Pb,Cu和Zn在自然水体生物膜中铁/锰氧化物等组分上的富集规律

用选择性萃取法萃取天然基质采集的生物膜中的铁/锰氧化物,考察生物膜上铁/锰氧化物对水体中Pb,Cu及Zn的富集作用.结果表明,锰氧化物对生物膜富集Pb起主要作用,而铁氧化物和除铁/锰氧化物以外的以有机质为主的其它组分的作用很小;膜上其它组分对Cu的富集贡献较大,锰氧化物的贡献与铁氧化物的接近;锰氧化物对Zn的富集贡献最大,铁氧化物和其它组分的贡献比较接近.锰氧化物对Pb,Cu及Zn的富集能力分别高于铁氧化物的富集能力,铁氧化物和锰氧化物对3种金属富集能力的大小顺序分别是Zn>Cu>Pb和Zn>Pb≥Cu.

铁/锰氧化物改性碳基催化剂的制备及其对甲苯的脱除性能

以甘蔗渣为原料,采用水热合成法制备了水热炭,再通过浸渍法负载上铁或锰的氧化物,得到具有吸附-催化氧化双功能的铁/锰氧化物改性碳基催化剂CMF,对催化剂进行了表征,并考察了其对甲苯的脱除性能。表征结果显示,CMF具有比表面积大、活性成分分布均匀等良好的表面结构。实验结果表明:CMF具有较高的甲苯脱除性能,当温度高于250 ℃时,CMF的甲苯去除率达80%以上,300 ℃时甲苯去除率达90%;在温度高于200 ℃后CMF催化氧化甲苯的产物中CO;产率高于80%,300 ℃时其产物中CO;产率达98%。

Enhancement of bio-oxidation of refractory arsenopyritic gold ore by adding pyrolusite in bioleaching system

Pyrolusite was added in the bioleaching process to enhance the bio-oxidation process. Bioleaching tests at different dosages of pyrolusite ore, pH and inoculation amounts of Acidithiobacillus ferrooxidans were studied. The results showed that the time of the bio-oxidation process was decreased obviously and the arsenic leaching rate reached 94.4% after the bioleaching. The bio-oxidation of arsenopyrite and the effective extraction of manganese from pyrolusite were achieved by the bioleaching process. After bioleaching, the leaching rate of gold from the reaction residues reached 95.8% by cyanide leaching. In the bio-oxidation process, pyrolusite increased the redox potential of the solution to accelerate the bioleaching rate. The experiment showed that there were two reaction modes in the bioleaching process.

Assessment of heavy metal pollution in sediments from Xiangjiang River(China) using sequential extraction and lead isotope analysis

The heavy metal(such as Cr,Ni,Cu,Cd,Pb,and Zn)concentration,speciation,and pollution source in 43 sediment samples from the Xiangjiang River were investigated using sequential extraction combined with Pb isotope analysis.Cu,Cd,Pb,and Zn concentrations are higher than their background values,while Cr and Ni concentrations are close to those.Sequential extraction demonstrates that heavy metals have different fractions,showing different bioavailabilities.The w(206Pb)/w(207Pb)ratio increases with decreasing bioavailability in the order of exchangeable<carbonate≈Fe-Mn oxides≈organic<residual(p<0.05).Wastewater,dust,and slag from mining and smelting areas,and the residual Pb are assumed to be the primary anthropogenic and natural sources of Pb,respectively.The percentages of anthropogenic Pb in the exchangeable,carbonate,Fe-Mn oxides,and organic fractions are(91.5±16.7)%,(61.1±13.9)%,(57.4±11.1)%,and(55.5±11.2)%,respectively,suggesting a significant input of anthropogenic Pb in these four fractions.

Enhancing storage performance of P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)cathode materials by Al_(2)O_(3)coating

The P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)materials were synthesized by an ultrasonic spray pyrolysis followed by solid-state sintering method.The structures,morphologies and electrochemical performances of Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)materials were characterized thoroughly by means of X-ray diffractometer,scanning electron microscope and electrochemical charge/discharge instruments.Moreover,a thin layer of Al_(2)O_(3),which was formed on the surface of Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2),can enhance the storage performance by preventing the formation of Na_(2)CO_(3)·H_(2)O,which is believed to enhance the electrochemical performances of Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2)materials.This facile surface modification method may pave a way to synthesize advanced cathode materials for sodium-ion batteries.

Combined Chemical and Mineralogical Evidence for Heavy Metal Binding in Mining- and Smelting-Affected Alluvial Soils

The binding of metallic contaminants （Pb, Cd, and Zn） and As on soil constituents was studied on four highly contaxninated alluvial soil profiles from the mining/smelting district of Pribram （Czech Republic） using a combination of mineralogical and chemical methods. Sequential extraction analysis （SEA） was supplemented by mineralogical investigation of both bulk samples and heavy mineral fractions using X-ray diffraction analysis （XRD） and scanning electron microscopy with an energy dispersive X-ray spectrometer （SEM/EDS）. The mineralogy of Fe and Mn oxides was studied by voltammetry of microparticles （VMP） and diffuse reflectance spectrometry （DRS）. Zinc and Pb were predominantly bound in the reducible fraction attributed to Fe oxides and Mn oxides （mainly birnessite, Na4Mn14O27.9H2O）, which were detected in soils by XRD and SEM/EDS. In contrast, Cd was the most mobile contaminant and was predominantly present in the exchangeable fraction. Arsenic was bound to the residual and reducible fractions （corresponding to Fe oxides or to unidentified Fe-Pb arsenates）. SEM/EDS observations indicate the predominant affinity of Pb for Mn oxides, and to a lesser extent, for Fe oxides. Thus, a more suitable SEA procedure should be used for these mining-affected soils to distinguish between the contaminant fraction bound to Mn oxides and Fe oxides.

Removal of tungsten from molybdate solution by Fe-Mn binary oxide adsorbent

Considering the different geochemical enrichment behaviors of W and Mo,Fe?Mn binary oxide(FMBO),ferric hydroxide(Fe(OH)3)and manganese dioxide(MnO2)were studied to separate W from molybdate solution,respectively.The experimental results demonstrated that Fe?Mn binary oxide(FMBO)was the most suitable adsorbent for the separation.Under a wide pH(6.9?11.3)region,more than80%W removal efficiency and less than3%Mo loss could be obtained.In addition,the Fe?Mn binary oxide adsorbent can be regenerated by treating with3mol/L NaOH,and the W adsorption efficiency was retained after five adsorption?desorption?regeneration cycles.All these indicate that the Fe?Mn binary oxides have the potential for the separation of W from molybdate solution.

Comparative Study on Characteristics of P Fixation by Mn, Fe and Al

An experiment was conducted to examine the role of Mn in P fixation through comparing with Al and Fe. Hydroxides and oxides of Al, Fe and Mn were prepared in lab under opened and closed conditions to react with phosphate. The newly formed Mn hydroxide showed the strongest P-fixing abilityl even several times higher than Fe hydroxide, but became the lowest rapidly due to ageing when exposed to air. Mn oxide showed the lowest p-fixing ability. Therefore, a sound consideration on P fixation should be based on both quantities and p-fixing abilities of the compounds of Fe, Al and Mn. The importance of Mn on P availability should receive more attention especially under oxidation-reduction dynamic conditions.

Distribution of rare earth elements of granitic regolith under the influence of climate

The distribution and anomalies of rare earth elements(REEs) of granitic regolith were studied in Inner Mongolia and Hainan Island, China. One profile showed slight REE enrichment of an upper layer and no obvious light REE/heavy REE(LREE/HREE) fractionation(La_N/Yb_N of 0.9). The second profile was significantly enriched in REEs and enriched in LREEs in the upper portion(La_N/Yb_N>1.8). Eu, Ce, and Gd anomalies of the two profiles are different. Slightly negative Eu, Ce, and Gd anomalies in NMG-3-1 indicate slow dissolution of primary minerals and little secondary products; in contrast, a positive Eu anomaly in HN-2 suggests the vegetation cycle may contribute to soil. The Ce anomaly of HN-2 reflects oxidation of Ce and coprecipitation by Fe-and Mn-oxides and organic matter. Correlation between Ce and Gd anomalies in HN-2 suggests Ce and Gd are both influenced by redoxreduction.

Fe-Si-Mn-Oxyhydroxide Encrustations on Basalts at East Pacific Rise near 13°N:An SEM-EDS Study

Fe-Si-Mn-oxyhydroxide encrustations at the East Pacific Rise （EPR） near 13°N were analyzed using the scanning electron microscope （SEM） with an energy dispersive spectrometer （EDS）. These encrustations are mainly composed of amorphous Fe- Si-Mn-oxyhydroxides forming laminated, spherical, porous aggregates with some biodetritus, anhydrite, nontronite, and feldspar particles. Anhydrite particles and nontronite crystals in the Fe-Si-Mn-oxyhydroxide encrustations imply that the Fe-Si-Mn-oxyhy- droxide may have formed under relatively low- to high-temperature hydrothermal conditions. The Fe-Si-Mn-oxyhydroxide encrusta- tions on pillow basalts are 1-2mm thick. The growth rate of ferromanganese crusts in the survey area suggests that these encrusta- tions are an unlikely result of hydrogenic deposition alone having a hydrothermal and （Fe/Mn ratio up to 7.7 and Fe/（Fe＋Mn＋A1） ratio exceeding 0.78） hydrogenic origin （0.22 Fe/Mn ratio close to the mean value of 0.7 for open-ocean seamount crusts）. The varying Fe/Mn ratios indicate that the Fe-Si-Mn-oxyhydroxide encrustations have formed through several stages of seafloor hydrother- malism. It is suggested that, at the initial formation stage, dense Fe-Si-oxyhydroxides with low Mn content deposit from a relatively reducing hydrothermal fluid, and then the loose Fe-Si-Mn-oxyhydroxides deposit on the Fe-Si-oxyhydroxides. As the oxidation degree of hydrothermal fluid increases and Si-oxide is inhibited, Mn-oxide will precipitate with Fe-oxyhydroxides.

Specific Adsorption of Trivalent La, Ce and Y by Soils and Ferro-manganese Oxides and Its Mechanism

In this paper, the adsorption-desorption variations of trivalent La, Ce, Y and mixed rare earths are discussed. The curves of pH-rare earth element adsorption were very well fitted to the equation: InD =a+b pH. The selectivity of RE (rare earth element) ions by the samples decreased in the following order: Ce> RE> La> Y, but the sequences were: La> Ce> Y on kaolinite and Y> La on amorphous iron oxide. Since the trivalent RE ions existed in the form of RE(OH)2+ in the solutions from pH < 5.45 to 7.0, the ratio of H+ displaced to RE3+ adsorbed in micromole was proposed to be about 2. The specific adsorption mechanism for RE was proposed to be that the RE ions complexed with oxide surface and the ion-surface complex of Ce3+ promoted oxidization on Mn hydroxide.

Influence of Long-Term Fertilization on Selenium Accumulation in Soil and Uptake by Crops

Continuous applications of organic and inorganic fertilizers can affect soil and food quality with respect to selenium （Se） concen- trations. A long-term （over 20 years） experimental field study, started in 1989, was conducted to investigate the changes in soil Se fractions and its uptake by crops, as affected by different fertilizer practices, in the North China Plain with an annual crop rotation of winter wheat and summer maize. The long-term experiment was arranged in a complete randomized block design consisting of 4 replications with 7 fertilizer treatments： 1） organic compost （OC）, 2） half organic compost plus half N-P-K chemical fertilizers （OC ＋ NPK）, 3） N-P-K fertilizers （NPK）, 4） N-P fertilizers （NP）, 5） P-K fertilizers （PK）, 6） N-K fertilizers （NK）, and 7） an un-amended control. Soil samples from the surface （20 cm） were collected in 1989, 1994, 1999, 2004 and 2009 to characterize Se and other soil properties. In 2009, the average soil Se concentrations in the treatments （149 ± 8 beg kg-1） were higher than those in the soil samples collected in 1989 at the beginning of the experiment （112 4- 4 beg kg-1）, and decreased in the order of OC 〉 OC ＋ NPK 〉 NPK NP 〉 PK NK 〉 control. Sequential extraction showed the oxidizable fraction （50.06%± 3.94%） was the dominant form of Se in the soil, followed by the residual fraction （24.12% ± 2.89%）, exchangeable fraction （15.09% ± 4.34%） and Fe-Mn oxides fraction （10.73%±4.04%）. With an increase of soil K, the exchangeable Se concentrations in the soil increased. The Se concentrations in the soil tillage layer （0-20 cm） were mainly related to soil organic carbon （SOC）, although different contributions came from atmospheric deposition, irrigation and fertilizers. With the accumulation of SOC, the uptakes of soil Se by two crops were inhibited. For the OC and OC ＋ NPK treatments, Se concentrations in wheat grains were lower than the critical standard of Se in stable food （100 μg kg·1]. Additionallv. Se concentrations in grains were also decreased by the deficiencies of major soil nutrients, especially P.

Mo marine geochemistry and reconstruction of ancient ocean redox states

Molybdenum(Mo) proxies, including bulk concentration and isotopic composition, have been increasingly used to reconstruct ancient ocean redox states. This study systematically reviews Mo cycles and their accompanying isotopic fractionations in modern ocean as well as their application in paleo-ocean redox reconstruction. Our review indicates that Mo enrichment in sediments mainly records the adsorption of Fe-Mn oxides/hydroxides and chemical bonding of H2 S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2 S in the water column or pore waters. In addition to the effect of euxinia, sedimentary Mo enrichment is related to the size of the oceanic Mo reservoir. Given these primary mechanisms for oceanic Mo cycling, Mo abundance data and Mo/TOC ratios acquired from euxinic sediments in geological times show that fluctuations of the oceanic Mo reservoir are well correlated with oxygenation of the atmosphere and oceans and suggest that oxygenation occurred in phases. Mo proxies suggest that Mo isotopes in strongly euxinic sediments reflect the contemporaneous Mo isotopic composition of seawater, but other processes such as iron-manganese(Fe-Mn) adsorption and weak euxinia can result in different fractionations. Diagenesis may complicate Mo enrichment and its isotopic fractionation in sediments. With appropriate constraints on the Mo isotopic composition of seawater and various outputs, a Mo isotope mass-balance model can quantitatively reconstruct global redox conditions over geological history. In summary, Mo proxies can be effectively used to reconstruct oceanic redox conditions on various timescales due to their sensitivity to both local and global marine redox conditions. However, given the complexity of geochemical processes, particularly the effects of diagenesis, further work is required to apply Mo proxies to ancient oceans.

Multiferroics and magnetoelectric effects in charge ordered compounds

The coexistence of magnetic ordering and ferroelectricity, ing on the origin of ferroelectricity, multiferroic materials known as multiferroics, has drawn a lot of research effort. Depend can be classified into different groups. In this paper, we review re cent progress in the field of multiferroics induced by different forms of charge ordering. In addition to a general description of charge order and electronic ferroelectricity, we focus on two specific systems： （1） charge order with frustration in RFe2O4 （R=Lu, Yb） system; （2） charge ordered perovskite manganites of the type （R1-xCax）MnO3 （R=La, Pr）. The charge ordering can be tuned by external electric fields, which results in pronounced magnetoelectric effects and strong dielectric tunability. Other materials and possible candidates with charge order induced multiferroics are also briefly summarized.