Melt composition control of Zr/Hf fractionation in magmatic processes

Zircon (ZrSiO₄) and hafnon (HfSiO₄) solubilities in water-saturated granitic melts have been determined as a function of melt composition at 800° and 1035°C at 200 MPa. The solubilities of zircon and hafnon in metaluminous or peraluminous melts are orders of magnitude lower than in strongly peralkaline melt. Moreover, the molar ratio of zircon and hafnon solubility is a function of melt composition. Although the solubilities are nearly identical in peralkaline melts, zircon on a molar basis is up to five times more soluble than hafnon in peraluminous melts. Accordingly, calculated partition coefficients of Zr and Hf between zircon and melt are nearly equal for the peralkaline melts, whereas for metaluminous and peraluminous melts D_Hf/D_Zr for zircon is 0.5 to 0.2. Consequently, zircon fractionation will strongly decrease Zr/Hf in some granites, whereas it has little effect on the Zr/Hf ratio in alkaline melts or similar depolymerized melt compositions.The ratio of the molar solubilities of zircon and hafnon for a given melt composition, temperature, and pressure is proportional to the Hf/Zr activity coefficient ratio in the melt. The data imply that this ratio is nearly constant and probably close to unity for a wide range of peralkaline and similar depolymerized melts. However, it changes by a factor of two to five over a relatively small interval of melt compositions when a nearly fully polymerized melt structure is approached. For most ferromagnesian minerals in equilibrium with a depolymerized melt, D_Hf > D_Zr. Typical values of D_Hf/D_Zr range from 1.5 to 2.5 for clinopyroxene, amphibole, and titanite. Because of the change in the Hf/Zr activity ratio in the melt, the relative fractionation of Zr and Hf by these minerals will disappear or even be reversed when the melt composition approaches that of a metaluminous or peraluminous granite. It is thus not surprising that fractional crystallization of such granitic magmas leads to a decrease in Zr/Hf, whereas fractional crystallization of depolymerized melts tends to increase Zr/Hf. There is no need to invoke fluid metasomatism to explain these effects. Results demonstrate that for ions with identical charge and nearly identical radius, crystal chemistry does not alone determine relative compatibilities. Rather, the effect of changing activity coefficients in the melt may be comparable to or even larger than elastic strain effects in the crystal lattice.     

S- and O-isotopic character of dissolved sulphate in the cover rock aquifers of a Zechstein salt dome

Sulfur and O isotope analyses of dissolved SO₄ were used to constrain a hydrogeological model for the area overlying the Gorleben–Rambow Salt Structure, Northern Germany. Samples were collected from 80 wells screened at different depth-intervals. The study area consists of a set of two vertically stacked aquifer systems. Generally, the isotope data show a good spatial correlation, outlining well-defined groundwater zones containing SO₄ of characteristic isotopic composition. Highly saline waters from deeper parts of the lower aquifer system are characterized by rather constant SO₄ isotopic compositions, which are typical of Permian Zechstein evaporites (δ³⁴S=9.6–11.9‰; δ¹⁸O=9.5–12.1‰). Above this is a transition zone containing ground waters of intermediate salinity and slightly higher isotopic values (average δ³⁴S=16.6‰; δ¹⁸O=15.3‰). The confined groundwater horizon on the top of the lower aquifer system below the low permeable Hamburg Clays is low in total dissolved solids and is characterized by an extreme ³⁴S enrichment (average δ³⁴S=39.1‰; δ¹⁸O=18.4‰), suggesting that bacterially mediated SO₄ reduction is a dominant geochemical process in this zone. Two areas of distinct isotopic composition can be identified in the shallow ground water horizons of the upper hydrogeological system. Sulfate in groundwaters adjacent to the river Elbe and Löcknitz has a typical meteoric isotopic signature (δ³⁴S=5.2‰; δ¹⁸O=8.2‰), whereas the central part of the area is characterized by more elevated isotopic ratios (δ³⁴S=12.7‰; δ¹⁸O=15.6‰). The two major SO₄ pools in the area are represented by Permian seawater SO₄ and a SO₄ of meteoric origin that has been mixed with SO₄ resulting from the oxidation of pyrite. It is suggested that the S-isotope compositions observed reflect the nature of the SO₄ source that have been modified to various extent by bacterial SO₄ reduction. Groundwaters with transitional salinity have resulted from mixing between brines and low-mineralized waters affected by bacterial SO₄ reduction.     

Chemical, biological and hydrological controls on the C content of cold seep carbonate crusts: numerical modeling and implications for convection at cold seeps

Understanding the hydrology of cold seep environments is crucial to perform accurate estimates of fluid and chemical fluxes at sedimentary wedges. Shallow convection processes may affect fluid flux estimates and could favor the destabilization of gas hydrate accumulations, increasing the sediment-ocean methane flux. Evidence for the occurrence of convection at cold seeps, however, is still limited. We use the concentration of ¹⁴C (D¹⁴C) in carbonate crusts formed at cold seeps of the eastern Mediterranean Sea as a tracer for convective recirculation of seawater-derived fluids. A numerical model is applied to investigate the controls on ¹⁴C incorporation in cold seep carbonates. Our simulations show that increased amounts of CH₄ in the expelled fluids result in elevated crust D¹⁴C, while high Ca²⁺ and HCO₃⁻ concentrations produce the opposite effect. Convection is the only transport process that can significantly increase crust D¹⁴C. Advection, bioirrigation, eddy diffusion and bioturbation instead, have little effect on, or produce a decrease of, crust D¹⁴C. In addition, the presence of old or modern carbon (MC) in host sediments prior to cementation and the ¹⁴C-decay associated to the time needed to form the crust contribute in defining the D¹⁴C of carbonate crusts. We then use the model to reproduce the ¹⁴C content of the eastern Mediterranean Sea crusts to constrain the chemical and hydrological conditions that led to their formation. Some crusts contain relatively low amounts of ¹⁴C (−945.0<D¹⁴C ‰<−930.2) which, assuming no ageing after crust formation, can be reproduced without considering convection. Other crusts from two sites (the Amsterdam and Napoli mud volcanoes), instead, have a very high ¹⁴C-content (−899.0<D¹⁴C ‰<−838.4) which can only be reproduced by the model if convection mixes deep fluids with seawater. Order-of-magnitude calculations using the Rayleigh criterion for convection suggest that the slow seepage (about 10 cm year⁻¹) of low salinity (20‰) fluids at the Amsterdam sites could trigger haline convection there. On the Napoli mud volcano, where high-density brines are expelled, density-driven convection cannot take place and other processes, possibly involving the rapid movement of free gas in the sediment, could be important.     

Shopping behaviour in the ?resund region before and after the establishment of the fixed link between Denmark and Sweden

In July 2000 the 15.5 km long fixed link across the Øresund was opened, connecting the Danish capital Copenhagen and the Swedish city of Malmö. With the decrease of the barrier an enlarged flow of shoppers was expected with Swedish customers availing themselves of the range of opportunities in the Copenhagen area and Danish customers making use of the much longer shop opening hours in Sweden. However, experience from other European border areas shows that customers tend to do their ordinary shopping in their home countries and that there must be significant differences in prices or ranges of goods to overcome the barrier of the border. Does the typical situation result from the rural nature of many border areas, and will matters be quite different in a metropolitan area? The purpose of the present paper is to describe the level and character of cross-border shopping by the residents of the Øresund region before and after the opening of the fixed link. Responses from about 4,000 people form the basis of the conclusion that a little less than a year after the opening of the fixed link the number of shopping trips across the Øresund had increased, but there was still no heavy flow of customers doing ordinary shopping in the neighbouring countries. In order to assess the level of cross-border shopping across the Øresund the findings are compared to those from surveys across the Danish-German land border.     

In situ experiments and seismic analysis of existing buildings. Part II: Seismic integrity threshold

The interest of in situ measurements (presented in Part I paper) for a seismic assessment of existing buildings is analysed in this paper. It is shown that the experimental modal characteristics obtained on regular concrete structures are described successfully by suited Timoshenko beam modelling. For a given structure, taking into account the experimental data, the corresponding beam model, and choosing the maximum tensile strain of concrete as damage criterion for key structural elements, a maximum level of the ground acceleration can be determined. This so‐called seismic integrity threshold is directly related to the onset of structural damages. This new approach is illustrated on one of the studied buildings. The advantages of using ambient vibrations survey for the vulnerability assessment of existing buildings are discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

A coupled simple climate model and its global analysis

Summary An atmosphere-land coupled simple climate model is constructed and its climatic properties are analyzed by introducing a global analysis method, cell mapping. The simple model is a nonlinear six order simplified climate model featured with chaotic dynamics, dissipation, and forcing source, which are the main features of the real climate system. The cell mapping method is applied with this coupled system. Numerical experiments are carried out for investigating the interactions between the fast-changing atmospheric variables and slow-changing underlying surface variables. The predictability of the system is also investigated via the global analysis, with which the evolution of the system is translated to the evolution of probability transition on a Markov Chain. An effective scheme is proposed for computing the probability transition matrix for the coupled system. Predictions can be made based on the combination of dynamics and statistics. The importance of constructing the coupled model is shown by globally analyzing the predictability of the coupled system. The coupling mechanism prolongs the memorization of initial information, and then the predictability as well.     

European VOC Emission Estimates Evaluated by Measurements and Model Calculations

Observations and model calculations of the concentration of hydrocarbonsat five Scandinavian rural sites during March–June 1993are reported.Decreasing concentrations from March to June are observedat all sites. The highest concentrations of hydrocarbons were found in air massescoming in from the southwest to southeast, indicating that long rangetransport fromcontinental Europe and the U.K. is important in pollution episodes. An episode of elevated concentrations of hydrocarbons observed at three of the sites in the middle of Marchis described and discussed in relation to the synoptic situation and thepresenceof other chemical compounds (NO₂, PAN, total nitrate andozone).A Lagrangian numerical model is used to calculate the concentrations of theindividual hydrocarbons at the fivesites and comparison with observations is made.The calculated concentrations for nonmethane hydrocarbons with quite longchemicallifetimes agree well with the observations.For the sum of observed and calculated hydrocarbons the correlationcoefficientsare in the range of 0.65–0.88 for the five sitesand the ratio between calculated and measured concentrations was0.72–0.97, indicating thatthe European VOC emission inventory is quite well estimated.     

Spinel peridotite xenoliths from the Atsagin-Dush volcano, Dariganga lava plateau, Mongolia: a record of partial melting and cryptic metasomatism in the upper mantle

Spinel peridotite xenoliths from the Atsagin-Dush volcanic centre, SE Mongolia range from fertile lherzolites to clinopyroxene(cpx)-bearing harzburgites. The cpx-poor peridotites typically contain interstitial fine-grained material and silicate glass and abundant fluid inclusions in minerals, some have large vesicular melt pockets that apparently formed after primary clinopyroxene and spinel. No volatile-bearing minerals (amphibole, phlogopite, apatite, carbonate) have been found in any of the xenoliths. Fifteen peridotite xenoliths have been analysed for major and trace elements; whole-rock Sr isotope compositions and O isotope composition of all minerals were determined for 13 xenoliths. Trace element composition and Sr-Nd isotope compositions were also determined in 11 clinopyroxene and melt pocket separates. Regular variations of major and moderately incompatible trace elements (e.g. heavy-rare-earth elements) in the peridotite series are consistent with its formation as a result of variable degrees of melt extraction from a fertile lherzolite protolith. The Nd isotope compositions of LREE (light-rare-earth elements)-depleted clinopyroxenes indicate an old (≥ 1 billion years) depletion event. Clinopyroxene-rich lherzolites are commonly depleted in LREE and other incompatible trace elements whereas cpx-poor peridotites show metasomatic enrichment that can be related to the abundance of fine-grained interstitial material, glass and fluid inclusions in minerals. The absence of hydrous minerals, ubiquitous CO₂-rich microinclusions in the enriched samples and negative anomalies of Nb, Hf, Zr, and Ti in primitive mantle-normalized trace element patterns of whole rocks and clinopyroxenes indicate that carbonate melts may have been responsible for the metasomatic enrichment. Low Cu and S contents and high δ³⁴S values in whole-rock peridotites could be explained by interaction with oxidized fluids that may have been derived from subducted oceanic crust. The Sr-Nd isotope compositions of LREE-depleted clinopyroxenes plot either in the MORB (mid-ocean-ridge basalt) field or to the right of the mantle array, the latter may be due to enrichment in radiogenic Sr. The LREE-enriched clinopyroxenes and melt pockets plot in the ocean island-basalt field and have Sr-Nd isotope signatures consistent with derivation from a mixture of the DMM (depleted MORB mantle) and EM (enriched mantle) II sources. Received: 18 January 1996 / Accepted: 23 August 1996     

Partial fusion of basic granulites at 5 to 15 kbar: implications for the origin of TTG magmas

Partial fusion experiments with basic granulites (S6, S37) believed to represent the lower crust beneath the Eifel region (Germany) were performed at pressures from 5 to 15 kbar. Water-undersaturated experiments were carried out in the presence of 1 wt% H₂O plus 2.44 or 0.81 wt% CO₂ equivalent to mole fractions of H₂O/(H₂O + CO₂) of 0.5 and 0.75, respectively, of the volatile components added. At temperatures from 850 to 1100 °C the weight proportions of melt range from 7 to 30 %. Melt compositions change from trondhjemitic over tonalitic to dioritic with increasing degree of partial melting. Crystalline residua are plagioclase/pyroxene dominated at 5 kbar to garnet/pyroxene dominated at 15␣kbar. Dehydration melting was studied in granulite S35 similar in composition to S6. The magmatic precursors of the granulite xenoliths used in this study had geochemical characteristics of cumulate gabbro (metagabbro S37) and evolved melts (metabasalts S6, S35), respectively. Melts from granulite S37 match the major element compositions of natural trondhjemites and tonalites. At 5 kbar, their Al₂O₃ is relatively low, similar to tonalites from ophiolites. At 15 kbar, Al₂O₃ in the melts is high due to the near absence of plagioclase in the crystalline residua. The Al₂O₃ concentrations in 15 kbar melts from S6 (˜20 wt%) are higher than in natural tonalites. Depth constraints on the formation of tonalitic magmas in the continental crust are provided by REE (rare earth element) patterns of the synthetic melts calculated from the known REE abundances in metagabbro S37 and metabasalt S6 assuming batch melting and using partition coefficients from the literature. The REE patterns of tonalites from active continental margins and Archean trondhjemite-tonalite-granodiorite␣associations low in REE with La_N (chondrite normalised) from 10 to 30 and Yb_N from 1 to 2 are reproduced at pressures of 10 and 12.5 kbar from metagabbro S37 which displays a slightly L(light)REE enriched pattern with La_N = 8 and Yb_N = 3. Natural tonalites with La_N from 30 to 100 require a source richer in REE than granulite S37. At 15 kbar, H(heavy)REE_N in melts from granulite S37 are depressed below the level observed in natural tonalites due to the high proportion of garnet (>30 wt%) in the residue. Melts from metabasalt S6 (enriched in REE with La_N = 38 and Yb_N = 16) do not match the REE characteristics of natural tonalites under any conditions. Received: 1 July 1994 / Accepted: 11 September 1996