The solubility of fluorite in hydrothermal solutions,an experimental study

The solubility of fluorite in NaCl solutions increases with increasing temperature at all ionic strengths up to about 100°C. Above this temperature, the solubility passes through a maximum and possibly a minimum with increasing temperature at NaCl concentrations of 1.0M or less, and increases continuously with increasing temperature at NaCl concentrations above 1.0M. At any given temperature, the solubility of fluorite increases with increasing salt concentration in NaCl, KCl and CaCl₂ solutions. The solubility follows Debye-Hückel theory for KCl solutions. In NaCl and CaCl₂ solutions, the solubility of fluorite increases more rapidly than predicted by Debye-Hückel theory: the excess solubility is due to the presence of NaF^c, CaF⁺, and possibly of Na₂F⁺. The solubility of fluorite in NaCl-CaCl₂ and in NaCl-CaCl₂-MgCl₂ solutions is controlled by the common ion effect and by the presence of NaF^c, CaF⁺, and MgF⁺. The solubility of fluorite in NaCl-HCl solutions increases rapidly with increasing initial HCl concentration; the large solubility increase is due to the presence of HF^c. It seems likely that complexes other than those identified in this study rarely play a major role in fluoride transport and fluorite deposition at temperatures below 300°C.     

Fluorite deposition in hydrothermal systems

During the formation of fluorite deposits fluorite is precipitated either as a consequence of changes in temperature and pressure along the flow path of hydrothermal solutions or due to fluid mixing, or as the result of the interaction of hydrothermal solutions with wall rocks.A decrease in temperature in the flow direction is the most appealing, though still unproven, mechanism of fluorite deposition in Mississippi Valley fluorite deposits.Mixing can produce solutions which are either undersaturated or supersaturated with respect to fluorite. The most important parameters are the temperature, the salinity, and the calcium and fluoride concentration of the fluids prior to mixing.A variety of wall rock reactions can lead to fluorite precipitation. Among these reactions which increase the pH of initially rather acid (pH ≤ 3) hydrothermal solutions are apt to be particularly important.     

Xxth International Congress of Photogrammetry and Remote Sensing

The XXth International Congress of Photogrammetry and Remote Sensing was held at the Istanbul Convention and Exhibition Centre (ICEC), Turkey, from 12th to 23rd July 2004. Reports are given on the Congress as a whole, including the General Assembly, some Technical Commission activities and the Congress Exhibition. Papers from the Congress are published in Volume XXXV of the International Archives of Photogrammetry, Remote Sensing and Spatial Information Sciences.     

Xenon isotopes in size separated nanodiamonds from Efremovka: Xe*, Xe-P3, and Xe-P6

Xenon isotopic data were acquired by high resolution step pyrolysis and combined step pyrolysis/combustion of aliquots of size separated nanodiamonds. ¹²⁹Xe excess (¹²⁹Xe*) from in situ decay of ¹²⁹I is preferentially associated with the larger grain size separates. This observation rules out trapping by recoil from surrounding material. The releases of Xe-P3 and ¹²⁹Xe occur in the same low temperature pyrolysis steps and exhibit similar distributions among the size separates. These observations imply a common site for the components and, in consequence, suggest a common incorporation event.Whether one component or two, our observations require that ¹²⁹Xe* and Xe-P3 were incorporated into a subpopulation of nanodiamonds before nanodiamonds were mixed and incorporated into parent bodies. Their susceptibilities to loss during heating in the laboratory are similar, but the ratio of ¹²⁹Xe* to Xe-P3 varies among nanodiamond separates from different meteorites (literature data). We conclude that the ¹²⁹Xe* we observe today was present as ¹²⁹I during parent body processing. Furthermore, the range of ¹²⁹Xe*/¹³²Xe_P3 ratios across all the separates requires that even nanodiamonds from CI chondrites were at least 5-10× more rich in Xe-P3 during ¹²⁹I decay than they are today.We present a simple model involving one degassing event per parent body between incorporation of nanodiamonds and final decay of ¹²⁹I. The observed variations among parent bodies require degassing events separated by several ¹²⁹I half lives (∼50Ma), consistent with low-temperature processing on parent bodies but longer than expected for nebular processing. In this model, nanodiamonds from ALHA77307 degassed at an unusually early stage, suggesting they alone may retain the signature of processing in the nebula in their P3 and ¹²⁹Xe* abundances.The isotopic signature associated with Xe-P6 is also found only in the larger size separates. Concentration of Xe-HL increases with increasing grain size, but its relative abundance with respect to Xe-P3 and P6 is higher in smaller grain-size fractions. We argue that Xe-P6 is best seen as a variant of Xe-HL, and that they are both mixtures of a “normal” component akin to solar xenon and a slightly variable exotic component. We show that both current models of Xe-H formation can account for the observed variability, and propose a scenario according to which Xe-HL and P6 were implanted into separate diamond populations before incorporation of Xe-P3 and ¹²⁹I.     

Flow rates in the axial hot springs of the East Pacific Rise (21°N): Implications for the heat budget and the formation of massive sulfide deposits

The first in-situ measurements of flow rates in submarine hot springs (temperatures between 275° and 350°C) were made in the hot springs of the East Pacific Rise at 21°N during November, 1981. The flow rates ranged between 0.7 and 2.4 m/s. We estimate that the total rates at which heat and mass are transported from the three hot spring areas—OBS, National Geographic, and Southwest Vents—are ca. 2.2×10⁸ W and 150 kg of fluid/s respectively. The very high rate of heat loss precludes the existence of hot springs as steady state features of the East Pacific Rise at 21°N. We estimate that hot springs are active for a maximum of ca. 40,000 years. Chemical and/or mechanical clogging of the vents can drastically reduce the lifetime of the hot springs.Using a simple model of plume development [1], we calculated that less than 3% of the sulfide particles that are entrained in the hydrothermal plumes at 21°N settle from the plumes before dispersal by a lateral submarine current at a height of ca. 250 m above the seafloor [2]. The time that is required to form the sulfide mounds that surround the hot springs by the accumulation of sulfide particles that settle from the plumes is ca. 70–85 years. The current rate at which sulfide particles settle from the hydrothermal plumes and accumulate near the hot springs appears to be too small to lead to the formation of large massive sulfide deposits such as the Mavrouni deposit on Cyprus [3], within the time limits that are suggested by our thermal energy balance calculations.     

Cumulus mergers in the maritime continent region

Summary We examine a family of tall (up to 20 km) cumulonimbus complexes that develop almost daily over an adjacent pair of flat islands in the Maritime Continent region north of Darwin, Australia, and that are known locally as Hectors. Nine cases observed by a rawinsonde network, surface observations (including radiation and soil measurements), the TRMM/TOGA radar, and one day of aircraft photography are used to analyse the development, rainfall, surface energy budgets, and vertical structure of these convective systems.The systems undergo convective merging which is similar to that observed in previous Florida studies and is multiplicative in terms of rainfall. About 90% of the total rainfall comes from the merged systems, which comprise less than 10% of convective systems, and this has implications for the manner in which tropical rainfall is parameterised in largerscale numerical models. By comparison to the West Indies, GATE, and Florida, the Hector environment contains a weaker basic flow, with less vertical shear. The main thermodynamic difference is that the Darwin area has an unstable upper troposphere and very high tropopause. Numerical modelling results support earlier observations of updraughts in excess of 30 ms^–1 in this region, but show that only modest convective drafts are experienced below the freezing level (5 km).The surface fluxes over the islands are estimated from a Monash University study to be mainly in latent form from evapotranspiration, with a Bowen ratio only slightly larger than that commonly observed over oceans. These surface fluxes are crucial to the development of a suitable mixed layer to support deep convection. The flux estimates agree with the observed changes below the cloud base and provide sufficient information for calculations of the bounds on precipitation efficiency. Of particular interest are the observations of Hector development on a day when the islands were under a dense cirrus overcast. We find that the islands still provide sufficient net sensible and latent heat fluxes to initiate convection.With 10 Figures     

Chemical evolution of seawater during the Phanerozoic: Implications from the record of marine evaporites

The chemical evolution of seawater during the Phanerozoic is still a matter of debate. We have assembled and critically analyzed the available data for the composition of fluid inclusions in marine halite and for the mineralogy of marine evaporites. The composition of fluid inclusions in primary marine halite reveals two major long-term cycles in the chemistry of seawater during the past 600 myr. The concentration of Mg²⁺, Ca²⁺, and SO₄²⁻ has varied quite dramatically. The Mg²⁺ concentration in seawater during most of the early Paleozoic and Jurassic to Cretaceous was as low as 30 to 40 mmol/kg H₂O; it reached maximum values ≥50 mmol/kg H₂O during the Late Neoproterozoic and Permian. The Ca²⁺ concentration in seawater during the Phanerozoic has reached maximum values two to three times greater than the concentration in seawater today (10.6 mmol/kg H₂O), whereas SO₄²⁻ concentrations may have been as low as 5 to 10 mmol/kg H₂O (a third to a fifth of the modern value) during the Jurassic and Early Paleozoic. The Mg²⁺/Ca²⁺ ratio in seawater ranged from 1 to 1.5 during the early to middle Paleozoic and Jurassic-Cretaceous to a near-modern value of 5.2 during the Late Neoproterozoic and Permian. This change in seawater Mg²⁺/Ca²⁺ ratio is consistent with the notion of alternating “calcite-aragonite seas” recorded in oölites and marine carbonate cements.Several models have been proposed to explain the chemical evolution of seawater. These have invoked significant changes in one or more of the major geochemical processes that control the composition of seawater. The pattern and magnitude of the variations in the composition of seawater proposed in this study are similar to those proposed elsewhere that suggest that seawater fluxes through midocean ridges have played a major role in the evolution of seawater during the past 600 myr. Two Phanerozoic supercycles of the Earth’s exogenic processes were recognized in the literature that are caused by mantle convection and plate activity. The composition of seawater has apparently undergone dramatic secular changes in phase with these supercycles and as a consequence of biological evolution. Analyses of fluid inclusions containing unevaporated seawater and a better understanding of the processes that affect the composition of seawater are needed to refine our understanding of the history of Phanerozoic seawater.     

Volcanic gases, black smokers, and the great oxidation event

This paper proposes that gradual changes in the composition of volatiles that have been added to the atmosphere-ocean system are responsible for the Great Oxidation Event (G.O.E.) ca. 2.3 Ga. Before ca. 2.3 Ga, the composition of these volatiles was probably such that 20% of the carbon gases could be reduced to organic matter and all of the sulfur gases could be reduced to pyrite. Since 2.3 Ga, the composition of these volatiles has been such that 20% of the carbon gases could be reduced to organic matter, but only a fraction of the sulfur gases could be reduced to pyrite. This change led to the oxygenation of the atmosphere and to a large increase in the SO₄⁻² concentration of seawater. A considerable body of observational data supports these proposals.