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V – Vanadium
Vanadium is one of the lightest members of the abundance of detrital Fe oxides, clay minerals, first row transition elements, consisting of Sc, Ti, hydrous oxides of Fe and Mn, and organic matter. V, Cr, Mn, Fe, Co, Ni, Cu and Zn, and belongs to The redox regime is important, V remaining group 5 of the periodic table, along with Nb and mobile under oxidising conditions but being Ta. The element has an atomic number of 23, an subject to precipitation just above the atomic mass of 51, three main oxidation states sulphate/sulphide redox threshold within a pH (+3, +4 and +5) and two naturally occurring range of 5.0–8.0 (Brookins 1988). The average V
isotopes (50V, and 51V), of which 51V is the most content of quartzitic sandstone and pure carbonate abundant at 99.8% of the total mass. sediments is low (<15 mg kg-1), with higher Vanadium is a lithophile metallic element at values in greywacke (40–150 mg kg-1), shale (90–
low pressure, but may be siderophile at the 260 mg kg-1), and clay (ca. 200 mg kg-1). Coal elevated pressures suggested for core formation in may also contain appreciable amounts of V. The the Earth. It is incompatible in most silicate most V-rich sedimentary rock is black shale, minerals, although it may be moderately reflecting both the affinity of the element for compatible in some pyroxenes (Snyder 1999). It organic sorption sites and its relative immobility forms several minerals including magnetite under reducing conditions. Cited average values (Fe,V)304, vanadinite Pb5(VO4)3Cl, and carnotite for loess and river particulates are 73 and 170 K2(UO2)2(VO4)2.3H2O. It is also present as a trace mg kg-1 V respectively (McLennan and Murray element in mica, apatite, pyroxene and amphibole. Montroseite VO(OH) occurs across a wide pH Vanadium is a highly mobile element. It range under reducing conditions, exhibiting V in displays both cationic character under acid its lowest valency (V3+), and acts as a source for a conditions, as vanadyl VO2+ and VO 2+ wide range of V3+, V4+ and V5+ oxides and anionic character under less acid to alkaline hydroxides. Sulphides of V4+ are found in ore conditions, as vanadate HVO 2- (Brookins 1988). The solubility of V is strongly The trivalent ion V3+ has an ionic radius (64 controlled by its oxidation state. Its solubility is pm) almost identical to that of Fe3+ (65 pm). highest in oxic environments, where vanadyl Because of this, V is frequently found as a cations predominate. Complexes with fluoride, substitute for Fe in magnetite and in the sulphate and oxalate may also act to increase V ferromagnesian silicate minerals formed during solubility under oxidising conditions (Wanty and primary magmatic processes (Curtis 1964). Mafic Goldhaber 1992), although the presence of U and rocks are typically enriched in V relative to most phosphates can result in the formation of highly intermediate and felsic rocks. Primitive magma insoluble V5+ complexes. Under more reducing types including calc-alkaline, alkaline and conditions, the relatively immobile V3+ state tholeiitic rocks have broadly similar V concentrations (Taylor et al. 1969). Mielke Kabata-Pendias (2001) reports that the (1979) cites values: ultramafic 40 mg kg-1, behaviour of V in soil has received little attention. basaltic 250 mg kg-1, granitic 44–88 mg kg-1, and
It appears that Fe oxides hold a reasonable with an average crustal abundance of 136 mg kg-1. fraction of soil V, however, the role of clay In ultramafic rocks, the V content generally minerals as well organic acids may be more reflects the abundance of minerals, such as Fe-Ti- significant than the V fraction adsorbed by Fe Cr oxides and pyroxene. Elevated V values are, oxides. The highest concentrations of V in soil therefore, indicative of mafic rocks. Although are reported for soil developed on mafic rocks described as a trace element, V is relatively (150 to 460 mg kg-1 V), while the lowest were abundant even though it only rarely forms found in peat soil (5 to 22 mg kg-1 V). The independent minerals in igneous rocks. average V content of soil worldwide has been Vanadium is largely immobile during estimated to vary from 18 mg kg-1 for histosols to metamorphism (Condie 1976). The V content of 115 mg kg-1 for rendzinas (Kabata-Pendias sedimentary rocks reflects primarily the Well-drained, lowland areas are likely to host environmental contamination. the highest V concentrations in stream water and, Vanadium is biologically active and is an in almost all instances, the dispersal of V will be essential nutrient for many animals. Its precise controlled by the prevailing rates of sorption to biochemical function is still in some doubt (WHO hydrous Fe and Mn oxides, clay and organic 1996), but Frausto da Silva and Williams (1991, matter (Krauskopf 1956). As a result, although V 1994, 2001) suggest a role in peroxidase enzymes. concentrations as high as 70 µg l-1 have been An intake of over 10 mg V per day can be toxic found in some natural water, most surface and for adults, but this greatly depends on its groundwater rarely exceed 10 µg l-1 (Hem 1992). speciation and oxidation state; the source is Anthropogenic sources of vanadium include usually airborne anthropogenic V (WHO 1996). oil and coal combustion, steel alloy tool In severe cases, toxic levels of V causes the production and traffic pollution. Vanadium has a inhibition of certain enzymes with animals, which variety of industrial uses in metallurgy, has several neurological effects, and can cause electronics and dyeing. Although the amounts of breathing disorders, paralyses and negative effects V used are small and are insignificant in terms of on the liver and kidneys. any direct anthropogenic input, the combustion of Table 72 compares the median concentrations coal and the waste from such processes, e.g., fly- of V in the FOREGS samples and in some ash, make a significant contribution to reference datasets. Table 72. Median concentrations of V in the FOREGS samples and in some reference data sets. Origin – Source
Number of
Size fraction
(V)
mm
Upper continental Total (ICP-MS)
Aqua regia (ICP-MS)
Total (ICP-MS)
Aqua regia (ICP-MS)
Soil, C-horizon3) Aqua regia (ICP-AES) 24.2 Filtered <0.45 µm
0.46 (µg l-1)
Stream sediment
<0.15
Total (XRF)
Stream sediment
<0.15
Aqua regia (ICP-AES)
Floodplain sediment
Total (XRF)
Floodplain sediment
Aqua regia (ICP-AES)
Stream sediment5) Aqua regia (ICP-AES) 38 1)Rudnick & Gao 2004, 2)Koljonen 1992, 3)Salminen et al. 2004, 4)Ivanov 1996, 5)Garret 2006.

The median values for total vanadium (ICP- MS analysis) are 63.0 mg kg-1 in subsoil and 60.0 The V subsoil distribution map shows many mg kg-1 in topsoil, with a range from 1.28 to 325 similarities to the Fe map. Low V areas in subsoil mg kg-1 in subsoils and 2.71 to 537 mg kg-1 in (<36 mg kg-1) are located mainly in the glacial topsoils. The average ratio topsoil/subsoil is drift covered sandy plains from Poland to the Netherlands, and throughout much of the Baltic states, and large parts of southern Finland and The topsoil V map shows some differences with respect to the subsoil map. In particular, the High V values in subsoil (>96 mg kg-1) are subsoil anomaly disappears completely in the present in north-western Spain (mainly associated topsoil in eastern Slovakia; there is enrichment in with the ultramafic Ordenes ophiolite complex, the illuvial layer of the podzolic topsoil in and intermediate plutonic rocks), the western northern Fennoscandia, because metals are bound Pyrenees (black shales), Brittany, Central Massif to organic matter; in the Spanish Sierra Nevada, (soils over Quaternary basalt), a north-south band the central Pyrenees and Gran Canaria, topsoilis in Italy from north of the Garda Lake to the Roman Alkaline Province, southern Sicily, Greece In subsoil, V shows a very strong positive north of the Gulf of Corinth (terra rossa soil, correlation with Fe (0.91) and Sc (0.91), a strong ophiolite, bauxite and base metal mineralisation), correlation (>0.6) with Co, Cu, Ti, Al, Ga, In, Eu the Dalmatian coast of Croatia, Slovenia and and some of the heavy REEs, and a good southern Austria (strong enrichment in karstic correlation (>0.4) with Mn, Cr, Ni, Nb, Te, Zn, Y residual soil), eastern Slovakia (soils over and the remaining REEs. It has a good negative volcanic rocks and Palaeogene flysch with correlation with SiO2 (-0.43). The correlations ultramafic clasts), parts of Norway, the ice divide pattern is the same in topsoil. area of north-central Finland (which is rich in The analysis with ICP-AES after aqua regia mica), the west coast of Wales and Scotland, and extraction yields a median V content of 33 northern Ireland (over the Antrim basalt). High V mg kg-1 in both subsoil and topsoil, with ranges values express crystalline rocks of intermediate to from 2 to 234 and from 1 to 281 mg kg-1 mafic or alkaline affiliation, including greenstone respectively. It can be concluded that only about belts, and also karst with soil on carbonate rocks half the vanadium was extracted with aqua regia. (Greece, Croatia, Slovenia). In northern Finland The subsoil distribution pattern shows overall V-bearing iron ores are present, and magnetite has similarity with total V but some areas (including a tendency to be enriched during weathering. Galicia in north-west Spain, Wales, Slovakia, and Vanadium in subsoil is also enhanced in southern southern Norway) show fewer high values for Portugal, and the French-Belgian Ardennes. In extractable vanadium. On the topsoil distribution central and eastern England, high V levels in map, extractable V is much lower in north-west subsoil are associated with Mesozoic sedimentary Spain, the western Pyrenees, south-west England ironstone. A point V subsoil anomaly in central and south-central Norway. Spain is in igneous rocks of the Cordillera V in stream water
Vanadium values range over three orders of lowest V values, indicating a strong topographic magnitude, from <0.05 to 19.5 µg l-1, with a and climatic control factor. median value of 0.460 µg l-1. Vanadium High V concentrations stream water (>1.25 distribution resembles that of As, Mo, Sb, Se, U µg l-1) occur in central and south-west Finland and and W. Concentrations in alkaline stream water southernmost Sweden on Svecofennian rocks, in in the Mediterranean region tend to be enhanced. Denmark, north-west Germany on glacial deposits Lowest V values stream water (<0.016 µg l-1) and in the Netherlands on Quaternary. In are found in central and northern Sweden, almost southern and western coast of Finland, the stream entire Norway (Precambrian and Caledonian catchments are dominated by V-bearing clay soil, rocks), western Scotland, Wales and western and some V occurrences are known in the central Ireland on Caledonides, and in north-west of parts of the country with anomalies in stream Iberian Peninsula on Variscan rocks. In Alpidic sediment. In Variscan Europe, enhanced V occurs Europe they occur in the western Alps of south- in the south-eastern tip of England, in Lorraine east France and north-west Italy, in western and in an area from Paris to Brittany in France, in Austria and on Crete. Typically high-relief, high the Iberian Pyrite Belt of southern Portugal and rainfall areas in north-west Europe show the Spain. In the Alpidic part of Europe, high V in stream water occurs in eastern Czech Republic distribution opposite to the one in solid sample (partly Variscan), eastern Austria, south-western media; it is controlled by pH, Eh and climate, with Slovakia and across Hungary to eastern Croatia, in the highest values found in alkaline stream the latter two mostly on Quaternary deposits of water with much dissolved organic carbon Pannonian basin. In Italy, moderately high V stream water values in the Po River valley, and The discussed patterns of V in stream water of widely distributed in central and southern Italy are Europe are distributed according to two major in part associated with alkaline volcanism, in models, the Major-ions and the REEs distribution western Sicily, and eastern and north-eastern patterns. Both of them are mainly exogenic, in Greece bordering the Aegean Sea (Plant et al. response to the climatic N-S zonation of the 2005). Isolated high V values in central and the continent, and to rainfall and infiltration in extreme south-east of England may be associated connection with topography. The much stronger with ironstone and the Weald district respectively. Major-ions pattern explains most of the V High V point anomalies in Greece are related to distribution in southern and central Europe, and ophiolite, amphibolite, Fe-Ni and base metal the REEs pattern anomalies in Finland, Sweden, mineralisation. Anomalous stream water V Denmark and adjacent Germany. Geogenic contents in south-central Slovakia are caused by features include high V concentrations in stream Tertiary volcanic rocks of predominantly andesitic water in the Italian and Greek alkaline volcanic composition. An isolated stream water V provinces (Plant et al. 2005). The anomalies anomalous point in Hungary has no apparent appear also in the solid sample media of these regions. In other areas the concordance of stream In Spain and Portugal, vanadium shows a water and solid media patterns is very rare. V in stream sediment
Total vanadium in stream sediment has a the Bohemian Massif, an area in the highest median value of 62.0 mg kg-1 (XRF analysis), western Alps (ophiolites near Mont Blanc and with a range from < 2 to 407 mg kg-1. Matterhorn), the Roman Alkaline Province in The V stream sediment distribution map shows Italy, a point anomaly at Roccamonfina in low V areas (<37 mg kg-1) located mainly in the Campania, and north-eastern and central Greece sandy plains from Poland to the Netherlands, (ophiolite, lignite, Fe-Ni, Cr, phosphorite and throughout much of the Baltic states, south-central base-metal mineralisation). In addition, scattered Sweden, western Ireland, eastern France and most V stream sediment point anomalies throughout parts of central southern and eastern Spain. Europe could be caused by local geological High V values in stream sediment (>89 substrate or by coprecipitation conditions in mg kg-1) are located mainly in southern Finland, stream sediment, and should be investigated northern Fennoscandia (iron ores), central Norway (Caledonian layered mafic intrusions such as Although vanadium is generally a lithophile Sulitjelma), and the Caledonides of Norway element in the primary (igneous) environment generally. The North-Atlantic Tertiary volcanic (except in magnetite and some Fe-silicates), it province shows high V stream sediment values in occurs with the siderophile element iron in the western Scotland (central complexes of Skye, secondary environment, adsorbed or in Mull, Rhum and Ardnamurchan) and in northern coprecipitation with Fe-oxides/hydroxides. The Ireland (Antrim plateau basalt). Most of Britain distribution of V on the stream sediment map is shows high V values, which may be caused by very similar to that of Fe. The correlation coprecipitation with iron in stream sediment. In coefficient Fe-V is 0.87 (very strong) in stream central and southern Europe, in contrast, V sediment. Vanadium also shows a strong anomalies are scarce and are limited to southern correlation (>0.6) with Al, Ga, Ti and Co, and a Portugal and adjacent Spain (Palaeozoic flysch good correlation (>0.4) with Eu, Ni, Cu, Zn and sediments and Ossa Morena metamorphic zone), north-western Spain (ultramafic rocks of the The analysis of stream sediment samples by Ordenes ophiolite complex), the Central Pyrenees, ICP-AES after aqua regia extraction yields a median extractable V content of 29 mg kg-1, and a distribution pattern is the same everywhere except range from 4 to 306 mg kg-1. This indicates that in the Pyrenees (black shale) and northern about 70% of the total V is extracted on average. Portugal-Spain (mafic/ultramafic rocks) where the The aqua regia extractable V stream sediment extractable V is lower. V in floodplain sediment
Total V values in floodplain sediment, complex, and intermediate plutonic rocks); in determined by XRF, vary from <2 to 266 mg kg-1, France, the Armorican Massif, part of Massif with a median of 56 mg kg-1, and the aqua regia Central (basaltic volcanics in Auvergne), the extractable from 3 to 140 mg kg-1 V, with a western Pyrenees, and the Jura Mountains the median of 29 mg kg-1. The aqua regia leach mineralised Erzgebirge and Bohemian Massif; in extracts on average 52% of the total V. The the Alpine realm, high V values are found in general distribution across the continent is roughly southern and eastern parts of Austria, most of similar, but varies in detail. Slovakia, Hungary and Croatia, northern Corsica, Low total V values in floodplain sediment north-western Italy and the upper Po River basin (<34 mg kg-1) occur over the glacial drift covered and the Roman alkaline magmatic province; plain from Elbe river in Germany across the Albania and northern Greece with ophiolite, whole of Poland and Lithuania to western Latvia; lignite, Fe-Ni, Cr, base-metal and phosphorite in central and eastern Spain on mostly Mesozoic mineralisation. A very high V value in floodplain and Tertiary rocks (clastics and carbonates); on sediment occurs on the basalt of Canary Islands carbonate and clastic rocks of Aquitaine and Rhône basins in France; on loose molasse basin The highest floodplain sediment V value is deposits of central-north Austria. Low total V found in the mineralised Oslo Rift (266 mg kg-1). values in floodplain sediment also occur in south- High V values that occur in England on the east Finland, south Sweden and southernmost Blackwater River to the north-east of London may Norway on largely granitic rocks of the be due to industrial pollution, and in Germany on Fennoscandian Shield, and over metamorphic and the Weser river (224 mg kg-1) to the north of granitic rocks and Old Red Sandstone in the Bremen to coal and oil combustion. The high northern half of Scotland. floodplain sediment V value in western Croatia is High total V values in floodplain sediment explained by enrichment in karstic soil. (>81 mg kg-1) occur in the Precambrian Shield Vanadium in floodplain sediment has a very rocks of Fennoscandia on old marine clay areas of strong positive correlation with Fe2O3 and Ti2O, a southern, central and northern Finland (e.g., strong correlation with Al2O3, Ga, Co, Nb, Ce, La, Koitelainen Cr-V-PGE); in northern Sweden (e.g., Eu, Sm, Gd and Y, and a good correlation with Li, Kirunavaara-Norrbotten mineralised area), central Ta, Cu, Th and the remaining REE. and southern Sweden (also near Taberg V-Ti-Fe The aqua regia V floodplain sediment deposit); in greenstone belts of central and distribution map is similar to the total XRF map, northern Norway, and in the Caledonides part, in but with a more pronounced anomaly in southern north and south-central Norway, partly over England, southern Italy and Sicily, southern and gabbroic areas; the Midland Valley of Scotland northern Finland, and north-east France. On the (mafic volcanics, 200 mg kg-1), Wales (mafic other hand the area with high V values is less volcanics) and south-east England (possibly conspicuous in central Norway, in Austria, industrial pollution). In Variscan Europe, high V Hungary and Slovenia, southern Portugal and in values in floodplain sediment are found over Brittany in France. rocks of the Iberian Portuguese-Spanish Pyrite It is concluded that the V spatial distribution in Belt extending into the Córdoba-Pedroches Zn-Pb floodplain sediment is related to bedrock geology district with Carboniferous black shale; and the and mineralisation, especially mafic and north-west part of Spain and adjacent Portugal ultramafic lithology, but also to clay-rich soil with (mafic and ultramafic rocks of the Ordenes high Al2O3 contents.

V comparison between sample media
Patterns in V distribution between all solid Patterns between total and leachable (aqua regia) sample media are broadly similar, although stream V concentrations are broadly similar, except in sediment concentrations are higher than in other north-eastern Portugal and over the Pyrenees, sample media throughout most of Britain and where leachable V data are lower than total data in Ireland and in southern Norway (Fe and Mn oxide all sample media (no explanation). precipitation induced by low pH, high rainfall A boxplot comparing V variation in subsoil, conditions). These patterns are similar to those topsoil, stream sediment and floodplain sediment seen for Fe, but weaker. Lower V is present in is presented in Figure 51. stream sediment throughout Croatia, Slovenia and Stream water V data show similar patterns to southern Austria (possibly explained by the those observed in solid sample media throughout removal of fine-grained material from the residual most of southern and eastern Europe, but opposite soils). Vanadium values in subsoil in north- patterns occur throughout Fennoscandia western Spain are higher than in other solid (relatively immobile V3+ associated with reducing sample media. Vanadium is higher in stream conditions), the Quaternary sediments of northern sediment in southern Portugal compared to other mainland Europe and most of the Iberian solid sample media. Lower V values are observed Peninsula (in the south, higher concentrations in floodplain sediment throughout the Pyrenees associated with oxic conditions). compared to the other solid sample media. Figure 51. Boxplot comparison of V variation in subsoil, topsoil, stream sediment and floodplain sediment.

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