Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3− and SiO2(OH)22−. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH^? was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 ? B ? 0.008 M and 2.5 ? -log[H⁺] ? 11.7, respectively. Within these ranges the formation of SiO(OH)₃^? and SiO₂(OH)₂^2? with formation constants log β_?11(Si(OH)₄ ? SiO(OH)₃^? + H⁺) = ?9.472 ±0.002 and log β_?21(Si(OH)₄ ? SiO₂(OH)₂^2? + 2H⁺) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with $\text{-}\text{log[H}{}^{\mathrm{+}}\text{] ? 10.7}$ their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Map Comparison or Traditional Mass-balance Measurements: Which Method is Better?

A number of Norwegian glaciers were selected in the 1960s for long-term mass-balance measurements, to produce necessary hydrological information for hydropower exploitation. Special large-scale glacier maps were produced for field work and data processing, and some glaciers have been mapped more than once. Thus, comparison of glacier maps can be used to calculate changes in glacier volume for some of the glaciers, provided they are of sufficient accuracy.
Conventional mass-balance measurements were carried out on all the selected glaciers. A cumulative calculation of net balances for a series of years is used to indicate the change in a glacier's volume during that period. However, various errors originate in the field, some of which are systematic, particularly on glaciers with large winter accumulation.
The present study indicates that certain errors are difficult to define and determine, For the maritime glacier Ålfotbreen, a cumulative mass-balance calculation gives a positive total balance (+3.4 m water equivalent in the period 1968–88), whereas the map comparison indicates a total negative balance (−5.8 m water equivalent). This indicates a discrepancy between the methods, which must be accounted for.
Determination of errors in mass-balance measurements is difficult. Sinking of stakes in the accumulation area and the use of sounding sticks (steel probes) in heavy snowlayers cause problems.     

Environmental responses to Lateglacial climatic fluctuations recorded in the sediments of pre‐Alpine Lake Mondsee (northeastern Alps)

Investigation of the sedimentary record of pre‐Alpine Lake Mondsee (Upper Austria) focused on the environmental reaction to rapid Lateglacial climatic changes. Results of this study reveal complex proxy responses that are variable in time and influenced by the long‐term evolution of the lake and its catchment. A new field sampling approach facilitated continuous and precisely controlled parallel sampling at decadal to sub‐annual resolution for µ‐XRF element scanning, carbon geochemistry, stable isotope measurements on ostracods, pollen analyses and large‐scale thin sections for microfacies analysis. The Holocene chronology is established through microscopic varve counting and supported by accelerator mass spectrometry ¹⁴C dating of terrestrial plant macrofossils, whereas the Lateglacial age model is based on δ¹⁸O wiggle matching with the Greenland NGRIP record, using the GICC05 chronology. Microfacies analysis enables the detection of subtle sedimentological changes, proving that depositional processes even in rather large lake systems are highly sensitive to climate forcing. Comparing periods of major warming at the onset of the Lateglacial and Holocene and of major cooling at the onset of the Younger Dryas reveals differences in proxy responses, reflecting threshold effects and ecosystem inertia. Temperature increase, vegetation recovery, decrease of detrital flux and intensification of biochemical calcite precipitation at the onset of the Holocene took place with only decadal leads and lags over a ca. 100 a period, whereas the spread of woodlands and the reduction of detrital flux lagged the warming at the onset of the Lateglacial Interstadial by ca. 500–750 a. Cooling at the onset of the Younger Dryas is reflected by the simultaneous reaction of δ¹⁸O and vegetation, but sedimentological changes (reduction of endogenic calcite content, increase in detrital flux) were delayed by about 150–300 a. Three short‐term Lateglacial cold intervals, corresponding to Greenland isotope substages GI‐1d, GI‐1c2 and GI‐1b, also show complex proxy responses that vary in time. Copyright © 2011 John Wiley & Sons, Ltd.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3 and SiO2(OH)2. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH⁻ was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H⁺] 11.7, respectively. Within these ranges the formation of SiO(OH)₃⁻ and SiO₂(OH)₂²⁻ with formation constants log β₋₁₁(Si(OH)₄ SiO(OH)₃⁻ + H⁺) = −9.472 ±0.002 and log β₋₂₁(Si(OH)₄ SiO₂(OH)₂²⁻ + 2H⁺) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H⁺] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Long-period (30 days1 year) electromagnetic sounding and the electrical conductivity of the lower mantle beneath Europe

The C -response connects the magnetic vertical component and the horizontal gradient of the horizontal components of electromagnetic variations and forms the basis for deriving the conductivitydepth profile of the Earth. Time-series of daily mean values at 42 observatories typically with 50 years of data are used to estimate C -responses for periods between 1 month and 1  yr. The Z : Y method is applied, which means that the vertical component is taken locally whereas the horizontal components are used globally by expansion in a series of spherical harmonics.
In combination with results from previous analyses, the method yields consistent results for European observatories in the entire period range from a few hours to 1  yr, corresponding to penetration depths between 300 and 1800  km.
1-D conductivity models derived from these results show an increase in conductivity with depth z to about 2  S  m^-1 at z =800  km, and almost constant conductivity between z =800 and z =2000  km with values of 310  S  m^-1, in good agreement with laboratory measurements of mantle material. Below 2000  km the conductivity is poorly resolved. However, the best-fitting models indicate a further increase in conductivity to values between 50 and 150  S  m^-1.     

Effects of Short‐term and Long‐term Aluminium Stress on Photosynthesis,Respiration, and Reproductive Capacity in a Unicellular Green Flagellate (Euglena gracilis)

Effects of short‐term (1 h exposure) and long‐term (7 d exposure) aluminium stress on photosynthesis and reproductive capacity have been studied in Euglena gracilis strain Z. Following concentrations of Al_tot (added as AlCl₃) were tested: 0.5 mg L^‐1, 1.0 mg L^‐1, 1.5 mg L^‐1, 2.5 mg L^‐1, 5.0 mg L^‐1, 7.5 mg L^‐1, 10.0 mg L^‐1, and 15.0 mg L^‐1 Al, respectively. Growth rates at different aluminium concentrations did not show significant differences, except at 15.0 mg L^‐1Al. Initial respiration was higher in long‐term than in the short‐term experiments. It is supposed that an energy‐dependent mechanism of excretion of aluminium ions has been active in the stressed cells. Consequently, the cells of E. gracilis after long‐term exposure to aluminium are believed to be more acclimatised to the aluminium stress. Photosynthetic efficiency (PE) has been negatively affected by aluminium in all experiments performed. Differences between control algae and those treated with aluminium were significant in all cases. PE in long‐term experiments was in general significantly higher at all concentrations of aluminium studied, compared to the short‐term experiments. The aluminium concentrations tested led only to a general decrease in PE while the level of decrease was not especially concentration‐dependent. In general, aluminium tolerance of E. gracilis can be estimated as low, especially by short‐term exposure. However, good acclimatisation capacity of this green flagellate to aluminium doses by long‐term exposure can be supposed.     

Atmospheric CO2 consumption by chemical weathering in North America

CO₂ consumption by chemical weathering is an integral part of the boundless carbon cycle, whose spatial patterns and controlling factors on continental scale are still not fully understood. A dataset of 338 river catchments throughout North America was used to empirically identify predictors of bicarbonate fluxes by chemical weathering and interpret the underlying controlling factors. Detailed analysis of major ion ratios enables distinction of the contributions of silicate and carbonate weathering and thus quantifying CO₂ consumption. Extrapolation of the identified empirical model equations to North America allows the analysis of the spatial patterns of the CO₂ consumption by chemical weathering.Runoff, lithology and land cover were identified as the major predictors of the riverine bicarbonate fluxes and the associated CO₂ consumption. Other influence factors, e.g. temperature, could not be established in the models. Of the distinguished land cover classes, artificial surfaces, dominated by urban areas, increase bicarbonate fluxes most, followed by shrubs, grasslands, managed lands, and forests. The extrapolation results in an average specific bicarbonate flux of 0.3 Mmol km⁻² a⁻¹ by chemical weathering in North America, of which 64% originates from atmospheric CO₂, and 36% from carbonate mineral dissolution. Chemical weathering in North America thus consumes 50 Mt atmospheric CO₂-C per year. About half of that originates from 10% of the area of North America.The estimated strength of individual predictors differs from previous studies. This highlights the need for a globally representative set of regionally calibrated models of CO₂ consumption by chemical weathering, which apply very detailed spatial data to resolve the heterogeneity of earth surface processes.     

Experimental evidence of fast groundwater responses in a hillslope/floodplain area in the Black Forest Mountains,Germany

Analysis of water flow pathways from hillslopes to streams is essential for the optimal protection of water resources as well as for ecohydrological studies. This study addresses runoff generation processes at a hillslope and near‐stream shallow groundwater system in the Black Forest Mountains, southwestern Germany. The changing spatial and temporal flow patterns during differing hydrological situations were examined using a combined hydraulic and hydrochemical approach. Groundwater levels at 10 wells, discharge at a near‐stream saturated area, and several natural tracers (deuterium, dissolved silica, and major anions and cations) were observed at different locations during high and low flows. The importance of the groundwater component during flood formation was clearly demonstrated: its contribution was about 80% during a double peak flood event at the saturated area. In addition, a rapid change of the shallow groundwater levels was observed along two transects of groundwater wells in the floodplain. This led to an enhanced groundwater discharge into the saturated area located at the end of one study transect. The amount of groundwater additionally activated during the event was about 30% of total discharge recorded at the outlet of the saturated area. Two alternative hypotheses are discussed to explain this phenomenon: the establishment of locally confined conditions and the development of a pressure wave (hypothesis A), or the significant change of the three‐dimensional groundwater flow lines that caused a large increase of the groundwater catchment at the saturated area during the investigated event (hypothesis B). Even if the exact flow paths and mechanisms could not be clearly identified, the importance of rapid responding hillslope groundwater was undoubtedly demonstrated by a combination of tracer and hydrometric methods. Copyright © 2004 John Wiley & Sons, Ltd.     

The axial rotation of planets and transfer of mass and angular momentum from a satellite system to its primary

The main topic of this paper is to investigate the exchange of mass and angular momentum between a satellite or planetary system and its primary, and the effects of this exchange to axial rotations and satellite orbits. Various applications on the calculation of axial rotations, present and past satellite masses and orbits and other implications of the theory are presented.