Mobility of trace elements in a coastal contaminated site under groundwater salinization dynamics.

Water pollution is a significant issue resulting from past long-term actions. The remediation projects carried out under law constraints for industrial plants, which have been the major contributors to environmental and water pollution, are currently providing a significant amount of data about contaminated soil, surface waters, and groundwater. Most of such plants worldwide are in coastal zones. Based on a significant amount of chemical and environmental data for a coastal contaminated site subject to variable groundwater salinization, this study aimed to understand the mobility of some trace elements because of coastal zone dynamics. Data concerned 688 groundwater samples, including As, Hg, Cd, Crtot, Cu, Ni, Pb, V, Se, Zn, pH, electrical conductivity, chlorides, total organic carbon and organic contaminants as quantitative variables, enhanced by additional qualitative variables such as groundwater salinity, season, water level, precipitation, and industrial activity type to make the dataset as representative as possible of the site under investigation. The study used robust multivariate statistical analyses to analyse the complex dataset and explain the relevant factors influencing contaminant behaviour under different environmental conditions. The Multivariate Statistical Analysis distinguished three clusters of trace elements with diverse reactivity to changes in groundwater salinization. The first includes Se, Cu, Crtot, V, and Ni, showing the highest correlation with electrical conductivity and chlorides because of their high affinity to form chloride or organic chloride complexes and for ion competition. Zn and Pb cluster in the second group: they are less reactive to groundwater salinization and more influenced by cation and anion competition and organic matter. The mobility of Hg and As (third cluster) significantly correlates with Fe and Mn, underlining the dominant role of reductive dissolution of trace elements-bearing minerals (Fe/Mn/Al-oxy-hydroxides) and metal-organic complexes. The correlation between the clustering of variables in groundwater and soils shows the influence of sediment structure, mineral composition, and physical and chemical soil conditions on the distribution in soils of trace elements and their transport to groundwater. The study proposes a valuable approach for assessing the effects of salinization in contaminated coastal aquifers. It supports planning multi-purpose characterization and monitoring campaigns of contaminated coastal sites and provides guidance on the correct associated remediation projects.

Assessment of environmental parameters effect on potentially toxic elements mobility in foreshore sediments to support marine-coastal contamination prediction.

Potentially toxic elements (PTEs) presence in marine sediments can significantly affect the environmental quality and negatively influence economy and recreational activities in related areas. Accordingly, contamination monitoring and control in the marine environment is a fundamental task. In this work, four PTEs behavior (i.e. As, Hg, Pb, and Zn) in sandy foreshore sediments (SFSs) was thoroughly investigated at different pH, redox potential and temperature conditions of the marine water. For all the tests, the released As was 2.7-6 times higher than its initial concentration in water. Nonetheless, final mass balances showed that preferential release in the liquid phase occurred for Pb and Hg (up to 10 % and 9.1 %, respectively). Moreover, final Zn and Hg content increase in SFSs labile fractions indicated their higher bioavailability after the tests. The obtained results outline an approach useful to predict the contaminants behavior in marine matrices and support environmental monitoring and preservation strategies.

Improved identification of pollution source attribution by using PAH ratios combined with multivariate statistics.

Polycyclic aromatic hydrocarbons (PAHs) are contaminants introduced by different pathways in the marine ecosystem, affecting both aquatic and sediment bodies. Identification of their sources is of vital importance for protecting the marine ecosystem. The attribution of the pollution sources is usually made by using diagnostic molecular ratios of PAHs isomers. The reliability of this approach diminishes when PAHs contents are measured far from their original source, for example in water bodies or in bottom sediments. Conventionally the source attribution is based on time consuming univariate methods. In the present work coupling of molecular ratios with advanced supervised statistical techniques was used to increase the accuracy of the PAH source attribution in bottom sediments. Data on PAHs distribution within 5 port areas, with known pattern port activity, were collected. Evaluation of multiple PAHs ratios at once by means of supervised OPLS-DA technique was performed. A robust descriptive and predictive model was set up and successfully validated. The proposed methodology helps identify PAH transport pathways, highlighting interactions between pollution patterns, port activities and coastal land-use supporting decision makers in defining monitoring and mitigation procedures.

Characterising contaminants distribution in marine-coastal sediments through multivariate and nonparametric statistical analyses: a complementary strategy supporting environmental monitoring and control.

This work investigates a statistical approach analysing data from monitoring activities on marine-coastal areas for environmental quality determination and surveillance. Analyses were performed on a database of the Environmental Protection and Prevention Agency of the Puglia Region. As, Cr, Ni, and Pb concentration values in marine sediments and biota from 2013 to 2015 and 2017 were processed to investigate different contaminant characteristics. Hierarchical cluster analysis identified three contaminant distribution classes with (1) highest Cr, Ni, and Pb concentrations, (2) highest As concentration, and (3) lowest contaminants concentration. The Kruskal-Wallis and Friedman tests showed that contaminant distributions were statistically different when considering the monitoring years and classes. However, statistical similarities resulted during the 2013-2017 and 2014-2015 periods. Spearman's coefficients displayed positive correlations among the pollutants in each matrix and mainly negative correlations for matrices comparison. This methodology aims to provide a practical support for monitoring to identify potential environmental deterioration over time and correlations with specific contamination sources.

Multivariate tools to investigate the spatial contaminant distribution in a highly anthropized area (Gulf of Naples, Italy).

The Gulf of Naples located in a high anthropized coastal area is subjected to an infrastructural intervention for the installation of a submarine power pipeline. In order to evaluate the distribution of contaminants in the seafloor sediments, a preliminary study has been conducted in the area using multivariate techniques. The statistic approach was performed to gain insights on the occurrence of organic and inorganic contaminants within the area, aiming to identify the relevant hot spots. Three geographical sub-areas influenced by different contaminant association were recognized: Torre Annunziata (TA), Capri (CA), and middle offshore (MO). TA and CA resulted marked by a severe contamination pattern due to anthropogenic pressures. In addition, the influence of the depositional basin in governing the contamination trend has been pointed out. The supervised technique PLS_DA resulted to be a powerful tool in addressing the complexity of the huge dataset acquired during the marine survey, highlighting the main trends in the variability of quality indicators, orienting thus the deeper investigations during follow-up monitoring activities.

Data on long-term monitoring programs to assess environmental pressures on coastal area.

The concentration of six metals/metalloids, five congeners of high molecular weight Polycyclic Aromatic Hydrocarbons (PAHs), and sum of five congeners of Polychlorinated Biphenyls (PCBs) determined within marine-coastal sediments of the Apulia Coast during a 5-year long-term monitoring program, are reported through tables and radial graphs. The data are referred to the pollutant concentration determined within 70 sites alongside two marine transects (500 m from coastline and 1750 m of coastline) representing different morphologic features of the coast and different pollution stressors loading [1]. Concentration variability during the five monitored years and data generated by the non-parametric correlation analyses among sediment physical-chemical main parameters and metal concentrations are also included.

Influence of hydrodynamic features in the transport and fate of hazard contaminants within touristic ports. Case study: Torre a Mare (Italy).

The environmental quality of Torre a Mare port (Italy) was assessed evaluating on one side, the chemical concentration of nine metals and metalloids within bottom sediments and on the other one, by exploring the impact of hydrodynamic conditions in contaminant's transport within the most polluted basins. The investigated port was selected as case study because it resulted much more polluted than it was expected based on the touristic port activities and related stressors loading on it. In order to determine the origin and fate of contaminants in the port basin, 2D numerical simulations were carried out by MIKE21 software. The hydrodynamic module (HD) based on a rectangular grid was initially used to characterize the flow field into two domains that cover the inner and offshore harbor area. Then, advection-dispersion (AD) and water quality (WQ) modules were coupled in order to simulate the simultaneous processes of transport and dispersion of hypothetical pollutant sources. The dissolved/suspended sediment particulates (DSS) were selected as contaminant tracers. The comparative analysis between simulation responses and the real metal contaminant distribution showed high agreement, suggesting that contaminants mainly come from outside port and tend to accumulate in the inner basin. In fact, hydrodynamic circulations cause inflowing streams toward the harbor entrance and the particular port morphology hampers the exit of fine sediments from the inner basin, enhancing thus the accumulation of sediment-associated contaminants within the port area. The study confirms that the quality of touristic port areas strongly depends on both pollution sources located within and outside the port domain and it is controlled mainly by the hydrodynamic-driven processes.

Combining chemometric tools for assessing hazard sources and factors acting simultaneously in contaminated areas. Case study: "Mar Piccolo" Taranto (South Italy).

Almost all marine coastal ecosystems possess complex structural and dynamic characteristics, which are influenced by anthropogenic causes and natural processes as well. Revealing the impact of sources and factors controlling the spatial distributions of contaminants within highly polluted areas is a fundamental propaedeutic step of their quality evaluation. Combination of different pattern recognition techniques, applied to one of the most polluted Mediterranean coastal basin, resulted in a more reliable hazard assessment. PCA/CA and factorial ANOVA were exploited as complementary techniques for apprehending the impact of multi-sources and multi-factors acting simultaneously and leading to similarities or differences in the spatial contamination pattern. The combination of PCA/CA and factorial ANOVA allowed, on one hand to determine the main processes and factors controlling the contamination trend within different layers and different basins, and, on the other hand, to ascertain possible synergistic effects. This approach showed the significance of a spatially representative overview given by the combination of PCA-CA/ANOVA in inferring the historical anthropogenic sources loading on the area.

Assessment and source identification of pollution risk for touristic ports: Heavy metals and polycyclic aromatic hydrocarbons in sediments of 4 marinas of the Apulia region (Italy).

The Apulia region in Italy has the longest Adriatic coastline; thus, maritime tourism is the driving force for its economic development. Pollution risk for four representative touristic ports of the region was assessed by determining the concentrations of 10 metals, 16 polycyclic aromatic hydrocarbons (PAHs) congeners, and the main nutrients. The cumulative mean Effects Range-Median quotient (mERMq) was used to assess the hazard degree, while the distribution patterns and content ratios of different PAH sediment concentrations were investigated to identify the pollution sources. Principal component analyses indicated an anomalous pollution trend for one of the small touristic ports assessed; this trend emerged from contamination by heavy metals and PAHs to a larger extent than expected, considering the main activity in this port, especially in its inner basin. The reason of this anomaly is thought to be the hydrodynamic and/or other stress factors.

Resin-Immobilized Palladium Nanoparticle Catalysts for Organic Reactions in Aqueous Media: Morphological Aspects.

An insight into the nano- and micro-structural morphology of a polymer supported Pd catalyst employed in different catalytic reactions under green conditions is reported. The pre-catalyst was obtained by copolymerization of the metal-containing monomer Pd(AAEMA)2 [AAEMA-=deprotonated form of 2-(acetoacetoxy) ethyl methacrylate] with ethyl methacrylate as co-monomer, and ethylene glycol dimethacrylate as cross-linker. This material was used in water for the Suzuki-Miyaura cross-coupling of aryl bromides, and for the reduction of nitroarenes and quinolines using NaBH4 or H2, as reductants. TEM analyses showed that in all cases the pristine Pd(II) species were reduced in situ to Pd(0), which formed metal nanoparticles (NPs, the real active species). The dependence of their average size (2-10 nm) and morphology on different parameters (temperature, reducing agent, presence of a phase transfer agent) is discussed. TEM and micro-IR analyses showed that the polymeric support retained its porosity and stability for several catalytic cycles in all reactions and Pd NPs did not aggregate after reuse. The metal nanoparticle distribution throughout the polymer matrix after several recycles provided precious information about the catalytic mechanism, which was truly heterogeneous in the hydrogenation reactions and of the so-called "release and catch" type in the Suzuki coupling.

Are conventional statistical techniques exhaustive for defining metal background concentrations in harbour sediments? A case study: The Coastal Area of Bari (Southeast Italy).

Sediment contamination by metals poses significant risks to coastal ecosystems and is considered to be problematic for dredging operations. The determination of the background values of metal and metalloid distribution based on site-specific variability is fundamental in assessing pollution levels in harbour sediments. The novelty of the present work consists of addressing the scope and limitation of analysing port sediments through the use of conventional statistical techniques (such as: linear regression analysis, construction of cumulative frequency curves and the iterative 2σ technique), that are commonly employed for assessing Regional Geochemical Background (RGB) values in coastal sediments. This study ascertained that although the tout court use of such techniques in determining the RGB values in harbour sediments seems appropriate (the chemical-physical parameters of port sediments fit well with statistical equations), it should nevertheless be avoided because it may be misleading and can mask key aspects of the study area that can only be revealed by further investigations, such as mineralogical and multivariate statistical analyses.