Soil Profile Concentration Distributions of Aluminum, Gallium, Indium and Thallium across Southeastern Missouri

The soil chemistry of gallium, indium, and thallium is not well defined, particularly with emerging evidence that these elements have toxic properties and may influence food safety. The purpose of this investigation was to estimate the soil concentrations of gallium, indium, and thallium and determine if these elements have a soil chemistry like aluminum and therefore demonstrate significant concentration correlations with aluminum. Twenty-seven soil series were selected, and the elemental concentrations were determined using aqua regia digestion with analytical determination performed using inductively coupled plasma emission-mass spectroscopy. The concentrations of gallium, indium, and thallium generally compared with the known literature. Aluminum-gallium and aluminum-thallium exhibited significant concentration correlations across the soil horizons of the sampled soils. Aluminum, gallium, and thallium did demonstrate concentration increases in soil horizons having illuviation of phyllosilicates, implying these phyllosilicates have adsorption and isomorphic substitution behaviors involving these elements.

基于神经网络和GIS的耕地土壤铊含量分布及其驱动因素

采用多元统计、GIS和神经网络相结合的方法研究了耕地土壤Tl含量的空间分布格局及其主要驱动因素.结果表明,研究区耕地土壤Tl环境质量较好.研究区耕地土壤Tl含量范围为0.01~7.33mg/kg,算术平均值(0.91±0.40)mg/kg,超过湖南省土壤Tl含量背景值(0.61mg/kg),耕地Tl含量累积特征明显,但明显低于2017年全国农用地土壤污染状况详查工作中土壤Tl含量评价参考值(1.0mg/kg).耕地土壤中Tl含量流域分布特征明显,耕地土壤Tl含量呈现“东高西低,南高北低”趋势,高值聚类区主要分布湘江流域南部地区和武水流域.武水流域耕地土壤Tl含量算术均值达到1.10mg/kg,存在潜在污染风险.研究区耕地土壤Tl含量积累和分布格局受水力、工业活动和自然因素的综合影响.高海拔和水网密度区耕地土壤Tl累积明显.黄棕壤的土壤Tl含量显著高于其他类型土壤.

滇东北火德红MVT矿床中铊的差异性富集机制:来自EBSD、LA-ICPMS和TEM证据

铊(Tl)是一种战略性关键金属,在高科技领域具有重要用途。作为“稀散元素”之一,Tl主要富集于低温贱金属硫化物矿床中,黄铁矿和白铁矿是其主要载体矿物。滇东北火德红MVT铅锌矿床中黄铁矿和白铁矿显示Tl的富集,其中白铁矿中Tl含量显著高于黄铁矿,为探究Tl在不同矿物之间的差异性富集机制提供了理想对象。本文对火德红矿床共生黄铁矿-白铁矿开展系统的结晶学、矿物学和地球化学研究。电子背散射衍射(EBSD)结果表明,热液黄铁矿、白铁矿晶粒组构具有一定继承性,与闪锌矿紧密共生,暗示为同一成矿事件的产物。激光剥蚀耦合等离子体质谱(LA-ICPMS)原位微量元素含量分析结果显示,黄铁矿和白铁矿中的Tl含量分别为127×10^(-6)~516×10^(-6)和356×10^(-6)~1046×10^(-6),不同含量测点Tl的激光剥蚀时间分辨元素信号曲线均较为平滑,暗示Tl主要以类质同象形式进入黄铁矿和白铁矿晶格。透射电镜(TEM)进一步证实Tl类质同象直接替换Fe为主,即2Tl^(+)←→□(空位)+Fe^(2+)。结合黄铁矿和白铁矿中Tl与Zn含量的正相关关系,本文认为白铁矿中Tl的超常富集可能与偏酸性条件下富Tl、Zn和Fe等金属成矿流体有关。综合研究表明,火德红矿床黄铁矿与白铁矿中Tl的差异性富集与晶体结构、Tl赋存状态无关,而是流体成分、物化条件共同制约的结果,受到矿物和矿床等不同尺度苛刻成矿条件的影响。与闪锌矿共生的白铁矿是未来寻找铊资源的重要方向。

Paraffin wax as a diluent for extraction and separation of trivalent gallium, indium, and thallium with 2,6-bis-(l'-phenyl-3'-methyl-5'-oxopyrazole-4') pyridineacyl

A method is proposed for the extraction and separation of trivalent gallium,indium and thallium from their corresponding aqueous solutions at 65 deg C with 2,6-bis-(1'-phenyl-3'-methyl-5'-oxopyrazole-4') pyridineacyl (H_2PMBPP or H_2A) using molten paraffinwax as a diluent. The values of pH_(1/2) for extraction of gallium, indium and thallium are2.62,4.32 and 4.93, respectively. Gallium can he extracted by H_2PMBPP at a lower acid medium. Theeffect of solvent and the composition of the extracted species are reported. And the thermodynamicdata of the extraction are also obtained.

Early diagnosis, treatment, and outcomes of five patients with acute thallium poisoning

BACKGROUND Thallium poisoning is rare and difficult to recognize.Early diagnosis and treatment of thallium-poisoned patients are essential to prevent morbidity and mortality.AIM To evaluate the efficacy of treatments and outcomes of five patients with early diagnosis of acute thallium poisoning.METHODS Five patients who consumed a thallium-contaminated meal were hospitalized in succession,and underwent clinical examinations such as blood tests and electromyography tests.Urine and blood tests confirmed the diagnosis of thallotoxicosis,revealing the occurrence of food poisoning.All patients underwent detoxification treatment,including hemoperfusion(HP)and treatment with Prussian blue(PB).A 24-mo follow-up was performed to evaluate the long-term outcomes on the patients after discharge.RESULTS Initially,the patients presented with symptoms of acute thallium poisoning including hyperalgesia of the limbs and abdominalgia,which may differ from common peripheral neuropathy.Accompanying symptoms such as hepatic damage and alopecia were observed in all the patients,which further confirmed the diagnosis of poisoning.Treatment with chelating agents was ineffective,while HP and treatment with PB drastically decreased the thallium concentration in the urine and blood.With early diagnosis and intervention,four patients had a good prognosis and no permanent sequelae.One patient developed blindness and disability during the 24-mo follow-up period.CONCLUSION Identification of incident cluster and characteristic symptoms is extremely important for early diagnosis of acute thallium poisoning.HP plus PB is essential to improve the prognosis of thallium-poisoned patients.

Thallium in Low Temperature Ore Deposits, China

This paper deals with thallium in typical low-temperature deopits of Au, Tl, As,Sb and Hg in South China with respect to its mode of occurrence, minerals and geochemicalcorrelations with many other coexisting major and trace elements. Criteria are proposed for i-dentifying independent thallium deposits and thallium-bearing deposits and the Nanhua realgardeposit is classified for the first time as an independent thallium deposit. Tl, F, Cl, I and B aresuggested as indicators for low-temperature mineralization with examples furnished for their ap-plications.

Physical properties of ternary thallium chalcogenes Tl2MQ3（M = Zr, Hf; Q = S, Se, Te） via ab-initio calculations

We have reported a first principles study of structural, mechanical, electronic, and thermoelectric properties of the monoclinic ternary thallium chalcogenes Tl2MQ3(M = Zr, Hf;Q = S, Se, Te). The electronic band structure calculations confirm that all compounds exhibit semiconductor character. Especially, Tl2ZrTe3 and Tl2HfTe3 can be good candidates for thermoelectric materials, having narrow band gaps of 0.169 eV and 0.21 eV, respectively. All of the compounds are soft and brittle according to the second-order elastic constant calculations. Low Debye temperatures also support the softness. We have obtained the transport properties of the compounds by using rigid band and constant relaxation time approximations in the context of Boltzmann transport theory. The results show that the compounds could be considered for room temperature thermoelectric applications(ZT ~ 0.9).

Investigations of Thallium(Ⅰ) Underpotential Deposition on the Silver Rotating Disk Electrode and Its Analytical Application

The cyclic voltammetry(CV) and the square wave technique were used for the investigations of thallium(Ⅰ) underpotential deposition(UPD) on the silver electrode. A solution of 10 \{mmol/L\} HClO 4+10 mmol/L NaCl was selected as the supporting electrolyte. The calibration plots for Tl(Ⅰ) concentration in the range of 2×10 -9 -1×10 -7 mol/L were obtained. The detection limit was 5×10 -10 mol/L. For the solutions of 4 0×10 -9 mol/L thallium added before the urine sample pretreatment procedure, the average recovery was 105 6% with a relative standard deviation(RSD) of 15 5%.

Novel Monomeric Phenanthroline - Thallium(III) Complexes Multinuclear NMR Characterization in Organic Solvents

A novel complex of monomeric thallium(III) with the nitrogen donor ligand phenanthroline (phen) has been prepared and characterized by multinuclear NMR (1H, 13C, 205Tl). The three complexes exist in equilibria in DMSO and acetonitrile solution, which was proved by the 205Tl NMR spectra. The 1H and 13C NMR spectra of tris-phen Tl(III) complex have been measured, where the spin-spin coupling between Tl (I = 1/2) and 13C or 1H signals were observed with the 1H and 13C NMR spectroscopy in acetonitrile. The coupling constants are presented and the chemical shifts of complexes are discussed in detail.

Analysis of Nine Cases of Acute Thallium Poisoning

In this study nine cases of thallium poisoning in a series of homicidal poisoning were analyzed in order to provide more information concerning thallium poisoning. It was found that the most common clinical feature of thallium poisoning was peripheral neuropathy and paraesthesia was more common than amyasthenia. Understanding of these clinical characteristics of thallium poisoning was helpful to early identification and differential diagnosis. Since the early administration of Prussian Blue, as a specific antidote for thallium poisoning, can substantially improve the prognosis, it is of great importance to establish a correct and early diagnosis.

Flame Atomic Absorption Spectrometric Determination of Trace Amounts of Zinc and Thallium in Different Matrixes after Solid Phase Extraction on Modified Multiwalled Carbon Nanotubes

The potential of modified multiwallcd carbon nanotubes, as a solid-phase extraction sorbent for the simultaneous separation and preconcentration of zinc and thallium has been investigated. Zinc and thallium were adsorbed quantitatively onto modified multiwalled carbon nanotubes in the pH range of 3 - 6.5. Parameters influencing the simultaneous preconcentration of Zn(II) and Tl(I) ions such as pH of the sample, sample and eluent flow rate, type and volume of elution solution and interfering ions, have been examined and optimized. Linearity was maintained between 0.1 to 20.0 μg?mL–1 for thallium and 20.0 ng?mL–1 to 5.0 μg?mL–1 for zinc in the final solution. The defection limits based on three times the standard deviation of the blank signal (n = 8) for thallium and zinc were 5.1 and 1.4 ng?mL–1, respectively. Seven replicate determination of a mixture of 5.0 and 0.2 μg?mL–1 of thallium and zinc in the final solution gave a mean absorbance of 0.085 and 0.074 with relative standard deviation 1.5% and 1.7%, respectively. The method has been applied for the determination of trace amounts of zinc and thallium in biological and water sample with satisfactory results.

Nucleation and Growth of Thallium on Thin Film Mercury Electrode: Voltammetric, Scanning Electron Microscopy, Chronoamperometric and Electrochemical Impedance Studies

Thallium is a heavy metal highly toxic to the biosphere. It can be determined by anodic stripping voltammetry after deposition on mercury film. The aim of this work is to study the conditions and mechanisms of deposition of Hg on glassy carbon electrode and Tl on Hg film by cyclic voltammetry, scanning electron microscopy, chronoamperometry and impedance techniques. The results showed a germination and growth of a 3D Hg phase on glassy carbon electrode. Similarly, the electrodeposition of Tl on Hg follows a 3D three-dimensional nucleation with diffusion controlled growth. The impedance measurements reveal an easier charge transfer on the Tl film.

Research and Safety Evaluation of Thallium in Cosmetic Products

By standard method to determine thallium content in 34 batches of cosmetic products sold in Shenzhen,including cushions and sunscreens for children,all results of samples are within the range of not detected to 0.62 mg/kg.By calculating the Maximum Theoretical Safety Limit,according to guidance of Scientific Committee on Consumer Safety(SCCS)of European Union and Toxicological Review of Thallium and Compounds 2009 of United States Environmental Protection Agency(EPA)to assess the risk of cosmetic products.As a result,if the mean concentration of thallium in different kind of cosmetic products does not exceed 0.031 mg/kg,the products will not show significant toxicological risk for consumers.

Hydrogeochemical processes of thallium in a rural area of Southwest Guizhou,China

The water system in a rural area of Lanmuchang in Southwest Guizhou is facing a risk of thallium (Tl) contamination due to Tl mineralization around the area. The major trace elements and Tl in the water system are studied to understand the hydrogeochemical processes of Tl constrained by Tl mineralization. The results showed that the dispersion pattern of Tl follows a descending order in concentration from mine groundwater (deep groundwater) →stream water→shallow groundwater→background water, reflecting the impact of Tl mineralization on the hydrogeochemical composition. Tl concentrations in stream water in both regimes are remarkably higher (2-30 fold) downstream than up- and mid-streams, probably caused by the unidentified discharge of deep groundwater. Low Tl levels are detected in the current drinking water, however, the highly elevated Tl in stream water and ground water may pose a potential environmental risk through daily washing and agricultural irrigation. This study suggests that human activities, such as agricultural irrigation, could intensify the environmental risk of Tl.

Lanmuchangite, a New Thallium (Hydrous) Sulphate from Lanmuchang, Guizhou Province, China

Lanmuchangite is a new thallium hydrous sulfate from the oxidation zone hosting rich thallium ore bodies in the Lanmuchang thallium(mercury) ore deposit, Xinren County, Guizhou Province, China. This new mineral is named after the locality where it was discovered. The mineral is associated with melanterite, pickeringite, potassium alum, jarosite, gypsum, arsenic blane, sulphur and some unknown minerals. The aggregates of lanmuchangite range from 2 to 10 mm in size. In general, the aggregates are compact and massive in form and are composed of anhedral granular crystals measuring in size from 40 to 90μm, but the single crystal grains show distinct boundaries. Parallel columnar aggregates are occasionally seen, which are composed of subhedral to euhedral columnar crystals ranging in size from 15 to 65μm. White, light yellow to white in color, glassy in luster and transparent. Hv-{mess.}=94-124 kg/mm+2, Hm={3.1}-{3.4}, density={2.22} g/cm+3. Under the polarization microscope the mineral is colorless and homogeneous, with N-{meas.}={1.495}. It is easily water-soluble. The average chemical composition is: Tl-2O={33.25}, Al-2O-3={8.07}, SO-3={25.19}, SiO-2={0.10}, K-2O={0.35}, CaO={0.08}, MgO={0.06}, FeO={0.04} and H-2O={33.46} [the crystal water (H-2O) was measured by thermogravimetery (TG) while the other composition were determined by electron microprobe], totaling {100.60%}. The empirical formula is (Tl-{1.00}K-{0.05})-{1.05} (Al-{1.01}Si-{0.01}Ca-{0.01}Mg-{0.01})-{1.04}-{2.01}·{11.88} H-2O and the simplified formula is TlAl-2·12H-2O. The compatibility of lanmuchangite is {-0.03} and its value falls within the range of {±0.020}-{±0.039}, so the compatibility is excellent. Its TG curve demonstrated that the crystal water was lost (i.e., dewatering) in stages at 101, 130 and 230℃. At the temperature of 243℃ the process of dewatering came to the end and the sum of lost crystal water reaches {33.30} wt%. IR spectroscopic analysis showed that the absorption bands 3374-3147 cm+{-1} and 1655-1648 cm+{-1} are due to tensile and bending vibration of crystal water molecules (H-2O) whereas those at 1131 cm+{-1} and 605 cm+{-1} are attributed to tensile and bending vibration of group +{2-}. Lanmuchangite is of the isometric system, with space group=Pa3, a={12.212(5)}, v=1821(2)+3, and Z=4. The strongest diffraction lines from the X-ray power diffraction data are {4.314}(100, 220), {2.801}(70, 331), {7.03}(54, 111), {2.731}(35, 420), {6.11}(27, 200), {3.524}(24, 222), {3.676}(22, 311), {3.051}(22, 400), {2.350}(21, 511), {3.263}(20, 321), {2.494}(20, 422), {1.932}(19, 620).

KINETIC STUDY ON THE EXTRACTION OF THALLIUM(Ⅲ) WITH DI(2-ETHYLHEXYL) SULFOXIDE FROM HYDROCHIORIC ACID MEDIA

The extraction of thallium (Ⅲ) with di (2-ethylhexyl) sulfoxide from hydrochloric acid media was studied by means of single-drop method.An extraction rate expression and the activation energysupport a mechanism,in which the ratelimiting step is HTlCl4+DEHSO(i) =HTlCl4DEHSO(i).

电感耦合等离子体原子发射光谱(ICP-AES)法测定再生锌中铊

铊是一种典型的危险废物,在选冶过程中,再生锌原料中的铊以氧化物或粉尘的形式排放到环境中,严重污染环境并危害人类健康。再生锌成分复杂,若样品消解不完全,直接影响测定结果的准确性。通过比较微波消解和电热板常压消解对样品的处理效果表明,微波消解法快速环保,但是对于难消解的再生锌样品,因无高氯酸的加入,其氧化性能降低,无法将样品消解完全,导致铊测定结果偏低。而采用高氯酸-硝酸-盐酸-氢氟酸构成的混合酸并于低温加聚四氟乙烯盖电热板常压消解,能够有效地解决再生锌样品前处理难题。采用四酸法消解样品,5%盐酸进行浸取,选择Tl 190.794 nm为分析谱线,用电感耦合等离子体原子发射光谱(ICP-AES)法测定再生锌中铊。在仪器设定的最佳测定条件下,当Tl质量浓度为0.10~5.00μg/mL时,与发射强度线性关系良好,线性回归方程为y=180.77 x-0.46,相关系数为0.99998。干扰实验表明,在设定的共存离子干扰上限,Pb、Zn、Cu、Fe、Ca、Bi、Sb、Sn、As、Al、Cd、Si、Ag等对再生锌中铊的测定基本无影响。按照实验方法,对5个不同铊含量水平的再生锌样品进行11次独立测定,其测定范围为0.004%~0.21%,方法检出限为0.004μg/mL,相对准偏差(RSD)为2.1~3.2%,加标回收率为97.3%~108%。方法简单,操作性强,能够快速准确测定再生锌中铊。