Heat capacity and phase equilibria of wadeite-type K2Si4O9     

Wenjun Yong  E. Dachs  A. C. Withers  E. J. Essene 《Contributions to Mineralogy and Petrology》2008,155(2):137-146

The low-temperature heat capacity (C _p) of Si-wadeite (K<;sub>2Si₄O₉) synthesized with a piston cylinder device was measured over the range of 5–303 K using the heat capacity option of a physical properties measurement system. The entropy of Si-wadeite at standard temperature and pressure calculated from the measured heat capacity data is 253.8 ± 0.6 J mol⁻¹ K<;sup>−1, which is considerably larger than some of the previous estimated values. The calculated phase transition boundaries in the system K<;sub>2O–Al₂O₃–SiO₂ are generally consistent with previous experimental results. Together with our calculated phase boundaries, seven multi-anvil experiments at 1,400 K and 6.0–7.7 GPa suggest that no equilibrium stability field of kalsilite + coesite intervenes between the stability field of sanidine and that of coesite + kyanite + Si-wadeite, in contrast to previous predictions. First-order approximations were undertaken to calculate the phase diagram in the system K<;sub>2Si₄O₉ at lower pressure and temperature. Large discrepancies were shown between the calculated diagram compared with previously published versions, suggesting that further experimental or/and calorimetric work is needed to better constrain the low-pressure phase relations of the K<;sub>2Si₄O₉ polymorphs. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Seasonal variations of alkenones and U₃₇ in the Chesapeake Bay water column     

Jennifer L. Mercer  Meixun Zhao  Steven M. Colman   《Estuarine, Coastal and Shelf Science》2005,63(4):675-682

Alkenone unsaturation indices (U^{K<;/sup>₃₇ and UK′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between UK<;/sup>₃₇ (and UK′₃₇) values and temperature, and a significant negative correlation between UK<;/sup>₃₇ (and UK′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. UK<;/sup>₃₇ relationships (UK<;/sup>₃₇=0.018 (T)−0.162, R2=0.84, UK′₃₇=0.013 (T)−0.04, R2=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index UK′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the UK<;/sup>₃₇ vs. temperature slope, or nutrient levels are the main controller of the UK<;/sup>₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.  相似文献}   

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple     

Luke M. Mosley  Shamus L.G. Husheer  Keith A. Hunter   《Marine Chemistry》2004,91(1-4):175-186

The conditional acid dissociation constants (pK<;/i>_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK<;/i>_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK<;/i>_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.  相似文献