Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Lamellar nigerite in Zn-rich spinel from the Falun deposit,Sweden

Lamellar nigerite is found in Zn-rich spinel from a sample that contains chiefly anthophyllite + spinel + cordierite, lesser amounts of quartz and chlorite, as well as sphalerite, pyrite, pyrrhotite, and galena, and rare cassiterite and rutile. Nigerite can be described as interlayering of spinel-like (R²⁺Al₂O₄) and nolanite-like ((Sn, Ti)Al₄O₈) structures. In nigerite, the spinel-like part is also compositionally related to spinel, but in the nolanite-like part only the structural analogy exists. Stoichiometric assumptions that relate the anhydrous cation sum to the amount of R⁴⁺ cations present, allow Fe³⁺ estimates from microprobe analyses, and a representative analysis gives the following anhydrous formula: Mg_1.30Fe _0.65 ²⁺ Zn_3.03Mn_0.03Al_11.65Fe _0.35 ³⁺ Sn_0.32Ti_0.18O₂₄.The nigerite is Zn-rich with a Zn ratio (Zn/(Zn+Mg+ Fe²⁺)) of about 0.59, and the Sn ratio (Sn/(Sn+Ti)) that ranges from about 0.63 to 0.41. The Fe³⁺ content in these samples ranges from 0.35 to 0.52 (24 oxygen basis).Textures suggest that the nigerite could have formed by the breakdown of R ₂ ²⁺ (Sn, Ti)O₄ and R²⁺Al₂O₄ spinel components during more complex reactions. An experimental investigation of the MgAl₂O₄-Mg₂SnO₄ join indicates that the solubility of Mg₂SnO₄ component in spinel over the T interval 500 to 900° C is about 0.5 to 3.0 mole %. This, coupled with the increased solubility expected from the presence of Ti, gives good agreement with the 2.4 to 2.6 mole % R ₂ ²⁺ (Sn, Ti)O₄ component in spinel that is estimated to be the maximum necessary to form the compositions and amounts of observed nigerite.     

Arsenic speciation and turnover in intact organic soil mesocosms during experimental drought and rewetting

Wetlands are significant sources and sinks for arsenic (As), yet the geochemical conditions and processes causing a release of dissolved arsenic and its association with the solid phase of wetland soils are poorly known. Here we present experiments in which arsenic speciation was determined in peatland mesocosms in high spatiotemporal resolution over 10 months. The experiment included a drought/rewetting treatment, a permanently wet, and a defoliated treatment. Soil water content was determined by the TDR technique, and arsenic, iron and sulfate turnover from mass balancing stocks and fluxes in the peat, and solid phase contents by sequential extractions. Arsenic content ranged from 5 to 25 mg kg⁻¹ and dissolved concentrations from 10 to 300 μg L⁻¹, mainly in form of As(III), and secondarily of As(V) and dimethylated arsenic (DMA). Total arsenic was mainly associated with amorphous iron hydroxides (R² > 0.95, α < 0.01) and deeper into the peat with an unidentified residual fraction. Arsenic release was linked to ferrous iron release and primarily occurred in the intensely rooted uppermost soil. Volumetric air contents of 2-13 % during drought eliminated DMA from the porewater and suppressed its release after rewetting for >30 d. Dissolved As(III) was oxidized and immobilized as As(V) at rates of up to 0.015 mmol m⁻³ d⁻¹. Rewetting mobilized As(III) at rates of up to 0.018 mmol m⁻³ d⁻¹ within days. Concurrently, Fe(II) was released at depth integrated rates of up 20 mmol m⁻³ d⁻¹. The redox half systems of arsenic, iron, and sulfur were in persistent disequilibrium, with H₂S being a thermodynamically viable reductant for As(V) to As(III). The study suggests that rewetting can lead to a rapid release of arsenic in iron-rich peatlands and that methylation is of lesser importance than co-release with iron reduction, which was largely driven by root activity.     

Soil properties controlling Zn speciation and fractionation in contaminated soils

We determined the speciation of Zn in 49 field soils differing widely in pH (4.1–7.7) and total Zn content (251–30,090 mg/kg) by using extended X-ray absorption fine structure (EXAFS) spectroscopy. All soils had been contaminated since several decades by inputs of aqueous Zn with runoff-water from galvanized power line towers. Pedogenic Zn species identified by EXAFS spectroscopy included Zn in hydroxy-interlayered minerals (Zn-HIM), Zn-rich phyllosilicates, Zn-layered double hydroxide (Zn-LDH), hydrozincite, and octahedrally and tetrahedrally coordinated sorbed or complexed Zn. Zn-HIM was only observed in (mostly acidic) soils containing less than 2000 mg/kg of Zn, reflecting the high affinity but limited sorption capacity of HIM. Zn-bearing precipitates, such as Zn-LDH and Zn-rich trioctahedral phyllosilicates, became more dominant with increasing pH and increasing total Zn content relative to available adsorption sites. Zn-LDH was the most abundant Zn-precipitate and was detected in soils with pH > 5.2. Zn-rich phyllosilicates were detected even at lower soil pH, but were generally less abundant than Zn-LDH. Hydrozincite was only identified in two calcareous soils with extremely high Zn contents. In addition to Zn-LDH, large amounts of Zn in highly contaminated soils were mainly accumulated as sorbed/complexed Zn in tetrahedral coordination. Soils grouped according to their Zn speciation inferred from EXAFS spectroscopy mainly differed with respect to soil pH and total Zn content. Clear differences were observed with respect to Zn fractionation by sequential extraction: From Zn-HIM containing soils, most of the total Zn was recovered in the exchangeable and the most recalcitrant fractions. In contrast, from soils containing the highest percentage of Zn-precipitates, Zn was mainly extracted in intermediate extraction steps. The results of this study demonstrate that soil pH and Zn contamination level relative to available adsorption sites are the most important factors controlling the formation of pedogenic Zn-species in aerobic soils and, consequently, Zn fractionation by sequential extraction.     

Natural speciation of Zn at the micrometer scale in a clayey soil using X-ray fluorescence, absorption, and diffraction

Combined use of synchrotron-based X-ray fluorescence (SXRF), diffraction (XRD), and absorption (EXAFS) with an X-ray spot size as small as five micrometers allows us to examine noninvasively heterogeneous soils and sediments. Specifically, the speciation of trace metals at low bulk concentrations and the nature of host minerals can be probed with a level of detail unattainable by other techniques. The potential of this novel analytical approach is demonstrated by determining the Zn species in the solid phases of a pristine horizon of a clayey acidic soil (pH 4.5-5.0) having a Zn concentration of 128 mg/kg. The sample presents a differentiated fabric under the optical microscope with traces of localized manganiferous, ferriferous and argillaceous accumulations. The high chemical and textural heterogeneity of this soil offers an opportunity to identify new Zn species and to confirm the existence of others proposed from published least-squares fits of bulk averaged EXAFS spectra. As many as five to six Zn species were observed: sphalerite (ZnS), zincochromite (ZnCr₂O₄), Zn-containing phyllosilicate and lithiophorite, and Zn-sorbed ferrihydrite or Zn-phosphate, the results being less definitive for these two last species. Bulk EXAFS spectroscopy applied to the powdered soil indicated that Zn is predominantly associated with phyllosilicates, all other species amounting to < ∼10 to 20% of total zinc. The role of lithiophorite in the sequestration of zinc in soils had been inferred previously, but the firm identification of lithiophorite in this study serves as an excellent demonstration of the capabilities of combined micro-SXRF/XRD/EXAFS measurements. The micro-EXAFS spectrum collected in an area containing only phyllosilicates could not be simulated assuming a single Zn structural environment. Two distinct octahedrally-coordinated crystallographic sites (i.e., two EXAFS components) were considered: one site located within the phyllosilicate structure (isomorphic cationic substitution in the octahedral sheet) and another in the interlayer region in the form of a Zn-sorbed hydroxy-Al interlayered species. This second subspecies is less certain and further investigation of the individual EXAFS spectrum of this component is needed to precise its exact nature and the uptake mechanism of zinc in it.     

Undications of current action in late Jurassic limestones,radiolarian limestones,saccocoma limestones and associated rocks from the subbetic of SE Spain

In the Vélez Blanco region (province of Almeia), filament limestones occur associated with pellet limestones, crinoidal limestones, radiolarian limestones, Saccocoma limestones and tintinnid limestones. These predominantly Late Jurassic rocks are underlain by Middle Jurassic oolitic limestones and overlain by Cretaceous pelagic limestones and marls.A distinction can be made between long and short filaments. The former are interpreted as undamaged valves, the latter as shell fragments of the pelagic pelecypod Bositra buchi. Bositra valves and fragments have been sorted by weak current (and/or wave) action.In the Saccocoma limestones, evidence for similar sorting of Saccocoma debris has been found.The radiolarian limestones represent a low-energy basin environment, but are not comparable with recent deep-sea radiolarian oozes.Nodular limestone intercalations and hiatuses represent a current- (and/or wave-) swept environment.The occurrence of filament-rich and Radiolaria-bearing, but benthos-poor, intervals within the oolitic limestone indicates that the deposition of such rocks can take place at moderate sea depths.     

Contact metamorphism of siliceous dolomite and impure limestones from the Werfen formation in the eastern Monzoni contact aureole

Summary ?The intrusive complex of Monzoni in the western central Dolomites (northern Italy) comprises a suite of pyroxenites, monzogabbros and monzodiorites with solidus temperatures in excess of 1000 °C which intruded previously unmetamorphosed Permotriassic sediments at less than 5 km depth. At the eastern intrusive contact an approximately 860 m wide contact aureole is developed in the carbonate country rocks. The prograde sequence of mineral parageneses in a siliceous dolomite of the Cencenighe member and in marly limestones of the Val Badia and Cencenighe members of the Lower Triassic Werfen formation indicate peak metamorphic temperatures in excess of 698 °C at 185 m from the intrusive contact and an outward temperature decrease of approximately 65 °C per 100 m. The high temperatures in the inner aureole caused formation of periclase from the prograde breakdown of dolomite and formation of melilite and esseneite-rich clinopyroxene. Present address: Mineralogisch-Petrographisches Institut, Universit?t Basel, Switzerland Received April 7, 2001; revised version accepted December 6, 2001     

Origin of high Zn contents in Jurassic limestone of the Jura mountain range and the Burgundy: evidence from Zn speciation and distribution

In order to better understand the origin and enrichment mechanisms leading to elevated Zn concentrations in Jurassic limestone of the Jura mountain range (JMR) and the Burgundy (B), we investigated four locations of Bajocian age (JMR: Lausen–Schleifenberg, Gurnigel; B: Vergisson–Davayé, Lucy-le-Bois) and two locations of Oxfordian age (JMR: Dornach, Pichoux) for their Zn distribution and speciation. Measurements of the acid-extractable and bulk Zn contents showed that Zn is stratigraphically and spatially heterogeneously distributed, in association with permeable carbonate levels. Up to 3,580 and 207 mg/kg Zn was detected in Bajocian and Oxfordian limestone, respectively, with numerous limestone samples having Zn contents above 50 mg/kg. Using X-ray absorption near edge structure spectroscopy and micro-X-ray fluorescence spectrometry, the speciation and micro-scale distribution of Zn was investigated for selected limestone samples. In Bajocian limestone sphalerite and/or Zn-substituted goethite and a minor fraction of Zn-bearing carbonates were identified. In contrast, Zn-bearing carbonates (Zn-substituted calcite and hydrozincite) were accounting for most of the total Zn in Oxfordian limestone. The micro-scale distribution of Zn for Bajocian and Oxfordian limestone was however similar with localized Zn-rich zones in the limestone cement and at the rim of oolites. The stratigraphic sporadicity and microscale heterogeneity of the Zn distribution together with the Zn speciation results point to a hydrothermal origin of Zn. Occurence of Zn-goethite is probably linked to the oxidative transformation of framboidal pyrite and hydrothermal sphalerite in contact with meteoritic waters. Difference in speciation between Bajocian limestone and Oxfordian limestone may be related to differences in rock permeability and/or to various hydrothermal events. Isotopic dating of the different mineralizations will be needed to decipher differences in Zn speciation and the precise chronology of hydrothermal episodes.     

Zn-rich högbomite formed from gahnite in the metabauxites of the Menderes Massif,SW Turkey

Gahnite, ZnAl₂O₄, present as an accessory mineral in regionally metamorphosed low-grade diasporites, has reacted in adjacent higher-grade, corundum-bearing metabauxite equivalents (emeries) to form Zn-rich högbomite, (Zn,Fe²⁺,Mg,Ni)_t-2x (Ti,Sn)_xAl₂O₄, of the 4H polytype. Commonly, the initial högbomite crystals grew epitactically along the octahedral faces of gahnite, which was subsequently dissolved, so that högbomite now forms spectacularly intergrown sets of eight crystals in perfect crystallographic orientation to each other. This indicates a metamorphic reaction, probably involving a fluid, transporting mainly the elements Zn and Al. Reactant Ti minerals in the diasporites were rutile and titanian hematite (10–15 mol% FeTiO₃). In the emeries högbomite coexists with still more Ti-rich hematites containing between 26 and 37 mol% FeTiO₃. The overall reaction relations involving partial reduction may be subdivided into the intial univariant reaction, gahnite+diaspore+Ti-hematite+rutile=högbomite+H₂O+O₂. This was followed, in the absence of gahnite, by compositional readjustments of högbomite and Ti-hematite and the appearance of magnetite. Core to rim zoning profiles indicate that, with continued growth, the högbomite crystals became poorer in Zn and Ti, but richer in Fe²⁺, while the Ti-contents of coexisting hematite increased. Högbomite formation at the expense of gahnite started at temperatures as low as about 400° C for an estimated pressure of 5–6 kbar.     

Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high “background” metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.     

Transformation of metal speciation in purple soil as affected by waterlogging

This study was conducted to investigate the effect of waterlogging on copper, lead and cadmium fractionation in Chinese purple soil. Heavy metals were added to purple soil at 80 % field capacity and waterlogging regimes as nitrate salts of 500 mg kg^?1 of copper and lead, and 5 mg kg^?1 of cadmium. Metals in the incubated soil samples were fractionated termly from 1 to 35 days by the sequential extraction procedure. Under both treatments, the heavy metals spiked in the soil were transformed slowly from the exchangeable fractions into more stable fractions, whereas their residual fractions barely changed. The transformation process of exchangeable fraction in soil was estimated by Elovich kinetic equation for the above incubation periods, and the constant B in Elovich equation was applied to reflect the transformation rates of metal speciation. It was found that waterlogging incubation could immobilize heavy metals, resulting in decreased lability and availability of the metals in purple soil. The effect of waterlogging on the redistribution of heavy metals in purple soil might be mainly related to the changes of pH, potential redox and hydrous oxides in varying soil-water systems.     

Mercury speciation in soil in vicinity of coal beds using sequential extraction

The sequential extraction procedure was proposed and used to study of mercury speciation in real samples of soil. Samples of soil profiles together with bedrock and coal were taken from sampling spots in the vicinity of surficial coal beds in an area with natural coal outcrops. The proposed sequential extraction procedure involves the following fractionation: organic mercury compounds, extractable mercury in an acidic medium, mercury bound to humic substances, elemental Hg and mercury bound to complexes, HgS and residual mercury. The significant distribution of mercury between the two portions—mercury bound to humic substance and HgS was determined in the majority of samples. The mercury bound to humic substances created a significant contribution, especially to the top layer of soil. On the other hand, HgS was the dominant form in the samples from lower layers of the soil profile. The mercury content in the samples did not show a distinct mobility. The influence of soil parameters on the mercury distribution in the studied samples was investigated and discussed.     

冰透镜体形成过程中的土体破裂驱动力研究综述

随着寒区工程高等级化和变形限制要求的进一步严格化,冻胀问题已经成为寒区工程建设考虑的关键问题。造成冻胀的原因在于外界水分迁移冻结并形成冰透镜体,因此,深入认识冰透镜体形成问题对解决实际工程中的冻害问题具有重要的意义。由于冰透镜体的形成受控于土体破裂驱动力,因此,深入开展冻结过程中的土体破裂驱动力研究对阐明冰透镜体的生长机理以及解决工程冻胀问题具有重要的指导意义。通过对国内外在土体冻结过程中的土体破裂驱动力方面的研究进行综合评述,指出各研究结果之间的异同点。基于各研究结果的相同点,分析了目前土体破裂驱动力研究中存在的不足,并提出了今后研究发展的方向。     

Changes in microstructure and water retention property of a lime-treated saline soil during curing

Acta Geotechnica - This study aims at investigating the lime treatment effect on the changes in microstructure and water retention property of compacted saline soil, with consideration of the...     

Natural speciation of Mn, Ni, and Zn at the micrometer scale in a clayey paddy soil using X-ray fluorescence, absorption, and diffraction

The natural speciation of Mn (0.19 g/kg), Ni (46 mg/kg), and Zn (42 mg/kg) in the argillic horizon (120 cm depth, pH = 5.6) of an Ultisol from a paddy soil in northern Taiwan was investigated by advanced X-ray synchrotron techniques. Microchemical associations were imaged by synchrotron-based X-ray microfluorescence, host minerals were identified by standard and micrometer-resolved X-ray diffraction, and the local coordination environment of Mn, Ni, and Zn was probed using extended X-ray absorption fine structure (EXAFS) spectroscopy on a powdered sample and a soil thin section, and polarized EXAFS spectroscopy on a highly textured self-supporting clay film from the <2 μm fraction of the soil. Manganese was concentrated in Fe-Mn soft mottles (44.4 g/kg) as turbostratic hexagonal birnessite and lithiophorite having Mn³⁺/Mn⁴⁺ atomic ratios of ∼20% and 50%, respectively. Quantitative analysis of high-order scattering paths of the EXAFS spectrum for natural and synthetic lithiophorite revealed that Mn³⁺ and Mn⁴⁺ are ordered in the layer. A structural model is proposed, in which Mn⁴⁺ and Mn³⁺ are ordered similarly to Al and Li in the layer, with Mn³⁺ cations being surrounded by six Mn⁴⁺, and Mn⁴⁺ cations by three Mn³⁺ and three Mn⁴⁺. Similar cation ordering in the manganese and aluminum layers likely provides a more homogeneous local balance of the excess and deficit of charges in each layer and increases the stability of lithiophorite. Ni (r = 0.70 Å) substitutes for Mn (r(Mn⁴⁺) = 0.54 Å, r(Mn³⁺) = 0.65 Å) in the manganese layer in the natural lithiophorite. In contrast, Zn (r = 0.74 Å) fills vacant sites in the gibbsitic layer of natural lithiophorite, in a similar manner as lithium (r = 0.74 Å) in synthetic lithiophorite. The partitioning of Ni and Zn between the two layers is a result of the general preference of Ni, whose size is intermediate between those of Mn³⁺ and Li⁺, for slightly smaller sites. In contrast with nickel, which is detected only where there is lithiophorite, the Zn-lithiophorite association found in Fe-Mn mottles is not representative of the bulk soil. The combined use of X-ray diffraction, and powder and polarized EXAFS spectroscopy revealed that Zn is predominantly bound to hydroxy-Al interlayers sandwiched between 2:1 vermiculite layers in the fine soil matrix. The incorporation of Zn in the gibbsitic layer of both lithiophorite and vermiculite helps increase the stability of these minerals by providing positive charge to balance the negative charge from the 2:1 phyllosilicate layer and the layer of lithiophorite. This binding environment for zinc is probably the main mechanism by which zinc is sequestered in acidic to near-neutral aluminum-rich clayey soils.     

Phosphorus in foraminiferal sediments from North Atlantic Ridge cores and in pure limestones

Samples of foraminiferal ooze from two North Atlantic cores were cleaned and progressively dissolved. Most of the P, Fe, and Mn was released during the first of two reductive cleaning steps. Most of the remainder of these elements and most of the Ca were released during the final acid dissolution step. The P in these samples is present largely in Fe- and Mn-rich coatings, not as a constituent of the foraminiferal shells themselves. Our results are consistent with those of earlier studies.The concentration of P in carbonate oozes in which it is clearly associated with coatings is similar to that of modern calcareous sediments in general, and with that of reasonably pure limestones of all ages. Phosphorus is apparently associated with (Fe, Mn)-oxide coatings in many carbonate sediments. The rate of removal of P from the oceans as a constituent of such sediments depends on the rate of formation of (Fe, Mn) coatings, not on the rate of incorporation of P into calcium carbonate.     

Tertiary remagnetization of normal polarity in Mesozoic marly limestones from SE France

The results of our new paleomagnetic investigations on 21 sites in the Cévennes and Lure regions as well as previous studies demonstrate that all Mesozoic marly limestones of SE France exhibit similar paleomagnetic behavior with remagnetization disputed in age. The studied areas have the particularity to have been folded before (Late Eocene), the Alpine folding (Oligo–Miocene). Samples (201 marly limestones) dated from Lower Jurassic to Lower Cretaceous have been demagnetized by thermal treatment. They all present a well-defined component with a normal polarity which was mostly obtained between 200 and 350 °C. Numerous arguments lead from pretectonic to syntectonic widespread remagnetization related to orogenic fluid circulation affecting the whole basin. An Eocene age (between 35 and 40 Ma) is obtained for this remagnetization thanks both to the comparison of the average inclination of all regional paleomagnetic studies (+54.9°/−1.5°) with the expected paleomagnetic inclination and the syntectonic character of remagnetization.     

Changes in mobility and speciation of heavy metals in clay-amended incinerator fly ash

The generation of municipal solid waste incinerator fly ash (MSWIF) has been increasing significantly over the recent past, and its disposal is problematic and costly due to high concentration of leachable heavy metals present in the material. This study explored a potential stabilization of MSWIF by blending with a natural sorbent material with low permeability, clay, and assessed the potential release of heavy metals from the stabilized mixtures under various simulated subsurface environments. The leachability of heavy metals such as Pb, Cd, Cr, Zn and Cu in the MSWIF-clay mixtures cured for 1 to 360 days was investigated by performing leaching tests and sequential chemical extractions (SCE). Leaching tests were performed at acidic, neutral and alkaline pH values. The leaching test results suggested that the natural clay could turn the MSWIF into non-hazardous material. All the MSWIF-clay mixtures demonstrated leaching behavior different from that of the original MSWIF. SCE results revealed that the acidic and reducing conditions were the most unfavorable to the immobilization of the heavy metals in the stabilized MSWIF-clay matrix. Conversely, the oxidizing and alkaline conditions were not critical to the stabilized MSWIF-clay mixtures. Apparently, clay in the mixtures could function as an adsorptive micro-barrier to retain the heavy metals within the MSWIF-clay matrices.     

Predicting the activity of Cd and Zn in soil pore water from the radio-labile metal fraction

Cadmium and zinc were added at 3 and 300 mg kg⁻¹, respectively, to 23 soils and incubated at 16°C and 80% field capacity for 818 d. Following addition of metal, changes in the radio-labile concentrations of both elements were examined on seven separate sampling occasions over 818 d. At each sample time, soil pore water was extracted using Rhizon soil solution samplers, and concentrations of Cd, Zn, dissolved organic carbon, and major cations and anions were determined. The chemical speciation program WHAM 6 was used to determine free metal ion activity, (M²⁺). Similar measurements were made on a set of historically contaminated soils from old mining areas, sewage sludge disposal facilities, and industrial sources. The two data sets were combined to give a range of values for p(Cd²⁺) and p(Zn²⁺) that covered 5 and 4 log₁₀ units, respectively. A pH-dependent Freundlich model was used to predict Zn²⁺ and Cd²⁺ ion activity in soil pore water. Total and radio-labile metal ion concentration in the solid phase was assumed to be adsorbed on the “whole soil,” humus, or free iron oxides to provide alternative model formats. The most successful models assumed that solubility was controlled by adsorption on soil humus. Inclusion of ionic strength as a model variable provided small improvements in model fit. Considering competition with Ca²⁺ and between Zn²⁺ and Cd²⁺ produced no apparent improvement in model fit. Surprisingly, there was little difference between the use of total and labile adsorbed metal as a model determinant. However, this may have been due to a strong correlation between metal lability and pH in the data set used. Values of residual standard deviation for the parameterized models using labile metal adsorbed on humus were 0.26 and 0.28 for prediction of p(Cd²⁺) and p(Zn²⁺), respectively. Solubility control by pure Zn and Cd minerals was not indicated from saturation indices. However there may have been fixation of metals to non-radio-labile forms in CaCO₃ and Ca-phosphate compounds in the soils in the higher pH range. Independent validation of the Cd model was carried out using an unpublished data set that included measurements of isotopically exchangeable Cd. There was good agreement with the parameterized model.