Accumulation of Potentially Toxic Elements in Mosses Collected in the Republic of Moldova
Abstract
:1. Introduction
2. Results and Discussion
2.1. Comparison of the Obtained Values with Data from the Previous Moss Survey
2.2. Association of Chemical Elements
2.3. Pollution Assessment of the Examined Moss Samples
3. Materials and Methods
3.1. Studied Area
3.2. Sampling
3.3. Sample Preparation
3.4. Analysis
3.4.1. Neutron Activation Analysis
3.4.2. Atomic Absorption Spectrometry
3.4.3. Quality Control
3.4.4. Statistical Analysis and Mapping
3.5. Pollution Indices
4. Conclusions
- During the second moss survey study in Moldova, the mass fractions of 35 elements were determined using NAA and AAS. The mass fractions of the determined elements varied in a wide range and the highest concentrations were determined in urban areas, mainly in Chisinau and Balti.
- Comparison of the obtained results with data from the previous moss survey revealed a significant decrease of the mass fractions of Cr, As, Se, Br, Sb, Cd, Pb, and Cu in the present moss survey.
- Compared with moss survey results from neighboring countries, the mass fractions of the elements As, Al, Ni, V, Cr, and Fe were the highest in samples collected in Moldova, while of Cd and Pb they were among the lowest.
- According to factor analysis to the main air pollution sources ascertained during the 2015/2016 moss survey in Moldova, namely, transport, industrial activity, and thermal power plants, were added mining and industrial activities.
- Contamination factor and Pollution load index values revealed unpolluted to moderately polluted conditions. The Balti and Chisinau municipalities were found to be the most contaminated. It was determined that Cr, Ni, Cu, As, Cd, Zn, and Pb pose a low potential ecological risk.
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
AAS | atomic absorption spectrometry |
CF | contamination factor |
CV | coefficients of variation |
FA | factor analysis |
MAD | Median Absolute Deviation |
NAA | neutron activation analysis |
PLI | Pollution load index |
RI | Potential ecological risk index |
SD | standard deviation |
References
- Kłos, A.; Ziembik, Z.; Rajfur, M.; Dołhańczuk-Śródka, A.; Bochenek, Z.; Bjerke, J.W.; Tømmervik, H.; Zagajewski, B.; Ziółkowski, D.; Jerz, D.; et al. Using moss and lichens in biomonitoring of heavy-metal contamination of forest areas in southern and north-eastern Poland. Sci. Total Environ. 2018, 627, 438–449. [Google Scholar] [CrossRef]
- Lee, C.S.L.; Li, X.; Zhang, G.; Peng, X.; Zhang, L. Biomonitoring of trace metals in the atmosphere using moss (Hypnum plumaeforme) in the Nanling Mountains and the Pearl River Delta, Southern China. Atmos. Environ. 2005, 39, 397–407. [Google Scholar] [CrossRef] [Green Version]
- Barandovski, L.; Stafilov, T.; Šajn, R.; Frontasyeva, M.; Andonovska, K.B. Atmospheric heavy metal deposition in north macedonia from 2002 to 2010 studied by moss biomonitoring technique. Atmosphere 2020, 11, 929. [Google Scholar] [CrossRef]
- Mahapatra, B.; Dhal, N.K.; Dash, A.K.; Panda, B.P.; Panigrahi, K.C.S.; Pradhan, A. Perspective of mitigating atmospheric heavy metal pollution: Using mosses as biomonitoring and indicator organism. Environ. Sci. Pollut. Res. 2019, 26, 29620–29638. [Google Scholar] [CrossRef] [PubMed]
- Conti, M.E.; Tudino, M.B. Lichens as Biomonitors of Heavy-Metal Pollution. Compr. Anal. Chem. 2016, 73, 117–145. [Google Scholar] [CrossRef]
- Kularatne, K.I.A.; De Freitas, C.R. Epiphytic lichens as biomonitors of airborne heavy metal pollution. Environ. Exp. Bot. 2013, 88, 24–32. [Google Scholar] [CrossRef]
- Alexandrino, K.; Viteri, F.; Rybarczyk, Y.; Guevara Andino, J.E.; Zalakeviciute, R. Biomonitoring of metal levels in urban areas with different vehicular traffic intensity by using Araucaria heterophylla needles. Ecol. Indic. 2020, 117. [Google Scholar] [CrossRef]
- Pakeman, R.J.; Hankard, P.K.; Osborn, D. Plants as biomonitors of atmospheric pollution: Their potential for use in pollution regulation. Rev. Environ. Contam. Toxicol. 1998, 157, 1–23. [Google Scholar] [CrossRef]
- Vergel, K.; Zinicovscaia, I.; Yushin, N.; Frontasyeva, M.V. Heavy Metal Atmospheric Deposition Study in Moscow Region, Russia. Bull. Environ. Contam. Toxicol. 2019, 103, 435–440. [Google Scholar] [CrossRef]
- Stihi, C.; Popescu, I.V.; Frontasyeva, M.; Radulescu, C.; Ene, A.; Culicov, O.; Zinicovscaia, I.; Dulama, I.D.; Cucu-Man, S.; Todoran, R.; et al. Characterization of Heavy Metal Air Pollution in Romania Using Moss Biomonitoring, Neutron Activation Analysis, and Atomic Absorption Spectrometry. Anal. Lett. 2017, 50, 2851–2858. [Google Scholar] [CrossRef]
- Qarri, F.; Lazo, P.; Allajbeu, S.; Bekteshi, L.; Kane, S.; Stafilov, T. The Evaluation of Air Quality in Albania by Moss Biomonitoring and Metals Atmospheric Deposition. Arch. Environ. Contam. Toxicol. 2019, 76, 554–571. [Google Scholar] [CrossRef]
- Stafilov, T.; Šajn, R.; Barandovski, L.; Andonovska, K.B.; Malinovska, S. Moss biomonitoring of atmospheric deposition study of minor and trace elements in Macedonia. Air Qual. Atmos. Health 2018, 11, 137–152. [Google Scholar] [CrossRef]
- Hristozova, G.; Marinova, S.; Svozilík, V.; Nekhoroshkov, P.; Frontasyeva, M.V. Biomonitoring of elemental atmospheric deposition: Spatial distributions in the 2015/2016 moss survey in Bulgaria. J. Radioanal. Nucl. Chem. 2020, 323, 839–849. [Google Scholar] [CrossRef]
- Zinicovscaia, I.; Hramco, C.; Duliu, O.G.; Vergel, K.; Culicov, O.A.; Frontasyeva, M.V.; Duca, G. Air Pollution Study in the Republic of Moldova Using Moss Biomonitoring Technique. Bull. Environ. Contam. Toxicol. 2017, 98, 262–269. [Google Scholar] [CrossRef] [PubMed]
- Stanković, J.D.; Sabovljević, A.D.; Sabovljević, M.S. Bryophytes and heavy metals: A review. Acta Bot. Croat. 2018, 77, 109–118. [Google Scholar] [CrossRef]
- Nordic Council of Ministers. Atmospheric Heavy Metal Deposition in Europe:–Estimation Based on Moss Analysis; Nordic Council of Ministers: Copenhagen, Denmark, 1994. [Google Scholar]
- Frontasyeva, M.; Harmens, H.; Uzhinskiy, A. Mosses as Biomonitors of Air Pollution: 2015/2016 Survey on Heavy Metals, Nitrogen and POPs in Europe and Beyond; LRTAP: Châtelaine, Switzerland, 2020; ISBN 9785953005081. [Google Scholar]
- Zhou, X.; Chen, Q.; Liu, C.; Fang, Y. Using moss to assess airborne heavy metal pollution in Taizhou, China. Int. J. Environ. Res. Public Health 2017, 14, 430. [Google Scholar] [CrossRef]
- Zhao, H.; Wang, X.; Li, X. Quantifying grain-size variability of metal pollutants in road-deposited sediments using the coefficient of variation. Int. J. Environ. Res. Public Health 2017, 14, 850. [Google Scholar] [CrossRef] [Green Version]
- Kłos, A.; Czora, M.; Rajfur, M.; Wacławek, M. Mechanisms for translocation of heavy metals from soil to epigeal mosses. Water. Air. Soil Pollut. 2012, 223, 1829–1836. [Google Scholar] [CrossRef] [Green Version]
- Čeburnis, D.; Valiulis, D. Investigation of absolute metal uptake efficiency from precipitation in moss. Sci. Total Environ. 1999, 226, 247–253. [Google Scholar] [CrossRef]
- Ministry of Ecology and Natural Resources. National Institute of Ecology Republic of Moldova State of the Environment Report 2004 Chişinău; Ministry of Ecology and Natural Resources: Beijing, China, 2005.
- Kabata-Pendias, A. Trace Elements in Soils and Plants; CRC Press: Boca Raton, FL, USA, 2010; ISBN 0849315751. [Google Scholar]
- Zinicovscaia, I.; Sturza, R.; Duliu, O.; Grozdov, D.; Gundorina, S.; Ghendov-Mosanu, A.; Duca, G. Major and trace elements in moldavian orchard soil and fruits: Assessment of anthropogenic contamination. Int. J. Environ. Res. Public Health 2020, 17, 7112. [Google Scholar] [CrossRef] [PubMed]
- Martins, G.; Miot-Sertier, C.; Lonvaud-Funel, A.; Masneuf-Pomarède, I. Grape berry bacterial inhibition by different copper fungicides. BIO Web Conf. 2016, 7, 01043. [Google Scholar] [CrossRef] [Green Version]
- Fernández, J.A.; Carballeira, A. Evaluation of contamination, by different elements, in terrestrial mosses. Arch. Environ. Contam. Toxicol. 2001, 40, 461–468. [Google Scholar] [CrossRef]
- Wu, W.; Wu, P.; Yang, F.; Sun, D.L.; Zhang, D.X.; Zhou, Y.K. Assessment of heavy metal pollution and human health risks in urban soils around an electronics manufacturing facility. Sci. Total Environ. 2018, 630, 53–61. [Google Scholar] [CrossRef]
- Air Quality in Europe-Publications Office of the EU. Available online: https://op.europa.eu/en/publication-detail/-/publication/d17e4630-aefa-11e7-837e-01aa75ed71a1/language-en (accessed on 1 March 2021).
- Harmens, M.H. United Nations Economic Commission for Europe Convention on Long-Range Transboundary Air Pollution Monitoring of Atmospheric Deposition of Heavy Metals, Nitrogen and Pops in Europe Using Bryophytes Monitoring Manual 2010 Survey Icp Vegetation Coordination. Available online: https://icpvegetation.ceh.ac.uk/get-involved/manuals/moss-survey (accessed on 27 February 2021).
- Pavlov, S.S.; Dmitriev, A.Y.; Frontasyeva, M.V. Automation system for neutron activation analysis at the reactor IBR-2, Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Russia. J. Radioanal. Nucl. Chem. 2016, 309, 27–38. [Google Scholar] [CrossRef] [Green Version]
- Greenberg, R.R.; Bode, P.; De Nadai Fernandes, E.A. Neutron activation analysis: A primary method of measurement. Spectrochim. Acta Part B At. Spectrosc. 2011, 66, 193–241. [Google Scholar] [CrossRef]
- Wilcoxon, F. Individual Comparisons by Ranking Methods. Biom. Bull. 1945, 1, 80. [Google Scholar] [CrossRef]
- Carballeira, A.; Couto, J.A.; Fernández, J.A. Estimation of background levels of various elements in terrestrial mosses from Galicia (NW Spain). Water. Air. Soil Pollut. 2002, 133, 235–252. [Google Scholar] [CrossRef]
- Hakanson, L. An ecological risk index for aquatic pollution control.a sedimentological approach. Water Res. 1980, 14, 975–1001. [Google Scholar] [CrossRef]
2020/2022 | 2015/2016 | ||||||
---|---|---|---|---|---|---|---|
Range | Md ± MAD & | Q1 | Q3 | Percentile 90 | Md ± MAD | Analytical Technique | |
Al | 1280–11,700 | 3400 ± 1200 | 2515 | 4780 | 8784 | 3120 ± 1100 | NAA |
As * | 0.31–2.03 | 0.77 ± 0.23 | 0.56 | 1.06 | 1.35 | 0.85 ± 0.27 | NAA |
Ba | 24–117 | 50 ± 15 | 40.8 | 71.5 | 84 | 60 ± 24 | NAA |
Br * | 1.07–7.6 | 3.2 ± 1.6 | 1.78 | 4 | 5.72 | 4.7 ± 1.0 | NAA |
Ca | 5740–17,200 | 9300 ± 1500 | 8165 | 11,050 | 16,200 | 9900 ± 1100 | NAA |
Cd * | 0.06–0.56 | 0.12 ± 0.04 | 0.078 | 0.16 | 0.25 | 0.39 ± 0.08 | AAS |
Ce | 1.83–16 | 4.6 ± 1.8 | 3.47 | 7.7 | 9.42 | 4.4 ± 1.7 | NAA |
Cl | 23–453 | 110 ± 30 | 67.5 | 139 | 174 | 100 ± 40 | NAA |
Co | 0.4–3.24 | 0.98 ± 0.29 | 0.7 | 1.32 | 1.96 | 0.79 ± 0.29 | NAA |
Cr * | 3.2–21.3 | 5.5 ± 1.06 | 4.4 | 8.95 | 11.7 | 7.2 ± 3.1 | NAA |
Cs | 0.18–1.5 | 0.42 ± 0.13 | 0.29 | 0.6 | 0.79 | 0.33 ± 0.14 | NAA |
Cu * | 5.7–22.2 | 8.7 ± 1.0 | 7.12 | 9.42 | 11.7 | 15± 3.0 | AAS |
Eu | 0.02–0.27 | 0.08 ± 0.04 | 0.058 | 0.12 | 0.15 | 0.08 ± 0.04 | NAA |
Fe | 951–7810 | 2200 ± 600 | 1740 | 3125 | 4524 | 2100 ± 900 | NAA |
Hf | 0.14–1.83 | 0.56 ± 0.19 | 0.41 | 0.86 | 1.15 | 0.45 ± 0.22 | NAA |
K | 4170–12,100 | 7250 ± 1000 | 5535 | 7830 | 9896 | 7100 ± 1500 | NAA |
La | 0.78–8.1 | 2.3 ± 0.6 | 1.71 | 3.05 | 4.58 | 2.1 ± 0.8 | NAA |
Mn | 41–335 | 90 ± 30 | 73.5 | 148 | 199 | 120 ± 50 | NAA |
Na | 119–965 | 400 ± 120 | 248 | 506 | 670 | 308 ± 122 | NAA |
Ni | 2.2–14.3 | 4.1 ± 1.0 | 3.27 | 5.4 | 7.74 | 4.7± 2.0 | NAA |
Pb * | 1.56–8.82 | 3.1 ± 0.4 | 2.76 | 3.74 | 5.12 | 12 ± 2.5 | AAS |
Rb | 3.2–26.6 | 9.9 ± 2.1 | 7.5 | 12.1 | 17.8 | 9.8 ± 3.9 | NAA |
Sb * | 0.09–0.85 | 0.19 ± 0.04 | 0.15 | 0.26 | 0.41 | 0.25 ± 0.06 | NAA |
Sc | 0.28–2.84 | 0.76 ± 0.24 | 0.59 | 1.07 | 1.61 | 0.69 ± 0.31 | NAA |
Se * | 0.11–0.43 | 0.23 ± 0.04 | 0.18 | 0.26 | 0.29 | 0.32 ± 0.05 | NAA |
Sm | 0.15–1.3 | 0.39 ± 0.14 | 0.28 | 0.57 | 0.77 | 0.31 ± 0.13 | NAA |
Sr | 26.5–107 | 50 ± 15 | 38.3 | 68.5 | 92 | 40 ± 10 | NAA |
Ta | 0.02–0.21 | 0.06 ± 0.02 | 0.046 | 0.095 | 0.12 | 0.06 ± 0.03 | NAA |
Tb | 0.02–0.15 | 0.04 ± 0.01 | 0.032 | 0.068 | 0.087 | 0.05 ± 0.02 | NAA |
Th | 0.23–2.5 | 0.73 ± 0.22 | 0.53 | 1 | 1.49 | 0.65 ± 0.27 | NAA |
Ti | 80–1020 | 290 ± 80 | 207.5 | 379 | 668 | 230 ± 110 | NAA |
U | 0.08–0.62 | 0.21 ± 0.07 | 0.16 | 0.29 | 0.35 | 0.22 ± 0.09 | NAA |
V | 2.4–18.8 | 5.4 ± 1.6 | 3.9 | 8.2 | 13.7 | 5.5 ± 2.3 | NAA |
Zn | 25–86 | 39 ± 7 | 32.3 | 47 | 70.4 | 37.2 ± 8.5 | NAA |
Al | As | Cd | Cr | Cu | Fe | Ni | Pb | Sb | V | Zn | |
---|---|---|---|---|---|---|---|---|---|---|---|
Moldova | 3400 | 0.7 | 0.1 | 5.4 | 8.7 | 2200 | 4.1 | 3.1 | 0.2 | 5.4 | 40 |
Belarus | 595 | 0.23 | 0.39 | 5.52 | 392 | 1.3 | 2.18 | 0.096 | 0.95 | 35 | |
Bulgaria | 2290 | 0.44 | 0.12 | 2.76 | 7.28 | 1125 | 2.21 | 10.7 | 0.11 | 3.81 | 28.1 |
Poland | 967 | 0.38 | 0.21 | 2.22 | 7.6 | 535 | 2.94 | 4.98 | 0.2 | 1.59 | 50.6 |
Romania | 2895 | 1.08 | 0.27 | 4.72 | 5.77 | 1535 | 3.11 | 4.2 | 0.2 | 4.32 | 40.1 |
Russia | 1450 | 0.49 | 0.28 | 4.13 | 6.03 | 925 | 2.55 | 0.81 | 0.2 | 2.65 | 43.1 |
Ukraine | 938 | 0.7 | 0.31 | 3.65 | 10.4 | 700 | 2.89 | 3.81 | 0.19 | 2.52 | 33.7 |
Element | Factor 1 | Factor 2 | Factor 3 | Factor 4 | Communality, % |
---|---|---|---|---|---|
Na | 0.93 | 0.18 | 0.14 | −0.02 | 98 |
Mg | 0.53 | 0.68 | 0.26 | 0.17 | 95 |
Al | 0.60 | 0.54 | 0.41 | 0.27 | 100 |
Cl | −0.18 | 0.18 | 0.82 | −0.07 | 82 |
K | 0.08 | 0.03 | 0.86 | −0.15 | 85 |
Ca | 0.02 | −0.81 | −0.06 | 0.38 | 76 |
Sc | 0.97 | 0.14 | 0.12 | −0.07 | 100 |
Ti | 0.62 | 0.55 | 0.36 | 0.25 | 98 |
V | 0.58 | 0.56 | 0.42 | 0.20 | 100 |
Cr | −0.91 | −0.21 | −0.09 | 0.11 | 94 |
Fe | −0.97 | −0.14 | −0.08 | 0.06 | 99 |
Co | −0.95 | −0.12 | −0.01 | 0.10 | 98 |
Ni | −0.86 | 0.02 | −0.14 | 0.28 | 89 |
Zn | 0.05 | −0.13 | −0.25 | 0.84 | 87 |
As | −0.87 | −0.27 | 0.00 | 0.22 | 95 |
Br | 0.46 | −0.09 | 0.67 | −0.22 | 91 |
Rb | 0.89 | −0.17 | 0.23 | −0.02 | 94 |
Sr | 0.24 | 0.81 | −0.13 | −0.19 | 87 |
Sb | −0.62 | −0.14 | 0.00 | 0.61 | 92 |
Cs | −0.94 | −0.24 | −0.01 | 0.13 | 99 |
Th | 0.96 | 0.11 | 0.15 | −0.05 | 99 |
U | 0.91 | 0.22 | 0.10 | −0.25 | 98 |
Cd | −0.14 | 0.55 | −0.19 | 0.61 | 85 |
Pb | 0.38 | 0.12 | 0.15 | −0.72 | 85 |
Cu | −0.45 | 0.10 | −0.66 | 0.32 | 82 |
Expl.Var, % | 47 | 14 | 12 | 11 |
Element | Background Values, mg/kg | Moldova | Chisinau | Balti |
---|---|---|---|---|
CF | ||||
Cu | 9.4 | 0.9 ± 0.3 * | 2.4 | 1.4 |
V | 5.7 | 1.2 ± 0.7 | 2.5 | 3.2 |
Cr | 5.5 | 1.3 ± 0.8 | 3.0 | 3.9 |
Fe | 1820 | 1.5 ± 0.8 | 3.4 | 3.8 |
As | 0.52 | 1.6 ± 0.7 | 3.7 | 3.9 |
Cd | 0.26 | 0.5 ± 0.4 | 0.4 | 0.5 |
Zn | 42 | 1.0 ± 0.3 | 1.1 | 1.4 |
Sb | 0.15 | 1.6 ± 1.1 | 5.4 | 5.6 |
Pb | 4.8 | 0.7 ± 0.3 | 1.1 | 1.4 |
U | 0.13 | 1.8 ± 0.9 | 4.0 | 4.1 |
PLI | 1.1 ± 0.4 | 2.4 | 2.3 | |
PER | 44.1 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
Share and Cite
Zinicovscaia, I.; Hramco, C.; Chaligava, O.; Yushin, N.; Grozdov, D.; Vergel, K.; Duca, G. Accumulation of Potentially Toxic Elements in Mosses Collected in the Republic of Moldova. Plants 2021, 10, 471. https://doi.org/10.3390/plants10030471
Zinicovscaia I, Hramco C, Chaligava O, Yushin N, Grozdov D, Vergel K, Duca G. Accumulation of Potentially Toxic Elements in Mosses Collected in the Republic of Moldova. Plants. 2021; 10(3):471. https://doi.org/10.3390/plants10030471
Chicago/Turabian StyleZinicovscaia, Inga, Constantin Hramco, Omari Chaligava, Nikita Yushin, Dmitrii Grozdov, Konstantin Vergel, and Gheorghe Duca. 2021. "Accumulation of Potentially Toxic Elements in Mosses Collected in the Republic of Moldova" Plants 10, no. 3: 471. https://doi.org/10.3390/plants10030471