利用X射线吸收近边结构光谱(XANES)研究水泥窑共处置产品中Ni和Cd的微观组成

在模拟水泥窑中高温煅烧掺有Ni、Cd化学试剂的水泥生料,并由制取的水泥熟料制备水泥净浆片.利用X射线吸收近边结构光谱（XANES）对水泥窑共处置产品中Ni、Cd的微观组成进行了研究.结果表明：Ni在水泥窑煅烧过程中发生了较为彻底的化学变化,形成了Ni-Mg化合物,该化合物可能是以氧化物、氢氧化物或碳酸盐的形式存在;水泥...     

Characterization of extracellular polymeric substances in the biofilms of typical bacteria by the sulfur K-edge XANES spectroscopy

A combined approach of physicochemical extraction and sulfur K-edge X-ray absorption near-edge structure（XANES） spectroscopy was applied to characterize the extracellular polymeric substances（EPS） of typical bacterial biofilms in this study. Physicochemical analysis showed variation of the contents of DNA,polysaccharide and protein in different fractions of EPS in different mediums. The sulfur K-edge XANES analysis yielded a variety of spectra.Spectral fitting of the XANES spectra utilizing a large set of model compounds showed that there was more reduced sulfur in both LB-EPS（loosely bound EPS） and TB-EPS（tightly bound EPS） of all the biofilms in LB medium than in R2 A medium. More oxidized sulfur was identified in LB-EPS than that in TB-EPS,suggesting different niches and physiological heterogeneity in the biofilms. Our results suggested that the sulfur K-edge XANES can be a useful tool to analyze the sulfur speciation in EPS of biofilms.     

Inorganic iodine incorporation into soil organic matter: evidence from iodine K-edge X-ray absorption near-edge structure

The transformation of inorganic iodine (I⁻ and IO₃⁻) incubated in soils with varying amounts of organic matter (Andosols from the surface layer of an upland field and forest, as well as Acrisols from surface and subsurface layers of an upland field) was investigated by using the iodine K-edge X-ray absorption near-edge structure (XANES). After 60 d of reaction, both I⁻ and IO₃⁻ were transformed into organoiodine in surface soils containing sufficient amounts of organic matter, whereas IO₃⁻ remained unchanged in the subsurface soil of Acrisols with low organic matter contents. Transformation of IO₃⁻ into organoiodine was not retarded when the microbial activity in soil was reduced by γ-ray irradiation, suggesting that microbial activity was not essential for the transformation of inorganic iodine into organoiodine. Soil organic matter has the ability to transform inorganic iodine into organoiodine.     

二种高硫煤中硫氮化学形态的研究

利用ＸＰＳ技术研究了贵定煤和西班牙Ｍｅｑｕｉｅｎｚａ煤中硫和氮化学形态的分布，并结合硫Ｋ－边ＸＡＮＥＳ和Ｍｏｓｓｂａｕｅｒ谱着重考察贵定煤中硫化学形态。结果表明，贵定煤中含硫化合物主要以噻吩形态存在，其次为有机硫化物；而Ｍｅｑｕｉｅｎｚａ煤中以有机硫化物含量最大，噻吩硫次之，有关含氮化合物，Ｍｅｑｕｉｅｎｚａ煤以吡咯和吡啶氮为主，但在贵定煤中观察到较大浓度的氧化氮化合物。     

砷氧化菌对胡敏酸络合As (Ⅲ)的氧化作用

土壤砷与土壤微生物相互作用是土壤砷形态转化中需要重点关注的内容之一.为了研究砷氧化菌对胡敏酸络合三价砷[HA-As(Ⅲ)]的作用,设置了不同p H值反应体系,研究砷氧化菌HN-2对HA-As(Ⅲ)作用下,砷的形态变化及其在固液两相中的分配.结果表明,在HA与As(Ⅲ)络合过程中,HA可以将一部分游离态As(Ⅲ)氧化为As(Ⅴ).其中,在p H=7的体系中,As(Ⅲ)被HN-2和HA氧化成As(Ⅴ)的效率最高.在含有砷氧化菌株和不含砷氧化菌株的体系中,0~10 h振荡过程中,HA-As材料均可以释放一部分As(Ⅲ)及As(Ⅴ)进入液相中,同时砷氧化菌可以快速地将As(Ⅲ)氧化为As(Ⅴ),而胡敏酸可以较缓慢地将As(Ⅲ)氧化为As(Ⅴ);反应10~24 h期间,HN-2砷氧化菌可以将络合态HA-As(Ⅲ)转化为游离态As(Ⅲ)并氧化为As(Ⅴ);48 h后反应逐渐达到平衡.固相同步辐射结果可以进一步证明HN-2砷氧化菌对络合态As(Ⅲ)的释放及氧化作用.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

Characteristics of secondary inorganic aerosol and sulfate species in size-fractionated aerosol particles in Shanghai

Sulfate, nitrate and ammonium(SNA) are the dominant species in secondary inorganic aerosol, and are considered an important factor in regional haze formation. Size-fractionated aerosol particles for a whole year were collected to study the size distribution of SNA as well as their chemical species in Shanghai. SNA mainly accumulated in fine particles and the highest average ratio of SNA to particulate matter(PM) was observed to be 47% in the fine size fraction(0.49–0.95 μm). Higher sulfur oxidation ratio and nitrogen oxidation ratio values were observed in PM of fine size less than 0.95 μm. Ion balance calculations indicated that more secondary sulfate and nitrate would be generated in PM of fine size(0.49–0.95 μm). Sulfur K-edge X-ray absorption near-edge structure(XANES) spectra of typical samples were analyzed. Results revealed that sulfur mainly existed as sulfate with a proportion(atomic basis) more than 73% in all size of PM and even higher at 90% in fine particles. Sulfate mainly existed as(NH4)2SO4 and gypsum in PM of Shanghai. Compared to non-haze days, a dramatic increase of(NH4)2SO4 content was found in fine particles on haze days only, which suggested the promoting impact of(NH4)2SO4 on haze formation. According to the result of air mass backward trajectory analysis, more(NH4)2SO4 would be generated during the periods of air mass stagnation. Based on XANES, analysis of sulfate species in size-fractionated aerosol particles can be an effective way to evaluate the impact of sulfate aerosols on regional haze formation.     

焚烧飞灰预处理工艺及其无机氯盐的行为研究

研究表明WCCB(水洗+烧结)预处理工艺能更高效更节能地去除飞灰中的氯化物,以利于其作为水泥原料的使用.水洗工艺条件为两次水洗、水固比均为3∶1,搅拌速度均为150 r.min-1,第一次水洗时间5 min,第二次水洗时间10 min;利用原焚烧炉进行烧结处理,温度为1 000℃,10%氧气含量,停留时间1 h.本研究尝试了3种焚烧飞灰:节煤器出来的飞灰、石灰干法中和酸性气体后布袋收集的飞灰、NaHCO3中和酸性气体后布袋收集的飞灰.经该工艺处理后,焚烧飞灰残渣量减少20%以上,氯减少94%以上,尤以NaHCO3中和得到的飞灰削减量为最,分别达到了72.1%和99.8%.采用同步辐射的X射线吸收近边精细结构(X-ray absorption near edge structure,XANES)和普通X射线衍射(X-ray Diffraction,XRD)相结合的方法研究分析无机氯盐在工艺过程中的行为,发现焚烧飞灰中主要的氯盐主要有NaCl、KCl和CaCl2.焚烧炉烟气净化系统的酸中和剂会影响无机氯盐的生成.焚烧飞灰中难溶性无机氯盐的结构与Friedel’s盐相似,并且与CaCl2有关系.     

同步辐射XRF和XANES研究重金属污染环境中小羽藓体内硫元素的生物指示作用

在实验室将小羽藓(Haplocladium)暴露于不同浓度的铅、铁、铬重金属环境下进行培育,分别应用同步辐射X射线荧光(SRXRF)方法测定小羽藓植株硫元素的含量和X射线吸收近边结构(XANES)分析不同价态的硫所占的相对含量.结果表明,暴露于铅、铁下的小羽藓植株内硫的含量明显增加,铅、铁浓度分别为400 mg/L和200 mg/L时,硫元素含量下降.培养周期为15 d时,小羽藓在100 mg/L铅胁迫下,低价硫由对照组的17.8%升高到23.6%,而同时以硫酸盐形式存在的硫由对照组的56.3%下降到51.2%.在400 mg/L铅胁迫时,低价硫含量增加到24.8%,硫酸盐中的硫所占的比例下降到48.4%.小羽藓植株内的胱氨酸、半胱氨酸、甲硫氨酸和谷胱甘肽中所含低价态硫的总相对含量增加,以硫酸盐态存在的硫相对含量明显下降.研究表明,重金属污染环境导致小羽藓硫吸收同化过程中硫元素含量和价态变化特征具有一定的生物指示作用.     

A novel concept of Fe-mineral-based magnetoreception: histological and physicochemical data from the upper beak of homing pigeons

Animals make use of the Earth’s magnetic field for navigation and regulation of vegetative functions; however, the anatomical and physiological basis for the magnetic sense has not been elucidated yet. Our recent results from histology and X-ray analyses support the hypothesis that delicate iron-containing structures in the skin of the upper beak of homing pigeons might serve as a biological magnetometer. Histology has revealed various iron sites within dendrites of the trigeminal nerve, their arrangement along strands of axons, the existence of three dendritic fields in each side of the beak with specific 3D-orientations, and the bilateral symmetry of the whole system. Element mapping by micro-synchrotron X-ray fluorescence analysis has shown the distribution of iron and its quantities. Micro-synchrotron X-ray absorption near-edge-structure spectroscopy has allowed us to unambiguously identify maghemite as the predominating iron mineral (90 vs 10% magnetite). In this paper, we show that iron-based magnetoreception needs the presence of both of these iron minerals, their specific dimensions, shapes, and arrangements in three different subcellular compartments. We suggest that an inherent magnetic enhancement process via an iron-crusted vesicle and the attached chains of iron platelets might be sufficient to account for the sensitivity and specificity required by such a magnetoreceptor. The appropriate alignment between the Earth’s magnetic field and the maghemite bands would induce a multiple attraction of the magnetite bullets perpendicular to the membrane, thus, triggering strain-sensitive membrane channels and a primary receptor potential. Due to its 3D architecture and physicochemical nature, the dendritic system should be able to separately sense the three vector components of the Earth’s local field, simultaneously—allowing birds to detect their geographic position by the magnetic vector, i.e., amplitude and direction of the local magnetic field, irrespective of the animal’s posture or movement and photoreception.