Cross-media transfer of polycyclic aromatic hydrocarbons in the Naples metropolitan area, southern Italy.

At present, an in-depth knowledge of polycyclic aromatic hydrocarbons (PAHs) in the multimedia system of the urban environment remains limited. Taking the Naples metropolitan area (NMA) for instance, we simulated the cross-media transfer of PAHs using a multimedia urban model, involving air, water, soil, sediment, vegetation, and impervious film. The results indicated that the predicted PAH values in 2015 match well with their corresponding in-situ monitoring data. The PAH emission inventory and the simulated mass in various media all showed a downward trend from 2015 to 2020 due to national energy conservation policies and Corona Virus Disease 2019. The simulated mass of PAHs in the soil and sediment phases was 896.8 and 232.7 kg in 2020, respectively, contributing together to 96.7% of PAHs in the NMA. And they were identified as the greatest sinks for PAHs, and exhibited the longest retention duration, with values of PAH persistence reaching approximately 548.8 - 2,0642.3 hours. The results of transfer fluxes indicated that local emissions and atmospheric advection were the primary routes affecting the distribution of PAHs. The sensitivity analysis indicated that atmospheric advection rate was the most critical parameter for air, soil, vegetation, and film, whereas water concentration and sediment degradation rate were vital for water and sediment, respectively. This study offered valuable insights into how human activity contributes to the status and fate of PAHs in the urban environment.

Screening and optimization of interpolation methods for mapping soil-borne polychlorinated biphenyls.

There is yet no scientific consensus, and for now, on how to choose the optimal interpolation method and its parameters for mapping soil-borne organic pollutants. Take the polychlorinated biphenyls (PCBs) for instance, we present the comparison of some classic interpolation methods using a high-resolution soil monitoring database. The results showed that empirical Bayesian kriging (EBK) has the highest accuracy for predicting the total PCB concentration, while root mean squared error (RMSE) in inverse distance weighting (IDW) is among the highest in these interpolation methods. The logarithmic transformation of non-normally distributed data contributed to enhance considerably the semivariogram for modeling in kriging interpolation. The increasing of search neighborhood reduced IDW's RMSE, but slightly affected in ordinary kriging (OK), while both of them resulted in over smooth of prediction map. The existence of outliers made the difference between two points increase sharply, and thereby weakening spatial autocorrelation and decreasing the accuracy. As predicted error increased continuously, the prediction accuracy of different interpolation methods reached unanimity gradually. The attempt of the assisted interpolation algorithm did not significantly improve the prediction accuracy of the IDW method. This study constructed a standardized workflow for interpolation, which could reduce human error to reach higher interpolation accuracy for mapping soil-borne PCBs.

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.

A new approach to assess the degree of contamination and determine sources and risks related to PTEs in an urban environment: the case study of Santiago (Chile).

In 2017, a geochemical survey was carried out across the Commune of Santiago, a local administrative unit located at the center of the namesake capital city of Chile, and the concentration of a number of major and trace elements (53 in total) was determined on 121 topsoil samples. Multifractal IDW (MIDW) interpolation method was applied to raw data to generate geochemical baseline maps of 15 potential toxic elements (PTEs); the concentration-area (C-A) plot was applied to MIDW grids to highlight the fractal distribution of geochemical data. Data of PTEs were elaborated to statistically determine local geochemical baselines and to assess the spatial variation of the degree of soil contamination by means of a new method taking into account both the severity of contamination and its complexity. Afterwards, to discriminate the sources of PTEs in soils, a robust Principal Component Analysis (PCA) was applied to data expressed in isometric log-ratio (ilr) coordinates. Based on PCA results, a Sequential Binary Partition (SBP) was also defined and balances were determined to generate contrasts among those elements considered as proxies of specific contamination sources (Urban traffic, productive settlements, etc.). A risk assessment was finally completed to potentially relate contamination sources to their potential effect on public health in the long term. A probabilistic approach, based on Monte Carlo method, was deemed more appropriate to include uncertainty due to spatial variation of geochemical data across the study area. Results showed how the integrated use of multivariate statistics and compositional data analysis gave the authors the chance to both discriminate between main contamination processes characterizing the soil of Santiago and to observe the existence of secondary phenomena that are normally difficult to constrain. Furthermore, it was demonstrated how a probabilistic approach in risk assessment could offer a more reliable view of the complexity of the process considering uncertainty as an integral part of the results.

Potentially toxic elements in the soils of Campi Flegrei (south Italy) and the immediate surroundings: Spatial distribution, origin and probabilistic human health risk.

Campi Flegrei is an active volcanic field in south Italy where the potentially toxic elements (PTEs) are of growing concern because the intensive anthropogenic and volcanic activities might pose adverse human health effects. In this article, 394 topsoils (0-15 cm) are collected for instrumental analysis of the <2 mm fraction. The geochemical maps indicate that higher concentrations of Pb, Zn, Cd, Cr, Hg, Ni and Sb are related to the urban area, but greater levels of As, Tl, Co, Cu, Se and V are observed in the other parts. A robust principal component analysis detected: (1) the Pb-Zn-Hg-Cd-Sb-Cr-Ni association that probably highlights anthropogenic activities such as heavy traffic load and fossil fuel combustion in the urbanized area; (2) the Al-Fe-Mn-Ti-Tl-V-Co-As-U-Th association that mostly reveals the contribution of pyroclastic deposits; and (3) the Na-K-B association that feasibly indicates the weathering degree. The probabilistic health risk modeling for the children under 6 years old shows negligible Pb and Zn non-carcinogenic risk and unexpected Pb carcinogenic risk for exposure through soil ingestion. However, for the inhalation pathway, the children aged <1 year old have the highest chance (90%) of acceptable (i.e. between 1E-6 and 1E-4) Pb carcinogenic health risk. This should not be overlooked because Naples is under high environmental pressure and previous studies reported the increased Pb and Zn quantities in soil over a 26-year timespan. Overall, the results of geostatistical interpolation, compositional data analysis and probabilistic health risk modeling potentially uncover the link between soil geochemistry and human health.

High spatial resolution measurements of passive-sampler derived air concentrations of persistent organic pollutants in the Campania region, Italy: Implications for source identification and risk analysis.

Because most relevant studies have used small sample sizes, to date, representative atmospheric monitoring of persistent organic pollutants (POPs) on a regional scale has been very limited, which makes it difficult to precisely identify "hotspots" and possible pollution sources. In this study, an ultrahigh resolution monitoring technique was used to measure the atmospheric spatial variations in POP concentrations on a regional scale, throughout Campania, Italy. The occurrence of specific POPs-including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and phthalate esters (PAEs)-were investigated using polyurethane foam-based passive air samplers (PUF-PAS), which were deployed at 129 sites across the Campania Territory between April and July 2016. The results show that the highest POP levels occurred in the Naples metropolitan area (NMA), although there were other problematic spots throughout the Territory. More specifically, hotspot areas in the NMA that depict serious POP pollution were found in the Bagnoli brownfield site, Sarno River Basin, and parts of the northeastern NMA sector. The atmospheric POP contamination in Campania is jointly controlled by the contributions of local emissions and long-range atmospheric transport. Diffusion model was employed to identify the potential sources of various POPs. The simulation showed that all the POP sources are located in the NMA and are closely related to industrial sites. This study demonstrates the advantage of using large sample sizes to identify POP source locations and achieve geospatial visualization of POP concentration and risk assessment levels.

Arsenic: Geochemical distribution and age-related health risk in Italy.

This study is the first attempt to evaluate occurrence, distribution and potential health impacts of As at a national scale in Italy. In various environmental matrices, As geochemical distribution was investigated and carcinogenic and non-carcinogenic risks were assessed with respect to different exposure routes and age groups. Both deterministic and probabilistic methods were used to determine the health risks. Geochemical mapping at a sub-continental scale provided a useful tool to spatially represent As concentration and the critical areas posing a health threat to inhabitants. The results show that significant As concentrations in tap water and soil (up to 27.20 µg/l and 62.20 mg/kg, respectively) are mainly governed by geological features. In the central parts of Italy, where alkaline volcanic materials and consequently high levels of As occur, the residents are prone to health issues. Daily exposure to As in tap water is unparalleled playing an important role in the potential cancer and non-cancer risks. The Incremental Lifetime Cancer Risk for skin cancer and also lung and bladder cancer associated with tap water ingestion interestingly shows that (i) almost 80% of the computed values fall above the internationally accepted benchmark value of 1 × 10-5; (ii) majority of the data exceed the acceptable risk proposed by most jurisdictions, such as that of Italian law (1 × 10-6). Further, geographical variation of health risk highlights high carcinogenic and non-carcinogenic risk associated with water ingestion for those living in the northern Alps (including the city of Trento) and the central and southern Italy (including the capital Rome and the cities of Napoli and Catanzaro). According to the results, application of the probabilistic method which considers variability and uncertainty is preferred to the deterministic approach for risk assessment. The sensitivity analysis showed that As concentration in drinking water and exposure duration are the factors with the greatest impact on the outcome of risk assessment (for all age groups). The results of the current study may be a good starting point for authorities to urgently decide about the needed policy actions in order to prevent the adverse health effects and to reduce the human health risk due to As exposure.

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.

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.

Organochlorine pesticides in the soils from Benevento provincial territory, southern Italy: Spatial distribution, air-soil exchange, and implications for environmental health.

This study comprehensively interprets the contamination status of organochlorine pesticides (OCPs) in the soils from Benevento provincial territory, southern Italy, and its implications for environmental health by means of a systematic grid sampling method and geostatistics. The total concentrations of OCPs in the soils ranged from 0.058 to 16.9 ng/g, with a geometric mean (GM) of 0.72 ng/g and an arithmetic mean (AM) of 1.71 ng/g. The levels of OCPs were dominated by p,p'-DDE, p,p'-DDD, HCB, contributing together to 73.5% of the total OCPs. The higher levels of HCB, DDTs, and HCHs found in southwestern, central and east Benevento provincial territory, all occurring adjacent to landfill sites. The residues of OCPs in soil are largely ascribed to their historical use. The OCP inventories in soils of Benevento provincial territory ranged from 0.13 to 4.84 metric tons, with GM = 0.42 metric tons and AM = 0.44 metric tons. The soil is likely to be a sink for DDTs under the influence of regional air transport from pollution hotspots and has the potential to release other chemicals with a high vapor pressure, e.g., HCB, HCHs, and α-Endosulfan. And the mean level of the air-soil exchange flux of HCB, HCHs, and DDTs is estimated to be -1.59, -0.72, and 0.10 ng/m2/day respectively. The potential ecological and human health risks caused by OCPs in the soils are deemed essentially negligible in Benevento provincial territory.

The occurrence of OCPs, PCBs, and PAHs in the soil, air, and bulk deposition of the Naples metropolitan area, southern Italy: Implications for sources and environmental processes.

I am often reminded of the famous saying of Goethe: "Vedi Napoli e poi muori! - See Naples and die!". Sadly, Naples is now confronted with a number of serious, ongoing problems with a need to alleviate pressure on the worsening environment. One serious problem facing the environment is the presence of the potentially hazardous persistent organic pollutants (POPs), although few systematic studies at regional scale have been conducted. In this study, samples of soil, air, and bulk deposition were collected in Naples metropolitan area (NMA) to characterize the status of POPs, including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). The results obtained showed that most of these compounds are pervasive in all the studied environmental matrices, especially in some hotspot areas, such as the Bagnoli Brownfield Site and the infamous "Triangle of the Death", where unwanted ecological risk conditions for PAHs and Endosulfan were determined, respectively. The interactional complexity between urban and the surrounding rural areas was also confirmed, as is the role that urban areas play in the migration and transformation process of POPs. High urban-rural gradients for atmospheric PAHs and PCBs were observed in the NMA, and the urban areas were identified as the emission source of these contaminants. Similarly, the OCP residues, historically originated from the nearby agricultural regions, experience long-term soil re-emission and continuously influence the connected urban environment via atmospheric transport processes.

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. 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. Total PAHs and individual molecular compounds from the US Environmental Protection Agency priority pollutants list were identified and measured. Results showed that 16 PAHs 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-1 (mean = 84.85 ng g-1), whilst rural areas presented ranges from 1.87 to 11,353 ng g-1 (mean = 333 ng g-1). 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: LWMPAHs/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 (TEQBAP) levels for the various locations sampled, highlighting that the highest values were found in the Campania region, with 661 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.

Ecological and human health risk assessment of toxic metals in street dusts and surface soils in Ahvaz, Iran.

This study aimed to examine the concentrations and environmental health risk of the potentially toxic metals including Pb, Zn, Cu, Cd, Cr, and As in street dusts and surface soils of Ahvaz, the capital of Khuzestan province, located in the southwest of Iran. To this end, a total of 81 street dusts and 96 surface soils were collected from Ahvaz urban areas. Toxic metals were measured by inductively coupled plasma-mass spectrometry and evaluated using enrichment factors, potential ecological risk index and human health risk assessment. Lead in street dusts and Pb and Cu in surface soil showed the highest enrichment factor. The results revealed that there are two major sources of toxic metals in Ahvaz, including industrial activities and road traffic emissions and also resuspension of soil and dust particles. Cu, Pb, Zn, and Cr in Ahvaz soil and dust particles are strongly influenced by anthropogenic activity, mainly industrial and traffic emissions, while As and Co originate from resuspension of soil natural parent particles. The potential ecological risk index (RI) values for dust samples indicated that 58.02% of all samples showed low potential ecological risk. Moreover, 33% and 9% of samples showed moderate and considerable ecological risk, respectively. In addition, the RI values for soil samples indicated that 57% and 40% of all samples had low and moderate ecological risk, respectively, and 3% had a high ecological risk. The hazard index (HI) values of studied potentially toxic metals showed that there is no non-carcinogenic risk for children and adults. Furthermore, the HI value for children was 2-7 times upper than those for adults, which confirm that children show more potential health risks for exposition to these potential toxic metals. Cancer risks of the studied potential toxic elements for both adults and children decreased in the following order Crdust > Crsoil > Cddust > Cdsoil > Asdust > Assoil > Pbdust > Pbsoil. The carcinogenic risk values of Cd, As, and Pb for adults and children was lower than 1 × 10-6, suggesting carcinogenic risk of potentially toxic metals in the street dust and surface soil could be neglected. On the other hand, the carcinogenic risk value of Cr was greater than 1 × 10-6 for both adults and children revealing that the carcinogenic risks of Cr essentially need more consideration for environmental management control.

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.

U-Th signatures of agricultural soil at the European continental scale (GEMAS): Distribution, weathering patterns and processes controlling their concentrations.

Agricultural soil (Ap-horizon, 0-20cm) samples were collected in Europe (33 countries, 5.6millionkm2) as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil-mapping project. The GEMAS survey area includes diverse groups of soil parent materials with varying geological history, a wide range of climate zones, and landscapes. The soil data have been used to provide a general view of U and Th mobility at the continental scale, using aqua regia and MMI® extractions. The U-Th distribution pattern is closely related to the compositional variation of the geological bedrock on which the soil is developed and human impact on the environment has not concealed these genuine geochemical features. Results from both extraction methods (aqua regia and MMI®) used in this study support this general picture. Ternary plots of several soil parameters have been used to evaluate chemical weathering trends. In the aqua regia extraction, some relative Th enrichment-U loss is related to the influence of alkaline and schist bedrocks, due to weathering processes. Whereas U enrichment-Th loss characterizes soils developed on alkaline and mafic bedrock end-members on one hand and calcareous rock, with a concomitant Sc depletion (used as proxy for mafic lithologies), on the other hand. This reflects weathering processes sensu latu, and their role in U retention in related soils. Contrary to that, the large U enrichment relative to Th in the MMI® extraction and the absence of end-member parent material influence explaining the enrichment indicates that lithology is not the cause of such enrichment. Comparison of U and Th to the soil geological parent material evidenced i) higher capability of U to be weathered in soils and higher resistance of Th to weathering processes and its enrichment in soils; and, ii) the MMI® extraction results show a greater affinity of U than Th for the bearing phases like clays and organic matter. The comparison of geological units with U anomalies in agricultural soil at the country scale (France) enables better understanding of U sources in the surficial environment and can be a useful tool in risk assessments.

Polycyclic aromatic hydrocarbons in the sediments of the Gulfs of Naples and Salerno, Southern Italy: Status, sources and ecological risk.

This study investigated the spatial distribution, potential sources, and toxic effects of polycyclic aromatic hydrocarbons (PAHs) in the sediments of the Gulfs of Naples and Salerno (NaSa Gulfs), Southern Italy. The investigation focused on the coastal sea sediments of the Bagnoli brownfield site within the Gulf of Naples. The ∑16PAHs in the sediments of the NaSa Gulfs outside of the Bagnoli brownfield site have concentrations that ranged from 9.58 to 15,818 µg/kg, with a geometric mean (Gmean) of 234 µg/kg. High-molecular weight PAHs (HMW PAHs) contributed to over 80% of the ∑16PAHs. The concentration of ∑16PAHs in the Gulf of Naples was twice as high as that in Salerno (768 µg/kg and 317 µg/kg, respectively), and the ∑16PAHs levels in the Bagnoli brownfield site exceeded that in the NaSa Gulfs by over three orders of magnitude. The molecular distributions of PAHs studies suggested biomass/coal combustion as their main sources. Based on the analysis of the toxic equivalent quantity and sediment quality guideline quotient, the contamination of PAHs in sediments may pose significant toxicity and biological risks to marine organisms.

Residues of hexachlorobenzene and chlorinated cyclodiene pesticides in the soils of the Campanian Plain, southern Italy.

A systematic grid sampling method and geostatistics were employed to investigate the spatial distribution, inventory, and potential ecological and human health risks of the residues of hexachlorobenzene (HCB) and chlorinated cyclodiene pesticides in soils of the Campanian Plain, Italy, and explore their relationship with the soils properties. The geometric mean (Gmean) concentrations of HCB and cyclodiene compounds followed the order CHLs (heptachlor, heptachlor epoxide, trans-chlordane, and cis-chlordane) > DRINs (aldrin, dieldrin, and endrin) > SULPHs (α-endosulfan, ß-endosulfan, and endosulfan sulfate) > HCB. The residual levels of most cyclodienes in agricultural soils were generally higher than those of corresponding counterparts in the other land uses. Significant differences in the concentration of HCB and cyclodienes in the soils across the region are observed, and the Acerra-Marigliano conurbation (AMC) and Sarno River Basin (SRB) areas exhibit particularly high residual concentrations. Some legacy cyclodienes in the Campanian Plain may be attributed to a secondary distribution. The Gmean inventory of HCB, SULPHs, CHLs, and DRINs in the soil is estimated to be 0.081, 0.41, 0.36, and 0.41 metric tons, respectively. The non-cancer and cancer risks of HCB and cyclodienes for exposed populations are deemed essentially negligible, however, endosulfan poses significant ecological risks to some terrestrial species.

An Integrated Approach for the Environmental Characterization of a Wide Potentially Contaminated Area in Southern Italy.

This paper deals with the environmental characterization of a large and densely populated area, with a poor reputation for contamination, considering the contribution of environmental features (air, soil, soil hydraulic and groundwater) and the potential effects on human health. The use of Geographic Information System (GIS) has made possible a georeferenced inventory and, by overlaying environmental information, an operational synthesis of comprehensive environmental conditions. The cumulative effects on environmental features were evaluated, taking into account superposition effects, by means of the Spatial MultiCriteria Decision Analysis (S-MCDA). The application of the S-MCDA for converging the combination of heterogeneous factors, related to soil, land and water, deeply studied by heterogeneous groups of experts, constitutes the novelty of the paper. The results confirmed an overall higher potential of exposure to contaminants in the environment and higher mortality rates in the study area for some tumours, but hospital admissions for tumours were generally similar to the regional trend. Besides, mortality data may be strictly dependent on the poor socioeconomic conditions, quality of therapy and a lack of welfare in the area relative to the rest of Italy. Finally, as regards the possible relationship between presence of contaminants in the environment and health conditions of the population no definite conclusions can be drawn, although the present study encourages the use of the new proposed methods, that increase the possibilities for studying the combined effect of more environmental factors.

Arsenic: Association of regional concentrations in drinking water with suicide and natural causes of death in Italy.

Arsenic, as a toxin, may be associated with higher mortality rates, although its relationship to suicide is not clear. Given this uncertainty, we evaluated associations between local arsenic concentrations in tapwater and mortality in regions of Italy, to test the hypothesis that both natural-cause and suicide death rates would be higher with greater trace concentrations of arsenic. Arsenic concentrations in drinking-water samples from 145 sites were assayed by mass spectrometry, and correlated with local rates of mortality due to suicide and natural causes between 1980 and 2011, using weighted, least-squares univariate and multivariate regression modeling. Arsenic concentrations averaged 0.969 (CI: 0.543-1.396) µg/L, well below an accepted safe maximum of 10µg/L. Arsenic levels were negatively associated with corresponding suicide rates, consistently among both men and women in all three study-decades, whereas mortality from natural causes increased with arsenic levels. Contrary to an hypothesized greater risk of suicide with higher concentrations of arsenic, we found a negative association, suggesting a possible protective effect, whereas mortality from natural causes was increased, in accord with known toxic effects of arsenic. The unexpected inverse association between arsenic and suicide requires further study.

Assessment of potentially harmful elements pollution in the Calore River basin (Southern Italy).

The geographical distribution of concentration values for harmful elements was determined in the Campania region, Italy. The study area consists of the drainage basin of the River Calore, a tributary of the river Volturno, the largest Southern Italian river. The results provide reliable analytical data allowing a quantitative assessment of the trace element pollution threat to the ecosystem and human health. Altogether 562 stream sediment samples were collected at a sampling density of 1 site per 5 km2. All samples were air-dried, sieved to <100 mesh fraction and analyzed for 37 elements after an aqua regia extraction by a combination of ICP-AES and ICP-MS. In addition to elemental analysis, gamma-ray spectrometry data were collected (a total of 562 measurements) using a hand-held Scintrex GRS-500 spectrometer. Statistical analyses were performed to show the single-element distribution and the distribution of elemental association factor scores resulting from R-mode factor analyses. Maps showing element distributions were made using GeoDAS and ArcGIS software. Our study showed that, despite evidence from concentrations of many elements for enrichment over natural background values, the spatial distribution of major and trace elements in Calore River basin is determined mostly by geogenic factors. The southwestern area of the basin highlighted an enrichment of many elements potentially harmful for human health and other living organisms (Al, Fe, K, Na, As, Cd, La, Pb, Th, Tl, U); however, these anomalies are due to the presence of pyroclastic and alkaline volcanic lithologies. Even where sedimentary lithologies occur, many harmful elements (Co, Cr, Mn, Ni) showed high concentration levels due to natural origins. Conversely, a strong heavy metal contamination (Pb, Zn, Cu, Sb, Ag, Au, Hg), due to an anthropogenic contribution, is highlighted in many areas characterized by the presence of road junctions, urban settlements and industrial areas. The enrichment factor of these elements is 3-4 times higher than the background values. The southwestern area of the basin is characterized by a moderate/high degree of contamination, just where the two busiest roads of the area run and the highest concentration of industries occurs.