INAA for determination of trace elements in bottom sediments of the Selenga river basin in Mongolia

Instrumental neutron activation analysis (INAA) was used for the determination of major, minor and trace elements in samples of bottom sediments of the inflows of the Selenga river basin to assess the impact of the contamination from the industrial complex Erdenet and other industrial enterprises in Mongolia. A total of 42 elements (Na, Mg, Cl, K, Ca, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Sr, Rb, Sr, Zr, Nb, Sb, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, Dy, Tm, Hf, Ta, W, Au, Hg, Th, and U) was determined by combination of conventional and epithermal neutron activation analysis at the IBR-2 reactor, FLNP JINR, Dubna. For the first time such a large set of elements was used for characterization of the bottom sediments as accumulating media which may reflect industrial contamination of the water basin. The concentrations of heavy metals and other trace elements in the samples from three inflows of the Selenga river basin were compared with data from the previous studies. It was shown that the industrial zone of the Erdenet Mining Corporation (EMC) and gold mining zone Zaamar are the sources of strong environmental contamination. The concentrations of Cu and Sb determined in sediment samples of the River Khangal and Govil near the EMC exceed average crustal rock and soil values by factors of 50 and 15, respectively. In the area of the gold mining zone Zaamar concentrations of Au, As, and Sb exceed crustal rock and soil values by factors of 4, 25, and 6, respectively. The relatively high levels of As, V, Zn, V, and Sr in the sediments of the studied rivers are obviously due to the discharges of untreated wastewater of desalination plant, electrical power station, textile industry and mining activities as well as domestic wastewater.     

LiMBO3 : Dy3+材料的发光特性

采用固相法制备了LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料,并研究了材料的发光特性。LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料的发射光谱均呈多峰发射,对应于Ca,Sr,Ba,其主发射峰分别是Dy³⁺的⁴F_9/2→⁶H_15/2(484,486,486 nm),⁶H_13/2(577,578,578 nm)和⁶H_11/2(668,668,666 nm)跃迁。监测黄色发射峰时,所得激发光 谱峰值位置相同,主激发峰分别为331,368, 397,433,462,478 nm,对应Dy³⁺的⁶H_15/2→ ⁴D_7/2,⁶P_7/2,⁶M_21/2,⁴G_11/2,⁴I_15/2和⁶F_9/2跃迁。研究了敏化剂Ce³⁺及电荷补偿剂Li⁺、Na⁺和K⁺对LiM(M=Ca, Sr, Ba)BO₃ : Dy³⁺材料发光强度的影响。结果显示:加入敏化剂Ce³⁺提高了材料的发光强度,发光强度最大处对应的Ce³⁺浓度为3%;加入电荷补偿剂Li⁺、Na⁺和K⁺后,材料的发光强度也得到了明显提高,但发光强度最大处对应的Li⁺、Na⁺和K⁺浓度不同,依次为4%、4%和3%。     

Estimating groundwater mixing and origin in an overexploited aquifer in Guanajuato, Mexico, using stable isotopes (strontium-87, carbon-13, deuterium and oxygen-18)

Stable Isotopes (strontium-87, deuterium and oxygen-18, carbon-13) have been used to reveal different sources of groundwater and mixing processes in the aquifer of the Silao-Romita Valley in the state of Guanajuato, Mexico. Calcite dissolution appeared to be the main process of strontium release leading to relatively equal (87)Sr/(86)Sr ratios of 0.7042-0.7062 throughout the study area which could be confirmed by samples of carbonate rocks having similar Sr ratios (0.7041-0.7073). delta(13)C values (-11.91- -6.87 per thousand VPDB) of groundwaters confirmed the solution of carbonates but indicated furthermore influences of soil-CO(2). Deuterium and (18)O contents showed a relatively narrow range of-80.1- -70.0 per thousand VSMOW and -10.2- -8.8 per thousand, VSMOW, respectively but are affected by evaporation and mixing processes. The use of delta(13)C together with (87)Sr/(86)Sr revealed three possible sources: (i) carbonate-controlled waters showing generally higher Sr-concentrations, (ii) fissure waters with low-strontium contents and (iii) infiltrating water which is characterized by low delta(13)C and (87)Sr/(86)Sr ratios. The third component is affected by evaporation processes taking place before and during infiltration which might be increased by extraction and reinfiltration (irrigation return flow).     

ICP-OES和ICP-MS测定中日两国大米中27种矿质元素含量

收集了16种中国大米和11种日本大米,经过微波消解或干灰化法处理后,采用电感耦合等离子体发射光谱法(ICP-OES)和电感耦合等离子体质谱法(ICP-MS)测定了其中Al,As,B,Ba,Ca,Cd,Co,Cr,Cs,Cu,Fe,Hg,K,Mg,Mn,Mo,Na,Ni,P,Pb,Rb,S,Se,Sr,Tl,V和Zn等27种矿质元素的含量,并用生物标准参考物质大米(GBW10010)评价了分析方法的准确度。研究结果表明,基于碰撞反应池技术(CCT)的ICP-MS能有效降低一些多原子离子对低m/z元素离子计数的干扰;与日本大米相比,中国大米中Al,S,Sr等元素含量显著偏高,而B,Cd,Cs,Mg,Mo,P,Pb,Zn等元素含量显著偏低(P0.05),采用聚类分析(最小方差法)对矿质元素含量进行处理,可正确判别两国大米。另外,还发现大米中Mg和P含量之间存在很强的线性相关性,相关系数高达0.9552。     

Application of total reflection X-ray fluorescence spectrometry for trace elemental analysis of rainwater

Applicability of total reflection X-ray fluorescence (TXRF) spectrometry for trace elemental analysis of rainwater samples was studied. The study was used to develop these samples as rainwater standards by the National University of Singapore (NUS). Our laboratory was one of the participants to use TXRF for this study. The rainwater sample obtained from NUS was analysed by TXRF and the trace elements Mn, Fe, Ni, Cu, Zn, V and Pb were determined as required by the NUS. The average precision was found to be within 16% and the TXRF-determined elemental concentrations of these elements were below 20 μg/l. The average deviation of TXRF-determined values from the certified values were 20% (excluding the deviation for Fe and V which were comparatively high). Apart from the above elements, S, K, Ca, Rb, Sr, Ba and Br were also determined by TXRF and were found to be in the range of 0.2 to 191 μg/l. TXRF-determined values of our laboratory played an important role in the certification of concentration of seven elements in this rainwater sample which was later developed as a rainwater standard.     

电荷补偿对Sr2SiO4∶Eu3+材料光谱特性的影响

采用溶胶-凝胶法制备了Sr2SiO4∶Eu3+发光材料.测量了Sr2SiO4∶Eu3+材料的激发与发射光谱,发射光谱主峰位于618 nm处;监测618 nm发射峰时,所得材料的激发光谱主峰分别为320 nm、397 nm、464 nm和518 nm.研究了Sr2SiO4∶Eu3+材料发射峰强度随电荷补偿剂Li+、Na+和K+掺杂浓度的变化情况.结果显示,随电荷补偿剂浓度的增大,材料发射峰强度均表现出先增大后减小的趋势,但不同电荷补偿剂下,材料发射峰强度最大处对应的补偿剂浓度不同,补偿剂Li+、Na+和K+的浓度分别为8 mol%、7.5 mol%和7 mol%.     

Na2GdPO4F2:Tb3+绿色荧光粉阴极射线发光研究

通过高温固相法制备Na2GdPO4F2:Tb3+绿色荧光粉,并利用X射线粉末衍射(XRD)和阴极射线光谱分别对其物相、阴极射线发光性能进行研究.结果表明,Tb3+作为绿色发光中心进入到Na2Gd2PO4F2的晶格中取代Gd3+的格位,在低电子束(0.5～5 kV)激发下主要表现出Tb3+的特征跃迁(5D3.4→7FJ,J=6～2),其中以5D4→7F5跃迁(546 nn)为主.样品Na2Gd0.95Tb0.05PO4F2在阴极射线激发下的色坐标为(0.240 3,0.438 6).随着电压、电流和掺杂量的增加,荧光粉的发光强度逐渐提高,其中,最佳的样品为Na2Gd0.9Tb0.1PO4F2.     

铁(Ⅲ)的硅胶H相反射散射光度法研究

本文提出了胡椒基荧光酮 (PIF)硅胶H相反射散射光度法测定铁的新方法。在溴化十六烷基三甲基铵的存在下 ,PIF与铁 (Ⅲ )形成稳定的蓝色配合物并且能被硅胶H吸附 ,其最大反射散射吸收波长位于 6 4 0nm ,铁 (Ⅲ )的浓度在 0～ 2 5ng·mL- 1 范围内呈线性关系 ,方法用于氧化镁中微量铁的测定 ,结果满意。     

新型红色荧光粉Sr2ZnMoO6:Sm3+的制备与发光性能

采用高温固相法合成了Sr₂ZnMoO₆:Sm³⁺新型红色荧光材料,并对其发光特性进行了研究。XRD测量结果表明所制备样品为纯相Sr₂ZnMoO₆晶体。样品的发射光谱由一系列锐谱组成,分别位于563 nm(⁴G_5/2→⁶H_5/2)、598 nm(⁴G_5/2→⁶H_7/2)、607 nm(⁴G_5/2→⁶H_7/2)和645 nm(⁴G_5/2→⁶H_9/2),最强发射为645 nm。样品激发光谱由电荷迁移带CT和Sm³⁺离子的特征激发峰组成,主激发峰位于284 nm(CT)和403 nm(⁶H_5/2-⁴L_13/2)。 随着Sm³⁺浓度的增大, Sr_2-xZnMoO₆:xSm³⁺材料的发光强度先增大后减小, 在x≥2%时,发生浓度猝灭现象。根据Dexter理论分析其猝灭机理为电偶极-电偶极相互作用。比较了Li⁺、Na⁺和K⁺作为电荷补偿剂的作用,发现均使Sr₂ZnMoO₆:Sm³⁺材料的发射强度得到增强,但以Li⁺补偿效果最为显著。     

Elemental composition of fine particulate matter (PM2.5) in Skopje,FYR of Macedonia

Aerosol samples were collected at an urban background site in Skopje, Former Yugoslavic Republic of Macedonia, during four measurement campaigns from December 2006 to October 2007. An impactor was used to collect particulate matter (PM_2.5) aerosol particles and the samples were analyzed for the concentrations of particulate mass, black carbon (BC), and 17 elements. The 12‐h average PM_2.5 concentrations varied in the range 10–140 µg m^?3 with the highest concentrations measured during wintertime pollution episodes and during the summer period. Pair‐wise correlations and crustal enrichment were studied and the data set was analyzed by factor analysis and positive matrix factorization. Major aerosol components were identified as mineral dust (main observed tracers Si, K, Ca, Ti, Fe, Sr, and Rb), combustion (BC, S, K, V, and Ni), traffic‐related aerosol (Pb and Zn), and secondary sulfate combined with mineral dust. Combustion sources dominated during wintertime and were likely due to heavy oil combustion, biomass burning, and other industrial activities within the city area. Mineral dust was observed throughout the year, but the concentrations peaked during the unusually hot and dry summer of 2007. It is concluded that Skopje suffers from serious air pollution due to central and residential heating, the transport sector, and industrial activities within the city, and contributions from mineral dust increase the PM_2.5 concentrations under dry periods. Topography and meteorological conditions aggravate the problems and make the air quality comparable with the conditions in other highly polluted cities in Southern Europe and worldwide. Copyright © 2011 John Wiley & Sons, Ltd.     

Levels and sources of heavy metal contamination in road dust in selected major highways of Accra,Ghana

Environmental studies have revealed significant contributions of vehicular exhaust emissions to high pollution levels in urban dwellings. The levels and sources of heavy metal contaminations of some major roads in Accra have been investigated in this work. Street dust samples collected from four major roads in Accra (Mallam Junction‐Weija road, John Teye‐Pokuase road, Tema Motorway and Tetteh Quarshie Interchange in Accra) were analysed for their elemental concentrations using energy‐dispersive X‐ray fluorescence. Twenty elements were identified: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr and Pb. Significant concentration levels were obtained for K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Br, Rb, Sr, Y, Zr and Pb in all the samples and were used for the source identification. Enrichment factors and principal component analysis were used to verify the anthropogenic contribution to road dust. Results obtained for the enrichment factors showed moderate enrichment for V, Cr and Cu, while Zn, Br, Zr and Pb were significantly enriched. Principal component analysis identified four sources and their contributions to the elemental contents in the road dust. Natural crust, brake wear, tyre wear and vehicle exhaust emission were the four sources identified. The contribution of vehicular non‐exhaust emissions to heavy metal contamination in the road dust was found to be greater than that of exhaust emissions. Copyright © 2012 John Wiley & Sons, Ltd.     

流动注射在线清理MPT-AES测定钯、铂和金的研究

本文研究了在大理Li^ 、Na^ 、K^ 、Ca^ 和Mg^2 离子存在时,通过在线清理用微波等离子体炬原子发射光谱法（MPT－AES）测定Pb,Pt和Au三种元素的可能性。实验结果表明,样品溶液通过阳离子交换树脂柱后,这些离子的干扰基本消除了,将所建立的方法用于一些实际样品分析,得到的结果满意。     

LnZr(BO3)2:Eu3+(Ln=Ba,Sr)的真空紫外光谱特性的研究

采用高温固相法合成了Ba(1-x)SrxZr(BO3)2:Eu3 系列样品,样品Ba(1-x)SrxZr(BO3)2:Eu3 激发谱在130～170nm和230 nm区域有两个很强的吸收带,位于130～170nm的吸收带主要是硼酸盐基质的吸收;位于230nm附近的吸收主要是Eu3 电荷转移态的吸收.当在样品中以Al部分取代Zr时,电荷转移态的吸收明显增强,并且Ba(1-x)SrxZr(BO3)2:Eu3 发射强度也会明显增强;随着x的增大,硼酸盐基质的吸收强度减弱,基质吸收带的主峰值向低能方向移动了大约30 nm.样品Ba(1-x)SrxZr(BO3)2:Eu3 在147nm激发下,发射出主峰值位于616nm的强红光,对应Eu3 电偶极(5D0→7F2)跃迁发射.     

Temperature controlled synthesis of SrCO3 nanorods via a facile solid-state decomposition rout starting from a novel inorganic precursor

Strontium carbonate nanorods have been successfully synthesized via solid-state decomposition of a new precursor, [Sr(Pht)(H₂O)₂]. The obtained nanorods were found to be orthorhombic with the length of 70-100 nm and the diameter of about 10-15 nm. The Effect of calcinations temperature on morphology and purity of the products has been investigated. Strontium carbonate nanorods were formed at 500 °C. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR) spectroscopy. In addition, further evidence for the purity and stoichiometry of the product was obtained by XPS (X-ray photoelectron spectroscopy) spectrum.     

利用三维荧光光谱和吸收光谱研究雨水中CDOM的光学特性

利用荧光激发-发射矩阵光谱(excitation-emission matrix spectroscopy,EEMs)技术并结合吸收光谱初步研究了2007年厦门梅雨季节期间雨水中有色溶解有机物(CDOM)的光学特性.结果表明,雨水CDOM的吸收光谱随波长旱指数衰减,代表雨水CDOM相对含量的吸收系数α(300)范围在0.27～3.45 m-1,均值为1.08 m-1;且降雨初期CDOM含量高于降雨后期.这表明人类活动和当地的大气污染或空气质基对雨水中CDOM的贡献.雨水CDOM的EEMs光谱揭示出2类4个主要荧光峰(2个类腐殖质荧光A和C与2个类蛋白质荧光B和S)的存在.其中2个类腐殖质荧光A和c之间以及2个类蛋白质荧光B和S之间均存在一定的正相关性,说明其具有相同来源或存在某种内部联系.2个类腐殖质荧光与吸收系数α(300)之间的强正相关性,说明其控制吸收特性的基团可能与控制其荧光特性的基团具有相似性质.结果表明雨水CDOM高吸收和荧光特性在大气化学中的作用不容轻视,在受大气水体影响的太阳辐射的光谱衰减中可能起着潜在的重要作用.     

[ONSO]型Salen化合物的合成、单晶结构及金属离子识别

一些重金属离子即使在较低浓度时也会对环境、生物体产生毒性,所以研究痕量金属离子识别具有重大意义。荧光传感器由于具有选择性好、灵敏度高、成本低、实时响应等优点, 得到了广泛关注。以2,4-二叔丁基苯酚,3,5-二叔丁基水杨醛和邻氨基苯硫酚为原料合成了类Salen配体L1, 并用1H NMR,13C NMR,IR,元素分析及X射线单晶衍射等手段对其进行了表征。并通过自由挥发法得到了配体L1的单晶结构,实验表明L1是三斜晶、P-1空间群的一个空穴平面[ONSO]四配位环境。通过荧光光谱考察了类Salen配体与金属离子(Li+,Na+,K+,Cd2+,Cs+,Co2+,Cu2+,Hg2+,Mn2+,Ni2+,Zn2+,Ag+)的识别与配位性能。光谱滴定分析表明L1与Zn2+以1∶1的化学计量数配位。另外,L1与Zn2+结合后荧光显著增强,荧光检测限达到5.01×10-5 mol·L-1,而上述提到的其他常见金属离子不引起荧光光谱变化。结果表明L1是一个对检测Zn2+的选择性高,灵敏度强的荧光增强型探针。     

Temperature-dependent photoluminescence properties of Sr2CeO4:Eu3+ and its modification for use in fluorescence thermometry

The efficient red material Sr2CeO4:Eu3+ (SCOE) has been studied as a potential thermographic phosphor for application in the single-color fluorescence thermometry technique. The temperature-dependent photoluminescence spectra and the integrated emission intensity of SCOE at different temperatures indicate that this red-light-emitting phosphor is extremely sensitive to ambient temperature. On this basis, we designed another three red materials as potential thermographic phosphors that have higher brightness and temperature sensitivity than SCOE, by means of adding Li+, Na+, and K+ ions into the lattice.     

南海砗磲Sr/Ca比值测试：XRF和ICP-OES方法对比研究

对采自中国南海的5个砗磲(1个现代砗磲、4个化石砗磲)进行了两种高分辨率Sr/Ca比值分析。电感耦合等离子体发射光谱法(ICP-OES)得到的Sr/Ca比值呈现出年周期变化，且与海表面温度呈现负相关关系，这表明Sr/Ca可作为良好的SST替代性指标。ICP-OES是测试砗磲壳体Sr/Ca常用的方法，但大量的样品需要钻样及预处理，相当耗时。而同步辐射X射线荧光分析(SR-XRF)可以克服这些缺点，它只需要前期的样品制备，并允许固态样品原位无损快速分析，具有高空间分辨率(微米级)、高灵敏度和多元素分析的特点。在本研究中，我们用SR-XRF方法测试砗磲样品化学元素的可行性。据查阅，目前尚未有类似的相关研究文献。本文实验结果显示SR-XRF 数据能够揭示元素含量及其比值变化。且SR-XRF测得的砗磲Sr/Ca比值与ICP-OES分析方法测得的Sr/Ca通过相关统计分析发现其显著性水平p值(5个砗磲样品的p值均<0.05)非常显著，表明高分辨率SR-XRF测得的砗磲Sr/Ca比值在一定程度上代替ICP-OES分析方法的可能性非常大。SR-XRF方法在砗磲重建古气候领域有很大的应用前景。     

Morphology and optical properties of Mg and Sr doped CaF2 nanocrystals

Magnesium (Mg) and Strontium (Sr) doped Calcium fluoride nanocrystals were synthesized by co-precipitation method. The cubic structure of the samples was confirmed by Powder X-ray diffraction. The average crystallite size of Mg doped samples was found to be ~ 25 nm whereas in Sr doped one it was ~ 35 nm. The morphological features revealed that the nanocrystals were agglomerated, crispy and porous. The as-prepared samples showed the presence of hydroxyl groups. The optical absorption spectrum of as-prepared Mg doped samples showed a strong absorption band peaked at ~ 233 nm whereas the Sr doped one showed a prominent absorption peak at 248 nm. A strong PL emission was observed at ~ 300 nm in Mg doped samples. However, the Sr doped samples showed two prominent emissions at ~ 345 and 615 nm.     

LiM(M=Ca,Sr,Ba)BO_3∶Tb~(3+)材料光谱特性研究

采用固相法制备了绿色LiM(M=Ca,Sr,Ba)BO3:Tb3+发光材料.测量结果显示材料均可被紫外(350～410 nm)光激发,发射绿光.研究了Tb3+浓度对材料发射光谱的影响,结果显示,随Tb3+浓度的增大,发射光谱峰位未发生变化,但其强度呈现出先增大后减小的趋势,即:存在浓度猝灭效应.加入电荷补偿剂Li+,Na+和K+提高了LiM(M=Ca,Sr,Ba)BO3:Tb抖材料的发射强度.