Heavy metal geochemistry and mineral magnetic characterization of urban soil in Xuzhou,China

In the present study, the enrichment, availability, speciation of heavy metals including Pb, Zn, Cu, Cd, Ni and Sb and magnetic properties of urban soils of Xuzhou (China) were investigated. All analyzed metals showed elevated concentrations compared to local background concentrations. Cadmium and Sb are the metals most enriched in the analyzed area, presenting enrichment factor, on average, of 16.5 and 8.3, respectively. By self-organizing map in combination with diagnostic ratios, the source of Sb, Cd, Cu and Pb in soils might be mainly from traffic emissions. Sequential extractions indicate that metals were primarily associated with the reducible fraction with the exception of Ni. The order of extraction efficiency of various metals was SBET (simplified physiologically based extraction test) > DTPA (diethylenetriaminepentaacetic acid) > CaCl₂. The magnetic results show that soil samples were dominated by a strong ferrimagnetic mineral component with multi- and single-domain magnetic grains. Only CaCl₂ extractable Sb was found to show significant correlations with χlf and SIRM. For both DTPA and SBET extractions, all metals investigated showed significant associations with both χlf and SIRM (saturation isothermal remanent magnetization).     

Heavy metals in Xuzhou urban roadside topsoils (China): magnetic characterization and enrichment mechanism

Heavy metal contamination is prevalent in urban areas where soil represents a significant sink. Urban topsoil samples were collected and metal concentrations including Pb, Zn, Cu, Cd, Ni and Co were measured by inductively coupled plasma mass spectrometry. All analyzed metals showed elevated concentrations compared to local background concentrations with the exception of Co. Cadmium was the metal most enriched in the analyzed area, presenting enrichment factor, on average, of 16.5. Mineral magnetic concentration parameters (χlf and SIRM) exhibited significant relationships with Pb, Zn, Cu and Cd, respectively. Zinc, Co and Ni exhibited a substantial build-up in the finest particles (<28 μm). Enrichment was positively correlated with carbonate complexation constants (but not bulk solubility products) and suggests that the dominant mechanism controlling metal enrichment in these samples is a precipitation of carbonate surfaces that subsequently adsorb metals.     

中亚地区现代表土磁学特征及其古环境意义*

在中国西北地区主要沙漠、绿洲和戈壁及蒙古国南部戈壁等亚洲中部粉尘源区采集了表土(包括沙漠和土壤)样品,系统分析了样品的磁学性质(包括磁化率、无磁滞磁化率、等温剩磁、磁滞回线和热磁曲线)。结果表明,中亚地区表土样品中主要磁性矿物是铁磁矿,含有赤铁矿和磁赤铁矿,并伴有少量顺磁性矿物;磁性矿物粒度主要是准单畴(PSD)和多畴(MD),超顺磁性颗粒含量较低,接近于中国西部黄土地层含量。中亚地区表土磁性矿物含量总体都较低,磁性矿物含量在空间上与降雨量成正比。研究结果指示西部地区(准噶尔盆地和南部塔里木盆地)表土样品较北部地区(鄂尔多斯高原、阿拉善高原以及蒙古高原)表土样品,其粗颗粒磁性矿物含量高,而细颗粒磁性矿物含量低。本研究结果为黄土地层古土壤磁性增强源自成土过程提供了最直接的证据。     

Magnetic mineralogical variability along Deccan trap basalt borehole (KBH07), Koyna deep continental drilling program,western Maharashtra,India

A 1248 m long core (KBH 07, 17°18′07″ N; 73°47′28.2″E, 960m above msl) drilled up to basement in the Deccan traps from Koyna region was sampled at ～10m interval for magnetic mineralogical studies.Analysis of routine rock magnetic parameters (mass specific magnetic susceptibility: χ_lf, frequency dependence of susceptibility: χ_fd, susceptibility of anhysteretic remanance: χ_ARM, saturation isothermal remanance: SIRM, remanance coercivty: B_(0)CR, Soft_IRM, Hard_IRM, S-Ratio, SIRM/χ_lf, χ_ARM/χ_lf) and density (σ, gm/cc) depicted significant higher order temporal variation. The χ_lf varies between 13 and 309 x 10-8m3/kg and is independent of density variation. The χ_ARM, B_(0)CR and S-Ratios indicate majority of SD-PSD ferrimagnets with episodes of MD ferrimagnetic concentration and few hard coercivity components. The giant plagioclase lath bearing (GPB) horizons show highest variability of ferrimagnetic concentration marked by anomalous peaks. Overall the variability of rock magnetic parameters independent of lava flow units suggest that the changeover in magnetic mineral concentration, composition and domain size occur at major episodes in magma composition (e.g., primary source, crustal contamination and fractional crystallization). The studied parameters are therefore examined to mark intervals of (i) magma compositional changes, (ii) zones of oxidative conditions and (iii) rapid/slow cooling intervals demanding detailed petrologic studies. We identified one I order trend, four II order cycles and eight III order cycles for the purpose of correlation. Notable peak in χ_lf at 650–700m, the changeover in rock magnetic parameters at ～930 m and ～280 m can facilitate marker intervals while several higher order variations can be adopted for high resolution correlation to other boreholes in the region. The complex variation in rock magnetic parameters independent of flow units reflect temporal magnitudes of compositional variability, cooling and emplacement history that needs detailed petro-mineralogical attempts; and the present data is useful for high order inter-core correlations under the deep drilling program.     

Study of pocyclic aromatic hydrocarbons at a pressure of 6–9 GPa with X-ray diffraction and synchrotron radiation

This work is one of the stages of study of the deep C-O-H fluid and investigates the behavior of polycyclic aromatic hydrocarbons (PAHs) under conditions of the Earth’s mantle. The composition of the C-O-H fluid in the upper mantle is estimated as a mixture of H₂O and CH₄ with a minor amount of H₂ and heavier hydrocarbons. Some theoretical calculations show that the stability of heavy hydrocarbons (alkanes, alkenes, and PAHs) increases with an increase in temperature. This paper presents the results of an XRD study of PAHs stability in multianvil presses on a Spring-8 accelerator (Japan). The primary compositions were chosen according to the abundance of PAHs in nature. In situ diffraction spectrums were recorded to determine the PAHs stability field. It was established that the PAHs become unstable at a pressure of 6–9 GPa and a temperature of 873–1073 K.     

High hafnium members of the zircon-hafnon series from the granite pegmatites of Zambézia,Mozambique

A mineralogical nomenclature applicable to the natural binary isomorphous series ZrSiO₄-HfSiO₄ is proposed. It is suggested that (Hf, Zr)SiO₄ with more than 90 mol.-% hafnium component be called hafnon. Zoned crystals ranging in composition from hafnian zircon to hafnon were found in the heavy mineral concentrates from the tantalum pegmatites of the Morrua area, Conco, Moneia and Muiane mines in the district of Zambézia, Mozambique. The density (Berman balance), Hf/Zr ratio (XRF analysis) and unit-cell parameters (X-ray powder pattern) of the samples are determined and discussed. Two microprobe analyses of hafnon from Muiane are presented.     

Electrical conductivity measurements on olivines and pyroxenes under defined thermodynamic activities as a function of temperature and pressure

Electrical conductivities of Ni₂SiO₄, Fe₂SiO₄, and MgSiO₃ were measured on synthetic powders in the temperature range 340° to 1,100° C and at pressures up to 20 kbars. For ternary compounds such as olivines and pyroxenes the control of two further variables, like the chemical activities of two components are needed, besides temperature and pressure. The activities of the corresponding binary oxides were controlled by equilibrating the samples with their neighbour-phases. Control of the oxygen partial pressure was achieved by buffer techniques. From the slopes of the lg σ vs. 1/T lines the activation energies were calculated for 10 kbar: 0.56 eV and 2.7 eV for Ni₂SiO₄ in equilibrium with SiO₂ and Ni/NiO-buffer for the temperature range 500°–800°C and 800°–1,000°C resp. 0.52 eV for Fe₂SiO₄ in equilibrium with SiO₂ and metallic iron, and 0.38 eV in equilibrium with SiO₂ and magnetite; 1.11 eV for MgSiO₃ in equilibrium with SiO₂, and 1.25 eV in equilibrium with Mg₂SiO₄.     

Decomposition of fayalite (Fe2SiO4) in an oxygen potential gradient at 1,418 K

The decomposition of fayalite (Fe₂SiO₄) in oxygen potential gradients is studied at T=1,418 K. The compound will be decomposed into its component oxides wüstite, Fe_1?δO, and silica, SiO₂, by the simultaneous action of two different oxygen partial pressures, exceeding a critical ratio, despite the fact that fayalite is stable at both the lower and the higher oxygen potential. A quantitative analysis of the decomposition process caused by defect fluxes within the bulk Fe₂SiO₄ is given.     

The problem of rock assimilation by Somma-Vesuvius magma

New chemical and modal analyses are presented of magmatic rocks and pyroxenes nodules from the Somma-Vesuvius volcano and of trachytes from the surrounding area. Geochemical evidence is employed in checking the generally accepted suggestion that magma composition develops from that of trachyte into phonolitic tephrite and finally into tephritic leucitite (vesuvite) by assimilation of dolomite. At the Somma stage of the volcano, phonolitic tephrites (tephritic phonolites) alone have been produced. Vesuvius lavas (tephritic leucitites) are comparatively high in K₂O, CaO, F, Cl, Mn, Cu, Sr and Ba and low in SiO₂ and Nb. The formation of vesuvites by assimilation of dolomitic sedimentary rocks, combined with gravity-separation of early-formed pyroxenes from a trachytic or tephritic magma, is improbable as shown by chemical balances between the respective igneous and sedimentary rocks.     

Climatic periodicities recorded in lake sediment magnetic susceptibility data: Further evidence for solar forcing on Indian summer monsoon

The Indian summer monsoon exhibits considerable spatio-temporal variability.It is therefore important to understand its dynamics and the inherent periodicities.In this study,we have performed spectral and wavelet analyses of magnetic susceptibility data for sediments from Thimmannanayakanakere(TK)-a small lake in southern India.The main objective of this investigation is to identify and explain the possible origin of the prominent periodicities present in the magnetic susceptibility data.Significant periodicities in the TK χ_(lf)data are centered at 906,232,147,128,96,61,54 and 44 years,which might have a solar origin.The wavelet power spectrum of the raw and detrended χ_(lf)data confirms the findings of spectral analysis and also provides temporal variations of the significant cyclicities during the past3700 cal.years B.P.Positive correlation is documented between sunspot activity and TK xif data;crossspectral analysis of the reconstructed sunspot data and TK xif data suggest that there is a strong coherence between the two datasets as significant periodicities are documented in both.There is a good match between the TK xif and the reconstructed total solar irradiance data for the past 1200 years.However,an out-of-phase relationship is documented at certain time-intervals,which may be attributed to uncertainties in the age-depth model.The results obtained from this study show that solar variations are the main controlling factor of the southwest monsoon and,like other archives from different regions in India,the TK lake sediments have also recorded these solar signatures.     

Synthetic Mn3+-kyanite and viridine, (Al2-xMn x 3+ ) SiO5, in the system Al2O3-MnO-MnO2-SiO2

Experiments on the join Al₂SiO₅-“Mn₂SiO₅” of the system Al₂O₃-SiO₂-MnO-MnO₂ in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn₂O₃, and high purity SiO₂ as starting materials and using /_O2-buffer techniques to preserve the Mn³⁺ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al_1.88Mn _0.12 ³⁺ )SiO₅ and, thus, equals approximately that on the join Al₂SiO₅-“Fe₂SiO₅” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn³⁺ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a _o, b _o, c _o, and V _o to increase by 0.015, 0.009, 0.014 Å, and 1.6 ų, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn³⁺-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusite_ss (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al_1.86Mn _0.14 ³⁺ )SiO₅-(Al_1.56Mn _0,44 ³⁺ )SiO₅. Thus, Al→Mn³⁺ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn³⁺ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a _o, b _o, c _o, and V _o to increase by 0.118, 0.029, 0.047 Å and 9.4 ų, resp. At “Mn₂SiO₅”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn₂SiO₅”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn²⁺Mn³⁺[O₈/Si0₄]), pyrolusite and SiO₂ were found to coexist with the Mn³⁺-saturated ky _ss or and _ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn³⁺). Pure synthetic braunites had the lattice constants a _o 9.425, c _o, 18.700 Å, V _o 1661.1 ų (ideal compn.) and a _o 9.374, c _o 18.593 ų, V _o 1633.6 ų (1 Al for 1 Mn³⁺). Stable coexistence of the Mn²⁺-bearing phase braunite with the Mn⁴⁺-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO₂-SiO₂.     

A thermochemical data base for phase equilibria in the system Fe-Mg-Si-O at high pressure and temperature

A thermochemical data base for phases in the system Fe-Mg-Si-O at high pressures up to 300 kbar is established by supplementing the available calorimetric data with data calculated from experimental high pressure synthesis studies. Phases included in the data base are the SiO₂ polymorphs, rock salt solid solutions (Fe-Mg-O), Fe₂O₃, Fe₃O₄, (Mg, Fe)₂SiO₄ olivine, spinel, modified spinel and (Mg, Fe)SiO₃ perovskite and pyroxene. Phases not included are the MgSiO₃-ilmenite and -garnet. Fe-Mg solution properties of olivine, spinel, perovskite and wustite (rock salt) are estimated. The wüstite solid solution has been modeled as a nonideal solution of three end members; FeO, FeO_1.5 and MgO. The new data base is made consistent with most of the available information on high pressure phase studies. The data base is useful in generating phase diagrams of various different compositions for the purpose of planning new experiments and analysing existing phase synthesis data.     

The lattice energy of forsterite. Charge distribution and formation enthalpy of the SiO 4 4− ion

In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z _o, the hardness parameter ρ and the repulsive radii r _Mg and r _Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO ₄ ^4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z _o=?1.34, ρ=0.27 Å, r _Mg=0.72 Å, r _Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol^?1 were obtained, respectively, for the lattice energy E _Land for its ionic component E _L ⁰ ,which accounts for interactions between Mg²⁺ and SiO ₄ ^4? ions only. The charge distribution calculated on the SiO ₄ ^4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO ₄ ^4? were estimated to be: ΔH _f(SiO ₄ ^4? )=2117.6 and E(SiO ₄ ^4? )=708.6 kJ mol^?1, respectively.     

Boninite primary magmas: Evidence from the Cape Vogel Peninsula,PNG

Boninites from Cape Vogel, PNG, are dominantly pyroxene-glass rocks, but many contain olivine, sometimes as refractory as Fo₉₄. We derive a parental magma for this suite (in equilibrium with Fo₉₄) which contains 20 wt.% MgO and is quartz-normative. This liquid is hydrous, and from petrographie evidence and whole rock H₂O⁺ values, we estimate it to contain 2–3 wt.% H₂O. These data suggest olivine fractionation and primary magmatic water are important in boninite genesis, but both are often obscured by later alteration. The derived parental magma has probably formed at 1,250–1,300° C and low pressures (< ?10kB) and is similar to those which gave rise to olivine-clinoenstatite phyric boninites from New Caledonia and from Howqua, Australia, and possibly to a proposed parental magma for the Bushveld Complex.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

Raman scattering and lattice vibrations of Ni2SiO4 spinel at elevated temperature

Raman spectra of Ni₂SiO₄ spinel (O _h ⁷ Z=8) have been measured in the temperature range from 20 to 600 °C and the Raman active vibrations (A _1g +E _g +3F _2g ) have been assigned. A calculation of the optically active lattice vibrations of this spinel has been made, assuming a potential function which combines general valence and short range force constants. The values of the force constants at 20 and 500 °C have been calculated from the vibrational frequencies of the observed Raman spectra and infrared (IR) spectral data. The Ni spinel at 20 °C has a prominently small Si-O bond stretching force constant of K(SiO)=2.356 ～ 2.680 md/Å and a large Ni-O bond stretching constant of K(NiO)=0.843 ～ 1.062 md/Å and these force constants at 500 °C decrease to K(SiO)=2.327 ～ 2.494 md/Å and K(NiO)=0.861 ～ 0.990 md/Å. The Si-O bond is noticeably weakened at high temperatures, despite the small thermal expantion from 1.657 Å (20 °C) to 1.660 Å (500 °C). These changes of the interatomic force constants of the spinel at high temperatures are in accord with the thermal structure changes observed by X-ray diffraction study. The weakened Si-O bond is consistent with the fact that Si atoms in the spinel lattice can diffuse at significant rates at elevated temperature.     

Zircon and sphene as fission track geochronometer and geothermometer: A reappraisal

The data published earlier on zircon and sphene fission track ages and annealing are discussed in the light of different etching conditions used for age determination and annealing experiments in order to explain the age discordances of some zircon and sphene pairs, as well as numerous closing temperatures obtained for individual minerals. Using the new set of simple etching conditions, zircon (KOH melt) and sphene (HF+HCl), the annealing experiments indicate that tracks in sphene are annealed more easily than in zircon. The closing temperature of zircon and sphene have been calculated at 300° and 250° C respectively. The study reveals that both the fission track age and the closing temperature of a mineral can vary considerably if different etchants are used. For different etching conditions the closing temperatures (T) of sphene have the following order: ^T NaOH> ^T HF+HCl+HNO₃+H₂O> ^THF+HCl>^THCl. An alternative method can be used to obtain thermal histories of rocks by selectively applying various etchants on the same mineral.     

Thermodynamic properties of the forsterite-fayalite (Mg2SiO4-Fe2SiO4) solid solution. determination of heat of formation

A high temperature calorimetric solution method involving the use of a sodium and lithium metaborate (NaBO₂+LiBO₂) molten bath at 1,180 K, has been developed in order to measure the enthalpy of formation of the forsterite-fayalite (Mg₂SiO₄-Fe₂SiO₄) system. The samples used for these measurements have been obtained by synthesis. They have been carefully controlled by chemical and X-ray analysis and Mössbauer spectroscopy. The results obtained for forsterite and fayalite agree closely with the data commonly found in the literature. Owing to the uncertainty of the experimental results, it is not possible to determine conclusively whether an enthalpy of mixing exists in this system.     

Polycyclic aromatic hydrocarbons in surface sediments of Binacional Itaipu Lake,Brazil: characteristics,sources and toxicity evaluation

Itaipu Lake, which includes the Itaipu hydroelectric power plant, is one of the largest dams in the world and has a strong relationship with its surroundings. The flooded area has multiple uses such as navigation, recreation, water abstraction for industrial, urban and agricultural irrigation. The lake is located at the frontier between Brazil, Argentina and Paraguay. In this study, superficial sediments collected from nine sampling sites were analysed for grain size, organic matter and 16 priority polycyclic aromatic hydrocarbons (PAHs) using high-performance liquid chromatography (HPLC) with fluorescence detector. The total concentration of PAHs in the dry sediment ranged from 35.21 to 685.37 µg kg^?1. Diagnostic ratios showed that the possible source of PAHs in the Itaipu Lake could be pyrolitic and petrogenic. The potential toxicity of sediment of PAHs varied from not detected to 127.70 µg g^?1, suggesting that some adverse ecological effects would arise due to PAHs in these sediments.