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.
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.
Mercury (Hg) is a global pollutant, being highly persistent in the atmosphere, in particular gaseous elemental mercury (GEM), which can easily be emitted and then transported over long distances. In ...the Gulf of Trieste (northern Adriatic Sea, Italy), contamination by Hg is well characterised but little is known regarding the concentrations, sources and fate of GEM in the atmosphere. In this work, discrete measurements of GEM were recorded from several sites at different times of the year. The database is consistent with temporal night-day variations monitored using a continuous real-time device. The meteorological conditions were collected as ancillary parameters. GEM levels varied from <LOD (2.0 ng m−3) to 48.5 ng m−3 (mean 2.7 ng m−3), with no significant differences found among sites. A clear daily pattern emerged, with maximum values reached just after sunset. Air temperature, relative humidity, wind speed and direction were identified as the main micrometeorological factors influencing both the spatial and temporal variation of GEM. Our results show that average atmospheric GEM values are higher than the natural background of the Northern Hemisphere and will be useful in future selection regarding the most suitable sites to monitor atmospheric Hg depositions and fluxes from soil and water.
The Marano and Grado Lagoon (Northern Adriatic Sea) has been affected by mercury (Hg) contamination coming from two sources, mining activity and discharges from a chlor-alkali plant (CAP). Sediments ...and water contamination have been previously well characterised, but little is known about the atmospheric compartment, where Hg is easily emitted and can persist for a long time as gaseous elemental mercury (GEM). In this work, atmospheric GEM levels and its spatial distribution over the lagoon were monitored at several sites by means of both continuous discrete instrumental measurements over several months and the determination of Hg bioaccumulated in lichens (Xanthoria parietina L.). Average GEM levels varied from 1.80 ± 0.74 to 3.04 ± 0.66 ng m−3, whereas Hg in lichens ranged between 0.06 to 0.40 mg kg−1. In both cases, the highest values were found downwind of the CAP, but excluding this point, spatial patterns of Hg in the atmosphere and lichens reflected the concentration of this metal in the sediments of the lagoon, showing a decrease moving westward. These results could indicate that the lagoon acts as a secondary source of Hg into the atmosphere: future work is needed to characterise the quantity of releases and depositions at different environments inside the lagoon.
High amounts of mercury (Hg) can be released into the atmosphere from soil surfaces of legacy contaminated areas as gaseous elemental mercury (Hg0). The alluvial plain of the Isonzo River (NE Italy) ...suffered widespread Hg contamination due to the re-distribution of Hg-enriched material discharged by historical cinnabar mining at the Idrija mine (Slovenia), but an assessment of Hg0 releases from the soils of this area is still lacking. In this work, Hg0 fluxes at the soil-air interface were evaluated using a non-steady state flux chamber coupled with a real-time Hg0 analyser at 6 sites within the Isonzo River plain. Measurements were performed in summer, autumn, and winter both on bare and grass-covered soil plots at regular time intervals during the diurnal period. Moreover, topsoils were analysed for organic matter content and Hg total concentration and speciation. Overall, Hg0 fluxes tracked the incident UV radiation during the sampling periods with daily averages significantly higher in summer (62.4 ± 14.5–800.2 ± 178.8 ng m−2 h−1) than autumn (15.2 ± 4.7–280.8 ± 75.6 ng m−2 h−1) and winter (16.9 ± 7.9–187.8 ± 62.7 ng m−2 h−1) due to higher irradiation and temperature, which favoured Hg reduction reactions. In summer and autumn significant correlations were observed between Hg0 fluxes and soil Hg content (78–95% cinnabar), whereas this relationship was not observed in winter likely due to relatively low emissions found in morning measurements in all sites coupled with low temperatures. Finally, vegetation cover effectively reduced Hg0 releases in summer (∼9–68%) and autumn (∼41–78%), whereas the difference between fluxes from vegetated and bare soils was not evident during winter dormancy due to scarce soil shading. These results suggest the opportunity of more extended spatial monitoring of Hg0 fluxes particularly in the croplands covering most of the Isonzo River alluvial plain and where bare soils are frequently disturbed by agricultural practices and directly exposed to radiation.
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•Field study of mercury evasion from soils contaminated by historic cinnabar mining.•Highest mercury releases in summer driven by UV radiation and temperatures.•Fluxes variability function of soil mercury and organic matter content.•Slow activation of mercury evasion from cinnabar in winter under low temperatures.•Living native grass vegetation cover significantly limits mercury volatilisation.
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.
The flooding regime of saltmarshes strongly affects organic matter mineralisation, representing a unique situation where oxygen diffusion is either impeded by submersion or favoured by retreating ...water in regular cycles within the same day. Decomposition of Limonium vulgare Mill. residues in saltmarsh soils was evaluated measuring CO2 and CH4 emissions. Four different saltmarshes from the Grado Lagoon (Northern Adriatic Sea) were investigated. Soils were characterised by a similar vegetation (Sarcocornietea class) and similar high coverage of L. vulgare (70-75%) but differed in redox potential, texture and organic carbon content. Hydromorphic conditions were reproduced in mesocosms, and soils were 20 incubated under fully aerobic, fully anaerobic and transient (6 hours cycles) tidal states. Partially decomposed litter (leaves) of L. vulgare was added and 22 decomposition processes were monitored through CO2 and CH4 emissions. Larger CO2 emissions were measured under aerobic conditions, in particular in soil samples with coarse texture. Fully anoxic and tidal regimes showed a similar behaviour. On the contrary, CH4 emissions were less dependent upon flooding, showing only slightly larger values under completely submerged conditions. Larger CH4 emissions have been obtained in fine textured soils. Soil organic matter content also influenced gas emissions: larger values corresponded to higher emissions of both CO2 and CH4.
Among potential toxic elements (PTEs), arsenic (As) and mercury (Hg) are well known for the toxicity of their different chemical species and diffusion in the environment via several anthropic sources ...(i.e., industrial settlements, mining activity). Bottom sediments often become a repository for As and Hg, although they may be considered a potential secondary source of these elements into the water column depending on their speciation and mobility. Focusing on the most recent studies (since 2019) on the occurrence of As and Hg in contaminated aquatic sediments, the aim of this review is to give an overview of the current understandings on the complex biogeochemical cycle of these elements in this environmental media. The main biogeochemical factors governing the transformations of As and Hg among their different chemical species were synthesized, highlighting those driving the formation of more mobile and/or bioavailable forms. Additionally, the most advanced analytical techniques for the determination of the different chemical species of As and Hg in sediments are briefly presented.
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•Sediments are sink or secondary source of arsenic (As) and mercury (Hg).•Mobility of As and Hg is strongly related to their speciation in sediments.•Various techniques are available for As and Hg speciation assessment.•Redox conditions, sulphur, and iron strongly affect As and Hg cycles.•Resuspension is a critical redistribution pathway for As and Hg in the water column.
The northern Adriatic Sea is well known for mercury (Hg) contamination mainly due to historical Hg mining which took place in Idrija (Slovenia). The formation of dissolved gaseous mercury (DGM) and ...its subsequent volatilisation can reduce the amount of Hg available in the water column. In this work, the diurnal patterns of both DGM production and gaseous elemental Hg (Hg0) fluxes at the water-air interface were seasonally evaluated in two selected environments within this area, a highly Hg-impacted, confined fish farm (VN: Val Noghera, Italy) and an open coastal zone less impacted by Hg inputs (PR: Bay of Piran, Slovenia). A floating flux chamber coupled with a real-time Hg0 analyser was used for flux estimation in parallel with DGM concentrations determination through in-field incubations. Substantial DGM production was observed at VN (range = 126.0–711.3 pg L−1) driven by both strong photoreduction and possibly dark biotic reduction, resulting in higher values in spring and summer and comparable concentrations throughout both day and night. Significantly lower DGM was observed at PR (range = 21.8–183.4 pg L−1). Surprisingly, comparable Hg0 fluxes were found at the two sites (range VN = 7.43–41.17 ng m−2 h−1, PR = 0–81.49 ng m−2 h−1), likely due to enhanced gaseous exchanges at PR thanks to high water turbulence and to the strong limitation of evasion at VN by water stagnation and expected high DGM oxidation in saltwater. Slight differences between the temporal variation of DGM and fluxes indicate that Hg evasion is more controlled by factors such as water temperature and mixing conditions than DGM concentrations alone. The relative low Hg losses through volatilisation at VN (2.4–4.6% of total Hg) further confirm that static conditions in saltwater environments negatively affect the ability of this process in reducing the amount of Hg retained in the water column, therefore potentially leading to a greater availability for methylation and trophic transfer.
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•Direct investigation of 24 h gaseous mercury fluxes in highly impacted coastal area.•Floating flux chamber coupled with a real-time spectrometer was used in the field.•Notable Hg dark reduction and evasion during night at impacted confined fish farm.•Relevant emissions due to turbulence at open coastal site despite low Hg levels.•Static conditions can increase Hg residence time and availability in water column.
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.
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•Hypoxia strongly affects nutrient and metal(loid)s remobilisation from sediments•The effectiveness of forced aeration to recycling of nutrients was investigated•Forced aeration interrupts bottom water hypoxic conditions•Forced aeration mitigates fluxes of solutes from the sediment to the water column
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