Thallium minerals

Occurrence. Thallium can be associated to heavy metals that occur in sulphidic ores (chalcophilic element behaviour) or to alkali metals in minerals such as car-nallite, sylvite, mica (the Tl+1 ion behaves as an alkali metal ion), or in true, but very rare, thallium minerals such as lorandite (T1AsS2), chalcothallite (Cu3T1S2). 

In contrast to the occurrence of thallium as trace element, thallium minerals are very rare. Crookesite (from Skrikerum/ Sweden) is a mixture of the selenides of copper, thallium, and silver. Similar chemical compositions have been found in berze-lianite (Germany) and lorandite (Macedonia). Thallium has also been found in extraterrestrial material meteoric stones contain 0.001 to 0.2 tgg whilst lunar minerals contain 0.0006 to 0.0024 pgg (Urey 1952, Wedepohl 1974). 

Thallium minerals are rare too. N. A. E. Nordenskiold found one in Sweden in 1866. 

Some elements found in body tissues have no apparent physiological role, but have not been shown to be toxic. Examples are mbidium, strontium, titanium, niobium, germanium, and lanthanum. Other elements are toxic when found in greater than trace amounts, and sometimes in trace amounts. These latter elements include arsenic, mercury, lead, cadmium, silver, zirconium, beryUium, and thallium. Numerous other elements are used in medicine in nonnutrient roles. These include lithium, bismuth, antimony, bromine, platinum, and gold (Eig. 1). The interactions of mineral nutrients with... 

Uses. Tballium compounds have limited use in industrial appHcations. The use of thaHous sulfate in rodenticides and insecticides has been replaced by other compounds less harmful to animals (see Insect control technology Pesticides). Tb allium sulfide has been used in photoelectric cells (see Photovoltaic cells). A thallium bromide—thallium iodide mixture is used to transmit infrared radiation for signal systems. ThaHous oxide is used in the manufacture of glass (qv) that has a high coefficient of refraction. Tb allium formate—malonate aqueous solutions (Cletici s solution) have been used in mineral separations. Many thallium compounds have been used as reagents in organic synthesis in researchlaboratoti.es. 

Zinc minerals tend to be associated with those of other metals the most common ate zinc—lead or lead—zinc, depending upon the dominant metal, zinc— copper or copper—zinc, and base metal such as silver. Zinc does occur alone, most often in the northeastern district, and here, as elsewhere, recoverable amounts of cadmium (up to 0.5%) are present. Other minor metals recovered from zinc ores are indium, germanium, and thallium. 

Indium (0.24 ppm) is similar in abundance to Sb and Cd, whereas T1 (0.7 ppm) is close to Tm and somewhat less abundant than Mo, W and Tb (1.2 ppm). Both elements are chalcophiles (p. 648), indium tending to associate with the similarly sized Zn in its sulfide minerals whilst the larger T1 tends to replace Pb in galena, PbS. Thallium(I) has a similar radius to Rb and so also concentrates with this element in the late magmatic potassium minerals such as feldspars and micas. 

While the above examples demonstrate that product control to a significant extent is possible in oxythallation by careful choice of substrate or reaction conditions, the synthetic utility of oxythallation has been illustrated most convincingly by the results obtained with highly ionic thallium(III) salts, especially the nitrate (hereafter abbreviated TTN). Unlike the sulfate, perchlorate, or fluoroborate salts (165), TTN can easily be obtained as the stable, crystalline trihydrate which is soluble in alcohols, carboxylic acids, ethers such as dimethoxyethane (glyme), and dilute mineral acids. Oxidations by TTN can therefore be carried out under a wide variety of experimental conditions. 

Reference has been made earlier to scattered rare metals, the five most important members of this particular group being gallium, indium, thallium, rhenium, and germanium. A common feature of these metals is that they do not form commercially significant mineral sources of their own, but are invariably produced from the processing of other mineral sources. The description given here pertains to rhenium, and serves as one example of these dispersed metals. 

Berndt et al. [740] have shown that traces of bismuth, cadmium, copper, cobalt, indium, nickel, lead, thallium, and zinc could be separated from samples of seawater, mineral water, and drinking water by complexation with the ammonium salt of pyrrolidine- 1-dithiocarboxylic acid, followed by filtration through a filter covered with a layer of active carbon. Sample volumes could range from 100 ml to 10 litres. The elements were dissolved in nitric acid and then determined by atomic absorption or inductively coupled plasma optical emission spectrometry. 

Al, Ga, In and T1 differ sharply from boron. They have greater chemical reactivity at lower temperatures, well-defined cationic chemistry in aqueous solutions they do not form numerous volatile hydrides and cluster compounds as boron. Aluminium readily oxidizes in air, but bulk samples of the metal form a coherent protective oxide film preventing appreciable reaction aluminium dissolves in dilute mineral acids, but it is passivated by concentrated HN03. It reacts with aqueous NaOH, while gallium, indium and thallium dissolve in most acids. 

Thallium is the 59th most abundant element found in the Earths crust. It is widely distributed over the Earth, but in very low concentrations. It is found in the mineral/ores of crooksite (a copper ore CuThSe), lorandite (TLAsS ), and hutchinsonite (lead ore, PbTl). It is found mainly in the ores of copper, iron, sulfides, and selenium, but not in its elemental metallic state. Significant amounts of thallium are recovered from the flue dust of industrial smokestacks where zinc and lead ores are smelted. 

It was originally stated that CaCOa activated with manganese cannot be excited by UV radiation, but CaCOa activated with lead, thallium or cerium and manganese shows an orange-red manganese luminescence under UV irradiation at room temperature (Bolden 1952). Nevertheless, in many minerals luminescence of Mn " " has been found with excitation spectra typical for this center without additional bands of Pb or Ce impurities. 

Crookesite. In 1866 Baron Nils Adolf Erik Nordenskiold found among the collections at the Royal Museum in Sweden a rare mineral from Skrikerum, which C. G. Mosander had regarded as a copper selenide. When Baron Nordenskiold analyzed it, he found it to be a selenide of copper, silver, and thallium. Because it was the first mineral of which the recently discovered element thallium was shown to be an essential constituent, he named it crookesite in honor of Sir William Crookes, the discoverer of thallium (31). Although crookesite is very rare, selenium and thallium are often found associated in nature, and both of these elements, so different in chemical properties, were originally discovered in the same source, namely the slime in the lead chambers of sulfuric acid plants using seleniferous and thalliferous pyrite. 

Many elements are present in the earth s crust in such minute amounts that they could never have been discovered by ordinary methods of mineral analysis. In 1859, however, Kirchhoff and Bunsen invented the spectroscope, an optical instrument consisting of a collimator, or metal tube fitted at one end with a lens and closed at the other except for a slit, at the focus of the lens, to admit light from the incandescent substance to be examined, a turntable containing a prism mounted to receive and separate the parallel rays from the lens and a telescope to observe the spectrum produced by the prism. With this instrument they soon discovered two new metals, cesium and rubidium, which they classified with sodium and potassium, which had been previously discovered by Davy, and lithium, which was added to the list of elements by Arfwedson. The spectroscopic discovery of thallium by Sir William Crookes and its prompt confirmation by C.-A. Lamy soon followed. In 1863 F. Reich and H. T. Richter of the Freiberg School of Mines discovered a very rare element in zmc blende, and named it indium because of its brilliant line in the indigo region of the spectrum. 

One of the most famous applications in forensic science is the analysis of Napoleon s hair by ICP-MS after mineralization in concentrated nitric acid whereby an arsenic concentration about 40 times higher than normal (about 40p,gg 1) was measured (see Section 9.5). Ingested arsenic is known to be stored in sulfydryl rich tissue, like hair, nails or skin. ETV-ICP-MS combined with isotope dilution has been employed to measure thallium in human scalp hair from a person poisoned by thallium compared to control subjects, whereby several longitudinal concentration gradients for the analyzed segments (length 10 mm) were obtained.28... 

Thallium occurs in small amounts in pyrite, zinc blende, and hematite of certain localities, and in a few rare minerals in Sweden and Macedonia. 

Because of low oxidation potential of thallium to form 1 1+, thallium is quite reactive, dissolving slowly in most dilute mineral acids to form thallium(I) solutions. The thallium(I) halides are insoluble in water, but thallium trihalides are soluble die latter are formed by treatment of the thallium(I) halide in solution with the corresponding halogen. Thallium(III) iodide, however, does not exist, TII3 being [Tl-lfl3— 1-... 

In an interlab oratory study involving 160 accredited hazardous materials laboratories reported by Kimbrough and Wakakuwa [28], each laboratory performed a mineral acid digestion on five soils spiked with arsenic, cadmium, molybdenum, selenium and thallium. Analysis of extracts was carried out by atomic emission spectrometry, inductively-coupled plasma mass spectrometry, flame atomic absorption spectrometry and hydride generation atomic absorption spectrometry. 

Thallium — Metal (atomic weight 204.383 gmol-1) found in nature mostly associated with minerals of copper, zinc, lead, and iron. Industrial production is based on electrolytic reduction from solutions of thallium in sulfuric acid obtained by dissolution of dust and cementation residues generated during lead and zinc production. 

The elements below boron in Group IIIA of the periodic table include one of the most common and useful metals and three others that are much less important. Aluminum is the third most abundant element, and it occurs naturally in a wide variety of aluminosilicates, some of which will be described in more detail in Chapter 11. It also occurs in the minerals bauxite, which is largely AIO(OH), and cryolite, Na3AlF6. Although a few relatively rare minerals contain gallium, indium, and thallium, they are usually found in small quantities and are widely distributed. As a result, these elements are generally obtained as by-products in the smelting of other metals, especially zinc and lead. 

For elements like radium, arsenic, beryllium, thallium, molybdenum and many others, not only the low solubility of the related minerals but also the coprecipitation or adsorption with other minerals, plays an important role. For instance radium is co-precipitated with iron hydroxides and barium sulfate. 

Hydrogen sulphide no precipitate in the presence of dilute mineral acid. Incomplete precipitation of black thallium(I) sulphide, T12S, occurs in neutral or acetic acid solution. 

Ammonium sulphide solution black precipitate of thallium(I) sulphide, T12S, soluble in mineral acids. The precipitate is oxidized to thallium(I) sulphate, T12S04, upon exposure to air. 

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