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.

Carcinogenic and non-carcinogenic risk assessment of trace elements and POPs in honey from Shirak and Syunik regions of Armenia.

Honey is a highly nutritious natural product widely produced and consumed by people in Shirak and Syunik regions of Armenia. Unlike Shirak, Syunik is under the impact of mining industry. Since the environmental pollution can adversely impact the safety of honey and entail a probable risk to human health, it is important to evaluate the presence of potentially toxic trace elements in honey samples from both regions and draw comparisons. This study assesses the dietary exposure to trace elements and persistent organic pollutants through the intake of honey for the first time among people in Shirak and Syunik regions. 24-hour dietary recall method was used to investigate the consumption of honey. The presence of seven trace elements (Pb, Cd, As, Hg, Cu, Zn, and Ni) and persistent organic pollutants (hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its metabolites) were determined in honey samples using atomic absorption spectrometry and gas chromatography-mass spectrometry, respectively. In several samples, the concentrations of Cu were above the maximum allowable level. Non-carcinogenic risk values did not exceed the acceptable level, while carcinogenic risk values for Ni and As exceeded the risk level of 10-6 in both regions. Moreover, among the persistent organic pollutants, only the concentration of DDT in honey from Shirak was above the European Union maximum residue level.

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.