Comparison of active measurements, lichen biomonitoring, and passive sampling for atmospheric mercury monitoring.

The number of atmospheric mercury (Hg) monitoring stations is growing globally. However, there are still many regions and locations where Hg monitoring is limited or non-existent. Expansion of the atmospheric Hg monitoring network could be facilitated by the use of cost-effective monitoring methods. As such, biomonitoring and passive monitoring offer a unique alternative to well-established monitoring by active measurements, since they do not require a power supply and require minimal workload to operate. The use of biomonitoring (lichens and mosses) and passive air samplers (PASs) (various designs with synthetic materials) has been reported in the literature, and comparisons with active measurement methods have also been made. However, these studies compared either biomonitoring or PASs (not both) to only one type of active measurement. In our work, we used transplanted (7 sampling sites) and in situ lichens (8 sampling sites) for biomonitoring, two PASs from different producers (3 sampling sites), and two different active measurement types (continuous and discontinuous active measurements, 1 and 8 sampling sites, respectively) to evaluate their effectiveness as monitoring methods. In the 9-month sampling campaign, 3 sampling locations with different characteristics (unpolluted, vicinity of a cement plant, and vicinity of a former Hg mine) were used. The results obtained with lichens and PASs clearly distinguished between sampling locations with different Hg concentrations; using both PASs and lichens together increased the confidence of our observations. The present work shows that biomonitoring and passive sampling can be effectively used to identify areas with elevated atmospheric Hg concentrations. The same can be said for discontinuous active measurements; however, the discrepancy between atmospheric Hg concentrations derived from PASs and discontinuous active measurements should be further investigated in the future.

Nonlinear shallow water investigation of atmospheric disturbances generated by strong seismic events.

The upper portions of the Earth's atmospheric layer, e.g., the ionospheric plasma layer, can be significantly affected by perturbations generated in the lower layers. In fact, all perturbations formed within the troposphere can easily propagate, not only horizontally within the layer but also vertically reaching the highest regions of the atmosphere far from the Earth's surface, as depicted by the Wentzel-Kramers-Brillouin (WKB) approximation of atmospheric waves. Because all perturbations generated in the atmospheric boundary layer must take into account the effects of the medium's nonlinearity and thus the effects of atmospheric turbulence, in this work the impact of a strong seismic event and the disturbances generated in the flow are analyzed by means of a fully nonlinear model which incorporates a simple parametrization of the seismic event and is based on the classical shallow water. A strict dependence was observed between the model control parameters and the vertical nonvanishing modes from the WKB approximation, and only few specific bands of excited modes are nonvanishing and can eventually propagate to the ionosphere. Moreover, the flow disturbance, generated by a seismic event, presents a multiscale nature characterized by two fixed wavelengths, and the excited modes are harmonics of such distinctive scales.

Triazine Herbicide and NPK Fertilizer Exposure: Accumulation of Heavy Metals and Rare Earth Elements, Effects on Cuticle Melanization, and Immunocompetence in the Model Species Tenebrio molitor.

The increasing use of agrochemicals, including fertilizers and herbicides, has led to worrying metal contamination of soils and waters and raises serious questions about the effects of their transfer to different levels of the trophic web. Accumulation and biomagnification of essential (K, Na, Mg, Zn, Ca), nonessential (Sr, Hg, Rb, Ba, Se, Cd, Cr, Pb, As), and rare earth elements (REEs) were investigated in newly emerged adults of Tenebrio molitor exposed to field-admitted concentrations of a metribuzin-based herbicide and an NPK blend fertilizer. Chemical analyses were performed using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) supported by unsupervised pattern recognition techniques. Physiological parameters such as cuticle melanization, cellular (circulating hemocytes), and humoral (phenoloxidase enzyme activity) immune responses and mass loss were tested as exposure markers in both sexes. The results showed that NPK fertilizer application is the main cause of REE accumulation in beetles over time, besides toxic elements (Sr, Hg, Cr, Rb, Ba, Ni, Al, V, U) also present in the herbicide-treated beetles. The biomagnification of Cu and Zn suggested a high potential for food web transfer in agroecosystems. Gender differences in element concentrations suggested that males and females differ in element uptake and excretion. Differences in phenotypic traits show that exposure affects metabolic pathways involving sequestration and detoxification during the transition phase from immature-to-mature beetles, triggering a redistribution of resources between sexual maturation and immune responses. Our findings highlight the importance of setting limits for metals and REEs in herbicides and fertilizers to avoid adverse effects on species that provide ecosystem services and contribute to soil health in agroecosystems.

Seven-year monitoring of mercury in wet precipitation and atmosphere at the Amsterdam Island GMOS station.

Mercury (Hg) fate and transport research requires more effort to obtain a deep knowledge of its biogeochemical cycle, particularly in the Southern Hemisphere and Tropics that are still missing of distributed monitoring sites. Continuous monitoring of atmospheric Hg concentrations and trend worldwide is relevant for the effectiveness evaluation of the Minamata Convention on Mercury (MCM) actions. In this context, Gaseous Elemental Mercury (GEM) and total mercury (THg) in precipitations were monitored from 2013 to 2019 at the Amsterdam Island Observatory (AMS - 37°48'S, 77°34'E) to provide insights into the Hg pathway in the remote southern Indian Ocean, also considering ancillary dataset of Rn-222, CO2, CO, and CH4. GEM average concentration was 1.06 ± 0.07 ng m-3, with a slight increase during the austral winter due to both higher wind speed over the surface ocean and contributions from southern Africa. In wet depositions, THg average concentration was 2.39 ± 1.17 ng L-1, whereas the annual flux averaged 2.04 ± 0.80 µg m-2 year-1. In general, both GEM and Volume-Weighted Mean Concentration (VWMC) of THg did not show an increasing/decreasing trend over the seven-year period, suggesting a substantial lack of evolution about emission of Hg reaching AMS. Air masses Cluster Analysis and Potential Source Contribution Function showed that oceanic evasion was the main Hg contributor at AMS, while further contributions were attributable to long-range transport events from southern Africa, particularly when the occurrence of El Niño increased the frequency of wildfires.

First atmospheric mercury measurements at a coastal site in the Apulia region: seasonal variability and source analysis.

In the framework of the Italian Special Network for Mercury (ISNM) "Reti Speciali", a sampling campaign to monitor atmospheric mercury (Hg) was carried out at Monte Sant'Angelo (MSA). This is a coastal monitoring station in the Apulia region, representative of the Southern Adriatic area, within the Mediterranean basin. This work presents continuous Gaseous Elemental Mercury (GEM) measurements over about three years at MSA, using the Lumex RA-915AM mercury analyzer. The aim was to obtain a dataset suitable for the analysis of Hg concentrations in terms of source and transport variation. Diurnal cycles of GEM were evaluated to observe the influence of local atmospheric temperature and wind speed on potential re-emissions from surrounding sea and soil surfaces. Data were also analyzed in terms of long-range transport, using backward trajectory cluster analysis. The spatial distribution of potential sources, contributing to higher measured GEM values, was obtained employing Potential Source Contribution Function (PSCF) statistics. The influence of major Hg anthropogenic point sources, such as mining activities and coal-fuel power plants, both regionally and continentally, from mainland Europe, was observed. The role of the vegetation GEM uptake in modulating the seasonal GEM variability was also investigated. The potential of wildfire influence over the highest detected GEM levels was further examined using active fire data and the evaluation of the vegetation dryness index during the selected episodes.

Recent applications and novel strategies for mercury determination in environmental samples using microextraction-based approaches: A review.

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.

Mediterranean Mercury Assessment 2022: An Updated Budget, Health Consequences, and Research Perspectives.

Mercury (Hg) and especially its methylated species (MeHg) are toxic chemicals that contaminate humans via the consumption of seafood. The most recent UNEP Global Mercury Assessment stressed that Mediterranean populations have higher Hg levels than people elsewhere in Europe. The present Critical Review updates current knowledge on the sources, biogeochemical cycling, and mass balance of Hg in the Mediterranean and identifies perspectives for future research especially in the context of global change. Concentrations of Hg in the Western Mediterranean average 0.86 ± 0.27 pmol L-1 in the upper water layer and 1.02 ± 0.12 pmol L-1 in intermediate and deep waters. In the Eastern Mediterranean, Hg measurements are in the same range but are too few to determine any consistent oceanographical pattern. The Mediterranean waters have a high methylation capacity, with MeHg representing up to 86% of the total Hg, and constitute a source of MeHg for the adjacent North Atlantic Ocean. The highest MeHg concentrations are associated with low oxygen water masses, suggesting a microbiological control on Hg methylation, consistent with the identification of hgcA-like genes in Mediterranean waters. MeHg concentrations are twice as high in the waters of the Western Basin compared to the ultra-oligotrophic Eastern Basin waters. This difference appears to be transferred through the food webs and the Hg content in predators to be ultimately controlled by MeHg concentrations of the waters of their foraging zones. Many Mediterranean top-predatory fish still exceed European Union regulatory Hg thresholds. This emphasizes the necessity of monitoring the exposure of Mediterranean populations, to formulate adequate mitigation strategies and recommendations, without advising against seafood consumption. This review also points out other insufficiencies of knowledge of Hg cycling in the Mediterranean Sea, including temporal variations in air-sea exchange, hydrothermal and cold seep inputs, point sources, submarine groundwater discharge, and exchanges between margins and the open sea. Future assessment of global change impacts under the Minamata Convention Hg policy requires long-term observations and dedicated high-resolution Earth System Models for the Mediterranean region.

Analytical study on the primary and secondary organic carbon and elemental carbon in the particulate matter at the high-altitude Monte Curcio GAW station, Italy.

This study provides a thorough investigation of the trends of organic carbon (OC) and elemental carbon (EC) in particulate matter (PM)10 and PM2.5 samples collected at the Monte Curcio Observatory (1780 m a.s.l.), a station of the Global Atmosphere Watch (GAW) program and Global Mercury Observation System (GMOS) network. Although the drawn attention toward these pollutants, there is still a lack of data for southern Italy, and this work is a contribution toward the filling of this gap. PM was sampled daily in 2016 and analyzed by thermo-optical transmittance method, while equivalent black carbon (eBC) concentrations in PM10 were simultaneously measured using a multiangle absorption photometer. The results showed that in PM10, the average values of OC and EC were 1.43 µgC/m3 and 0.12 µgC/m3, whereas in PM2.5, these concentrations were 1.09 µgC/m3 and 0.12 µgC/m3, respectively. We detected a clear seasonal variability in OC and EC with higher concentrations during the warm period. Moreover, the analysis of the OC/EC ratio revealed that most of the carbonaceous aerosol was transported by long-range air masses, as further confirmed by the use of the concentration-weighed trajectory (CWT) model. The mass absorption cross-section at 632 nm of EC (MACEC) over the entire period was 9.67 ± 4.86 m2/g and 8.70 ± 3.18 m2/g in PM2.5 and PM10, respectively, and did not exhibit a clear seasonal variation. The concentrations for OC and EC were also used for the computation of the secondary organic carbon (SOC) content, whose outcomes resulted in a seasonal trend similar to those obtained for OC and EC. As regards the eBC, its weekly pattern showed a slight increase during the weekend in the warm period, consistent with the anthropic activities in the touristic area surrounding the observatory.

An innovative green protocol for the quantification of benzothiazoles, benzotriazoles and benzosulfonamides in PM10 using microwave-assisted extraction coupled with solid-phase microextraction gas chromatography tandem-mass spectrometry.

Benzothiazoles (BTHs), benzotriazoles (BTRs), and benzenesulfonamides (BSAs) are chemicals used in several industrial and household applications. Despite these compounds are emerging pollutants, there is still a lack of information about their presence in outdoor air samples. In this paper, we developed a new method for the quantification of BTHs, BTRs, and BSAs in airborne particulate matter (PM10). The extraction of fourteen analytes from PM10 was accomplished by microwave-assisted extraction (MAE) using an environmentally friendly mixture of water and ethanol. SPME was used to analyze the target compounds from the MAE extract by gas chromatography-tandem mass spectrometry (SPME-GC-MS/MS), eliminating additional sample clean-up steps. The best working conditions for MAE and SPME were examined multivariately by experimental design techniques. The target compounds were quantified in selected reaction monitoring acquisition mode. The proposed method was carefully validated, and the achieved results were satisfactory in terms of linearity, lower limit of quantification (picograms per cubic meter), intra- and inter-day accuracy (81-118% and 82-114%, respectively), and precision (repeatability and reproducibility in the range 2.3-17% and 7.4-19%, respectively). The application in a real monitoring campaign showed that the developed protocol is a valuable and eco-friendly alternative to the methods proposed so far.

Multiscale assessment of the impact on air quality of an intense wildfire season in southern Italy.

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.

Characteristics and Performances of a Nanostructured Material for Passive Samplers of Gaseous Hg.

Passive air samplers (PASs) have been used for mapping gaseous mercury concentration in extensive areas. In this work, an easy-to-use and -prepare gold nanoparticle (NP)-based PAS has been investigated. The PAS is constituted of a microfibrous quartz disk filter impregnated of gold NP photo-growth on TiO2 NPs (Au@TiO2) and used as gaseous mercury adsorbing material. The disk was housed in a cylinder glass container and subjected to an axial diffusive sampling. The adsorbed mercury was measured by thermal desorption using a Tekran® instrument. Different amounts of Au@TiO2 (ranging between 4.0 and 4.0 × 10-3 mg) were deposited by drop-casting onto the fibrous substrate and assessed for about 1 year of deployment in outdoor environment with a mercury concentration mean of about 1.24 ± 0.32 ng/m3 in order to optimize the adsorbing layer. PASs showed a linear relation of the adsorbed mercury as a function of time with a rate of 18.5 ± 0.4 pg/day (≈1.5% of the gaseous concentration per day). However, only the PAS with 4 mg of Au@TiO2, provided with a surface density of about 3.26 × 10-2 mg/mm2 and 50 µm thick inside the fibrous quartz, kept stability in working, with a constant sampling rate (SR) (0.0138 ± 0.0005 m3/day) over an outdoor monitoring experimental campaign of about 1 year. On the other hand, higher sampling rates have been found when PASs were deployed for a few days, making these tools also effective for one-day monitoring. Furthermore, these PASs were used and re-used after each thermal desorption to confirm the chance to reuse such structured layers within their samplers, thus supporting the purpose to design inexpensive, compact and portable air pollutant sampling devices, ideal for assessing both personal and environmental exposures. During the whole deployment, PASs were aided by simultaneous Tekran® measurements.

Agrochemical treatments as a source of heavy metals and rare earth elements in agricultural soils and bioaccumulation in ground beetles.

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.

Modification of the EPA method 1631E for the quantification of total mercury in natural waters.

To support the effectiveness of the Minamata Convention, the accurate determinations of mercury (Hg) in natural waters is an important but certainly challenging task due to the low concentrations expected in ambient samples. Mercury contamination may occur from many sources such as the unproperly-cleaning of storage bottles or the use of reagents for sample analysis with Hg traces, thus leading the analyst to easily run into errors. In our work, we propose some key modifications to the United States Environmental Protection Agency(EPA) method 1631E aimed at reducing the Hg contamination of reagents, storage containers, and minimizing the carryover effect in the instrumental line of sampling. The changes introduced have been tailored for the use of the method with cold vapor atomic fluorescence spectroscopy (CV-AFS) instrumentation and tested as part of a United Nations Environment Program (UNEP) ring test. Although the edited method was tested with natural water samples, the proposed method improvements can also apply to the Hg analysis in solid matrices that require the prior acid digestion of the samples.•A customized version of the EPA method 1631E is proposed for the analysis of aqueous samples.•New protocols for the reduction of contamination in the storage bottles and reagents used for the preparation of BrCl solution are provided.•A useful strategy for the control of the memory effect is included.

Artisanal and small-scale gold mining, meandering tropical rivers, and geological heritage: Evidence from Brazil and Indonesia.

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 km2 along the Marupa River and ~30,427 km2 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.

Sources of mercury in deep-sea sediments of the Mediterranean Sea as revealed by mercury stable isotopes.

Mercury (Hg) and its stable isotope composition were used to determine the sources of Hg in deep-sea sediments of the Mediterranean Sea. Surface and down-core sediment δ202Hg values varied widely between -2.30 and +0.78‰, showed consistently positive values for mass independent fractionation of odd Hg isotopes (with average values of Δ199Hg = +0.10 ± 0.04‰ and Δ201Hg = +0.04 ± 0.02‰) and near-zero Δ200Hg values, indicating either multiple Hg sources or a combination of different Hg isotope fractionating processes before and after sediment deposition. Both mass-dependent and mass-independent fractionation processes influence the isotopic composition of Hg in the Mediterranean Sea. Positive Δ199Hg values are likely the result of enhanced Hg2+ photoreduction in the Mediterranean water column before incorporation of Hg into sediments, while mass-dependent fractionation decreases δ202Hg values due to kinetic isotope fractionation during deposition and mobilization. An isotope mixing model based on mass-dependent and mass-independent fractionation (δ202Hg and Δ199Hg) suggests at least three primary Hg sources of atmospheric deposition in the surface sediments: urban, industrial and global precipitation-derived. Industry is the main source of Hg in Algerian and Western Basin surface sediments and at two sites in the Adriatic Sea, while the urban contribution is most prominent at the Strait of Otranto (MS3) and in Adriatic surface sediments. The contribution from precipitation ranged from 10% in Algerian to 37% in W Basin sediments. Overall, results suggest that atmospheric Hg deposition to Mediterranean surface sediments is dominated by gaseous elemental mercury (58 ± 11%) rather than wet deposition.

Spatial and taxonomic variation of mercury concentration in low trophic level fauna from the Mediterranean Sea.

Studies of mercury (Hg) in the Mediterranean Sea have focused on pollution sources, air-sea mercury exchange, abiotic mercury cycling, and seafood. Much less is known about methylmercury (MeHg) concentrations in the lower food web. Zooplankton and small fish were sampled from the neuston layer at both coastal and open sea stations in the Mediterranean Sea during three cruise campaigns undertaken in the fall of 2011 and the summers of 2012 and 2013. Zooplankton and small fish were sorted by morphospecies, and the most abundant taxa (e.g. euphausiids, isopods, hyperiid amphipods) analyzed for methylmercury (MeHg) concentration. Unfiltered water samples were taken during the 2011 and 2012 cruises and analyzed for MeHg concentration. Multiple taxa suggested elevated MeHg concentrations in the Tyrrhenian and Balearic Seas in comparison with more eastern and western stations in the Mediterranean Sea. Spatial variation in zooplankton MeHg concentration is positively correlated with single time point whole water MeHg concentration for euphausiids and mysids and negatively correlated with maximum chlorophyll a concentration for euphausiids, mysids, and "smelt" fish. Taxonomic variation in MeHg concentration appears driven by taxonomic grouping and feeding mode. Euphausiids, due to their abundance, relative larger size, importance as a food source for other fauna, and observed relationship with surface water MeHg are a good candidate biotic group to evaluate for use in monitoring the bioavailability of MeHg for trophic transfer in the Mediterranean and potentially globally.

Passive Sampling of Gaseous Elemental Mercury Based on a Composite TiO2NP/AuNP Layer.

Passive sampling systems (PASs) are a low cost strategy to quantify Hg levels in air over both different environmental locations and time periods of few hours to weeks/months. For this reason, novel nanostructured materials have been designed and developed. They consist of an adsorbent layer made of titania nanoparticles (TiO2NPs, ≤25 nm diameter) finely decorated with gold nanoparticles. The TiO2NPs functionalization occurred for the photocatalytic properties of titania-anatase when UV-irradiated in an aqueous solution containing HAuCl4. The resulting nanostructured suspension was deposited by drop-casting on a thin quartz slices, dried and then incorporated into a common axial sampler to be investigated as a potential PAS device. The morphological characteristics of the sample were studied by High-Resolution Transmission Electron Microscopy, Atomic Force Microscopy, and Optical Microscopy. UV-Vis spectra showed a blue shift of the membrane when exposed to Hg° vapors. The adsorbed mercury was thermally desorbed for a few minutes, and then quantified by a mercury vapor analyzer. Such a sampling system reported an efficiency of adsorption that was equal to ≈95%. Temperature and relative humidity only mildly affected the membrane performances. These structures seem to be promising candidates for mercury samplers, due to both the strong affinity of gold with Hg, and the wide adsorbing surface.

A green approach for organophosphate ester determination in airborne particulate matter: Microwave-assisted extraction using hydroalcoholic mixture coupled with solid-phase microextraction gas chromatography-tandem mass spectrometry.

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.

Global Sources and Pathways of Mercury in the Context of Human Health.

This paper reviews information from the existing literature and the EU GMOS (Global Mercury Observation System) project to assess the current scientific knowledge on global mercury releases into the atmosphere, on global atmospheric transport and deposition, and on the linkage between environmental contamination and potential impacts on human health. The review concludes that assessment of global sources and pathways of mercury in the context of human health is important for being able to monitor the effects from implementation of the Minamata Convention targets, although new research is needed on the improvement of emission inventory data, the chemical and physical behaviour of mercury in the atmosphere, the improvement of monitoring network data, predictions of future emissions and speciation, and on the subsequent effects on the environment, human health, as well as the economic costs and benefits of reducing these aspects.

Particulate-phase mercury emissions from biomass burning and impact on resulting deposition: a modelling assessment.

Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg(Hg(g)0) . However, little is known about the fraction of Hg bound to particulate matter (HgP) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric HgP concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improvement when considering a fraction of HgP from BB. The set of sensitivity runs also showed how the quantity and geographical distribution of HgP emitted from BB has a limited impact on a global scale, although the inclusion of increasing fractions HgP does limit Hg(g)0 availability to the global atmospheric pool. This reduces the fraction of Hg from BB which deposits to the world's oceans from 71 to 62 %. The impact locally is, however, significant on northern boreal and tropical forests, where fires are frequent, uncontrolled and lead to notable Hg inputs to local ecosystems. In the light of ongoing climatic changes this effect could be potentially be exacerbated in the future.