Dissemination of heavy metal contamination in surface sediments of batlama stream Giresun Turkey

0.09. 20.70

20.61 GV: Guidelines Values, LEL (Lowest Effect Level), TEL (Threshold Effect Level), MET (Minimal Effect Threshold), TET (Toxic Effect Threshold), SAV (Shale Average Value), TS= This study Since there are not any criteria specified in our country to evaluate sediment quality of freshwater, data acquired in the study was evaluated in accordance with the sediment quality criteria published by MacDonald et al. [12], Persaud et al. [13] and with the average heavy metal content of crust reported by Krauskopf [14] . According to effect levels of sediment quality criteria, LEL (Lowest Effect Level) is the limit; below this limit, generally no negative effects are observed on creatures in sediments. TEL (Threshold effect level) is the limit; below this limit, negative effects on creatures in sediments are rarely observed. MET (Minimal effect threshold) is the limit; below this limit, negative effects are not generally observed on most of the creatures in sediments. TET is known as Toxic

Sigma Journal of Engineering and Natural Sciences, Research Article, Vol. 39, No. 1, pp. 13-23, March, 2021 effect threshold. Above this limit, negative effects are generally observed in most of the creatures in sediments [12] (Table 2). Iron (Fe) is the most commonly found element in the earth’s crust with an average value of 47000 ppm [14]. In this study, the element which was found most in the sediment is Fe with its average value of 9724 (mg/dry kg). The minimum value was found in St. 2 in spring as 9523 (mg/dry kg), and the maximum value was found in St 1 as 10126 (mg/dry kg) (Figure 2). As one of the sediment quality criteria, LEL value (20000 ppm) was not exceeded in any station (Fig.2). Based on this data, it can be stated that river sediment is at a level that does not pose a threat to aquatic ecosystems (Fig. 2). In accordance with the stations specified in the sediment, average manganese (Mn) amount is 374.30 (mg/dry kg). The minimum value was found in St.3 as 333.33 (mg/dry kg), and the maximum value was found in St.1 as 443.07 (mg/dry kg). The average Mn amount is well below 850 ppm, which is the average of the earth’s crust. Additionally, as one of the sediment quality criteria reported by Persaud et al. (1993), LEL value (460 mg/dry kg) was not exceeded in any station and in any season (Fig. 2).

Figure 2. Boxplot graphics and levels of heavy metals in the sediment The annual average zinc (Zn) amount found in the sediment is 49.60 (mg/dry kg). The minimum value was recorded in St. 1 as 26.32 (mg/dry kg), and the maximum value was recorded in St. 2 as 64.28 (mg/dry kg) (Figure 2). These values are considerably lower than the naturally existing zinc value in the sediment (100 mg / dry kg) [15]. In addition, the LEL limit value of 120 (mg / dry kg), which is one of the sediment quality criteria, was not exceeded 16

Sigma Journal of Engineering and Natural Sciences, Research Article, Vol. 39, No. 1, pp. 13-23, March, 2021 in any station and in any season. Based on these findings, it can be concluded that basin sediments were not exposed to zinc contamination. Annual average chrome (Cr) amount found in the sediments which were collected seasonally from three stations in Batlama Stream is 7.08 (mg/dry kg). The minimum value was recorded in St. 1 as 6.59 (mg/dry kg), and the maximum value was recorded in St. 3 as 7.49 (mg/dry kg). These values are considerably lower than the average chrome value which naturally exists in the earth’s crust (100 mg / dry kg) (Table 2). Additionally, LEL (26 mg / dry kg) and TEL (37.3 mg / dry kg) limit values, which are among sediment quality criteria, were not exceeded in any stations and in any seasons (Fig. 2). Based on these findings, it can be concluded that the stream was not exposed to chrome contamination. Cobalt (Co) is found at an average rate of 8 ppm in the earth’s crust [13]. In this study, it was calculated to be 5.47 (mg/dry kg). The minimum value was found in St. 3 as 5.11 (mg/dry kg), and the maximum value was found in St. 1 as 6.04 (mg/dry kg). As can be understood from these values, river sediment does not contain any danger for aquatic ecosystem in terms of cobalt element. Ni concentration is 4.99 (mg/dry kg) on average. The minimum value was found in St. 2 as 4.89 (mg/dry kg), and the maximum value was found in St. 1 as 5.06 (mg/dry kg). Compared to the Çömlekçi Stream, Batlama Stream has a lower concentration Cadmium (Cd) is an element which is not obligatory for living things, and causes genetic and ecological toxicity on animals as well as negatively affecting plant growth and development. Its release to nature is mainly through power plants, metal industry, geological decomposition, atmospheric deposition, phosphate fertilizers used, incinerated solid wastes, toxic wastes from industrial plants and sewages [16, 17]. The average Cd content annually detected in the sediment of the river is 0.09 ppm. The maximum value was recorded in St.3 as 0.17 (mg/dry kg). The obtained values are in the range of 0.1 - 0.5 mg / kg which is the average Cd value in the earth’s crust [17]. Additionally, these results are well below the LEL (0.6 ppm) value of the sediment quality criteria in all stations and in all seasons. Consequently, sediment values of the streams are appropriate for freshwater ecosystems in terms of Cd. Table 3. Comparison of heavy metal concentrations in sediments of Batlama Stream with other world rivers. Location Mangonbangon River , Philippines Ganga River , India Gomti River, India Korotoa River , Bangladesh Langat River, Malaysia Huaihe River, China Jialu River, China Shur River, Iran Tigris River, Turkey Batlama River, Turkey

Mn Co Fe References 261 15.31 22006 [46] 372 31988 [47] [48] [35] 28300 [49] 876 33388 [50] [51] 26000 [52] [53] 343 5.47 7829 This study

Studies on sediment quality in our country and in the world have increased in recent years. Average concentrations of heavy metal were compared with the studies carried out on Ganga and Gomti rivers in India, Korotoa River Bangladesh, Langat River in Malaysia, Huaihe and Jialu rivers in China, Şur River in Iran, Dicle River in Turkey, and Mangonbangon River in Philippines. It was found out that most of the pollution was related to industrial development in the rivers we compare. Especially Zn and Cu are high in Dicle and Şur rivers. Similarly, Cr and Ni concentrations did not exceed the values in Dicle and Korota rivers; it is rather low compared to other rivers listed. Ganga and Huaihe rivers are the ones with the highest Mn levels among the rivers compared. Similarly, average Fe concentrations reported in Ganga, Langat, Huaihe and Shur rivers are high. Ustaoğlu and Tepe [18] found in the research of heavy metal levels in the sediment of Pazarsuyu Brook that Fe, Mn, Zn, Cu, Pb, Cr, Co, Cd elements were the most abundant in the sediment. They were found respectively as 8312 ppm, 155.83 ppm, 32.74 ppm, 19.69 ppm, 17.79 ppm, 10.64 ppm, 4.26ppm, and 0.16ppm. The heavy metal levels detected in the sediment of Pazarsuyu Brook, which is subjected to the pressure of domestic, agricultural wastes, agricultural fertilizers and pesticides and HEPP constructions, and stone and gravel pits, are not at a level that is dangerous for aquatic life. Fe and Mn are the metals which are found abundantly in the earth’s crust [19, 20]. Akbulut and Tunçer [21] found in the 17

Sigma Journal of Engineering and Natural Sciences, Research Article, Vol. 39, No. 1, pp. 13-23, March, 2021 study they carried out that Fe and Mn accumulation was high in the sediment. In our study, it was detected that these metals are higher than others. Anoymous [22] indicated that pesticides which are commonly used in agricultural areas and have Cu and Mn as active agent, and artificial fertilizers which are high in Cr, Ni, Mn [23,24] can mix in the brook as a result of rain and human activities; and it could be considered the reason of high accumulation levels. Pb exists in lead mineral along with Cu and Zn [22], and in our study, it was found to be high in 2 St. It is thought that the increase in the number of gas stations in the region is effective in the increase of lead. Statistical Analyses Pearson’s correlation analysis: According to the results of Pearson’s correlation test which is carried out to determine the relationships of variables with each other, although many metals are related to each other, Mn, Ni, Cu showed no correlation with other metals. Co and Mn shows medium level of correlation (r=0.665, P<0.05), and Co and Fe shows high level of correlation (r=0.761, P<0.01). Zn and Ni shows high level of correlation (r=0.738, P<0.01). Pb and Zn shows high level of correlation in a positive way (r=0.765, P<0.01). Zn, on the other hand, shows Fe and Co and Pb shows Fe negative correlation (Table 3). The results of correlation analysis applied to heavy metal data acquired from the stream sediment are similar to the information in the literature. Cr, Mn, Cu, Ni, Zn, and Cd elements are grouped together and it is understood that these heavy metals result from anthropogenic sources [25]. The negative correlation between Pb and other metals in the sediment shows that contamination sources of Pb are different from other metals. Table 4. Pearson correlation matrix for metals in sediments of the Batlama Stream N=12

In the factor analysis applied to heavy metals detected in the sediment, 3 factors which have eigenvalues higher than 1 and explain 83.07% of the total variance were detected. While all elements (Zn, Cd, Cu) found in the 1st factor which explains 40.506% of the total variance have a powerful positive charge, Mn and Co and powerful negative charge supports such situation. In the 2nd factor which forms 25.682% of the total variance, Fe and Cr have powerful positive charge, and Pb has negative charge. Ni itself forms the 3 rd factor which has 16.88% share in the total variant (Table 4). According to Suresh et al. [26], if the coefficient relationship between metals is high, it shows that these metals have similar transportation behaviours and come from the same source. The weak relationship between other metals indicates that these metals are not controlled by one element. Instead, geochemical support and mergence exist by being controlled one combination [27]. Inverse relationship between Mn and Zn is an indicator of Zn’s external input of heavy metal which can be related to anthropogenic sources [28]. Table 4 Rotation component matrix for metals in surface sediments from Batlama stream. Cluster analysis: Clustering analysis was applied to the data so as to observe variables’ relationships with each other and clustering of variables. According to clustering dendrogram, two big clustering draw attention (Figure 2). First group includes Co, Ni, and Cr. It means that transportation mechanisms and/or sources of these elements are similar. The second group represents possible common sources/processes of Cu, Pb, Zn. Cd, Fe and Mn are located away from these two groups (Figure 3).

Sigma Journal of Engineering and Natural Sciences, Research Article, Vol. 39, No. 1, pp. 13-23, March, 2021

Figure 3. Cluster analysis (CA) dendrogram of the Batlama Stream sediments Enrichment Factor (EF): Enrichment factor is a frequently used index to determine the possible sources of metals, anthropogenic effect and grade. Average enrichment factors of the metals studied in Batlama stream are as follows in a decreasing way: Pb> Zn> Cu> Mn> Cd>Co>Fe>Cr>Ni. In general, the highest enrichment values were detected in St.2. While Pb showed significant degree enrichment in St.2, moderate degree enrichment was detected in St.1 and 3. While Zn showed moderate enrichment in St. 2 and 3, it showed minimum enrichment in St.1. While Cu had moderate enrichment in St. 2 and 3, it had minimum enrichment in St.1. While Mn showed moderate enrichment in St. 1, it showed minimum enrichment in St. 2 and 3. Cd showed moderate enrichment in St. 2 and minimum enrichment in St.3, and its enrichment level was found to be 0 in St. 1. Co, on the other hand, showed minimal increase in all stations. Fe showed minimal increase in all stations. It was observed that Cr and Ni elements did not show an increase in general (Table 5). These increases of Pb observed in St.2 indicated anthropogenic based input and it must be paid attention for the health of ecosystem. Additionally, this area is well known with natural Pb deposits [29,30]. Table 5. Enrichment (EF) in the Batlama Stream by sample stations enrichment factors (EF) grade standards for EF Sutherland (2000) B1 Cr 0.36 Mn 2.53 Fe 1.04 Co 1.54 Ni 0.36 Cu 1.82 Zn 1.34 Cd 0 Pb 2.21

Value EF<2 Minimal enrichment 2≤EF<5 Moderate enrichment 5≤EF<20 Significant enrichment 20≤EF<40 Very high enrichment EF≥40 Extremely high enrichment.

Enrichment factor (EF) is used in evaluating origins of elements [31,32]. Enrichment factor is a convenient tool to differentiate between anthropogenic and natural sources of elements [33]. If EF values are between 0.05 and 1.5, elements are natural; if they are 1.5 >, it means it has anthropogenic sources [34-38]. In our study, the value of Mn, Cu, Zn, and Pb concentration is >1.5. Contamination Factor (CF): As an index used to make an evaluation about the sources of metals, CF values are sorted in a decreasing way as follows: Pb> Zn> Cu> Mn> Cd> Co> Fe> Cr> Ni. According to CF values, all elements apart from Pb showed low contamination. On the other hand, Pb showed moderate contamination in St. 2. As can be observed from 19

Sigma Journal of Engineering and Natural Sciences, Research Article, Vol. 39, No. 1, pp. 13-23, March, 2021 average values, all elements apart from Pb have values less than 1 (Table 6). These index values were < 1 in all stations; the concentration of these elements is less than the background values in stations and for this reason, it is categorized as uncontaminated. Distribution of metals depends not only on their sources but also on hydromechanical flow of the water [39-41]. Table 6. Contamination factor (CF) in the Batlama Stream sediment sample stations Contamination Factor (CF) B 1 B2 B3

In order to interpret the degree of contamination detected in Batlama Stream, Geo-accumulation index values (Igeo) were calculated (Chart 5.6). In Batlama Stream, no contamination was observed in all elements but Pb. Insignificant contamination was found in Pb. While Pb was -1.73 only in St. 1, it was 0.18 in St. 2 and 0.66 in St. 3. The average value was calculated as insignificant contamination with 0.53. I geo showed that all metals are between 0 and 1 (Table 7). In Batlama stream, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Cd elements did not change because of anthropogenic effects. However, it was found out that for Pb, this value was on the limit in stations apart from St.1. This metal might come from cars and industrial wastes. Also, this Pb might be caused by agricultural activities across the stream. The high Pb levels in St.2 might be related to the location of these stations. Additionally, this area is well known with natural Pb deposits [42-44]. Table 7. Geoaccumulation index values (Igeo) in the Batlama stream by sample sations. Geoaccumulation index B1 B2 -4.32 -4.32 Cr

Grade standards for Igeo Müller [48] Value Igeo status Mean -4.32 Igeo≤0 Practically uncontaminated 0<Igeo<1 Uncontaminated to moderately -1.78 contaminated -2.83 1<Igeo<2 Moderately contaminated -2.39 2<Igeo<3 Moderately to heavily contaminated -4.32 3<Igeo<4 Heavily contaminated -1.68 4<Igeo<5 Heavily to extremely contaminated -1.51 Igeo≥5 Extremely contaminated -2.25 0.53

Ecological risk factor (Eri): Eri indicator was used to evaluate potential ecological risks (Table 8). Based on the results of Er i index, all elements are in the limit of low ecological risk. Based on Er i indexes in general, it can be stated that there is not any potential environmental danger in terms of the elements analysed in the region. Results are close to the results acquired in Zarrin Gol River [34] and Tajan River [45].

Sigma Journal of Engineering and Natural Sciences, Research Article, Vol. 39, No. 1, pp. 13-23, March, 2021 Table 8. Ecological risk factor (Eri) Batlama stream sediment by samples stations [46].

Value Er < 40 40 ≤ Er < 80 80 ≤ Er < 160 160 ≤ Er < 320 Er ≥ 320

Ecological risk factor for an individual metal Low risk Moderate risk Considerable risk High risk Very high risk