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 on the source of geochemical anomalies in the sediments of the Changjiang river (China), using a modified enrichment factor based on multivariate statistical analyses.

Rivers can be sinks for potential toxic elements (PTEs) inputted in their systems by both natural and anthropic processes. Many indices have been proposed to assess the contamination degree of sediments and the environmental conditions of surficial water bodies. Above all, enrichment factor (EF) is the most used tool, but also it is the most debated for its limitations. The need for a reference element and for a background/baseline composition makes the EF method dependent on the researcher's expertise, implying that its repeatability may not be granted. Starting from the awareness that geochemical processes, bringing to compositional changes in the environmental matrices, involve multiple elements rather than individual variables, we developed a modified EF (mEF) based on the use of elemental associations. Different multivariate statistical methods (i.e. Robust Principal Component Analysis and Fuzzy Clustering), in a compositional data analysis (CoDA) perspective, were used to set all the terms of the mEF. The mEF was applied to 101 sediment samples collected from a 2 m-long core, covering a sedimentation period of about 150 years (1850-2007), located in the lower Changjiang River (China). The method resulted effective in recognizing most of the signals proceeding from the main natural and anthropogenic events which affected the lower river basin in the considered timespan. The largest geochemical variations recorded fit well the flooding events occurred; besides, the effects produced on the system by the recent socio-economic development (following the end of the civil war in 1949 and the beginning of economic reforms in 1978) and the start-up of the Three Gorges Dam (the world's largest power station since 2012) were also intercepted. The proposed method represents a step forward to enhance the effectiveness of the EF in discriminating geochemical anomalies that may be significant to assess the human historical impact on the environment.

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.

Investigation of polycyclic aromatic hydrocarbons in soils from Caserta provincial territory, southern Italy: Spatial distribution, source apportionment, and risk assessment.

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils from Caserta provincial territory, southern Italy, were systematically investigated along with their correlations with soil properties and health risk. The concentrations of ∑16PAHs ranged from 10.0 to 4191 ng/g, with a median (1 st quartile, Q1; 3rd quartile, Q3) of 28.5 (17.5-65.0) ng/g; Four-ring PAHs were the most abundant and contributed an average of ∼50.2% of the ∑16PAHs. Significant differences in the spatial distributions of PAHs in soil were observed, with higher levels of PAH contamination found in Caserta city and the surrounding areas. According to the positive matrix factorization (PMF) model, three sources were identified: chemical production and metal smelting, vehicle emissions, and coal/biomass combustion. Soil total organic carbon was significantly correlated with the concentration of total PAHs and the concentrations of PAHs with three-, four-, and five-rings. In contrast, only the concentration of ∑4DBPs (dibenzo(a,e)pyrene, dibenzo(a,h)pyrene, dibenzo(a,i)pyrene, dibenzo(a,l)pyrene) was well correlated with population density. The soil mass inventory of ∑16PAHs was estimated to be 6.87 metric tons (geometric mean). The ecological risks posed by PAHs in the study are negligible; however, health risks of exposure to soil-borne PAHs were identified based on a probabilistic risk model.

Assessment of the concentrations of polycyclic aromatic hydrocarbons and organochlorine pesticides in soils from the Sarno River basin, Italy, and ecotoxicological survey by Daphnia magna.

We studied the contamination level of the soils of the Sarno River basin in southwestern Italy by combined acute toxicity test with Dapnia magna and chemical extraction of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs). For the ecotoxicological assessment, 188 samples were taken and coincided with those of a previous study (2013) where heavy metals were surveyed. For the organics assessment, 21 samples were selected nearby representative areas of elevated anthropic pressure. About 10.1 % of the samples showed noticeable sign of D. magna mortality, 61-100 %, and fall along the potentially floatable areas of Sarno and Solofrana basins with high degree of contamination by Cr, As, Zn, and Hg. High levels of ecotoxicity, 61-100 %, were determined in the lower Sarno River basin in areas of moderate or low degree of contamination by Cd, Cu Hg, Pb, Sb, Sn, and Zn. Benzo(a)pyrene, indenopyrene, and benzo(g,h,i)perylene were present at concentrations of 0.32, 0.23, and 0.18 mg kg(-1), respectively, 2- to 3-fold the law limits with most of the samples falling nearby the points where the ecotoxicity output was close to 100 %. Among OCPs, pp'-DDT had a mean of 0.225 mg kg(-1) and hence about more than 200- and 2-fold the residential, 0.01 mg kg(-1), and commercial/industrial limits, 0.1 mg kg(-1) and determined mainly in the central Sarno valley in an area where elevated concentrations of benzopyrene and D. magna mortality were also observed. The study evidenced the high rate of contamination by PAHs and OCPs of the soils and the need of urgent remediation actions.

Assessment of the environmental conditions of the Sarno river basin (south Italy): a stream sediment approach.

The Sarno river basin covers an area of 500 km(2) collecting the waters of Solofrana and Cavaiola tributaries. Originally it manly represents a source of livelihood for inhabitants by fishing and transporting goods; currently, the Sarno river, still partially used for irrigation, is affected by an extreme environmental degradation as a result of uncontrolled outflow of industrial waste. Within the framework of a wider geochemical prospecting project aiming at characterizing the whole territory of the Campania region, 89 stream sediment samples with a sampling density of 1 sample per 5 km(2) were collected in the river basin and analyzed by means of inductively coupled plasma-mass spectrometry in order to assess the environmental conditions at a regional scale. A GIS-aided technique, based on both the actual distribution of potentially harmful elements and their regional background values, was used to generate the maps of the contamination factors and of the contamination degrees for As, Cd, Cr, Cu, Hg, Pb and Zn. Furthermore, a factor analysis was performed to assess the nature and the extent of contamination sources for the river sediments. Results showed that the Sarno river basin could be divided in two "environmental status" units: one, low contaminated, corresponding to the hilly and mountain areas, and the second, from moderately to very highly contaminated, corresponding to the economically developed areas of the valley floor characterized by a high population density. This work was developed within a project that aims to investigate the relationships between environmental pollution and human health by analyzing environmental media (stream sediments, water, soil and vegetation) together with human hair of resident population. In this context, the spatial correlation between the extremely compromised environmental conditions of developed areas and the incidence rate of liver cancer in the same area was also explored posing the need of a careful costs/benefits analysis to assess whether the deterioration of the environment, that could adversely affect the conditions of public health, is worth the economic development.