天然褐铁矿处理含Hg（Ⅱ）废水的实验研究

利用水合金属氧化物和氢氧化物矿物表面重金属离子发生吸附作用的原理，进行了天然褐铁矿处理含Hg(Ⅱ)废水的实验。结果表明：试样用量、粒径、废水浓度、pH值、离子强度、反应时间、振荡器转速等因素对Hg(Ⅱ)的吸附率有一定的影响，其中pH值的影响最大；Hg(Ⅱ)在天然褐铁矿上的吸附等温曲线不同于Langmuir和Fre-undlich等温线，而为台阶型，符合分级离子／配位子交换等温曲线。     

Speciation of Cr and V within BOF steel slag reused in road constructions

Basic Oxygen Furnace (BOF) steel slag is a residue from the basic oxygen converter in steel-making operations, which is partially reused as an aggregate for road constructions. It is essentially composed of calcium, silicon and iron but also contains potential toxic elements present as traces, like chromium (Cr, 2600 mg kg^− 1) and vanadium (V, 690 mg kg^− 1), which can be released. The linked results of chemical analysis, XRD and SEM-EDX enabled to identify the main mineral phases composing BOF slag and EDX micro-analyses indicated that V and Cr were associated to dicalciumferrite. A 47-days static leaching test at a laboratory scale with a controlled pH of 5 (pH_stat leaching test) showed that Cr was little released, while V was significantly released. Finally, X-ray absorption near-edge structure (XANES) spectra of 3 BOF slag samples were recorded (“raw”, leached 47 days at pH 5 and aged 2 years in a lysimeter). XANES spectra showed that Cr is present at octahedral coordination in the trivalent form, the less mobile and less toxic one, and that its speciation does not evolve during natural ageing and leaching at pH 5. They also indicated that V is predominantly present in the + 4 oxidation state and seems to become oxidized to the pentavalent form (the most toxic form) during natural ageing.     

天然磁铁矿处理含Hg（Ⅱ）废水实验研究

利用重金属离子可在水合金属氧化物和氢氧化物矿物表面产生吸陵作用的原理，进行了天然磁铁矿处理含Hg(Ⅱ）废水的实验研究，结果表明：当温度为25℃，吸附平衡时间为60分钟、试样用量为20g/L，试样粒径为200目以下、pH值为6.40，离子强度为零时，Hg(Ⅱ）初始浓度为1.12mg/L的溶液的吸附率可达98%，使废水中Hg(Ⅱ）的浓度达到国家排放标准。pH值、离子强度、粒径、试样用量、废水浓度、温度、时间均对Hg(Ⅱ）的吸附率有一定的影响，其中pH值的影响最大，Hg(Ⅱ）在天然磁铁矿上的吸附等温曲线不同于Langmuir和Freundlich等温曲线，而是表现为台阶段，符合分级离子/配位子交换等温曲线。     

东海内陆架沉积物中有机硫形态的K边XANES谱分析

有机硫是海洋沉积物重要的硫形态,与有机质保存及多种元素的地球化学循环密切相关。利用硫的K边XANES谱从分子水平研究了东海内陆架沉积物中腐殖酸硫(HA-S)、富里酸硫(FA-S)以及铬不可还原有机硫(non-CROS)的形态及相对含量。结果表明,HA-S和FA-S总体上均以氧化态有机硫为主,其相对平均含量分别为56%和69%,而non-CROS则以还原态有机硫为主(86%)。HA-S和FA-S的强还原态硫为还原态有机硫的主要组成,磺酸盐和硫酸酯为HA-S中氧化态有机硫的主要组分,硫酸酯为FA-S中氧化态有机硫的主要组分。FA-S的强还原态有机硫为硫化成因,HA-S的强还原态硫可能与硫化和生物成因有关,而non-CROS的强还原态有机硫则主要为生物成因。如non-CROS能近似代表海洋沉积物中的有机硫总量,则表明该沉积物中总有机硫以还原态硫为主;而腐殖质硫(HA-S+FA-S)较高比例的氧化态硫则表明腐殖质硫不能全面反映沉积物中有机硫的组成和来源。     

汞银黝铜矿Ag6 (Cu4Hg2) Sb4S13——黝铜矿族新矿物

作为黝铜矿族矿物的新成员,汞银黝铜矿(Argentotetrahedrite-(Hg),IMA 2020-079),Ag6(Cu4 Hg2) Sb4S13,发现于湘黔汞矿带北段之保靖东坪Hg-Ag矿床中,是该矿床的主要矿石矿物和回收对象.汞银黝铜矿单晶晶体尺寸约为5～20 μm,呈粒径20～300 μm的粒状、片状集合...     

Experimental and theoretical study of the structural environment of magnesium in minerals and silicate glasses using X-ray absorption near-edge structure

X-ray absorption spectroscopy at the Mg K-edge is used to obtain information on magnesium environment in minerals, silicate and alumino-silicate glasses. First-principles XANES calculations are performed for minerals using a plane-wave density functional formalism with core-hole effects treated in a supercell approach. The good agreement obtained between experimental and theoretical spectra provides useful information to interpret the spectral features. With the help of calculation, the position of the first peak of XANES spectra is related to both coordination and polyhedron distortion changes. In alumino-silicate glasses, magnesium is found to be mainly 5-fold coordinated to oxygen whatever the aluminum saturation index value. In silicate glasses, magnesium coordination increases from 4 in Cs-, Rb- and K-bearing glasses to 5 in Na- and Li-bearing glasses but remains equal as the polymerization degree of the glass varies. The variation of the C feature (position and intensity) is strongly related to the alkali type providing information on the medium range order.

高压下天然菱铁矿的压缩性和电子结构研究

采用同步辐射光源和金刚石对顶砧(DAC)技术,对天然菱铁矿的压缩性和电子结构进行了原位X射线衍射(XRD)和X射线吸收近边结构谱(XANES)测试研究。在室温下随着压力逐渐升高至50.2 GPa,菱铁矿保持方解石型结构不变,但是逐渐向Na Cl型结构转变;刚性[CO3]2-基团平行于ab-平面定向排列使c轴的压缩性大于a轴。菱铁矿在44.6~47.1 GPa之间发生电子由高自旋态(HS)向低自旋态(LS)的转变,表现为体积塌陷8%。HS菱铁矿的等温状态方程参数为K0=112(5)GPa和K'0=4.6(3)。首次采用XANES技术对菱铁矿中Fe2+的电子结构进行了研究,结果表明:随着压力升高至37.3 GPa,Fe2+的配位和局域对称并未发生明显变化;此后电子结构开始转变,Fe2+的3d轨道分裂能降低,电子跃迁概率增大,呈现LS特性。     

Natural attenuation of TCE, As, Hg linked to the heterogeneous oxidation of Fe(II): an AFM study

Hydrous ferric oxide (HFO) colloids formed, in strictly anoxic conditions upon oxidation of Fe²⁺ ions adsorbed on mineral surface, were investigated under in situ conditions by contact mode atomic force microscopy (AFM). Freshly cleaved and acid-etched large single crystals of near endmember phlogopite were pre-equilibrated with dissolved Fe(II) and then reacted with Hg(II), As(V) and trichlorethene (TCE)-bearing solutions at 25 °C and 1 atm. HFO structures are found to be of nanometer scale. The As(V)–Fe(II) and Hg(II)–Fe(II) reaction products are round (25 nm) microcrystallites located predominantly on the layer edges and are indicative of an accelerated Fe(II) oxidation rate upon formation of Fe(II) inner sphere surface complexes with the phyllosilicate edge surface sites. On the other hand, TCE–Fe(II)–phlogopite reaction products are needle-shaped (45 nm long) particles located on the basal plane along the Periodic Bond Chains (PCBs) directions. Experiments with additions of sodium chloride confirm the importance of the Fe(II) adsorption step in the control of the overall heterogeneous Fe(II)–TCE electron transfer reaction.

Kinetic measurements at the nanomolar level of Hg° formed upon reduction of Hg(II) by Fe(II) in presence of phlogopite particles provide further convincing evidence for reduction of Hg(II)_aq coupled to the oxidation of Fe(II) adsorbed at the phlogopite–fluid interface, and indicate that sorption of Fe(II) to mineral surfaces enhances the reduction rate of Hg(II) species. The Hg(II) reduction reaction follows a first-order kinetic law. Under our experimental conditions, which were representative of many natural systems, 80% of the mercury is transferred to the atmosphere as Hg° in less than 2 h.

The reduction of a heavy metal (Hg), a toxic oxyanion (arsenate ion) and a chlorinated solvent (TCE) thus appear to be driven by the high reactivity of adsorbed Fe(II). This is of environmental relevance since these three priority pollutants are that way reductively transformed to a volatile, an immobilizable and a biodegradable species, respectively. Such kinetic data and reaction pathways are important in the evaluation of natural evaluation scenarios, in the optimization of Fe(II)/mineral mixtures as reductants in technical systems, and in general, in predicting the fate and transport of pollutants in natural systems.     

Adsorption of Lead (II), Copper (II) on tourmaline from Altai mine in China's Sinkiang

Tourmaline from Altai mine in China's Sinkiang was used to remove lead (II), copper (II) from aqueous solution. The results demonstrate that tourmaline contains Na(Mg,V)3Al6(BO3)3Si6O18(OH)4, NaFe3Al6(BO3)3Si6O18(OH)4. The data show that Tourmaline from Altai mine in China's Sinkiang can be used natural adsorbent for lead (II), copper (II).It is observed that the adsorption data fitted to the Langmuir isotherm. Furthermore, both Pb (II) and Cu (II) absorbed by tourmaline and tourmaline were characterized by X-ray diffraction, Laser Raman Spectrum, Fourier transform infrared spectroscopy, X-ray energy dispersive spectrometer, Transmission electron microscopy and Zeta potential.     

Two-dimensional reactive transport modeling of the alteration of a fractured limestone by hyperalkaline solutions at Maqarin (Jordan)

Two-dimensional reactive transport modeling of the Maqarin Eastern Springs site, a natural analogue for the alteration of a fractured limestone by high-pH Portland cement waters, has been performed using the CrunchFlow code. These 2D calculations included transport by advection–dispersion–diffusion along a single fracture and diffusion in the wall rock. Solute transport was coupled to mineral dissolution and precipitation. A limited sensitivity analysis evaluated the effect of different values of primary mineral surface areas, flow velocity and sulfate concentration of the inflowing high-pH solution.Major secondary minerals include ettringite–thaumasite, C–S–H/C–A–S–H and calcite. C–S–H/C–A–S–H precipitation is controlled by the dissolution of primary silicates. Ettringite precipitation is controlled by diffusion of sulfate and aluminum from the wall rock to the fracture, with aluminum provided by the dissolution of albite. Calcite precipitation is controlled by diffusion of carbonate from the wall rock. Extents of porosity sealing along the fracture and in the fracture-wall rock interface depend on assumptions regarding flow velocity and composition of the high-pH solution. The multiple episodes of fracture sealing and reactivation evidenced in the fracture infills were not included in the simulations. Results can qualitatively reproduce the reported decrease in porosity in the fractures and in the wall rock next to the fractures. Instances of porosity increase next to fractures caused by carbonate dissolution were not reproduced by the calculations.     

Boron K-edge XANES of boron oxides: tetrahedral B–O distances and near-surface alteration

Synchrotron radiation boron K-edge XANES spectra collected in fluorescence yield mode are reported for monoclinic metaboric acid [HBO₂(II)], sinhalite (MgAlBO₄), and a selection of boron oxides in which B is exclusively in trigonal coordination (^[3]B). The anomalously high divergence of tetrahedral (^[4]B–O) bond lengths in HBO₂(II) and sinhalite is used to resolve fine structure at the ^[4]B K edge due to splitting of σ*(t₂) antibonding orbitals. For HBO₂(II), XANES peaks at 196.9 and 199.3?eV are assigned to ^[4]B–O distances of 1.564 and ～1.440 (×3) Å, respectively, and, for sinhalite, peaks at 196.8, 197.9, and 199.6?eV are assigned to distances of 1.586, 1.483 (×2), and 1.442?Å, respectively. A correlation between peak splitting at the ^[4]B K edge and divergence of tetrahedral bond length is established for borates and borosilicates using data for sinhalite, HBO₂(II), ferroaxinite, danburite, datolite, and BPO₄. B K-edge XANES spectra collected in total electron yield mode, which probes to <60?Å, show that almost all ^[4]B in HBO₂(II) and about one-third of the ^[4]B in sinhalite are converted to ^[3]B in the near-surface structure. Moreover, HBO₂(II), HBO₂(III), sassolite (boric acid; H₃BO₃), and v-B₂O₃, which have markedly different bulk structures, have a similar near-surface layer composed of a relaxed anhydrous network of BO₃ groups.     

西藏甲玛铜多金属矿硫同位素地球化学研究

西藏墨竹工卡县甲玛铜多金属矿床位于冈底斯成矿带东段,Cu、Mo、Pb+Zn、Au、Ag均达大型规模,并伴生Co、Bi、W、Ni等多金属矿化。黄铜矿、斑铜矿、辉钼矿、方铅矿、闪锌矿、黝铜矿、辉铜矿等硫化物为主要的矿石矿物,硫酸盐矿物以硬石膏为主,含矿岩浆岩以花岗斑岩、二长花岗斑岩和花岗闪长斑岩为主。通过对甲玛矿区主要硫化物和硬石膏的硫同位素分析,并结合前人研究,甲玛矿区硫化物的硫同位素δ34S值变化于13.6‰～+12.5‰,平均值1.33‰(样品数86)、硬石膏δ34S值+0.5‰～+1.8‰,平均值+1.13‰(样品数3)、岩浆岩δ34S值0.7‰～0.2‰,平均值0.5‰(样品数3),与岩浆硫δ34S值0±3‰一致。闪锌矿-方铅矿-黄铜矿矿物对的硫同位素地质温度计,显示成矿温度为408～433℃,说明其形成时硫同位素处于平衡状态。冈底斯成矿带上的驱龙等斑岩型矿床中硫化物和岩浆岩硫同位素,均具有δ34S值变化范围小,平均值接近0值,与岩浆硫特征一致的特点,反映了甲玛铜多金属矿床具有矽卡岩-斑岩型矿床硫同位素地球化学特征,硫以岩浆来源为主。     

独居石和磷钇矿晶体结构的精确测定

本文用强功率四圆单晶衍射仪精确地修正了独居石和磷钇矿的晶体结构。独居石［Ｍｏｎａｚｉｔｅ－（Ｃｅ），ＣｅＰＯ４］属单斜晶系，ａ＝６．７８４３（１７），ｂ＝６．９８９１（１２），ｃ＝６．４５９２（１０），β＝１０３．６２６（１６）°，Ｚ＝４，空间群为Ｐ２１／ｎ。使用１１０６个［Ｆ≥３σ（Ｆ）］的独立衍射点，经多轮最小二乘法修正后，最终获得偏离因子Ｒ＝０．０６０。独居石的结构由孤立的［ＰＯ４］四面体构成，Ｃｅ位于［ＰＯ４］四面体包围之中，Ｃｅ的配位数为９，独居石的Ｃｅ—Ｏ平均键长为２．５５２，Ｐ—Ｏ平均键长为１．５２８。磷钇矿（Ｘｅｎｏｔｉｍｅ，ＹＰＯ４）属四方晶系，其晶格常数为：ａ＝６．８７９１（２４），ｃ＝６．０１４７（１９），Ｚ＝４，空间群为Ｉ４Ｉ／ａｍｄ（Ｎｏ．１４１）。使用１４２个［Ｆ≥３σ（Ｆ）］的独立衍射点，经多轮最小二乘法修正后，最终获得偏离因子Ｒ为０．０４８３。磷和氧形成四面体配位，其Ｐ—Ｏ平均键长为１．５４３；稀土钇与氧原子相连构成八次配位，其Ｙ—Ｏ平均键长为２．３３３。     

海洋沉积物甲烷厌氧氧化作用(AOM)及其对无机硫循环的影响

甲烷厌氧氧化作用(AOM)在调控全球甲烷收支平衡以及缓解因甲烷引起的温室效应等方面扮演着十分重要的角色,成为近些年来海洋生物地球化学领域的研究热点之一.一般而言,海洋沉积物孔隙水硫酸盐还原主要是通过2种反应途径来完成,即氧化有机质途径和AOM途径.长期以来,与有机质氧化途径相关的硫酸盐还原作用研究已有充分展示,而由AOM驱动的硫酸盐还原及其对自生硫化铁形成与埋藏的重要贡献却被严重低估.侧重从生物地球化学、同位素地球化学等角度,综述近些年来不同环境条件下海洋沉积物AOM作用发生的地球化学证据和AOM对沉积物孔隙水硫酸盐消耗比例的贡献大小及其调控因素.AOM过程产生的H2S会与沉积物中活性铁结合形成自生铁硫化物.与沉积物浅表层条件相比,AOM过程固定的自生铁硫化物不容易发生再氧化,更利于在沉积物中埋藏保存起来.AOM与海洋沉积物硫酸盐还原作用相偶联,由AOM驱动的硫酸盐还原过程对海底自生铁硫化物形成与埋藏的重要贡献不容忽视.该综述有助加深对海洋沉积物AOM作用的认识及其对硫循环的全面理解.     

Mercury contents in the vertical profiles through alluvial sediments as a reflection of mining in Idrija (Slovenia)

The influence of geomorphological factors to Hg contamination of the Idrijca River alluvial sediments because of the historical mining and ore roasting activities has been studied. Main source of Hg in alluvial sediments was dumping of ore roasting residues and mining waste into the river channel and its erosion downstream. The position of the material in relation to the geomorphological properties is highly related with its Hg content. Floodplains were found to be the most contaminated geomorphological units (mean Hg content 335 mg/kg), with Hg concentration rapidly dropping in the first terrace (155 mg/kg). The least contaminated material was found in the higher terraces (3.8 mg/kg). Sampling upstream Idrija (average Hg content is 22.1 mg/kg) shows that not only mine and ore roasting plant increased Hg levels in alluvial deposits but also contaminated sites upstream Idrija contribute to Hg contamination. Geochemical background for alluvial sediments for this area is estimated to be 0.75 mg/kg. Downstream Idrija, 9 hotspots were determined where highly contaminated material is actively eroded and carries a high risk of further contamination of the So?a River and northern Adriatic Sea ecosystems.     

Lepidocrocite-catalyzed Mn(II) oxygenation by air and its effect on the oxidation and mobilization of As(III)

Manganese (oxy)hydroxides (MnO_X) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnO_X in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnO_X species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.     

铁(II)-5-Br-PADAP-乳化剂OP体系析相光度法测定微量铁的应用研究

研究了铁 (Ⅱ ) 5 Br PADAP 乳化剂OP体系中的析相、显色反应的条件及其吸收光谱的分析特征 ,拟定了直接测定不同种类样品中痕量铁的分析方法。在pH =5 .0的HAC NaAC缓冲溶液中 ,Fe(Ⅱ ) 5 Br PADAP络合物具有两个吸收峰 ,分别位于λ1 =5 6 1nm与λ2 =75 4nm处。本文选择λ =75 4nm进行测定 ,其摩尔吸光系数为 :ε75 4 =3.9× 10 4L·mol- 1 ·cm- 1 。铁含量在 0～ 2 4μg范围内服从比尔定律。此方法用于样品中痕量铁的测定 ,结果准确     

Sb–Hg ore deposit distribution controlled by brittle structures: The case of the Selvena mining district (Monte Amiata, Tuscany, Italy)

This paper deals with the tectonic control on the hydrothermal system that gave rise to Sb–Hg ore deposits in the Monte Amiata area that was one of the most relevant mining district for the exploitation of mercury in Italy. The study area (Selvena mining district) is located in southern Tuscany (inner Northern Apennines) one of the most important mineralized area in the western Mediterranean region. Southern Tuscany was severely affected by Middle–Late Miocene low-angle normal faults, later dissected by Pliocene–Pleistocene faults, coeval magmatism (Late Miocene–Pleistocene) and hydrothermal activity (Pliocene–Present). The Selvena mining district is located south of Middle Pleistocene Monte Amiata volcanic complex. Our structural and kinematic study is based on the integration among fieldwork, borehole and mine data. The results highlight two Pleistocene–Holocene left-lateral transtensional shear zones linked by normal faults, defining a coeval pull-apart structure. Here, the Sb–Hg mineralization, transported by meteoric hydrothermal fluids mainly, is particularly diffuse and concentrated in the cataclasites and in damage zones of the normal faults. Furthermore, a widespread mineralization also occurs in the cataclasites of Miocene low-angle normal faults. Mine evidence suggests that ore-bearing fluids percolated through structural conduits located along the fault planes and resulting parallel to the intermediate stress axis. Geological structures and ore deposit distribution are related to a single hydrothermal circuit, with meteoric water channelled to depth through conduits parallel to the intermediate stress axis of the transcurrent shear zones; then, hydrothermal fluids mainly ascended through the almost vertical deformation zones located at the intersection between normal and strike-slip faults. Thus, hydrothermal fluids permeated also the Middle–Late Miocene cataclasites. This study shed light on the relationships between geological structures and mineralization in southern Tuscany and underlines the importance to investigate mine areas to understand hydrothermal fluids path.     

白杨河超大型铍(铀)矿床中蓝柱石(BeAlSiO4(OH))的矿物特征与地质意义

蓝柱石作为一种较为罕见的含铍矿物,通常产在过铝-准铝性的岩浆-热液演化系统中,或发育于富铝质岩石的低级变质过程中。本文通过偏光显微镜、电子探针、X射线粉晶衍射、激光拉曼光谱和红外光谱等多种手段方法,在白杨河超大型铍(铀)矿床首次发现了除羟硅铍石以外的另一种含铍矿物-蓝柱石。系统的矿物学研究表明蓝柱石应由花岗斑岩岩浆分异的岩浆热液直接沉淀而成,且形成于富F环境中。结合前人关于矿床地质特征、成矿年代学和地球化学等方面的研究,认为白杨河矿床中的铍矿化应是花岗斑岩深部岩浆房分异的岩浆热液,在不断演化过程中形成的,而与后期流体(包括幔源流体和大气降水)的淋滤作用无关或关系很小。     

原子吸收法测定炼银炉渣中的金

采用HF－H2SO4除硅,萃取－原子吸收法测定炼银炉渣中的金。样品加标回收率为92.0％－104.0％,相对标准偏差为3.8％（n＝11）。将该法应用到炼银炉渣中金的测定,结果符合分析质量要求。