Rayleigh scattering by aqueous colloidal silica as a cause for the blue color of hydrothermal water

Thermal waters in hydrothermal ponds, bathing pools and the brines of geothermal electric power plants commonly have a characteristic blue color. Although many researchers have assumed that the blue color is due to a colloidal suspension and/or absorption by dissolved ferrous iron or by water itself, there has been no specific effort to identify the physical nature of this phenomenon. We have tested, in synthetic and natural solutions, whether aqueous colloidal silica is responsible for the blue color. Aqueous colloidal silica is formed by silica polymerization in thermal waters of the neutral-chloride type which contain initially monomeric silica in concentrations up to three times above the solubilities of amorphous silica. The hue of the blue thermal waters in the pools tested agrees with that of a synthesized colloidal silica solution. Grain-size analyses of aqueous colloidal silica in the blue-colored thermal waters demonstrate that the color is caused by Rayleigh scattering from aqueous colloidal silica particles with diameters (0.1–0.45 μm) smaller than the wavelengths of visible radiation.     

Sorption of Eu<Superscript>3+</Superscript>onto nano-size silica-water interfaces

The sorption of Eu species onto nano-size silica-water interfaces is investigated at pH range of 1―8.5 and the initial Eu concentrations (C_Eu) of 2×10⁻⁵, 2×10⁻⁴ and 2×10⁻³ M using fluorescence spectroscopy. The sorption rate of Eu is initially low, but significantly increases at pH > 4. For the initial C_Eu of 2×10⁻⁵, 2×10⁻⁴ and 2×10⁻³ M, the dissolved Eu species are completely sorbed onto silica-water interfaces at pH = 4.75, −5.8 and 6.6, respectively, with the respective sorption densities of −1.58×10⁻⁸, 1.58×10⁻⁷ and 1.58×10⁻⁶ mol/m². The sorbed Eu species at pH < 6 is aquo Eu³⁺, which is sorbed onto silica-water interfaces as an outer-sphere complex at pH < 5, but may be sorbed as an inner-sphere bidentate complex at 5 < pH < 6, due to the decrease of the N_H2O to −6 at pH = 6. At pH = 6 – 8, Eu(OH)²⁺, Eu(CO₃)⁺and Eu(CO₃)₂ ⁻ form in the solutions, and Eu(CO₃)⁺is dominant at pH = −7.5. These ions may be sorbed onto silica-water interfaces as inner-sphere bidentate complexes or multi-nuclear pre-cipitates.     

Toward an Understanding of Biogenic-silica Dissolution in Seawater – An Initial Rate Approach Applied between 40 and 90 °C

Summary The kinetics of phytoplankton frustule dissolution has generally been studied as the appearance of silicic acid in a batch reactor. Unfortunately, this approach, though often illuminating, has not so far been successful because of the difficulty of parameterising the full reaction curve. This current study shows how the initial rate approach to chemical kinetics offers a way around this bottleneck, thereby allowing much chemical kinetics information about frustule dissolution to be collected. The technique is shown to be flexible and suited to short reaction times which facilitate detailed quantitative kinetics investigation, indeed, as would be expected in a solution phase, kinetics study. The technique is exemplified by a dissolution study of uncleaned frustules of Cyclotella crypticaat 40 °C and above. The frustules were found to yield the same dissolution rate after 5 weeks dark storage, at 4 °C. Meanwhile, log dissolution rate was found to vary linearly with pH, with gradient 0.38 ± 0.01 (r ²=0.990). Linearity was upheld even at pHs as high as 14. Finally, a robust Arrhenius plot was established between 40 and 90 °C yielding an activation energy for dissolution of 84 ± 3 kJ mol ⁻¹. Follow through with the Eyring equation yielded an activation enthalpy, ΔH ^‡, and an activation entropy, ΔS ^‡, of 81 and 85 J mol ⁻¹ K ⁻¹, respectively. The discussion brings salient aspects of existing knowledge about diatom frustule dissolution kinetics into the wider context of silicate mineral dissolution.     

Influence of climate fluctuation on clay formation in the Baikal drainage basin

Sedimentary cores BDP 96 and 98 and VER 96-2 St. 3 from Academician Ridge in Lake Baikal were investigated to investigate the effect of climatic fluctuations on rock weathering and clay formation in the Baikal drainage basin. Illite, smectite, vermiculite, and kaolinite were identified as the major clay minerals in the sediments by X-ray diffraction analysis. Biotite in gravels in alluvial soils of the Baikal drainage area weathers through illite to vermiculite, smectite, and finally to kaolinite. To investigate the relationship between weathering and climate, we measured the clay content and the concentration of biogenic silica in the sediments. High surface productivity (increased biogenic silica) and high chemical weathering (decreased clay content) occurred simultaneously, showing that crustal weathering and soil formation were enhanced under warm climatic conditions.Clay formation was enhanced in the watershed from the Late Miocene to the Middle Pliocene, and mechanical weathering of rocks increased during glacial intervals after the climate began to cool in Late Pliocene time. This change in the weathering mode in the watershed reduced the nutrient flux and aquatic productivity of Lake Baikal.     

The behaviour of dissolved silica during the mixing of river and sea waters in Tokyo Bay

The behaviour of dissolved silica was studied in Tokyo Bay during six surveys in 1979 and 1980. The data from late spring and mid-summer samples showed concave mixing curves of silica versus salinity, whereas for the winter samples a simple conservative dillution curve was obtained. Plots of particulate silicon to particulate aluminium showed that even for winter samples as well as summer ones there were some processes removing silica from solution. The processes could not be adequately explained by adsorption onto suspended solids. The data are indicative of uptake by diatoms as the principal removal mechanism. Most of the diatom skeletons settled to the bottom where dissolution was rapid. The silica-salinity curves in this study thus demonstrate an apparent removal process for dissolved silica. This is because during summer the displacement rate of biogenic silica from a unit water column to the bottom as fecal pellets or by sinking is greater than the supply rate of dissolved silica by the action of diffusion and mixing of bottom water enriched with dissolved silica whereas in winter these rates are reasonably balanced.     

Silicon transfers in a rice field in Camargue (France)

We conducted a study of the biogeochemical cycle of silicon in a rice field in Camargue (France) in order to evaluate the role of biogenic silicon particles (BSi) in the cycle. Opal-A biogenic particles (phytoliths, diatoms…), which dissolve more rapidly than other forms of silicate usually present in soils, are postulated to represent the easiest bioavailable Si for rice. We found 0.03–0.06 wt.% of BSi in soils (mainly phytoliths). This value is lower than other values from the literature. Each year, the exportation of BSi from rice cultivation is 270 ± 80 kg Si ha^− 1. We show that BSi input by irrigation is mostly composed of diatoms and we estimate it at 100 kg Si ha^− 1 year^− 1. This value is more than a third of the annual Si need for rice. The budget of the dissolved silicon (DSi) fluxes gives the following results: the atmospheric and irrigation inputs represents 1% and roughly 10%, respectively, of the annual need for rice; the drainage and infiltration outputs represent 17 ± 14 and 12 ± 9 kg Si ha^− 1 year^− 1, respectively; the balance of our budget shows that at least 170 kg Si ha^− 1 year^− 1 are exported from the soil. If we consider the soil BSi as the only source of dissolved silicon, this stock could be exhausted in 5 years.     

Siliceous microfossil record of late Holocene oceanography and climate along the west coast of Vancouver Island, British Columbia (Canada)

Diatoms, silicoflagellates, and biogenic silica (BSi) were analyzed from two piston cores recovered from Effingham Inlet, British Columbia. Relatively productive marine conditions from 4850 to 4000 cal yr BP were followed by a transition to the modern ocean-climate regime marked by a decreased siliceous microfossil production since 2800 cal yr BP. This change in the northeast Pacific climate was characterized by an apparent cooling associated with higher rainfall and lower light levels. The reduced abundance of most spring-summer bloom diatom taxa (Skeletonema-Thalassiosira-Chaetoceros) was coupled with a decreased abundance of diatoms normally associated with incursions of offshore water into coastal inlets. This pattern reflected a weaker summer upwelling along Vancouver Island associated with the insolation-related increase in the strength of the Aleutian Low and a weakened North Pacific High. After ca. 2800 cal yr BP, diatom assemblages also indicated more frequent periods of relatively low spring-summer surface water salinity and a disruption of the typical bloom sequence, indicative of increased climatic variability. A period of warmer and drier climate conditions and possibly increased coastal upwelling offshore occurred ca. 1450-1050 cal yr BP. The most recent 500 yr are marked by reduced diatom production and the appearance of three distinct diatom biomarkers in the stratigraphic record (Rhizosolenia setigera ca. AD 1940; Minidiscus chilensis ca. AD 1860; Thalassionema nitzschioides morphotype A, ca. AD 1550). The oceanographic changes recorded in Effingham Inlet are correlative with other marine and terrestrial paleoenvironmental records in the northeast Pacific Ocean.     

Decadal-scale autumn temperature reconstruction back to AD 1580 inferred from the varved sediments of Lake Silvaplana (southeastern Swiss Alps)

A quantitative high-resolution autumn (September-November) temperature reconstruction for the southeastern Swiss Alps back to AD 1580 is presented here. We used the annually resolved biogenic silica (diatoms) flux derived from the accurately dated and annually sampled sediments of Lake Silvaplana (46°27′N, 9°48′E, 1800 m a.s.l.). The biogenic silica flux smoothed by means of a 9-yr running mean was calibrated (r = 0.70, p < 0.01) against local instrumental temperature data (AD 1864-1949). The resulting reconstruction (± 2 standard errors = ± 0.7 °C) indicates that autumns during the late Little Ice Age were generally cooler than they were during the 20th century. During the cold anomaly around AD 1600 and during the Maunder Minimum, however, the reconstructed autumn temperatures did not experience strong negative departures from the 20th-century mean. The warmest autumns prior to 1900 occurred around AD 1770 and 1820 (0.75 °C above the 20th-century mean). Our data agree closely with two other autumn temperature reconstructions for the Alps and for Europe that are based on documentary evidence and are completely unrelated to our data, revealing a very consistent picture over the centuries.     

Biogeochemistry of silica in Devils Lake: implications for diatom preservation

Diatom-salinity records from sediment cores have been used to construct climate records of saline-lake basins. In many cases, this has been done without thorough understanding of the preservation potential of the diatoms in the sediments through time. The purpose of this study was to determine the biogeochemistry of silica in Devils Lake and evaluate the potential effects of silica cycling on diatom preservation. During the period of record, 1867–1999, lake levels have fluctuated from 427 m above sea level in 1940 to 441.1 m above sea level in 1999. The biogeochemistry of silica in Devils Lake is dominated by internal cycling. During the early 1990s when lake levels were relatively high, about 94% of the biogenic silica (BSi) produced in Devils Lake was recycled in the water column before burial. About 42% of the BSi that was incorporated in bottom sediments was dissolved and diffused back into the lake, and the remaining 58% was buried. Therefore, the BSi accumulation rate was about 3% of the BSi assimilation rate. Generally, the results obtained from this study are similar to those obtained from studies of the biogeochemistry of silica in large oligotrophic lakes and the open ocean where most of the BSi produced is recycled in surface water. During the mid 1960s when lake levels were relatively low, BSi assimilation and water-column dissolution rates were much higher than when lake levels were high. The BSi assimilation rate was as much as three times higher during low lake levels. Even with the much higher BSi assimilation rate, the BSi accumulation rate was about three times lower because the BSi water-column dissolution rate was more than 99% of the BSi assimilation rate compared to 94% during high lake levels. Variations in the biogeochemistry of silica with lake level have important implications for paleolimnologic studies. Increased BSi water-column dissolution during decreasing lake levels may alter the diatom-salinity record by selectively removing the less resistant diatoms. Also, BSi accumulation may be proportional to the amount of silica input from tributary sources. Therefore, BSi accumulation chronologies from sediment cores may be effective records of tributary inflow.     

Synthetic Silica Glass for Trace Aluminium Determination in Quartz by Electron Microprobe

Five synthetic silica glasses have been prepared for microprobe determination of trace aluminium in quartz. The glasses were synthesized from tetraethoxysilane (TEOS) into which between 0 and 1431 μg g-¹ aluminium had been doped. The aluminium concentrations of the glasses were independently determined by ICP-AES analysis. X-ray wavelength shift in the Al Kα peak was minimised relative to unknown quartz samples when these glasses were used for calibration. A set of these five glasses yielded a linear calibration line, and are available for trace aluminium analysis of quartz in routine microprobe systems.