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)