Can Sediments Contaminated by Mining be a Source of Mercury in the Coastal Environment Due to Dredging? Evidence from Thermo-Desorption and Chemical Speciation.

The sediments in the Gulf of Trieste (northern Adriatic Sea, Italy) are contaminated by mercury (Hg) due to historic mining which took place in Idrija (Slovenia). Despite many studies having been done regarding Hg, no information is available on the potential impact of dredging required along the main channel approaching the Port of Monfalcone. Sixteen surface sediment samples were collected along the channel to determine both total Hg concentration and chemical species using the thermo-desorption (TD) technique. Six samples were also chosen to apply a selective sequential extraction (SSE). The TD technique showed the maximum Hg release approximately at 260 and 335°C, corresponding to metacinnabar (ß-HgS) and cinnabar (α-HgS), respectively. The SSE demonstrated that Hg was mainly associated with poorly soluble or insoluble compounds (98.7%). A resuspension event over a limited period of time can be considered of negligible impact to the water column due to the scarce Hg mobility from sediments.

Bioaccumulation of thallium and other trace metals in Biscutella laevigata nearby a decommissioned zinc-lead mine (Northeastern Italian Alps).

The mineral body exploited in Salafossa (Eastern Dolomites) was one of the largest lead/zinc-containing mineral deposits in Europe. Both metals were mainly present as sulphides (sphalerite, ZnS and galena, PbS). Mining activity started around 1550, but it was only around 1960 that the richest veins of the minerals were discovered. The mine closed in 1985, and concentrations of several trace metals, such as thallium (Tl), iron (Fe), manganese (Mn), lead (Pb) and zinc (Zn), were detected in the soils and plant samples (Biscutella laevigata L.) that were collected from eighteen sites selected outside the mine. B. laevigata is a pseudometallophyta species, and it often grows near mining areas where the soil's metal concentrations are significantly higher than those of soil with a natural geochemical background. The total metal concentrations in the plant tissue (roots and leaves of Biscutella laevigata) and in the soil samples - both bulk-soil and the B. laevigata root system (rhizo-soil) - were determined through Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The metal extractability and leachability of the soil samples were estimated using soil extractions with DTPA (Diethylenetriaminepentaacetic acid). In addition, metal mobility caused by rainwater runoff was estimated by using a leaching test with a dilute solution of H2SO4 and HNO3. The results showed that metals were present in a chemical form available for uptake by the plants' roots. In fact, high concentrations of the metals were also found in the plant tissue (roots and leaves) of B. laevigata, and these concentrations were higher than those whose soils present natural geochemical background levels in the corresponding rhizo-soil. Thus, B. laevigata has shown a marked ability to bioaccumulate trace metals, especially Tl and, to a lesser extent, Zn, Pb, Fe and Mn, and it can influence metal mobility in the rhizo-soil. To assess the uptake and translocation processes of the trace metals, resulting in their bioaccumulation, two different indices were calculated: the enrichment factor in roots (EFr), as the ratio between the metal concentration in belowground biomass and in the respective rhizo-soil, and the translocation factor (TF), as the ratio between the metal concentration in the leaves and the corresponding roots. For both indices, values > 1 denoted enrichment of the metal in the roots or its translocation to the upper tissues. The results showed that EFr and TF were considerably high only for Tl, reaching a maximum value of 60 for EFr and 11.6 for TF. Conversely, the other investigated metals did not show significant bioaccumulation (EFr < 1), and they showed TF > 1 only at a few sites.

Effect of forced aeration on the biogeochemical cycle of nutrients and metal(loid)s as a remedy for hypoxia in a permanently stratified estuary (Gulf of Trieste, northern Adriatic Sea).

The Timavo River estuary (northern Adriatic Sea) is characterised by strong thermohaline stratification that keeps the deep waters hypoxic. The consequence is an harmful algal bloom at the surface in summer that can be mitigated with a forced aeration system installed at the bottom to improve water oxygenation. The nutrient and metal(loid) cycle was investigated, before and during reoxygenation, using an in situ benthic chamber coupled with sampling and analyses of the water column, sediments and porewater. Dissolved oxygen (DO) decreased along the water column and quickly within the benthic chamber when aeration was not in operation, resulting in hypoxia (2.29 mg L-1) at the bottom and consequent increase in nutrient and metal(loid) concentrations. In contrast, DO levels increased during the activation of the forced aeration system, which proved effective in mitigating oxygen depletion and the efflux of metal(loid)s and nutrients into the overlying water.

Environmental impact of potentially toxic elements on soils, sediments, waters, and air nearby an abandoned Hg-rich fahlore mine (Mt. Avanza, Carnic Alps, NE Italy).

The decommissioned fahlore Cu-Sb(-Ag) mine at Mt. Avanza (Carnic Alps, Italy) is a rare example of exploited ore deposits, as the tetrahedrite (Cu6[Cu4(Fe,Zn)2]Sb4S13) is the main ore mineral found. This multi-compartmental geochemical characterisation approach provides one of the first case studies regarding the geochemical behaviour and fate of Hg, Sb, As, Cu, and other elements in solid and water matrices and of Hg in the atmosphere in an environment affected by the mining activity of a fahlore ore deposit. Elevated concentrations of the elements (Cu, Sb, As, Pb, Zn, Hg) associated with both (Zn-Hg)-tetrahedrite and to other minor ore minerals in mine wastes, soils, and stream sediments were observed. Concentrations in waters and stream sediments greatly decreased with increasing distance from the mining area and the Igeo index values testify the highest levels of sediment contamination inside the mine area. Thallium and Ge were associated with the "lithogenic component" and not to sulfosalt/sulphide minerals. Although mine drainage water often slightly exceeded the national regulatory limits for Sb and As, with Sb being more mobile than As, the relatively low dissolved concentrations indicate a moderate stability of the tetrahedrite. The fate of Hg at the investigated fahlore mining district appeared similar to cinnabar mining sites around the world. Weak solubility but the potential evasion of gaseous elemental mercury (GEM) into the atmosphere also appear to be characteristics of Hg in fahlore ores. Although GEM concentrations are such that they do not present a pressing concern, real-time field surveys allowed for the easy identification of Hg sources, proving to be an effective, suitable high-resolution indirect approach for optimising soil sampling surveys and detecting mine wastes and mine adits.

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.

Interactions of airborne graphene oxides with the sexual reproduction of a model plant: When production impurities matter.

The increasing use of graphene-related materials (GRMs) in everyday-life products raises concerns for their possible release into the environment and consequent impact on organisms. GRMs have widely varying effects on plants and, according to recent evidences, graphene oxide (GO) has the potential to interfere with the sexual reproduction owing to its acidic properties and production residues. Here, stigmas of the model plant Cucurbita pepo (summer squash) were subjected to simulated dry depositions of GO and GO purified from production residues (PGO). Stigmas were then hand-pollinated and GRM deposition was checked by ESEM and confocal microscopy. Analysis of stigma integrity, pH homeostasis and pollen-stigma interactions did not reveal negative effects. Fruit and seed production were not affected, but GO depositions of 22.1 ± 7.2 ng mm-2 affected the normal development of seeds, decreasing seed dimensions, seed germination and germination speed. The elemental analysis revealed that GO has significant quantities of production residues, such as strong acids and oxidants, while PGO has only traces, which justifies the differences observed in the effects caused by the two materials. Our results show that GO depositions of up to 11.1 ± 3.6 ng mm-2, which fall within the variation range of total dry particulate matter depositions reported in the literature, are safe for reproduction of C. pepo. This is the first "safety" limit ever recorded for depositions of "out-of-the-box" GO concerning the reproduction of a seed plant. If confirmed for wind-pollinated species, it might be considered for policymaking of GRMs emissions in the air.

Percutaneous metals absorption following exposure to road dust powder.

The skin constitutes a protective barrier to external physical and chemical aggressions. Although it is constantly exposed to various xenobiotics, it is generally considered poorly permeable to them, as for example metal ions, becoming unfortunately an entry route of such substances. Metals may penetrate inside the skin inducing more or less local effects such as skin sensitization and potential metals diffusion into the bloodstream. The objective of the study was to investigate the percutaneous penetration of metals in vitro - ex vivo in Franz cell with intact as well damaged skin applying a road dust powder. Moreover, porcine and human skins were compared. This study demonstrated that, after the application of a road dust powder on the skin, metals can penetrate and permeate this cutaneous membrane. From this experimental analysis, in intact skin lead (Pb) achieved the highest skin absorption in both human and porcine skin, while skin absorption profile of cobalt (Co) was the lowest in human skin than the one in porcine model. The concentrations of Ni present in receiving solution were higher compared to other metals in all experiments performed. The present work, definitely shows that metals permeation through damaged skin is accelerated than intact skin, as a result of the weaker cutaneous barrier function. According to published data, pig skin appeared as a suitable model for human skin. Our results confirmed that skin absorption of metals can be relevant in environmental exposures.

Occupational exposure to mercury from cinnabar enriched sand in workers of Grado Beach, Gulf of Trieste (North-eastern Italy, upper Adriatic Sea).

Health and safety of occupations entailing extensive skin contact with cinnabar-enriched sand in beaches of Friuli-Venezia Giulia (FVG) Region (North-eastern Italy) have been questioned for possible skin absorption of mercury (Hg). One hundred mg hair was collected from the occipital scalp of 50 male workers of Grado beach and 121 males from FVG general population. Factors associated with hair Hg content were investigated by multivariable logistic (considering Hg levels >1 vs ≤1 mg/kg) and log-transformed linear regression. The median hair concentration of Hg in male beach workers was 0.70 (IQR = 0.42; 1.34) mg/kg, lower than FVG general population's [1.29 (IQR = 0.87-2.06) mg/kg (p < 0.001)]. In both regression models the hair Hg increased with fish consumption, both among beach workers of Grado and FVG general population. The mean Hg levels in beach workers of Grado fell within an acceptable range, not requiring restrictions of their occupational activities.

Is airborne graphene oxide a possible hazard for the sexual reproduction of wind-pollinated plants?

Products containing graphene-related materials (GRMs) are becoming increasingly common, allowing GRM nanoparticles (NPs) to enter the environment during their life cycle. Thanks to their lightness and bidimensional geometry, GRM NPs can be easily dispersed in the air and travel very long distances. The flowers of wind-pollinated plants may be exposed to airborne GRMs, being apt to intercept pollen from the air and, inevitably, other airborne particles. Here, stigmas of four wind-pollinated plants (Corylus avellana, common hazel; Juglans regia, walnut; Quercus ilex, holm oak; Zea mays, maize) were exposed to airborne graphene oxide (GO) and GO purified from production residues (PGO) at a concentration of 3.7 ng m-3. Subsequently, the stigmas were pollinated and the adhesion of GOs and their effects on stigma integrity and pollen-stigma interaction were examined. The effect of GO NPs in presence of liquid water on the stigma of C. avellana was also investigated. GOs NPs were intercepted by all species, but their effect varied among them. GO reduced pollen adhesion in J. regia and Q. ilex, whereas pollen germination was unaffected in all four species. The presence of a film of water neither completely removed GO NPs from the stigma, nor it enhanced the toxic effect of GO acidity. PGO never affected pollen-stigma interaction, indicating that the phytotoxic substances used for the production of GO, still in traces in commercial GO, are the main cause of GO toxicity. These results reconfirm the need to verify GRMs effects also on key biological processes beside single model organisms.

The Legacy of the Idrija Mine Twenty-Five Years after Closing: Is Mercury in the Water Column of the Gulf of Trieste Still an Environmental Issue?

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/Soca 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 (

Use of single particle ICP-MS to estimate silver nanoparticle penetration through baby porcine mucosa.

Children are potentially exposed to products that contain nanoparticles (NPs). In particular, silver NPs are commonly present both in products used by and around children, primarily due to their antibacterial properties. However, very few data are available regarding the ability of silver NPs to penetrate through the oral mucosa in children. In the present work, we used baby porcine buccal mucosa mounted on vertical Franz diffusion cells, as an in vitro model to investigate penetration of silver NPs (19 ± 5 nm). Permeability experiments were performed using pristine physiologically-relevant saline solution in the receiver chamber and known concentrations of NPs or ions in the donor chamber; conditions mimicked the in vivo physiological pH conditions. After physicochemical characterization of silver nanoparticles dispersed in physiological solution, we evaluated the passage of ions and NPs through the mucosa, using single particle inductively coupled plasma mass spectrometry. A flux of 4.1 ± 1.7 ng cm-2 min-1 and a lag time of 159 ± 17 min were observed through mucosa exposed to silver nanoparticles. The latter suggests nanoparticle penetration through the baby porcine mucosa and release Ag+ ions in the receptor fluid, as confirmed by computational model. Due to physiological similarity between human and pig membranes it is reasonable to assume that a trans-oral mucosa penetration could occur in children upon contact with silver nanoparticles.

Mercury and arsenic mobility in resuspended contaminated estuarine sediments (Asturias, Spain): A laboratory-based study.

Estuarine sediments must be dredged to allow for navigation, and where these sediments are placed after dredging depends upon guidelines based only on the total concentration of contaminants. However, resuspension events could seriously affect the mobility and speciation of contaminants, including potentially toxic trace elements stored in sediments. The effects of resuspension on the cycling of mercury (Hg) and arsenic (As) between the sediment and water column was investigated in a mesocosm study. Four experiments were conducted in three estuaries in northern Spain based on samples collected from sites which have been impacted by decommissioned Hg and As mines and periodically subjected to dredging activities. Designed to mimic the resuspension of particles, each of the experiments revealed that the release of Hg and As species does not only depend on the total concentration in the sediments (16.3-50.9 mg kg-1, for As and 0.52-5.01 mg kg-1 for Hg). The contribution from porewaters and the subsequent reductive dissolution and/or desorption appear to be the main processes responsible for the abrupt increase in dissolved Hg and As species (maximum release of 427% and 125%, respectively). In some cases, As and Hg continued to remain at high concentrations in the water column even after the experiments were completed, thus testifying to their critical persistence in the dissolved form. Conversely, at the other sites, the restoration of pre-resuspension conditions was observed only a few hours after resuspension, mainly due to the role of Fe oxy-hydroxides which provides suitable surfaces for adsorption and/or co-precipitation involving dissolved Hg (maximum removal of -58%) and As (maximum removal of -25%) species. The results of this research could be helpful to take appropriate decisions regarding dredging especially at the Nalòn estuary, where the release of dissolved As(V) and MeHg appeared to be favoured by sediment resuspension.

Trace elements in the estuarine systems of the Gulf of Trieste (northern Adriatic Sea): A chemometric approach to depict partitioning and behaviour of particulate, colloidal and truly dissolved fractions.

Estuaries are transitional water systems where the hydrodynamic processes governing water circulation actively influence suspended particle transport and deposition. In the estuarine mixing zone, the strong physico-chemical gradients resulting from the interaction between river freshwater and seawater may affect the distribution, mobility and fate of several potentially toxic compounds, among which trace elements are of major concern. Knowledge regarding the partitioning behaviour of trace elements would provide essential scientific support for the environmental management of estuaries. In this study, trace element occurrence and phase partitioning among suspended particulate matter, colloidal material and the truly dissolved fraction were investigated in the main Italian and Slovenian estuarine environments of the Gulf of Trieste (northern Adriatic Sea). Further information about the water quality at the river mouths was provided and, in addition to the traditional evaluation of single chemical parameters, a multi-way principal component analysis was employed in order to depict disparities among sampling sites, water layers and seasonal conditions with the final aim of evaluating trace element phase partitioning. Results indicated that the suspended particulate matter acts as the main effective vehicle for Cu, Cr, Fe, Ni and Pb, and enhanced adsorption processes resulted in elevated partitioning coefficients, especially for Fe and Pb. Although disparities occurred between sampling sites and seasons, trace elements showing affinity for the solid phase appeared to be partially bound to the colloidal material. Conversely, As and Cs prevailed in the truly dissolved fraction, especially in seawater and showed scarce affinity for both the suspended particles and colloids.

Mobility of metal(loid)s at the sediment-water interface in two tourist port areas of the Gulf of Trieste (northern Adriatic Sea).

One of the main environmental issues affecting coastal marine environments is the accumulation of contaminants in sediments and their potential mobility. In situ benthic chamber experiments were conducted at two tourist ports (marinas) located in the Gulf of Trieste, one in Slovenia and one in Italy. The aim was to understand if and where recycling at the sediment-water interface (SWI) may affect metal(loid)s. Short sediment cores were also collected near the chamber to investigate the solid (sediments) and dissolved phases (porewaters). Both diffusive and benthic fluxes were estimated to elucidate the release of metal(loid)s at the SWI. Total element concentrations and their labile fractions were determined in sediments to quantify their potential mobility. The total element contents were found to be two orders of magnitude higher in the Italian marina than in the Slovenian one, especially for Hg (up to 1000 mg kg-1), whereas the labile fraction was scarce or null. The opposite occurred in the Slovenian marina. Metal(loid)s in porewaters showed a clear diagenetic sequence and a close dependence upon the suboxic/anoxic conditions of sediments. The results suggest that although the sediments of the Italian marina exhibit the highest total metal(loid) concentration, these elements are scarcely remobilisable. Conversely, in the Slovenian marina, sediments seem to be comparatively more prone to release metal(loid)s at the SWI.