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 (β-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.
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.
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.
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•Hg spatial distribution and speciation in the groundwater of the Isonzo River alluvial plain were investigated.•Two sampling methods (static and dynamic) were compared to study Hg mobility.•Hg content in the groundwater was not affected by the enriched alluvial deposits.•Hg speciation showed that Cl− has a key role in the formation of soluble species.•Hg as cinnabar (HgS) was found to be the dominant form in alluvial sediments.
The Marano and Grado Lagoon (northern Adriatic Sea, Italy) is contaminated mainly by mercury (Hg) of mining and industrial origin. This work aims to investigate the sedimentary records of Hg of a ...tidal flat–saltmarsh (TF–S) system and to understand the role played by tidal fluxes in terms of the transport, accumulation and release of Hg due to the periodic flow of the tide. The complex history of the sources of Hg in the area of the TF–S system has resulted in several fluctuations of Hg in sediments over time; due to its higher sedimentation rate (1.3 cm year
−1
) than the subtidal areas of the Grado lagoon, the outer area of the TF–S system is more active in terms of accumulation (from 56 to 81 mg m
−2
year
−1
) than the inner area. Fluxes were estimated at the mouth of a principal tidal creek by combining discrete hourly tidal flow measurements with weighed measurements of dissolved (DHg) and particulate (PHg) mercury obtained via water sample collection. Mercury, mainly in particulate form, is drained by the tidal creek from the marsh during a tidal semi-cycle. The highest flux of PHg was recorded during ebb tide in July (1071 mg). The calculation of the quantitative flows of PHg and DHg highlighted a tendency for Hg to be exported from the TF–S to the lagoon channel during a tidal semi-cycle. However, the results obtained here for the Hg fluxes do not allow for the depiction of a constant positive or negative budget as that found in the literature for macro-scale budget calculations at lagoon tidal inlets. A possible explanation for there being no constant trend in the PHg and DHg budget is that our TF–S system is located in a lagoon area where previous findings reported accretion or a balance situation between erosion and sedimentation processes.
The cycling of metal(loid)s at the sediment–water 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.
The Cananéia-Iguape estuarine–lagoon complex (São Paulo state, Brazil) is a natural laboratory to study metal binding by humic substances (HS) in subtropical settings. This transitional environment ...is evolving into a freshwater environment due to water input from the Ribeira River, funneled through the Valo Grande Canal (Iguape). Past mining activities in the Ribeira River basin and maritime traffic are suspected to be potential sources of trace metals in the system. In this study, the trace metal contents of Free Humic Acids (FHA), Bound Humic Acids (BHA), and Fulvic Acids (FA) extracted from sedimentary organic matter were investigated. Moreover, the sources of HS were traced using their stable carbon isotope compositions and C/N ratios. The results suggested a mixed marine–terrestrial source of FHA, BHA, and FA. Copper and Cr were the most abundant trace metals bound to HS. On average, Cu showed concentrations of 176, 115, and 37.9 μg g−1 in FHA, BHA, and FA, respectively, whereas Cr showed average concentrations of 47.4, 86.3, and 43.9 μg g−1 in FHA, BHA, and FA, respectively. Marine FHA showed the highest binding capacity for trace metals, whereas terrestrial FA derived from the decay of mangrove organic matter showed the lowest binding capacity.
A crucial step towards developing a more complete understanding of mercury (Hg) biogeochemical cycling in coastal environments is the measurement of the fluxes of gaseous elemental mercury (GEM), at ...the water-air interface (W-A interface). A floating flux chamber coupled with a real-time atomic adsorption spectrometer (Lumex-RA 915M) was applied to measure GEM concentrations, and to estimate the diurnal evasion flux at the W-A interface during three seasonal campaigns at four selected sites: two in a lagoon-based fish farm, one in an open lagoon environment highly impacted by long-term activities from the Idrija mercury mine (Slovenia), and an uncontaminated area of the Gulf of Trieste, the Bay of Piran (Slovenia). In this study, the regional background concentration measured at the uncontaminated site of atmospheric GEM (from 1.60 ± 0.95 to 2.87 ± 1.52 ng m−3) was determined. GEM fluxes at the W-A interface were found to be significantly higher during the summer (from 51.2 ± 8.8 ng m−2 h−1 to 79.9 ± 11.4 ng m−2 h−1) and correlated to incident solar radiation and water temperature. This finding confirms the importance of these two parameters in the photoreduction and biotic reduction of Hg2+ to dissolved gaseous mercury (DGM), which is volatile and easily released to the atmosphere in the form of GEM. These new insights will be of help for future estimates of Hg mass balance in one of the most contaminated areas in the Adriatic Sea.
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•Diurnal fluxes of elemental mercury were investigated at the water-air interface.•A dynamic floating chamber and absorption spectrometer were used in the field.•Solar radiation and water temperature significantly influenced mercury evasion.•Highest fluxes of gaseous elemental mercury were found during summer season.•Night testing is needed to detect possible mercury evasion without sunlight.
Mercury (Hg) in aquatic environments accumulates in sediments in several chemical forms, both inorganic and organic, which are often determined through time-consuming selective and sequential ...extraction procedures. Thermal desorption technique (pyrolysis) coupled with continuous determination by atomic absorption spectrometry (AAS) may be an easy-to-use alternative technique for the rapid identification and quantification of Hg species in the solid matrix. This technique is based on the gradual heating of a sample that releases Hg at different temperature intervals depending on its chemical form. Thus, a single Hg species that desorbs at a specific temperature may be identified via a thermogram of the sample.
In this work, several commercial pure Hg compounds, natural Hg mineral species (red cinnabar, α-HgS) and one compound synthesised in the lab (α-FeOOHHg) were mixed with synthetic calcium carbonate (CaCO3), silica (SiO2) and natural matrices (silicate and carbonate marine sediments) which were then desorbed in order to determine the desorption peak temperatures corresponding to each Hg species. Moreover, possible interference caused by the matrix was also considered. The results obtained from 52 desorbed MIX samples displayed different desorption temperatures for the same Hg species depending on the matrix used. Indeed, Hg species mixed with synthetic SiO2 desorbed at a temperature lower than the same species mixed with synthetic CaCO3 with a difference of approximately 100 °C.
The analytical approach was applied to selected coastal sediments from the Gulf of Trieste (Northern Adriatic Sea, Italy), contaminated by Hg from the five centuries of cinnabar (α-HgS) mining activity from Idrija (Slovenia), in order to identify the unknown Hg species. The results revealed the presence of two peaks with a distinct temperature of desorption (∼250 and 350 °C). The highest temperature corresponds to the mostly refractory red cinnabar (α-HgS) compound, whereas the lowest temperature is related to other species (e.g. β-HgS) that may also include Hg associated with more mobile and potentially bio-accessible species (e.g. α-FeOOHHg) if compared to α-HgS. This methodological approach is a rapid and cost-effective technique useful to preliminarily quantify more stable Hg species (mainly α-HgS), underlining the relevance in considering the chemical form of the element rather than merely the total concentration for simplifying the environmental management of Hg-contaminated sediments.
•Thermodesorption technique facilitates rapid identification of Hg species in solid matrix.•Commercial pure Hg compounds mixed with synthetic and natural matrices are desorbed.•Several desorption peak temperatures of each Hg species were obtained.•β-HgS (210–250 °C) and α-HgS (350–360 °C) was mainly identified in marine sediments.•Hg compounds with very low concentration are more difficult to be detected.
The long term vertical and horizontal mobility of mercury (Hg) in soils of agricultural areas of a historically contaminated Italian National Relevance Site (SIN Brescia-Caffaro) was investigated. ...The contamination resulted from the continuous discharge of Hg in irrigation waters by an industrial plant (Caffaro S.p.A), equipped with a mercury-cell chlor-alkali process. The contamination levels with depth ranged from about 20 mg/kg dry weight (d.w.) of soil in the top (plow) layer to less than 0.1 mg/kg d.w. at 1 m depth. The concentrations varied also spatially, up to one order of magnitude within the same field and showing a decreasing trend from the Hg source (i.e., irrigation ditches). The concentration profiles and gradients measured were explained considering Hg loading, soil properties, such as the texture, organic carbon content, pH and cation exchange capacity. A Selective Sequential Extraction (SSE) was also applied on soil samples from an ad hoc greenhouse experiment to investigate the role of different plant species in influencing Hg speciation in soils. Although most of the extracted Hg was included in scarcely mobile or immobile forms, some plant species (i.e., alfalfa) showed to importantly increase the soluble and exchangeable fractions with respect to the unplanted control soils, thus affecting mobility and potential bioavailability of Hg.
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•Mercury (Hg) was measured in soils of a highly contaminated agricultural area in Brescia, Italy.•Contamination was due to the use of contaminated irrigation water from a chlor-alkali plant.•Soil cores up to 1 m and spatial analysis evidenced gradients with depth and field length.•A greenhouse experiment allowed to evaluate how plant species could change Hg speciation.•Alfalfa importantly increased the soluble fractions of Hg and therefore its mobility in soil.
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
) 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
) and PHg (0.39-12.5 ng L
) 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.
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