Vanadium magnetite–melt oxybarometry of natural,silicic magmas: a comparison of various oxybarometers and thermometers

To test a recently developed oxybarometer for silicic magmas based on partitioning of vanadium between magnetite and silicate melt, a comprehensive oxybarometry and thermometry study on 22 natural rhyolites to dacites was conducted. Investigated samples were either vitrophyres or holocrystalline rocks in which part of the mineral and melt assemblage was preserved only as inclusions within phenocrysts. Utilized methods include vanadium magnetite–melt oxybarometry, Fe–Ti oxide thermometry and -oxybarometry, zircon saturation thermometry, and two-feldspar thermometry, with all analyses conducted by laser-ablation ICP–MS. Based on the number of analyses, the reproducibility of the results and the certainty of contemporaneity of the analyzed minerals and silicate melts the samples were grouped into three classes of reliability. In the most reliable (n = 5) and medium reliable (n = 10) samples, all fO₂ values determined via vanadium magnetite–melt oxybarometry agree within 0.5 log units with the fO₂ values determined via Fe–Ti oxide oxybarometry, except for two samples of the medium reliable group. In the least reliable samples (n = 7), most of which show evidence for magma mixing, calculated fO₂ values agree within 0.75 log units. Comparison of three different thermometers reveals that temperatures obtained via zircon saturation thermometry agree within the limits of uncertainty with those obtained via two-feldspar thermometry in most cases, whereas temperatures obtained via Fe–Ti oxide thermometry commonly deviate by ≥50 °C due to large uncertainties associated with the Fe–Ti oxide model at T-fO₂ conditions typical of most silicic magmas. Another outcome of this study is that magma mixing is a common but easily overlooked phenomenon in silicic volcanic rocks, which means that great care has to be taken in the application and interpretation of thermometers and oxybarometers.     

Geological and geochemical factors affecting radon concentrations in dwellings located on permeable glacial sediments—a case study from Kinsarvik,Norway

In 1996–1997, indoor radon values of more than 40,000 Bq/m³ and large seasonal and geographical variations in indoor air radon were reported from a residential area located on a highly permeable ice-marginal deposit. Geochemical analyses of bedrock, groundwater and sediments and comparisons between indoor radon values and soil radon values indicate that the indoor radon concentrations in this area are strongly affected by subterranean airflows caused by temperature differences between soil air and atmospheric air. The airflows concentrate the radon-laden soil air towards the topographic highest part of the deposit in winter and towards the topographic lowest part in summer. In areas where subterranean airflows are likely to occur, radon measurements performed both in summer and in winter provide the best estimate of annual average indoor radon concentrations, and assessments of indoor radon concentrations based on single soil gas measurements are not recommended.     

The mobility of U and Th in subduction zone fluids: an indicator of oxygen fugacity and fluid salinity

The solubility of U and Th in aqueous solutions at P-T-conditions relevant for subduction zones was studied by trapping uraninite or thorite saturated fluids as synthetic fluid inclusions in quartz and analyzing their composition by Laser Ablation-ICPMS. Uranium is virtually insoluble in aqueous fluids at Fe-FeO buffer conditions, whereas its solubility increases both with oxygen fugacity and with salinity to 960 ppm at 26.1 kbar, Re-ReO₂ buffer conditions and 14.1 wt% NaCl in the fluid. At 26.1 kbar and 800°C, uranium solubility can be reproduced by the equation: log\textU = 2.681 + 0.1433logf\textO₂ + 0.594\textCl, \log {\text{U}} = 2.681 + 0.1433\log f{\text{O}}_{2} + 0.594{\text{Cl,}} where fO₂ is the oxygen fugacity, and Cl is the chlorine content of the fluid in molality. In contrast, Th solubility is generally low (<10 ppm) and independent of oxygen fugacity or fluid salinity. The solubility of U and Th in clinopyroxene in equilibrium with uraninite and thorite was found to be in the order of 10 ppm. Calculated fluid/cpx partition coefficients of Th are close to unity for all conditions. In contrast, D^fluid/cpx for uranium increases strongly both with oxygen fugacity and with salinity. We show that reducing or NaCl-free fluids cannot produce primitive arc magmas with U/Th ratio higher than MORB. However, the dissolution of several wt% of oxidized, saline fluids in arc melts can produce U/Th ratios several times higher than in MORB. We suggest that observed U/Th ratios in arc magmas provide tight constraints on both the salinity and the oxidation state of subduction zone fluids.     

Transport and sedimentation of Cu in a microtidal estuary, SE Norway

The transport and sedimentation of copper in the Glomma estuary, SE Norway during a period of 90% reduction in the industrial input of Cu, was studied from sediment trap material and compared to samples of the bottom sediments. Traps were deployed at four stations for several monthly periods during 1990, 1994 and 1995. Trapped material was analysed for suspended particulate matter (SPM), total organic carbon (TOC) and nitrogen (TN), Cu, and Al. Only about 10% of the Cu from the river is trapped in the estuary. Still there was a moderate but significant reduction in Cu concentration in the trap SPM from 1990 to 1994, reflecting the industrial reductions, but only if excluding summer samples apparently influenced by antifouling Cu from boat paint. Settling matter therefore seems appropriate and sensitive for monitoring changes in the Cu load. The results supported the view that TOC is the main carrier of Cu to the sediments.     

Characterisation of a Natural Quartz Crystal as a Reference Material for Microanalytical Determination of Ti,Al, Li,Fe, Mn,Ga and Ge

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP‐MS, electron probe microanalysis (EPMA) and solution ICP‐MS to determine the concentration of twenty‐four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium‐in‐quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA‐ICP‐MS laboratories, three EPMA laboratories and one solution‐ICP‐MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g^?1), Al (154 ± 15 μg g^?1), Li (30 ± 2 μg g^?1), Fe (2.2 ± 0.3 μg g^?1), Mn (0.34 ± 0.04 μg g^?1), Ge (1.7 ± 0.2 μg g^?1) and Ga (0.020 ± 0.002 μg g^?1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.     

The contribution of urban runoff to organic contaminant levels in harbour sediments near two Norwegian cities

The main aim of the present study was to compare the quality of particle emissions (urban runoff and settling particles in rivers and harbours) to the quality of top-layer bed sediments, for two Norwegian harbours (Oslo and Drammen). A sub-aim was to investigate whether non-industrial urban runoff contributed to the organotin load of sediments, apart from leaching from ship hulls. Time-integrated samples of stormwater runoff were obtained in an innovative manner, by sampling man-holes in the stormwater system. Settling particles were sampled with sediment traps. The study focused on PAHs, PCBs and organotin compounds. Contaminant levels were generally a factor of 2-10 (PAHs) and 3-30 (TBT) lower in emitted riverine and runoff particles than in top-layer bed sediments, except for PCBs in Oslo harbour (only 20-30% lower). Significant levels of tributyltin (TBT; median 140mug/kg) were shown in runoff particles, showing that TBT can also be emitted via urban sources, since the sampled man-holes were not in areas where dry-docking activities take place. Possible land-based TBT sources include long-lasting house paint and use of TBT as PVC stabilizer and timber preservative. Since there are ongoing emissions into the two studied harbour areas, it is concluded that the addition of an actively sorbing capping material such as activated carbon might be the best remediation alternative.     

Quantitative analysis of melt and fluid inclusions by LA-ICP-MS: Practical aspects and selected results

Quantitative analysis of melt and fluid inclusions by LA-ICP-MS: Practical aspects and selected resultsAudétatA.,GüntherD.,andHeinrichC.A.1998.Formation of a m agm atic- hydrothermal ore deposit:Insights withL A-ICP-MS analysis of fluid inclusions.Science,279:2091～2094 AudétatA .,GüntherD.,andHeinrichC.A.2000 a.Causes for large- scale m etal zonation around mineralized plutons:FluidinclusionL A-ICP-MS evidence from theMoleGranite,Australia.EconomicGeology,(in press) …     

Mobility and H2O loss from fluid inclusions in natural quartz crystals

Petrographic observations on quartz crystals from the Mole Granite (Australia) and other localities shed new light on the mechanisms of post-entrapment modification of fluid inclusions. These modifications include migration away from pseudosecondary trails, changes in fluid salinity and density, shape distortion and the formation of “sweat-haloes” around strongly deformed inclusions. Increases in fluid salinity, which usually are associated with inclusion migration, indicate water-losses of up to 50%. However, LA-ICP-MS-analysis of unmobilized and mobilized inclusions of the same trail reveals basically unchanged ratios of major – and trace element cations, with the exception of Li, which seems to be incorporated into the crystal lattice during migration. Despite the fact that all these modifications are closely related to deformation processes, they occur not only in mechanically deformed quartz, but also in free-standing crystals. In the latter samples, stress has been generated internally as a result of brazil-twinned growth and compositional zonation. These observations and their interpretation leads to a list of practical criteria that should help in differentiating between reliable and suspect fluid inclusions in other samples. Received: 17 November 1998 / Accepted: 16 April 1999