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(Belgrade), 23 (2008) 195-200
UDC: 631.8:543.632.495(497.11). Scientific paper * Naučni rad
Concentrations of Heavy Metals in NPK Fertilizers Imported in Serbia
Jelena Milinović1, Vesna Lukić2 , Snežana Nikolić-Mandić3 and Dimitrije Stojanović1 Serbia (email@example.com) 2 Belgrade Waterworks and Sewerage, Water Quality Control Department, 11000 Belgrade, Obrenovački put bb, Serbia 3Faculty of Chemistry, University of Belgrade, 11000 Belgrade, Studentski trg 12-16, Serbia
1Institute of Pesticides and Environmental Protection, 11080 Belgrade, Banatska 31b,
Concentrations of Pb, Cd, Cu and Mn in sixteen NPK fertilizers imported and widely used in Serbia were determined by flame atomic absorption spectrometry (AAS). The results show that contents of heavy metals varied significantly in different fertilizers depending on N:P:K ratio and fertilizer origin. Pb and Cd contents in water solution of fertilizers occurred at low ranges: 2.0-3.1 and 0.03-1.56 mg/kg, respectively. An NPK (15:15:15) fertilizer from Romania was found to contain the highest concentration of Pb and Cd as impurities. Cu content, ranging from 7.1 to 974.7 mg/kg, was the highest in coloured fertilizers from Hungary, the Netherlands and Greece. Mn value in a Hungarian NPK product (10:10:20) exceeds the average Mn value in soil. The data indicate variable contents of heavy metals in fertilizers, some of which are significantly higher than natural concentrations in soil, which suggests that they need to be continuously monitored. Keywords: Heavy metals; NPK fertilizers; Flame atomic absorption spectrometry
Adding fertilizers to soil and plants is a common agricultural practice aimed at improving soil fertility and plant production. The FAO in Rome warned in 2005 that Serbia might become dependent on food imports. Enlarged food production volume begins by increasing crop yields through the use of higher amounts of fertilizers. Although fertilizers are predominantly beneficial in terms of plant production, they may also be po-
tentially harmful as substances contaminating soil and both groundwater and surface waters. Fertilizers usually get insufficiently purified in the manufacturing process and therefore often contain various levels of impurities, including heavy metals, depending on the quality of raw materials used for their production. As a result of accumulation of heavy metals in soil, groundwater and plants, toxic effects of these elements can become very harmful (Jagodin et al., 1991; Gupta and Gupta, 1998). Pb and Cd, for instance, 195
MATERIAL AND METHODS Pb. an amount of about 1 g of each sample was dissolved in 100 mL of deionised water and the solutions were heated at 95oC for 30 minutes. The same procedure was performed for fertilizer extraction with acetic solutions at pH 4.. one Greek (19:9:27). under optimal conditions (Table 1).1-0. has recently sustained severe damages.. two Hungarian (10:10:20 and 14:11:25). all fertilizers used in Serbia are still not being analysed for heavy metal contents in compliance with Standard Regulatives. Cu and Mn concentrations in inorganic NPK fertilizers were investigated by flame atomic absorption spectrometry (SpectrAA 220 – Varian) in oxidizing air-acetylene flame. two Romanian (15:12:15 and 15:15:15).0 0. i.0 1. which in Serbia totals some 300-600 kg of the main components per ha of soil cultivated. The results obtained provided a basis for an assessment of risks from heavy metal toxicity in representative European and one American samples.000 tons annually. Cu and Mn determination by flame AAS Tabela 1. 1980. Table1. Instrumentalni parametri tokom određivanja Pb. four products from the Netherlands (18:11:18.0 0. the leading manufacturer HIP-Azotara in Pančevo.7 7. Boeckx. Savage et al. but should their concentrations exceed the respective average concentrations in soil.5 Cd 228. 1981. Pb. In this work. Cu i Mn metodom plamene AAS Instrumental parameters Instrumentalni parametri Wavelength Talasna dužina (nm) Lamp current Struja lampe (mA) Slit width Širina otvora (nm) Working range Radni opseg standarda (mg/kg) Pb 217. and one American (15:11:29) NPK fertilizer.e.0 0. All reagents used in the experiments were of analytical grade and were checked for possible trace metal contamination.5 5. the solutions were filtered with Milipore filters. A high input of fertilizers in soil.. Cu and Mn are essential elements for plants and living organisms generally. Cu and Mn concentrations in sixteen commercial NPK fertilizers of different types and origins were determined. which puts several NPK fertilizer products on the market. 1986).01-0. 2006). Cd. plants would uptake high amounts of these metals through the root system and so become harmful (Clark et al. Cd. Cd. Nebulization rate was 5 mL/min in all measurements. two Russian (16:13:16 and 16:16:16). The samples.0 5.2 1-6 196 .0 and 4. Sixteen commercial NPK fertilizers with different N:P:K ratios were analysed. The fertilizer samples were homogenized and grounded well in a blender.5 1-5 Mn 279. Chen et al.5 0.08 Cu 324. Instrumental parameters during Pb. originating from different countries. On the other hand. 1981). 600-800.Jelena Milinović i saradnici belong to a group of very toxic metals that can disturb metabolic processes (Travis and Haddock. Despite the fact that heavy metal concentrations in fertilizers have been limited in several European countries. 15:9:9. In addition. The residues were washed by deionised water. 1997. Deionized water was used in preparing stock solutions. After cooling at room temperature. particularly NPK.0 0. In Serbia. After drying at 105°C for 2 hours. two Croatian (10:30:20 and 15:15:15). were: two Austrian samples (15:15:15). Imported fertilizers tend to be of poor quality and are often delivered without appropriate quality control certificates. in 50 mL volumetric flasks. may cause excessive additions of heavy metals in soil through the impurities of raw materials (Raven and Loeppert. We are therefore forced to import mineral fertilizers from various European and other countries.5. many fertilizer manufactures have closed down over the past decades. The choice of a solution was made upon the known fact that soils in Serbia are predominantly neutral to medium acid. Cd.8 4. 16:15:25 and 12:13:12).
Cu values were found to vary on a large scale from 4. i.e.9 10. Evidently. Pb contents in two NPK fertilizer products of the same origin (from Romania). The data additionally confirm that contaminated raw materials were used for producing these samples. Attention should be paid to the uncoloured NPK 14:11:25 sample from Hungary.5 nd 9.44 mg Cd/kg fertilizer which means that about 650 mg Cd per hectar is put into neutral soil annually. similar to the Pb content in the same samples.1 8. Considering the two NPK samples from Romania. Copper contents in the analysed samples are presented in Table 4. which is more than 240 times.4 mg Pb/kg).4 2. i.0 nd 2.03 to 1.5 Na pH 4.0 nd nd nd 8. Cadmium was detected in almost all of the analysed fertilizers and the levels in water solutions varied from Table 2. both Austrian.0 2. belong to a group of coloured mixed fertilizers in which copper sulfate was used as a colouring additive. one Hungarian (14:11:25) and one Russian (16:13:16). which means that the raw materials used for preparing the series were of better quality. Cd was found in higher concentration in the sample with higher P percentage. In the sample with the higher P content.5.5 At pH 4. As expected. the Netherlands and Hungary. Pb was not found at all.4 nd 5. Pb concentration was the highest in one of the NPK samples from the Netherlands (6.7 nd 9.1 nd nd nd 2.0 5. Pb was not detected. the risk of contamination with fertilizers rich in Cd increases rapidly. 15:12:15 and 15:15:15.3 At pH 4. differed greatly. It shows that in seven samples.0 Na pH 4.e.4 3. Sample No.70 mg/kg (at pH 4.1 nd 3. In the remaining samples. the levels of this metal in the examined fertilizers.6 3. Pb was found in concentrations ranging from 2. At pH 4.4 2.5 nd nd nd 3. The lowest contents of Pb were found in a Croatian (15:15:15) and the second Hungarian (10:10:20) NPK samples. while the highest were detected in Romanian and Russian samples. As Cd readily leaches through deeper soil layers. Br. extracted in water solution. This positive correlation was not dectected in all cases. Pb concentration was higher. In acetic buffer solution at pH 4.1 mg/kg.6 4. (Beograd). Koncentracija Pb u NPK đubrivima (mg/kg) 0. getting into groundwater and then to surface waters. three Dutch. Pb contents in the investigated samples were higher in acid solutions.3 nd nd nd 6. Interestingly. extracted in water and acid solutions.Pestic.04 (in water solution) to 974.0 to 3. such as those from Croatia (10:30:20).56 mg Cd/kg (Table 3).6 11. Hungary (14:11:25) and Russia (16:13:16).5 197 .5 9. Pb concentrations in NPK fertilizers (mg/kg) Tabela 2. which contained more than 90 mg Cu/kg.1 mg Pb/kg.2 nd 4. The mean value of Cd concentrations is about 1. especially in more acid soils.6 nd nd nd 10. are highly variable depending on fertilizer type and origin.0) in one of the Hungarian samples.0 the detected values were on a scale from 8. uzorka 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NPK fertilizer NPK đubrivo 15:15:15 15:15:15 10:30:20 15:15:15 19:9:27 10:10:20 14:11:25 15:12:15 15:15:15 16:13:16 16:16:16 12:13:12 15:9:9 16:15:25 18:11:18 15:11:29 Origin Poreklo Austria Austria Croatia Croatia Greece Hungary Hungary Romania Romania Russia Russia The Netherlands The Netherlands The Netherlands The Netherlands USA In water U vodi nd nd nd 2. such as the NPK samples from Greece. The explanation for this considerable range is that some mixed fertilizers. fitomed. in several other samples.2 4.5 to 11. 23 (2008) 195-200 RESULTS AND DISCUSSION Pb concentrations in sixteen fertilizer samples analysed are presented in Table 2.
Br.10 0.10 0.20 nd nd 0.05 20.81 609.93 8.30 At pH 4. 1994). soil will accumulate more rapidly with the element used as a colouring reagent.35 nd 0.50 nd 0.62 1 15:15:15 Austria 2 15:15:15 Austria 3 10:30:20 Croatia 4 15:15:15 Croatia 5 19:9:27 Greece* 6 10:10:20 Hungary* 7 14:11:25 Hungary 8 15:12:15 Romania 9 15:15:15 Romania 10 16:13:16 Russia 11 16:16:16 Russia 12 12:13:12 The Netherlands* 13 15:9:9 The Netherlands* 14 16:15:25 The Netherlands* 15 18:11:18 The Netherlands* 16 15:11:29 USA * Mixed fertilizers with copper sulfate as colouring additive * Mešana đubriva sa dodatim bakar-sulfatom kao sredstvom za bojenje 198 .20 0.15 0.0 18. Koncentracija Cd u NPK đubrivima (mg/kg) Sample No.55 13.24 nd 0.1 mg/L.5 Na pH 4.57 10.03 0.02 128.30 nd 0.12 3.53 9.62 0. uzorka 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NPK fertilizer NPK đubrivo 15:15:15 15:15:15 10:30:20 15:15:15 19:9:27 10:10:20 14:11:25 15:12:15 15:15:15 16:13:16 16:16:16 12:13:12 15:9:9 16:15:25 18:11:18 15:11:29 Origin Poreklo Austria Austria Croatia Croatia Greece Hungary Hungary Romania Romania Russia Russia The Netherlands The Netherlands The Netherlands The Netherlands USA In water U vodi 0.10 nd nd 0.62 14.31 0.44 3.26 11.27 0. uzorka NPK fertilizer NPK đubrivo Origin Poreklo In water U vodi 10.0 91.76 208.35 At pH 4.5 Na pH 4.17 0.2 449.70 112.76 2.43 13.15 10.33 0.18 24.26 At pH 4.25 2.43 227.38 1.74 36.87 10.0 Na pH 4.97 239.49 376.41 Copper contents in nine NPK fertilizers is less than 30 mg/kg.73 218.50 215. which is satisfactory because the maximum allowed concentration for copper in soil and drinking water are 100 mg/kg and 0.33 209.0 3.94 456.15 0. Cd concentrations in NPK fertilizers (mg/kg) Tabela 3.22 0.15 206.04 23.70 15.56 0. The mean value of copper concentration in air-dried soil samples permissible by our Official Gazette is 50 mg/kg.62 1.62 16.46 nd 0.20 4.45 14. By using coloured mixed fertilizers. Koncentracija Cu u NPK đubrivima (mg/kg) Sample No.53 0. Cu concentrations in NPK fertilizers (mg/kg) Tabela 4.20 0.39 30. which is sig- Table 4.Jelena Milinović i saradnici Table 3.56 7.6 8.40 nd nd 0.0 Na pH 4.2 974.20 0.5 3.08 125.10 0.93 At pH 4.33 18. Br.26 0. respectively (OGRS.32 13.64 851.5 13.2 98.06 17.85 185.66 201.01 161.30 11. so the application of coloured mineral fertilizers should be heavily restricted.42 nd 0.
S.22 128.80 72. Yang.Pestic. This value must be significantly lowered by rigorously controlling the manufacturing process of fertilizers.61 566.: Leaching potential of heavy metals (Cd.0 is more than ten times higher than the average Mn level that can be found in soil (about 800 mg/kg).60 58. (Beograd). This is important particularly in terms of a need to use greater quantities of fertilizers in crops grown on neutral and acid soils. Communications in Soil Science and Plant Analysis.5 34. P.71 828. attention should also be directed to the quality of raw materials in order to prevent highly toxic concentrations.. 29: 1491-1522.51 10. Table 5.52 485.44 14.72 13.0 Na pH 4. Ni. Data acquired in this study of Pb.20 52. R.75 64. S. Journal of Trace Elements in Medicine and Biology. 58: 274-288.65 mg Mn/kg of fertilizer (Hungarian 10:10:20 sample) in water solution.83 548.Y.53 9.57 8..57 10.32 450.17 9.52 554. Chen. Yang. Gupta.03 125. Knudsen.64 565. and Gupta.43 23.: Trace element toxicity relationships to crop production and livestock and human health: Implications for management.W. X. Stoffella.E.75 (Austrian 15:15:15 sample) to 5236. He.75 13.14 600.L. 1998. as it is often the case in our country.94 720.L..: Effect of Trace Element Deficiencies and Excesses on Mineral Nutrients in Sorghum.62 14. 1986. and Maranville. fitomed..B. Mn concentrations in NPK fertilizers (mg/kg) Tabela 5...60 646. 2006.11 590.93 At pH 4. Mn levels in the fertilizers investigated cover the widest range (Table 5).27 513. P. Concentrations of this potentially toxic metal vary from 8.C. which is especially important for soils with lower pH. 1981.95 161.86 14.: Lead Poisoning in Children. Clark.27 9569.20 5236.71 17. The data shown in Table 4 also indicate that lower pH enables better solution capacity of copper. Pb. D.14 18. Yu.01 9. The extremely high Mn level of 9569. U. REFERENCES Boeckx.65 751.A.00 759.26 At pH 4.V.62 199 . G. J. Cd. Heavy metal concentrations exceeding the average values for normal soils can be very harmful. as expected.5 Na pH 4.20 125. 23 (2008) 195-200 nificantly lower than the concentrations determined in samples (OGRS. Journal of Plant Nutrition. Hence.82 128. Cu and Zn) from acidic sandy soil amended with dolomit phosphate rock (DPR) fertilizers.71 mg Mn/kg in a Hungarian NPK (10:10:20) sample extracted in a buffer at pH 4.. Br. surface and groundwaters and the biosphere in general.30 61.C.0 38. Pier. Analytical Chemistry.64 7099. Cd.62 10. 1994). The reason for such a high variability in concentrations is the composition of raw materials used for fertilizers products. 3: 357-374.J. Z. uzorka 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 NPK fertilizer NPK đubrivo 15:15:15 15:15:15 10:30:20 15:15:15 19:9:27 10:10:20 14:11:25 15:12:15 15:15:15 16:13:16 16:16:16 12:13:12 15:9:9 16:15:25 18:11:18 15:11:29 Origin Poreklo Austria Austria Croatia Croatia Greece Hungary Hungary Romania Romania Russia Russia The Netherlands The Netherlands The Netherlands The Netherlands USA In water U vodi 18.C. 20: 127-133. Cu and Mn suggest that fertilizer chemical characterisation should be carried out on a regular basis in order to minimize persistent contamination of soils.47 228. These variable contents of Pb. D. J.94 219.46 74. R. and Calvert. Koncentracija Mn u NPK đubrivima (mg/kg) Sample No. Cu and Mn contents in mineral NPK fertilizers imported in Serbia show considerable variation in their concentrations in water and acid solutions.
and Haddock. podzemnih i površinskih voda.A.V. A. and Loeppert. 1: 128-158. u cilju smanjenja zagađenosti zemljišta. jer je nekim mešanim đubrivima dodat bakar-sulfat kao sredstvo za bojenje. Berry. Najveći sadržaj Cu je nađen u obojenim. 23/94. 1991. 553 (in Serbian). Ključne reči: Teški metali. Sadržaj Mn u mađarskom NPK đubrivu (10:10:20) je veći od prosečnog sadržaja Mn u zemljištu čak deset puta.1.: Nickel in the soil-fertilizer-plants-animals-man system.L. Savage.7 mg/kg. Cu i Mn u šesnaest uvoznih NPK đubriva. p. Journal of Environmental Quality. Agrohimija. NPK đubrivo (15:15:15) uveženo iz Rumunije sadrži veoma visoke koncentracije Pb i Cd. Govorina. Koncentracije teških metala u uvoznim NPK đubrivima u Srbiji REZIME Koncentracije Pb. kao i od samog porekla đubriva. No. C. Official Gazette of the Republic of Serbia. and Reed.C. Grčke i Holandije. što zavisi od odnosa N:P:K u ispitivanim uzorcima đubriva. Raven. Cd. Dobijeni rezultati pokazuju da sadržaj teških metala u uzorcima različitih đubriva značajno varira. Sadržaj Cu varira u znatno većem opsegu: od 7. respektivno. plamena atomska apsorpciona spektrometrija 200 . koja se najčešće koriste u Srbiji.A.: Effects of trace element stress on the morphology of developing seedlings of lettuce as shown by scanning electron microscopy. Environmental Research. su određene metodom plamene atomske apsorpcione spektrometrije. NPK đubriva.: Trace Element Composition of Fertilizers and Soil Amendments..P. and Vinogradova.H.56 mg/kg. Travis. B.: Interpretation of the observed age-dependency of cadmium body burdens in man.03-1. 1981. V.B. odnosno 0. 22: 46-60.1 do 974. R. 1980. 1997. koji se nalaze kao nečistoće u sirovinama za dobijanje ovog đubriva. mešanim NPK đubrivima poreklom iz Mađarske. 26: 551-557. S. K.0-3. Journal of Plant Nutrition.G.Jelena Milinović i saradnici Jagodin. i prevazilazi vrednost maksimalno dozvoljene koncentracije Cu koja se može naći u zemljištu. W. OGRS: Guideline values for allowed concentrations of dangerous and toxic substances in soil and irrigation water and methods for their investigations.. C. Ovi podaci ukazuju da je neophodno permanentno kontrolisati sadržaj teških metala u uvoznim đubrivima. 3: 129-138. Koncentracije Pb i Cd su u uskom intervalu: 2. W.
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