Ar and Ar recoil loss during neutron irradiation of sanidine and plagioclase

The ⁴⁰Ar/³⁹Ar dating technique requires the activation of ³⁹Ar via neutron irradiation. The energy produced by the reaction is transferred to the daughter atom as kinetic energy and triggers its displacement, known as the recoil effect. Significant amounts of ³⁹Ar and ³⁷Ar can be lost from minerals leading to spurious ages and biased age spectra. Through two experiments, we present direct measurement of the recoil-induced ³⁹Ar and ³⁷Ar losses on Fish Canyon sanidine and plagioclase. We use multi-grain populations with discrete sizes ranging from 210 to <5 μm. One population consists of a mixture between sanidine and plagioclase, and the other includes pure sanidine.We show that ³⁹Ar loss (depletion factor) for sanidine is ∼3% for the smallest fraction. Age spectra of fractions smaller than ∼50 μm show slight departure from flat plateau-age spectrum usually observed for large sanidine. This departure is roughly proportional to the size of the grain but does not show typical ³⁹Ar loss age spectra. The calculated thickness of the total depletion layer d₀(sanidine) is 0.035 ± 0.012 (2σ). This is equivalent to a mean depth of the partial depletion layer (x₀) of 0.070 ± 0.024 μm. The latter value is indistinguishable from previous values of ∼0.07-0.09 μm obtained by argon implantation experiments and simulation results.We show that it is possible to adequately correct ages from ³⁹Ar ejection loss provided that the d₀-value and the size range of the minerals are sufficiently constrained. As exemplified by similar calculations performed on results obtained in a similar study of GA1550 biotite [Paine J. H., Nomade S., and Renne P. R. (2006) Quantification of ³⁹Ar recoil ejection from GA1550 biotite during neutron irradiation as a function of grain dimensions. Geochim. Cosmochim. Acta70, 1507-1517.], the d₀(biotite) is 0.46 ± 0.06 μm. The significant difference between empirical results on biotite and sanidine, along with different simulation results, suggests that for biotite, crystal structures and lattice defects of the stopping medium and possibly subsequent thermal degassing (due to ∼150-200 °C temperature in the reactor or extraction line bake out) must play an important role in ³⁹Ar loss.The second experiment suggests that ³⁷Ar recoil can substantially affect the age via the interference corrections with results that suggest up to ∼98% of ³⁷Ar can be ejected from the ∼5 μm grain dimension.Further investigation of silicates of various compositions and structures are required to better understand (and correct) the recoil and recoil-induced effects on both ³⁹Ar and ³⁷Ar and their influences on ⁴⁰Ar/³⁹Ar dating.     

Calibration of GA1550 biotite standard for K/Ar and 40Ar/39Ar dating

The mineral separate GA1550 biotite has become an international standard for K/Ar and ⁴⁰Ar/³⁹Ar dating studies, although it was prepared as an intralaboratory standard at ANU to monitor tracer depletion from a gas pipette. It is one of a small number of samples that has been calibrated against ³⁸Ar tracers, some of which had been mixed with known amounts of atmospheric argon, so that a so-called primary calibration has been performed. By measuring GA1550 biotite against additional tracers from the same batch we have determined the radiogenic argon content of this sample as 1.342 (± 0.007) × 10^? 9 mol/g, and together with the measured K content of 7.645 (± 0.050) weight percent, we derive a best estimate for the K/Ar age as 98.5 ± 0.5 Ma, where the error is derived from averaging the ages determined relative to the ³⁸Ar tracer.     

Ammonium loss and nitrogen isotopic fractionation in biotite as a function of metamorphic grade in metapelites from western Maine, USA

Ammonium fixed in micas of metamorphic rocks is a sensitive indicator both of organic-inorganic interactions during diagenesis as well as of the devolatilization history and fluid/rock interaction during metamorphism. In this study, a collection of geochemically well-characterized biotite separates from a series of graphite-bearing Paleozoic greenschist- to upper amphibolite-facies metapelites, western Maine, USA, were analyzed for ammonium nitrogen () contents and isotopic composition (δ¹⁵N_NH4) using the HF-digestion distillation technique followed by the EA-IRMS technique. Biotite separates, sampled from 9 individual metamorphic zones, contain 3000 to 100 ppm with a wide range in δ¹⁵N from +1.6‰ to +9.1‰. Average contents in biotite show a distinct decrease from about 2750 ppm for the lowest metamorphic grade (∼500 °C) down to 218 ppm for the highest metamorphic grade (∼685 °C). Decreasing abundances in are inversely correlated in a linear fashion with increasing K⁺ in biotite as a function of metamorphic grade and are interpreted as a devolatilization effect. Despite expected increasing δ¹⁵N_NH4 values in biotite with nitrogen loss, a significant decrease from the Garnet Zones to the Staurolite Zones was found, followed by an increase to the Sillimanite Zones. This pattern for δ¹⁵N_NH4 values in biotite inversely correlates with Mg/(Mg + Fe) ratios in biotite and is discussed in the framework of isotopic fractionation due to different exchange processes between or , reflecting devolatilization history and redox conditions during metamorphism.     

Shear wave velocity as function of cone penetration resistance and grain size for Holocene-age uncemented soils: a new perspective

For feasibility studies and preliminary design estimates, field measurements of shear wave velocity, V _s, may not be economically adequate and empirical correlations between V _s and more available penetration measurements such as cone penetration test, CPT, data turn out to be potentially valuable at least for initial evaluation of the small-strain stiffness of soils. These types of correlations between geophysical (Vs) and geotechnical (N-SPT, q _c-CPT) measurements are also of utmost importance where a great precision in the calculation of the deposit response is required such as in liquefaction evaluation or earthquake ground response analyses. In this study, the stress-normalized shear wave velocity V _s1 (in m/s) is defined as statistical functions of the normalized dimensionless resistance, Q _tn-CPT, and the mean effective diameter, D ₅₀ (in mm), using a data set of different uncemented soils of Holocene age accumulated at various sites in North America, Europe, and Asia. The V _s1–Q _tn data exhibit different trends with respect to grain sizes. For soils with mean grain size (D ₅₀) < 0.2 mm, the V _s1/Q _tn ^0.25 ratio undergoes a significant reduction with the increase in D ₅₀ of the soil. This trend is completely reversed with further increase in D ₅₀ (D ₅₀ > 0.2 mm). These results corroborate earlier results that stressed the use of different CPT-based correlations with different soil types, and those emphasized the need to impose particle-size limits on the validity of the majority of available correlations.     

Characteristics of normal fatty acids from sediments as a function of geologic-geochemical factors

Forty-nine samples from Mesozoic rocks of Northern Bulgaria and from recent marine muds of the Black Sea have been analyzed for fatty acids (FA), using extraction, treatment with ion exchange resin and gas chromatography. There is a higher concentration of normal (n) FA in the recent marine sediments, as well as in their bitumen extracts than in the rocks as a whole. There is twice as much n-FA in the rocks containing dispersed organic matter (DOM) formed mainly by benthonic organisms as compared to ancient sediments with planktonic DOM. The content of n-FA has decreased nine and five times, respectively in planktonic DOM in the sequence: limestones-marls-argillites and clayey siltstones, while the amount of organic carbon has risen four and two times. The n-FA are chiefly represented by C₁₆ and C₁₈ and in the recent sediments also by C₂₂ molecules. However when the level of maturity of DOM corresponds to the katagenetic degrees of MK₃ and MK₄, maximum is in n-FA with 19 and 20 carbon atoms. A gradual decrease in the amount of the n-FA with even-numbered carbon atoms was noted as maturity of the planktonic DOM increases from early diagenesis in recent marine sediments to the katagenetic degrees of MK₃ and MK₄ in ancient rocks. The ratios $\text{FA}\text{HC}$ and $\text{FA}\text{HC}\text{+ FA}$ have also decreased when the katagenetic maturity of DOM changes from PK₃ degree to MK₄ degree. These geochemical features may be used as an additional criterion in determining the principal phase of oil formation.     

Characterization of the CO2 fluid adsorption in coal as a function of pressure using neutron scattering techniques (SANS and USANS)

Small angle neutron scattering techniques have been applied to investigate the phase behavior of CO₂ injected into coal and possible changes in the coal pore structure that may result from this injection. Three coals were selected for this study: the Seelyville coal from the Illinois Basin (R_o = 0.53%), Baralaba coal from the Bowen Basin (R_o = 0.67%), and Bulli 4 coal from the Sydney Basin (R_o = 1.42%). The coals were selected from different depths to represent the range of the underground CO₂ conditions (from subcritical to supercritical) which may be realized in the deep subsurface environment. The experiments were conducted in a high pressure cell and CO₂ was injected under a range of pressure conditions, including those corresponding to in-situ hydrostatic subsurface conditions for each coal. Our experiments indicate that the porous matrix of all coals remains essentially unchanged after exposure to CO₂ at pressures up to 200 bar (1 bar = 10⁵ Pa). Each coal responds differently to the CO₂ exposure and this response appears to be different in pores of various sizes within the same coal. For the Seelyville coal at reservoir conditions (16 °C, 50 bar), CO₂ condenses from a gas into liquid, which leads to increased average fluid density in the pores (ρ_pore) with sizes (r) 1 × 10⁵ ≥ r ≥ 1 × 10⁴ Å (ρ_pore ≈ 0.489 g/cm³) as well as in small pores with size between 30 and 300 Å (ρ_pore ≈ 0.671 g/cm³). These values are by a factor of three to four higher than the density of bulk CO₂ (ρ_CO2) under similar thermodynamic conditions (ρ_CO2 ≈ 0.15 g/cm³). At the same time, in the intermediate size pores with r ≈ 1000 Å the average fluid density is similar to the density of bulk fluid, which indicates that adsorption does not occur in these pores. At in situ conditions for the Baralaba coal (35 ^OC, 100 bar), the average fluid density of CO₂ in all pores is lower than that of the bulk fluid (ρ_pore / ρ_CO2 ≈ 0.6). Neutron scattering from the Bulli 4 coal did not show any significant variation with pressure, a phenomenon which we assign to the extremely small amount of porosity of this coal in the pore size range between 35 and 100,000 Å.     

Volatile organic compounds emitted from hardwood drying as a function of processing parameters

During the drying of wood, volatile organic compounds are emitted. These emissions contribute, in the presence of nitrogen oxides and sunlight, to the formation of ground level ozone and other harmful photo-oxidants. Emissions of volatile organic compounds from the drying of birch sawdust in a spouted bed were analyzed with a flame ionization detector and with a gas chromatograph-mass spectrometer. A D-optimal model of the emissions showed that the emissions increased exponentially with decreasing sawdust moisture content and that the final sawdust moisture content was influencing emissions about twice as much as the inlet drying medium temperature and the month of logging. At inlet temperatures of 140–170 °C, the emissions increased steeply when the moisture content of the sawdust reached 10%, whereas an inlet temperature of 200 °C caused a surge of thermal degradation products at 15% moisture content. The results of this study should help to reduce the emissions of volatile hydrocarbons during the drying of hardwood sawdust and wood chips.     

The non-oxidative dissolution of galena nanocrystals: Insights into mineral dissolution rates as a function of grain size, shape, and aggregation state

The acidic, non-oxidative dissolution of galena (PbS) nanocrystals has been studied in detail using transmission electron microscopy (TEM) to follow the evolution of the size and shape of the nanocrystals before and after dissolution experiments, X-ray photoelectron spectroscopy (XPS) to follow particle chemistry, and dissolution rate analysis to compare dissolution rates between nanocrystalline and bulk galena. Dissolution characteristics were also studied as a function of nanocrystal access to bulk vs. confined solution due to the degree of proximity of next-nearest grains. Nearly monodisperse galena nanocyrstals with an average diameter of 14.4 nm were synthesized for this study, and samples were exposed to pH 3, deoxygenated HCl solutions for up to 3 h at 25 °C. Detailed XPS analysis showed the nanocrystals to be free of unwanted contamination, surface complexes, and oxidative artifacts, except for small amounts of lead-containing oxidation species in both pre- and post-dissolution samples which have been observed in fresh, natural bulk galena. Depending on the calculation methods used, galena nanocrystals, under the conditions of our experiments, dissolve at a surface area normalized rate of one to two orders of magnitude faster than bulk galena under similar conditions. We believe that this reflects the higher percentage of reactive surface area on nanocrystalline surfaces vs. surfaces on larger crystals. In addition, it was shown that {1 1 1} and {1 1 0} faces dissolve faster than {1 0 0} faces on nanocrystals, rationalized by the average coordination number of ions on each of these faces. Finally, dissolution was greatly inhibited for galena nanocrystal surfaces that were closely adjacent (1-2 nm, or less) to other nanocyrstals, a direct indication of the properties of aqueous solutions and ion transport in extremely confined spaces and relevant to dissolution variations that have been suspected within aggregates.     

The geological significance of 40Ar/39Ar and Rb–Sr white mica ages from Syros and Sifnos,Greece: a record of continuous (re)crystallization during exhumation?

The Attic‐Cycladic crystalline belt in the central Aegean region records a complex structural and metamorphic evolution that documents Cenozoic subduction zone processes and exhumation. A prerequisite to develop an improved tectono‐metamorphic understanding of this area is dating of distinct P–T–D stages. To evaluate the geological significance of phengite ages of variably overprinted rocks, ⁴⁰Ar/³⁹Ar and Rb–Sr analyses were undertaken on transitional blueschist–greenschist and greenschist facies samples from the islands of Syros and Sifnos. White mica geochronology indicates a large age variability (⁴⁰Ar/³⁹Ar: 41–27 Ma; Rb–Sr: 34–20 Ma). Petrologically similar samples have either experienced greenschist facies overprinting at different times or variations in ages record variable degrees of greenschist facies retrogression and incomplete resetting of isotopic systematics. The ⁴⁰Ar/³⁹Ar and Rb–Sr data for metamorphic rocks from both islands record only minor, localized evidence for Miocene ages (c. 21 Ma) that are well documented elsewhere in the Cyclades and interpreted to result from retrogression of high‐pressure mineral assemblages during lower pressure metamorphism. Field and textural evidence suggests that heterogeneous overprinting may be due to a lack of permeability and/or limited availability of fluids in some bulk compositions and that retrogression was more or less parallel to lithological layering and/or foliation as a result of, possibly deformation‐enhanced, channelized fluid ingress. Published and new ⁴⁰Ar/³⁹Ar and Rb–Sr data for both islands indicate apparent age variations that can be broadly linked to mineral assemblages documenting transitional blueschist‐to‐greenschist‐ and/or greenschist facies metamorphism. The data do not record the timing of peak HP metamorphism, but may accurately record continuous (partial) resetting of isotopic systematics and/or (re)crystallization of white mica during exhumation and greenschist facies retrogression. The form of ⁴⁰Ar/³⁹Ar phengite age spectra are complex with the lowest temperature steps yielding Middle to Late Miocene ages. The youngest Rb–Sr ages suggest maximum ages of 20.6 ± 0.8 Ma (Syros) and 22.5 ± 0.6 Ma (Sifnos) for the timing of greenschist facies overprinting. The results of this study further accentuate the challenges of interpreting isotopic data for white mica from polymetamorphic terranes, particularly when mixing of populations and/or incomplete resetting of isotopic systematics occurs during exhumation. These data capture the full range of isotopic age variations in retrogressed HP rocks documented in previous isotopic studies, and can be interpreted in terms of the geodynamic evolution of the Aegean.     

从沉积速率和沉积物粒度看冰后期海侵以来珠江三角洲西江大鳌沙的形成

大鳌沙处于珠江三角洲西江河口的近口段,洪季西江河口的潮区界西线在其顶端附近。冰后期海侵以来,大鳌沙顶端的PRD05和中部的PRD04两个钻孔的沉积速率和沉积物粒度有着极大的差别。7 630 a BP以前,PRD04孔的沉积速率小于PRD05孔的沉积速率;但7 630 a BP以来,PRD04孔的沉积速率大于PRD05孔的沉积速率。从粒度分析看,埋深12.28 m以下,PRD04孔沉积物比PRD05孔的粗,分选性比PRD05孔的差;埋深12.28 m以上,PRD04孔的沉积物比PRD05孔的细,分选性相对比PRD05孔的好。分析表明,9 000～4 200a BP, 沉积物由南（中部）向北（顶部）输运,涨潮流冲蚀老沉积物,在喷出磨刀门通道后,流速迅速降低,粗颗粒泥沙先沉积,而细颗粒泥沙被涨潮流搬运至更北的区域沉积。近3500年以来,河流动力占优势,沉积物由北（顶部）向南（中部）输运。大鳌沙的形成与涨潮射流密切相关。涨潮射流口的位置在蛇地山和右岸纵向山地之间,宽约2200 m。     

Albite dissolution kinetics as a function of distance from equilibrium: Implications for natural feldspar weathering

Determining the kinetics of many geologic and engineering processes involving solid/fluid interactions requires a fundamental understanding of the Gibbs free energy dependency of the system. Currently, significant discrepancies seem to exist between kinetic datasets measured to determine the relationship between dissolution rate and Gibbs free energy. To identify the causes of these discrepancies, we have combined vertical scanning interferometry, atomic force microscopy, and scanning electron microscopy techniques to identify dissolution mechanisms and quantify dissolution rates of albite single crystals over a range of Gibbs free energy (−61.1 < ΔG < −10.2 kJ/mol). During our experiments, both a previously dissolved albite surface exhibiting etch pits and a pristine surface lacking dissolution features were dissolved simultaneously within a hydrothermal, flow-through reactor. Experimental results document an up to 2 orders of magnitude difference in dissolution rate between the differently pretreated surfaces, which are dominated by different dissolution mechanisms. The rate difference, which persists over a range of solution saturation state, indicates that the dissolution mechanisms obey different Gibbs free energy dependencies. We propose that this difference in rates is the direct consequence of a kinetic change in dissolution mechanism with deviation from equilibrium conditions. The existence of this kinetic “switch” indicates that a single, continuous function describing the relationship between dissolution rate and Gibbs free energy may be insufficient. Finally, we discuss some of the potential consequences of our findings on albite’s weathering rates with a particular focus on the sample’s history.     

Porphyroblast nucleation, growth and dissolution in regional metamorphic rocks as a function of deformation partitioning during foliation development

Abstract In regional metamorphic rocks, the partitioning of deformation into progressive shearing and progressive shortening components results in strain and strain-rate gradients across the boundaries between the partitioned zones. These generate dislocation density gradients and hence chemical potential gradients that drive dissolution and solution transfer. Phyllosilicates and graphite are well adapted to accommodating progressive shearing without necessarily building up large dislocation density gradients within a grain, because of their uniquely layered crystal structure. However, most silicates and oxides cannot accommodate strain transitions within grains without associated dislocation density gradients, and hence are susceptible to dissolution and solution transfer. As a consequence, zones of progressive shearing become zones of dissolution of most minerals, and of concentration of phyllosilicates and graphite. Exceptions are mylonites, where strain-rates are commonly high enough for plastic deformation to dominate over diffusion rates and therefore over dissolution and solution transfer. Porphyroblastic minerals cannot nucleate and grow in zones of active progressive shearing, as they would be dissolved by the effects of shearing strain on their boundaries. However, they can nucleate and grow in zones of progressive shortening and this is aided by the propensity for microfracturing in these zones, which allows rapid access of fluids carrying the material presumed to be necessary for nucleation and growth. Zones of progessive shortening also have a number of characteristics that help to lower the activation energy barrier for nucleation, this includes a build up of stored strain-energy relative to zones of progressive shearing, in which dissolution is occuring. Porphyroblast growth is generally syndeformational, and previously accepted criteria for static growth are not valid when the role of deformation partitioning is taken into account. Porphyroblasts in a contact aureole do not grow statically either, as microfracturing, associated with emplacement, allows access of fluids in a fashion that is similar to microfracturing in zones of progressive shortening. The criteria used for porphyroblast timing can be readily accommodated in terms of deformation partitioning, reactivation of deforming foliations, and a general lack of rotation of porphyroblasts, with the spectacular exception of genuinely spiralling garnet porphyroblasts.     

Vanadium and niobium behavior in rutile as a function of oxygen fugacity: evidence from natural samples

Vanadium occurs in multiple valence states in nature, whereas Nb is exclusively pentavalent. Both are compatible in rutile, but the relationship of V–Nb partitioning and dependence on oxygen fugacity (expressed as fO₂) has not yet been systematically investigated. We acquired trace-element concentrations on rutile grains (n = 86) in nine eclogitic samples from the Dabie-Sulu orogenic belt by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and combined them with published results in order to assess the direct and indirect effects of oxygen fugacity on the partitioning of V and Nb into rutile. A well-defined negative correlation between Nb (7–1,200 ppm) and V concentrations (50–3,200 ppm) was found, documenting a competitive relationship in the rutile crystal that does not appear to be controlled by bulk rock or mineral compositions. Based on the published relationship of ^RtD_V and V valence with ?QFM, we suggest that the priority order of V incorporation into rutile is V⁴⁺ > V³⁺ > V⁵⁺. The inferred Nb–V competitive relationship in rutile from the Dabie-Sulu orogenic belt could be explained by decreasing fO₂ due to dehydration reactions involving loss of oxidizing fluids during continental subduction: The increased proportion of V³⁺ (expressed as V³⁺/∑V) and attendant decrease in ^RtD_V is suggested to lead to an increase in rutile lattice sites available for Nb⁵⁺. A similar effect may be observed under more oxidizing conditions. When V⁵⁺/∑V increases, ^RtD_V shows a dramatic decline and Nb concentration increases considerably. This is possibly documented by rutile in highly metasomatized and oxidized MARID-type (MARID: mica–amphibole–rutile–ilmenite–diopside) mantle xenoliths from the Kaapvaal craton, which also show a negative V–Nb covariation. In addition, their Nb/Ta covaries with V concentrations: For V concentrations <1,250 ppm, Nb/Ta ranges between 35 and 45, whereas for V > 1,250 ppm, Nb/Ta is considerably lower (5–15). This relationship is mainly controlled by a change in Nb concentrations, suggesting that the indirect dependence of ^RtD_Nb on fO₂, which is not mirrored in ^RtD_Ta, can exert considerable influence on rutile Nb–Ta fractionation.     

The leaching of major and trace elements from MSWI bottom ash as a function of pH and time

In this paper, the leaching behaviour of major components (Al, Ca, SO₄, Mg, Si, Fe, Na and DOC) and trace elements (Ni, Zn, Cd, Cu, Pb, Mo and Sb) from MSWI bottom ash is studied as a function of time over a wide range of pH, under pH-controlled conditions. Equilibrium geochemical modelling using the modelling framework ORCHESTRA is used to enable a process-based interpretation of the results and to investigate whether ‘equilibrium’ is attained during the time scale of the experiments. Depending on the element and setpoint-pH value, net concentration increases or decreases of up to one order of magnitude were observed. Different concentration–time trends (increase or decrease) are observed in different pH ranges. The direction of the concentration–time trends depends on: (1) the shape of the ‘equilibrium’ solubility curve, and (2) the position of the setpoint-pH in the leaching test relative to the natural pH of the sample. Although the majority of the elements do not reach steady state, leached concentrations over a wide pH range have been shown to closely approach ‘equilibrium’ model curves within an equilibration time of 168 h. The different effects that leaching kinetics may have on the pH dependent leaching patterns have been identified for a wide range of elements, and can generally be explained in a mechanistic way. The results are in support of the currently prescribed equilibration time of 48 h in the European standard for the pH-static leaching test (TS14997). Finally, this study demonstrates that pH-static leaching experiments such as described in the European standards (TS14497 and TS14429), in combination with selective chemical extractions and a mechanistically based modelling approach, constitute a powerful set of tools for the characterization of leaching processes in waste materials over a wide range of conditions.     

Element partitioning in calcite as a function of solution flow rate: a study on vein calcites from the Harz Mountains

A semi-empirical treatment of isothermal element partitioning caused by flow rate-dependent calcite growth from hydrothermal solutions yields element/Ca ratios that are qualitatively similar to those observed in calcite bands of the Pb-Zn banded ores from the Harz Mountains, Germany. The comparison of the calculations with the analytical results suggests that flow rates varied between episodes of calcite precipitation as well as during formation of individual bands. Based on a flow rate-dependent element partition coefficient, changing element/Ca ratios in precipitates from a hydrotherm are therefore not necessarily indicative of changing compositions of the fluid. The variations in element/Ca ratios to be envisaged could be as much as a factor of three.Notation A defined by Eq. 8 - a, b individual values of any element in Eq. 1 - c concentration in moles/m³ - C ₀ initial concentration moles/m³ - i running parameter - F area of precipitation in m² - k _p rate constant of pth order reaction in s · m³/moles^p - R linear (one-dimensional) growth rate in moles/m² · s - p order of growth reaction - s distance from entry of solution in m - s ₀ vertical extension of a vein in m - t time in s - v flow rate of hydrothermal solution in m/s - v₀ standard flow rate in m/s - _r relative flow rate in multiple of v₀ - fraction of total precipitation - ₀ fraction of precipitation under reference conditions when the hydrothermal solution leaves the vein - defining the sign in Eq. 1 for elements that are en riched (= +1) or impoverished (= -1) - logarithmic partition coefficient in Eq. 10 - (R) logarithmic partition coefficient as a function of variable growth rate - [ ], { } concentration ratios of fluids and solids, respectively - EL/Ca calculated ratio of El/Ca in the calcite surface zone after Eq. 11     

Mobility of heavy metals as a function of pH of samples from an overbank sediment profile contaminated by mining activities

Parts of the flood plains north of the Harz Mountains are contaminated with heavy metals, such as Pb, Cu, Zn and Cd derived from mining, which has been carried out in the Harz Mts. since the Middle Ages. It is important to know the mobility of the heavy metals in these overbank sediments in order to estimate the danger to the environment arising from this source. This paper deals with the effect of pH on heavy-metal mobility, using a constant-pH method. The investigations were carried out on an overbank sediment profile near Salzgitter Bad, north of the Harz Mts. The mobility of the heavy metals in the overbank sediment profile is described as a function of pH and depth. Besides the mobile heavy-metal fraction at a certain pH, the buffering capacity of the sediment at this pH must be taken into consideration. The different layers of the overbank sediment profile show distinct differences in buffering capacity and a natural pH harrier could be identified in the upper part of the profile. Therefore, to avoid increasing heavy-metal mobility the natural layering of the overbank sediment profile should not be disturbed. Two different kinds of desorption experiments at constant pH are also discussed, as well as the conversion of the heavy-metal species in the ore minerals into the species in the sediment.     

Compositional variation of muscovite as a function of metamorphic grade and assemblage in metapelites from N.W. Maine

Chemical data are presented for 49 muscovites from high and low Al specimens collected form N.W. Maine at metamorphic grades ranging from the upper staurolite to the upper sillimanite zone. Data also are presented for two muscovite from St. Paul Island, two muscovites+three paragonites from Gassetts, Vermont, and one muscovite from an adamellite in N. W. Maine.These data given further information on the effects of P, T, and bulk composition on muscovite composition. Specifically, temperature clearly influences the Na/Na+K ratio of muscovite in limiting assemblages but may not have much effect on the phengite content. Increase in pressure clearly does cause an increase in phengite content. Bulk composition (assemblage) has a very great effect on both Na/Na+K ratio and phengite content so that attempts to use either of these factors to monitor metamorphic grade should generally be done in the context of a limiting assemblage.     

An experimental study of illite dissolution kinetics as a function of ph from 1.4 to 12.4 and temperature from 5 to 50°C

Dissolution rates of natural illite (Illite du Puy) were measured from Si release rates during closed system experiments at pH ranging from 1.4 to 12.4 and temperatures ranging from 5 to 50°C. Experiments performed at 4<pH<11 exhibited reactive fluid Si/Al concentration ratios that were inconsistent with stoichiometric illite dissolution likely due to secondary phase precipitation. In contrast, after an initial preferential release of aluminum relative to silicon, the reactive fluid Si/Al concentration ratio evolution was consistent with stoichiometric illite dissolution for all experiments conducted at 4>pH>11. Si release rate decreased with time during all experiments; for those experiments performed at 4>pH>11 this observation can be attributed to either 1) changing reactive surface area; 2) the effect of initial fine particle dissolution; or 3) a negative order of the illite dissolution reaction with respect to aqueous Al and/or Si. Measured dissolution rates exhibited a typical variation with pH; rates decrease with increasing pH at acid conditions, minimize at near to neutral pH and increase with increasing pH at basic conditions. An empirical expression describing rates obtained in the present study is given by

     

Ilmenite as a Source for Zirconium during High-grade Metamorphism? Textural Evidence from the Caledonides of Western Norway and Implications for Zircon Geochronology

The Proterozoic Lindås Nappe, part of the Caledonidesof western Norway, was affected by penetrative Sveconorwegiangranulite-facies metamorphism, followed by a fluid-driven eclogite-and amphibolite-facies Caledonian overprint, spatially restrictedalong fractures and shear zones. In mafic granulites and amphibolites,a luminescent anhedral zircon overgrowth, which gives an averageage of 924 ± 58 Ma (Th/U = 0·52; secondary ionmass spectrometry data), surrounds a magmatic zoned core withan age of 952 ± 32 Ma (Th/U = 1·27). In the granulites,a continuous rim of zircon or a discontinuous corona of