Elisa Petranich

Evaluation of mercury biogeochemical cycling at the sediment–water interface in anthropogenically modified lagoon environments

The Marano and Grado Lagoon is well known for being contaminated by mercury (Hg) from the Idrija mine (Slovenia) and the decommissioned chlor-alkali plant of Torviscosa (Italy). Experimental activities were conducted in a local fish farm to understand Hg cycling at the sediment-water interface. Both diffusive and benthic fluxes were estimated in terms of chemical and physical features. Mercury concentration in sediments (up to 6.81μg/g) showed a slight variability with depth, whereas the highest methylmercury (MeHg) values (up to 10ng/g) were detected in the first centimetres. MeHg seems to be produced and stored in the 2-3cm below the sediment-water interface, where sulphate reducing bacteria activity occurs and hypoxic-anoxic conditions become persistent for days. DMeHg in porewaters varied seasonally (from 0.1 and 17% of dissolved Hg (DHg)) with the highest concentrations in summer. DHg diffusive effluxes higher (up to 444ng/m2/day) than those reported in the open lagoon (~95ng/m2/day), whereas DMeHg showed influxes in the fish farm (up to -156ng/m2/day). The diurnal DHg and DMeHg benthic fluxes were found to be higher than the highest summer values previously reported for the natural lagoon environment. Bottom sediments, especially in anoxic conditions, seem to be a significant source of MeHg in the water column where it eventually accumulates. However, net fluxes considering the daily trend of DHg and DMeHg, indicated possible DMeHg degradation processes. Enhancing water dynamics in the fish farm could mitigate environmental conditions suitable for Hg methylation.

Benthic nutrient cycling at the sediment-water interface in a lagoon fish farming system (northern Adriatic Sea, Italy)

Metabolism and carbon, oxygen, and nutrient fluxes (DIC, DOC, DO2, NO2-, NO3-, NH4+, PO43- and SiO44-) were studied during three surveys at two sites (VN1 and VN3) located at a fish farm at the Marano and Grado Lagoon (northern Adriatic Sea), using an in situ benthic chamber. Field experiments were conducted in July and October 2015 and March 2016 at a depth of approximately 2 m along the main channels of the fish farm. Water samples were collected by a scuba diver every 2 h in order to investigate daily fluxes of solutes across the sediment-water interface (SWI). Regarding the solid phase, Corg/Ntot and Corg/Porg molar ratios suggested an autochthonous marine origin of the organic matter and a minor preservation of P in the sediments, respectively; high values of sulphur (Stot) were also encountered (0.8-2%). The conditions at VN3 were mostly anoxic with high NH4+ levels (30-1027 μM) and the absence of NO3-. Substantial daily patterns of all solutes occurred especially in autumn and winter. On the contrary, fluxes at VN1 were less pronounced. Usually, inverse correlations appeared between dissolved O2 and DIC trends, but in our system this was observed only at VN3 in autumn and accomplished by a parallel increase in NH4+, PO43- and SiO44- during intense nutrient regeneration. These results are significantly different than those reported for open lagoon environments, where nutrient regeneration at the SWI and in surface sediments is the primary source of nutrients available for assimilation processes, especially during the warmer period of the year when the natural nutrient input by fresh water inflows is limited. Due to the importance of this site for aquaculture, biodiversity and ecosystem services, useful suggestions have been provided from this study in order to improve the quality of this unique aquatic system.

Mercury uptake by halophytes in response to a long-term contamination in coastal wetland salt marshes (northern Adriatic Sea)

Mercury (Hg) distribution in saltmarsh sediments and in three selected halophytes (Limonium narbonense, Sarcocornia fruticosa and Atriplex portulacoides) of a wetland system (Marano and Grado Lagoon, Italy) following a contamination gradient in sediments was investigated. The Hg uptake was evaluated at the root system level by calculating the enrichment factor (EF) and in the aboveground tissues by means of the translocation factor (TF). The related methylmercury (MeHg) concentrations in the halophytes were also investigated with regard to the location of the sites and their degree of contamination. Hg concentration in halophytes seemed poorly correlated both with the total Hg in rhizo-sediments and with the specific plant considered, supporting the evidence that the chemico-physical parameters of sediments could significantly affect metal availability for plants. Hg concentrations in roots increased with depth and were 20-fold higher than content measured in related rhizo-sediments (high EF). A low content of Hg is translocated in aboveground tissues (very low TF values), thus highlighting a kind of avoidance strategy of these halophytes against Hg toxicity. MeHg values were comparable between the two sites and among species, but the translocation from below- to aboveground plant tissues was more active.

Mercury in the unconfined aquifer of the Isonzo/Soca River alluvial plain downstream from the Idrija mining area

This work aims at evaluating mercury (Hg) occurrence, spatial distribution and speciation in groundwater of the Isonzo/Soča River upper alluvial plain downstream from the Idrija Hg mine (Western Slovenia). Several wells and piezometers were sampled both in static and dynamic mode. Total (THg) and filtered (FHg) concentrations were generally higher in static (THg, 1.87-855 ng L-1; FHg, 0.20-13.61 ng L-1) than in dynamic mode (THg, 0.08-78.77 ng L-1; FHg, 0.28-6.65 ng L-1). The estimated background value accounts for 2-3 ng L-1. On the basis of hydrochemistry and isotopic composition, the main sources of groundwater were established. Hg concentrations in the Slovenian sector, supplied by local rainfall, are comparable to values measured close to the Isonzo River. Possible further Hg local sources have been suggested. Stability field analysis for the aqueous Hg species revealed that in the presence of chloride Hg solubility may be increased by the formation of chlorocomplexes. Mercury that rarely enters reduced surrounding conditions can be bound to sulphur to form polysulphide species depending on the pH of water. Since Hg-contaminated alluvial sediments of the Isonzo River may act as a secondary Hg source in groundwater, a borehole was dug down to the water table. Mercury content and speciation revealed that cinnabar (HgS) is the prevalent form followed by the matrix-bound Hg (Hgbound). Variations of the physico-chemical boundary conditions, as well as the raising/lowering of the water table, may be locally responsible for the slight variability of Hg concentrations in the aquifer.

Suspended particulate mercury associated with tidal fluxes in a lagoon environment impacted by cinnabar mining activity (northern Adriatic Sea)

The Isonzo River has been demonstrated to be a continuing point source of mercury (Hg) in the Gulf of Trieste although the Idrija mine was last active in 1996. The present study aims to investigate the role of the suspended particulate matter (SPM) associated with tidal fluxes to disperse particulate Hg (PHg) into the Grado coastal lagoon system. PHg concentrations (avg. 3.11±2.62μg/g, d.w.), notwithstanding the ebb or flood tides, were significantly higher than the local sediment background (0.13μg/g). The relative affinity of Hg for the particulate phase in surface waters was confirmed by higher average distribution coefficient (Kd) values (5.6-6.7). PHg contents showed the highest values in ebb tide conditions, thus suggesting their origin from the erosion of tidal flats and saltmarshes of the lagoon. When compared to river discharge, high PHg surface concentrations in flood tide are related to rainfall events occurring within the river basin. Results can be used to make an indicative assessment of the amount of Hg bound to SPM which is transported in and out of the lagoon basin following the action of tidal fluxes. A simple estimation provides a negative budget for the Grado lagoon sub-basin which loses between 0.14 and 1.16kg of PHg during a tidal semi-cycle. This conclusion is in agreement with the evidence of morphological deterioration which has emerged from recent studies on the lagoon environment, and which testifies to a current sedimentary loss from the lagoon into the northern Adriatic Sea.