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The Sarno river basin covers an area of 500 km 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 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. [ABSTRACT FROM AUTHOR]

Abstract: Arsenic concentrations are reported for the <2mm fraction of ca. 2200 soil samples each from agricultural (Ap horizon, 0–20cm) and grazing land (Gr, 0–10cm), covering western Europe at a sample density of 1site/2500km2. Median As concentrations in an aqua regia extraction determined by inductively coupled plasma emission mass spectrometer (ICP-MS) were 5.7mg/kg for the Ap samples and 5.8mg/kg for the Gr samples. The median for the total As concentration as determined by X-ray fluorescence spectrometry (XRF) was 7mg/kg in both soil materials. Maps of the As distribution for both land-use types (Ap and Gr) show a very similar geographical distribution. The dominant feature in both maps is the southern margin of the former glacial cover seen in the form of a sharp boundary between northern and southern European As concentrations. In fact, the median As concentration in the agricultural soils of southern Europe was found to be more than 3-fold higher than in those of northern Europe (Ap: aqua regia: 2.5 vs. 8.0mg/kg; total: 3 vs. 10mg/kg). Most of the As anomalies on the maps can be directly linked to geology (ore occurrences, As-rich rock types). However, some features have an anthropogenic origin. The new data define the geochemical background of As in agricultural soils at the European scale. [Copyright &y& Elsevier]

Abstract: The Bagnoli brownfield site, one of the largest Italian dismantled industrial areas undergoing remediation, is located in the western sector of the urban territory of the city of Naples (Southern Italy) inside the active volcanic field of Campi Flegrei. The remediation project, funded by the Italian government, started in 1996 and was extended to the coastal area sea sediments facing the brownfield site in 2001. A total of 384 sea sediment samples were collected from 128 boreholes at different depths (0–20cm, 20–30cm, 30–50cm, 100–120cm, 150–180cm, 180–200cm, 280–300cm, and 380–400cm) down the seabed along the coastline. Analyzed samples show that the coastal area facing the Bagnoli brownfield site is strongly contaminated by metals whose distribution seems to be controlled by the grain size of the sea sediments, and by the presence of organic compounds (PAHs and PCBs). Geochemical mapping and R-mode factor score analysis allowed us to identify the groundwaters, emanating from the brownfield site to the sea across an artificial structure (“Colmata a mare”) limited by two piers and filled by scum, slag and landfill material, as the main source of contaminants. Since the groundwaters metal contamination was proven to be mostly dependent on a natural hydrothermal enrichment process related to the volcanic activity of Campi Flegrei, a remediation project would be needed primarily for PAHs and PCBs, which occur well above the concentration levels permitted by the Italian Law in the sea sediments facing the Bagnoli coastline. [Copyright &y& Elsevier]

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. [Display omitted] • Variations in spatial concentration of POPs in air of the Campania are significant. • Higher levels of POPs found in Campania are linked to pollution hotspots. • The joint influence of local vs. long-range atmospheric transport was validated. • The POPs' simulated source locations are all in the Naples metropolitan area. A high-resolution monitoring technique was implemented to measure spatial variations in atmospheric POP concentrations on a regional scale, for the purpose of identifying sources and determining human exposure risk. [ABSTRACT FROM AUTHOR]

When dealing with environmental problems, it is of fundamental importance to establish reference values (geochemical baselines) against which to determine the presence or absence of active contamination processes. In the effort to develop a method to assess the geochemical baselines for territories featuring complex geological settings and a well-established anthropic environmental pressure, we combined compositional data analysis (CoDA) with geolithological information to reduce the degree of uncertainty possibly affecting the results. The proposed approach comprises (1) a knowledge-driven step to select a number of sample subsets from a geochemical dataset each with a high probability of having its composition strongly influenced by only one of the lithologies outcropping in the study area; (2) a data-driven step to compute compositional principal balances and define geochemical indicators to be used to assign each of the observations in the dataset to one of the geochemical domains associated to a mayor lithologies outcropping in the study area; (3) the determination for each geochemical domain of baseline values based on the samples assigned to them by the data-driven step. The method was tested using the geochemical data referring to 887 stream sediment samples collected across the Volturno River catchment basin (Southern Italy), featuring a relevant lithological heterogeneity. The results obtained were easily interpretable as they fitted well with the geomorphological, geochemical, and geodynamic processes characterizing the study area. Despite the use of stream sediments for the specific case study presented, the application principles of the method hold for any environmental media and for any territory for which there is a need to define baseline values. However, for a successful application of the method, it is crucial to have a fair knowledge of the geological settings of the study area. • A novel method to define areas with different natural background is proposed. • A method to build compositional indicators of natural phenomena is proposed. • Indicators are obtained by combining expert knowledge and statistical approaches. • Compositional indicators enable four geochemical domains to be recognized. • Geochemical domains clearly differ from geological units. [ABSTRACT FROM AUTHOR]

The Irpinia Fault, also known as the Monte Marzano Fault System, located in the Southern Apennines (Italy), is one of the most seismically active structures in the Mediterranean. It is the source of the 1980, Ms 6.9, multi-segment rupture earthquake that caused significant damage and nearly 3,000 casualties. Paleoseismological surveys indicate that this structure has generated at least four Mw ~ 7 surface-rupturing earthquakes in the past 2 ka. This paper presents a comprehensive, high-resolution geophysical investigation focused on the southernmost fault segment of the Monte Marzano Fault System, i.e., the Pantano-Ripa Rossa Fault, outcropping within the Pantano di San Gregorio Magno intramontane basin. The project, named TEst Site IRpinia fAult (TESIRA), was supported by the University of Napoli Federico II to study the near-surface structure of this intra-basin fault splay that repeatedly ruptured co-seismically in the past thousands of years. Our imaging approach included 2D and 3D electrical and seismic surveys, gravimetry, 3D FullWaver electrical tomography, drone-borne GPR and magnetic surveys, and CO2 soil flux assessment across the surface rupture. This multidisciplinary investigation improved our understanding of the basin shallow structure, providing an image of a rather complex subsurface fault and basin geometry. Seismic data suggest that fault activity at the Pantano segment of MMFS is characterized by a near-surface cumulative displacement greater than previous estimations, calling into question earlier assumptions about the timing of its activation. Despite some challenges with our drone-mounted survey equipment, the integrated dataset provides a comprehensive and reliable image of the subsurface structure. This work demonstrates the utility of developing an integrated approach at high-resolution geophysical imaging and interpretation of fault zones with weak morphological expressions. [ABSTRACT FROM AUTHOR]

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 km 2 , 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. [ABSTRACT FROM AUTHOR]

Abstract Organochlorine pesticides (OCPs) have the potential to concentrate in the marine environment and threaten the local marine life. Here, we present the results of a study of the contamination profiles, spatial distribution, possible sources, and potential ecological risk of OCPs in marine sediments from Gulfs of Naples and Salerno, Southern Italy. The total concentrations of OCPs ranged from 0.54 to 99.6 ng/g (average mean: AM = 7.80 ± 16.3 ng/g). The concentration of OCPs from gulf of Salerno (AM = 9.20 ± 20.7 ng/g) was higher than Naples (AM = 7.49 ± 15.3 ng/g). The sediment levels of individual OCPs were (in sequence of concentration) dichlorodiphenyltrichloroethanes (DDTs, including p , p' -DDD, p , p' -DDE, o , p' -DDT and p , p' -DDT) > CHLs (heptachlor, heptachlor epoxide, trans-chlordane, and cis-chlordane) > hexachlorocyclohexanes (HCHs, including α - β - γ -and δ -HCH) > DRINs (aldrin, dieldrin, and endrin) > hexachlorobenzene (HCB) > SULPHs (α -endosulfan, β -endosulfan, and endosulfan sulfate). DDTs and heptachlor were the highest in proportion among the OCPs. High concentrations of OCPs were observed in the coastal area especially near the cities of Naples and Salerno as a result of terrigenous supply. The occurrence of high residual levels of OCPs found in this study may be attributed to their historical application. Marine dynamics influence the distribution of OCPs, in particular the HCHs, as they are less lipophilic and more soluble. According to established sediment quality guidelines, DDTs may cause ecological risk. Highlights • OCPs levels in sediments from gulfs of Naples and Salerno were first reported. • DDTs was the most dominant contaminant in the study area. • Higher residues of OCPs in near shore were observed. • The concentrations of DDTs pose significant ecological risks. [ABSTRACT FROM AUTHOR]

Abstract The Sarno River Basin (south-west Italy), nestled between the Somma–Vesuvius volcanic complex and the limestone formations of the Campania–Apennine Chain, is one of the most polluted river basins in Europe due to widespread industrialization and intensive agriculture. Water from the Sarno River, which is heavily contaminated by the discharge of human and industrial wastes, is partially used for irrigation on the agricultural fields surrounding it. We apply compositional data analysis to 319 soil samples, collected during two field campaigns along the river course and throughout the basin, to determine the concentration and possible origin (anthropogenic and/or geogenic) of the elemental anomalies, including potentially toxic elements (PTEs). The concentrations of 53 elements were determined using ICP-MS and, subsequently, log-transformed. Using hierarchical clustering, clr-biplot and a principal factor analysis, the variability and the correlations between a subset of extracted variables (26 elements) were identified. Factor score interpolated maps were then generated using both lognormal data (NDR) and clr-transformed data to better visualize the distribution and potential sources of the patterns in the Sarno Basin. The underlying geology substrata appear to be associated with raised levels of Na, K, P, Rb, Ba, V, Co, B, Zr, and Li, due to the presence of pyroclastic rocks from Mt. Somma–Vesuvius. Similarly, elevated Pb, Zn, Cd, and Hg concentrations are most likely related to the geological and anthropogenic sources, the underlying volcanic rocks, and contamination from fossil fuel combustion associated with nearby urban centers. Interpolated factor score maps and the clr-biplot show a clear correlation between Ni and Cr in samples taken along the Sarno River, and Ca and Mg near the Solofra district. After considering nearby anthropogenic sources, the Ni and Cr are PTEs most likely originating from the Solofra tannery industry, while Ca and Mg correlate to the underlying limestone-rich soils of the area. This study shows the applicability of the log-ratio transformations to these studies, as they clearly show relationships and dependencies between elements which can be lost when univariate and classical multivariate analyses are employed on raw and lognormal data. Highlights • Cluster based clr-data unveils interrelationships between groups of elements related with their possible sources. • Clr-biplot displays groups of variables related to the lithological background and main human activities. • Factor scores maps enhance the dominant underlying lithology and anthropogenic element associations. • Clr-data in factor analysis highlights the release of Ni and Cr from Solofra tannery industries in the Sarno River. [ABSTRACT FROM AUTHOR]

Abstract The objective of this study is to demonstrate the combined use of point pattern, multifractal and digital image processing analysis in order to recognise and characterise spatial patterns of Ni concentration in topsoil in the Campania Region (Italy). After an exploring univariate statistical analysis, spatial clusters and outliers were revealed by Moran-I autocorrelation among the original measurement points. The linear and accurate Triangular Irregular Network (TIN) interpolation of Ni concentrations fitted at 3663 sample points was used. Successive moving average smoothing was applied to generalise the TIN model and to suppress small irregularities. The resulting raster map was the subject of multifractal analysis to classify the TIN-based Ni raster concentration map and to define Ni-baseline values. Digital Image Processing including lineament density and spatial variability index calculation was performed not only on the TIN-based total Ni raster map but also on its baseline map to recognise spatial patterns. The Ni-baseline map was given particular attention because the spatial distribution and variance in this map are assumed to be related to different geogenic processes. The highest spatial variability zones of total Ni concentrations are located in Campi Flegrei and around Napoli where low Ni values and spatial outliers are clustered. The highest variability zones can be found in topsoils over volcanoclastic rocks and they are related to urbanised and agricultural land use areas. The lowest variability zones coincide with the Eocene-Miocene argillaceous sediments of the Apennine Mts where the highest Ni values were measured. The highest spatial variability in the Ni-baseline map is in a NW-SE zone following the carbonate outcrops of the Apennine Mts (e.g. Mt. Alburni, Mt. Picentini). Another interesting NW-SE trending moderate to high variability zone was also identified following the alluvial plains of the Apennine's rivers. The Apennine's rivers seem to have played a crucial role in the redistribution of Ni through sediment transport processes resulting in higher spatial variability of Ni in the studied soils. The lowest variability zone is located south of Campi Flegrei and Napoli and it occupies the vast area of the Campanian Plain. Highlights • Combination of multifractal and digital image processing analysis • Spatial pattern recognition of Ni and its baseline values in topsoil of Campania • Low variance zones of Ni are related to argillaceous sediments of the Apennine Mts. • High variance zones of Ni-baseline values are related to carbonate massifs. • NW-SE high-variance corridor revealed along the alluvial plains of Apennine Mts. [ABSTRACT FROM AUTHOR]

One of the main objectives of environmental geochemistry is to reveal the source and spatial patterns of different inorganic and organic elements/compounds with special emphasize on potentially toxic elements. In the last couple of decades, environmental geochemists mainly focused on the identification and separation of geochemical anomalies from background/baseline values of potentially toxic heavy metals and the estimation of their ecological and human health risks. However, the main concern with previously published papers on this issue is that the majority of them simply neglected the compositional nature of geochemical data; hence results became spurious and biased and can be interpreted with reservations. Our goal is to identify, interpret and discriminate the source patterns of 4 potentially toxic elements in the Campania Region (Italy) emphasising on their ratios and spatial abundance using multivariate compositional data analysis. This study contributes to understand the compositional behaviour and relative proportion of 4 potentially toxic elements whose precise contamination sources have been unclear before. A workflow of compositional data analysis including a new discrimination index has been elaborated to identify their possible sources of contamination and enrichment. The investigated data set includes 18 elements derived from 3669 topsoil samples, collected at an average sampling density of 1 site per 3.2 km 2 . First, robust biplots and factor analysis were performed to get an overview of elemental associations and reduce the dimensionality of the data set. They revealed that the 4 PTEs belong to different groups. The multivariate regression analysis using alr-transformed (additive logratio) data proved the strong linear relationship between Fe, Mn (independent) and each investigated PTE (dependent), but also unveiled deviation trends in case of Zn and Pb. Based on the multivariate regression result, a sequential binary partition was performed by means of 6 variables (the 4 PTEs, Fe, and Mn) to obtain balances. Balances are ilr-coordinates (isometric-logratio) which can be interpreted as ratios of specific groups of elements. They were used to generate interpolated maps by using multifractal method to see spatial patterns and proportions of elemental associations. A new index has been elaborated based on the bivariate regression of balances and their standardised residuals, which was particularly useful to identify and separate the sources of anthropogenic contamination and geogenic enrichment of respective elemental associations. The large urban and industrial areas (e.g. Naples, Salerno) along the coastline are mainly contaminated by Pb and Zn due to heavy traffic and alloy production. Some Cr and Ni contamination was discerned in the Sarno Basin where the Solofra industrial district is likely to be the principal source through releases from tannery industry. The large volcanic complexes (e.g. Mt. Somma-Vesuvius, Phlegraean Fields, Mt. Roccamonfina) are all characterised by geogenic enrichment of Zn and Pb. In contrast, Cr and Ni-geogenic enrichment is mainly related to the siliciclastic deposits. [ABSTRACT FROM AUTHOR]

In this study, 500 bottom soils and 7300 topsoils samples were collected to determine the major elements concentrations and to evaluate the correspondence of soil chemical contents and the local geology and to better identify background values. The <2 mm fraction of each sample was analysed for a total of 52 elements combining ICP-MS and ICP-ES techniques. This study focuses on the concentration and distribution of major elements: Al, Ca, Fe, K, Mg, Mn, Na, P and Ti. A combined methodological approach, which involved compositional data analysis, multifractal data interpolation, as well as enrichment factor analysis, was applied to the geochemical dataset. Results indicate that the compositional approach in the multivariate data analysis allows to better interpret the behaviour of elements in natural environment and in geochemical processes as compared to raw data and to improve the quality of related maps. The study has shown that the soils of the Campania region generally contain higher concentrations of investigated major elements than those assessed for European and Italian agricultural soils. In Campania, both bottom soils and topsoils contain higher concentrations of Al, K, Na, P and Ti in volcanic areas. Limestone and dolostone are responsible for higher Ca and Mg contents, while soils formed on siliciclastic deposits generally contain higher levels of Fe and Mn. P and Na concentrations are higher in volcanic soils, but the contribution of fertilizers, which is evident in some areas, should not be underestimated. Weathering processes play an essential role in the distribution of elements in soils, and this appears very evident mostly in volcanic areas. The observations are consistent with the results of the enrichment factors analysis. • The paper describes the major elements distribution in soils of Campania. • Compositional data analysis together with geochemical mapping is an effective approach. • The chemical composition of soils generally reflects the underlying bedrock chemistry. • At some sites, the concentrations of some elements are higher due to the use of fertilizers. • A key role in the distribution of the elements is played by their geochemical behaviour in the surface environment. [ABSTRACT FROM AUTHOR]

Polyurethane foam (PUF) disk passive air samplers (PAS) were deployed to measure spatiality and seasonality of atmospheric OCPs in Jianghan Plain (JHP) and Western Hubei Mountain (WHM), to make a preliminary explorative study of the source–sink relationship of organochlorine pesticides (OCPs) and their association with the monsoon. The concentrations of individual OCPs in the JHP were generally higher than those in the WHM. Significantly high levels of DDTs and Endosulfan were found in the spring and summer, HCB was found in autumn and winter, and HCHs displayed uniform distributions. Compared with the levels of 2005, a significant decrease of atmospheric HCHs, DDTs and HCB was observed, whereas an increase in Endosulfan was observed. The air–soil equilibrium status of OCPs suggested that Dajiuhu (DJH) soils are likely to be a sink for OCPs, and JHP soils are acting as the emitter, contaminating the atmosphere at certain monitoring stations. Backward air trajectory analysis demonstrated that the seasonal fluctuation of atmospheric DDTs, HCB and Endosulfan at the DJH site were closely associated with the variations of the East Asian monsoon. [ABSTRACT FROM AUTHOR]

Sn and Cu are proposed to have their mineralization potential predetermined by their contents in initial fluids of granite-related magmatic-hydrothermal systems. However, it remains ambiguous whether the giant Sn-mineralized skarn system is applicable, and whether the Sn-Cu association in some deposits is predominantly determined by their initial metal contents. The Gejiu orefield is one of the most essential Sn-polymetallic districts worldwide, with proven resources of 3.27 million tons of tin, 3.25 million tons of copper, 4.29 million tons of lead and zinc, and >20 other metals with economic significance. Sn-polymetallic mineralization at Gejiu constitutes a composite skarn ore system that includes proximal skarn and related cassiterite-sulfide, greisen, and tourmaline-vein types. The Laochang Sn-polymetallic deposit hosts several largest skarn and cassiterite-sulfide orebodies in the eastern part of Gejiu. Recent exploitation at Laochang discovered Sn-mineralized quartz veins hosted in the concealed granite, providing a valuable opportunity to characterize the proximal magmatic-hydrothermal process of the mineralizing granitic system. Here, fluid inclusion analysis is carried out on these veins to discuss the fluid evolution, cassiterite precipitation mechanism and whether metal content in early proximal magmatic fluids determines the metal association and endowment in the deposit. Based on the paragenesis of ore and gangue minerals, three hydrothermal stages are distinguished, including quartz-tourmaline stage (Stage I), cassiterite-arsenopyrite-quartz stage (Stage II) and late sulfide stage (Stage III). Fluid evolution controlling vein formation is constrained by microthermometry and LA-ICP-MS analysis of four fluid inclusions generations successively entrapped in quartz and cassiterite. The fluids involved during vein formation show an interplay between single-sourced magmatic fluids and meteoric water. The intermediate-density single phase fluid recorded at stage I quartz is derived from initial fluids directly exsolving from granitic magma. At stage II, fluid immiscibility occurred and the separated brines were entrapped in quartz and early-formed cassiterite. Along with cassiterite precipitation, brines were mixed with low-salinity and cooler meteoric water, leading to entrapment of low-salinity aqueous fluid in outer growth zones of cassiterite at stage II. The constructed fluid evolution history suggests that fluid immiscibility may have facilitated the nucleation of cassiterite crystals at the onset of deposition while mixing of magmatic fluid with meteoric water likely dominate later cassiterite mineralization. Compared with the fluid dataset of barren and mineralized granitic systems worldwide, pre-ore fluids of the studied quartz veins are enriched in Sn, confirming that high Sn content in the initial magmatic fluid can serve as indicator to distinguish mineralized system. In contrast, although Cu mineralization is economically important in the Laochang deposit, predicted Cu contents in pre-ore proximal magmatic fluids are as low as those obtained from Cu-barren system. This implies introduction of Cu into the hydrothermal system from other sources. • Sn mineralization veins in Laochang are controlled by proximal magmatic fluids • Fluid immiscibility and fluid mixing in the vein probably facilitate cassiterite precipitation • Enrichment of Sn in pre-mineralization fluids is necessary for formation of Sn deposit • Significant Cu mineralization in Sn ores is attributed to introduction of Cu from other sources. [ABSTRACT FROM AUTHOR]

Abstract: Rare earth elements (REEs) are quickly gaining more and more relevance as important chemical resources due to the large number of technical applications, and as a consequence, scientific interest on REE-bearing minerals is increasing. In this work, REE data from the FOREGS Geochemical Atlas of Europe database on solid sample media (topsoil, subsoil, stream sediment, and floodplain) and stream water for Italy and Sweden are used to plot distribution maps, and Principal Component Analysis to identify patterns within the data set. The careful investigation of the spatial distribution of REEs in all sample media for both countries allowed us to identify the prominent role played by the geogenic component. Despite a similar REE content of bedrocks (alkaline igneous products, both intrusive and effusive in Italy, alkali granites and pegmatites in Sweden), several distinct differences emerged between the two countries. We identified factors like climate, geomorphology, age of deposits, presence of mineralisation, types of soil and presence of till, as responsible for the different REE enrichments in solid and aqueous sample media in the two countries. Italian palaeosols, developed in volcanic areas, were identified as a possible future source for REE extraction using low pollutant extraction techniques. [Copyright &y& Elsevier]

Abstract: The city of Huelva and surrounding areas are affected by several sources of pollution such as acid mine drainage, industrial complexes, urban wastes and agriculture activities that could pose an important environmental risk. For this reason, the modified BCR (three steps) sequential extraction method was applied to evaluate the mobility and bioavailability of the trace elements in 25 representative samples of the study area. The operational scheme of the BCR was classified into three steps: water/acid soluble fraction, reducible and oxidisable fraction. The mobility sequence based on the sum of three first phases was: Cu (82.01%)>Zn (71.14%)>Cd (68.35%)>Ni (50.44%)>Pb (36.39%)>Cr (29.22%)>As (18.82%). Among metals, Cd poses a serious threat to human health and the environment due to the calculated high percentage of mobility. Additionally, multivariate statistical techniques (principal components and cluster analyses) were applied to the chemical results to evaluate the degree of metallic pollution and the levels of association between the variables (metal-metalloids) at the different steps of sequential extraction and to recognise possible sources of potential contamination. The PCA suggests that the study area is influenced by four sources of anthropogenic contributions: acid mine drainage, industrial activities, traffic, and agriculture, aside from the natural sources characteristic of the zone. Calculated environmental risk index reveal a considerable-high ecological risk in the saltmarshes of the Huelva estuary probably related to acid mine drainage and the industrial complexes located in these areas, while in the north sector of Huelva the metallic content is more closer to the natural sources values. The results obtained suggest the need for corrective remediation measures due to the higher accumulation of potentially dangerous metals, which in most cases exceed the limits established by certain legislation. [Copyright &y& Elsevier]

Abstract: In this work we compare the inorganic content of bottled mineral water, steadily increasing as a source of drinking water, and tap water which is often affected by intensive chemical treatment Bottled mineral water should be representative of the hydrogeochemical composition of groundwater, whereas tap water could derive from multiple sources such as groundwater or surface water including rivers and reservoirs. The data of this paper were collected within a project carried out by the EuroGeoSurvey Geochemistry Expert Group aimed at the characterization of groundwater geochemistry using bottled mineral waters purchased in supermarkets all over Europe which included also the analysis, for comparative purposes, of tap water. The comparison of two extensive databases of 69 elements on 157 tap water samples and 178 bottled mineral waters on Italian territory enabled the recognition of very wide ranges of variation in both databases. The elements with the highest variation are Y, Li, U, I, HCO3 −, Be, Yb, Tm, Zr, Lu, F, and Cs in the bottled mineral database and Ga, PO4 3−, Zn, Mg, Ti, Th, Cd, Pb, and Cu in the tap water database. The first group of elements in bottled mineral water includes elements with localized very high concentration due to prolonged interaction with unusual rock types, whereas the second group of elements in tap water includes elements that are released by corrosion reaction with the material of the distributing systems. Aside from these differences, tap water displayed a much more restricted range of variation for major ions compared to bottled mineral water because of quality guidelines imposed by Italian Law for selected major ions (Ca, Cl−, SO4 2−). Some elements do not display statistically different distributions between the two databases (As, Cr, I, Li, Mo, Rb, Sr, Se, U, V) and for some of these (e.g., Cr and V) non-natural sources cannot be excluded in both databases (e.g. pipeline corrosion or container leaching). The spatial distribution of the ionic species provides similar information as far as the role of geology, groundwater condition and, additional sources is concerned. Among the elements displaying significant differences, Al, Cd, Cu, Fe, Ni, Pb and Zn are strongly enriched in tap water samples, whereas Be, Cs, Sb, Sn and Tl are significantly enriched in the bottled mineral water. The group of elements enriched in tap water is controlled also by corrosion processes, so their spatial distribution is random and virtually unrelated to geological or geochemical conditions. Among the elements enriched in the bottled mineral water group, Sb derives from PET container leaching, whereas the other elements likely derive from water–rock interaction. [Copyright &y& Elsevier]

Abstract: Tap water is a fundamental resource for everyday life, it is subjected to several routine controls and needs to fulfill many compliance scheme. Several elements are monitored on a regular basis, but many trace chemical elements are not usually analyzed, so there is the need to have some kind of indication about their concentration and variation ranges in order to better assess the water quality. An opportunity for such investigations has been provided by a project of the EuroGeoSurvey Geochemistry Expert Group aimed at the characterization of groundwater geochemistry using bottled mineral waters purchased in supermarkets all over Europe which included also the analysis for comparative purpose, of tap water. The initial tap water database of 24 sites has been subsequently increased to the final number of 157 distributed all over Italy and representative of end-user situations (either private houses and public places). In the samples, pH, conductivity and concentrations of 69 elements (Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Pb, Pr, Rb, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, Br−, HCO3 −, Cl−, F−, NH4 +, NO2 −, NO3 −, PO4 3−, SO4 2−,SiO2) were measured at the BGR geochemical laboratories. Some major elements (Ca, HCO3 −, Mg), the dominant water type, display limited range of variation whereas for others (Na, Cl−) the scattering is wider (3 orders of magnitude). Only one sample for Cl and two samples for NO3 − are above the recommended EU and Italian guidelines. Clear influence of bedrock geology and/aquifer composition is clear for some elements (e.g. As, F, Rb, V, U), other elements are indicator of mixing with deep formation water or sea-spray contribution (e.g. Br, I), others reflect also peculiar geographic area (e.g. B in Tuscany, Se in Emilia-Romagna). Factor analysis enabled the identification of a “corrosion” factor which includes Pb, Zn, Cd, Cu, Mn, Sn and Fe, all elements which are preferentially related to interaction with the distributing system pipelines. [Copyright &y& Elsevier]

Abstract: At present, environmental geochemical cartography using GIS-GeoDAS combined software has become an important tool in the study of polluted soils. Huelva Township, where several sources of pollution (related to acid mine drainage, industrial complexes, urban wastes…) take place is a singular environment to determine the geogenic natural content (background) and the anthropogenic contribution (baseline) applying the GIS-GeoDAS analysis. For this purpose, 150 surficial soil samples and 6 soil profiles were collected and analyzed using ICP-MS and ICP-ES for major and trace elements. The statistic analysis and the background values established have allowed to discriminate two ground of elements: a) anthropic sources (F1: Ag, As, Cd, Cu, Pb, Zn and Hg, among others) and b) natural sources (F2: mainly Al, Co, Cr, Ni, V and Be). Additionally, baseline maps show several elements sources related to AMD processes in the floodplain of the Tinto–Odiel estuary (As, Cd, Cu, Pb, and Zn, among others) and also associated with those areas where intense industrial activity has been developed. Arsenic, Cd, Cu, Pb, Ag and Zn baselines values are above the threshold values recommended by the Directive Commission of the European Community for soils and sludge and therefore represent a risk to human health. The established background and baseline values by GIS-GeoDAS could be used as generic values for the proper application of environmental soil regulations in the future. [Copyright &y& Elsevier]

The Tianbaoshan deposit, located in the Sichuan–Yunnan–Guizhou (SYG) metallogenetic belt, is one of famous Pb Zn deposits of Southwest China, with an established reserve of 2.6 Mt. Pb and Zn. According to the detailed field geological survey and microscopic petrography observation, three distinct ore fluid evolution stages can be divided. In this contribution, sphalerite and associated quartz from above diverse stages were carefully chosen for systematic fluid inclusion (FI) petrography, microthermometry, individual FI LA-ICP-MS analysis, Raman microspectroscopy, and in situ trace element investigation of sphalerite. The sphalerite only defines a two-phase aqueous FI type, while the FIs hosted in quartz exhibit diverse types, including two-phase aqueous FIs, vapor-rich FIs, and pure aqueous fluid inclusions. Our microthermometry results indicate that the homogenization temperature (Th) and salinity of FIs in sphalerite from the stage 1 are 109.6‐182.2 °C and 12.51–21.61 wt% NaCl equiv., respectively. The Th of the sphalerite-hosted fluid inclusions in stage 2 ranges from 97 to 158.3 °C, with a salinity range of 14.46–19.76 wt% NaCl equiv. The FIs trapped in sphalerite exhibited medium-high salinity and low Th, and Raman spectrum analysis shows that vapor composition of the FI is mainly H 2 O, reflecting the typical characteristics of basin brine. Measurements on quartz-hosted FIs yield homogenization temperatures from 134.3 to 233.1 °C, with a salinity from 4.49 to 12.62 wt% NaCl equiv. The gas phase composition of these inclusions is complex and consists of several components, such as CH 4 , N 2 , CO 2 , and H 2 O. The results indicate that the FIs present in quartz are dissimilar from those in sphalerite, and the sphalerite mineralization fluid has typical characteristics of basin brine and represents the ore-forming fluid. The significantly high Na and Ca of the mineralizing fluid is revealed, suggesting that the mineralizing fluid may be of the Na Ca system. Combined with Ca/K, K/Na and Rb/Na ratio, typical basinal brines origin was constrained by fluid composition analysis. The gradual enrichment of Ca, Mg, and Sr in the mineralizing fluid emphasizes the positive effect of fluid-rock reactions on the precipitation of Zn. The trace element in sphalerite of the Tianbaoshan deposit is distinct from SEDEX-, skarn-, and volcanogenic massive sulfide (VMS)-type deposits and notably similar to MVT deposits. Combining with fluid inclusion and sphalerite trace elements feature, we define the Tianbaoshan deposit as a typical MVT Pb Zn deposit. • Homogenization and freezing temperatures are similar to those of typical MVT brines. • Water-rock reactions play a positive role on the precipitation of Zn. • The ratios of K, Na, Cl, Br in ore-forming fluid also show the typical characteristics of basin brine. • The Tianbaoshan deposit is a typical MVT Pb Zn deposit. [ABSTRACT FROM AUTHOR]

Analysis of stream sediment geochemical data has undergone a series of developments during last decades. As a matter of fact, many factors can potentially influence the chemical composition of these sediments and the existing techniques are not able to fully explain compositional variations occurring along with their transport. By applying some recently developed equations, this paper takes into account the topographical relief and the morphological surface areas of outcropping lithological units to both estimate local geochemical background values and delineate promising zones in terms of mineral exploration. Specifically, through the combination of a three-dimensional sample catchment analysis with dilution correction equation, the process of delineating catchment basins featured by economically relevant Cu occurrences has been improved. The effectiveness of the technique has been evaluated through the application of the prediction-area plot obtaining better results than applying the two-dimensional approach. • Comparison is made between 2D and 3D analysis of sample catchment basin techniques. • Results were evaluated through normalized density to find out the efficiency of techniques. • Incorporation of real surface areas (3D approach) delivered more acceptable results. [ABSTRACT FROM AUTHOR]

This work discusses the results of a geochemical survey conducted in the Salerno urban area to determine the sources patterns of major, minor, trace and ultra-trace elements in soils. In particular, the study focused on elements that are potentially toxic and listed in the environmental Italian legislation (D.L. 152/06), in order to effectively monitoring an important aspect of environment health. A total of 151 topsoil samples were collected, air-dried and sieved (<2 mm). After aqua regia digestion the samples were analyzed for 42 elements by ICP-MS and ICP-AES. Geostatistical analyses were carried out in order to show the single element spatial distribution and the distribution of factor scores elemental associations from R-mode factor analysis. In performing factor analysis, the additive logratio (alr) transformation was applied to the whole dataset in order to deal with the closure effects of the investigated geochemical data, avoiding artefacts and spurious correlation. The use of alr-transformed data instead of the normal data in the factor analysis allowed for a better interpretation of the distribution patterns, since this produced four factor models which, once mapped, were easier to interpret. The study revealed that major and minor elements (Al, Ca, Fe, K, Mg, Na, P, S and Ti) have a perfectly natural distribution with no discernible association to any human activity or presence. In contrast, many trace and ultra-trace elements (Ag, As, Au, Ba, Be, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Pd, Pt, Rh, Sb, Sn, Tl, V and Zn) show anomalous concentration values located almost exclusively in highly inhabited areas, industrial sites and along high traffic roads. Other trace and ultra-trace elements (B, Bi, Ga, La, Sc, Se, Sr, Te, Th, Tl, U and W) show concentrations compatible with the natural background levels. Some potentially toxic elements (e.g. Pb and Zn) reach concentration levels tens of times higher than the legal limits in the busiest areas of the city. Exposure to high concentrations of these contaminants may cause health problems to people living in these zones. • The soils of the Salerno urban area are affected by moderate to high contamination. • Pollutants are found within highly populated areas, industrial sites and along high traffic roads. • Palladium and Pt pollution is evident in all the areas where high traffic flow is present. • The reached level of contamination requires the strict attention of the authorities. [ABSTRACT FROM AUTHOR]

Uranium, thorium and potassium are distinguished in different compartments of the environmental media according to the inputs, the fate and the distribution patterns that occur in the ecosystems. Thus, an understanding of the sources patterns and behaviours of these elements in soils, their rock-soil relationships and potential toxicity or deficiency problems associated with them is nowadays a relevant concern for environmental protection and human health. A robust compositional computation analysis coupled with frequency spatial-method (Fractal model) is applied on 3 selected elements (U, Th and K), based on a large dataset of 7134 topsoil samples over the whole Campania region, and investigated elements concentrations were analysed (after aqua regia extraction) by inductively coupled plasma mass spectrometry (ICP-MS). In this survey, U concentrations ranged from 0.05 to 43.2 mg kg−1 with a mean value of 3.35 mg kg−1, Th concentrations ranged from 0.3 to 64.30 mg kg−1 with a mean values of 11.95 mg kg−1 and K concentrations ranged from 0.03 to 5.97% with a mean value of 0.68%. The mean values for U and Th are slightly above the mean crustal abundances, while K is slightly below them. Fractal mapping of Centred-log transformed (clr) data of investigated elements show that the U, Th and K geochemical anomalies can be ascribed to geology-related volcanic sources. Indeed, the highest values in soils were assessed in the surveyed alkaline magmatic areas in the central-western part of the region characterized by volcanic rocks, whereas lowest values are found in areas characterized by silico-clastic and carbonate deposits, occurring mostly in the southern and eastern part of the region. Evidence from this study showed that compositional data transformations such as clr transformation could help to avoid artefacts, prior to statistical computations. • U, Th and K concentrations were estimated on Campania Region soils. • Compositional data analysis and frequency spatial-method were applied on U, Th and K. • Geology-related volcanic sources control the U, Th and K geochemical anomalies. [ABSTRACT FROM AUTHOR]