聚合氯化铝铁中Al(Ⅲ)对Fe(Ⅲ)稳定性的保护作用

对以NaOH为碱化剂合成的聚合氯化铝铁(PAFC)及其合成前体聚合氯化铝(PAC)、聚合氯化铁(PFC)的低温干燥胶体进行了表征。红外光谱证实PAFC中存在Fe-O-HAl基团;X射线衍射结果证实了PAFC中有着与PAC、PFC不同形态的Al(Ⅲ)、Fe(Ⅲ)羟基配合物,这些Fe-Al羟合异核多核共聚物是长程无序的;扫描电镜能谱分析表明:短程有序的Al-OH-Fe羟合物在Fe(Ⅲ)、Al(Ⅲ)继续水解的过程中与它们一起随机排列,形成长程无序的Fe-Al羟合异核多核共聚物无定形胶体。Al(Ⅲ)对Fe(Ⅲ)的保护作用包括三个方面:Al(Ⅲ)对Fe(Ⅲ)的水解有催化作用,使Fe(Ⅲ)形成更多细微的结晶中心而不是相互聚集生成较大的结晶;大量Al(Ⅲ)的存在使Fe(Ⅲ)羟合物之间的碰撞受到制约,相当于降低了Fe(Ⅲ)的有效浓度,延缓了Fe(Ⅲ)的迅速水解;大量短程有序的Al-OH-Fe羟合物的存在破坏了Al13相及-βFeOOH相的生成环境,有效地保护了Fe(Ⅲ)胶团并使它们在水溶液中的稳定时间大大增加。     

含钙聚硅氯化铁铝的表征与絮凝研究

用X粉晶衍射、红外光谱对以Ca（OH）2为碱化剂合成的含硅聚合氯化铝铁（PAFSCCa）、比较样聚合氯化铝铁（PAFCCa）、及其合成前体聚合氯化铝（PACCa）、聚合氯化铁（PFCCa）的低温干燥样进行了表征。XRD衍射结果显示．PAFSCCa中有Ca-Si-O-Al化合物存在,加热可促进Ca-Si-O-Al化合物的结晶和生长。Si/Al摩尔比在1：1时有利于Ca（Ⅱ）、Fe（Ⅲ）、Al（Ⅲ）与OH^-之间的共聚,无论是在加热、常温合成条件下,PAFSCCa中均有短程有序而长程无序的Ca（Ⅱ）、Fe（Ⅲ）、Al（Ⅲ）羟合物大量存在。Ca-Si-O-Al化合物的存在会抑制Ca-O-Fe之间的键合,破坏Fe（Ⅲ）羟合物的结晶,但促进低聚合度Fe（Ⅲ）羟合物的生成。红外光谱证实,PAFSCCa中硅铝之间通过Si-O-Al氧桥的键合程度随Si/Al摩尔比的增加而上升。在Si/Al摩尔比1：1及加热合成条件下,硅铝之间通过Si-O-Al氧桥的键合程度最高。絮凝实验证实PAFSCCa水解形成絮体时,含硅高的样品其絮体更大,絮凝效果好,硅铝共聚物对抑制微絮体再稳定的贡献大。     

楚雄盆地六苴上白垩统马头山组大村段沉积地球化学

上白垩统马头山组大村段是云南楚雄盆地的主要含铜层位之一。通过六苴zK24401钻孔岩芯样品地球化学研究,认为大村段是半干旱-半潮湿气候条件下盆地边缘的湖泊沉积形成,沉积物距物源区较近,其沉积演化过程与物源区具有一致性。主元素组成的W（SiO2＋Al2Oa＋K2O＋Na2O）占49．64％～81．84％,n（SiO2）／n（Al2O3）平均值为3．65,n（Al）／n（Al＋Fe＋Mn）值为0．71～0．78,n（Si）／n（Si＋Al＋Fe）值为0．69～0．87,反映出沉积物物源以陆源为主;n（Al2O3）／n．（Al2O3＋Fe3O3）值为0．79～0．91,显示了大陆边缘沉积环境的特点;K2O／Na2O多大于1,表明物源区主要为偏酸性的花岗质岩石。沉积旋回造成多层泥页岩中Cu、Zn、Sb等元素初始富集。稀土总量ω（EREE）为104．12×10^-6～181．69×10^-6,n（La）N／n（Yb）N〉1,轻重稀土分异程度较高,稀土配分模式为Eu、Ce亏损——轻稀土富集右斜型。     

中国坡缕石晶体化学研究

本研究通过对坡缕石化学成分分析数据的系统数理统计分析及结合透射电镜研究提出了Al2O3、Fe2O3、Mgo同SiO2一样为坡缕石的自身氧化物组分，而CaO、K2O、Na2O、TiO2等为主要以吸附态存在的非自身氧化物成分。相应的坡缕石晶体化学式为（Mg、Al、Fe、）5SiO20。（OH）2：·4（H2O）·nH2O（□—空位）。Ala3 、Fe3 、Mg2 异价类质同象置换的线性方程为Mg2 =4．978－1．519（Al3 ＋Fe3 ）。穆斯堡尔谱、红外光谱及（020）面网晶格条纹象的分裂研究表明了阳离子占位形式：MIM2M3M3M1，其中边缘M1=（Fex3＋）（Mg），中间M3=（A13 ＋Fe3＋），M2=Al3 （缺Fe3 ）或M2=（Fe3 ＋Al3 ）或等于（Fe3 ）和（□）。坡缕石的Mg2 －Al3 －Fe3 组分三角形图解揭示了：富Fe外生沉积成因为主的土状坡缕石和贫Fe富Al的热液交代蚀变充填作用为主的纤维状坡缕石的成分成因分类。     

水成型铁锰成矿的纳米成因研究进展

新生代深海铁锰矿床的大规模成矿是地质历史上特有的现象,其形成的海底铁锰结核/结壳因富含巨量的有用金属而备受关注。水成型铁锰成矿的胶体成因模型自20世纪90年代中期提出以来已被广泛接受并采用。随着近20年来纳米地球科学的迅速发展,人们意识到纳米颗粒作为胶体的最小部分,能够以其独特的性质显著影响铁锰成矿过程。通过总结已有研究,发现铁氧化物与锰氧化物会以纳米颗粒的形式普遍共存于多种表生地质环境,还证实了水成型铁锰结核/结壳中的主要铁锰矿物（如水羟锰矿和水铁矿）都是纳米颗粒。铁氧化物纳米颗粒对二价锰[Mn(Ⅱ)]的表面催化氧化可能是水成型铁锰矿物通常在纳米尺度密切共生的原因。此外,在铁锰结壳中还观测到大量在以往研究中被普遍忽视的三价锰[Mn(Ⅲ)]矿物,其含量在结壳顶部最高,随深度增加逐渐下降,四价锰[Mn(Ⅳ)]矿物的含量则呈相反的变化趋势。不同价态锰氧化物纳米颗粒的表面能差异导致Mn(Ⅲ)矿物在Mn(Ⅱ)的氧化过程中最先沉淀,并可能在沉淀之后逐渐转化为Mn(Ⅳ)矿物。相信随着纳米地球科学与高精度原位实验技术的发展,必将不断深化对海水铁锰循环及海底铁锰成矿的认识。     

配位体对地下环境中Fe（Ⅱ）衰减硝基苯的强化作用

通过静态实验研究了配位体对地下环境中Fe（Ⅱ）衰减硝基苯的影响。实验结果表明,配位体的种类、浓度均对Fe（Ⅱ）衰减硝基苯有重要影响。在Fe（Ⅱ）浓度为5 mmol/L的条件下,以半胱氨酸为配位体形成的络合物对硝基苯衰减效果最好,对硝基苯的去除率为86.16%;在配位体浓度变化的条件下,配位体浓度为50 mmol/L时,对硝基苯的衰减效果相对较好,去除率均在65%以上;另外,在Fe（Ⅱ）和配位体浓度一定的条件下,硝基苯的浓度对其衰减也有影响,100 mg/L的硝基苯衰减效果最好,之后随着硝基苯浓度增加,衰减效果呈现逐渐变差的趋势;在Fe（Ⅱ）的络合物衰减硝基苯的过程中,Fe（Ⅱ）被氧化成Fe（Ⅲ）。     

氢气还原处理对天然金红石可见光吸收的影响机制

天然半导体矿物金红石因结构中含有类质同象替代杂质元素V和Fe,具有一定的可见光吸收和光催化活性。为改善金红石的日光光催化性能,在H2还原气氛下,对天然金红石粉末进行500～900℃不同温度的热处理改性研究。紫外-可见漫反射吸收光谱（UV-Vis diffuse reflectance absorption spectra）表明H2还原处理显著改善了金红石在可见光区460～750 nm波段的光吸收,其中900℃处理样品的光吸收提升最为明显。电子顺磁共振（EPR）和X射线光电子能谱（XPS）测试表明,随着还原温度升高,杂质元素V和Fe从高价态（V5＋,Fe3＋）向较低的价态（V4＋,V3＋,Fe2＋）转化,同时金红石表面的化学吸附水含量也有所增加。本文认为H2还原热处理引起的过渡金属元素价态的改变,尤其是较低氧化态V离子（V4＋和V3＋）的形成,可能是导致金红石样品可见光吸收显著增加的主要原因。     

负载型纳米Pd/Fe对挥发性氯代烃的去除

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1,1-二氯乙烯（1,1-DCE）、林丹（γ-HCH）为主要目标污染物,探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备,透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性,当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时,1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关,与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程,速率常数分别为0-528 3 h^-1及2-012 9 h^-1,反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中,Fe腐蚀产生的H2为主要还原剂,Pd是良好的加氢催化剂,在金属颗粒表面形成高浓度反应相,使反应短时间内完成。     

冀北张家口地区汉诺坝玄武岩中麻粒岩捕虏体的硫化物相

捕虏体麻粒岩是了解下地壳形成和演化的重要样品。汉诺坝新生代玄武岩中的二辉麻粒岩捕虏体样品中富含各种硫化物相，主要类型有：①孤立产出的球状出溶硫化物；②矿物颗粒之间或颗粒内的粗晶硫化物；③次生硫化物包裹体群；④裂隙充填硫化物。电子探针分析表明，硫化物的矿物成分均为贫镍磁黄铁矿，（Ni＋Co＋Cu）／Fe（原子比）远小于0．2；（Fe＋Cu＋Co＋Ni）／S（原子比）比地幔岩的磁黄铁矿小，多小于0．875，反映了一种S过饱和环境。各种产状的磁黄铁矿中Au、Ag都有一定的含量，其平均值分别为0．19％～0.22％（Au）、0．01％～0．02％（Ag），反映下地壳的麻粒岩化与金矿化的成因联系。磁黄铁矿的Ni、Co、Cu含量与S正相关，说明微量重金属元素与S具有同源的关系，由于地幔去气伴随S而进入下地壳。     

试谈富钴结壳的成矿机制

富钴结壳的形成是“物理化学成矿”的结果。在海水中存在一个最低含氧带（OMZ），在此带内，来自内源、外源和水成等多种来源的Fe、Mn等成矿元素含量丰富。在OMZ下方，由于氧化作用，Fe、Mn首先形成水合氧化物胶体，同时Pt也可能在此时从海水中分离出来；在Fe-Mn氧化物沉淀过程中，由于表面吸附作用，具有合适表面电荷的Co^2 、Ni^2 等离子，被吸附到胶体颗粒表面，逐步富集成矿；在微生物和上升海流的作用下，磷酸盐组分加入到结壳中，形成夹层。因此,富钴结壳是多组分分阶段物理化学成矿的产物。     

Effect of phosphate, silicate, and Ca on the morphology, structure and elemental composition of Fe(III)-precipitates formed in aerated Fe(II) and As(III) containing water

We investigated Fe(III)-precipitates formed from Fe(II) oxidation in water at pH 7 as a function of dissolved Fe(II), As(III), phosphate, and silicate in the absence and presence of Ca. We used transmission electron microscopy (TEM), including selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX) to characterize the morphology, structure and elemental composition of the precipitates. Results from our companion X-ray absorption spectroscopy (XAS) study suggested that the oxidation of Fe(II) leads to the sequential formation of distinct polymeric units in the following order: Fe(III)-phosphate oligomers in the presence of phosphate, silicate-rich hydrous ferric oxide (HFO-Si) at high Si/Fe (>0.5) or 2-line ferrihydrite (2L-Fh) at lower Si/Fe (∼0.1-0.5), and lepidocrocite (Lp) in the absence of phosphate at low Si/Fe (<0.1). Results from this study show that the size of the polymeric units increased along the same sequence and that the aggregation of these polymeric units resulted in spherical particles with characteristic surface textures changing from smooth to coarse. The diameter of the spherical particles increased from 15 to 380 nm as the molar ratio (P + Si + As)/Fe(II) in the starting solution decreased and larger spherical particles precipitated from Ca-containing than from Ca-free solutions. These trends suggested that the size of the spherical particles was controlled by the charge of the polymeric units. Spherical particles coagulated into flocs whose size was larger in the presence than in the absence of Ca. Further observations pointed to the importance of Fe(II) oxidation and polymerization versus polymer aggregation and floc formation kinetics in controlling the spatial arrangement of the different polymeric units within Fe(III)-precipitates. The resulting structural and compositional heterogeneity of short-range-ordered Fe(III)-precipitates likely affects their colloidal stability and their chemical reactivity and needs to be considered when addressing the fate of co-transformed trace elements such as arsenic.     

Synthesis and phase transformations involving scorodite, ferric arsenate and arsenical ferrihydrite: Implications for arsenic mobility

Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 °C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO₄)_1.5 solutions also containing 0.02-0.2 M Na₂HAsO₄. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO₄·4-7H₂O, is a precursor to scorodite formation. As defined by As XAFS and Fe XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH)₆ octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1-4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate. Arsenate adsorption appears to retard ferrihydrite growth in the precipitates with molar Fe/As ratios of 1-4, whereas increased reaction gradually transforms two-line ferrihydrite to six-line ferrihydrite at Fe/As ratios of 5 and greater.     

铬铁矿中的次近邻效应

本文使用穆斯堡尔效应对三个铬铁矿进行了研究,测量了铬铁矿L-1在150K和298K温度下的穆斯堡尔谱和铬铁矿L-2和L-3在298K温度下的谱。使用次近邻效应解释了铬铁矿中的多重Fe~(2+)双峰,并使用二项式分布计算了Cr~(3+)、Fe~(3+)和Al占据次近邻位置的几率。在穆斯堡尔面积和二项式分布计算的基础上做出了Fe~(2+)双峰的指派。铬铁矿L-1谱在150K下进一步分裂,表明用来解释铬铁矿谱的模型是正确的。     

山东昌乐蓝宝石的颜色成因与优化

本文对昌乐蓝宝石进行了大量的颜色指数测量。各样品的主波长虽多落在蓝紫—蓝—蓝绿区,但其纯度均很低,以致肉眼观察十分暗淡,近乎黑色。蓝宝石的颜色主要由全铁含量和Fe~(2+)/Fe~(3+)值决定。随Fe~(2+)含量的增多,蓝宝石的颜色由黄逐渐变为蓝紫色。热处理难以改变蓝宝石中全铁的含量,但可使不同价态铁的含量发生改变。昌乐蓝宝石中全铁含量太高,通常热处理效果不很理想。     

金绿宝石和变石的呈色机理

对24块世界主要产地的金绿宝石和变石进行X荧光能谱分析,得到其所含的主要微量元素分别是Fe、Ga、Ti和Fe、Cr、Ti。金绿宝石和变石各1块样品的同步辐射X荧光能谱半定量分析表明金绿宝石中Fe含量平均为17 800×10^-6,Cr为855×10^-6;变石中Fe含量为16 060×10^-6,Cr含量达13 333×10^-6。对15个样品的可见吸收光谱进行测试及解释表明金绿宝石的可见吸收光谱是由Fe³⁺引起,变石的可见吸收光谱由Cr³⁺和Fe³⁺共同引起。色度学的分析和系列计算表明具有440～470 nm间最大吸收和540～630 nm宽吸收带的双峰形状的可见吸收光谱,可产生红-绿色的变石效应,通过向着该双峰形状的可见光谱的方向进行变石的优化处理可以获得宝石的变石效应。     

Interpreting nanoscale size-effects in aggregated Fe-oxide suspensions: Reaction of Fe(II) with Goethite

The Fe(II)/Fe(III) redox couple plays an important role in both the subsurface fate and transport of groundwater pollutants and the global cycling of carbon and nitrogen in iron-limited marine environments. Iron oxide particles involved in these redox processes exhibit broad size distributions, and the recent demonstrations of dramatic nanoscale size-effects with various metal oxides has compelled us, as well as many others, to consider whether the rate and extent of Fe(II)/Fe(III) cycling depends upon oxide particle size in natural systems. Here, we investigated the reaction of Fe(II) with three different goethite particle sizes in pH 7.5 suspensions. Acicular goethite rods with primary particle dimensions ranging from 7 by 80 nm to 25 by 670 nm were studied. Similar behavior with respect to Fe(II) sorption, electron transfer and nitrobenzene reduction was observed on a mass-normalized basis despite almost a threefold difference in goethite specific surface areas. Scanning electron microscopy (SEM) images, dynamic light scattering (DLS) and sedimentation measurements all indicated that, at pH 7.5, significant aggregation occurred with all three sizes of goethite particles. SEM images further revealed that nanoscale particles formed dense aggregates on the order of several microns in diameter. The clear formation of particle aggregates in solution raises questions regarding the use of primary particle surface area as a basis for assessing nanoscale size-effects in iron oxide suspensions at circum-neutral pH values. In our case, normalizing the Fe(II) sorption densities and rate constants for nitrobenzene reduction by BET surface area implies that goethite nanoparticles are less reactive than larger particles. We suspect, however, that aggregation is responsible for this observed size-dependence, and argue that BET values should not be used to assess differences in surface site density or intrinsic surface reactivity in aggregated particle suspensions. In order to realistically assess nanoscale size-effects in environmentally relevant systems that are likely to aggregate, new methods are needed to quantify the amount of surface area accessible for sorption and reaction in wet nanoparticle suspensions, rather than assuming that this value is equivalent to the surface area determined from the characterization of dry nanoparticles.     

海南蓬莱蓝宝石的光致发光谱学特征及意义

从光致发光光谱角度探讨了海南蓬莱蓝宝石的呈色机理.结果发现:与蓝宝石吸收光谱的500～700 nm吸收宽带相比,在500～720 nm发光波段内存在566.8 nm锐峰、600 nm左右肩峰和Cr~(3+)的694.2 nm特征峰.600 nm肩峰与其吸收峰镜像对称,566.8 nm处锐峰的产生原因复杂.600 nm肩峰可能与Fe~(2+)-Fe~(2+)离子对的电子跃迁有关;566.8 nm锐峰因532 nm激光激发Fe~(2+)-Ti~(4+)或Fe~(2+)-Fe~(3+)间的电荷迁移带,通过晶格造成Si~(4+)、Mg~(2+)等微量杂质离子敏化而产生.光致发光谱中呈现更多谱峰,能呈现离子跃迁时不同离子间发生的相互作用,为500～700 nm吸收宽带由不同致色机制的叠加给出了直接证明,是一种能全面地研究宝石矿物中致色元素能级结构的有效方法.     

含钙铝铁水解聚合产物的矿物学研究Ⅲ:陈化对形态的影响

用透射电镜、扫描电镜、热分析及矿物谱学等手段对含钙铝铁水解聚合产物(含微量硅)合成初期样品及其陈化9年后样品组成物相的形态演化进行了观察对比研究。结果表明,含钙铝铁溶液合成初期迅速形成类钙矾石双羟合结构体,其结构中部分Al3+被Fe3+取代、SO42-阴离子被Cl-离子替代,无定形的铝铁共聚物、铝硅共聚物和多种铝、铁、钙氢氧化物(氧化物)微晶竞争存在。缺氧条件下铝铁水解产物的演化由于氯、钙离子的存在而与文献的报道有所不同。陈化改变了含钙聚合铝(铁)溶液中的长程有序结构。其中的类钙矾石双羟合结构体在高Cl-、低pH环境下长期陈化过程经历了溶解-再结晶作用。大量的铁微晶相溶解形成富铝水羟合铁(ferrihydrite)胶体结构,Cl-与Ca2+以键合或共沉淀方式进入富铝水羟合铁(ferrihydrite)相。富铝水羟合铁(ferrihydrite)胶体最终的结晶相还是β-FeOOH。     

用对氧的电子探针定量分析值测定石榴子石中Fe~(2+)与Fe~(3+)的含量

本文用对氧的电子探针定量分析值测定了几种石榴子石中Fe~(2+)与Fe~(3+)的含量,讨论了这种新方法中氧的测量精度,详细叙述了实验过程,并与常用的电价差值法和剩余氧计算法进行了比较。     

Determination of bioavailable Fe(III) content in column experiments with the reactive tracer phosphate

Different methods were compared to evaluate the oxidation capacity of ferric iron in column studies. The specific adsorption of the reactive tracer phosphate on the Fe(III) oxide surface was used as an alternative approach to determine the oxidation capacity utilizing the linear correlation between the long-term extent of Fe(III) reduction and the specific surface area of the oxide. Although a low crystalline form of ferric iron (two-line ferrihydrite) was used as electron acceptor and toluene as a carbon source, only 31 and 24% respectively of the total iron was reduced by Geobacter metallireducens in parallel experiments. The results of the phosphate tracer tests were in good agreement with the Fe(III) that was actually reduced and the microbially oxidized toluene. The oxidation capacity of ferric iron is therefore overestimated by the chemical extraction methods, which completely dissolve the ferrihydrite and neglect surface-dependent limitations.