The paper presents data from studies aiming at determination of individual elements in the soils in some 

valleys in Macedonia, with particular reference to the concentration of Mg, which is one of the most important bio­ 

gene elements in the process of photosynthesis in plants. 

The authors detemined concentrations of individual microelements and toxic elements in some soils in 

the territory of the Republic of Macedonia. The aim of the studies was to determine the amounts of those elements 

that exceed the values allowed and are toxic and harmful for the normal growth and development of plant strains

Boev, Blazo

Lepitkova, Sonja

UGD Academic Repository

GEOME2 Manuscript received: April 22, 1997 Accepted: May 14, 1997 Geologica Macedonica, Vol. 11, pp. 51-56 (1997) ISSN 0352 - 1206 UDC: 551.42 (437.17) Original scientific paper GEOCHEMICAL INVESTIGATIONS OF THE SOILS IN THE REPUBLIC OF MACEDONIA Blazo Boev and Sonja Lepitkova Faculty ofMining and Geology, Stip, Republic ofMacedonia The paper presents data from studies aiming at determination of individual elements in the soils in some valleys in Macedonia, with particular reference to the concentration of Mg, which is one of the most important bio­gene elements in the process of photosynthesis in plants. The authors detennined concentrations of individual microelements and toxic elements in some soils in the territory of the Republic of Macedonia. The aim of the studies was to determine the amounts of those elements that exceed the values allowed and are toxic and harmful for the normal growth and development of plant strains. Key words: soils; microelements; magnesium INTRODUCTION Soil is the top part of the lithosphere and basic factor of life. It is an important natural source that conditions the status, social and economic develop­ment of society. Scientists dealing with the nature of soil con­sider that soil is "a natural body of minerals and organic components, divided into horizons differing from the matter lying in the basement in morphol­ogy, composition, chemistry and biology. A specific feature of soils is that they have different composi­tion and characteristics in individual layers at depth. This must be taken in consideration when ana­lysing the composition and the character of soils. The characteristics of soils are different from those of the source material ensuing them. This is due to biological activity since the influence of cer­tain organic components in the development and growth of plants is sometimes greater than that of the source rock. Since soil, its nature, setting and influence are a component part of the biosphere and a product of joint action between biogene and abiogene environ­ment, the soil - organism system becomes an im­portant mechanism for the formation and produc­tivity of biosphere. Therefore, determination of the character of soil is of particular importance to the development of some plant strains making possible the improvement of the composition of the soil through certain mechanisms. METIIODS OF WORK Analytical method Forty samples collected from the three largest valleys in Macedonia were studied. Samples were collected from six sections, from 0 to 70 cm in depth and analysed by ICP-AES method. This method was chosen following the large number of reports presenting good results in the determination of trace elements in some soils (Dahlquist and Knoll , 1978; Horwitz, 1980; David, 1978; Lyons and Lynch, 1985; Willet and Zarcinas, 1986). The advantages of this method compared with other methods for trace elements analysis (i .e. AAS by flame atomization) are as follows: i l I RI 52 B. Boev - S. Lepitkova - the possibility to obtain spectra for more elements or multi-element analyses after one excit­mg;• - low detection limits for several elements, even for elements such as V, P etc .; - lower probability for chemical interference; - greater range of concentrations for which there is linear dependence of instrumental signal from concentrations of elements or the possibility for simultaneous determination of major and trace elements; - high precision. The ICP-AES method can determine up to 75 elements. With samples collected from agricultural material several elements can be determined directly in extracted solutions, whereas some need pre­conditioning by ion exchangers. Since soil samples can differ, it is necessary to provide a representative sample. This can be achieved by drying the sample with no 2 mm frac­tion at room temperature in well-aired premises for several days, taking smaller sample by quartering and screening with sieves of200 meshes . Soil samples can be treated in a variety of ways applying a number of reagents depending on whether the total concentration or the amount of elements available to plants are analysed. The total amount ofelements in soil samples is the concentration of elements obtained after their complete and thorough digestion . Content of elements obtained by acid liquid extraction from soils investigated combined with inorganic acids can be regarded as approximate indicators of the concentration of elements available to plants. This is so because analysis of samples in such "rigorous" conditions is not consistent with the conditions in which biological processes take place. The content of so called accessible elements is a logical estimate of the amount of elements in the soil available to plants and is obtained by extraction of weak acids from the soil such as acetic acid or complexon III . The M CaCI solution and 0.1 M thriethano­lamine puffered 0.005 M dyethilene-thriamine­pentaacetic acid (DTPA) adjusted to pH 7.3 is used to determine accessible forms of metals such as Fe, Cu and Mn. For the exchangeable cations such as Ca, Mg, Na and K extraction was made with neu­tral I M ammonium acetate (Dahlquist and Knoll, 1978) . Extraction for Fe, Al and P was made using ammonium oxalate-oxalic acid solution (known as Tamm's reagent), (Novozamski, Van Esk, Houba, Van der Lee, 1986). ANALYTICAL METHODS Approach Air-dried sample prepared in accordance with ISO 11464 (ground sample and sieved through the sieve the aperture the size 150 f.1m, is extracted with a HClIHN03acid mixture at room temperature for a period of 16 hours followed by distillation for a period of 2 hours . After this the extract is diluted with nitric acid. After this step the contents of trace elements are determined by ISP-AES method. Reagents Reagents used are of sufficient purity required by ISP-AES determinations, confirmed by con­ducting a blank test. Water must comply with de­gree 2 purity ISO 3696. Hydrochloric acid, c(HCI) - 12.0 moUl, p - 1.19 glml, Nitric acid, C(HN03) - 15 .8 mol/I, Nitric acid, C(HN03) - 0.5 moUU. Apparatus Glass apparatuses are carefully cleaned with warm nitric acid for at least 6 hours and then rinsed with water. Grinding mill dry samples, to a size less than 150 f.1m without contamination by the elements to be determined. Test sieve the aperture the size 150 f.1m made of plastics materials. Disiccator-Exicator, the volume of 2 I . Reaction vessel, the volume 250 ml. Reflux condenser with conical ground joints. Absorption vessel, non-return type if mercury is determined. Glass beads, the diameter of 2 mm. Heating apparatus. Volumetric flask, the volume of 110 ml. Filter paper, the pore size of 8 f.1m and a di­ameter of 150 rnm. Geologica Macedonica, 11, p. 51 - 56 (1997) cording sieve tt san1ple s~ and put T several TikveS T The prl AI) am Cd etc sampl il distribl taken i some e R centratl shows gene cl b low l (6300 I o 1I1creas as In a ofMg indicatt nia are should velopm c: is high detectel in Petal Ire pecial1) centrali the dete Only 51 cated v. in soils area un, Geologic.. Geochemical illvestigatioll Ofthe soils ill the Republic ofMacedollia 53 )Ies is their liquid with :imate lilable lIes in th the ,lace. :nts is in the action Did or :hano­mme­; used as Fe, Ich as 1 neu­Knoll, using Ml as louba, with 'nsed !than tsto made ts. rcury a di­(1997) Preparation ofsample Representative portion of air dried sample ac­cording to ISO 11464 is ground and screened with sieve the meshes of 150 11m in order to obtain a sample approximately 20 g in size. Procedure Sample of 3 g is weighed by analytical scale and put in a distillation vessel. The sample is mois­tened with 0.5 - I ml water and mixed with 21 ml HCI and 7 ml HN03 drop by drop in order to reduce foaming. Fifteen ml HN03 is added to the absorp­tion flask and distillation apparatus is assembled. The sample in the flask is extracted at room tem­perature for 16 hours and then distilled at boiling temperature for 2 hours. The distilled material is placed into a volumetric flask the size of 110 ml and filled with nitric acid c(HN03 ) - 0.5 mol/I. RESULTS AND DISCUSSION The samples under study were collected from several sites, e.g. Vardar - Gradsko, Rosoman; Tikves - Kraiste, Lozovo and ZK Pelagonia. The results obtained are shown in Tables 1-3 . The presence of some major elements (Mg, Fe, Ca, AI) and trace elements (B, Co, Ni , Mo, Pb, Zn, Cu, Cd etc) was studied in samples collected from 40 sampling sites. The influence of pH factor on the distribution of individual elements in some soils was taken into account in the study of concentration of some elements. Results were compared with measurable con­centrations allowed for such elements . Table I shows that Mg, as one of the most important bio­gene elements in most of the samples studied, is below the average value for individual types of soils (6300 ppm) . Only in measurement sites 13, 14, 21 and 22 increased concentrations of Mg were found, where as in all other measurement sites the concentration of Mg is below the average value in the soil. This indicates that the soils in the Republic of Macedo­nia are poorly magnesic, and magnesic fertilizers should be used in soils in order to improve the de­velopment and growth of plants. Calcium concentration in most of the samples is higher than the allowed, the highest values were detected in the Tikves - Kraiste site, and the lowest in Pelagonia. Iron is also an important biogene element, es­pecially to many functions with plants and its con':: centration in soils is an important precondition to the determination of the kind and quality of soil. Only some probes in the measurement sites indi­cated values closer to the average Fe concentration in soils (of 38000 ppm), indicating that soils in the area under survey are poor in iron. Geologica Macedonica, 11, p. 51-56 (1997) Table I Total amounts ofB and Mg in the soil (mg/kg) No B Mg No B Mg 36.7 6066 21 32.2 10109 2 -33.2 5597 22 42.5 12798 3 38.4 5925 23 33.1 3648 4 38.7 5833 24 41.2 2867 5 51.9 7665 25 41.5 4304 6 32.6 6328 . 26 49.8 3774 7 34.8 5484 27 43.1 4390 8 39.4 6340 28 41.5 5618 9 54.8 8323 29 64.0 7141 10 43.6 9927 30 73.2 7102 II 43 .0 7428 31 69.0 7637 12 36.4 81 IS 32 72.9 5322 13 32.1 14608 33 59.0 6573 14 26.3 14896 34 70.2 6342 15 43.7 5977 35 50.7 5077 16 33.3 6246 36 78.6 5172 17 33.3 6791 37 60.1 4778 18 30.5 5620 38 69.3 3700 19 65.2 4114 39 61.3 4606 20 33.5 3778 40 80.9 5504 Sulphur is also a biogene clement important to the development of plants and animal life. In soils under survey the concentration of sulphur ranges below average values, only in measurement sites II, 12, 13, 16, 17, 21 and 22 being over the average (of 850 ppm) . The concentration of Al is also below the average in all measurement sites (Table 2}. The contents of individual microelements are given in Tables 2 and 3. Data indicate that most of the microelements are below the average measur­able concentrations allowed. , , 54 B. Boev ­ S. Lepitkova Table 2 Table 3 The concentration ojPb, Cu, Zn, Cd, Fe, Mn The concentration ojCo, Ni, As, Ca, Mo and S and Al in the soil (mg/kg) in the soil (mglkg) No Ph Cu Zn Cd Fe Mn Al No Co Ni As Ca Mo S 34 .5 31 43 0.61 12807 803 11910 13.10 83.6 < 0.50 4182 < 0.20 145 2 20.8 24 .5 43 .3 0.90 11601 574 11914 2 10.15 63.3 <0.50 29337 <0.20 540 3 22.4 17.7 37.6 0.70 15172 804 13807 3 13.59 88.5 < 0.50 4186 <0.20 153 4 22 25.6 40 0.77 13977 788 12860 4 13.16 85.5 <0.50 4119 < 0.20 151 5 21.1 15.7 46 1.03 17385 768 16075 5 14.20 103.5 < 0.50 4390 <0.20 147 6 14.5 15 .7 34.1 0.56 10875 790 11140 6 9.80 60.7 < 0.50 47064 <0.20 652 7 19.6 20 33 .1 0.75 10704 503 10931 7 9.28 58.7 <0.50 30374 <0.20 560 8 20.6 24 .6 42.4 0.79 12052 526 12276 8 10.50 63 < 0.50 29032 < 0.20 591 9 15.4 10.2 33.4 0.61 11817 574 8075 9 9.31 58.4 3.50 20151 <0.20 441 10 15 .9 16.2 55 1.06 15344 447 11903 10 13 .23 86.8 1.65 25299 <0.20 592 II 12.2 22.2 37 0.73 12182 673 9824 II 9.05 5 I. 9 < 0.50 53795 <0.20 992 12 25 .2 13 .8 36.9 0.85 14280 511 11257 12 9.41 56.7 < 0.50 62231 <0.20 1091 13 11.1 18.8 33.9 0.79 11563 425 6790 13 8.05 47.5 < 0.50 108000 < 0.20 1072 14 5.1 16.4 31 0.63 7405 520 7669 14 6.82 42.6 < 0.50 109000 <0.20 1895 15 14 JO.5 42.2 0.77 1078 694 9776 15 7.72 45.6 <0.50 29918 <0.20 808 16 12.7 10.5 33 .3 0.71 10969 487 10619 16 8.34 43.7 < 0.50 52263 < 0.20 920 17 6.2 10.3 35.4 0.95 11854 433 9715 17 8.93 44.9 < 0.50 69601 <0.20 1219 18 5.5 7.6 32 0.66 10410 417 8127 18 7.49 42.8 < 0.50 56870 <0.20 1000 19 9.7 6.3 44 .5 0.58 8891 340 6965 19 6.86 43.2 < 0.50 22260 <0.20 432 20 4.3 4.7 27.7 0.63 7929 265 6119 20 5.83 41.7 <0.50 29404 <0.20 514 21 9.3 9.7 27.7 0.73 8445 199 6257 21 6.96 37 < 0.50 62598 < 0.20 1050 22 15.7 16.4 43.8 1.11 14953 401 10161 22 10.29 36.2 < 0.50 78976 <0.20 1329 23 19 10.6 30.6 0.53 11499 614 12313 23 10.61 44.1 < 0.50 4189 <0.20 130 studied i24 17.6 16.4 44.4 0.58 10712 690 10401 24 10.56 42.7 < 0.50 2829 < 0.20 127 25 24.3 10.6 52.4 0.98 16230 650 16680 25 11.02 53 .3 < 0.50 3754 <0.20 149 26 21 17.1 38.3 0.69 12633 605 13577 26 12.61 52 < 0.50 4302 <0.20 166 27 13 .9 13.0 38.9 0.95 12284 711 12839 27 10.91 59.7 < 0.50 18606 <0.20 385 28 13.9 15 .2 45.4 0.99 13367 601 13771 28 11.29 76.5 < 0.50 24227 <0.20 4% 29 22.1 28.9 69.1 1.69 26288 635 13423 29 19.22 39.5 < 0.50 2490 <0.20 195 [I J Beet Map30 26.1 33.3 74.3 1.81 29100 869 14294 30 19.37 40.3 < 0.50 2363 <0.20 234 HOj ( 31 26.5 31.3 74.7 1.84 29299 894 14603 31 19.43 41.4 <0.50 2638 <0.20 221 [2J Dlivi 32 19.6 21.8 58 1.46 21950 862 10701 32 16.16 33.3 < 0.50 2222 < 0.20 133 alld Sp!!C33 17.8 20.4 52.3 1.57 20343 747 10260 33 13.40 30.6 < 0.50 3045 <0.20 168 [3J Duh!34 20.1 24.1 57.7 1.30 22355 639 11901 34 15.49 34.7 < 0.50 4574 <0.20 171 piasl 35 9.9 23.2 41.5 1.24 21658 763 10692 35 19.53 31.2 <0.50 1631 < 0.20 103 log;c 36 	 13 .5 23.8 45.9 1.47 25734 679 13564 36 23.65 34 .9 < 0.50 1896 < 0.20 102 Appl (4J Lyon37 13.9 24.7 44 .3 1.52 21102 796 10694 37 22.11 31.8 < 0.50 1364 <0.20 96 chan 70 39 18.1 24.2 44.7 1.57 27175 764 13535 39 23.27 36.1 < 0.50 1778 < 0.20 104 40 12.4 20.5 45 .5 1.20 18876 644 9194 40 19.13 29.5 < 0.50 1290 <0.20 81 38 8 24 .2 41.2 1.18 18924 695 8973 38 20.32 26.1 < 0.50 888 <0.20 Geologica ~Geologica Macedonica.l1. p. 51 - 56 (1997) 55 Geochemical illvestigatioll ofthe soils ill the Republic ofMacedollia The average distribution of lead amounts to 70 ppm and in samples studied lead concentration ranges from 4 to 34 .5 ppm. This indicates that the soils in the areas under survey are not contaminated by the metal. This is an important precondition for the quality of soils and plant growth because Pb is one of the most toxic heavy metals. Zn contents are within the concentrations al­lowed (ranging from 30 to 370 ppm) depending on pH (Veselinovic et ai, 1996). This indicates that the soils in the Republic of Macedonia have normal Zn values. It is an important fact since Zn is one of the most important biogene elements. Cd was found in limits allowed (ranging from 0.5 to 2 ppm) and is one of the important precondi­tions to the quality of soils since Cd is one of the most toxic heavy metals. The concentrations of Co and N i were found in increased values compared with the average con­centration in the soils (Co ranging from 10 to 15 ppm, and Ni from 20 to 30 ppm) due to the proximity to the FENIMAK-Kavadarci flotation plant where these metals are processed. Arsenic was found in lower amounts than the average. Taking in consideration the fact that arse­nic is one of the very toxic heavy metals it is a good fact that the sampling sites in this study are not af­fected by human activities. Copper contents were detected within the val­ues allowed (from 20 to 120 ppm depending on pH) ranging from 6.3 to 33.3 ppm (Table 2). Legend of samples: 1-8, samples from Rosoman; 9-10, samples from Ribarci; 11-22, samples from Tikves - Kraiste; 23-28, san1ples from Gumaja - Lozovo; 29-40, samples from Pelagonia CONCLUSION Considering the results of the studies carried besides their biophilic character the concentrations out on the contents of the major elements affecting of some microelements over the values allowed are the soil it can be inferred that the soils in the terri­ extremely harmful for the normal growth and de­tory of the Republic of Macedonia are poorly mag­ velopment of plants. Increased concentrations over nesic and all other concentrations of microelements the allowed were found for Ni and Co in all meas­are lower than the average. urement sites studied. Ni was detected in the soils in The contents of some microelements were the Tikves - Kraiste, and Rosoman sites, whereas studied in order to determine their values, because Co was detected in the Pelagonia site. REFERENCES [11 	BeCeJIIfHOBIfK, ,0: ., rplKeTIfK, 11., KapMaTIf , III., MapKoBIfK, ,0:., 1996: CiuGlbe u iipOljeCll y JlCU6VlU­Noj cpeollNu. Klblfra 1, EeorpaA. [21 	David, D. J., 1978: Analysis of soil, plallts, fertilizers and other agrocultural materials, Prog. Analyt. Atom. Spectroscopy, I, 225-254 . [3) Dahlquist, R. L., Knoll, J. w., 1978: Induktive coupled plasma-atomic emission spectrometry: analysis of bio­logical materials and soils for major, trace elemellts. Applied Spectroscopy, 32, 1-29. [4 J Lyons, 1. J., LYllCh, P. J., 1985: Detemlination of ex­changeable cations (Ca, Mg, Na, K) in aqueous and al-Geologica Macedonica, 11, p. 51 - 56 (1997) coholic NCI extracts of solid using ICP-AES. Commun in soil Sci. Plant. Anal., 16 (1),15-26. [5] Horwitz, W., 1980: Methods ofanalysiS of the associa­tion of official analytical chemists. Washington: Asso­ciation of olicial analytical chemists, 13th edition. [6J Novozamsky, 1., Van Esk, R., Houba, V. J. G., Van der Lee, J. J., 1986: Use of ICP-AES for detennination of iron, aluminium and phosphoros in Tamm's soil ex­tracts. Neth. Jour. Agri . Sci ., 34,185-191, [7] Willet, !' R. , Zarcinas, B. A., 1986: Natric acid disso­lution multi-element analysis of soil. Sci. Plant. Anal., 17 (2),183-193. l 56 B. Boev ­ S. Lepilkova Pe3f1Me rEOX~~MHCKH HCIIHTYBAILA HA nOqBHTE BO PEnYBJlHKA MAKEIlOHHJA M8.lKO lioeB H COILa JIenHTKoBa PyoapcKo-ieoJlOw,KU f/JaKYJliiieiii, miiiuu, Peiiy6J1uKa MaKeooltuja Bo TpYAOT ce rrpe3eHTHpaaT nOAaTOl.\H OA H3Y'!YBa­Iha Haco'!eUH KOH At:TepMHHHpalhe Ha oAAe.nHH eJleMeH­TH BO nO'!BHTt: BO HeKOH KOTJlHUH BO Peny6J1HKa MaKe­AOHHja . nOce6Ho BHHMaHHt:. e 06pHaTO Ha Mg Koj e eAeH OA MHory Oa)l(HHTe 6Hort:HH eJleMeHTH 80 npouecoT ua CPOTocHHTe3aTa Kaj paCTeuHjaTa. I..J.eJlTa 6ewe Aa ce YTBPAH npHCYCTBOTO oa OBHe eJleMeHTH BO nO'!BaTa BO KOJlH'!eCTBa KOH ce WTeTHH HJlH TOKCH'!HH 3a pa3BojoT Ha pacTeHHjaTa. Geologica Macedonica, 11, p. 51-56 (1997) Pelago and th mm basic 

Geochemical investigations of the soils in the republic of Macedonia

Abstract

Similar works

Full text

Available Versions

UGD Academic Repository