Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

GGR Critical Review of Analytical Developments in 2008–2009: An Introduction

This collection of articles represents the fourth in a series of reviews in which authors have aimed at capturing the key advances in a range of analytical fields ( Hergt et al. 2005, 2006, 2008 ). The publication period under review is 2008–2009 and the intention here is to provide readers with a summary of the most influential developments published during this period, across a broad range of topics appropriate to the Earth and environmental sciences. Most authors comment on the ways in which the emphases of research in their specific fields of examination have changed over time. All note an increase in rigour and focus on data quality. Whether advances have taken place in instrumentation, sample manipulation or data deconvolution, there are a large number of dedicated scientists out there contributing to the high quality of geochemical data employed in geological and environmental research.     

Cambro-Ordovician Magmatism in SE Brazil: U-Pb and Rb-Sr Ages, Combined with Sr and Nd Isotopic Data of Charnockitic Rocks from the Varzea Alegre Complex

In the central-southern region of Espírito Santo State, southeastern Brazil, several granitoids with a variable composition intruded high-grade metamorphic rocks, in the northern segment of the Ribeira fold belt. A close relationship between hydrous and anhydrous facies is present in some of the plutons, including the Varzea Alegre Igneous Complex, which has an inner domain formed by gabbro, diorite and granite, and an irregular outer ring of charnockitic rocks. These green megaporphyritic charnockites have primary anhydrous mineral assemblage, I-type and metaluminous character, and high-K calc-alkaline signature. U-Pb zircon single crystal ages obtained by TIMS indicate crystallization at about 500 Ma, similar to other late tectonic plutons of this part of the Ribeira belt. Sr and Nd isotopic ratios ranging from 0.7078 to 0.7096 and 0.5114 to 0.5116 respectively, are interpreted to be indicative of a hybrid origin from crustal and mantle-derived magmas. A binary diagram using Sr isotope ratios also demonstrates that the genesis of the charnockites probably included both magma mixing and fractional crystallization processes.     

Seasonal variation of polychlorinated biphenyl concentrations in the southern part of the Baltic Sea

The impact of seasonal fluctuations in forcing factors such as atmospheric concentration, temperature, and biological productivity on the concentration of polychlorinated biphenyls (PCBs) in the surface water of the southern part of the Baltic Sea was investigated. Water samples were collected on eight cruises over 2 years. A clear seasonal variability in dissolved PCB concentrations was observed with higher levels in summer than in winter and spring. This was attributed to changes in atmospheric concentrations and water temperature, based on measurements showing the PCB levels in the atmosphere and surface water to be close to a partitioning equilibrium. Concentrations in the suspended particulate material (SPM) fraction were also variable, and when the quotient of the organic carbon normalised concentration in SPM and the dissolved concentration was calculated (i.e., the bioaccumulation factor (BAF)), a seasonal pattern was observed which was consistent with kinetic limitations on partitioning into particles caused by plankton growth. However, seasonal variability in the partitioning properties of the SPM may also contribute to this variability.     

Adsorption of thorium and protactinium onto different particle types: experimental findings

Here we present the results of experiments investigating the adsorption of Protactinium and Thorium onto different particle types in natural seawater. Particle types studied were smectite as a representative of clay, biogenic opal from a cleaned diatom culture, manganese dioxide precipitate, and calcium carbonate. The particles were added to three different types of natural seawater (0.5 mg/L) which were first 0.2 μm-filtered, and the distribution of Pa and Th between dissolved and particulate phase (>0.2 μm) was monitored for 4 to 5 d at increasing time intervals. The tracers applied were the β-emitters ²³³Pa and ²³⁴Th. The measurement technique via β-counting for both nuclides in the same sample is reported here for the first time.The observed recoveries during the experiment range from 40 to 99 (±5) % for Th and from 51 to 105 (±6) % for Pa. The distribution coefficients (K_d) after establishment of an equilibrium cover a wide range for Th from 0.5 to 107 × 10⁶ ml/g, and from 0.03 to 166 × 10⁶ ml/g for Protactinium, depending on particle type and on the type of seawater used.Thorium revealed a specific affinity for all particle types investigated, with varying degree and adsorption kinetics. The results suggest that all particle types investigated may serve as Th carrier phases in the sediment. Pa was found to be less particle reactive than Th in most cases. Th/Pa fractionation factors (F_Th/Pa) were also obtained. Weakest fractionation was found on MnO₂ (F_Th/Pa=1), followed by the chemically cleaned biogenic opal (2.8) and smectite (5.4). The results for calcium carbonate were highly variable. Our experimental results imply that particle composition is indeed playing a role in the differing marine geochemistry of Th and Pa. We conclude that experiments with filtered natural seawater using particle concentrations on a natural level are a helpful approach when investigating the geochemical behaviour of strongly particle-reactive elements like Th and Pa in the marine environment.     

Fluid-mineral equilibria in a hydrothermal system,Roosevelt hot springs,Utah

The availability of fluids and drill cuttings from the active hydrothermal system at Roosevelt Hot Springs allows a quantitative comparison between the observed and predicted alteration mineralogy, calculated from fluid-mineral equilibria relationships. Comparison of all wells and springs in the thermal area indicates a common reservoir source, and geothermometer calculations predict its temperature to be higher ($\text{288°C ± 10°}$) than the maximum measured temperature of 268°C.The composition of the deep reservoir fluid was estimated from surface well samples, allowing for steam loss, gas release, mineral precipitation and ground-water mixing in the well bore. This deep fluid is sodium chloride in character, with approximately 9700 ppm dissolved solids, a pH of 6.0, and gas partial pressures of O₂ ranging from 10^?32 to 10^?35 atm, CO₂ of 11 atm, H₂S of 0.020 atm and CH₄ of 0.001 atm.Comparison of the alteration mineralogy from producing and nonproducing wells allowed delineation of an alteration pattern characteristic of the reservoir rock. Theoretical alteration mineral assemblages in equilibrium with the deep reservoir fluid, between 150° and 300°C, in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-H₄SiO₄-H₂O-H₂S-CO₂-HCl, were calculated. Minerals theoretically in equilibrium with the calculated reservoir fluid at $\text{>240°C}$ include sericite, K-feldspar, quartz, chalcedony, hematite, magnetite and pyrite. This assemblage corresponds with observed higher-temperature ($\text{>210°C}$) alteration assemblage in the deeper parts of the producing wells. The presence of montmorillonite and mixed-layer clays with the above assemblage observed at temperatures <210°C corresponds with minerals predicted to be in equilibrium with the fluid below 240°C.Alteration minerals present in the reservoir rock that do not exhibit equilibrium with respect to the reservoir fluid include epidote, anhydrite, calcite and chlorite. These may be products of an earlier hydrothermal event, or processes such as boiling and mixing, or a result of errors in the equilibrium calculations as a result of inadequate thermochemical data.