Uptake of dissolved Cd by biogenic and abiogenic aragonite: a comparison with sorption onto calcite

The uptake of Cd²⁺ by aragonite and calcite is investigated by combining macroscopic measurements with some qualitative sorption experiments performed in a hydrogel medium. Both biogenic and abiogenic aragonites were studied in order to evaluate the process on materials with different textures. Assuming that sorption occurs by surface precipitation of metal-bearing solids, the gel produces a drastic decrease in the nucleation density, which allows for the precipitation of crystallites that are large enough to be analysed by scanning electron microscopy and characterized by glancing-incidence X-ray techniques. The macroscopic study reveals that aragonite is a powerful sorbent for cadmium in aqueous environments. Microscopic observations indicate that cadmium is sorbed onto aragonite by surface precipitation of (Cd, Ca)CO₃ solid solutions with a calcite-type structure. The precipitating individuals grow randomly oriented on the surface to reach sizes in the micrometre range. As a consequence, the concentration of cadmium in the aqueous solution decreases dramatically to values controlled by the low solubility of the cadmium-rich end member. This mechanism involves simultaneous dissolution-crystallization and is the same for both abiogenic and biogenic aragonites, the only difference being a result of the higher specific surface area of the biogenic starting material. Long-term uptake of cadmium by calcite occurs through a similar dissolution-crystallization mechanism, the final outcome being virtually the same, that is, surface precipitation of (Cd,Ca)CO₃ solid solutions. In this case, however, substrate and precipitate are isostructural and the process occurs by oriented overgrowth of thin lamellar crystallites, which spread to quickly cover the surface by a layer a few nanometers thick. This epitaxial layer armors the substrate from further dissolution, so that the process stops when only a small amount of cadmium has been removed from the fluid. As a result, the “sorption capacity” of calcite is considerably lower than that of aragonite. The study illustrates reaction pathways and “partial” equilibrium endpoints in surface-precipitation processes involving solid solutions.     

A method for determining both diffusion and sorption coefficients of rock medium within a few days by adopting a micro-reactor technique

Migration properties characterized by physico-chemical factors such as distribution coefficient (K_d) and diffusion coefficient (D_e) are of great concern in performance assessment of high-level radioactive waste disposal in a deep geologic environment. These coefficients are normally obtained with different sample geometries using conventional methods, i.e., crushed samples by the batch sorption method for K_d determination and block samples by the through-diffusion method for D_e. A size dependence on both K_d and D_e has been reported and an additional correction due to size difference is required to maintain consistency of the data set. A fast method was developed, hereafter referred to as the micro-channel method, to determine both the sorption coefficient (R_d) and D_e using non-crushed rock sample by adopting the micro-reactor technique. In this method, a radionuclide solution is injected into a micro-channel (20 mm length, 4 mm width, 160 μm depth), which is in contact with a plate-shaped rock sample. A part of the injected radionuclide can diffuse into the rock matrix and/or adsorb on the rock surface and this results in an inlet-outlet concentration difference. A breakthrough curve is easily obtained with a short observation period because the injection amount is extremely small and is comparable to that escaping by diffusion into the matrix. The breakthrough curve is analyzed by a two-dimensional diffusion-advection equation to evaluate R_d and D_e.In the present study, tritiated water (specific activity, 1.2 × 10⁴ Bq/mL; pH, 6) was injected into the micro-channel, and the breakthrough curve of ³H obtained. A series of experiments was carried out by changing the flow rate of the tritiated water (2.6 × 10⁻⁵–7.7 × 10⁻⁴ m/s). Rock samples were biotite granite from the Makabe area, Japan. The diffusion coefficient evaluated by least squares fitting to the numerical solutions (D_e = 1.5 × 10⁻¹¹ m²/s) agreed well with that obtained by the through-diffusion method (1.3 × 10⁻¹¹ m²/s). The breakthrough curve of Cs ([Cs] = 1.0 × 10⁻⁷ mol/L, pH 6) labeled with ¹³⁴Cs (specific activity adjusted to 4.9 × 10¹ Bq/mL) was also obtained. A nearly constant R_d value (5.5 × 10⁻² m³/kg) was found when the flow rate was less than 2.5 × 10⁻⁴ m/s. This implied that the sorption equilibrium is reached and K_d is obtained by the present method. This value was almost identical to K_d obtained by the batch sorption method (5.0 × 10⁻² m³/kg), but the testing period was very different; 1 day and 7 days, respectively. It is concluded that application of the micro-channel method provided advantages when compared with the conventional methods.     

The Ge/Si ratio as a tool to recognize biogenic silica in chert

Germanium and silicon, dissolved in seawater, are considered to be incorporated into biogenic opal with no or little fractionation, which permitted to use diatoms as reliable recorders of seawater Ge/Si. Does some fractionation occur during diagenesis, preventing the use of Ge/Si in ancient sediments? We examined the Ge/Si ratio of fossil sponges and flint nodules of the Cretaceous Chalk Formation of northern France. Though disputed, silica in this formation is considered to originate from sponges. No fractionation is observed between sponges and diagenetic flints, which allows us to observe whether Ge/Si bears a biogenic or detrital signature. We may thus confirm that sponges were the main silica supplier during the chalk deposition. The Ge/Si ratio may be used to identify a biogenic signature in cherts where the origin of silica is dubious.     

A wastewater treatment using a biofilm airlift suspension reactor with biomass attached to supports: a numerical model

A mathematical model of the biological process occurring in a modified biofilm airlift suspension reactor is presented. When compared with a traditional wastewater treatment plant, a biofilm airlift suspension process has major advantages, such as higher oxygen levels in the bulk fluid and lower space requirements. The limited volumes obtained with this technique generally do not allow to reach the high times of contact required for an efficient removal of nitrogen that normally are characterized by a slower kinetics than carbonaceous compounds. To avoid this problem, supports for attached biomass growth were inserted in the reactor. Both physical and biological aspects were incorporated into the presented model to simulate the removal processes of the substrates. A sensitivity analysis was performed, and the model was validated using experimental results obtained at a lab-scale plant. This model can accurately estimate the removal rate in different boundary conditions providing the details of the water quality profiles through the reactor and in the attached biomass. The model thus represents a valid aid for design purposes and for the management of treatment plants that use these uncommon reactors. The model also provides the required hydraulic retention time for a complete nitrification and the appropriate recirculation ratio. The results have shown the full-scale applicability of this treatment due to its efficiencies coupled to the advantages of its low impact, low space requirement and low sludge production.     

Swelling-induced volumetric strains internal to a stressed coal associated with CO2 sorption

It is generally accepted that typical coalbed gases (methane and carbon dioxide) are sorbed (both adsorbed and absorbed) in the coal matrix causing it to swell and resulting in local stress and strain variations in a coalbed confined under overburden pressure. The swelling, interactions of gases within the coal matrix and the resultant changes in the permeability, sorption, gas flow mechanics in the reservoir, and stress state of the coal can impact a number of reservoir-related factors. These include effective production of coalbed methane, degasification of future mining areas by drilling horizontal and vertical degasification wells, injection of CO₂ as an enhanced coalbed methane recovery technique, and concurrent CO₂ sequestration. Such information can also provide an understanding of the mechanisms behind gas outbursts in underground coal mines.The spatio-temporal volumetric strains in a consolidated Pittsburgh seam coal sample were evaluated while both confining pressure and carbon dioxide (CO₂) pore pressure were increased to keep a constant positive effective stress on the sample. The changes internal to the sample were evaluated by maps of density and atomic number determined by dual-energy X-ray computed tomography (X-ray CT). Early-time images, as soon as CO₂ was introduced, were also used to calculate the macroporosity in the coal sample. Scanning electron microscopy (SEM) and photographic images of the polished section of the coal sample at X-ray CT image location were used to identify the microlithotypes and microstructures.The CO₂ sorption-associated swelling and volumetric strains in consolidated coal under constant effective stress are heterogeneous processes depending on the lithotypes present. In the time scale of the experiment, vitrite showed the highest degree of swelling due to dissolution of CO₂, while the clay (kaolinite) and inertite region was compressed in response. The volumetric strains associated with swelling and compression were between ± 15% depending on the location. Although the effective stress on the sample was constant, it varied within the sample as a result of the internal stresses created by gas sorption-related structural changes. SEM images and porosity calculations revealed that the kaolinite and inertite bearing layer was highly porous, which enabled the fastest CO₂ uptake and the highest degree of compression.     

Attachment of individual particles to a stationary air bubble in model systems

A particle–bubble attachment apparatus, similar to that used by Whelan and Brown [Bull. Inst. Min. Met. Trans. 65 (1956) 181] is developed to study free falling glass beads (d_p=131 μm) with different surface treatment attaching to a stationary air bubble (d_b=3 mm). The entire process of the particle–bubble attachment is photographically recorded using a high framing-rate camera and analyzed frame by frame. It is found that the hydrophilic particle slides on the top half of the bubble, and then the particle leaves the bubble, as anticipated. The particle sliding velocity increases with increasing angular position on the bubble surface. For the hydrophobic particle, it was found that the particle slides over the entire bubble surface without detaching from the bubble. The sliding velocity, however, reaches a maximum at an angular position of 90–100°, and then slows down to zero. A smaller sliding velocity is obtained for the hydrophobic particle than that of the hydrophilic particle at a given angular position. The attachment efficiency for the hydrophobic particle reduces with increasing initial angular positions, suggesting that the hydrophobicity alone does not directly guarantee the attachment to a bubble. Adding surfactant (sodium dodecyl sulfate [SDS]) to the test solution makes the hydrophobic particle become less hydrophobic or even hydrophilic, thereby decreasing the attachment efficiency. A much longer induction time is obtained in our present work than that reported in the literature. A simplified particle sliding velocity and attachment model is developed, and a good agreement between the theoretical prediction and experimental measurement is obtained.     

Experimental sorption of Ni, Cs and Ln onto a montmorillonite up to 150°C

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs⁺, Ni²⁺ and 14 lanthanides (Ln³⁺) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution.The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni²⁺ and Ln³⁺ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol⁻¹ and 39 ± 15 kJ.mol⁻¹ for Ni²⁺ and Eu³⁺, respectively. On the other hand, the temperature effect on Cs⁺ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs⁺ on the montmorillonite is −19 ± 5 kJ.mol⁻¹.Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature.The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.     

Zinc availability in relation to selected soil properties in a crude oil polluted eutric tropofluvent

The study investigated zinc availability in relation to selected soil properties in a crude-oil-polluted Eutric Tropofluvent in Egbema, Southeastern Nigeria. For this purpose, three treatments have been applied: unpolluted soil, polluted without vegetation and polluted with vegetation with five replicates arranged in a randomized complete block design. Guided by transect sampling technique, soil sampling was carried out in June 2008. Soil samples were collected from the three different land units using soil auger at a depth of 0–20 cm. Standard laboratory procedures were adopted in analysing the soils. Soil generated data were subjected to analysis of variance and correlation analysis. Results showed highly significant variation (p = 0.01) in bulk density, porosity, silt: clay ratio, pH, effective cation exchange capacity, percent base saturation, total nitrogen, organic matter, available phosphorus, calcium: magnesium ratio and zinc. It was found that zinc was higher in crude oil polluted soils than in non-polluted soil and it was below critical limits. Zinc availability in relation to selected soil properties in the crude oil polluted soils indicated that clay and organic matter did not affect zinc availability, while pH and effective cation exchange capacity did. A study on zinc dynamics in crude-oil-polluted soils will certainly provide further information on the management of crude-oil-polluted soils since it is one of the key micronutrient for crop productivity.     

Rate and extent of cobalt sorption to representative aquifer minerals in the presence of a moderately strong organic ligand

There is an increasing awareness that rate-limited sorption reactions can play an important role in the transport of solutes in groundwater. The rate and extent of reactions between aqueous metals and mineral surfaces are affected by many factors, including the temperature, the presence of organic chelating agents, and adsorbent mineralogy. Cobalt sorption was investigated in terms of temperature, citrate concentration, and silica sand surface coating. The kinetic sorption data were described well by two simultaneous second-order reactions. The results suggested that decreasing temperature or the presence of citrate resulted in a slower approach to equilibrium for Co sorption to the uncoated silica sand that contained small amounts of secondary minerals. Using the same sand coated with an amorphous Fe(III) oxide, increasing temperature or the presence of citrate resulted in a faster approach to equilibrium for Co sorption. The equilibrium adsorption isotherms were described well by a generalized two-layer surface complexation model. Citrate decreased the extent of Co sorption to the uncoated silica; the effect was most pronounced at low temperature. Conversely, citrate increased the extent of Co sorption to the Fe-coated silica. These results suggest that citrate decreased the rate and extent of adsorption to the uncoated silica through the formation of a stable anionic aqueous complex that has a lower affinity for the surface than Co²⁺. Conversely, the higher anion sorption capacity of the Fe-coated silica increased the rate and extent of Co sorption with citrate present, presumably through the formation of an organo-metallic ternary surface complex.     

On the exact evaluation of displacements within a semi-infinite solid due to a buried line source

Garvin’s variant of the Cagniard technique has been used to evaluate exactly the displacements at points within a homogeneous, isotropic, perfectly elastic, solid half space due to a buried explosive line source. The disturbance at any given time is confined to a region bounded by the free surface of the half space and theP wave front within it. The disturbance associated with the Rayleigh pulse affects a smaller region bounded by the free surface and the PP wave front.     

Sensitivity of incipient particle motion to fluid flow penetration depth within a packed bed

A discrete element method is applied to a three‐dimensional analysis related to sediment entrainment on a micro‐scale. Sediment entrainment is the process by which a fluid medium accelerates particles from rest and advects them upward until they are either transported as bedload or suspended by the flow. Modelling of the entrainment process is a critically important aspect for studies of erosion, pollutant resuspension and transport, and formation of bedforms in environmental flows. Previous discrete element method studies of sediment entrainment have assumed the flow within the particle bed to be negligible and have only allowed for the motion of the topmost particles. At the same time, micro‐scale experimental studies indicate that there is a small slip of the fluid flow at the top of the bed, indicating the presence of non‐vanishing fluid velocity within the topmost bed layers. The current study demonstrates that the onset of particle incipient motion, which immediately precedes particle entrainment, is highly sensitive to this small fluid flow within the topmost bed layers. Using an exponential decay profile for the inner‐bed fluid flow, the discrete element method calculations are repeated with different fluid penetration depths within the bed for several small particle Reynolds numbers. For cases with slip velocity corresponding to that observed in previous experiments with natural sediment, the predicted particle velocity is found to be a few percent of the fluid velocity at the top of the viscous wall layer, which is a reasonable range of velocities for observation of incipient particle motion. This method for prescribing the fluid flow within the particle bed allows for the current discrete element method to be extended in future studies to the analysis of sediment entrainment under the influence of events such as turbulent bursting. Additionally, predictions for the slip velocities and fluid flow profile within the bed suggest the need for further experimental studies to provide the data necessary for additional improvement of the discrete element method models.     

Microseismicity within a karstified rock mass due to cracks and collapses as a tool for risk management

Seismometer arrays have been widely applied to record collapse by controlled explosion in mines and caves. However, most underground failures are natural events, and because they can occur abruptly, underground failures represent a serious geological hazard. An accelerometric array installed on 4 September 2008 has been used to manage the geological risk of the Peschiera Springs drainage plant of Rome??s aqueduct, which is located in the Central Apennines approximately 80?km from Rome, Italy. The plant occupies a karstified carbonatic slope that is extensively involved in gravitational deformations, which are responsible for underground failures such as cracks and collapses. To distinguish among different types of recorded events, an automated procedure was implemented based on the duration, peak of ground acceleration (PGA) and PGA variation in the recordings of the plant??s accelerometric stations. The frequencies of earthquakes and micro-earthquakes due to underground failures are, in general, well correlated. Nevertheless, many underground failure sequences can be directly associated with the continuous deformations that affect the slope. The cumulative Arias intensity trend derived for the underground failures combined with the failure and earthquake frequencies enabled the definition of a control index (CI) that identifies alarming or emergency conditions. The CI can be used as a tool for managing the geological risk associated with the deformational processes that affect the drainage plant.     

二维饱和多孔介质因点汇诱发比奥固结的解析解

给出了有限二维饱和多孔介质因点汇诱发的Biot固结的一个解析解。其中假设多孔介质为均匀各向同性和线弹性,假设孔隙压力场符合第1类边界条件,数学模型采用可压缩多孔介质模型。利用傅里叶和拉普拉斯变换及相应反演获得了双重无穷项级数和形式的精确解。然后特别探讨了定流量点汇诱发的稳态解析解,并用文献现有解析解进行了验证。所提出的解析解适合于验证数值解,并可用于深入分析有限二维多孔介质的流-固耦合行为。     

Grain-size sorting within river bars in relation to downstream fining along a wandering channel

The textural variability of river bed gravels at bar scales is poorly understood, as are the relations between variability at this scale and at reach and river scales. Surface and subsurface grain‐size distributions were therefore examined at reach, bar and bedform scales along lower Fraser River, British Columbia, Canada. Grain‐size variations within compound bars are conditioned by longitudinal position, elevation and morphological setting. Surface and subsurface sediments tend to decrease in median size from bar head to bar tail by 33% and 17%, respectively. Sediment size is constrained at some upper limit that is inversely related to bar surface elevation and which is consistent with competence considerations. The surface sediments on unit bars are finer and better sorted than the bed materials in bar‐top channels and along the main bar edges. Secondary unit bars tend to have a lower sand content than other features, a consequence of sediment resorting. Individual unit bars and gravel sheets exhibit streamwise grain‐size fining and lee‐side sand deposition. Over time, significant amounts of cut and fill do not ipso facto cause changes in surface grain sizes; yet, sediment characteristics can change without any significant morphological adjustment taking place. At the reach scale there is a clear downstream fining trend, but local variability is consistently high due to within‐bar variations. The surface median grain‐size range on individual bars is, on average, 25% of that along the entire 50 km reach but is 68% on one bar. While the overall fining trend yields a downstream change in surface median size of 0·76 mm km^?1, the average value for ‘head‐to‐tail’ size reduction on individual bars is 6·3 mm km^?1, an order of magnitude difference that highlights the effectiveness of bar‐scale sorting processes in gravel‐bed rivers. Possibilities for modelling bar‐scale variability and the interaction of the different controls that are identified are discussed.     

Contrasting the sorption of Zn by oxyhydroxides of Mn and Fe,and organic matter along a mineral-poor to mineral-rich fen gradient

The geochemistry of Mn and Fe in surface pools, pore-waters and surface peats and the sorption of Zn by the surface peats was contrasted among 15 peatlands sampled along a mineral-poor to mineral-rich fen gradient. Sorption of Zn by surficial peats was compared via distribution coefficients, both total (K_DT) and partial (K_DERMn, K_DRFe and K_DORG), where ER Mn, R Fe and ORG are amounts of Zn recovered from the easily reducible Mn oxides, reducible Fe oxides, and organic components of peat, respectively. Apparent stability constants (K_As) for Zn sorption onto oxides of Fe recovered from the surface peats were also calculated and compared along the same gradient. Peat geochemistry was peatland dependent; mineral-poor fens had less easily reducible Mn and greater amounts of organic matter (%Loss on Ignition; LOI) versus mineral-rich fens (range of 0.66–8.6 mm kg⁻¹ for ER Mn and 20–88% LOI for organic matter). Reducible Fe also varied among peatlands (range 51–315 mm kg⁻¹) but was independent of the mineral-poor to mineral-rich fen gradient. Comparison of partial K_Ds for amounts of Zn sorped onto the ER Mn, R Fe and ORG components of peat indicated that sorption was dominated by R Fe in all peatlands. K_DTs ranged from 0.54–2.00. In contrast to other aquatic systems, however, the range in K_DTs was not related to either surface or pore-water pH. K_As ranged from 0.36 to 3.06 and were also independent of surface or pore-water pH. However, average K_As (but not K_DTs), were greater for mineral-poor fens (P<0.02), suggesting greater Zn binding by surface peats of mineral-poor fens versus either the moderately poor or mineral-rich peatlands. Other water chemistry variables, such as pore-water base cation concentrations, weakly correlated to Zn partitioning onto R Fe (r=−0.35, P=0.05), but did not fully explain differences in Zn partitioning among peatlands. Greater average K_As for the mineral-poor peatlands may in part be due to the presence of strong metal-organic matter-Fe oxide complexes in the Sphagnum dominated peatlands as well as lower pore-water base cation concentrations that occur in the mineral-poor peatland as compared to the more mineral-rich fens.     

Evidence for a transgressive barrier within a regressive strandplain system: Implications for complex coastal response to environmental change

Clastic, depositional strandplain systems have the potential to record changes in the primary drivers of coastal evolution: climate, sea‐level, and the frequency of major meteorological and oceanographic events. This study seeks to use one such record from a southern Brazilian strandplain to highlight the potentially‐complex nature of coastal sedimentological response to small changes in these drivers. Following a 2 to 4 m highstand at ca 5·8 ka in southern Brazil, falling sea‐level reworked shelf sediment onshore, forcing coastal progradation, smoothing the irregular coastline and forming the 5 km wide Pinheira Strandplain, composed of ca 500 successive beach and dune ridges. Sediment cores, grab samples and >11 km of ground‐penetrating radar profiles reveal that the strandplain sequence is composed of well‐sorted, fine to very‐fine quartz sand. Since the mid‐Holocene highstand, the shoreline prograded at a rate of ca 1 to 2 m yr^?1 through the deposition of a 4 to 6 m thick shoreface unit; a 1 to 3 m thick foreshore unit containing ubiquitous ridge and runnel facies; and an uppermost beach and foredune unit. However, the discovery of a linear, 100 m wide barrier ridge with associated washover units, a 3 to 4 m deep lagoon and 250 m wide tidal inlet within the strandplain sequence reveals a period of shoreline transgression at 3·3 to 2·8 ka during the otherwise regressive developmental history of the plain. The protected nature of Pinheira largely buffered it from changes in precipitation patterns, wave energy and fluvial sediment supply during the time of its formation. However, multiple lines of evidence indicate that a change in the rate of relative sea‐level fall, probably due to either steric or ice‐volume effects, may have affected this coastline. Thus, whereas these other potential drivers cannot be fully discounted, this study provides insights into the complexity of decadal‐scale to millennial‐scale coastal response to likely variability in sea‐level change rates.     

黔西北铅锌矿稀土元素组成特征——兼论黔西北地区铅锌矿成矿与峨眉山玄武岩的关系

通过对黔西北地区铅锌矿中硫化物稀土元素组成特征、峨眉山玄武岩中成矿元素铅锌的含量、铅锌矿硫同位素及锶同位素组成分析表明,该区铅锌矿成矿物质不是来源于峨眉山玄武岩,由于峨眉山玄武岩的喷出时代与本区铅锌矿成矿时代相差较远,也不可能为本区铅锌矿的形成提供热源。