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.

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Date of Discussion: / / 2013

‏

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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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9

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

14

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