云南兰坪金顶超大型铅锌矿区镉的环境地球化学研究

矿产资源开采利用过程中导致的重金属环境污染问题日益严重。我国铅锌矿资源丰富，其开采利用过程中镉的环境污染也日益突出。本文通过对云南兰坪金顶Pb-Zn矿区矿床开采利用过程中镉等重金属元素的环境地球化学行为及矿区生态环境的研究，得出如下主要结论。 1. 矿石淋滤实验表明矿区部分氧化铅锌矿石可以很快被再次氧化或者被溶解并释放出大量镉等有害元素，滤出元素可以迅速发生沉淀或被沉淀物包裹，其释放能力表现为Zn>Pb>Cd。铅锌氧化矿石中菱锌矿组分含量是影响镉淋失的主要因素。在开放体系的水-岩作用下，矿区岩石、矿物的自然风化极易造成当地水系统中镉污染。 2. 矿区不同岩（矿）石中镉含量分布差异比较大，围岩中镉含量为50-650 ppm，平均310 ppm，原生矿中镉含量为14-2800 ppm，平均767 ppm，氧化矿中镉含量为110-8200 ppm，平均1661 ppm，其平均值最高。Zn、Cd地球化学性质的差异导致了二者在原生矿和氧化矿中的不同地球化学分配特点，原生矿Zn/Cd高于氧化矿Zn/Cd，表明氧化环境中镉更容易在氧化矿中富集，而锌更容易被氧化析出到环境中。氧化矿中Cd与Ca呈负相关，这表明Cd的富集和Ca的氧化淋失是同时进行的，并且还可能有Cd对Ca的类质同像代替存在。 3. 矿区上游对照区土壤中的高含量Cd浓度是因土壤母质层重金属高背景值造成的，而非人为污染。矿区中心区土壤受到严重Cd污染，可能与选厂、采场废石堆、尾矿库和露采矿山大范围暴露有关。矿区沿沘江下游两岸土壤中Cd含量远远超出上游土壤背景值和金顶全区土壤背景值，这可能是与污水灌溉有关。通过加权综合污染指数评价法发现矿区土壤污染的主要因子是Cd，其次是Zn和Pb，矿区土壤重金属污染贡献顺序为：Cd>Zn>Pb。矿区土壤污染主要表现为：矿区土壤污染有从中心区向沘江下游扩散区土壤中蔓延的趋势。 4. 矿区水体中出现较高含量的镉，高出天然河流中镉含量的50-100倍。矿区架崖山、北厂和跑马坪等采矿区水体中镉浓度范围在15-30 µg/L之间。矿区水体中镉含量水平表现为：矿山浅层地下水>矿山溪流水>沘江河水。研究结果表明，矿区沘江下游河段水体明显受镉污染，其中水体中镉的平均含量为15.7 µg/L，悬浮物中镉含量为49.3 mg/kg，沉积物中镉含量为203.7 mg/kg。矿区载镉岩石和矿物的自然风化是造成矿区水环境中镉污染的直接原因。 5. 跑马坪采场的废弃石具有较低的Cd含量，而北厂、架崖山采场的废弃石具有较高的Cd浓度，可能与废弃矿石类型本身差异有关。尾矿剖面中的Cd含量，在表层中随剖面深度呈递减趋势，在中层随剖面深度变化不明显，而在底层中明显富集。尾矿库表层尾矿样品中弱酸提取态和可还原态Cd高于底层尾矿样品，相比之下，表层尾矿中Cd等重金属元素易于释放到环境中，对环境的潜在危害大。老尾矿库尾矿砂中Cd金属总量高于新尾矿库尾矿砂，可能还是因为选矿工艺、技术的差异造成的。 6. 矿区污染段水体中硫同位素值较低，远远低于上游非污染区硫同位素值。矿区水体中δ34S值保持了金顶铅锌矿山源区矿山物质硫同位素的特征，显示了矿山来源物质的影响。根据水体硫酸盐中硫同位素稀释原理，研究发现沘江下游水体SO42-中85 %的硫来源于矿山物质。 7. 从矿区筛选出Cd、Zn、Pb的超富集植物共有4种：其中Cd超富集植物有2种，分别是本地生条裂萎陵菜（Potentilla lancinata Card. In Lecomte）和辣子草（Galinsoga parviflora Cav.）；Zn超富集植物仅发现有1种植物，为节节草（Equisetum ramosissmum Desf.）；Pb超富集植物发现了1种植物，为毛莲菜（Picris hieracioides L.）。这些植物均具备了超富集植物的基本特征，在污染土壤治理与修复方面具有一定的实践意义。 8. 建立了金顶铅锌矿山（床）地质环境模型。Cd的释放、迁移扩散模式为：雨水淋滤时，矿山固体废弃物产生富Cd的酸性或弱酸性矿山排水，通过下渗淋滤发生测向和垂向迁移，进入周边水体和土壤，然后被水系沉积物中针铁矿、方解石等吸附，并在沉降物中沉淀富集，导致矿区主要河流沘江水体的自净能力下降，加速水体的进一步恶化，破坏生物生存环境。矿区受污染水体、土壤和大气中的有害物质通过生物链进入动植物体内，进而危害人类健康。

Colorimetric and ratiometric fluorescence sensing of fluoride: Tuning selectivity in proton transfer

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Analyses of patterns of copper and lead mineralisation in human skeletons excavated from an ancient mining and smelting centre in the Jordanian desert

Grattan, J.P., Al-Saad, Z., Gilbertson, D.D., Karaki, L.O., Pyatt, F.B 2005 Analyses of patterns of copper and lead mineralisation in human skeletons excavated from an ancient mining and smelting centre in the Jordanian desert Mineralogical Magazine. 69(5) 653-666.

Determinação de cádmio e chumbo em brinquedos para crianças com idade inferior a 3 anos

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

Occupational lead neurotoxicity: A behavioural and electrophysiological evaluation. study design and year one results.

To evaluate the effects of chronic lead exposure on the nervous system in adults, a set of neurobehavioural and electrophysiological tests was administered to 99 lead exposed foundry employees and 61 unexposed workers. Current and past blood lead concentrations were used to estimate the degree of lead absorption; all previous blood lead concentrations had been less than or equal to 90 micrograms/100 ml. Characteristic signs (such as wrist extensor weakness) or symptoms (such as colic) of lead poisoning were not seen. Sensory conduction in the sural nerve was not affected. By contrast, various neurobehavioural functions deteriorated with increasing lead burden. Workers with blood lead concentrations between 40 and 60 micrograms/100 ml showed impaired performance on tests of verbal concept formation, visual/motor performance, memory, and mood. Thus impairment in central nervous system function in lead exposed adults occurred in the absence of peripheral nervous system derangement and increased in severity with increasing lead dose.

Occupational lead neurotoxicity: Improvement in behavioural effects after reduction of exposure.

To evaluate critical exposure levels and the reversibility of lead neurotoxicity a group of lead exposed foundry workers and an unexposed reference population were followed up for three years. During this period, tests designed to monitor neurobehavioural function and lead dose were administered. Evaluations of 160 workers during the first year showed dose dependent decrements in mood, visual/motor performance, memory, and verbal concept formation. Subsequently, an improvement in the hygienic conditions at the plant resulted in striking reductions in blood lead concentrations over the following two years. Attendant improvement in indices of tension (20% reduction), anger (18%), depression (26%), fatigue (27%), and confusion (13%) was observed. Performance on neurobehavioural testing generally correlated best with integrated dose estimates derived from blood lead concentrations measured periodically over the study period; zinc protoporphyrin levels were less well correlated with function. This investigation confirms the importance of compliance with workplace standards designed to lower exposures to ensure that individual blood lead concentrations remain below 50 micrograms/dl.

Comparing impacts of new cropping systems on biodiversity in traditional rural China

This study selected six geographically-similar villages with traditional and alternative cultivation methods (two groups of three, one traditional and two alternatives) in two counties of Henan Province, China—a representative area of the Huang-huai-hai Plain representing traditional rural China. Soil heavy metal concentrations, floral and faunal biodiversity, and socio-economic data were recorded. Heavy metal concentrations of surface soils from three sites in each village were analysed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS, chromium, nickel, copper, cadmium, and lead) and Atomic Absorption Spectrophotometer (AAS, zinc). The floral biodiversity of four land-use types was recorded following the Braun-Blanquet coverage-abundance method using 0.5×0.5m quadrats. The faunal biodiversity of two representative farmland plots was recorded using 0.3×0.3m quadrats at four 0.1m layers. The socio-economic data were recorded through face-to-face interviews of one hundred randomly selected households at each village. Results demonstrate different cultivation methods lead to different impact on above variables. Traditional cultivation led to lower heavy metal concentrations; both alternative managements were associated with massive agrochemical input causing heavy metal pollution in farmlands. Floral distribution was significantly affected by village factors. Diverse cultivation supported high floral biodiversity through multi-scale heterogeneous landscapes containing niches and habitats. Faunal distribution was also significantly affected by village factor nested within soil depth. Different faunal groups responded differently, with Acari being taxonomically diverse and Collembola high in densities. Increase in manual labour and crop number in villages using alternative cultivation may positively affect biodiversity. The results point to the conservation potential of diverse cultivation methods in traditional rural China and other regions under social and political reforms, where traditional agriculture is changing to unified, large-scale mechanized agriculture. This study serves as a baseline for conservation in small-holding agricultural areas of China, and points to the necessity of further studies at larger and longer scales.

Policy-induced technology adoption: Evidence from the U.S. lead phasedown

Theory suggests that economic instruments, such as pollution taxes or tradable permits, can provide more efficient technology adoption incentives than conventional regulatory standards. We explore this issue for an important industry undergoing dramatic decreases in allowed pollution - the U.S. petroleum industry's phasedown of lead in gasoline. Using a duration model applied to a panel of refineries from 1971-1995, we find that the pattern of technology adoption is consistent with an economic response to market incentives, plant characteristics, and alternative policies. Importantly, evidence suggests that the tradable permit system used during the phasedown provided incentives for more efficient technology adoption decisions.

Atherosclerosis: Viewing the problem from a different perspective including possible treatment options

This paper proposes that atherosclerosis is initiated by a signaling event that deposits calcium hydroxyapatite (Ca-HAP). This event is preceded by a loss of mechanical structure in the arterial wall. After Ca-HAP has been deposited, it is unlikely that it will be reabsorbed because the solubility product constant (K sp) is very small, and the large stores of Ca +2 and PO 4-3 in the bones oppose any attempts to dissolve Ca-HAP by decreasing the common ions. The hydroxide ion (OH -) of Ca-HAP can be displaced in nature by fluoride (F -) and carbonate (CO 3-2) ions, and it is proposed that anions associated with cholesterol ester hydrolysis and, in very small quantities, the enolate of 7-ketocholesterol could also displace the OH -of Ca-HAP, forming an ionic bond. The free energy of hydration of Ca-HAP at 310 K is most likely negative, and the ionic radii of the anions associated with the hydrolysis of cholesterol ester are compatible with the substitution. Furthermore, examination of the pathology of atherosclerotic lesions by Raman and NMR spectroscopy and confocal microscopy supports deposition of Ca-HAP associated with cholesterol. Investigating the affinity of intermediates of cholesterol hydrolysis for Ca-HAP compared to lipoproteins such as HDL, LDL, and VLDL using isothermic titration calorimetry could add proof of this concept and may lead to the development of a new class of medications targeted at the deposition of cholesterol within Ca-HAP. Treatment of acute ischemic events as a consequence of atherosclerosis with denitrogenation and oxygenation is discussed. © the author(s), publisher and licensee Libertas Academica Ltd.

Modelling the performance of lead-Free solder interconnects for copper bumped flip-chip devices

Traditionally, before flip chips can be assembled the dies have to be attached with solder bumps. This process involves the deposition of metal layers on the Al pads on the dies and this is called the under bump metallurgy (UBM). In an alternative process, however, Copper (Cu) columns can be used to replace solder bumps and the UBM process may be omitted altogether. After the bumping process, the bumped dies can be assembled on to the printed circuit board (PCB) by using either solder or conductive adhesives. In this work, the reliability issues of flip chips with Cu column bumped dies have been studied. The flip chip lifetime associated with the solder fatigue failure has been modeled for a range of geometric parameters. The relative importance of these parameters is given and solder volume has been identified as the most important design parameter for long-term reliability. Another important problem that has been studied in this work is the dissolution of protection metals on the pad and Cu column in the reflow process. For small solder joints the amount of Cu which dissolves into the molten solder after the protection layers have worn out may significantly affect solder joint properties.

Numerical simulation of vacuum dezincing of lead alloy

Removing zinc by distillation can leave the lead bullion virtually free of zinc and also produces pure zinc crystals. Batch distillation is considered in a hemispherical kettle with water-cooled lid, under high vacuum (50 Pa or less). Sufficient zinc concentration at the evaporating surface is achieved by means of a mechanical stirrer. The numerical model is based on the multiphysics simulation package PHYSICA. The fluid flow module of the code is used to simulate the action of the stirring impeller and to determine the temperature and concentration fields throughout the liquid volume including the evaporating surface. The rate of zinc evaporation and condensation is then modelled using Langmuir’s equations. Diffusion of the zinc vapour through the residual air in the vacuum gap is also taken into account. Computed results show that the mixing is sufficient and the rate-limiting step of the process is the surface evaporation driven by the difference of the equilibrium vapour pressure and the actual partial pressure of zinc vapour. However, at higher zinc concentrations, the heat transfer through the growing zinc crystal crust towards the cold steel lid may become the limiting factor because the crystallization front may reach the melting point. The computational model can be very useful in optimising the process within its safe limits.

Intermetallic phase detection in lead-free solders using synchrotron X-ray diffraction

The high-intensity, high-resolution x-ray source at the European Synchrotron Radiation Facility (ESRF) has been used in x-ray diffraction (XRD) experiments to detect intermetallic compounds (IMCs) in lead-free solder bumps. The IMCs found in 95.5Sn3.8Ag0.7Cu solder bumps on Cu pads with electroplated-nickel immersion-gold (ENIG) surface finish are consistent with results based on traditional destructive methods. Moreover, after positive identification of the IMCs from the diffraction data, spatial distribution plots over the entire bump were obtained. These spatial distributions for selected intermetallic phases display the layer thickness and confirm the locations of the IMCs. For isothermally aged solder samples, results have shown that much thicker layers of IMCs have grown from the pad interface into the bulk of the solder. Additionally, the XRD technique has also been used in a temperature-resolved mode to observe the formation of IMCs, in situ, during the solidification of the solder joint. The results demonstrate that the XRD technique is very attractive as it allows for nondestructive investigations to be performed on expensive state-of-the-art electronic components, thereby allowing new, lead-free materials to be fully characterized.

Modelling the Performance of Flexible Substrates for Lead-Free Applications

In this paper, the performance of flexible substrates for lead-free applications was studied using finite element method (FEM). Firstly, the thermal induced stress in the flex substrate during the lead free solder reflow process was predicted. The shear stress at the interface between the copper track and flex was plotted. This shear stress increases with the thickness of the copper track. Secondly, an ACF flip chip was taken as a typical lead-free application of the flex substrate. The reflow effect on the reliability of ACF interconnections was analyzed. Higher stress was identified along the interface between the conductive particle and the metallization, and the interfacial stress increases with the reflow peak temperature and the coefficient of thermal expansion (CTE) of the adhesive. The moisture effect on the reliability of ACF joints were studied using a macro-micro modeling technique, the predominantly tensile stress found at the interface between the conductive particle and metallization could reduce the contact area and even cause the electrical failure. Modeling results are consistent with the findings in the experimental work