Nitrite reduction by Fe(II) associated with kaolinite

Interactions of iron (Fe) with the nitrogen (N) cycle have emerged and contain elements of abiotic and biological reactions. One such abiotic reaction which has received little study is the reactivity of NO₂ ^? and Fe(II) associated with a major clay mineral, kaolinite. The main objective of this study was to evaluate the reactivity of NO₂ ^? with Fe(II) added to kaolinite under anoxic conditions. Stirred batch reactivity experiments were carried out with 10 g L^?1 kaolinite spiked with 25 and 100 µM Fe(II) at pH 6.45 in an anaerobic chamber. Approximately 500 µM NO₂ ^? was added to initiate the reaction with Fe(II)-loaded kaolinite. The rate of nitrite removal from solution was 2.4-fold slower in the high Fe(II) treatment when compared with the low Fe(II) treatment. A large portion of the NO₂ ^? removed from solution was confirmed to be reduced to N₂O_(g) in the Fe(II)-kaolinite slurries. However, NO₂ ^? reduction was also noticed in the presence of kaolinite-alone and to somewhat lesser extent in the presence of dithionite-citrate-bicarbonate (DCB)-treated kaolinite. Chemical extractions coupled with infrared spectroscopy suggest that Fe(III) oxide mineral impurities and structural Fe(III) in kaolinite may participate in NO₂ ^? removal from solution. Furthermore, a magnetite mineral was identified based on X-ray diffraction analysis of untreated kaolinite and DCB-treated kaolinite. Our findings reveal a novel pathway of NO₂ ^? transformation in the environment in the presence of Fe(II) associated (sorbed and impurity) with kaolinite.     

山西晋城和阳泉地区石炭系太原组铵伊利石矿物特征及成因

铵伊利石是伊利石层间域的K+被NH+4替代而形成的类质同象.文中运用X射线衍射分析、傅里叶红外光谱分析以及热重—热流—红外光谱同步分析等手段,对山西晋城及阳泉地区的15号煤层夹矸及煤中矿物进行了研究,发现15号煤层夹矸和煤低温灰中黏土矿物以铵伊利石和高岭石为主,铵伊利石含量为21％～74％;X射线衍射图谱上d(001)...     

O-H stretching vibrations in kaolinite,and related minerals

The grades of ordering as represented by I.R. and X-ray spectra for platy kaolinite, fire clay mineral, ball clay, dickite, nacrite and tubular dehydrated halloysite samples of various origin, are related.Well ordered kaolinite, has four bands 3,693, 3,668, 3,652 and 3,620 cm^–1. In less ordered kaolinite, fire clay mineral and ball clay these bands have shifted a little or of the middle two, which are the weakest, only one band may be left (between brackets): less ordered kaolinite: 3,695, 3,667, 3,652 (3,653) and 3,620 cm^–1; fire clay mineral 3,696, 3,668, 3,653 (3,653) and 3,621 cm^–1; ball clay 3,697, 3,652 and 3,621 cm^–1.Dehydrated halloysite has 3,693–3,698, 3,668, 3,650–3,654 and 3,620–3,626 cm^–1 bands. In the most disordered dehydrated halloysite samples (Martinsberg and Baia Mare) only two bands are left at 3,696 and 3,624 cm^–1.Dickite has four bands: 3,708, 3,656, 3,627 and 3,622 cm^–1. For the lesser ordered Mexico sample it is 3,701, 3,652, 3,627 and 3,621 cm^–1. Nacrite also has four bands i.e.: 3,700, 3,650, 3,627 and 3,620 cm^–1.There is, apart from orientation effects, a wide variation in the absolute and especially in the relative intensities of the I.R. bands and X-ray reflections for each of the mineral groups investigated here, but of various origin. The need of a nomenclature adapted to the level of our knowledge about this matter to day and comprising all these variations included those in morphology is emphasized.Quantitative analyses, the adjective meant in the sense of an accuracy of minimal 5%, constitute a difficult problem which is perhaps even wholly impossible to solve with the conventional methods of today.     

Distribution and Influence of Iron Phases on the Physico—Chemical Properties of Phyllosilicates

Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-band Electron Spin Resonance(ESR) spectroscopies.The purity of the samples and the degree of structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm^-1 assigned as Al-OH-Fe which is present after chemical dissolution of free iron.The Moessbauer spectra of these clays sow two doublets with isomer shift and quadrupole splitting typical of octahedral coordinated Fe^3 ,in addition to third doubler with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H)sample.6-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octaedral symmetry and as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activaiton of investigated montmorillonite samples by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,amounts and site occupation of Fe associated with kaolinite samples show a negative correlation with the parameters used to describe the degree of crystalline perfection,color,brightness and vitrification range of these kaolinite samples.     

Distribution and Influence of Iron Phases the Physico—Chemical Properties of Phyllosilicates

Clay minerals from different Cretaceous stratigraphic successions of Egypt were investigated using XRD,DTA,dissolution analysis(DCB),IR,Moessbauer and X-ray Electron Spin Resonance(ESR) spectroscopes.The purity of the samples and the degree of their structural order were determined by XRD.The location of Fe in the octahedral sheet is characterized by absorption bands at-875cm^-1 assigned as Al-OH-Fe which persist after chemical dissolution of free iron.The Moessbauer spectra of these clays show two doublets with isomer shift and quadrupole splitting typical of octahedrally coordinated Fe^3 ,in addition to third doublet with hyperfine parameter typical of Fe^2 in the spectra of Abu-Had kaolinite (H) sample.Six-lines magnetic hyperfine components which are consistent with those of hematite are confirmed in the spectra of both Isel and Rish kaolinite samples.Goethite was confirmed by both IR and DTA.Multiple nature of ESR of these clays suggested structural Fe in distorted octahedral symmetry as well as non-structural Fe.Little dispersion and low swelling indices as well as incomplete activation of the investigated montmorillonite samplas by NaCO3 appear to be due to incomplete disaggregation of montmorillonite particles.This can be explained by the ability of Fe-gel to aggregate the montmorillonite into pseudo-particles and retard the rigid-gel structure.However,extraction of this ferric amorphous compound by dithonite treatment recovers the surface properties of the montmorillonite samples.On the other hand,the amount and site occupation of Fe associated with kaolinite samples show an inverse correlation with the parameters used to describe the degree of crystallinity perfection,color,brightness and vitrification range of these kaolinite samples.     

Reduction of Expansive Index,Swelling and Compression Behavior of Kaolinite and Bentonite Clay with Sand and Class C Fly Ash

Swelling behavior of expansive soil has always created problems in the field of geotechnical engineering. Generally, the method used to assess the swelling potential of expansive soil from its plasticity index, shrinkage limit and colloidal content. Alternative way to evaluate swelling behavior is from its expansive index (EI) and swelling pressure value. The present study investigates the reduction of EI and swelling pressure for kaolinite and bentonite clay when mixed with various percentages of Ottawa sand and Class C fly ash. The percentages of Ottawa sand and Class C fly ash used were 0–50 % by weight. The results show that there is a significant reduction in the swelling properties of expansive soil with the addition of Ottawa sand and Class C fly ash. The reduction in EI ranged approximately from 10 to 50 and 4 to 49 % for kaolinite and bentonite clay, respectively. Also the maximum swelling pressure of kaolinite and bentonite clay decreased approximately 93 and 64 %, respectively with the addition of various percentages of Ottawa sand and Class C fly ash. Standard index properties test viz., liquid limit, plastic limit and linear shrinkage test were conducted to see the characteristics of expansive soil when mixed with less expansive sand and fly ash. Also, for these expansive soils one dimensional consolidation test have been conducted with sand and fly ash mixtures and the results were compared with pure kaolinite and bentonite clay.     

Aqueous dissolution,solubilities and thermodynamic stabilities of common aluminosilicate clay minerals: Kaolinite and smectites

Determinations of the aqueous solubilities of kaolinite at pH 4, and of five smectite minerals in suspensions set between pH 5 and 8, were undertaken with mineral suspensions adjusted to approach equilibrium from over- and undersaturation. After 1,237 days, Dry Branch, Georgia kaolinite suspensions attained equilibrium solubility with respect to the kaolinite, for which K_eq = (2.72 ± 0.35) × 10⁷. The experimentally determined Gibbs free energy of formation (ΔG_f,298⁰) for the kaolinite is −3,789.51 ± 6.60 kj mol⁻¹. Equilibrium solubilities could not be determined for the smectites because the composition of the solution phase in the smectite suspensions appeared to be controlled by the formation of gibbsite or amorphous aluminum hydroxide and not by the smectites, preventing attempts to determine valid ΔG_f⁰ values for these complex aluminosilicate clay minerals. Reported solubility-based ΔG_f⁰ determinations for smectites and other variable composition aluminosilicate clay minerals are shown to be invalid because of experimental deficiencies and of conceptual flaws arising from the nature of the minerals themselves. Because of the variable composition of smectites and similar minerals, it is concluded that reliable equilibrium solubilities and solubility-derived ΔG_f⁰ values can neither be rigorously determined by conventional experimental procedures, nor applied in equilibriabased models of smectite-water interactions.     

Transformational changes of clay minerals, zeolites and silica minerals during diagenesis

Diagenetic transformation of clay minerals, zeolites and silica minerals in Cretaceous and Tertiary argillaceous rocks from deeply drilled wells in Japan were studied. Transformations of these minerals during diagenesis were as follows: in clay minerals, montmorillonite → montmorillonite-illite mixed-layer mineral → illite; in zeolites, volcanic glass → clinoptilolite → heulandite and/or analcite → laumontite and/or albite; in silica minerals, amorphous silica → low-cristobalite → low-quartz. Maximum overburden pressures and geothermal temperatures corresponding to these transformations in each well studied were calculated. For clay minerals, a pressure of approximately 900 kg cm^?2 and a temperature of about 100°C are necessary for the transformation from montmorillonite to mixed-layer mineral and 920 kg cm^?2 and 140°C for mixed-layer mineral to illite. Transformation from kaolinite to other minerals requires much higher pressures and temperatures than from montmorillonite to mixed-layer mineral. For zeolites, 330 kg cm^?2 and 60°C are required for the transformation from volcanic glass to clinoptilolite, 860 kg cm^?2 and 120°C for clinoptilolite to heulandite and/or analcite, and 930 kg cm^?2 and 140°C for heulandite and/or analcite to laumontite and/or albite. For silica minerals, 250 kg cm^?2 and 50°C are necessary for the transformation from amorphous silica to low-cristobalite and 660 kg cm^?2 and 70°C for low-cristobalite to low-quartz. Based on these diagenetic mineral transformations, seven mineral zones are recognized in argillaceous sediments. On the other hand, from the porosity studies of argillaceous sediments in Japan, the process of diagenesis is classified into the following three stages. The early compaction stage is marked by shallow burial and viscous rocks with more than 30% porosity. The late compaction stage is characterized by intermediate burial and plastic rocks with 30-10% porosities. The transformation stage is marked by deep burial and elastic rocks with less than 10% porosity.     

Fate of riverine nitrate entering an estuary: I. Denitrification and nitrogen burial

Fate of riverine nitrate entering a well defined turbid estuary receiving discharges from the Atchafalaya River, a distributary of the Mississippi River, was determined. Seasonal distribution of NO₃ and its transformations were measured in Four League Bay (9,300 ha). Denitrification was estimated by incubating wet samples in the presence of acetylene and monitoring N₂O production. The annual sediment accumulation of N was also determined within the bay and within the adjacent marshes. Nitrogen accumulation ranged from 6.0 to 23 gN per m² per yr on the marsh and 6.1 to 11.2 gN per m² per yr in the bay. Denitrification in this system was controlled by the availability of NO₃ ^? with fluxes ranging from 2 to 70 ngN per g per hr. The annual (N₂O +N₂)-N emission was equivalent to 142 and 120 μg per g or 2.1 and 1.7 gN per m² from the 5 bay and 5 marsh stations, respectively. Approximately 1.95×10⁵ kgN, predominantly as N₂, is being returned to the atmosphere via denitrification. We estimate this to be equivalent to 50% of the riverine NO₃ ^? entering this estuary. A significant amount was also assimilated within the estuary.     

Occurrence of Li,B, Cu and Zn in some Egyptian Nile sediments

Lithium, boron, copper and zinc have been determined on cored and surface sediments from the delta and the drainage valley of the Nile River. The clay size fraction separated from the samples consists of montmorillonite and kaolinite as the predominant clay components, followed by illite and chlorite. Quartz and calcite are the non-clay admixtures.Lithium content varies between 7 and 48 ppm in the bulk sediments and between 28 and 61 ppm in the clay fractions, being clearly enriched in the clay material. In the clay fractions, concentration of lithium in kaolinite is indicated by a close relation between the lithium and kaolinite contents and is further supported by a close correlation with A1₂O₃.Boron in the clay fraction (62–112 ppm) appears to be concentrated in detrital illite.The concentrations of copper (26–900 ppm) and zinc (65–333 ppm) in the clay fractions correlate positively with the CO₂ percentage. Both elements tend to occur in or on the claysized grains of caleite.     

An infrared study of clay minerals, 2. The identification of kaolinite-group clays in deep-sea sediments

The kaolinite-group mineral in deep-sea sediments is usually identified as kaolinite, and occasionally as halloysite. A study has been made of the infrared spectra of these two minerals; their absorption bands have been described, and compared to those of the other principal clay groups, i.e., illites, montmorillonites and chlorites, found in deep-sea sediments. It is shown that kaolinite and halloysite have diagnostic absorption bands at ca. 915 cm^?1 and ca. 3700 cm^?1. These bands are made the basis of a rapid infrared technique for the identification of kaolinite and or halloysite in deep-sea sediments.     

Evidences of felsic volcanism and hydrothermal activities from clays associated with the Palaeoproterozoic Porcellanite Formation of the Vindhyan Supergroup,Central India

Chemico-mineralogical attributes of authigenic clays associated with the altered volcanic tuffs that occur in the Palaeoproterozoic Porcellanite Formation contain evidences of hydrothermal alteration and diagenetic processes in a marine environment. Previous sedimentological and geochemical studies on Porcellanite Formation were restricted to the Chopan area, but, the details related to provenance, nature and source of volcanism archived in these clays have not been ascertained. In order to understand these aspects, present study on these authigenic clays were carried out. Clay minerals represent dominance of illite with subordinate amount of montmorillonite. Moreover, low abundance of kaolinite is also noticed. The illite fibers and plates associated with the kaolinite indicate illitization. The kaolinite to illite transformation is favoured by incorporation of K⁺ ions, derived from the K-feldspar dissolution and its overgrowth. Major oxide contents of these clays and their ratios when plotted over diagrams marked with standard illite, kaolinite, smectite and chlorite compositional fields show clustering within or close to the illite field. Thermodynamic components calculated for these clays when plotted over AR₂³⁺AlSi₃O₁₀(OH)₂ − R₂³⁺Si₄O₁₀(OH)₂ − AR²⁺R³⁺Si₄O₁₀(OH)₂ ternary diagram, data plots lie within the illite, mixed layer I/S and smectite fields. Binary major oxide data plots between bulk rock and authigenic clay compositions showed felsic affinity. Montmorillonite and illite predominated in the eastern and western marginal areas of the Vindhyan Basin, respectively. However, former resulted from the hydrothermal alteration of volcanic glass associated with the ferruginous breccia and altered tuffs and remnants of the volcanic vents, whereas, later is associated with the tuffaceous beds. Owing to the adsorption, Ba, Rb and Sr is enriched in clays comparing to the bulk rock composition. Low (< 15 ppm) Sc values suggested major contribution from the felsic component. Also, low Rb/Sr and Th/U values revealed moderate insitu weathering. The dominance of K-feldspar alteration and insitu weathering is also evident from clustering of clay data plots in the A-CN-K ternary diagram. Pronounced negative Eu anomaly together with higher LREE/HREE values associated with these clay minerals implied proximity to source and their possible derivation from the silicified felsic tuffs available in the provenance.     

Seasonal and spatial changes in water and sediment quality variables in Bafa Lake

The brackish Bafa Lake located in the southwestern part of Turkey is under stress because of both natural and untreated wastewater effluents. The purpose of this research is to determine spatiotemporal distributions of some physicochemical variables in water column (temperature, salinity, pH, conductivity, dissolved oxygen, NH₄–N, NO₂–N, NO₃–N, oPO₄–P, TPO₄–P, chlorophyll-a, total suspended solids) and sediment (TN, TC, TOC, TP) and their relationships at coastal stations. In the water column, nitrate and phosphate concentrations showed seasonal variations with high values recorded in winter period. Ammonium was determined as a main source of TIN component. During summer period, a large amount of total phosphorus was found as dissolved organic form. However, in the winter period, inorganic phosphate levels increased at sampling stations. N limitation was a common feature throughout the lake where P-limitation was only observed in summer period. The total phosphorus levels which showed hypereutrophic condition at the western part of the lake changed between 1.55 and 4.99 μM and did not remain in the range for uncontaminated condition. In the lake sediment, a strong relationship was found between TOC and TC levels. Generally, the mean TOC concentrations constitute small amount of TC values in the sampling stations. The results also indicated that a strong correlation exists between TOC and TN values, and TN was greatly regulated by organic sources. In the lake, TOC:TN ratios changed between 5 and 13; the ratio greater than 10 could be an indicator of algal and land plant sources mixing as an organic matter.     

An experimental study of lake water-sediment interaction rates

Dissolution rates of sediments obtained from the Oued Cherf reservoir were measured in closed-system batch reactors at 25 °C in fluids sampled concurrently from the same locations as the sediments. The BET surface areas of the sediments ranged from 16 to 45 m²/g and consisted primarily of quartz, calcite, and clay minerals. After a brief initial period, release rates of Si, Mg, Ca, Cl, SO₄, and NO₃ from these sediments are approximately linear with time over the course of the experiments, which lasted from 3 to 5 months. BET surface area normalized Si release rates ranged from 10^–17.4 to 10^–18.4 mol/cm²/s. These release rates match closely Si release rates from quartz and clay minerals determined from laboratory dissolution rates reported in the literature. This coherence suggests that laboratory measured silicate dissolution rates can be used with confidence to predict the dissolution behavior of sediments in natural surface waters.     

Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO₂ partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L⁻¹ to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.     

Zinc mobility and speciation in soil covered by contaminated dredged sediment using micrometer-scale and bulk-averaging X-ray fluorescence, absorption and diffraction techniques

The mobility and solid-state speciation of zinc in a pseudogley soil (pH = 8.2-8.3) before and after contamination by land-disposition of a dredged sediment ([Zn] = 6600 mg kg⁻¹) affected by smelter operations were studied in a 50 m² pilot-scale test site and the laboratory using state-of-the-art synchrotron-based techniques. Sediment disposition on land caused the migration of micrometer-sized, smelter-related, sphalerite (ZnS) and franklinite (ZnFe₂O₄) grains and dissolved Zn from the sediment downwards to a soil depth of 20 cm over a period of 18 months. Gravitational movement of fine-grained metal contaminants probably occurred continuously, while peaks of Zn leaching were observed in the summer when the oxidative dissolution of ZnS was favored by non-flooding conditions. The Zn concentration in the <50 μm soil fraction increased from ∼61 ppm to ∼94 ppm in the first 12 months at 0-10 cm depth, and to ∼269 ppm in the first 15 months following the sediment deposition. Higher Zn concentrations and enrichments were observed in the fine (<2 μm) and very fine (<0.2 μm) fractions after 15 months (480 mg kg⁻¹ and 1000 mg kg⁻¹, respectively), compared to 200 mg kg⁻¹ in the <2 μm fraction of the initial soil. In total, 1.2% of the Zn initially present in the sediment was released to the environment after 15 months, representing an integrated quantity of ∼4 kg Zn over an area of 50 m². Microfocused X-ray fluorescence (XRF), diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy techniques were used to image chemical associations of Zn with Fe and Mn, and to identify mineral and Zn species in selected points-of-interest in the uncontaminated and contaminated soil. Bulk average powder EXAFS spectroscopy was used to quantify the proportion of each Zn species in the soil. In the uncontaminated soil, Zn is largely speciated as Zn-containing phyllosilicate, and to a minor extent as zincochromite (ZnCr₂O₄), ^IVZn-sorbed turbostratic birnessite (δ-MnO₂), and Zn-substituted goethite. In the upper 0-10 cm of the contaminated soil, ∼60 ± 10% of total Zn is present as ZnS inherited from the overlying sediment. Poorly-crystalline Zn-sorbed Fe (oxyhydr)oxides and zinciferous phyllosilicate amount to ∼20-30 ± 10% each and, therefore, make up most of the remaining Zn. Smaller amounts of franklinite (ZnFe₂O₄), Zn-birnessite and Zn-goethite were also detected. Further solubilization of the Zn inventory in the sediment, and also remobilization of Zn from the poorly-crystalline neoformed Fe (oxyhydr)oxide precipitates, are expected over time. This study shows that land deposition of contaminated dredged sediments is a source of Zn for the covered soil and, consequently, presents environmental hazards. Remediation technologies should be devised to either sequester Zn into sparingly soluble crystalline phases, or remove Zn by collecting leachates beneath the sediment.     

Intercalation of kaolinite with acetamide

Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH₂ groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm^–1. Secondly, the appearance of additional bands at ∼3600 cm^–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm^–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH₂ deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm^–1 become a single band at 1680 cm^–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm^–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group. Received: 4 February 1998/ Revised, accepted: 30 June 1998     

The geochemistry of iron in Recent tidal-flat sediments of the Wash area,England: a mineralogical,Mössbauer,and magnetic study

Undisturbed core samples of Recent sediments from the Wash tidal flats, East Anglia, England, obtained using a Delft corer, were studied with special reference to the diagenesis and geochemical behaviour of iron. The Mössbauer effect in ⁵⁷Fe was used to monitor the distribution of Fe between different phases as a function of depth, together with the magnetic mineralogy and palaeomagnetic properties.The cores consist of, successively downwards: 0.36 m brown clay; 1.5 m finely laminated silts and fine sands, and 7.14 m homogeneous fine sands. The dominant minerals are quartz, feldspar, calcite and clay minerals, and chemical analysis for Al, Si, Mg, Mn, Ca, Fe, Na, K showed variations closely linked to lithological changes. Illite is the most abundant clay mineral (mean 48%), followed by mixed layer illite-montmorillonite and montmorillonite, kaolinite and chlorite. Chlorite is the major iron-bearing clay mineral and represents 4 to 10% of the <2 μm fraction throughout the core. Sulphide minerals are present throughout the core, including framboidal pyrite.Computer fit analysis of the Mössbauer spectra of best quality showed contributions from Fe²⁺ and Fe³⁺ in clay minerals (essentially chlorite), low-spin Fe²⁺ in pyrite, and magnetically ordered iron in greigite (Fe₃S₄). Systematic variations, as a function of sample depth, indicate a relative increase in the amount of Fe in pyrite at the expense of the clay minerals.Magnetite and titanium-bearing magnetite are the carriers of natural magnetic remanence in these sediments.The direction and intensity of natural remanence in the samples compare well with the known secular variation of the Earth's magnetic field derived from the historic-archaeomagnetic record and this enables the samples to be dated and sedimentation rates to be determined (1.5 mm yr^?1 for the upper 2 m and ~7.7 mm yr^?1 for the lower 7 m).     

Clay mineralogy and geochemistry and their palaeoclimatic interpretation of the Pleistocene deposits in the Xuancheng section,southern China

A red soil profile in Xuancheng, Anhui province, southern China, in the middle to lower reaches of the Yangtze River, was investigated using X‐ray diffraction, X‐ray fluorescence spectrometer, and scanning electron microscopy. The mobile components K₂O and Na₂O and trace elements Ba and Sr of the Xuancheng section exhibit a general trend of decrease downward along the red soil profile, together with an increase downward of chemical index of alteration (CIA) values, suggesting more intense depletion in the lower portion than in the upper portion. The major components SiO₂, Al₂O₃ and Fe₂O₃, as well as SiO₂/Al₂O₃, SiO₂/Fe₂O₃ and Al₂O₃/Fe₂O₃ ratios, show notable fluctuations along the soil profile, indicating intense climatic oscillations in the area during the Pleistocene age. The clay mineral assemblage of the Xuancheng section can be generally subdivided into three groups, suggesting a general trend of three stages of climate changes. The lower portion of ～10.4–6.3 m depth has a lower illite content and higher abundance of kaolinite and illite–smectite (I/S) clays, indicating that a warm and wet climate prevailed over the episode of ca. 600–350 ka BP. A decrease in abundance of kaolinite and I/S clays and increase in illite content at a depth of ～6.3–2.2 m probably indicate a transition stage of climate change from warm/humid to cool/dry in the period ca. 350–80 ka BP. The higher illite content and lower abundance of kaolinite and I/S clays in the upper portion of ～2.2–0 m depth suggest that a relatively cool and dry climate dominated since ca. 80 ka BP. Based on changes in clay mineralogy and chemical indices of the sediments, seven warm/cold fluctuations were determined in the area since the Middle Pleistocene. Climate changes documented in the Xuancheng section are in agreement with the δ¹⁸O records of sediments from the equatorial Pacific Core V28‐238 and the loess–palaeosol sequences in the Loess Plateau of northwestern China. Correlated to the episode of S4 and S5 soil units in the Loess Plateau, the period of ca. 600–350 ka BP in the Xuancheng area was dominated by the particularly strong East Asia summer monsoon, as indicated by its most abundant kaolinite and I/S clays. Fluctuations in clay mineralogy along the Xuancheng soil profile were mainly controlled by both the East Asia summer and winter monsoons in response to the global changes in the Middle–Late Pleistocene. Copyright © 2009 John Wiley & Sons, Ltd.     

Parameters controlling the partitioning of tributyltin (TBT) in aquatic systems

In the present study the distribution of TBT between solid and water phase as a function of several parameters was determined. Two types of clay minerals (Na-montmorillonite SWy and kaolinite KGa) and quartz sand were used as sorbents in conventional batch experiments. Sorption coefficients (K_d) followed the order montmorillonite (89 l/kg) > kaolinite (51 l/kg) > quartz (25 l/kg), while for sorption coefficients normalized to the surface area (Kd′) an opposite trend was observed, with the lowest value determined for montmorillonite (2.79 × 10⁻³ l/m²) and the highest for quartz sand (8.04 × 10⁻² l/m²). The results demonstrate that numerous environmental parameters influence the adsorption process of TBT, such as solid/solution ratio, clay content and salinity. Another important factor governing TBT adsorption is pH, because it affects both the TBT species in the water phase as well as the surface properties of the mineral phase. The maximum of TBT adsorption onto clays was always around pH 6–7. According to the data, it is evident that the content of organic matter in the solid phase plays an important role on TBT adsorption, either as particulate organic matter (POM) or organic matter adsorbed to mineral particles (AOM). Experiments were carried out with well characterized organic matter and the results showed a linear increase of K_d from 51 up to 2700 l/kg upon the addition of 5% of particulate organic matter to pure phased kaolinite. TBT adsorption onto mineral surfaces, which were previously enriched with adsorbed organic matter, was investigated at different pH. The present study points to the importance of identifying and characterizing sorbents and envrionmental conditions, in order to predict and model TBT distribution in natural systems.