Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

Experimental study of the selective adsorption of heavy metals onto clay minerals

The interaction between minerals and heavy metals has been a hot object of study in environmental science,mineralogy and soil science,Through the selective adsorption experiment of Ca-montomorillonite,illite and kaolinite to Cu2 ,Pb^2 ,Zn^2 ,Cd^2 ,and Cr^3 ions at certain conditions,it could be concluded that Cr^3 is most effectively sorbed by all the three minerals.Also,it can be found that Pb^2 shows a strong affinity for illite and kaolinite while cu^2 for montmorillonite .Based on the adsorption experiment at varying pH of solution,it can be found that the amount of heavy etals sorbed by minerals increases with increasing pH of the solution.     

A study on the adsorption characteristics of cadmium and zinc onto acidic and alkaline soils

The adsorption of cadmium (Cd) and zinc (Zn) with similar chemical properties is examined onto three soil samples: one is alkaline and the others are acidic. The distribution coefficient (K _d) and the Freundlich constant (K _F) for Zn are slightly higher than those for Cd, implying that the adsorption affinity of Zn is a little greater and less mobile. However, Cd and Zn usually show comparable results in the kinetic, isotherm, and envelope experiments. The adsorption of the heavy metals is relatively rapid and the reaction is almost completed within 15 min. The kinetics for both Cd and Zn are very well explained by the parabolic diffusion model. The maximum adsorption of the heavy metals is obtained at high pH, high temperature, and low ionic strength. The adsorption capacity on the alkaline soil is more significantly affected by the temperature as compared to the acidic soil. It is found that the adsorption affinity of the two heavy metals is mainly affected by the soil properties, such as pH, pH_PZC, organic matter, and total carbon. It is also confirmed that the chemical properties of the heavy metals are important factors in their adsorption onto soil. The adsorption isotherms of Cd and Zn are well described in both Freundlich and Langmuir models at the usual pH (soil pH). Under acidic and alkaline pHs, however, only the Freundlich model describes the adsorption of both heavy metals satisfactorily.     

Diagenesis and Very Low‐grade Metamorphism of the Upper Permian Yangjiagou Formation in Eastern Changchun,China: Evidence from Clay Mineral Geothermobarometers

The metamorphic conditions of the Upper Permian Yangjiagou Formation in eastern Changchun, China, were evaluated based on the mineral assemblage, illite crystallinity, illite polytypism,the b dimension of illite, and the chemical composition of chlorite. The pelitic rocks in the Yangjiagou Formation are characterized by illite + kaolinite + chlorite ± mixed-layer chlorite/smectite and detrital quartz + plagioclase. Illite in the formation has a crystallinity of 0.38-0.55 and comprises mixed 2 M_1 and1 M_d polytypes, indicating a metamorphic temperature of 200℃. Based on the chemical composition of chlorite and the chlorite geothermometer, we estimated diagenetic to very low-grade metamorphic conditions with temperatures of 185℃～204℃. The b dimension of illite varies from 8.992 A to 9.005 A.We used a mathematical algorithm to extend Guidotti and Sassi's(1986) diagram relating illite b dimension with temperature and pressure, and used this diagram, together with illite crystallinity and chlorite chemical composition, to semi-quantitatively estimate the formation pressure at1.2 kbar. These reveal that the Yangjiagou Formation has experienced very low-grade metamorphism.     

Cation exchange capacity of loess and overlying soil in the non-carbonate loess sections, North-Western Croatia

The adsorption properties in terms of cation exchange capacity and their relation to the soil and sediment constituents (clay minerals, Fe-, Mn-, and Al-oxyhydroxides, organic matter) were investigated in loess, soil-loess transition zone, and soil at four loess-soil sections in North-Western Croatia. Cation exchange capacity of the bulk samples, the samples after oxalate extraction of Fe, Mn and Al, and after removal of organic matter, as well as of the separated clay fraction, was determined using copper ethylenediamine. Cation exchange capacity (pH～7) of the bulk samples ranges from 5 to 12 cmol _c /kg in soil, from 7 to 15 cmol _c /kg in the soil-loess transition zone, and from 12 to 20 cmol _c /kg in loess. Generally, CEC values increase with depth. Oxalate extraction of Fe, Mn, and Al, and removal of organic matter cause a CEC decrease of 3–38% and 8–55%, respectively, proving a considerable influence of these constituents to the bulk CEC values. In the separated clay fraction (<2 μm) CEC values are up to several times higher relative to those in the bulk samples. The measured CEC values of the bulk samples generally correspond to the clay mineral content identified. Also, a slight increase in muscovite/illite content with depth and the vermiculite occurrence in the loess horizon are concomitant with the CEC increase in deeper horizons, irrespective of the sample pretreatment.     

Chlorite crystallinity: an empirical approach and correlation with illite crystallinity, coal rank and mineral facies as exemplified by Palaeozoic and Mesozoic rocks of northeast Hungary

Abstract Fairly strong (r= 0.75–0.85) positive linear correlations were found between crystallinity indices (peak widths) measured on the first two basal reflections of chlorite and those of illite–muscovite in <2-μm fractions of a representative shale–slate–phyllite series from Palaeozoic and Mesozoic formations of northeast Hungary. The metamorphic grade ranges from late or deep diagenesis through anchizone to epizone conditions. Chlorite crystallinity values measured on air-dried and ethylene-glycol-solvated samples suggest that the effects of expandable interlayers are negligable, especially in the higher grade (～temperature) part of the series. However, the greater scattering of crystallinity values for the chlorite 001 reflection compared to those of the 002 reflection may be related to the effects of minor amounts of interlayered and/or discrete smectite and/or vermiculite. With increasing metamorphic grade and advancing equilibrium recrystallization, the chlorite compositions in different samples become more homogenous. No correlation exists between crystallinity and changes in chlorite composition as estimated from the intensity ratios of basal reflections. Hence an increase of domain size and a decrease of lattice distortion with increasing grade (～temperature) may be decisive factors affecting chlorite crystallinity. Chlorite crystallinity can be applied as a reliable regional, statistical technique complementary with, or instead of, the illite crystallinity method. The illite and chlorite crystallinity scales used here are related to Kübler's epi-, anchi- and diagenetic zones and correlated with coal rank, conodont colour alteration and mineral facies data. As the effects of the detrital white mica can be observed even in the <2-μm fractions of anchizonal metapelites, the anchizone boundaries determined solely on the base of ‘fixed’illite crystallinity values may vary with amounts of detrital and newly formed muscovite–illite. Hence a complex approach utilizing more than one method for determination of grade is preferred for petrogenetic purposes, even if relationships between crystallinity scales, coal rank and mineral facies also vary strongly in different tectonic settings and lithologies.     

不同粘土矿物对赖氨酸的吸附行为对比研究

以皂石、高岭石、绿泥石和伊利石为原材料,分别与赖氨酸进行反应,研究赖氨酸在上述粘土矿物上的吸附行为, 并运用粉末X-射线衍射技术（XRD）、傅里叶变换红外吸收光谱术（FTIR）和热重（TG）等分析方法,表征反应前后粘土 矿物的变化。实验结果表明,不同粘土矿物对赖氨酸的吸附等温线均符合Freundlich等温方程,且不同粘土矿物对赖氨酸的 饱和吸附量大小顺序为：皂石>蒙脱石>绿泥石>高岭石>伊利石;XRD结果表明皂石对赖氨酸的吸附发生在矿物层间,而绿 泥石、高岭石和伊利石对赖氨酸的吸附主要在矿物表面进行;FTIR和TG结果表明赖氨酸主要取代粘土矿物层间吸附水,以 氢键的形式与Si-O-Si(IVAl)键合。实验结果将有助于进一步探明环境中粘土矿物对有机质的吸附机理。     

Assessment of contamination load on water,soil and sediment affected by the Kongjujeil mine drainage,Republic of Korea

Environmental pollution in the Kongjujeil mine creek was determined on the basis of physicochemical and mineralogical properties for various kinds of waters, soils, precipitates and sediments collected in August and December 1998. The hydrochemistry of water is characterized by an enrichment in concentrations of Ca ²⁺, Si, alkali ions, NO ₃ ^- and Cl ^- in ground and surface water, where relatively the mine waters are significantly enriched in Ca ²⁺+Mg ²⁺, Al, heavy metals and SO ₄ ^2- concentrations. The mine waters have lower pH (3.24) and higher EC (613 µS/cm) compared with those of ground and surface water. The ranges of dD and d ¹⁸O values (SMOW) in the water are -50.2 to -61.6‰ and -7.0 to -8.6‰. Using a computer code, the saturation indices of albite, calcite and dolomite in the mine water show that it is undersaturated, and has progressively evolved toward the equilibrium state. Ground and surface water are nearly saturated. The gibbsite, kaolinite and smectite are supersaturated in the surface and groundwater. Geochemical modeling shows that mostly toxic metals exist largely in the form of metal sulfates and free metals in mine water. These metals in the surrounding fresh water could be formed of carbonate or hydroxide complex ions. Minerals within the soil and sediment near the mining area were partly variable consisting of quartz, mica, alkali feldspar, plagioclase, chlorite, vermiculite, berthierine and clay minerals. The separated heavy minerals, soil and sediment are composed of some pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, malachite, goethite and various hydroxide minerals. Some potentially toxic elements (As, Cd, Cu, Pb, Sb and Zn) are found in extremely high concentrations in the surface soils in the vicinity of the mine. The enrichment index of heavy metals in sediment and surface soil of the mine drainage was very severe, while it was not so great in the cultivated soil.     

Removal of zinc(II) from aqueous solutions using modified agricultural wastes: kinetics and equilibrium studies

In recent years, the need for safe and economical methods to eliminate heavy metals from contaminated waters has necessitated research on the production of low-cost alternatives to commercially available activated carbon. In the present work, in order to enhance the removal of heavy metals from contaminated water, Zizyphus vulgaris wastes were modified chemically to produce an adsorbent rich in carboxylic groups to enhance the removal of heavy metals from contaminated water. Adsorption of Zn(II) ions on the produced adsorbent was then optimized. The optimal ratio for esterification involved the treatment of Z. vulgaris wastes (1 g) with 0.0037 mmol malic acid in the presence of a very small amount of water for 2 h at 140 °C. The maximum values for adsorption capacity, q _max, were 28.7 and 164.6 mg/g on native and modified Z. vulgaris wastes, respectively, at pH 5 and 30 °C with a contact time 2 h and an initial metal ion concentration of 400 mg/L. The equilibrium data were well fitted by the Langmuir and Freundlich adsorption models and demonstrated the significant capacity for Z. vulgaris wastes in the removal of Zn(II) ions from aqueous solutions.     

Clay petrology of the Upper Triassic/Lower Jurassic terrestrial strata of the Newark Supergroup,Connecticut Valley,U.S.A.

The clay mineralogy of the Newark Supergroup (Upper Triassic/Lower Jurassic) in the Connecticut Valley was studied by X-ray diffraction analysis. Clay minerals identified in 126 samples are illite, chlorite, smectite, kaolinite, vermiculite, expandable chlorite, mixed-layer illite/smectite, mixed-layer chlorite/smectite, and mixed-layer chlorite/vermiculite. In general, the rocks are illitic with subordinate amounts of chlorite. However, the various lithofacies in the Newark Supergroup are characterized by distinct clay-mineral assemblages. Red beds of floodplain origin contain clays mainly of detrital nature with 2M illite most abundant. Subordinate amounts of chlorite, smectite, vermiculite, kaolinite and mixed-layer illite/smectite are also present. An interstratified chlorite/vermiculite occurs in red mudstone underlying basalt flows. Lacustrine gray beds are generally characterized by the clay-mineral assemblage 1Md illite + chlorite with minor amounts of smectite ane expandable chlorite. An interstratified chlorite/smectite predominates in gray mudstone associated with perennial lake cycles in the East Berlin Formation. Black shales of deeper lacustrine origin contain the assemblage 1Md ifillite + trioctahedral smectite and traces of chlorite. Illite and smectite also occur as mixed-layer phases.In many respects, the distribution of clay minerals in the Connecticut Valley can be likened to the general scheme proposed for the Permo-Triassic basins of Europe and Africa. These display both vertical and horizontal variations in clay-mineral assemblages that reflect the chemical and spatiotemporal evolution of intrabasin depositional and diagenetic environments. Chemical data indicate that magnesium, especially, was concentrated in the black muds of large perennial lakes that intermittently occupied the Connecticut rift valley. Pore waters derived from these sediments played an important role in the development of Mg-rich 2 : 1 and interstratified clay minerals during early diagenesis.     

Mineralogical attenuation for metallic remediation in a passive system for mine water treatment

Passive systems with constructed wetlands have been consistently used to treat mine water from abandoned mines. Long-term and cost-effective remediation is a crucial expectation for these water treatment facilities. To achieve that, a complex chain of physical, chemical, biological, and mineralogical mechanisms for pollutants removal must be designed to simulate natural attenuation processes. This paper aims to present geochemical and mineralogical data obtained in a recently constructed passive system (from an abandoned mine, Jales, Northern Portugal). It shows the role of different solid materials in the retention of metals and arsenic, observed during the start-up period of the treatment plant. The mineralogical study focused on two types of materials: (1) the ochre-precipitates, formed as waste products from the neutralization process, and (2) the fine-grained minerals contained in the soil of the wetlands. The ochre-precipitates demonstrated to be poorly ordered iron-rich material, which gave rise to hematite upon artificial heating. The heating experiments also provided mineralogical evidence for the presence of an associated amorphous arsenic-rich compound. Chemical analysis on the freshly ochre-precipitates revealed high concentrations of arsenic (51,867 ppm) and metals, such as zinc (1,213 ppm) and manganese (821 ppm), indicating strong enrichment factors relative to the water from which they precipitate. Mineralogical data obtained in the soil of the wetlands indicate that chlorite, illite, chlorite–vermiculite and mica–vermiculite mixed-layers, vermiculite, kaolinite and goethite are concentrated in the fine-grained fractions (<20 and <2 μm). The chemical analyses show that high levels of arsenic (up to 3%) and metals are also retained in these fractions, which may be enhanced by the low degree of order of the clay minerals as suggested by an XRD study. The obtained results suggest that, although the treatment plant has been receiving water only since 2006, future performance will be strongly dependent on these identified mineralogical pollutant hosts.     

Mineral weathering and elemental transport during hillslope evolution at the Susquehanna/Shale Hills Critical Zone Observatory

Located in the uplands of the Valley and Ridge physiographic province of Pennsylvania, the Susquehanna/Shale Hills Critical Zone Observatory (SSHO) is a tectonically quiescent, first-order catchment developed on shales of the Silurian Rose Hill Formation. We used soil cores augered at the highest point of the watershed and along a subsurface water flowline on a planar hillslope to investigate mineral transformations and physical/chemical weathering fluxes. About 25 m of bedrock was also drilled to estimate parent composition. Depletion of carbonate at tens of meters of depth in bedrock may delineate a deep carbonate-weathering front. Overlying this, extending from ∼6 m below the bedrock-soil interface up into the soil, is the feldspar dissolution front. In the soils, depletion profiles for K, Mg, Si, Fe, and Al relative to the bedrock define the illite and chlorite reaction fronts. When combined with a cosmogenic nuclide-derived erosion rate on watershed sediments, these depletion profiles are consistent with dissolution rates that are several orders of magnitudes slower for chlorite (1-5 × 10⁻¹⁷ mol m⁻² s⁻¹) and illite (2-9 × 10⁻¹⁷ mol m⁻² s⁻¹) than observed in the laboratory. Mineral reactions result in formation of vermiculite, hydroxy-interlayered vermiculite, and minor kaolinite. During weathering, exchangeable divalent cations are replaced by Al as soil pH decreases.The losses of Mg and K in the soils occur largely as solute fluxes; in contrast, losses of Al and Fe are mostly as downslope transport of fine particles. Physical erosion of bulk soils also occurs: results from a steady-state model demonstrate that physical erosion accounts for about half of the total denudation at the ridgetop and midslope positions. Chemical weathering losses of Mg, Na, and K are higher in the upslope positions likely because of the higher degree of chemical undersaturation in porewaters. Chemical weathering slows down in the valley floor and Al and Si even show net accumulation. The simplest model for the hillslope that is consistent with all observations is a steady-state, clay weathering-limited system where soil production rates decrease with increasing soil thickness.     

The spatial distribution of potassium status and clay mineralogy in relation to different land-use types in a calcareous Mediterranean environment

In order to investigate changes caused in clay mineralogy and potassium (K) status by different land-use types, 42 soils samples (0–30 cm) were monitored and analyzed. Soil samples belonging to Reference Soil Groups of Cambisols and Vertisols were collected from three neighboring land uses involving cropland (under long-term continuous cultivation), grassland, and forestland. The soils reflected an alkaline and calcareous aspect as were characterized by high pH (mean of 7.1 to 7.5) and calcium carbonate equivalent (mean of 35 to 97 g?kg^?1) in the three land-use types. X-ray diffraction patterns of the clay fraction showed that the soils were mainly composed of illite, smectite, chlorite, and kaolinite. Chlorite and kaolinite remained unweathered irrespective of land use and soil types, soil processes, and physicochemical attributes assessed. Some changes in the XRD diffractograms of illite and smectite (the intensity or the position of peaks) were observed in the cultivated soils compared to those of the adjoining grassland that may explain the dynamics of the K trapped in illite interlayer sites. Potassium issues reflected a heterogeneous response to changes in land-use types. In light of this, a pronounced variation in soluble K (4–22 mg?kg^?1), exchangeable K (140–558 mg?kg^?1), and non-exchangeable K (135–742 mg?kg^?1) appeared among the land-use types for both Cambisols and Vertisols, corresponding to variability in clay content, nature and type of clay mineral (mainly illite and smectite), cation exchange capacity (CEC), and soil organic carbon (SOC). In general, the largest amounts of soluble K and exchangeable K were recorded in the forestland, whereas the highest contents of non-exchangeable K were found in the grassland for both Cambisols and Vertisols. Exchangeable K, available K, CEC, and clay contents in the soils with higher smectite values (25–50 %) were significantly different (P?≤?0.05) compared to those of the lower smectite values (10–25 %). This suggests that smectite is a major source for surface sorption of K in the studied soils.     

德兴铜矿地区土壤的基本特征及其对重金属元素的吸附研究

本文首先分析了江西德兴铜矿区周围土壤的微量元素和矿物组成特征,结果显示该地区重金属元素富集,且表层土中重金属元素含量与粘土矿物相对含量变化具有较好的一致性。室内土柱淋滤实验结果表明,当总淋滤时间为451 h时,土壤对Pb²⁺的总吸附量为2 584.75 mg/kg,淋滤实验的前半期存在多种竞争吸附机制,后半期土壤对Pb²⁺的吸附基本达到动态平衡。淋滤后土壤矿物的相对质量分数发生了改变,粘土矿物有所减少。粘土矿物在不同土壤层对Pb²⁺的吸附能力也各异。     

Vermiculite bio-barriers for Cu and Zn remediation: an eco-friendly approach for freshwater and sediments protection

The increase in heavy metal contamination in freshwater systems causes serious environmental problems in most industrialized countries, and the effort to find eco-friendly techniques for reducing water and sediment contamination is fundamental for environmental protection. Permeable barriers made of natural clays can be used as low-cost and eco-friendly materials for adsorbing heavy metals from water solution and thus reducing the sediment contamination. This study discusses the application of permeable barriers made of vermiculite clay for heavy metals remediation at the interface between water and sediments and investigates the possibility to increase their efficiency by loading the vermiculite surface with a microbial biofilm of Pseudomonas putida, which is well known to be a heavy metal accumulator. Some batch assays were performed to verify the uptake capacity of two systems and their adsorption kinetics, and the results indicated that the vermiculite bio-barrier system had a higher removal capacity than the vermiculite barrier (+34.4 and 22.8 % for Cu and Zn, respectively). Moreover, the presence of P. putida biofilm strongly contributed to fasten the kinetics of metals adsorption onto vermiculite sheets. In open-system conditions, the presence of a vermiculite barrier at the interface between water and sediment could reduce the sediment contamination up to 20 and 23 % for Cu and Zn, respectively, highlighting the efficiency of these eco-friendly materials for environmental applications. Nevertheless, the contribution of microbial biofilm in open-system setup should be optimized, and some important considerations about biofilm attachment in a continuous-flow system have been discussed.     

Biosorption of cadmium(II) from aqueous solution onto <Emphasis Type="Italic">Hydrilla verticillata</Emphasis>

Biosorption is an effective method to remove heavy metals from wastewater. In this work, the biosorption of Cd(II) onto Hydrilla verticillata was examined in aqueous solution with parameters of initial pH, adsorbent dosage, contact time, initial Cd(II) concentration, temperature, and co-existing ion. Linear Langmuir and Freundlich models were applied to describe the equilibrium isotherms, and both of the two models were fitted well. The monolayer adsorption capacity of Cd(II) was found to be 50 mg/g at pH 6 and 20°C. Dubinin–Radushkevich isotherm model was also applied to the equilibrium data. The mean free energy of adsorption (11.18 kJ/mol) indicated that the adsorption of Cd(II) onto H. verticillata might be carried out via chemical ion-exchange mechanism. Thermodynamic parameters, including free energy (∆G ⁰), enthalpy (∆H ⁰), and entropy (∆S ⁰) of adsorption, were also calculated. These results showed that the biosorption of Cd(II) onto H. verticillata was a feasible, spontaneous, and exothermic process in nature. Desorption experiments indicated that 0.01 mol/L EDTA and HNO₃ were efficient desorbents for the recovery of Cd(II) from biomass. IR spectrum analysis suggested that amido, hydroxyl, C=O and C–O could combine strongly with Cd(II). EDX spectrum analysis suggested that an ion exchange mechanism might be involved.     

Burial Metamorphism of the Ordos Basin in Northern Shaanxi

Burial metamorphism has been found in the Ordos basin of northern Shaanxi. On the basis of a rather intensive study of burial metamorphism of sandstone, it has been shown that the evolution from diagenesis to metamorphism involves four stages: cementation of clay minerals, regrowth of pressolved quartz and feldspar, cementation of carbonates and formation of laumontite. On that basis it has been put forward that the laumontite is formed by burial metamorphism of clay and carbonate minerals. According to the thermodynamic data of minerals, the conditions under which laumontite is formed are T<250℃ and X_(CO_2)<0.17. High-resolution SEM and TEM studies of clay minerals in mudstone show that there occur a mixed layer assemblage of bertherine and illite/chlorite and transformation from bertherine to chlorite. On that basis coupled by the X-ray diffraction analysis the author suggests the following transformation of clay minerals during burial metamorphism: the earliest smectite-kaolinite assemblage changes into the bertherine-illite mixture with increasing depth, then into the illite/chlorite mixed layer assemblage and finally into dispersed individual illite and chlorite. The reaction of the transformation is:smectite+kaolinite+K~+=illite+chlorite+quartz According to the study of the oxygen isotope thermometry of the coexisting illitequartz pair, the temperature of the above transformation is lower than 180℃.     

Alteration mineralogy,lithochemistry and stable isotope geochemistry of the Murgul (Artvin,NE Turkey) volcanic hosted massive sulfide deposit: Implications for the alteration age and ore forming fluids

The Murgul (Artvin, NE Turkey) massive sulfide deposit is hosted dominantly by Late Cretaceous calc-alkaline to transitional felsic volcanics. The footwall rocks are represented by dacitic flows and pyroclastics, whereas the hanging wall rocks consist of epiclastic rocks, chemical exhalative rocks, gypsum-bearing vitric tuff, purple vitric tuff and dacitic flows. Multi-element variation diagrams of the hanging wall and footwall rocks exhibit similar patterns with considerable enrichment in K, Rb and Ba and depletion in Nb, Sr, Ti and P. The chondrite-normalized rare earth element (REEs) patterns of all the rocks are characterized by pronounced positive/negative Eu anomalies as a result of different degrees of hydrothermal alteration and the semi-protected effects of plagioclase fractionation.Mineralogical results suggest illite, illite/smectite + chlorite ± kaolinite and chlorite in the footwall rocks and illite ± smectite ± kaolinite and chlorite ± illite in the hanging wall rocks. Overall, the alteration pattern is represented by silica, sericite, chlorite and chlorite–carbonate–epidote–sericite and quartz/albite zones. Increments of Ishikawa alteration indexes, resulting from gains in K₂O and losses in Na₂O and the chlorite–carbonate–pyrite index towards to the center of the stringer zone, indicate the inner parts of the alteration zones. Calculations of the changes in the chemical mass imply a general volume increase in the footwall rocks. Abnormal volume increases are explained by silica and iron enrichments and a total depletion of alkalis in silica zone. Relative K increments are linked to the sericitization of plagioclase and glass shards and the formation of illite/smectite in the sericite zone. In addition, Fe enrichment is always met by pyrite formation accompanied by quartz and chlorite. Illite is favored over chlorite, smectite and kaolinite in the central part of the ore body due to the increase in the (Al + K)/(Na + Ca) ratio. Although the REEs were enriched in the silicification zone, light REEs show depletion in the silicification zone and enrichment in the other zones in contrast to the heavy REEs' behavior. Hydrothermal alteration within the hanging wall rocks, apart from the gypsum-bearing vitric tuffs, is primarily controlled by chloritization with proportional Fe and Mg enrichments and sericitization.The δ¹⁸O and δD values of clay minerals systematically change with increasing formation temperature from 6.6 to 8.7‰ and − 42 to − 50‰ for illites, and 8.6 and − 52‰ for chlorite, respectively. The O- and H-stable isotopic data imply that hydrothermal-alteration processes occurred at 253–332 °C for illites and 136 °C for chlorite with a temperature decrease outward from the center of the deposit. The positive δ³⁴S values (20.3 to 20.4‰) for gypsum suggest contributions from seawater sulfate reduced by Fe-oxide/-hydroxide phases within altered volcanic units. Thus, the hydrothermal alteration possibly formed via a dissolution–precipitation mechanism that operated under acidic conditions. The K–Ar dating (73–62 Ma) of the illites indicates an illitization process from the Maastrichtian to Early Danian period.     

Potential of natural bed soil in adsorption of heavy metals in industrial waste landfill

Development of higher welfare could not be realized unless by energy consumption and other natural resources. Growth of industrial complexes has shown an unprecedented trend during recent years. Many of these towns have no treatment systems for the industrial wastes leachates. Besides, the chemical composition of wastes in such complexes varies considerably due to the different kinds of industries. It is endeavored in the present work to study the natural potential of soil to treat leachate of such industrial wastes. For this purpose, the Aliabad industrial complex in Tehran — Garmsar road was selected as the study area. The potential of adsorption of elements such as nickel, copper, cadmium, zinc, chromium, lead and manganese was investigated. The results indicated that the soil potential to adsorb heavy metals (except for manganese) was very high (95 %) in the adsorption of heavy metals (except for manganese). Further, chemical partitioning studies revealed that heavy metals are associated with various soil phases such as loosely bonded ions, sulfide and organics to various extents. Among the mentioned soil phases, one can deduce that major portion of metal contaminants is absorbed as loosely bonded ions. Organic bond and sulfide bond are in the 2^nd and 3^rd positions of metal contaminants adsorption, respectively. The results of the present study apparently showed that soil column had ample capacity to adsorb metal contaminants. Thus, determination of soil potential in adsorption of heavy metals during site selection is as important criteria.     

Very low grade metamorphism of the Taveyanne formation of western Switzerland

The andesitic early Oligocene Taveyanne metagreywacke of the Helvetic nappes of western Switzerland shows an increase of metamorphic grade from zeolite facies through lower greenschist facies. Electron microprobe analysis, fluid inclusion thermometry, stable isotope analysis, coal rank, illite and chlorite crystallinity and thermodynamic calculations were carried out to determine metamorphic conditions. Evaluation of all techniques used in this study suggest that only combinations of different parameters yield reliable information to constrain very low-grade metamorphic conditions. Electron microprobe analyses are presented for actinolite, chlorite, epidote, phengite, laumontite, prehnite, pumpellyite, and titanite. With increasing metamorphic grade, chlorite is enriched in tetrahedral Al, pumpellyite becomes poorer in Fe_tot and more homogeneous in chemical composition, and titanite tends to incorporate Ti at the expense of Al and Fe³⁺. Metamorphic P-T conditions were determined by a combination of fluid inclusion microthermobarometry, stable isotope thermometry on quartz-calcite veins, chlorite “geothermometry” and thermodynamic calculations. Peak temperatures range from 210–250 °C for zeolite facies to 270–300 °C for prehnite-pumpellyite facies to 300–360 °C for pumpellyite-actinolite facies. An evaluation of 289 chlorite analyses indicates that the tetrahedral Al content is negatively correlated with the saponite component. Temperatures derived from chlorite “geothermometry” match maximum temperature conditions mentioned above. Illite crystallinity data for shales and slates intercalated with the Taveyanne metagreywacke indicate that the diagenetic zone correlates with the zeolite facies, the upper anchizone with the prehnite-pumpellyite facies, and the lower epizone with the pumpellyite-actinolite facies. A comparison of coal rank and illite crystallinity data (n=12,r=0.91) yielded R _max values of 2.9 and 5.5% for the lower and upper boundary of the anchizone, respectively. Received: 2 August 1996 / Accepted: 16 July 1997