黄河下游山东段沿岸土壤中重金属元素异常的成因

山东省多目标区域地球化学调查发现,沿黄河两岸分布有As、Cd、Cr、Cu、Pb、Zn、Ni等重金属元素异常,这类异常衬度不大,并多沿河呈不连续分布。研究结果表明,异常区土壤重金属元素的含量与SiO2、Al2O3Fe2O3等常量组分间具有显著的相关性,多数微量重金属元素随SiO2含量的增加而降低,随Al2O3Fe2O3含量的增加而增加。根据常量组分与土壤质地的密切关系可以推断。土壤质地对重金属元素异常的形成具明显的控制作用。     

山东灵山岛青山群硅质岩的地球化学特征及地质意义

山东东部灵山岛地区发育一套火山碎屑岩、硅质岩、火山碎屑岩夹火山弹的特殊沉积层,为查明这套地层中硅质岩的形成原因及其大地构造背景,对硅质岩进行岩相学和地球化学分析。结果表明,研究区SiO2平均含量为70. 08%,Fe/Ti、(Fe+Mn)/Ti、δEu、Ba/Sr、Ni/Co及地球化学示踪投影指示其为热水成因;Al/(Al+Fe+Mn)、Al2O3/(Al2O3+Fe2O3)、MnO/TiO2、V/Cr、Ni/Co、Th/Sc、U/Th、δCe、(La/Ce)N表明其形成于大陆边缘环境;K2O/Na2O、Al2O3/TiO2、SiO2/Al2O3、SiO2/MgO、Ni/Co值暗示其形成与火山作用有关。研究区硅质岩应为热水成因,且形成过程中受到陆源物质和火山作用的双重影响,形成于大陆边缘裂谷沉积环境。     

黎塘岩溶区土壤铁锰结核的地球化学特征研究

对黎塘岩溶区土壤铁锰结核的地球化学特征研究表明:与土壤相比,铁锰结核的化学组成中仍以SiO2、Al2O3和Fe2O3为主,但Fe2O3的含量明显增加,成为铁锰结核中含量最多的氧化物,MnO含量也有一定程度增加,它们富集系数分别为5．19和3．40;铁锰结核对重金属具有明显的富集效应,其富集顺序为Cr（M）〉Pb〉Co〉Zn〉Ni〉Ba〉Li,它在土壤中的含量受成土母质及浅层地下水活动的影响。元素的相关分析及因子分析表明,铁锰结核在形成过程中还具有成核富集效应、专性吸附效应和成核易淋溶效应。      

贵州松桃道坨锰矿含锰岩系地球化学特征 和沉积环境分析

道坨锰矿床是贵州锰矿整装勘查过程中新发现的全隐伏超大型锰矿床,其含锰岩系赋存于南华系大塘坡组第一段底部黑色页岩中,呈层状、似层状、透镜状产出。对含锰岩系主量及微量元素地球化学特征分析:其V/(V+Ni)、V/(V+Cr)、V/Cr、Ce/La值,及U、V、Ni、Mo等氧化还原敏感元素的富集程度显示其形成于缺氧环境。含锰岩系富集As、Mo、Ag、Sb,及Al/(Al+Fe+Mn)、(Fe+Mn)/Ti、Co/Zn值均显示热水沉积物特征,且在(Cu+Ni+Co)×10—Fe—Mn、Co/Zn—(Cu+Ni+Co)关系图解中,岩矿样品投影点均落在热水沉积区内,反映了热水作用对锰的富集和成矿影响甚重。此外,Al2O3/(Al2O3+Fe2O3)、Al/(Al+Fe)、Al/(A1+Fe+Mn)、(La/Ce)N值及(K2O+NaO2)—SiO2、La/Ce—Al2O3/(Al2O3+Fe2O3)图解指示含锰岩系形成于被动大陆边缘背景。     

Minipal 4便携式能量色散X射线荧光光谱仪在勘查地球化学中的应用

使用粉末样品压片制样，用Minipal 4便携式能量色散X射线荧光光谱仪测定化探样品尹的Na2O、MgO、Al2O3、SiO2、CaO、Fe2O3、K2O、As、Ba、Br、Ce、Co、Cr、Cu、Ga、La、Mn、Nb、Ni、P、Pb、Rb、Sr、Th、V、Y、Zn、Zr、Ti、Mo等30种组分。方法简便、快速，分析结果的精度和准确度能满足野外现场分析的要求。     

新疆达坂城西南一带奇尔古斯套组硅质岩地球化学特征及成因讨论

奇尔古斯套组硅质岩SiO2含量较高,Al2O3、TiO2含量变化较大,反映出较多的外来物质的加入;Si/ (Al+Fe+Mn)、Al/ (Al+ Fe+ Mn)、MnO/TiO2、Al2 O3/(Al2 O3+ Fe3 O2)值较高,反映其为生物化学成因,形成于大陆边缘环境;Fe2O3/TiO2对Al2O3/(Al2 O3+ Fe2O3)图解同样说明其形成于大陆边缘环境.REE较高,HREE富集不明显,北美页岩标准化后的稀土配分模式曲线较为平坦,向左倾斜不明显,(La/Ce)shale值较低,δCeshale值较高,无明显Ce负异常,反映奇尔古斯套组硅质岩属生物化学成因硅质岩,形成于大陆边缘环境; (La/Ce)shale对Al2 O3/(Al2 O3+Fe2 O3)图解亦说明其形成于大陆边缘环境.微量元素中Hf含量高,而Be、Li、Nb、Rb、Sr、Ta、Th、U、V、Zr含量低;Ba元素含量低;Co、Ni贫富相当,Co/Ni值较高,U/Th值低,说明奇尔古斯套组硅质岩属于正常的生物化学成因的硅质岩.     

X射线荧光光谱法测定多种铁矿和硅酸盐中主次量组分

采用熔融玻璃法,用Axios型X射线荧光光谱仪测定铁矿和硅酸盐中Fe2O3、SiO2、A l2O3、TiO2、CaO、MgO、SO3、MnO、V2O5、K2O、P2O5、Na2O、Co和N i等组分含量。使用理论α系数和经验系数法校正基体效应,经标准物质检验,分析结果与标准值基本吻合。用钒钛磁铁矿GBW 07225国家一级标准物质进行精密度试验,统计结果除K2O、P2O5、N i的RSD<15%,其余大多数组分的RSD<4.0%(n=12)。     

平阴县土壤中重金属元素异常成因研究

通过对平阴县周边及其西部农田区采样调查,平阴县周边元素异常具有异常衬度较高,富集系数大等特征,西部农田区异常具有各元素套合关系好,多数异常衬度不高,富集系数小的特点。结果表明,西部农田区异常是以As,Cd为主要成分的异常,元素含量与SiO2,Al2O3,Fe2O3等常量组分间具有显著的相关性,随SiO2含量的增加而降低,随Al2O3,Fe2O3含量的增加而增加,说明土壤常量组分及其所决定的土壤质地是导致异常形成的主要因素;而平阴城区异常是以S,Hg,As,Zn,Mn等元素为主的异常,是典型的人为综合因素（化工烟尘、工厂污水、生活垃圾）产生的异常。     

河南济源大峪槐圪塔岭二叠—三叠系元素地球化学特征及古环境

本文对河南济源盆地大峪槐疙瘩岭二叠系上石盒子组(P3sh)、孙家沟组(P3s)和三叠系刘家沟组(T1l)剖面岩石样品进行了元素、频率磁化率、碳酸盐以及总有机质等的分析研究,结果表明在二叠系孙家沟组(P3s)底部济源动物群化石层、以及三叠系刘家沟组(T1l)底部界线(P/T)附近,其微量和常量元素发生了较明显的变化。化石层中Ba,Cr,Hf,Nb,Th,Ti,V,Y,Tl,Zn,Cu,Ga,Pb,Ni,La,Rb,Nd,以及K2O,Al2O3,Fe2O3含量相对较高,Zr,W,Sr,Bi,Co,Ce,以及SiO2,Na2O含量较低,MgO,CaO,Mn则没有明显的变化。Ba,Hf,Nb,Th,Ti,V,Y,W,K2O,Al2O3,SiO2,Na2O,Bi,Fe2O3,Ni,Co,La,Nd,Ce,及有机碳含量在三叠系底部含量明显上升,Cu,Ga,Pb,Tl,Zn,Cr,Zr,Sr,MgO,CaO,以及岩石频率磁化率Xfd、碳酸盐含量则明显下降。该剖面不仅记录了二叠—三叠纪的生物灭绝事件,而且有明显的二叠—三叠系界线,事件及界线的形成可能与沉积环境和古气候有关,水体的变浅、炎热气候和风化作用加强可能是直接的原因。石盒子组(P3sh)主要为河流—三角洲沉积环境,古气候相对温暖湿润;孙家沟组(P3s)为三角洲平原相,前期和后期有强烈风化作用,并且炎热多雨。中期则水平面上升,水下三角洲前缘砂质沉积为主;三叠系刘家沟组(T1l)则水体进一步扩张,气温相对下降。     

X射线荧光光谱法测定多目标地球化学调查样品中主次痕量组分

采用低压聚乙烯镶边垫底的粉末样品压片制样,用PW2440X射线荧光光谱仪对多目标地球化学调查样品中Na2O、MgO、Al2O3、SiO2、P、K2O、CaO、Ti、Mn、Fe2O3、Co、Nb、Zr、Y、Sr、Rb、Pb、Th、Zn、Cu、Ni、V、Cr、Ba、La等组分进行测定。重点讨论了微量元素的背景选择和谱线重叠校正问题。使用经验系数法和康普顿散射线作内标校正基体效应,经标准物质分析检验,结果与标准值吻合,用GBW07308和GBW07310水系沉积物国家一级标准物质作精密度试验,统计结果RSD(n=12)除La、Cr、Co和Th<14.00%以外,其余各组分均小于6.00%。     

富碲马营矿[Ir（Te,Bi）2]——马营矿的新变种

富碲马营矿产在纯橄榄岩铬矿体中。在铝矿石及矿体附近的砂矿中均可找到。呈粒状自形结构,直径0．01～0．15mm。与硫铱矿（IrS2）、双峰矿、高台矿、马营矿及（Fe,Ni）9Cu3Ir6S20等紧密共生。有的呈脉状,宽0．1～0．2mm,长1．2mm。金属光泽。不透明,钢灰色,粉末黑色。HM＝3．7。VHN50＝161kg／mm2（范围132～215kg／mm2）。无解理。无断口。性脆。计算密度为12．2g／cm3。反射色亮白带淡黄色调,内反射无,均质性,双反射与反射多色性无。5个电子探针分析数据平均为（％）：Cu0．3,Te32．9,Ir34．7,Pt2．7,Bi28．2,总量98．9。实验式根据原子数3计算为：（Ir(0．92)Pt(0．92)Cu(0．01)）;(1．00)Bi(0．68)Te(1．31)。简化后的理论式为Ir（Te,Bi）2,而（Ir：Bi：Te＝3：2：4）。6条富碲马营矿是强X射线衍射hki、d、I为：210,2．89（60）;311,1．95（100）;511,1．246（70）;520,1．204（60）;440,1．145（60）;533,0．9891（60）。根据X射线粉晶指标化求得马营矿为等轴晶系,空间群：Pa3,a＝0．6486（4）um,V＝0．2729nm3,Z＝4。富碲马营矿是本文作者对马营矿研究的继续与补充。     

X射线荧光光谱法快速分析镁质耐火材料中硅铝铁钛钙镁

采用X射线荧光光谱法快速测定镁质耐火材料（包括原料镁砂及其制品镁砖）中的SiO₂、Al₂O₃、Fe₂O₃、TiO₂、CaO、MgO等6种组分。利用粉末直接压片法制取试样,确定仪器最佳参数,系列标样建立工作曲线,经验系数法对基体效应进行校正。对于主次组分,方法精密度低于5%（n=10）。方法用于实际样品的测定,结果与实验室化学法和其他单位的X射线荧光光谱法相符。方法适用于厂矿企业大批量生产的镁质耐火材料化学组成分析。     

Crystal structures and cation distributions in simple spinels from powder XRD structural refinements: MgCr2O4, ZnCr2O4, Fe3O4 and the temperature dependence of the cation distribution in ZnAl2O4

The crystal structure and cation distributions in the spinels MgCr₂O₄, ZnCr₂O₄, Fe₃O₄ and a suite of ZnAl₂O₄ samples annealed at 900 to 1400° C and then rapidly quenched, have been determined by powder X-ray diffraction, using several different X-ray procedures and both conventional structure-factor refinement and whole-pattern (or Rietveld) refinement methods. The chromite spinels are expected from crystal chemical considerations to have an almost completely normal cation distribution (inversion parameter, x, equal to zero). In agreement with this expectation, three samples of MgCr₂O₄ annealed at 900, 1100 and 1300° C, and ZnCr₂O₄ were all found to have x=0 within two estimated standard deviations (esd), suggesting that the accuracy with which cation distributions in spinels may be determined by powder XRD is close to the estimated precision. Slightly better results are obtained assuming neutral-atom scattering curves rather than half-ionized or fully ionized, but the differences are small (within the esd). The results from the Rietveld refinements are similarly in good agreement with those using the conventional structure factor refinement approach (agreement within the combined esd's), although in detail the Rietveld procedure sometimes produces small systematic differences in refined parameters. The suite of ZnAl₂O₄ spinels show a smooth increase in x from 0.01 at 900° C to 0.05 at 1300° C, and this behaviour is well described by the simple thermodynamic model for disordering in spinels with α_Zn-Al=89 kJ/mol, assuming β=?20 kJ/mol. The oxygen positional parameters for Fe₃O₄ are similar to those from published single crystal studies, indicating that the powder method also yields accurate interatomic distances in spinels.     

Surinamite analogs in the MgO-Ga2O3-GeO2 and MgO-Al2O3-GeO2 systems

New germanate analogs of the mineral surinamite, Mg₃Al₄BeSi₃O₁₆, have been synthesized with composition Mg₄A₄Ge₃O₁₆ (A=Al, Ga) and have been characterized by powder X-ray diffraction and transmission electron microscopy. The Al surinamite phase crystallizes with a primitive unit-cell (P2/n, a=10.153(1), b=11.708(2), c=9.920(1) Å, β=110.18 (2)° and Z=4) similar to that of the silicate mineral. The Ga surinamite-like phase crystallizes with a larger unit-cell (C2/c, a=10.308(2), b=23.690(5), c=10.057(l) Å, β=110.23 (2)° and Z=8). High-resolution electron microscopy has shown the common formation of intergrowths between the surinamite and sapphirine structures, illustrating the polysomatic structural relationship between them. Observations of disordered microstructures in the Al surinamite suggest the occurrence of a P2/n?C2/c transformation.     

A Preliminary Study on the Preparation of Four Pacific Ocean Polymetallic Nodule and Sediment Reference Materials: GSPN-2, GSPN-3, GSMS-2 and GSMS-3

The research project for the preparation of two polymetallic nodule (GSPN-2, GSPN-3) and two marine sediment (GSMS-2, GSMS-3) reference materials was completed in 1996. The samples were collected from the Eastern and Central Pacific Ocean and prepared to less than 74 μm fine powder. The homogeneity of the materials was tested by X-ray fluorescence spectrometry. The relative standard deviations (RSD %) of measurements of selected elements in samples taken from thirty bottles selected at random were less than 0.5%. Thirty four laboratories worldwide participated in the collaborative analysis programme. The number of elements or constituents analysed was seventy nine for nodules and eighty one for sediments. Among those, sixty three elements were certified in each sample. The sum of major elements or components is 99.7% for GSPN-2, 99.5% for GSPN-3, 99.8% for GSMS-2 and 99.8% for GSMS-3.     

Abramovite, Pb2SnInBiS7, a new mineral species from fumaroles of the Kudryavy volcano, Kurile Islands, Russia

Abramovite, a new mineral species, has been found as fumarole crust on the Kudryavy volcano, Iturup Island, Kuriles, Russia. The mineral is associated with pyrrhotite, pyrite, würtzite, galena, halite, sylvite, and anhydrite. Abramovite occurs as tiny elongated lamellar crystals up to 1 mm long and 0.2 mm wide (average 300 × 50 μ m), which make up chaotic intergrowths in the narrow zone of fumarole crust formed at ～600°C. Most crystals are slightly striated along the elongation. The new mineral is silver gray, with a metallic luster and black streak. Under reflected light, abramovite is white with a yellowish gray hue. It has weak bireflectance; anisotropy is distinct without color effects. The chemical composition (electron microprobe) is as follows, wt %: 20.66 S, 0.98 Se, 0.01 Cu, 0.03 Cd, 11.40 In, 12.11 Sn, 37.11 Pb, 17.30 Bi; the total is 99.60. The empirical formula calculated on the basis of 12 atoms is Pb_1.92Sn_1.09In_1.06Bi_0.89(S_6.90Se_0.13)_7.03. The simplified formula is Pb₂SnInBiS₇. The strongest eight lines in the X-ray powder pattern [d, Å (I)(hkl)] are 5.90(36)(100), 3.90(100)(111), 3.84(71)(112), 3.166(26)(114), 2.921(33)(115), 2.902(16)(200), 2.329(15)(214), 2.186(18)(125). The selected area electron diffraction (SAED) patterns of abramovite are quite similar to those of the homologous cylindrite series minerals. The new mineral is characterized by noncommensurate structure composed of regularly alternated pseudotetragonal and pseudohexagonal sheets. The structure parameters determined from the SAED patterns and X-ray powder diffraction data for pseudotetragonal subcell are: a = 23.4(3), b = 5.77(2), c = 5.83(1) Å, α = 89.1(5) °, β = 89.9(7)°, γ = 91.5(7)°, V = 790(8) ų; for pseudohexagonal subcell: a = 23.6(3), b = 3.6(1), c = 6.2(1) Å, α = 91(2)°, β = 92(1)°, γ = 90(2)°, V = 532(10) ų. Abramovite is triclinic, space group P(1). The new mineral is named in honor of Russian mineralogist Dmitry Abramov. The type material of abramovite has been deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

铂双峰矿—双峰矿的新变种

铂双峰矿产在纯橄榄岩铝矿体中。在铝矿石及矿体邻近的砂矿中均可找到。呈块状聚集体或板片状自形晶,与疏钻矿、含锇自然铱紧密共生。脉状的宽20～301μm,长400～500μm,一般10μm×20μm。金属光泽。条痕黑色。HM=3．05。VHN20=92kg／mm2（平均）。{0001}解理完全。性脆。计算密度为10．21g／cm2。反射色;亮黄白带淡蓝色。内反射无。非均质性中等,偏光色为淡蓝或淡黄。双反射或反射多色性在空气中或油中均未见。5个电子探针分析数据平均（wt％）：Cu0．2,Te57.2,Ir24.5,Pt17．2,Bi0．4,总量99．5。实验式为：（IR0．57Pt0.39Cu0.01）0．98（Te1.99Bi0.01）2.00。简化理论式为（11,Pt）Te2。4条最强X射线粉晶衍射线hkl,d,I为：101,2．87（100）;102,2．10（70）;110,1．98（60）;103,1．58O（50）。根据X射线粉晶数据进行指标化,获得铂双峰矿晶胞数据：三方晶系,P3ml,a=0．3973（5）,c＝0．5315（5）um,V＝0．0727nm3,Z=1。铂双峰矿是笔者对双峰矿研究的继续与补充。     

A Single Step Acid Assisted Microwave Digestion Method for the Complete Dissolution of Bauxite and Quantitation of its Composition (Al2O3, Fe2O3, SiO2, TiO2, Cr2O3, MgO,MnO and V2O5) by ICP-AES

An acid assisted microwave-based method for the complete dissolution of bauxite using mixture of H₂SO₄, H₃PO₄ and HF acids in a single step was developed for the determination of various analytes (Al₂O₃, Fe₂O₃, SiO₂, TiO₂, Cr₂O₃, MgO, MnO and V₂O₅) using ICP-AES. The method was validated with respect to ruggedness, linearity, trueness, precision, limit of detection (LOD), limit of quantification (LOQ), working range and measurement uncertainties by analysing a bauxite reference material (Alcan BXT-12) and four certified reference materials (IPT-131, BXBA-4, NIST SRM 600, NIST SRM 697). The expanded uncertainties obtained for Al₂O₃ (40.0%), Fe₂O₃ (17.0%), SiO₂ (20.3%), TiO₂ (1.31%), Cr₂O₃ (0.024%), MgO (0.05), MnO (0.013), and V₂O₅ (0.60%), were 0.80, 0.40, 0.50, 0.033, 0.0008, 0.002, 0.0007 and 0.002 respectively, which are fit for the intended use to characterise bauxite. The developed method was also evaluated through participation in an interlaboratory comparison exercise organised by the Jawaharlal Nehru Aluminium Research Development and Design Centre (JNARDDC), Nagpur, India, using bauxite sample (BXT-JNA), with satisfactory z-scores achieved.     

Mariinskite, BeCr2O4, a new mineral, chromium analog of chrysoberyl

A new mineral, mariinskite, BeCr₂O₄, the chromium analog of chrysoberyl, has been found at the Mariinsky (Malyshevo) deposit, the Ural Emerald Mines, the Central Urals, Russia. The mineral is named after its type locality. It was discovered in chromitite in association with fluorphlogopite, Cr-bearing muscovite, eskolaite, and tourmaline. Mariinskite occurs as anhedral grains ranging from 0.01 to 0.3 mm in size; in some cases it forms pseudohexagonal chrysoberyl-type twins. The mineral is dark-green, with a pale green streak; the Mohs’ hardness is 8.5, microhardness VHN = 1725 kg/mm². D _meas = 4.25(2) g/cm³, D _calc = 4.25 g/cm³. Microscopically, it is emerald-green, pleochroic from emerald-green (γ) to yellow-green (β) and greenish yellow (α). The new mineral is biaxial (+), γ = 2.15(1), β = 2.09(3), and α = 2.05(1), 2V _meas = 80 ± (10)°, 2V _calc = 80.5°. In reflected light, it is gray with green reflections; R _max (589) = 12.9%; R _min (589) = 12.3%, and there are strong, internal green reflections. The strongest absorption bands in the IR spectrum are as follows (cm^?1): 935, 700, 614, 534. Space group Pnma, a = 9.727(3), b = 5.619(1), c = 4.499(1) Å, V = 245.9(3) ų, Z = 4. The strongest reflections in the X-ray powder diffraction pattern are as follows (d Å, I, hkl): 4.08(40)(101), 3.31(90)(111), 2.629(50)(301), 2.434(50)(220), 2.381(40)(311), 2.139(60)(221), 1.651(100)(222). The average chemical composition of mariinskite (electron microprobe, wt %) is as follows: BeO 16.3, Al₂O₃ 23.89, Cr₂O₃ 58.67, Fe₂O₃ 0.26, V₂O₃ 0.26, TiO₂ 0.61, total is 99.98. The empirical formula, calculated on the basis of four O atoms is Be_1.03(Cr_1.22Al_0.74Ti_0.01Fe_0.01V_0.01)_1.99O₄. The compatibility index 1 ? (K_p/K_c), 0.019, is excellent. The type specimens are deposited in the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, and the Ural Geological Museum, Yekaterinburg, Russia.     

Improvements in Digestion Protocols for Trace Element and Isotope Determinations in Stream and Lake Sediment Reference Materials (JSd-1, JSd-2, JSd-3, JLk-1 and LKSD-1)

Total dissolution is a critical step in geochemical analysis. Despite the number of published protocols, this issue still draws attention for sediment samples, which are particularly difficult to dissolve due to the common occurrence and high abundance of refractory phases such as zircon. We present tests of different chemical digestion procedures carried out on reference materials (RM) of stream (JSd-1, JSd-2 and JSd-3) and lake (JLk-1 and LKSD-1) sediments from the Geological Survey of Japan (GSJ) and the Canadian Certified Reference Material Programme (CCRPM). We demonstrate that the fusion technique is not appropriate for our studies as not all elements of interest were recovered and blank levels were too high to permit further Sr and Pb isotopic composition measurements. Similarly, conventional HF+HNO₃ dissolution methods were not efficient enough for detrital samples. Our preferred method involved using high pressure Teflon® vessel bombs in association with HClO₄. This protocol ensured a complete dissolution of the powder, as well as a complete recovery of trace elements. Moreover, blank levels were sufficiently low that Sr or Pb isotope compositions could be measured from the same mother solution. We also tested the homogeneity of RM powders by performing tests on various amount of powder.