Macronutrients and heavy metals contents in the leaves of trees from the devastated lands at Kryvyi Rih District (Central Ukraine)

M -- Arithmetic mean, m -- Standard error of mean, CV% -- Coefficient of variability.

The average Manganese content in all vegetation is 200mg*kg^-1 d.w. [9, 12, 20]. We found that at a control site in the leaves of all tree species, the concentrations of this metal were well below than this range. Zinc concentrations in vegetation are around 30mg*kg^-1 d.w., and in the leaves of trees that have grown outside by industrial enterprises influence, they are at range 25-50mg*kg^-1 d.w. [8, 9, 12, 20]. According to our research, Zinc content in Birch leaves is within the same range. It should also be noted that the concentrations of this metal in the leaves of Black locust and Maple were significantly lower (Table 2).

In the Vegetation of the World, the average Copper contain is about 8mg*kg^-1 d.w. [9, 12, 20]. We found that the concentrations of this metal in the leaves of all tree species were significantly below this level. Average Lead content in the vegetation is around 1,25mg*kg^-1 d.w. [9, 12], and in the leaves of trees it is at the level of 0,5-1,0mg*kg^-1 d.w. [12, 20]. The analysis of obtained results shows that at a control site the concentrations of this metal in the leaves of all the investigated tree species were below these values (Table 2).

The similar consistent patterns were found for Cadmium concentrations. In all the vegetation its content is 0,03-0,05 mg*kg^-1 d.w. At a control site, the concentrations of this metal in the leaves of all the tree species were below these values (Table 2).

Thus, at a control site in the leaves of the trees, the only Ferrum and partially Zinc concentrations lie within the range of average values established for the vegetation. While, the concentrations of other metals (Manganese, Copper, Lead and Cadmium) are 2-7 times lower than the average values. In our opinion, this phenomenon can be explained by the effect of regional geochemical and biogeochemical anomaly, which is characterized by the increased content of Ferrum and Zinc. In addition, we believe that casual autumn dynamics of chemical elements in plants has the effect on the concentration of heavy metals in the leaves of trees.

Macronutrients and heavy metals content in leaves at a devastated lands. In the devastated lands at Kryvyi Rih iron-ore & metallurgical district, the content of Potassium in the leaves of the trees is less than control values (Fig. 2).

We found that, in the leaves of trees from the devastated lands at Kryvyi Rih region Potassium concentrations were less than the control values in Maple - by 15-70% (P<0,05), in Birch - by 15-55% (P<0,05). In the leaves of Black locust, both potassium content reduction (plots II III -- by 10-45% (P<0,05) less) and accumulation of this element (plots IV -- by 20% (P<0,05) higher) were detected.

Calcium content in the leaves emerged below than control values too (Fig. 2): in Birch -- by 19-54% (P<0,05) and in Black locust -- by 5162% (P<0,05). It should be noted that the concentrations of this metal in Maple's leaves at the plots II, IV, V were at the level of control values, while at the plot III they were by 40% (P<0,05) less than the control values (Fig. 2).

Figure 2. The relative K, Ca, Mg content in the leaves of trees from the devastated lands at Kryvyi Rih district The element content in the control is 100%.

Research areas: C _ control, I, II, III, IV, V plots on devastated land.

Acer _ Ash-leaved maple, Betula _ Silver Birch, Robinia _ Black locust

The analysis of obtained results (Fig. 2) shows that the Magnesium content was both higher and lower than the control values. Thus, in the leaves of Birch the accumulation of this element is predominant, the excess of control values is by 25-70% (P<0,05). In Maple's leaves, Magnesium concentrations at plot II were by 14% (P<0,05) above control and at plots

I and III they were 10-55% (P<0,05) less than control values. The content of this element in Black locust's leaves was within the control values (plots

II and V) or by 17% (P<0,05) less (plot II).

It was found that the Phosphorus content in the leaves of trees from devastated lands was less than control values (Fig. 3): by 21-61% (P<0,05) for Maple and by 46-63% (P<0,05) for Robinia. The content of this element in the Birch's leaves in most cases (plots II, II, IV) was below the control values by 44-54% (P<0,05), but at the plot V it emerged by 55% (P<0,05) higher than the control value. The data on Figure 3 show that in all cases the content of Sulphur in the leaves of trees from the devastated lands at Kryvyi Rih region were notably, 2-12 times, higher than the control values (P<0,05).

Figure 3. The relative P „y S content in the leaves of trees from the devastated lands at Kryvyi Rih district The element content in the control is 100%.

Research areas: C _ control, I, II, III, IV, V plots on devastated land.

Acer _ Ash-leaved maple, Betula _ Silver Birch, Robinia _ Black locust

The analysis of obtained results shows that in the leaves of trees from the devastated lands at Kryvyi Rih region only accumulation of Ferrum is statistically significant (Fig. 4). Thus, the concentrations of this metal in the leaves were higher than the control values: in Black locust by 1,7-2,4 times (P<0,05), in Birch by 1,9-4,0 times (P<0,05), in Maple by 1,2-5,0 times (P<0,05).

Figure 4. The relative heavy metals content in the leaves of trees from the devastated lands at Kryvyi Rih district The element content in the control is 100%.

Research areas: C _ control, I, II, III, IV, V plots on devastated land.

Acer _ Ash-leaved maple, Betula _ Silver Birch, Robinia _ Black locust

Manganese content exceeds the control values in Black locust leaves (by 2,7-8,1 times (P<0,05)) and in Birch (by 13-49 times (P<0,05)). While, in the Maple leaves, both accumulation of this metal (at plots I and II by 1,5-1,7 times above the control (P<0,05)) and its “leaching” (at plots III and IV by 15-19% below control (P<0,05)) were found.

In most cases, the Zinc contents in the leaves of trees were higher than the control values: by 11-19% (P<0,05) in Maple, by 1,4 times (P<0,05), in Black locust and 1,7-3.2 times (P<0,05) in Birch. It was also found that at plot III concentrations of this metal were below the control values: in Maple by 37% (P<0,05) and in Black locust by 48% (P<0,05).

It is established that only Copper accumulation was statistically significant in the leaves of Black locust. The concentration of this metal was by 1,2-2,3 times (P<0,05) above the control values. In the leaves of other tree species both high and low Copper content were detected. Thus, the concentrations of this metal exceed the control values: by 1,4-2,0 times (P<0,05) at plots I, II, III and V in Maple, by 16,9 times (P<0,05) at plots I and V in Birch. At the same time, the Copper content in the leaves was lower than the control values: by 46% (P<0,05) at plots III in Maple, by 31-39% at plots III and IV in Birch.

Our findings (Fig. 4) show that Lead concentrations in Birch leaves at all the plots were higher than the control values by 1,6-2,3 times (P<0,05). In Maple leaves at plots I, II, IV and V this metal's concentrations were also higher than control values, by 1,5-2,3 (P<0,05). But at plot III the Lead content was below than control by 23% (P<0,05). In Black locust leaves, this metal accumulation was detected only at plot V, where its content was 1,6 times higher than control (P<0,05). At the same time at plots III and IV, the Led concentrations were below than control values by 14-16% (P<0,05). Cadmium content in the leaves of woody plants exceed the control values: by 9-25 times (P<0,05) in Birch, by 5,4-6,6 times (P<0,05) in Black locust and by 5,4-6,6 times (P<0,05) in Maple. It should also be noted that at plots III, the concentration of this metal is below the control values in the leaves of Maple and Black locust a, respectively by 32% and 45% (P<0,05).

Discussions

All macronutrients that we have studied (K, Ca, Mg, P, and S) are biologically significant chemical elements. Therefore, these elements have a significant influence on all the important processes of life, growth and development of woody plant species [5, 12, 15]. In the course of evolution, for each chemical element, a certain interval of optimum was formed. The information about this interval is very important for the biological evaluation of the element content [8, 9].

According to scientific publications, the optimal Potassium concentration in plants is from 10000 to 14000mg*kg ¹ d.w., while the content of this element exceeding 25 000mg*kg^-1 d.w. is considered as phytotoxic [6, 8, 9, 20]. According to the results of our research, at a control site in the leaves of Black locust and Birch, the Potassium concentration was below the biological optimum (4 200-4 700mg*kg^-1 d.w.). The content of this metal in the leaves of Ash-leaved maple was slightly higher (about 10 000mg*kg^-1 d.w.), but it was at the lower level of biological optimum.

On devastated lands at Kryvyi Rih iron-ore & metallurgical district, the Potassium concentration ranges from 200 to 870mg*kg d.w., which is much less than the values of biological optimum. This is undoubtedly indicative of a deficiency of Potassium content for these plants.

The average optimal Calcium concentration in plants is between 10000 and 20000mg*kg^-1 d.w., and its phytotoxic amount is over 40000mg*kg^-1 d.w. [6, 8, 9, 20]. At the control site, the concentration of this element was within the biological optimum. On devastated lands, the growth and development of woody plants occur with some deficiency of this macroelement. The Calcium concentration in Birch leaves is 6400- 11300mg*kg^-1 d.w., in Black locust leaves is 7 800-16400mg*kg^-1 d.w.

The average Magnesium concentration in plants actually coincides with the range of biological optimum (1 000-3 200 mg*kg^-1 d.w.), and the phytotoxic concentration is more than 5 500mg*kg^-1 d.w. [6, 8, 9, 20]. According to the results of our studies, the content of this metal in the leaves of trees at the control site is near the upper limit of the biological optimum (2800-3600mg*kg^-1 d.w.), but does not exceed the threshold of its phytotoxicity. On devastated lands, the Magnesium concentration in the leaves of trees in most cases was above the upper limit of the biological optimum (3 200mg*kg^-1 d.w.) but was below the phytotoxicity threshold (5 500mg*kg^-1 d.w.).

According to scientific publications, the optimal Phosphorus concentration in plants is 1000-3000mg*kg^-1 d.w., the content of this element greater than 5 000mg*kg^-1 d.w. is considered as phytotoxic [6, 8, 9, 20]. We found that at the control site the Phosphorus, content in the leaves of trees was at the minimum level of its biological optimum 950-1 500mg*kg^-1 d.w. On devastated lands, in most cases, its concentration was much lower than the values of the biological optimum 350-750 mg*kg^-1 d.w. This fact indicates a deficit of this macronutrient.

The range of biological optimum for Sulfur content in plants is 1 500-2 500 mg*kg^-1 d.w. and the phytotoxicity threshold is greater than 5 000mg*kg d.w. and [6, 8, 9, 20]. We found that at a control site in the leaves of trees, the Sulfur content was below the values of the biological optimum (650-950mg*kg^-1 d.w.). On devastated lands, in all cases, the Sulfur concentration in the leaves of trees was higher than control. However, the content of this element, with rare exceptions (Black locust at plot II), was in the range of biological optimum and did not exceed the phytotoxicity threshold.

According to the scientific literature [3, 12, 13, 27], 100-250 mg*kg^-1 d.w. Ferrum concentration in plants is considered optimal, and the phytotoxicity threshold is 500-550 mg*kg^-1 d.w. We find that woody plants in all study areas contain extremely high concentrations of Ferrum in leaves: 300-500 mg*kg^-1 d.w. at a control site and 650-2010 mg*kg^-1 d.w. at devastated lands. Therefore, it can be assumed that woody plants are clearly exposed to the phototoxic effects of high concentrations of this metal.

Manganese content in plants from 50 to 200mg*kg^-1 d.w. considers as optimal, and if metal content is more than 300-400 mg*kg^-1 d.w. a stable phytotoxic effect was observed [3, 10, 12, 29]. We found that at a control site a Manganese concentrations in the leaves of trees for all species was in the optimality range -- 50-90 mg*kg^-1 d.w. On devastated lands, the content of this metal in the Maple's leaves was slightly higher than the control values (70-170mg*kg^-1 d.w.), but does not go beyond the optimum. While, the Manganese concentrations in Black locust's leaves and in Birch's leaves significantly exceed the toxicity threshold (300-800 and 2300-5000mg*kg^-1 d.w., respectively). Hence, the plants are influenced by Manganese phytotoxicity.

For Zinc, the optimum range of its content in plants is 10- 50mg*kg^-1 d.w. and its phytotoxicity threshold is 100mg*kg^-1 d.w. [10, 12, 26, 30]. According to our studies results, the concentrations of this metal in the leaves of Maple and Black locust were in the optimum range (both at the control site and on the devastated lands (except for plot V)). In Birch leaves, Zinc concentrations reach 100-280mg*kg ¹ d.w., which actually exceeds the phytotoxicity threshold.

Data from scientific publications indicate that Copper concentrations in plants of 5-10mg*kg^-1 d.w. are maintained optimal, and the phytotoxical threshold is greater than 20mg*kg^-1 d.w. [3, 11, 25, 26]. The results of our studies have shown that the concentrations of this metal in the leaves of all three tree species do not exceed the lower threshold of the optimum zone: at a control site -- 1,4-2,4 mg*kg^-1 d.w. and at devastated lands -- 0,8-4,6 mg*kg^-1 d.w. Therefore, we can assume that there is a deficiency of this important trace element.

The biological optimum range for Lead concentration in plants is 5- 10mg*kg^-1 d.w., and the phytotoxical threshold is 30mg*kg^-1 d.w. [4, 11, 13, 20]. We have found that the content of this metal in the leaves of trees does not exceed the minimum value of the biological optimum: 0,13-0,21 mg*kg^-1 d.w. at the control site and 0,1-0,48 mg*kg^-1 d.w. at devastated lands.

According to scientific publications, the optimal Cadmium concentration in plants is 0,005-0,020 mg*kg^-1 d.w., the content of this element greater than 0,200mg*kg^-1 d.w. is considered as phytotoxic [3, 10, 25, 28]. We found that at a control site, the content of this metal in the leaves of all three species was within the optimum range: 0,0029-0,0306 mg*kg^-1 d.w. At devastated lands, Cadmium concentration was also in the optimum range for Maple (0,0103-0,0234 mg*kg^-1 d.w.) and for Black locust (0,0029-0,0200 mg*kg^-1 d.w.). For Birch leaves, the content of this metal in all cases exceeds the values of the phytotoxicity threshold 0,25080,4897 mg*kg^-1 d.w.

Among the woody plants species that we have investigated, the maximum concentrations of macronutrients have been identified in Black locust and Ash-leaved maple. The maximum concentrations of heavy metals were found in the Silver birch.

Conclusions

Macronutrient (K, Ca, Mg, P, S) and heavy metals (Fe, Mn, Zn, Cu, Pb, Cd) contents in leaves of three tree species indicate a difficult ecological conditions on the Petrovsky waste rock dump devastated lands at the Kryvyi Rih iron-ore & metallurgical district. The growth and development of trees on these devastated lands is carried out with a clear nutrient's shortage (especially K and P) and metal's excess (especially Fe, Mn and Zn).

Taking into account the revealed values of macronutrients optimal concentrations and revealed the heavy metals lowest content in the leaves, we assume that Ash-leaved maple Acer negundo and Black locust Robinia pseudoacacia (compared to the Silver Birch Betula pendula) are more resistant to the geochemical conditions of devastated lands. Therefore, species of trees can be recommended for the creation of artificial tree plantations on devastated lands.

Reference

1. Adams, M. B. (ed.). (2017). The forestry reclamation approach: guide to successful reforestation of mined lands. U.S. Department of Agriculture, Forest Service. https://doi.org/10.2737/NRS-GTR-169

2. Ajasa, Al. M., Bello, O.M.O., Ibrahim, A.O., Ogunwande, I. A., & Olawore, N.O. (2004). Heavy trace metals and macronutrients status in herbal plants of Nigeria. Food Chemistry, 85 (1), 67-71. https://doi.org/10.1016/jioodchem.2003.06.004

3. Ali, H., Khan, E., & Sajad, M.A. (2013). Phytoremediation of heavy metals --concepts and applications. Chemosphere, 91, 869-881. https://doi.org/10.1016/j.chemosphere.2013.01.075

4. Amanifar, S., Aliasgharzad, N., Toorchi, M., & Zarei, M.

(2014). Lead phytotoxicity on some plant growth parameters and proline accumulation in mycorrhizal tomato (Lycopersicon esculentum L.). International Journal of Biosciences, 4 (10), 80-88. http://dx.doi.org/10.12692/ijb/4.10.80-88

5. Barker, A.V., & Pilbeam, D. J. (2010). Handbook of plant nutrition. Taylor & Francis Group.

6. Bashkin, V. N., & Kasimov, N. S. (2004). Biogeohimiya

[Biogeochemistry]'. Scientific World. (in Russian).

7. Bielyk, Yu.V., Savosko, V. M., & Lykholat, Yu.V. (2019). Taxonomic composition and synanthropic characteristic of woody plant community on Petrovsky waste rock dumps (Kryvorizhzhya)]. Ecological Bulletin of Kryvyi Rih District, 4, 104-113. https://doi.org/10.31812/eco-bulletin- krd.v4i0.2565 (in Ukrainian).

8. Dmytruk, Yu. M., & Berbets M. A. (2009). Fundamentalna

bioheokhimiia [Fundamentals of Biogeochemistry]. Book-XXI. (in Ukrainian).

9. Dobrovolskiy, V. V. (2003). Fundamentalnaya biogeohimiya [Fundamentals of Biogeochemistry]. Publishing Center “Academy”. (in Russian).

10. Emamverdian, A., Ding, Y., Mokhberdoran, F., & Xie, Y. (2015). Heavy metal stress and some mechanisms of plant defense response. The Scientific World Journal, 2015, 1-18. https://doi.org/10.1155/2015/756120

11. Gjorgieva-Ackova, D. (2018). Heavy metals and their general

toxicity for plants. Plant Science Today, 5 (1), 14-18.

https://dx.doi.org/10.14719/pst.2018.5.1.355

12. Kabata-Pendias, A. (2011). Trace elements in soils and plants. Taylor and Francis Group.

13. Katrin, V. (2014). How plants cope with heavy metals. Botanical Studies, 55, 35. https://doi.org/10.1186/1999-3110-55-35

14. Kivinen, S. (2017). Sustainable post-mining land use: are closed metal mines abandoned or re-used space? Sustainability, 9, 1705. https://doi.org/10.3390/su9101705

15. Maathuis, F. J.M. (2009). Physiological functions of mineral macronutrients. Current Opinion in Plant Biology, 12, 250-258 (2009). https://doi.org/10.1016/j.pbi.2009.04.003

16. Macdonald, S.E., Landhausser, S.M., Skousen, J., Franklin, J., Frouz, J., Hall, S., Jacobs, D., & Quideau S. (2015). Forest restoration following surface mining disturbance: challenges and solutions. New Forests, 46, 703-732. https://doi.org/10.1007/s11056-015-9506-4

17. MCdonald, J. H. (2014). Handbook of biolological statistics. Sparky house publishing.

18. Pietrzykowski, M. (2019). Tree species selection and reaction to mine soil reconstructed at reforested post-mine sites: Central and eastern European experiences. Ecological Engineering, 3, 100012. https://doi.org/10.1016/j.ecoena.2019.100012

19. Ranjan, V., Sen, P., Kumar, D., & Singh, B. (2016). Reclamation and rehabilitation of waste dump by eco-restoration techniques at Thakurani iron ore mines in Odisha. International Journal of Mining and Mineral Engineering, 7 (3), 253-264. https://doi.org/10.1504/IJMME.2016.078372

20. Rudyshyn, S.D. (2013). Fundamentalna bioheokhimiia [Fundamentals of Biogeochemistry]. Academia Publishing Center. (in Ukrainian).

21. Savosko, V. M., Lykholat, Yu. V., Domshyna, K. M., & Lykholat, T.Yu. (2018). Ekolohichna ta heolohichna zumovlenist poshyrennia derev i chaharnykiv na devastovanykh zemliakh Kryvorizhzhia [Ecological and geological determination of trees and shrubs' dispersal on the devastated lands at Kryvorizhya]. Journal of Geology, Geography and Geoecology, 27 (1), 116-130. https://doi.org/10.15421/111837 (in Ukrainian).

22. Savosko, V. M., Lykholat, Y. V., Bielyk, Yu. V., & Lykholat, T. Yu. (2019b). Ecological and geological determination of the initial pedogenesis on devastated lands in the Kryvyi Rih Iron Mining & Metallurgical District (Ukraine). Journal of Geology, Geography and Geoecology, 28 (4), 738-746. https://doi.org/10.15421/111969

23. Skousen, J., & Zipper, C.E. (2014). Post-mining policies and practices in the Eastern USA coal region. International journal of coal science & technology, 1 (2), 135-151. https://doi.org/10.1007/s40789-014-0021-6

24. Tripathi, D.K., Singh, V. P., Chauhan, D.K., Prasad, S.M., & Dubey, N. K. (2014). Role of macronutrients in plant growth and acclimation: recent advances and future prospective. In: P. Ahmad, M.Wani, M.Azooz, L. S.Phan Tran (eds) Improvement of crops in the era of climatic changes (Vol. 2, pp. 197-216). Springer. https://doi.org/10.1007/978-1-4614-8824-8_8

25. Versieren, L., Evers, S., Abd Elgawag, H., Asard, H., & Smolders, E. (2017). Mixture toxicity of copper, cadmium, and zinc to barley seedlings is not explained by antioxidant and oxidative stress biomarkers. Environmental Toxicology and Chemistry, 36, 220-230. https://doi.org/10.1002/etc.3529

26. Yadav, S. (2010). Heavy metals toxicity in plants: an overview on the role of glutathione and phytochelatins. South African Journal of Botany, 76, 167-179. https://doi.org/10.1016/j.sajb.2009.10.007

27. Zengin, F.K., & Munzuroglu, O. (2005). Effects of some heavymetals on content of chlorophyll, proline and some antioxidant chemicals in bean (Phaseolus vulgaris L.) seedlings. Acta Biologica Cracoviensia Series Botanica, 47 (2), 157-164.

28. Zhou, B., Yao, W., Wang, S., Wang, X., & Jiang, T. (2014). The metallothionein gene TaMT3 from Tamarix androssowii confers Cd²+ tolerance in Tobacco. International Journal of Molecular Sciences, 15 (6), 10398-10409. https://doi.org/10.3390/ijms150610398

29. Zipper, C.E., Burger, J., Skousen, J. G., Angel, P. N., Barton, C.D., Davis, V., & Franklin, J. (2011). Restoring forests and associated ecosystem services on appalachian coal surface mines. Environmental Management, 47, 751-765 (2011). https://doi.org/10.1007/s00267-011- 9670-z

30. Zivkovic, J., Razic, S., Arsenijevic, J., & Maksimovi, Z. (2012). Heavy metal contents in Veronica species and soil from mountainous areas in Serbia. Journal of the Serbian Chemical Society, 77 (7), 959-970. https://doi.org/10.2298/jsc111225221z

31. Zika, M., & Erb, K. H. (2009). The global loss of net primary production resulting from human-induced soil degradation in drylands. Ecological Economics, 69, 310-318. https://doi.org/10.1016Zj.ecolecon.2009.06

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