Proton-induced X-ray emission measurements of trace elements in water samples collected from an Indiana coal mining locality

A new method of simultaneous multi-elemental analysis, Proton Induced X-ray Emission (PIXE), was used to detect trace elements in waters associated with a coal strip-mining operation in southern Indiana. Stream, pond, and ground water samples were collected and analyzed monthly from, or near, Sulphur Creek in Sullivan County. The concentrations of 26 major and trace elements were determined in samples from eleven locations: K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Cd, Sn, Sb, I, Ba, Hg, Pb, and U. Elemental concentrations fluctuated considerably throughout the 13-month sampling period and also among sampling sites. Nickel, Zn, As, Cd, Mn, Fe, and Ca were highest in the upstream water which was most acidic (pH = 2.9–4.0) because of old unreclaimed mining operations. The highest values recorded were Ni = 1662 ppb, Zn = 4953 ppb, As = 26 ppb, Cd = 93 ppb, Mn = 5063 ppb, Fe = 63 ppm, and Ca = 325 ppm. The concentrations of these elements decreased downstream as the pH of Sulphur Creek increased which was likely due to the influence of the calcareous glacial till cover in the area and the recent mining activity which disturbed overburden containing a high percentage of calcareous materials. Lead, I, Br, and Ti values were highest (661 ppb, 86 ppb, 70 ppb, and 45 ppb, respectively) in the ground water from the coal seam (pH approximately 7). Other elements which were relatively high in the pH 7 waters closest to the current mining operations (pond, stream, and groundwater) included K (17 ppm), Sr (3408 ppb), Ba (173 ppb), As (14 ppb), Rb (16 ppb), Sn (14 ppb), and Cu (3840 ppb). The highest Cu concentration was recorded at the point where drainage water from the mine entered Sulphur Creek. Gallium, U, Hg, and Mo were found in low (< 13 ppb for Ga and Hg; < 205 ppb for Mo and U) concentrations and only in the ponds within the mine.     

The geochemistry of the volatile trace elements As, Cd, Ga, In and Sn in the Earth’s mantle: New evidence from in situ analyses of mantle xenoliths

The abundances of 30 trace elements, including the volatile chalcophile/siderophile elements As, Cd, Ga, In and Sn were determined by laser ablation ICP-MS in minerals of 19 anhydrous and 5 hydrous spinel peridotite xenoliths from three continents. The majority of samples were fertile lherzolites with more than 5% clinopyroxene; several samples have major element compositions close to estimates of the primitive mantle. All samples have been previously analysed for bulk-rock major, minor and lithophile trace elements. They cover a wide range of equilibration temperatures from about 850 to 1250 °C and a pressure range from 0.8 to 3.0 GPa. A comparison of results from bulk-rock analyses with concentrations obtained from combining silicate and oxide mineral data with modal mineralogy, gave excellent agreement, with the exception of As. Arsenic is the only element analysed that has high concentrations in sulphides. For all other elements sulphides can be neglected as host phases in these mantle rocks. The major host phase for Cd, In and Sn is clinopyroxene and if present, amphibole. Cadmium and In appear to behave moderately incompatibly during mantle melting similar to Yb.The data yield new and more reliable mantle abundances for Cd (35 ± 7 ppb), In (18 ± 3 ppb) and Sn (91 ± 28 ppb). The In value is similar to the Mg and CI-normalized Zn abundance of the mantle, although In is cosmochemically more volatile than Zn. The high In content suggests a high content of volatile elements in general in proto-Earth material. The lower relative abundances of volatile chalcophile elements such as Cd, S, Se and Te might be explained by sulphide segregation during core formation. The very low relative abundances of volatile and highly incompatible lithophile elements such as Br, Cl and I, and also C, N and rare gases, imply loss during Earth accretion, arguably by collisional erosion from differentiated planetesimals and protoplanets.     

Determination of Trace Element Mass Fractions in Ultramafic Rocks by HR‐ICP‐MS: A Combined Approach Using a Direct Digestion/Dilution Method and Preconcentration by Coprecipitation

A procedure is described for the determination of thirty‐seven minor and trace elements (LILE, REE, HFSE, U, Th, Pb, transition elements and Ga) in ultramafic rocks. After Tm addition and acid sample digestion, compositions were determined both following a direct digestion/dilution method (without element separation) and after a preconcentration procedure using a double coprecipitation process. Four ultramafic reference materials were investigated to test and validate our procedure (UB‐N, MGL‐GAS [GeoPT12], JP‐1 and DTS‐2B). Results obtained following the preconcentration procedure are in good agreement with previously published work on REE, HFSE, U, Th, Pb and some of the transition elements (Sc, Ti, V). This procedure has two major advantages: (a) it avoids any matrix effect resulting from the high Mg content of peridotite, and (b) it allows the preconcentration of a larger trace element set than with previous methods. Other elements (LILE, other transition elements Cr, Mn, Co, Ni, Cu, Zn, as well as Ga) were not fully coprecipitated with the preconcentration method and could only be accurately determined through the direct digestion/dilution method.     

Trace element chemistry of Apollo 14 lunar soil from Fra Mauro

Analytical data are presented for Apollo 14 fines ( < 1 mm) sample 14163,136 for 31 trace elements. The heavy REE are enriched monotonically by factors of 105 ± 10 over chondrites. Eu shows a large depletion (30 × chondrites) and the light REE show a smooth progressive enrichment with a slight fall at La. Ba, Cs, Th, U, Nb, Zr and Hf are strongly enriched, relative to chondritic abundances. Thus the outer portions of the moon sampled by the Imbrium event, and now represented by the Fra Mauro Formation, possessed high concentrations (100–200 × chondrites) for many elements, prior to the excavation of the mare basins. A correlation may exist between Gd/Eu and Zr/Hf ratios in lunar materials.     

Experimental sorption of Ni, Cs and Ln onto a montmorillonite up to 150°C

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs⁺, Ni²⁺ and 14 lanthanides (Ln³⁺) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution.The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni²⁺ and Ln³⁺ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol⁻¹ and 39 ± 15 kJ.mol⁻¹ for Ni²⁺ and Eu³⁺, respectively. On the other hand, the temperature effect on Cs⁺ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs⁺ on the montmorillonite is −19 ± 5 kJ.mol⁻¹.Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature.The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.     

Minor and trace-element data of iron oxides from iron-formations of the Iron Quadrangle,Minas Gerais,Brazil

Summary Chemical investigations of 192 hand-picked iron-oxide concentrates from banded iron-formation of the Iron Quadrangle, Brazil, did not yield any significant difference in minor and trace-element contents between itabirite and iron-ore samples (Fe >63%). Mean values (171–177 samples) are: Ca 82 ± 12 ppm; Co 120 ± 8; Cr 77 ± 8; Cu 40 ± 2; Mg 40±5; Mn 170±L28; Ni 167±7; P 905±23; Ti 114±13; V 138±8; Al 1068 ± 174 ppm (52 samples) and Au 33 ± 8 ppb (50 samples). Microprobe results indicate different trends of Fe-substitution by minor elements depending on the different lattice types of magnetite and hematite. Mg and Mn are much more concentrated in magnetite than in hematite whereas hematite is distinctly enriched in titanium due to the isostructural nature of the hematite and ilmenite lattices.

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Zusammenfassung Chemische Analysen von 192, unter dem Binokular ausgelesener Eisenoxidkonzentrate von Proben aus den Eisenerzlagerstätten des Eisernen Vierecks in Brasilien, ergaben keinerlei Unterschiede in den Neben- und Spurenelementgehalten zwischen den Itabiriten und den Reicherzen (Fe >63%). Die Mittelwerte von jeweils 171–177 Elementbestimmungen ind folgende: Ca 82± 12 ppm; Co 120± 8; Cr 77± 8; Cu 40± 2; g 40±5; Mn 170±28; Ni 167±7, P 905±23; Ti 114:L13; V 138±8, Al 1068 ± 174 ppm (52 Proben) und Au 33 ± 8 ppb (50 Proben).Aus Mikrosondenuntersuchungen ergeben sich in Abhängigkeit von den unterschiedlichen Kristallgittertypen des Magnetits und Hämatits verschiedene Substitutionsraten des Eisens durch Nebenelemente. So zeigen Mg und Mn in Magnetiten um eine Vielfaches höhere Werte als in Hämatiten, während Ti im Hämatit wegen der Isotypie des Hämatit-Ilmenit-Gitters deutlich angereichert ist.

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With 1 Figures     

固相萃取掺氧空气-乙炔火焰原子吸收光谱法测定水和植物样品中的痕量镓

目前研究萃取分离富集镓大多偏向在强酸性体系中,一定程度上给操作带来安全风险,另需耐酸器皿设备,易污染,空白背景值高。本文开发了一种在弱酸性条件下萃取分离富集痕量镓的方法。以大孔吸附树脂为载体,十六烷基三甲基溴化铵调节其表面极性,热固化负载2-乙基己基磷酸(2-乙基己基)酯,制备了镓的萃取树脂。动态考察了固相萃取镓的吸附容量,优化选择固相萃取分离富集条件,实验表明萃取条件温和,分离富集痕量镓效果理想。当溶液酸度为pH 2.5时,Ga(Ⅲ)达到最大的回收率99%,并确定了掺氧空气乙炔火焰原子吸收光谱法(FAAS)测定镓的最佳参数,提升了常规空气乙炔FAAS测定镓的灵敏度。方法检出限(3σ)为2.6ng/mL,相对标准偏差(RSD,n=7)为2.87%,加标回收率在95.7%～102.0%之间,理论富集倍数为40。本方法已应用于自来水、中药材和水培蔬菜样品中痕量镓的测定,简便、快速、可靠。     

Statistical assessment of geochemical pattern in overbank sediments of the river Sava,Croatia

Four overbank profiles from the three terraces of different age were sampled in 10 to 20 cm intervals for the bulk content of major and minor (Ca, Mg, Fe, Ti, Al, Na, K and P) and trace (Mo, Cu, Pb, Zn, Ni, Co, Mn, As, U, Th, Sr, Cd, Sb, V, La, Cr, Ba, W, Zr, Ce, Sn, Y, Nb, Ta, Sc, Li, Rb and Hf) elements in the minus 0.125 mm fraction. Univariate statistics together with analysis of variance discriminated between the lower-lying carbonate (CA) population dominantly composed of carbonates and the overlying silicate (SI) population being dominantly of silicate mineralogy. This stratified pattern resulted from the intensive erosive action of melting glaciers exerted on limestones and dolomites in the alpine region, followed by local inputs mainly of silicate composition. Elements exhibiting the greatest between-population variability are Ca and Mg being enriched in the CA population and Fe, Mn, P, Sr, Al, Na, K, Li, Rb, Y, Zr, Ni, Cr and Ti being enriched in the SI population. Anomalously high Hg, Pb and Ba concentrations (maximum values: 6,500±2,860 ppb, 225±13 ppm and 1,519±91 ppm, respectively) in the lowermost part of the profile S7, which is nearest to the Croatian-Slovenian border, derive from the mineralized Slovenian catchment area. This profile also contains trimodal frequency distributions of Fe, Mn and P whose highest concentrations coincide with increased values of Zn and Cu which are bimodally distributed. Geochemical patterns of majority of elements in all four profiles consistently reflect the average compositions of the upstream drainage basins.     

Case studies on the origin of basalt: III. Petrogenesis of the Mauna Ulu eruption,Kilauea, 1969–1971

During the Mauna Ulu flank eruption on Kilauea, Hawaii, the concentrations in the lavas of the minor elements K, P, Na and Ti, and the incompatible trace elements (analyzed by isotope dilution) K, Rb, Cs, Ba, Sr, and the REE (except Yb) decreased monotonically and linearly with the time (or date) of the eruption. At the same time, the concentrations of the major elements and of Yb, and the ratios of K/Rb, K/Cs, Ba/Rb, ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd remained constant. Most of the scatter in the raw concentration data is removed by a simple correction for olivine (plus chromite) fractionation previously established by Wright et al. (1975). These results are explained by simple equilibrium partial melting of a uniform source. The degree of melting increased by about 20% of the initial value during the course of the eruption. The trace element data are inverted by the method originated by Minster and Allègre (1978) and simplified by Hofmann and Feigenson (1983). The source has the following element (or isotope) ratios: K/Rb=501±7, Ba/Rb=14.0±0.5, Rb/Cs=95±7, Rb/Sr=0.0193 (+0.0045, –0.0090), (Ce/Ba)_CN= 1.1±0.1, (Sr/Ba)_CN=1.19 (+0.30, –0.19), ⁸⁷Sr/⁸⁶Sr=0.703521±0.000016, and ¹⁴³Nd/¹⁴⁴Nd=0.512966±0.000008. The REE pattern of the source has a nearly flat or slightly negative slope (=relative LREE enrichment) between Ce and Dy and a strongly positive slope between Dy and Yb. However, this relative HREE enrichment is poorly constrained by the analytical data, is highly model dependent and may not be a true source feature. The Yb concentration in the source is particularly poorly constrained because it is essentially constant in the melts. On the other hand, this special feature demonstrates that Yb must be buffered by a mineral phase with a high partition coefficient for Yb, namely garnet. The calculated clinopyroxene/garnet ratio in the source is roughly equal to one. In contrast, the source of Kohala volcano had previously been found to contain little or no garnet.     

Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano

Rhenium (Re) is one of the least abundant elements in Earth, averaging 0.28 ppb in the primitive mantle. The unique occurrence of rheniite ReS₂ (74.5 wt% of Re) in Kudryavy volcano precipitates raises questions about recycling of Re-rich reservoirs within the Kurile-Kamchatka volcanic Island arc setting. The sources of this unique Re enrichment have been inferred from studies of Re-Os isotope systematic and trace elements in volcanic gases, sulphide precipitates and host volcanic rocks. The fumarolic gas condensates are enriched in hydrophile trace elements relative to fluid-immobile elements and exhibit high Ba/Nb (133-204), Rb/Y (16-406) and Th/Zr (0.01-0.25) ratios. They are characterised by high Re (7-210 ppb) and Os abundances (0.4-0.9 ppb), with ¹⁸⁷Os/¹⁸⁸Os ratios in a range 0.122-0.152. This Os isotopic compositional range is similar to that of the peridotite xenoliths from the metasomatised mantle wedge above the subducted Pacific plate, the radiogenic isotopic signature of which is probably due to radiogenic addition from a slab-derived fluid.Re- and Os-rich sulphide and oxide minerals precipitate from volcanic gases within fumarolic fields. Molybdenite (MoS₂), powellite (CaMoO₄) and cannizzarite (Pb₄Bi₆S₁₃) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb of Re, respectively. Both molybdenite and rheniite contain normal Os concentrations, with total Os abundances in a range from 0.6 to 3.1 ppm for molybdenite, and 2.3-24.3 ppb for the rheniite samples. Repeated analyses of osmium isotope ratios for two rheniite samples form a best-fit line with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.32 ± 0.15 and an age of 79 ± 11 yr, which is the youngest age ever measured in natural samples. The high Re contents in molybdenite and rheniite led to high radiogenic ¹⁸⁷Os values, even in the limited period of time, with ¹⁸⁷Os/¹⁸⁸Os ratios up to 3.3 for molybdenite and up to 4.4 for rheniite.The Os isotopic compositions of andesite-basaltic rocks from the Kudryavy volcano (¹⁸⁷Os/¹⁸⁸Os up to 0.326) are more radiogenic than those of residual peridotites and fumarolic gas condensates that are mainly constituted from magmatic vapor. Such radiogenic values can be attributed either to the addition of a radiogenic Os-rich subduction component to the depleted mantle, or to the assimilation of older dacitic caldera walls (¹⁸⁷Os/¹⁸⁸Os = 0.6) during arc magma ascent and emplacement. The latter hypothesis is supported by the correlation between ¹⁸⁷Os/¹⁸⁸Os ratio and indicators of fractionation such as MgO or Ni, and by low contents of potentially hydrophile trace elements such as Ba, Rb and Th relative to fluid-immobile elements such as Nb, Zr and Y. The high Re flux in the Kudryavy volcano (estimated at ∼46 kg/yr) can be explained by remobilisation of Re by Cl-rich water from an underplated mantle wedge and subducted organic-rich sediments of the Pacific plate.     

The Svalbard western coast: site of baseline geochemistry and incipient contamination

 Potentially toxic metals tracked by the Arctic Monitoring and Assessment Program were analysed in sediments from the Svalbard western coastal zone. These include As and Hg found as contaminants in other Arctic seas as well as other elements (e.g. Pb, V, Cu, Zn, Cr, Ni). Svalbard shelf sediments contain average values of 12 ppm As, 12 ppm Pb, 56 ppb Hg and 114 ppm V. These values increase in Isfjorden sediments to 15 ppm As, 28 ppm Pb, 99 ppb Hg and 210 ppm V. Cluster analysis yields a major cluster that is likely related to clay minerals (Al, K, Ti, Mg) and sorption onto them of transition (Cu, V, Cr, Sc) and other elements (Pb, Rb). A second significant cluster includes Ca, Sr and plagioclase. The Svalbard western shelf is a natural geochemical environment. The possible incipient contamination of fjord sediments by As, Pb, Hg and V should be evaluated for possible links to anthropogenic sources. If links are found, remediation must be used to stop the input and preserve a pristine Svalbard fjord environment. Received: 21 December 1998 · Accepted: 15 March 1999     

New chelating resin for preconcentration and determination of molybdenum by inductive couple plasma atomic emission spectroscopy

A chelating resin is prepared by condensation polymerization of aniline with formaldehyde and characterized by Fourier transform infrared spectrometer, elemental analysis and thermogravimetric analysis and studied for the preconcentration and determination of trace Molybdate ion from environmental water sample using inductive couple plasma atomic emission spectroscopy. The optimum pH value for sorption of the metal ion was 5. The sorption capacity of functionalized resin is 3.1 mg/g. The chelating sorbent can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. The best desorption of the metal ions from resin was obtained by 0.5 mol/L nitric acid as eluting agent. The profile of molybdenum uptake on this sorbent reflects good accessibility of the chelating sites in the aniline-formaldehyde. Scatchard analysis revealed that the homogeneous binding sites were formed in the polymers. The equilibrium adsorption data of Molybdate ion modified resin were analyzed by five isotherm models such as Langmuir, Freundlich and Temkin. Langmuir isotherm parameters obtained from the four Langmuir linear equations by using linear method. Based on the Langmuir isotherm analysis, the monolayer adsorption capacity was determined to be 4.03 mg/g at 20 °C. The method was applied for molybdenum ions determination from river water sample.     

Natural speciation of Ni, Zn, Ba, and As in ferromanganese coatings on quartz using X-ray fluorescence, absorption, and diffraction

The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the ^VIZn/^IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn⁴⁺ vacancies (i.e., no Mn³⁺ for Mn⁴⁺ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.     

铀(Ⅵ)分析中的分离富集技术

本文归纳总结了近10年来国内外铀分析中的分离富集方法.依据分离富集原理的不同,将其划分为浮选、毛细管电泳、吸附分离、萃取4类方法.着重讨论了它们的分离富集条件、吸附容量、富集倍数以及方法的检测限等主要参数,并对未来铀的分离富集技术进行了展望.     

白云岩风化剖面元素地球化学特征:对黔中九架炉组“三稀金属”富集机制的启示

黔中早石炭世九架炉组铝土矿含矿岩系富集Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th和稀土(REEs)等"三稀金属",具有成为独立矿床或伴生资源的潜力。这些元素大部分与九架炉组共有同一母岩,且富集程度受母岩的成分和风化作用控制。本研究选取九架炉组母岩乌当娄山关群白云岩和纳雍牛蹄塘组泥质白云岩的现代风化剖面为研究对象,研究元素在风化作用过程中的迁移特征及分布规律,进而为九架炉组微量元素的富集机制提供启示。研究获得以下认识:1)依据剖面结构、ZrHf、Nb-Ta、Y-Ho二元图特征及REE配分曲线和Eu/Eu*值的相似性表明研究区土层主要来源于基底或母岩的风化; 2)白云岩风化成土过程中Si、Fe、Cr、As、Sb、Ti、Nb、Ta、Zr、Hf、Th、REEs等元素化学性质相对稳定,富集程度较高,而Ca、Mg、Na、K、Sr、P、Mo、Cd等元素化学性质活泼,容易淋失亏损; 3)纳雍剖面REEs~(3+)和Ca~(2+)半径差与REEs富集系数相关性良好,表明碳酸盐岩风化过程中,含钙矿物磷灰石是稀土元素分配的重要控制因素; 4)九架炉组的母岩也是Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th等微量元素的主要物质来源,母岩风化过程中,这些微量元素首先在副矿物、黏土矿物、铝矿物及磷灰石等矿物相中初步富集,之后随风化碎屑物一起沉积形成微量元素超常富集地层; 5)纳雍剖面地表和地下水提供了部分P、Be、Zn、Sb、Pb、Y及REEs来源,指示水体迁入作用也是九架炉组REEs富集的重要原因。研究表明黔中九架炉组微量元素的来源较复杂,风化-沉积过程中,化学性质稳定的元素残留在风化碎屑物中并被搬运-沉积在负地形中,而化学性质活泼的元素首先被带入水体,在沉积-成岩过程中特定条件下发生二次富集作用(例如次生矿物的形成及吸附)形成微量元素富集的地层。     

桂西南早-中三叠世东平-足荣大型锰矿床地球化学、年代学及成因研究

广西东平-足荣大型锰矿床位于桂西南锰矿带上,是广西重要的锰矿富集区。其含矿地层为三叠系北泗组,是一套以硅-泥-灰为主浅海台盆相含锰碳酸盐岩沉积,含锰矿物主要为钙菱锰矿、锰方解石和锰白云石。本文对矿区锰矿层顶部的沉凝灰岩及含锰岩系开展了详细的岩石学、岩石地球化学和锆石U-Pb年代学研究,进而对锰矿成矿时代、成因、沉积环境、沉凝灰岩源区和大地构造背景进行了探讨。锆石SHRIMP U-Pb定年结果显示,3件沉凝灰岩样品的锆石呈自形-半自形板柱状,发育良好的岩浆锆石振荡环带结构。~(206) Pb/~(238)U年龄加权平均值分别为250.8±2.1Ma(MSWD=0.98)、250.6±2.2Ma(MSWD=0.49)和243.6±2.3Ma(MSWD=0.44)。进一步限定了"东平"式锰矿的成矿时代为早-中三叠世(不晚于241～246Ma的范围内)。沉凝灰岩的构造环境判别图解及微量、稀土元素特征显示其岩浆可能形成于与俯冲消减作用相关的碰撞-弧相关或活动大陆边缘相关背景,推测东平-足荣锰矿的形成可能受到广西凭祥-东兴火山作用的影响。含锰岩系的U、V和Mo元素含量及U/Th、V/Cr、V/(V+Ni)、Ni/Co 比值显示东平-足荣锰矿形成于氧化-次氧化的沉积环境。logU-logTh、Fe/Ti-Al/(Al+Fe+Mn)图解及微量元素Ba含量、Ba/Sr值均指示成矿作用受到热水作用的影响。综合矿床地质研究,东平-足荣锰矿形成于弧后盆地拉张构造背景中,锰成矿受同期火山及海底热液作用影响,水体沉积环境为氧化-次氧化条件。     

Conversion,sorption, and transport of arsenic species in geological media

This work addresses the inter-conversion and sorption of inorganic As species in representative geological media. Through the sensitive quantification of As(III) and As(V) with liquid chromatography–inductively coupled plasma-mass spectrometry, and through integrated batch and column approaches, it is shown that natural media can either reduce or oxidize As species. Oxidation of As(III) to As(V) is shown in the Hanford sediment, while reduction of As(V) to As(III) is shown for the surface soil of Savannah River Site. Overall, the sorption distribution coefficient of As(V) onto geological media is much larger than that of As(III), and a reduction of the more sorptive As(V) to As(III) will lead to groundwater enrichment with As. Coupled with the different sorption behavior of As(III) and As(V), the inter-conversion of these species will strongly affect the geochemical cycling of redox-sensitive As in the subsurface.     

Quantitative trace element analysis of single fluid inclusions by proton-induced X-ray emission (PIXE): application to fluid inclusions in hydrothermal quartz

Single fluid inclusion analogues with known elemental composition and regular shape were analyzed for trace element contents by particle-induced X-ray emission (PIXE)—a nondestructive method for the analysis of single fluid inclusions—to evaluate the accuracy and detection limits of this type of analysis. Elements with concentrations of 10 to 1000 ppm were measured with average estimated relative error of ±7%. For natural fluid inclusions with 30 μm radius and 20 μm depth in quartz, the total analytical errors were estimated to be ±40% relative for Ca, ±16% for Fe, ±13% for Zn, ±12% for Sr, and ±11% for Br and Rb, by considering uncertainties in microscopic measurements of inclusion depths. Detection limits of 4 to 46 ppm for elements of mass numbers 25-50 were achieved for analyses of a spherical fluid inclusion with 30 μm radius and 20 μm depth in quartz, at an integrated charge of 1.0 μC. The trace element compositions of single fluid inclusions in a hydrothermal quartz crystal were also determined. The elemental concentrations in the inclusions varied widely: 0.2-9 wt.% for Ca and Fe, 300-8000 ppm for Mn and Zn, 40-3000 ppm for Cu, 100-4000 ppm for Br, Rb, Sr, and Pb, and less than 100 ppm for Ge. Elemental concentrations of secondary fluid inclusions on the same trail varied over an order of magnitude, even though all these inclusions were formed from the same fluid. Elemental concentrations in inclusions on the same trail are positively correlated with each other, except for Cu and Rb. Ratios of almost all elements in the inclusions on the trail were essentially unchanged; thus, the elemental ratios can provide original information on trace element compositions of a hydrothermal fluid.     

痕量钍分析进展近况

本文综述了10年来痕量钍的分离富集方法和测定方法,包括分光光度法、荧光光度法、极谱法、中子活化法、X射线荧光法等,应用这些方法测定ppb级的针,能得到满意的结果。     

Analysis of Sulfides for Gold and Associated Trace Metals by Direct Neutron Activation With a Low-Flux Reactor

A routine method for the direct determination of Au and associated trace metals in sulfides has been developed for use with a low-flux nuclear reactor (SLOWPOKE II Reactor Facility, University of Toronto). Small samples (100–200 mg) are analysed simultaneously for Au, Ag, As, Sb, Mo, Co, Se, Cd, Fe, and Zn. Sulfides containing finely divided gold can be analysed with a high degree of precision and yield results which agree closely with commercial fire assay-atomic absorption analyses for Au. Favourable comparisons with other analytical techniques (flameless atomic absorption and emission spectrometry) are also indicated for Ag, As, and Sb. Neutron activation has the advantage of providing precise and accurate results for these elements without chemical separation or preconcentration. Analyses of 10 sulfide-bearing reference materials from CANMET, Ottawa are compared with published best values for selected trace metals including Au.