Origin and palaeo‐environments of calcareous sediments in the Moshaweng dry valley,southeast Botswana

Quaternary sedimentation in the Moshaweng dry valley of southeastern Botswana is evaluated on the basis of geomorphological evolution and sedimentological analyses. Stratigraphic evidence reveals an upper surface (1095 m) containing abundant sil‐calcrete, an intermediate surface (1085 m) in which sil‐calcrete underlies nodular calcrete and lower (1075 m) surface in which sil‐calcrete and nodular calcrete are interbedded. This subdivision is reflected in the geochemical composition of the sediments which show an overall trend of decreasing SiO₂ content (and increasing CaCO₃ content) with depth from the highest to the lowest surface levels. The calcretes and sil‐calcretes represent modifications of pre‐existing detrital Kalahari Group sand and basal Kalahari pebbles which thinned over a Karoo bedrock high. Modification took place during wet periods when abundant Ca⁺⁺‐rich groundwater flowed along the structurally aligned valley system. With the onset of drier conditions, water table fluctuations led to the precipitation of nodular calcretes in the phreatic layer to a depth of about 20 m. A major geochemical change resulted in the preferential silicification of the nodular calcrete deposits. Conditions for silica mobilization may be related to drying‐induced salinity and in situ geochemical differentiation brought about by pebble dissociation towards the top of the sediment pile. As calcretization and valley formation progressed to lower levels, silica release took place on a diminishing scale. Thermoluminescence dating infers a mid‐Pleistocene age for sil‐calcrete formation suggesting that valley evolution and original calcrete precipitation are much older. Late stage dissolution of CaCO₃ from pre‐existing surface calcretes or sil‐calcretes led to the formation of pedogenic case‐hardened deposits during a time of reduced flow through the Moshaweng system possibly during the upper or late Pleistocene. Copyright © 2002 John Wiley & Sons, Ltd.     

The phase diagram of CaCO3 in relation to shock compression and decomposition

The phase diagram for calcite (CaCO₃) is re-evaluated in relation to dynamic compression and following release from shock. Available shock compression data on Hugoniot dynamic measurements, analysis of recovered samples, and observation at terrestrial impact sites are compared with theoretically derived equations of state (EOS) for CaCO₃ and its decomposition products CaO and CO₂. The study results in a refined phase diagram for CaCO₃ in which the major change is the extension of the liquid field of CaCO₃. A general outcome of this analysis is that release of CO₂ from naturally shocked carbonates to the atmosphere is (grossly) overestimated if based on the calcite phase diagram constructed from thermodynamic equilibrium conditions.     

Shock temperature in calcite (CaCO3) at 95-160 GPa

The temperatures induced in crystalline calcite (CaCO₃) upon planar shock compression (95-160 GPa) are reported from two-stage light gas gun experiments. Temperatures of 3300-5400 K are obtained by fitting six-channel optical pyrometer radiances in the 450-900 nm range to the Planck gray-body radiation law. Thermodynamic calculations demonstrate that these temperatures are some 400-1350 K lower than expected for vibronic excitations of the lattice with a 3R/mole-atom specific heat (R is gas constant). The temperature deficit along the Hugoniot is larger than that expected from only melting. In addition to melting, it appears likely that shock-induced decomposition of calcite occurs behind the shock front. We modeled disproportionation of calcite into CaO (solid) plus CO₂ (gas). For temperature calculations, specific heat at constant volume for 1 mole of CO₂ is taken to be 6.7R as compared to 9R in the solid state; whereas a mole of calcite and a mole of CaO have their solid state values 15R and 6R, respectively. Calculations suggest that the calcite decomposes to CaO and CO₂ at ∼110±10 GPa along the Hugoniot. Recent reanalysis of earlier VISAR measurements of particle velocity profiles [1] indicates that calcite shocked to 18 GPa undergoes disproportionation at much lower pressures upon isentropic expansion.     

The join grossularite-calcite through the system CaO—Al2O3—SiO2—CO2 at 30 kilobars: Crystallization range of silicates and carbonates on the liquidus

At 30 kbar, calcite melts congruently at 1615°C, and grossularite melts incongruently to liquid + gehlenite (tentative identification) at 1535°C. The assemblage calcite + grossularite melts at 1450°C to produce liquid + vapor, with piercing point at about 49 wt.% CaCO₃. Vapor phase is present in all hypersolidus phase fields except for those with less than about 7% CaCO₃ or 8% Ca₃Al₂Si₃O₁₂. These results, together with known liquidus data for CaO—SiO₂—CO₂ and inferred results for CaO—Al₂O₃—CO₂ and Al₂O₃—SiO₂—CO₂, permit construction of the position of the CO₂- saturated liquidus surface in the quaternary system, and estimation of the positions of liquidus field boundaries separating some of the primary crystallization fields on this surface. The field of calcite is separated from those for grossularite and quartz by a field boundary with about 50% dissolved CaCO₃. Crystallization paths of silicate liquids in the range Ca₂SiO₄—Ca₃Al₂Si₃O₁₂—SiO₂, with some dissolved CO₂, will terminate at a quaternary eutectic on this field boundary, with the precipitation of calcite together with grossularite and quartz, at a temperature below 1450°C. Addition of Al₂O₃ to CaO—SiO₂—CO₂ in amounts sufficient to stabilize garnet thus causes little change in the general liquidus pattern as far as carbonates and silicates are concerned. With addition of MgO, we anticipate that silicate liquids with dissolved CO₂ will also follow liquidus paths to fields for the precipitation of carbonates; we conclude that similar paths link kimberlite and some carnbonatite magmas.     

Processes of silicate karstification associated with pan formation in the Darwin–Koolpinya area of northern Australia

Lyons Lagoon, one of many small pans near Darwin, Northern Australia, occurs in lateritized terrain. Formation by structurally facilitated silicate karsti?cation of the parent Cretaceous sandy sediments was earlier proposed. This paper presents the results of thin section microscopy and scanning electron microscopy with energy‐dispersive X‐ray study of pan sediments with a view to assessing the extent to which they re?ect the geomorphological/hydrogeological history. Severe corrosion was found to overprint the impact features of the primary sands, attributed to aggressive leaching and consistent with formation of the depression by karsti?cation when the water table was low. Formation of a smectitic matrix is considered to have followed when the water table was high. Upon subsequent lowering of the water level leaching was resumed, altering smectite to kaolinite and resulting in incongruent dissolution of kaolinite to leave a siliceous residuum. At least two cycles of high followed by low water levels are recognized. Such periodic changes of levels are considered essential to pan formation within freely draining lateritic terrain. The processes of pan formation and alteration of pan sediments (essentially residual deposits) is ongoing, biocorrosion being implicated as an important mechanism. Incongruent kaolinite dissolution, to leave a silica residuum, a hitherto apparently unrecognized process, raises the possibility that silcrete may form as a relative accumulation which is synchronous with lateritic leaching in more elevated topographic positions. Copyright © 2004 John Wiley & Sons, Ltd.     

Biosilicium (BSi) in Sedimenten Mecklenburger Seen (Deutschland) und das Calciumcarbonat-Biosilicium-Verhältnis als Trophie- und Wasserstandsindikator Biogenic Silica (BSi) in Sediments of the Mecklenburgian Lake District (Germany) and the Calcite-Silica-Relation as Indicator for Trophy and Water Level

The BSi content has been investigated in the surface sediments of lakes of different trophic state in the Mecklenburgian Lake District. The BSi content differs between 1 to 1000 mg BSi/g dry matter. High values were found in deep eutrophic lakes. Litoral sediments and shallow eutrophic lakes have lower contents. BSi content was found to be correlated with lake morphometry, depth, trophic level, sediment composition and especially with calcite. With the CaCO₃/BSi-value, 3 groups of lakes can be characterized:

• CaCO₃/BSi = 0 oligotrophic and dystrophic lakes
• CaCO₃/BSi ≤ 10 mesotrophic and eutrophic deep lakes
• CaCO₃/BSi ≤ 10 eutrophic shallow lakes

The results from the recent sediments have been compared with those from older sediments. Using the CaCO₃/BSi-value, climatic change, trophic state, and sea level can be detected.     

Isovolumetric weathering and silcrete formation,southern Cape Province,South Africa

Calculations of absolute elemental gains and losses based on isovolumetric bedrock alteration are applied to deep weathering profiles and silcrete developed on Dwyka Tillite and Bokkeveld Shale. Bedrock weathering to kaolinite and illite yields sufficient SiO₂ to account for observed thicknesses of associated silcrete. Absolute accumulation of SiO₂ in silcrete is complemented by substantial absolute depletion of Al₂O₃. Absolute accumulation of TiO₂ in both silcrete and associated weathered material together with authigenic anatase concentrations in silctete recorded during micromorphological investigations indicate TiO₂ mobilization in a low pH environment (pH < 3·75) during silcrete formation. Under these low pH conditions increased Al₂O₃ solubility led to replacement of kaolinite and illite by a proportion of SiO₂ retained in the weathering profile through restricted drainage.     

The nature of calcareous deposits along pan margins in eastern central Namibia

In a region along the western margin of the Kalahari in eastern Namibia and western Botswana, many pan basins have mainly calcareous deposits along part of their margins. These are typically lined by low vertical scarps. In Namibia, these pans are mainly located in dry river beds. The petrographical study of these deposits demonstrates that they consist of lacustrine sediments that have to a varying extent been affected by early‐diagenetic processes and by the formation of late‐diagenetic features. The original composition of the deposits ranges from highly calcareous sediments, typically with ostracod, diatom and charophyte remains, to entirely non‐calcareous diatomites. The deposits generally show an upward increase in total carbonate content, which is mainly a synsedimentary feature. The early‐diagenetic processes that affected the deposits include the formation of orthic siliceous nodules. At a later stage, secondary calcite enrichment occurred, leaving only the silica‐impregnated sections unaffected. This enrichment partly accounts for the upward increase in total carbonate content in some profiles and often resulted in the development of a highly calcareous surface horizon. Sepiolite and amorphous silica that are part of the groundmass of the deposits may also partly have formed at this stage. Late‐diagenetic features include various forms of secondary calcite and silica. This study of pan basins in eastern central Namibia indicates that a lacustrine rather than purely pedogenic origin should also be considered for calcareous deposits that commonly occur along pan margins in other parts of southern Africa. Copyright © 2002 John Wiley & Sons, Ltd.     

Holocene calcrete crust deposits on the moraine of Batura Glacier, northern Pakistan

Abstract   Calcretes can be observed on the surface of old moraines around Batura Glacier in the upper Hunza Valley, Karakoram Mountains, Pakistan. They develop as a calcareous crust cementing small gravels under boulders. In order to understand the genesis of the calcrete crust, a variety of methods were employed: (i) study of mineralogy and geochemistry of a calcrete crust precipitated on the lateral moraine using X-ray diffractometer and electron probe microanalysis; (ii) analysis of solute chemistry of surface water and ice bodies around the Batura Glacier; and (iii) accelerator mass spectrometry ¹⁴C dating of the crust itself. The results indicate that the calcrete crust has definite laminated layers composed of a fine-grain and compact calcite layer, and a mineral fragment layer. The chemical composition of the calcite layer is approximately 60% CaO and 1% MgO. The mineral fragment layer consists of rounded grain materials up to 0.2 mm in diameter. It shows a graded bedding structure with fine grains of quartz, albite and muscovite. Meanwhile, as the Paleozoic Pasu limestone is distributed around the terminal of Batura Glacier, Ca cations dissolve in the melt water of the glacier. Accordingly, the calcrete crust is precipitated by decreases in CO₂ partial pressure from glacier ice and evaporation of the melt water, including high concentration of Ca²⁺ at ephemeral streams and small ponds stagnating between the moraine and glacial ice. On the basis of the AMS ¹⁴C age, the calcrete is considered to have formed approximately 8200 calibrated years bp under the Batura glacial stage.     

Factors controlling the chemical evolution of travertine‐depositing rivers of the Barkly karst,northern Australia

Groundwaters feeding travertine‐depositing rivers of the northeastern segment of the Barkly karst (NW Queensland, Australia) are of comparable chemical composition, allowing a detailed investigation of how the rate of downstream chemical evolution varies from river to river. The discharge, pH, temperature, conductivity and major‐ion concentrations of five rivers were determined by standard field and laboratory techniques. The results show that each river experiences similar patterns of downstream chemical evolution, with CO₂ outgassing driving the waters to high levels of calcite supersaturation, which in turn leads to widespread calcium carbonate deposition. However, the rate at which the waters evolve, measured as the loss of CaCO₃ per kilometre, varies from river to river, and depends primarily upon discharge at the time of sampling and stream gradient. For example, Louie Creek (Q = 0·11 m³ s^?1) and Carl Creek (Q = 0·50 m³ s^?1) have identical stream gradients, but the loss of CaCO₃ per kilometre for Louie Creek is twice that of Carl Creek. The Gregory River (Q = 3·07 m³ s^?1), O'Shanassy River (Q = 0·57 m³ s^?1) and Lawn Hill Creek (Q = 0·72 m³ s^?1) have very similar gradients, but the rate of hydrochemical evolution of the Gregory River is significantly less than either of the other two systems. The results have major implications for travertine deposition: the stream reach required for waters to evolve to critical levels of calcite supersaturation will, all others things being equal, increase with increasing discharge, and the length of reach over which travertine is deposited will also increase with increasing discharge. This implies that fossil travertine deposits preserved well downstream of modern deposition limits are likely to have been formed under higher discharge regimes. Copyright © 2002 John Wiley & Sons, Ltd.     

Early Cretaceous I‐type granites in the southwest Fujian Province: new constraints on the late Mesozoic tectonic evolution of southeast China

Zircons from two samples of the Sukeng pluton in the southwest Fujian Province, China, were analyzed by LA–ICP–MS with the aim of determining the timing of formation. The zircons from the two samples yield similar U–Pb ages of 100.47 ± 0.42 and 102.46 ± 0.69 Ma, indicating that the Sufeng pluton is contemporaneous with the Sifang and Luoboling plutons, all of which are also related to Cu–Au–Pb–Zn–Mo mineralization within the study area. All three plutons have geochemical features of I‐type granites, are high‐ to mid‐K calc‐alkaline metaluminous rocks, and have average molar Al₂O₃/ (CaO+Na₂O+K₂O) values of 0.95, initial ⁸⁷Sr/⁸⁶Sr ratios of 0.70465–0.70841, εNd(t) values at 101 Ma from –1.72 to –7.26, and two‐stage Nd model ages (T_2DM) from 1.16 to 1.60 Ga. Zircons within these plutons have εHf(t) values at 101 Ma from –3.5 to 6.25 and T_2DM ages from 0.74 to 1.46 Ga, suggesting these I‐type granites formed from magmas generated by partial melting of Mesoproterozoic to Neoproterozoic continental crust that mixed with mantle‐derived magmas. The magmatism was associated with thickening of the lower crust caused by collisions between microcontinents in the Cathaysian Block, which were driven by Early Cretaceous subduction of the Pacific Plate.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Lower crustal melting via magma underplating: Elemental and Sr–Nd–Pb isotopic constraints from late Mesozoic intermediate–felsic volcanic rocks in the northeastern North China Block

Ar–Ar dating, major and trace element analyses, and Sr–Nd–Pb isotope results of two groups of Lower Cretaceous (erupted at 126 and 119 Ma, respectively) intermediate–felsic lava from the northeastern North China Block (NCB) suggest their derivation from melting of mixtures between the heterogeneous lower crust and underplated basalts. Both groups exhibit high‐K calc‐alkaline to shoshonitic affinities, characterized by light rare earth element (LREE) and large ion lithophile element (LILE) enrichment and variable high field strength element (HFSE, e.g. Nb, Ta and Ti) depletion, and moderately radiogenic Sr and unradiogenic Nd and Pb isotopic compositions. Compared with Group 2, Group 1 rocks have relatively higher K₂O and Al₂O₃/(CaO + K₂O + Na₂O) in molar ratio, higher HFSE concentrations and lower Nb/Ta ratios, and higher Sr–Nd–Pb isotope ratios. Group 1 rocks were derived from a mixture of an enriched mantle‐derived magma and a lower crust that has developed radiogenic Sr and unradiogenic Nd and Pb isotopic compositions, whereas the Group 2 magmas were melts of another mixture between the same mantle‐derived component and another type of lower crust having even lower Sr, Nd, and Pb isotopic ratios. Shift in source region from Group 1 to Group 2 coincided with a change in melting conditions: hydrous melting of both the underplated basalt and the lower crust produced the earlier high‐Nb and low‐Nb/Ta melts with little or no residual Ti‐rich phases; while the younger low‐Nb and high‐Nb/Ta magmas were melted under a water‐deficient system, in which Ti‐rich phases were retained in the source. Generation of the two groups of intermediate–felsic volcanic rocks was genetically linked with the contemporaneous magma underplating event as a result of lithospheric thinning in the eastern NCB.     

Groundwater mineralisation processes in Mediterranean semi‐arid systems (Cap‐Bon,North east of Tunisia): hydrogeological and geochemical approaches

The groundwater of the Korba plain represents major water resources in Tunisia. The Plio‐Quaternary unconfined aquifer of the Cap‐Bon (north‐east Tunisia) is subject to the intensive agricultural activities and high groundwater pumping rates due to the increasing of the groundwater extraction. The degradation of the groundwater quality is characterized by the salinization phenomena. Groundwater were sampled and analysed for physic‐chemical parameters: Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^‐, SO₄^2‐, HCO₃^‐, NO₃^‐, pH, electrical conductivity (EC), and the temperature (T°). The hydrochemical analysis is coupled with the calculation of the saturation indexes (SI gypsum, SI halite, SI calcite and SI dolomite), ionic derivation and with the ion correlations compared to chloride concentrations: Na⁺/ Cl^‐, Ca²⁺/ Cl^‐ and Mg²⁺/ Cl^‐ ratios. Seawater fractions in the groundwater were calculated using the chloride concentration. Those processes can be used as indicators of seawater intrusion progression. EC methods were also conducted to obtain new informations on the spatial scales and dynamics of the fresh water–seawater interface of coastal groundwater exchange. The mixing zone between freshwater and saltwater was clearly observed from the EC profile in the investigated area where a strong increase in EC with depth was observed, corresponding to the freshwater and saltwater interface. Results of hydrochemical study revealed the presence of direct cation exchange linked to seawater intrusion and dissolution processes associated with cations exchange. These results, together with EC investigation, indicated that the groundwater is affected by seawater intrusion and is still major actor as a source of salinization of the groundwater in Korba coastal plain. Further isotopic and hydrological investigations will be necessary to identify and more understood the underlying mechanisms. Copyright © 2012 John Wiley & Sons, Ltd.     

Aragonite dissolution on the Bermuda pedestal: Its depth and geochemical significance

The depth distribution of pteropod and planktonic foram tests, and fine-grained (<62 μm) aragonite, high-Mg calcite (12 mode mol.% MgCO₃), and low-Mg calcite has been determined for surface sediments of an area of the eastern slope of the Bermuda pedestal. Over the range 1800–3000 m, fine-grained aragonite and fine-grained high-Mg calcite gradually disappear relative to fine-grained low-Mg calcite, and pteropods gradually disappear relative to planktonic forams. This is interpreted as preferential dissolution of aragonite (and high-Mg calcite) relative to low-Mg calcite over this depth range. Coarse aragonitic debris derived from shallow-water organisms living on the Bermuda platform does not show consistent disappearance over the same depth zone. Chemical analyses of bottom water samples taken at the same time as some of the sediment samples indicate that the degree of saturation with respect to aragonite Ω_A over the zone of aragonite disappearance ranges from 0.55 to 0.85; i.e. major dissolution occurs only at Ω_A values distinctly less than one. These results lend credence to the hypothesis that CaCO₃ dissolution in the oceans, both as aragonite and as calcite, takes place mainly as a response to complex chemical kinetic phenomena and not as a result of the simple attainment of undersaturation (thermodynamic hypothesis) or the resuspension of bottom sediment (hydrodynamic hypothesis).     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

The influence of diurnal temperatures on the hydrochemistry of a tufa‐depositing stream

At‐a‐station diurnal variations in carbonate hydrochemistry were measured during four observation periods at Davys Creek, a tufa‐depositing stream in central NSW, Australia. Major ion concentrations and continuously logged measurements of specific conductivity, pH and temperature showed that changes in the amount of CaCO₃ deposited upstream of the study reach were directly related to changes in diurnal water temperatures, which control the rate of CO₂ efflux to the atmosphere. The greatest upstream losses occurred during the mid‐afternoon water temperature peak, whereas the lowest upstream losses occurred at sunrise, when water temperatures were at their lowest. Cloudy days at all times of the year produced small diurnal water temperatures ranges (c. 2–5°C) and, consequently, relatively small changes in upstream CaCO₃ loss (23–50 mg L^?1) through the day. Clear sunny days, especially during summer months, produced large diurnal water temperature changes (up to c. 11°C), which in turn triggered diurnal changes in upstream CaCO₃ loss of up to 100 mg L^?1. By implication, the active reach of tufa deposition must advance downstream and increase in length during the evening and vice versa during the day. Given that the temperature of Davys Creek waters are a function of insolation, changes in the reach of tufa deposition under baseflow conditions are a direct function of the prevailing weather. This has implications for the palaeoclimatic interpretation of fossil tufa deposits. Copyright © 2003 John Wiley & Sons, Ltd.     

Geochemical evidence of hydrothermal recharge in Lake Baringo,central Kenya Rift Valley

Lake Baringo, a freshwater lake in the central Kenya Rift Valley, is fed by perennial and ephemeral rivers, direct rainfall, and hot springs on Ol Kokwe Island near the centre of the lake. The lake has no surface outlet, but despite high evaporation rates it maintains dilute waters by subsurface seepage through permeable sediments and faulted lavas. New geochemical analyses (major ions, trace elements) of the river, lake, and hot spring waters and the suspended sediments have been made to determine the main controls of lake water quality. The results show that evaporative concentration and the binary mixing between two end members (rivers and thermal waters) can explain the hydrochemistry of the lake waters. Two zones are recognized from water composition. The southern part of the lake near sites of perennial river inflow is weakly influenced by evaporation, has low total dissolved species (TDS), and has a seasonally variable load of mainly detrital suspended sediments. In contrast, waters of the northern part of the lake show evidence for strong evaporation (TDS of up to eight times inflow). Authigenic clay minerals and calcite may be precipitating from those more concentrated fluids. The subaerial hot‐spring waters have a distinctive chemistry and are enriched in some elements that are also present in the lake water. Comparison of the chemical composition of the inflowing surface waters and lake water shows (1) an enrichment of some species (HCO₃^?, Cl, SO₄^2?, F, Na, B, V, Cr, As, Mo, Ba and U) in the lake, (2) a depletion in SiO₂ in the lake, and (3) a possible hydrothermal origin for most F. The rare earth element distribution and the F/Cl and Na/Cl ratios give valuable information on the rate of mixing of the river and hydrothermal fluids in the lake water. Calculations imply that thermal fluids may be seeping upward locally into the lake through grid‐faulted lavas, particularly south of Ol Kokwe Island. Copyright © 2006 John Wiley & Sons, Ltd.     

Modelling residence‐time response to freshwater input in Apalachicola Bay,Florida, USA

Residence time of an estuary can be used to estimate the rate of removal of freshwater and pollutants from river inflow. In this study, a calibrated three‐dimensional hydrodynamic model was used to determine residence time in response to the change of freshwater input in Apalachicola Bay. The bay is about 40 km long and 7 km wide, with an average 3 m water depth. Through hydrodynamic model simulations, the spatial and temporal salinity and the total freshwater volume in the bay were calculated. Then the freshwater fraction method was used to estimate the residence time. Results indicate that the residence time in Apalachicola Bay typically ranges between 3 and 10 days for the daily freshwater input ranging from 177 m³/s to 4561 m³/s. Regression analysis of model results shows that an exponential regression equation can be used to correlate the estuarine residence time to changes of freshwater input. Copyright © 2002 John Wiley & Sons, Ltd.     

Estimating daily inflows of large lakes using a water‐balance‐based runoff coefficient scaling approach

Daily river inflow time series are highly valuable for water resources and water environment management of large lakes. However, the availability of continuous inflow data for large lakes is still relatively limited, especially for large lakes situated within humid plain regions with tens or even hundreds of tributaries. In this study, we choose the fifth largest freshwater Lake Chaohu in China as our study area to introduce a new approach to reconstruct historical daily inflows at ungauged subcatchments of large lakes. This approach makes use of water level, lake surface rainfall, evaporation from the lake, and catchment rainfall observations. Rainfall–runoff relationship at a reference catchment was analysed to select rainfall input and estimate run‐off coefficient firstly, and the run‐off coefficient was then transferred to ungauged subcatchments to initially estimate daily inflows. Run‐off coefficient was scaled to adjust daily inflows at ungauged subcatchments according to water balance of the lake. This approach was evaluated using sparsely measured inflows at eight subcatchments of Lake Chaohu and compared with the commonly used drainage area ratio method. Results suggest that the inflow time series reconstructed from this approach consistent well to corresponding observations, with mean R² and Nash–Sutcliffe efficiency values of 0.69 and 0.6, respectively. This approach outperforms drainage area ratio method in terms of mean R² and Nash–Sutcliffe efficiency values. Accuracy of this approach holds well when the number of water‐level station being used decreased from four to one.