Connections between Phosphate

Fertilizer Production and the

Uranium Fuel Cycle

Richard A. Brand
Department of Physics
& Responsible for radiation safety
University of Duisburg-Essen
(Multifos: Tricalcium Phosphate)
 Plan
• Naturally occurring radioactive materials (NORM)

• Technologically enhanced natural radioactivity:

Phosphate Fertilizers & distribution of contaminants

• NORM or Technologically enhanced radioactivity?

• Health effects from use of phosphate fertilizers?

• Example of Uranium and Radium Removal

• Waste Products of Phosphate Fertilizers: phosphogypsum

• Interest in recovering uranium

• Rekindled Interest in recovering uranium and cleaning

phosphogypsum

• What should be done

•Naturally occurring radioactive materials (NORM)
Biggest problem high-LET exposure: Radon

Ref: BEIR VII Health Risks from Exposure to Low Levels of

Ionizing Radiation, National Research Council 2006
 • Typical risk calculation based on low-LET exposure!
Radiation protection:
Linear no-threshold model generally accepted.
Dilution among the general public does not help matters.

Generally little governmental control

for materials with less than
1000 Bq/kg.

Approximant limits for no control:

U238+ (Th,Pa) 500Bq/kg
U238sec (Th, … Po) 10 Bq/kg
Ra226++ (Rn, … Po) 10 Bq/kg

Ref: BEIR VII Health Risks from Exposure to Low Levels of Ref: Strahlenschutzverordnung 2001
Ionizing Radiation, National Research Council 2006
Natural environmental radioactivity

Bundesamt für Strahlenschutz, Berlin

Natural environmental radioactivity

Bundesamt für Strahlenschutz, Berlin

•Technologically enhanced natural radioactivity:
Production of Phosphate Fertilizers
Sulfuric acid process:

Ref: W. E. Falck & D. Wymer, I.A.E.A. Vienna

 Sulfuric acid process:

All radioisotopes land up somewhere!

Radium in the gypsum!

Natural uranium (no daughter isotopes): 25 Bq/mg

Ref: W. E. Falck & D. Wymer, I.A.E.A. Vienna

 Nitric acid process:

All radioisotopes land up in the fertilizer!

Natural uranium (no daughter isotopes): 25 Bq/mg

Ref: W. E. Falck & D. Wymer, I.A.E.A. Vienna

•Natural environmental radioactivity
Or
Technologically enhanced
natural environmental radioactivity?

If much of the uranium in farmed

soil is of anthropogenic origin,

why is it listed under “Natural

environmental radioactivity”?

Bundesamt für Strahlenschutz, Berlin

 •Situation in Germany:
Verwendung von Phosphatdüngemitteln
Die in Deutschland eingeführten Rohphosphate, die
vorwiegend aus den USA, Nordafrika und Israel kommen,
weisen … gegenüber ….der Böden einen bis zu fünfzigfach
erhöhten Gehalt an U-238 und Ra-226 auf.

Die spezifischen Aktivitäten der daraus hergestellten

mineralischen Phosphatdünger betragen für :

U-238 280 - 920 Bq/kg (TSP max. 3000 Bq/kg),

Radium-226 160 - 520 Bq/kg (TSP max. 1150 Bq/kg )
K-40 30 - 6200 Bq/kg…

Messungen ergaben für Lagerarbeiter … 2,3 mSv pro Jahr

und … in der Landwirtschaft maximal 1 mSv pro Jahr.

Technologically enhanced natural environmental radioactivity

Bundesamt für Strahlenschutz, Berlin
RICHTLINIE 96/29/EURATOM DES RATES vom 13. Mai 1996

Artikel 13
Dosisgrenzwerte für Einzelpersonen der Bevölkerung

(1) Unbeschadet des Artikels 14 sind die in den Absätzen 2 und 3 festgelegten
Dosisgrenzwerte für Einzelpersonen der Bevölkerung einzuhalten.

(2) Der Grenzwert der effektiven Dosis beträgt 1 mSv pro Jahr. Allerdings kann
unter besonderen Umständen ein höherer Wert der effektiven Dosis pro Jahr
zugelassen werden, sofern der Mittelwert über fünf aufeinanderfolgende Jahre
1 mSv pro Jahr nicht überschreitet.

Question: do farmers carry film dosimeters?

 •Health effects from use of phosphate fertilizers?
One example: Tobacco

… tobacco grown in India averaged only 0.09 pCi per gram

of polonium 210, whereas tobacco grown in the United
States averaged 0.516 pCi per gram.

One factor in the difference between India and the United

States may be the extensive use of apatite as fertilizer for
tobacco in the United States…;

The amount of polonium 210 inhaled from a pack of 20

cigarettes is therefore about 0.72 pCi. …independent of
any form of filtering or 'low tar' cigarette.

Compared to nonsmokers, heavy smokers have four times

greater radioisotope density throughout their lungs.

… the alpha particle dosage from polonium 210 received

by smokers of two packs a day was .. 150 times higher
than .. from natural background radiation.

Apatite: Ca5(PO4)3(OH,F,Cl)
Source: National Institute of Health
http://en.wikipedia.org/wiki/Health_effects_of_tobacco_smoking
 Examples of Uranium and Radium Removal
Options for the extraction of U from phosphoric acid

1. Precipitation of U from phosphoric acid,

using an organic reagent (e.g. acetone) as dispersant, and ammonium fluoride (NH4F) as
precipitant. Reduction of U6+ to U4+ by addition of Fe powder. Recovery of U (for the production
of „yellow cake“) from the precipitate by dissolution in diluted H2SO4 or HNO3 and subsequent
purification by ion exchange or solvent extraction.

2. Ion exchange separation with a chelating resin

(with subsequent elution and precipitation to produce „yellow cake“)

3. Membrane separation of U, using liquid membranes with a strong affinity for U (as yet still
in experimental development stage)

4. Froth flotation
complexing U with a surface active agent of hydrophobic nature (froth needs to be purified to
produce high grade „yellow cake“)

5. Solvent extraction (capable to be practiced on a large commercial scale)

using various synergistic mixtures of organic solvents such as DNPPA (di nonyl phenyl
phosphoric acid)+TOPO (tri n octyl phosphine oxide), followed by purification and precipitation
=> U extraction rates of >90% can be realized

Thanks to Sylvia Kratz et al. after Singh et al. (2001), Gupta & Singh (2003)
Examples of Uranium and Radium Removal

Nitric acid attack:

1) No gypsum formed.
2) all radioisotopes in liquid
3) Radium removed by copercipitation
with BaSO4
4) Uranium and rare earths removed
using solvent extraction

Environmental Considerations On Uranium And

Radium From Phosphate Fertilizers
T.M. CIOROIANU, F. BUNU, D. FILIP, Gh. FILIP

in

Impact of new environmental and safety regulations

on uranium exploration, mining, milling and
management of its waste
Proceedings of a Technical Committee Meeting, 1998,
IAEA
 •Waste Products of Phosphate Fertilizers:
phosphogypsum.

For 1 Kilo fertilizer, 5 kilos phosphogypsum (calcium sulfate)

• Florida: 32 million tones per year

• Most of phosphogypsum lands on stacks

• Much is dumped (oceans) or used in agriculture!

• Efforts to create secondary markets hampered by

contamination with radium.

• Possible uses (when not contaminated):

• Construction
• Agriculture
• Landfill
 Phosphogypsum Stacks

•Stacks need to be sealed:

similar to uranium mine tailings.
•Source of radon.
•Can contaminate aquifer system.
•Sinkholes
 Disposal into the oceans:

Example:
Lebanese
Chemical
Company

Greenpeace
Research
Laboratories
2002
 • Commercial interest in
recovering uranium depends on
market price

Thanks to Ewald Schnug

 •Interest in recovering uranium and in
cleaning up phosphate:

past

Uranium has been recovered from fertilizer production in several countries:

•USA, IMC Global (now Mosaic) up to 1999

•Belgium up to 1996
•Kazakhstan, Ulbinski & Shevchenko
•Pakistan, Multan
•Iraq: Al-Quaim
•Israel

Commercial recovery ceased due to price of uranium.

 Industrial Facilities for Uranium Recovery
Information from http://www.wise-uranium.org/pfac.html
Outdated!!
 • Possible recoverable uranium:

Advantage of U extraction:
Potential U resources in phosphate rock are estimated to range between 15
and 22 Mio t U (WISE, 2000; UIC, 2005). At the current global rate of
consumption (68000 t U/year; UIC, 2005), phosphatic uranium could meet the
global demand for about 220 to 324 years. As a „side effect“, U input into
agricultural soils with mineral P fertilization would be reduced.

Known conventional U resources, on the other hand, are around 3.5 Mio t U,
and will only last for about 50 years (UIC, 2005).

=> Sustainable resource management

Disadvantage: Higher market price for P containing mineral fertilizers

Thanks to Sylvia Kratz et al.

 •Interest in recovering uranium for
military and clandestine purposes:
•Iraq

al Qaim phosphate plant

and uranium extraction
facility (Unit-340).

The unit was designed to

produce 54 tonnes of
uranium peroxide per
year.

http://www.isis-online.org/publications/iraq/alqaim.html
 •Interest in recovering uranium for
military and clandestine purposes:
•Israel

Israel has also devised a

method of extracting uranium
from the phosphate deposits in
the Negev desert, where there
is an estimated 30000 to
60000 tons of uranium in
phosphate ores.

Active mining of phosphate

deposits takes place in the
Negev near Beersheba.
Negev: Contamination of water resources
Immediately adjacent to
in Southern Israel
Dimona reactor.
http://www.iued.org.il
 •Could be an Interest in recovering uranium for
military and clandestine purposes:
Possible to hide U enrichment in fertilizer production:

Histogram of R(235U/238U)-isotope ratio Histogram of R(234U/238U)- isotope ratio in

in different types of samples different types of samples
50 25 Secular equilibrium
Typical R(235U/238U) = 0 .007202

40 20

30 15

20 10

Sample with possible

10 Mean = 5.521E-5
depleted uranium Mean = 0.0072 5
Std. Dev. = 1.2606E-
Std. Dev. =
5.0168E-5 N = 67

0 N = 65 0
0.0068 0.0069 0.0070 0.0071 0.0072 5.1E-5 5.2E-5 5.3E-5 5.4E-5 5.5E-5 5.6E-5 5.7E-5 5.8E-5

R(235U/238U)- isotope ratio R(234U/238U)- isotope ratio

Fig. 10: Frequency histogram (frequency distribution) of Fig. 11: Frequency histogram of R(234U/238U) in
R(235U/238U) in fertilisers samples of different type 67 fertilisers samples of different type

Sattouf et al., (2006) U and Sr isotope ratios in rock phosphates

& talk at this symposium
• Rekindled Interest in recovering uranium:

• Started with $1M AEC-funding of IMC plant in Florida

(Time Magazine Apr. 12, 1954)

• Phosphate industry may restart uranium mining as price soars

(Tampa Tribune, May 11, 2007, Tampa Florida)

• Florida fertilizer production:

1) CF Industries
2) Mosaic Corp. (IMC Global + Cargill Cop.)
3) Potash Corp.

Other industrial units considering uranium recovery:

1) Yarimca Phosphoric Acid Plant, Turkey

Solvent extraction, Önal and Atak
Radiation Safety Problems, NATO Science Series

2) Nuclear Materials Corp. Egypt

L.A. Guirguis, Can. J. Chem. 61 (1983)

3) Phosphate Research Center, Morocco

“Towards a desalination initiative … uranium recovered
from Moroccan phosphoric acid production”
Lung et al., Int. J. Nuclear Desalination 2005
 • Rekindled Interest in cleaning phosphogypsum:

Presently:

Phosphogypsum stacks
capped with plastic

Cost: 10 to 20 M$/stack
Dr. Bill Burnett surveys the crater-like summit
of Florida's largest GYP stack at IMC-Agrico Constant monitoring
necessary

Danger to aquifer systems

Any use proposed must consider:
Radon emission
• Potential of release of Ra into environment
• Radon emitted into atmosphere
• Potential re-use and loss of institutional control
 Conversion of phosphogypsum to Sulfate fertilizer using
Merseberg process:

Radionuclide flow during the conversion of phosphogypsum to ammonium sulfate

W. C. Burnett et al., Journal of environmental radioactivity 1996
& The Florida Institute of Phosphate Research
 • Recovering phosphogypsum for use:

Main problems:

• Application of phosphogypsum, …in building materials

has been limited by the presence of minor components
that are hazardous, such as radioactive substances, ..,.

The worldwide use of phosphogypsum in building

materials is probably well below 15% of output. In the
US, use was banned in 1990 and in the
European Union, it was discontinued by 1992.

Recently, uranium levels in .. phosphogypsum have

increased due to reduced uranium extraction.

… use in building materials of another type of waste

gypsum, generated by flue gas desulphurization, has
rapidly increased.

L. Reijnders, Building and Environment 42 (2007) 1036.

 Recovering phosphogypsum for use:

. separation techniques may reduce the concentrations of

such [radioactive] components.

Higher waste disposal costs, tighter regulations and higher prices

for competing virgin minerals could make the use of the purified
phosphogypsum … in building materials more attractive.

L. Reijnders, Building and Environment 42 (2007) 1036.

 In Line Purification of Process Slurries

.. Two methods have been investigated:

(i) supported liquid membrane extraction, and
(ii) ion exchange bars.
Mechanical, Maritime
And Materials Engineering Both methods have successfully been applied to
the solvent-mediated recrystallization of calcium
sulphate.

C. Koopman, G. J. Witkamp, G. M.
Van Rosmalen,
Removal of heavy metals and
lanthanides from industrial
phosphoric acid process liquors,
Separ. Sci. Technol. 1999, 34(15),
2997-3008
 What should be done

• Technical means for clean up and recovery exist

• What is urgently needed:

1. Monitoring and limits for total radioisotopes in fertilizers!

2. Necessity for monitoring: avoid uranium black market,

utilize an important raw material!

3. Clean-up of radioisotopes in both fertilizer and byproducts.

4. Controlled commercial usage or burial of radioisotopes

extracted.