Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth's surface environments

Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ~(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ~(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ~(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ~(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ~(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.     

Predicting summer hypoxia in the northern Gulf of Mexico: riverine N, P, and Si loading

We conducted a statistical analysis to discern the relative strengths of the loading of various forms of nitrogen, phosphorus, dissolved silicate and their molar ratios on the variance in the size of the summertime low oxygen zone found off the Mississippi River, northern Gulf of Mexico. A stable statistical model that included Year and riverine nitrate+nitrite loading for the 2 months prior to the measurement of hypoxic zone size described 82% of its variation in size from 1978 to 2004. The usefulness of the term Year is consistent with the documented increase in carbon stored in sediments after the 1970s, which is when the hypoxic zone is predicted to have become a regular feature on the shelf and to have expanded westward. The increased carbon storage is anticipated to cause a sedimentary respiratory demand influencing the size of the zone, and whose temporal influence is cumulative and transcends the annual variations in nitrogen loading. The variable Year is negatively correlated with the TN:TP ratio in a way that suggests N, not P, has become more important as a factor limiting phytoplankton growth in the last 20 years. Nitrogen, in particular nitrate+nitrite, and not phosphorus, dissolved silicate, or their molar ratios, appears to be the major driving factor influencing the size of the hypoxic zone on this shelf. This conclusion is consistent with cross-system analyses that conclude that the TN:TP ratio in the Mississippi River, currently fluctuating around 20:1, is indicative of nitrogen, not phosphorus, limitation of phytoplankton growth. Nutrient management that places stronger emphasis on reducing nitrogen loading as compared to phosphorus loading, is justified.     

Variability of the dissolved nutrient (N,P, Si) concentrations in the Bay of Annaba in relation to the inputs of the Seybouse and Mafragh estuaries

Dissolved inorganic nitrogen (DIN), phosphate (PO₄) and silicic acid (Si(OH)₄) loads from the Seybouse and the Mafragh estuaries into the Bay of Annaba, Algeria, were assessed at three stations of the Bay over three years. The Seybouse inputs had high levels of DIN and PO₄, in contrast to the Mafragh estuary’s near-pristine inputs; Si(OH)₄ levels were low in both estuaries. The DIN:PO₄ molar ratios were over 30 in most samples and the Si(OH)₄:DIN ratio was less than 0.5 in the Seybouse waters, but nearly balanced in the Mafragh. The specific fluxes of Si–Si(OH)₄ (400–540 kg Si km⁻² yr⁻¹) were comparable in the two catchments, but those of DIN were several-fold higher in the Seybouse (373 kg N km⁻² yr⁻¹). The inner Bay affected by the Seybouse inputs had high levels of all nutrients, while the Mafragh plume and the outer marine station were less enriched.     

Interrelations between Si and P biogeochemical cycles—a new approach to the solution of the eutrophication problem

Because the biogeochemical cycles of P and Si in temperate lakes are strongly connected by the dynamics of primary producers, it should be possible to influence the former cycle by causing changes in the latter. It is shown using the mathematical model ‘Rostherne’ that winter levels of ambient Si have a major influence both on spring levels of ambient P and on the summer cyanobacterial maxima. Additions of Si to the lakes could be used for the fine regulation of the biogeochemical balance and may prescribe a recipe for improvement of water quality, as well as a new solution to the problem of eutrophication. Copyright © 2000 John Wiley & Sons, Ltd.     

Bioavailability and Interaction of Si and P in a Coastal Saline Soil Amended with Pig Slurry

The effects of widely applied organic waste amendment on soil Si and P bioavailability and their interaction have rarely been investigated. The study examined bioavailability and interaction of Si and P in response to pig slurry (PS) amendment in a coastal saline (CS) soil. The final purposes of the study are to assess fertilizer Si and P needs and to ensure environmental quality. The results show that PS amendment can cause accumulation of bioavailable Si in surface soil (0–20 cm), and significantly improve both soil bioavailable P content and soil P lability through PS‐Si and P input, and by the input of PS‐organic matter (OM) and enhancing the complexation of OM with soil Si and P. As a result of the Si‐P competitive sorption, Si shows a more rapid increase in bioavailability than P at the preliminary stage of PS amendment. However, under the weakly alkaline conditions as a result of relatively long term PS amendment, the fixation capacity of Si by soil solid components increases causing a rapider decline of Si bioavailability than that of P.     

Reed litter Si content affects microbial community structure and the lipid composition of an invertebrate shredder during aquatic decomposition

The decomposition of plant litter is an important mechanism in regard to energy and nutrient dynamics of ecosystems. Silicon concentration of plant tissue can affect these processes by changing litter quality, i.e. nutrient stoichiometry and cellulose and phenols content. To determine which group of microbial decomposers benefits from high Si content in plants and how this impacts on animal decomposers, a batch experiment was conducted with reed leaf litter (Phragmites australis) differing in Si content in the presence/absence of invertebrate shredders (Gammarus pulex). Lipid concentration of G. pulex, in reed litter and fine particulate matter (FPOM) were examined. High Si concentration in reed resulted in a decline of gram positive bacteria in the heterotrophic biofilm and of gram negative bacteria in FPOM. The lipid composition in the next trophic level, the decomposer G. pulex, changed too, indicating a diet shift in favor of bacteria and algae with increasing litter Si concentration. Thus, basal decomposers were affected by the Si availability in plant resources, and these effects likely persist along the food chain, as FPOM is a dominant food supply for other groups, e.g. collectors. This impact of Si content on plant substrate quality for decomposer food webs may have global relevance, due to related modifications in carbon and nutrient cycling during litter decomposition.     

Production de26Al dans Fe et Si par protons de 0.6 et 24 GeV

A total of 139 breccia and crystalline rock fragments in the size range 2–4 mm from four Apollo 15 soil samples have been examined. Two of the sample stations are on the mare surface (4 and 9A) and two are on the Apennine Front (2 and 6). Approximately 90% of the fragments from the Apennine Front are brown-glass “soil” breccias, but those from the mare surface are 60%–70% basalt. Several textural varieties of mare basalt have been recognized, but within experimental error there is no difference in their⁴⁰Ar-³⁹Ar ages. The major non-mare (Pre-Imbrian) crystalline rock types in the Apennine Front regolith are KREEP basalt, anorthositic rocks, recrystallized norite (including anorthositic norite) and recrystallized polymict breccias; however, such crystalline rocks are rare in the samples examined. Apparently, the near surface Imbrium ejecta below the regolith has not been thermally recrystallized, and probably there are no outcrops of crystalline rocks upslope from the sample stations.     

Geochemical and geochronological studies of the Muong Hum alkaline granitic pluton from the Phan Si Pan Zone,northwest Vietnam: Implications for petrogenesis and tectonic setting

The Phan Si Pan zone in northwest Vietnam is an important tectonic unit for understanding the geological evolution of the southeast Asian Block. Numerous late Permian A‐type granites outcrop in this zone. In this study, new geochemical and geochronological data derived from the Muong Hum alkaline granitic pluton in the Phan Si Pan zone were investigated for its petrogenesis and tectonic setting. Zircon U–Pb analyses of three samples yielded ²⁰⁶Pb/²³⁸U ages of (251.1 ±3.5) Ma, (251.2 ±3.8) Ma, and (253.9 ±1.5) Ma, respectively, coinciding with the ages of the acid member of magma from Emeishan large igneous province, southwest China. The Muong Hum granite has 10 000 × Ga/Al and A/CNK values of 4.70–4.93 and 0.87–0.90, respectively, as well as negative Eu anomalies. It shows significant depletion of Ba, Sr, Ti, and P, similar to features of A‐type granite. Zircons have positive ε_Hf(t) values (+1.9 to +8.6) and Hf model ages (T_DM1) of 595–846 Ma, originating a mantle source. Compared with the Panzhihua A‐type granite of the southwest China domain and other A‐type plutons of the Phan Si Pan zone, including Ye Yen Sun, Phu Sa Phin, Nam Xe, Tam Duong Phan Si Pan, and Taihe, the geochemical characteristics and zircon Hf isotopic compositions of the Muong Hum granite demonstrate an affinity of mantle magma. It is believed that the Phan Si Pan zone is an important part of Emeishan large igneous province. It was reworked by the Cenozoic Aillaoshan‐Red River shear fault to its present location.     

Elasticity of (Mg, Fe)(Si, Al)O3-perovskite at high pressure

The most abundant mineral on Earth has a perovskite crystal structure and a chemistry that is dominated by MgSiO₃ with the next most abundant cations probably being aluminum and ferric iron. The dearth of experimental elasticity data for this chemically complex mineral limits our ability to calculate model seismic velocities for the lower mantle. We have calculated the single crystal elastic moduli (c_ij) for (Mg, Fe^3 +)(Si, Al)O₃ perovskite using density functional theory in order to investigate the effect of chemical variations and spin state transitions of the Fe³⁺ ions. Considering the favored coupled substitution of Mg²⁺-Si^4 + by Fe³⁺-Al³⁺, we find that the effect of ferric iron on seismic properties is comparable with the same amount of ferrous iron. Ferric iron lowers the elastic moduli relative to the Al charge-coupled substitution. Substitution of Fe³⁺ for Al³⁺, giving rise to an Fe/Mg ratio of 6%, causes 1.8% lower longitudinal velocity and 2.5% lower shear velocity at ambient pressure and 1.1% lower longitudinal velocity and 1.8% lower shear velocity at 142 GPa. The spin state of the iron for this composition has a relatively small effect (< 0.5% variation) on both bulk modulus and shear modulus.     

Fractional crystallization trends in the system Mg2SiO4-CaAl2Si2O8-FeO-Fe2O3-SiO2 over the range of oxygen partial pressures of 10−11 to 10−0.7 atm

A brief report is made of current laboratory investigations on phase relations among olivine, pyroxene, anorthite, magnetite, tridymite, liquid and gas in the system Mg₂SiO₄-CaAl₂Si₂O₈-FeO-Fe₂O₂-SiO₂ over a wide range of oxygen partial pressures. Courses of fractional crystallization under various conditions of oxygen partial pressure are depicted using an anorthite saturation diagram. Starting with a basalt-like composition in the system, fractional crystallization at a moderate oxygen partial pressure (10 atm.) results in an andesite-like residual liquid of composition 55 SiO₂, 14 iron oxide, 6 MgO, 9 CaO, 16 Al₂O₃ at a temperature of 1155°C. With fractional crystallization in a closed system, the end liquid approaches the composition of 45 SiO₂, 38 iron oxide, 6 CaO and 11 Al₂O₃, at a temperature of 1050°C and oxygen partial pressure of about 10^?12 atm. The andesitic final liquid in this system would be expected to further differentiate toward dacitic and rhyolitic compositions if alkalies and water were present in the system. On the basis of these studies, the derivation of liquids of andesitic, dacitic or rhyolitic composition from primary basalts by fractional crystallization seems entirely possible if the oxygen partial pressure is maintained at a moderate or high level.     

Caractérisation de la Variabilité Spatiale et Temporelle des Précipitations Annuelles sur le Bassin du Lac Tchad au Cours du 20ème Siècle/Spatial and Temporal Variability of Annual Rainfall in the Lake Chad Basin During the 20th Century

Abstract

The study of changes in annual rainfall in the Lake Chad basin during the 20th century is based on the analysis of 47 stations, i.e. a total of about 1600 station-years for the time series with more than 25 years of data. As previously observed in western and Sahelian Africa, robust tests of shift in time series identify a significant change in mean from the beginning of the 1960s between the latitudes 11 and 13°N, and a little later in this decade for the northern stations. The analysis of decadal rainfall shows that the 1950s decade was very humid and the next three decades were drier. These dry conditions were more and more severe until the 1980s. Data available after 1990 do not show any inversion in the trend. The annual rainfall decreases from south to north, and the regional gradient has changed from 1.5 mm km^?1 in the 1950s to 1.2 mm km^?1 in the 1980s between the latitudes 10 and 14°N.     

Dynamics of dissolved major (Na,K, Ca,Mg, and Si) and trace (Al,Fe, Mn,Zn, Cu,and Cr) elements along the lower Orinoco River

This study addresses the changes in dissolved major and trace element concentrations along the Orinoco River, including the mixing zone between the Orinoco and Apure Rivers. Water samples from the Apure and Orinoco Rivers were collected monthly in four sectors over a period of 15 months. Auxiliary parameters (pH, dissolved oxygen, conductivity, and temperature), total suspended sediments, dissolved organic carbon (DOC), and major (Na, K, Ca, Mg, and Si) and trace (Al, Fe, Mn, Zn, Cu, and Cr) element concentrations were measured in all sectors. The relative contribution of both rivers after the Apure–Orinoco confluence was determined using Ca as a tracer. Moreover, a mixing model was developed to determine whether dissolved species exhibit a conservative behavior during mixing. The results indicate that DOC is removed from waters during the Apure–Orinoco mixing, probably due to absorption of DOC on mineral phases supplied by the Apure River. Dissolved Na, Ca, and Mg behave conservatively during the mixing processes, and their concentrations are controlled by a dilution process. The anomaly in the temporal pattern of K in the Orinoco is caused by the input of biogenic K originating from the Apure River during the high‐water stage. The loss of dissolved Si during the low‐water stage can be explained by the uptake of Si by diatoms. Dissolved Mn, Zn, Al, and Fe showed a non‐conservative behavior during the Apure–Orinoco mixing. The removal of Mn and Zn from the dissolved phase can be explained by the formation of Mn‐oxyhydroxides and the scavenging of Zn onto Mn oxides. Dissolved Fe is controlled by redox processes, although the removals of Fe and Al due to the preferential adsorption of large organometallic complexes by mineral surfaces after the Apure–Orinoco confluence can affect the mobility of both elements during transport. The conservative behavior shown by Cu and Cr can be related to the tendency of both elements to be complexed with small organic colloids, which are not preferentially adsorbed by clays.     

On the synchronism in the events within the core and on the surface of the earth: the changes in the organic world and in the polarity of the geomagnetic field in the phanerozoic

The data on geomagnetic reversals are compared with the changes in the organic world and with the lower-mantle plumes. The times of the formation of plumes and the times of their appearance on the Earth’s surface relate to the intervals characterized by the different frequencies of geomagnetic reversals, i.e., there is no interrelation between the formation of plumes and the frequency of the changes in the geomagnetic field polarity. At the same time, a certain synchronism is observed between the frequency of the geomagnetic reversals and the boundaries of the biostratigraphic ages, i.e., the changes in the organic world in the long-period range. A hypothesis is proposed, which explains the change in the sign of the geomagnetic field by the combined effect of the irregular rotation of the internal core relative to the mantle and the changes in the slope angle of the axis of the Earth’s rotation, which, in turn, results in synchronous events on the Earth’s surface: the rates of changes in the organic world.     

Anomalies in the secular variations in the main geomagnetic field in the context of the hierarchic dipole model

The developed dynamic model of the main geomagnetic field (MGF) includes the sources of three levels, which have existed and continuously changed during the 100-year period. The spatial-temporal dynamics of the secular variations in MGF has been considered based on this model. It has been indicated that, at different times, the formation of anomalies (located in similar regions) depended on the total dynamics of different combinations of sources, including a change in the parameters of the dipoles of the secondorder smallness. Anomalies generated by the dynamics of the dipoles of the third-order smallness do not evidently manifest themselves in the total secular variations but are responsible for the specific shapes of isodynamic lines. Based on the stability and continuity of the constructed model, the conclusion is made that long-living turbulent flows of different scales can exist in the liquid core.     

The changes in the electric conductivity of the lithosphere in the source region of the strongest Olyutora earthquake in the Koryak highlands

The results of the magnetotelluric (MT) soundings before and after an earthquake are analyzed. The interpretation is based on the longitudinal and transverse MT curves (along and across the strike of the main tectonic elements, respectively). The MT curves are distorted by the ρ- and coast effect. The distortions due to the coast effect are estimated by the testing three-dimensional (3D) model. It is established that the coast effect distortion at the periods up to 1000 s is small and can be disregarded. The divergence of the longitudinal and transverse MT curves, which points to the presence of the deep faults, is thoroughly studied. The inversion of the MTsounding curves is carried out by the REBOCC program of the numerical two-dimensional modeling. This program implements the procedures of elimination of the ρ-effect and the joint inversion of the longitudinal and transverse MT sounding curves. The obtained geoelectrical cross sections provide an insight into the structure of electrical conductivity of the lithosphere before and after the earthquake. The more intense variations in the electric conductivity are observed in the zone of the deep faults. These variations are related to the changes in the porosity and saturation of the rocks by the highly mineralized fluids.     

Hydrological changes in the Ganges system in Bangladesh in the post-Farakka period

Abstract

The basin area of the Ganges River in Bangladesh is extremely dependent on a regular water supply from upstream to meet requirements for agriculture, fisheries, navigation, salinity control, and domestic and industrial sectors. In 1975, India commissioned a barrage on the Ganges River at Farakka to divert a significant portion of the dry season flow in order to make the Calcutta Port navigable. Statistical analyses of discharge and water level data have been carried out to determine if significant changes have occurred in the hydrology of the Ganges system in Bangladesh in the post-Farakka period. Siltation of the Gorai River (an offtake of the Ganges River) has also been examined using the stage-discharge relationship and regression analysis. The analyses show that the diversion has caused considerable hydrological changes in the Ganges system in Bangladesh. The water supply in the dry season has been reduced substantially, while siltation of the Gorai River has increased significantly.     

Changes in sediment transport in the Kuye River in the Loess Plateau in China

In this paper, the changes in sediment transport over 51 years from 1955 to 2006 in the Kuye River in the Loess Plateau in China are assessed. Key factors affecting sediment yield and sediment transport, such as precipitation depth, discharge, and human activities are studied. To investigate the changes in sediment yield in this watershed, a trend analysis on sediment concentration, precipitation depth, and discharge is conducted. Precipitation depths at 2 Climate Stations （CSs）, as well as discharge and sediment transport at 3 Gauging Stations （GSs） are used to assess the features of sediment transport in the Kuye River. The rtmoff modulus （defined as the annual average discharge per unit area, L/（s·km^2）） and the sediment transport modulus （defined as the annual suspended sediment transport per unit area, t/（yr km^2）） are introduced in this study to assess the changes in runoff and sediment yield for this watershed. The results show that the highest average monthly discharge during the study period in the Kuye River is 66.23 m^3/s in August with an average monthly sediment concentration of 88.9 kg/m^3. However, the highest average monthly sediment concentration during the study period in the Kuye River is 125.34 kg/m^3 and occurs in July, which has an average discharge of 42.6 m^3/s that is much less than the average monthly discharge in August. It is found that both the runoff modulus and sediment transport modulus at Wenjiachuan GS on the Kuye River has a clear downward trend. During the summer season from July to August, the sediment transport modulus at Wenjiachuan GS is much higher than those at Toudaoguai and Longmen GSs on the Yellow River. The easily erodible loess in the Kuye River watershed and the sparse vegetation are responsible for the extremely high sediment yield from the Kuye River watershed. The analyses of the grain size distribution of suspended load in the Kuye River are presented. The average monthly median grain size of suspended load in the Kuye River is largest in February and then decreases until June. In July, the average monthly median grain size of suspended load approaches another peak and decreases until September. Then, the median grain size of suspended load starts to increase until February of the following year. However, the average monthly median grain size of suspended load in the Yellow River at Toudaoguai and Longmen GSs is the smallest between early summer and late fall The median grain size in the Yellow River starts to increase in November and approaches the largest size in January.     

Trends in the characteristics of the annual and semiannual variations observed in the radio wave absorption in the lower ionosphere

The continuous increase in concentration of greenhouse gases in the atmosphere is expected to cool higher levels of the atmosphere. There is some direct and indirect experimental evidence of long-term trends in temperature and other parameters in the mesosphere and lower thermosphere (MLT). Here we look for long-term trends in the annual and semiannual variations of the radio wave absorption in the lower ionosphere, which corresponds to the MLT region heights. Data from central and southeastern Europe are used. A consistent tendency to a positive trend in the amplitude of the semiannual wave appears to be observed. The reality of a similar tendency in the amplitude of the annual wave is questionable in the sense that the trend in the amplitude of the annual wave is probably induced by the trend in the yearly average values of absorption. The phases of both the annual and semiannual waves display a forward tendency, i.e. shift to an earlier time in the year. A tentative interpretation of these results in terms of changes of the seasonal variation of temperature and wind at MLT heights does not contradict the trends observed in those parameters.