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CHAPTER - II GEOCHEMISTRY OF URANIUM Uranium is one of the most abundant element found in the Earth's crust. It can be found almost everywhere in rock and soil, in rivers and oceans. Traces of uranium are even found in food and human tissue. However, concentrated uranium ores are found in just a few places, usually in hard rock or sandstone (Abhas Singh, 2010). Naturally occurring uranium consists of three different isotopes: U238, U235 and U234. No natural isotopic fraction of U238 and U235 has been observed, and totally all natural materials have a ratio of U238/U235. The third isotope of uranium U234 is an intermediate in decay series of U238 and is formed from U238 by emission of an alpha followed by two beta particles. The formation of uranium valence states between 2+ and 6+. In minerals, only the valences 4+, 5+ and 6+ are known (Wedepohl, 1969). The present chapter deals the geochemistry of Uranium in rocks, soils, plants and water. 2.1. Lithogeochemistry of Uranium: Uranium occurs in a variety of minerals but characteristically is concentrated in a few of minor abundance. Uranium generally formed in Di – valent (UO), Tri – valent (UF3), Tetra – valent (UCl4), Penta – valent (UF5), Hexa – valent (UF6). Uranium is present as trace amount in such major minerals as quartz and feldspars, its mode of occurrence is uncertain, though following possibilities are 1. Isomorphous substitution in the lattice, 2. Concentration in lattice defects, 3. Adsorption along crystal imperfections and grain borders, 4. Inclusion as microcrystals of uranium minerals (Ali, 2001). The fact that the uranium and thorium concentration of igneous rocks are both closely related to the compositions of those rocks makes it difficult to subdivide igneous rocks into meaningful radiometric groups (Assaf et al., 1997). In the igneous environment, uranium is mobile element and tends to accumulate in the late differentiates of igneous melts, primarily because the uranous (U4+) ion has a high charge, which prevents it from substituting for any element its own size. The abundance of uranium 4 ppm in granite (Table 2.1), 0.10 ppm in Oceanic tholeiitic basalt, 0.01 ppm in Dunite and peridotite, 0.53 ppm in Plateau basalt, 0.45 ppm in sand stones, 0.20 ppm in metamorphic rocks (Wedepohl, 1969). 19 Table 2.1 abundance of uranium in various sources (Levinson, 1980) Granite 4.8 ppm Sedimentary rock 2 ppm Average in earth continental crust 2.8 ppm Soil 1 ppm Vegetation Ash 0.5 ppm Sea water 1- 4 X 10 -3 ppb Drinking water 30 ppb Uranium (IAEA, 1996) is ubiquitous. Its concentration, however, is conditioned by its specific properties such as its high affinity to oxygen, its stability in tetravalent form under conditions of high temperature and pressure and its stable because of large ionic radii and absence of crystallo - chemical analogue (Jayaram, 1978). The low polarizing properties of uranium and the consequent high solubility result in its enrichment as are forming solutions in the late stage of magmatic crystallization in the pegmatoid and hydrothermal phases. Although uranium occurs under diverse conditions it is primarily associated with magmatic rocks. At crustal depths, however, it decreases because of the increase in the content of mono and bivalent elements. The concentration of uranium varies according to the substances it is mixed with and the places where it is found. For example, when uranium is mixed with granite that covers 60% of the Earth's crust, there are approximately four parts of uranium per million, i.e. 999,996 parts of granite and four parts of uranium. General abundance ratio (content in percent) of uranium in the Earth crust according to A.P. Vinogradov is 2.5 x 10-4%. It forms part of all rock forming the Earth crust and is also present in natural waters and living organisms. The lowest concentration of uranium is present in ultrabasic rocks, the highest in sedimentary rocks (phosphate rock and carbon shale). Due to radioactive decay the amount of uranium in the Earth crust in the geological history is reducing. When plutonic rock crystallizes uranium is squeezed out in the residual liquor and concentrates in accessory minerals (Abdel Warith, 2000). Proximity of ionic radius of U4+ to ionic radius of Th, Ca, determines a broad spectrum of isomorphous substitutions of uranium in thorium and rare-earth minerals. 20 During the hydrothermal process uranium actively migrates in the form of uraniumcarbonate complexes. Decrease of oxidation-reduction potential of solutions, decrease of partial pressure of carbon dioxide, change of pH of solutions lead to dissipation of such complexes and precipitation of uranium in the form of mineral phases. Temperature intervals where hydrothermal uranium minerals are formed are estimated at 100 - 220оС, sometimes at 300 - 350оС. Metamorphic processes from amphibolitic to granulite facies are commonly accompanied by carry over of uranium. Ultrametamorphism sometimes is accompanied by some addition. 2.2. Pedogeochemistry of Uranium: Uranium (U) is predominantly found in the +VI and +IV oxidation states in the environment. U (VI) is generally more soluble and consequently more mobile than U (IV) in soil. Depending on the redox conditions and the pH of the environment, uranium can exist in different predominant forms; under oxic conditions uranium are primarily present as the uranyl ion UO2, 2+ and its associated hydroxyl complexes for low pH values. For sufficiently high total uranium concentrations at near-neutral pH, U (VI) can precipitate as schoepite [UO3· 2H2O]. In the presence of high phosphate concentrations, U (VI) can form uranyl phosphate solids that are less soluble than other U (VI) solids. For under saturated conditions, U (VI) can be solubilized by forming dissolved uranyl- phosphate complexes (Abhas Singh, 2010). U (VI) can readily adsorb to iron (III) oxyhydroxides such as ferrihydrite, goethite, and hematite and clay minerals. Adsorption to iron-bearing minerals is favored by the high binding affinity of uranyl ion to geomedia. Iron (III) oxyhydroxides like goethite are common minerals in soil and groundwater. They act as strong adsorbents for heavy-metals because of their reactive surfaces and high specific surface areas [10]. U (VI) adsorption to iron oxides typically increases from low to near neutral pH conditions. However, at higher pH values, in the presence of inorganic carbon, U (VI) forms stable dissolved complexes with carbonates that can limit U (VI) adsorption to iron oxyhydroxides and increase the solubility of U (VI) precipitates. At reducing conditions, uranium exists primarily as the mineral uraninite, UO2, which may be oxidized to more mobile U (VI) species when exposed to oxidizing conditions (El Mansi, 2000). 21 In-situ immobilization is also likely to promote the most stable solid associated forms of uranium. Based on its geochemistry there are different potential approaches to immobilizing U (VI). It can be reduced to the relatively immobile U (IV) under reducing conditions by microbial activity and by chemical reductants. When sustaining reducing conditions is not feasible, reduced U (IV) may remobilize by oxidizing to U (VI) species, other in-situ remediation approaches are needed. Phosphate addition is a potential strategy for in-situ uranium immobilization for oxidizing conditions. The injection of phosphate-containing compounds may facilitate formation of uranyl phosphate solids; these solids have relatively low solubilities and are expected to form stable precipitates. This strategy could be particularly useful for sites at low pH when carbonate effects are not dominant and uranyl phosphates may precipitate out readily. Because phosphate is not abundant in most soils and aquatic systems, a source of orthophosphate must be added to the subsurface. Orthophosphate can be obtained from minerals or from organic compounds. A recent study reported uranyl phosphate precipitation as a result of bacterial phosphates activity; bacteria use an organophosphate compound for their metabolism and in-turn produce 4 orthophosphate that can combine with uranium. Uranyl phosphate precipitates were also observed in an oxidizing bedrock aquifer resulting from interactions with iron oxyhydroxide, the abundance of uranium 1 ppm in soil. 2.3. Hydrogeochemistry of Uranium: Organic material in the pore spaces of rocks creates a reducing environment in the water. The oxidizing, uranium-bearing water is passing through the rock precipitate uranium in the rock where the reducing environment exists. Sometimes whole logs (organic matter) buried in the rocks become rich in uranium deposited through this process. Uranium is a widespread and ubiquitous element. It has a crustal abundance of 2.8 parts per million, slightly more than tin. Primary deposits of uranium tend to concentrate in granitic or alkalic volcanic rocks, hydrothermal veins, marine black shales, and Precambrian age placers (Lidman et al., 2012). Secondary (or epigenetic) deposits of uranium are formed later than the surrounding rocks that host the mineral deposit. Uranium is soluble in oxidizing aqueous solutions, especially the U6+ valence state, and can be redistributed from primary source rocks into porous sedimentary 22 rocks and structures by groundwater and form secondary (epigenetic) uranium mineral deposits. Uranium concentrations are constant in sea water and are in the range 1- 4 x 10 -3 ppb (1 – 4 ppm). These values may be compared with an average of 10 -5 to 10 -6 ppm for thorium. Concentrations of uranium in fresh water are considerably more variable than in the oceans. The concentrations are clearly controlled by the variety of factors, such rock type leached by the water, rate of flow and rate of evaporation (Wedepohl, 1969). Natural waters carrying the uranium carbonate and phosphate will also carry many other anions, such as the sulphate, fluoride and chloride which may also form complexes with uranium. Uranium complexes of some of these anions are important under specific environmental conditions: (a) Uranous fluoride in reducing water below pH 3-4. (b) Uranyl fluoride, uranyl ion (UO2 2+), in oxidized water at Eh values of + 0.2 to 0.1 volt, and pH values 1-7. (c) Hydroxide complexes in neutral to alkaline environments. It is now clear that uranium in natural waters is normally complexed. The nature of the complexing inorganic ions, such as carbonate, phosphate, hydroxide and fluoride, will depend on the relative activities of these anions and the specific conditions of Eh-pH. They are also affected by other variables such as the total dissolved solids content and the presence of other ions. Therefore, there is a trend toward analyzing for many of the variables found in water samples collected for uranium surveys in an attempt to assistant in interpretation of the results. These includes: U, PO4, HCO3, SO4, Cl, F, Ca, Mg, K, total dissolved solids, conductivity, pH, Eh, and pathfinder elements (Levinson, 1980). 2.4. Biogeochemistry of Uranium Uranium is low in the list of element abundance, comprising only 0.0027% of the earth's crust. Apart from ore deposits, uranium is most abundant in high silica igneous rocks and in shales, especially black shales. Black shales are commonly enriched in 23 uranium with respect to other sedimentary rocks, sometimes to the extent of causing these rocks, rich in organic matter, to be considered as possible commercial sources of uranium. With atomic number 92 and atomic weight 238.03, uranium is the heaviest naturally occurring element. There are eleven known isotopes, of which three—with atomic weights 234, 235, and 238—occur in nature. The uranium content of coals is highly variable and its occurrence sporadic; where higher than average, the uranium tends to be concentrated in the stratigraphically highest coals or in the vicinity of an unconformity. It is thus most probable that virtually all the uranium in coals has been extracted from solution long after the deposition of peat and that almost no uranium was associated with the original vegetation (Levinson, 1980). The plants ash contains 0.5 ppm of uranium general limit. No plants have been recognized that are direct indicators of U mineralization, although in Alaska it has been noted that lupine tends to favour U-rich soil (Kovalevsky, 1972). Several indirect indicators are known (notably Astragalus) which have an affinity for selenium, and therefore are actually selenium indicators. U is associated with Se in the sandstone roll-front type deposits of the mid-western USA, where Se indicator plants (Anderson et al., 1954) have been used successfully in the discovery of U mineralization in plants. Another geobotanical indicator of U mineralization is the development of abnormal growth patterns, which have been observed in the field and in laboratory experiments (Bakhit, 1989). Such morphological changes are not, however, a reliable guide to U mineralization, since many other physical and chemical parameters may effect similar changes. Three studies have noted changes from normal flower colours near U mineralization (P.W. Swarzenskia et al., 1999). Shacklette noted a paling in the pink hue of fireweed; Kovalsky and Vorotnitskaya noted albinism and varicoloured flowers of Caragana; and Brooks indicated that U anthocyanins may give a bluish tint to flowers which are typically red or pink (Anderson et al., 1954). The fixation of U by plants and other organic matter in general. Plants grown in soils spiked with U accumulated more U in their roots than in their aerial parts, although the amount of U in the branch tips was found to bear a definite relationship to that available in the soil. Roots with a high cation exchange capacity can absorb the most U. Another study suggested that U compounds in plants probably form as a result of 24 ion-exchange reactions between metal-bearing solutions and plant tissues. Organic compounds can bind and transfer U. Studies have shown that U occurs as oxonium complexes in cellulose and lignin, and as chelates. Humic and fulvic acids are the dominant concentrators and transporters of U and they are believed to play a significant role in the formation of secondary U deposits. Low levels of soil phosphate greatly increase the ability of plants to accumulate U, whereas high levels of carbonate have a similar effect. U is effectively absorbed by plants that take up very little potassium (e.g. rose and pine families). Where formation waters have a high salt content U tends to stay in solution, and in the presence of salts and calcium, U can migrate considerable distances. Important observations for biogeochemical prospecting are: 1) U is absorbed best by plants which have a fairly acid cell sap and a high cation exchange capacity in the root. This acidity is estimated to be pH 5, pH 4-5 and less than pH 5.2. One Russian study found the highest U uptake to take place in peat at pH 6; and 2) plants with high transpiration rates transport most ions to their upper parts. Kovalevsky indicated that plants in the boreal forests of Siberia appeared to have a physiological barrier to U uptake, whereas Ra migrated readily from the soils to the plants and no barrier seemed present. He noted that physiological barriers are much more significant in the aerial portions of plants than their roots, and that the barriers are absent in the roots of high-order plants and of low significance in the lower plants. A later study defined U as a "low barrier" element (i.e. only small quantities can be taken up by the high-order plants), but noted that element absorption by plants is, on average, 3000 times more vigorous from aqueous solutions than from the solid phase of soils. Thus where U is dissolved in groundwater, much higher U concentrations in plants may result than where U is present in the soils. This study concluded that the "barrier" exists not in the roots but in the twigs, where U dissolved in fluids passing up the xylem tissues precipitates due to a change in pH that occurs during photosynthesis U is in low concentrations in the soils, but available in the formation waters that the roots are tapping (IAEA, 1996). Thus there is a wide spectrum of results from a good to poor correlation, perhaps dependant upon the porosity, permeability and hydrology regime of the substrate. Each study area must be treated on its own merits. If a better geochemical profile is obtained from soils than plants, then the soils should be collected. If a similar 25 response is found in both sample media, then whichever is more practical should be collected. If the U in the bedrock is incorporated in the crystal lattices of resistate minerals (Levinson, 1972), there is likely to be no more than a subtle biogeochemical response to the mineralization, despite the highly corrosive micro-environment established around rootlets. However, if the U is labile (e.g. as pitchblende or other U oxides in fractures and at crystal boundaries) then it can be readily assimilated by some plants and a strong biogeochemical response may result. 2.5. Uranium mineralogy Uranium is amphoteric (Frondel, 1958; IAEA, 1974). On account of this, in acid and neutral media its forms cations, (bivalent uranyl ions UO2++) and in alkaline media it forms urinate and polyuranate anions. The large ionic radii, variable valency of uranium and its amphoteric property explain the complex chemical behavior of uranium and the consequent large number of mineralogical, varieties. There are on record over hundred identified uranium minerals. Uranium is most stable in hexavalent state. In oxygen rich systems the hexavalent uranium forms (U6O2++) ions. Minerals having (U6O2++) are stable but relatively more soluble in leachants. They form fluorescent yellowish – green coloured compounds, characteristic of uranyl ions. Tetravalent uranium minerals, on the other hand, require suitable redox conditions before them can be solubilised. The compounds of pentavalent uranium are transitory and quickly disproportionate to U4+, and U6+ ions. Thus, no stable minerals of pentavalent uranium are formed in nature. Uranium is associated with Th, Ra, Zr in simple and multiple oxides because U4+ is diadochic with them. Nb, Ta and Ti are found multiple oxides, although uranium is not isomorphous with them because of the valency state and ionic radii. Thus it also occurs in monazite, zircon, columbite – tantalite, samarskite etc. 2.6. Uranium ore minerals An ore mineral, is a “mineral which may be used for the extraction of one or more metals”. A uranium ore mineral is therefore a mineral possessing such physical and chemical properties and occurring in a deposit in such concentrations that it may be used for the profitable extraction of uranium, either alone or together with one or 26 more other metals. There are only a few of the many uranium minerals that meet these qualifications and still fewer in which uranium is the major constituent. Pitchblende and uraninite contains theoretically up to 85 per cent uranium but actually between 50 and 80 percent; Carotids, torbernite, tyuyamunite, autunite, uranophane, and brannerite are 45 to 60 percent. Davidite, samarskite, and euxenite, for example contains only 1 to 18 per cent. The majorities of uranium-bearing minerals however contain uranium in small or trace amounts. 2.7. Primary Uranium ore minerals Uraninite (combined with UO2 and UO3; 50-85 percent U3O8). Uraninite is a naturally occurring uranium oxide with cubic or octahedral crystal form. It has a specific gravity of 8-10.5 (iron = 7.85), a grayish-black color sometimes with a greenish cast and a, it is also an important constituent of nearly all important primary deposits, occurring closely associated with its massive variety, pitchblende Hardness of 5-6, about the same as steel. Its streak is black. Its most widespread occurrence is in pegmatites, in which it is found in small amounts, throughout the world. Pitchblende (combined with UO2 and UO3; 50-80 percent U3O8). Pitchblende is the massive variety of uraninite, without apparent crystal form, that occurs most abundantly in the rich primary vein deposits of uranium. It is the chief constituent of nearly all high-grade uranium ores and has provided the largest part of all uranium produced throughout the world. Davidite (rare earth-iron-titanium oxide; 7-10 percent U3O8). Davidite is a dark brown to black mineral with a glassy to sub metallic luster. It has about the same hardness as pitchblende (5-6) and is somewhat lighter in weight (specific gravity, 4.5). It occurs most commonly in angular, irregular masses, sometimes with crystal outlines, but never in round, botryoidal shapes like pitchblende. 27 Coffinite Coffinite is a uranium-bearing silicate mineral with formula: U (SiO4)1-x (OH)4x. It occurs as black incrustations, dark to pale-brown in thin section. It has a grayish black streak. It has a brittle to conchoidal fracture. The hardness of coffinite is between 5 and 6.It was first described in 1954 for an occurrence at the La Sal No. 2 Mine, Beaver Mesa, America and named for American geologist Reuben Clare Coffin (1886 -1972). It has widespread global occurrence in Colorado Plateau-type uranium ore deposits of uranium and vanadium. It replaces organic matter in sandstone and in hydrothermal vein type deposits. It occurs in association with uraninite, thorite, pyrite, marcasite, roscoelite, clay minerals and amorphous organic matter. Coffinite's chemical formula is U (SiO4)1-x (OH)4 ray powder patterns from samples of coffinite allowed geologists to classify it as a new mineral in 1955. A comparison to the x-ray powder pattern of zircon (Zr SiO4) and thorite (Th SiO4) was the basis for this classification. Preliminary chemical analysis indicated that the uranous silicate exhibited hydroxyl substitution. The results of Sherwood’s preliminary chemical analysis were based on samples from three locations. Hydroxyl bonds and siliconoxygen bonds also proved to exist after infrared absorption spectral analyses were performed The hydroxyl substitution occurs as (OH)44- for (SiO4)2-. The hydroxyl constituent in coffinite later proved to be nonessential in the formation of a stable synthetic mineral. Recent electron microprobe analysis of the submicroscopic crystals uncovered an abundance of calcium, yttrium, phosphorus, and minimal lead substitutions along with traces of other rare earth elements. Coffinite was first discovered in sedimentary uranium deposits in the Colorado Plateau region, but has also been discovered in sedimentary uranium deposits and hydrothermal veins in many other locations. Samples of coffinite from the Colorado Plateau were found with black fine-grained low-valence vanadium minerals, uraninite and finely dispersed black organic material. Other materials associated with later finds from the same region were clay and quartz. In vein deposits of the Copper King Mine in Colorado, coffinite was also found to occur with uraninite and pitchblende. Formation of coffinite requires a uranium source, and may happen in reducing conditions, as evidenced by the associated 28 presence of low-valence vanadium minerals. Silica-rich solution provides such a reducing condition in cases where coffinite results as an alteration product of uraninite. This finding is consistent with the coffinite samples of the Colorado Plateau, which included fossilized wood. In China, coffinite can be found in granite in addition to sandstone. Concluded that coarse-grained coffinite most likely forms in high temperature environments. Coffinite and uraninite precipitate inside brecciated and fractured regions of altered granite at pressures between 500 to 800 bars and temperatures at 126 to 178 °C. 2.8. Secondary Uranium ore minerals Carnotite (K2O 2UO3 V2O5 nH2O; 50-55 percent U3O8). Carnotite, a potassium uranium vanadate, is the most important of the secondary uranium ore minerals, having provided possibly 90 percent of the uranium production from secondary deposits. It is a lemon-yellow mineral with an earthy luster, a yellow streak, and a specific gravity of about 4. Tyuyamunite (CaO 2UO3 V2O5 nH2O; 48-55 percent U3O8).Tyuyamunite is closely related to carnotite as indicated by the chemical formula, which is the same except that calcium substitutes for the potassium of carnotite. The physical properties of tyuyamunite are the same except for a slightly more greenish color than carnotite and, in some cases, a very weak yellow-green fluorescence not found in carnotite. Torbernite and Meta-torbernite (CuO U2O3 P2O5 nH2O; 60 percent with U3O8). Torbernite and meta-torbernite are hydrous copper uranium phosphates, the only difference between the two being the number of water molecules present; their physical properties are identical. Autunite and Meta-Autunite (CaO2UO3 P2O5 nH2O; 60 percent U3O8. Reference to the chemical formula will show that these two minerals have the same composition as torbernite, with calcium substituting for copper. Uranophane (CaO2 UO3 2SiO2 6H2O; 65 percent U3O8) Uranophane is a hydrated calcium uranium silicate containing silica in place of the phosphate of autunite. 29 Schroeckingerite (NaCa3 (UO2) (CO3)3(SO4) F 10 H2O; 30 percent with U3O8). Schroeckingerite is a complex hydrated sulfate, carbonate, and fluoride of calcium, sodium, and uranium. 2.9. Ore genesis of Uranium There are several themes of uranium ore deposit formation, which are caused by geological and geochemical features of rocks and the element uranium. The basic themes of uranium ore genesis are host mineralogy, reduction-oxidation potential, and porosity. Uranium is a highly soluble, as well as a radioactive, heavy metal. It can be easily dissolved, transported and precipitated within ground waters by soluble changes in oxidation conditions. Uranium also does not usually form very insoluble mineral species, which is a further factor in the wide variety of geological conditions and places in which uranium mineralization may accumulate. Uranium is an incompatible element within magmas, and as such it tends to become accumulated within highly fractionated and evolved granite melts, particularly alkaline examples. (Rogers et al., 1969) These melts tend to become highly enriched in uranium, thorium and potassium, and may in turn create internal pegmatite or hydrothermal systems into which uranium may dissolve. 30