A kinetic model of metamorphism: an application to siliceous dolomites

We use a kinetic model of a metamorphic system to study the effect of competing rates of reaction, fluid injection, and heating on the evolution of the reaction pathway in temperature/composition space at constant pressure. We show that for rocks in contact with mixed volatile (e.g., CO₂-H₂O) fluids the reaction path may be quite different from what is expected from equilibrium-based petrologic models. Equilibrium-based models, used to understand the development of rock systems undergoing mineral reactions during a metamorphic event, rely on the Gibbs phase rule and only consider stable phases. For constant pressure, the temperature-composition paths follow univariant curves and significant reactions may occur at invariant points. By contrast, the more general kinetic treatment is not constrained by equilibrium, although with the proper competing rates equilibrium is a possible endmember of the kinetic approach. The deviation from equilibrium depends on the competing rates of reaction, heating, and fluid injection. A key element required by the kinetic approach is the inclusion of metastable reactions in the formulation, whereas such reactions are irrelevant for equilibrium-based models. Metastable reactions are often involved in a complex interplay with common prograde stable metamorphic reactions. We present model results for the well-studied CaO-MgO-SiO₂-CO₂-H₂O (CMS) system to show how the system evolves under kinetic control. Our simulations and discussion focus on the behavior of the CMS system under a number of closed and open system conditions. Special attention is paid to closed system behavior in the vicinity of the (first) isobaric invariant point (with Dol, Qtz, Tlc, Cal, and Tr). Also, for open systems with massive fluid infiltration we consider heating rates varying from contact to regional metamorphic conditions. For some geologically reasonable rates of reactions, heating, and fluid injection, our results demonstrate that equilibrium conditions may be significantly overstepped in metamorphic systems. We used overall mineral reactions in this model with rates based on experimental results. Future models could rely on more fundamental dissolution and precipitation reactions. Such an extension would require additional kinetic rate data, as well as mineral solubilities in mixed volatile fluids.Editorial responsibility: J. Hoefs     

Primary fractionation of elements among iron meteorites

The primary fractionation process in iron meteorites is that responsible for the distribution of elements between the groups, most notably Ga and Ge, which show concentration ranges of 10³ and 10⁴ respectively. To investigate the cause of the primary fractionation, concentrations of 16 elements were converted to relative abundances by dividing the element/Ni ratio by the CI chondrite ratio. These abundances were plotted on logarithmic graphs with data for each group (except IB and IIICD) and each cluster of closely related anomalous irons averaged.Co, P, Au, As, Cu, Sb, Ge and Zn are positively correlated with Ga. For most groups (except IA, IC and IIAB) relative abundances of these elements tend to decrease from about 1 in approximately the order listed above. This is the expected order in which these elements will condense into Fe, Ni during equilibrium nebular condensation. Mean relative abundances of refractory elements in groups generally lie within a narrow range of 0.5–2, and are uncorrelated with Ga. Although the equilibrium model may be only a gross approximation, it suggests that most primary fractionation did occur during nebular condensation.The anomalous irons are essential for defining many of the primary fractionation trends. On several element-Ga graphs the displacements of the anomalous irons from the primary curves indicate that these irons experienced the same secondary fractionation process (probably fractional crystallization) that produced the trends within most groups. The anomalous irons appear to be samples from over 50 minor groups, which have similar histories to the 12 major groups.     

Determining Paleosol Topography Using Seismic Refraction

The seismic refraction reversed profiling technique has been used to investigate the topography of the last interglacial soil (paleosol S1) within the central Chinese Loess Plateau near Xifeng. The results suggest an essentially flat-lying soil at a depth which varies by only a few meters over an area of more than 10 km². In addition, the results indicate a high-velocity layer at 50-60 m depth which is thought to coincide with a layer of carbonate concretions at the base of paleosol S5. The results agree well with the local loess-paleosol stratigraphy for this area and indicate that the seismic refraction method is a rapid technique for investigating paleotopography.     

Calculations of horizontal mixing rates using222Rn and the controls on hypoxia in western Long Island Sound, 1991

Late summer hypoxia (<3 ppm oxygen) in western Long Island Sound (WLIS) is a persistent environmental and management issue whose controlling processes are poorly understood. Measured rates of sediment and water-column oxygen consumption in the bottom water suggest that a condition of no oxygen should be attained on the time scale of 13–30 d. Observations, however, indicate the onset of hypoxia is of the order 150 d. Therefore, horizontal and/or vertical transport of oxygen into the area of hypoxia must play an important role. Hypoxia decreases benthic activity and the sediment flux of²²²Rn. The resulting horizontal gradient in bottom water²²²Rn was measured and used to estimate the effective horizontal transport rate (>5–50 m² s^?1), which is considerably slower than previous estimates. Scale analysis of the hypoxia process indicates that horizontal transport rates alone can explain the slow progression of hypoxia in XLIS but that vertical processes may also be capable of delaying the onset of hypoxia especially under conditions of weak stratification or weak intermediate layer oxygen consumption. This scale analysis indicates a delicately balanced process that is sensitive to both climatologically-driven variability in the rates of horizontal and vertical transport as well as the biologically-driven rates of oxygen consumption. An improved ability to predict and/or control hypoxia must be based on a better understanding of temporal and spacial variations in circulation, mixing, and stratification as well as the biological processes in the water column and the sediments.     

Using groundwater noble gas measurements to confirm paleorecharge hypotheses at Pahute Mesa,Nevada National Security Site,Nevada, USA

Hydrogeology Journal - Pahute Mesa (Nevada, USA) was the site of 85 underground nuclear tests between 1965 and 1992 whose residual radiochemical inventory poses a contaminant threat to local...     

含硫化物镁铁质-超镁铁质侵入体中橄榄石Mg、Ni含量的制约:原理、模式及Voisey's Bay侵入体样品研究

镁铁质-超镁铁质岩浆结晶分离早期形成镁铁矿物,镁铁矿物中的Ni和Mg是相容元素。随着结晶分离作用的进行,Ni、Mg在硅酸盐岩浆及后形成的硅酸盐物质中的丰度下降。橄榄石中Ni含量及硅酸盐物质MgO/FeO比值都与母岩浆的相关值相关,据此可推断母岩浆的信息,它们之间可由实验测得的系数相联系。当岩浆饱和硫化物时,在结晶分离过程中硫化物珠滴会与镁铁硅酸盐物质一道析出,同时,与硫化物非饱和岩浆相比,过多的Ni会随之析出。这也反映在Ni、Mg含量比无硫化物分离时有更迅速的降低上。Ni、Mg含量变化值可以在VoiseysBay侵入体的模式曲线上反映出,加拿大Labrador的这一侵入体赋存了一个世界级的Ni-Cu-Co硫化物矿床。过去的作法是将侵入体中橄榄石的Ni、Mg含量与Simkin和Smith得出的各种火成岩中橄榄石的Ni、Mg含量相比较以确定Ni亏损,进而假定橄榄石来自硫化物饱和、有经济价值的岩浆。现在的研究显示这种简单的对比会导致错误。将样品数据与模式曲线对比并反映出侵入体矿物结晶堆积特征是重要的方法。使用这一方法,样品数据能很好地被模式曲线拟合。以在VoiseysBay的研究为例,当硫化物液相与硅酸盐矿物被去除后,硫化物非饱和的分离作用期就会显现出来,随后是硅酸盐结晶作用期。