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The Pollution from a Phosphate fertilizer Plant
ByBy
Prof.Dr. Tarek ElnimrProf.Dr. Tarek Elnimr
(Tanta University, EGYPT)(Tanta University, EGYPT)
The Pollution from a Phosphate fertilizer Plant and its Effects on Human and ecological Health
ByBy
Prof.Dr. Tarek ElnimrProf.Dr. Tarek Elnimr
(Tanta University, EGYPT)(Tanta University, EGYPT)
In 1900In 1900 14% 14%NowNow ~ 47% (3 billion people) ~ 47% (3 billion people)
The strong industrialization that normally occurs with The strong industrialization that normally occurs with intense urbanization heightens health and intense urbanization heightens health and environmental problems of cities.environmental problems of cities.
Continued exposure to low-level Continued exposure to low-level environmental pollution may be a environmental pollution may be a much more serious problem.much more serious problem.
Many industries are the source of Many industries are the source of low-level environmental pollution low-level environmental pollution with different types of pollutantswith different types of pollutants
• Non-nuclear industries such as phosphate Non-nuclear industries such as phosphate fertilizer industry use raw material containing fertilizer industry use raw material containing significant levels of natural radionuclides. significant levels of natural radionuclides.
• Also, the phosphate fertilizer industry is one of Also, the phosphate fertilizer industry is one of activities leading to environmental pollution activities leading to environmental pollution with fluoride and heavy metals.with fluoride and heavy metals.
Selected industry
is tois to assess the impact of a production plant of assess the impact of a production plant of phosphate fertilizers on the environment.phosphate fertilizers on the environment.
Through determine the contents of fluoride, heavy Through determine the contents of fluoride, heavy metals and radioactivity inmetals and radioactivity in
1.1. various types of environmental samples (sediment, water various types of environmental samples (sediment, water and plant) around the outlet of the wastewater discharge and plant) around the outlet of the wastewater discharge pipes of this plant.pipes of this plant.
2.2. raw materials, end and by-products of phosphate fertilizer raw materials, end and by-products of phosphate fertilizer industry.industry.
The main objective of this workThe main objective of this work
FertilizerSediment
WaterPlant
Experimental Methods (I)
Sampling
Samples Characteristics
Sample Preparation
FertilizerSediment
WaterPlant pH
TOMFluoride
TDS(total dissolved salt)
Bicarbonate
- For fertilizer samples- For fertilizer samples 3gm + 20 ml H3gm + 20 ml H22OO
• Preparation forPreparation for XRF Measurment ground sieved pressed at 9 ton sieved pressed at 9 ton
1 cm diameter pellet1 cm diameter pellet• Preparation forPreparation for F Content Measurment - - For sediment samplesFor sediment samples 1gm + 10 gm(Na1gm + 10 gm(Na22COCO33) melting at 1000) melting at 1000
dissolved to prepare 20 ml dissolved to prepare 20 ml
Radiation hazard indices calculations
Absorbed dose rate: (world average value = 59 nGy h-1)
D (nGy h-1) = 0.462 CU (Bq kg-1) + 0.604 CTh (Bq kg-1) + 0.0417 CK (Bq kg-1)
Radium equivalent (world average value = 370 Bq kg-1)
Raeq (Bq kg-1) = CRa (Bq kg-1) + 1.43 CTh (Bq kg-1) + 0.077 CK (Bq kg-1)
external hazard index Hex :
internal hazard index Hin :
4810259370
KThRa
ex
AAAH
4810259185
KThRa
in
AAAH
ResultsResults
Characteristicsof samples
Radioactivity contentmeasurements
pH, TOM, TDSand Bicarbonate
Fertilizer, sediment, water and plant
XRFmeasurements
Fertilizer andsediment
concentration - correlation - comparison
Fcontent
Fig. 3.1. The fluoride concentration (mg/g) for sediment samples collected from up stream, wastewater discharge pipe and down stream locations. The solid and dotted lines show the mean value for each group and one standard deviation (1σ), respectively.
S6 S7 S80
1
2
3
S1 S2 S3
Flu
ori
de
Con
cen
trati
on
(m
g/g
)
0
1
2
3
S4 S50
1
2
3
mean = 0.91
mean = 1.5
mean = 0.94
Sample Location
W1 W2 W3
F
luor
ide
Con
cen
trat
ion
(m
g/l)
0
1
W4 W5-5
0
5
10
15
W6 W7 W8-5
0
5
10
15
mean = 3.9
mean = 0.45
mean = 2.8
Sample Location
Fig. 3.2. The fluoride concentration
(mg/l) for water samples collected from up stream, wastewater discharge pipe and down stream locations. The solid and dotted lines show the mean value for each group and one standard deviation (1σ), respectively.
Pb
(1
0.5
4 k
eV)
Pb
(12
.63
keV
)S
r (1
4.4
keV
)
Sr
(15
.83
keV
)
Sn
(2
5.2
7 k
eV)
Sb
(2
6.3
5 k
eV)
Ba
(36
.35
keV
)
Ba
(36
.35
keV
)
Pb
(1
0.5
4 k
eV)
Ac
(12
.64
kev
)
Sr(
14
.4 k
eV)
Sr
(15
.83
keV
)
Sn
(2
5.2
7 k
eV)
Sb
(2
6.3
5 k
eV)
Ba
(36
.35
keV
)
Ba
(36
.35
keV
)
Pb
(1
0.5
4 k
eV)
Ac
(12
.64
kev
)
F3
Ba
(36
.35
keV
)
Ba
(36
.35
keV
)
Sb
(2
6.3
5 k
eV)
Sn
(2
5.2
7 k
eV)
Sr
(15
.83
keV
)
Sr
(14
.4 k
eV)
Pb
(1
0.5
4 k
eV)
Ac
(12
.64
keV
)
200 300 400 500 600
Co
un
t R
ate
/Ch
an
nel
0
1
F5
Sr
(14
.17
keV
)
Sr
(15
.83
keV
)
Sn
(2
5.2
7 k
eV)
Sb
pea
k
Ba
(32
.19
keV
)
Ba
(36
.35
keV
)
Pb
fro
m t
he
sourc
e ho
lder
In p
eak
200 300 400 500 600
0
1
Ba
(31
.8 k
eV)
Channel Number
200 300 400 500 600
0
1
Background
F3Fig. 3.3. Examples of some selected X-ray spectra of the fertilizer samples (F3 and F5) and background measured with the Si(Li) detector.
0
100
200
300
400
500
600
S1 S2
1000
2000
3000
4000
5000
Sample Location
S4 S5 S6 S7 S8
Sr
Sn
Ba
Ele
men
t C
once
ntra
tion
(m
g/kg
)
40
60
80
100
120
140 Sn
Fig. 3.4. The elemental concentration (mg/kg) for sediments samples collected from different locations. The solid and dotted lines show the mean value for each group and one standard deviation (1σ), respectively
Table 3.3. The correlation coefficients between the concentrations of any two elements determined in phosphate fertilizer and sediment samples assuming a linear relation.
Sr Sn Ba Fe
Phosphate Fertilizer Samples
Sr 1.00
Sn 0.15 1.00
Ba 0.11 0.3 1.00
Sediment Samples
Sr 1.00
Sn 0.55 1.00
Ba 0.07 0.14 1.00
Fe 0.76 0.29 0.10 1.00
Table 3.5. Continued.
609.
3(21
4B
i)
HPGe
2000 4000 6000 8000
Cou
nts/
Cha
nnel
0
200
400
600
800
1000
NaI(Tl)
0 1000 2000 3000 400010
100
1000
10000
Channel Number
2000 4000 6000 80000
200
400
600
800
1000
0 1000 2000 3000 400010
100
1000
10000
1764
.5
214
Bi
1460
.8
40K11
20.3
21
4Bi
609.
3 21
4Bi
351.
9 21
4Bi
186.
2 22
6R
a
583.
2 20
8Tl
1460
.8
40K
609.
3 21
4Bi
609.
3 21
4Bi
1764
.5
214
Bi
1120
.3
214
Bi
2614
.5
208
Tl
2204
.1 +
244
7.7
214
Bi
1460
.8
40K
F4 Sample F4 Sample
Background Background
511
anni
hila
tion
radi
atio
n
Fig.3.5. Gamma-ray spectra of the fertilizer sample (F4) and background measured using HPGe and NaI(Tl) detectors. All energies are in keV.
Fig. 3.6. The concentrations of 226Ra,
232Th and 40K in phosphate raw (F1 and F2), fertilizer products (F3, F4, F5 and F6), waste product (F7) known as phosphogypsum measured using NaI(Tl) and HPGe detectors.
Sample Code
F1 F2 F3 F4 F5 F6 F70
20
40
60
80
100
120
140
232Th
40K Act
ivit
y C
on
cen
tra
tio
n (
Bq
/kg
)
0
5
10
15
20
25
30
35
226Ra
0
200
400
600
800
1000
1200
1400
1600
232Th
226Ra
NaI
HP
Ge
0
10
20
30
40
50
Act
ivit
y C
on
cen
tra
tio
n
(Bq
/kg
)
0
5
10
15
20
25
Sample Location
S1 S2 S3 S4 S5 S6 S7 S80
100
200
300
400
NaI
HP
Ge
226Ra
232Th
40K
Fig. 3.7. The concentrations of
226Ra, 232Th and 40K for sediment samples collected from different locations measured using NaI(Tl) and HPGe detectors.
0
10
20
30
40
Act
ivit
y C
once
ntr
atio
n (
Bq
/kg)
0
10
20
S1 S2 S30
100
200
300
S6 S7 S8
226Ra
232Th
40K
Sample Location
S4 S5
Fig. 3.8. The activity concentrations of 226Ra, 232Th and 40k for sediment samples collected from different locations. The solid and dotted lines show the mean value for each
group and one standard deviation (1σ), respectively.
Act
ivit
y C
once
ntr
atio
n (
Bq
/l)
-0.2
-0.1
0.0
0.1
0.2
0
1
2
W1 W2 W30
1
Samples Locations
W4 W5 W6 W7 W8
226Ra
232Th
40K
Fig. 3.9. The activity concentrations of 226Ra, 232Th and 40k for water samples collected from different locations. The solid and dotted lines show the mean value for each group
and one standard deviation (1σ), respectively.
0
5
10
15
20
25
Act
ivit
y C
once
ntra
tion
(B
q/kg
)
0
10
20
30
40
50
P1 P2 P3
600
700
800
900
1000
1100
P6 P7 P8
226Ra
232Th
40K
Sample Location
P4 P5
Fig. 3.10. The activity concentrations of 226Ra, 232Th and 40k for plant samples collected from different locations. The solid and dotted lines show the mean value for each group and one standard deviation (1σ), respectively.
Mea
n
Act
ivit
y C
on
cen
tra
tio
n
(Bq
/kg
)
0
5
10
15
20
25
Sample Location
0
100
200
300
400
0
10
20
30
40
0
10
20
30
40226Ra
232Th
40K
up stream wastewater pipe down stream
Fig. 3.11. The mean concentration
of 226Ra, 232Th and 40K for sediment samples collected from different locations. The ranges are shown as boxes while mean values are shown as solid circles.
0
500
1000
1500
2000
226
RaC
once
ntra
tion
(Bq/
kg)
0
500
1000
1500
2000
Super Phosohate Raw SIingle Super Phosphate Triple Super Phospate
Reference Number
Phosphogypsum
Fig. 3.14. The concentration of 226Ra for super phosphate raw, single super phosphate, triple super phosphate and phosphogypsum samples. The ranges are shown as boxes while mean or single values are shown as close circles.
Plant Samples
226
Ra
Con
cent
ratio
n (B
q/kg
) for
Sed
imen
t and
Pla
nt S
ampl
es
0
50
100
150
200
250
0
50
100
150
200
250
Sediment Samples
Reference Number
226R
a C
once
ntra
tion(
Bq/
l) fo
r W
ater
Sam
ples
-0.4
-0.2
0.2
0.4
0.6
0.8
1.2
1.4
0.0
1.0
Water Samples
Fig. 3.17. The concentration of 226Ra for sediment, plant and water samples. The ranges are shown as boxes while mean or single values are shown as close circles.
Table 3.8. The correlation coefficients between the concentration of any isotope in fertilizer, sediment and water samples, and Sr, Sn, Ba and Fe heavy metals concentrations and other characteristics.
226Ra 232Th 40K
Super Phosphate Fertilizer Samples
Sr 0.85 0.55 0.0005
Sn 0.06 0.18 0.03
Ba 0.49 0.86 0.39
F 0.79 0.41 0.34
pH 0.51 0.06 0.19
Sediment Samples
Sr 0.19 0.11 0.60
Sn 0.28 0.47 0.50
Ba 0.82 0.09 0.13
Fe 0.23 0.82 0.04
F 0.56 0.06 0.44
pH 0.01 0.23 0.04
TOM 0.22 0.75 0.30
Water Samples
F 0.19 0.13 0.27
pH 0.55 0.27 0.53
Bicarbonate 0.6 0.29 0.52
Salinity 0.1 0.5 0.77
Fig. 3.20. The concentration of Raeq for super phosphate raw material and super phosphate fertilizer samples. The ranges are shown as boxes while mean or
single values are shown as close circles.
Reference Number
Super phosphate Fertilizer
200
400
600
800
1000
1200
1400
Super phosphate raw
Ra e
q C
on
cen
trati
on
(B
q/k
g)
ConclusionConclusion The phosphate fertilizer showed higher values of fluoride
concentration than those for other types of fertilizers..
The lowest fluoride content was found in Abu-Tartor phosphate raw materials.
The highest fluoride concentration was found in wastewater discharge pipe locations.
The results indicated that the wastewater polluted with fluoride produced from the fertilizer company may be affecting the environment.
No clear results were deduced for heavy metals to allow No clear results were deduced for heavy metals to allow testing of this possible effect because of the limited testing of this possible effect because of the limited number of samples. number of samples.
The results indicated that the The results indicated that the 226226Ra activity concentration Ra activity concentration of the phosphate fertilizer samples is higher than that in of the phosphate fertilizer samples is higher than that in other types of fertilizer. other types of fertilizer.
There is a great variation in the There is a great variation in the 226226Ra concentration of Ra concentration of phosphate raw material (F1 and F2) because the geological phosphate raw material (F1 and F2) because the geological origin of the phosphate ore is not the same.origin of the phosphate ore is not the same.
The environment may be slightly affected with low The environment may be slightly affected with low concentrations of concentrations of 226226Ra and Ra and 232232Th isotopes due to the Th isotopes due to the discharged wastewater from the phosphate fertilizer discharged wastewater from the phosphate fertilizer industry. industry.
The results showed that there is a correlation between the The results showed that there is a correlation between the 226226Ra and F concentrations in fertilizer samples (liner Ra and F concentrations in fertilizer samples (liner correlation coefficient, r = 0.79) due to the elemental correlation coefficient, r = 0.79) due to the elemental composition of phosphate raw materials.composition of phosphate raw materials.
RecommendationsRecommendations The treatment of the wastewater produced from the The treatment of the wastewater produced from the
phosphate fertilizer industry is an important way to reduce phosphate fertilizer industry is an important way to reduce the impact of this industry on the environment.the impact of this industry on the environment.
Using raw materials that contain low levels of natural Using raw materials that contain low levels of natural radioctivities, heavy metals and fluoride for the phosphate radioctivities, heavy metals and fluoride for the phosphate fertilizer industry is preferable.fertilizer industry is preferable.
A good ventilation of the industrial area of the phosphate A good ventilation of the industrial area of the phosphate fertilizer plant and the storage places of the end products fertilizer plant and the storage places of the end products and by-products is necessary to avoid radon accumulation.and by-products is necessary to avoid radon accumulation.
We should encourage the reinvestigation of the same We should encourage the reinvestigation of the same studied region with extending area and larger numbers of studied region with extending area and larger numbers of environmental samples and other similar industrial regions environmental samples and other similar industrial regions to obtain a larger view about the impact of different to obtain a larger view about the impact of different
industries on the Egyptian environment.industries on the Egyptian environment.
Thank youThank you for your attention for your attention
Study Area
Table 2.1. Some information of the collected fertilizer samples.
Samples code
Commercial Name
Composition Comments
F1 Read sea raw materials (31%)
31% P2O5 Collected from selected company
F2 Abu-Tartor raw materials (29%)
29% P2O5 Collected from selected company
F3 Single super phosphate (end product)
18.20% P2O5 Collected from selected company
F4 Triple super phosphate
40 - 48 % P2O5 Collected from local market
F5 Super phosphate (abo nakla)
18.20% P2O5 Collected from local market
F6 Improved super phosphate
0.5 P2O + 23 Ca + 18 S Collected from local market
F7 Phosphogypsum CaSO4. x H2O Collected from local market
F8 Fero Fert )19 N -19 P - 19K + (Mg + T.E
Collected from local market
F9 Crystal Nasser )20 N- 20 P- 20 K + (T.E
Collected from local market
F10 Chema 33.5% 33.5 N + 0.06 Ca + 2 MgNO3 + 0.2 S
Collected from local market
F11 Chema 33.5% azote 33.5% azote Collected from local market
F12 Urea 46% azote + 0.2%S Collected from local market
Fertilizer
Sampling
Sediment
Plant
Water
~24l: ~0.3l
V=300 cc
~1.5l for characteristics
20 ml (F, pH, TDS, Bicarbonate)
~2 kg with depth~20-30cmV=150cc
10 gm (TOM)0.5 gm (F)
2 gm (pH )~1 gm (XRF)
~5 kg fresh weight V=300cc
0.5 kgV=150cc3 gm (F)10 gm (pH)~1 gm (XRF)
Characteristic Measurements
TDS &Bicarbonate
pH TOM
• Crison 501 pH/mV-meter
Adsorption, Solubility and migration
• Loss on ignitionat 550 ºC
Why?
• Using a Ds meter
• Using acid titration
Fluoride Measurment
Fertilizer, sediment and water samples
Ion Selectivity Meter (Orion EA 940)at Water & Soil Analysis Unit,
Central Lab., Desert Research Center
Table 2.1. Some information of the collected fertilizer samples.
Samples code
Commercial Name
Composition Comments
F1 Read sea raw materials (31%)
31% P2O5 Collected from selected company
F2 Abu-Tartor raw materials (29%)
29% P2O5 Collected from selected company
F3 Single super phosphate (end product)
18.20% P2O5 Collected from selected company
F4 Triple super phosphate
40 - 48 % P2O5 Collected from local market
F5 Super phosphate (abo nakla)
18.20% P2O5 Collected from local market
F6 Improved super phosphate
0.5 P2O + 23 Ca + 18 S Collected from local market
F7 Phosphogypsum CaSO4. x H2O Collected from local market
F8 Fero Fert )19 N -19 P - 19K + (Mg + T.E
Collected from local market
F9 Crystal Nasser )20 N- 20 P- 20 K + (T.E
Collected from local market
F10 Chema 33.5% 33.5 N + 0.06 Ca + 2 MgNO3 + 0.2 S
Collected from local market
F11 Chema 33.5% azote 33.5% azote Collected from local market
F12 Urea 46% azote + 0.2%S Collected from local market
Radioactivity concentration measurements
Using γ-ray spectrometer employing 5"×5" NaI(Tl) and 10%HPGe detector
Experimental Methods (II)
XRF spectrometeremploying Si(Li) detector
Heavy metal concentration measurements
Gamma-Ray MeasurementsGamma-Ray Measurements
Low BG lead shieldLow BG lead shield 10% HPGe10% HPGe
Fig. 2.3. A block diagram of electronics used for the γ-ray spectrometer employing NaI(Tl) or HPGe detector
Detector Preamplifier Amplifier MCA
Bias Supply
For HPGe PC
Bias supplyfor NaI(Tl)
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