磷灰石对湖泊沉积物中水铁矿稳定性的制约

通过在滇池开展原位实验,研究探讨了湖泊沉积物中磷灰石制约水铁矿分解和转化的机制,以及二者共存时的环境效应。结果表明:将水铁矿放置到沉积物中1个月,矿物保持稳定;放置时间达到3个月时,添加磷灰石实验中水铁矿发生了显著物相转变。冬天(12—2月)实验中,转化产物随深度的变化趋势为针铁矿+磁(赤)铁矿→针铁矿+纤铁矿→针铁矿;夏天(6—9月)实验中,转化产物随深度的变化趋势为针铁矿+纤铁矿+磁(赤)铁矿→针铁矿+纤铁矿→未转化。透射电镜分析结果显示冬天实验中生成的磁性铁氧化物为纳米磁铁矿和磁赤铁矿,夏天实验中产生的则主要为纳米磁铁矿。X射线光电子能谱分析结果显示冬天表层实验样品具有较高P含量。分析表明的湖泊沉积物中磷灰石促进水铁矿转化的过程为:(1)微生物促进磷灰石溶解;(2)磷灰石溶解释放的P促进铁还原菌生长;(3)铁还原菌促进水铁矿还原;(4)水铁矿还原产生的溶解态Fe²⁺催化水铁矿向针铁矿、纤铁矿和磁铁矿转化。冬天及沉积氧化-还原界面最适宜磷灰石分解菌和铁还原菌生长,水铁矿的转化和P释放能力也更强,相应地内源磷释放的风险也更大。     

水铁矿的结构、组成及环境地球化学行为

水铁矿广泛分布于水、土壤、沉积物和生物体中,它具有大比表面积和高表面活性,控制和影响着环境中某些污染物质和营养元素的形态、迁移和转化。此外,它也是环境中其他晶质铁(氢)氧化物形成的前驱体。然而,人们对水铁矿在环境中的作用和重要性的认识还存在不足,主要表现在：(1)水铁矿通常被混淆为无定形铁氢氧化物或水合铁氧化物,环境中的水铁矿因难以分离和进行定量分析而使其含量常被低估;(2)水铁矿结晶弱,结构表征困难,对其在环境中的分布、组成、结构及性质的认识较欠缺。水铁矿以弱晶质的纳米颗粒形式存在,其XRD(X射线衍射)线少且宽、强度弱。根据衍射线的条数可将水铁矿分为结晶较弱的2 线水铁矿(2LFh)和结晶较好的6 线水铁矿(6LFh)。目前,普遍接受的水铁矿化学式为Fe5HO8·4H2O,但大量实验表明H2O不是水铁矿结构的必要成分,且容易被吸附的外来物质取代。有人提出水铁矿是一种二元结构,中心为八面体配位Fe,表面以四面体配位Fe为主,这有待论证。最近,通过PDF(配对分布函数)研究水铁矿的结构表明,理想水铁矿结构包含20%四面体配位Fe和80%八面体配位Fe,化学式为Fe10O14(OH)2。然而, 不少学者对这一新的水铁矿结构模型提出了质疑。对近年来水铁矿的分布、组成、结构和环境行为方面的研究和存在的问题进行了综述和讨论,并且对水铁矿的未来研究方向进行了展望。     

模拟厌氧水稻土中氮、砷变化及迁移研究

矿渣和酸性矿山废水的排放会使矿区周围的农田受到污染。为研究厌氧条件下矿区农田中氮和砷之间的联系,本文通过摇瓶实验探究了含砷水铁矿在厌氧含氮农田中释放的砷形态的变化,通过柱实验探究了水稻生长对氮、砷形态和浓度的影响。研究结果发现,在厌氧条件下,外源氮的加入促进了砷污染水稻土中As(Ⅴ)的还原,使生成的As(Ⅲ)浓度最高达396μg/L;在柱实验模拟的厌氧农田不同层位中,水稻的生长过程促进了氮和砷的还原以及砷向下层位的迁移,使装置中的As(Ⅲ)浓度最高达517μg/L;摇瓶实验和柱实验在相近的厌氧条件下,NO^-₃的存在能够直接参与As(Ⅴ)还原。研究结果为农田砷污染的治理提供了一定的参考价值。     

Feldspar dissolution in the presence of organic acid anions under diagenetic conditions: an experimental study

Previous experiments to determine the aqueous solubility of lead-rich orthoclase in the presence of the ethanoic acid anion (acetate) at 150°C and 50 MPa have shown that the observed fluid compositions are essentially controlled by the presence of secondary mineral precipitates, which buffer dissolved species apart from lead. Data for lead suggest that dissolution increased with increasing fluid ethanoic acid anion content, but the ethanoic acid anion was unstable under the experimental conditions. Additional experiment have now been carried out using pure natural albite and ethanoic acid anion solutions at 150°C and 50 MPa, in which the ethanoic acid anion remains stable. The results for albite again demonstrate the influence on fluid composition of secondary mineral precipitates, but data for silica allow the rates of dissolution to be estimated. Values obtained for the dissolution rate constant increase from 1.8 × 10⁻⁷ to 5.3 × 10⁻⁷ s⁻¹ with increasing fluid ethanoic acid anion content (0.1–2.5 molal) and approximate to values for quartz and orthoclase dissolution rates for similar PT conditions, reflecting similarity in the mechanisms of dissolution of the minerals' three dimensional (alumino)silicate frameworks. However, these experiments provide no other evidence that the ethanoic acid anion enhances equilibrium solubilities of feldspars or quartz. In contrast to the results for the ethanoic acid anion, data for albite dissolution experiments in the presence of the ethanedioic acid anion (oxalate) at 150°C and 50 MPa show an inhibitionn of solubility (apart from aluminium), while data for the 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion (citrate) show considerable enhancement of solubility for aluminium and silicon, and titanium derived from the reaction vessel. The 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion is unstable, decaying according to first order kinetics (half life = 1.5 days). In their application to problems of diagenesis in the presence of organic acid anions, these results suggest that the ethanoic acid anion may influence feldspar dissolution by accelerating diagenetic reactions, while geologically short-lived species such as the 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion and its decay products may dramatically enhance aluminosilicate solubility.     

Effect of groundwater fulvic acid on the adsorption of arsenate by ferrihydrite and gibbsite

Adsorption studies have been conducted at pH 4, 6 and 8 to assess the effect of fulvic acid on arsenate adsorption to ferrihydrite and gibbsite. The studies compared the adsorption of arsenate on the mineral surfaces in the absence of fulvic acid, to those cases where increasing concentrations of fulvic acid (0.3–60 μM) were added to the mineral–arsenate suspensions. Experiments where arsenate was added to mineral–fulvate suspensions were also conducted. The results suggest that arsenate adsorption on both gibbsite and ferrihydrite decreases with increasing concentrations of fulvic acid. This effect was highest at pH 4, and decreased at pH 6 and 8. Ferrous ion concentrations were very low during the ferrihydrite experiments and support the view that fulvic acid can both displace arsenate from and inhibited its adsorption to mineral surfaces. The experiments also indicated that the amount of arsenate adsorbed was lower if fulvic acid was added before rather than after arsenate. This may reflect the relative size of arsenate and fulvic acid molecules and their ability to penetrate the crystal matrices of the minerals.     

Arsenate and arsenite adsorption onto Al-containing ferrihydrites. Implications for arsenic immobilization after neutralization of acid mine drainage

Natural ferrihydrites (Fh) often contain impurities such as aluminum, especially in acid mine drainage, and these impurities can potentially impact the chemical reactivity of Fh with respect to metal (loid) adsorption. In the present study, we have investigated the influence of aluminum on the sorption properties of ferrihydrite with respect to environmentally relevant aqueous arsenic species, arsenite and arsenate. We have conducted sorption experiments by reacting aqueous As(III) and As(V) with synthetic Al-free and Al-bearing ferrihydrite at pH 6.5. Our results reveal that, when increasing the Al:Fe molar ratio in Fh, the sorption density dramatically decreased for As(III), whereas it increased for As(V). Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy analysis at the As K-edge indicated that the As^IIIO₃ pyramid binds to FeO₆ octahedra on both Al-free Fh and Al-bearing Fh, by forming bidentate mononuclear edge-sharing (²E) and bidentate binuclear corner-sharing (²C) surface complexes characterized by As–Fe distances of 2.9 Å and 3.4 Å, respectively. The decrease in As(III) sorption density with increasing Al:Fe ratio in Fh could thus be explained by a low affinity of the As(OH)₃ molecule for Al surface sites compared to Fe ones. In contrast, on the basis of available literature on As(V) adsorption mechanisms, we suggest that, in addition to inner-sphere ²C arsenate surface complexes, outer-sphere arsenate surface complexes forming hydrogen bonds with both Al–OH and Fe–OH surface sites could explain the enhancement of As(V) sorption onto aluminous Fh relative to Al-free Fh, as observed in the present study. The presence of aluminum in Fh may thus enhance the mobility of arsenite with respect to arsenate in Acid Mine Drainage impacted systems, while mixed Al:Fe systems could present an alternative for arsenic removal from impacted waters, provided that As(III) would be oxidized to As(V).     

天然矿物低温催化脂肪酸酯生烃反应动力学研究

选择十八烷酸甲酯为模型化合物,以 10种天然矿物为载体,通过动力学方法考察了天然矿物对脂肪酸酯生烃反应的催化作用.结果表明,地质低温条件下天然矿物对脂肪酸酯生烃反应具有催化作用.矿物的催化作用主要体现在对反应活化能和指前因子的影响上.粘土、碳酸盐和金属元素对于脂肪酸酯生烃反应具有不同的催化作用,碳酸盐矿物相对于粘土矿物使生烃反应的活化能降低,过渡金属化合物矿物存在时,催化反应活化能介于碳酸盐和粘土矿物之间.天然矿物的存在能够升高或降低反应指前因子.     

Uranium(VI) sorption to hematite in the presence of humic acid

A long-standing problem in aquatic geochemistry has been the incorporation of natural organic matter (NOM) into speciation models. The general effect of NOM on metal ion sorption by particles has been understood for some time, and significant progress has been made in elucidating some of the details of the role of NOM through the use of surrogate organic acids such as citric acid. However, a gap exists between the general observations that have been made of NOM behavior and the inclusion of NOM in surface chemical models for metal ion sorption. In this paper, we report on the results of a study on the sorption of U(VI) by hematite in the absence and presence of Suwannee river humic acid (HA) and over a range of other system conditions (e.g., pH, I). Essential HA characteristics (e.g., its acid/base, metal binding, and surface chemical properties) were “captured” by representing the HA as an assembly of monoprotic acids with assumed pK values and without explicit correction for electrostatic effects. The ternary system (hematite/HA/U(VI)) was simulated through the combination of the binary submodels (i.e., CO₃²⁻/hematite, U(VI)/HA, U(VI)/hematite, and HA/hematite) with model constants fixed at the values determined from simulations of the respective experimental systems. However, the “summed-binary” approach undersimulated experimental results, and the ternary system model required the postulation of two ternary surface (Type A) complexes composed of the uranyl ion, hematite surface sites, and the model ligands comprising the HA. Consideration of the HA in this manner permitted the simulation of HA effects on U(VI) sorption by hematite over a range of solution conditions using a general speciation model.     

微波辅助萃取技术在有机锡砷汞化合物形态分析中的应用

文章总结了近10年来萃取技术在有机锡、有机砷和有机汞化合物形态分析中的应用，对各种萃取技术进行了比较，并指出微波辅助萃取技术具有快速、高效、试剂消耗少、基体干扰少的优点。     

乙酸和碳酸对粘土土工性状影响的试验

对加入不同浓度乙酸和碳酸的土样做室内土工试验,并进行机理分析。试验结果表明:乙酸根、碳酸根通过改变粘土颗粒双电层的厚度、极性水分子的吸附量,使土的结构发生凝聚或分散,引起压实粘土的塑性、渗透性等变化。其中,乙酸根是通过溶解粘土矿物中的铝,提高了粘土的渗透系数和塑性指数;而碳酸根是以其与金属离子发生化学反应生成难溶性碳酸盐的方式,降低了粘土的渗透系数。这为判断垃圾堆放场粘土衬垫工程的稳定性提供了依据。     

The mechanism of fatty acid adsorption in the presence of fluorite,calcite and barite

The interaction of oleic acid with fluorite, calcite and barite has been studied using solubility, oleate abstraction, electrophoretic mobility and Hallimond-tube flotation measurements. Abstraction of oleate from aqueous solution corresponds to the precipitation of the metal oleate. Multilayers of metal oleate inhibits the dissolution of the minerals and prevents true equilibrium from being obtained. Flotation is not only dependent on the amount of oleate abstracted but also on the strength of adhesion of the precipitated metal oleate to the minerals. Selectivity between the flotation of calcite, fluorite and barite is unlikely to be obtained by varying the pH because similar responses are observed.     

金云母-蛭石间层矿物的酸浸取物与酸蚀机理研究

对采自新疆尉犁蛭石矿的金云母蛭石间层矿物样品进行了酸处理实验研究。在样品化学成分和XRD分析的基础上,研究了样品酸处理后酸浸取物的化学组成、含量及结构变化特征;分析讨论了金云母蛭石间层矿物在酸处理过程中不同阳离子浸出率的变化规律和酸蚀机理。结果表明,层间可交换性阳离子的氧化物CaO和Na2O的酸浸取率最高,层间不可交换性阳离子的氧化物K2O次之,八面体中阳离子的氧化物MgO、Fe2O3和Al2O3具有较高的酸浸取率,而四面体阳离子的氧化物Si O2的酸浸取率最低;金云母蛭石间层矿物中蛭石晶层含量高的样品酸浸取率高,金云母蛭石间层矿物的耐酸蚀性能不如金云母。     

金川铜镍矿山尾矿砂酸溶性实验研究

为研究金川铜镍矿山酸性废水溶解尾矿砂实现综合治理废液与废固的可能性,进行了尾矿砂在硫酸中的溶解实验。结果表明,尾矿砂在硫酸浓度大于3mol/L、温度保持90℃以上并在液固比6.0下强力搅拌,能够较好地溶解于硫酸中,生成无定形二氧化硅;300℃的马弗炉焙烧4h有助于尾矿砂中绿泥石的溶解,对透闪石的溶解影响不大。尾矿砂中橄榄石、蛇纹石和透辉石较容易被硫酸溶解,透闪石、斜长石则比较难溶解,这与尾矿砂中矿物性质有密切关系。     

硫酸型酸雨参与碳酸盐岩溶蚀的研究进展

碳酸盐岩的H2CO3溶蚀产生岩溶碳汇,占整个岩石风化碳汇的 94%。西南岩溶区硫酸型酸雨严重,硫酸型酸雨广泛参与碳酸盐岩的溶蚀。H2SO4参与的碳酸盐岩风化是一个大气CO2净释放过程,具有减汇作用巨大。另一方面,岩溶区石灰土壤和地下水具有较高的pH值及盐基饱和度,对H+有巨大的缓冲作用,大气酸沉降在碳酸盐岩地区可能并不会造成地下水的HCO3-和pH降低;相反,较高浓度的SO42-所产生的盐效应和SO2-4与各种阳离子形成的离子对会增大方解石、白云石溶解度,可增强H2CO3对碳酸盐的溶蚀,这可能会使岩溶作用产生更大的碳汇效应。因此,硫酸型酸雨参与碳酸盐岩风化的减汇效应不仅可能被高估,硫酸型酸雨还可能增强碳酸盐岩的H2CO3溶蚀,具有增加岩溶碳汇效应的作用。应结合石灰土壤对大气酸沉降的缓冲容量和阈值及大气酸沉降的H+与土壤中盐基离子的交换量,并综合考虑盐效应、离子对作用、同离子效应,客观评价硫酸型酸雨流经石灰土壤层后对碳酸盐岩溶蚀吸收大气/土壤CO2的影响      

Possibility of the discovery of eolian gold placers in Tuva

Issue of the influence of eolian processes on the formation of gold placers in the Tuva region is considered. It has been revealed that the formation of placers is related not only to hydrodynamic processes but also to eolian processes, which are reflected in the formation of relief, redistribution of metal, and reworking of the useful component. Study of typomorphic features of the eolian gold and regularities of its redistribution revealed the possibility of discovery of a new type of placer gold (eolian and heterogeneous placers).     

In situ atomic force microscopy measurements of biotite basal plane reactivity in the presence of oxalic acid

We have used a direct imaging technique, in situ atomic force microscopy (AFM), to observe the dissolution of the basal biotite surface by oxalic acid over a range of temperatures close to ambient conditions, using a specially designed AFM liquid cell and non-invasive intermittent contact mode of operation. From the 3-dimensional nanometre-resolution data sets, we observe a process characterised by the slow formation of shallow etch pits in the (0 0 1) surface and fast growth of etch pits from the resulting steps, which represent proxies for the {h k 0} surface. Measurements of dissolution rates as a function of temperature allow a determination of an apparent activation energy (E_a,app) for the process, via mass-loss calculations from image analysis. We obtain a value of E_a,app = 49 ± 2 kJ mol⁻¹, which is consistent with separate calculations based on planar area etch pit growth, and measurements of etch pit perimeters, indicating that this value of E_a,app is representative of {h k 0} surface dissolution. The measurement of etch pit perimeters also enables an estimation of apparent activation energy as a function of step density indicating substantially higher apparent activation energy, up to E_a,app = 140 kJ mol⁻¹, on extrapolation towards a pristine surface with no defects. We suggest that this higher value of E_a,app represents the slow formation of etch pits into the (0 0 1) surface.     

How to use the groundwater resources at the area polluted by organoarsenic compounds for Old Japanese Army Toxic Gas Weapon in Japan

从医学地质学角度看,在日本地质污染的地方如何使用地下水资源,我们面临许多问题.本文讨论了地质污染学(geo-pollution science)作为医学地质学中一门学科的概念以及在受二苯亚砷酸污染的地方成功使用农业地下水的案例.     

A detailed study of the transformation of ferrihydrite to hematite in an aqueous medium at 92°C

The transformation of ferrihydrite to hematite by ageing at 92°C in solution has been studied using computer-fitted ⁵⁷Fe Mössbauer spectra, together with X-ray diffraction and electron microscopy. The X-ray diffraction patterns show hematite is first discernible after 10 minutes ageing and after 30 minutes the hematite peaks are sharp and definite. Mössbauer spectroscopy at room temperature shows it is discernible after 60 minutes ageing but can be detected at liquid nitrogen temperature by 30 minutes. With further ageing the ferrihydrite progressively transforms to hematite and at 116 hours hematite is the only component. The electron micrographs show the ferrihydrite particles of 3–5 nm diameter coalesce to form hexagonal hematite platelets, initially of some 20 nm diameter, which increase to 30–40 nm with ageing.The Mössbauer spectra show the broadened ferric doublet resonance of ferrihydrite and the six-line magnetic hyperfine hematite resonance. Two closely overlapping ferric doublets were computer-fitted to the ferrihydrite resonance, the widths and dips of the component peaks within each doublet being constrained initially to be equal. As these constraints were relaxed, the widths and dips became unequal. This effect is related to the progressive ordering of the ferrihydrite structure as it ages to produce a partially magnetically ordered hematite structure, with a reduced magnetic field at room temperature of initially 473 kOe, increasing to 499 kOe with time. These results suggest a direct transformation of ferrihydrite to hematite, initiated by the coalescing of the ferrihydrite particles.     

Dissolution kinetics of probertite in boric acid solution

Probertite (NaCaB₅O₉·5H₂O) and ulexite (NaCaB₅O₉·8H₂O) posses identical chemical formula except for their water content. In this study, the dissolution of probertite in boric acid solution was investigated as a function of temperature and time. As the boric acid concentration increased, the dissolution of probertite also increased. However, the boric acid concentrations above 5 wt.% at 60 °C and 80 °C did not significantly affect the dissolution of probertite. The stirring speed had almost no effect on the dissolution of probertite. The dissolution kinetics of probertite in boric acid solution was controlled by first order pseudo homogeneous reaction. The activation energies for different probertite particle sizes varied from 25.25 kJ/mol K to 28.25 kJ/mol K, indicating that particle size had minor effect on the dissolution of probertite.