Quantitative high resolution cathodoluminescence spectroscopy of diagenetic and hydrothermal dolomites

A combination of high resolution cathodoluminescence-spectroscopy (HRS-CL=high resolution spectroscopy of cathodoluminescence emission) with spatial resolving trace element analyses (PIXE=proton induced X-ray emission) is used to establish a method for the quantitative determination of the Mn-content of diagenetic and hydrothermal dolomites using the measurements of peak areas of Mn-activated CL emission bands. This method takes into account the overlap of the CL broad bands of Mn²⁺ in the Mg- and the Ca-lattice-position of dolomite. There is a linear correlation between the peak areas and Mn concentration up to approx. 1000–1500 ppm. Thus, CL spectroscopy allows a determination of Mn concentrations below the abilities of PIXE (10–15 ppm) to less than 1 ppm by extrapolation of this linear relation.

Up to an Fe-content of approx. 2000 ppm, no quenching effect of Fe on this linear relationship occurs. However, Fe-contents above 2000 ppm result in a decrease of Mn-induced luminescence. Even at Fe-concentration >25,000 ppm spectroscopy reveals that Mn-activated CL of dolomite is not entirely extinguished.     

Petrology and geothermometry of retrograded Hercynian charnockites and host gneisses, Agly Massif, French Pyrenees

Abstract A Hercynian charnockite occurs within high-grade gneisses in the Agly Massif, French Pyrenees. Its thermal history has been evaluated using the Fe-Mg distribution coefticient ( K _D) between garnet and biotite. These minerals have different origins but similar compositions in the charnockites and host gneisses. In the charnockite, the Bi–Ga pairs are the retrograde products of Opx alteration. This Opx reaction with feldspar can be written. Opx + PI + Fluid 1(H₂O + Al + K + Fe + Ti) = Bi + Ga + Q + Fluid 2(H₂O + Na). The garnets are relatively Ca poor (4–2.5% grossular); they are automorphic and zoned in the gneisses and poikiloblastic in the charnockites. Both types show a retrograde rim (of few hundred microns'width) across which Fe and Mn increase as Mg decreases. The biotites show a good correlation between the octahedral cations (Ti⁴⁺+ Fe²⁺) and (Mg²⁺+ Al³⁺_VI); Ti and Fe both increase, whereas Mg and Al_VI decrease. There is an inverse linear correlation between Fe²⁺ and Mg²⁺ and the Fe/Mg ratio increases as Ti increases. The relation between Ti and K ^Ga-Bi_DFe-Mg is less clear: it seems that K _D slightly decreases as Ti increases. The equilibration temperatures of Ga–Bi pairs are discussed: the charnockite Ga-Bi pairs have equilibrated between 550°C and 600°C; whereas those of the gneisses have equilibrated between 550°C and 650°C. Two main thermal steps appear: one in the gneisses between 600-650°C and a second one in both the gneisses and the charnockites between 550°C and 600°C.     

The influence of the limestone-quarry Čertovy schody (Czech Republic) on the precipitation chemistry and atmospheric deposition

Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na⁺, K⁺, Mg²⁺, Ca²⁺, F⁻, Cl⁻, NO₃⁻, HCO₃⁻, SO₄²⁻) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis.     

Mineralogical Characteristics and Cationic Exchange Properties of a Zeolite Mineral from Romana, NW Sardinia, Italy

An investigation was conducted into the Tertiary ignimbrite formations in the Romana area in NW Sardinia. Scanning electron microscopy–energy-dispersive spectrometry indicated the presence of clinoptilolite and subordinate smectite, quartz, mordenite and calcite. Laboratory analyses of representative samples collected from the deposit indicated a cation exchange capacity ranging from 85 to 135 mEq per 100 g. Ion exchange experiments conducted in flasks containing different initial cation concentrations and in columns supplied with solution having constant cation concentration, showed different selectivity towards the cations examined, in the order: NH₄⁺> Pb²⁺> Cd²⁺> Cu²⁺> Zn²⁺> Mn²⁺> Ni²⁺. Compared to the untreated material, under the experimental conditions used and considering the eluate, and the Italian regulatory limits for discharge into surface waters, the zeolite treated with a 1-N NaCl solution yielded a 1.3–5-fold increase in the volume of treated water, depending on the cation examined. The experimental results obtained show that the cationic exchange properties of the zeolite rock from the Romana deposit are comparable with the average quality of zeolites currently imported into Italy from non-European countries.     

湖南栗山铅锌铜多金属矿床闪锌矿微量元素特征及成矿指示意义

位于江南造山带中段的湘东北地区是我国华南重要的金铅锌铜钴多金属矿产地之一,栗山铅锌铜多金属矿床是该区近年来找矿勘查新发现的一大型矿床。该矿床位于晚侏罗世—早白垩世幕阜山岩体南缘,矿体主要赋存于岩体及其与地层接触带的构造破碎带内,空间上与岩体关系密切,然而目前关于该矿床的研究十分薄弱。本文采用电子探针和激光剥蚀电感耦合等离子质谱仪开展了闪锌矿的原位微区微量元素分析。微量元素组成分析结果表明,闪锌矿以富集Co、Ga而贫Fe、Cd、Ge为特征,其中Fe、Mn、Cd、Co、Ga等元素以类质同象形式产出,而Cu、Pb、Ag和Sn等元素则还以包裹体形式赋存于闪锌矿中。根据不同微量元素间的相关关系,认为闪锌矿中可能存在Zn²⁺↔Fe²⁺、4 Zn²⁺↔2 Fe²⁺+Ge⁴⁺+□(其中□表示空位)、3 Zn²⁺↔2 Cu⁺+Ge⁴⁺、2 Zn²⁺↔Ag⁺+Sb³⁺等简单和复杂替代关系。闪锌矿的Zn/Fe、Ga/Ge、Ge/In、Ga/In比值和Fe温度计等指示闪锌矿形成于中低温(240~250 ℃)、低硫逸度(lgf(S₂)=-13.3~-9.6)环境。栗山矿区闪锌矿的微量元素组成特征有别于金顶砂岩型、SEDEX型、VMS型、MVT型和夕卡岩型铅锌矿,结合低的Cd/Fe(0.03~0.14,平均0.06)、Cd/Mn(1.54~6.30,平均2.91)比值和Ge含量,暗示该矿床成矿作用与岩浆活动有关。综合矿区地质特征和区域构造-岩浆演化,认为该矿床是在太平洋板块俯冲后撤引起的伸展构造背景下形成的与燕山期幕阜山岩体有关的中低温岩浆热液充填交代型矿床。该类型矿床闪锌矿具有鲜明的微量元素组成特征,可为判别具相似地质特征的矿床成因提供借鉴。     

Quantitative temperature-time information from retrograde diffusion zoning in garnet: constraints for the P–T–t history of the Central Black Forest, Germany

Garnet from a kinzigite, a high-grade gneiss from the central Black Forest (Germany), displays a prominent and regular retrograde diffusion zoning in Fe, Mn and particularly Mg. The Mg diffusion profiles are suitable to derive cooling rates using recent datasets for cation diffusion in garnet. This information, together with textural relationships, thermobarometry and thermochronology, is used to constrain the pressure–temperature–time history of the high-grade gneisses. The garnet–biotite thermometer indicates peak metamorphic temperatures for the garnet cores of 730–810  °C. The temperatures for the outer rims are 600–650  °C. Garnet–Al₂SiO₅–plagioclase–quartz (GASP) barometry, garnet–rutile–Al₂SiO₅–ilmenite (GRAIL) and garnet–rutile–ilmenite–plagioclase–quartz (GRIPS) barometry yield pressures from 6–9  kbar. U–Pb ages of monazite of 341±2  Ma date the low- P high- T metamorphism in the central Black Forest. A Rb/Sr biotite–whole rock pair defines a cooling age of 321±2  Ma. The two mineral ages yield a cooling rate of about 15±2  °C Ma⁻¹. The petrologic cooling rates, with particular consideration of the f O₂ conditions for modelling retrograde diffusion profiles, agree with the geochronological cooling rate. The oldest sediments overlying the crystalline basement indicate a minimum cooling rate of 10  °C Ma⁻¹.     

Determination of Rare Earth Elements and Y in Ultramafic Rocks by ICP-MS After Preconcentration Using Fe(OH)3 and Mg(OH)2 Coprecipitation

A simple and reliable method to separate rare earth elements (REE) from Mg, Fe, K, Na, Ca and Ba in ultramafic rocks has been developed, thereby concentrating their abundances. The sample (0.3 g) was digested with HF and HNO₃ in a PTFE bomb, placed in a stainless steel container and, after drying, the insoluble residue was dissolved in 6 ml of 10% v/v HNO₃. Following the addition of 50% triethanolamine and 30% m/v NaOH solution, the REE were precipitated along with Mg(OH)₂, such that the majority of Fe, K and Na in the solution could be separated by centrifuging. The precipitate was dissolved in 1 ml HNO₃ and a buffer solution of NH₄Cl/NH₄OH at pH = 9.0 was added to precipitate the REE along with any remaining Fe as Fe(OH)₃, and so achieve separation from Mg, Ca and Ba, which remained in the solution. In this way, REE could be separated from major elements and were concentrated by a factor of about 60. The recovery of REE was more than 95% using this method. Four ultramafic rock reference materials, PCC-1 (USGS), JP-1 (GSJ), DZE-1, DZE-2 (IGGE) and one new proficiency testing sample GeoPT12 (GAS Serpentinite) were analysed by ICP-MS using indium as an internal standard. The quantitation limits were about 0.02–0.2 ng g⁻¹. Smooth chondrite-normalised REE patterns were obtained with a precision for REE determination of about 2–9%.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

Effects of secular variation in seawater Mg/Ca ratio (calcite–aragonite seas) on CaCO3 sediment production by the calcareous algae Halimeda, Penicillus and Udotea– evidence from recent experiments and the geological record

Independent lines of geological evidence suggest that fluctuations in the Mg/Ca ratio of seawater between 1.0 and 5.2 have caused the oceans to alternate between favouring the precipitation of the aragonite and high-Mg calcite polymorphs of calcium carbonate ( m Mg/Ca > 2; aragonite seas) and the low-Mg calcite polymorph ( m Mg/Ca < 2; calcite seas) throughout Phanerozoic time. The rise of aragonite-secreting bryopsidalean algae as major producers of carbonate sediments in middle Palaeogene time, a role that they maintained through to the present, has been attributed to a transition from calcite-to-aragonite seas in early Cenozoic time. Recent experiments on the modern, carbonate-sediment-producing bryopsidales Halimeda , Penicillus and Udotea reveal that their rates of calcification, linear extension and primary production decline when reared in experimental calcite seawaters ( m Mg/Ca < 2). These normally aragonite-secreting algae also began producing at least one-quarter of their CaCO₃ as calcite under calcite sea conditions, indicating that their biomineralogical control can be partially overridden by ambient seawater chemistry. The observation that primary production and linear extension declined along with calcification in the mineralogically unfavourable seawater suggests that photosynthesis within these algae is enhanced by calcification via liberation of CO₂ and/or H⁺. Thus, the reduced fitness of these algae associated with their low rates of calcification in calcite seas may have been exacerbated by concomitant reductions in tissue mass and algal height.     

The pressure dependence of the zirconium-in-rutile thermometer

The solubility of ZrO₂ in rutile is strongly temperature-dependent and has been identified as a potentially powerful thermometer when the rutile coexists with an appropriate buffer assemblage, e.g. zircon + quartz. In combination with experimental data at 10 kbar, previous consideration of data on natural rutile has not identified a pressure dependence for the thermometer. However, the expected volume change as a result of substitution of the larger Zr⁴⁺ cation for Ti⁴⁺ suggests that the Zr content of rutile should decrease with increasing pressure. To investigate the pressure dependence of the thermometer, piston cylinder (at 10, 20 & 30 kbar) and 1 atm furnace experiments were performed in the system ZrO₂-TiO₂-SiO₂. The solubility of ZrO₂ in rutile, in the presence of zircon and quartz was reversed at each pressure value. From these experiments, the thermodynamics of the end-member reaction ZrSiO₄ = SiO₂ + ZrO₂ (in rutile) have been determined. There is a secondary pressure effect accompanying the primary temperature dependence of the Zr content of rutile. New thermometer equations are, in the α -quartz field: in the β -quartz field and in the coesite field in which φ is ppm Zr, P is in kbar and R is the gas constant, 0.0083144 kJ K⁻¹. Thermometric results using these equations are shown for a range of geological settings.     

利用碳酸盐岩的Fe/Mn比值恢复海洋的氧化还原状态

碳酸盐岩的Fe/Mn元素比值,作为一项新的地球化学指标,可以用于恢复海洋的氧化还原状态.在氧化条件下,Fe³⁺和Mn⁴⁺均不可溶,因此氧化海水中的溶解Fe和Mn的含量均很低.Fe³⁺和Mn⁴⁺在还原条件下可以被细菌还原为可溶的Fe²⁺和Mn²⁺,而氧化还原电位的计算表明,Mn⁴⁺的还原要早于Fe³⁺的还原,因此细菌的Mn还原过程发生在沉积物的更浅层.可溶的Fe²⁺和Mn²⁺向上扩散到海水中,替代碳酸盐岩晶格里的Ca²⁺,因此碳酸盐岩晶格中的Fe²⁺和Mn²⁺的含量受控于来自沉积物孔隙水的扩散,而后者又与水岩界面的氧化还原状态相关.因此可以预测,随着海水变得逐渐缺氧,碳酸盐岩中的Fe/Mn比值会逐渐增高.为了验证这一假说,我们分析了中元古代高于庄组白云岩的Fe/Mn比值.研究发现,几乎所有的样品的Fe/Mn比值介于20～30之间,显著高于泥盆纪末期深水碳酸盐岩和浅水台地碳酸盐岩的Fe/Mn比值.高于庄组碳酸盐岩高的Fe/Mn比值一方面可能指示了中元古代低的大气氧气浓度和海洋的广泛缺氧,也可能反映了白云岩形成于缺氧的沉积物空隙水里.     

Diffusion-controlled corona reaction and overstepping of equilibrium in a garnet granulite, Yenisey Ridge, Siberia

Diffusion modelling is applied to layered garnet–pyroxene–quartz coronas, formed by a pressure-induced reaction between plagioclase and primary pyroxene in a metabasic granulite. The reconstructed reaction involves some change in composition of reactant minerals. The distribution of minerals between layers is satisfactorily explained by diffusion-controlled reaction with local equilibrium, in which the diffusion coefficient for Al was smaller than those for Fe, Mg and Ca by a factor of approximately four. Diffusion of Mg towards plagioclase implies a chemical-potential gradient for MgO component in a direction opposite to the changing Mg content of garnet; this is explained by the influence of Al₂O₃ on the chemical potential of the pyrope end-member. Grain-boundary diffusion is suggested to have operated, possibly with composition gradients different from those in the bulk minerals. Chemical-potential differences across the corona are estimated from the variation in garnet composition, enabling affinity (the free energy change driving the reaction) to be estimated as 6.9±1.8  kJ per 24-oxygen mole of garnet produced. This implies that the pressure for equilibrium among the minerals was overstepped by 1.4±0.4  kbar. The probable P–T conditions of reaction were in the range 650–790  °C, 8–10  kbar. Assuming a timescale of reaction between 10⁶ and 10⁸ years, estimated diffusion coefficients for Fe, Mg and Ca are in the range 9×10⁻²³ to 5×10⁻²⁰ m² s⁻¹. These are consistent with experimental values in the literature for solid-state diffusion, including grain-boundary diffusion.     

Zircon U–Pb age, trace element and Hf isotope composition of Kongling terrane in the Yangtze Craton: refining the timing of Palaeoproterozoic high-grade metamorphism

U–Pb age, trace element and Hf isotope compositions of zircon were analysed for a metasedimentary rock and two amphibolites from the Kongling terrane in the northern part of the Yangtze Craton. The zircon shows distinct morphological and chemical characteristics. Most zircon in an amphibolite shows oscillatory zoning, high Th/U and ¹⁷⁶Lu/¹⁷⁷Hf ratios, high formation temperature, high trace element contents, clear negative Eu anomaly, as well as HREE-enriched patterns, suggesting that it is igneous. The zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2857 ± 8 Ma, representing the age of the magmatic protolith. The zircon in the other two samples is metamorphic. It has low Th/U ratios, low trace element concentrations, variable HREE contents (33.8 ≥ Lu_N≥2213; 14.7 ≤ Lu_N/Sm_N ≤ 354) and ¹⁷⁶Lu/¹⁷⁷Hf ratios (0.000030–0.001168). The data indicate that the zircon formed in the presence of garnet and under upper amphibolite facies conditions. The metamorphic zircon yields a weighted mean ²⁰⁷Pb/²⁰⁶Pb age of 2010 ± 13 Ma. These results combined with previously obtained Palaeoproterozoic metamorphic ages suggest a c. 2.0 Ga Palaeoproterozoic collisional event in the Yangtze Craton, which may result from the assembly of the supercontinent Columbia. The zircon in two samples yields weighted mean two-stage Hf model ( T _DM2) ages of 3217 ± 110 and 2943 ± 50 Ma, respectively, indicating that their protoliths were mainly derived from Archean crust.     

Control on the emplacement of the andesite lava dome of the Soufriere Hills volcano, Montserrat by degassing-induced crystallization

Lava solidification is controlled by two mechanisms: external cooling and gas exsolution, the latter inducing crystallization due to increasing liquidus temperature. The andesite lava dome of the Soufriere Hills Volcano, Montserrat, is an extrusion dominated by crystallization caused by gas exsolution where cooling is unimportant in controlling emplacement. In the magma chamber the magma has an estimated viscosity of 7 × 10⁶ Pa s. During ascent, gas exsolution caused the magma to extrude in a highly crystalline state, with only 5–15% residual melt, viscosities in the range 10¹³–10¹⁴ Pa s and mechanical strength > 1 MPa. Deformation can be heterogeneous with extrusion along shear zones. Rheological stiffening in the upper conduit also causes large overpressures, shallow seismicity, and cyclic patterns of dome extrusion. Gas-rich porphyritic andesites tend to be the least mobile kind of lava, because transition from magma into hot crystalline material was reached during ascent.     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

福建碧田Au-Ag-Cu矿床含金石英脉中磷灰石的阴极发光研究

碧田Au Ag Cu矿床含金石英脉中的磷灰石在阴极射线激发下发明亮的黄绿色光 ,特征峰波长为 5 70～5 80nm。阴极发光 (CL)图像揭示了磷灰石的内部环带结构 ,不同环带微量和稀土元素含量具有明显的差异。发光带w(MnO) >0 .4%、n(Mn) /n(Fe) >2、n(Mn) /n(La+Ce) >4;Mn2 + 为CL的主要激发元素。磷灰石晶体结构中以LREE3 + +Si4+ =Ca2 + +P5+ 为主要的元素替代形式。磷灰石微量与稀土元素的分布特征表明 ,该矿床形成于近地表的低温热液体系 ,成矿流体在矿物共沉淀的晚期向富Si、Na方向演化。     

Metamorphic evolution of the Naga Hills eclogite and blueschist, Northeast India: implications for early subduction of the Indian plate under the Burma microplate

Tectonic slices and lenses of eclogite within mafic and ultramafic rocks of the Early Cretaceous–Eocene Naga Hills ophiolite were studied to constrain the physical conditions of eastward subduction of the Indian plate under the Burma microplate and convergence rate prior to the India–Eurasia collision. Some of the lenses are composed of eclogite, garnet-blueschist, glaucophanite and greenschist from core to margin, representing a retrograde hydrothermal alteration sequence. Barroisite, garnet, omphacite and epidote with minor chlorite, phengite, rutile and quartz constitute the peak metamorphic assemblage. In eclogite and garnet-blueschist, garnet shows an increase in Mg and Fe and decrease in Mn from core to rim. In chlorite in eclogite, Mg increases from core to rim. Inclusions of epidote, glaucophane, omphacite and quartz in garnet represent the pre-peak assemblage. Glaucophane also occurs profusely at the rims of barroisite. The matrix glaucophane and epidote represent the post-peak assemblage. The Fe³⁺ content of garnet-hosted omphacite is higher than that of matrix omphacite, and Fe³⁺ increases from core to rim in matrix glaucophane. Albite occurs in late stage veins. P – T pseudosection analysis indicates that the Naga Hills eclogites followed a clockwise P – T path with prograde metamorphism beginning at ∼1.3 GPa/525 °C and peaking at 1.7–2.0 GPa/580–610 °C, and subsequent retrogression to ∼1.1 GPa/540 °C. A comparison of these P – T conditions with numerical thermal models of plate subduction indicates that the Naga Hills eclogites probably formed near the top of the subducting crust with convergence rates of ∼ 55–100 km Myr⁻¹, consistent with high pre-collision convergence rates between India and Eurasia.     

Development of a Field Preconcentration/Elution Unit for Routine Determination of Dissolved Metal Concentrations by ICP-OES in Marine Waters: Application for Monitoring of the New Caledonia Lagoon

An iminodiacetate chelating resin was optimised for the rapid determination of Co, Cu, Fe, Mn and Ni in seawater. Using inexpensive, high-capacity, reusable cartridges allowed high flow rates of up to 25 ml min⁻¹. High preconcentration factors, of up to 500, were obtained in order to analyse samples using an ICP-OES. The requirement for a buffer was eliminated due to the high tolerance of the ICP-OES to interfering matrix elements, thereby further reducing the potential for contamination. Quantification limits in seawater were: Co = 6 ng l⁻¹, Cu = 8 ng l⁻¹, Fe = 6 ng l⁻¹, Mn = 5 ng l⁻¹ and Ni = 6 ng l⁻¹. The method was verified by the analysis of near shore seawater (CASS-4) and open ocean seawater (NASS-5) reference materials. In order to satisfy the high sampling demands using the iminodiacetate cartridges, a portable off-line preconcentration unit was developed for routine analysis. The multi-channel preconcentration unit, was capable of treating up to eight samples simultaneously with concentrating times as little as 30 minutes. The technique was also used to determine dissolved metals in fresh and interstitial waters. The technique has been successfully used in a number of environmental studies and impact assessments to evaluate the effects of mining on the New Caledonian lagoon.     

The Determination of Major Oxide and Trace Element Concentrations in Eighteen Chinese Standard Reference Samples by X-ray Fluorescence Spectrometry

Eighteen Chinese geologic reference samples (stream sediments GSD 9–12, soils GSS 1–8, and rocks GSR 1–6) were analyzed by wavelength-dispersive X-ray fluorescence spectrometry (XRFS) for major elements Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, and P, and by energy-dispersive XRFS for trace elements Ba, Ce, Cr, Cu, La, Nb, Ni, Rb, Sr, Y, Zn, and Zr. Major element analysis followed gravimetric determination of loss on ignition, and samples were prepared by fusion with Li₂B₄O₇. A loose-powder sample preparation was used for trace element analysis. The results reported in this study are, generally, in good agreement with concentrations compiled by X. Xie of the Geochemical Standard Reference Group and the Institute of Geophysical and Geochemical Exploration (People's Republic of China).     

Cu–Fe Bearing Zinc Sulfide from Laloki Stratabound Massive Sulfide Deposit, Papua New Guinea: Chemical Characterization

Abstract: A strange, unidentified, Cu-Fe bearing zinc sulfide occurs in the Laloki massive sulfide deposit, Papua New Guinea. The mineral is optically uniform in texture but is chemically variable and zoned even within a single grain. Copper contents vary from 0.1 up to 8.85 wt%. Iron reaches 18.31 wt% at maximum and decreases as Cu increases. It is remarkable, however, that the total Fe+Cu remains essentially unchanged between roughly 18 and 20 wt%. Zn and S are least variable, giving 45.85–47.84 wt% and 33.48–34.58 wt%, respectively. Other trace elements such as Cd and Mn are in general less than 0.2 wt%. It is strongly suggested that the mineral in question constitutes a unique Fe-Cu substitutional solid solution series belonging essentially to the Zn–Fe–Cu–S system.
The ideal chemical formula of the solid solution series can well be presented as Zn₁₀(Fe, Cu)₅S₁₅ or Zn₂(Fe, Cu)S₃, where Fe is always greater than Cu. It is intriguing that chalcopyrite blebs are recognizable restrictively only in nearby portions of the Cu-rich end member with the ideal composition close to Zn₁₀Fe₃Cu₂S_15. It has been confirmed by vacuum-sealed heating experiments that this mineral is decomposed to produce chalcopyrite and Fe-bearing normal sphalerite at temperatures below 200C. This would provide another evidence for the existence of such distinct phase as suggested here.