Does acute exposure to thimerosal, an organic mercury compound, affect the mitochondrial function of an infant model?

BACKGROUND: Thimerosal (TM) is a toxic, organometallic mercury compound (which releases ethyl-mercury-containing compounds in aqueous solutions) used as a preservative in vaccines. Mitochondria are organelle which are highly vulnerable to many chemical compounds, including mercury (Hg) and its derivatives. METHOD: Wistar rats (at 21 days of age) were used to model a child's TM exposure following childhood vaccination, divided in two groups: TM exposed (20 µg/kg/day) and unexposed controls (saline solution), both for 24 h. Atomic Fluorescence Spectrometry was used to quantify the amounts of mercury in tissues. The electron transport chain (ETC) from isolated mitochondria was evaluated using an oxygen electrode. The mitochondrial membrane potential and H2O2 production were analyzed using selective fluorescence probes. The activity of some enzymes (SOD, CAT, GPx, and AChE) and secondary markers of oxidative stress (GSH, GSSG, total free thiol) were also examined in tissues. RESULTS: Hg accumulation in the brain and liver was higher in exposed animals when compared to the control. Liver-isolated mitochondria showed that TM improved respiratory control by 23%; however, states 3 and 4 of the ETC presented a decrease of 16% and 37%, respectively. Furthermore, brain-isolated mitochondria presented an improvement of 61% in respiratory control. Brain enzyme activities were significantly impacted in TM-exposed rats compared to unexposed rats as follows: decreases in SOD (32%) and AChE (42%) and increases in GPx (79%) and CAT (100%). GPx enzyme activity in the liver was significantly increased (37%). Among secondary oxidative stress markers, the brain's total reduced thiol (SH) concentration was significantly increased (41%). CONCLUSION: Acute TM treatment exposure in a Wistar rat model mimicking TM exposure in an infant following childhood vaccination significantly damaged brain bioenergetic pathways. This study supports the ability of TM exposure to preferentially damage the nervous system.

Multimedia fate simulation of mercury in a coastal urban area based on the fugacity/aquivalence method.

Due to intensive industrial production and living activities, urban areas are the main anthropogenic mercury (Hg) emission sources. After entering the environment through exhaust gases, wastewater or waste residues, Hg can migrate and transform among different environmental compartments in various species, such as elemental mercury (Hg0), divalent mercury (Hg2+) and methylmercury (MeHg). Studies have yet to report on the multimedia behaviors of Hg in urban areas due to the complexity of the processes involved. In this study, the atmospheric Hg emission in Dalian, a coastal city in Northeast China, was estimated by an anthropogenic emission inventory, and a Level III multimedia model was constructed based on the fugacity/aquivalence method to simulate the fate of Hg in air, water, soil, sediment, vegetation and film. The total annual atmospheric emission was 9.91 t, of which coal combustion and non-coal sources accounted for 70.1 % and 29.9 %, respectively. Atmospheric emission and advection were dominated by Hg0, and aquatic emission and advection were dominated by Hg2+. The migration of air-vegetation, vegetation-soil and soil-air were three important pathways of Hg in urban areas. The model was validated by collecting local soil and vegetation samples and regional air, seawater and sediment monitoring data. The scenario simulation indicated that the local load would decrease to different extents with a 21.0 % reduction in atmospheric Hg emission by implementing the "coal-to-gas" measures. Our developed model can characterize the fate of Hg in coastal urban areas and provide a reference for control strategies.

Health risk assessment for human mercury exposure from Cinnabaris-containing Baizi Yangxin Pills in healthy volunteers Po administration.

BACKGROUND: Cinnabaris (α-HgS), a mineral traditional Chinese material medica, has been used in combination with other herbs manifesting some definite therapeutic effects for thousands of years. But the currently reported mercury poisoning incidents raised the doubts about the safety of Cinnabaris-containing traditional Chinese medicines (TCMs). Baizi Yangxin Pills (BZYXP) is a Cinnabaris-containing TCM widely used in clinical practice. This study evaluated the health risk of mercury exposure from BZYXP in healthy volunteers based on the total mercury and mercury species analysis of blood and urine after single and multiple doses of BZYXP. METHODS: Blood pharmacokinetics and urinary excretion studies of mercury were compared between single (9 g, once daily) and multiple doses (9 g, twice daily, continued for 7 days) of BZYXP. The whole blood and urine samples were collected at the specific points or periods after the administration of BZYXP. The total mercury and mercury species in blood and urine samples were determined by cold vapor-atomic fluorescence spectrometry (CV-AFS) and HPLC-CV-AFS, respectively. RESULTS: The mercury was excreted slowly and accumulated obviously after continuous exposure of BZYXP. Moreover, the well-known neurotoxin methylmercury (MeHg) was detected in blood samples after 7 days' administration of BZYXP. In the urine samples, only Hg(II) was detected. Therefore, long-term use of BZYXP will cause mercury poisoning due to mercury's high accumulative properties and MeHg formation. CONCLUSION: Cinnabaris-containing TCMs such as BZYXP should be restricted to cases in which alternatives are available, and the blood mercury species profile should be monitored during the long-term clinical medication.

Assessment of thimerosal effects in sublethal concentrations on zebrafish (Danio rerio) embryos exploring NMR-based metabolomics profile.

Thimerosal, a preservative commonly used in the pharmaceutical and cosmetic industry, has raised concerns regarding its potentially toxic effects as an organic mercury compound. Within this context, using an NMR-based metabolomics profile and chemometric analysis, zebrafish embryos were used as an in vivo model to study the effects of thimerosal in metabolic profiles after exposure to sublethal concentrations of the mercury compound. The thimerosal concentrations of 40 and 80 nM were employed, corresponding to 40% and 80% of the LC50, respectively, for zebrafish embryos. The most significant alterations in the metabolic profile included changes in carbohydrates, amino acids, nucleotides, trimethylamine-N-oxide, ethanolamine, betaine, and ethanol. Furthermore, thimerosal exposure affects various metabolic pathways, impairing the nervous system, disrupting protein metabolism, and potentially causing oxidative damage. Therefore, adopting a metabolomics approach in this investigation provided insights into the potentially implicated metabolic pathways contributing to the deleterious effects of thimerosal in biological systems.

[Mercury species analysis and tissue distribution in rats after continuous administration of Cinnabaris].

Cinnabaris is a traditional Chinese medicine(TCM) commonly used for sedation and tranquilization in clinics, and its safety has always been a concern. This study intends to investigate the species and tissue distribution of mercury in rats after continuous administration of Cinnabaris. In the experiment, 30 rats were randomly divided into the control group(equivalent to 0.5% carboxy-methyl cellulose sodium), low-dose Cinnabaris group(0.2 g·kg~(-1)), high-dose Cinnabaris group(2 g·kg~(-1)), pseudogerm-free control group(equivalent to 0.5% sodium carboxymethyl cellulose), and pseudogerm-free Cinnabaris group(2 g·kg~(-1)). They were orally administered for 30 consecutive days. Ultrasound-assisted acid extraction method combined with high performance liquid chromatography and inductively coupled plasma-mass spectrometry(HPLC-ICP-MS) was adopted to determine inorganic mercury [Hg(Ⅱ)], methylmercury(MeHg), and ethylmercury(EtHg) in different tissue, plasma, urine, and feces of rats. The optimal detection conditions and extraction methods were optimized, and the linearity(R~2>0.999 3), precision(RSD<7.0%), and accuracy(spike recoveries ranged from 73.05% to 109.5%) of all the mercury species were satisfied, meeting the requirements of analysis. The results of mercury species detection showed that Hg(Ⅱ) was detected in all the tissue of the five experimental groups, and the main accumulating organs were the intestinal tract, stomach, and kidney. MeHg existed at a low concentration in most tissue, and EtHg was not detected in all groups. In addition, pathological examination results showed that hepatocyte vacuolar degeneration, loose cytoplasm, light staining, and mononuclear cell infiltration were observed in the high-dose Cinnabaris group, low-dose Cinnabaris group, and pseudogerm-free Cinnabaris group, with slightly milder lesions in the low-dose Cinnabaris group. Hydrous degeneration of renal tubular epithelium could be seen in the high-dose Cinnabaris group and pseudogerm-free Cinnabaris group, but there was no significant difference between the other groups and the control group. No abnormal changes were found in the brain tissue of rats in each group. This paper studied the different mercury species and tissue distribution in normal and pseudogerm-free rats after continuous administration of Cinnabaris for 30 days and clarified its effects on the tissue structure of the liver, kidney, and brain, which provided supporting evidence for the safety evaluation of Cinnabaris.

An improved method for rapid and safe preparation and measurement of dimethylmercury using gas chromatography-atomic fluorescence spectrometry.

Transformations between dimethylmercury (DMHg) and other mercury (Hg) species have been one of the critical knowledge gaps in the Hg global biogeochemical cycle due to the lack of detailed studies. The preparation and measurement of DMHg are challenging due to the high toxicity and volatility of DMHg. In this work, we invented a new DMHg generator for successfully preparing high-purity DMHg in a highly controllable and safe way. The DMHg could be spontaneously volatilized and diffused from the original preparation solution to the solution to be studied. The parameters for generating DMHg were optimized to be the pH value of 4.0 with a MeCo/Hg2+ molar ratio of 10 at 20 °C. The following measurement method of DMHg in the presence of various species of Hg was also investigated and optimized. Hg0 and DMHg could be separated effectively with the carrier gas flow rate of 15 mL min-1 and the gas chromatography column temperature of 30 °C. The interferences of Hg0, monomethylmercury and other species were excluded by systematic control experiments. A sensitive and reliable approach for quantifying trace DMHg in water was developed. Under the optimal conditions, the limits of detection for Hg0, MMHg and DMHg were 0.03, 0.002 and 0.024 ng L-1, respectively, with the relative standard deviation below 8.2%. The developed method was validated by the determination Hg species of different natural water samples. This work is expected to provide a new and safe strategy for DMHg preparation and a verified method for DMHg measurement.

Mercury sources, contaminations, mercury cycle, detection and treatment techniques: A review.

Mercury is considered a toxic pollutant harmful to our human health and the environment. Mercury is highly persistent, volatile and bioaccumulated and enters into the food chain, destroying our ecosystem. The levels of mercury in the water bodies as well as in the atmosphere are affected by anthropogenic and natural activities. In this review, the mercury species as well as the mercury contamination towards water, soil and air are discussed in detail. In addition to that, the sources of mercury and the mercury cycle in the aquatic system are also discussed. The determination of mercury with various methods such as with modified electrodes and nanomaterials was elaborated in brief. The treatment in the removal of mercury such as adsorption, electrooxidation and photocatalysis were explained with recent ideologies and among them, adsorption was considered one of the efficient techniques in terms of cost and mercury removal.

Incorporating soil mercury species and fractions into multi-objective risk assessment of a residue disposal site in China.

Environmental problems in soil and water caused by solid waste dumps have become a growing concern. This study proposes an integrated risk assessment model aimed at multi-objectives including human, ecology and groundwater and develops remediation target values at different tiers associated with soil mercury species and fractions in a typical residue disposal site of China. The results show that the residue disposal site was severely contaminated with mercury, with the maximum mercury content in the soil reaching 579.14 mg/kg. The average concentration of vapour mercury, bioaccessible mercury, bioavailable mercury and leachable mercury tested in laboratory was 87.65 mg/kg, 3.15 mg/kg (intestinal phase), 1.654 mg/kg and 0.045 mg/L, respectively. The hazard index calculated using total mercury, bioaccessible mercury and vapour mercury was 7.43 E + 01, 4.42 E + 01, and the remediation target values were7.79 mg/kg and 13.1 mg/kg, respectively. The ecological risk for total mercury and bioavailable mercury was calculated using measured site soil mercury background values of 6390.92 and 94.52, and the remediation target was 0.7 mg/kg and 47.33 mg/kg, respectively. Under Class IV water conditions, the measured and three-phase equilibrium model simulations of leachable mercury resulted in remediation targets of 6 mg/kg and 10 mg/kg for soil mercury. Compared to total mercury, the remediation target values calculated using mercury species and fractions were significantly larger under human health protection, ecology protection and groundwater protection. This results in a reduction in the area of soil to be remediated by 20.3-85.7%, resulting in significant savings in remediation costs. It was concluded that when conducting risk assessment and reuse of mercury-contaminated sites, it is important to consider the species and fractions of mercury in the soil in order to reasonably determine the remediation criteria and scale of remediation to avoid over-remediation and incomplete remediation. At the same time, a comprehensive protection target remediation mechanism should be established by combining different receptors.

Metalloproteomic approach to liver tissue of rats exposed to mercury.

The aims of this study were to identify mercury-associated protein spots in the liver tissue of rats exposed to low concentrations of mercury and to elucidate the physiological and functional aspects of the proteins identified in the protein spots. Therefore, proteomic analysis of the liver tissue of Wistar rats exposed to mercury chloride (4.60 µg kg-1 in Hg2+) was performed for thirty days (Hg-30 group) and sixty days (Hg-60 group). The proteomic profile of the liver tissue of the rats was obtained by two-dimensional electrophoresis (2D-PAGE), and the determinations of total mercury in the liver tissue, pellets and protein spots were performed by graphite furnace atomic absorption spectrometry (GFAAS). ImageMaster 2D Platinum 7.0 software was used to identify the differentially expressed mercury-associated protein spots, which were then characterized by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The determinations by GFAAS indicated a total mercury bioaccumulation of 2812% in the Hg-30 group and 3298% in the Hg-60 group and 10 mercury-associated protein spots with a concentration range of 51 ± 1.0 to 412 ± 6.00 mg kg-1 in the 2D PAGE gels from the liver tissue of the Hg-60 group. The LC-MS/MS analyses allowed the identification of 11 metal binding proteins in mercury-associated protein spots that presented fold change with upregulation >1.5, downregulation < -1.7 or that were expressed only in the Hg-60 group. Using the FASTA sequences of the proteins identified in the mercury-associated protein spots, bioinformatics analyses were performed to elucidate the physiological and functional aspects of the metal binding proteins, allowing us to infer that enzymes such as GSTM2 presented greater mercury concentrations and downregulation < -3; Acaa2 and Bhmt, which showed expression only in the Hg-60 group, among others, may act as potential mercury exposure biomarkers.

Mercury species analysis and tissue distribution in rats after continuous administration of Cinnabaris / 中国中药杂志

Cinnabaris is a traditional Chinese medicine(TCM) commonly used for sedation and tranquilization in clinics, and its safety has always been a concern. This study intends to investigate the species and tissue distribution of mercury in rats after continuous administration of Cinnabaris. In the experiment, 30 rats were randomly divided into the control group(equivalent to 0.5% carboxy-methyl cellulose sodium), low-dose Cinnabaris group(0.2 g·kg~(-1)), high-dose Cinnabaris group(2 g·kg~(-1)), pseudogerm-free control group(equivalent to 0.5% sodium carboxymethyl cellulose), and pseudogerm-free Cinnabaris group(2 g·kg~(-1)). They were orally administered for 30 consecutive days. Ultrasound-assisted acid extraction method combined with high performance liquid chromatography and inductively coupled plasma-mass spectrometry(HPLC-ICP-MS) was adopted to determine inorganic mercury [Hg(Ⅱ)], methylmercury(MeHg), and ethylmercury(EtHg) in different tissue, plasma, urine, and feces of rats. The optimal detection conditions and extraction methods were optimized, and the linearity(R~2>0.999 3), precision(RSD<7.0%), and accuracy(spike recoveries ranged from 73.05% to 109.5%) of all the mercury species were satisfied, meeting the requirements of analysis. The results of mercury species detection showed that Hg(Ⅱ) was detected in all the tissue of the five experimental groups, and the main accumulating organs were the intestinal tract, stomach, and kidney. MeHg existed at a low concentration in most tissue, and EtHg was not detected in all groups. In addition, pathological examination results showed that hepatocyte vacuolar degeneration, loose cytoplasm, light staining, and mononuclear cell infiltration were observed in the high-dose Cinnabaris group, low-dose Cinnabaris group, and pseudogerm-free Cinnabaris group, with slightly milder lesions in the low-dose Cinnabaris group. Hydrous degeneration of renal tubular epithelium could be seen in the high-dose Cinnabaris group and pseudogerm-free Cinnabaris group, but there was no significant difference between the other groups and the control group. No abnormal changes were found in the brain tissue of rats in each group. This paper studied the different mercury species and tissue distribution in normal and pseudogerm-free rats after continuous administration of Cinnabaris for 30 days and clarified its effects on the tissue structure of the liver, kidney, and brain, which provided supporting evidence for the safety evaluation of Cinnabaris.

One-pot fabrication of functional magnetic adsorbent for efficient capture of mercury species in aqueous samples prior to HPLC analysis.

Efficient extraction is a vital step in mercury speciation. In this context, using 4-vinylbenzeneboronic acid and 9-vinylanthracene as functional monomers, a new magnetic adsorbent was fabricated according to one-pot hydrothermal approach. Various characterization results prove the as-prepared adsorbent presented abundant functional groups and saturation magnetism. Combining with magnetic solid phase extraction (MSPE), the adsorbent exhibited satisfactory entrapment performance towards different mercury species which had been pre-coordinated with dithizone to form metal-organic coordination. A series of parameters influencing the extraction performance were inspected in detail. Under the most beneficial conditions, sensitive and reliable approach to quantify trace methylmercury, ethylmercury, phenylmercury and inorganic mercury in aqueous samples was developed by the combination of HPLC/DAD. Limits of detection and precision located in the ranges of 0.012-0.074 µg/L and 2.5-9.8%, respectively. Recoveries with low, medium and high fortified contents in actual waters varied from 79.8 to 119%. Confirmatory experiments were performed to evidence the accuracy and reliability of established approach. In addition, a possible mechanism was suggested based on the chemical nature of analytes, extraction conditions and characterization results.

Revealing the mechanisms of mercury adsorption on metal-doped kaolinite(001) surfaces by first principles.

Natural kaolinite exhibit high affinity for heavy metals while the interaction mechanisms in the presence of heteroatoms remain largely elusive, which are tackled by first principles. In this paper, three common dopants (Mg, Ca, Fe) were employed to construct metal-doped kaolinite(001) (K(001)) surfaces. We found that Mg-doped K(001) was the most stable surface in terms of thermal stability and structural analysis, consistent with the pervasive isomorphic substitution in kaolinite minerals. The interaction of mercury with Mg-doped K(001) surface was investigated in the form of predominant top-site and bridge-site models. The effects of chloride on the interaction were also studied. The results demonstrated that the strongest adsorption occured in the present of dopants and the absence of chloride. The electronic properties revealed a significant charge transfer (up to 1.28 electrons) and chemisorption character at the interfaces when dopants were introduced, which could be ascribed to the overlapping of Hg-5d and Os-2p (surface O) orbitals in the range of -7.5 eV to +0.5 eV. Additionally, the chloride had a profoundly adverse influence on mercury adsorption due to the upward shift of Hg-6s and Hg-6p orbitals. The studies are beneficial to understand the interaction mechanisms of natural minerals toward environmental pollutants in actual applications.

Appraising ecotoxicological risk of mercury species and their mixtures in sediments to aquatic biota using diffusive gradients in thin films (DGT).

Mercury (Hg) is a global, persistent and inevitable pollutant, the toxicity of which is mostly reflected in its species including inorganic Hg (InHg) and methyl mercury (MeHg). Using diffusive gradients in thin films (DGT) is deemed as a reliable technique to determine the bioavailability of pollutants. This study is the first attempt to assess the integrated toxicity of mercury species mixtures in sediments to the aquatic biota based on the DGT technique. In the course, the Daya Bay under serious anthropogenic influences was selected as the study case. The results showed that the DGT concentrations of InHg and MeHg were detected as 0.30-1.93 µg/L and 0.28-1.94 µg/L respectively in the surface sediments collected from the Daya Bay. In terms of the toxicity of single mercury species, the risk quotient (RQ) values of InHg and MeHg significantly exceeded 1, indicating that the adverse effects of InHg and MeHg should not be ignored. In terms of the integrated toxicity of mercury species mixtures, the probabilistic biological risk assessment results demonstrate that Daya Bay features low (3.32%) probability of toxic effects in its surface sediments to the aquatic biota.

The underappreciated role of natural organic matter bond Hg(II) and nanoparticulate HgS as substrates for methylation in paddy soils across a Hg concentration gradient.

Rice consumption is the major pathway for human methylmercury (MeHg) exposure in inland China, especially in mercury (Hg) contaminated regions. MeHg production, a microbially driven process, depends on both the chemical speciation of inorganic divalent mercury, Hg(II), that determines Hg bioavailability for methylation. Studies have shown that Hg(II) speciation in contaminated paddy soils is mostly controlled by natural organic matter and sulfide levels, which are typically thought to limit Hg mobility and bioavailability. Yet, high levels of MeHg are found in rice, calling for reconsideration of the nature of Hg species bioavailable to methylators in paddy soils. Here, we conducted incubation experiments using a multi-isotope tracer technique including 198Hg(NO3)2, natural organic matter bond Hg(II) (NOM-199Hg(II)), ferrous sulfide sorbed Hg(II) (≡FeS-200Hg(II)), and nanoparticulate mercuric sulfide (nano-202HgS), to investigate the relative importance of geochemically diverse yet relevant Hg(II) species on Hg methylation in paddy soils across a Hg concentration gradient. We show that methylation rates for all Hg(II) species tested decreased with increasing Hg concentrations, and that methylation rates using NOM-199Hg(II) and nano-202HgS as substrates were similar or greater than rates obtained using the labile 198Hg(NO3)2 substrate. ≡FeS-200Hg(II) yielded the lowest methylation rate in all sites, and thus the formation of FeS is likely a sink for labile 198Hg(NO3)2 in sulfide-rich paddy soils. Moreover, the variability in the methylation data for a given site (1 to 5-fold variation depending on the Hg species) was smaller than what was observed across the Hg concentration gradient (103-104 fold variation between sites). These findings emphasize that at broad spatial scales, site-specific characteristics, such as microbial community structure, need to be taken into consideration, alongside the nature of the Hg substrate available for methylation, to determine net MeHg production. This study highlights the importance of developing site-specific strategies for remediating Hg pollution.

Task specific monolith for magnetic field-reinforced in-tube solid phase microextraction of mercury species in waters prior to online HPLC quantification.

In this study, a novel sorbent based on task specific monolith doped with Fe3O4 was in situ fabricated in capillary and acted as the extraction medium of magnetic field-reinforced in-tube solid phase microextraction (MFR/IT-SPME) to trap and preconcentrate mercury species which were coordinated with dithizone to form chelates. Various characterization technologies evidenced that the obtained monolithic adsorbent presented porous and super paramagnetic properties, and possessed abundant functional groups. Results evidenced that the implementation of magnetic field during extraction stages enhanced the extraction efficiency of studied Hg chelates from 48.5% to 75.3% to 69.9-94.4%. Under the optimized extraction parameters, the introduced MFR/IT-SPME was online coupled to HPLC/DAD to quantify mercury species at ultra-trace levels in various water samples. Limits of detection varied from 0.0067 µg/L to 0.016 µg/L, and the RSDs for precision were below 7.5%. Additionally, related extraction mechanism was deduced and revealed multiple forces co-contributed to the enrichment. The reliability and accuracy of suggested online approach for speciation analysis of mercury was well proved by confirmatory experiments.

Selective and efficient removal of Hg (II) from aqueous media by a low-cost dendrimer-grafted polyacrylonitrile fiber: Performance and mechanism.

Polyacrylonitrile fiber was successfully modified with triazine-based dendrimer via grafting method as a promising adsorbent for removal of mercury species from aqueous media. The prepared adsorbent was characterized by elemental analysis, scanning electron microscope, Fourier transform infrared spectroscopy, porous structure analysis and X-ray photoelectron spectroscopy, providing the evidence of successful fabrication. The adsorption conditions were found via varying pH, dosage, coexisting substances, contact time, temperature and concentration. Adsorption performance, described better by the pseudo-second-order kinetics with intraparticle diffusion as rate controlling step and Langmuir isotherm model, indicated a chemisorption process with the maximum Langmuir adsorption amount of 227.64 mg g-1 for mercury ions. Thermodynamically, adsorption of mercury ions was spontaneous and endothermic. Desorption and regeneration experiments demonstrated that it could be reused in five successive adsorption cycles without significant loss of its original performance. Experimental data and density functional theory calculation disclosed the coordination geometries and chelating mechanism between the adsorbent and mercury ions. The proposed study would provide a new prospect for the purification of mercury in aqueous system by functionalizing commercial polyacrylonitrile fiber with dendrimers.

Mercury species and potential leaching in sludge from coal-fired power plants.

Wet flue gas desulfurization (WFGD) sludge, generated from the WFGD effluent treatment process, is suitable for multiple uses in various industries. However, risk assessments of its utilization are limited. Systematic study of Hg species occurrences, partitioning and risks of leaching is required, and these concerns were addressed in the present study. Hg temperature-programmed decomposition (Hg-TPD) and an improved European Community Bureau of Reference (BCR) method indicated residual Hg in WFGD sludge was related to HgS, and the content of this fraction was from 2 to 3%. HgCl2, HgO and HgSO4 were assigned to the water/acid-soluble fractions, and reducible Hg was related to Fe species in the sludge. Leachate evaluation of the WFGD sludge indicated potentially high Hg leaching risk. WFGD sludge with higher Hg concentrations and smaller particulate diameters exhibited greater leaching potential. Leaching of Hg from WFGD sludge in China into the environment was estimated at 7.46 t/yr.

Magnetic solid-phase extraction for speciation of mercury based on thiol and thioether-functionalized magnetic covalent organic frameworks nanocomposite synthesized at room temperature.

A simple and practical magnetic solid-phase extraction high-performance liquid chromatography-inductively coupled plasma mass spectrometry (MSPE-HPLC-ICP-MS) method for extraction and determination of trace mercury species, including inorganic mercury (IHg), monomethylmercury (MeHg) and ethylmercury (EtHg), was developed. The MSPE adsorbent, urchin-like thiol and thioether-functionalized magnetic covalent organic frameworks (Fe3O4@COF-S-SH), was synthesized by coating covalent organic frameworks (COFs) on the surface of Fe3O4 nanoparticles at room temperature and then easily grafting 1,2-Ethanedithiol on the COFs. The as-prepared Fe3O4@COF-S-SH has strong adsorption capacity for IHg, MeHg and EtHg, with excellent static adsorption capacity: 571, 559 and 564 mg g-1, respectively. The parameters influencing the extraction and enrichment had been optimized, including pH, adsorption and desorption time, composition and amount of the eluent, co-existing ions and dissolved organic materials etc. Under the optimized condition, the limit of detection (3δ) of the proposed method were 0.96, 0.17 and 0.47 ng L-1 for IHg, MeHg and EtHg, and the developed method has high actual enrichment factors of 370, 395, 365-fold for IHg, MeHg and EtHg based on 200 mL samples, respectively. The high accuracy and reproducibility has been proved by the spiked recoveries (96.0‒108 %) in real water samples and determination of the certified reference material. Both the adsorption and desorption process can be completed within 5 min. The proposed method with simple operation, short pre-concentration time and high sensitivity has been successfully applied to mercury speciation at trace levels in the samples with complicated matrices, including underground water, surface water, sea water and fish samples.

Relating trophic ecology and Hg species contamination in a resident opportunistic seabird of the Bay of Biscay.

Methylmercury (MeHg) is the most bioavailable and toxic form of the globally distributed pollutant Hg. Organisms of higher trophic levels living in aquatic ecosystems have potentially higher concentrations of MeHg. In this work, we analysed both MeHg and inorganic Mercury (Hg(II)) concentrations from dorsal feathers of chicks from ten colonies of Yellow-legged Gull (Larus michahellis) in the south-eastern part of the Bay of Biscay. Overall, we detected a high mean MeHg concentration that, however, differed among colonies. Additionally, based on stable isotopes analysis (δ13C and δ15N) and conducting General Linear Mixed Models, we found that chicks which were mostly/mainly fed with prey of marine origin had higher levels of MeHg. We propose Yellow-legged Gull as a reliable biomonitor for Hg species, as it is easy for sampling and in compliance with the Minamata convention on Mercury.