Multistress Interplay: Time and Duration of Ocean Acidification Modulate the Toxicity of Mercury and Other Metals.

The current understanding of multistress interplay assumes stresses occur in perfect synchrony, but this assumption is rarely met in the natural marine ecosystem. To understand the interplay between nonperfectly overlapped stresses in the ocean, we manipulated a multigenerational experiment (F0-F3) to explore how different temporal scenarios of ocean acidification will affect mercury toxicity in a marine copepod Pseudodiaptomus annandalei. We found that the scenario of past acidification aggravated mercury toxicity but current and persistent acidification mitigated its toxicity. We specifically performed a proteomics analysis for the copepods of F3. The results indicated that current and persistent acidification initiated the energy compensation for development and mercury efflux, whereas past acidification lacked the barrier of H+ and had dysfunction in the detoxification and efflux system, providing a mechanistic understanding of mercury toxicity under different acidification scenarios. Furthermore, we conducted a meta-analysis on marine animals, demonstrating that different acidification scenarios could alter the toxicity of several other metals, despite evidence from nonsynchronous scenarios remaining limited. Our study thus demonstrates that time and duration of ocean acidification modulate mercury toxicity in marine copepods and suggests that future studies should move beyond the oversimplified scenario of perfect synchrony in understanding multistress interaction.

Effects of sulfur nanoparticles on rhizosphere microbial community changes in oilseed rape plantation soil under mercury stress.

In the present study, experiments were conducted to assess the influence of nanoscale sulfur in the microbial community structure of metallophytes in Hg-contaminated rhizosphere soil for planting rapeseed. The results showed that the richness and diversity of the rhizobacteria community decreased significantly under Hg stress, but increased slightly after SNPs addition, with a reduction in the loss of Hg-sensitive microorganisms. Moreover, all changes in the relative abundances of the top ten phyla influenced by Hg treatment were reverted when subjected to Hg + SNPs treatment, except for Myxococcota and Bacteroidota. Similarly, the top five genera, whose relative abundance decreased the most under Hg alone compared to CK, increased by 19.05%-54.66% under Hg + SNPs treatment compared with Hg alone. Furthermore, the relative abundance of Sphingomonas, as one of the dominant genera for both CK and Hg + SNPs treatment, was actively correlated with plant growth. Rhizobacteria, like Pedobacter and Massilia, were significantly decreased under Hg + SNPs and were positively linked to Hg accumulation in plants. This study suggested that SNPs could create a healthier soil microecological environment by reversing the effect of Hg on the relative abundance of microorganisms, thereby assisting microorganisms to remediate heavy metal-contaminated soil and reduce the stress of heavy metals on plants.

In this manuscript, we first comprehensively investigated the changes in the rhizosphere microbial community structure of metallophytes in Hg-contaminated soil with SNPs addition, as well as the relationship between soil microbiology and plant resistance to Hg stress. Our results demonstrated that SNPs exhibit a significant advantage in improving rhizosphere microecology by increasing the abundance of beneficial rhizobacteria, thereby alleviating heavy metal toxicity, and promoting plant growth. This study is the first study describing the response of soil microorganisms coexposed to heavy metals and SNPs, providing valuable information for the potential use of SNPs to assist phytoremediation of toxic metal pollution and its impact on soil microbial communities.

Accumulation and risk assessment of mercury in soil as influenced by mercury mining/smelting in Tongren, Southwest China.

To investigate the influence of mercury (Hg) mining/smelting on the surrounding soil environment, ninety soil samples were collected around Hg mining/smelting areas in Tongren city, Guizhou Province, Southwest China. The total mercury (THg), methylmercury (MeHg), bioavailability and fractions of Hg in the soil and their potential risk were evaluated. The results showed that Hg mining/smelting significantly increased the soil pH and decreased the soil organic matter content (p < 0.05). The THg content in the surrounding soil was much higher than that at the control site, with almost all the samples exceeding the national standard in China (3.4 mg/kg, GB15618-2018). Similarly, the concentrations of MeHg (0.09-2.74 µg/kg) and bioavailable Hg (0.64-62.94 µg/kg) in these soil samples were also significantly higher than those in the control site. However, the MeHg/THg ratio was significantly lower in mining/smelting influenced soils (0.01-0.68%) than in control soils (0.60-3.72%). Fraction analysis revealed that residual (RES-Hg) and organic matter-bounded (OM-Hg) Hg accounted for more than 50% of the THg. Ecological risk assessment revealed that the potential ecological risk for most of the Hg mining/smelting-influenced soils (30.16 ≤ Er ≤ 2280.02) were higher than those at the control site (15.12 ≤ Er ≤ 27.1). In addition, these Hg mining/smelting-influenced soils posed acceptable noncarcinogenic risks to adults (except for two soil samples), with hazard indices (HIs) ranging from 0.04 to 1.11 and a mean HI of 0.44. However, children suffer serious noncarcinogenic risks, with HIs ranging from 0.34 to 7.43 and a mean HI of 3.10.

Mercury in multimedia system of Itacaiúnas Basin, Brazilian Amazon: An integrated approach to understand its distribution, origin, and ecological risk.

This study presents the first integrated study on total Hg (THg) level in surface soil (SS), bottom soil (BS), stream sediments (SD), lake sediments (LS), stream water (SW), and lake water (LW) of Itacaiúnas River Watershed (IRW), Brazil to investigate the source and distribution of Hg in different environmental media considering contrasts of geological domains and sub-basins and its potential ecological and human risk. Hg content in most of the soils and sediments were above the upper crustal average values (56 µg/kg), however, when compared to the legal limits set by the Resolution CONAMA (Conselho Nacional de Meio Ambiente: soil 500 µg/kg; sediment 486 µg/kg), only 1 soil sample from Parauapebas sub-basin and 4 sediment samples from Violão Lake exceeded the limit. None of the SW and LW samples (<0.2 µg/L; CONAMA limit for Class II freshwater) are markedly contaminated by Hg. The SS and BS show similar contents and spatial distribution of Hg with higher contents being registered mostly in the Itacaiúnas and Parauapebas sub-basins, which are closely correlated with SD. This suggests that Hg levels are largely of geogenic origin and anthropogenic effect is highly limited. Principal Component Analysis (PCA) results show that Hg is strongly associated with total organic carbon (TOC), loss on ignition (LOI), and SO3, indicating organic matter as the main factor controlling the distribution of Hg and this is the major cause of accentuated Hg enrichment in lake sediments. The ecological risk index revealed a low pollution risk for most of the solid samples, except 11% LS and <1.5% SS and SD samples, which registered moderate risk. Health risk assessment indicated no adverse non-carcinogenic health effect on either adults and children in terms of Hg contamination. This information will be useful for Hg risk assessment in the Carajás region and future environmental research in this direction in the Amazonia.

Total mercury in different egg tissues provides insights to mercury metabolisms in bird bodies.

Mercury (Hg) pollution in birds has been widely reported, but the metabolism of Hg in bird bodies remains unclear. Measurement of Hg concentrations in bird tissues (muscles and organs) could provide insights into the metabolism of Hg in bird bodies, however, this approach is often invasive. To avoid invasive procedures, we conducted feeding experiments using chickens and used eggs as a proxy for understanding Hg metabolism in chicken bodies. For the control group, various THg concentrations were observed in egg whites, egg yolks, and eggshells, but the THg concentration trends for different egg tissues were not statistically different (P > 0.05). For the Hg feeding group (0.3 mg/kg body weight, feeding once), Hg peaks were observed in egg yolks and egg whites at different time periods, suggesting different response time to dietary Hg in chicken body tissues. Mercury in egg yolks peaked at Day 6, suggesting their quick response to dietary Hg. Egg whites reached Hg peak at Day 20, exhibiting a slower response to dietary Hg. Eggshells did not show a Hg peak, perhaps due to their predominant inorganic components that do not trigger Hg bioaccumulation. We measured THgyolk/THgwhite ratios in various chicken eggs purchased from three areas in Guizhou, SW China. The THgyolk/THgwhite ratios for Huaxi, Hezhang and Wuchuan were 1.33 (0.57-2.41), 7.89 (4.27-19.47) and 2.64 (1.68-4.22), respectively, to suggest different exposure history for chickens. This study provides new insights into the metabolism and lifetime of Hg in bird bodies.

Bridged EGFET Design for the Rapid Screening of Sorbents as Sensitisers in Water-Pollution Sensors.

We further simplify the most 'user-friendly' potentiometric sensor for waterborne analytes, the 'extended-gate field effect transistor' (EGFET). This is accomplished using a 'bridge' design, that links two separate water pools, a 'control gate' (CG) pool and a 'floating gate' (FG) pool, by a bridge filled with agar-agar hydrogel. We show electric communication between electrodes in the pools across the gel bridge to the gate of an LND150 FET. When loading the gel bridge with a sorbent that is known to act as a sensitiser for Cu2+ water pollution, namely, the ion exchanging zeolite 'clinoptilolite', the bridged EGFET acts as a potentiometric sensor to waterborne Cu2+. We then introduce novel sensitisers into the gel bridge, the commercially available resins PurometTM MTS9140 and MTS9200, which are sorbents for the extraction of mercury (Hg2+) pollution from water. We find a response of the bridged EGFET to Hg2+ water pollution, setting a template for the rapid screening of ion exchange resins that are readily available for a wide range of harmful (or precious) metal ions. We fit the potentiometric sensor response vs. pollutant concentration characteristics to the Langmuir-Freundlich (LF) model which is discussed in context with other ion-sensor characteristics.

The spatial analysis, risk assessment and source identification for mercury in a typical area with multiple pollution sources in southern China.

Mercury (Hg) has always been a research hot spot because of its high toxicity. This study conducted in farmland near rare earth mining area and traffic facilities, which considered multiple pollution sources innovatively. It not only analyzed Hg spatial characteristics using inverse distance weighting and self-organizing map (SOM), but also assessed its pollution risk by potential ecological risk index (Er) as well as geoaccumulation index (Igeo), and identified the pollution sources with positive matrix factorization. The results showed that there was no heavy Hg pollution in most farmland, while a few sampling sites with Hg pollution were close to highway, railway station and petrol station in Xinfeng or in the farmland of Anyuan, which were divided into the cluster with highest Hg concentration in SOM. The vehicle exhaust emission and pesticide as well as fertilizer additions significantly contributed to the local Hg pollution. Besides, there was moderate pollution and high ecological risk in Anyuan assessed by Igeo and Er, respectively. In contrast, Xinfeng had the moderate and considerable ecological risks in a larger scale. The enriched Hg might harmed not only the nearby ecological environment, but also the human health when it entered human body through food chain. The three factors that contributed to mercury concentration in this area according to positive matrix factorization were natural source, traffic source and agricultural source, respectively. This study about Hg pollution in the typical area would provide scientific evidence for the particular treatment of Hg pollution from various pollution sources like traffic source, agricultural source, etc.

Responses of bacterial taxonomic attributes to mercury species in rhizosphere paddy soil under natural sulphur-rich biochar amendment.

Biochar and sulphur (S) are important factors regulating the level, speciation and transformation of mercury (Hg), leading to alterations in the assemblage of the soil microbial community. However, variations in the taxonomic attributes of the rhizosphere soil bacterial community arising from the Hg speciation in paddy soil, amended with natural S-rich biochar (NSBC) derived from the pyrolysis of S-rich oilseed rape straw, remain unclear. Herein, a rice pot experiment was conducted. Hg-polluted paddy soils were amended with NSBC and low-S biochar (LSBC) to evaluate the role of Hg chemical form affected by NSBC in regulating the taxonomic attributes of rhizosphere soil, including microbial abundance, composition, and ecological clusters within the co-occurrence network of microbial communities. Results showed that microbial abundance was higher in soils with lower Hg levels, and mean increases of 149 observed operational taxonomic units (OTUs) and 238 predicted OTUs (Chao 1) were observed, with a 1 mg kg-1 decrease in the total Hg (T-Hg) content. Among the 13 predictor variables, the T-Hg content was the strongest and most consistent predictor of the bacterial taxonomic attributes. This finding may be attributed to the fact that the drastic reduction in T-Hg and Hg bioavailability induced by NSBC results in the decrease of Hg stress on the soil microbiome. Moreover, NSBC amendment shifted the ecological clusters toward the amelioration of Hg pollution.

Health risk assessment of gaseous elemental mercury (GEM) in Mexico City.

Emissions of gaseous elemental mercury (GEM or Hg0) from different sources in urban areas are important subjects for environmental investigations. In this study, atmospheric Hg measurements were conducted to investigate air pollution in the urban environment by carrying out several mobile surveys in Mexico City. This work presents atmospheric concentrations of GEM in terms of diurnal variation trends and comparisons with criteria for pollutant concentrations such as CO, SO2, NO2, PM2.5, and PM10. The concentration of GEM was measured during the pre-rainy period by using a high-resolution active air sampler, the Lumex RA 915 M mercury analyzer. In comparison with those for other cities worldwide, the GEM concentrations were similar or slightly elevated, and they ranged from 0.20 to 30.23 ng m-3. However, the GEM concentration was significantly lower than those in contaminated areas, such as fluorescent lamp factory locations and gold mining zones. The GEM concentrations recorded in Mexico City did not exceed the WHO atmospheric limit of 200 ng m-3. We performed statistical correlation analysis which suggests equivalent sources between Hg and other atmospheric pollutants, mainly NO2 and SO2, emitted from urban combustion and industrial plants. The atmospheric Hg emissions are basically controlled by sunlight radiation, as well as having a direct relationship with meteorological parameters. The area of the city studied herein is characterized by high traffic density, cement production, and municipal solid waste (MSW) treatment, which constantly release GEM into the atmosphere. In this study, we included the simulation with the HYSPLIT dispersion model from three potential areas of GEM release. Emissions from industrial corridors and volcanic plumes localized outside the urban area contribute to the pollution of Mexico City and mainly affect the northern area during specific periods and climate conditions. Using the USEPA model, we assessed the human health risk resulting from exposure to inhaled GEM among residents of Mexico City. The results of the health risk assessment indicated no significant noncarcinogenic risk (hazard quotient (HQ) < 1) or consequent adverse effects for children and adults living in the sampling area over the study period. GEM emissions inventory data is necessary to improve our knowledge about the Hg contribution and effect in urban megacity areas with the objective to develop public safe policy and implementing the Minamata Convention.

Predicted Near-Future Oceanic Warming Enhances Mercury Toxicity in Marine Copepods.

The effects of acute mercury exposure (118 µg/L) on the marine copepod Tigriopus japonicus were examined at 22 and 25 °C for 24 h and compared with controls. Mercury accumulation and seven genes related to antioxidant/stress responses were analyzed after exposure. The 24-h LC50 value decreased in the warmer environment and mercury accumulation was elevated. Under both temperatures, mercury significantly affected the expression of all analyzed genes and probably caused oxidative stress. Intriguingly, at the same mercury concentration, most genes were upregulated at the higher relative to the lower temperature, and the copepods likely initiated more compensatory reactions to counteract increased mercury toxicity associated with the warmer temperature. Overall, this study suggests a molecular mechanism by which marine copepods could respond to future oceanic warming and mercury pollution.

Highly Resolved Inventory of Mercury Release to Water from Anthropogenic Sources in China.

This study developed an up-to-date and point-source-based inventory of mercury (Hg) releases to water in China by applying probabilistic release factors that combined industry removal efficiencies, reuse of reclaimed water, and receiving water types. In 2017, the national mercury release to water was estimated to be 50 (35-66) tons, in which 47%, 8%, 7%, and 25% were from nonferrous metal smelting, vinyl chloride monomer (VCM) production, coal-fired boilers, and domestic sewage, respectively. Approximately 95% of mercury was released to inland rivers, and the rest was discharged to lakes or coastal water. The significant sources were identified based on their mercury releases to water. The control of mercury release to water in China shall focus on zinc smelting plants, municipal sewage treatment plants, and the VCM production process. For zinc smelting plants, China can tighten the limit of mercury concentration in discharged wastewater and combine Hg-catcher device in traditional integrated treatment. For municipal sewage treatment plants and the VCM production process, promoting processes of Hg-free production can reduce mercury inputs at the source. Our study provides insights for other parties to identify the relevant sources of mercury release to water and to conduct control measures, so as to promote the global convention implementation.

Influence of Legacy Mercury on Antibiotic Resistomes: Evidence from Agricultural Soils with Different Cropping Systems.

Agricultural soils are important reservoirs for antibiotic resistance genes (ARGs), which have close linkage to human health via crop production. Metal stress in environments may function as a selection pressure for antibiotic resistomes. However, there is still a lack of field studies focusing on the effect of historical mercury (Hg) contamination on antibiotic resistomes in agricultural soils. Here, we explored the ARG profile in soils with different cropping systems (paddy and upland) and linked them to legacy Hg exposure. We found that ARG profiles were significantly different between paddy and upland soils. However, both paddy and upland soils with long-term field Hg contamination harbored higher diversity and abundance of ARGs than non-polluted soils. The co-occurrence network reveals significant associations among Hg, Hg resistance genes, mobile genetic elements (MGEs), and ARGs. Together with path analysis showing legacy Hg possibly affecting soil resistomes through the shifts of soil microbiota, Hg resistance genes, and MGEs, we suggest that legacy Hg-induced potential co-selection might elevate the ARG level. Redundancy analysis further supports that legacy Hg pollution had a significant association with ARG variations in the paddy and upland soils (P < 0.01). Collectively, our results highlight the underappreciated role of legacy Hg as a potential persistent selecting agent in contributing to soil ARGs in agroecosystems.

Status and environmental management of soil mercury pollution in China: A review.

The harm from mercury pollution to human health and the environment has long been known. In recent years, the combination of industrial activities and long-term atmospheric transport has resulted in a sustained increase in mercury concentrations in soils. However, soil remediation and mercury-contaminated soil management in China are still in its infancy, and there is ample space for the development of related research. We systematically reviewed several pertinent topics and found that soil mercury pollution around mines and industrial soil in China is the most serious. The highest mercury content is found in the soil around the Tongren mercury mine in Guizhou Province and the thermometer factories. The average content of soil mercury is similar to that of atmospheric mercury emission in China. Mercury content in soil gradually decreases from the southeast to the northwest. In order to repair the mercury-contaminated soil, solidification and stabilization technology have been developed in China and applied in the engineering of restoration. In the future, we will study more effective stabilizer materials and select plants highly rich in mercury, to develop low-cost and high-repair-rate remediation technology. China has also developed a series of policies, regulations, and regulatory documents to manage mercury pollution, such as the Agricultural Land Standard and the Construction Land Standard. Compared with other countries, the screening values for soil mercury in China are relatively low. China has also established control standards for methylmercury in soils of residential and industrial land. In addition, China has issued emission standards and control notices related to the mercury industry. However, there are still shortcomings in soil remediation technology and environmental management systems for mercury pollution in China. In the future, China will formulate standards according to local conditions and improve the responsibility mechanism, financial mechanism, and level of public participation.

Rapid field testing of mercury pollution by designed fluorescent biosensor and its cells-alginate hydrogel-based paper assay.

With increasing industrial activities, mercury has been largely discharged into environment and caused serious environmental problems. The growing level of mercury pollution has become a huge threat to human health due to its significant biotoxicity. Therefore, the simple and fast means for on-site monitoring discharged mercury pollution are highly necessary to protect human beings from its pernicious effects in time. Herein, a "turn off" fluorescent biosensor (mCherry L199C) for sensing Hg2+ was successfully designed based on direct modification of the chromophore environment of fluorescent protein mCherry. For rapid screening and characterization, the designed variant of mCherry (mCherry L199C) was directly expressed on outer-membrane of  Escherichia coli cells by cell surface display technique. The fluorescent biosensor was characterized to have favorable response to Hg2+ at micromole level among other metal ions and over a broad pH range. Further, the cells of the fluorescent biosensor were encapsulated in alginate hydrogel to develop the cells-alginate hydrogel-based paper. The cells-alginate hydrogel-based paper could detect mercury pollution in 5 min with simple operation process and inexpensive equipment, and it could keep fluorescence and activity stable at 4 °C for 24 hr, which would be a high-throughput screening tool in preliminarily reporting the presence of mercury pollution in natural setting.

Snakes as Novel Biomarkers of Mercury Contamination: A Review.

Mercury (Hg) is an environmental contaminant that has been reported in many wildlife species worldwide. The organic form of Hg bioaccumulates in higher trophic levels, and thus, long-lived predators are at risk for higher Hg exposure. Although ecological risk assessments for contaminants such as Hg include pertinent receptor species, snakes are rarely considered, despite their high trophic status and potential to accumulate high levels of Hg. Our current knowledge of these reptiles suggests that snakes may be useful novel biomarkers to monitor contaminated environments. The few available studies show that snakes can bioaccumulate significant amounts of Hg. However, little is known about the role of snakes in Hg transport in the environment or the individual-level effects of Hg exposure in this group of reptiles. This is a major concern, as snakes often serve as important prey for a variety of taxa within ecosystems (including humans). In this review, we compiled and analyzed the results of over 30 studies to discuss the impact of Hg on snakes, specifically sources of exposure, bioaccumulation, health consequences, and specific scientific knowledge gaps regarding these moderate to high trophic predators.

Interfacial oxygen nanobubbles reduce methylmercury production ability of sediments in eutrophic waters.

Eutrophication can induce hypoxia/anoxia and rich organic matter at the sediment-water interface in surface waters. When eutrophic waters are impacted with mercury (Hg) pollution, methylmercury (MeHg) production ability (MPA) of surface sediment would increase and more MeHg might be produced. To tackle this risk, this study firstly collected samples of surface sediment and overlying water from a typical eutrophic lake-Taihu Lake. Then from a sediment-water simulation system, we demonstrated that eutrophic waters were able to methylate Hg spontaneously, and that sediment is the major Hg sink in the system. After the addition of HgCl2 solution (approximately 1 mg L-1 in the slurry), MeHg concentrations in the sediment increased by 11.7 times after 48 h. The subsequent column experiments proved that O2 nanobubbles could significantly decrease the MPA of surface sediment, by up to 48%. Furthermore, we found that O2 nanobubbles could remediate anoxia mainly by increasing dissolved oxygen (from 0 to 2.1 mg L-1), oxidation-reduction potentials (by 37% on average), and sulfate (by 31% on average) in the overlying water. In addition, O2 nanobubbles could also help decrease organic matter concentration, as was revealed by the decline of dissolved organic carbon in the overlying water (by up to 57%) and total organic carbon in surface sediment (by up to 37%). The remediation of anoxia and reduction of organic matter could contribute to the decrease of hgcA gene abundance (by up to 86%), and thus result in the reduction of MPA after the addition of O2 nanobubbles. This study revealed the risk of MeHg production in case Hg pollution occurs in eutrophic waters and proposed a feasible solution for MeHg remediation.

Multi-pathway human exposure risk assessment using Bayesian modeling at the historically largest mercury mining district.

The largest mercury (Hg) mining district in the world is located in Almadén (Spain), with well-known environmental impacts in the surrounding ecosystem. However, the impact of mercury on the health of the inhabitants of this area has not been documented accordingly. This study aims to carry out a probabilistic human health risk assessment using Bayesian modeling to estimate the non-carcinogenic risk related to Hg through multiple exposure pathways. Samples of vegetables, wild mushrooms, fish, soil, water, and air were analyzed, and adult residents were randomly surveyed to adjust the risk models to the specific population data. On the one hand, the results for the non-carcinogenic risk based on Hazard Quotient (HQ) showed unacceptable risk levels through ingestion of Hg-contaminated vegetables and fish, with HQ values 20 and 3 times higher, respectively, than the safe exposure threshold of 1 for the 97.5th percentile. On the other hand, ingestion of mushrooms, dermal contact with soil, ingestion of water, dermal contact with water and inhalation of air, were below the safety limit for the 97.5th percentile, and did not represent a risk to the health of residents. In addition, the probabilistic approach was compared with the conservative deterministic approach, and similar results were obtained. This is the first study conducted in Almadén, which clearly reveals the high levels of human health risk to which the population is exposed due to the legacy of two millennia of Hg mining.

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.

Determination of Metals in Tree Rings by ICP-MS Using Ash from a Direct Mercury Analyzer.

Elemental profiles in cores of tree trunks (bole wood) have been used for environmental monitoring and reconstruction of metal pollution history. Mercury (Hg) is a global pollutant that can be accurately measured in tree rings in a simple and pragmatic fashion using a direct mercury analyzer (DMA) that is based on thermal decomposition, amalgamation, and atomic absorption spectrophotometry. In this feasibility study, we demonstrate that the ash remaining after the DMA analyses can be used to quantify a wide range of other non-volatile elements (Ba, Be, Co, Cr, Cu, Fe, Ga, Mg, Mn, Ni, Pb, Sr, Th, and U) in that same sample of wood by inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted acid digestion. Other elements (Ag, Cd, Cs, Rb, Tl, and V) exhibited poor recoveries, possibly due to losses during sample preparation. We assessed the accuracy with reference materials, spikes, and by comparison with EPA Method 3052 (Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices). For the first group of elements (deemed suitable for the method), recoveries ranged between 80% and 120% and the relative standard deviation was generally < 15%, indicating acceptable precision. We applied the method to five species of trees: eastern red cedar (Juniperus virginiana), loblolly pine (Pinus taeda), shortleaf pine (Pinus echinata), white oak (Quercus alba), and tulip poplar (Liriodendron tulipifera) from Holly Springs National Forest in north Mississippi, USA. Mercury concentrations (ng/g ± SE) were highest in the cedar (1.8 ± 0.3; n = 5), followed by loblolly pine (1.6 ± 0.3, n = 3), shortleaf pine (1.2 ± 0.2; n = 3), oak (1.1 ± 0.2; n = 5), and poplar (0.5 ± 0.1; n = 5). Concentrations of other elements were generally Fe > Mg > Ba ≈ Sr ≈ Mn > Cr ≈ Cu > Ni ≈ Rb > Co > Ga ≈ Ag, with the other elements generally below the method detection limit (MDL). Overall, we showed that the DMA can be used to not only determine total Hg in segments of tree core, but can serve as the ashing step in the preparation of wood for ICP-MS analysis, thus allowing the determination of non-volatile elements along with Hg in the very same sample.

Studying absorbance properties and mercury remediation capabilities of gold-graphene oxide-iron oxide (Au-GO-Fe3O4) nanoparticle systems.

Mercury pollution is a rampant problem in many economically significant Philippine freshwater ecosystems. Communities dependent on these freshwater sources are therefore at risk for exposure to harmful levels of mercury. Various formulations of a novel gold-graphene oxide-iron oxide (Au-GO-Fe3O4) hybrid nanoparticle system were created and subjected to UV-Vis spectroscopy to determine optimal formulations that would best serve as potential substrates for Surface-Enhanced Raman Spectroscopy (SERS) detection of mercury. Optimal formulations of Au-GO-Fe3O4 were also introduced into mercury-polluted environments to evaluate its ability to remove mercury from both water and biological tissues. Spectroscopic analysis revealed that Fe3O4-rich formulations of Au-GO-Fe3O4 had the greatest potential to boost Raman signal intensities of mercury due to red shifting of absorbance peaks and overall increased absorbance across visible wavelengths resulting in the inclusion of greater areas underneath absorbance peaks. Mercury remediation experiments likewise demonstrated Au-GO-Fe3O4 to significantly reduce average concentrations of mercury from 1.67 to 0.82 ppm in polluted water samples - corresponding to a mercury removal efficiency of 50.9% and a mercury adsorption capacity of 5.89 mg/g. The results highlight the viability of Au-GO-Fe3O4 to function as both substrate for SERS detection of mercury and as effective adsorbent for mercury remediation.