Compositional-geochemical characterization of lead (Pb) anomalies and Pb-induced human health risk in urban topsoil.

Urban areas are characterized by a constant anthropogenic input, which is manifested in the chemical composition of the surface layer of urban soil. The consequence is the formation of intense anomalies of chemical elements, including lead (Pb), that are atypical for this landscape. Therefore, this study aims to explore the compositional-geochemical characteristics of soil Pb anomalies in the urban areas of Yerevan, Gyumri, and Vanadzor, and to identify the geochemical associations of Pb that emerge under prevalent anthropogenic influences in these urban areas. The results obtained through the combined use of compositional data analysis and geospatial mapping showed that the investigated Pb anomalies in different cities form source-specific geochemical associations influenced by historical and ongoing activities, as well as the natural geochemical behavior of chemical elements occurring in these areas. Specifically, in Yerevan, Pb was closely linked with Cu and Zn, forming a group of persistent anthropogenic tracers of urban areas. In contrast, in Gyumri and Vanadzor, Pb was linked with Ca, suggesting that over decades, complexation of Pb by Ca carbonates occurred. These patterns of compositional-geochemical characteristics of Pb anomalies are directly linked to the socio-economic development of cities and the various emission sources present in their environments during different periods. The human health risk assessment showed that children are under the Pb-induced non-carcinogenic risk by a certainty of 63.59% in Yerevan and 50% both in Gyumri and Vanadzor.

Increasing obsidian diversity during the Chalcolithic Period at Yeghegis-1 Rockshelter (Armenia) reveals shifts in land use and social networks.

The newly excavated rockshelter of Yeghegis-1 in Armenia reflects an occupation of five centuries, as attested by radiocarbon dates from ∼ 4100 to 4000 cal BCE in the lowest layer to ∼ 3600-3500 cal BCE at the top. It is a partially collapsed cave in which pastoralists, we hypothesize, wintered with their herds. The stone tool assemblage is predominantly obsidian (92.1%), despite the shelter being > 60 km on foot from the nearest sources. We use obsidian sourcing to investigate two purported trends in the Southern Caucasus during the Chalcolithic Period: (1) occupation of more varied high-altitude environments and (2) more expansive social networks. Our data show both trends were dynamic phenomena. There was a greater balance in use of the nearest pasturelands over time, perhaps linked to risk management and/or resource sustainability. During later occupations, artifacts from distant sources reveal more extensive connections. This increase in connectivity likely played a central role in the shifts in societal complexity that gave rise to widely shared material culture throughout the Armenian Highlands around the start of the Early Bronze Age. In such a model, greater social connectivity becomes a key mechanism for, rather than a product of, the spread of cultural and/or technological innovations.

Geospatial patterns and geochemical compositional characteristics of molybdenum in different mediums of an urban environment.

Urban areas are characterized by the presence of certain potentially toxic elements including molybdenum (Mo). Therefore, compositional data analysis combined with geospatial mapping was applied in this study to reveal the spatial distribution characteristics of Mo in courtyard surface dust (dust), soils, and river sediments (sediments), to identify potential sources of Mo, and to reveal Mo geochemical associations in different urban environmental mediums. The mean contents of Mo decreased in the following order: dust (11.9 mg/kg) - soil (5.84 mg/kg) - sediment (4.87 mg/kg). The highest maximum Mo content among the studied mediums (61.8 mg/kg) was detected in dust. It was the only investigated medium where a very high level of Mo enrichment was observed (4.4% of samples). Moreover, a significant level of enrichment predominated in dust (47% of samples) whereas in soil, moderate enrichment prevails (68.5%). A significant correlation of Mo contents was observed with Zn contents in all the studied mediums, and with Ca contents in soil and sediments. A significant negative correlation was observed only between Mo contents in dust and sampling site altitudes suggesting that high-rise buildings might play the role of geochemical barriers. Principal component analysis, k-means and hierarchical clustering showed that in the geogenic elements soil group Mo showed an affinity to be bound by Fe/Mn oxide/hydroxides whereas the Mo coprecipitation, complexation and absorption by carbonates predominated in the Mo-related soil group (geochemical compositional association of Mo, Zn, Cu, Pb, and Ca) under anthropogenic influence. For dust, the geochemical compositional association was the same, but in the geogenic-related group, Cu was the most closely associated element instead of Zn. The spatial location of the Mo-related group of samples identified by k-means clustering indicates that Mo concentrate processing plant may be a potential source of Mo introduction into the urban environment.

The pattern of stability of African swine fever virus in leeches.

African swine fever virus (ASFV) can accumulate and survive in leeches for a long time. The reasons for the survival of ASFV in leeches are not entirely clear. Here, we elucidate the virus survival pathway in infected leeches. One of the questions reported previously is addressed in this article. How the virus concentration in the body of the leech is equal to or higher than in the water infected with ASFV? Examination of blood swallowed by leeches reveals that the blood cells retain their morphological characteristics for several weeks. It can explain the long-term persistence of the high levels of ASFV in the leeches that ingested ASFV-infected pig blood. qRT-PCR assay showed the transcription of ASFV genes in infected leeches. However, the infectious particles of the virus measured by HADU haven't increased. Quantitative studies of the ASFV revealed a high content of both viral genes and infectious particles in the skin of leeches compared with other body parts. Electron microscopy analysis revealed the ability of the ASFV to effectively bind to the skin surface of the leeches, which explained the high concentrations of ASFV in the leeches' skin. A significant difference in the transcriptional activity between early and late viral genes indicates that the virus entered the initial stage of replication, but for some reason failed to complete it, which is typical of abortive infections.

Exploring relationship of soil PTE geochemical and "VIS-NIR spectroscopy" patterns near Cu-Mo mine (Armenia).

PTE contamination of soils remains one of the global environmental concerns. The ways of detecting and monitoring PTE concentrations in soils varies including traditional field sampling accompanied by sample preparation and chemical analysis and state of the art visible and near-infrared (Vis-NIR) spectroscopic approaches. Among the different Machine Learning (ML) to extract soil information from spectra and to explore the relationship between spectral reflectance data and soil PTE content PLSR method is a well-established one to construct a soil PTE estimation model. This study aimed to explore the relationship of soil PTE geochemical and VIS-NIR spectroscopy characteristics in agricultural soils near Cu-Mo mine area in Armenia. PLSR method is applied to identify the links between the spectra and agricultural soil Ti, V, Cr, Mn, Fe, Co, Ba, Pb, Zn, Cu, Sr, Zr and Mo contents to reveal the potential of VIS-NIR spectroscopy in ex-situ monitoring of Kajaran soils. The results show that different portions of VIS-NIR spectra are responsible for Ti (1100-1200 nm, 2350-2500 nm), V (350-500 nm, 700-750 nm, 1000-1100 nm, 1400-2500 nm), Cr (1300-1400 nm, 1900-2100 nm) and Ba (450-500 nm, 600-800 nm, 1050-1700 nm, 2000-2100 nm, 2350-2400 nm) estimations through PLSR correspondingly. However, among the studied PTEs Ti and V, which shows significant negative correlations in VIS-NIR spectra registered at around 400-600 nm and 850-1150 nm regions, are remarkable and promising with the PLSR estimation results using VIS-NIR spectra Ti (R2Test = 0.74), V (R2Test = 0.71). This study shows that VIS-NIR spectroscopy has a high potential for the estimation of at least several PTE in soils and PLSR modelis reliable for deriving information from there.

Factors conditioning soil PTE contents and the associated health risk in an area with mixed land use.

The study of soil chemical composition and geochemical characterization is of great concern. In 2020, a soil survey of the Ararat region (Armenia) was conducted to study the contents of soil elements (Cr, V, Ti, As, Zn, Cu, Co, Fe, Mn, Ba, Pb, Mo, Ca, and K), identify pollution sources and factors conditioning their spatial distribution patterns, and assess the health risk associated with potentially toxic elements (PTEs). The combined application of compositional data analysis and geospatial mapping allowed to reveal three subsamples with unique chemical signatures. Group I included soils in which Fe, Co, Ti, Mn, V, Ba, Pb, and Zn had mainly a natural origin. Soils of Group II are localized in heavily urbanized and industrialized parts of the region, and their spatial distribution is in line with relatively high contents of Cu and partially As, Cr, and K. The spatial distribution of Group III coincides with positions of soils with relatively high contents of Ca and is in line with the geological features and the locations of stone quarries. The human health risk assessment showed that As contents pose a mono-elemental noncarcinogenic health risk to children in two sites (near the Gold Factory and Tigranashen village), whereas a multi-elemental health risk to children was identified on almost the entire region's territory. Moreover, the comparatively high level of As risk was identified in Group III and linked to the travertine quarries exploitation. The results of this study indicated the need for additional in-depth studies targeting As contents and its unrevealed features linked to the travertine quarries exploitation.

Last glacial loess dynamics in the Southern Caucasus (NE-Armenia) and the phenomenon of missing loess deposition during MIS-2.

The Marine Isotope Stage (MIS) 2 is considered the coldest, driest and stormiest period during the last Glacial-Interglacial cycle in large parts of Eurasia. This resulted from strongly decreased northern hemisphere temperature and related maximum extension of northern ice sheets that strongly reinforced large-scale circulation modes such as westerlies and East Asian Winter Monsoon driven by the Siberian High. Normally, this intensified circulation is reflected by maximum loess deposition in numerous loess regions spanning Europe and Asia. However, here we present a new loess record from the Caucasus region in NE-Armenia providing evidence in support of heavily reduced or even lacking loess formation during the MIS-2. Owing to implementations of comprehensible luminescence dating work and a provenance survey using rock magnetic and geochemical data, we are able to define distinct loess formation phases and to retrace sediment transport pathways. By comparing our results to other Eurasian palaeo-records, we unveil general atmospheric circulation modes that are most likely responsible for loess formation in the Southern Caucasus. Moreover, we try to test different scenarios to explain lacking loess formation during MIS-2. In line with other archive information, we suggest that loess formation was hampered by higher regional moisture conditions caused by a southward-shift of westerlies and renewed moisture absorption over the Black Sea. Our results show that modifications of MIS-2 circulation modes induced a very heterogeneous moisture distribution, particularly in the lower mid-latitudes of Eurasia producing a juxtaposition of very dry (morphodynamically active) and moderately dry (morphodynamically stable) areas.

Compositional features of Pb in agricultural soils and geochemical associations conditioning Pb contents in plants.

Soil geochemical data is compositional. Hence the studies targeting the potential of accumulation of toxic elements (TE) in plants have to consider the compositional nature of soil chemical environment. In this study, the combined application of compositional data analysis and geospatial mapping was used to investigate Pb geochemical associations in agricultural soils, revealing the link between these associations and Pb contents in plants, as well as identifying source-specific transfer of Pb from soil to plants. The obtained results showed that soil chemical composition was conditioned by the geological peculiarities of the study area and the potential sources of chemical elements' release. Particularly, k-means clustering and CoDa-biplot allows to identify three distinct subsamples and the application of HCA showed that both Pb soil and plants contents were in the same cluster in all subsamples. However, the geochemical association of elements in subsamples I and III suggested that Pb contents in plants were conditioned by the geochemical behaviors of carbonates whereas in subsample II Pb plant contents were presented in a geochemical association (K, Rb, Pb, and Zn) typical for both fertilizers and the potassium feldspar. The transfer factor (TF) for the comparatively higher values is observed for the subsample linked to K, Rb, Pb, and Zn geochemical association. At the same time, the negative influence of carbonates on the Pb availability in the plants was evidenced. The results of this study can serve as a good example for other investigations targeting the role of soil chemical elements compositional features in elements transfer to plant.

Assessment of the mutagenic potential of the water of an urban river by means of two Tradescantia-based test systems.

River pollution can be caused by anthropogenic or natural factors. When testing water quality for the presence of toxic substances, higher plants as bioindicators for the genotoxic effects of complex mixtures are effective and appropriate. Hence, in this work the Tradescantia (clone 02) stamen hair mutations (Trad-SHM) and Tradescantia micronuclei (Trad-MCN) were used to determine mutagenic and clastogenic potential of an urban river. A significant increase in the level of all studied endpoints as well as morphological changes, including pink cells (PC) and colorless cells (CC) in stamen hairs, stunted hairs (SH), tetrads with micronuclei (MN) and MN in tetrads of pollen microspores in the Tradescantia was observed compared to the negative control (tap water). As an example riverine system, part of the River Hrazdan (Armenia) flowing through a highly urbanized and industrial area was studied. The positive control (10 mM CrO3) showed the highest genotoxicity for the SHM assay (PC: 5.1 / 1000, CC: 17.9 / 1000) and for the MCN assay (12 MN / 100 tetrads and 9.4 ± 0.53 tetrads with MN). Genetic responses were analyzed in conjunction with the concentrations of select elements in the riverine water. Reasons for observing such a high level of genetic markers in the riverine water and applicability of the Tradescantia (clone 02) test-systems in environmental risk assessment and biomonitoring are discussed.

Multifractal features of activity concentration and stochastic risk assessment of naturally occurring and technogenic radionuclides in the soil of Yerevan, Armenia.

Spatial patterns and background ranges of naturally occurring radionuclides (NORs) (i.e. U-238, Th-232, K-40) and Cs-137 were studied in the urban soils of Yerevan, the capital city of Armenia. Multifractal Inverse Distance Weighting (MIDW) was used to generate and analyze distribution patterns of radionuclide activities. Based on Fourier transformation of radioactivity data, a spectral analysis was also applied to separate, where possible, background/baseline patterns from local anomalies: two ranges of background values were found to characterise the Yerevan territory. Specifically, in the south and south-east of Yerevan, the lower background ranges of U-238, Th-232 and K-40 comprised in the intervals 2.60-36.42 Bq/kg, 4.04-30.63 Bq/kg and 147.7-396.7 Bq/kg, respectively, were observed in association with the presence of sedimentary formations. In contrast, the higher ones were found, instead, in the central and northern parts of the city where andesite-basalt lavas and ignimbrite tuffs occur. Here, the background values rise to 142.4 Bq/kg, 138.76 Bq/kg and 1502 Bq/kg, respectively. As for the distribution of artificial Cs-137, its baseline levels in Yerevan seem to depend mostly on the global radioactive fallout and some local technogenic sources. Its distribution patterns partially differ from those of NORs. In the framework of this paper, Radium equivalent activity (RaEq), outdoor absorbed dose rate in air (ODRA) and annual effective dose equivalent (AEDEs) were also determined and mapped. They show a good coincidence of their spatial variations with those of NORs. The Monte Carlo simulation was used to assess excess lifetime cancer risk from a stochastic perspective. The related sensitivity analysis revealed that, among NORs, U-238 and Th-232 give the greatest contribution to the total variance (45.7% 42.8%, respectively). In comparison, K-40 has the lowest share (11.3%). Regarding Cs-137, a highly negligible contribution to the onset of health risks (accounting for 0.02%) was observed.

Toxic element contents and associated multi-medium health risk assessment in an area under continuous agricultural use.

Soils and contaminated plants are in the group of significant environmental pathways of human exposure to toxic elements (TEs). This study aimed to assess the soil-to-plant transfer of TEs (Pb, As, Cd, Hg), as well as the plausible health risks via different exposure pathways in the Armavir region of Armenia. The contents of TEs were determined in soil, fruit and vegetable samples using X-ray fluorescence and atomic absorption spectroscopy, respectively, and the soil-to-plant transfer of TEs and induced chronic non-carcinogenic risks were evaluated. The detected TE contents did not exceed the available national and international regulatory levels. Moreover, the evaluated soil-to-plant transfer of these TEs was negligible. The obtained results indicated the absence of a single-element non-carcinogenic risk via one single ingestion pathway. Meanwhile, in the case of multi-food and multi-soil ingestion, the combined non-carcinogenic risk estimates for Pb and As exceeded the precautionary level of 0.1 indicating a low health risk. Similarly, the multi-element hazard index (HI) showed a low level of non-carcinogenic risk through a multi-pathway ingestion. Thus, the outcomes highlighted that there was a need for precautionary measures to prevent plausible health issues for the adult population in Armavir.

Potentially toxic elements contents and the associated potential ecological risk in the bottom sediments of Hrazdan river under the impact of Yerevan city (Armenia).

This research aims to assess the ecological status of the Hrazdan river (Armenia) section that flows through Yerevan. The distribution of potentially toxic elements (PTE) (Cr, V, As, Zn, Cu, Ni, Co, Mn, Pb, Ti, Mo, Fe, and Ba), the bottom sediments pollution level, and the ecological risk were assessed employing the single pollution index (SPI), the enrichment factor (EF), the geo-accumulation index (Igeo), and the potential ecological risk index (RI). On sampling sites, water quality parameters (turbidity, DO, electrical conductivity (EC), salinity, TDS, pH, temperature °C) were measured as well. The correlation analysis revealed a significant correlation between Zn-Cu, Pb; Cu-Pb, Mo; Co-Fe, Ti pointing out similar sources and origination of these elements. The results indicated that the content of the studied elements in the Hrazdan bottom sediments exceeded the background content in urban soils, which was due to a set of geological and anthropogenic factors. High contents of elements were determined on the sampling sites spatially confined to the residential and industrial areas. According to EF and Igeo data, the priority bottom sediment contaminants are As, Pb, Mo, Zn, V, and Cu. The RI value varies from 196 to 316 with the mean of 246 which corresponds to the moderate-level ecological risk. On the whole, a moderate (77.8%) and a considerable (22.2%) ecological risk was revealed. The major source of Pb, Cu, Zn, and Mo contents was identified as the surface runoffs in the urban environment. This was verified by the cluster analysis results.

Revealing XRF data quality level, comparability with ICP-ES/ICP-MS soil PTE contents and similarities in PTE induced health risk.

Portable X-ray fluorescence spectroscopy (XRF) was recognized as an efficient and promising tools to study the contents of chemical elements in various media including soils under the impact of anthropogenic activities. However, the quality of data and the equality of chemical elements with other common analytical methods such as aqua-regia extraction vary depending on site, sample conditions, and analysis time. In this study, we examine the adequacy of XRF and ICP-ES/ICP-MS aqua-regia extractable (AR) results obtained for lab-type pretreated samples (N = 15) for Ti, Fe, Mn, Co, V, Pb, Zn, Cu, Cr, Mo, Sr, and As contents in soils under the impact of copper smelter and assess the equality of PTE contents induced health risk. The obtained results suggested that XRF reached definitive data quality level for As, Zn, and Mn and screening (quantitative) data quality level established for Cu, Pb, Fe, Mo, Cr, V, and Ti. Moreover, in some cases (i.e., for Ti) XRF overperformed AR indicating the high efficiency of XRF application when sparingly soluble mineral matrices are presented. At the same time, PTE induced health risk assessment at the established data quality level showed that equality of non-carcinogenic children health risk was observed for As, Zn, Cu, Pb, Mn, and V. The latter indicating the applicability of XRF to generate reliable base for risky sites identification and characterization.

Revealing Soil and Tree Leaves Deposited Particulate Matter PTE Relationship and Potential Sources in Urban Environment.

Trees play a pivotal role in improving urban environmental quality and provide several ecosystem services including the removal of pollutants from the air, such as particular matter (PM) and potentially toxic elements (PTE). Therefore, understanding the tree PM and PTE capturing potential, also in connection with plant species, is of great concern, especially in urban areas. This study aims to reveal the link between the elemental composition of PM deposited on tree leaves and soils PTE contents, as well as to rank the PM capturing efficiency of 10 different tree species growing under the impact of urban environments. This also allowed us to test the efficiency of PM deposited on tree leaves as a PTE biomonitoring and pollution source identification tool, in the two biggest urban areas of Armenia. Indeed, high contents of PTE are detected in both soil- and leaf-deposited PM from sites characterized by the presence of localized and active pollution sources (i.e., industrial unites, high traffic, etc.), which are identified by specific tracers (such as Mo, Cu, Zn, Pb, and Cd). Among the studied tree species, the highest PM amount per unit leaf area is observed for Platanus orientalis, but elm species are also identified as promising canditates to be considered for their PM removing potential, and need to be included in future more details studies.

Yerevan soil radioactivity: Radiological and geochemical assessment.

Spatial pattern of naturally occurring radionuclides (NOR): 226Ra, 232Th, 40K, and artificial 137Cs was studied using soil samples of the multipurpose geochemical survey of the city of Yerevan, capital of Armenia. High purity Ge detector-based gamma spectrometry system was used for the determination of radionuclides activity concentrations in urban soils. A combination of compositional data analysis, geochemical mapping and radiological assessment were applied to reveal potential factors of technologically enhanced natural radioactivity and excess lifetime cancer risk for Yerevan's population due to NOR and artificial 137Cs in the urban environment. Statistical methods with the geochemical mapping revealed the great contribution of soil-forming rocks to NOR distribution in urban soils. The spatial distribution of calculated radiological indices and dose rates levels follows the distribution patterns of NOR. The activity concentration of fallout radionuclide 137Cs was within the range typical for the studied altitudes. Above baseline activity of 137Cs was observed in the north-western and western part of the city that is in typical ranges of 137Cs content in soil derived from global radioactive fallout. Urban soils of Yerevan were found radiologically safe, however, igneous rock derived soils are a sink of NOR and the main environmental source of continuous exposure to the residents. Values of excess lifetime cancer risk were higher than mean global value.

Identification of spatial patterns, geochemical associations and assessment of origin-specific health risk of potentially toxic elements in soils of Armavir region, Armenia.

The study of soil potentially toxic elements (PTE) contents and establishment of the geochemical characterization of areas which have never been studied is of great concern. In 2019, soil survey of the Armavir region (Armenia) was conducted in order to investigate the spatial pattern of PTE, reveal PTE geochemical associations and assess the origin-specific health risks. The application of compositional data analysis and geospatial mapping allowed to identify two clusters of samples. The first cluster was spatially located on volcanic rocks and was represented by Fe, Co, Mn, Ti, Zn, Ba, Pb suggesting a natural origin of PTE in these areas. The second cluster was allocated on the alluvial, deluvial, and proluvial sediments and represented by As, Cu, Cr, Ni. Such combination of elements in the same group indicates the anthropogenic introduction of some quantities of PTE. The latter is confirmed by the presence of outliers and extreme values for As, Cu and Ni, as well as by the spatial colocation of Fe, Mn, Co, Pb, Zn outliers and extreme contents. The health risk assessment showed that for children the multi-elemental non-carcinogenic risk was detected, while for the adults the non-carcinogenic risk and carcinogenic risk were below the allowable level. The detailed study of the risk levels showed that in first cluster comparatively higher risk were observed for Pb, V, Ba, Zn while in the second cluster: Fe, Co, Mn, As, Cr, Cu, Ni. The results indicated the necessity of additional in-depth studies with special focus on bioavailability of PTE.

Combination of compositional data analysis and machine learning approaches to identify sources and geochemical associations of potentially toxic elements in soil and assess the associated human health risk in a mining city.

Mining activities change the chemical composition of the environment and have negative reflection on people's health and there is no single measure to deal with adverse consequences of mining activities, as each case is specific and needs to be understood and mitigated in a unique way. In this study, the combination of compositional data analysis (CoDA), k-means algorithm, hierarchical cluster analysis applied to reveal the geochemical associations of potentially toxic elements (PTE) in soil of Alaverdi city (Armenia) (Ti, Fe, Ba, Mn, Co, V, Pb, Zn, Cu, Cr, Mo, As). Additionally, to assess PTE-induced health risk, two commonly used approaches were used. The obtained results show that the combination of CoDA and machine learning algorithms allow to identify and describe three geochemical associations of the studied elements: the natural, manmade and hybrid. Moreover, the revealed geochemical associations were linked to the natural pattern of distribution of the element concentrations including the influence of the natural mineralization of the parent rocks, as well as the emission from the copper smelter and urban management related activities. The health risk assessment using the US EPA method demonstrated that the observed contents of studied elements are posing a non-carcinogenic risk to children in the entire territory of the city. In the case of adults, the non-carcinogenic risk was identified in areas situated close to the copper smelter. The Summary pollution index (Zc) values were in line with the results of the US EPA method and indicated that the main residential part of the city was under the hazardous pollution level suggesting the possibility of increase in the overall incidence of diseases among frequently ill individuals, children with chronic diseases and functional disorders of vascular system. The obtained results indicated the need for further in-depth studies with special focus on the synergic effect of PTE.

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

Soils samples collected during different geochemical surveys of the city of Kajaran located near the biggest Cu-Mo mining area in Armenia were subjected to the multivariate geostatistical analysis and geochemical mapping in order to reveal soil heavy metals spatial distribution pattern and assess human health risk level under continuous impact of mining activities. In addition, human health risk assessment was done for the contents of Pb, Cu, Zn, Co, Mo, Mn, Ti, and Fe. The results of Principal Component Analysis and Cluster Analysis verify each other and were also complemented by the spatial distribution features of studied heavy metals indicating that two groups of elements have been generated. The first anthropogenically predominated group includes the main industrial elements Mo and Cu, and their accessories Pb and Zn while Ti, Mn, Fe and Co with the naturally predominant contents were observed in the second group. Moreover, the study reveals that the superposition of geogenic and anthropogenic components lead to the alteration of the shapes of areas with the high natural contents of heavy metals and formation of polluted 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 >1 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.

Human health risk assessment and riskiest heavy metal origin identification in urban soils of Yerevan, Armenia.

The pollution of urban soils by heavy metals remains a topical issue because of the risks it represents to human health. Heavy metal pollution levels of Yerevan's soils were evaluated using Pollution index and Enrichment factor, while associated health risk was assessed by US EPA model. The heavy metals with significant amount of PI > 1 values were observed for V (100%), Cr (95.4%), Ni (92.5%), Cu (95.6%), Zn (92.9%), Hg (89.0%), Pb (99.9%), As (72.0%), and Ba (61.6% of samples). EF showed that Yerevan topsoils were significantly contaminated with Hg, and moderately contaminated with V, Ni, Cu, Zn, Cr, and As. Topsoils near the smelting plants of molybdenum concentrate have moderately to extremely high contamination levels for Mo. Topsoils were moderate to extremely highly contaminated with Pb, too. The high amounts of samples with heavy metal contents greater than Maximum Acceptable Concentrations were observed for Pb, Cr, Zn, Ni, and Cu. Pb and Cr exceeded corresponding Soil Screening Levels in 3.39% and 2.43% of samples, correspondingly. The risk assessment showed children's multi-elemental non-carcinogenic risk and low level of arsenic carcinogenic risk in the whole Yerevan. The riskiest element was Pb which high contents in 72 risky sites correlate only with the metals having a natural origin. Moreover, its main source is historically polluted soils and Pb supposed to be redistributed in the city environment linked to the sorption complexes of Fe and Mn oxides.