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Th – Thorium

Introduction

Thorium is a member of the actinide series of resistate in character, as its major host minerals,
elements, along with U and the human-made such as monazite and zircon, are highly resistant
elements such as Pu. The element has an atomic to both chemical and physical breakdown. Any
number of 90, an atomic mass of 232, one main Th released by weathering has a transient
oxidation state (+4) and one naturally occurring existence in solution as it is strongly sorbed by
isotope (232Th). Like U, it is a radioactive element clay minerals. Thus, sandstone, arkose and
and its most stable isotope, 232Th, has a very long graywacke may have up to 10 mg kg-1, and
half-life of 1.4 x 1010 years. normal shale and mudstone 10–13 mg kg-1.
Thorium is the most abundant of the heavy Mielke (1979) cites levels of Th in shale,
elements, i.e., elements with atomic number sandstone and carbonate rocks as 12, 1.7 and 1.7
greater than Bi (83). It has a crustal abundance of mg kg-1 respectively. Black shale may have
9.6-12 mg kg-1, which is more abundant than Sn higher Th levels, but never as high as the U
and only slightly less than Pb. It is strongly content, because of the much stronger affinity of
lithophilic, and is more abundant in crustal rocks U for organic material and the greater mobility of
than in meteorites and mantle-type rocks, such as oxidised UO22+ in solution. Placer deposits, such
dunite. It forms several minerals including as monazite sands, however, may be exceptionally
monazite (Ce,La,Nd,Th)(PO4,SiO4), the rarer rich in Th and constitute one of the major ores of
thorite ThSiO4 and thorianite ThO2, but is more Th. Limestone is normally very low in Th, since
widely dispersed as an accessory element in Th4+ cannot form a stable carbonate, unlike UO22+;
zircon, sphene, epidote, uraninite, allanite and similarly, Th is almost completely absent from
apatite in igneous rocks. Although Th is a evaporite deposits. Marine Mn nodules are often
transition element, possessing more than one enriched in Th (24–124 mg kg-1) and Atlantic
valency state, its geochemistry is dominated by pelagic clay have been noted to contain 30 mg kg-
the Th4+ ion, which has an ionic radius of 94 pm, 1
(Wedepohl 1978). The average value for loess is
and shows greatest affinity to other M4+ elements quoted as 11.3 mg kg-1 (McLennan and Murray
such as U, Ce and Zr. The minerals of these 1999).
elements are often isostructural, with replacement Kabata-Pendias (2001) report there is very
and solid-solution gradations between the end- little information with respect to Th in soil. The
members, e.g., thorianite ThO2, cerianite CeO2 global average for soil is given as 3.4 to 10.5
and uraninite UO2; thorite ThSiO4 and zircon mg kg-1. The mobility of Th in soil, like U, is
ZrSiO4; and monazite (Ce,La,Th,U)PO4. governed by the formation of the hydrated cation
Thorium is generally higher in granitic than Th4+, which is responsible for its solubility over a
mafic igneous rocks. Since it can enter some wide range of soil pH. Organic acids increase the
rock-forming minerals, such as biotite, it is not as solubility of Th in soil, but its mobility may be
strongly concentrated in the incompatible limited due to the formation of slightly soluble
pegmatite phase like U, although some Th- precipitates (e.g., phosphates, oxides) and by
containing minerals, such as allanite do occur in adsorption on clay minerals and organic matter.
pegmatite. Granite typically contains 10-40 Thorium has low mobility under all
mg kg-1 Th, although there is much local and environmental conditions, mainly due to the high
provincial variation. Intermediate rocks, such as stability of the insoluble oxide ThO2 and the
andesite have about 1–4 mg kg-1 Th, while gabbro strongly resistate nature of its carrier minerals
usually has less than 3.5 mg kg-1, and basalt less such as monazite and zircon. Unlike U, Th cannot
than 1 mg kg-1. In metamorphic rocks, the Th be oxidised to a stable cation equivalent to the
content is generally immobile up to the highest highly mobile uranyl ion UO22+. The soluble
grades, but anatexis will result in concentration in species Th(SO4)2+ may form below pH 3, and
the mobile granitic phase. High Th values, under oxidising conditions (Brookins 1988), e.g.,
therefore, indicate the presence of felsic rocks, in acid mine water. Any Th released into solution
especially intrusives. will be rapidly sorbed by clay minerals and
Thorium in sedimentary rocks is essentially hydrolysed to the hydrous oxide Th(OH)4, which
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will be intimately associated with the clay-mineral coal combustion (Reimann and de Caritat 1998).
fraction, unless it can be mobilised by other The amounts of Th in the environment may
inorganic or organic ligands (Hem 1992). Thus, increase as a result of accidental releases of Th
Th is essentially insoluble in surface and from nuclear processing plants.
groundwaters, and levels are extremely low at Thorium has no known biological function. It
0.01-1 µg l-1 (Hem 1992). Because of this, Th is a is chemotoxic, radiotoxic and a carcinogen. In the
useful pathfinder element in stream sediment for environment, Th behaves similarly to the REEs,
locating uranium deposits associated with especially Ce, substituting for Ca in bones and
magmatic rocks, since almost all the Th is teeth. Long-term exposure to Th increases the
transported as solid mineral material with minimal chances of developing lung diseases and lung,
loss to solution. The average Th content in river pancreas and bone cancer.
particulates is given as 14 mg kg-1 (McLennan and Table 67 compares the median concentrations
Murray 1999). of Th in the FOREGS samples and in some
Anthropogenic sources of thorium include reference datasets.
fertilisers, uranium mining and processing, and

Table 67. Median concentrations of Th in the FOREGS samples and in some reference data sets.
Thorium Origin – Source Number of Size fraction Extraction Median
(Th) samples mm mg kg-1
Crust1) Upper continental n.a. n.a. Total 10.5
Subsoil FOREGS 790 <2.0 Total (ICP-MS) 7.63
Topsoil FOREGS 843 <2.0 Total (ICP-MS) 7.24
2)
Soil World n.a. n.a. Total 9.4
Water FOREGS 807 Filtered <0.45 µm 0.009 (µg l-1)
Water3) World n.a. n.a. <0.001 (µg l-1)
Stream sediment FOREGS 852 <0.15 Total (XRF) 10.0
Floodplain sediment FOREGS 747 <2.0 Total (XRF) 8.00
4)
Stream sediment Canada 26 227 <0.18 Total (INAA) 8.1
1)
Rudnick & Gao 2004, 2)Koljonen 1992, 3)Ivanov 1996, 4)Garret 2006.

Th in soil

The median Th content is 8.00 mg kg-1 in High Th values in subsoil (>11 mg kg-1) appear
subsoil and 7.24 mg kg-1 in topsoil; the range in the crystalline basement of the Iberian Massif
varies from <0.1 to 71.7 mg kg-1 in subsoil and in Portugal and western Spain, in the alkaline
0.30 to 75.9 mg kg-1 in topsoils. The average ratio magmatic province of Italy, the Massif Central in
topsoil/subsoil is 0.925. France, Slovenia, Croatia, and northern Bavaria.
Northern Europe generally shows Th contents Elevated Th values in north-eastern Greece are
in subsoil below the median, with low values (<5 related to granitic intrusions. As Th normally has
mg kg-1) in the glacial drift area from Poland to a higher background in granite, gneiss and
the Netherlands, in central Finland, in northern alkaline rocks, its geological distribution seems to
Norway, western Ireland, and southern Spain. be overprinted in northern Europe by climate- or
The southern margin of the formerly glaciated pH-determined pedogenic processes, notably
area through the Netherlands, Germany and leaching. These processes are responsible for
Poland is well marked on the map, with low taking more Th out of the soil and transferring it
subsoil Th values to the north of it. to stream water, which shows relatively high

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values in northern Europe (see below). The Th U, Nb, Ta, Ga, Sc, Nd, Sm, Gd and Tb, and a
subsoil and topsoil patterns are overall similar. good correlation (>0.4) with Pb, Ag, Bi, Sn, Al,
Thorium in subsoil shows a very strong In, K, Y and the remaining (heavy) REEs. This
correlation (>0.8) with the light REEs Ce, La and pattern of correlations is similar in topsoil, but for
Pr, a strong correlation (>0.6) with Be, Rb, Cs, Tl, Sn and Ag it is much weaker.

Th in stream water

Thorium values in stream water range over and in northern Ireland and Scotland, in the
four orders of magnitude, from <0.002 µg l-1 to Caledonides, and in France (Brittany and Massif
0.37 µg l-1, with a median value of 0.009 µg l-1. Central), characterised by Variscan terrains. In
Thorium data correlate most closely with the northern Ireland, the isolated Th anomaly is
lanthanides. associated with the Mourne granite. The
Lowest Th values in stream water (<0.002 enhanced point value in the Roman
µg l-1) are predominantly found on Variscan province is controlled by recent alkaline
terrains in south-western and north-eastern Spain volcanism.
and in north and south France, and on Alpine The described Th distribution on the stream
Orogen in all northern Italy, in central Austria, water map shows clearly the similarity with the
and in Albania and Greece. REEs and associated elements patterns in acidic,
Highest Th concentrations in stream water low-mineralisation and high-organic-matter
(>0.11 µg l-1) are predominantly found on stream water. The pattern is climate controlled.
Precambrian Shield (mostly intrusive and The association with the patterns of alkaline rocks
metamorphic rocks) in southern Norway, southern elements is, however, largely geogenic, and
and eastern Sweden and southern Finland, and appears to be responsible for high Th
mainly on Precambrian Shield derived glacial drift concentrations in Italy including Sicily and
in north-eastern Germany. The high Th Sardinia, and in Germany.
concentration in stream water in Fennoscandia is In comparison with Th in soil and sediments,
in contrast with low values in soils and sediments, the Th patterns in stream water differ entirely.
pointing to leaching of Th under the existing Notable exceptions are the high Th values in both
conditions of climate and high DOC content. stream water and solid sample media over the
Enhanced values in stream water (>0.05 Massif Central in France and the Italian province
µg l-1) also occur in north central Fennoscandia, of alkaline volcanism.

Th in stream sediment

The median Th content in stream sediment is High Th stream sediment areas (>13 mg kg-1)
10 mg kg-1, and the range varies from <1 to 253 include the Variscan crystalline basement in
mg kg-1. northern Portugal and Spain, and in the Massif
Low Th values in stream sediment (<7 Central in France. High values also occur in the
mg kg-1) are found in the glacial drift covered area Variscan part of Germany, the Bohemian Massif,
of northern Europe extending from the Corsica; in the western Alps; in the Roman
Netherlands through to Poland, in southern alkaline magmatic province, in southern Italy and
Sweden, central Norway, parts of northern Sicily, in north-eastern Greece (associated with
Sweden and northern and eastern Finland, western granite and U mineralisation), northern Estonia
Ireland, the Po valley in northern Italy, south- (black shale), southern Finland, southern Norway
eastern Spain and most of Greece. The southern and small areas in northern Finland and northern
margin of the ice-age glaciated area through the Norway. A point anomaly characterises the
Netherlands, Germany and Poland is well marked Mourne granite in northern Ireland.
on the map, with low Th stream sediment values Thorium in stream sediment has a very strong
just north of it. to strong correlation with Y and the REEs (except

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Eu), a strong correlation with U (0.77), a good and a weak correlation with Be, Hf, W, Al, Ga
correlation with Ta, Nb, Tl, Sn, Eu, K, Rb and Zr, and Cs.

Th in floodplain sediment

Thorium values in floodplain sediment range intrusives and mineralisation, and often associated
from <1 to 38 mg kg-1, with a median of 8 with U; Swiss-Italian border area with granitic
mg kg-1. The variation in the lower Th values is rocks; the Roman Alkaline Province, eastern
somewhat constrained by the detection limit of the Sicily volcanics, clastic rocks in Croatia, and
XRF analytical method. central Macedonia and Thrace of north-east
Low Th values in floodplain sediment (<5 Greece with granite, gneiss, schist and U
mg kg-1) occur over the glacial drift covered plain mineralisation.
extending from north Germany and almost the Highly anomalous Th values in floodplain
whole of Poland to Lithuania and Latvia; on the sediment occur in granitic areas of northern
crystalline rocks of the Precambrian Shield in Portugal (34 and 38 mg kg-1) and northern Massif
south-eastern Finland, northernmost and central Central in France (34 mg kg-1). Further
Norway; on mostly limestone and crystalline anomalous Th values are found in the
rocks in Ireland. The molasse basins in southern metallogenic provinces of south-east Sweden, the
Germany and central Austria; in France over the Roman alkaline magmatic province, and in the
fluvial deposits of the lower Garonne river; a Czech Republic west of Brno on the Jihlava River
small area in eastern Spain on clastic and draining the mineralised area of the Moravian
carbonate rocks; in south Albania and western Hills. The isolated Th point anomaly in south-
Greece in areas of limestone, flysch and ophiolite. west Norway is situated on the Kvina River,
The southern margin of the ice-age glaciated area which drains the Knaben Mo deposit hosted in
through Germany and Poland is well marked on felsic gneiss. The high Th value in west Croatia is
the map, with low to very Th values just north of explained by accumulation in residual karstic soil.
it. Thorium in floodplain sediment shows a very
High Th values in floodplain sediment (>11 strong correlation with Rb (0.85), strong
mg kg-1) occur in Fennoscandia draining gneiss correlations with Al2O3, Ga, K, Nb, Ta, Tl, Y and
and granite terrains in most of central Sweden and U, and good correlations with Be, Li, W, Zr, Cs,
south-western Finland, across mainly Variscan Fe, Ti and V. Correlations with the REEs are
north-western and central Europe with variable good to strong.
lithology in Wales, south-west England; the It is concluded that the distribution map of Th
crystalline rocks of the Iberian Massif in central to in floodplain sediment reflects patterns related to
western Spain and Portugal; France (Poitou, the geological substratum. It generally maps areas
Massif Central, Vosges, Corsica), the Bohemian with felsic intrusives, and known U mineralised
Massif, most of the Czech Republic, western parts areas.
of Slovakia and Hungary, areas with granite

Th comparison between sample media

In general, there are broad similarities between case for stream sediment in coastal Croatia and
all solid sample media; patterns in topsoil and Slovenia and in the western parts of Austria
subsoil are almost identical. In stream sediment, (explained by the probable removal of fine-
the average values are generally higher than in grained material from the residual soil and karst).
soil and in floodplain sediment. The anomalies in In southern Norway, southern and south-western
the Massif Central and the Czech Republic are Finland and northern Estonia, stream sediment Th
more pronounced in floodplain and stream concentrations are higher than in the other solid
sediments. On the other hand, the Italian Alkaline sample media, possibly the result of heavy
Province has lower Th values in both floodplain mineral concentration in stream sediment. In
and stream sediments than in soil; this is also the floodplain sediment, central eastern Sweden

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shows higher Th values than in soil. Also, south- sample media. Thorium is not normally mobile
western Finland has higher Th in floodplain except in the presence of DOC, and tends towards
sediment than in all other media. low concentrations in Mediterranean
A boxplot comparing Th variation in subsoil, environments, especially in northern Italy, Greece
topsoil, stream sediment and floodplain sediment and Albania, and higher concentrations occur in
is presented in Figure 47. the more DOC rich environments of southern
Sweden and Finland, as well as in parts of
Patterns in stream water Th content are Germany and Brittany.
virtually opposite to those observed in all solid

Figure 47. Boxplot comparison of Th variation in subsoil, topsoil, stream


sediment and floodplain sediment.

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