基于知识图谱的土壤重金属快速监测技术进展

为了解当前国际土壤重金属快速监测研究现状及趋势，以Web of science数据库为基础，以X射线荧光光谱法（XRF）为例利用CiteSpace进行知识图谱可视化分析，并在此基础上对国际土壤重金属快速监测进行研究综述.结果表明，从Web of science数据库资料来看，当前对土壤重金属快速监测的研究机构以中国科学院和西班牙国家科学研究委员会发文量最多，而发文从属国家以美国为最多，中国和德国居其次；研究热点主要集中于快速监测仪器的技术开发、实际应用、定量化监测影响因素的识别及校正等方面；针对土壤重金属污染快速监测的未来研究趋势主要集中于监测仪器的小型化智能化研发、农田土壤重金属快速监测、区域土壤重金属空间分布监测等方面.认清和了解当前国际土壤重金属快速监测研究状况，可为国内相关研究提供参考.     

土壤重金属X射线荧光光谱非标样测试方法研究

采用粉末压片制样,用X射线荧光光谱非标样测试方法测定土壤中Ti、V、Cr、Mn、Fe、Ni、Cu、Zn、Ga、As、Cd、Sn、Sb、Pb、Hg等15种重金属元素。研究了样品制备方法和元素测量条件等影响测试准确度的因素。结果表明此方法不需对固体样品进行消化处理,无需制备标准样片,快速、简便、效率高,是一种非破坏性的分析方法,方法的检出限、准确度和精密度基本能够满足土壤中有毒有害重金属的快速筛查要求。     

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: a geoenvironmental perspective

Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. Key findings: at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.     

ICP-MS与XRF测定PM_(2.5)中重金属含量的对比分析

目前,大气颗粒物中重金属含量分析方法很多,现有环境空气质量标准并未对重金属分析方法进行统一规定,在实际监测过程中各地选择的分析方法都不尽相同。因此,确定合适的分析方法,满足快速准确测定PM_(2.5)中金属元素含量的需求显得极为重要。文章采用ICP-MS与XRF分别测定PM_(2.5)滤膜样品中Al、As等15种金属的含量,并对2组实验结果进行对比及相关性分析。结果显示,2种方法测定元素Al、Mn、Fe、Cu、Zn、As、Se、Pb的相关性系数R在0.818 5~0.953 6之间,趋势线斜率在0.787 9~1.252之间,可比性较好,测定上述元素时2种分析方法均可选用;Ti、V、Cr、Co、Ni、Cd、Ba相关性系数R和趋势线斜率较低,2种方法分析数据差异较大,测定时应选用灵敏度更高的分析方法如ICP-MS。在测定大气颗粒物中重金属元素时,应根据样品实际情况选择合适的分析方法。     

Rapid evaluation of arsenic contamination in paddy soils using field portable X-ray fluorescence spectrometry

Arsenic (As) in paddy fields is deteriorating food security and human health through rice ingestion. Rice is the dominant food source of arsenic exposure to half of the world''s population. Therefore, an in situ effective method for As risk evaluation in paddy soil is strongly needed to avoid As exposure through rice ingestion. Herein, we developed a rapid analytical methodology for determination of As in plant tissues using field portable X-ray fluorescence spectrometry (FP-XRF). This method was applied to rice roots in order to evaluate the As contamination in paddy soils. The results showed that rice roots with iron plaques were superior to rhizosphere soils for generating FP-XRF signals, especially for field sites with As concentrations lower than the soil detection limit of FP-XRF (30.0 mg/kg). Moreover, the strong linear relationships of As concentrations between the rice roots and corresponding leaves and grains proved that the rice root, rather than the soil, is a better predictor of As concentrations in rice grains. The research provides an efficient As monitoring method for As contaminated paddy fields by using wetland plant roots with iron plaques and XRF-based analytical techniques.     

中国四城市空气中粗细颗粒物元素组成特征

采集280多个来自中国4城市粗细颗粒物样品,用X一荧光光谱法分析了其中的42种元素报道了空气颗粒物中元素的组成特征,并对元素进行聚类分析,结果表明,主要可分成地壳元素及燃煤或燃油污染元素两大类污染点颗粒物中污染元素的浓度比对照点的要高,而且,这些污染元素在细颗粒物中的富集因子比在粗颗粒物中的富集因子要高出许多倍但城市内污染元素的富集团子在污染点与对照点之间的差别不如同一种元素在两城市间的差别明显     

给水管网中管内壁腐蚀管垢特征分析

使用扫描电镜(SEM)、X荧光光谱分析(XRF)、X射线衍射分析(XRD)以及X光电子能谱(XPS)对给水管网中铸铁管和镀锌钢管上的管内壁腐蚀管垢进行微观形态、化学组成、晶体结构和化合物构成等物理化学特征分析.发现管垢外部平滑而致密,内部为多孔结构.铁是管垢最重要的化学组成,管垢基本上是含铁的化合物.外层管垢可能的化学组成是α-FeOOH、γ-FeOOH、α-Fe₂O₃、γFe₂O₃、FeCl₃等三价铁化合物,而内层管垢则为Fe₃O₄、FeCl₂、FeCO₃等二价铁及二价铁与三价铁共同存在的化合物.管垢的特征取决于管网水力条件、水质条件和管材本身特性.     

The Orange-Brown Patina of Salisbury Cathedral (West Porch) Surfaces: Evidence of its Man-Made Origin (5 pp)

Goal, Scope and Background In this paper, we attempt to elucidate the composition and origin of the orange patina on the surfaces of the West-Porch of Salisbury Cathedral by comparison to other known patinas: (i) the orange-brown patina on the marble surfaces of the Acropolis in Athens and the Arch of Titus in Rome whose analyses have shown very high amounts of phosphates, and generally amino acids from animal-skin glue or other protein binders; (ii) the phosphated patinas which also contain oxalates, found in 1996 on Catalonian calcareous sandstones and in the calcareous dolomites of the Monastery of Silos, Spain, whose origin is either the application of calcium caseinate, or egg yolk and animal glue; and (iii) the patinas with only oxalates found in some of Verona's monuments (St Zeno) and Spanish sites as in the Monastery of Guadalupe and Cuenca cathedral, formed either by the mineralization of algal filaments or by biological reactions yielding oxalate from yolk egg (added to stone as part of preservative empirical treatments). Methods In the winter of 2003, the West-Porch of Salisbury Cathedral received conservation works, but the old patina was not entirely removed. This fact has allowed us to collect the samples for its study. The IR spectra were registered with a Golden Gate ATR Mk II system using attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectrometry. Mineral composition was determined by XRD (Philips PW 1710 spectrometer with Cu tube), whereas major and trace elements analyses were performed by XRF (Philips PW1480 PW). Microscopy examination was performed on a Leica M655 microscope. Phosphate, oxalate, calcium and sulphate contents were analysed by usual chemical methods. Results ATD-FTIR spectra of the Salisbury's patina exhibit peaks at 2361, 2341 and 671 cm–1 (assigned to phosphates); 3410, 1680, 1620, 1122 and 602 cm–1 (assigned to sulphates); and 1447/1437 and 876 cm–1 (attributed to carbonates). The little peaks at 1620 and 798 cm–1 could be assigned to oxalates. XRD and XRF have led to identify the carbonates, phosphates and sulphates as pertaining to the species dolomite, hydroxyapatite and gypsum, respectively. Oxalates are detected only in small amounts by chemical analyses but wewellite and weddellite have not been well identified. The interface between the patina and the calcareous dolomite is very uneven and full of cavities in certain cases, but well-defined and rather smooth in other cases. In accord with the very small amounts of the oxalates found, remnants of micro-organisms are not detected in the patinas. Discussion The Salisbury's patina is a composite material formed by particulates and matrix constituents. Regarding the patina particulate, e.g. animal bones, it is necessary to refer to the apatite phase composition. The bone mineral contains 4–8 wt % of carbonate in animal body and its presence in the apatite phase is advantageous as it increases the mechanical strength. We think that FTIR bands at around 1440 and 876 cm–1 arise from vibration of CO32– ions, but not necessarily from the limestone. They could be attributed to carbonated hydroxyapatite through the substitution of groups PO43– for CO32– in the lattice of hydroxyapatite. Concerning the matrix and also from the FTIR spectra, the absence of specific bands of the following species: proteins (3350–3225, 1660, 1550–1535, 1270–1230 and 620 cm–1), oils (1778, 1738 and 1051 cm–1), bee waxes (3000, 1470, 720–730 and 1700 cm–1) and aged egg-yolk (2954, 2920, 2850, 1650, 1549, 1465 and 1240 cm–1) had led us to exclude these usual binders. On the other hand, the amount of sulphates in the paste that covers the walls of the Salisbury's Cathedral is excessively high (above 20% in weight) to consider it as a biotransformation product of calcium oxalate from fungal biofilms. Consequently, we must think that the gypsum found in the samples has a man-made origin (it was deliberately added as part of a protective paste) and that it is the matrix searched for. Thus, we deduce that the patina of Salisbury's Cathedral is a special stucco made mixing plaster with powdered bone (the colour of the bones is the same that it exhibits in the patina), low quantities of an uncharacterized binder (collagen, possibly) and water. Conclusion We believe that the patina of the Salisbury's Cathedral is a variant of the Greco-Latin empirical protective treatment that included bone as a hardening material. Nevertheless, we also think that the presence of the bones in the paste could be related to an aesthetical intention: gaining a warm tone for the original stone through the ochre colour of the bones. Recommendation and Perspective Our results have been an excuse to contribute to the controversy started at the 80's on the origin of orange-brown patinas observed on stone surfaces of Greco-Latin and medieval monuments. There are two major theories on provenance: biological vs. man-made. In Salisbury Cathedral, neither of them has been proven through scientific evidence as yet. Our opinion is that Salisbury patina can be classified into the man-made group.     

Characterization of phosphogypsum wastes associated with phosphoric acid and fertilizers production

The present work is directed to characterize the phosphogypsum (PG) wastes associated with phosphoric acid produced by the wet process in industrial facility for the production of fertilizers and chemicals in Egypt. The PG waste samples were characterized in terms of spectroscopic analysis (X-ray diffraction, X-ray fluorescence, IR spectra) and radiometric analysis (γ- and α-measurements). The γ-ray measurements showed that the average activity concentrations are 140 ± 12.6, 459 ± 36.7, 323 ± 28.4, 8.3 ± 0.76 and 64.3 ± 4.1 Bq/kg for U-238, Ra-226, Pb-210, Th-232 and K-40, respectively. The α-particle measurements of uranium isotopes showed that the average activity concentrations of U-238, U-235 and U-234 were 153 ± 9.8, 7 ± 0.38, 152 ± 10.4 Bq/kg, respectively. The average radiochemical recovery (%) of the destructive α-particle measurements is ∼70% with a resolution (FWHM) of ∼30 keV. Activity ratios of U-238/Ra-226 and U-238/Pb-210 were less than unity (i.e., <1) and equal to 0.31 ± 0.02 and 0.47 ± 0.16, respectively. The isotopic ratios of U-238/U-235 and U-238/U-234 (in PG and PR samples) were close to the normal values of ∼21.7 and ∼1, respectively and are not affected by the wet processing of phosphate rock (PR). The obtained results of PG waste samples were compared with phosphate rock (PR) samples. The radiation hazard indices are namely, radium activity index (Ra-Eq > 370 Bq/kg), total absorbed gamma dose rate (D_γr > 5 nGy/h) and radon emanation fraction (Rn-EF > 20%). Uncertainty of the sample counting was 95% confidence level of σ. The results indicated the necessity to find suitable routes to decrease and/or redistribute the radionuclide of environmental interest (i.e., Ra-226) in PG wastes, consequently to reduce its radiation impacts in the surrounding environment.     

滇中抚仙湖沉积物元素特征与流域侵蚀研究

通过对云南滇中盆地高原深水湖泊抚仙湖沉积岩芯进行X射线荧光光谱（XRF）元素与磁化率连续扫描,结合聚类分析、主成分分析方法和其它相关环境代用指标,探讨了抚仙湖流域自1840年以来的流域侵蚀与人类活动特征.研究结果表明,抚仙湖XRF元素扫描的聚类分析结果具有明显的阶段性特征,可将其大致划分为3个阶段,即34~24cm（约1715~1813年）,24~9cm（约1813~1947年）和9~0cm（约1947~2018年）.基于抚仙湖沉积物岩芯中元素比值和低频磁化率的主成分分析,识别出的主成分1与主成分2的方差贡献分别为37.72%和25.73%.指示抚仙湖流域侵蚀强度的元素比值Rb/Sr、Ti/Sr、Ti/Rb公因子载荷较大（>0.6）,该结果表明,抚仙湖外源碎屑沉积物的元素比值对流域侵蚀与人类活动具有良好的指示意义.因此,本文使用湖相沉积中的环境代用指标对抚仙湖流域侵蚀与人类活动强度进行重建.研究结果表明,1840年以来人类活动加剧了流域侵蚀强度.自1990年以来随着流域生态环境的逐步恢复,侵蚀强度总体较弱.