ICP-MS研究黄河河曲段表层沉积物对Pb(Ⅱ)和Cr(Ⅵ)的吸附-解吸特性

表层沉积物易于富集和释放水中重金属,是污染水体中重金属的源和汇,研究表明黄河河曲段水体中Pb和Cr重金属污染严重。以电感耦合等离子体质谱(ICP-MS)为检测手段,研究了在优化实验条件下,黄河河曲段表层沉积物对Pb(Ⅱ)和Cr(Ⅵ)的吸附特性和解吸特性。结果表明：黄河河曲段沉积物对Pb(Ⅱ)和Cr(Ⅵ)具有较强的吸附作用,在吸附初始5 min时吸附率均达到98%以上,且是自发的吸热过程(ΔG<0,ΔH>0)。动力学实验显示,两种离子的吸附过程均符合准二级吸附动力学。等温吸附方程拟合发现,Pb(Ⅱ)的吸附符合Langmuir模型,而Cr(Ⅵ)的吸附符合Freundlich模型。解吸过程符合Elovich方程,且受pH的影响较大。Pb(Ⅱ)和Cr(Ⅵ)二元体系竞争效应研究表明,Pb(Ⅱ)的吸附率大于Cr(Ⅵ),且均低于单离子吸附率。扫描电子显微镜(SEM)和孔径及比表面积分析显示,黄河河曲段表层沉积物表面结构不规则,且具有相对较高比表面积。该研究揭示了Pb(Ⅱ)和Cr(Ⅵ)在黄河河曲段沉积物上的吸附-解吸行为,对评估沉积物污染风险和污染修复、掌握重金属离子与沉积物之间的作用机理具有一定指导意义。     

黄河甘宁蒙段表层沉积物中重金属元素含量及其形态分析

到目前为止,关于水环境中重金属浓度和形态分布的研究有许多报道。但是关于黄河上游,特别是对黄河甘宁蒙段区域重金属的研究报道仍需进一步深入。在相关研究工作的基础上,使用HR-ICP-MS和BCR连续提取法主要对2011年丰水期黄河甘宁蒙段12个采样点表层沉积物Cd,Pb,Cr,V,Co,Ni,Cu和Zn重金属元素的含量,形态和潜在风险进行测定与分析。结果表明：所有采样点各重金属元素含量顺序相同：Cr>V>Zn>Cu>Ni>Pb>Co>Cd,与各采样点所在区域土壤中背景值相比,S5采样点Cd元素的含量水平最高(1.30 μg·g-1) 约为背景值(0.103 μg·g-1)的13倍。通过I_geo对重金属进行污染评价,结果显示S5采样点Cd元素为强污染水平(I_geo=3.08),内蒙古段四个采样点(S1—S4)Cd表现为中强度污染水平,I_geo位于2.02~2.90之间;此外,富集因子(EF)评价结果发现,研究区域表层沉积物中八种重金属均受到人为活动的污染。根据潜在生态风险指数(RI)结果,S5和S3采样点为高生态风险,其他采样点为中等生态风险。BCR连续提取法结果显示Cd的有效性最高,其次为Co和Ni,V和Cr有效性最低。根据形态分析风险评估准则 (RAC),Cd在S1—S4采样点有高风险,在S5采样点有很高风险;而对于Ni和Co来说,12个采样点中均表现为中等风险。研究结果和结论可为相关政府部门提供重要的研究信息。     

HR-ICP-MS研究黄河三个连续区域段表层沉积物中重金属污染的空间分布和季节变化

采用高分辨电感耦合等离子体质谱(HR-ICP-MS) 和地积累指数法(I_geo) 对黄河甘肃、宁夏和内蒙古自治区连续三段表层沉积物中重金属(Cr,Pb,Cd,Cu,Zn 和 Ni)的空间分布和季节性波动(丰水期、枯水期和平水期) 以及污染状况进行系统研究分析,研究结果表明：内蒙古段三个季节中沉积物重金属含量都高于甘肃和宁夏段,同时,除Cd外,丰水期所有点的沉积物重金属含量都高于枯水期和平水期,而枯水期和平水期的重金属含量相近。I_geo结果显示丰、枯水期的Cd,Cu和Cr元素的I_geo值在内蒙古段最高,而在甘肃段最低;所有重金属的I_geo值在丰水期高于枯水期,除Cd外,都在平水期降低,而ICd_geo在平水期各采样点明显上升;丰水期的甘肃段、枯水期的甘肃和宁夏段以及平水期的所有采样点中的Pb,Zn和Ni的I_geo值都小于0,表明这些元素在这些点几乎无污染。就研究区域而言,内蒙古段的重金属含量以及生态风险最高,Cr,Cd和Cu是最具有潜在风险的三个元素;就研究季节而言,丰水期的重金属含量和潜在风险高于枯水期和平水期,可能是跟丰水期沉积物的pH和总有机碳(TOC)含量较高有关。相关性分析(CCA)用来探究重金属与pH/TOC间的关系以及重金属的潜在来源。CCA的结果表明Pb,Cu,Zn和Ni互相相关,并且这四种元素容易受到周围环境pH和TOC的影响,除此之外,Cr,Cd以及TOC 三者相关,且这两种元素受到人类活动影响较严重。该研究工作可为研究区域表层沉积物重金属在不同季节的环境行为提供有效的信息,同时,研究重金属、pH和TOC之间的相关性可有效揭示重金属的潜在来源。     

ICP-MS研究太湖过滤水和表层沉积物中重金属的含量水平及污染评价

采用电感耦合等离子体质谱法(ICP-MS)对太湖22个采样点过滤水和18个采样点表层沉积物中镉(Cd)、铬(Cr)、铜(Cu)、镍(Ni)、铅(Pb)和锌(Zn)六种重金属元素含量进行测定。同时,采用单因子指数法(I_i)、内梅罗综合指数法(I)、地质累积指数法(I_geo)、潜在生态风险指数法(RI)和平均可能影响浓度商法(mPEC-Q)分别对过滤水和表层沉积物进行了污染评价。结果表明, 除S₃,S₄,S₂₀,S₂₂采样点外过滤水中Cu,Ni和Zn元素含量最高。其重金属平均含量水平大小排序为：Zn>Ni>Cu>Cr>Cd>Pb。研究区域的I_i和I值均小于1, 表明所有采样点五种重金属元素(Ni无标准限值)均处于清洁状态。而在表层沉积物中六种元素含量均超过当地背景值, 其平均含量大小排序为：Zn>Cr>Pb>Ni>Cu>Cd, 其中S₁₂采样点(渔民生态园)六种元素含量最高,且它们具有最大的I_geo,RI(327)和mPEC-Q(0.605),表明沉积物存在不同程度的污染。源分析的结果表明, 六种重金属具有较大的相关性,且Cd,Cu,Pb和Zn受电镀、冶炼工业生产及农业活动中化肥使用的影响较大。研究结果对追溯太湖重金属来源、迁移规律、生物效应和综合治理提供可信的实验依据。     

宿州城市土壤重金属污染特征及其健康风险评价

选取宿州市不同功能区(工业区、商业区、车站附近、居民区以及城市绿地)采集表层土壤样品55个,利用XRF测定出土壤中重金属Cu、Zn、Pb、Cr、Mn、Ni的含量,并借助健康风险评价模型,分别评价了土壤重金属在不同暴露途径下的健康风险。结果表明,Cu、Zn、Pb和Cr的平均含量均超出安徽省土壤背景值,说明宿州城市土壤中已受到不同程度的重金属污染;工业区、商业区和车站附近土壤重金属含量普遍较高,Cu、Zn、Pb与交通运输、工业生产关系密切,Cr主要来源于工业废弃物排放,Ni则受到生活污染和交通污染的双重影响;土壤重金属的非致癌风险指数(HI)和致癌风险指数(Risk)均低于危害水平界限,未形成明显的健康风险。     

ICP-MS研究黄河三湖河口表层沉积物对Cd~(2+)和Cu~(2+)的吸附-解吸特性

为了研究黄河上游表层沉积物与Cd~(2+)和Cu~(2+)的相互作用机理,以黄河三湖河口表层沉积物(简称样品)为研究对象,采用电感耦合等离子体质谱(ICP-MS)技术,优化样品对Cd~(2+)和Cu~(2+)的吸附固液比、时间、pH等条件。并在此条件下研究了Cd~(2+)和Cu~(2+)在样品上的吸附特性和解吸特性。结果表明:两种金属的优化吸附条件不同,在各自优化吸附条件下,样品对Cu~(2+)和Cd~(2+)的平衡吸附量分别为0.88和0.13 mg·g~(-1);对两种金属的吸附动力学符合伪二级吸附动力学模型,且样品对Cu~(2+)的吸附速率大于对Cd~(2+)的吸附速率;吸附热力学拟合结果显示吸附过程符合Freundlich模型,对两种金属的吸附均属于优惠型吸附,且吸附过程属于吸热过程,可自发进行;解吸动力学研究表明,两个金属的解吸过程均符合Elovich方程,属于非均相扩散;在多离子竞争吸附-解吸实验中发现,样品对Cu~(2+)的吸附-解吸受到共存离子的影响更大。研究结果揭示了黄河三湖河口表层沉积物对Cd~(2+)和Cu~(2+)吸附和解吸的作用机理以及共存离子对吸附解吸特性的影响。对于分析重金属在水体与沉积物之间的作用机理、固液两相分布规律以及重金属迁移能力提供了理论依据,同时也为制定研究区域针对性的重金属防控措施具有一定指导意义。     

ICP-MS研究太湖表层沉积物对Cd2+和Zn2+的吸附-解吸特性

前期研究发现太湖过滤水和表层沉积物中Zn含量最高,且表层沉积物中Cd存在强生态危害。因此,在优化实验条件下,以电感耦合等离子体质谱(ICP-MS)为分析手段研究了太湖苏州湾大桥东表层沉积物(标记为SES)对Cd2+和Zn2+的吸附-解吸特性。吸附动力学结果表明：SES对Cd2+和Zn2+的吸附能力相差不大,在吸附时间t<120 min时,吸附是一个快速阶段,而当t≥120 min时则相反,吸附趋于动态平衡;Cd2+和Zn2+的吸附更符合伪二级动力学模型。吸附热力学实验表明,沉积物对Cd2+的吸附更符合Freundlich模型,而对Cd2+的吸附更符合Langmuir模型。沉积物中Cd2+和Zn2+的解吸动力学研究发现,二者均更符合Elovich方程,为非均相扩散过程。且当pH值增大时,沉积物中Cd2+和Zn2+的解吸量逐渐减小,并在pH=9时趋于稳定。结合Cd2+和Zn2+的吸附-解吸特性发现,SES对Cd2+和Zn2+的吸附速率远远大于其解吸速率,与作者前期研究结果一致。揭示了太湖表层沉积物对Cd2+和Zn2+的吸附-解吸作用机理及不同因素对吸附-解吸行为的影响。对研究太湖固-液两相界面重金属的分配和污染水体修复具有重要指导意义。     

HR-ICP-MS研究丰水期黄河甘宁蒙段表层沉积物中重金属的形态分析与污染评价

为连续、系统地研究不同年份丰水期黄河甘宁蒙段表层沉积物中重金属的含量、污染状况和潜在生态风险,在前期工作的基础上,采用三级四步提取法(BCR)和高分辨电感耦合等离子体质谱(HR-ICP-MS)对2012年丰水期黄河甘宁蒙段包头浮桥(S2)、石嘴山陶乐镇(S6)和乌金峡(S9)等10个采样点水体表层沉积物中Cd,Pb,Cr,Ni,Cu,V,Co,Zn和Mn九种重金属元素进行含量测定和形态分析,并对重金属元素的污染作出评价。结果表明：各重金属元素在每个采样点分布趋势相同,平均含量顺序依次为：Mn＞V＞Zn＞Cr＞Cu＞Ni＞Pb＞Co＞Cd;表层沉积物中重金属主要以残渣态形式存在,表明重金属的生物有效性低,对环境影响较小;地积累指数法 (I_geo) 的评价结果显示Cd元素的I_geo值最高,对环境污染程度较高,其余元素对环境影响较小,其中Mn元素影响最小;富集因子法(EF)评价结果表明,Cd和Cu元素在某些采样点表现为显著富集,尤其是Cd在S5点处EF值高达4.69,表明该点处Cd受人类活动影响较为明显,其余元素均为非富集元素,这与I_geo评价结果吻合;潜在生态风险指数法(RI)表明,黄河甘宁蒙段S1,S2和S5点的RI值在150~300之间,为中等危害范畴,其余各采样点RI值均小于150,为轻微危害。研究结果为相关部门提供可信的实验数据和理论依据,也为建立该河段泥沙-污染物输移数学模型和系统研究持久性有毒污染物迁移转化规律及环境评价提供技术支撑。     

Multivariate statistical approaches as applied to environmental physics studies

The present communication deals with the application of the most important environmetric approaches like cluster analysis, principal components analysis and principal components regression (apportioning models) to environmental systems which are of substantial interest for environmental physics — surface waters, aerosols, and coastal sediments. Using various case studies we identify the latent factors responsible for the data set structure and construct models showing the contribution of each identified source (anthropogenic or natural) to the total measure of the pollution. In this way the information obtained by the monitoring data becomes broader and more intelligent, which help in problem solving in environmental physics.     

Phase-controlled preparation of iron (oxyhydr)oxide nanocrystallines for heavy metal removal

Obtaining cost-effective iron (oxyhydr)oxide nanocrystallines is the essential prerequisite for their future extensive applications in environmental remediation, such as the removal of heavy metals from contaminated waters. Here, various phases of iron (oxyhydr)oxide nanocrystallines were simply synthesized from the phase-controlled transformation of amorphous hydrous ferric- or ferrous-oxide in thermal solution with a certain ethanol/water ratio and with the presence of oleic acid. According to this method, goethite nanorods in diameter of 3–4 nm, hematite nanocubes sized 20–30 nm, and magnetite nanoparticles in diameter of 6–7 nm were successfully obtained. The final products of this transformation can be conveniently controlled by adjusting the reaction parameters, such as pH, temperature, and ethanol/water ratio. Due to the enhanced specific surface area and probably the modifications of the surface structure of nanocrystallines, the as-synthesized goethite nanorods and magnetite nanoparticles demonstrated extremely strong As(III) affinity, with 5.8 and 54 times of As(III) adsorption, respectively, higher than the micron-sized relatives. The cost-effective feature of as-synthesized nanocrystallines and their remarkably enhanced affinity toward arsenic made them potentially applicable for the removal of arsenic and such like heavy metals from the contaminated environment.     

A numerical simulation of the transport of surface ozone along a Mediterranean coastal area

Summary A simple numerical simulation of daily summer circulation in W-NW and E-SE directions was applied to a coastal area of Greater Ravenna in Northern Italy to assess the influence on ozone levels of the transport mechanism in the land-sea breeze system. Field measurements of ozone concentration and micrometeorological data collected over a ten-year period (1978–1989) by a coastal monitoring station were processed to identify meteorological and climatic situations. The diurnal pattern of a ?pure? off-shore-in-shore circulation system was reconstructed by applying a simple model in which data were considered or rejected as a function of the prevailing wind direction. Only data collected under W-NW and E-SE wind direction conditions became part of the ?reconstructed wind circulation system?. The findings show that the relative concentration values and the time duration of the simulated transport phenomenon are in good agreement with the recorded episodes of transport and of severe continuous fumigation, occurring during the night, at the polluted area.     

通辽地区污灌区土壤重金属污染状况的调查与评价

对内蒙古东部通辽市污水灌溉区的土壤进行了采样,用电感耦合等离子体-质谱法(ICP-MS)分析了土壤中Cu、Zn、Pb、Cr、Cd 5种元素的含量.根据GB15618-1995土壤环境质量标准对检测结果进行了单因子分析与评价,结果表明,调查区内重金属元素污染较轻,只有孔家区Cr、Cd的含量超标.     

广州珠江水体微表层与次表层中重金属的分布特征

采用ICP-AES对广州珠江水体微表层与次表层中Cu、As、Zn、Cr、Pb和Cd的质量浓度进行为期一年的调查研究。结果表明：珠江广州段水体均不同程度地受到6种重金属的污染,重金属浓度的季节性变化比较明显,在春季和冬季时浓度较高,夏季时浓度较低;重金属浓度的空间变化也比较明显。除Zn外,微表层对其余5种重金属均具有较强的富集作用。     

Comparison of standard‐based and standardless methods of quantification used in X‐ray fluorescence analysis: Application to the exoskeleton of clams

In this work, we aim at achieving the most accurate quantitative determination of the composition of exoskeletons of bivalves from Tagus estuary with Energy Dispersive X‐ray Fluorescence. Samples from the shells of clams ranging from the Bronze Ages to the 16th century A.D . belonging to the Museu Arqueológico de Almada, and also from the shells of clams collected recently in the same region, were analyzed for comparison of the trace element composition and detection of heavy metals. The analysis was performed with 2 Energy Dispersive X‐ray Fluorescence setups, one with triaxial geometry and another with a conventional geometry and vacuum capabilities. Samples were pressed as pellets, and the spectra collected with both setups were evaluated using standardless fundamental parameter based software's implemented in each setup, and by comparing with standard reference materials of similar matrix. The comparison of the results obtained with different methods lead to the conclusion that the most realistic results were obtained with calibration curves obtained with external standards and correction the fluorescent intensities with the Compton scattering peak. When comparing the obtained concentrations for all the analyzed periods, results showed a decrease of Fe in the 12th Century. Regarding the environmental current state of the Tagus estuary, there were no heavy metals detected above the safety regulations.     

Ultrasonic processes for the advanced remediation of contaminated sediments

Sediments play a fundamental role in the aquatic environment, so that the presence of contaminants poses severe concern for the possible negative effects on both environmental and human health. Sediment remediation is thus necessary to reduce pollutant concentrations and several techniques have been studied so far. A novel approach for sediment remediation is the use of Advanced Oxidation Processes, which include ultrasound (US). This paper focuses on the study of the ultrasonic effects for the simultaneous reduction of both organic and inorganic contaminants from sediments. To this end, the US technology was investigated as a stand-alone treatment as well as in combination with an electro-kinetic (EK) process, known to be effective in the removal of heavy metals from soil and sediments. The US remediation resulted in higher organic compound degradation, with an average 88% removal, but promising desorption yields (47–84%) were achieved for heavy metals as well. The combined EK/US process was found to be particularly effective for lead. Experimental outcomes highlighted the potential of the ultrasonic technology for the remediation of contaminated sediments and addressed some considerations for the possible scale-up.     

Ferromagnetic alignment of iron nanostructures on the silicon surface

The phase composition, electronic structure, and magnetic properties of nanostructures formed upon deposition of iron on the surface of the Si(556) vicinal face coated by a submonolayer silver film with a √3×√3-Ag structure have been studied using high-energy-resolution photoelectron spectroscopy and analysis of magnetic linear dichroism in photoemission of Fe 3p electrons. The effective thickness of the deposited iron layer is varied from 1 to 25 ?. It has been shown that a 1- to 2-? Fe coverage leads to the formation of a metastable iron silicide thin layer with a CsCl-type structure on the surface of the sample. A further deposition of Fe (up to ≈7 ?) brings about the formation of chains consisting of nonmagnetic islands of the Fe—Si solid solution on this layer, which are oriented along the steps of the substrate. A ferromagnetic alignment of the system along the surface of the sample appears only at coverages of approximately 10 ?, when larger (≈100 nm) iron islands start to grow on the solid solution layer.     

Equation of state of the transitive layer in a one-component system and some of its applications

We obtain the equation of state relating the interphase tension at the planar interface of a crystal—the melt proper with the surface tension of free surfaces in one-component system. Numerical calculations for metals are performed at the temperature of the triple point. Using the obtained equation, we solve a number of problems, including determination of the work of adhesion, the limiting wetting angle of a crystal by the melt proper, the diffluence coefficient due to Harkins, and construction of a Neumann triangle.     

Erosion of the GaAs target under irradiation by a high-power pulsed ion beam

The results of examination of the GaAs-target erosion under irradiation by a high-power pulsed ion beam are reported. In the experiments, use was made of a high-power pulsed ion source with the following parameters: ion energy — 250 keV, target current density — 350 A/cm², pulse duration — 80 ns, target energy density — up to 7 J/cm². The target erosion coefficient and its dependence on the number of successive pulses are measured. It is found that the surface roughness parameter is increased with the number of successive beam pulses. A regular structure of surface relief is observed to form in the case where the number of pulses > 20–40. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 66–70, January, 2007.     

利用荷花与睡莲对沉积物中重金属的修复研究

选取水景植物荷花、睡莲对黑臭河道沉积物中重金属进行修复,用ICP-AES全谱直读电感耦合等离子发射光谱法测定沉积物、植物中重金属镉、铬、铜、镍、铅的总量与形态的量,重金属在植物中分布。结果表明：荷花对沉积物中重金属平均去除率为20.42%,睡莲为18.23%;睡莲、荷花种植后沉积物重金属形态的量呈减小趋势,经植物修复后沉积物中铬、铅、镍的主要形态为残渣态,镉、铜的主要形态为弱酸溶解态。铜、镍在睡莲中的分布特征为茎<叶<根,镉和铅为叶<茎<根,铬为茎<根<叶。铬、镍在荷花中分布为根<叶<茎, 铜为叶<根<茎,镉、铅主要积累在荷花的叶部组织。     

4-Geodesy

Summary As familiar geodesy determines the shape of the Earth from measurements of distances between selected points, so 4-geodesy has for ideal to determine spacetime geometry—and through it masses of celestial objects—by measurements of distances of selected stars from the Earth and from each other. Crucial to this enterpise is a means for determining distances transverse to the line of sight. A ?lighting-profile? method is outlined for determining transverse distance: 1) trace the flash of light from a supernova as the resulting illumination makes its way to the distant galaxy, and 2) compare the observed ?lighting profile? with the canonical shape calculated in the appendix. Paper presented at the Congress ?Galactic and Extragalactic Dark Matter?, Roma, 28 to 30 June 1983.