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.

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.

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.

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.

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.

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.

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.

Heavy metals pollution levels and children health risk assessment of Yerevan kindergartens soils.

Children, the most vulnerable urban population group, are exceptionally sensitive to polluted environments, particularly urban soils, which can lead to adverse health effects upon exposure. In this study, the total concentrations of Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti, V, and Zn were determined in 111 topsoil samples collected from kindergartens in Yerevan. The objectives of this study were to evaluate heavy metal pollution levels of kindergarten's soils in Yerevan, compare with national legal and international requirements on heavy metal contents in kindergarten soil, and assess related child health risk. Multivariate geostatistical analyses suggested that the concentrations of Ag, As, Ba, Cd, Cu, Hg, Mo, Pb, and Zn observed in the kindergarten's topsoil may have originated from anthropogenic sources, while Co, Cr, Fe, Mn, Ni, Ti, and V mostly come from natural sources. According to the Summary pollution index (Zc), 102 kindergartens belong to the low pollution level, 7 to the moderate and only 2 to the high level of pollution. Summary concentration index (SCI) showed that 109 kindergartens were in the allowable level, while 2 featured in the low level of pollution. The health risk assessment showed that in all kindergartens except for seven, non-carcinogenic risk for children was detected (HI>1), while carcinogenic risk from arsenic belongs to the very low (allowable) level. Cr and multi-element carcinogenic risk (RI) exceeded the safety level (1.0E- 06) in all kindergartens and showed that the potential of developing cancer, albeit small, does exist. Therefore, city's kindergartens require necessary remedial actions to eliminate or reduce soil pollution and heavy metal-induced health risks.