Science of the Total Environment 639 (2018) 900–909

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Science of the Total Environment

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Continuous impact of mining activities on soil heavy metals levels and human health

Gevorg Tepanosyan ⁎, Lilit Sahakyan, Olga Belyaeva, Shushanik Asmaryan, Armen Saghatelyan

The Center for Ecological-Noosphere Studies, National Academy of Sciences, Abovian-68, Yerevan 0025, Armenia

HIGHLIGHTS GRAPHICAL ABSTRACT

• Anthropogenically predominant groups of elements include Mo, Cu, Zn and Pb. • Superposition of natural and anthropo- genic factors formed highly polluted areas. • Multi-elemental non-carcinogenic risk to children health detected.

article info abstract

Article history: Soils samples collected during different geochemical surveys of the city of Kajaran located near the biggest Cu-Mo Received 30 January 2018 mining area in Armenia were subjected to the multivariate geostatistical analysis and geochemical mapping in Received in revised form 11 May 2018 order to reveal soil heavy metals spatial distribution pattern and assess human health risk level under continuous Accepted 17 May 2018 impact of mining activities. In addition, human health risk assessment was done for the contents of Pb, Cu, Zn, Co, Available online xxxx Mo, Mn, Ti, and Fe. The results of Principal Component Analysis and Cluster Analysis verify each other and were also complemented Keywords: Geochemical survey by the spatial distribution features of studied heavy metals indicating that two groups of elements have been gen- Heavy metals erated. The first anthropogenically predominated group includes the main industrial elements Mo and Cu, and Soil pollution their accessories Pb and Zn while Ti, Mn, Fe and Co with the naturally predominant contents were observed in Multivariate geostatistical analysis the second group. Moreover, the study reveals that the superposition of geogenic and anthropogenic components Mining area lead to the alteration of the shapes of areas with the high natural contents of heavy metals and formation of pol- Health risk assessment luted areas with the intensive anomalies of elements. Health risk assessment showed that Mo was the only studied element which poses a non-carcinogenic risk to adult and children's health in some sampling sites during the whole period of investigations. Moreover, in all studied locations multi-elemental non-carcinogenic risk to children health from all studied heavy metals were detected. Special attention was given to the soils of kindergarten territories, and the results indicated that Hazard Index in kindergartens was N1 indicating an adverse health effect to children. The results obtained can serve as a basis for the development and implementation of risks reduction measures and systematic monitoring program planning. © 2018 Elsevier B.V. All rights reserved.

1. Introduction

Mining industry is both a leading factor of economic development in a country and a significant source of environmental pollution by heavy ⁎ Corresponding author. metals (Anju and Banerjee, 2012; Carkovic et al., 2016; Chakraborty E-mail addresses: [email protected],(G.Tepanosyan), [email protected], (L. Sahakyan), [email protected], (O. Belyaeva), et al., 2017; Ding et al., 2017; Li et al., 2014; Martínez López et al., [email protected],(S.Asmaryan),[email protected] (A. Saghatelyan). 2008). In this respect, the anthropogenic contents of heavy metals

https://doi.org/10.1016/j.scitotenv.2018.05.211 0048-9697/© 2018 Elsevier B.V. All rights reserved. G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909 901

Fig. 1. Soils sampling points in 2005, 2011 and 2015 of the city of Kajaran. may become a human health risk factor. It has been repeatedly demon- 2. Materials and methods strated through the investigations of cities (Gabari and Fernández- Caliani, 2017; Kamunda et al., 2016; Lee et al., 2006; Martínez López 2.1. Study area and local geology et al., 2008; Saghatelyan et al., 2010; Wu et al., 2010) located near min- ing complexes. To describe the integrated fingerprint of long-term pol- The city of Kajaran (N 39°9′ and E 46°9′) is the biggest mining center lution, soils of such cities should be studied first, as they accumulate of the Republic of Armenia and is situated in the south of the country, in both pollutions through the diffusion and emission from the point the province of Syunik. The establishment of the city of Kajaran is linked sources (Chakraborty et al., 2017; Johnson et al., 2011; Protano and to the exploitation of the mine and creation of “Zangezur Copper Mo- Nannoni, 2018). Moreover, peculiarities of heavy metal migration in lybdenum Combine (ZCMC).” Today, ZCMC produces 18.5 mln. tons of the environment of cities, as well as final shapes of polluted areas and ore per year which constitutes N60% of the mining industry of conditions of their formation highly depend on the accumulative and Armenia (Worldbank, 2016). The city covers an area of 2.74 km2 barrier features of the soils (Golovin et al., 2004). (7061 inhabitants) (NSS RA, 2016), has a rugged relief and is situated The city of Kajaran is the biggest mining industrial center of the at the height of 1750–1800 m. The city is located in the temperate Republic of Armenia and accommodates the Zangezur Copper Molybde- mountainous climatic zone (maximum in summer: +35 °C; minimum num Combine (ZCMC). In the city, systematic multipurpose geochemi- in winter: −30 °C). The amount of precipitation is approximately cal studies were performed since 2005 by The Center for Ecological- 650 mm and is distributed round the year unevenly with most quanti- Noosphere Studies (CENS) (Saghatelyan et al., 2010). The results of ties during May and June. Northwestern and western winds are domi- the studies indicated that Kajaran soils are polluted by heavy metals nant in the city (The atlas of conditions and resources of Armenian (Ghazaryan et al., 2017; Saghatelyan et al., 2008, 2010). Moreover, the SSR. Climate, 1975). Artsvanic tailing repository of the ZCMC is located 42 km away north- In the territory of Kajaran, two types of erosion landforms are distin- west from Kajaran. The so-called “clean” water of the tailing repository guished: U-shaped river valleys in the middle and lower course of the is discharging into the main river Voghchi through its effluents, thus river and V-shaped river valleys in the riverheads. polluting the agroecosystems irrigated by the water of the river and Due to the heavy spring floods in the southern and partly in the its affluents (Saghatelyan et al., 2008, 2010). western slopes, the soil layer is missing. Up to the height of 1800 m, The impact of the mining activities of ZCMC was also traced in Yere- the soils are brown, while from 1800 to 2400 m chestnut soils predom- van, the capital and industrial center of Armenia. Particularly, the “Plant inate. The northern slope is covered with gray mountain-forest skeletal of Pure Iron” and “Armenian Molybdenum Production” located in the soils (Klopotovski, 1947). southern industrial district of Yerevan is operating on the base of mo- The geological base includes volcanogenic sedimentary and intru- lybdenum concentrate (containing 50% of molybdenum) received sive rocks of the Tertiary period, particularly monzonites and porphyry from Kajaran. The products of the “Plant of Pure Iron” include granites. The Kajaran sulfide copper molybdenum deposit is timed to ferromolybdenum, molybdenum powder, metal molybdenum briskets the monzonites, which were significantly altered by the hydrothermal and alloys, as well as rhenium salts (Zangezur Copper Molybdenum processes, and two types of metallizing is observed: stringer- Combine, 2017). Therefore, Mo mining and processing activities impact disseminated (the main type) and vein (subordinate type). The main both Kajaran and Yerevan population. ore minerals are molybdenite (MoS2) and chalcopyrite (CuFeS2), and Although the city of Kajaran is located within the natural biogeo- the accessory minerals pyrite (FeS2), magnetite (FeO·Fe₂O₃), hematite chemical province (Saghatelyan et al., 2010) which implies the high contents of Mo and Cu in soils, the results of previous studies have Table 1 shown that main industrial elements are of primary environmental con- Levels of single- and poly-element pollution (RA Government, 2005). cern. Moreover, besides Cu and Mo, within the soil pollutants the acces- Element Contents corresponding to pollution level, mg/kg sory elements such as Pb and Zn have also been found (Saghatelyan Level 1 Level 2 Level 3 Level 4 Level 5 et al., 2008, 2010). However, studies targeting the assessment of risk Allowable Low Medium High Extremely high arising from heavy metal contents of soils are insufficient. Therefore, Pb b65 65–130 130–250 250–600 N600 the goal of this study was: 1) to investigate the spatial distribution pecu- Zn b220 220–450 450–900 900–1800 N1800 liarities of heavy metals in the Kajaran city soil and identify possible Cu b132 132–200 200–300 300–500 N500 sources, 2) to assess the human health risk the heavy metals pose, Mo b132 132–200 200–300 300–500 N500 using the databases of the multipurpose geochemical studies of 2005 Mn b1500 1500–2000 2000–3000 3000–4000 N4000 SCI b88–16 16–32 32–128 N128 (Saghatelyan et al., 2008), 2011 (Asmaryan et al., 2014)and2015. 902 G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909

Table 2 2007) were calculated to determine the accuracy error and precision Defined oral reference doses (RfD) of the studied elements (European Food Safety of analysis. The obtained results showed that PD and RPD were within Authority, 2010; RAIS, 2017). 0.1–14.6% and 2.4–14.8%, respectively. Elements Reference doses (RfD, mg/kg−1 day−1)

Fe 0.7 2.4. Assessment of pollution with heavy metals in soil Pb 0.0005 Cu 0.04 To study the levels of heavy metals pollution in Kajaran soils, the Zn 0.3 content of elements were compared with Maximum acceptable concen- Mo 0.005 Co 0.0003 trations (MAC) for soils accepted in Armenia (RA Government, 2005). Mn 0.024 Ti 4 Ci KMAC ¼ ; ð1Þ CMAC

where: K is a concentration coefficient based on MAC; C – content of (Fe2O3), sphalerite (ZnS), tetrahedrite (Cu12Sb4S13), bismuthine (Bi2S3), MAC i ith metalinsoilsample;C – local MAC value of the ith metal in soil. In wulfenite (Pb(MoO4)), vanadinite (Pb5(VO4)3Cl), galena (PbS) etc., as MAC well as native Te and Au. Besides that, ore and ore concentrates contain Armenia MAC values are set for Mn, Cu, Zn, Mo, Pb (RA Government, Re, Se, Ag (Saghatelyan et al., 2008). 2005). To describe multi-element pollution of city soils, the Summary con- 2.2. Topsoil sampling centration index (SCI) was calculated. X ¼ ; ð Þ The database used for this study incorporates the results of 2005 (53 SCI KMAC 2 samples) and 2011 (23 samples) multipurpose geochemical surveys and kindergartens (12 samples) from the study conducted in 2015 KMAC and SCI classification levels are provided in Table 1 (RA (Fig. 1). Government, 2005). Different in years, these studies were done based on the same sam- pling methods developed and based on international guidelines 2.5. Data analysis and geochemical mapping (Darnley et al., 1995; Revich et al., 1982; Saet et al., 1990) and ISO (Fomin and Fomin, 2001; ISO, 2005), US EPA (US EPA, 1999) standards. The descriptive statistics of datasets are summarized in Table 3. In particular, the top 10 cm of the soil layer were sampled using hand Shapiro-Wilk normality tests were used to check the normality of shovel. 3–5 subsamples were mixed to obtain a bulk sample. All col- data. Based on the results of normality tests, the two-sample t-test lected bulk samples were stored in plastic bags. Once taken to the lab, and the Mann-Whitney U test were performed to compare the central soil samples were air-dried, homogenized, sieved (b1 mm) and milled values of underlying distributions of data of 2005 and 2011 respectively. in compliance with ISO-11464 (ISO, 2006) and then stored in sealed Levene's Test was used to check the Equality of Variances. To identify bags for further analysis. outliers and extreme values, box-plots of heavy metals were created. Cluster Analysis (CA) and Principal Component Analysis (PCA) were 2.3. Analytic methods and QA/QC performed to group the studied heavy metals and to identify the poten- tial sources of origin. The total contents of heavy metals (Ti, Mn, Fe, Co, Cu, Zn, Mo and Pb) Element concentrations below the detection limit were given a value in soils were determined using X-ray fluorescence spectrometry of 1/2 of the detection limit as proposed by Reiman et al. (2008). (EDXRF X-5000) (Innov-X Systems, 2003; US EPA, 2007) in 2005 and Geochemical mapping was conducted. To illustrate the spatial distri- 2011, while in 2015 atom absorption spectroscopy (AAnalyst 800 AAS bution of pollution levels and to identify the riskiest locations, geochem- PE, USA) was used. The analysis was done in the Environmental Geo- ical maps were created using the ArcGIS software. Because some chemistry Department and at the Central Analytical Laboratory of samples with high values surrounded by low values were not reflected CENS accredited by ISO-IEC 17025. in the color surface maps, color surface maps were combined with As part of the QA/QC procedure the Relative percent difference (RPD growing-dot maps for the better visualization of problematic areas. %) of duplicate samples and the Percent difference (PD%) of standard Color surface maps were created using the Inverse Distance Weighting reference materials (Cicchella et al., 2008; US EPA Method 6200, method (the power - 2, the number of neighboring samples - 8).

Table 3 Descriptive statistics of studied heavy metals in Kajaran city topsoil in 2005 and 2011.

Elements Ti Mn Fe Co Cu Zn Mo Pb

2005 Mean 7011.5 1340.4 60,581.2 20.4 784.9 166.5 887.9 82.4 Median 6888.0 1322.0 59,252.0 19.7 542.0 126.0 143.1 28.7 SD 1709.7 406.2 16,786.2 4.7 717.6 108.8 2543.8 323.9 Min 4005.0 619.0 30,733.0 11.5 63.0 63.2 2.3 6.1 Max 11,780.0 2501.0 133,489.0 39.7 4001.0 702.0 17,863.2 2388.0 Skew. 0.7 0.9 1.5 1.2 2.4 2.7 6.0 7.2 CV, % 24.4 30.3 27.7 22.7 91.4 65.3 286.5 393.2

2011 Mean 6809.2 1247.3 61,521.7 21.8 1061.1 173.0 1417.6 36.6 Median 6551.0 1215.0 60,000.0 21.1 842.0 142.0 598.0 31.7 SD 1509.5 320.3 19,033.2 5.9 1016.9 81.2 1905.9 22.5 Min 3937.0 508.0 39,000.0 15.3 153.0 72.0 13.5 6.2 Max 9687.0 1818.0 133,000.0 45.9 4886.0 350.0 6880.0 90.5 Skew. 0.3 −0.1 2.5 3.3 2.6 0.7 2.2 0.9 CV, % 22.2 25.7 30.9 26.8 95.8 47.0 134.4 61.6 G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909 903

Table 4 Table 6 Shapiro-Wilk normality test results for studied heavy metals in 2005 and 2011. Principal components loadings for varimax rotated PCA of studied heavy metals.

Elements 2005 2011 Elements Component

Statistic df Sig. Statistic df Sig. 12

Raw dataset Ti −0.618b 0.712a Ti 0.957 53 0.056 0.967 23 0.616 Mn −0.660b 0.235 Mn 0.944 53 0.015 0.974 23 0.774 Fe −0.217 0.920a Fe 0.904 53 0.000 0.767 23 0.000 Co 0.002 0.922a Co 0.918 53 0.001 0.644 23 0.000 Cu 0.651b 0.533b Cu 0.756 53 0.000 0.736 23 0.000 Zn 0.662b −0.237 Zn 0.746 53 0.000 0.918 23 0.059 Mo 0.829a 0.246 Mo 0.334 53 0.000 0.688 23 0.000 Pb 0.741a −0.343 Pb 0.171 53 0.000 0.930 23 0.110 Eigen value 2.96 2.78 Variance % 37.05 34.73 Log(10) transformed dataset Cumulative % 71.78 Ti –– a Mn 0.989 53 0.896 – Strong (N0.7) loading. b Fe 0.981 53 0.542 0.914 23 0.050 Moderate (0.5–0.7) loading. Co 0.969 53 0.187 0.809 23 0.001 Cu 0.981 53 0.571 0.980 23 0.898 RBA is considered to be 1. RfDi is the oral reference dose of the studied Zn 0.944 53 0.015 – Mo 0.987 53 0.814 0.952 23 0.324 elements (Table 2). In the case of Kajaran kindergartens soils, ED for Pb 0.844 53 0.000 – 3 years - a period over which children attend kindergartens in Armenia; EF - exposure frequancy: 253 days/year considering days off Bold are values p N 0.05 significance level. and vacation over three years and attendance hours per day. In the case of non-carcinogenic risk HQ/HI N 1 means that adverse 2.6. Human health risk assessment health effect can be expected, while when HQ/HI b 1 there is no possibil- ity of adverse health effect (RAIS, 2017). The non-carcinogenic risk to human health arising from heavy metal The RfD of studied elements (see Table 2), as well as other exposure contents in Kajaran city soils was assessed based on the methodology parameters used for the risk assessment, were taken from RAIS and US proposed in the US Risk Assessment Information System (RAIS) (RAIS, EPA Human health risk assessment guidance (RAIS, 2017; US EPA, 1989, 2017). As a preferential route of exposure, ingestion pathway was 2004). Only the RfD of Pb was taken from European FoodSafety Author- considered. ity (European Food Safety Authority, 2010). Single-element (HQ) and multi-elemental (HI) non-carcinogenic risk to children and adults risk levels were estimated using the follow- 3. Results and discussion ing equations (RAIS, 2017). 3.1. Statistical data treatment and analysis CDIchildren adults ¼ ðÞC EF ED IngR RBA CF =ðÞAT BW ; ð3Þ The descriptive statistics of heavy metal contents of Kajaran soil i i i HQ ¼ CDI =RfD ; ð4Þ dated 2005 and 2011 are outlined in Table 3. The average values of Cu, Zn, Mo, and Pb both in 2005 and 2011 were ¼ ∑n i: ð Þ HI i¼1HQ 5 greater than the corresponding median values. Moreover, for Cu, Mo and Pb comparatively high CV values of 91.4%, 286.5%, 393.2% and in which: C is the concentration of heavy metals in the soil sample 95.8%, 134.4%, 61.6% were observed in 2005 and 2011, respectively. In (mg/ kg), IngR is the ingestion rate (200 and 100 mg day−1 for children both cases, negligible differences between the average and median and adults, respectively). EF is the exposure frequency values of Ti, Mn, Fe and Co, as well as low CV values were observed. (350 day year−1). ED is the exposure duration (6 and 26 years for chil- The results of Shapiro-Wilk normality test (Table 4)showedthatin dren and adults, respectively). BW is the average body weight (15 and 2005 Ti had a normal distribution and Mn, Fe, Co, Cu and Mo followed 70 kg for children and adults, respectively). AT is the average time a lognormal distribution, while Zn and Pb showed an abnormal distribu- (365 days), for non-carcinogenic risk - AT = ED × 365 day year−1.CF tion. In 2011, normal distribution was observed for Ti, Mn, Zn and Pb, is the conversion factor (1 × 10−6 kg mg−1). RBA is the relative bioavail- and Fe, Cu, Mo, and Pb showed lognormal distribution. Co was the ability factor. For arsenic, RBA is 0.6 while for other studied elements only element having abnormal distribution in 2011.

Table 5 Two-sample t-test and Mann-Whitney U test results for studied heavy metals in 2005 and 2011.

Elements Ti Mn Fe Cu Mo

Levene's test for equality of variances F 0.000 0.060 0.179 1.768 0.006 Sig. 0.989 0.807 0.673 0.187 0.937 T-test for equality of means T 1.597 1.805 0.937 −0.147 −1.719 Df 79 79 79 79 79 Sig. (2-tailed) 0.114 0.075 0.351 0.884 0.090 Mean Difference 631.48 0.05 0.03 −0.01 −0.31 Std. Error Difference 395.52 0.03 0.03 0.09 0.18 95% Confidence Interval of the Difference Lower −155.79 −0.01 −0.03 −0.19 −0.66 Upper 1418.75 0.11 0.08 0.16 0.05

Mann-Whitney U test

Sig. Co Zn Pb 0.762 0.702 0.306

Significance level p b 0.05. 904 G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909

Fig. 2. 2D loading plot for the rotated components.

To further study the distribution peculiarities of heavy metals in Fig. 4. Cluster analysis of heavy metals in Kajaran soils. 2005 and 2011, the Two-sample t-test and Mann-Whitney U test were performed (see Table 5). The Two-sample t-test and Mann-Whitney U test results indicate group 2 (2011) with 95% of confidence for all studied heavy metals. that the central values of the underlying distribution of group 1 Moreover, these two samples are the representatives of the same gen- (2005) are equal to the central values of the underlying distribution of eral population. Therefore, within this study, the identification of

Fig. 3. Spatial distribution of the PC1 and PC2 scores. G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909 905 potential sources of origin of the studied elements and the mapping of elements have high CV values indicating the presence of anthropogenic their spatial distribution were done based on the joint database of impute. However, the fact is that in Kajaran area, Mo and Cu are the 2005 and 2011. main industrial elements in the ore, while Pb and Zn are accessory ele- ments suggesting that the observed concentrations of these elements 3.2. Principal component analysis and cluster analysis are the outcome of both natural and predominant anthropogenic sources. In the multivariate data, to reduce data dimensionality and to re- The processes of extraction, transportation and ore dressing lead to move possible “noise” prior to CA, PCA should be done as the first step the penetration of Mo, Pb, Cu, and Zn to the surface environment and (Reiman et al., 2008). In this study, the KMO (0.67) and Bartlett's test further accumulation into soils. Another source of the contents of (p b 0.001) results showed that PCA could be used to analyze the these elements may be the northwestern winds which cross the closed dataset. tailing repository of Voghchi situated near the city in its northeastern PCA results showed that only the eigenvalues of first two compo- part. Moreover, the contents of Pb, Cu, and Zn in the city's environment nents (PC1 = 2.96 and PC2 = 2.78) were N1. According to the varimax are vehicular emissions (Chabukdhara and Nema, 2013; Sun et al., 2010; rotation results (Table 6 and Fig. 2), PC1 and PC2 explained 71.78% of the Yuan et al., 2014). The latter is typical also for Kajaran, because of the total variance. mining transport. Also, the north-south main highway of the republic PC1 explaining 37.05% of total variance, showed a strong positive passes through the city of Kajaran. The sources of Pb in transport may loading for Mo, Pb, moderate positive loading for Cu, Zn and negative be brake lining (Winther, 2010) and car batteries (Steinnes, 2013), for moderate loading for Ti and Mn suggesting other dominant sources of Zn the vehicle tires (Li et al., 2001), and for Cu vehicle brake lining origin of Ti and Mn than those in the case of Mo, Pb, Cu, and Zn. These (Lindström, 2001).

Fig. 5. Spatial distribution of heavy metals in Kajaran city soils. 906 G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909

Fig. 6. Spatial distribution of MAC excesses and SCI levels.

In the case of PC2 (34.73% of total variance) strong positive loadings high values are observed in the western industrial part of the city. The observed for Ti, Fe, Co suggest the predominant geogenic input of these high values of PC1 and PC2 scores are partially overlapping near the elements. This was confirmed by low values of CV. In the PC2 moderate ZCMC (Fig. 3), indicating that the processes of ore crushing and milling, positive loading was observed for Cu. The presence of Cu both in PC1 as well as, ore dressing may be one of the potential sources for the an- and PC2 indicated the presence of different sources of this element in thropogenic contents of studied heavy metals in the city of Kajaran. the study area. Hierarchical CA results presented in the dendrogram (Fig. 4) and ob- The spatial distribution maps of factor scores make it especially evi- tained for the log, the transformed and standardized (Z score) values of dent that high values of the anthropogenically predominant group (PC1 studied heavy metals showed that two distinct clusters were formed. including Mo, Pb, Cu, and Zn) are spatially allocated in the residential The first cluster includes Fe, Co, Ti, and Mn, while the second cluster part of the city, while in the case of PC2 (including Ti, Fe, Co, and Cu) combines Zn, Pb, Cu and Mo at the rescaled distance of 20. Thus, it is

Table 7 Children and adults' health non-carcinogenic risk of heavy metals in Kajaran soils in 2005.

Elements Adults Children

Min Max Mean HQ/HI N 1 Min Max Mean HQ/HI N 1

Ti_HQ 1.37E−03 4.03E−03 2.40E−03 – 1.28E−02 3.77E−02 2.24E−02 – Mn_HQ 3.53E−02 1.43E−01 7.65E−02 – 3.30E−01 1.33E+00 7.14E−01 6 Fe_HQ 6.01E−02 2.61E−01 1.19E−01 – 5.61E−01 2.44E+00 1.11E+00 33 Co_HQ 5.25E−02 1.81E−01 9.34E−02 – 4.90E−01 1.69E+00 8.71E−01 14 Cu_HQ 2.16E−03 1.37E−01 2.69E−02 – 2.01E−02 1.28E+00 2.51E−01 1 Zn_HQ 2.89E−04 3.21E−03 7.60E−04 – 2.69E−03 2.99E−02 7.10E−03 – Mo_HQ 6.16E−04 4.89E+00 2.43E−01 2 5.75E−03 4.57E+01 2.27E+00 19 Pb_HQ 1.67E−02 6.54E+00 2.26E−01 1 1.56E−01 6.11E+01 2.11E+00 22 HI 2.93E−01 7.14E+00 7.87E−01 6 2.74E+00 6.66E+01 7.35E+00 53

In italic HQ/HI N 1 values are given. G. Tepanosyan et al. / Science of the Total Environment 639 (2018) 900–909 907

Table 8 Children and adults' health non-carcinogenic risk of heavy metals in Kajaran soils in 2011.

Elements Adults Children

Min Max Mean HQ/HI N 1 Min Max Mean HQ/HI N 1

Ti_HQ 1.35E−03 3.32E−03 2.33E−03 – 1.26E−02 3.10E−02 2.18E−02 – Mn_HQ 2.90E−02 1.04E−01 7.12E−02 – 2.71E−01 9.68E−01 6.64E−01 – Fe_HQ 7.63E−02 2.60E−01 1.20E−01 – 7.12E−01 2.43E+00 1.12E+00 16 Co_HQ 6.99E−02 2.10E−01 9.96E−02 – 6.52E−01 1.96E+00 9.30E−01 4 Cu_HQ 5.24E−03 1.67E−01 3.63E−02 – 4.89E−02 1.56E+00 3.39E−01 1 Zn_HQ 3.29E−04 1.60E−03 7.90E−04 – 3.07E−03 1.49E−02 7.37E−03 – Mo_HQ 3.70E−03 1.88E+00 3.88E−01 2 3.45E−02 1.76E+01 3.63E+00 15 Pb_HQ 1.70E−02 2.48E−01 1.00E−01 – 1.59E−01 2.31E+00 9.36E−01 7 HI 3.37E−01 2.35E+00 8.19E−01 4 3.14E+00 2.19E+01 7.65E+00 23

In italic HQ/HI N 1 values are given. evident that the results of CA are identical with the results of PCA, sug- (Fig. 6) are also located in the residential part of the city and ZCMC. gesting different levels of the predominance of geogenic and anthropo- Therefore, there is a need for human health risk assessment to delineate genic factors of origin for these two groups of metals. areas where observed concentrations of the studied heavy metals can become risk factors to human health. 3.3. Heavy metals spatial distribution 3.5. Human health risk assessment The spatial distribution maps of studied heavy metals (Fig. 5)arein line with multivariate analysis results. One group includes Mo, Cu, Pb The non-carcinogenic risk to human health from the ingestion path- and Zn. For these elements, concentrations N50% were spatially allo- way was assessed based on the contents of Ti, Fe, Co, Mn, Mo, Cu, Pb and cated mainly in the residential part. Another group included Fe, Co, Ti Zn in the soils of Kajaran in 2005, 2011 and 2015 (Table 7). and Mn and in this case N50% concentrations outline the residential The non-carcinogenic risk assessment of adults showed that both in part of the city. However, in both cases, element contents N50% were ob- 2005 and 2011 only Mo contents in 2 sampling sites per each year posed served also near the ZCMC. an adverse health effect to adults (Tables 7 and 8). The multi-elemental risk was detected in 4 and 6 sampling sites for 3.4. Kajaran soils pollution levels both cases, and the riskiest sites located in the western part of the Com- bine (1 sampling site per year) and the residential part of the city (5 and The average contents of Mn, Zn in 2005 and 2011, as well as Pb in 3 sampling sites per year, respectively). The average value of multi- 2011 are lower than the corresponding values of MAC. In 2005 excesses elemental risk in 2005 (HI = 7.14) was 3.04 times greater than in vs. MAC were detected for Cu, Mo, and Pb, and in 2011 for Cu and Mo: 2011. The latter is mainly associated with comparably low contents of However, maximal contents of all elements exceeded MAC values. Pb in 2011 as leaded gasoline sales has ceased in Armenia since 2001. Moreover excesses vs. MAC were observed for 60.5%, 98.7%, 15.8%, In the case of non-carcinogenic risk threatening children, the mono- 26.3% and 26.3% of Mo, Cu, Pb, Zn, and Mn, respectively. The observed elemental risk was observed for Fe, Co, Cu, Mo, Pb (2005 and 2011) and excesses vs. MAC prove that all studied heavy metals have concentra- Mn (2005). Moreover, in 2005 the risk was detected in 6, 33, 14, 1, 19 tions which may pose an adverse health effect to the local population. and 22 sampling sites for Mn, Fe, Co, Cu, Mo and Pb, while in 2011 in From Fig. 6 it is evident that the areals of high and very high levels of 16, 4, 1, 15 and 7 sampling sites for Fe, Co, Cu, Mo and Pb, respectively. excesses vs. MAC are spatially allocated and include the residential part In 2005, the Mn HQ N 1 sampling sites were spatially located outside of of the city and ZCMC. The areals of Pb and Zn excesses vs. MAC are lo- the residential parts of the city. For Pb, 22 sites posing a risk to children cated in the residential part of the city. In the case of Mn areals of ex- are situated in the city's residential part and its outskirts. Both in 2005 cesses vs. MAC are located adjacent to the query in the northern and and 2011 the sampling sites of Fe and Mo having HQ N 1 values were western parts of Combine and city, respectively. The spatial distribution near the Combine and in the residential part of the city. For Co HQ N 1 map of SCI iterates Mo and Cu maps because the proportion of these el- values were near the Combine and outside the residential part, and in ements in SCI values is 74.1%. The moderate and high levels of SCI have the case of Cu - near the Combine. dominated in the built up areas of the city. Similar results obtained by The multi-elemental risk was detected both in 2005 and 2011 in all Ghazaryan et al. (2017). The areals of high and very high levels of SCI studied sites indicating an adverse health effect to children. The average

Table 9 Children health non-carcinogenic risk of heavy metals in Kajaran kindergartens soils in 2015.

Kindergarten Ti_HQ Mn_HQ Fe_HQ Co_HQ Cu_HQ Zn_HQ Mo_HQ Pb_HQ HI_8

N1 7.56E−03 7.83E−02 2.48E−01 1.97E−01 8.83E−02 1.22E−03 7.96E−01 3.19E−01 1.73E+00 6.83E−03 8.96E−02 2.93E−01 2.58E−01 4.74E−02 6.16E−04 7.00E−02 5.25E−01 1.29E+00 6.96E−03 1.23E−01 1.81E−01 2.22E−01 5.98E−02 1.57E−03 9.40E−02 3.75E−01 1.06E+00 7.07E−03 8.93E−02 1.64E−01 2.00E−01 5.51E−02 7.52E−04 9.50E−02 2.16E−01 8.26E−01 6.21E−03 1.07E−01 2.07E−01 3.57E−01 5.48E−02 9.58E−04 3.30E−01 5.32E−01 1.59E+00 6.27E−03 7.41E−02 1.31E−01 2.98E−01 4.43E−02 1.08E−03 3.11E−01 5.02E−01 1.37E+00 N1 mean 6.82E−03 9.36E−02 2.04E−01 2.55E−01 5.83E−02 1.03E−03 2.83E−01 4.11E−01 1.31E+00 N2 7.22E−03 9.63E−02 2.14E−01 2.07E−01 7.49E−02 2.47E−03 8.71E−01 4.40E−01 1.91E+00 5.66E−03 1.11E−01 1.53E−01 2.31E−01 6.26E−02 1.80E−03 1.93E−01 3.21E−01 1.08E+00 5.97E−03 1.22E−01 1.65E−01 2.28E−01 1.06E−01 1.93E−03 3.72E−01 4.63E−01 1.46E+00 5.35E−03 1.42E−01 1.79E−01 2.69E−01 5.78E−02 1.46E−03 5.22E−01 4.58E−01 1.64E+00 5.90E−03 1.28E−01 1.92E−01 2.01E−01 5.78E−02 1.51E−03 2.76E−01 4.55E−01 1.32E+00 5.75E−03 9.77E−02 1.66E−01 2.22E−01 5.79E−02 1.64E−03 2.82E−01 4.24E−01 1.26E+00 N2 mean 5.98E−03 1.16E−01 1.78E−01 2.27E−01 6.94E−02 1.80E−03 4.19E−01 4.27E−01 1.44E+00 908 G. 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