Integrated stratigraphy and <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar chronology of the Early to Middle Miocene Upper Freshwater Molasse in eastern Bavaria (Germany)

A detailed integrated stratigraphic study was carried out on middle Miocene fluvial successions of the Upper Freshwater Molasse (OSM) from the North Alpine Foreland Basin, in eastern Bavaria, Germany. The biostratigraphic investigations yielded six new localities thereby refining the OSM biostratigraphy for units C to E (sensu; Heissig, Actes du Congres BiochroM’97. Mem Trav EPHE, Inst Montpellier 21, 1997) and further improving biostratigraphic correlations between the different sections throughout eastern Bavaria. Radioisotopic ages of 14.55 ± 0.19 and 14.88 ± 0.11 Ma have been obtained for glass shards from the main bentonite horizon and the Ries impactite: two important stratigraphic marker beds used for confirming our magnetostratigraphic calibration to the Astronomical Tuned Neogene Time Scale (ATNTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). Paleomagnetic analysis was performed using alternating field (AF) and thermal (TH) demagnetization methods. The AF method revealed both normal and reverse polarities but proofs to yield unreliable ChRM directions for the Puttenhausen section. Using the biostratigraphic information and radioisotopic ages, the magnetostratigraphic records of the different sections are tentatively correlated to the Astronomical Tuned Neogene Time Scale (ATNTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). This correlation implies that the main bentonite horizon coincides to chron C5ADn, which is corroborated by its radioisotopic age of 14.55 Ma, whereas the new fossil locality Furth 460, belonging to OSM unit E, probably correlates to chron C5Bn.1r. The latter correlation agrees well with the Swiss Molasse locality Frohberg. Correlations of the older sections are not straightforward. The Brock horizon, which comprises limestone ejecta from the Ries impact, possibly correlates to C5ADr (14.581–14.784 Ma), implying that, although within error, the radioisotopic age of 14.88 ± 0.11 Ma is somewhat too old. The fossil localities in Puttenhausen, belonging to the older part of OSM unit C, probably coincide with chron C5Cn.2n or older, which is older than the correlations established for the Swiss Molasse. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users.     

How to cut a sediment core for 210Pb geochronology

²¹⁰Pb geochronology is described mathematically, but how to cut a sediment core is not explicit. Thick sectioning may reduce dating reliability; but on the contrary, thin sectioning is time-consuming. Considering the counting error of excess ²¹⁰Pb, a new method was proposed for the determination of meaningful thickness for sectioning. The authors applied this method to a core from Tokyo Bay. To increase the thickness with depth, the treatment is helpful in reducing the sample number for measurement and improving the dating accuracy. In addition, the averaging effect involved in sectioning was discussed, and it was confirmed that the averaging effect in the new method on ²¹⁰Pb geochronology may generally be neglected.     

Detailed <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating of geologic events associated with the Mantos Blancos copper deposit,northern Chile

The ⁴⁰Ar/³⁹Ar geochronological method was applied to date magmatic and hydrothermal alteration events in the Mantos Blancos mining district in the Coastal Cordillera of northern Chile, allowing the distinction of two separate mineralization events. The Late Jurassic Mantos Blancos orebody, hosted in Jurassic volcanic rocks, is a magmatic-hydrothermal breccia-style Cu deposit. Two superimposed mineralization events have been recently proposed. The first event is accompanied by a phyllic hydrothermal alteration affecting a rhyolitic dome. The second mineralization event is related to the intrusion of bimodal stocks and sills inside the deposit. Because of the superposition of several magmatic and hydrothermal events, the obtained ⁴⁰Ar/³⁹Ar age data are complex; however, with a careful interpretation of the age spectra, it is possible to detect complex histories of successive emplacement, alteration, mineralization, and thermal resetting. The extrusion of Jurassic basic to intermediate volcanic rocks of the La Negra Formation is dated at 156.3 ± 1.4 Ma (2σ) using plagioclase from an andesitic lava flow. The first mineralization event and associated phyllic alteration affecting the rhyolitic dome occurred around 155–156 Ma. A younger bimodal intrusive event, supposed to be equivalent to the bimodal stock and sill system inside the deposit, is probably responsible for the second mineralization event dated at ca. 142 Ma. Other low-temperature alteration events have been dated on sericitized plagioclase at ca. 145–146, 125, and 101 Ma. This is the first time that two distinct mineralization events have been documented from radiometric data for a copper deposit in the metallogenic belt of the Coastal Cordillera of northern Chile. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Timing and duration of supergene mineralization at the Xinrong manganese deposit,western Guangdong Province,South China: cryptomelane <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar dating

Supergene Mn-oxide deposits are widely distributed in Guangxi, Guangdong, Yunnan, and Hunan Provinces, South China, accounting for 18% of the total Mn reserves in the country. Direct dating of supergene Mn enrichment, however, is lacking. In this paper, we present high-resolution ⁴⁰Ar/³⁹Ar ages of Mn oxides from the Xinrong Mn deposit, western Guangdong, to place numerical constraints on the timing and duration of supergene Mn enrichment. A total of ten cryptomelane samples, spanning a vertical extent of 67 m, were dated using the ⁴⁰Ar/³⁹Ar laser incremental heating technique, with seven samples yielding well-defined plateau or pseudo-plateau ages ranging from 23.48 ± 0.91 to 2.06 ± 0.05 Ma (2σ). One sample yields a staircase spectrum that does not reach a plateau; the spectrum, however, indicates the presence of two or more generations of Mn oxides in the sample, whose ages are best estimated at 22.34 ± 0.31 and 10.2 ± 0.86 Ma, respectively. The remaining two samples gave meaningless or uninterpretable results due to significant ³⁹Ar recoil and contamination by old phases. The ⁴⁰Ar/³⁹Ar data thus reveal a protracted history of weathering and supergene Mn enrichment that started at least in the end of the Oligocene or beginning of Miocene and extending into the latest Pliocene. Staircase-apparent age spectra, resulting from banded or botryoidal samples, yield an average growth rate of Mn oxides at 0.6–0.7 × 10⁻³ mm kyr⁻¹. The values indicate that a 1-mm grain of Mn oxides may host minerals precipitated during a time span of ca. 1.5 m.y., and accumulation of Mn oxides to form economic deposits under weathering environments may take millions of years. The distribution of weathering ages shows that the oldest Mn oxides occur on the top of the profile, whereas the youngest minerals are found at the bottom, suggesting downward propagation of weathering fronts. However, two samples located at the intermediate depths of the profile yield ages comparable with those occurring at the highest elevations. Such a complexity of age distribution is interpreted in terms of preferential penetration of Mn-rich weathering solutions along more permeable fault zones, or as a result of multi stages of dissolution and re-precipitation of Mn oxides. A synthesis of geochronological and geological data suggests that formation of the Xinrong deposit was a consequence of a combination of favorable lithological, climatic, and structural conditions. Because the climatic and structural conditions are similar among the provinces of South China during the Cenozoic, the geochronological results obtained at Xinrong may also have implications for the timing of supergene Mn enrichment throughout South China.     

40^Ar／39^Ar Ages of Auriferous Quartz Veins from the Fengyang and Zhangbaling Regions and Their Geological Significance

Geotectonically the Fengyang and Zhangbaling regions belong to the North China craton and the Dabie-Sulu oragene, respectively. Neo-Archean gneiss and amphibolite and metamor-phosed sea-facies sodic volcanic rocks axe the main outcrops in the two regions, respectively. The Zhangbaling terrane strike-skipped along the Tancheng-Lujiang fault zone in Mesozoic and Cenozo-ic eras and got close to the Fengyang terrane. Mesozoic Yanshanian intrusions occur broadly in thetwo regions. Gold-beating quartz veins occur in the metamorphic rocks in the Fengyang region and in the granodiorite and metamorphosed sea-facies sodic volcanic rocks in the Zhanghaling region.Generally, the formation of the auriferous quartz veins involved three stages. At the first stage,gold-poor sulfide quartz veins were formed; at the second stage gold-rich quartz sulfide veins wereformed; and at the third stage gold-poor barite and/or carbonate veins were formed. The 40^Ar/29^Ar step-heating plateau ages of the first-stage and the second-stage quartz aggregates from the Zhuding, Maoshan and Shangeheng gold deposits range between 116.1 0.6 Ma and 118.3 0.5 Ma and are pretty close to their least apparent ages and isoehronal ages, respectively. All plat-eau, least apparent and isoehronal ages range between 113.4 0.4 Ma and 118.3 0.5 Ma,which are considered as the formation age range of the quartz. It is reasonable and reliable to takethe 40^Ar/39^Ar age range of the quartz as the formation age range of gold-bearing quartz veins onthe basis of spatial relationship between gold-bearing quartz veins and their country rocks. Thegold deposits in the two regions were formed in Aptian, Cretaceous, when the Tancheng-Lujiangfault zone moved as a normal fault with slightly right-lateral strike-skip, was extensional and expe-rienced very strong magnmtic process. It is shown that the magnmtic hydrothermal fluid is a veryimportant part of the gold ore-forming hydrothermal fluid in the Fengyang and Zhanghaling re-gions. The formation of the gold ore deposits in the Fengyang and Zhanghaling regions had genetic relations with the extensional movement of the Tancheng-Lujiang fault zone and magmatic activities and took place under the extensional dynamic condition in Late Cretaceous. Therefore, the exten-sional movement of the Tancheng-Lujiang fault zone presented the energy and space for magmatic and gold ore-forming processes.     

<Superscript>40</Superscript>Ar-<Superscript>39</Superscript>Ar dating of lamprophyre dykes in the Baimazhai nickel deposit,Yunnan Province,China, and its geological significance

The Baimazhai nickel deposit, Yunnan Province, China, is located in the southern part of the Sanjiang （Tri-river） alkali-rich intrusive rock belt （Sanjiang ARIR）. In this paper was conducted ^40Ar-^39Ar dating of two phlogopites in lamprophyres which are, as dikes, widely distributed in the orefield, and two plateau ages were acquired, i.e., 32.46±0.62 Ma and 32.01±0.60 Ma, respectively （averaging 32.23±0.60 Ma）. The ages are obviously younger than those of the ore-hosted complex and mineralization of the Baimazhai nickel deposit. In combination with the characteristics, it is indicated that lamprophyres in the orefield and those in the Sanjiang ARIR are similar in tectonic setting, mineral assemblage and geochemistry. It is considered that lamprophyres in the orefield are the important component of the Sanjiang ARIR, and the lamprophyres and ore-hosted complex in the orefield represent the products of two times of different magmatic activity from different mantle sources. On the other hand, the age of lamprophyres in the orefield is older than that of the strike-slip shearing of the Ailaoshan-Honghe fault belt, suggesting that the strike-slip shearing of the Ailaoshan-Honghe fault belt is not the factor leading to magmatic activity of lamprophyres in the orefield, while it is more possible that magmatic activity of the Sanjiang ARIR promoted strike-slip shearing of the fault belt.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

Tectono-thermal evolution of the India-Asia collision zone based on<Superscript>40</Superscript>Ar-<Superscript>39</Superscript>Ar thermochronology in Ladakh,India

New⁴⁰Ar-³⁹Ar thermochronological results from the Ladakh region in the India-Asia collision zone provide a tectono-thermal evolutionary scenario. The characteristic granodiorite of the Ladakh batholith near Leh yielded a plateau age of 46.3 ± 0.6 Ma (2σ). Biotite from the same rock yielded a plateau age of 44.6 ± 0.3 Ma (2σ). The youngest phase of the Ladakh batholith, the leucogranite near Himya, yielded a cooling pattern with a plateau-like age of ∼ 36 Ma. The plateau age of muscovite from the same rock is 29.8 ±0.2 Ma (2σ). These ages indicate post-collision tectono-thermal activity, which may have been responsible for partial melting within the Ladakh batholith. Two basalt samples from Sumdo Nala have also recorded the post-collision tectono-thermal event, which lasted at least for 8 MY in the suture zone since the collision, whereas in the western part of the Indus Suture, pillow lava of Chiktan showed no effect of this event and yielded an age of emplacement of 128.2 ±2.6 Ma (2σ). The available data indicate that post-collision deformation led to the crustal thickening causing an increase in temperature, which may have caused partial melting at the base of the thickened crust. The high thermal regime propagated away from the suture with time.     

Rapid migration of heavy metals and <Superscript>137</Superscript>Cs in alluvial sediments,Upper Odra River valley,Poland

The studies presented explore post-depositional changes of zinc, cadmium, lead, manganese and ¹³⁷Cs distribution in alluvial sediments accumulated in the upper Odra River valley in southern Poland. The rate of these changes was estimated by comparing metal and ¹³⁷Cs distributions in four vertical alluvial profiles with a history of river pollution and sediment deposition. The untypical ¹³⁷Cs distribution with peaks in the surface 40–60 cm and lower down, even at a depth of 2.5 m in strata deposited before the beginning of nuclear tests in 1954, indicates rapid post-depositional migration of this isotope from the surface and its retention in lower, less permeable layers. Moreover, the highest concentrations of lead, zinc and cadmium were found at a depth of 4 m in sediments accumulated in the mid-nineteenth century in spite of the growth of industrialization and the pollution of the Odra River with heavy metals until the end of the twentieth century. The post-depositional changes in heavy metals and ¹³⁷Cs are rapid in comparison with the slow element migration usually observed in uninundated soils. This difference is explained by the frequent and easy infiltration of polluted river water into the gravelly and sandy sediments present in the profiles.     

Fine structure in photoluminescence spectrum of S<Subscript>2</Subscript><Superscript>−</Superscript> center in sodalite

The photoluminescence and excitation spectra of sodalites from Greenland, Canada and Xinjiang (China) are observed at 300 and 10 K in detail. The features of the emission and excitation spectra of the orange-yellow fluorescence of these sodalites are independent of the locality. The emission spectra at 300 and 10 K consist of a broad band with a series of peaks and a maximum peak at 648 and 645.9 nm, respectively. The excitation spectra obtained by monitoring the orange-yellow fluorescence at 300 and 10 K consist of a main band with a peak at 392 nm. The luminescence efficiency of the heat-treated sodalite from Xinjiang is about seven times as high as that of untreated natural sodalite. The emission spectrum of the S₂ ⁻ center in sodalite at 10 K consists of a band with a clearly resolved structure with a series of maxima spaced about 560 cm⁻¹ (20–25 nm) apart. Each narrow band at 10 K shows a fine structure consisting of a small peak due to the stretching vibration of the isotopic species of ³²S³⁴S⁻, a main peak due to that of the isotopic species of ³²S₂ ⁻ and five peaks due to phonon sidebands of the main peak.     

210Pb and 137Cs measurements in the Circum Bohai Sea coastal region: sedimentation rates and implications

The representative ²¹⁰Pb and ¹³⁷Cs age-depth profiles were selected from more than 100 sites in the Circum Bohai Sea (CBS) coastal region to examine the sedimentation rates and associated environmental changes. There are three unique ²¹⁰Pb_exc distribution patterns: 1) ideal-decaying type, representing relatively constant sediment supply and quieter environmental setting; 2) wiggling type, but with approximately equivalent amplitude, representing coarser sediments and associated stronger flow current environment; and 3) episodic-eventinfluencing type, each representing typhoon storm-influenced depositional environment. Our results also show that there is a lower sedimentation rate (ca. 0.1 cm/a) in the coastal lowlands, a higher sedimentation rate (ca. 0.5–3 cm/a) in the intertidal flat and an intermediate rate of ca. 0.58 cm/a in the subtidal zone near the Huanghua Harbor. The interbedded silt layer occurring in the core sediment reveals lower ²¹⁰Pb activities, indicating a discontinuous sedimentation mostly due to typhoon events which dwarfs against ²¹⁰Pb and ¹³⁷Cs applicability. Overall, the ²¹⁰Pb and ¹³⁷Cs measurements of the present study provide physical insight into the evaluation of the coastal-marine ecological environment and associated management.     

<Superscript>226</Superscript>Ra, <Superscript>232</Superscript>Th and <Superscript>40</Superscript>K activities in soils of Cuihua Mountain National Geological Park,China

Gamma activity from the naturally occurring radionuclides namely, ²²⁶Ra, ²³²Th, the primordial radionuclide ⁴⁰K was measured in the soil of Cuihua Mountain National Geological Park, China using γ-ray spectrometry technique. The mean activity of ²²⁶Ra, ²³²Th and ⁴⁰K were found to be 27.2 ± 6.5, 43.9 ± 6.2 and 653.1 ± 127.6 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil. The radium equivalent activity, the air absorbed dose rate, the annual effective dose rate, and the external hazard index were evaluated and compared with the internationally approved values. All the soil samples have Ra_eq lower than the limit of 370 Bq kg⁻¹ and H _ex less than unity. The overall mean outdoor terrestrial gamma dose rate is 66.3 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.081 mSv.     

Thermal decomposition of NH<Subscript>4</Subscript><Superscript>+</Superscript>-vermiculite from Santa Olalla (Huelva,Spain) and its relation to the metal ion distribution in the octahedral sheet

The investigation of the NH₃ loss in the NH₄⁺-vermiculite (Santa Olalla) by thermogravimetry, evolved gas analysis, chemical analysis, X-ray diffraction and IR spectroscopy is reported here. The mass loss during heating takes place in two steps at about 650 and 825 °C. Additionally, the releases of H₂O and NH₃ occurs simultaneously. The experimental results indicate that the protons remaining in the interlayer space after NH₃ removal trigger the H₂O release. X-ray diffraction shows that during the decomposition of NH₄⁺-vermiculite there are two domains with different interlayer spaces at ~9 and ~10 Å. As the decomposition proceeds, the intensity of the 9 Å peak increases at the expense of the second one. The change in the IR-stretching modes of the structural OH groups during heating indicates that the OH groups surrounded by 3Mg²⁺ or 2Mg²⁺Fe²⁺ are released at lower temperatures than those with environments like 2Mg²⁺Fe³⁺, 2Mg²⁺Al³⁺ or more complex ones.     

High-pressure electronic absorption spectroscopy of natural and synthetic Cr<Superscript>3+</Superscript>-bearing clinopyroxenes

Comparison of polarized optical absorption spectra of natural Ca-rich diopsides and synthetic NaCrSi2O6 and LiCrSi2O6 clinopyroxenes, evidences as vivid similarities, as noticeable differences. The similarities reflect the fact that in all cases Cr3+ enters the small octahedral M1-site of the clinopyroxene structure. The differences are due to some iron content in the natural samples causing broad intense near infrared bands of electronic spin-allowed dd transitions of Fe2+(M1, M2) and intervalence Fe2+/Fe3+ charge-transfer transition, and by different symmetry and different local crystal fields strength of Cr3+ in the crystal structures. The positions of the spin-allowed bands of Cr3+, especially of the low energy one caused by the electronic 4 A 2g → 2 T 1g transition, are found to be in accordance with mean M1–O distances. The local relaxation parameter ε calculated for limCr 3+ → 0 from the spectra and interatomic á Cr - O ñ \left\langle {Cr - O} \right\rangle and á Mg - O ñ \left\langle {Mg - O} \right\rangle distances yields a very high value, 0.96, indicating that in the clinopyroxene structure the local lattice relaxation around the “guest” ion, Cr3+, deviates greatly from the “diffraction” value, ε = 0, than in any other known Cr3+-bearing systems studied so far. Under pressure the spin-allowed bands of Cr3+ shift to higher energies and decrease in intensity quite in accordance with the crystal field theoretical expectations, while the spin-forbidden absorption lines remain practically unshifted, but also undergo a strong weakening. There is no evident dependence of the Racah parameter B of Cr3+ reflecting the covalence of the oxygen-chromium bond under pressure: within the uncertainty of determination it may be regarded as practically constant. The values of CrO6 octahedral modulus, k\textpoly\textloc k_{\text{poly}}^{\text{loc}} , derived from high-pressure spectra of natural chromium diopside and synthetic NaCrSi2O6 kosmochlor are very close, ~203 and ~196 GPa, respectively, being, however, nearly twice higher than that of MgO6 octahedron in diopside, 105(4) GPa, obtained by Thompson and Downs (2008). Such a strong stiffening of the structural octahedron, i.e. twice higher value of k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} comparing with that of k\textMg2 + \textloc k_{{{\text{Mg}}^{2 + } }}^{\text{loc}} , may be caused by simultaneous substitution of Ca2+ by larger Na+ in the neighboring M2 sites at so-called jadeite-coupled substitution Mg2+ + Ca2+ → Cr3+ + Na+. It is also remarkable that the values of CrO6 octahedral modulus of NaCrSi2O6 kosmochlor obtained here are nearly twice larger than that of 90(16) GPa, evaluated by high-pressure X-ray structural refinement by Origlieri et al. (2003). Taking into account that the overall compressibility of the clinopyroxene structure should mainly be due to the compressibility of M1- and M2-sites, our k\textCr3 + \textloc k_{{{\text{Cr}}^{3 + } }}^{\text{loc}} -value, ~196 GPa, looks much more consistent with the bulk modulus value, 134(1) GPa.     

Application of the <Superscript>137</Superscript>Cs tracer technique to study soil erosion of alpine meadows in the headwater region of the Yellow River

The ¹³⁷Cs tracer technique was used to study soil erosion of alpine meadow grassland in two small river basins in the headwater region of the Yellow River. The results show that the levels of ¹³⁷Cs in soil samples from this alpine meadow vegetation zone exhibit an exponential distribution, generally within a depth of approximately 20 cm. Due to strong winds, freeze-thaw cycles and water, soil erosion was found to be stronger on the upper slope than on the lower slope, and except for the slope crest, the intensity of soil erosion at other sites was as follows: upslope < midslope < downslope. There was a significant negative correlation between the intensity of soil erosion and the extent of alpine meadow vegetation cover (P < 0.01). The mean soil erosion modulus exhibited a linear reduction trend with an increase in vegetation cover, and the correlation coefficient R ² was ≥ 0.997. The higher the degradation degree of the alpine meadow grassland, the greater is the soil erosion. The mean erosion modulus in the severely degraded meadow zone was 2.23 times greater than the one in the slightly degraded zone, and the maximum erosion modulus reached 2.96 × 10⁶ kg/km²/a.     

Structural localization of Al<Superscript>3+</Superscript> ions in aluminosilicates: application of heteronuclear chemical shift correlation to 2:1 phyllosilicates

The main objective of this paper is to apply an NMR-based methodology to clay minerals that provides resolution enhancement in ²⁷Al NMR spectra, permitting the differentiation of aluminum ions with one same coordination number, but with different chemical environments. For this purpose, we have performed two-dimensional ¹H²⁷Al cross-polarization experiments, which facilitate the identification of the different aluminum crystallographic sites by means of the nature of the proton polarization source. For the development of this methodology, we have carried out a systematic study of a set of well-characterized 2:1 phyllosilicates with aluminum in different crystallographic sites. The structural locations of aluminum in the selected layered silicates have been established unequivocally. Once the correlation between all different aluminum and proton sites in smectite was well established, an unknown material was examined, the utility of this methodology being illustrated. This methodology can be applied to a great variety of materials, such as zeolites, ALPOs and mesoporous aluminosilicates, in which a precise determination of the aluminum location is demanded.     

Disproportionation of Fe<Superscript>2+</Superscript> in Al-free silicate perovskite in the laser heated diamond anvil cell as recorded by electron probe microanalysis of oxygen

Experimental evidence is reported for Fe²⁺ disproportionation in Al-free perovskite (Pv), when submitted to large temperature gradients (i.e., under off-equilibrium conditions) in a laser heated diamond anvil cell (LHDAC). To enable this effect, the experimental procedure was designed to produce large radial and axial temperature gradients. In the Pv and ferropericlase (Fp) assemblage synthesized after dissociation of natural olivine, the three chemical states of iron (i.e., Fe⁰, Fe²⁺ and Fe³⁺) could be evidenced by electron probe microanalysis (EPMA), through variations of oxygen contents attached to the Fe cations. Despite inherent difficulties for determination of O-contents and Fe³⁺/ΣFe ratios using EPMA, we recorded significant changes in iron oxidation state across the laser-heated strip. These changes are correlated with variations in composition for the major elements (Fe, Mg, and Si), which evidences that the Pv/Fp assemblage experienced large segregation under the strong temperature gradients. Grains of metallic iron were detected in parts of the laser-heated strip coexisting with a Pv phase with Fe/(Mg + Fe) = 6 at% and most of its iron as Fe³⁺. This Fe²⁺-disproportionation reaction involves insertion of Fe³⁺-defects in the Pv lattice. This Fe³⁺-bearing Pv phase is presumably unstable and decomposes into a mineral assemblage including magnesioferrite, which is detected at the border of the laser-heated strip.     

Effect of multifactors interaction on competitive adsorption of Zn<Superscript>2+</Superscript> and Cd<Superscript>2+</Superscript> by response surface methodology

The problem associated with multi-metals contaminated soils has generated increasingly more attention. Thus, it is necessary within the field to study the mutual influence of environmental factors on competitive adsorption. The majority of studies carried out to date have concentrated on the variation of adsorption capacity or the removal efficiency, with only a single factor changed (including pH, ionic strength, and metal concentration). However, the interaction effect among various environmental factors was ignored in these studies. The purpose of this study was mainly aimed toward the investigation of the interaction of two influential factors, as well as the influential degree of each factor (such as the initial pH, ionic strength, initial metal concentration, and the competitive metal concentration) on competitive adsorption using the response surface method. These results demonstrated that the influential degree of each factor studied on the competitive adsorption of Zn²⁺ and Cd²⁺ followed the trend of having the initial concentration of the target metal?>?initial pH?>?concentration of competitive metal?>?ionic strength. When the metal concentration was held constant, we found that the competitive adsorption of Zn²⁺ initially increased, followed by a decrease with increasing initial pH. However, this was found to change minimally with increasing ionic strength. When the initial pH or ionic strength was held constant, the competitive ability was observed to increase with increasing Zn²⁺ concentration. However, with increasing Zn²⁺ or Cd²⁺ concentrations, the variation degree of the competitive adsorption was found to become smaller. These results provide novel information toward a better understanding of the effect of multifactors on the competitive adsorption of Zn²⁺ and Cd²⁺.     

Differential behavior of components of the <Superscript>238</Superscript>U-<Superscript>206</Superscript>Pb and <Superscript>235</Superscript>U-<Superscript>207</Superscript>Pb isotopic systems in polymineralic U ores

U-Pb systems were examined in samples (ranging from 4 to 10 cm³ in volume) of ore material taken from along a 3.5-m profile across a zone of U mineralization exposed in an underground mine at the Strel’tsovskoe U deposit in eastern Transbaikalia. The behaviors of two isotopic U-Pb systems (²³⁸U-²⁰⁶Pb and ²³⁵U-²⁰⁷Pb) are principally different in all samples from our profile. While the individual samples are characterized by a vast scatter of their T(²⁰⁶Pb/²³⁸U) age values (from 112 to 717 Ma), the corresponding T(²⁰⁷Pb/²³⁵U) values vary much less significantly (from 127 to 142 Ma) and are generally close to the true age of the U mineralization. The main reason for the distortion of the U-Pb system is the long-lasting (for tens of million years) migration of intermediate decay products in the ²³⁸U-²⁰⁶Pb(RD²³⁸U) in the samples. This process resulted in the loss of RD²³⁸U from domains with high U concentrations and the subsequent accommodation of RD²³⁸U at sites with low U concentrations. The long-term effect of these opposite processes resulted in a deficit or excess of ²⁰⁶Pb as the final product of ²³⁸U decay. The loss or migration of RD²³⁸U are explained by the occurrence of pitchblende in association with U oxides that have higher Si and OH concentrations than those in the pitchblende and a higher ⁺⁶U/⁺⁴U ratio. The finely dispersed character of the mineralization and the loose or metamict texture of the material are the principal prerequisites for RD²³⁸U loss and an excess of ²⁰⁶Pb in adjacent domains with low U concentrations. Domains with low U contents in the zone with U mineralization serve as geochemical barriers (because of sulfides contained in them) at which long-lived RD²³⁸U(²²⁶Ra, ²¹⁰Po, ²¹⁰Bi, and ²¹⁰Pb) were accommodated and subsequently caused an excess of ²⁰⁶Pb. The ²³⁵U-²⁰⁷Pb system remained closed because of the much briefer lifetime of the ²³⁵U decay products. This may account for the significant discrepancies between the T(²⁰⁶Pb/²³⁸U) and T(²⁰⁷Pb/²³⁵U) age values. RD²³⁸U was most probably lost via the migration of radioisotopes at the middle part and end of the ²³⁸U family (starting with ²²⁶Ra). The heavy Th, Pa, and U radioisotopes (²³⁴Th, ²³⁴Pa, ²³⁴U, and ²³⁰Th) that occur closer to the beginning of ²³⁸U decay, before ²²⁶Ra, only relatively insignificantly participated in the process. Our results show that the loss and migration of RD²³⁸U are, under certain conditions, the main (or even the only) process responsible for the distortion of the U-Pb system.     

Extreme <Superscript>15</Superscript>N Depletion in Seagrasses

Seagrass beds form an important part of the coastal ecosystem in many parts of the world but are very sensitive to anthropogenic nutrient increases. In the last decades, stable isotopes have been used as tracers of anthropogenic nutrient sources and to distinguish these impacts from natural environmental change, as well as in the identification of food sources in isotopic food web reconstruction. Thus, it is important to establish the extent of natural variations on the stable isotope composition of seagrass, validating their ability to act as both tracers of nutrients and food sources. Around the world, depending on the seagrass species and ecosystem, values of seagrass N normally vary from 0 to 8?‰ δ¹⁵N. In this study, highly unusual seagrass N isotope values were observed on the east coast of Qatar, with significant spatial variation over a scale of a few metres, and with δ¹⁵N values ranging from +2.95 to ?12.39?‰ within a single bay during March 2012. This pattern of variation was consistent over a period of a year although there was a seasonal effect on the seagrass δ¹⁵N values. Seagrass, water column and sediment nutrient profiles were not correlated with seagrass δ¹⁵N values and neither were longer-term indicators of nutrient limitation such as seagrass biomass and height. Sediment δ¹⁵N values were correlated with Halodule uninervis δ¹⁵N values and this, together with the small spatial scale of variation, suggest that localised sediment processes may be responsible for the extreme isotopic values. Consistent differences in sediment to plant ¹⁵N discrimination between seagrass species also suggest that species-specific nutrient uptake mechanisms contribute to the observed δ¹⁵N values. This study reports some of the most extreme, negative δ¹⁵N values ever noted for seagrass (as low as ?12.4?‰) and some of the most highly spatially variable (values varied over 15.4?‰ in a relatively small area of only 655 ha). These results are widely relevant, as they demonstrate the need for adequate spatial and temporal sampling when working with N stable isotopes to identify food sources in food web studies or as tracers of anthropogenic nutrients.