Behaviour of Metal(loid)s at the Sediment-Water Interface in an Aquaculture Lagoon Environment (Grado Lagoon, Northern Adriatic Sea, Italy)

The cycling of metal(loid)s at the sediment\u2013water interface (SWI) was evaluated at two selected sites (VN1 and VN3) in an active fish farm in the Grado Lagoon (Northern Adriatic, Italy). In situ experiments using a transparent benthic chamber and the collection of short sediment cores were performed, to investigate the behavior of metal(loid)s in the solid (sediments) and dissolved (porewaters) phases. Total and labile concentration of metal(loid)s were also determined in sediments, to quantify their potential mobility. Comparable total concentrations were found at both sites, excluding As, Mn, Pb and V, which were higher at VN3. Metal(loid) porewater profiles showed a diagenetic sequence and a close dependence with redox (suboxic/anoxic) conditions in the surface sediments. Positive diffusive fluxes along with benthic fluxes, particularly at the more oxic site, VN1, were found for almost all metal(loid)s, indicating their tendency to migrate towards the overlying water column. Despite sediments at two sites exhibiting high total metal(loid) concentrations and moderate effluxes at the SWI, the results suggest that they are hardly remobilized from the sediments. Recycling of metal(loid)s from the SWI would not constitute a threat for the aquatic trophic chain in the fish farm

Legacy of Past Mining Activity Affecting the Present Distribution of Dissolved and Particulate Mercury and Methylmercury in an Estuarine Environment (Nalón River, Northern Spain)

At the Nalón River estuary (Asturias, Northern Spain), the occurrence of Hg is due to historical mining activity which has resulted in environmental issues of great concern. Although several studies have investigated the sediment compartment regarding Hg contamination, no information is currently available on the fate of Hg and MeHg in the water column. Considering different hydrodynamic/seasonal conditions, water samples were collected along the estuary to evaluate Hg and MeHg distribution and partitioning behaviour between solid and aqueous phases. The complementary effect of the river discharge and tidal currents contributed to the prevalence of the dissolved (4.02 +/- 1.33 ng L-1) or particulate (8.37 +/- 4.20 ng L-1) Hg under different conditions of discharge in summer and autumn, respectively. Conversely, particulate MeHg prevailed when the river flow was low, especially at the estuary mouth (25.8 +/- 19.1 pg L-1) and most likely due to the resuspension of fine particles promoted by a stronger tidal current. In comparison with the total Hg concentration, extremely low amounts of dissolved and particulate MeHg were observed, and strong interactions between MeHg and organic carbon highlighted a negligible risk of increased mobility and potential bioaccumulation of MeHg

Fluxes of settling sediment particles and associated mercury in a coastal environment contaminated by past mining (Gulf of Trieste, northern Adriatic Sea)

Purpose: As the result of historical mining at Idrija (Slovenia), mercury (Hg) contamination in the Gulf of Trieste (northern Adriatic Sea) is still an issue of environmental concern. The element has been conveyed into the coastal area by the Isonzo/Soča River inputs of freshwater and suspended particles for centuries. This research aims to investigate the occurrence of Hg bound to the settling sediment particles (SSP) in the coastal water and to assess the sedimentary Hg fuxes. Methods: Settling sediment particles were collected at four sites located in the innermost sector of the Gulf, a shallow and sheltered embayment where the accumulation of fine sediments is promoted. Six sampling campaigns were performed under different environmental conditions in terms of discharge from the Isonzo River and 12 sediment traps were installed in the upper and bottom water column for SSP collection. Settling sediment particles (SSP) were collected approximately every 2 weeks and analysed for grain size and total Hg. Results: Settling sediment particles (SSP) consisted predominantly of silt (77.7±10.1%), showing a concentration of Hg ranging overall between 0.61 and 6.87 µg g−1. Regarding the daily SSP fuxes, the minimum (7.05±3.26 g m−2 day−1) and the maximum (92.4±69.0 g m−2 day−1) values were observed under conditions of low and high river discharge, respectively. The daily Hg fluxes displayed a notable variability, up to an order of magnitude, both in the surface water layer (3.07–94.6 µg m−2 day−1) and at the bottom (11.3–245 µg m−2 day−1), reaching the maximum values following periods of high river flow. Conclusions: The Isonzo River inputs of suspended particulate matter continue to convey Hg into the Gulf of Trieste, especially following river flood events, which represent one of the most relevant natural factors affecting the variations of the Hg flux in the investigated area

Mobility and fate of Thallium and other potentially harmful elements in drainage waters from a decommissioned Zn-Pb mine (North-Eastern Italian Alps)

The potential impact of decommissioned mining areas on the quality of water resources is an issue of major concern for local communities. Acid mine drainage resulting from hydrolysis and oxidation of metal sulphides associated with mineral veins or mining wastes is often responsible for leaching large amounts of potentially harmful elements (PHEs) in solution, which can be dispersed into the surrounding environment and affect the quality of the recipient water bodies. The aim of the present study was to investigate the geochemical properties of the mine drainage waters at the decommissioned Salafossa mine (North-Eastern Italian Alps), to highlight anomalous concentrations of PHEs outflowing from the currently flooded galleries and to elucidate their speciation. In spite of the Zn-Pb sulphides still present in the body ore, there is no evidence of acid drainage waters from the mine galleries as a result of the buffering effect produced by carbonate host rocks. Due to their high mobility, however, Zn and Tl are present in solution mostly in ionic form. Conversely, the less mobile Pb, is referably partitioned in the solid phase. Additionally, the oxidising conditions of the drainage waters also allow the precipitation of some PHEs (As, Cd, Pb, Tl, Zn) in the form of Fe-Mn oxy-hydroxides and carbonates, which accumulate at the bottom of the mine galleries as fine \u201csediments\u201d or concretions. Drainage waters inside the mine were found to be highly enriched in Zn (up to 16 mg L\u20101), Fe (up to 5 mg L\u20101) and Tl (up to 260 \u3bcg L\u20101). Their concentrations, however, are partially diluted in the mine due to a mixing with less mineralised waters before being discharged into the Piave River, the major tributary downstream from the mining area. Although drainage waters are still characterised by high concentrations of Tl (about 30 \u3bcg L\u20101) at their outflow, dilution in the Piave River seems to be the only natural process mitigating the impact of PHEs within the drainage basin

Two-year monitoring of water hydrochemistry in a Pb-Zn Mississippi Valley-Type mine (MVT) in the Southeastern Alps (Raibl, Friuli Venezia Giulia)

The recent and past mining activities are among the main anthropic sources of dispersion of potentially toxic trace elements (PTEs) in the environment. In this study, a two year monitoring of different water bodies in a decommissioned mining site located in the Southeastern Alps (Friuli Venezia Giulia, Raibl mine) was performed. Results have allowed to provide a characterisation of the hydrogeochemistry, the chemical signatures and the temporal-spatial variations of PTEs in a carbonate-hosted Pb-Zn Mississippi Valley-Type (MVT) mine, where no acid mine drainages (AMD) occur. Besides mineralogy and pH-Eh conditions, strong rainfalls and high-flow events are the main factors affecting the temporal variability of dissolved PTEs, promoting their dissolution and dispersion. Anomalous concentrations of trace metals (Zn, Pb, Tl) were found in near neutral pH-buffered groundwaters entrapped in tailings impoundments, whereas concentrations of metalloids (As, Sb and Ge) were more abundant in low-flow water drainage from mine adits. High concentrations of Tl were found in the saturated area of the tailings impoundments, related to relatively lower pH and sulfate ions contents, thus suggesting Tl-bearing pyrite/marcasite oxidation. At the same time, low concentrations of dissolved Ge and Cd in groundwaters entrapped in tailings are possibly associated to sphalerite-depleted post-flotation tailings. Based on chemical data, modeling and literature, attenuation processes of dissolved PTEs (mainly Pb) are mainly attributed to sorption onto Fe-oxy-hydroxides, which is pH-dependent, and precipitation of mineral phases (e.g., dissolved Zn to hydrozincite: Zn5(CO3)2(OH)6). The Tl/Zn and Tl/Pb ratios show that enrichments occur without notable attenuation inside the tailings impoundments, possibly indicating that Tl attenuation needs higher pH to effectively promote adsorption onto Fe-oxy-hydroxides, as, conversely, occurs in the Rio del Lago stream waters

Effects of hypoxia on biogeochemical cycling of nutrients and trace elements in a stratified estuarine system (Gulf of Trieste, northern Adriatic Sea)

Estuaries can be thought as a sedimentary trap leading to the accumulation of potentially toxic trace elements (PTEs) in sediments. However, biogeochemical processes at the sediment-water interface (SWI) may also be responsible for the release of dissolved PTEs and nutrients in the overlying water column affecting the water quality. The estuarine system of the Timavo River (Gulf of Trieste, northern Adriatic Sea) is a semi-closed aquatic environment where a long-lasting oxic-hypoxic interface along the water column occurred due to the scarce water circulation in the innermost sector. To prevent bloom-forming and potential production of toxins and off-flavours, artificial mixing has been provided with a bubble plume installation connected to pressurised air and built on the sediment surface aiming at reoxygenating the water column. The aim of this research was to evaluate the behaviour of PTEs (As, Cr, Hg, Fe, Mn, Ni, Pb, V) and nutrients (NO3, NO2, NH4 and SRP) along the water column and at the SWI before (June) and during (September) the activation of the forced aeration system. Water samples were collected at different depths along the water column, in situ benthic chamber experiments were performed at the SWI and short sediment cores were sampled to investigate both the sediment and porewater. Dissolved oxygen decreased along the water column, especially in June when hypoxia (2.29 mg/L) and reductive conditions (58 mV) were observed at the bottom resulting in increasing dissolved PTE and nutrient concentrations. Accordingly, a gradual oxygen depletion was observed in the benthic chamber testifying to intense organic matter remineralisation processes. Moreover, the highest concentrations of dissolved PTEs in porewater were restricted to the top of the sedimentary sequence, especially in June when hypoxic conditions may promote PTE and nutrient effluxes from the sediment to the water column

Correction to: Concentration of mercury in human hair and associated factors in residents of the Gulf of Trieste (North‑Eastern Italy)

The Gulf of Trieste (Northern Adriatic Sea, Italy) is the coastal area of the Mediterranean Sea most highly contaminated by mercury (Hg) due to fluvial inputs from the Isonzo/Soča River system, draining over 500 years’ worth of cinnabar extraction activity from the Idrija mining district (Western Slovenia). The aim of this research is to investigate the concentration of Hg in hair samples taken from the general population of the Friuli Venezia Giulia (FVG) Region coastal area, as a marker of chronic exposure to Hg. Three hundred and one individuals — 119 males and 182 females — were recruited by convenience sampling in Trieste in September 2021. An amount of approximately 100 mg of hair was collected from the occipital scalp of each participant to measure the respective Hg concentrations (expressed as mg/kg). Moreover, participants completed a self-report questionnaire collecting extensive socio-demographic and life-style information. A multiple linear regression analysis was employed to investigate factors associated with increased levels of Hg concentration in hair. A mean Hg concentration in hair of 1.63 mg/kg was found, slightly above the 1.0 mg/kg threshold recommended by the WHO for pregnant women and children, although still well below the no observed adverse effects level (NOAEL) of 10 mg/kg. Among respondents, 55.6% showed a Hg concentration in hair > 1 mg/kg, 22.9% > 2 mg/kg, and 2 participants exhibited Hg levels > 10 mg/kg. The adjusted mean hair Hg level increased in those subjects who reported a preference for shellfish/crayfish/mollusks (RC = 0.35; 95%CI: 0.16; 0.55), whereas it decreased in those who reported a preference for frozen fish (RC = -0.23; 95%CI: − 0.39; − 0.06). Though a risk alert for Hg exposure for coastal residents from FVG is deemed unnecessary at this time, it is recommended that pregnant women limit their ingestion of locally caught fish to < 4 servings/month

Concentration of mercury in human hair and associated factors in residents of the Gulf of Trieste (North-Eastern Italy)

The Gulf of Trieste (Northern Adriatic Sea, Italy) is the coastal area of the Mediterranean Sea most highly contaminated by mercury (Hg) due to fluvial inputs from the Isonzo/Soca River system, draining over 500 years' worth of cinnabar extraction activity from the Idrija mining district (Western Slovenia). The aim of this research is to investigate the concentration of Hg in hair samples taken from the general population of the Friuli Venezia Giulia (FVG) Region coastal area, as a marker of chronic exposure to Hg. Three hundred and one individuals - 119 males and 182 females - were recruited by convenience sampling in Trieste in September 2021. An amount of approximately 100 mg of hair was collected from the occipital scalp of each participant to measure the respective Hg concentrations (expressed as mg/kg). Moreover, participants completed a self-report questionnaire collecting extensive socio-demographic and life-style information. A multiple linear regression analysis was employed to investigate factors associated with increased levels of Hg concentration in hair. A mean Hg concentration in hair of 1.63 mg/kg was found, slightly above the 1.0 mg/kg threshold recommended by the WHO for pregnant women and children, although still well below the no observed adverse effects level (NOAEL) of 10 mg/kg. Among respondents, 55.6% showed a Hg concentration in hair > 1 mg/kg, 22.9% > 2 mg/kg, and 2 participants exhibited Hg levels > 10 mg/kg. The adjusted mean hair Hg level increased in those subjects who reported a preference for shellfish/crayfish/mollusks (RC = 0.35; 95%CI: 0.16; 0.55), whereas it decreased in those who reported a preference for frozen fish (RC = -0.23; 95%CI: - 0.39; - 0.06). Though a risk alert for Hg exposure for coastal residents from FVG is deemed unnecessary at this time, it is recommended that pregnant women limit their ingestion of locally caught fish to < 4 servings/month

Portable X-ray Fluorescence (pXRF) as a Tool for Environmental Characterisation and Management of Mining Wastes: Benefits and Limits

Portable X-ray fluorescence (pXRF) is one of the main geochemical techniques employed in multi-elemental analysis screening for contaminated sites management. As the confidence of pXRF analyses are matrix-specific, efforts are made to provide studies of pXRF quality on different geochemical datasets, focusing on less investigated elements such as mercury (Hg) and antimony (Sb), to help both new and experienced users. The analysis of environmental solid samples from two decommissioned mining sites in NE Italy, characterised by Pb-Zn and (Hg-rich) Cu-Sb ore deposits, were prepared with two different protocols and compared with traditional destructive analyses. Sample composition was found strictly dependent to the occurrence of false positives and overestimation at low concentrations. In contrast, milling the sample did not produce major variations in the overall quality. Lead (Pb), Sb, and Zn reached the definitive data quality in at least one of the two datasets. Consequently, as far as a thorough QA/QC protocol is followed, pXRF can rapidly produce chemical data that is as accurate as that produced by destructive standard laboratory techniques, thus allowing to identify potential sources of contamination that could be reprocessed for the extraction of valuable elements and mitigating the dispersion of contaminants and ecological or health risks

Importance of a tidal flat-saltmarsh system as a source-sink of mercury in a contaminated coastal lagoon environment (northern Adriatic Sea)

Saltmarshes are important constituents of marine-coastal transitional environments that provide several services to the ecosystem. Due to anthropogenic activities, several contaminants are increasingly introduced into these environments where are disperse and can accumulate in the saltmarsh sediments. The Marano and Grado Lagoon (northern Adriatic Sea) is affected by Hg contamination, which mainly coming from historical regional mining activities (Idrija, western Slovenia) and, subordinately, from more recent industrial input due to a chlor-alkali plant. Several studies have also demonstrated the Hg contamination of saltmarsh sediments and halophyte vegetation that cover them. Moreover, saltmarshes not only trap contaminated sediments, but can act as a secondary source of contamination. This work aims at determining the potential role of the tidal flat-saltmarsh (TF-S) system as a sink or secondary source of Hg in this coastal lagoon in relation to the chemical-physical processes leading their remobilisation. The main objective was to understand the role played by periodic flow of tide in a TF-S pilot site in terms of transport, accumulation and release of Hg. Tidal flows and water chemistry were measured at the mouth of a principal tidal creek which collect the waters of a dense channel network draining a 5.5-ha tidal flat-saltmarsh system. Tidal fluxes were estimated by combining discrete hourly tidal flow measurements with weighted measurements of particulate (PHg) and dissolved (DHg) mercury obtained by water samples. The highest values of DHg and PHg were recorded during ebb tide and the quantitative fluxes estimated for all parameters highlighted a tendency for metal to be exported from the TF-S system due to the tidal flows in ebb tide conditions. The results obtained for the PHg fluxes, in particular, are in agreement with those observed on a macro-scale at one of the lagoon tidal inlets considering an annual mass-balance of PHg performed via several water column sampling campaigns. A simple estimation provides a negative sedimentary budget for the TF-S system, which loses PHg towards the main lagoon channel during a tidal semi-cycle thus confirming other evidence of serious morphological deterioration of this critical coastal environment