The accumulation of contaminants and their potential mobility represent two of the main environmental issues facing coastal environments. Sediments often act as “reservoirs” of contaminants, including potentially toxic trace elements, but they can also be considered a secondary source of contamination due to remobilisation processes at the sediment-water interface which may affect the quality of the coastal water and aquatic biota. This research aims to provide a geochemical characterisation of the estuarine system of the Timavo/Reka River, focusing on the occurrence of trace elements in different environmental matrices with the purpose of highlighting potential critical conditions in terms of environmental quality. The surface sediments were found to be enriched in several trace elements especially in the innermost sector of the area. There, sulphate-reductive conditions in the bottom saltwater testify to potential anoxia at the sediment-water interface, driving trace element accumulation in the residual fraction of the sediments. However, Fe and Mn redox behaviour appears to play a crucial role in the recycling of dissolved trace elements in the water column. With the lone exception of the saltwater in the innermost sector, trace elements were found to be mainly associated with suspended particles due to oxidation and precipitation processes, whereas a common lithogenic origin was identified for Cr, Ni, and Co, which are significantly correlated both in the surface sediments and in the suspended particles.

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.

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.

Considerable amounts of gaseous elemental mercury (Hg⁰) can be released into the atmosphere from Hg-enriched substrates, such as those from former mining areas, posing a potential environmental threat. In this work, Hg⁰ fluxes at the soil–air interface under natural vegetation covers were measured in various locations within the Idrija Hg mining area (Slovenia) and its surroundings. Sites were selected in order to compare Hg⁰ fluxes from both forest soils heavily impacted by historical ore roasting and urban soils characterised by a different degree of Hg enrichment due to the natural occurrence of Hg in rocks or recent mining and roasting processes. Replicate measurements at each site were conducted using a non-steady state flux chamber coupled with a real-time Hg⁰ analyser (Lumex RA-915M). Moreover, topsoil samples (0–2 cm) were analysed for Hg total concentration and speciation. Cinnabar was the predominant Hg form in almost all the sites. Despite Hg⁰ being undetectable in soils using thermo-desorption, substantial emissions were observed (70.7–701.8 ng m⁻² h⁻¹). Urban soils in a naturally enriched area showed on average the highest Hg⁰ fluxes, whereas relatively low emissions were found at the historical roasting site, which is currently forested, despite the significantly high total Hg content in soils (up to 219.0 and 10,400 mg kg⁻¹, respectively). Overall, our findings confirm that shading by trees or litter may effectively limit the amount of Hg⁰ released into the atmosphere even from extremely enriched soils, thus acting as a natural mitigation.

Mercury (Hg) contamination in the Gulf of Trieste (northern Adriatic Sea) due to mining activity in Idrija (Slovenia) still represents an issue of environmental concern. The Isonzo/Soča River’s freshwater inputs have been identified as the main source of Hg into the Gulf, especially following periods of medium-high discharge. This research aims to evaluate the occurrence and distribution of dissolved (DHg) and particulate (PHg) Hg along the water column in the northernmost sector of the Gulf, a shallow and sheltered embayment suitable for the accumulation of fine sediments. Sediment and water samples were collected under unperturbed and perturbed environmental conditions induced by natural and anthropogenic factors. Mercury in the sediments (0.77–6.39 µg g⁻¹) and its relationship to grain size were found to be consistent with previous research focused on the entire Gulf, testifying to the common origin of the sediment. Results showed a notable variability of DHg (<LOD–149 ng L⁻¹) and PHg (0.39–12.5 ng L⁻¹) depending on the interaction between riverine and marine hydrological conditions. Mercury was found to be mainly partitioned in the suspended particles, especially following periods of high discharge, thus confirming the crucial role of the river inputs in regulating PHg distribution in the Gulf.

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 fluxes. 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 fluxes, 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.