Sagged phosphatic Nantgarw porcelain (ca. 1813–1820): Casualty of overfiring or a fertile paste?

Nantgarw phosphatic (bone-ash) porcelain (ca. 1813–1820) is renowned for its translucency and the high quality of its enamel decoration. However, only a small proportion of its wares (perhaps 10%) were successfully fired due to sagging (body distortion) and other problems. This indicates that: (1) In terms of its potential for generating a minimum melt, the Nantgarw paste had an unusually fertile composition, or (2) Nantgarw's staff had difficulties in controlling kiln temperatures, so that its wares tended to be overfired. This issue has been addressed using analytical data for sherds excavated from the factory site. Detailed modal, petrographic, and geochemical data demonstrate that extensively sagged wasters contain a high proportion (∼43–63 vol %) of a former melt phase but are surprisingly porous (7–25 vol % pores). In terms of minimum melt generation, the sagged samples have a more fertile bulk composition than their successfully fired counterparts. Most of the wasters contain subsolidus anorthite (∼An₉₅) enclosed by a melt phase with (once corrected for entrained silica polymorph crystallites) a eutectic (minimum melt) composition. The anorthite, however, was completely resorbed by the melt in some of the sagged samples, which subsequently crystallized liquidus anorthite that displays a quenched morphology. These samples were therefore fired above (T_max <1430°C, as estimated from melt compositions) the eutectic (T∼1290°C) in the anorthite–tricalcium phosphate–silica system. The fact that other wasters contain subsolidus anorthite and a minimum melt shows that firing at the eutectic did not guarantee a successful firing, regardless of the melt fertility of the paste. It is likely that the duration of firing near T_max and character of the object (i.e., flatware vs. hollow-ware) were also important variables in this regard. In addition to producing their well-known phosphatic wares, Nantgarw's proprietors apparently also experimented with silicious pastes with compositions akin to true porcelain. Some of silicious sherds found at the site have a lead-bearing (∼15 wt % PbO) glaze, indicating that they survived an early, high temperature biscuit firing, after which they were fired at lower temperature in the glost kiln (i.e., a “soft-paste type” firing sequence). Evidence that the Nantgarw kiln could achieve temperatures in the order of 1400°C further suggests that these silicious sherds are b.f. wasters. © 1999 John Wiley & Sons, Inc.     

Microstructures of phosphatic porcelain from sintering to vitrification: Evidence from sherds excavated in Charleston,South Carolina

Eight phosphatic porcelain sherds recovered from various historical sites in Charleston were analyzed by electron microprobe. Some sherds contain sulfur (2.3–3.1wt.% SO₃); others contain only traces of this component. The analytical data suggest that the sulfurous sherds are Bow porcelain (London, Bowcock period, ca. 1755–1769). The origin(s) of the low‐S samples remains unidentified; one compositionally resembles “gold‐anchor period” (phosphatic) Chelsea porcelain (London, ca. 1756–1769) but its decoration is inconsistent with known wares produced by this factory during that era. The degree of vitrification is highly variable, particularly among the SO₃‐poor samples. The melt phase is strongly enriched in incompatible elements (Ti, Fe, Na, K). The phosphate phase [calcined bone ash (hydroxyapatite)] in poorly vitrified samples hosts minute melt blebs, but remains porous. With increasing vitrification, these melt blebs increase in size and begin to coalesce, ultimately forming ameboid patches up to ∼10 μm in diameter. In the most vitrified samples, the coalesced melt “leaks” into the matrix, leaving behind a phosphate phase that lacks pores and melt and has a lower CaO/P₂O₅ ratio (=2.7, molecular proportions) than either hydroxyapatite (3.3) or β‐whitlockite (3.0). The two varieties of phosphate occur in some poorly vitrified samples, suggesting the recycling of high‐fired wasters (as “grog”) in their ceramic pastes. Melt compositions vary with contiguous mineralogy, accounting for their divergence from the ternary eutectic in the Ca₃(PO₄)₂‐CaAl₂Si₂O₈‐SiO₂ system. The resorption of phosphate by the matrix melt virtually precludes recognition of anorthite formed by the “non‐phosphate glass equation.” © 2011 Wiley Periodicals, Inc.     

Geochemistry of major and trace elements and Pb–Sr isotopes of a weathering profile developed on the Lower Cambrian black shales in central Hunan,China

This paper reports a geochemical study on the major and trace elements and Pb–Sr isotopes of a weathering profile developed in the Lower Cambrian black shales in central Hunan (China). Six weathering horizons were identified and sampled vertically throughout the profile. The chemical composition of the profile consists of variable concentrations of the major elements Fe₂O₃, FeO, MnO, MgO, CaO, Na₂O, and P₂O₅ and of less variable concentrations of SiO₂, TiO₂, Al₂O₃, and K₂O. The chemical change caused by weathering is estimated by mass-balance calculations, and the results show that the element mobility is characterised by substantial loss of SiO₂, FeO, CaO, K₂O, Na₂O, LOI, Cr, V, Ba, Cs, Rb, Sr, U, and Th, and moderate loss of Al₂O₃, MgO, Fe₂O₃, Ni, Cu, Pb, Tl, Sn, Sc, Ge and REE (Y). The high field strength elements TiO₂, Sn, Sc, U, Ga, Ge, Zr, Hf, Nb, and Ta were immobile during weathering. The chemical changes and the Pb–Sr isotopic data suggest that four types of chemical reactions occurred: the oxidation of sulphide minerals (e.g., pyrite) and organic carbon (OS), the dissolution of less resistant clinochlore-Ia, calcite, and P-bearing minerals (DL), the dissolution of detrital albite and microcline (DA), and the transformation of clay (TC) minerals (e.g., muscovite and illite–smectite). These chemical reactions then led to two stages of geochemical processes, an early stage of chemical differentiation and a later stage of chemical homogenisation. The chemical differentiation dominated by the OS, DL, and DA reactions, led to the leaching of mobile elements (e.g., MgO, Na₂O, K₂O, P₂O₅, Sr, and REE) and the redistribution of some less mobile elements (e.g., SiO₂ and Al₂O₃). In contrast, the chemical homogenisation, which was caused by TC reactions, led to the leaching of both mobile and less mobile elements from the system and ultimately transformed the weathered black shales into soil. Soils derived from black shales in South China might result from the above two geochemical processes.     

Palaeoweathering characteristics of an intrabasaltic red bole of the Deccan Flood Basalts near Shrivardhan of western coast of India

An intrabasaltic red bole horizon is studied for its weathering characteristics with respect to the underlying and overlying basalts. The study indicates that all the three units have been considerably weathered; the red bole unit, however shows some distinctive characteristics. The red boles show a higher cation exchange capacity (CEC) and lower sodium adsorption ratio (SAR) and organic carbon (OC) as compared to the weathered basalts. The lower values of Al₂O₃, TiO₂ and Fe₂O₃(T) in red boles indicate their lesser weathering than the underlying and overlying basalts, which is further corroborated by the weathering intensity measured by the indices like chemical index of alteration (CIA) and statistical empirical index of chemical weathering (W). It is also evident that the red bole samples show more retention of original mafic and felsic components. While K₂O exhibits an erratic behaviour, the MgO and CaO do not show much leaching in red boles. Lesser leaching and salinity in the red boles is indicated by the higher values of calcification and lower values of salinization. The SiO₂–Al₂O₃–Fe₂O₃ plot indicates that red bole samples are close to the basalt field, while the weathered upper basalt is more kaolinized than the weathered lower basalt. These observations reveal that the post-formational weathering processes have least affected the original palaeoweathering characters of the red bole horizon and hence the intrabasaltic palaeosols (weathering horizons) can effectively be used to constrain the palaeoweathering and palaeoclimates during the continental flood basalt episodes in the geologic past.     

Wall-Rock alteration of biotite hornfels at the Tyrnyauz deposit,Russia

A new zonation type of W–Mo-bearing altered biotite hornfels at the Tyrnyauz deposit is reported. The review of zonation indicates a subsequent transition into the mobile state of CaO, MgO, FeO, and Al₂O₃ and retention of volume owing to dissolution or deposition of quartz as an excess mobile mineral. The main features of zonation are similar to those in acid leaching columns; the input of strong CaO base into the outer zone is unusual.     

Major element geochemistry of purple soils/rocks in the red Sichuan Basin, China: implications of their diagenesis and pedogenesis

Major element compositions and chemical weathering features of the purple soils and their corresponding rocks in the Red Sichuan Basin, China were studied in this paper to infer the diagenetic features of the purple rocks and the pedogenetic features of the purple soils. The results showed that all of the rock and soil samples, except those from Yibin, have strongly similar major element compositions and the distribution patterns of their major element compositions are similar to those of the upper continental crust. Chemical index of alteration, chemical index of weathering and Na₂O/K₂O indicate that the purple soils and rocks have similar chemical weathering intensities, whereas the Al₂O₃–CaO* + Na₂O–K₂O (A–CN–K) relationship, suggests that chemical weathering was strong during diagenesis of the purple rocks, but weak during pedogenesis of the purple soils. Variations in major element compositions of the purplish rock samples, except that from Yibin, do not primarily reflect differences in compositions of the sediment source, sediment recycling and potassium metasomatism, and therefore the effects of chemical weathering on the major element compositions were mainly dependent on climate condition and the residence time of material exposed to chemical weathering. Chemical weathering of the purple rocks reached only moderate degrees under the general influence of warm and humid climate during Jurassic and Cretaceous. Warmer and more humid climate conditions partly resulted in stronger chemical weathering of rocks in the southern region of the basin than in the central and western region, whereas shorter residence time of material in upslope position partly resulted in weaker chemical weathering of rocks in the eastern region than in the central and western region. The same climate and stable tectonic setting led to comparable chemical weathering intensities of rocks in the Ziliujing and Jiaguan Formations. Gradually colder and dryer climate from Early Jurassic to Middle Jurassic then to Late Jurassic and shorter residence time in tectonically active setting of Middle Jurassic and late Late Jurassic resulted in the following order of chemical weathering intensity of the purple Jurassic rocks: Ziliujing Formation ? Shaximiao Formation ≈ Suining Formation > Penglaizhen Formation.     

Theoretical approach to evaluating plagioclase dissolution mechanisms

The more rapid dissolution of Ca-rich feldspars relative to Na, K-rich feldspars has been attributed to the preferential leaching of Al deep within the feldspar structure. Evidence from surface microanalysis (e.g., Hellmann et al., 2003), however, shows that preferential dissolution of Al is confined to the top layers of the feldspar lattice and that the amorphous surface layer most likely results from precipitation versus dissolution. It is thus critical to examine the extent of preferential Al removal. Here we present a theoretical study of plagioclase dissolution behavior using parameterized Monte Carlo simulations. Two different dissolution mechanisms, a mechanism involving preferential leaching of Al and an interfacial dissolution-reprecipitation mechanism, are tested using compositions representing the entire plagioclase solid solution series. Our modeling results indicate that under the control of the preferential Al leaching mechanism, the influence of (Al, Si) disorder on the dissolution rate is significant. At a fixed composition, an increase in the degree of (Al, Si) disorder yields an increased dissolution rate, with an 8-fold increase in dissolution rate observed for highly disordered albite (An₀) compared to low albite. Increasing anorthite content tends to decrease the variation in the dissolution rate due to disorder. The difference in the dissolution rate of 293 tested oligoclase configurations with a composition of An₂₀ is 3-fold, and the difference is reduced to 2-fold among 107 andesine configurations of An₃₀. Furthermore, feldspar configurations with completely disordered (Al, Si) distributions yield a consistent log-linear dependence of dissolution rate on the anorthite content (An), while other feldspar configurations with modest degrees of (Al, Si) disorder exhibit rates less than this trend. In contrast, when Al removal is confined to the top surface layers, a variety of feldspar configurations with different (Al, Si) disorder but a single fixed composition have similar dissolution rates; and the dissolution rate of Ca-rich feldspars departs positively from its log-linear relationship with anorthite content. This departure occurs around An₈₀ and is in good agreement with previous experimental studies. Subsequent modeling results of aluminum inhibition, ΔG dependence, and formation of altered surface layers in the framework of the interfacial dissolution-reprecipitation mechanism are all comparable with experimental investigations, and these results suggest that an interfacial dissolution-reprecipitation mechanism governs the dissolution of plagioclase feldspars.     

X-ray photoelectron studies of the mechanism of iron silicate dissolution during weathering

Iron silicate minerals (bronzite, fayalite), exposed to aqueous dissolution in the laboratory for up to 60 days at room temperature and pH 1, 1.5, and 6, have been studied for evidence of changes in surface composition, using XPS, and these results compared with those obtained from solution chemical analysis. In the absence of dissolved O₂ or at low pH (1–1.5) dissolution proceeds congruently after the initial formation of a thin (<10 Å) protonated surface layer depleted in Fe relative to Si. This layer is unstable and does not grow with time as attested to by long term congruent dissolution and by the formation of an amorphous silica surficial breakdown product at pH 1 and 1.5. In bronzite the layer is also slightly depleted in Mg but much less than it is in Fe due to the preferential occupation by Fe⁺² of more weakly bonded M₂ sites. The behavior of the layer is similar to that found earlier on iron-free pyroxene (Schottet al., 1981); in other words, because of its thinness and instability it is not diffusion-inhibiting or protective toward dissolution.In the presence of dissolved O₂, as would be the case in most weathering solutions, dissolution of bronzite and fayalite results in the formation of two surface layers whose compositions were deduced by measurements of XPS binding energies. The outer layer, consisting of hydrous ferric oxide, is readily removed by ultrasonic cleaning and, most likely, is not protective toward dissolution. The inner layer consists of Fe⁺³ in a protonated or hydroxylated silicate (Mg-silicate in the case of bronzite) matrix. This layer appears to impede dissolution over the time scale of the experiment as attested to by parabolic dissolution rates. However, the layer does not continue to grow on the time scale of weathering because ultrasonically cleaned soil grains (Berner and Schott, 1982) exhibit surface compositions similar to those found in the present month-long laboratory experiments. In other words, a thick, highly altered, diffusion-inhibiting, protective surface layer does not form at the acidic pH of most soils.     

A mechanism for pyroxene-pyroxenoid and pyroxenoid-pyroxenoid transformations

A mechanism for the solid state replacement of clinopyroxene by pyroxenoids has been derived from consideration of the crystal structures. The mechanism involves the propagation of partial dislocations, with Burgers vectors of 1/4 \([2\bar 3\bar 1]\) , through the clinopyroxene matrix to generate a resultant shear; the passage of one dislocation gives rise to a single chain-repeat unit of wollastonite in each silicate chain. Pyroxenoids may thus be formed from clinopyroxene by the periodic introduction of these dislocations on parallel slip-planes, and pyroxenoid to pyroxenoid inversions may proceed by the introduction and removal of such shears by the propagation of the correct combination of partial dislocations. The Burgers vectors for these dislocations in each of the pyroxenoid mineral structures has been calculated. A two step mechanism is proposed for clinopyroxene to bustamite, and pyroxenoid to bustamite inversions, which utilises the same shear as above which generates a wollastonite structure. The second step is a shear of 1/2[001] on the plane \((1\bar 10)\) of this wollastonite intermediate, to give a bustamite structure.     

Volatility inversion of silicon and magnesium oxides during the evaporation of HASP glasses on the moon

An inversion of SiO₂ and MgO volatility occurs during high-temperature melt evaporation in the CaO–MgO–Al₂O₃–SiO₂ (CMAS) system. This results in that SiO₂, which is usually more volatile than MgO, becomes less volatile during the evaporation of melts enriched in the refractory oxides CaO and Al₂O₃. The volatility inversion is adequately explained within the theory of acid–base interaction of silicate melt components developed by D.S. Korzhinskii. The compositions of high-Al₂O₃ and SiO₂-poor glasses (known as HASP glasses) from the lunar regolith show a systematic decrease in MgO/SiO₂ with increasing CaO content, which is a direct consequence of the influence of acid–base effects.     

Diffusive dissolution in ternary systems: analysis with applications to quartz and quartzite dissolution in molten silicates

Exact solutions to equations governing isothermal diffusive dissolution of a crystalline slab in a ternary liquid were obtained to include the effect of coupled chemical diffusion in the liquid. These analytical results, supplemented by approximate solutions valid for slow dissolving, provide new insights into the characteristics of diffusive dissolution in ternary systems. Dissolution rate is proportional to square root of time in diffusive dissolution. The coefficient of proportionality is a function of diffusion coefficients, liquidus relation, melt composition at the crystal–melt interface, and compositions of the dissolving crystal and starting melt. In the limit of slow dissolving, the dissolution rate can be written in terms of three dimensionless parameters that are functions of the aforementioned parameters. Dissolution rate is proportional to the diffusion rate of the slow eigen component in the melt when the diffusion rate of the minor eigen component is much slower than the diffusion rate of the major eigen component.Laboratory experiments of diffusive dissolution of single crystals and polycrystalline aggregates of quartz in a haplodacitic melt (25 wt.% CaO, 15 wt.% Al₂O₃, and 60 wt.% SiO₂) were conducted at 1500°C and 1 GPa. Measured dissolution distances (X_b, in microns) are proportional to the square root of experimental run time (t, in seconds), X_b = −0.620 (±0.019) √t. Chemical concentration profiles measured from quenched melts are invariant with time when displayed against the distance (measured from the crystal–melt interface) normalized by the square root of time. The melt compositions at the crystal–melt interface, extrapolated from the measured diffusion profiles in the quenched melts, are within 0.2 wt.% of the independently measured quartz liquidus in the ternary CaO–Al₂O₃–SiO₂ at 1500°C and 1 GPa. These results suggest that crystal and melt are in chemical equilibrium at their interface shortly after the onset of dissolution. Diffusive dissolution of quartz and quartzite is characterized by slow dissolving. Using quartz liquidus as one of the boundary conditions, it has been shown that the calculated dissolution distances and concentration profiles are in good agreement with the experimentally measured ones. Coupled diffusion played an essential role in quartz and quartzite dissolution in haplodacitic to haplobasaltic melts, and is likely to play an important role in diffusion-limited kinetic processes such as crystal growth and dissolution in natural melts of basaltic–rhyolitic compositions.     

Calcic hydrosilicate metasomatic rocks at the Gumeshevsk skarn-porphyry copper deposit in the central Urals,Russia

The body of hydroxylellestadite metasomatic rock penetrated by a borehole drilled at the Gumeshevsk deposit at depths of 530–534 m includes a thin interval of younger lower temperature tobermorite-plombierite metasomatic rock with subordinate amounts of Ca-Si gel, tacherenite, cubic lime, and thaumasite. Hydroxylellestadite has never before been found in calc skarns. The hydroxylellestadite metasomatic rock is cut by gypsum and fukalite veinlets, and the tobermorite-plombierite metasomatic rock is intersected by thaumasite veinlets. The pristine rock of the metasomatics was marble, and the metasomatic rock replaced andradite-bearing wollastonite skarn (with wollastonite replaced by foshagite). The ore minerals (chalcopyrite, valleriite, sphalerite, and others) were formed after the hydroxylellestadite metasomatite but most probably before the tobermorite-plombierite metasomatic rock and the veinlets of calcic minerals. The metasomatic rock was produced at significant variations in the oxygen, sulfur, and carbon dioxide fugacities. The composition of the hydroxylellestadite is, according to its microprobe analysis, as follows (wt %): SiO₂ 17.10, TiO₂ 0.01, Al₂O₃ 0.02, FeO 0.20, MnO 0.00, MgO 0.04, CaO 55.40, Na₂O 0.14, K₂O 0.09, P₂O₅ 0.12, CO₂ 1.90 (chemical analysis), SO₃ 21.60, F 0.16, Cl 0.14, total 96.92. The plombierite (SiO₂ 43.8–44.1 wt %, CaO 30.5–31.1 wt %) in the metasomatic rock notably differs from rare plombierite (SiO₂ 48.18 wt %, CaO 39.19 wt %) contained in the veinlets of thaumasite (SiO₂ 12.70 wt %, CaO 30.69 wt %, SO₃ 17.78 wt %).     

Weathering rates from top to bottom in a carbonate environment

This study investigates U-series, Sr isotopes, major and trace elements in a chalk aquifer system located in Eastern France. Soil and rock samples were collected along depth profiles down to 45 m in four localities as an attempt to investigate the weathering processes in the soil, the unsaturated zone and the saturated zone of the aquifer. Interstitial water was extracted from soils and rocks by a centrifugation technique. U-series offer a powerful tool to calculate weathering rates because the relative mobility of the U- and Th-isotopes can be precisely measured and it does not require the determination of a reference state as in other approaches. As expected, the data show very large mobile element depletion in the soil with large ²³⁰Th excess relative to ²³⁸U, while the rocks show more limited but not insignificant mobile element depletion. The U-series data have been used to constrain weathering rates based on a 1-D reactive transport model. Weathering rates in the near surface are about 10–100 times faster than at depth. However, when integrated over the depth of the cores, including the unsaturated and the saturated zones, this underground weathering represents more than 30% of the total weathering flux, assuming congruent dissolution of carbonates. The (²³⁴U/²³⁸U) ratios in interstitial water are consistent with solid samples showing ²³⁴U depletion near the surface and an excess ²³⁴U at depth. A leaching experiment performed on chalk shows that the excess ²³⁴U in natural waters percolating through carbonate rocks results both from preferential ²³⁴U leaching and direct recoil in the interstitial water. A new approach was used to derive the recoil ejection factor based on BET measurements and the fractal dimension of chalk surface. Consideration of preferential leaching and recoil allows a more accurate modeling of weathering rates.     

A preferred method for the determination of bulk compositions of coarse-grained refractory inclusions and some implications of the results

Analyses of coarse-grained refractory inclusions typically do not have the solar CaO/Al₂O₃ ratio, probably reflecting nonrepresentative sampling of them in the laboratory. Many previous studies, especially those done by instrumental neutron activation analysis (INAA), were based on very small amounts of material removed from those restricted portions of inclusions that happened to be exposed on surfaces of bulk meteorite samples. Here, we address the sampling problem by studying thin sections of large inclusions, and by analyzing much larger aliquots of powders of these inclusions by INAA than has typically been done in the past. These results do show convergence toward the solar CaO/Al₂O₃ ratio of 0.792. The bulk compositions of 15 coarse-grained inclusions determined by INAA of samples >2 mg have an average CaO/Al₂O₃ ratio of 0.80 ± 0.18. When bulk compositions are obtained by modal recombination based on analysis of thin sections with cross-sections of entire, large, unbroken inclusions, the average of 11 samples (0.79 ± 0.15) also matches the solar value. Among those analyzed by INAA and by modal recombination, there were no inclusions for which both techniques agreed on a CaO/Al₂O₃ ratio deviating by >∼15% from the solar value. These results suggest that: individual inclusions may have the solar CaO/Al₂O₃ ratio; departures from this value are due to sample heterogeneity and nonrepresentative sampling in the laboratory; and it is therefore valid to correct compositions to this value. We present a method for doing so by mathematical addition or subtraction of melilite, spinel, or pyroxene. This yields a set of multiple, usually slightly different, corrected compositions for each inclusion. The best estimate of the bulk composition of an inclusion is the average of these corrected compositions, which simultaneously accounts for errors in sampling of all major phases. Results show that Type B2 inclusions tend to be more SiO₂-rich and have higher normative Anorthite/Gehlenite component ratios than Type B1s. The inclusion bulk compositions lie in a field that can result from evaporation at 1700-2000K of CMAS liquids with solar CaO/Al₂O₃, but with a wide range of initial MgO (30-60 wt%) and SiO₂ (15-50 wt%) contents.     

From London to Liverpool: Evidence for a Limehouse–Reid porcelain connection based on the analysis of sherds from the Brownlow Hill (ca. 1755–1767) factory site

The diversity of Brownlow Hill porcelains of the W^m Reid & Co. era is due to the remarkably wide range in the composition of their pastes and glazes and inferred firing conditions relative to the initial vitrification temperature. Sixteen of 21 analyzed sherds from the factory site are bone‐ash wares that display large variations in their bulk chemical composition. The remaining samples have silicious‐aluminous (akin to “stone china” sensu Richard Pococke in 1750) and silicious‐aluminous‐calcic (“S‐A‐C”) compositions that resemble Limehouse (London) and Pomona (Staffordshire) porcelains produced during the 1740s. The mineralogy of the Brownlow Hill S‐A‐C sherds suggests firing at a relatively high temperature (T_max approaching 1400°C, based on relations on the SiO₂‐Al₂O₃‐CaO phase diagram), thereby obscuring the identity of some of the ingredients (e.g., the source of CaO) used in their manufacture. Limehouse and Brownlow Hill may have been linked through the activities of William Ball, who is mentioned in connection with both factories, or indirectly via former Limehouse staff later employed at the Pomona factory, located not far from a W^m Reid & Co. branch factory in Shelton, Stoke‐on‐Trent. In terms of a time line, knowledge of these pastes appears to have spread first from London to Staffordshire, and then to Liverpool. © 2003 Wiley Periodicals, Inc.     

Experimental study of igneous and sedimentary apatite dissolution: Control of pH, distance from equilibrium, and temperature on dissolution rates

Apatite dissolution experiments were conducted using both a fluidized bed and stirred tank reactor over a range of pH, temperature, solution saturation state, and on non-carbonated and carbonated apatite compositions: igneous fluorapatite (FAP) and sedimentary carbonate fluorapatite (CFA), respectively. From 2 <pH <6, the rate of release from dissolution of all apatite components [calcium (Ca), phosphorus (P), and fluoride (F)] increased with decreasing pH for FAP. From 6 < pH < 8.5, the FAP dissolution rate is pH independent. Measuring apatite dissolution rates at pH > 8.5 were not possible due to detection limits of the analytical techniques used in this study and the high insolubility of FAP. For the CFA compositions studied, the dissolution rate decreased with increasing pH from 4 < pH < 7. During early stages of the dissolution reaction for both FAP and CFA, mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P and Ca:F being greater than mineral stoichiometric ratios, suggesting that Ca was preferentially released compared to P and F from the mineral structure during the early stages of dissolution. An increase in reacted solution pH accompanies this early elevated release of Ca. As the dissolution reaction proceeded to steady state, dissolution became congruent. When normalized to BET measured surface area, FAP dissolved faster from 4 < pH < 7 compared to CFA. The apparent Arrhenius activation energy (E_a) of FAP dissolution over the temperature range of 25-55°C at pH = 3.0, I = 0.1, and pCO₂ = 0 is 8.3 ± 0.2 kcal mol⁻¹. Both the apparent exchange of solution H⁺ for solid-bound Ca at low pH in the early stage of dissolution and the E_a of dissolution suggest a surface and not a diffusion controlled dissolution reaction for FAP and CFA. The degree of undersaturation of the solution, ΔG_R, with respect to FAP was important in determining the dissolution rate. At pH = 3.0, I = 0.1, and pCO₂ = 0, the dissolution rate of FAP was ∼ 5× greater in the far-from-equilibrium region compared to the near-equilibrium slope region.A simple apatite weathering model incorporating the experimental results from this study was constructed, and numerical calculations suggest that during the Phanerozoic both the surface area of igneous rock available for weathering and the average global temperature were important factors in determining the P weathering flux from apatite dissolution. It is possible that elevated global temperatures coupled with relatively high surface area of igneous rock during the early- to mid-Paleozoic resulted in elevated P weathering fluxes, which along with climatic evolutionary pressures of the Neoproterozoic, facilitated the radiation of multicellular organisms, large-scale phosphorite deposition, and abundance of calcium phosphate shelled organisms during the early Cambrian.     

The role of acidity–basicity in evaporating refractory inclusions in chondrites

When melts of Ca–Al inclusions in chondrites, which are dominated by the oxides SiO₂, MgO, CaO, and Al₂O₃, evaporate at high temperatures, the SiO₂ and MgO fugacities are inverted: SiO₂, which is more volatile than MgO, becomes less volatile when melts rich in refractory CaO and Al₂O₃ evaporate. This fugacity inversion can be realistically explained within the framework of D.S. Korzhinskii’s theory of acid–base interaction between components in silicate melts. According to this theory, an increase in CaO concentration in the melt increases its basicity, and this, in turn, increases the activity (and hence, also fugacity) of MgO and decreases those of SiO₂. In the real compositions of the Ca–Al inclusions in chondrites, the MgO/SiO₂ ratio systematically decreases with an increase in the CaO concentration under the effect of acid–base interaction.     

An evaluation of acid deposition on cation leaching and weathering rates of an Andosol and a Cambisol

An evaluation of the response of an Andosol and a Cambisol to acid deposition and weathering rates was studied by using a controlled laboratory leaching experiment. Both soils where derived from mafic parent material, a Histic Andosol from Western Iceland and a Cambisol from North East Scotland. De-ionized water and water acidified with H₂SO₄ (pH 3) was leached through reconstructed soil columns to simulate 34 years of precipitation.Acidic input increased cation leaching and weathering rates in both soil types and reduced pH levels. The Andosol proved generally to have higher weathering rates, leaching potential, ion exchange and acid-buffering capacity as well as maintaining a relatively steady pH despite intense acidic input. This was due to differences in parent material and mineral composition. The Andosol was developed from basaltic volcanic tephra, which had higher dissolution rates due to its amorphous mineral structures. The Cambisol was developed from gabbro with more stable mineral structures.     

Chemical and Isotopic Characteristics of the Water and Suspended Particulate Materials in the Yangtze River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials（SPM） in the Yangtze River were investigated on the samples collected from 25 hydrological monitoring stations in the mainsteam and 13 hydrological monitoring stations in the major tributaries during 2003 to 2007. The water samples show a large variation in both δD（ 30‰ to 112‰） and δ18O（ 3.8‰ to 15.4‰） values. Both δD and δ18O values show a decrease from the river head to the Jinsha Jiang section and then increase downstream to the river mouth. It is found that the oxygen and hydrogen isotopic compositions of the Yangtze water are controlled by meteoric precipitation, evaporation, ice（and snow） melting and dam building. The Yangtze SPM concentrations show a large variation and are well corresponded to the spatial and temporal changes of flow speed, runoff and SPM supply, which are affected by the slope of the river bed, local precipitation rate, weathering intensity, erosion condition and anthropogenic activity. The Yangtze SPM consists of clay minerals, clastic silicate and carbonate minerals, heavy minerals, iron hydroxide and organic compounds. From the upper to lower reaches, the clay and clastic silicate components in SPM increase gradually, but the carbonate components decrease gradually, which may reflect changes of climate and weathering intensity in the drainage area. Compared to those of the upper crust rocks, the Yangtze SPM has lower contents of SiO2, CaO, K2 O and Na2 O and higher contents of TFe2 O3 and trace metals of Co, Ni, Cu, Zn, Pb and Cd. The ΣREE in the Yangtze SPM is also slightly higher than that of the upper crust. From the upper to lower reaches, the CaO and MgO contents in SPM decrease gradually, but the SiO2 content increases gradually, corresponding to the increase of clay minerals and decrease of the carbonates. The δ30SiSPM values（ 1.1‰ to 0.3‰） of the Yangtze SPM are similar to those of the average shale, but lower than those of the granite rocks（ 0.3‰ to 0.3‰）, reflecting the effect of silicon isotope fractionation in silicate weathering process. The δ30SiSPM values of the Yangtze SPM show a decreasing trend from the upper to the middle and lower reaches, responding to the variation of the clay content. The major anions of the river water are HCO 3, SO 4 2, Cl, NO 3, SiO 4 4 and F and the major cations include Ca2＋, Na＋, Mg2＋, K＋ and Sr2＋. The good correlation between HCO3-content and the content of Ca2＋may suggest that carbonate dissolution is the dominate contributor to the total dissolved solid（TDS） of the Yangtze River. Very good correlations are also found among contents of Cl, SO4 2, Na＋, Mg2＋, K＋and Sr2＋, indicating the important contribution of evaporite dissolution to the TDS of the Yangtze River. High TDS contents are generally found in the head water, reflecting a strong effect of evaporation in the Qinghai-Tibet Plateau. A small increase of the TDS is generally observed in the river mouth, indicating the influence of tidal intrusion. The F and NO3 contents show a clear increase trend from the upstream to downstream, reflecting the contribution of pesticides and fertilizers in the Chuan Jiang section and the middle and lower reaches. The DSi shows a decrease trend from the upstream to downstream, reflecting the effect of rice and grass growth along the Chuan Jiang section and the middle and lower reaches. The dissolved Cu, Zn and Cd in the Yangtze water are all higher than those in world large rivers, reflecting the effect of intensive mining activity along the Yangtze drainage area. The Yangtze water generally shows similar REE distribution pattern to the global shale. The δ30SiDiss values of the dissolved silicon vary from 0.5‰ to 3.7‰, which is the highest among those of the rivers studied. The δ30SiDiss values of the water in the Yangtze mainsteam show an increase trend from the upper stream to downstream. Its DSi and δ30SiDiss are influenced by multiple processes, such as weathering process, phytolith growth in plants, evaporation, phytolith dissolution, growth of fresh water diatom, adsorption and desorption of aqueous monosilicic acid on iron oxide, precipitation of silcretes and formation of clays coatings in aquifers, and human activity. The δ34SSO4 values of the Yangtze water range from 1.7‰ to 9.0‰. The SO4 in the Yangtze water are mainly from the SO4 in meteoric water, the dissolved sulfate from evaporite, and oxidation of sulfide in rocks, coal and ore deposits. The sulfate reduction and precipitation process can also affect the sulfur isotope composition of the Yangtze water. The87Sr/86Sr ratios of the Yangtze water range from 0.70823 to 0.71590, with an average value of 0.71084. The87Sr/86Sr ratio and Sr concentration are primary controlled by mixing of various sources with different87Sr/86Sr ratios and Sr contents, including the limestone, evaporite and the silicate rocks. The atmospheric precipitation and anthropogenic inputs can also contribute some Sr to the river. The δ11B values of the dissolved B in the Yangtze water range from 2.0‰ to 18.3‰, which is affected by multifactors, such as silicate weathering, carbonate weathering, evaporite dissolution, atmospheric deposition, and anthropogenic inputs.     

Effects of temperature on silicate weathering: Solute fluxes and chemical weathering in a temperate rain forest watershed,Jamieson Creek,British Columbia

Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO₂, and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients.When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area.