Study of the Effect of Sample Preparation on the Determination of Heavy Metals in Bottom Sediments of the Danube River (Ukraine)

IJEP 43(4): 313-320 : Vol. 43 Issue. 4 (April 2023)

Valentyna Loboichenko1*, Nataliia Nikitina2, Nataliia Leonova2,3, Olga Konovalova2,3 and Daryna Martyniuk4

1. Lutsk National Technical University, Department of Civil Security, Lvivska street, 75, 43018, Lutsk, Ukraine
2. V. N. Karazin Kharkiv National University, Chemical Metrology Department, Svobody Square, 4, 61022, Kharkiv, Ukraine
3. Water Research Institute, Nábrezie Arm. Gen. L. Svobodu, 5, 81249, Bratislava, Slovakia
4. Ukrainian Research Institute of Environmental Problems, Bakulina Street, 6, 61166, Kharkiv, Ukraine


In the paper the modern methods of the heavy metals determination in bottom sediments were briefly analyzed and the options for the sample preparation were considered. It is noted that the atomic adsorption methods and methods using inductively coupled plasma are the most common. Acid digestion for preparing the sediment samples is predominantly used with or without additional microwave digestion of the samples. There is a lack of unification in the sample preparation of bottom sediments. For this sutdy, a number of samples of bottom sediments of the Danube river (Ukraine), options for sample preparation with acid decomposition, microwave decomposition in acid and microwave decomposition in a mixture of acids were analyzed. It was found that with an increase in the intensification of sample preparation for iron, chromium and manganese, the completeness of extraction increases; the effect of the intensity of sample preparation is most pronounced in the determination of iron and the least in the determination of manganese. For zinc and copper, there is no such dependence and for cobalt, the use of microwave decomposition slightly increases the completeness of extraction. In the Fe-Mn-Zn-Cr-Cu-Co series, the decrease in the accumulation of these metals in bottom sediments was observed.


Heavy metal, Environment, Water, Sample preparation, Microwave decomposition, Acid decomposition, Bottom sediment


  1. Rene, E.R., et al. 2021. Green technologies for sustainable environment: an introduction. Env. Sci. Poll. Res., 28(45): 63437-63439. doi: 10.1007/s11 356-021-16870-3.
  2. Oláh, J., et al. 2020. Impact of industry 4.0 on environmental sustainability. Sustain., 12(11): 4674-4695. doi: 10.3390/su12114674.
  3. Dreval, Y., et al. 2020. The problem of comprehensive analysis of organic agriculture as a factor of environmental safety. Env. Climate Tech., 24(1): 58–71. doi: 10.2478/rtuect-2020-0004.
  4. Lu, Z., et al. 2018. The impact of agricultural chemical inputs on environment: global evidence from informetrics analysis and visualization. Int. J. Low Carbon Tech., 13(4): 338–352. doi :10. 1093/ ijlct/cty039.
  5. Tudi, M., et al. 2021. Agriculture development, pesticide application and its impact on the environment. Int. J. Env. Res. Public Health. 18(3): 1112-1135. doi: 10.3390/ijerph18031112.
  6. Strelets, V., et al. 2022. Analysis of the influence of anthropogenic factors of the urbanized territory of Poltava region (Ukraine) on the state of river water. Ecol. Eng. Env. Tech., 23(2): 185–192. doi: 10.12912/ 27197050/146019.
  7. Pegg, J., et al. 2022. Impacts of alien invasive species on large wetlands. In Fundamentals of tropical freshwater wetlands (chapter 16). Ed T. Dalu and R.J. Wasserman. Elsevier. pp 487-516. doi: 10.1016/B978-0-12-822362-8.00018-9.
  8. Popov, O., et al. 2020. Emergencies at potentially dangerous objects causing atmosphere pollution: Peculiarities of chemically hazardous substances migration. In Systems, decision and control in energy I (SSDC, vol. 298). Ed V. Babak, V. Isaienko and A. Zaporozhets. Springer Cham, New York. pp 151–163. doi:10.1007/978-3-030-48583-2_10.
  9. Slepuzhnikov, E., et al. 2019. Procedure for implementation of the method of artificial deposition of radioactive substances from the atmosphere. Nuclear Radiation Safety. 3(83): 13–25. doi: 10.32918/nrs.2019.3(83).02.
  10. Chandrappa, R. and U.C. Kulshrestha. 2015. Air pollution and disasters. In Sustainable air pollution management: Theory and practice. Springer Cham, New York. pp 325–343. doi: 10.1007/978-3-319-21596-9_8.
  11. Strelets, V.V., et al. 2021. Comparative assessment of environmental parameters of foaming agents based on synthetic hydrocarbon used for extinguishing the fires of oil and petroleum products. SOCAR Proceedings. 1: 001-010.
  12. Migalenko, K., et al. 2018. Development of the technique for restricting the propagation of fire in natural peat ecosystems. Eastern-European J. Enterprise Tech., 1(10 (91)): 31–37. doi: 10.15587/1729-4061.2018.121727.
  13. The war in Donbas: realities and prospects of settlement. 2019. In National security and defence (vol 1-2). Ed Rasumkov Centre. Kyiv. pp 89–104. Available at : 2019_eng.pdf.
  14. Schillinger, J., et al. 2020. Water in war: Understanding the impacts of armed conflict on water resources and their management. WIREs Water. 7(6): 1-19. doi: 10.1002/wat2.1480.
  15. Razegheh, A., et al. 2021. Abandoned Covid-19 personal protective equipment along the Bushehr shores, the Persian Gulf: An emerging source of secondary microplastics in coastlines. Marine Poll. Bull., 168: 112386-112394. doi: 10.1016/j.mar-polbul.2021.112386.
  16. Ana, L., et al. 2022. Implications of Covid-19 pandemic on environmental compartments: Is plastic pollution a major issue? J. Hazard. Mater. Adv., 5: 100041-100049. doi: 10.1016/j.hazadv.2021. 100041.
  17. Leonova, N., et al. 2022. Study of short-term effects on the soil of disposable protective face masks used in the Covid-19 pandemic. Key Eng. Mater., 925: 197–210. doi: 10.4028/p-zjo35h.
  18. Jane, A., et al. 2005. Chemicals in the environment: implications for global sustainability. Appl. Earth Sci.,114(2): 65-97. DOI: 10.1179/0371 74505X62857.
  19. Zhanyun, W., et al. 2020. Toward a global understanding of chemical pollution: A first comprehensive analysis of national and regional chemical inventories. Env. Sci. Tech., 54(5): 2575–2584. doi: 10.1021/acs.est.9b06379.
  20. Wieczorek, J. and A. Baran. 2022. Pollution indices and biotests as useful tools for the evaluation of the degree of soil contamination by trace elements. J. Soils Sediments.22:559-576. doi: 10.1007/s11368-021-03091-x.
  21. Walter, K.D. and M.R. Whiles. 2020. Responses to stress, toxic chemicals and other pollutants in aquatic ecosystems (chapter 16). In Aquatic ecology, freshwater ecology (3rd edn). Academic Press. pp 453-502.
  22. Adeola, F.O. 2021. Global impact of chemicals and toxic substances on human health and the environment. In Handbook of global health. Ed I. Kickbusch, D. Ganten and M. Moeti. Springer, Cham. pp 2227-2256. doi : 10.1007/978-3-030-45009-0_96.
  23. Tchounwou, P.B., et al. 2012. Heavy metal toxicity and the environment. Experientia supplementum. 101: 133–164. doi: 10.1007/978-3-7643-8340-4_6.
  24. Zinabu, M., et al. 2022. Evaluating concentrations of major elements and heavy metals in surface and groundwater resources in reference to the WHO (2011). Drinking Water Quality Guideline Hitsats Mayhanse Areas. 42(2): 149-157.
  25. Da Silva Jr., J.B., et al. 2022. A risk assessment by metal contamination in a river used for public water supply. Marine Poll. Bull., 179: 113730-113737. doi: 10.1016/j.marpolbul.2022.113730.
  26. Misha, R., S. Farzana and P. Dey. 2022. Quality assessment of drinking water, sanitation practices and associated health hazards: Case study in rural districts of West Bengal, India. Indian J. Env. Prot., 42(1): 15-24.
  27. Masindi, V. and K.L. Muedi. 2018. Environmental contamination by heavy metals. In Heavy metals. Ed H.E.M. Saleh and R.F. Aglan. IntechOpen, London. pp 153-178. doi: 10.5772/intechopen. 76082.
  28. Lordache, A.M., et al. 2022. Accumulation and ecotoxicological risk assessment of heavy metals in surface sediments of the Olt river, Romania. Sci. reports.12(1): 880-891. doi: 10.1038/s41598-022-04865-0.
  29. Liu, X., et al. 2022. Heavy metal distribution and bioaccumulation combined with ecological and human health risk evaluation in a typical urban plateau lake, southwest China. Front. Env. Sci., 10: 814678-814691. doi: 10.3389/fenvs.2022.814 678.
  30. Fernandez-Maestre, R., B. Johnson-Restrepo and J. Olivero-Verbel. 2018. Heavy metals in sediments and fish in the Caribbean coast of Colombia: Assessing the environmental risk. Int J. Env. Res., 12: 289–301. doi: 10.1007/ s41742-018-0091-1.
  31. Harikumar, P.S., et al. 2010. Assessment of heavy metal contamination in the sediments of a river draining into a Ramsar site in the Indian subcontinent. J. Adv. Laboratory Res. Biol., 1(2): 120-129.
  32. Sardans, J., F. Montes and J. Peñuelas. 2011. Electrothermal atomic absorption spectrometry to determine As, Cd, Cr, Cu, Hg and Pb in soils and sediments: A review and perspectives. Soil Sediment Contam. Int. J., 20(4): 447-491. doi : 10.1080/15320383.2011.571526.
  33. Luo, P., et al. 2021. Heavy metals in water and surface sediments of the Fenghe river basin, China: assessment and source analysis. Water Sci. Tech., 84 (10-11): 3072–3090. doi: 10.2166/wst.2021. 335.
  34. Astatkie, H., A. Ambelu and E. Mengistie. 2021. Contamination of stream sediment with heavy metals in the Awetu watershed of southwestern Ethiopia. Front. Earth Sci., 9: 658737-658750. doi: 10.3389/feart.2021.658737.
  35. Arroyo, L., et al. 2009. Optimization and validation of a laser ablation inductively coupled plasma mass spectrometry method for the routine analysis of soils and sediments. Spectrochimica Acta Part B: Atomic Spectroscopy. 64(1): 16-25.
  36. Sakan, S., et al. 2011. A study of trace element contamination in river sediments in Serbia using microwave-assisted aqua regia digestion and multivariate statistical analysis. Microchem. J., 99(2): 492-502.
  37. Sergio, L.C., et al. 2022. Use of pollution indices and ecological risk in the assessment of contamination from chemical elements in soils and sediments – Practical aspects. Tr. EAC. 35: e00169. doi: 10.1016/j.teac. 2022.e00169.
  38. De Groot, A.J., K.H. Zschuppel and W. Salomons. 1982. Standardization of methods of analysis for heavy metals in sediments. Hydrobiologia. 91: 689–695. doi: 10.1007/BF02391984.
  39. Khan, W.R., et al. 2020. Risk assessment of heavy metal concentrations in sediments of Matang mangrove forest reserve. Trop. Conserv. Sci., 13: 1-12. doi: 10.1177/1940082920933122.
  40. Duncan, A.E., N. de Vries and K.B. Nyarko. 2018. Assessment of heavy metal pollution in the sediments of the river Pra and its tributaries. Water Air Soil Poll., 229(8): 272: 1-10. doi: 10.1007/s11270-018-3899-6.
  41. Li, F., et al. 2022. Assessment of heavy metal pollution in surface sediments of the Chishui river basin, China. PLoS ONE. 17(2): e0260901: 1-15. doi: 10.1371/journal.pone.0260901.
  42. Balarama Krishna, M.V., et al. 2012. A cost-effective and rapid microwave-assisted acid extraction method for the multi-elemental analysis of sediments by ICP-AES and ICP-MS. Anal. Methods. 4: 3290-3299. doi:10.1039/C2AY25393C.
  43. Chand, V. and P. Surendra. 2013. ICP-OES assessment of heavy metal contamination in tropical marine sediments: A comparative study of two digestion techniques. Microchem. J., 111: 53-61. doi: 10.1016/j.microc.2012.11.007.
  44. Yuhu, L. and Q. Jia. 2021. Pollution and risk assessment of heavy metals in the sediments and soils around Tiegelongnan copper deposit, northern Tibet, China. J. Chem., 2021: 1-13. doi: 10. 1155/2021/8925866.
  45. EPA report. 1996. Method 3050B: Acid digestion of sediments, sludges and soils. EPA SW-846. Revision 2. U.S. Environmental Protection Agency, Washington, D.C., U.S.A.
  46. Galí Navarro, E.M., et al. 2011. Comparison of USEPA 3050B and ISO 14869-1: 2001 digestion methods for sediment analysis by using FAAS and ICP-OES quantification techniques. Química Nova. 34(8): 1443-1449. doi:10.1590/S0100-40422 011000800025.
  47. EPA report. 1996. Method 3052: Microwave assisted acid digestion of siliceous and organically based matrices. EPA SW-846. Revision 0. U.S. Environmental Protection Agency, Washington, D.C., U.S.A.
  48. Remeteiová, D., et al. 2020. Evaluation of US EPA method 3052 microwave acid digestion for quantification of majority metals in waste printed circuit Boards. Metals. 10(11): 1511-1523. doi: 10. 3390/met10111511.
  49. Brandelero, S.M., et al. 2018. Evaluation of analytical methods for lead (Pb) (USEPA 3051) and zinc (Zn) (HR-CS AAS) in sediments. Revista Virtual Química. 10(3): 518-528. doi:10.21577/1984-6835.20180039.
  50. Chen, M. and L.Q. Ma. 1998. Comparison of four USEPA digestion methods for trace metal analysis using certified and Florida soils. J. Env. Quality. 27(6): 1294-1300. doi: 10.2134/jeq1998.004724 25002700060004x.
  51. ISO 5667-12. 2017. Water quality – Sampling – Part 12: Guidance on sampling of bottom sediments from rivers, lakes and estuarine areas. International Organization for Standardization.
  52. ISO 11464. 2006. Soil quality — Pretreatment of samples for physico-chemical analysis. International Organization for Standardization.
  53. EPA report. 2007. Method 3051A: Microwave assisted acid digestion of sediments, sludges and oils. EPA SW-846. Revision 1. U.S. Environmental Protection Agency, Washington, D.C., U.S.A.
  54. Guedes, L. and A.H. Batista. 2020. The classic aqua regia and EPA 3051A methods can mislead environmental assessments and certifications: Potentially harmful elements resorption in short-range order materials. Chemosphere. 251: 126356-126371. doi: 126356.10.1016/j.chem-osphere.2020.126356.