晶安高科“三废”治理及综合利用

介绍了晶安高科污染源的来源、采取的措施及综合治理、利用方法.使废水指标由PH11～12;SS<1000mg/l;CODcr≤200mg/l;氨氮≤200mg/l降到PH6～9;SS<70mg/l;CODcr≤100mg/l;氨氮≤15mg/l;酸雾指标由HCl500～800mg/m3达到小于25～40mg/m3;炉窑烟气由林格曼黑度5,烟尘浓度2700～5191mg/Nm3降到林格曼黑度1,烟尘浓度小于200mg/Nm3;硅渣可生产复合絮凝剂和白炭黑,不仅可改善环境影响,而且可回收盐酸和利用废资源,可给企业带来经济效益.     

考虑降解效应的城市固体废弃物非线性本构模型

基于城市固体废弃物(MSW)的降解及土力学特征,在应力降解模型、等向压缩特性和邓肯-张模型的理论基础上,建立了一个能够描述MSW应力和降解耦合作用的全量非线性本构模型。给出了不同应力状态下单元体体积和轴向变形随时间变化的数学表达,同时给出了所有参数的确定方法。采用该模型对不同龄期和不同围压条件下填埋场现场试样的三轴CD应力-应变曲线以及室内长期一维降解压缩试验进行了模拟。结果表明,模型概念合理、参数明确,能够较全面地描述不同降解龄期垃圾的本构关系,可用于分析填埋场的长期变形。     

高能偏振能量色散-X射线荧光光谱法测定PM10大气颗粒物的组成

为配合X射线衍射分析(XRD)方法对可吸入大气颗粒悬浮物(PM10)的结晶物相进行定性和定量分析的研究工作,本文应用高能偏振能量色散X射线荧光光谱(HE-P-EDXRF)对Whatman玻璃纤维滤膜采集的PM10颗粒物中主、次量元素进行定量分析,着重研究了空气滤膜空白值对测定PM10颗粒物中组成的影响。结果表明,当玻璃纤维滤膜空白值中元素的面密度大于0.1μg/cm2时,需使用玻璃纤维滤膜为载体的标准样品;元素的面密度小于0.1μg/cm2时,可用聚碳酸脂膜为载体的标准样品。对HE-P-EDXRF谱仪测定PM10颗粒物中痕量重元素进行探讨,将测定元素范围扩展到62个元素,其中Na、Mg、S、Y、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu的检岀限>0.1μg/cm2;Ca、Cr、Mn、Fe、Co、Ni、Cu、Zn、Br和Rb的检岀限<0.01μg/cm2;Cl、Al、Si、P、K、Sc、Ti、V、Ge、As、Br、Se、Sr、Zr、Mo、Pd、Rh、In、Nb、Ag、Cd、Te、Sb、Sn、Ba、Cs、La、Ce、Pr、Au、Pt、W、Tl、Pb、Bi、Th和U等元素检出限为0.1～0.01μg/cm2。     

X射线荧光光谱分析技术在过程分析中的应用

X射线荧光光谱(XRF)分析作为过程分析化学中一门富有成效的分析技术,在现场分析、流程控制中发挥了积极的作用。文章评述了XRF分析在冶金、地质、采矿、选矿等方面的应用概况以及在国内此领域的发展。     

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.     

X射线荧光光谱法测定地质样品中的氯和硫

使用粉末压片-X射线荧光光谱法测定地质样品中的Cl和S，探讨了样品放置时间、环境以及建立真空的时间对测量结果的影响。Cl的精密度(RSD，n=6)小于10％，S的精密度(RSD，n=6)小于5％。Cl和S的方法检出限分别为14和11μg／g，采用国家标准物质分析验证方法，其结果与标准值相符。     

熔融制片-X射线荧光光谱法测定锰矿样品中主次量元素

采用混合熔剂熔融制备样片,加入碘化铵粉末,有效地驱赶了锰矿熔融制样时产生的大量气泡,用Axios型X射线荧光光谱仪测定锰矿样品中的Mn、Fe、Si、Al、Ti、Ca、Mg、Na、K、P、Ba、Cu、Zn、Ni等元素的氧化物含量,用理论a系数校正基体效应,方法简便快捷。用国家一级锰矿石标准物质GBW 07266验证,结果与标准值相符;以锰矿石考察方法的精澈（RSD,n=12）,除CuO为10．05％,其余各组分均≤8％。     

国外XRFA中计算机软件和数据处理方法的研究

本文从定量分析软件、解谱技术、专家系统和化学统计学四个方面介绍了国外文献中X-射线荧光分析领域内数据处理与计算机软件开发的研究近况。     

同步辐射X射线荧光微探针测定岩石中的元素分布

同步辐射X射线(白光)荧光微探针在大气环境下,光斑尺寸为(50×50)μm~2,位移为1mm/步,计数时间30s,扫描测量了含石榴石紫苏花岗岩中多元素(K、Ca、Ti、Cr、Mn、Fe、Cu、Zn、Rb和Sr)的分布并绘制成图。检测限达x×10ppm,绝对量为10~(-10)—10~(-11)g范围。     

Mechanism of Hg(II) immobilization in sediments by sulfate-cement amendment

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO₄ amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L_III- and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca₆Al₂(SO₄)₃(OH)₁₂^.26H₂O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20–25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg–Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg–Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a polynuclear chloromercury(II) salt as the primary immobilization mechanism.     

Geochemical investigations of slags from the historical smelting in Freiberg, Erzgebirge (Germany)

The Freiberg area in the Saxon Erzgebirge (Ore Mountains) represents one of the oldest mining districts in Germany. Argentiferous ore mineralizations with lead, zinc and copper are dominating in this region. Various waste products of mining can be found around Freiberg. In particular, the slags from ore smelting were and are regarded as unusable waste products. However, they preserve information on the smelting and weathering behaviour of slag, which makes them very useful sources of information for our purposes. To reconstruct the chemical processes during ore smelting, historical slag represents a most valuable archive. Therefore, the historical slag dump in Halsbach (Germany) was examined exemplarily for the Freiberg deposit. The slag was dumped approx. 400 years ago and is rich in lead. An interrelation between the slag and the metallurgical process applied can be made on the basis of chemical composition, appearance and microscopic results. The slags of the heap in Halsbach contain high concentrations of heavy metals (average contents in mg kg⁻¹: Zn 40,000; Pb 10,000; Cu 1500; U 1000). Enrichments of heavy metals in the organic-rich soil horizons within the range of the dump foot (maximum contents in the A-horizon in mg kg⁻¹: Zn 3719; Pb 9198; As 3017; Cu 963) imply a faint discharge of metals from the dump.     

pXRF原位分析在柴北缘鱼卡金红石矿床勘查中的应用

便携式X射线荧光分析(pXRF)具有快速、高效、绿色、便捷等优点, 在矿产勘查中的应用越来越广泛。样品的不平度效应和不均匀效应等问题, 使得pXRF现场原位分析结果与实验室分析结果存在一定偏差。将该技术运用于柴北缘鱼卡金红石矿床勘查找矿, 对pXRF原位分析的稳定性进行试验, 并与实验室XRF法测试结果进行对比分析。结果表明, pXRF原位分析单点重复测量结果稳定, 分析测试最优时间为25~30 s; pXRF和实验室XRF法对样品Ti含量具有显著相关性, 存在线性关系。野外快速分析, 评价榴辉岩的Ti含量, 结果表明, 当pXRF原位分析榴辉岩中Ti含量在0~0.52%时, 对应非矿化榴辉岩; Ti含量在0.52%~0.86%时, 对应金红石贫矿体; Ti含量大于0.86%时, 对应的榴辉岩为金红石工业矿体。在槽探编录和钻探施工过程中, 使用pXRF分析可在野外快速判断榴辉岩的含矿性, 辅助找矿工作中圈定矿体, 大大减少样品采集的工作量, 节约成本和时间, 提高对榴辉岩型金红石矿床的勘查效率。     

古琉璃着色元素的同步辐射X荧光分析

用同步辐射X射线荧光对陕西不同年代和地层出土的各色古琉璃釉中的主量和微量元素进行了分析，用SPSS统计软件对实验数据进行多元统计分析。结果表明，各色琉璃釉中主要着色元素是Fe、Cu和Co，琉璃中的多样釉色是由三种主要着色元素的含量决定。元素相关性分析表明，Fe和Co可能来自一种原料，而Cu可能来自另一种原料。     

微孔滤膜制片X射线荧光光谱法测定矿石中银

在氨性介质中以水合联氨还原,Au兼作载体和内标,微孔滤膜制片,XRF测定Ag的方法应用于银矿标准物质及铜矿、铅锌矿、低品位金矿样品中x～xxxμg/g含量Ag的测定。分析结果的RSD优于3％,准确度与常规方法相当。     

GCL对垃圾渗滤液中阳离子和有机质的吸附能力

通过对渗透前后垃圾填埋场渗滤液进行化学成分的测定和分析,研究了GCL的吸附能力及其变化规律,并采用X射线荧光光谱分析对试验结果进行了验证。研究结果表明在渗透过程中GCL对渗滤液中的有机物和阳离子存在吸附作用,水化液对GCL的吸附能力有一定影响;在渗透开始阶段,GCL对垃圾渗滤液中阳离子和有机物的吸附能力比较强,而后逐渐达到吸附饱和状态而丧失吸附能力,因此用GCL作为防渗屏障,主要是依靠其低渗透特性,而非其对溶液中有机质和有害离子的吸附作用。通过对膨润土进行X射线荧光光谱分析也发现:经过渗透后的膨润土中除常见氧化物外,还有来自渗透液中被吸附的物质,但含量不大。     

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。     

波长色散X射线荧光分析的新发展

除了继续发展波长色散X射线荧光分析装置在主、次量元素分析上高精度、高稳定性的固有特点之外,进一步提高灵敏度,使分析范围扩展到痕量分析;开拓微区面分布的元素成像分析;进一步对传统分析因难的轻元素和中、重金属元素的探讨,开发新的高级次谱线分析方法;适应新材料特别是纳米材料的分析要求,对薄膜分析的开拓等方面,已经有了长足的发展。在介绍商品化的分析装置方面的发展状况的同时,对无标样分析的基本参数法目前发展状况也做了介绍。