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Soil Contamination Compositional Index a New Approach to Quantify Applied Geochemistry 96 (2018) 264–276 Contents lists available at ScienceDirect Applied Geochemistry journal homepage: www.elsevier.com/locate/apgeochem Soil contamination compositional index: A new approach to quantify contamination demonstrated by assessing compositional source patterns of T potentially toxic elements in the Campania Region (Italy) ∗ Attila Petrika, , Matar Thiombanea, Annamaria Limaa, Stefano Albanesea, Jamie T. Buscherb,c, Benedetto De Vivod,e a Dipartimento di Scienze della Terra, dell'Ambiente e delle Risorse, Università degli Studi di Napoli "Federico II", Complesso Universitario Monte S. Angelo, Via Cintia snc, 80126, Naples, Italy b Andean Geothermal Center of Excellence (CEGA), Universidad de Chile, Plaza Ercilla 803, Santiago, Chile c Department of Geology, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Plaza Ercilla 803, Santiago, Chile d Pegaso University, Piazza Trieste e Trento 48, 80132 Napoli, Italy e Benecon Scarl, Dipartimento Ambiente e Territorio, Via S. Maria di Costantinopoli 104, 80138 Napoli, Italy ARTICLE INFO ABSTRACT Editorial handling by C. Reimann Potentially toxic elements (PTEs) are a major worldwide threat to the environment due to the constant global Keywords: increase in industrial activity and urbanisation. Several studies have provided detailed maps and a better un- Campania region (Italy) derstanding of the spatial distribution patterns of PTEs in different matrices, but the majority of these studies Potentially toxic elements have simply neglected the compositional nature of geochemical data. The aims of this study are to reveal the Spatial abundance compositional behaviour and relative structure of 15 PTEs (subcomposition) in Campania, one of the most Source discrimination contaminated regions in Italy, and to quantify the spatial abundance and identify the possible origins of these Soil contamination compositional index PTEs. Robust compositional biplots were used to understand the natural grouping and origin of the PTEs. Ratios of specific subcompositions (balances) of PTEs were calculated to map the spatial patterns and identify the spatial variability of the PTEs. This study presents the preliminary steps needed to quantify and analyse the relative difference in the spatial abundance of PTEs by applying a compositional abundance index. In addition, a new soil contamination compositional index (SCCI) was elaborated to quantify topsoil contamination by the 15 PTEs and related subgroups following the compositional structure of the geochemical data. The elevated spatial abundance of the 15 PTEs is related to highly urbanised (Naples and Salerno), highly industrialised (Solofra) and intensely cultivated areas (Sarno River Basin), where the high dominance of ele- ments from the anthropogenic subgroup (Pb, Sb, Sn and Zn) and high SCCI values suggest that contamination is from anthropogenic sources. The high spatial dominance of elements from the volcanic rock subgroup (As, Be, Se, Tl and V) in these same areas is likely related to geogenic sources, including alkalic pyroclastic rocks. Although the high spatial abundance of Group B elements (Cd, Cr, Co and Ni) is related to Terra Rossa soils and shaley facies of siliciclastic rocks of the southern Apennines, these same elements can also reach high abun- dances and reflect contamination (i.e. high SCCI values) from urbanised and industrialised areas due to e.g., tanneries and alloy production. Other high spatial abundances of the 15 PTEs with little or no contamination (i.e. very low SCCI values) can be related to nearby carbonate massifs, where a mixture of geogenic factors including weathering, advanced pedogenic processes, adsorption and co-precipitation with Fe-/Mn-oxyhydroxides and the presence of pyr- oclastic material might all be responsible for an increase in abundance. The lowest spatial dominance of the 15 PTEs occurs in the northeastern and southwestern siliciclastic zones of the Campania Region, where there is a low level of urbanisation and industrialisation and therefore con- tamination from any source can be excluded. ∗ Corresponding author. Dipartimento di Scienze della Terra, dell'Ambiente e delle Risorse, Università degli Studi di Napoli "Federico II", Complesso Universitario Monte S. Angelo, Via Cintia snc, 80126, Naples. Italy. E-mail address: [email protected] (A. Petrik). https://doi.org/10.1016/j.apgeochem.2018.07.014 Received 28 March 2018; Received in revised form 19 July 2018; Accepted 21 July 2018 Available online 23 July 2018 0883-2927/ © 2018 Elsevier Ltd. All rights reserved. A. Petrik et al. Applied Geochemistry 96 (2018) 264–276 1. Introduction 1980; Muller, 1981), to quantify the contamination status of different environmental media. Indices using background/baseline values (e.g., One of the main objectives of environmental geochemistry research Single Pollution Index) for reference are straightforward, but are not is to constrain the spatial distribution patterns of various organic and scale-invariant meaning that the change in units of the concentrations inorganic elements and compounds to determine whether sources are modifies the results of the analysis (Aitchison and Egozcue, 2005; geogenic and/or anthropogenic. Geochemical mapping and the deli- Pawlowsky-Glahn et al., 2015). The critical reviews of element ratio mitation of mineralisation or contamination/pollution areas has always variations and Enrichment factors (EFs) were made by Reimann and de been the focus of exploration and environmental geochemistry. Several Caritat (2000, 2005) claiming that their values vary and are dependent graphical techniques including proportional dots (Björklund and on the different parent rock materials and chosen reference media as Gustavsson, 1987), statistical methods like Mean + 2 Standard De- well as reference elements. In addition, these indices do not take into viation (Hawkes and Webb, 1962; Reimann and Garrett, 2005) and account the different biogeochemical processes, the natural fractiona- Median + 2 Median Absolute Deviation (Reimann et al., 2005), cu- tion of elements or differential solubility of minerals which may have mulative probability plots (Tennant and White, 1959; Lepeltier, 1969; remarkable impact on elemental enrichment/contamination (Reimann Sinclair, 1974), upper-fence criteria in Tukey's boxplots (Tukey, 1977) and de Caritat, 2000, 2005). Sucharovà et al. (2012) emphasised that and stated percentiles (e.g., 95th, 98th) in box-and-whiskers plots high EFs or top-/bottom soil ratios reflect the geochemical decoupling (Kürzl, 1988) have all been used to define geochemical threshold values of the lithosphere from the biosphere rather than contamination. They and outliers. The separation of elemental anomalies from baseline and concluded that regional distribution of the raw data from multi-medium background values using various fractal methods such as the Con- provides a better indication of the extent and impact of pollution than centration-Area (C-A) or Spectrum-Area (S-A) techniques and local ratios calculated based on misconceptions. singularity analysis have been successfully applied (Cheng, 1999; Fabian et al. (2017) introduced a new method for detecting and Cheng et al., 1994, 2000; Lima et al., 2003a, 2005; Albanese et al., quantifying diffuse contamination based on the analysis of cumulative 2007, 2015; Zuo et al., 2015; Zuo and Wang, 2016; Parsa et al., 2017; distribution functions. This method revealed local contamination Minolfi et al., 2018; Rezza et al., 2018). sources and efficiently monitored diffuse contamination at the con- Potentially Toxic Elements (PTEs) have always been given special tinental to regional scale. emphasis because the accumulation of these elements in different ma- However, geochemical data are inherently compositional data; trices can cause soil and land degradation that can then be transferred therefore indices measuring the contamination/pollution should be to the human body from dermal contact, inhalation or ingestion considered the main principles of compositional data analysis. through the food chain and drinking water (Lim et al., 2008; Ji et al., This study aims to better understand the compositional behaviour 2008; Varrica et al., 2014). PTEs are a major environmental concern and relative structure of a subcomposition of 15 elements, which are because concentrations are constantly rising due to accelerated popu- listed as PTEs for the Campania Region (D. Lgs. 152/2006), and to lation growth and therefore increased urbanisation and industrialisa- quantify the spatial abundance and identify the possible origins of PTEs. tion that generate a wide range of anthropogenic contamination sources We put special emphasis on the ratios of specific subcompositions (Albanese et al., 2010; Guillén et al., 2011; Wang et al., 2012; Wu et al., (balances) of PTEs by mapping the spatial patterns and making profiles 2015). PTE compounds are generally non-biodegradable with long to reveal the spatial variability. This study presents the preliminary biological half-lives that tend to accumulate in soils by adsorption to steps to analyse the spatial abundance of PTEs by applying a compo- clay minerals and organic matter (Kabata-Pendias, 2011). However, sitional abundance index. A new soil contamination compositional PTE bioavailability is influenced by different physicochemical processes index was elaborated to quantify the topsoil contamination from the 15 (e.g., pH, Eh) and physiological adaptations (Yang et al., 2004; Skordas PTEs and associated
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