studies on elemental contents of some biological …
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1
STUDIES ON ELEMENTAL CONTENTS
OF SOME BIOLOGICAL AND ENVIRONMENTAL MATERIALS
USING NUCLEAR AND ATOMIC TECHNIQUES
BY
WALAA MOSTAFA MOHAMED ABD-EL AZIZ (M. SC.)
REACTORS PHYSICS DEPARTMENT,
ATOMIC REACTORS DIVISION-NUCLEAR RESEARCH CENTER,
ATOMIC ENERGY AUTHORITY- CAIRO – EGYPT.
FOR
THE DEGREE OF PHILOSOPHY DOCTOR IN SCIENCE
(NUCLEAR PHYSICS)
SUBMITED TO
PHYSICS DEPARTMENT- FACULITY OF SCIENCE
ZAGAZIG UNIVERSITY
ZAGAZIG- EGYPT
2013
2
STUDIES ON ELEMENTAL CONTENTS
OF SOME BIOLOGICAL AND ENVIRONMENTAL MATERIALS
USING NUCLEAR AND ATOMIC TECHNIQUES
BY
WALAA MOSTAFA MOHAMED ABD-EL AZIZ
(M. SC.)
Supervisors:
1- Prof. Dr. I.I. BASHTER, Professor of Nuclear Physics, Physics Department,
Faculty of Science, Zagazig University – ZAGAZIG - EGYPT
Signature
2- Prof. Dr. N. Ashoub, Professor of Theoretical Physics, Reactors Physics
Department- Nuclear Research Center, (Atomic Energy Authority) - CAIRO –
EGYPT.
Signature
3- Prof. Dr. A. M. Hassan, Professor of Nuclear Physics, Reactor Physics
Department, Reactors Division, Nuclear Research Center, Atomic Energy
Authority (Died)
3
Approval Sheet
Student Name: Walaa Mostafa Mohamed Abdel Aziz
Thesis Title: "Studies on elemental Contents of Some Biological and
Environmental Materials using Nuclear and Atomic
Techniques"
Degree of study: The degree of Philosophy Doctor in science.
Approved by:
Name
Profession
Signature
1-
2-
3- Prof. Dr. I.I. BASHTER
Prof. of Nucl. Phys. Faculty of
Science – Zagazig University.
4- Prof. Dr.N.ASHOUB
Prof. of theoretical Phys. Nuclear
Research Center- Atomic Energy
Authority.
Date of Discussion: / / 2013
4
Thesis Content
The five chapters of this thesis were as follows:
1- General Introduction.
2- Experimental techniques and basis of calculations.
3- Experimental set-up.
4- Results and Discussion.
5- Comments on the results obtained and Conclusions.
5
List of Abbreviations
Neutron Activation Analysis
NAA
Inductively Coupled Plasma-Mass Spectrometry
ICP-MS
X-Ray Fluorescence
XRF
Energy Dispersive X-Ray
EDX
Atomic Absorption Spectrometry
AAS
Flame Absorption Spectrometer FAAS
Environmental Protection Agency
EPA
Monte Carlo code
MCNP
Flame Absorption Spectrometer
FAAS
Hyper Pure Germanium Detector
HPGe
delayed neutron activation analysis
DNAA
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List of Tables
Table No. Subject
Page
Table (4- 1)
Table (4-2)
Table (4-3)
Table (4-4)
Table (4-5)
Table (4-6)
Table (4-7)
Table (4-8)
Table (4-9)
Table (4-10)
The elemental concentration of values using the Short
lived radionucluide in the samples under investigation
Elemental content of sample 1 as obtained by NAA,XRF
and ICP, for long lived isotopes.
Elemental content of sample 2 as obtained by NAA,XRF
and ICP, for long lived isotopes.
Elemental content of sample 3 as obtained by NAA,XRF
and ICP, for long lived isotopes.
Elemental content of sample 1(super triple) and sample
2(super phosphate) as obtained by INAA for long lived
isotopes.
Elements concentration (%) in the three samples of kohl as
detected by EDX.
Heavy Elements Concentration in (mg/L) (ppm) in the
samples of kohl as measured by atomic absorption
spectroscopy AA- MS
Concentration of (C, O, S) in the above sample (%) using
elemental analyzer
The elemental concentration values for the Short lived
radionuclide in sample 3 under investigation
The elemental concentration values for the long lived
radionuclide in sample 3 under investigation
48
49
50
51
62
68
70
70
72
72
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List of Figures
Fig. No. Subject
Page
Fig.(2-1)
Fig.(2-2)
Fig.(2-3)
Fig.(3-1)
Fig.(3-2)
Fig.(3-3)
Fig.(4-1)
Fig.(4-2)
Fig.(4-3)
Fig.(4-4)
Fig.(4-5)
Fig.(4-6)
Fig.(4-7)
Fig.(4-8)
Schematic of ICP torch
Generation principle of characteristic X-ray
Energy dispersive x-ray fluorescence spectrometer.
Excitation by X–rays from (a) an x-ray tube and (b) a
radioactive substance
Energy Calibration (using Co-60, Cs-137 and Ba-133
isotopes)
Energy calibration curve for HPGe spectrometer system
Efficiency curve for the HPGe detector
Major elements in the investigated samples.
Trace elements in the investigated samples.
Heavy metals and rare earth elements in the investigated
samples.
Gamma -Ray Spectrum of sample 3 (calcium sulfate) as
received for short irradiation facility of ET-RR-2 reactor
Gamma-Ray Spectrum of sample 1 (vercum 4) as received
for short irradiation facility of ET-RR-2 reactor
Gamma-Ray Spectrum of sample 2 (vercum 9) as received
for short irradiation facility of ET-RR-2 reactor
Gamma -Ray Spectrum of sample 3 (calcium sulfate) as
received for long irradiation facility of ET-RR-2 reactor
Gamma-Ray Spectrum of sample 1 (vercum 4) as received
for long irradiation facility of ET-RR-2 reactor
32
34
37
43
44
46
52
53
54
55
56
57
58
59
8
Fig.(4-9)
Fig.(4-10)
Fig.(4-11)
Fig.(4-12)
Fig.(4-13)
Fig.(4-14)
Fig.(4-15)
Gamma-Ray Spectrum of sample 2 (vercum 9) as received
for long irradiation facility of ET-RR-2 reactor
Change average concentrations of different elements in
plant samples with distance
Change average concentrations of different elements in
soil samples with distance
Change the concentrations of different elements in the
plant samples with distance
Elements concentration (%) in the three samples of kohl as
detected by EDX.
Elements Concentration in (mg/L) in the samples of kohl
as measured by atomic absorption spectroscopy AA- MS.
Gamma-Ray Spectrum of sample 3 (Galena) as received
for long irradiation facility of ET-RR-2 reactor.
60
64
65
66
69
71
73
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SUMMARY
In the last few decades, the elemental investigation in different materials has a
great importance for industrial and medical applications. One can find hundreds of
papers and many of special conferences around this work. The development in
gamma–ray spectroscopy technique as well as the diffraction technique make it much
easier and give a very promising data for such investigations. So this thesis deals with
the elemental investigations and microstructure studies of some strategic materials in
industrial, environmental using the following techniques: Neutron Activation Analysis
(NAA), Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), X-Ray
Fluorescence (XRF), Energy Dispersive X-Ray (EDX), Atomic Absorption
Spectrometry (AAS).
Neutron activation analysis is considered as one of the most important
analytical technique, which yield very accurate and precise results for trace and ultra-
trace elemental concentrations in complex samples. Along the past several decades,
this has been applied for determination of a great variety of elements in many
disciplines including environmental (1)
, biological (2)
, geological as well as material
science (3)
. Also it is considered as a method for qualitative and quantitative
determination of elements based on the measurement of characteristic radiation from
radionuclides formed directly or indirectly by neutron irradiation of samples (4)
. The
most suitable source of the neutrons is usually the nuclear research reactor. The high
resolution gamma-ray detection systems are used as well for analysis of the complex
gamma-ray spectra obtained by neutron capture.
A neutron flux in the order of 1.3x1011
cm-2
s-1
for long and 2.7x1011
cm-2
s-1
for
short irradiation times are still quite acceptable for many of Neutron Activation
Analysis purposes, as has been demonstrated in many laboratories.(5)
11
The research reactor facilities offer more advantages for neutron activation
analysis, such as, relatively low gamma-ray dose and allowing for relatively long
irradiation with samples packed in Aluminum foils and polyethylene capsules.
The potential use of ICP-MS for the determination of isotopic ratio was
demonstrated early in the stage of its development (6)
. ICP-MS is used for isotope ratio
determination in a wide range of fields including earth sciences, medical applications,
environmental studies, and in nuclear industry. The range and combination of
elements, which can be analyzed by ICP-MS, is very broad. Modern instruments
provide the possibility for the simultaneous determination of most elements in the
periodic table at major, trace and ultra trace levels in single or multielement
determinations.
For Atomic Absorption Spectrometry which is used for measuring the
concentration of elements in the liquid and the solid samples, by Flame Absorption
Spectrometer (FAAS) and Graphite Furnace Atomic Absorption Spectrometer
(GFAAS), respectively. The detection limit of this technique reaches part per trillion
in gram (ppt), in the case of (GFAAS). A hydride system is attached to the Atomic
Absorption Spectrometer (HG-AAS), which gives the ability to analyze the elements:
Selenium, Tellurium, Antimony, Arsenic and Mercury by changing their oxidation
state.
The X-ray Fluorescence Spectrometer allows nondestructive rapid analysis of
samples in the form of solid samples, powder and liquid. The range of elements that
can be measured is from Sodium (Na) to Uranium (U). The XRF spectrometer has the
capability of a quantitative analysis of elements, oxides and compounds. The XRF has
a wide range for the elemental analysis in different fields such as materials, metals,
rocks, ceramics, food polymers fertilizers, cosmetics, paint, plant waist, mineral water,
environmental applications, industrial applications, medical applications, petroleum
and semiconductors.
11
For Energy Dispersive X-Ray Fluorescence Spectrometer (EDX-Ray), the SEM
equipped with EDX spectrometer acts as a microprobe for solid surfaces (7)
. The
analysis is a nondestructive method in the range from major to 100 ppm for the whole
elements of the periodic table (except: hydrogen, helium, lithium and beryllium). The
SEM has the ability for imaging with magnification up to 300,00 times. A low
vacuum technique allows observation and analysis for any insulator specimen without
conductive coating (8)
.
There are three samples of domestic fertilizers from Delta Gypsum Company
and the International Company of Fertilizers. Because phosphate fertilizers are
manufactured from rock phosphates, they may contain various trace and minor
elements (9)
. These elements, when applied to the soil, may persist due to their long
life-time in soils, and could be readily available for plants, especially in acidic soils (10)
with a potential risk of transfer to the plants and human food chain (11)
. Biologically,
these heavy metals are toxic to living systems particularly when present in high
concentrations. Thus the objective of this work is to evaluate the concentrations of
elements in some domestic fertilizer samples.
And two samples of domestic fertilizers from the Abu-Zabal phosphate factory
in El-Qalubia governorate, Egypt and 19 samples of plants and soil from area around
the Abu-Zabal phosphate factory. Samples were grinded and prepared for neutrons
irradiation. The weight of each sample in case of long irradiation was 0.3 g. The
samples were encapsulated in the polyethylene containers and irradiated for different
times in the core of ET-RR-2 and the concentrations of elements in all these samples
were evaluated.
Pollution of agricultural soils with fertilizers can be solved by limiting the total
load of each heavy metal, taking into consideration pH, organic matter and clay
contents, and other properties that reflect binding capacity of soil components, so that
12
soil could be maintained as a multi-functional system, without affecting biodiversity,
another important quality that could be adversely affected by fertilizers (9)
.
Knowledge of metal concentrations in fertilizers must be assessed in the case of
fertility trials or in continuous cropping systems where phosphate fertilizers are added
to soils. These concerns are very important in agricultural systems.
Also three different Samples of kohl used in this work were purchased from the
local Egyptian market and pharmacies in Cairo. The African natural untreated kohl
was in big crystallized stone form, while the American and French synthetic kohl
were in pencil forms. The samples were crushed, finely grounded into powder form.
The scope of this thesis
Studies on the elemental investigation of some biological and environmental
materials by gamma-ray spectroscopy, and other analytical techniques.
13
CHAPTER 1
GENERAL INTRODUCTION
1.1 Introduction
Fertilizers enhance soil chemistry by introducing nutrients deficient in or
lacking in soils. Fertilizers often contain a mixture of nitrogen, phosphorus and
potassium in varying quantities, depending on the application. All of these chemicals
occur naturally in the environment. Other ingredients may also be included.
According to the Economic Research Service, fertilizer use has steadily increased
since 1960. While fertilizer application improves soil health and food quality, overuse
has serious environmental impact.
Nitrites and Nitrates: when excess nitrites and nitrates enter aquatic ecosystems,
a deadly increase in the ammonia cycle occurs resulting in excessive ammonia in the
water, which can kill aquatic plants and organisms.
Phosphorus Excessive: phosphorus in aquatic ecosystems causes algal blooms,
which in turn create a cycle where by dissolved oxygen, is depleted, resulting in plant
and fish kills. Livestock Populations rising food demand results in increases in
livestock population and consequently livestock fodder through fertilizer use, causing
a proliferation of harmful bacteria such as E. coli in water resources.
Water Pollution: the U.S. Environmental Protection Agency (EPA) identified
agriculture, with its high use of pesticides and fertilizers, as the primary cause of
water pollution.
Balance: when fertilizers enter the environment, they disrupt the chemical
balance of ecosystems, sometimes to the point where the ecosystem cannot recover.
Infertile Soil: the synthesized materials manufacturers use in their chemical
fertilizers may help plants grow, but they do not help the soil they grow in. In fact,
they can do quite the opposite. According to Garden Counselor Lawn Care, the
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unnaturally high levels of nutrients that some chemical fertilizers contain can over
saturate soil and cancel out the effectiveness of other vital nutrients.
Another way chemical fertilizers can make soil infertile is by increasing its
acidity. Many chemical fertilizers contain sulfuric and hydrochloric acid, which if
used in excess can cause serious harm to microorganisms (specifically the type that
helps supply plants with nitrogen). This can have a serious impact on the soil's pH and
adversely affect plant growth.
Increased Microorganisms Nitrogen-rich chemical fertilizers can have the
complete opposite effect on soil in comparison to more acidic fertilizers. Too much
nitrogen can lead to a microorganism population boom. In large enough numbers,
these microorganisms, instead of helping plants, will hurt them, as they will consume
all of the organic material and nutrients in the surrounding soil.
Groundwater Pollution plants can only absorb a certain amount of nutrients. So
if you over apply a chemical fertilizer, not all of the chemically synthesized nutrients
within it will actually contribute to the plant's health and growth. Instead, the unused
fertilizer will seep into the ground, where it can be carried by rain and irrigation
ditches into streams, rivers, lakes, reservoirs and oceans. The chemical compounds in
the fertilizer can contaminate drinking water supplies and disrupt ecosystems.
Chemical fertilizers are often very salty. The over-application of chemical
fertilizers can thus contribute to plants developing unsightly "salt burns." These occur
when an over saturation of salt leads to certain areas of the plant becoming
dehydrated, and plant tissues dry out.
Due to the high potency of chemical fertilizers, they can sometimes lead to plants
becoming too big for their own health. Larger limbs and thicker foliage translates to a
considerable increase weight, which can put stress on a plant's roots.
15
1.2 Review of Previous Work
1.2.1 For fertilizers
In (1988), A. j. Jeffrey and D. j. Lyons, (12)
were analyzed and centrifuged Soil
samples at 800 gm for 45 min, and the supernatant soln. Were filtered ( 0.2 micro m
filter ) . The filtrates were diluted with H2O (1: 9), and were analyzed by ICP AES
(details given). Calcium , Mg , Na , K , Mn and Si were determined with limits of 0.3
, 0.2 , 0.4 , 1.0 , 0.01 and 0.5 micro g ml-1
, respectively, coefficient of variation were
> 2% ( n = 6 ). Recoveries were ~ 100%. Iron and Al could not be determined because
of spectral interference by Ca and Mg.
In (1989), J. D. Ardis and A. M. Baker, (13)
could be determined all species of
P and S , as well as metals , rapidly by ICP emission spectrometry with use of a
Perkin-Elmer Plasma ll spectrometer with a vacuum system and dual
monochromators. Effluent samples were prepared by US Environmental Protection
Agency test method No. 200. 7 and analyses were performed with qualitative
scanning or quantitatively. Total P was determined regardless of the species present
(lower oxides, ortho-or poly-phosphate or organic) and sensitivity was 0.08 micro g
ml-1
. Sulphur could be determined with sensitivity of 0.1micro g ml-1
. Detection limits
for metals ranged from 0.3 to 75micro g ml-1
.
In (1989), S. S. Ismail and F. Grass, et al, (14)
were determined Twenty-two
elements in three such fertilizer materials by NAA with detection of short medium or
long-lived nuclides. For short-lived products samples were irradiated in a flux of 1.3 ×
1012
n cm-2
s-1
for 10 s and counted for 10 s after 20 ms, and for 60 s after 10 s, and
were then re irradiated for 60 s with counting for 10 s after 20 ms and 180 s after 10 s
with a 16% HPGe detector. For long-lived nuclides irradiation was in a flux of 1.8 ×
1012
n cm-2
s-1
for 4 h with counting for 15 min after 7 days. Results showed good
16
agreement with certified values. Precision was only within 5% owing to the in
homogeneity of the samples.
In (1992), D. W. Averitt and G. F. Wallace, (15)
had been developed microwave
dissolution – ICP MS procedure for the determination at a wide range of traces
elements and concentration. Dissolution was with ultrapure HNO3 at 100% power
(MDS-81 D from CEM Corp.) , MS was with a Perkin-Elmer SCIEX ELAN 500 ICP
spectrometer fitted with a nickel sampler and skimmer cones (full operating details
given). The method was applied to phosphate fertilizer, feeding-stuffs and river
sediment. Results agreed with those of AAS and ICP AES.
In (1992), X. G. Lou, et al, (16)
were wetted powdered phosphate rock (1 g) with
H2O, mixed with 10 ml of HF and 3 ml of HClO4 and heated on a hot plate to
fumeless and analyzed by ICP AES at 213.618 nm for P. This method was also
applied to the determination of P, Mg, K, Na, Fe and Al in fertilizers with a
coefficient of variation of > = 0.51%.
In (1993), Y. Fu. and W. Wang, (17)
were studied the effects of spectral
interference, Based on the characteristics of the single-channel scan ICP AES , base
effect, nebulizer pressure and different power on determination of rare-earth elements.
The selected analytical lines, background calibration and observation heights for 16
elements are tabulated. The recoveries were 90 to 110% and the coefficient of
variation were 2.7%, detection limits were 0.012 to 0.495 ppm.
In (1995), R. Matilainen and J. Tummavuori, (18)
were determined boron in two
commercial fertilizers in four independent laboratories, NPK 20-4-8 and NPK 25-4-,
by ICP AES. There are four analytical lines for boron: 249.773, 249.678, 208.959 and
208.893 nm. Two of the most sensitive lines: 249.773 and 249.678 nm have severe Fe
interferences (cf Xu and Rao, Fresenius J. Anal. Chem. 1986, 325, 534), other
interferences were due to P and K. The interference effects were studies by adding
17
matrix element typically found in fertilizers to real fertilizer samples. If the levels of
added matrix correlate > 0.2 to each other the effect of the added element on the boron
determination can be calculated by multiple linear regressions. The best analytical line
for the determination of boron in fertilizer was at 208.959 nm.
In (1995), R. Matilainen and J. Tummavuori, (19)
were prepared samples for
water-soluble and acid-soluble Mg as described earlier ( cf. “ Official Methods of
Analysis “ , 15th
Ed., AOAC, Arlington, VA, USA, 1990 ) except the samples were
filtered before making up to volume. Four wavelengths, viz., 202.528 , 285.213 ,
383.826 ( Mg l ) and 279.553 ( Mg ll ) were evaluated for the determination of Mg
and the effects of fertilizer matrix components such as P , Ca , K , Na , S and Fe were
investigated. Measurements were performed with use of a Perkin-Elmer ICP
1000/2000 instrument. Interferences were both interelement and spectral. K caused
interelement effects at all wavelengths, Ca caused interelement effects at 202.582 ,
279.559 and 285.213 nm , and Na caused interelement effects at 205.582 , 279.553
and 285.213 nm , and Na caused interelement effects at 205.582 , 279.553 and
383.826 nm , S and P caused interelement and spectral effects. The best wavelength
for Mg determination in fertilizers was 383.826 nm (Mg l).
In (1996), A. R. Mermut, et al, (20)
were available limited information on the
trace element contents of soils and crops in Saskatchewan. Trace elements to a large
extent are derived from soil parent materials and partially from anthropogenic
activities such as agricultural application of fertilizers. The objective of this study was
to establish levels of trace element concentrations of the surface horizons and parent
materials of selected soils fertilizers and durum wheat (Tritium durum Deaf.).
Inductively coupled plasma mass spectrometry (ICP-MS) having the capacity to
determine 60 elements simultaneously at very low detection levels was used. Trace
elements for this work are among the most frequently reported in the recent literature.
A positive relationship between the total contents of traces elements and percent of
18
clays in the soils except Se was found. This suggests that the major part of the
elements studied is associated with the clay minerals in soils. In two Regina heavy
clay soils, total Cu, Zn, Se and Pb were higher in the surface soil than the subsoil, but
this increase was statistically not significant. All the elements except Zn, Cd and Pb
were depleted in soils that have lower clay content in the surface horizon than the
parent material. Soils having similar clay contents in the surface horizon and subsoil
total V, Cr, Co, Ni, Zn, Cd, Sn, Sb, Tl and Pb concentrations were higher in the
surface horizon relative to parent material . Only Zn and Cd increases were
significant. Enrichment of elements in the surface horizons was in part attributed to
anthropogenic additions. Experiments with EDTA and DTPA extraction techniques
showed that almost half of Co, As and Cd and other elements in fertilizers were
between 4 and 50% in somewhat available from for plants indicating their potential
for soil pollution.
In (1999), U. El-Ghawi, et al, (21)
were used ICP and NAA to determine the
concentrations of 35 elements in six different artificial granular fertilizers. Samples
were ground in a mortar. For analysis by ICP, considerable effort was made to bring
the samples into solution and here three different procedures were employed. The first
step involved acid treatment where the sample (700 mg) was added to 3 ml
concentrated HNO3 and heated at 120 degree C for 30 min: complete dissolution was
normally achieved by adding a little HCl and heating and the solution was made up to
25 ml with H2O. In the second one dissolution of sample ( 150 mg ) in 2 ml
concentrated HCl , 1 ml concentrated HNO3 and 1 ml concentrated HF in a PTFE
bomb at 130 degree C for 4 h was performed . H3BO3 was added to complex the
residual HF and the solution made up to 50 ml with 6% H3BO3 solution. The third
step involved the dissolution of sample ( mass not given ) was irradiated in a thermal
flux of up to 2 × 1012
n/cm 2/s : details have been published elsewhere ( Molnar et al.,
Periodica Polytechnica, 1992 , 13 , 45 ) . The irradiated samples were left for 4 weeks
before analysis by gamma-ray spectrometry.
19
In (1999), M. Sohrabpour, et al, (22)
had been performed a borehole experiment
using prompt gamma neutron activation analysis in a large sample box having a
volume of 1 m3. Brine solutions having a salt concentration in the range of 0±10 wt%
of sodium chloride has been used. Chlorine prompt gamma spectral response as a
function of the salt concentrations has been obtained. A simulation of the above
experiments has also been carried out using the MCNP4A Monte Carlo code.
Comparison of the experimental spectral response versus the simulated MCNP4A data
has produced excellent agreement. In view of the good benchmark data it is proposed
that due to the inherent problems associated with the ordinary calibration procedures
for the borehole logging tools, one could employ a combined calibration/simulation
scheme to circumvent these diculties and achieve more elective results.
In (2001), A.S. Abdel- Haleem, et al, (23)
were applied the technique of
instrumental neutron activation analysis as a sensitive nondestructive analytical tool
for the determination of heavy metals and rare earth elements in phosphate fertilizer
ingredients. The contents of heavy metals Fe , Zn , Co , Cr and Sc as well as rare earth
elements La, Ce, Hf, Eu, Yb and Sm were determined in four samples representing the
phosphate fertilizer components ( e.g. rock phosphate, limestone and sulfur ). These
samples were collected from the Abu-Zabal phosphate factory in El-Qalubia
governorate, Egypt. The aim of this study was to determine the elemental pattern in
phosphate ingredients as well as in the produced phosphate fertilizer. Fair agreement
was found between the results obtained for the standard reference material Soil-7 and
the certified values reported by the International Atomic Energy Agency. The results
for the input raw materials (rock phosphate, limestone and sulfur) and the output
product as final fertilizer were presented and discussed.
In (2002), W.M. Yang, et al, (24)
were developed the determination of
phosphorus in fertilizers using an inductively coupled plasma atomic emission
21
spectrometry (ICP-AES) method. Total phosphorus, direct extraction available
phosphorus (EDTA), and water-soluble phosphorus, reported as phosphorus pent
oxide (P2O5), in 15 Magruder check fertilizers were measured by ICP-AES, and the
results were compared with those obtained by the AOAC official method. Five
analytical wavelengths of phosphorus, 177.49, 178.287, 213.618, 214.914 and
253.565 nm, were tested for the determination of phosphorus in fertilizers, and their
detection limits were obtained. Acid effects of perchloric acid and possible matrix
effects of aluminum, calcium, magnesium, potassium, and sodium were negligible for
phosphorus determination. Wavelength 213.618 nm was the best analytical
wavelength for phosphorus determination by all 3 sample preparation methods for the
selected magruder fertilizers. The results demonstrated that the accuracy and precision
of the ICP AES method were comparable with those of the official methods.
In (2003), M.R. Wang, et al,
(25) had been proposed the simultaneous
determination of Fe, Mn, Cu, B and Mo in the foliar microelement fertilizer using an
inductively coupled plasma atomic emission spectrometry (ICP-AES) and the
analytical results were in accordance with those using national standard method. The
method is simple and rapid.
In (2004), M. A. Rauf, et al, (26)
were used Industrial fertilizers to study selected
essential and non-essential metals by two analytical techniques, namely atomic
absorption spectroscopy and neutron activation analysis. Out of eight metals namely
Pb, Cu, Fe, Zn, Ni, Cd, Mn and Cr, which were determined by atomic absorption
technique, Fe showed maximum concentration, whereas Cd and Pb showed minimum
value. In the case of neutron activation analysis, 16 elements namely Cr, Fe, Zn, Co,
Th, Sc, La, Ba, Rb, Cs, Sb, Yb, Ce, Mn, Na and Eu were analyzed. In this group, Na
exhibited maximum concentration value, while Sb and Eu showed the minimum
value. Cr, Fe, Zn and Mn were the four commonly studied elements by the two
techniques. Within this group, Fe showed the highest concentration values, while the
21
lowest was shown in the case of Cr. The comparison of overall data generally showed
lower concentrations of trace metals in nitrogenous fertilizers as compared to potash
and phosphate fertilizers.
In (2005), Serena Righi, et al, (27)
were estimated the effective doses to the plant
workers and to members of the population surrounding the industrial site. The authors
had considered external irradiation, inhalation and ingestion of dust and inhalation of
radon and radon daughters as the main occupational exposure routes. After estimating
the single contributions, the total effective dose had been calculated as the sum of said
contributions. Calculations had been differentiated according to the different tasks of
the company employees. Annual individual effective doses to local residents, resulting
from internal and external irradiation caused by particulate matter emitted into the
atmosphere by the plant had been estimated.
In (2007), LZU Jim-ling, et al, (28)
were applied Phosphorus (P) from fertilizer
and manure is important in increasing crop yield and soil fertility; however, excessive
uses of phosphate fertilizer and manure may also increase P loss from agricultural
soils, posing environmental impact. A long term experiment was conducted on a
calcareous soil (meadow cinnamon) in Hebei Province, China, from 2003 to 2006 to
investigate the effects of phosphate fertilizer and manure on the yield of Chinese
cabbage, soil P accumulation, P sorption saturation, soluble P in runoff water, and P
leaching. P fertilizer (P, O) application at a rate of 360 kg ha-1 or manure of 150 t ha-
1 significantly increased Chinese cabbage yield as compared to the unfertilized
control. However, no significant yield response was found with excessive phosphate
or manure application. Soil Olsen-P, soluble P, bio available P, the degree of
phosphorus sorption saturation in top soil layer (0-20 cm), and soluble P in runoff
water increased significantly with the increase of phosphate fertilizer and manure
application rates, where the maximum phosphorus sorption capacity decreased with
the phosphate fertilizer and manure application rates. Soil Olsen-P and soluble P also
22
increased significantly in the sub soil layer (20-40 cm) with the high P fertilizer and
manure rates. It indicates that excessive P application over crop demand can lead to a
high environmental risk owing to the enrichment of soil Olsen-P, soluble P, bio
available P, and the degree of phosphorus sorption saturation in agricultural soils.
In (2008), A. M. Hassan, et al, (29)
were applied Radiometry techniques to
evaluate the activity and concentration values of 283
U, 232
Th and 40
K in four types of
Egyptian made fertilizers. Also, radon and thorium concentration values were
estimated for the same samples. The Hyper-Pure Germanium Detection System (HP
Ge DS) installed at the hot laboratories of Inchas, Cairo and the Solid State Nuclear
Track Detection System (SSNTDS) facility in Girls College were used for
measurements. A comparative study on the concentration values obtained in this work
for the four fertilizer samples was presented.
In (2009), S. Javied, et al, (30)
were studied Phosphate rock belongs mainly to
sedimentary, slightly igneous, and negligibly to metamorphic rocks. It is used for the
production of phosphorous based fertilizers, acids, detergents and many products of
common use. The rock is mainly composed of phosphorous and minutely of many
other elements. The concentration of Cd, Cu, Cr, Ni, Pb, Zn (environmental pollutants
i.e. toxic elements) were determined, and Co, K, Mg, Mn, Na (common elements) in
phosphate rocks used for production of fertilizer in Pakistan. Rock samples of local
origin were collected from the geological rock formations around the city of
Abbottabad and those of foreign origin were obtained from the fertilizer factories and
research institutes in Pakistan. Analysis of phosphate rock for all the elements of
interest was carried out with Flame Atomic Absorption spectrometer (FAAS) except
for sodium which was analyzed using Flame Photometer, while the concentration of
potassium was determined using both techniques. The results showed that heavy
metal content was lower in Pakistani phosphate than that in imported rock and were
below the safe limits with the exception of lead whose concentration was found to be
23
higher in local phosphate deposits than that in imported rock samples. Phosphate rock
is a source of heavy metal pollution of air, soil, water, food chain etc, therefore
requires removal of heavy metals (HMs) from the rock prior to its use.
In (2010), A. El-Taher, (31) were determined Uranium isotopes found in soil,
rock, water, plants, air, etc., contribute to the natural radiation exposure of the
population. U concentrations in some Egyptian environmental samples like Toshki
soil, Aswan iron-ore, and phosphate samples from El-Sibayia in the Nile Valley and
El-Quseir in the Red Sea coast using instrumental neutron activation analysis (INAA)
and delayed neutron activation analysis (DNAA) in the Mainz TRIGA research
reactor. The results showed that the phosphate rocks are rich natural sources of
uranium among the other minerals forming the earth crust.
In (2011), W. Boukhenfouf, et al, (32)
were evaluated the fluxes of natural
radionuclides in local production of phosphate fertilizers to determine the content of
radioactivity in several commercial fertilizers produced in Algeria and to estimate
their radiological impact in a cultivated soil even for the long-term exposure due to
their application. Because of their mineral content, soils are naturally radioactive and
one of the sources of radioactivity other than those of natural origin is mainly due to
the extensive use of fertilizers. For these purposes, virgin and fertilized soils were
collected from outlying Setif region in Algeria and from phosphate fertilizers used in
this area. Gamma spectrometry was exploited to determine activity concentration due
to naturally occurring 226Ra, 232Th and 40K in five types of samples (two different
sorts of fertilizers, virgin and fertilized soils and well water used for irrigation) taken
from Setif’s areas. The results show that these radionuclides were present in an. For
well water, the values were 1.93 and 0.12 Bq/kg; however the third value was below
the Minimum Detectable Activity. The radium equivalent activity and the
representative level index for all samples were also calculated. The data were
discussed and compared with those given in the literature.
24
In (2012), E. Bulska, et al, (33)
were investigated and compared analytical
performance of inductively coupled plasma mass spectrometry (ICP-MS) for
determination of lanthanides in plant materials with neutron activation analysis
(NAA) as well as ion chromatography (IC) with UV–VIS detection. Two sample
preparation protocols were tested: (i) microwave assisted digestion by concentrated
nitric acid; (ii) microwave digestion involving silica and fluoride removal, followed
by the selective and quantitative lanthanides group separation from the plant matrix.
Several Certified Reference Materials (CRM) of plant origin were used for the
evaluation of the accuracy of the applied analytical procedures. The consistency of
results, obtained by various methods, enabled to establish the tentative recommended
values (TRV) for several missing elements in one of CRMs. The ICP-MS, due to its
very high sensitivity, has the potential to contribute to this aim. The discrepancy of the
results obtained by various methods was discussed in a view of possible matrix effects
related to the composition of investigated materials.
1.2.2 For kohl samples
In (1991), Carol Parry and Joseph Eaton (34)
were investigated traditional kohl
used in Asia, Africa, and the Middle East. It may be a pervasive source of lead
poisoning in those areas. Samples of kohl were purchased In Morocco, Mauritania,
Great Britain, and the United States. Some of these samples originated at from
Pakistan, India, and Saudi Arabia. Kohl is widely believed consist of antimony (Sb),
but analysis consistently revealed only trace amounts of antimony. Nine of the twenty-
two samples tested contained less than 0.6% lead; however, seven samples had lead
levels in excess of 50%. The remainder ranged from 3.31 to 37.3%. Third-world-
manufactured kohl's were used in the United States and Britain, suggesting that this
hazard is no longer confined to the third world. Kohl's which contained lead were
sold in violation of laws on lead in cosmetics in both of these nations. Third-word
physicians and health care workers appear to be unaware of possible lead uptake from
25
unsuspected traditionally used items. Physicians in developed nations with patients
from Asia, the Middle East, and North Africa need to factor in the possibility of past
or present lead intake from unorthodox sources such as kohl.
In (2001), N. Lekoucha, et al., (35)
were investigated the use of traditional
cosmetics and remedies such as kohl and henna is very common in Morocco,
especially among women, children and babies. Kohl is a dangerous eye cosmetic. It is
usually mixed with other harmful substances, then applied on women’s eyebrows and
used in skin treatments for infants. Henna is another traditional product, with religious
associations, which has been widely used over the centuries for cosmetic and medical
purposes. Many people add various herbs or other substances to the henna in order to
strengthen it or to give it a stronger color. Our results were reassuring in that the
concentrations of lead found in non-elaborate henna only. Samples of henna were low.
However, when henna was mixed with other products elaborate henna, these
concentrations increased. Lead concentrations in kohl were very high however, unlike
henna, were lower in mixed kohl as mixing with other products diluted the
concentration of lead. Nevertheless, in both types of kohl, lead concentrations were
very high and consequently constitute a risk for public health, particularly for
children.
In (2003), R.M. Al-Ashban, et al., (36)
were investigated kohl (surma) used as
eyeliner a popular practice in Saudi Arabia and people firmly believe that it is safe to
use. A total of 107 kohl samples (branded and unbranded) were collected from
different regions of Saudi Arabia, and analyzed for exist lead. In addition, aluminum
and antimony levels were also determined. Lead levels up to 53% were detected in
some kohl preparations, and some samples were found to contain camphor and
menthol. The blood analyses of regular kohl users revealed a high lead concentration
and relatively low hemoglobin levels. Due to the health risk, an official public
awareness campaign is suggested to encourage the use of lead-free kohl.
26
In (2004), A. D. Hardy, et al (37),
were analyzed a total of 18 kohl samples using
X-ray Powder Diffraction (XRPD) and Scanning Electron Microscopy (SEM). All the
samples were purchased in Cairo and eleven of them originated in Egypt. The main
component of six samples was found to be galena (PbS); where four of these samples
originated in Egypt and two in India. For a further ten samples the main component
was found to be one of the following: amorphous carbon, calcite (CaCO3), cuprites
(Cu2O), goethite (Fe O (OH)), elemental silicon or talc (Mg3Si4O10 (OH) 2). For the
last two samples the main component of each was an unknown amorphous organic
compound.
In (2004), M. S. Ghamsari, et al. (38)
had been deposited high quality poly
crystalline nanostructure PbS thin film on a glass substrate by chemical deposition
technique. The hydrazine hydrate as a reducing agent for lead ion has been used for
preparation of the film. After deposition, the film has been annealed, and then the
influence of hydrazine hydrate on the dark resistivity and photosensitivity of film have
been investigated. It was found that in the presence of hydrazine hydrate in chemical
deposition bath, the resistance of the prepared film increases to mega ohm. The
measured room temperature of the film is 4×109W
−1Hz
1/2cm at the wavelength of 2.4
μm.The experimental results have shown that the PbS film, which has been prepared
according to this procedure, can be applied as an infrared detector in the range of 1.0–
3.0 μm.
In (2005), A. A. Rempel, et al., (39)
were produced powders and solid film of
lead sulfate (PbS) by chemical bath deposition from aqueous solutions at a
temperature of 325K. By a Rietveld-like analysis of the X-ray spectra, it was shown
that nano crystalline PbS has the same rock salt structure B1 (space group Fm-3m) as
coarse grained or single crystalline PbS. Nevertheless, this B1 structure is a much
distorted structure with root mean square displacements up to 0.011 nm and with a
27
micro strain up to 0.3%. The particle sizes in the PbS powders and films measured by
scanning electron microscopy (SEM) are found to be in agreement with those
determined by Bragg–Brentano X-ray diffraction (XRD) on powders and by glancing
incident diffraction (GID) on film. It was found that by changing the chemical affinity
in the range from 31.4 to 38.7kJ/mol; it is possible to regulate the particle size of the
chemically deposited sulfate powders from 100 to 300 nm.
In (2006), R. R. Hawaldar, et al., (40)
were reported the self-assembly of nano
crystalline PbS at the liquid–liquid interface. The PbS nano crystals were,
subsequently, transformed in the form of thin films by dip coating. The resultant films
were characterized by SEM-EDAX, TEM-SAED, XPS and UV–visible spectroscopy.
Pyramidal features at the nanometer scale and a sharp excitonic peak at 656 nm are
the salient aspects of this work. The band gap of the order of 1.8 eV (associated with
the excitonic feature) is ideally suited for solar photovoltaic applications.
In (2007), F. A. Fern´andez-Lima, et al. (41)
were characterized Polycrystalline
thin films of lead sulfide (PbS) grown using substrate colloidal coating chemical bath
depositions by RBS, XPS, AFM and GIXRD techniques. The films were grown on
glass substrates previously coated with PbS colloidal particles in a polyvinyl alcohol
solution. The PbS films obtained with the inclusion of the polymer showed non-
oxygen-containing organic contamination. All samples maintained the Pb : S 1:1
stoichiometry throughout the film. The amount of effective nucleation centers and the
mean grain size have being controlled by the substrate colloidal coating. The analysis
of the polycrystalline PbS films showed that a preferable (1 0 0) lattice plane
orientation parallel to the substrate surface can be obtained using a substrate colloidal
coating chemical bath deposition, and the orientation increases when a layer of colloid
is initially dried on the substrate.
In (2012), A. F. Haider, et al.,(42)
were performed elemental analyses of kohl
(stone) samples collected from three different parts of the world using laser-induced
28
breakdown spectroscopy (LIBS). The analyses indicated that lead (Pb), copper (Cu),
silver (Ag), iron (Fe), calcium (Ca), aluminum (Al), silicon (Si), and sodium (Na)
were present in all the kohl samples. In addition to these elements, the sample from
Madina, Kingdom of Saudi Arabia (KSA), contained the elements tin (Sn), zirconium
(Zr), and antimony (Sb). The sample from Mount Toor, Egypt, also contained Sn.
Also, quantitative analysis for lead was carried out by the standard addition method
using the LIBS technique. The result showed the presence of 14.12 ± 0.28% by weight
of Pb in the sample from Madina, which compares well with the measurement done
using atomic absorption spectroscopy (AAS) (13.31 ± 0.46%). The standard addition
method used three calibration curves drawn for three emission lines of the LIBS
spectra of Pb. The limits of detection for these calibration curves varied from 0.27%
to 1.16% by weight. The lead contents of the samples from Mount Toor and the local
market of Bangladesh were also measured by the AAS technique, and the results were
14.61 ± 0.48% and 8.98 ± 0.35% by weight, respectively.
In this work, three samples of domestic fertilizers and three samples of
kohl have been elementally investigated. The NAA, ICP-MS, XRF, EDX, AAS a
have been used for this purpose.
Two samples of domestic fertilizers from the Abu-Zabal phosphate factory in
El-Qalubia governorate, Egypt and 19 samples of plants and soil from area around
the Abu-Zabal phosphate factory. The samples were encapsulated in the polyethylene
containers and irradiated for different times in the core of ET-RR-2 reactor.
The concentrations of elements in these samples were evaluated.
29
CHAPTER 2
EXPERIMENTAL TECHNIQUES
2.1 Using the Neutron Activation Techniques (NAA)
As mentioned above It is a sensitive analytical technique, useful for performing
both qualitative and quantitative multi-element analysis of major, minor, and trace
elements in samples from almost every conceivable field of scientific or technical
interest. (43)
Neutron activation analysis was discovered in 1936 when Hevesy and Levi
found that samples containing certain rare earth elements became highly radioactive
after exposure to a source of neutrons. Neutron activation is the general term for
irradiating material with a flux of low–energy neutrons to create radionuclides. (44)
Three steps are involved:
a. Neutron bombardment of the sample.
b. Recording the energy spectrum of the produced gamma radiation.
c. Analysis of significance of the spectrum features.
The energies of the spectral peaks identify the present elements and the areas of
the peaks define the quantities of each element. The sample is placed in a neutron
source for a long time to produce enough radionuclide products that can be measured
with the desired statistical precision (45)
. Neutron activation analysis is a physical
method of analysis of materials for elemental composition. A sample is exposed to
neutrons, resulting in activation of many of the constituent elements. Specific
radiations emitted by activated products are detected to determine the amount of the
elements present in the sample. Instrumental neutron activation analysis (INAA) is a
technique in which gamma, Beta and positron are detected. Gamma ray emissions are
usually distinctive enough that elements may be determined without chemical
separations or special sample preparation. Neutron activation analysis is capable of
simultaneous determination of many elements in most samples even when parameters
31
are selected to optimize detection sensitivity of one particular element. Information on
additional elements is obtained with no additional effort or expense.
For quantitative analysis, the well-resolved and pronounced γ-ray lines have
been selected to measure the concentrations of 31 elements of the fertilizer samples.
In order to estimate the concentration value of each element, the well-known
analytical equation was used. (46)
eeeNfI
MCm
tct irrt wmth
110
------------ (2-1)
Where,
m: is the mass of the element,
φm: is the thermal neutron flux measured by Gold foil technique (Au foils),
λ :s the decay constant,
C: is the activity (net peak area of the interested gamma-rayline),
M: is the atomic mass of the element,
ε: is the efficiency of the detection system at the selected full energy peak.
2.2 Inductively Coupled Plasma-Mass Spectrometry
The potential use of ICP-MS for the determination of isotopic ratio was
demonstrated early in the stage of its development (47).
ICP-MS is used for isotope ratio
determination in a wide range of fields including earth sciences, medical applications,
environmental studies, and in nuclear industry. The range and combination of
elements, which can be analyzed by ICP-MS, is very broad. Modern instruments
provide the possibility for the simultaneous determination of most elements in the
periodic table at major, trace and ultra trace levels in single or multielement
determinations.
31
2.2.1. Plasma sources for mass spectrometry
Plasma can be thought of as the co-existence in a confined space of the positive
ions, electrons and neutral species of an inert gas, like argon. Classification of the
common plasma sources is made according to the method of inputting power to the
gas. For example, the inductively coupled plasma is sometimes referred to as the radio
frequency RF; other types of plasma are the direct current plasma (DCP) and
microwave-induced plasma (MIP). The subject of plasma temperature still remains an
area for discussion. Although plasma is electrically neutral, it is not in a
thermodynamic equilibrium. Hence, it is not possible to characterize a single
temperature. Four temperatures can be used to characterize the plasma, namely
excitation, ionization, electron, and gas temperature as in the following.
1. Excitation temperature is a measure of the population density of the energy levels.
2. Ionization temperature is a measure of the population density of different
ionization states.
3. Electron temperature is a measure of the kinetic energy of the electrons.
4. Gas temperature is a measure of the kinetic energy of the atoms.
2.2.2 Inductively coupled plasma ion source
The inductively coupled plasma (ICP) is an electrodeless discharge in a gas
(commonly Argon) at atmospheric pressure, maintained by energy coupled to it from
a radio frequency generator (48(
. A suitable coupling coil, which acts as the primary of
a radio frequency transformer, while the secondary is created by the discharge itself.
The plasma is generated inside and at the open end of an assembly of quartz tubes
known as the torch. A typical arrangement of a torch used for mass spectrometry is
shown in Fig. (2-1).
32
Fig. (2-1): Schematic of ICP torch.
2.2.2.1 ICP ionization
If an electron absorbs sufficient energy, equal to its first ionization energy, it escapes
the atomic nucleus and an ion is formed. In the ICP the major mechanism by which
ionization occurs is thermal ionization. When a system is in thermal equilibrium, the
degree of ionization of an atom is given by the following equation:
(2-2)-
kT
E
h
Tmk
Z
Z
n
nn i
a
i
a
ei exp22
2/3
2
where ni , ne and na are the number densities of the ions, free electrons and atoms,
respectively, Z; and Za are the ionic and atomic partition functions, respectively, m is
the electron mass, k is the Boltzmann constant, T is the temperature; h is Planck's
constant and E1 is the first ionization energy.
2.2.2.2 ICP resolution
The main advantage of a magnetic sector is the high degree of resolution
obtainable. Resolution is defined as
(2-3)-----------------------M
MR
Normal analytical zone
(blue) Initial radiation zone
(red) Induction
region Outer gas
flow
Torch Load coil
Aerosol gas flow
(into axial channel)
33
Where;
R is resolution, M is mass (strictly m/z) and M is peak width at 5% peak height.
This is concept is illustrated better in Figure. The resolution obtainable with
quadruples is limited by the stability and uniformity of the RF/DC field and by the
spread in ion energies of the ions.
2.3 Atomic Absorption Spectrometry
The concept of atomic absorption spectrometry (AAS) was proposed in 1955 in
Australia (49(
and in the Netherlands . Their idea was to present the analyte as an
atomic vapor and to pass through it radiation of the right wavelength to excite atoms
from the ground state to an excited electronic level. Walsh used a hollow-cathode
lamp as an excitation source and the atomizer was a combustion flame. In 1961 L’vov
described an electrically heated carbon tube as an atomization system whereby
relatively small volumes of sample were introduced into the resistively heated tube,
through which the optical beam of the spectrometer passed. (50)
A drawback of the
graphite furnace was an increase in chemical interferences, molecular absorption and
scattering compared with the flame. Different methods were developed to solve these
problems (51).
2.3.1. Principle
When an atomic vapor containing free atoms of an element in the ground state
is illuminated by a light source that radiates light of a frequency characteristic of the
element present in the vapor, radiation will be attenuated at certain frequencies (52)
The
absorbed radiation excites electrons from the ground state to a higher energy level.
The degree of absorption is a quantitative measure for the concentration of the ground
state atoms in the vapor. These energy transitions correspond to radiation in the UV
and visible regions of the electromagnetic spectrum. As only atoms in the ground state
are involved in this process, ionization must be kept to a minimum. This can be
achieved by atomization in a flame (flame atomic absorption spectrometry; FAAS) or
34
in a graphite furnace (graphite furnace atomic absorption spectrometry; GFAAS),
where temperatures of 3000 K are seldom exceeded.
2.4. X-ray Fluorescence Spectrometer
X-ray fluorescence is one of the most widely used of all analytical methods for
the qualitative identification of elements having atomic numbers greater than that of
oxygen (> 8); in addition, it is often employed for semi quantitative or quantitative
elemental analysis as well (53)
. There are several types of X-ray fluorescence
instruments. The three basic types are wavelength dispersive, energy dispersive and
non dispersive (54)
.
2.4.1. Generation principle of fluorescence X- rays
The sample is irradiated by a primary beam of X-rays, which causes the
ejection of electrons from inner orbital shells. X-rays are emitted as electrons fall from
outer levels to vacant inner levels as shown in Fig. (2-2). The primary beam must
consist of photons with greater energy than the most energetic of the expected
secondary x-rays to be emitted by the sample (55).
Fig. (2-2): Generation principle of characteristic X-ray.
35
2.5. Energy Dispersive X-ray Fluorescence Spectrometers
2.5.1. Principle
When x-rays (primary x-rays) are illuminated from the x-ray tube to the
specimen, fluorescence x-rays having wavelengths (energies) peculiar to the
constituent elements of the specimen are generated from the elements. Qualitative
analysis can be made by investigating the wavelengths of the fluorescence x-rays and
quantitative analysis by investigating the x-ray dose. The energies are investigated by
using the energy separation characteristic of x-ray detector.
The energy E contained in a photon of a frequency is related to the
wavelength λ of the radiation by the equation:
E = h h c/ λ,
E λ = h c -------------------------------- (2-4)
Where h and c are constants, this formulation suggests the possibility that spectral
dispersion may be based on energy as well as on wavelength.
Energy dispersion depends on the availability of a detector that responds
linearly to the energy content of the individual photons incident upon it. This
requirement must be carefully distinguished from the response to the total average
energy or power, which depends on both the energy per photon and the number of
photons received per unit time. Those detectors that are designated as proportional,
namely scintillation counters, gas counters operated at an intermediate range of
voltages, and lithium- drifted silicon or germanium detectors are capable of measuring
photon energies. The development of practical solid state detectors that made possible
energy dispersive spectrometers in a useful form. The signal from the solid-state
detector is analyzed by a series of electronic energy discriminators that permit
36
separate counting of signal pulses of successive energy brackets (56)
.Certain
radioisotopes are x-ray emitters and thus can be used as excitation sources for
fluorescence. No high voltage supply or high vacuum equipment is necessary (57)
.
A basic energy–dispersive spectrometer with an x-ray tube and radioactive
source is shown in (Fig.2-3).( 58)
Many applications of Energy dispersive spectrometers have been reported
Hanson had described a comprehensive program for determining the elemental
composition of any object made of metal, glass and ceramic and included the
necessary data for 71 elements (59(
. Rasberry reported comparative data for four types
of portable energy dispersive x-ray fluorescence analyzers for in situ detection of Pb
in wall paint (60)
. Surkov et al. described a most interesting x-ray fluorescence
spectrometer with which they had carried out elemental analysises of rocks on the
surface of venus (61)
.
2.6 Accuracy and precision
The accuracy is used here as an estimate of the closeness of the measured
concentration or ratio, to the ‘true’ or agreed upon value. It may be defined as:
The term precision is used here to describe the short-term reproducibility of a signal,
concentration or ratio. It is expressed as a relative standard deviation of the mean or as
the relative standard deviation calculated as a percentage of the mean (SD/ X ) x100.
37
Fig.(2-3): Energy dispersive x-ray fluorescence spectrometer. Excitation by
X–rays from (a) an x-ray tube and (b) a radioactive substance
38
CHAPTER 3
EXPERIMENTAL SET-UP
3.1 Sample and Sampling
3.1.1 Fertilizers, plants and soil
Three samples of domestic fertilizers from Delta Gypsum Company and the
International Company of Fertilizers were grinded and prepared for irradiation. The
weight of each sample in case of short irradiation was 0.1 g while in case of long
irradiation was 0.3 g. Samples were encapsulated in the polyethylene containers and
irradiated for different times. The data obtained for some of the identified elements
are compared with the corresponding values obtained by the XRF and the ICP-MS
techniques for the same samples
Two samples of domestic fertilizers from the Abu-Zabal phosphate factory in
El-Qalubia governorate- Egypt and 18 samples of plants and soil from area around
the Abu-Zabal phosphate factory at different distances ( 0 m -5m- 50m-60m-70m-
300m). Samples were grinded and prepared for neutrons irradiation. The weight of
each sample in case of long irradiation was 0.2 g. The samples were encapsulated in
the polyethylene containers and irradiated for different times in the core of ET-RR-2
reactor and the concentrations of elements in these samples were obtained and
evaluated from the gamma spectra of the irradiated samples. The technique of
instrumental neutron activation analysis was applied as a sensitive nondestructive
analytical tool for the determination of heavy metals and rare earth elements in
phosphate fertilizer, plant and soil ingredients.
3.1.2 Kohl
Two samples of kohl used in this work were purchased from the local Egyptian
market and pharmacies in Cairo. One African natural untreated kohl sample had a big
39
crystallized stone form, while the American and French synthetic kohl were in pencil
forms. These samples were crushed, finely grounded into powder form.
In order to obtain more information on the composition and elemental content
of some natural and synthetic, commercially available kohl samples, Energy
Dispersive X-ray, Atomic Absorption Mass Spectroscopy, Neutron Activation
Analysis and elemental analysis measurements were performed.
Neutron Activation Analysis and elemental analysis at the ET-RR-1 reactor was
done for one of the samples (Galena from Africa) which prepared in dried powder
form. Briefly, neutrons can react with isotopes of various elements and produce
radioactive nuclides. The characteristic gamma ray emitted by the nuclides produced
can be used for qualitative and quantitative determination of various elements. Often
elements in part per million or percentage could be analyzed. Usually neutrons are
used as projectiles and -rays are emitted. Also the high resolution -ray detection
system together with the advanced computer programs can help in complete analysis
of the data obtained with high accuracy (62)
.
3.2 Set – Up of the Electronic Systems
3.2. 1 Neutron activation analysis
The electronic systems used for neutron activation analysis technique are:
3.2.2 Short irradiation
There are two computer pneumatic irradiation transfer systems to give precise
timing for the irradiation and analysis of short lived radio nuclides. One of the
irradiation sites for thermal neutron activation and the other for epithermal/fast
neutron activation. The position at the reflector area with thermal neutron flux
1.3x1011
n /cm2/sec is used for thermal neutron activation. A Supervision and control
system with data acquisition and recording modules are available for the facility
operation.
41
Samples requiring short irradiation times and low to moderate flux densities (1011
n.cm2.s
-1), are packed in virgin polyethylene vials and placed into larger transport
device known as rabbit. The rabbit travels from the laboratory to the irradiation
position (in thermal column by an air-driven pneumatic transport system into the core
of the reactor where the sample resides until it has been subjected to the specified
amount of radiation. The rabbit is then extracted from the core and transported back to
the laboratory where the vials are removed from the rabbit, and transferred to non-
irradiated vials for completion of the analytical process.
For analysis of short-lived radio nuclides there are two computer controlled
pneumatic irradiation transfer systems. The pneumatic transport system function is to
send capsules to irradiation position and return then to the loading station after the
pre-set time.
3.2.3 Long irradiation
For measurements of long-lived radio nuclides, there are many manually loaded
irradiation boxes for irradiation of samples. The samples requiring longer irradiation
times (hours or days), with moderate to high flux densities, are packaged in high-
purity quartz vials. Samples can be bundled into a watertight metal container called a
sample holder, which is manually lowered into the reactor for the specified irradiation
time. After irradiation, the sample holder is removed from the core to allow short-
lived radioactivity to dissipate to safe handling levels. There are many manually
loaded sites for irradiation of samples for several hours or days (63)
.
3. 3 Detector Characteristics
3.3.1 Energy resolution
Energy resolution of the gamma spectrometers is defined as full width at half
maximum (FWHM) in kilo electron volts (Kev) for peak of cobalt-60 at 1.33 Mev.
The resolution in neutron activation analysis in ETRR-2 is 2.1 Kev.
41
3.3.2 Relative efficiency
The relative efficiency of the hyper pure germanium detector is defined as the ratio
in percentage of the photo peak counting rate obtained from germanium detector to
photo peak counting rate of 3x3 inch sodium iodide NaI (Tl) crystal at distance 25cm
from Co-60 source. The relative efficiency of the two hyper pure germanium detectors
in the neutron activation analysis laboratory in ETRR-2 reactor is 100%.
3.3.3 Measurement system of gamma rays
The measurement system is carried out using the HPGe spectroscopy system. The
instrumentation used to measure gamma rays from radioactive samples generally
consists of a semiconductor detector, associated electronics, and a computer-based,
multi-channel analyzer (MCA/computer). Most NAA labs operate one or more hyper
pure germanium (HPGe) detectors which operate at liquid nitrogen temperatures (77
degrees K) by mounting the germanium crystal in a vacuum cryostat, thermally
connected to a copper rod or "cold finger". There are two coaxial HPGe detectors and
a Compton suppression system, each is 100% relative efficiency, and resolution
2.1keV for the 60Co gamma ray at 1332.5keV in NAA Labs at ETRR-2. Each
detector is shielded with 10cm thickness ultra low background lead shield with low
carbon steel casing.
3. 4 Counting System Calibration
The calibration of the gamma spectrometers defines these three relations: (1)
spectrum channel numbers to energy, (2) the FWHM of the peak and energy, and (3)
spectrum count rate and activity in Becquerel or other units. The data collected are in
counts/unit time/channel and, to be useful, these data need to be converted to activities
(which is decays per unit time at a given energy). The calibration parameters do this
conversion. These relationships are calculated from spectra, operator inputs, and with
other inputs from libraries and tables. it is important that the calibration, both energy
42
and efficiency, be done correctly because the calibration results will affect all analysis
employing these calibrations. The energy calibration data is used to define the
energies of the peaks in the spectrum. If incorrect data is used to define correspond to
the correct library entry and the peak may be incorrectly identified. The shape
parameters are used to define the expected shape for a single peak. If incorrect, peaks
will be labeled as having a bad shape. Peaks labeled with poor shape may not be
included in the activity calculations, resulting in loss of accuracy. An incorrect
efficiency calibration can cause the nuclide activity to be incorrectly reported (64)
.
3. 4.1Energy calibration
The energy calibration section calculates two sets of parameters: the energy vs.
channel number, and the peak shape or FWHM vs. energy. The inputs to this section
are spectrum with isolated peaks distributed over the energy range of interest. By
choosing four standard sources (Cs-137, Co-60, Na-22, and Ba-133) for energy
calibration, because the gamma ray emitted from these sources cover wide range in
the spectrum. The four standards sources are placed over the HPGe detector and start
counting for 1800 second and then mark the known peaks and inform the software
that this energy is the energy relating to channel number and repeating this steps until
finish all peaks. The final step in energy calibration is to save the energy calibration
(65). Once energy calibration points have been established over the entire energy range
of interest, calibration curves relating energy to channel and FWHM to energy are
normally derived. Figure (3-1), Figure (3-2), show the calibration spectrum,
calibration curves relating energy to channel and full width at half maximum FWHM
to energy, respectively.
2. 4.2 Efficiency calibration
The efficiency calibration section calculates the detection of the spectrometers as a
function of energy. The efficiency calibration includes effects from the detector itself,
43
Fig.(3.1) Energy Calibration (using Co-60, Cs-137 and Ba-133 isotopes)
44
Fig. (3.2) Energy calibration curve for HPGe spectrometer system
45
the detector-source geometry, the materials surrounding the detector and absorption in
the source material or matrix. In general, it is not good practice to use efficiency
calibrations from one detector-source geometry for different geometries. The
efficiency is defined as a function of energy, which means that the energy calibration
must be done first (66)
. For precise data, different standard sources are choosing to
have at least 10 points in the efficiency curve. The sources used in efficiency
calibration are (Na-22, Cs-137, Cd-109, Co-60, Ba-133, Mn-54 and Co-57), and the
procedure here is placing source by source because our unknown samples are point
source. Then by counting each source separately and mark the peak of interest and
calculate the activity of source corrected for decay time and inform the software the
activity and calculate the efficiency related to the energy of this peak, and repeat this
step until finishing. This gives all sources 10 points in the efficiency curve as shown
in figure (3-3).
Calibration or standardization is the determination of the proportionality factors that
relate the measured activity (peak-area in the γ-ray spectrum) (66)
to the amounts of the
elements present in the sample under experimental conditions. Basically there are two
standardizations used in NAA, viz. the relative and the non-relative methods.
46
Fig. (3-3) Efficiency curve for the HPGe detector
0 500 1000 1500 2000
0.005
0.010
0.015
0.020
0.025
0.030
Eff
icie
ncy
Energy (kev)
47
CHAPTER 4
EXPERIMENTAL RESULTS AND DISCUSSION
4.1 In Case of Fertilizers Delta Gypsum Company
Qualitatively, the results revealed a total of 31 elements. Six elements of the
following specific isotopes: 24
Na, 28
Al, 52V
, 5 6
Mn, 86
Rb, and 137m
Ba were determined.
All these isotopes are short half-life isotopes which were measured by rabbit
technique as shown in table 1. Other 25 elements have the isotopes (152
Eu, 109
Pd, 51
Cr,
181Hf,
131Ba,
124Sb,
95Zr,
46Sc,
59Fe,
182Ta,
60Co,
77Ge,
142Ce,
160Tb,
169Yb,
147Nd,
194Ir,
103Ru,
47Ca,
124mSb,
76As,
71mZn,
859Sr,
134Cs, and
86Rb) were determined.
For quantitative analysis, the well-resolved and pronounced -ray lines have
been selected to measure the concentrations of 31 elements of the fertilizer samples as
in tables (4-1), (4-2), (4-3) and (4-4).
Fig (4-1) shows the major elements in the investigated samples. It shows that
Ca and Fe have the highest concentrations in sample no. 3 (45.3%) and (18.02),
respectively. While Fig (4-2) shows trace elements in the investigated samples. It
shows that Ba has the highest concentration in sample no.1 (130.5ppm). While Rb
has the highest concentration in sample no. 2 (80.6ppm). Where Fe shows the
highest concentration in sample no. 3 (Fig 4- 3 (C)).
While the Gamma-Ray Spectrum of three samples of fertilizers as received
for long and short irradiation facility of ET-RR-2 reactor as in Figs. (4-4), (4-5), (4-
6), (4-7), (4-8),(4-9).
48
Table (4-1):The elemental concentration values for the Short lived
radionuclide in the fertilizer samples under investigation
Sample Element Nucl. Reaction ray
(kev)
I T1/2 INAA
(present
work)
XRF % ICP
(ppm)
S1
56Mn 55
Mn(n,)56
Mn 847.8
98.9 2.5h 0.109%
± 0.007 0.321 %
± 0.11
---
24Na 23
Na(n,)24
Na 1368.5
100 14.96h 20.6 ppm ±1.90
--- ---
52V 51
V(n,)52
V 1434.1
100 3.75m 20.7 ppm
±1.91
--- 8.63
28Al 27
Al(n,)28
Al 1779
100 2.25m 0.614%
±0.04
0.714 % ± 0.34
---
86Rb 85
Rb(n,)86
Rb 2111.2
0.12 17.8m 58.8 ppm
±5.44
--- 80.5
S2
56Mn 55
Mn(n,)56
Mn 847.8
98.9 2.5h 0.158% ± 0.01
0.504 % ± 0.17
---
24Na 23
Na(n,)24
Na 1368.5
100 14.96h 0.051% ±0.003
--- ---
52V 51
V(n,)52
V 1434.1
100 3.75m 31.5 ppm
± 2.91
--- 8.87
28Al 27
Al(n,)28
Al 1779
100 2.25m 3.53% ±0.23
3.366 % ± 0.66
---
86Rb 85
Rb(n,)86
Rb 2111.2
0.12 17.8m 80.6 ppm ±7.46
--- ---
S3
56Mn
55Mn(n,)
56Mn 847.8
98.9 2.5h 3.99 ppm
±0.36
--- ---
28Al 27
Al(n,)28
Al 1779
100 2.25m 60.67ppm
±5.61
--- ---
137mBa 136
Ba(n,)137m
Ba 661.6
28.4 3.94h 16.78ppm
±1.55
--- 16.25
49
Table (4-2): Elemental content of sample 1 (vercum 4) as obtained by
INAA, XRF and ICP, for long lived isotopes.
Element Nucl. Reaction ray
(kev) I T1/2 INAA
(present
work)
XRF
%
ICP
(ppm)
152Eu
151Eu(n,)
152Eu 121.8
28.4 13.3y 0.3185ppm
±0.02
--- 0.62
109Pd
108Pd(n,)
109Pd 311.4
0.03 13.46h 0.383ppm
±0.03
--- 0.37
51Cr
50Cr(n,)
51Cr 320.1
9.83 27.7d 21.1ppm
±1.95
--- 16.13
181Hf
180Hf(n,)
181Hf 482
85.5 42.4d 0.17ppm
±0.015
--- 0.11
131Ba
130Ba(n,)
131Ba 496.3
47.1 11.8d 130.5ppm
±12.08
--- 115.3
124Sb
123Sb(n,)
124Sb 602.7 98.4 60.2d 0.2ppm
±0.018
--- 0.5
95Zr
94Zr(n,)
95Zr 724.2
43.7 64.03d 2.9%
±0.26
--- ---
46Sc
45Sc(n,)
46Sc 889.2
100 83.82d 0.49ppm
±0.04
--- ---
59Fe
58Fe(n,)
59Fe 1099.3
56.3 44.5d 9.14%
±0.63
6.261
±0.09
---
182Ta
181Ta(n,)
182Ta 1121.3
35.0 115.0d 1.04%
±0.07
--- ---
60Co
59Co(n,)
60Co 1173.2 99.9 5.27y 11.8ppm
±1.08
--- 10.5
77Ge
76Ga(n,)
77Ga 2089.6 0.33 11.3h 0.662ppm
±0.05
--- 0.87
47Ca
46Ca(n,)
47Ca 530.4 0.1 4.54d 42.4%
±2.76
42.3
±0.45
---
51
Table (4-3): Elemental content of sample 2 (vercum 9) as obtained by
INAA, XRF and ICP, for long lived isotopes. Element Nucl. Reaction ray
(kev)
I T1/2 INAA
(present
work)
XRF
%
ICP
(ppm)
152Eu 151
Eu(n,)152
Eu
121.8 28.4 13.3y 0.184ppm ±0.06
--- 0.15
142Ce 141
Ce(n,)142
Ce 145.4 48.4
32.5d 12.7ppm
±1.26
--- 5.12
160Tb 159
Tb(n,)160
Tb 197 6.79
2.73y 0.15%
±0.01
--- 0.0013
169Yb 168
Yb(n,)169
Yb 307.7 11.1
32.02d 1.5% ±0.1
--- ---
147Nd 146
Nd(n,)147
Nd 319.4 1.95
10.98d 0.52ppm ±0.02
--- 0.75
194Ir 193
Ir(n,)194
Ir 328.4 92.8
171d 48.7ppm
±4.8
--- ---
175Hf 174
Hf(n,)175
Hf 344.0
4
86.6
70d 0.17ppm ±0.01
--- ---
103Ru 102
Ru(n,)103
Ru 443.8 0.32
39.25d 0.14ppm
±0.01
--- 0.5
131Ba 130
Ba(n,)131
Ba 486.5 2.09
11.8d 31.04ppm
±3.08
--- 24.38
47Ca 46
Ca(n,)47
Ca 530.4 0.1 4.54d 41.4%
±2.76
41.329
±0.45
---
124mSb 123
Sb(n,)124m
Sb 602.7 20.0 60.2d
0.25%
±0.01
--- ---
59Zr 94
Zr(n,)95
Zr 724.2 43.7 64.03d 0.072%
±0.005
0.073 ±0.06
0.073
76As 75
As(n,)76
As 867.6 0.13 26.32h 1.34ppm
±0.10
--- 1.25
46Sc 45
Sc(n,)46
Sc 889.2 100 83.82d 0.149%
±0.01
--- ---
77Ga 76Ga(n,)77Ga 925.5 0.74 11.3h 0.78ppm
±0.06
--- 0.73
71mZn 70
Zn(n,)71m
Zn 964.7 4.7 3.94h 4.6% ±0.32
1.012 ±0.11
---
59Fe 58
Fe(n,)59
Fe 1099.
3
56.3 44.5d 3.42% ±0.23
8.881 ±0.15
---
60Co 59
Co(n,)60
Co 1173.
2
99.9 5.27y 10.2ppm ±0.83
--- 8.25
51
Table (4-4): Elemental content of sample 3(calcium sulfate) as obtained
by INAA, XRF and ICP, for long lived isotopes.
Element Nucl. Reaction ray
(kev)
I T1/2 INAA
(present work)
XRF % ICP
(ppm) 47
Ca 46Ca(n,)
47Ca 489.2
6.74 4.54d 45.3%±3.02 59.098
±0.17
---
859Sr 84
Sr(n,)85g
Sr 514
99.3 64.84d 0.193%±0.007 0.119
±0.02
---
134Cs 133
Cs(n,)134
Cs 604.7 97.6
2.06y 0.58ppm±0.11 --- 0.5
152Eu 151
Eu(n,)152
Eu 778.9 13.0
13.33y 7.7ppm±0.76 --- ---
160Tb 159
Tb(n,)160
Tb 879.4
30.0 72.3d 7.25ppm±0.71 --- ---
46Sc 45
Sc(n,)46
Sc 889.2
100 83.82d 28.59ppm±2.83 --- ---
86Rb 85
Rb(n,)86
Rb 1076.6
8.78 18.66d 8.8ppm±0.87 --- 2.25
59Fe 58
Fe(n,)59
Fe 1099.3
56.3 44.5d 18.02%±1.20 --- ---
182Ta 181
Ta(n,)182
Ta 1121.3
35.0 115.0d 0.128ppm±0.02 --- 0.37
60Co 59
Co(n,)60
Co 1173.2
99.9 5.27y 28.5ppm±2.82 --- 9.25
72Ga 76
Ga(n,)77
Ga 1596.7
4.24 14.1h 5.342ppm±0.52 --- 6.125
124Sb 123
Sb(n,)124
Sb 1691
49.0 60.2d 10.3ppm±1.02 --- ---
52
Fig (4-1): Major elements in the investigated samples
53
Fig (4-2)Trace elements in the investigated samples
54
(A) Co and Sb concentrations in the investigated samples
(B) Contents of rare earth elements in the investigated
samples
(C): Average iron concentration in three samples under investigation
Fig(4-3) Heavy metals and rare earth elements in the investigated
samples
55
Figure (4-4) -Ray Spectrum of sample 3 (calcium sulfate) as received
for short irradiation facility of ET-RR-2 reaR56Y78tor
56
Figure (4-5) -Ray Spectrum of sample 1 (vercum 4) as received for
short irradiation facility of ET-RR-2 reactor
57
Figure (4-6) -Ray Spectrum of sample 2 (vercum 9) as received for
short irradiation facility of ET-RR-2 reactor
58
Figure (4-7) -Ray Spectrum of sample 3 (calcium sulfate) as received
for long irradiation facility of ET-RR-2 reactor
59
Figure (4-8) -Ray Spectrum of sample 1 (vercum 4) as received for
long irradiation facility of ET-RR-2 reactor
61
Figure (4-9) -Ray Spectrum of sample 2 (vercum 9) as received for
long irradiation facility of ET-RR-2 reactor
61
4-2 In Case of Fertilizers Abu-Zabal Phosphate Factory –plant –soil
The concentrations for the elements were determined by the neutron activation
method. The mean concentrations of heavy metals and rare earth elements in the two
fertilizer samples under investigation. Most of the tested elements accumulated in the
produced phosphate fertilizer were originally from the limestone except for Co, Sc
and Eu which were originally found in the raw rock phosphate.
For quantitative analysis, the well-resolved and pronounced -ray lines have been
selected to measure the concentrations of 15 elements have the isotopes (76
As, 141
Ce,
60Co,
51Cr,
152Eu,
181Hf,
42K ,
177Lu,
140La,
24Na,
59Fe
46Sc,
59Fe,
233Pa,
175YB,
153Sm
169Yb
and 65
Zn) as in table (4-5).
Variation of average concentrations of different elements in plant samples with
distance are in figure (4-10).
Change average concentrations of different elements in soil samples with
Distance are in Fig.(4-11)
Change the concentrations of different elements in the plant samples with
distance (60-70-300) are in fig. (4-12).
62
Table (4-5): Elemental content of sample 1(super triple) and sample
2(super phosphate) as obtained by INAA for long lived isotopes.
Element
Isotope
Nucl. Reaction T1/2 Sample 1
(mg/kg) sample 2
(mg/kg) 76
As 75As(n,)
76As 26.32h 2.30E-05
3.44E-05
141Ce 140
Ce(n,)141
Ce 32.5d 5.85E-04
4.29E-04
60
Co 59Co(n,)
60Co 5.27y 9.84E-06
9.40E-06
51
Cr 50
Cr (n,) 51
Cr 27.7d 6.88E-05
6.34E-05
152
Eu 151Eu(n,)
152Eu 13.33y 4.19E-05 3.17E-06
181Hf
180Hf(n,)
181Hf
70d 5.12E-06
3.75E-06
42K 41
K (n,) 42
K 12.36h 9.32E-02
4.42E-02
177
Lu 176Lu (n,)
177Lu 6.71d 9.26E-03
7.26E-03
140La 139
La (n,) 140
La 40.27h 2.89E-05
2.73E-05
24Na
23Na(n,)
24Na 14.96h 6.11E-03 6.30E-03
59Fe 58
Fe(n,)59
Fe 44.5d 3.34E-05
2.11E-05
46
Sc 45Sc(n,)
46Sc 83.82d 8.95E-08
8.60E-08
233
Pa 232Th(n,)
233Pa 27d 6.80E-08
5.38E-08
153
Sm 152Sm (n,)
153Sm 46.27h 5.76E-06
4.25E-06
175
Yb 174Yb(n,)
175Yb
1.88h 5.68E-06
6.34E-06
65
Zn 64Zn (n,)
65Zn 243.9d 4.34E-04
1.49E-04
63
0 50 100 150 200 250 300
0.00000
0.00001
0.00002
0.00003
0.00004 As
Conc
entra
ion
Destances
0 50 100 150 200 250 300
0.0000
0.0001
0.0002
0.0003
0.0004
0.0005
0.0006
0.0007
Conc
entra
ion
Ce
Destances
0 50 100 150 200 250 300
0.000000
0.000001
0.000002
0.000003
0.000004
0.000005
0.000006 Co
Con
cent
raio
n
distance
64
0 50 100 150 200 250 300
0.00000
0.00001
0.00002
0.00003
0.00004
Cr
Con
cent
raio
n
distance
0 50 100 150 200 250 300
0.000000
0.000001
0.000002
0.000003
0.000004
0.000005
0.000006
0.000007
Eu
Con
cent
raio
n
Distance
0 50 100 150 200 250 300
0.000000
0.000001
0.000002
0.000003
0.000004
0.000005
Con
cent
raio
ns
distance
Hf
Fig.(4-10) Change average concentrations of different elements in plant samples with
distance
65
0 50 100 150 200 250 300
0.00000
0.00005
0.00010
0.00015
0.00020
0.00025
0.00030
0.00035
Con
cent
ratio
n (m
g/kg
)
Distance (m)
Ce
0 50 100 150 200 250 300
0.000000
0.000005
0.000010
0.000015
0.000020
0.000025
0.000030
Con
cent
ratio
n (m
g/kg
)
Distance (m)
As
0 50 100 150 200 250 300
0.000000
0.000001
0.000002
0.000003
0.000004
0.000005
0.000006
Conc
entra
tion
(mg/
kg)
Distance (m)
Co
Fig.(4-11) Change average concentrations of different elements in soil samples with
distance
66
AS
-76
Ce-1
41
Co-6
0
Cr-
51
Eu-1
52
HF
-181
K-4
2
Lu-1
77
LA
-140
NA
-24
FE
-59
SC
-46
Pa-2
33
Sm
-153
Br-
82
1E-10
1E-9
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3
Co
nce
ntr
aio
n at 70m
at 60m
at 300m
Plant sampls
Fig.(4-12) Change the concentrations of different elements in the plant samples with
distance
67
4-3 In Case of Kohl:
Out of the three tested set of samples, one contained in excess of 87% lead
(from Africa), the other two samples from USA and France not detected. While the
percentage of Al was comparable in the three samples, the Cd concentration was in
excess in sample 3 (from Africa) and lowest in sample 1 (from France), as indicated
from EDX measurements see table (4-6) and Fig (4-13).
The elemental analyzer measurements showed that the prevailing element in
sample 1 is carbon (88.34 %), whilst it is minimal in sample 3 (0.25 %) see fig. (4-8).
the latter low ratio was not detected by EDX, but was detected by the elemental
analyzer techniques within the experimental error. The cupper and iron concentrations
were found to be comparable among the sets of samples as revealed by AA-MS (see
table (4-7), and Fig (4-14).
There were no significant concentration differences among other elements (e.g. Mn,
Zn, Si and K) in the three samples according to AA-MS measurements, which is also
consistent with EDX measurements. Of interest, among the the detected elements in
the composition of samples is Pb element, which constitutes the main hazardous
element. From the previously described measurements, one can note that the highest
concentration of Pb is found in the natural, unprocessed sample from African sources,
while the concentration of Pb was significantly reduced in the other two samples
manufactured in France and USA. Thus, the chemical treatment during manufacture
has its impact on Pb content of the processed product.
68
Table (4-6) Elements concentration (%) in the three samples of kohl as
detected by EDX.
Element Sample 1(France) Sample 2 (USA) Sample 3 ( Somalia,
Africa)
C 94.29± 4.7145
52.14± 2.607
ND
O ND
16.83± 0.8415
ND
Al 1.04±0.052
1.16± 0.058 0.84±0.042
Si 1.14±0.057
2.74± 0.137
ND
Ca ND
0.71±0.0355
ND
Mn ND
0.24±0.012
ND
S 0.05±0.0025
ND 12.34±0.617
K 0.48±0.024
ND ND
Ti 0.48±0.024
ND
ND
Fe 0.39±0.0195
24.39±1.2195
ND
Cu 1.27±0.0635
0.19±0.0095
ND
Zn 0.87±0.0435
1.59±0.0795
ND
Pb ND ND
86.82±4.341
* ND : Not Detected
69
Al Si Ca Mn S K Ti Fe Cu Zn Pb
0
20
40
60
80
Elem
ents
conc
entra
tion (
%)
Element
Africa
C O Al Si Ca Mn S K Ti Fe Cu Zn
0
20
40
60
80
100
Elem
ents
con
cent
ratio
n (%
)
Element
France
C O Al Si Ca Mn S K Ti Fe Cu Zn
0
10
20
30
40
50
Eleme
nts co
ncen
tratio
n (%)
Element
USA
Figure (4-13): Elements concentration (%) in the three samples of kohl
as detected by EDX.
71
Table (4-7) Heavy Elements Concentration in (mg/L) (ppm) in the samples of
kohl as measured by atomic absorption spectroscopy AA- MS
Element Sample 1(France) Sample 2 (USA) Sample 3 ( Somalia, Africa)
Cd
2.51±0.01 10.67±0.35 25.97±0.74
Pb
58.57±1.05 137.7±4.78 995.5±6.92
Mn
69.95±1.56 46.13±1.12 68.98±1.48
Cu
6.03±0.05 4.45±0.01 5.55±0.03
Zn
4920±23.5 3649±20.7 5173±26.2
Fe
2330±15.1 2325±15.2 2415±16.2
K
8412±49.2 6124±32.4 6651±35.8
Table (4-8) Concentration of (C, O, S) in the above sample (%) using elemental
analyzer
Element
Sample 1(France) Sample 2 (USA) Sample 3 ( Somalia,Africa)
C
88.34±4.417 52.07±2.6035 0.2584±0.01292
O
4.896±0.2448 8.733±0.43665 2.2522±0.11261
71
Cd Pb Mn Cu Zn Fe K
0
1000
2000
3000
4000
5000
6000
7000
Ele
men
ts C
once
ntra
tion
in (m
g/L)
Element
Africa
Cd Pb Mn Cu Zn Fe K
0
2000
4000
6000
8000
Elem
ents
Conc
entra
tion i
n (mg
/L)
Element
France
Cd Pb Mn Cu Zn Fe K
0
1000
2000
3000
4000
5000
6000
Elem
ents
Conc
entra
tion i
n (mg
/L)
Element
USA
Figure (4-14): Elements Concentration in (mg/L) in the samples of kohl
as measured by atomic absorption spectroscopy AA- MS
.
72
.
The Gamma-ray spectrum of sample 3 (Galena), obtained using long irradiation
facility of the ET-RR-2 reactor is given in Figure (4-15). Qualitatively, the Thermal
NAA results revealed main four different elements that were determined using short
and long lived isotopes measured by HPGe detector see table (4-9),(4-10).
For quantitative analysis, the well-resolved and pronounced -ray lines for each
isotope have been selected to measure the concentrations of the four elements of the
kohl sample. In order to estimate the concentration value of each element, the well-
known analytical equation (46)
was used. The thermal neutron flux of ET-RR-2 was
about 1011
n/cm2.s.
Table (4-9) The elemental concentration values for the Short lived radionuclide
in sample 3 under investigation
Element Concentration (ppm)
Al 07930
Mn 689800
V 1.7000
Th 0.1200
Table (4-10): The elemental concentration values for the long lived radionuclide
in sample 3 under investigation
Element Concentration (ppm)
Ag 11831.7
Sb 7145.30
Zn 6.82000
Cd 20.8300
73
Sb124
Ag110
Zn30
Sb124
Sb124
Sb124
Cd117m
Energy (K
eV)
Fig.(4-15) (Gamma-Ray Spectrum of sample no. 3 (Galena) received for long
irradiation facility of ET-RR-2 reactor)
74
CHAPTER 5
COMMENTS ON THE RESULTS OBTAINED AND
CONCLUSIONS
5-1 In Case of Fertilizers
Toxic elements such as Co and Sb have the great importance in toxicological
studies. The concentration of Cobalt in the samples under investigation ranges from
10.2 to 28.5 ppm. The highest concentration of Co was found in sample 3 (Fig. 3 (A)),
also the level of Antimony in sample no. 3 was much higher than other samples.
Figure 1 (B) shows the content of rare earth elements such as Ce, Hf, and Eu in the
investigated samples, where Ce was appeared only in sample no. 2, while the
concentration of Eu in sample no. 3 was much higher than others. But Hf was found
slightly high in sample no. 1 and sample 2 and does not appeared in sample no. 3.
Also, the contents of heavy metals Fe, Zn, Co, Cr, and Sc were determined, where Fe
shows the highest concentration in sample no. 3 (Fig. 3(C)). Biologically, Iron is
known to be essential for different physiological bioprocesses in plants and increase
shoot dry weight in soil. Zn, on the other hand increases the seeds yield. While Ca is
the major component of the phosphate rocks, because these rocks are mostly
phosphorus of marine sedimentary origin. Also Sr is abundant in sample 3 because its
chemistry is similar to Ca. Where, Chromium is naturally found in the environment,
occurring in soils, rocks and living organisms. The biological effects associated with
chromium uptake are diverse and depend on its oxidation state. The chromium state is
non-carcinogenic because of its inability to bind with carriers encountered in cell
membranes. While Aluminum was found in the three samples and have the
concentrations of 0.614%, 3.35%, and 60.67ppm in sample1, sample2, and sample3,
respectively. The concentration values have been determined by XRF & ICP just for
sake of comparison. Tables 1-4 show the discrepancies of the results. The elements
75
determined by inductively coupled plasma mass spectrometry (ICP-MS) were 52
V,
86Rb,
137mBa,
152Eu,
109Pd,
51Cr,
181Hf,
131Ba,
124Sb,
60Co,
77Ge,
142Ce,
160Tb,
147Nd,
103Ru,
131Ba,
59Zr,
76As,
77Ga,
134Cs,
85Rb, and
182Ta, and also elements determined by
x-ray fluorescence were 56
Mn, 28
Al, 59
Fe, 47
Ca, 59
Zr, 71m
Zn, and 859
Sr.
5-2 In Case of kohl
Of note, the Al and Cu concentration values obtained from Thermal NAA are
consistent with their corresponding values obtained using EDX and AA-MS
respectively.
Lead is harmful to all adults, children and infants. It is particularly harmful to
the developing brain and nervous system. Lead mainly enters the body through oral
ingestion or inhalation of lead dust. Of lead that reaches the digestive tract, adults
absorb about 11% and children absorb 30-75 %. Less than 1 % of lead is known to be
absorbed through digestive tract, adults absorb about 11 % and children absorb 30-75
%. Less than 1 % of lead is known to be absorbed through the skin. Lead poisoning is
a global problem, considered to be the most important environmental disease in
children. Pregnant women and children under 6 years of age absorb lead in the highest
quantities, and even low levels of lead exposure are considered hazardous to pregnant
women. Lead exposure during the first trimester of pregnancy has been found to
cause alterations in the developing retina, thus leading to possible defects in the visual
system in future. Lead poisoning has been linked to juvenile delinquency and
behavioral problems. Young children are particularly susceptible to lead poisoning
due to their normal hand-to-mouth activity and because of the high efficiency of lead
absorption by their gastrointestinal tracts. Chronic low-dose lead exposure was found
to cause renal tubular injury in children, while in adults, it was associated with poorly
controlled hypertension. The blood levels in 19 children ranged between 60 and 257
mg/dl. Two of these patients died before starting treatment, and three children died
76
during treatment. Among the children who recovered, four had neurological sequelae.
The source of lead in 11 patients was confirmed to be kohl. Recently, a seven-month-
old baby was found to have a blood lead level of 39 mg/dl due to use of kohl. In the
USA, kohl and "kajal" from the Middle East were considered among the unapproved
dyes in eye cosmetics that contained potentially harmful amounts of lead. Similarly,
certain traditional digestive remedies also contain harmful levels of lead. Little is
known about lead poisoning in Saudi Arabia. Studies have suggested that kohl in
Saudi Arabia might be a cause of lead toxicity, but no detailed investigation has been
undertaken to date.
In addition to lead, aluminum might also be toxic at both environmental and
therapeutic levels. Aluminum exposure, apart from causing cholinotoxicity, can
induce changes in other neurotransmitter levels since neurotransmitter levels are
closely interrelated.
Antimony, on the other hand, has been found to induce DNA strand lesions but
not DNA–protein crosslinks. Fumes from melting antimony cause dermatoses and
skin lesions . Bearing in mind the reports on aluminium and antimony toxicity and
many alarming reports on the association of kohl with lead poisoning in different
countries.
77
CONCLUSIONS
The elemental concentration values of 31 elements in the fertilizer samples, have
been determined by applying a sensitive nondestructive analytical techniques such as
INAA. It has also shown enough sensitivity to determine the concentrations of several
trace and rare earth elements, The concentration values of elements were compared
with the corresponding elements obtained by the ICP-MS and XRF techniques, for the
same samples.
Phosphorus fertilizers contain varying amounts of heavy metals and other rare
earth elements as contaminants from either phosphate rock ores or other ingredients
used in the phosphate fertilizer industry. As some heavy metals are potentially
harmful to human health, attention is being given to its avenues of entry into the
human food chain. Uptake of such elements by plants consumed directly or indirectly
by humans is one avenue of entry, so the effects of heavy metal contaminants in
phosphate fertilizers are of concern. Commercial fertilizers have been used for
decades and will probably continue to be used for many decades to come. Hence, even
low annual accumulations may finally build up undesired concentrations in soil,
especially where fertilizers with high heavy metal or rare earth element concentrations
are used.
Thus, a total of three synthetic and natural eye-liner samples of known origin
that are commercially available in the Egyptian market were analyzed using Energy
Dispersive X-ray (EDX), Atomic Absorption Mass Spectroscopy (AA-MS) and
elemental analysis using Thermal Neutron Activation Technique (TNAT) for the
natural one in powder form. It was found that lead (>86%) represents the main
hazardous element in the natural eye-liner from African sources. Aluminum and
Antimony were also found in the later sample in considerable concentration 0.92%
and 0.71% respectively. For the synthetic two samples from French and American
sources, the major hazardous element found to be Carbon in high concentration 94%
78
and 52% respectively. The study raises ethical and medical concerns about the
implications of using eye-liners with high toxic elemental content in Egypt.
79
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85
STUDIES ON ELEMENTAL CONTENTS
OF SOME BIOLOGICAL AND ENVIRONMENTALMATERIALS
USING NUCLEAR AND ATOMIC TECHNIQUES
دراسات حول المحتوى العناصرى لبعض المواد البيئية والبيولوجية
نات نووية وذريةاباستخدام تق
(باللغة العربية)لرسالة عام لملخص
باالتعر علاى العوا ار النةو اة حاياثاهتم الباحثون فى مجاا الييياااا الووةااة ةالتقبي ياة إ
مةو احهاا النختلياة ةكلاا باساتخيام الت ا اا النركباة ةحديااي ار حركييهاا فاى ة الصاواعية للنواد
ظهار فاى كناا , ة ةالتي ح تخيم أحيث ظم الةشا الام م لهاذا الغار نتقورالووةاة ةالذراة ال
. الآة ة الأخيرة مئا البدوث شارحة هذه الاوظم ةحقبي احهاا فاى الايةراا العلنياة الندلياة ةاليةلياة
سنية اليراعياة منثلاة للناواد البيئياة ةكاذلا ماواد الةدال حواةلت هذه الرسالة فدص ةحدليل مواد الأ
. ةالتى حنثل مواد بيولوجية
ااا ا ااا وةاااة ةكراااة بالغااة التقااور ةموهااا علااى ساابيل النثااا ح اهااذا الغاار ح لاسااتخيم
شاعة الأ ا اح ة التشيط التشعيعى بالويوحر ا ةح ا ة الامتصاص الذرى باستخيام البم ما الن تدثة
-: فى إاجا كل ح ا ة على حيةعلى ل ى الضوا ةفينا الي يةال يو
ح ا ااة التشااعيل بالويوحر ااا حياا ا ااتخيم النياعاال النصاار الثااا ى كنصااير للوتيوحر ااا -:أةلاً
النقلاو فدصاها ح ا ط هاذه الويوحرة اا علاى العيواا ةهواا فى قلر النياعل النتولية الدراراة
آشاعة الجاماا عوهاا اد ةحوات وتشعيل لتتعامل مل أ واة عوا ر هاذه الناالنتواجية داخل كب ولا الة
ةالةيااااة ليااتم حدياااي النعاااارة باسااتخيام مودويااا تااي حيدااص فينااا بعااي يااة ةالفااى شااةل أ يااا جام
ةكلاا لةال عيوال علاى حاية بتديااي ( n ,γ) حهاا ب ااً ل واعاي التياعال الواوة ا وعية العوا ر ةكني
بللااورا حاايث أ ااواك الةواشاا الجاميااة ةهااى ةا ااتخيم لااذلا أل ةال يااا فتاارا مويااة للتشااعي
الجرمااا يوم بااالن الو اااةة كنااا ا ااتي علااى وعيااة هااذه العوا اار ةكنيتهااا ببرمجااة بعاا النعااادلا
. عوا رىوظام الةش الب الخا ة
86
لبم مااا اجهااا مقيااا الةتلااة كة النوباال الأاااو ى ماا ح ا ااة الامتصاااص الااذرى باسااتخيام :ثا ياااً
(ICP- MS)الن تخيمة الن تدثة
م حعتبار ةهاى 12111ةقايرة فصالل ( JMS- PLASMAX2) ةا انى هاذا الجهاا
أعلى قيرا اليصل فى العالم لنثل هاذا الواوك ما الأجهاية مناا انةوال ما التغلار علاى
لعوا ااار ةالنركباااا كا الةتااال لمشااااكل التاااياخم الواشااائة أثوااااا عنلياااا التدليااال
كنا أن الجها ميةد بجها م ح لييرى انةول م حدليل العيوا الصلبة على . اربةالنت
حالتها بيةن أى معالجا كينيائية
AASح ا ة إستخيام جها مقيا الإمتصاص الذرى -: اثالث
Atomic Absorbtion Spectrometer
تدلياال العوا اار جهااا مقيااا الإمتصاااص الااذرى ةالناايةد بياارن جرافيتااى عبااارة عاا جهااا ل
ةا ااتخيم الجهااا ل يااا حركياايا العوا اار فااى . بإسااتخيام ياا الإمتصاااص الااذرى لةاال عوصاار
ةقيرحل التدليلية حصال . فى العياي م التقبي ا ةالن تخيمة مختل أ واك العيوا ال ائلة أةالصلبة
ة حنةوال ما حدليال ما البواحاا الجرافيتيا ااييالعةالجهاا مايةد ب. إلى جيا ما النلياون ما الجارام
العيوا الصلبة كنا هى ةبايةن أى معاامم كينيائياة ةالتاى حصال قايرة التدليال بهاا إلاى جايا ما
الترليون م النادة
(PPT ) ةالجها ميةد بوظام(HG-AAS ) الذى انةوال ما قياا عوا ار ال اليويوم ةالتلورااوم
. ة لهذه العوا رةالأ تنون ةالير يخ ةاليئبا ع راا حغيير حالة الأك ي
.استخيام الأشعة ال يوية -:رابعا
XRF X-ray fluorescence spectrometer))مقيا الأشعة ال يوية اليلوراة -1
ا ااوم هااذا الجهااا بعناال حدلياال لياار إحمفااى للعيوااا الصاالبة ةال ااائلة للعوا اار ماا الصااوداوم إلااى
مللينتار مربال ما 1حدليال موق اة قاي حصال إلاى كنا أن الجها ميةد بةاميرا حنةول ما . اليورا يوم
ةللجهاا مايى ةاسال . ةللجها إمةا ية عنل التداليل الةنياة للعوا ار ةالأكاسايي ةالنركباا . العيوة
واد النختلية مثل النعادن ةالأحجاار الةراناة ةالصاخور ةال ايراميا ةالألذااة م التقبي ا فى الن
87
ةالبولينااارا ةالأساانية ةم تدضاارا التجنياال ةالاايها ا ةالنياااه النعي يااة ةالتقبي ااا الصااواعية
. ةالقبية ةالبيئية ةالبترة ةأشباه النو م
Energy Dispersive Energy (EDX)مقيا الأشعة ال يوية كا القاقة النتشتتة -2
جاايا ماا النليااون ماا 111ا ااوم هااذا الجهااا بالتدلياال الاايقيا الغياار إحمفااى لىسااقح الصاالبة حتااى
ةكذا انةول أخاذ اور . الجرام م النادة لعوا ر الجية اليةرى بيأ م الةربون ةحتى اليورا يوم
ةالتصاوار فاى ظارة حيراان ةالجها مايةد بإمةا ياة التدليال. أل مرة 311مةبرة لىسقح حتى
موخي منا انةول م فدص جنيل العيوا العا لة للةهرباا بيةن ما مو ل ةكذا العيواا التاى
. حدتوى على ر م الر وبة بيةن أى حجهيي سابا ةاعتبر الجها كنجس حدليلى موضعى
:لأهدافهذاالعم
- :اهي العنل فى هذه الرسالة إلى
دااص العوا اارى الاايقيا لتدياااي وعيااة ة اار حركيااي العوا اار النةو ااة لاابع إجااراا الي :أةلاً
ةبع م عيوا الترباة ةالوباا النجااةرة الأسنية الن تخيمة مدلياً فى عنليا الت نيي اليراعى
ةكلاا بغار التعار علاى العوا ار الأساساية ةكاذلا العوا ار الغيار لنصول الأسنية اليراعياة
.مرلو فيها
إجراا اليدص ةالتدليل العوا رى لناواد الةدال الن اتورد ةالن اتخيم مدليااً للوقاو علاى :ثا ياً
وعيااة العوا اار النةو ااة لهااذه النااادة البيولوجيااة الهامااة ةالتااي لا لوااى عاا اسااتخيامها لى يااا
.ةالبالغي ةكلا لخقورة هذه العوا ر على قاك العي ةسممة العيون بصية عامة
تقبي ااا النثلااى لاسااتخيام الااوظم الووةاااة ةالذراااة فااى مجااا التقبي ااا العنليااة إجااراا ال :ثالثاااً
.ةاليدص العوا رى لنثل هذه النواد البيئية ة البيولوجية
كنا حواقش هذه الرسالة الوتائ العنلياة التاي حام الدصاو عليهاا ةحديااي مايى الاساتيادة موهاا ةكاذلا
.دياي ر حركييهاميى الخقورة النتوقعة للعوا ر التى حم ح
88
دراسات حول المحتوى العناصرى لبعض المواد البيئية والبيولوجية
نات نووية وذريةاباستخدام تق
رسالة م يمة م
عبدالعزيزولاءمصطفىمحمد
(النوويةماجستيرفىالفيزياء)
للدصو على درجة
دكتوراةالفلسفةفىالفيزياء
(اليييااا الووةاة)
قسمالفيزياء
جامعةالزقازيق-كليةالعلوم
1023
89
دراسات حول المحتوى العناصرى لبعض المواد البيئية والبيولوجية
نات نووية وذريةاباستخدام تق
رسالة م يمة م
ولاءمصطفىمحمدعبدالعزيز
(ماج تير فى اليييااا الووةاة)
للدصو على درجة
ةفىالفيزياءدكتوراةالفلسف
(اليييااا الووةاة)
:العلمىالإشرافلجنة
نجيبعبدالرحمنعشوب.د.أ(2)
بهيئةالطاقةالذريةالفيزياءالنظريةأستاذ
إبراهيمإسماعيلبشطر.د.أ(1)
جامعةالزقازيق–الفيزياءالنوويةبكليةالعلومأستاذ
دحسانعبدالمنعممحمو.د.أ((3)
(متوفى)بهيئةالطاقةالذريةالمتفرغالأستاذ
قسمالفيزياء
جامعةالزقازيق-كليةالعلوم
91
دراسات حول المحتوى العناصرى لبعض المواد البيئية والبيولوجية
نات نووية وذريةاباستخدام تق
رسالة م يمة م
عبدالعزيزولاءمصطفىمحمد
(ييااا الووةاةماج تير فى الي)
للدصو على درجة
دكتوراةالفلسفةفىالفيزياء
(اليييااا الووةاة)
ةقي حنت مواقشة الرسالة ةالنواف ة عليها
اللجوة
:الحكملجنة
نجيبعبدالرحمنعشوب.د.أ
بهيئةالطاقةالذريةظريةالفيزياءالنأستاذ
إبراهيمإسماعيلبشطر.د.أ
جامعةالزقازيق–تاذالفيزياءالنوويةبكليةالعلومأس
1023//تاريخالموافقة