Geogenic versus anthropogenic behaviour and geochemical footprint of Al, Na, K and P in the Campania region (Southern Italy) soils through compositional data analysis and enrichment factor

Geochemical studies that focus on environmental applications tend to approach the chemical elements as individual entities and may therefore offer only partial and sometimes biased interpretations of their distributions and behaviour. A potential alternative approach is to consider a compositional data analysis, where every element is part of a whole. In this study, an integrated methodology, which included compositional data analysis, multifractal data transformations and interpolation, as well as enrichment factor analysis, was applied to a geochemical dataset for the Campania region, in the south of Italy, focusing in particular on the behaviour, footprints and sources of a smaller pool of elements: Al, Na, K and P. The initial dataset included 3669 topsoil samples, collected at an average sampling density of 1 site per 2.3 km2, and analyzed (after an aqua regia extraction) by a combination of ICP-AES and ICP-MS for 53 elements. Frequency based methods (Clr biplot, Enrichment Factor computation) and frequency spatial-method (fractal and multifractal plots) allowed identifying the relationships between the elements and their possible source patterns in Campania soils in relation to a natural occurring concentrations in geogenic material (rocks, soils and sediments) or human input. Results showed how the interpretation of concentration and behaviour of Al, Na, K and P was enhanced thanks to the application of data log-ratio transformation in univariate and multivariate analysis compared to the use of raw or log-normal data. Multivariate analyses with compositional biplot allowed the identification of four element associations and their potential association with the underling geology and/or human activities. When focusing on the smaller pool of elements (Al, P, K and Na), these relationships with the unique geology of the region, were largely confirmed by multifractal interpolated maps. However, when the local background was used for the calculation of the enrichment factor, the resulting interpolated maps allowed to identify smaller areas where the greater concentrations of P could not be possibly associated to a mineralisation (e.g., ultrapotassic rocks) but were more likely to be associated to anthropogenic input such as agriculture activities with potentially extensive use of phosphate fertilizers. The integrated approach of this study allowed a more robust qualitative and quantitative evaluation of elemental concentration, providing in particular new and vital information on the distribution and patterns of P in soils of the Campania region, but also a viable, more robust, methodological approach to regional environmental geochemistry studies

Source patterns and contamination level of polycyclic aromatic hydrocarbons (PAHs) in urban and rural areas of Southern Italian soils

Polycyclic aromatic hydrocarbons (PAHs) are a group of persistent organic pollutants (POPs). They have been identified as a type of carcinogenic substance and are relatively widespread in environment media such as air, water and soils, constituting a significant hazard for human health. In many parts of the world, PAHs are still found in high concentrations despite improved legislation and monitoring, and it is therefore vital defining their profiles, and assessing their potential sources. This study focused on a large region of the South of Italy, where concentration levels, profiles, possible sources and toxicity equivalent quantity (TEQ) level of sixteen PAHs were investigated. The survey included soils from five large regions of the south of Italy: 80 soil samples (0–20 cm top layer) from urban and rural locations were collected and analysed by Gas chromatography-mass spectrometry (GC-MS). Total PAHs and individual molecular compounds from the US Environmental Protection Agency (EPA) priority pollutants list were identified and measured. Results showed that 16PAHs varied significantly in urban and rural areas, and different regions presented discordant characteristics. Urban areas presented concentrations ranging from 7.62 to 755 ng/g (mean = 84.85 ng/g), whilst rural areas presented ranges from 1.87 to 11, 353 ng/g (mean = 333 ng/g). Large urban areas, such as Rome, Naples and Palermo, exhibited high PAHs total concentration, but high values were also found in rural areas of Campania region. Different PAHs molecular ratios were used as diagnostic fingerprinting for source identification: L WMPAHs/HWMPAHs, Fluo/(Fluo +Pyr), BaA/(BaA +Chr), Ant/(Ant +Phe), and IcdP/(IcdP +BghiP). These ratios indicated that PAHs sources in the study area were mainly of pyrogenic origin, i.e. mostly related to biomass combustion and vehicular emission. On the other hand, values in Sicilian soils seemed to indicate a petrogenic origin, possibly linked to emissions from crude oil combustion and refineries present in the region. Finally, results allowed to calculate the Toxicity equivalent Quantity (TEQ BAP) levels for the various locations sampled, highlighting that the highest values were found in the Campania region, with 661 ng g-1 and 54.20 ng g-1, in rural and urban areas, respectively. These findings, which could be linked to the presence of a large solid waste incinerator plant, but also to well-documented illegal waste disposal and burning, suggest that exposure to PAH may be posing an increased risk to human health in some of the studied areas

Source patterns of potentially toxic elements (PTEs) and mining activity contamination level in soils of Taltal city (northern Chile)

Mining activities are among the main sources of potentially toxic elements (PTEs) in the environment which constitute a real concern worldwide, especially in developing countries. These activities have been carried out for more than a century in Chile, South America, where, as evidence of incorrect waste disposal practices, several abandoned mining waste deposits were left behind. This study aimed to understand multi-elements geochemistry, source patterns and mobility of PTEs in soils of the Taltal urban area (northern Chile). Topsoil samples (n = 125) were collected in the urban area of Taltal city (6 km2) where physicochemical properties (redox potential, electric conductivity and pH) as well as chemical concentrations for 35 elements were determined by inductively coupled plasma optical emission spectrometer. Data were treated following a robust workflow, which included factor analysis (based on ilr-transformed data), a new robust compositional contamination index (RCCI), and fractal/multi-fractal interpolation in GIS environment. This approach allowed to generate significant elemental associations, identifying pool of elements related either to the geological background, pedogenic processes accompanying soil formation or to anthropogenic activities. In particular, the study eventually focused on a pool of 6 PTEs (As, Cd, Cr, Cu, Pb, and Zn), their spatial distribution in the Taltal city, and the potential sources and mechanisms controlling their concentrations. Results showed generally low baseline values of PTEs in most sites of the surveyed area. On a smaller number of sites, however, higher values concentrations of As, Cd, Cu, Zn and Pb were found. These corresponded to very high RCCI contamination level and were correlated to potential anthropogenic sources, such as the abandoned mining waste deposits in the north-eastern part of the Taltal city. This study highlighted new and significant insight on the contamination levels of Taltal city, and its links with anthropogenic activities. Further research is considered to be crucial to extend this assessment to the entire region. This would provide a comprehensive overview and vital information for the development of intervention limits and guide environmental legislation for these pollutants in Chilean soils

Status, sources and contamination levels of organochlorine pesticide residues in urban and agricultural areas: a preliminary review in central–southern Italian soils

Organochlorine pesticides (OCPs) are synthetic chemicals commonly used in agricultural activities to kill pests and are persistent organic pollutants (POPs). They can be detected in different environmental media, but soil is considered an important reservoir due to its retention capacity. Many different types of OCPs exist, which can have different origins and pathways in the environment. It is therefore important to study their distribution and behaviour in the environment, starting to build a picture of the potential human health risk in different contexts. This study aimed at investigating the regional distribution, possible sources and contamination levels of 24 OCP compounds in urban and rural soils from central and southern Italy. One hundred and forty-eight topsoil samples (0–20 cm top layer) from 78 urban and 70 rural areas in 11 administrative regions were collected and analysed by gas chromatography–electron capture detector (GC–ECD). Total OCP residues in soils ranged from nd (no detected) to 1043 ng/g with a mean of 29.91 ng/g and from nd to 1914 ng/g with a mean of 60.16 ng/g in urban and rural area, respectively. Endosulfan was the prevailing OCP in urban areas, followed by DDTs, Drins, Methoxychlor, HCHs, Chlordane-related compounds and HCB. In rural areas, the order of concentrations was Drins > DDTs > Methoxychlor > Endosulfans > HCHs > Chlordanes > HCB. Diagnostic ratios and robust multivariate analyses revealed that DDT in soils could be related to historical application, whilst (illegal) use of technical DDT or dicofol may still occur in some urban areas. HCH residues could be related to both historical use and recent application, whilst there was evidence that modest (yet significant) application of commercial technical HCH may still be happening in urban areas. Drins and Chlordane compounds appeared to be mostly related to historical application, whilst Endosulfan presented a complex mix of results, indicating mainly historical origin in rural areas as well as potential recent applications on urban areas. Contamination levels were quantified by Soil Quality Index (SoQI), identifying high levels in rural areas of Campania and Apulia, possibly due to the intensive nature of some agricultural practices in those regions (e.g., vineyards and olive plantations). The results from this study (which is in progress in the remaining regions of Italy) will provide an invaluable baseline for OCP distribution in Italy and a powerful argument for follow-up studies in contaminated areas. It is also hoped that similar studies will eventually constitute enough evidence to push towards an institutional response for more adequate regulation as well as a full ratification of the Stockholm Convention

A new hazard assessment workflow to assess soil contamination from large and artisanal scale gold mining

Gold mining activities are undertaken both at large and artisanal scale, often resulting in serious ‘collateral’ environmental issues, including environmental pollution and hazard to human and ecosystem health. Furthermore, some of these activities are poorly regulated, which can produce long-lasting damage to the environment and local livelihoods. The aim of this study was to identify a new workflow model to discriminate anthropogenic versus geogenic enrichment in soils of gold mining regions. The Kedougou region (Senegal, West Africa) was used as a case study. Ninety-four soil samples (76 topsoils and 18 bottom soils) were collected over an area of 6,742 km2 and analysed for 53 chemical elements. Robust spatial mapping, compositional and geostatistical models were employed to evaluate sources and elemental footprint associated with geology and mining activities. Multivariate approaches highlighted anomalies in arsenic (As) and mercury (Hg) distribution in several areas. However, further interpretation with enrichment factor (EFs) and index of geoaccumulation (IGeo) emphasised high contamination levels in areas approximately coinciding with the ones where artisanal and small scale mining (ASGM) activities occur, and robust compositional contamination index (RCCI) isolated potentially harmful elements (PHE) contamination levels in very specific areas of the Kedougou mining region. The study underlined the importance of complementary approaches to identify anomalies and, more significantly, contamination by hazardous material. In particular, the analyses helped to identify discrete areas that would require to be surveyed in more detail to allow a comprehensive and thorough risk assessment, to investigate potential impacts to both human and ecosystem health

Source patterns of potentially toxic elements (PTEs) and mining activity contamination level in soils of Taltal city (northern Chile)

Mining activities are among the main sources of potentially toxic elements (PTEs) in the environment which constitute a real concern worldwide, especially in developing countries. These activities have been carried out for more than a century in Chile, South America, where, as evidence of incorrect waste disposal practices, several abandoned mining waste deposits were left behind. This study aimed to understand multi-elements geochemistry, source patterns and mobility of PTEs in soils of the Taltal urban area (northern Chile). Topsoil samples (n = 125) were collected in the urban area of Taltal city (6 km2) where physicochemical properties (redox potential, electric conductivity and pH) as well as chemical concentrations for 35 elements were determined by inductively coupled plasma optical emission spectrometer. Data were treated following a robust workflow, which included factor analysis (based on ilr-transformed data), a new robust compositional contamination index (RCCI), and fractal/multi-fractal interpolation in GIS environment. This approach allowed to generate significant elemental associations, identifying pool of elements related either to the geological background, pedogenic processes accompanying soil formation or to anthropogenic activities. In particular, the study eventually focused on a pool of 6 PTEs (As, Cd, Cr, Cu, Pb, and Zn), their spatial distribution in the Taltal city, and the potential sources and mechanisms controlling their concentrations. Results showed generally low baseline values of PTEs in most sites of the surveyed area. On a smaller number of sites, however, higher values concentrations of As, Cd, Cu, Zn and Pb were found. These corresponded to very high RCCI contamination level and were correlated to potential anthropogenic sources, such as the abandoned mining waste deposits in the north-eastern part of the Taltal city. This study highlighted new and significant insight on the contamination levels of Taltal city, and its links with anthropogenic activities. Further research is considered to be crucial to extend this assessment to the entire region. This would provide a comprehensive overview and vital information for the development of intervention limits and guide environmental legislation for these pollutants in Chilean soils

Source patterns of potentially toxic elements (PTEs) and mining activity contamination level in soils of Taltal city (northern Chile)

none7siMining activities are among the main sources of potentially toxic elements (PTEs) in the environment which constitute a real concern worldwide, especially in developing countries. These activities have been carried out for more than a century in Chile, South America, where, as evidence of incorrect waste disposal practices, several abandoned mining waste deposits were left behind. This study aimed to understand multi-elements geochemistry, source patterns and mobility of PTEs in soils of the Taltal urban area (northern Chile). Topsoil samples (n = 125) were collected in the urban area of Taltal city (6 km(2)) where physicochemical properties (redox potential, electric conductivity and pH) as well as chemical concentrations for 35 elements were determined by inductively coupled plasma optical emission spectrometer. Data were treated following a robust workflow, which included factor analysis (based on ilr-transformed data), a new robust compositional contamination index (RCCI), and fractal/multi-fractal interpolation in GIS environment. This approach allowed to generate significant elemental associations, identifying pool of elements related either to the geological background, pedogenic processes accompanying soil formation or to anthropogenic activities. In particular, the study eventually focused on a pool of 6 PTEs (As, Cd, Cr, Cu, Pb, and Zn), their spatial distribution in the Taltal city, and the potential sources and mechanisms controlling their concentrations. Results showed generally low baseline values of PTEs in most sites of the surveyed area. On a smaller number of sites, however, higher values concentrations of As, Cd, Cu, Zn and Pb were found. These corresponded to very high RCCI contamination level and were correlated to potential anthropogenic sources, such as the abandoned mining waste deposits in the north-eastern part of the Taltal city. This study highlighted new and significant insight on the contamination levels of Taltal city, and its links with anthropogenic activities. Further research is considered to be crucial to extend this assessment to the entire region. This would provide a comprehensive overview and vital information for the development of intervention limits and guide environmental legislation for these pollutants in Chilean soils.openReyes A; Thiombane M; Panico A; Daniele L; Lima A; Di Bonito M; De Vivo BReyes A; Thiombane M; Panico A; Daniele L; Lima A; Di Bonito M; De Vivo

Potentially toxic elements in soils of Campania region (Southern Italy): Combining raw and compositional data

Concern about health effect of Potentially Toxic Elements (PTEs) has led to an increasing global attention about their concentration levels in the environment. Soil geochemistry has been widely used as a tool for environment monitoring. This study investigates topsoil geochemistry of Campania region (Southern Italy) and (i) allows a reliable overview of the PTEs (As, Be, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Se, Sn, Tl, V and Zn) concentration in soils, (ii) enable the investigation of the main factors governing PTEs geochemical variation on a regional scale. Over 7300 topsoil samples were collected from the survey area, which occupies an area of about 13.600 km2. Samples were analyzed for pseudo-total content of 53 elements (major and trace elements) by ICP-MS after aqua regia digestion. Data analysis was performed taking into account both raw data and their compositional nature as a tool for the PTEs environmental evaluation and origin investigation. As, Be, Cu, Pb, Sn, Tl, V and Zn in soils of Campania region show higher median concentration levels than Italian and European ones. In addition, all PTEs exceed the residential/ recreational intervention limit (CSCA) set by Italian legislation. The variation structure of compositional data had been visualized using compositional (clr) biplots and displaying the individual sample observations according to their parent rock. Clr-biplot analysis allowed us to recognize geochemical processes controlling most of soil chemical signatures. Multivariate analysis has been performed and three principal components were determined. PC1 is controlled by enrichment of elements deriving from dominant parent rocks of the area (siliciclastics and volcanoclastics). On the other hand, PC1 reveals the presence of an elemental association dominated by Na, K, U, Th, Zr, Ti, Tl and Be (clr variables), which are pathfinder element of soils developed from volcanic parent material. The second (PC2) component well discriminates the geochemical mobility of the elements in soils. The third (PC3) component reveal the presence of an anthropogenic association (Hg, Sb, Pb, Sn, Au, Ag) which depict a marginal contribution in soil geochemistry of the study area. The generation of clr-biplot helped us in a deeper interpretation of single element spatial distribution patterns. As, Be, Sn, Tl and V spatial distribution shows dominance in soil developed from volcanic products of the main volcanic complexes. Our study showed that element such as Be, Sn and Tl naturally exceed the contamination thresholds in almost the entire territory, due to a quite elevated background concentration values. Hence, Campania region con not be considered entirely contaminated (at this scale) by such elements. Co, Cd, Cr and Ni are more abundant where siliciclastic parent rocks occur