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This study provides a review of 13 oceanographic campaigns between 2000 and 2017 to measure Hg in the Mediterranean, highlighting major findings from measurement and modelling activities during the Med-Oceanor program. The initial campaigns showed that high concentrations of RGM could be found far from industrial source regions and the observed daily variation in concentration, with peaks at midday and lower concentrations during darkness gave the first indications that photochemically mediated oxidation reactions were producing RGM in the MBL. Later atmospheric chemistry modelling studies showed the feasibility of Hg oxidation by bromine containing oxidants, which are released as a result of the acidification of sea salt aerosols in the Marine Boundary Layer (MBL). Spatial and seasonal variations of DGM were observed at different depths in the water column, with average DGM concentrations higher in the West and East Mediterranean deep and intermediate waters, than in overlaying Atlantic waters. DGM in water profiles typically increased with depth, together with nutrients and decreasing oxygen, indicating a possible bacterial and/or geogenic origin. Using measured DGM and meteorological variable values Hg fluxes can be calculated. When these are included in regional and global models they suggest that the net Hg evasion from the Mediterranean is around 30 Mg yr -1 . Repetition of these campaigns should be an extremely high priority, both to continue to monitor changes in atmospheric and aquatic Hg species concentrations, but also to perform RGM detection methodology intercomparisons so that the historical data is adequately contextualised and may be used to evaluate temporal trends., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2025 The Authors. Published by Elsevier B.V. All rights reserved.)

The growing need to monitor Hg levels in the environment to control its emissions and evaluate the effectiveness of reduction policies is driving the scientific community to focus efforts on creating analytical methods that are simpler, lower cost, more performing, and environmentally sustainable. In this context, an important contribution is provided by microextraction techniques, which have long proven to be simple, reliable, and to ensure an environmentally responsible sample preparation. This manuscript reviews the recent progress in the determination of environmental Hg using microextraction techniques. The considered studies involve all environmental compartments (i.e., air, water, soil, and biota) and have been discussed by grouping them according to the employed technique while pointing out the main advances achieved and the most important limitations. The ultimate goal is to provide an up-to-date overview of the analytical potential of microextraction techniques that can be exploited in various investigation fields and to highlight the most important knowledge gaps that should be addressed in the coming years, such as in-situ sampling, the use of natural materials, and the value of metrological support to obtain data SI-traceable and comparable., (Copyright © 2022. Published by Elsevier B.V.)

The summer of 2017 in the Calabria Region (South Italy) was an exceptional wildfire season with the largest area burned by wildfires in the last 11 years (2008-2019). The equivalent black carbon (EBC) and carbon monoxide (CO) measurements, recorded at the high-altitude Global Atmosphere Watch (GAW) Monte Curcio (MCU) regional station, were analyzed to establish the wildfires' impact on air quality, human health, and the ecosystem. A method was applied to identify the possible wildfires that influenced the air quality based on the integration of fire data (both satellite and ground-based) and the high-resolution WRF-HYSPLIT trajectories. The satellite-based fires applied to WRF-HYSPLIT with 10 km of spatial resolution allowed us to establish that for 52.5% of total cases, wildfires were located outside the Calabria Region, and they were influenced by long-range transport. Nonetheless, the impact on human health, qualitatively evaluated in terms of passively smoked cigarettes (PSC) corresponding to the EBC, was greater when wildfires were local. Indeed, for wildfires located mainly in Calabria, the equivalent PSC ranged from 2.75 to 11.08. This maximum PSC value was close to the daily number of smoked cigarettes in Calabria (approximately 12.4). Even if this analogy does not imply a proportional effect between the estimated number of cigarettes smoked and the effective wildfire EBC exposure, this result suggests that wildfire emissions may have negative effects on people's health. Moreover, a focus on the Calabria Region was conducted using high-resolution ground-based GPS and higher resolution WRF-HYSPLIT back-trajectories (2 km) to measure wildfires. The validity of the methodology was confirmed by the EBC and CO positive correlation with the ratio between the identified ground-based burned areas and the distance from the sampling station. Moreover, the impact on the ecosystem was studied by analyzing the land vegetation loss due to the wildfires that contributed to air quality reduction at the MCU station. A total of more than 1679 ha of vegetation burned, the main losses comprising forests and shrubland., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The continuous and extensive application of agrochemicals leads to the accumulation of heavy metals (HMs) and rare earth elements (REEs) in agricultural soils and their transfer in the food web with consequent relevant risks for human and ecosystem health. In this study, HM and REE concentrations were quantified in the soil of wheat crop fields conventionally managed in the agricultural areas of Sila Mountain (Southern Italy) and compared with the concentration in a field of wild herbs, used as control. Statistical analyses and principal component analysis suggested that the use of pesticides, herbicides and fertilizers contributes to the accumulation of HMs and REEs in the soil. Different accumulation patterns were recorded in treated fields as a consequence of the type and amount of agrochemical used and the crop rotation. The exposure risk associated with the transfer through the tropic levels of agroecosystem was carried out measuring the concentration of HMs and REEs in adults of Harpalus (Pseudoophonus) rufipes (De Geer, 1774) collected from each monitored site. Different accumulation patterns found in specimens from the monitored sites highlighted the ability of this generalist predator to regulate metal uptake under field conditions. The values of bioaccumulation factor (BAF) allow to defining the order of accumulation in P. rufipes which was classified as a macroconcentrator of Cd, Cu, Mg and Zn. Our results can supplement the limited information regarding the REE accumulation in soil invertebrates and may provide reference data for assessing potential environmental risks in croplands., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Artisanal and small-scale gold mining (ASGM) flourishes along many tropical rivers, and it still requires proper documentation in many countries, as well as interpretation in terms of rational resource exploitation and wildlife preservation. In this study we used remote sensing techniques to analyze two representative examples of ASGM: one along the Marupa River in Brazil (Tapajós Domain) and another one along the Kahayan River in Indonesia (Central Kalimantan). The documented spatial extent of ASGM is ~9175 km 2 along the Marupa River and ~30,427 km 2 along the Kahayan River. It was established these activities change rapidly (2-3 years) in space. Although active and inactive sites occur in both areas, a great number of inactive sites distinguish the Marupa River. It is very crucial that ASGM along the Marupa and Kahayan rivers link strongly to watercourse meanders, but also changes river valley morphology. This is an interesting evidence of coupled fluvial-anthropic morphodynamics of meandering river valleys. Geological phenomena represented in the study areas include gold resource exploitation (economic phenomenon), landforms and their dynamics (geomorphological phenomenon), and mercury environmental pollution (geochemical phenomenon). Due to remarkable spatial extent and evident interconnection, these phenomena seem to be unique and, thus, constituting geological heritage. Identification of the latter means that ASGM sites add value to the local environment. A paradox is that illegal and mercury-releasing ASGM needs termination, but such an action will result in the loss of the noted geological heritage value. Solution to this paradox requires careful development of plans for local management. However, it is clear that the presence of the noted heritage requires turning more attention to ASGM and their natural (river valley) context., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Particulate matter (PM) is among the most dangerous air pollutants, and there is a growing concern related to the effects of airborne particles on human health. Their harmful effects can be derived are directly linked to the size of particles themselves and the associated pollutants after they have been taken up by inhalation. In this work was developed a new analytical method for the quantification of organophosphorus esters (OPE) bound to airborne PM. The proposed protocol provides for the microwave-assisted extraction (MAE) of the analytes from the PM followed by solid-phase microextraction gas chromatography-tandem mass spectrometry determination (SPME-GC-MS/MS). Unlike to the traditional protocol, which provides for the use of tedious Soxhlet extraction with environmentally damaging organic solvents, the proposed method allows for a reliable quantification by using an eco-friendly hydroalcoholic mixture (water/ethanol; 50:50, v/v). The method was developed using as target compounds ten organophosphate esters, namely tripropyl phosphate (TPP), tri-n-butyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tributoxyethyl phosphate (TBEP), triphenyl phosphate (TPhP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tricresyl phosphate (TCP). The extraction performance of five SPME fibers was evaluated and the DVB/CAR/PDMS coating demonstrated to be the most suitable for the extraction of the target analytes. Experimental Design was used for the multivariate optimization of the parameters affecting the MAE process as well as the SPME extraction, and the optimal working conditions were determined by using Derringer's desirability function. The developed method was validated in terms of linearity, sensitivity (LLOQ values of 0.5 ng/mL for TDCPP and 0.1 ng/mL for the other analytes), matrix effect (81-117%), intra and inter day accuracy (83-115% and 80-115%, respectively), and precision (repeatability and reproducibility in the range 1.0-12.4% and 2.3-15.2%, respectively). The satisfactory performances reached make the proposed protocol a green and high-throughput alternative for OPE quantification in particulate matter., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM – dissolved gaseous Hg, RHg – reactive Hg, THg – total Hg, MeHg – monomethyl Hg and DMeHg – dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Global mercury emission inventories include anthropogenic emissions, contributing via current use or presence of mercury in a variety of products and processes, as well as natural source emissions. These inventories neglect the contribution of areas contaminated with mercury from historical accumulation, which surround mines or production plants associated with mercury production or use. Although recent studies have shown that releases of mercury from these historical sites can be significant, a database of the global distribution of mercury contaminated sites does not exist, nor are there means of scaling up such releases to estimate fluxes on a regional and global basis. Therefore, here we estimated for the first time the contribution of mercury releases from contaminated sites to the global mercury budget. A geo-referenced database was built, comprising over 3000 mercury contaminated sites associated with mercury mining, precious metal processing, non-ferrous metal production and various polluted industrial sites. In the assessment, mercury releases from these sites to both the atmosphere as well as the hydrosphere were considered based on data available for selected case studies, their number, the reported extent of contamination and geographical location. Annual average global emissions of mercury from identified contaminated sites amount to 198 (137-260) Mgyr(-1). Of that, 82 (70-95)Mgyr(-1) contribute to atmospheric releases, while 116 (67-165) Mgyr(-1) is estimated to be transported away from these sites by hydrological processes. Although these estimates are associated with large uncertainties, our current understanding of mercury releases from contaminated sites indicates that these releases can also be of paramount importance on the global perspective. This is especially important as it is known that these sites represent a long-term source of releases if not managed properly. Therefore, the information presented here is needed by governments and NGO's in order to re-focus resources in making decisions regarding mitigation and remediation strategies on a global level., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Atmospheric mercury emissions from mine-waste enriched soils were measured in order to compare the mercury fluxes of bare soils with those from other soils covered by native grasses. Our research was conducted near Mt. Amiata in central Italy, an area that was one of the largest and most productive mining centers in Europe up into the 1980s. To determine in situ mercury emissions, we used a Plexiglas flux chamber connected to a portable mercury analyzer (Lumex RA-915+). This allowed us to detect, in real time, the mercury vapor in the air, and to correlate this with the meteorological parameters that we examined (solar radiation, soil temperature, and humidity). The highest mercury flux values (8000ngm(-2)h(-1)) were observed on bare soils during the hours of maximum insulation, while lower values (250ngm(-2)h(-1)) were observed on soils covered by native grasses. Our results indicate that two main environmental variables affect mercury emission: solar radiation intensity and soil temperature. The presence of native vegetation, which can shield soil surfaces from incident light, reduced mercury emissions, a result that we attribute to a drop in the efficiency of mercury photoreduction processes rather than to decreases in soil temperature. This finding is consistent with decreases in mercury flux values down to 3500ngm(-2)h(-1), which occurred under cloudy conditions despite high soil temperatures. Moreover, when the soil temperature was 28°C and the vegetation was removed from the experimental site, mercury emissions increased almost four-fold. This increase occurred almost immediately after the grasses were cut, and was approximately eight-fold after 20h. Thus, this study demonstrates that enhancing wild vegetation cover could be an inexpensive and effective approach in fostering a natural, self-renewing reduction of mercury emissions from mercury-contaminated soils., (Copyright © 2013 Elsevier Inc. All rights reserved.)

An oceanographic cruise campaign on-board the Italian research vessel Urania was carried out from the 26th of August to the 13th of September 2010 in the Eastern Mediterranean. The campaign sought to investigate the mercury cycle at coastal and offshore locations in different weather conditions. The experimental activity focused on measuring mercury speciation in both seawater and in air, and using meteorological parameters to estimate elemental mercury exchange at the sea-atmosphere interface. Dissolved gaseous mercury (DGM), unfiltered total mercury (UTHg) and filtered total mercury (FTHg) surface concentrations ranged from 16 to 114, 300 to 18,760, and 230 to 10,990pgL(-1), respectively. The highest DGM, UTHg and FTHg values were observed close to Augusta (Sicily), a highly industrialized area of the Mediterranean region, while the lowest values were recorded at offshore stations. DGM vertical profiles partially followed the distribution of sunlight, as a result of the photoinduced transformations of elemental mercury in the surface layers of the water column. However, at some stations, we observed higher DGM concentrations in samples taken from the bottom of the water column, suggesting biological mercury production processes or the presence of tectonic activity. Moreover, two days of continuous measurement at one location demonstrated that surface DGM concentration is affected by solar radiation and atmospheric turbulence intensity. Atmospheric measurements of gaseous elemental mercury (GEM) showed an average concentration (1.6ngm(-3)) close to the background level for the northern hemisphere. For the first time this study used a numerical scheme based on a two-thin film model with a specific parameterization for mercury to estimate elemental mercury flux. The calculated average mercury flux during the entire cruise was 2.2±1.5ngm(-2)h(-1). The analysis of flux data highlights the importance of the wind speed on the mercury evasion from sea surfaces., (Copyright © 2012 Elsevier B.V. All rights reserved.)

A model describing the interaction of gas phase elemental atmospheric mercury, H(g)(o), with the ambient aerosol has been linked to hybrid single-particle Lagrangian integrated trajectory (HYSPLIT_4) a hybrid dispersion and deposition model. The integrated modelling system allows H(g)(o) emitted from an anthropogenic source in the presence(g) of the local aerosol to be followed and calculates the deposition fluxes to terrestrial and water receptors resulting from the interaction between the H(g)(o) and the aerosol. The model includes a source-based parameterized description of the ambient aerosol, a gas-phase diffusion and adsorption model for the interaction of H(g)(o) and the ambient particulate matter under conditions of low relative humidity, and an aqueous phase Hg chemistry model to allow for complete or partial deliquescence of the particles under conditions of high humidity. The model is, thus, able not only to calculate deposition fluxes, but also the speciation of the Hg compounds deposited; this is of great importance in the modelling of the atmospheric Hg cycle due to the difference in the properties of elemental and oxidized Hg.

Mercury evasion from seawaters is considered to be one of the main natural sources of mercury released to the atmosphere. The temporal evolution of this mechanism is related to biotic and abiotic processes that produce mercury in its elemental form and as DGM. The efficiency of these processes depends upon the intensity of the solar radiation, the ambient temperature of the air parcel above the seawater, and the water temperature. In the Mediterranean region, the magnitude of these mechanisms are particularly significant, due to favorable climate conditions and to the presence of large cinnabar deposits that cross the whole region; all these synergic factors yield significant evasional fluxes of mercury from the surface water during most of the annual period. In this work, mercury fluxes were measured by using a floating flux chamber connected to an atomic absorption analyzer. Photosynthetic active radiation (PAR) and UV components of the solar radiation were measured using the same system adopted in the EC 'ELDONet project'. The measurements of the mercury evasional fluxes were carried out at three sites of the northern Tyrrhenian Sea during 1998. Two sites were located at unpolluted and polluted coastal areas, and the third was an offshore site. The evasional flux showed a typical daily trend, highest at midday when the ambient temperature and solar radiation were at the maximum, and lowest, near to zero, during the night. Besides the day-night behavior, a seasonal trend was also observed, with minimum values during the winter period (0.7-2.0 ng/m2 h) and maximum values during the summer (10-13 ng/m2 h).

Emissions from volcanoes, fumaroles and solfataras as well as contributions from widespread geological anomalies could represent an important source of mercury released to the atmosphere in the Mediterranean basin. Volcanoes located in this area (Etna, Stromboli and Vulcano) are the most active in Europe; therefore, it is extremely important to know their mercury contributions to the regional atmospheric budget. Two main methods are used for the evaluation of volcanic mercury flux: a direct determination of the flux (by measuring in the plume) and an indirect one derived from the determination of the Hg/SO2 (or Hg/S) ratio value, as SO2 emissions are constantly monitored by volcanologists. An attempt to estimate mercury flux from the Vulcano volcano and to establish the Hg/S ratio value has been made along three field campaigns carried out in October 1998, in February and May 1999 sampling several fumaroles. Traditional sampling methods were used to collect both total Hg and S. The average Hg/S ratio value resulted to be 1.2 x 10(-7). From the Hg/S value we derived the Hg/SO2 value, and by assuming that all the volcanoes located in this area have the same Hg/SO2 ratio, mercury emissions from Vulcano and Stromboli were estimated to be in the range 1.3-5.5 kg/year and 7.3-76.6 kg/year respectively, while for Etna mercury flux ranged from 61.8 to 536.5 kg/year. Data reported in literature appear to be overestimated (Fitzgerald WF. Mercury emission from volcanos. In: 4th International conference on mercury as a global pollutant, August 4-8 1996, Hamburg, Germany), volcanic mercury emission does not constitute the main natural source of the metal.