystallization of Ap₁ and Ap_2core, which both have typical hydrothermal Sn-W deposit characteristics, whereas Ap_2rim is related to a carbonate stage of the mineralization in the Panasqueira deposit.     

Chemical oceanographic influences on sediment accumulations of a carbonate ramp: Holocene Yucatan Shelf,Mexico

Global controls on the oceanographic influences on the nature of carbonate factories are broadly understood. The details of the influences of changes in temperature and nutrients across individual carbonate shelves are less well constrained, however. This study explores spatial and temporal variations in chemical oceanography along and across the Yucatan Shelf, a modern carbonate ramp, and how these factors relate to variable bottom character, sediment and sediment geochemistry. In‐situ sensors and remote‐sensing data indicate the sporadic presence of cool, upwelled water with low dissolved oxygen and elevated Chlorophyll‐a. This current‐driven, westward flow of upwelled water is most evident in a zone just offshore of the northern peninsular shoreline, but its influence wanes ca 75 km offshore and as the shore turns southward. The impacts of this water mass include a transitional photozoan–heterozoan assemblage with biosiliceous components, relict grains and common thin Holocene sediment accumulations nearshore; further offshore are coralgal reefs and expansive sand plains. Geochemical proxies of bulk sediment, including high δ¹⁸O and elevated HREE/LREE (heavy rare‐earth element/light rare‐earth element) ratios near, and downcurrent of, the upwelling source, are interpreted to represent the signal of nearshore, westward movement of the cool and nutrient‐rich, upwelled water. Collectively, these data emphasize how local processes such as upwelling and longshore transport can variably influence carbonate sediment accumulations and their geochemical signatures, both along and across individual shelves. These data and insights provide an analogue for the influences of spatial variability of water masses in the geological record, and for accurate interpretation of stratigraphic changes of sedimentary and geochemical proxy data in carbonate archives.     

微波等离子体原子发射光谱法测定偏远矿区海泡石中的主微量元素

海泡石是具有层状结构的含水富镁硅酸盐黏土矿物,其中无机元素含量是揭示其成矿物质来源、成矿流体性质和矿床成因的重要依据,通常采用电感耦合等离子体发射光谱/质谱法(ICP-OES/MS)进行测定,等离子体(ICP)的高温激发会产生成大量谱线干扰,维持ICP稳定工作需使用高纯氩气,持续供气对于偏远矿区海泡石的检测还将面对气体采购和运输不便的问题。本文基于微波等离子体原子发射光谱(MP-AES)的低温激发技术减少光谱干扰,建立了准确测定偏远矿区海泡石中主量元素Mg、Al、Ca、Fe、K、Na和微量元素Cu、Zn、Mn、Pb含量的分析方法。利用硝酸-盐酸-氢氟酸混合酸对海泡石进行微波消解,避免了样品处理过程中分析元素的损失,加快了样品处理速度,同时提高了样品溶液的稳定性。通过选择各元素光谱线的分析波长,并利用快速线性干扰校正(FLIC)技术校正光谱干扰,以Lu为内标元素校正基体效应,提高了灵敏度和准确度。各元素的检出限为0.19～14.6μg/L。海泡石国家标准物质(GBW07138)各元素测定值与认定值的相对误差在-5.0%～6.7%之间。本方法具有检出限低、线性范围宽、结果准确等优点;MP-AES采用自带的氮气发生器为等离子体提供氮气作为工作气,无需引入复杂气体,提高了分析效率,尤其适用于气体采购和运输不便的偏远矿区。     

滇东南都龙超大型锡锌多金属矿床黄铁矿LA-ICPMS微量元素组成研究

滇东南马关都龙是一个以锡锌为主,共-伴生铟、铜、铅、钨、铁、银等多种元素的锡锌多金属超大型矿床。虽然前人从矿物学、矿床地球化学、年代学等不同角度开展了较多的研究,该矿床锡锌多金属矿化为燕山晚期岩浆热液活动的产物已是不争的事实,但关于该矿床是否存在热水沉积作用及其与锡锌多金属成矿作用的关系依然存在较大争议。本文选取都龙矿区广泛存在的黄铁矿作为主要研究对象,在矿相学基础上利用LA-ICPMS对不同阶段黄铁矿的微量元素组成开展了系统的研究。野外及显微鉴定结果表明,矿区存在四种类型(期次)的黄铁矿,即:鲕状黄铁矿Py1;穿切或交代Py1的细脉状黄铁矿Py2;与闪锌矿等硫化物共生的自形黄铁矿Py3;包裹早期黄铁矿或闪锌矿等硫化物的他形黄铁矿Py4。LA-ICPMS分析结果表明,该矿床黄铁矿中富集多种微量元素,其中Co、Ni、As、Ge等元素以类质同象的形式存在黄铁矿晶格中,而其余元素多以显微矿物包体形式赋存于黄铁矿中。上述四期黄铁矿微量元素组成存在较大差别,Py1相对富集Zn和As,而其余微量元素含量较低,Co与Ni含量较低,Co/Ni比值远低于1.00,其微量元素组成与典型沉积作用形成黄铁矿基本一致; Py2与Py1具有相似的微量元素组成特征,其Co/Ni比值接近Py1变化范围; Py3和Py4除富集Zn、As外,Mn、Co、Ni、Cu、Sb、Pb、Bi元素含量也相对较高,其Co/Ni比值相对较高,多大于1,与典型岩浆热液型黄铁矿微量元素组成相似,而与沉积型黄铁矿差异明显。结合各阶段黄铁矿产出地质特征,对比不同类型黄铁矿微量元素组成,本研究认为:Py1鲕状黄铁矿为热水沉积作用形成; Py2为Py1变质改造形成的细脉状黄铁矿,其微量元素继承了Py1; Py3为岩浆热液活动形成的自形黄铁矿; Py4为岩浆热液活动晚期形成的他形黄铁矿,Ag和Bi组成作为区分不同成因类型黄铁矿的化学指标的潜力。矿区早期沉积作用形成鲕状黄铁矿过程可能为后期成矿作用提供了部分硫源及少量Zn等成矿物质,海西-印支期区域变质改造作用对矿区成矿作用影响不大,而燕山晚期岩浆热液活动才是矿区锡多金属大规模成矿作用的主导因素。     

下庄竹山下铀矿床黄铁矿元素地球化学特征及其表征意义

竹山下铀矿床是粤北下庄铀矿田内大型铀矿床之一,铀矿化类型为"交点"型和硅化带型。在详细的野外地质调查基础上,对竹山下铀矿床4种不同类型黄铁矿进行元素含量分析及硫同位素测试,结果表明:"交点"型矿石中黄铁矿相对富集Pb、 Cu、 Co、 As、 Ni、 Se、 Bi、 U、 Sb、 Zn等微量元素;"交点"型铀矿化形成于中深部高温环境,成矿热液具有地幔流体特征,成矿过程硫来源与该区花岗岩中黄铁矿的硫来源一致或者相似,花岗岩中的黄铁矿可能为该期成矿事件的产物;竹山下矿床在垂向上表现出越往深部硫逸度越低的特征;"交点"型和硅化带型中黄铁矿具有相似的微量元素配分曲线,表明二者具有相同的成矿热液来源,且与辉绿岩中黄铁矿配分曲线相似,表明该区成矿热液具有深源性。     

关键元素与生命健康:中国耕地缺硒吗?

地球上的生命和非生命都是由自然界已发现的92种化学元素组成的,通过全国土壤地球化学基准值与人体血液元素含量对比研究,发现血液中40~50种化学元素平均值与土壤地球化学基准值的分布高度一致,表明这些关键元素与生命息息相关。近年大家持续关注的硒(Se)元素是人体必需的微量元素,缺乏会产生健康风险,但摄入过量也会导致中毒,因此被称为健康窗口元素。过去研究认为,中国耕地缺硒是造成健康危害的原因之一。本文通过对全国3 382个网格化点位土壤采样,获得Se的地球化学基准值和空间分布数据,发现中国贫硒国土面积,按照世界卫生组织推荐值(0.1 mg/kg)和中国规范(0.125 mg/kg)计算,分别占21.1%和31.6%;适宜区(0.125~0.40 mg/kg)面积大约555万km²,占国土面积约57.1%;富硒区(>0.40 mg/kg)面积达110万km²,占国土面积约11.2%。贫硒国土主要分布在青藏高原和内蒙古局部地区,而中国9大平原的粮食主产区耕地总体上不缺硒,其中珠江三角洲平原、广西平原、成都平原、长江中下游平原是富硒区(>0.40 mg/kg),华北平原、东北平原、三江平原、关中平原是硒边缘区-适量区(0.125~0.40 mg/kg),只有河套平原是缺硒区(<0.125 mg/kg)。根据覆盖全国的网格化土壤采样分析结果,发现低硒带呈不连续的片状分布于内蒙古东部至青藏高原一带,与传统认为“低硒带分布于东北三省至西南云贵高原”不完全一致。硒的空间分布模式主要受地质背景、岩石类型、土壤类型和自然地理景观控制。     

Hydro-geochemistry of groundwater and surface water in Dschang town(West Cameroon): Alkali and alkaline-earth elements ascertain lithological and anthropogenic constraints

This study focuses on the sources of alkali and alkaline-earth elements based on the geochemistry of groundwater and surface water in Dschang concerning environmental and anthropogenic constraints. A comprehensive set of 50 samples from groundwater and surface water were analyzed by ICPMS and processed by spatial interpolation in a GIS environment. The results highlight a geochemical anomaly at the center of the densely inhabited area subject to a profusion of open dumps discharges. This anomaly with the highest spatial contents of Be(Cs, Rb, Mg) suggests an anthropogenic source that demarcates with the lowest alkali and alkaline-earth elements on the peripheral area of Dschang. Other findings include lithological constraints with volcanic rocks being the main source compared to granitoid.The study points out good correlations between Be, Cs, Rb and Mg spatial distributions and physicochemical parameters of waters(K, EC, TDS), and inversely with the lowest p H. p H is established as the most functioning physico-chemical constraint of alkali and alkaline-earth mobility in Dschang. The p H lowest values within the geochemical anomaly also highlight the impact of human activities on water acidity, which later enhance elements mobility and enrichment. Despite low elements contents relative to WHO standards, our findings point out an example of anthropogenic impact on water geochemistry linked to solid waste pollution; it also demonstrates significant anthropogenic changes of environmental physicochemical parameters of prime importance in the mobility and distribution of elements in the study area.Similar assessments should be extended in major towns in Cameroon.