STUDY OF CHEMICAL ELEMENTS IN BLACK SAND
AND THEIR RELATIONSHIP WITH SOIL
VARIABLES ON EL-BROLIS –LAKE COAST –EGYPT.
Abd El-Salam M. Elwa
Soil Chemistry and Physics Department, Water Resources and Desert Soils Division,
Desert Research Center, El-Matariya 11753, Cairo, Egypt.
E-mail- abdelsalamelwa33@yahoo.com
Key Wards ; Black sand . El –Brolis , Rashid , Trace element.
ABSTRACT.
Three profiles were selected number 1,2 from EL-Brolis –Lake coast
and profile number 3 from Rashid where the samples are black sand and
every profile contain tow layer of surface and subsurface Physical and
chemical properties of the black sand are determined where the texture is
sand Soil reaction (pH) is alkaline, CaCO3% ranges from 0.55 to 1.10 % ,
organic matter varied from 1.74% to 4.04%, salinity of black sand is high
varied from 2.27 to 22.29 dSm-1. The cation and anion(mmolc/l ) followed
this order Cl - > Na+ > K+ >SO4
-- > Ca++> Mg++ > HCO3
- > CO3 -- . Total and
extractable of trace elements in international limits values and NPK in the
studied area varied form deficient to sufficient.
This study determine the concentration of trace elements ( Total
& extractable ) and find a relation between soil variables and the content
of trace elements.
Fig.(1)Location of the studied area
Egypt. J. of Appl. Sci., 36 (5-6) 2021 174-184
INTRODUCTION
The Egyptian black sands placer deposits on the Mediterranean
Coastal Plain contain many mineral species as they have been derived
from igneous and metamorphic rocks (Higazy and Naguib (1950).
Many studies were carried out dealing with the mineralogical
composition, grain size distribution, origin of the sediments as well as
their economic considerations. Black sand constituents include six heavy
economic minerals; namely magnetite, ilmenite, monazite, zircon, rutile
and garnet. Monazite, zircon and rutile minerals contain number of
elements necessary for the nuclear industry e.g. uranium, thorium,
zirconium, hafnium, titanium and rare earths elements. Thus, the
evaluation of these raw materials in the Egyptian black sands placer
deposits would be calculated on the basis of the reserves of monazite,
zircon and rutile mineral content in localities along the Mediterranean
Coastal Plain; namely Rosetta, Baltim, Damietta and north Sinai.
(Dabbour et al., ( 1990)
Late Miocene and before the completion of the High Dam in May
1964, the River Nile was discharging huge quantities of sediments
during the annual flood seasons in the Mediterranean Sea. These
sediments were the final products of the disintegrated materials from the
two main drainage areas of the Nile Basin which cover an area of about
3,000,000 km2 i.e. The Equatorial Plateau (igneous rocks) and the
Ethiopian Plateau (Said,(1981 ).
Missak, and Attia, (1981). Chosen four localities for geological
reserve evaluation for monazite, zircon and rutile are considered to be the
principal black sands deposits. The first locality is on both sides of
Rosetta promontory. It extends from Idku Lake outlet to El Burrullus
Lake openning. This stretch is about 70 km long and its width varies
from about 200 m to about 5000 m with an average width of about 800
m. The area is characterized mainly by beach deposits except west
Rosetta outpouring sector which has coastal plain sand dunes. The depth
of the black sands in this area reaches about 9 m. Beyond this depth, the
sand fraction decreases to be less than 40% while the clay fraction
constitutes the 193 major percentage. Above the mentioned depth, the
sand fraction generally exceeds 60% of the sediments.
The second locality is the coastal plain sand dune belt in which the
heavy minerals content reaches up to about 35% and covers the area from
Burg El Burrullus village eastward to El Gharbia Main Drainage, a
stretch of about 15 km long and average width of about 800m. The height
175 Egypt. J. of Appl. Sci., 36 (5-6) 2021
of the sand dunes in this area reaches up to 15m, however, an average
height of 5 m will be considered. Assuming that the beach sediments
under the sand dunes reach about 10m depth, the thickness of the deposit
in this area will be considered as 1 5 m.
The third locality is the north western part of El Manzalla Lake and
the beach area just east of Damietta outpouring. The depth of this deposit
will be 10 m and the area is about 30 km2. This area is characterized by a
series of parallel sand bars called "Barr" trending generally northwest
and are separated by longitudinal lagoons called "Tawal". The
mechanism of formation of these parallel sand bars was attributed to the
result of the accretion of the bottom sediments of the continental shelf by
the wave action and the continuous accumulation of these sands till the
sand bar became exposed on the surface of the sea water leaving a
longitudinal lagoon behind it.
The last locality is the north Sinai coastal plain sector which
extends between the eastern openning of El Bardawiel Lake at El Zaraniq
in the west and El Arish town in the east. This stretch is about 20 km in
length and about 500 m width It is characterized by beach deposits lined
from the south by north Sinai sand dune belt .. The depth of the deposit in
this area is about 10 m. (Missak, and Attia,(1981).
Monazite Mineral:
The mineral monazite is the world supply source for both rare
earth elements and thorium. Chemically the mineral is an orthophosphate
of rare earth elements and thorium; (REE, Th)PO4. The rare earth oxides
represent 60% of the mineral and consists mainly from the elements
which have low atomic numbers (e.g Lanthanum ”La”, Cerium ”Ce”,
Praseodymium ”Pr”, Neodymium ”Nd”) and known as light rare earths
group. The predominant component of the rare earths in monazite is
cerium, which often constitutes up to 45% of the total rare earths content,
so the rare earths known as “cerium group” (Ellis 1994). The rare earth
distribution in monazite was variable depending upon their location, i.e.
the rare earth elements from different locations had not exactly the same
distribution (Table 1).
Table (1): Rare Earth Distribution in Monazite from Different
Locations (Gupta and Krishnamurthy 2005)
Egypt
(Mostafa
2009)
Australia
Brazil
China
India
Rare U.S.A
earth
oxide
Capel Queensland
Mount
Idaho Florida Weld
La 26.23 17.50 23.00 23.35 24.00 26.00 23.9 21.50 23.2
Ce 46.14 43.70 46.00 42.70 47.00 51.00 46.0 45.8 44.7
Pr 6.02 5.00 5.50 4.10 4.50 4.00 5.0 5.3 4.7
Nd 16.98 17.50 20.00 17.00 18.50 15.00 17.4 18.6 17.6
Egypt. J. of Appl. Sci., 36 (5-6) 2021 176
Thorium “Th” together with the heavy rare earth element “yttrium Y”
are usually present substituting for cerium, etc, so, thorium amount
ranges from 4% up to 12% ThO2 are usually reported. Monazites are also
reported to be contain uranium which ranges from trace amounts up to
values as high as 1.0% U3O8
(Gupta and Krishnamurthy 2005).
Monazite Occurrence and Distribution:
Egyptian monazite was found in beach sands and sand dunes along
the Nile Delta recent shore line in a zone extending from Rafah to Abo
Qir, East of Alexandria. It was found also in sand bars isolating the
lagoon lakes of El-Bardawil, El-Manzalah, El-Burullus and Edku from
the Mediterranean Sea (Mostafa 2009). However, these black sand
deposits have actually been carried by the River Nile and laid down in
the Mediterranean Sea and later transported to its shores by water
currents, winds, waves or others. The chemical composition of the
Egyptian and the different monazite sands was shown in table (2).
Table (2): The Egyptian and Different Monazite Sands
Composition
Constituent, wt%
Egyptian (Mostafa
1995)
Australian (Gupta
2005)
Indian
(Gupta 2005)
RE2O3
ThO2
P2O5
SiO2
Others
61.17
5.75
27.8
0.7
4.58
58.5
6.4
27.5
2.83
4.77
58.60
8.8
30.1
1.7
0.8
PHYSICAL PROCESSING OF BLACK SANDS:
Monazite sand concentrate was obtained as a by product during the
successive separation and concentration of the different economic
minerals through physical processing techniques for black sands. These
separation procedures utilize a combination of the following well
established industrial techniques (Gupta and Krishnamurthy 1992):
1- Gravity separation using shaking tables ( utilizing differences in
specific gravity , shapes and grain size in fig.2.
177 Egypt. J. of Appl. Sci., 36 (5-6) 2021
Fig. (2): Separation of Valuable Minerals and Monazite from Black
Sands by Physical Methods
MATERIALS AND METHODS
Soil samples analyses.
Textured of the soil samples was determined with the dry sieving
method (Piper 1950) .
CaCO3 content was determined volumetrically using Collin's
calcimeter according to Jackson (1973).
Organic matter content was determined by the method outlined by
Jackson (1973).
Determination of pH in the soil extract was carried out by Beckman
glass electrode pH – meter, Black (1983).
Electrical conductivity (EC) of the soil saturation extract as well as
soluble anions and cations were determined following the methods
described by Jackson (1973). For convenience, CO3
--,Cl-, HCO3
-,
Shaking Tables
Heavy Minerals
Silicates
Low Intensity Magnetic
Separation
Magnetic
Magnetite
Nonmagnetic
High Intensity Magnetic
Separation (stage "1")
Conductor
High Intensity Magnetic
Separation (stage "3")
Magnetic
Nonconductor
High Intensity Magnetic
Separation (stage "2")
Nonmagnetic
Nonmagnetic
Magnetic
Zircon Monazite Ilmenit
Black Sands
Egypt. J. of Appl. Sci., 36 (5-6) 2021 178
were determined titrimetrically while SO4
-- was determined
gravimetrically by precipitation as barium sulfate.Soluble Ca++ and
Mg+ were determined titrimetrically using the versenate solution
while Na+ and K+ were determined by flame Photometry, as
described by Black (1983).
Cation exchange capacity (CEC) and exchangeable cations were
determined following the methods described by Jackson (1973).
Total trace metals contents in the soil samples (Zn, Cu, Ni, Co, Cr
and Cd) were determined by the Ionic Coupled Plasma (ICP), after
digestion of the samples with a ternary acids mixture of HNO3,
H2SO4 and HClO4, as recommended by Hesse (1971).
Chemically – extractable amounts of the same elements were
extracted from soils by Diethelene triamine pentaacetic acid
(DTPA) and determined by Inductively Coupled Plasma, (ICP).
Lindsay and Norvell (1978).
RESULTS AND DISCUSSION
1- Characterization of the studied soils;
Studied of the soil texture were indicated from Tables (3 and 4)
which the result reveal that the soil samples is sand varied form very
coarse sand to fine sand (VCS to FS) .Soil reaction in this studied soil is
alkaline as indicated by pH values which ranged from 8.09 to 8.74
.Calcium carbonate content ranes from 0.33 to 1.10 % .The organic
matter ranged form 3.01 to 4.04 % .CEC for the studied soils ranges from
1.18 to 2.74 mmol /100 g. Soil salinity is very high varied from 2.27 to
22.29 dS/m this due to the proximity of the profiler to the seashore. The
cations and inions of the studied soil are generally take this order Cl - >
Na + > K + > SO4 -- .Ca ++ >Mg++ .HCO3 - > CO3 –
Thus to use this regions of black sands in agriculture, it must be
treated to eliminate this salinity.
Table (3)Dry sieving of the studied soil on EL-Brolis Lake coast-
Egypt.
Location
Profile
.No.
Sample
No.
Depth
(Cm )
VCS %
CS
%
MS
%
FS
%
VFS
%
SI+CL
%
1 - El-Brolis
31o 30 / 20.2// N 1
1 0 – 30 1.33 7.59 21.49 62.26 6.43 0.90
30o 45.// 54.2 // E 2 30 – 60 2.93 7.73 59.92 28.38 0.42 0.62
2-El- Brolis
31o 27 / 13.3 // N
2
3 0 – 30 3.66 9.89 14.61 54.60 13.83 3.41
30o 35.// 31.6 // E 4 30 – 60 4.27 6.78 60.41 27.89 0.33 0.14
3- Rashid
31o 18 / 59 // N
3
5 0 – 30 0.52 0.20 3.55 87.60. 5.80 2.37
30o 16.// 38.1 // E 6 30 -60 0.20 0.15 17.56 76.76 4.31 1.02
.(VCS)Very coarse sand. (CS) Coarse sand , (MS 0 Medium sand, (FS) fine sand
(SL) Silt , (CL) clay .
179 Egypt. J. of Appl. Sci., 36 (5-6) 2021
Table (4) Chemical properties of the studied soils
Prof. Samp. Depth
pH
EC CaCO 3 O.M Cations (Me/l ) Anions (me/L ) CEC
NO. NO. (cm ) ds/m % % Na Me/100g + K+ Ca++ Mg++ CO3
-- HCO3
- Cl- SO4
--
1- El- Brolis
1 0 – 30 8.15 11.97 0.55 3.47 88.48 17.09 10.08 5.15 0.00 0.36 112.50 6.88 1.5
2 30 – 60 8.09 22.29 0.76 4.04 171.98 23.98 19.90 9.85 0.00 2.79 199.00 21.13 1.5
2- El- Brolis
3 0 – 30 8.34 13.66 0.65 3.41 96.47 25.28 11.53 5.06 0.00 1.55 110.60 24.42 2.74
4 30 – 60 8.35 15.59 0.33 3.99 110.87 25.28 13.08 5.97 0.00 1.52 139.99 14.39 1.18
3- Rashid
5 0 – 30 8.73 2.27 1.10 1.74 20.02 1.21 2.50 0.50 0.00 0.60 12.00 10.13 2.54
6 30 – 60 8.18 3.02 1.10 3.01 22.27 1.38 3.10 2.30 0.00 1.20 15.90 13.07 2.54
2- Total trace elements in the studied Black sands.
Data in table (5) listed some trace metals contents of Cd, Co, Cr ,
cu ,Fe , Ni , pb and Zn. The vertical distribution of these elements in all
profiles as Cd, Co and Cr metals content decrease from top to bottom and
the highest values in the surface layer while the lowest values were in
the second layer but as for Cu metal in profile 1. the lowest value in the
surface layer 3.16 mg/kg but the highest value in the second layer was
3.38 mg/kg .Cu in the profile 2 the vertical distribution the highest value
7.58 mg/kg in the surface later and the lower value in the subsurface
layer 0.76 mg/kg .Also in profile 3. the lower value in the surface layer
and the higher value in the subsurface layer. Fe metal content decrease
by increasing the depth of the profiles 1,2 but in profile 3, Fe content
decrease by increasing the depth of the profile.Ni content increasing by
increasing the depth of profile 2,3 but in profile 1 the concentration of Ni
metal increasing by increasing the depth of the profile. Pb metal content
increasing by the depth in all profiles . the highest value in sub surface
layer of profile 2 . 46.47 mg/ kg but the lowest value in the surface layer
in the profile 10.81mg/kg. in the end Zn metal content in profile 1,3 the
content increase by the depth of the profiles. But in profile 2 the content
of Zn metal decrease by increasing the depth of profile. the Maximum
permissible concentrations of trace elements reported by (Kabata-
Pendias and Pendias 2001) are : Cd (cadmium) 5 mg/kg, Co (cobalt) 50
mg/kg, Cr (chromium) 100 mg/kg, Cu (copper) 100 mg/kg, Ni (nickel)
100 mg/kg, Pb (lead) 100 mg/kg, and Zn (zinc) 300 mg/kg.
Table (5)Total trace elements content of black sand in the studied
area of El-Brolis Lake coast –Egypt.
Prof. Samp. Depth Cd Co Cr Cu Fe Ni pb Zn
NO. NO. (cm ) mg/kg
1-El-Brolis
1 0 – 30 2.77 20.9 108 3.16 14680 11.68 14.76 31.65
2 30 – 60 2.42 20.5 45.6 3.38 11720 16.21 22.66 76.35
2-El-Brolis
3 0 – 30 0.98 30.7 198 7.58 25.860 30.44 5.91 59.87
4 30 – 60 0.50 7.34 53.3 0.76 7133 8.68 46.47 17.29
3- Rashid
5 0 – 30 0.88 10.7 52.5 1.09 10520 20.26 0.81 22.17
6 30 – 60 0.75 4.83 37.8 2.70 10820 7.35 12.11 38.43
Egypt. J. of Appl. Sci., 36 (5-6) 2021 180
3- Chemically extractable of trace elements in black sand in the
studied area of EL-Brolis Lake coast –Egypt.
Data in table (6 ) listed concentration of available trace elements in
the studied area black sands Cd, Co, Cr , cu ,Fe , Ni , Si and Zn the
vertical distribution of the metals show Cd metal in profile 1, decrease by
increasing the depth of profile. But in profiles 2,3 Cd metal
concentration increase by increasing the depth of profiles. In Co metals
the distribution increasing by increasing the depth of all profiles ,in Cr ,
Fe , Ni , Zn and Cu metals the concentration decreasing by increasing
the depth of all profiles except Cu and Si metals in profile3. the surface
layer of Cu and Si content lower thane the subsurface layer . The
maximum permissible concentrations of extractable of trace metals in
soil are the following,: Pb – 6,0 mg/kg and Cr - 6,0 mg/kg Ni – 4,0
mg/kg Co – 5.0 mg/kg Zn – 23,0 mg/kg Cu – 3,0 mg/kg Kabata-Pendias
and Pendias 2001.
Table (6) Chemically extractable of trace elements in black sand in
the studied area of EL-Brolis Lake coast –Egypt.
Prof. Samp. Depth Cd Co Cr Cu Fe Ni Si Zn
NO. NO. (cm ) mg/kg
1-El-Brolis
1 0 – 30 0.063 0.090 0.032 0.493 26.98 0.170 23.84 2.63
2 30 – 60 0.024 0.150 0.004 0.397 11.51 0.154 29.28 1.42
2-El- Brolis
3 0 – 30 0.028 0.140 0.037 0.535 36.84 0.172 15.03 1.26
4 30 – 60 0.036 0.145 0.036 0.347 12.87 0.169 23.90 1.43
3- Rashid
5 0 – 30 0.091 0.074 0.032 0.369 47.36 0.190 15.80 1.32
6 30– 60 0.095 0.111 0.009 0.419 45.94 0.006 5.01 1.70
4 - Correlation between trace element and soil variables :
Significant correlations were calculated between trace element and
some physical and chemical properties.
The correlated highly significantly positively between EC / Na+
was (r =0.997), EC/ Ca++ (r =o.997), EC/ Mg++ (r =0.978),EC/K+
(r= 0.912),EC/Cl-1 (r =0.997), EC/ OM % (r=0. 861),EC/HCO3
-2
(r=0.737),EC/SO4
-2 ( r=0.553 ) ,EC/ total Cr (r =o.749), EC/ total Al
(r =0.588), and EC/ total Ca (r =o.950). EC / total. Co (r =0.809), CaCO3/
K+ (r =0.859), OM%/ Na+ (r =0.837), OM%/K (r =0.833), OM%/Ca++
(r =0.844), OM%/ Mg++- (r =0.886), OM%/ Cl-1 ( r =0.863 ) ,Na+ / Ca++
(r =o.999), Na+/ Mg++ (r =0.983), Mg++/Cl-1 (r =0.994), Na+/ K+
(r =0.879), K+/ Ca++ (r =0.883), K+/Mg++/ (r =0.828), K+/Cl- (r =0.903),
Ca++/Mg++ (r =0.984), Ca++ / Cl- ( r =0.993 ), Mg++/ Cl - (r =0.976), pH
/ total Li (r =0.684), pH/ total. Co (r =0.684), pH- /total Ca (r =0.652),
pH/SO4
2- (r =0.696). The statistical analysis revealed that correlated
significantly positively between pH/total Cd (r =0.563).
181 Egypt. J. of Appl. Sci., 36 (5-6) 2021
Data presented in Table (7), indicated that soil Nitrate-N values
were ranged from 17.5 to 66.5, according to Soil Mukashema (2007),
soil Nitrate-N values in the area Fall in the ranges in sufficient level,
expect profile No.1 fall in low level.(N-NO3 < 19 mg/kg ) very low , (19
-37 ) low, (38 – 51 ) moderate, ( 52- 70 ) high , > 70 mg/kg ) very high.
( Extraction method )
Table (7) NPK(mg/kg) in the studied area
K N- No3
P
Profile No. Sample No.
1 1 4.96 106.7 17.5
2 4.76 110.6 21
2 3 4.53 101.3 63
4 5.21 101.9 66.5
3 5 5.93 43.7 64.4
6 6.43 46.6 66.5
While Olsen-P Soil were ranged from 4.76 to 6.43 mg/kg refer that
all profiles are exit in deficient level. K availability (mg/kg) were ranged
from 43.7 to 110.6 refer that profiles are exit in sufficient level expect
profial No.3 fall in deficient level. Where,the critical level of them N as
nitrate in soil solution =50 mg/kg , P = 5 mg/kg and K =80 mg/kg but
they are differing among soils.
Based on the soil analysis, fertility stauts, it is preferable to use the
area for agricultural use. It is preferable to applying different fertilizers
with irrigation water in order to obtain the highest crop productivity
CONCLUSION:
1-The soil texture of the studied soil samples is sand. soil reaction is
alkaline calcium carbonate ,organic matter percent and CEC is very
low. The cationic and anionic ions take this order. Cl - > Na+ > K+
>SO4
-- > Ca++> Mg++ > HCO3
- > CO3 --
2- Total and extractable trace elements in international limits or lesser.
NPK in the studied area varied from deficient to Sufficient . the
Egyptian black sands need treatment to used in agriculture.
3- The Egyptian black sands contain monazite mineral which consider
the source of rear earth elements and thorium. Monazites are also
reported to be contain uranium which ranges from trace amounts up to
values as high as 1.0%
4- Must be removal this radio active elements as uranium , thorium,
zirconium, hafnium, titanium from black sands.
5- To eliminate this radio active elements its very expensive.
Egypt. J. of Appl. Sci., 36 (5-6) 2021 182
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د ا رسة بعض العناصر الکيميائية فى الرمال السوداء وعلاقتها بمتغي ا رت التربة
عمى ساحل بحيرة البرلس – مصر
عبدالسلام محمد عبدالسلام عموة
قسم کيمياء وطبيعة الأ ا رضى – شعبة مصادر المياه والأ ا رضى الصح ا روية-
مرکز بح وث الصح ا رء – المطرية - القاهرة.
تم اختيار ثلاث قطاعات من الرمال السوداء قطاعين من ساحل بحيرة البرلس وقطاع من ساحل
رشيد واظهرت نتائج التحاليل الأتى : -
- -1 قوام التربة رممى وان التربة قموية التفاعل ونسبة کربونات الکالسيوم تت ا روح مابين 5.00
1.51 % ومموحة التربة تت ا روح مابين -1.. %1.15 ونسبة المادة العضوية تت ا روح ما بين 1
.dsm-1 ....2 – ....
.- وکان ترکيز الکاتيونات والانيونات الذائبة کالاتى :
Cl - > Na+ > K+ >SO4
-- > Ca++> Mg++ > HCO3
- > CO3 --
-3 وان الترکيز الکمى والمستخمص لمعناصر الصغرى لمتربة فى مستوى الحدود المسموح بها او
اقل .
-1 واتضح أيضا أن الرمال السوداء تحتوى عمى معادن ذات اهمية اقتصادية کبيرة وتحتوى
عمى عناصر مشعة مثل ا ليو ا رنيوم وهذا يجعل من الصعب إستخدامها فى الز ا رعة الا بعد
التخمص من العناصر المشعة وهذه عممية مکمفة تکمفة عالية اکثر مما سيعود منها عند
ز ا رعتها.
0 – لذا يقتصر التعامل مع الرمال السوداء عمى انها مصدر من مصادر الدخل القومى وذلک
بفصل مافيها من معادن ثمينة واستخدامها فى الأغ ا رض الصناعية الهامة.
Egypt. J. of Appl. Sci., 36 (5-6) 2021 184
