Soil degradation involves the decline of soil quality and fertility due to the acidification, salinization or chemical contamination of soils from agricultural or industrial sources. In this study, spatial changes of topsoil quality were investigated in the lower basin of Arieș River, an area with a wide history of industrial activities. A sampling campaign has been done along the lower Arieș catchment, during a rainy season (November 2019). The topsoils pH and metals content were analysed. In order to asses the quality of the soil samples, soil contamination index Cd and enrichment factor EF were computed. The results of the present study showed that the topsoil samples from the former industrial sites had a high Cu, Pb and As content. According to the Cd, one sample presented a level of concern due to high level of heavy metals content, and EF assigned a considerable degree of soil enrichment - in case of two topsoil samples

Băbălău-Fuss Vanda

Micle Valer

Moldovan Ana

Török Anamaria Iulia

English

University of Szeged

26th International Symposium on Analytical and Environmental Problems 229  ASSESING THE SOIL QUALITY OF A FORMER INDUSTIAL AREA, USING POLLUTION LOAD INDEX AND ENRICHMENT FACTOR  Ana Moldovan1,2, Anamaria Iulia Török1, Băbălău-Fuss Vanda1, Valer Micle2  1 INCDO-INOE 2000, Research Institute for Analytical Instrumentation, 67 Donath Street, 400293 Cluj-Napoca, Romania; 2 Technical University, Faculty of Materials and Environmental Engineering, 103-105 Muncii Boulevard, 400641 Cluj-Napoca, Romania  e-mail: ana.moldovan@icia.ro  Abstract Soil degradation involves the decline of soil quality and fertility due to the acidification, salinization or chemical contamination of soils from agricultural or industrial sources. In this study, spatial changes of topsoil quality were investigated in the lower basin of Arieș River, an area with a wide history of industrial activities. A sampling campaign has been done along the lower Arieș catchment, during a rainy season (November 2019). The topsoils pH and metals content were analysed. In order to asses the quality of the soil samples, soil contamination index Cd and enrichment factor EF were computed. The results of the present study showed that the topsoil samples from the former industrial sites had a high Cu, Pb and As content. According to the Cd, one sample presented a level of concern due to high level of heavy metals content, and EF assigned a considerable degree of soil enrichment - in case of two topsoil samples.   Introduction Intensive anthropogenic land use activities have a negative impact on the land ecosystem and can lead to the land degradation. The quality of the soil is given by its capacity to function within land-use and ecosystem boundaries, with a balanced chemical composition (Fusaro et al., 2018, Paz-Kagan et al., 2014). The soil is an environmental segment that can store various pollutants, a witness of the historical anthropogenic activities with negative effects on the quality of the environment. Hence, it is crucial that methodologies assessing impacts caused by historical and actual anthropogenic activities to use related impacts in their frameworks (Turran et al., 2019, Ma et al., 2020). To assess soil quality, indicators have been used, evaluating different soil functions, utilizing chemical, physical, and biological attributes (Chavaz et al., 2017). The present study aims to establish the current quality of the six topsoils sampled from the lower Arieș River basin. Their quality was assessed with the help of two indices: soil contamination index Cd (Rehman et al., 2020) and enrichment factor EF (Siddiqhe et al., 2020).  Experimental 1. Study area The Arieș River catchment is an area affected by past mining and industrial activities. Although, in the last decade, most of the anthropogenic activities were stopped, the historical pollution is still leaving their mark on the soil quality (Levei et al., 2013, Butiuc-Keul et al., 2012).  26th International Symposium on Analytical and Environmental Problems 230  The lower basin begins at the border between Cluj and Alba counties and continues until Arieș River joins the Mureș River and overlap entirely to the Transylvanian Depression. The geomorphological substrate of the lower basin is a clay rich area (Costea, 2009). The history of the studied area is characterized by intense industrial activities, like extractive, chemical (Turda) and metallurgical industries (Câmpia Turzii). In the present, the land use is primarily managed for farming activities in the lower reaches of the Mures river (Frink, 2009). 2. Sampling and testing Soil samples were collected at the 0.10–0.20 m depths, from 6 different areas (Figure 1), in November 2019. Sampling locations were chosen with respect to the history of anthropic activities carried out in the area.  The soil samples were homogenized, dried at 105 °C for 24 h and passed through a 4 mm sieve. To analyze the pH, the samples were dispersed in water with a soil/water ratio of 1:5. The samples pH was determined using a 350I multiparameter (WTW). 3 g of soil samples were digested in a mixture of HCl and HNO3 (3:1) prior to measure the concentrations of metals. Fe, Ni, Cr, Cu, Zn, Cd, Pb, Na, Mg, K, Ca, Mn, Ba, Al, Sr, P concentrations were measured using Optima 5300 DV Spectrometer (Perkin Elmer), while As concentration was determined by ELAN DRC II Spectrometer (Perkin-Elmer). All chemicals were of analytical grade (Merck). 3. Soil quality assessment Two methods to calculate the potential ecological risk were used to evaluate the current quality of the soil samples collected in 2019. To identify the contributions of the heavy metals to soil pollution, soil contamination index Cd (Eqs. 1-2) and enrichment factor EF (Eqs. 3-4) were assessed. 𝐶𝑓 =𝐶𝐴𝑖𝐶𝑁𝑖− 1 (1) 𝐶𝑑 = ∑(𝑐𝑓)𝑛𝑖=1 (2) Where, CAi is the value of the concentration of ith metal ions in the analyte and CNi represents the maximum allowable concentration (MAC) of the elements, according to the national legislation (Law 756/1997). Cf and Cd results higher than 1.0 indicate a powerful contamination with metals (Ullah and Muhammad, 2020).  𝐸𝐹 = 𝑅𝑒𝑠𝑎/𝑅𝑒𝑏𝑘 (3) 𝑃𝐸𝑅 = ∑ 𝐸𝐹𝑛𝑖=1 (4) where, Resa is the value of the concentration of ith metal ions in the analyte and Rebk is the value of the concentration of ith metal ions in the background sample (Kabata-Pendias, 2011, Kukdrer et al., 2014).   Figure 1. The lower Arieș River basin and sampling points 26th International Symposium on Analytical and Environmental Problems 231  Results and discussion 1. Descriptive statistics of heavy metal concentrations Soil screening values for pH and metal content are presented in Table 1. The tested soil samples pH was neutral (in the range of 7.5 to 8.0 pH units). The high exceeding rates of heavy metals comparing with intervention threshold for sensitive soil indicated an obvious accumulation in topsoil, especially for Cu, Pb and As. The concentration of Cu was higher than the intervention concentration in S2 and S3, while the Pb and As admissible concentrations were exceeded in the soils sampled from S2 and S4. All other metals content fall within the permissible guideline values. Romanian environmental legislation has not established limiting values for Fe, Na, Mg, K, Ca and Al to soil quality, due to the natural presence of these elements in soils.  Table 1. The analyzed parameters in the tested soil sample   S1 S2 S3 S4 S5 S6 ITSS* BK** pH pH units 8.0 8.0 7.5 7.8 7.8 7.7 - - Fe mg/kg 10287 10428 10785 10677 10912 10426 - - Ni 31.6 44.8 42.4 38.5 30.8 24.5 100 15–50 Cr 28.4 43.1 37.2 35.8 48.2 26.1 300 42–200 Cu 146 216 204 175 87.3 82.8 200 11–13 Zn 202 305 291 356 104 111 600 31–90 Cd <0.20 <0.20 <0.20 <0.20 <0.20 <0.20 5.00 - Pb 22.3 157 58.3 117 16.8 33.2 100 10–35 Na 410 462 517 427 126 123 - - Mg 2456 2103 2871 2603 2737 2503 - - K 3274 3311 4279 3612 1654 1216 - - Ca 10062 1345 17532 12341 4276 5062 - - Mn 785 1127 1254 1096 513 349 2500 310–1007 Ba 100 84.7 124 97.2 49.8 49.7 625 315–500 Al 15262 19473 20004 18006 15312 9818 - - Sr 44.3 52.4 75.8 61.6 20.8 13.4 - - P 325 265 85.6 192 236 174 - - As 18.2 25.1 24.5 27.1 17.2 21.1 25 - * Intervention threshold for sensitive soils according to Law 756/1997 ** Heavy metal concentration (mg/kg) in background soils of the world (Semenkov et al., 2020) Comparing with the metal concentration background soils of the world, the content of Cu and Zn from all the samples analyzed exceeded, while Pb and Mn were higher than their corresponding background values in the perimeter of the former industrial areas. Ni, Cr and Ba content are similar to the indicated limits for the metals content of the background soils, (Semenkov et al., 2020).  It can be concluded that the topsoil samples with high concentration of metals  were obtain near from the former industrial areas of „Chemicals“ from Turda and „Wire Industry“ from Câmpia Turzii. In this study, the metal concentrations observed in soils of the studied area corresponded to base values found in the Iron Quadrangle region from Brazil, which is one of the richest mineral-bearing regions in the world (Souza et al., 2015).   26th International Symposium on Analytical and Environmental Problems 232  2. Soil pollution assessment using Cd and EF The indices Cf and EF were implemented to evaluate the level of metal pollution in the environment of industrial areas in the lower Arieș River basin. Contamination index Cd was computed for 8 heavy metals: Ni, Cr, Cu, Zn, Pb, As, Cd, Mn and it is presented in Table 2. For S2, Cf for Cu, Pb and As were higher than unity, and the value of Cd (1.53) indicated a powerful contamination with heavy metals. Cf indicated a high contamination for Pb in the sample S3, however the Cd was low (Cd<1), which indicates a moderate metal contamination. For S2 and S3, Cf mean values were observed as Pb > Cu > As > Zn > Ni > Mn > Cr > Cd.  Table 2. The contamination index computed for soil sampled from the lower Arieș River basin  Cf – Ni Cf – Cr Cf – Cu Cd – Zn Cf – Pb Cf – As Cf – Cd Cf – Mn Cd S1 -0.579 -0.716 0.460 -0.327 -0.554 0.213 -1.00 -0.686 -5.90 S2 -0.324 -0.547 1.12 0.214 1.48 1.07 -1.00 -0.476 1.53 S3 -0.487 -0.642 0.750 0.187 1.340 0.807 -1.00 -0.562 -1.70 S4 -0.435 -0.628 1.040 -0.030 0.166 0.633 -1.00 -0.498 -3.45 S5 -0.589 -0.518 -0.127 -0.653 -0.664 0.147 -1.00 -0.795 -6.65 S6 -0.673 -0.739 -0.172 -0.630 -0.336 0.407 -1.00 -0.860 -6.60   Figure 2. The enrichment factor EF computed for the soil samples  Enrichment factor (EF) is usually employed for differentiating metals originating from natural weathering from parent materials or human-induced processes (Kabala et al., 2020). Figure 2 showed that the values of EF were very high and varied greatly across different sited. According to Hossain Bhuiyan (2020), S1, S5 and S6 have a low degree of enrichment, S4, a medium degree, S2 and S3, a considerable degree of metal enrichment. The sequence of heavy metals as regards to calculated mean EF values was Cr > Pb > Ni > As > Zn > Cu > Cd. EF was an effective tool in proving the initial hypothesis: that the historical pollution is still very present in the topsoil of the studied area. Ciarkowska and Gambus (2020) suggested a high ecological risk in an industrial area from Nowa Huta district of Krakow, generated by the soil accumulation of Cr and Pb. In addition, a change in the management strategies applied to the sites is recommended by the authors.  Conclusion In the lower basin Arieş River, the geographic position and history of industrial activities carried out in the area had a major impact on the soil quality. The aim of the present study was to assess the current quality state of 6 topsoils sampled of different point from lower Arieș River 11.013.819.531.438.913.60.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0S1S2S3S4S5S6Moderate degree of soil enrichmentConsiderable degree of soil enrichmentLow degree of soil enrichment 26th International Symposium on Analytical and Environmental Problems 233  basin. Although the neutral pH, the soil samples from S2 and S3 Cu, Pb and As content was higher than the intervention threshold for sensitive soils. Furthermore, some metals content such as Cu, Zn, Pb and Mn, was higher than their corresponding background values. According to Cd, S2 presented a high level of metal contamination, with a computed value of 1.53. EF divided the 6 topsoil samples into three different enrichment categories: low degree (S1, S5, S6), medium degree (S4) and a considerable degree of soil enrichment (S2, S3). In the mentioned pollution index context, the sequence pollution state of the topsoil tested was S2 > S3 > S4 > S5> S1 > S6.  Acknowledgements This paper was supported by the Project “Entrepreneurial competences and excellence research in doctoral and postdoctoral programs -ANTREDOC”, project co-funded by the European Social Fund.  References [1] S. Fusaro, F. Gavinelli, F. Lazzarini, M.G., Paoletti, Ecol. Indic. 93 (2018), pp. 1276 – 1292.  [2] T. Paz-Kagan, M. Shachak, E. Zaassy, A. Karnieli, Geoderma 230 – 231 (2014), 171 – 184.  [3] I.D. Turam., O. Dengiz, B., Ozkan, Comput. Electron. Agric. 164 (2019), 104933. [4] L. Ma., T. Xiao, Z. Ning, Y. Liu, H. Chen, J. Peng, Sci. Total Environ. 724 (2020), 138176. 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Assessing the soil quality of a former industrial area, using pollution load index and enrichment factor

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Assessing the soil quality of a former industrial area, using pollution load index and enrichment factor

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