Organic Mercury Research Articles

UV Induced Advanced Oxidation Process For The Degradation Of Organic Mercury And Its Application To Mercury Speciation By Atomic Fluorescence Spectrometry

UV Induced Advanced Oxidation Process For The Degradation Of Organic Mercury And Its Application To Mercury Speciation By Atomic Fluorescence Spectrometry

The dynamics of mercury around an artisanal and small-scale gold mining area, Camarines Norte, Philippines.

To elucidate the dynamics of mercury emitted and released by artisanal and small-scale gold mining (ASGM) activity and to estimate its impact on the ecosystems of the bay, the distribution of mercury in the atmosphere, soil, water, and sediment around Mambulao Bay, Camarines Norte, Philippines, was investigated. The ASGM operations use mercury to extract gold from ore and are located on the east shore side of the bay. Samplings were conducted in August 2017 and September 2018. The samples were used for determination of total mercury (T-Hg) and organic mercury (org-Hg) concentrations, total organic carbon (TOC) content, and chemical composition. The atmospheric mercury concentration on the east shore side, 6.1-25.8ngm-3, was significantly higher than the value of 1.4-9.9ngm-3 observed on the west shore side. The average concentrations of T-Hg in the forest soils of the west shore side and those of the east shore side were 0.081 ± 0.028mgkg-1 and 0.496 ± 0.439mgkg-1, respectively. In the vertical distribution of T-Hg in the soil of the east shore side, a higher concentration was observed near the surface. For the vertical variations in T-Hg in the marine sediment, higher values were observed near the estuary, and the vertical variations in core samples showed an increase in mercury concentration toward the surface. The highest concentration of T-Hg in sediment, 9.5mgkg-1, which was 2 orders of magnitude higher than the background levels of this area, was found near the river mouth. The T-Hg, org-Hg, and TOC levels showed a positive correlation, suggesting that the rivers are the main sources of T-Hg and org-Hg in the bay. Although the fish sample containing a mercury content higher than the regulatory level for fish and shellfish of 0.4mgkg-1 in Japan was only one of 42 samples, the percentage of org-Hg in fish samples was 91 ± 18%. Mercury released into the surroundings by the ASGM activities can be converted into methylmercury and affect the bay's ecosystem.

Mercury and methylmercury differentially modulate hepatic cytochrome P450 1A1 and 1A2 in vivo and in vitro.

The cytochrome P450 1 A (CYP1A) subfamily enzymes are involved in the metabolic activation of several xenobiotics to toxic metabolites and reactive intermediates, resulting ultimately in carcinogenesis. Mercury and halogenated aromatic hydrocarbons (HAHs), typified by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), are persistent environmental pollutants involved in the modulation of aryl hydrocarbon receptor (AHR) gene battery, including cytochrome P450 (CYP) genes. We previously investigated the effect of coexposure to either inorganic or organic mercury (Hg+2 and MeHg) with TCDD on CYP1A1 in vitro. Thus, we examined the impact of coexposure to Hg+2 or MeHg and TCDD on AHR-regulated genes (Cyp1a1/1a2) in vivo and in vitro. Therefore, male C57BL/6 mice were injected intraperitoneally with MeHg or Hg+2 (2.5 mg/kg) in the absence and presence of TCDD (15 μg/kg) for 6 or 24 h. The concentration-dependent effect of MeHg was examined in murine hepatoma Hepa1c1c7 cells. In vivo, both MeHg and Hg2+ inhibited the TCDD-mediated induction of Cyp1a1/1a2 mRNA levels. However, Only Hg2+ was able to inhibit the TCDD-mediated induction at posttranscriptional levels of CYP1A1/1A2 protein and catalytic activity, suggesting differential modulation effects by Hg+2 and MeHg. In addition, the inhibitory role of HO-1 (Heme oxygenase-1) on CYP1A activity induced by TCDD was investigated using a HO-1 competitive inhibitor, tin-mesoporphyrin, that partially restored the MeHg-mediated decrease in CYP1A1 activity. This study demonstrates that MeHg, alongside Hg2+ , can differentially modulate the TCDD-induced AHR-regulated genes (Cyp1a1/1a2) at different expression levels in C57BL/6 mice liver and Hepa1c1c7 cells.

Dietary Selenomethionine Reduce Mercury Tissue Levels and Modulate Methylmercury Induced Proteomic and Transcriptomic Alterations in Hippocampi of Adolescent BALB/c Mice.

Methylmercury (MeHg) is a well-known environmental contaminant, particularly harmful to the developing brain. The main human dietary exposure to MeHg occurs through seafood consumption. However, seafood also contains several nutrients, including selenium, which has been shown to interact with MeHg and potentially ameliorate its toxicity. The aim of this study was to investigate the combined effects of selenium (as selenomethionine; SeMet) and MeHg on mercury accumulation in tissues and the effects concomitant dietary exposure of these compounds exert on the hippocampal proteome and transcriptome in mice. Adolescent male BALB/c mice were exposed to SeMet and two different doses of MeHg through their diet for 11 weeks. Organs, including the brain, were sampled for mercury analyses. Hippocampi were collected and analyzed using proteomics and transcriptomics followed by multi-omics bioinformatics data analysis. The dietary presence of SeMet reduced the amount of mercury in several organs, including the brain. Proteomic and RNA-seq analyses showed that both protein and RNA expression patterns were inversely regulated in mice receiving SeMet together with MeHg compared to MeHg alone. Several pathways, proteins and RNA transcripts involved in conditions such as immune responses and inflammation, oxidative stress, cell plasticity and Alzheimer’s disease were affected inversely by SeMet and MeHg, indicating that SeMet can ameliorate several toxic effects of MeHg in mice.

Simultaneously speciation of mercury in water, human blood and food samples based on pyrrolic and pyridinic nitrogen doped porous graphene nanostructure

A rapid and efficient method based on a novel nitrogen-doped porous graphene nanostructure (NDPG) was used for the speciation of mercury in water and human blood samples by the CV-AAS. The mixture of the NDPG, ionic liquid, and acetone was rapidly injected into the human blood, water, and food samples for mercury separation by the cloud point assisted dispersive ionic liquid-micro solid-phase extraction (CPA-DIL-μ-SPE) at pH 7.5. The UV-microwave accessory converted the organic mercury (R-Hg) to inorganic mercury, and total mercury (TM) was determined. Finally, the organic mercury was calculated by subtracting the inorganic and entire mercury contents. By optimizing, the linear range, LOD, and enrichment factor were obtained (0.01–6.80 µg/L; 0.005–3.60 µg/L), (2.6 ng/L; 1.2 ng/L) and (9.8; 20.2) for the mercury species in human blood and water/food samples, respectively (Mean of RSD < 1.9 %). The CRM samples obtained the validation of the procedure.

Bioaccumulation of inorganic and organic mercury in the cuttlefish Sepia officinalis: Influence of ocean acidification and food type

The bioaccumulation of mercury (Hg) in marine organisms through various pathways has not yet been fully explored, particularly in cephalopods. This study utilises radiotracer techniques using the isotope 203Hg to investigate the toxicokinetics and the organotropism of waterborne inorganic Hg (iHg) and dietary inorganic and organic Hg (methylHg, MeHg) in juvenile common cuttlefish Sepia officinalis. The effect of two contrasting CO2 partial pressures in seawater (400 and 1600 μatm, equivalent to pH 8.08 and 7.54, respectively) and two types of prey (fish and shrimp) were tested as potential driving factors of Hg bioaccumulation. After 14 days of waterborne exposure, juvenile cuttlefish showed a stable concentration factor of 709 ± 54 and 893 ± 117 at pH 8.08 and 7.54, respectively. The accumulated dissolved i203Hg was depurated relatively rapidly with a radiotracer biological half-life (Tb1/2) of 44 ± 12 and 55 ± 16 days at pH 8.08 and 7.54, respectively. During the whole exposure period, approximately half of the i203Hg was found in the gills, but i203Hg also increased in the digestive gland. When fed with 203Hg-radiolabelled prey, cuttlefish assimilated almost all the Hg provided (>95%) independently of the prey type. Nevertheless, the prey type played a major role on the depuration kinetics with Hg Tb1/2 approaching infinity in fish fed cuttlefish vs. 25 days in shrimp fed cuttlefish. Such a difference is explained by the different proportion of Hg species in the prey, with fish prey containing more than 80% of MeHg vs. only 30% in shrimp. Four days after ingestion of radiolabelled food, iHg was primarily found in the digestive organs while MeHg was transferred towards the muscular tissues. No significant effect of pH/pCO2 variation was observed during both the waterborne and dietary exposures on the bioaccumulation kinetics and tissue distribution of i203Hg and Me203Hg. Dietary exposure is the predominant pathway of Hg bioaccumulation in juvenile cuttlefish.

Organo-mercury species in a polluted agricultural flood plain: Combining speciation methods and polymerase chain reaction to investigate pathways of contamination

The analysis of organic mercury (Hg) species in polluted soils is a necessary tool to assess the environmental risk(s) of mercury in contaminated legacy sites. The artificial formation of monomethylmercury (MeHg) during soil extraction and/or analysis is a well-known limitation and is especially relevant in highly polluted areas where MeHg/Hg ratios are notoriously low. Although this has been known for almost 30 years, the thorough characterisation of artificial formation rates is rarely a part of the method development in scientific literature. Here we present the application of two separate procedures (inorganic Hg (iHg) spiking and double-spike isotope dilution analyses (DSIDA)) to determine and correct for artificial Hg methylation in MeHg-selective acid-leaching/organic solvent extraction procedure. Subsequently, we combined corrected MeHg and ethylmercury (EtHg) measurements with PCR amplification of hgcA genes to distinguish between naturally formed MeHg from primary deposited MeHg in soils from a legacy site in a Swiss mountain valley. We found the DSIDA procedure incompatible with the organomercury selective extraction method due to the quantitative removal of iHg. Methylation factors from iHg spiking were in the range of (0.0075 ± 0.0001%) and were consistent across soils and sediment matrices. Further, we suggest that MeHg was deposited and not formed in-situ in two out of three studied locations. Our line of evidence consists of 1) the concomitant detection of EtHg, 2) the elevated MeHg concentrations (up to 4.84 μg kg−1), and 3) the absence of hgcA genes at these locations. The combination of Hg speciation and methylation gene (hgcA) abundance analyses are tools suited to assess Hg pollution pathways at Hg legacy sites.

Selection of green remediation alternatives for chemical industrial sites: An integrated life cycle assessment and fuzzy synthetic evaluation approach

The concept of green site remediation calls for a model that can consider environmental impacts in the selection of site remediation alternatives. In this study, an integrated life cycle assessment (LCA)-fuzzy synthetic evaluation (FSE) model is developed to help practitioners select the optimal site remediation plan by incorporating life cycle impacts into the comprehensive suitability evaluation. The LCA module quantifies environmental and economic impacts using ReCiPe and Input-Output LCA methods, respectively. The impacts are evaluated along with other suitability considerations, presented in 32 indicators under ten criteria, by practitioners through a questionnaire survey. FSE is used to process the collected subjective judgments and generate a suitability index for informed selection. The integrated model is applied to a case study of an abandoned chemical industrial site contaminated by various organic chemicals and mercury. Four remediation alternatives, designed as the combined uses of ex-situ thermal desorption, in-situ thermal desorption, and in-situ containment, are evaluated. The LCA results show that the alternative with extensive use (treating 93.8 % of the contaminated soil) of in-situ thermal desorption is associated with the highest environmental and economic impacts, followed by the alternative with less extensive use (6.2 %) of in-situ thermal desorption. The FSE results show that the economic, technical, and environmental impact considerations are the top three important criteria. The integrated LCA-FSE results indicate that the alternative with mixed use of ex-situ thermal desorption and in-situ containment could be the optimal plan. Excluding LCA results could alter the suitability ranks of the alternatives.

Persistent organic pollutants and mercury in a colony of Antarctic seabirds: higher concentrations in 1998, 2001, and 2003 compared to 2014 to 2016

Over decades, persistent organic pollutants (POPs) and trace metals like mercury (Hg) have reached the remotest areas of the world such as Antarctica by atmospheric transport. Once deposited in polar areas, low temperatures, and limited solar radiation lead to long environmental residence times, allowing the toxic substances to accumulate in biota. We investigated the load of polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and metabolites (DDEs, DDDs) in embryos from failed eggs of the smallest seabird breeding in Antarctica, the Wilson's storm-petrel (Oceanites oceanicus) at King George Island (Isla 25 de Mayo). We compared samples of different developmental stages collected in 2001, 2003, and 2014 to 2016 to investigate changes in pollutant concentrations over time. We detected eight PCBs including the dioxin-like (dl) congeners PCB 105 and 118 (ΣPCBs: 59-3403 ng g−1 ww) as well as 4,4’-DDE, and 4,4’-DDD (ΣDDX: 19-1035 ng g−1 ww) in the embryos. Samples from the years 2001 and 2003 showed higher concentrations of PCBs than those from 2014 to 2016. Concentrations of DDX was similar in both time intervals. Furthermore, we determined Hg concentrations in egg membranes from 1998 to 2003, and 2014 to 2016. Similar to PCBs, Hg in egg membranes were higher in 1998 than in 2003, and higher in 2003 than in the years 2014 to 2016, suggesting a slow recovery of the pelagic Antarctic environment from the detected legacy pollutants. Embryos showed an increase in pollutant concentrations within the last third of their development. This finding indicates that contaminant concentrations may differ among developmental stages, and it should be taken into account in analyses on toxic impact during embryogenesis.

Effects of Mercury Concentration on the Health and Safety of Oil and Gas Workers

Introduction: The processing of crude oil is characterized by numerous hazards, which have significant health, safety, and environmental impacts on neighboring communities. The occurrence of mercury and its toxic derivatives is considered one of the many negative impacts of oil and gas operations. However, there is limited research on mercury and its negative effects on workers in the Gulf Cooperation Council (GCC) region. This study examines the occurrence, exposure, and symptoms of mercury on the health and safety of oil and gas workers in Oman. It also explores the acute/chronic effects of mercury poisoning on the maintenance and inspection workers, who are more prone to the adverse effects of mercury poisoning during oil and gas operations. Methods: The two-pronged approach of literature review and survey questionnaire was used to deduce the effects of mercury exposure and poisoning using 68 respondents with 1 – 6 years of working experience in the sector. Results: Based on the questionnaire response rate of 72%, the results showed that over 90% of participants had experienced symptoms of elemental, organic, and methyl mercury poisoning. The common symptoms experienced are headaches, insomnia, weakness, hearing impairment, visual and sensory abilities. However, the respondents who experienced methyl mercury (MeHg) symptoms are due to consuming seafood and cigarettes, whereas elemental and organic mercury symptoms are due to oil and gas operations. Conclusion: The findings highlight the need for robust health and safety measures to effectively detect, monitor and eliminate mercury compounds responsible for poisoning maintenance and inspection workers.

Design and synthesis of fluorescent peptide-based probes with aggregation-induced emission characteristic for detecting CH3Hg+ and Hg2+ in aqueous environment: Tuning fluorescent detection for CH3Hg+ by replacing peptide receptors

Even though methylmercury (CH3Hg+) is more toxic than Hg2+, it is more difficult to detect methylmercury than Hg2+ because of less charge and less thiophilicity. In the present study, we developed fluorescent probes for detecting CH3Hg+ and Hg2+ from the fluorescent peptide-based probe (1) for Hg2+ with aggregation induced emission (AIE) characteristic by replacing amino acids of the peptide moiety. The fluorescent probes (2–7) based on dipeptide receptors with AIE characteristics were synthesized for sensing CH3Hg+ and Hg2+ in aqueous environment. Probe 2, 4, 6, and 7 showed turn-on responses to CH3Hg+ and Hg2+ in aqueous solutions. Among them, probe 7 had the most desirable sensing features such as high solubility in water (<1% DMSO), sensitive Off-On response toward Hg2+ and CH3Hg+, high selectivity for Hg2+ and CH3Hg + among tested metal ions, reversibility, fast recognition (∼1 min), significant fluorescent signal changes, and low detection limits (1.4 ppb for Hg2+ and 152 ppb for CH3Hg+). Specially, the specific turn-on fluorescent signals to Hg2+ as well as CH3Hg+ were not significantly interference by coexisting Group I and II metal ions (1 mM) and most other heavy metal ions and the detection limit was lower than the maximum allowable levels of CH3Hg+ in food. The mechanism investigation using NMR, ESI mass spectrometer, and DLS measurements revealed that 7 formed nano-sized aggregates after complexation with Hg2+ and CH3Hg+, resulting in the enhanced fluorescent signals. The dipeptide receptor (AlaHis-OH) of 7 provided potent interactions with Hg2+ as well as CH3Hg+ in aqueous solutions. Probe 7 was successfully applied for the quantification of Hg2+ as well as CH3Hg+ in groundwater samples. We first developed fluorescent probes with AIE characteristics for reversibly detecting Hg2+ and CH3Hg+ in aqueous solution. The relationship between the peptide receptor structures and the specific interactions of Hg2+ and CH3Hg+ would provide useful information for further design of fluorescent detection systems for inorganic and organic mercury.

Using Carbon Paste Electrode Modified with Ion Imprinted Polymer and MWCNT for Electrochemical Quantification of Methylmercury in Natural Water Samples.

Methylmercury (MeHg) is one of the most toxic organic mercury compounds found in the environment. The continuous exposure of human beings to this highly toxic compound may damage their nervous system. The present work reports the development and application of a novel electrochemical sensing technique for the quantification of MeHg using a modified carbon paste electrode with multi-walled carbon nanotubes (MWCNTs) combined with ion imprinted polymer, which is highly selective toward MeHg (CPE/MWCNTs/IIP-MeHg) detection. The ion imprinted polymer was synthesized using 2-mercaptobenzothiazole (MBT), acrylic acid (AA) and MeHg employed as ligand, functional monomer and template ion, respectively, and the synthesized material was characterized by Raman spectroscopy and SEM-EDX. Both the proposed and control sensors were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrochemical measurements were carried out using differential pulse stripping voltammetry (DPSV), and a well-defined anodic peak observed at about +0.138 V (vs. Ag/AgCl) was recorded for MeHg. The application of the CPE/MWCNTs/IIP-MeHg sensor (which increased the charge transfer on the electrode surface) under the DPSV-based electrochemical method (which enhanced the signal intensity) made the detection technique highly sensitive and selective for the quantification of methylmercury. Under optimum experimental conditions, the proposed sensor exhibited a linear response range of 560–610 µg L−1 and a detection limit of 0.538 µg L−1, with acceptable relative error values ≤1% when applied for the detection of MeHg in real water samples.

Seasonal pollutant levels in littoral high-Arctic amphipods in relation to food sources and terrestrial run-off

Increasing terrestrial run-off from melting glaciers and thawing permafrost to Arctic coastal areas is expected to facilitate re-mobilization of stored legacy persistent organic pollutants (POPs) and mercury (Hg), potentially increasing exposure to these contaminants for coastal benthic organisms. We quantified chlorinated POPs and Hg concentrations, lipid content and multiple dietary markers, in a littoral deposit-feeding amphipod Gammarus setosus and sediments during the melting period from April to August in Adventelva river estuary in Svalbard, a Norwegian Arctic Aarchipelago. There was an overall decrease in concentrations of ∑POPs from April to August (from 58 ± 23 to 13 ± 4 ng/g lipid weight; lw), Hg (from 5.6 ± 0.7 to 4.1 ± 0.5 ng/g dry weight; dw) and Methyl Hg (MeHg) (from 5 ± 1 to 0.8 ± 0.7 ng/g dw) in G. setosus. However, we observed a seasonal peak in penta- and hexachlorobenzene (PeCB and HCB) in May (2.44 ± 0.3 and 23.6 ± 1.7 ng/g lw). Sediment concentrations of POPs and Hg (dw) only partly correlated with the contaminant concentrations in G. setosus. Dietary markers, including fatty acids and carbon and nitrogen stable isotopes, indicated a diet of settled phytoplankton in May–July and a broader range of carbon sources after the spring bloom. Phytoplankton utilization and chlorobenzene concentrations in G. setosus exhibited similar seasonal patterns, suggesting a dietary uptake of chlorobenzenes that is delivered to the aquatic environment during spring snowmelt. The seasonal decrease in contaminant concentrations in G. setosus could be related to seasonal changes in dietary contaminant exposure and amphipod ecology. Furthermore, this decrease implies that terrestrial run-off is not a significant source of re-mobilized Hg and legacy POPs to littoral amphipods in the Adventelva river estuary during the melt season.

Study on the difference of curative effect of conventional mercury displacement treatment on mercury in brain and kidney

Objective: To explore the expulsion effect of sodium dimercaptopropanesulfonate (DMPS) on mercury in different organs of mercury poisoning and the therapeutic effect of glutathione (GSH) combined with antioxidant therapy on mercury poisoning. Methods: In February 2019, 50 SPF male SD rats were randomly divided into 5 groups, 10 rats in each group: A (saline negative control group) , B (HgCL2 positive control group) , treatment group (C: intramuscular injection of DMPS 15 mg/kg treatment, D: intramuscular injection of DMPS30 mg/kg treatment, E: intramuscular injection of DMPS 15 mg/kg and intraperitoneal injection of GSH200 mg/kg treatment) . Rats in group B, C, D and E were subcutaneously injected with mercury chloride solution (1 mg/kg) to establish a rat model of subacute mercury poisoning kidney injury. Rats in group A were subcutaneously injected with normal saline. After the establishment of the model, rats in the treatment group were injected with DMPS and GSH. Rats in group A and group B were injected with normal saline. At 21 d (treatment 7 d) and 28 d (treatment 14 d) after exposure, urine and blood samples of 5 rats in each group were collected. Blood biochemistry, urine mercury, urine microalbumin and mercury content in renal cortex, cerebral cortex and cerebellum were detected. Results: After exposure to mercury, the contents of mercury in renal cortex, cerebrum and cerebellum of rats in group B, C, D and E increased, and urine microalbumin increased. Pathology showed renal tubular injury and renal interstitial inflammation. Compared with group B, urinary mercury and renal cortex mercury in group C, D and E decreased rapidly after DMPS treatment, and there was no significant decrease in mercury levels in cerebellum and cerebral cortex of rats, accompanied by transient increase in urinary albumin after DMPS treatment (P<0.05) ; the renal interstitial inflammation in group E was improved after GSH treatment. There was a positive correlation between urinary mercury and the contents of mercury in renal cortex, cerebral cortex and cerebellum (r=0.61, 0.47, 0.48, P<0.05) . Conclusion: DMPS mercury expulsion treatment can significantly reduce the level of metal mercury in the kidney, and there is no significant change in the level of metal mercury in the cortex and cerebellum.

Are fur farms a potential source of persistent organic pollutants or mercury to nearby freshwater ecosystems?

Farming of carnivorous animals for pelts potentially contaminates nearby ecosystems because animal feed and waste may contain persistent organic pollutants (POPs) and metals. Mink farms in Nova Scotia (NS), Canada, provide mink with feed partially composed of marine fish meal. To test whether mink farms potentially contribute contaminants to nearby lakes, we quantified organochlorine pesticides (OCP), polychlorinated biphenyls (PCB), and total mercury (THg) in mink/aquaculture feed, waste, and sediment collected from 14 lakes within rural southwest NS where mink farms are abundant and have operated for decades. Mercury, PCBs, dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), and dieldrin were present in mink/aquaculture feed and mink waste, indicating they are potential contaminant sources. Lakes with mink farms in their catchment exhibited significantly higher THgflux than lakes downstream of mink farming activity and reference lakes (p < 0.0001) after the intensification of mink farming in 1980, indicating mink farming activity is likely associated with increased lacustrine THgflux. Sedimentary ƩPCBflux was elevated in lakes with mink farms in their catchments, suggesting possible PCB contributions from mink farming, local agriculture, and atmospheric deposition. Elevated ƩDDT in lakes near mink farms relative to reference lakes suggests a possible enrichment related to mink farming, although mixed land use and historical DDT usage related to forestry in the region complicates DDT source attribution. Maximum dieldrinflux and HCHflux in lake sediment occurred coeval with peak worldwide usage in the 1970s and are unlikely to be associated with local mink farming. Lakes with mink farming activities in their catchments were associated with increased THgflux, ƩPCBflux, and possibly ƩDDTflux, suggesting a possible connection between marine fish meal, fur farms, and aquatic ecosystems in NS.

Mercury speciation in estuarine water using dithiol-based magnetic solid-phase extraction and cold vapor atomic fluorescence spectrometry

In this work, a method for mercury speciation using magnetic nanoparticles (MNPs) coated with dithiol and detection by cold vapor atomic fluorescence spectrometry (CV AFS) was developed. The magnetic Fe3O4 nanoparticles were coated with Al2O3 and sodium dodecyl sulfate (SDS) and functionalized with 1,3,4-thiadiazole-2,5-dithiol (TDT). The resulting functionalized MNPs (FMNPs, Fe3O4@Al2O3-TDT) were dispersed in the water samples, and the sorption performance with different mercury species was investigated. Once retained on the surface of Fe3O4@ Al2O3-TDT MNPs, the mercury species were magnetically separated from the sample and eluted with HCl. The organic mercury species were oxidized employing KBr-KBrO3 (100 and 17 mM, respectively) in an acid medium (HCl 1.0 M), and the results were expressed considering the total inorganic mercury concentration. It was successfully applied in mercury speciation analysis in the estuarine water, followed by CV AFS determination. In the proposed method under optimal conditions (pH 6), inorganic mercury was quantified in a linear range from 10 to 2000 ng L−1, with a limit of detection of 0.55 ng L−1, relative standard deviation (RSD) < 1.62%, and an enrichment factor of twelve. The recoveries in spiked estuarine water samples ranged from 94 to 106% for Hg(II), 85–91% for MeHg, 83–94% for EtHg, and 84–95% (PhHg) using two levels of concentration (100 and 500 ng L−1). The method is accurate, precise, and efficiently applied in mercury species determination in a complex matrix without laborious and time-consuming sample preparation.

Mercury, legacy and emerging POPs, and endocrine-behavioural linkages: Implications of Arctic change in a diving seabird

Arctic species encounter multiple stressors including climate change and environmental contaminants. Some contaminants may disrupt hormones that govern the behavioural responses of wildlife to climatic variation, and thus the capacity of species to respond to climate change. We investigated correlative interactions between legacy and emerging persistent organic pollutants (POPs), mercury (Hg), hormones and behaviours, in thick-billed murres (Uria lomvia) (N = 163) breeding in northern Hudson Bay (2016–2018). The blood profile of the murres was dominated by methylmercury (MeHg), followed by much lower levels of sum (∑) 35 polychlorinated biphenyls (PCBs), hexachlorobenzene (HCB) and p,p'-dichlorodiphenyltrichloroethylene (DDE), polybrominated diphenyl ethers (PBDEs) BDE-47, -99 and BDE-100; all other measured organochlorine pesticides and replacement brominated flame retardants had low concentrations if detected. Inter-annual variations occurred in MeHg, circulating triiodothyronine (T3), thyroxine (T4), and the foraging behaviours of the murres, identified using GPS-accelerometers. Compared to the 50-year mean date (1971–2021) for 50% of sea-ice coverage in Hudson Bay, sea-ice breakup was 1–2 weeks earlier (2016, 2017) or comparable (2018). Indeed, 2017 was the earliest year on record. Consistent with relationships identified individually between MeHg and total T3, and T3 and foraging behaviour, a direct interaction between these three parameters was evident when all possible interactions among measured chemical pollutants, hormones, and behaviours of the murres were considered collectively (path analysis). When murres were likely already stressed due to early sea-ice breakup (2016, 2017), blood MeHg influenced circulating T3 that in turn reduced foraging time underwater. We conclude that when sea-ice breaks up early in the breeding season, Hg may interfere with the ability of murres to adjust their foraging behaviour via T3 in relation to variation in sea-ice.

Immobilization of mercury in tailings originating from the historical artisanal and small-scale gold mining using sodium polysulfide.

A series of sodium polysulfides (SPSs) with different sulfur indexes was prepared as stabilizers to amend elemental mercury-contaminated artisanal small-scale gold mine (ASGM) tailings in Hubei, China, by controlling the molar ratio of sulfur and sodium sulfides as 1:1, 2:1, 3:1, and 4:1 during the synthesis. XRD, XPS, and laser Raman spectroscopy all suggested that the synthesized SPSs were a mixture of multiple polysulfides, sulfur, sodium sulfides, and sodium thiosulfate. Based on toxicity characteristic leaching procedure test (TCLP), mercury stabilization efficiency of SPSs was evaluated and proved to be more superior than sulfur, sodium sulfide, and also calcium polysulfide, with an optimal stabilization efficiency of 97.16% at SPS/THg = 1:2, SPSs pH = initial pH, and liquid-to-solid ratio = 20:7. A pseudo-second-order kinetic model was able to interpret the stabilization kinetics and demonstrated that mercury stabilization rate increased with the sulfur index in the SPSs, but excess SPSs were potentially to inhibit the precipitation of mercury. Speciation analysis results determined with sequential extraction indicated that the unstable mercury, elemental mercury, and organic-bound mercury fractions decreased respectively by up to 88.6%, 53.5%, and 26.3%. Pearson correlation analysis showed that the mercury stabilization in the mine tailings amended with SPSs mainly occurs from the precipitation of the elemental mercury, and the organic mercury fraction reduction was correlated with the decrease of the unstable mercury.

Thiophene-functional hierarchical carbons for the removal of ionic and organic mercury in light hydrocarbon liquids: Synthesis, evaluation and adsorption mechanism

A simple synthesis of thiophene-functional zeolite-templated carbons (ZTCs) is proposed to remove ionic mercury (Hg2+) and organic mercury (Hgorg) from gasoline. Microporous zeolite (Beta) and mesoporous zeolite (MCM-41) were used to prepare porous carbon by impregnating with 2-thiophenemethanol (ThM) to explore the influence of template type on the quality of templated carbon. The amount of strong acidic sites in MCM-41 zeolite was more than Beta zeolite which promoted the catalytic polymerisation of the ThM in the pores structure of the zeolite and highly templated carbon was obtained. The impregnation concentration of ThM on the structure and functional groups of the samples was explored. It was found that increasing the concentration of ThM properly can promote the filling of zeolite pores by ThM and form more ordered templated carbons. In addition, the increased ThM promoted the formation of the S = O and C-O oxygen-containing functional groups. The optimal impregnation concentrations of ThM were 25% for B-Al (25%-B-Al-ZTC) and 75% for M−Al (75%-M−Al−ZTC). The 75%-M−Al−ZTC with sufficient S = O and C-O oxygen-containing functional groups showed excellent mercury adsorption capacity (617.49 μg/g) and a high intra-particle diffusion rate (294.10 h−1). The simultaneous adsorption of Hg2+ and Hgorg was also conducted and it was found that Hgorg had competitive adsorption for Hg2+ which led the total adsorption capacity to decrease. In addition, the 25%-B-Al-ZTC and 75%-M−Al−ZTC adsorbents had good regeneration ability and the adsorption capacity remained over 75% and 71% for Hg2+ and Hgorg after five desorption-sorption cycles, respectively. Thus, the new adsorbents with stable and efficient Hg removal performance have the potential for practical application by oil refineries.

High concentrations of HgS, MeHg and toxic gas emissions in thermally affected waste dumps from hard coal mining in Poland

This study aims to provide numerous environmental research approaches to understand the formation of mineral and organic mercury compounds in self-heating coal waste dumps of the Upper Silesian Coal Basin (USCB). The results are combined with environmental and health risk assessments. The mineralogy comprised accessory minerals in the fine fraction of thermally affected waste, i.e., Hg sulfides, most likely cinnabar or metacinnabar. Moreover, other metals, e.g., Pb, Zn and Cu, were found as sulfide forms. Apart from Hg, the ICP-ES/MS data confirmed the high content of Mn, Zn, Pb, Hg, Cr and Ba in these wastes. The high concentration of available Hg resulted in elevated MeHg concentrations in the dumps. There were no correlations or trends between MeHg concentrations and elemental Hg, TS, TOC, and pH. Furthermore, we did not detect microbial genes responsible for Hg methylation. The organic compounds identified in waste and emitted gases, such as organic acids, or free methyl radicals, common in such burn environments, could be responsible for the formation of MeHg. The concentration levels of gases, e.g., benzene, formaldehyde, NH3, emitted by the vents, reached or surpassed acceptable levels numerous times. The potential ecological and human health risks of these dumps were moderate to very high due to the significant influence of the high Hg concentrations.