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Journal of Radioanalytical and Nuclear Chemistry, Vol. 242, No.

3 (1999) 693-701

Analysis of selected fertilizers imported to Libya for


major, minor, trace and toxic elements using ICP-OES and INAA
U. EI-Ghawi, 1. G. P~tzay, 1 N. Vajda, 2 D. B6dizs 2
l Department of Chemical Technology
2 Institute of Nuclear Techniques, Technical University of Budapest, H-1521, Budapest, Hungary
(Received June 8, 1999)

The concentration of 35 elements (AI, As, B, Ba, Be, Ca, Cd, Co, C1, Cr, Cu, Fe, K, Mg, Mn, Mo, N, Na, Ni, P, Pb, Rb, S, Sb, Sc, Si, Sr, Tb, Th,
Ti, U, V, Yb, Zn and Zr) in six different imported, NPK, NP and K fertilizers were determined by ICP-OES in two different laboratories and by
INAA. The fertilizers were labeled as 24/12 (Belgium), 46/18 (Morocco), 50% ammonium sulfate 50% K20 (Belgium), New 24/12 (Belgium),
16.8.24 (France) and 17.17.17 (France). It is clear that these fertilizers vary widely in their heavy metals and uranium content, and the
accumulation of certain elements in vitally important media such as water, soil and food is undesirable from the medical point of view. The results
obtained were acceptable and intercomparison between various methods was carried out.

Introduction imported to Libya. In addition, other elements as A1, Ba,


Be, Co, CI, Cr, Na, Ni, Rb, Sc, Si, Sr, Tb, Ti, V and Yb
Fertilizers are materials added to the soil, and were analyzed by using ICP-OES and INAA methods.
sometimes to foliage, to supply nutrients to sustain plants
and promote their abundant and fruitful growth. The
elements that constitute these plant foods are divided Experimental
into three classes: (1) primary nutrients, nitrogen (N),
phosphorus (as P205), and potassium (as I420); (2) Samples, samplepreparation
secondary nutrients, calcium (Ca), magnesium (Mg), and
sulfur (S); and (3) micronutrients, iron (Fe), manganese For this study six imported fertilizers were collected
(Mn), copper (Cu), zinc (Zn), boron (B), and l~om the Secretary of Agriculture during Feb. 1996.
molybdenum (Mo). In addition to their role as nutrients, These fertilizer labels content are presented in Table 1.
Ca and Mg are important in adjusting the pH of the All the products under investigation were granular
soil. 1,2 heterogeneous in nature, thus for the preparation of a
Due to the continuos population growth during this homogeneous sample a bore sample from each bag was
century, fertilizers and agrochemicals play a very mixed and pulverized in a glass mortar.
important role in increasing the land productivity and
fertility. The food-fertilizer-population linkage is the 1CP-OESanalysis
important underlying basis supporting demand; the
estimated fertilizers demand for the next year will be Sample dissolution: For the ICP-OES analysis the
about 200x106 metric tons of fertilizers nutrients N, samples have to be presented in the form of an aqueous
P205, and K20.1 The chemical world industries of solution. Ideally, complete dissolution is a prerequisite
fertilizers and agrochemicals involved 83 billion $ in the for accurate analytical results; however, often the
year 1989. 3 complete dissolution is replaced by partial extraction of
Environmental problems connected with fertilizers, the components of interest. Acid digestion is often used
especially phosphate fertilizers, are eutrophication and to determine the acid soluble part of the metal
the buildup of heavy metals (radioactive and toxic compounds of fertilizers.
elements). Solid samples have to be brought into solution before
The aim of the present paper is to check the level of the ICP-OES analysis, and this dissolution step is often
the primary nutrients, N, P and K, secondary nutrients, the most tedious, time-consuming part of the analysis
Ca, Mg and S, and micronutrients, Fe, Mn, Cu, Zn, B procedure.
and Mo as well as the level of heavy metals (radioactive In this work the dissolution and digestion were done
elements U and Th), and of stable environmental by three different techniques to check the solubility of
pollutants like As, Cd, Pb and Sb, in the fertilizers these fertilizers.

* On leave from Tajura Nuclear Research Center,


P. O. Box 84462 Tripoli, Libya,
E-mall: usama@reak.bme.hu

0236-5731/99/USD 17. O0 Elsevier Science B. V., Amsterdam


9 1999 Akaddmiai Kiad6, Budapest Akaddmiai Kiad6, Budapest
All rights reserved
U. EL-GHAWIet al.: ANALYSISOF SELECTEDFERTILIZERSIMPORTEDTO LIBYA

Table 1. The imported fertilizer labels

Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6

24/12 46/18 50%(NH4)2SO


4 New 24/12 16.8.24 17.17.17
s0% r2o
Belgium Morocco Belgium Belgium France France

(1) Dissolution in nitric acid or a mixture of nitric The resulting liquid samples are nebulized by a V-
and hydrochloric acid. 700 mg fertilizer sample powder groove nebuliser arrangement with an argon flow rate of
was measured into a glass flask on an analytical balance; 0.8 dm3/min, giving approximately a 3.0 cm3/min sample
then 3 cm 3 of high purity HNO 3 (70 m/v%) was added to uptake rate. The specification of the operating conditions are
the sample, the flask was placed into a block heater and given in Table 2. For calibration and quality control a set of
heated below the boiling point of the acid (set to 120 ~ multielement standard solutions was used.
for 30 min). This time was sufficient to dissolve most of
the samples. Sample No. 4 was not fully dissolved, some Instrumental neutron activation analysis (INAA)
black material was observed floating, by adding a few
drops of HC1 acid and heating for another 30 minutes The irradiations were performed in the Training
most of the residue was dissolved, but some black reactor of the Institute of Nuclear Techniques, Technical
material remained. By subjecting sample No. 4 to HPLC University of Budapest. The maximal thermal neutron
analysis, an oil layer coating the sample was observed. flux was 2"1012n'cm-2"s-1 and the maximal thermal
This oil was used for controlled-release of this type of power was 100 kW. The samples were irradiated in two
fertilizer. All the sample solutions were cooled down and steps and the ~/-spectra were detected by a HPGe well-
filtered into a volumetric flask and made up to a final type detector (FWHM: 2.1 keV, and 17.5% relative
volume of 25 cm 3 with distilled water for ICP analysis. efficiency at 1332.5 keV) for the analysis of short-lived
The solutions represent the acid soluble part of the nuclides, and a HPGe Pop Top type detector (FWHM:
fertilizers. 1.7 keV, and 26% relative efficiency at 1332.5 keV) for
(2) Dissolution in hydrofluoric acid. 0.150 g of the long-lived nuclides. The resulting T-spectra were
powdered sample was transferred into a PTFE bomb. analyzed by using Sampo 90.
Then, 2 cm 3 hydrochloric acid (36 m/v%), 1 cm 3 nitric Standards from NIST (SRM 1633a and 1571) and
acid (70 m/v%) and 1 cm 3 hydrofluoric acid (40 m/v%) IAEA soil-7 were used for calibration and quality
were added. The bomb was closed and the dissolution control. Detailed descriptions of the 1NAA procedures
was carried out under pressure at 130 ~ for 4 hours. have been published earlier. 4
Then the bomb was cooled down to room temperature Direct gamma-spectrometry: Samples and standards
and opened. Ten cm 3 of 6% by weight boric acid were placed in plastic tubes of 5 cm 3 volume capacity.
solution was added and the bomb was closed again and The cell was closed and left for at least four weeks
kept at 80 ~ for 30 minutes to complex the excess of before being counted to allow for radium and its short-
hydrofluoric acid. Then the solution was transferred into lived progeny to be in radioactive equilibrium when
a 50 ml volumetric flask made of polyethylene. The measured.
bomb was rinsed and filled up with 6% by weight boric The samples were counted, using a HPGe well type
acid solution. The ICP multielement standard solutions detector, with a well-volume of 5 cm 3, while the spectra
were also diluted with 6% by weight boric acid solution were analyzed using the Sampo-90 program.
for the measurement of these samples.
(3) Dissolution in water. 0.500 g of powdered sample Table 2. Operating conditions
was transferred into a glass beaker and 10 cm 3 deionised
Instrument Plasma lab. ICP spectrometer
water was added. The solution was heated at 95 ~ for
30 minutes using an electrical heating block. The Plasma (At-At) 27.12 MHz
Power 1.3 kW
solution was filtered into a 25 cm 3 volumetric flask. The Outer argon 10 I/min
residue was washed by deionised water. The filtered Intermediate argon 1.2 I/rain
solution was acidified by 3 cm 3 of high purity HNO 3 Inner argon 0.8 I/min
Observation height 13 mm
(70 m/v%) and the volume was set. For nebulisation the Sample flow rate 3 ml/min
same conditions were used. Integration time 5 s
Sample introduction by Gilson Minipuls pump

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