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ENVIRONMENTAL SAMPLES
By
RAMJEE KANDEL
My sincere thank goes to Prof. Dr Raja Ram Pradhananga, Head, Central Department of
Chemistry and Research committee of this Department for necessary guidelines and
facilities during my research work.
I am equally dept to Mr. Krishna Mani Bhandary, Chief, Central Library, Tribhuvan
University, to Superintendent Geologist Krishna Kafle, The Department of Mines and
Geology, Lainchaur and to Mr. Buddha Ram Shah, NAST for their co-operation and
advice.
Lastly, I would like to express heartfelt thanks to my beloved colleagues Mr. Bishnu
Bastakoti, Binaya, Daya Nidhi, Homnath and Tara for their help during this research
work.
Ramjee Kandel
ABSTRACT
Spectrophotometric method for the determination of thorium (IV) in the environmental
samples are investigated. This method, based on arsenazo III as the complexing agent in
acidic medium is found to be sensitive in the range of 0.02- 0.8 μg Th/ml at λmax 660nm.
The molar absorptivity is 11.59×104 Lmole-1 cm-1. The convenient process for the
extraction of thorium is the liquid – liquid extraction. Thorium is extracted into Isobutyl
Methyl Ketone (IBMK) from aluminium nitrate at the pH 0.8-0.9, in the presence of
hexadecayltrimethylammonium bromide (CTAB). Benzene is used to bring the thorium
in the aqueous phase as a result of which the extraction percentage is increased. This
method is used to determine the amount of water soluble thorium ions in the water, sand
and soil.
1.0 INTRODUCTION
Human beings have direct and inevitable relation with water. We depend
on different sources of water such as underground water, surface water as
well as rain water. The presence of dissolved radioactive substances like
thorium in drinking water prevails in minute quantities from continuous
weathering of such minerals which is present naturally in the
environment. Thorium was discovered in 1829 by Berzelius in a mineral,
now known as thorite. Natural thorium consists of two long lived
232
radioactive isotopes namely, Th (~100%) t1/2 = 1.405×1010y and trace
228
amounts of its descendant Th with t1/2 = 1.913y of atomic weight
232 238
232.08 (Haissinsky and Adloff, 1965).The decay of Th leads to Th
as follows –
With the discovery of U233 and its slow-neutron fission properties, a new
stimulus has been given to the detailed study of the thorium chemistry
(Katzin, 1955). It is used in atomic energy program. Because of its low
work function and high emissivity for electrons, thorium is used in a
number of gaseous discharge lamps. This metal has been continuously
used to generate strong monochromatic X-ray (Hampel, 1968)
1
Thorium is less abundant than lead but about three times as abundant as
uranium (Frondel, 1956) in contrast, the concentration of thorium in seas
and oceans are nearly a thousand times smaller than that of uranium
(Haissinsky and Adloff, 1965). Deposits of monazite containing sands
occur mainly in countries like India, Brazil, Australia, Malagasy, Ceylon,
South-Africa, the U.S. and Canada. Although the sands that extend along
the seacoast of Travoncore in India contain less than one percentage
monazite, this is considered as the worlds’ most important source of
thorium (Hampel, 1968). The concentration of thorium is 2×10-8g/l in
rivers and 4×10-5 percentage in stony meteorites and its cosmic
abundance is 0.02 atoms per 106 atoms of Si (Haissinsky and Adloff,
1965)
2
percent. Some of the important ores of thorium is given in Table 1.1
below:
3
in most igneous rocks is within 0-25 ppm; up to several 100 ppm has also
been reported. Thorium and uranium seem to be closely associated in
igneous rocks. The thorium-uranium ratio of various rocks throughout the
world is approximately uniform; the ratio ranging from 3-1 up to 0-20
(Twenhofel and Buck, 1956). The concentration of thorium in different
types of rock varies widely as shown in Table 1.2 below:
4
in which 11 cps was for thorium against background value 200 cps as
total count and 1 cps thorium was recorded (Shrestha, 2004)
5
ions. The complexing agents with thorium are Cl-, NO3-, ClO3-, BrO3-,
IO3-, HSO4-, PO43- and F-. Some ions of many organic acids that form
varities of complexes are oxalates, citrates, pthalates, maleates and even
EDTA. All of these are positively charged or cation complexes. In nitric
acid solution of >3M, however, thorium forms an anionic complex. At pH
values greater than three, thorium undergoes hydrolysis in aqueous
solution. The common insoluble compounds used in thorium separation
are the hydroxides, fluorides, chromates, phosphates and oxalates while
the soluble compounds include the chloride, nitrate and sulfate
(Fairbridge, 1972). Thorium forms numerous chelated compounds,
insoluble in water but soluble in organic solvents (Haissinsky and Adloff,
1965).
6
augmented by sorption and precipitation of radionuclides of incoming
water. The top level of about 0.25 m of soil contributes significantly to
background radiation dose. Background concentrations of radionuclides
in soil varies because of many factors. Soil may have been produced from
the weathered top layer of still-intact bedrock below or transported
laterally from the same rock unit. Some methods of transport are natural
phenomena such as- earthquakes, volcanoes, glaciers and changes in soil
composition from flooding. Water is the dominant transporting medium
in the environment. Outwash erosion products from mountain produces a
soil surface that is more radioactive than the underlying bedrocks. Wind
also play a significant role in the transportation of weathered radioactive
rocks from one location to another (www.whori.edu/education/gsp/
Mcg/BPE, 2005).
Breathing of air containing the thorium dust may increase the chance of
developing lung disease. On many years of exposure and in extreme
cases, cancer of the lung or pancreas can result. Even changes in the
genetic material of body cells have also been reported. If it is
accumulated in bones for a long period, bone cancer can result which is a
potential hazard. These factors, however include on the dose, the
duration, the pathway exposed of thorium inhalation and the food intake
etc. (www.abuse.com/environment/EPA-Home/Radition/ Information/
Radionuclides, 2005).
7
The Environment Protection Agency, USA, has set a drinking limit of 15
pCi/L for water with gross alpha particles and 4 millirems per year for
beta particles and photon activity. The tolerance value for natural thorium
are 10-5µC/mL of water, 2×10-13µC/cm3 in air, and 0.02 µC for the whole
body before developing radiotoxicity (Haissinsky and Adloff, 1965). The
Maximum Allowable Concentration (MAC) of 21 µg Th/gm of tissue is
calculated to give approximately the tolerance dose. However, if the
thorium is in partial equilibrium with its daughters, the tolerance dose rise
up to 25 µg per gram of tissue, a value numerically identical with that for
uranium (Hodge and Thomas, 1958).
8
by the help of known concentration of thorium following the Lambert-
Beer’s law and unknown concentration can be found by reading the
absorbance and using the calibration curve. In this method, thorium
present in the sample was extracted from acid-deficient aluminium nitrate
medium into isobutyl methyl ketone (IBMK). Further addition of
hexadecyltrimethyl ammonium bromide (CTAB) solution enabled the
quantitative extraction of thorium into isobutyl methyl ketone.
Sequentially extracted thorium from uranium was complexed with
arsenazo (III) and the concentration calculated from the measured
absorbance or optical density(Ramakrishna and Murthy, 1980).
Spectrophotometric Method:
Where,
A = Absorbance or optical density (O.D.)
a = Absorbtivity when c is expressed in gram per liter.
b = Length of the absorbing homogeneous medium.
c = Concentration of the absorbing species in gram per liter or
moles per liter.
Where,
Ii = Intensity of the incident radiation.
It = Intensity of the transmitted radiation.
Where,
ε = Molar extinction coefficient
The absorbance 'A' also depends upon the wavelength, λ, of the incident
light and there is particular wavelength for which the absorbance is
maximum called λmax which is characteristic of the colored absorbing
species.
11
plot gives a straight line at low concentration range and the deviation
from the linearity occurs as the concentration increases. Higher
concentrations of some other colourless salts even adversely affect
absorption of light (Khopkar, 1998). At high concentration, deviation
from Lambert Beer's law occurs which are due to the intermolecular
interactions and concentration dependent dissociations or associations.
The reaction with solvent or with hydrogen ions or formation of complex
ions with varying number of ligands also influence these results.
Before 1939, very little was known about the analytical chemistry of
thorium. During and since the World War II, however, the literature on
the analytical chemistry of thorium has grown tremendously. The first
comprehensive survey appeared in 1948 (Moeller et al., 1948). The
precipitation method by the use of sodium oxalate followed by digestion
with permanganate, the excess of which is measured colorimetrically had
the drawback as the solubility of thorium oxalate was approximately 0.1
mg/lit (Kall and Gordon, 1953). Colorimetry of the iodine released by
thorium iodate was not sufficiently sensitive for the analysis of low grade
ores (Rodden, 1950). Para-arsonic acid was excellent (Grimaldi and
Fairchild, 1945) but this reagent was not commonly found. In addition, it
was difficult to wash and filter the complex formed by the reagent with
the thorium. Determination of the color developed by the derivatives of
benzoic acid and particularly m-dinitrobenzoic acid (Rodden, 1950)
cannot be adopted owing to the lack of accuracy. Alizarine is easy to
obtain and highly sensitive and thorium-alizarin complex has high rate of
extinction to allow the determination of tens of micrograms of thorium in
common colorimetric devices. However, in order to reach this limit, it
12
was necessary to eliminate the interference factor. The resulted in
interference gives an error of about 10 percent (Suner, 1958).
The iodate method developed (Meyer and Speter, 1910) has been widely
used for separation and determination of thorium. Other metals that were
also precipitated as iodates under the same conditions were subsequently
removed by precipitating thorium as an oxalate (Rodden, 1950). When
oxalic acid was used as a precipitant, the losses of thorium were too high
(Clinch and Simpson, 1957). Photometric determination in weakly acidic
or neutral medium form with 1-(pyridyl-2'-azo)-resorcinol was found to
be suitable after separating the thorium in the form of the oxalate
(Alimarin et al., 1957). The use of aspartic acid as titrant and
bromophenol blue as indicator permited thorium to be determined in
presence of large amount based on spectrophotometric titration of their
anionic fluoride complexes in a 90 percent dimethylsulfoxide with
potassium salt solution in presence of nitchromazo as metalloindicator
(Sergeev and Korenman, 1978). Mesotartaric acid used as a masking
agent permited the determination of thorium with thorin in presence of
zirconium (Grimaldi and Fletcher, 1956). The colour reaction between
morin and thorium were also carefully studied during the determination
thorium (Fletcher and Milkey, 1956).
13
Tc-arsenazo with thorium along its application used 7.2 mol/lit. of HCl
have been also studied (Chen, 2002).
Extraction methods have not been extensively explored for the sequential
separation of uranium and thorium probably because their extraction
takes place from medium of widely differing composition. Synergistic
extraction of Th (IV) and U (VI) from nitric acid by using HBMPPT and
TOPO was found to be successful as the extraction increased on addition
of TOPO in toluene (Yu et al., 2001). In extraction of U (VI) and Th (IV)
with N, N-dibutyl alkylamide, the change in length of carbonyl chain was
found not to affect the extraction of U (VI) but extraction of Th (IV)
falled with increase in length of carbonyl chain (Sun et al., 1999).
Simultaneous determination of uranium and thorium with standard dual
addition method showed that the recoveries of (96.8-102.3)% of thorium
by spectroscopic analysis (He et al., 1998). Since, the extraction
behaviour of these metal ions is spectrophotometrically followed using
arsenazo III (Savvin, 1961) at present suitable conditions for the selective
and sequential extraction of thorium in the mixture of thorium and
uranium has been studied from acid deficient aluminium nitrate solution
into IBMK by the use of spectrophotometer.
14
4.0 Objectives of the Work
5.0 Experimentation
The following instruments and the steps for the procedure of preparation
of reagents were undertaken. Collection of the samples and extraction
proceeded.
5.1 Instrumentation
The details of the quality and manufacture of the respective chemicals are
given in Appendix I.
15
a) Stock Thorium Nitrate Solution (1000 µg Th/ml)
2.457 gm of Th(NO3)4.5H2O (G.R. grade, Loba-Chemie) was dried in a
desiccators and weighed out accurately. Then, this was dissolved in 10%
nitric acid which was prepared in double distilled water. The final volume
in 1000 ml volumetric flask was made up to the mark by adding 10
percent HNO3.
b) Working solution
Standard thorium solutions were prepared by appropriate dilution of stock
thorium nitrate solution in 25 ml volumetric flask.
c) Aluminium Nitrate
Saturated solution of Al(NO3)3.9H2O (G.R. grade, 98.5%) was prepared
in 100 ml beaker. Everyday, a fresh solution was prepared in distilled
water.
16
g) 0.02 Percent arsenazo III
0.02 gm of arsenazo III (G.R. grade), a coloring and complexing agent
was weighed out accurately and transferred to 100 ml volumetric flask.
The final volume was made up to the mark after it was dissolved.
0.9
0.8
0.7
Absorbance
0.6
0.5
0.4
0.3
0.2
0.1
0
620 630 640 650 660 670 680 690 700 710
Wavelength in nm
17
5.4 Calibration Curve for Thorium Determination
0.5
0.45
0.4
0.35
0.3
Absorbance
0.25
0.2
0.15
0.1
0.05
0
0 0.2 0.4 0.6 0.8 1 1.2
Concentraction (ppm)
18
5.5 Collection of Samples
The samples were collected from the northern part of the Kathmandu
valley at the Shivapuri hillside of Bramakhel and Chudikhel areas.
Samples of water, sand and some soils were taken for this study. There
were more than 1200 people in this village who are directly dependent on
the source of these samples. The villagers used water for drinking,
washing, bathing and irrigation. Domestic cattle were also found to be
consuming water of those sites. These source of water supplied the
nearby pond. The sand extracted from those sites were used for
construction work in Kathmandu city too. The grass grown on these study
sites were used for grazing of cattle. Vegetables and other food grown
here were sold in the capital city.
b. Method of Collection
Water sample were collected from the river where the bed of the running
water had stones and gravels of different formation. Collected water
samples were stored in 1 liter and 5 liter plastic jars in which about 1 ml
of concentrated HNO3 was added per liter as a preservative. Collection of
the sand and soil samples were determined at these locations with the
ground radiometric survey portable Scintillation Counter. At the field
with higher cps first 10 cm depth of the sample was discarded. Samples
of 1 kg from the banks of riversides were weighed in a spring balance and
kept in a plastic bag. The samples were immediately labelled as – w, st
and s for water, sand and soil respectively as shown in Table 6.5 and 6.6.
19
5.6 Extraction of Thorium
a) From Water
Two aqueous phases (I and II) obtained were taken in a 100 cc separating
funnel. Then 1 ml of CTAB solution and 10 ml of IBMK were added
into it and shaken for about 5 minutes. The aqueous phase was discarded
while the organic phase was retained for the recovery of thorium.
To the organic phase (5 ml), 0.1 M HCl each was added twice to strip the
thorium content. Few drops of concentrated H2SO4 was added to the
resulting aqueous phase collected in 25 ml of beaker. It was evaporated
till all fumes of sulfur trioxide ceased to evolve. The residue obtained was
dissolved in 5 ml of water, then this was transferred to the 25 cc
20
volumetric flask where 1:1 HCl was used for rinsing. 5 ml of 0.02 percent
of arsenazo III was added and to the rest, 1:1 HCl was used up to the
mark. After 35-40 minutes, the absorbance or optical density was read at
the λmax value of 660 nm. The concentration of thorium was calculated
directly from the calibration curve (Fig. 5.2).
The sand and soil samples collected from different places, were taken for
analysis. Firstly, homogeneous distribution of sand was made by
shoveling. Out of four fractions of sand, opposite side samples were
mixed and again homogeneously distributed. 100 ml of water was poured
in 200 gms of sand where, (2-3) drops of concentrated nitric acid was
added and stirred well. After sedimentation, it was filtered. The resulting
filtrate was evaporated, in such a way that only about 5 ml of liquid was
left over. Further work was performed as shown in the Flow Diagram Fig.
5.3 below:
21
1 ml Al (NO3)3
~10 gm of 5 ml of sample (NH4)2CO3 Sample .9H2O Sample in 100 cc
Added solution in 25 solution at separating funnel
aluminium ml beaker pH meter 5 ml. of IBMK
nitrate Solution
pH (0.8-0.9) Shaken
(3-5) minutes
5 ml of Al (NO3)3 . 9H2O
Added Organic
5 ml of benzene solution phase
Shaken
(2-3) minutes
(discarded)
Mixed
Shaken
5 minutes
0.1 M HCL
Organic Aqueous
Strip twice phase phase
(discarded)
5 ml of H2O
Added Residue
5 ml of arsenazo III
+ 1:1 HCl up to mark
22
6.0 Results and Discussion
23
latter did not give effective result. Among other reagents, an organic
reagent arsenazo III (Fig. 6.1 below), used in this method was more easily
available and cheaper than the reagent used in other method of extraction.
OH OH
N=N N=N
HO As OH SO3H SO3H
HO As OH
O O
(SO3H2)C10H2 (OH) [N-NC6H4 AsO (OH)2]2
24
(i) Effect of the pH
Effect of pH on thorium have been continuously studied for the last few
decades. In complexometric titration of thorium in presence of
1-(Pyridyl-2'-azo)-2-naphthol (Meyer and Speter, 1960), pH was
monitered at 1.8 and other values. The amount of aluminimum nitrate at
different pH was studied with and without addition of CTAB. When 10
grams of aluminum nitrate was added to 5 ml. of known sample, the raise
in volume was by ~10 cc and molarity of aluminium nitrate was 2.6 mol
per liter. The variation in pH were made by the help of ammonium
carbonate (Ramakrishna and Murthy, 1979). Table 6.1 below showed the
extraction percentage of thorium, when (NH4)2CO3 was not added only
64 percentage of thorium was extracted. The extraction percentage was
decreased with increase in pH of the solution. With addition of CTAB
there was remarkable difference in extraction behaviour. Although
addition of 1 ml of 0.5 percentage of CTAB at lower pH did not have
much effect, however, with increasing pH its extraction percentage
increased slowly and even up to 100 percentage at pH of 0.9. Thereafter,
again it decreased with further increase in pH. The addition of 2 m, 3 ml
etc. of 0.5 percent of CTAB resulted in the values same as those of 1 ml
of 0.5 percent of CTAB in the percentage of extraction. This confirmed
that addition of more CTAB has no further significance and pH value of
0.9 was found effective condition for cent percent extraction.
25
Table 6.1 : Effect of pH in Thorium Extraction with and without CTAB
With the use of
Without the use of CTAB
CTAB
pH of Th Th Th
% %
S.N. the taken Absorbance extraction extraction
extraction extraction
solution (µg/ml) (µg/ml) (µg/ml)
1 0.5 0.5 0.14 0.29 58 0.41 82
2 0.8 0.5 0.13 0.26 52 0.49 98
3 0.9 0.5 0.12 0.25 50 0.50 100
4 1.5 0.5 0.07 0.15 30 0.43 86
5 2.0 0.5 0.01 0.02 4 0.36 72
120
100
80
% Extraction
60
40
20
0
0 0.5 1 1.5 2 2.5
-3
pH of Al (NO3)3. 9H2O at 2.62 mol dm
Without CTAB in aluminium nitrate at different % extraction of the thorium With addition of CTAB in aluminium nitrate
26
(ii) Effect of Aluminium Nitrate Concentration
27
120
100
80
% Extraction
60
40
20
0
0 0.5 1 1.5 2 2.5 3 3.5
Molarity of aluminium nitrate
% Thorium in IBMK at pH of 0.8-0.9 without CTAB % Thorium in IBMK at pH of 0.8-0.9 with CTAB
28
ion was no more than thorium, and uranium had no effect in the whole
process.
Since the water and sand samples were collected from rivers and its bed, it
could have various anions present which as such might affect the
extraction. Qualitative tests of some anions like PO43-, SO42- and F- were
done. Test of PO43- was performed by adding 3 drops of HNO3 in a nitric
acid acidified sample, slightly warmed where slight excess of ammonium
molybdate was added. The sulfate test was performed by the use of lead
acetate and barium chloride solution. Similarly F- test was done by
acidifying test solution with CH3COOH and again CH3COOH in excess
then CaCl2 solution and warmed. No ppt in any sample solution was
observed; however, quantitative test of PO43- showed that up to 0.3 ppm of
phosphate was present. Spectrophotometric determination of phosphate
was performed by using stannous chloride (2.5 g SnCl2.2H2O in 100 ml
glycerol and ammonium molybdate (NH4)6 Mo7O24.4H2O in acidified
H2SO4) reagents. In 25 ml of sample solution, 1 ml ammonium molybdate
and 2 drops of SnCl2 reagent were added. It was shaken and left for color
development. Then spectrophotometric analysis of blue coloured sample
was performed between 10 minutes and 12 minutes at λmax of 690 nm
(Clesceri, 1998). This experiment showed presence of 0-0.3 ppm of
29
phosphate in water sample. Anions like chlorides and nitrates were not
studied as they do not interfere in thorium determination while PO43-, SO42-,
F- and also organic acid anions may form stable complex (Sergeev and
Korenman, 1978) but the organic reagent arsenazo III made it possible to
determine thorium in strongly acidic medium without the preliminary
separation of those ions (Leib, 1984).
30
Table 6.4 : Standardization of Method with known Quantities of Thorium
(Accuracy and Precision)
S.N. Th Absorbance Th Mean Standard Relative 95%
taken found deviation S.D. confidence
(µg/ml) (µg/ml) (S.D.) interval
1 0.02 0.01 0.02
0.02 0.01 0.02 0.02 - - 0.02 ± 0
0.02 0.01 0.02
2 0.06 0.02 0.05
0.056 ±
0.06 0.03 0.06 0.056 0.0047 7.14
0.011
0.06 0.03 0.06
3 0.1 0.05 0.09
0.093 ±
0.1 0.06 0.1 0.093 0.004 4.30
0.009
0.1 0.05 0.09
4 0.4 0.19 0.35
0.4 ±
0.4 0.20 0.40 0.40 0.04 10
0.099
0.4 0.21 0.45
5 0.8 0.40 0.80
0.783 ±
0.8 0.40 0.80 0.783 0.023 2.9
0.057
0.8 0.39 0.75
31
compounds, best results were obtained with ketone (Katzin, 1955).
Among so many ketones, IBMK was selected because of its lower
solubility in the aqueous phase and rapid separation of both phases
(Ramakrishna and Murthy, 1979). To the organic phase 5 ml of saturated
aluminum nitrate and 5 ml of benzene were added as the remainder of
thorium in organic phase would again get attached as the species
[Th(NO3)6]2- and the benzene as organic solvent was used because it
neither extract thorium nor uranium but had the property of bringing
down thorium in aqueous phase completely. The second aqueous phase
was separated and mixed with first aqueous phase, then 1 ml of 0.5
percentage of CTAB and 10 ml of IBMK were added. CTAB was
selected because it is an excellent cationic surfactant that has the property
of lowering surface tension and lower solubility when added in aqueous
phase in small quantity. It had the behaviour like that of TOPO used in
toluene, where extraction ability was increased in appreciable quantity
(Yu et al., 2001). The structure of CTAB(C19H42BrN) is as shown in Fig.
6.4 below.
CH3
N CH3
Br(-)
CH3
Organic phase was only taken after discarding aqueous phase for the
recovery of thorium. Thorium present was striped twice by the help of
0.1 M HCl. After addition of 2-3 drops of concentrated H2SO4, the solution
was evapourated till the fuming of sulfur trioxide ceased and the residue
was obtained to eliminated most of the acid (Suner, 1958) and oxidised any
organic matter (Andjelković and Rajković, 1958). The residue thus
32
obtained was dissolved in nearly 5 ml. of water then transferred to 25 cc
volumetric flask using 1:1 HCl for rinsing. 5 ml of arsenazo III was added
and the volume diluted up to the mark with 1:1 HCl. Eventually, the
concentration of thorium was determined by extraction process after the
lapse of 35-40 minutes of reagent added.
In Central Siwalik Region, thorium present was low to the value of ratio
Th/U = 0.0686, where total count rate was up to 27,437 cps in variable
weight (less than a kg), (Aryal, 1994). Ground radiometric survey in
Tinbhangale area (Makwanpur), the radioactive intensity (RI) by the use
of four channel Gamma-ray Spectrometer, the total count was up to
27,405 cps where thorium alone counts up to 30 cps (Kaphle and Khan,
2003). Similarly, by the use of this instrument up to 2,839 cps total count
out of which thorium present was 27 cps alone in (Mahadev Khola) of the
Brahmakhel area was reported (Shrestha, 2004).
Chemical test analysis of both water and sand were shown in Table 6.5
and 6.6 respectively collected from different sites of Bramakhel and
Chudikhel area. Out of fifteen water samples, six samples showed certain
quantities of thorium ranging from 20 ppb to 100 ppb where the gross
radioactive was from (100.8-163.7) Bq/lit (Shrestha, 2004).
The extraction of thorium from 200 mg of sand from the same site
depicits that 12 samples contained the thorium ranging from 20 ppb to 80
ppb out of 18 sand samples taken into analysis. The extraction of thorium
from second washed sand did not show the presence of thorium. That is
so because, either all the soluble thorium in sand were washed at first part
of the experiment or the thorium remained in the second wash were
below the detection limit of the experiment. The gross radioactive were in
33
range from (30.4 – 21655.7) Bq/kg (Shrestha, 2004). The results showed
that the homogenous content of thorium was more in sand in comparison
to water.
34
Table 6.6 : Chemical Analysis of Sand
S.N. Sample No. *Gross radioactive Bq/kg Absorbance Concentration (PPb)
1 RH/st 1 2643.1 0.02 40
2 RH/st 2 412.7 - -
3 RH/st 3 1740.2 0.01 20
4 RH/st 4 869.7 - -
5 RH/st 5 9230.7 - -
6 RH/s 6 - 0.01 20
7 RH/st 7 30.4 0.01 20
8 RH/st 8 21655.7 0.02 40
9 RH/st 9 346.0 0.02 40
10 RH/st 10 - - -
11 RH/st 11 - 0.01 20
12 RH/st 12 1570.4 - -
13 RH/st 13 17449.5 0.02 40
14 RH/st 14 14043.2 0.01 20
15 RH/st 15 7804.2 0.02 40
16 RH/st 16 1358.8 0.04 80
17 RH/st 17 11457.7 - -
18 RH/st 18 - 0.03 60
35
7.0 Conclusion
36
8.0 Suggestions for Further Work
37
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38
Collee, R.; Govaerts, J. and Winand, L., Quantitative Analysis of Thorium in
Ores and Thoriferous Products, by a Method Based on Radioactivity,
International Conference on the Peaceful uses of Atomic Energy,
Geneva, 3, 589, U.N., New York (1958).
Cui, Y; Zhang, Z.; Jiang, R. and Sun, G., Structural Effect of N-N-dialkylamide
on Thorium (IV) Solvent Extraction from HNO3 Solution, Journal of
Radioanalytical and Nuclear Chemistry, Kluwer Academic Pub. 288
(1), 171-173 (Eng.) (2003).
Grimaldi, F.S. and Fletcher, M.H., Thorin – Tartaric Acid System for
Spectrophotometric Determination of Thorium, Anal. Chem, 28, 812
(1956).
He, R.; Wang, J. and Wang, Y., Simultaneous Determination of U and Th with
Standard Dual-Addition Method, Rare Met. (Beijing), 17 (2), 154-159
(Eng.) (1998).
39
Hodge, H.C. and Thomas, R.G., Health Hazards from the Inhalation of
Insoluble Uraniun and Thorium Oxides, International Conference on
Peaceful uses of the Atomic Energy, Geneva, 23, 302, U.N., New York
(1958).
http:/www.abuse.com/environment/EPA-Home/Radiation/Information/
Radionuclides (2005).
http:/www.whoi.edu/education/gsp/MCG/BPE, (2005)
Kall, H.L. and Gordon, L., Quantitative Insolubility of Thorium Oxalate, Anal.
Chem., 25, 1256-58 (1953).
40
Meyer, R.J. and Speter, M., Chem. Ztg., 34, 606 (1910).
Moeller, T.; Schweitzer, G.K. and Star, D.D., Analytical Aspects of Thorium
Chemistry, Chem. Revs, 42, 63 (1948).
Nemodruk, A.A. and Kochetkova, N.E., Zh. Anal. Khim, 17, 330 (1962).
Savvin, S.B., Organic Reagents of the Arsenazo III group [in Russian],
Atomizdat, Moscow (1971).
41
Sun, G.; Bao, B. and Cui, Y., Extraction of U (VI) and Th (IV) with N, N-
dibutyl-alkylamides, He HuaxueYu Fangshe Huaxue 21 (2), 119-123
(ch) (1999)
230
Thomas, R.G., The Metabolism of Th (Ionium) Administered by
Intratracheal Injection to the Rat, University of Rochester Atomic Energy
Project Report, UR-980 (1956).
Twenhofel, W.S. and Buck, K.L, The Geology of Thorium Deposits in the
United States, International Conference on the Peaceful uses of Atomic
Energy, Geneva, 6, 586, U.N., New York (1956).
Yu, S.; Ma, L. and Bao, B., Synergistic Extraction of U (VI) and Th (IV) rom
nitric acid with HBMPPT and TOPO in Toluene, Solvent extraction for
the 21st century, proceeding of ISEC '99 Barcelona, Spain, 2, 1357-1359
(Eng.) (2001).
42
Appendix I
Chemical Assay Values
Thorium nitrate Loba Chemie
Minimum assay (gravimetric)- 99%
Maximum Limits of Impurities :
Chloride (Cl) - 0.002%
Sulphate (SO4) - 0.01%
Heavy metals (as Pb) - 0.002%
Iron (Fe) - 0.001%
Titanium (Ti) - 0.005%
Rare ground (as La) - 0.2%
by NH3 (as sulphate) - 0.2%
38
Benzene Extra Pure 78.11 S.d. fine chem.. Ltd.
Minimum Assay (GLC) - 99.0%
Boiling Range (79-81°C) - Min 95%
Freezing point - not below 5.2°C
Wt per ml at 20°C - 0.875-0.879g
Maximum limits of impurities
Non volatile matter - 0.002
Water - 0.1%
HNO3 - 63.01
Assay (HNO3) - 66-75%
Chloride (Cl) - < 0.005%
Sulfate - < 0.001%
Heavy metals (Pb) - 0.001%
39
REFERENCES
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Thorium by Some Pyrazolone Derivatives. New Variant of the
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Anal. Chem., 31 (12), Part 1, 1743-1745 (1977).
Carswell, D.J. and Lawrence, J.J., J. Inor. Nucl. Chem. 11, 69 (1959).
Chen, H., Study of the Colour Reaction of Tc-Arsenazo with Thorium and its
Application, Hubei Daxue Xuebao Ziran Kexueban, 24 (4), 329-331,
369 (Ch.) (2002).
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Estimation of Water and Wastewater, 20th edition, Washington D.C., p.
4-145 (1998).
40
Collee, R.; Govaerts, J. and Winand, L., Quantitative Analysis of Thorium in
Ores and Thoriferous Products, by a Method Based on Radioactivity,
International Conference on the Peaceful uses of Atomic Energy,
Geneva, 3, 589, U.N., New York (1958).
Cui, Y; Zhang, Z.; Jiang, R. and Sun, G., Structural Effect of N-N-dialkylamide
on Thorium (IV) Solvent Extraction from HNO3 Solution, Journal of
Radioanalytical and Nuclear Chemistry, Kluwer Academic Pub. 288
(1), 171-173 (Eng.) (2003).
Grimaldi, F.S. and Fletcher, M.H., Thorin – Tartaric Acid System for
Spectrophotometric Determination of Thorium, Anal. Chem, 28, 812
(1956).
He, R.; Wang, J. and Wang, Y., Simultaneous Determination of U and Th with
Standard Dual-Addition Method, Rare Met. (Beijing), 17 (2), 154-159
(Eng.) (1998).
41
Hodge, H.C. and Thomas, R.G., Health Hazards from the Inhalation of
Insoluble Uraniun and Thorium Oxides, International Conference on
Peaceful uses of the Atomic Energy, Geneva, 23, 302, U.N., New York
(1958).
http:/www.abuse.com/environment/EPA-Home/Radiation/Information/
Radionuclides (2005).
http:/www.whoi.edu/education/gsp/MCG/BPE, (2005)
Kall, H.L. and Gordon, L., Quantitative Insolubility of Thorium Oxalate, Anal.
Chem., 25, 1256-58 (1953).
42
Meyer, R.J. and Speter, M., Chem. Ztg., 34, 606 (1910).
Moeller, T.; Schweitzer, G.K. and Star, D.D., Analytical Aspects of Thorium
Chemistry, Chem. Revs, 42, 63 (1948).
Nemodruk, A.A. and Kochetkova, N.E., Zh. Anal. Khim, 17, 330 (1962).
Savvin, S.B., Organic Reagents of the Arsenazo III group [in Russian],
Atomizdat, Moscow (1971).
43
Sun, G.; Bao, B. and Cui, Y., Extraction of U (VI) and Th (IV) with N, N-
dibutyl-alkylamides, He HuaxueYu Fangshe Huaxue 21 (2), 119-123
(ch) (1999)
230
Thomas, R.G., The Metabolism of Th (Ionium) Administered by
Intratracheal Injection to the Rat, University of Rochester Atomic Energy
Project Report, UR-980 (1956).
Twenhofel, W.S. and Buck, K.L, The Geology of Thorium Deposits in the
United States, International Conference on the Peaceful uses of Atomic
Energy, Geneva, 6, 586, U.N., New York (1956).
Yu, S.; Ma, L. and Bao, B., Synergistic Extraction of U (VI) and Th (IV) rom
nitric acid with HBMPPT and TOPO in Toluene, Solvent extraction for
the 21st century, proceeding of ISEC '99 Barcelona, Spain, 2, 1357-1359
(Eng.) (2001).
44