Hydrogeological assessment of a major spring discharging from a calcarenitic aquifer with implications on resilience to climate change.

Groundwater is a vital source of freshwater, serving ecological, environmental, and societal needs. In regions with springs as a predominant source, such as the Northern Apennines (Italy), resilience of these springs to climate-induced recharge changes is crucial for water supply and ecosystem preservation. In this study, Nadìa Spring in the Northern Apennines is examined through an unprecedented array of multidisciplinary analyses to understand its resilience and unique characteristics. The Nadìa Spring's exceptional response, characterized by a sustained base flow even in the face of drought, is attributed to a combination of factors including a substantial groundwater reservoir, a complex network of faults/fractures, slope instabilities, and karst dissolution. The investigation reveals a dual porosity system in the aquifer, consisting of fast-flow conduits and a diffuse fracture network. While fast-flow conduits contribute to rapid responses during high-flow conditions, the diffuse system becomes predominant during low-flow periods. This dual porosity structure helps the spring maintain a consistent base flow in the face of climate-induced recharge fluctuations. The study shows that Nadìa Spring exhibits remarkable resilience to year-to-year variations in recharge, as evidenced by stable minimum discharge values. While the spring has undergone a decline in discharge over the past century due to long-term climate change, it is becoming more resilient over interdecadal timescales due to transition to a diffuse drainage system that mitigates the impact of reduced recharge. The availability of a century-long spring discharge monitoring was a crucial piece of information for understanding the spring's discharge response and drawing conclusions about its long-term resilience to recharge fluctuations. Continuing long-term monitoring and research in the future will be essential to validate and expand upon these findings in the context of changing climatic conditions. This research serves as a model for assessing strategic groundwater discharge points in geological settings similar to the Northern Apennines.

Butterflies as bioindicators of metal contamination.

Anthropogenic trace metal contamination has significantly increased and has caused many hazardous consequences for the ecosystems and human health. The Terni basin valley (Central Italy) shows a heavy load of pollutants from industrial activities, while the characteristic orography structure of the valley favours air stagnation, thus limiting air pollution dispersal. The present study conducted in 2014 aimed to determine the concentration of ten metals in five species of butterflies at nine sites in the Terni valley along a 21-km-long transect, including both relatively pristine and industrial areas. At sites where soil contamination was high for a given metal, such as for chromium as in the case of site 4 (the closest to the steel plant) and for lead as in the case of site 2 (contaminated by a firing range), higher levels of contamination were observed in the tissues of butterflies. We found a correlation between soil contamination and the concentration of Cr, Al and Sr in the tissues of some species of butterflies. The sensitivity to contamination differed among the five species; in particular, Coenonympha pamphilus was generally the species that revealed the highest concentrations of all the ten trace metals at the sites closer to the industrial area. It is known that C. pamphilus is a sedentary species and that its host plants are the Poaceae, capable of accumulating high quantities of metals in their rhizosphere region, thus providing the link with soil contamination. Therefore, monitoring the metal concentration levels in butterflies might be a good indicator and a control tool of environmental quality, specifically in areas affected by high anthropogenic pollution loads linked to a specific source.

Sediment quality of the Ridracoli fresh water reservoir in Italy: Insights from aqua regia digestion and sequential extractions.

The inter-element relationships and the forms in which metals exist strongly influence their mobility and, in turn, have a signature on the environment and human health. Located in the northern Apennines within the Emilia-Romagna region, the Ridracoli artificial lake is one of Italy's most important reservoirs that provides drinking water for about one million people. This work characterized the reservoir sediments by ICP-MS after aqua regia digestion (ARD), comparing the limits by law to assess environmental compliance and XRF data from the same sample-set taken as total concentrations. The Degree of Extraction (DE) from pseudo-total concentrations of ARD analysis allows assessing elements mobility and the associated environmental risk. Principal Component Analysis (PCA) on the obtained data helped to investigate inter-element relationships better; for example, we observed carbonate-sourced sediments, many trace elements (e.g., Ni, Zn) linked to FeMn oxyhydroxides, the importance of the grain size in elements distribution, and the central role of the organic matter in element partitioning. In addition, a Sequential Extraction Procedure (SEP) was applied to the sediment samples to understand the partitioning of many analytes, including Potentially Harmful Elements (PHE) such as Fe, Mn, Cu, Cr, Ni, Pb, and Zn. The results indicated that the most easily mobilized forms were predominant in the area near the dam, in correspondence to sediments affected by the formation of a seasonal anoxic layer.

A non-lethal method to assess element content in the endangered Pinna nobilis.

The fan shell Pinna nobilis is the largest bivalve endemic to the Mediterranean and is actually a strongly endangered species. Due to the biological, ecological, and historical relevance of this species, the research of a non-lethal method to relate the element content in organism's tissues and environment can provide information potentially useful to evaluate environmental pollution and organism physiological status. In this study, a screening on element concentration in the animal growing environment (seawater and sediments) and in four soft tissues (hepatopancreas, gills, mantle, and muscle), and two acellular tissues (calcite shell layer, and byssus) was performed. The comparison among these results was used to assess whether the no-lethal acellular tissue element concentration can be used to reveal the element presence in the environment and soft tissues. Elements, such as B, Ag, As, Mn, Mo, Pb, or Se, showed a possible relationship between their presence in the byssus and soft tissues. In the byssus Cr, Sb, Sn, and V have shown to be mostly related to the environment, more than the soft tissues, and might be used to draw a historical record of the exposure of the organism. The element concentration in the calcite shell layer did not relate with environmental element concentrations. Essential elements, like Cu, Fe, Ni, and Zn, were present in calcite shell layer and byssus and are likely related to their biological activity in the organism. The research also gave an overview on the presence of pollution and on the preferential intake route of the element. In summary, this study, performed on a limited number of specimens of this protected species, indicated that element concentration in the byssus can be applied as non-lethal method to monitor this endangered species and its interaction with the elements in the growing environment.

Sensitivity of foraminiferal-based indices to evaluate the ecological quality status of marine coastal benthic systems: A case study of the Gulf of Manfredonia (southern Adriatic Sea).

This paper aims to compare two foraminiferal based biotic indices generally used to evaluate the ecological quality status (EcoQS): the Foram-AMBI and the Foram Stress Index (FSI). For this purpose, we report the distribution and diversity of living foraminiferal assemblages and the environmental variables from a bathymetric transect in the Southern Adriatic Sea. The two indices agree well with the detected organic enrichment but indicate conflicting EcoQS as the Foram-AMBI detects good environmental conditions, whereas the FSI describes a poor-moderate quality. Many species not assigned (including soft-shelled foraminifera) are to blame for the different results. Also, both foraminiferal-based indices neglect the heavy metal increase encountered in the deepest stations. These findings suggest the need for a more in-depth analysis to improve the ecological status evaluation of marine benthic systems, including other descriptors as chemical pollutants in combination with biotic indices sensitive to organic matter enrichment.

Integration of physical, geochemical and biological analyses as a strategy for coastal lagoon biomonitoring.

Coastal lagoons are complex environments threatened by natural and anthropogenic stressors. Here, we tested the effectiveness of combining physical, geochemical and chemical measurements with biomarker data obtained in field-exposed marine mussels (Mytilus galloprovincialis) as a biomonitoring strategy for a highly pressured lagoon (Pialassa Baiona, Ravenna, Italy). Data showed a spatial trend of sediment contamination by Hg, Pt, Au, Ag, Mo, Re, Cd, Pd and Zn. Local conditions of high water temperature/low conductivity were detected among selected sites. After a 30-day in situ exposure, Ag and Hg were the most bioaccumulated elements (10 and 5 folds, respectively) in mussels followed by Sb, Al, Ti and Fe. Decreased survival, lysosomal dysfunctions, increased metallothionein content and peroxisome proliferation were observed in mussels in relation to metal spatial distribution and physico-chemical fluctuations. Overall, this study provides a further confirmation of the role of biomonitoring to reliably assess the environmental quality of highly pressured lagoons.

Bioaccumulation of trace elements affects chick body condition and gut microbiome in greater flamingos.

Elevated concentrations of trace elements represent a major concern to wetland ecosystems, since river estuaries are geochemical endpoints that accumulate pollution. Although the negative impact of environmental exposure of highly toxic elements such as Pb and Hg has received substantial attention, we still lack a comprehensive understanding of the effects that these and other common trace elements have on natural populations. We used greater flamingos as a study system within three sites that represent a gradient of pollution. Controlling for environmental sediment exposure, we assessed if signatures of bioaccumulation in feathers for ten trace elements (As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Sn and Zn) are associated with two known proxies of health: body condition and the gut bacterial microbiome. We found evidence of an adverse effect of Se, Hg, and Pb bioaccumulation on body condition. Furthermore, bioaccumulation of the elements As, Cu, Se, Pb and Zn influenced different aspects of the gut microbiome. Bioaccumulation of Se led to a shift in the microbiome composition, largely driven by an enrichment of Bacteroides plebeius, which is linked to the breakdown of sulphated polysaccharides of algae. Bacteroides plebeius was negatively associated with chick body condition, suggesting an adverse effect of a microalgae diet rich in Se. Pb bioaccumulation was linked with a decrease in microbial diversity (adjusted-R2 = 10.4%) and an increase in heterogeneity of the microbial community (adjusted-R2 = 10.5%), an indication of impaired gut homeostasis. As, Cu and Zn had more nuanced effects on gut microbiome heterogeneity according to breeding site and bioaccumulation concentration. Our results therefore suggest that in addition to well-studied elements, bioaccumulation of poorly studied elements also adversely affect health of natural populations.

Effect of biogenic jarosite on the bio-immobilization of toxic elements from sulfide tailings.

The discharge of toxic elements from tailings soils in the aquatic environments occurs chiefly in the presence of indigenous bacteria. The biotic components may interact in the opposite direction, leading to the formation of a passivation layer, which can inhibit the solubility of the elements. In this work, the influence of jarosite on the bio-immobilization of toxic elements was studied by native bacteria. In batch experiments, the bio-immobilization of heavy metals by an inhibitory layer was examined in the different aquatic media using pure cultures of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. A variety of analyses also investigated the mechanisms of metals bio-immobilization. Among different tests, the highest metal solubility yielded 99% Mn, 91% Cr, 95% Fe, and 78% Cu using A. ferrooxidans in 9KFe medium after ten days. After 22 days, these percentages decreased down to 30% Mn and about 20% Cr, Fe, and Cu, likely due to metal immobilization by biogenic jarosite. The formation of jarosite was confirmed by an electron probe micro-analyzer (EPMA), X-ray diffraction (XRD), and scanning electron microscope (SEM). The mechanisms of metal bio-immobilization by biogenic jarosite from tailings soil confirmed three main steps: 1) the dissolution of metal sulfides in the presence of Acidithiobacillus bacteria; 2) the nucleation of jarosite on the surface of sulfide minerals; 3) the co-precipitation of dissolved elements with jarosite during the bio-immobilization process, demonstrated by a structural study for jarosite. Covering the surface of soils by the jarosite provided a stable compound in the acidic environment of mine-waste.

Deposition processes over complex topographies: Experimental data meets atmospheric modeling.

The present paper describes the assessment of the atmospheric deposition processes in a basin valley through a multidisciplinary approach based on the data collected within an extensive physico-chemical characterization of the soils, combined with the local meteorology. Surface soil cores were collected on a NNW-SSE transect across the Terni basin (Central Italy), between the Monti Martani and the Monti Sabini chains (956 m a.s.l.), featuring the heavily polluted urban and industrial enclave of Terni on its bottom. Airborne radiotracers, namely 210Pb and 137Cs, have been used to highlight atmospheric deposition. We observed an increased deposition flux of 210Pb and 137Cs at sites located at the highest altitudes, and the associated concentration profiles in soil allowed to evaluate the role of atmospheric deposition. We also obtained a comprehensive dataset of stable anthropogenic pollutants of atmospheric origin that showed heterogeneity along the transect. The behavior has been explained by the local characteristic of the soil, by seeder-feeder processes promoted by the atmospheric circulation, and was reconciled with the concentration profile of radiotracers by factor analysis. Finally, the substantial impact of the local industrial activities on soil profiles and the role of the planetary boundary layer has been discussed and supported by simulations employing a Lagrangian dispersion model.

Geochemical and magnetic data on anthropogenic ashes from municipal solid waste incineration (MSWI).

This paper reports supplementary information to "Understanding room-temperature magnetic properties of anthropogenic ashes from municipal solid waste incineration to assess potential impacts and resources" [1]. The sample-set is composed of 47 samples of bottom (BA) and fly (FA) ashes from Municipal Solid Waste Incineration (MSWI), including eight magnetic extracts of selected BA and FA materials. The sampling relies on a simple random sampling strategy at four different MSWI sites in Northern Italy [2]. X-Ray Fluorescence (XRF) analysis on pressed powder pellets, microscopic observations on thin sections and stubs, and magnetic analysis were carried out. Various magnetic measurements are presented: the magnetic susceptibility measured at two different frequencies (0.47 and 4.7 kHz); the mass-specific susceptibility of ARM (χARM), expressed in m3/kg, calculated after mass-normalization and bias DC field correction; experiments for isothermal remanent magnetization (IRM) experimented were also conducted. The latter measurement allowed the calculation of additional parameters, such as the coercivity of remanence (B0cr) and the S-ratio [3]. The IRM acquired in a field of 1.0 T was regarded as the saturation IRM (SIRM). Mass-specific magnetic susceptibility (χ) was calculated by dividing the volume susceptibility by the sample mass. Finally, hysteresis loops and backfield curves at room temperature were measured on selected samples and are available. Data can be reused as groundwork information in future studies on MSWI residues. It would be essential to produce new data on geochemical and magnetic characteristics of MSWI residues to assure good coverage of data for enhanced sustainability of these heterogeneous streams of anthropogenic materials. This combination of methods will contribute to paving the way for quick and reliable resource assessment as well as to promote environmental sustainability.

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.

Assessing aquitard integrity in a complex aquifer - aquitard system contaminated by chlorinated hydrocarbons.

This study investigates for the first time the integrity of multiple stacked aquitards with different degrees of contaminant degradation. Aquitard integrity was assessed in a contaminated, multi-layered, alluvial aquifer-aquitard system (Ferrara, northern Italy). The system was contaminated by mixed organic contaminants of industrial origin (mostly chlorinated ethenes) that were illegally disposed in an urban dump four to five decades ago. High spatial resolution profiles of hydraulic head, geochemistry and chlorinated hydrocarbon concentrations were determined through the multi-layered system via discrete interval sampling of continuous cores and multilevel groundwater sampling, at three locations aligned along a transect adjacent to the buried waste to a maximum depth of 53 m below the water table. The profiles revealed that the two shallow aquitards had low integrity with respect to impeding downward migration of dense non-aqueous phase liquid (DNAPL), and provided little protection to the underlying aquifers against DNAPL contamination due to preferential pathways through imperceptible fractures and/or permeable micro-beds. However, both aquitards inhibited downward DNAPL migration to some extent due to DNAPL retention along its flow paths and accumulation at lower permeability interfaces, with decreasing peak concentrations at the top of successively deeper aquitard units. Moreover, both aquitards enhanced contaminant biodegradation due to the occurrence of organic rich sub-layers, influencing the contaminant plume composition, mobility and fate in the underlying and overlying aquifers. The deepest aquitard showed evidence of DNAPL accumulation at the top and slow diffusion-dominated transport consistent with 40 years of transport, suggesting higher integrity compared to the two shallower aquitards. However, the occurrence of micro-fractures and/or discontinuities in the aquitard upgradient under the dump (source) is the most likely explanation for contamination of the deepest aquifer. Analytical 1-D simulations of the diffusion profiles in the deepest aquitard revealed that DNAPL contamination down to the top of this aquitard occurred with minimal delay after DNAPL waste disposal began. The results highlight the necessity of high-resolution vertical profiling for assessing the presence of imperceptible features relevant to DNAPL migration and integrity of individual aquitards affecting organic contaminant source zone mass and phase distributions over decades.

Minimization of metal sulphides bioleaching from mine wastes into the aquatic environment.

The continuous presence of toxic elements in the aquatic environments around mine tailings occurs due to bioleaching or chemical extraction promoted by the mining operations. Biogenic passivation treatment of tailings dams can be a new environment-friendly technique to inhibit the solubility of heavy metals. In spite of current bioleaching researches, we tried to minimize the mobility of the trace elements in the laboratory scale through the formation of a passivation layer in the presence of a mixed culture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. The X-ray diffraction (XRD) and scanning electron microscope (SEM) represented the jarosite generation as an inhibitory layer on the mineral surfaces of the tested materials. More detailed observations on electron probe micro-analyzer (EPMA) showed the co-precipitation of metals with the passivation layer. Thereby, the passivation layer demonstrates potential in elements immobilization which, in turn, can be optimized in the natural systems. Our working hypothesis was to exploit and optimize the formation of the passivation layer to maximize the immobilization of heavy metals (e.g., Cu, Cr). The optimization process of bioleaching experiments using indigenous bacteria caused a reduced solubility for Cu (from around 20% to 4.5%) and Cr (from around 30% to 10.6%) and the formation of 6.5 gr passivation layer. The analyses finally represented the high efficiency of the passivation technique to minimize metals bioleaching in comparison to earlier studies.

Environmental implications of metal mobility in marine sediments receiving input from a torrent affected by mine discharge.

Acid Mine Drainage (AMD) is one of the most important sources of pollution in fluvial systems and can enrich rivers in dissolved and suspended metals of environmental concern. Colloidal particles may favour the transport of metals to the sea, where metals can be accumulated in bottom sediments. The aim of this paper was to evaluate the mobility of metals in the "Baia delle Favole" bottom sediments (Sestri Levante, Italy), which receive the input of the AMD impacted Gromolo Torrent, using chemical speciation (BCR sequential extraction). Basing on the Risk Assessment Code (RAC), our results showed a systematic and widespread high risk classification for Mn, whereas a medium risk is associated to Co, Cu, and Zn in the sediments collected near the mouth of the Gromolo Torrent. Moreover, in these sediments the occurrence of Fe oxyhydroxides has been observed, reflecting an increase of metals in the reducible fraction obtained with BCR.

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.

Sediment quality assessment in a coastal lagoon (Ravenna, NE Italy) based on SEM-AVS and sequential extraction procedure.

Sediments from the Pialassa Piomboni coastal lagoon (NE Italy) were studied to assess the degree of contamination and ecological risk related to trace metals by combining a geochemical characterization of bulk sediments with the assessment of the bioavailable forms of trace metals. With this purpose, sediment contamination (Cd, Cu, Hg, Ni, Pb, and Zn) was assessed by Enrichment Factors (EFs), and potential bioavailability by the Simultaneously Extracted Metals and Acid Volatile Sulfides (SEM-AVS) approach (Cd, Cu, Ni, Pb, and Zn), and by Sequential Extraction Procedure (Co, Cr, Cu, Ni, Pb, and Zn). On average, Cr and Ni exhibited no contamination (EF ≤1.5), and a predominance in the residual fraction of the sediment, indicating natural origin for these metals. Cu, Pb and Zn displayed a local contamination, which resulted in a higher proportion of Cu bound to the reducible and oxidizable fractions (~30% and ~40% as median, respectively), and Pb mostly associated with the reducible phase (~60% as median). Hence, Cu and Pb could be mobilized when environmental conditions become reducing or oxidizing. Zn resulted mainly partitioned into the reducible and residual fractions (~50% as median, in both fractions). The Risk Assessment Code (RAC) indicated that approximately 30% of samples had >10% of total Zn weakly bound to the sediment, suggesting a medium risk of exposure for aquatic organisms. RAC results were consistent with the ∑SEM-AVS findings, pointing to possible adverse effects for aquatic biota in ~30% of samples, with Zn mostly accounting for the total metal bioavailability. Hg showed a moderate to very severe enrichment, indicating that a substantial amount of this metal derives from anthropogenic sources and may pose adverse effects on the aquatic biota of the Pialassa Piomboni lagoon.

Occurrence and distribution of six selected endocrine disrupting compounds in surface- and groundwaters of the Romagna area (North Italy).

Endocrine disrupting compounds (EDCs) are a wide group of contaminants of emerging concern known to be harmful for organisms. The aim of the study was to assess the occurrence and distribution of six EDCs (estrone-E1, ß-estradiol-E2, 17α-ethinylestradiol-EE2, bisphenol A-BPA, perfluooctanoic acid-PFOA, perfluorooctane sulfonate-PFOS) in the Apenninic rivers and groundwaters of the Romagna area (North of Italy). Groundwaters were unaffected by EDC contamination, while all classes of compounds were detected at concentrations above the method quantification limit (MQL) in the majority of the river bodies. In detail, PFOA and PFOS concentrations varied between

Seasonal variations in the occurrence of perfluoroalkyl substances in water, sediment and fish samples from Ebro Delta (Catalonia, Spain).

The main objective of this study was to assess the concentration levels and the seasonal variations of 13 poly- and perfluoroalkyl substances (PFASs) in different compartments (water, sediments and fish) of the Ebro Delta (NE Spain) and surrounding coastal areas. Perfluorooctanoic acid (PFOA) was the most frequently detected compound in waters and sediments. Perfluorocarboxylic acids (PFCAs) were the compounds found at the highest concentrations in water samples. On the other hand, sediments were more enriched in perfluorooctanesulfonate (PFOS) (range<1.02-22.6ng/g dw). Waters and sediments showed a different seasonal trend. While waters were characterised by a substantial constant level of PFASs over the year, sediments showed a progressive decrease from autumn to summer, revealing the great influence that environmental conditions exert on PFAS distribution in sediments. As regards fish samples, in spite of the ban of its production, PFOS was the most frequently detected compound in seawater fishes, in agreement with its high persistency, bioaccumulation and biomagnification. Moreover, PFASs showed to be more distributed in the skin rather than in muscle tissues. In addition, river fishes were characterised by very high PFAS levels (∑PFAS range from 63.8ng/g ww to 938ng/g ww), with perfluoroalkyl carboxylic acids being more concentrated than sulfonates. The PFASs concentrations in water, sediment, and biota revealed that one of the studied sites, Isla de Buda was the most contaminated site of the Ebro Delta. These results are consistent with its location at the final part of the estuary, where many irrigation channels are collected together.

Metal transport and remobilisation in a basin affected by acid mine drainage: the role of ochreous amorphous precipitates.

Metal-polluted mine waters represent a major threat to the quality of waters and sediments in a downstream basin. At the confluence between acidic mine waters and the unpolluted waters of the Gromolo Torrent (Liguria, North-West Italy), the massive formation of an ochreous amorphous precipitate takes place. This precipitate forms a soft blanket that covers the torrent bed and can be observed down to its mouth in the sea. The aim of this work is to evaluate the dispersion of metals in the Gromolo Torrent basin from the abandoned Cu-Fe sulphide mine of Libiola to the Ligurian Sea and to assess the metal remobilisation from the amorphous precipitates. The mineralogy of the superficial sediments collected in the torrent bed and the concentrations of different elements of environmental concern (Cu, Zn, Cd, Co, Cr, Mn, Ni, Pb, As, and Sb) were therefore analysed. The results showed that the precipitates contain high concentration of Fe, Al, Cu, and Zn, significantly modifying the bulk chemistry of the Gromolo Torrent sediments. In order to evaluate the possible remobilisation of ecotoxic elements from the amorphous precipitates, bulk leaching tests were performed with both deionised and seawater. Bulk leaching tests with deionised water mobilised primarily high Pb amounts, but also relatively high concentrations of Fe, Al, Cu, and Zn are released in the leachate. In seawater tests, Fe, Al, Cu, and Zn were released in smaller amounts, while other elements like Mn, Cd, Co, and Ni increased in the released fraction. Pb was still strongly released as in deionised water experiments. The results show that the interaction of precipitates and seawater can remobilise high concentrations of metals, thus affecting the surrounding environment.

A comprehensive evaluation of the environmental quality of a coastal lagoon (Ravenna, Italy): Integrating chemical and physiological analyses in mussels as a biomonitoring strategy.

This study aimed at evaluating the environmental quality of a coastal lagoon (Pialassa Piomboni, NW-Adriatic, Italy) by combining analyses of biomarkers of environmental stress and bioaccumulation of contaminants in marine mussels (Mytilus galloprovincialis) transplanted for 28days to six selected sites. Assessed biomarkers encompassed lysosomal endpoints, oxidative stress and detoxification parameters, specific responses to metals, neuro- and genotoxic substances; chemical analyses focused on PAHs, metals, pesticide and pharmaceuticals. Results showed up to a 67-fold bioaccumulation of 4- to 6-ring PAHs, including pyrene, fluoranthene, chrysene and benzo(ghi)perylene in transplanted mussels compared to reference conditions (T0). A 10-fold increase of Fe, Cr and Mn was observed, while pesticides and pharmaceuticals were not or slightly detected. The onset of a significant (p<0.05) general stress syndrome occurred in exposed mussels, as outlined by a 50-57.7% decrease in haemocytes lysosomal membrane stability and an increased lysosomal volume (22.6-26.9%) and neutral lipid storage (18.9-48.8%) observed in digestive gland. Data also revealed a diffuse lipofuscin accumulation (86.5-139.3%; p<0.05) in digestive gland, occasionally associated to a catalase activity inhibition in gill, indicating an increased vulnerability toward pro-oxidant factors. Higher levels of primary DNA damage (258%; p<0.05) and PAH accumulation were found in mussels exposed along the eastern shoreline, hosting a petrochemical settlement. Bioaccumulated metals showed a positive correlation with increased metallothionein content (85-208%; p<0.05) observed in mussels from most sites. Overall, the use of physiological and chemical analyses detected chronic alterations of the mussel health status induced by specific toxicological pathways, proving a suitable approach in the framework of biomonitoring programs of coastal lagoons.