Reactive-transport modeling of fly ash–water–brines interactions from laboratory-scale column studies

Dynamic leaching tests are important studies that provide more insights into time-dependent leaching mechanisms of any given solid waste. Hydrogeochemical modeling using PHREEQC was applied for column modeling of two ash recipes and brines generated from South African coal utility plants, Sasol and Eskom. The modeling results were part of a larger ash–brine study aimed at acquiring knowledge on (i) quantification and characterization of the products formed when ash is in contact with water–brines in different scenarios, (ii) the mineralogical changes associated with water–brine–ash interactions over time, (iii) species concentration, and (iv) leaching and transport controlling factors. The column modeling was successfully identified and quantified as important reactive mineralogical phases controlling major, minor and trace elements’ release. The pH of the solution was found to be a very important controlling factor in leaching chemistry. The highest mineralogical transformation took place in the first 10 days of ash contact with either water or brines, and within 0.1 m from the column inflow. Many of the major and trace elements Ca, Mg, Na, K, Sr, S(VI), Fe, are leached easily into water systems and their concentration fronts were high at the beginning (within 0.1 m from the column inflow and within the first 10 days) upon contact with the liquid phase. However, their concentration decreased with time until a steady state was reached. Modeling results also revealed that geochemical reactions taking place during ash–water–brine interactions does affect the porosity of the ash, whereas the leaching processes lead to increased porosity. Besides supporting experimental data, modeling results gave predictive insights on leaching of elements which may directly impact on the environment, particularly ground water. These predictions will help develop scenarios and offer potential guide for future sustainable waste management practices as a way of addressing the co-disposal of brines within inland ash dams and heaps.     

Spectroscopic studies of synthetic and natural ringwoodite, γ-(Mg,Fe)<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Synthetic ringwoodite γ-(Mg_1?x Fe _x )₂SiO₄ of 0.4 ≤ x ≤ 1.0 compositions and variously colored micro-grains of natural ringwoodite in shock metamorphism veins of thin sections of two S6-type chondrites were studied by means of microprobe analysis, TEM and optical absorption spectroscopy. Three synthetic samples were studied in addition with Mössbauer spectroscopy. The Mössbauer spectra consist of two doublets caused by ^VIFe²⁺ and ^VIFe³⁺, with IS and QS parameters close to those established elsewhere (e.g., O’Neill et al. in Am Mineral 78:456–460, 1993). The Fe³⁺/Fe_total ratio evaluated by curve resolution of the spectra, ranges from 0.04 to 0.1. Optical absorption spectra of all synthetic samples studied are qualitatively very similar as they are directly related to the iron content. They differ mostly in the intensity of the observed absorption features. The spectra consist of a very strong high-energy absorption edge and a series of absorption bands of different width and intensity. The three strongest and broadest absorptions of them are attributed to splitting of electronic spin-allowed ⁵ T _2g → ⁵ E _g transitions of ^VIFe²⁺ and intervalence charge-transfer (IVCT) transition between ferrous and ferric ions in adjacent octahedral sites of the ringwoodite structure. The spin-allowed bands at ca. 8,000 and 11,500 cm^?1 weakly depend on temperature, whilst the Fe²⁺/Fe³⁺ IVCT band at ~16,400 cm^?1 displays very strong temperature dependence: i.e., with increasing temperature it decreases and practically disappears at about 497 K, a behavior typical for bands of this type. With increasing pressure the absorption edge shifts to lower energies while the spin-allowed bands shift to higher energy and strongly decreases in intensity. The IVCT band also strongly weakens and vanishes at about 9 GPa. We assigned this effect to pressure-induced reduction of Fe³⁺ in ringwoodite. By analogy with synthetic samples three broad bands in spectra of natural (meteoritic) blue ringwoodite are assigned to electronic spin-allowed transitions of ^VIFe²⁺ (the bands at ~8,600 and ~12,700 cm^?1) and Fe²⁺/Fe³⁺ IVCT transition (~18,100 cm^?1), respectively. Spectra of colorless ringwoodite of the same composition consist of a single broad band at ca. 12,000 cm^?1. It is assumed that such ringwoodite grains are inverse (Fe, Mg)₂SiO₄-spinels and that the single band is caused by the split spin-allowed ⁵ E → ⁵ T ₂ transition of ^IVFe²⁺. Ringwoodite of intermediate color variations between dark-blue and colorless are assumed to be partly inversed ringwoodite. No glassy material between the grain boundaries in the natural colored ringwoodite aggregates was found in our samples and disprove the cause of the coloration to be due to light scattering effect (Lingemann and Stöffler in Lunar Planet Sci 29(1308), 1998).     

Characterisation of the environmental impact of the Rodalquilar mine,Spain by ground-based reflectance spectroscopy

This study has investigated the utility of using field-based reflectance spectroscopy to characterise the distribution and nature of the dispersion of tailings material from the Rodalquilar mine, Spain. Field spectral measurements covering the visible to shortwave infrared wavelengths (0.35 to 2.5 m) and laboratory analyses were performed on samples collected along the length of the main river within the Rodalquilar valley. The nature and degree of contamination at locations within the river channel were calculated by a range of spectrometric analyses. The resulting mineral maps identified that tailings material with significant amounts of hematite with minor jarosite, ferrihydrite and goethite, and clays, primarily alunite and kaolinite, with minor smectite and illite, had been dispersed along the length of the river. These results have been used to improve understanding of the erosion and remediation history of the Rodalquilar mine. This study has shown the potential of field-based reflectance spectroscopy, integrated with ground positioning and digital mapping systems, as a real-time mapping methodology enabling immediate, accurate characterisation of the nature and scale of tailings material dispersion.     

Metal pollution in coarse sediments of Tuticorin coast,Southeast coast of India

Indian coastal waters are subjected to considerable pressure from sewage and industrial wastes, which are responsible for the contamination of the coastal sediments with consequent loss in biosphere. The present investigation attempts to study the significance of coarse material (Sand fraction) in the distribution of metals in polluted marine sediments. The study revealed that coarse Sand component contains a relatively significant proportion of the anthropogenic metals (Cd, Cu, Pb and Zn) and therefore it cannot be neglected in metal pollution studies of coastal sediments. Further, the distribution of anthropogenic metals in both Silt + Clay and Sand fraction follow the same suit indicating similar pollution sources. From the total sediment type (Silt + Clay and Sand fraction) all anthropogenic metals had a noticeable amount (>50%) in the acid extractable (and potentially bio-available) fraction. This article stresses the importance of coarse fraction in metal pollution studies in Indian coastal system.     

锡-银多金属成矿系统的基本特征、研究进展与展望

锡-银多金属成矿系统主要产于主动大陆边缘、板内伸展和造山后伸展等构造背景中。全球典型成矿带包括玻利维亚南部带、俄罗斯远东Sikhote-Alin带、我国大兴安岭南段、南岭和欧洲Erzgebirge地区。成矿相关岩浆岩主要为浅成中酸性侵入体或次火山岩体,包括流纹英安-流纹质火山/次火山岩、石英斑岩、花岗斑岩、花岗闪长斑岩等,并与同期火山岩和碱性基性岩脉密切共生。岩浆源区不仅有大量地壳物质的参与,还普遍存在不同比例地幔物质成分的加入。围岩蚀变由早到晚、由成矿中心向外依次发育电气石化/云英岩化、绢云母化、伊利石化和高级泥化,金属矿化组合相应的依次为Sn(-W)→Zn-CuPb-Sn→Ag-Pb-Zn-Sb-Sn→Ag-Sb-Pb,锡矿化产于电气石和云英岩化带内,银矿化产于伊利石化和高级泥化带内。以银为主矿体多在浅部呈多条陡立脉状产出,以锡为主的矿体在深部呈大脉状和热液角砾岩体产出,也可呈浸染状或细网脉状产出(此时称为斑岩型锡矿)。此类矿床还常伴生In、Cd、Ga等矿化,主要产于闪锌矿、黄铜矿和方铅矿为主的硫化物成矿阶段。对成矿金属起源的研究显示锡可能主要来自中上地壳富锡的变质沉积岩,但银的来源尚无明确解释,沉积岩、地幔、围岩地层可能都有贡献。岩浆较低的氧逸度条件和富Cl的成分有利于形成富锡和其它金属的成矿流体,成矿早期流体常具有较高的盐度,伴随温度的降低和天水流体的稀释过程,流体由早期的高温高盐度逐渐演化到晚期的低温低盐度,并伴随不同金属的依次沉淀,这一过程中,可能多期次流体的叠加作用对大型矿床的形成起重要作用。在前人研究基础上,提出了本类型矿床研究中存在的一些关键问题:(1)普遍存在的壳幔相互作用在成矿过程中的作用尚不明确,地幔物质可能是重要的热源、硫和金属的来源;(2)火山作用与成矿之间的关系及其所起的作用;(3)在同一锡-银多金属成矿带中,富锡贫银、富银贫锡、富锡又富银这三类矿床之间的成因联系如何?造成它们金属组合差异的原因如何?可能需要从岩体侵位深度、矿床剥蚀程度、成矿流体性质等方面进行研究探讨;(4)不同金属元素的起源与耦合成矿作用,Sn-Ag-In等重要的成矿元素可能不是相同的起源,其进入流体的时间及沉淀的物理化学条件也是有差异的,它们在同一矿床中耦合成矿的详细过程与机制尚不清楚,原位微区流体包裹体成分分析、硫化物微量元素和同位素原位分析和面扫描技术可能是解决这一难题的重要手段。上述问题的解决不仅有助于提高对锡-银多金属矿床成矿过程的认识,还可为相关矿床的勘查找矿工作提供理论支持。     

Mercury bioaccumulation in the spotted dogfish (Scyliorhinus canicula) from the Atlantic Ocean

The annual and life-cycle mercury bioaccumulation pattern in selected tissues of the economically relevant Elasmobranchii species Scyliorhinus canicula was studied, and the risks associated with its consumption evaluated.Preferential mercury bioaccumulation occurred in muscle tissue, and followed the order muscle > heart > liver > gills > pancreas. Total mercury in muscle tissue ranged from 0.13 mg kg⁻¹ (wwt) in 1+ year old males to 0.8 mg kg⁻¹ (wwt) in 8+ year old mature females, with no significant differences found between genders, and no clear lifespan bioaccumulation pattern observed, except for mature females. Organic mercury in the muscle ranged from 0.05 mg kg⁻¹ (wwt) to 0.52 mg kg⁻¹ (wwt), corresponding to an average of 70% of total mercury content. In mature females, a significant correlation (R = 0.99, P = 0.01) was found between size and organic mercury fraction, suggesting reproduction as an important factor controlling organic mercury bioaccumulation in the spotted dogfish.     

乌鲁木齐冬季大气细颗粒物水溶性离子特征及来源

为了探讨乌鲁木齐冬季大气细颗粒物的污染水平及其水溶性离子的特征,于2013年1-3月采集大气PM_2.5样品,并利用离子色谱仪分析其中的水溶性离子,采用硫转化率、离子相关性分析及后向轨迹模型对其可能来源进行了讨论。结果表明:观测期间采样点PM_2.5平均质量浓度为170.13±51.39 μg·m^-3,水溶性离子总浓度平均值为53.47±23.76 μg·m^-3,其中3种二次离子(SO₄^2-、NO₃^-和NH₄⁺)是水溶性离子的主要组分;不同天气类型下PM_2.5和离子浓度差异较大,雾、霾天气二次离子浓度占总浓度的81.99%和86.24%,硫转化率均大于0.1;春节期间由于燃放大量的烟花爆竹,使得PM_2.5可溶性离子K⁺和Cl^-浓度急剧上升;NH₄⁺与SO₄^2-、NO₃^-相关系数分别为0.975和0.748,(NH₄)₂SO₄、NH₄HSO₄和NH₄NO₃是细颗粒物水溶性组分的可能结合方式,Cl^-和K⁺的相关性显著,说明两者具有同源性;固定排放源仍然是乌鲁木齐大气污染物的主要来源,局地大气输送会使大气污染加重。     

用于阻尼器结构不锈钢丝金属橡胶元件力学性能试验研究

为研究金属橡胶材料用作土木工程结构消能减震阻尼器的力学性能,本文针对不同成型密度的金属橡胶阻尼元件,分别在静力、动力荷载作用下进行了压缩性能试验,测试加载幅值、循环加载次数、元件成型密度、动力加载频率等因素对金属橡胶元件阻尼耗能的影响规律。研究结果表明,金属橡胶材料有着良好的弹性和阻尼特性,其滞变耗能能力随着成型密度、加载幅值的增加而增大;加载频率和加载次数对金属橡胶滞变性能几乎没有影响。