Non-chromatographic screening method for the determination of mercury species. Application to the monitoring of mercury levels in Antarctic samples

A simple non-chromatographic method for the determination of mercury (Hg²⁺), methylmercury (MeHg⁺), dimethylmercury (Me₂Hg), and phenylmercury (PhHg⁺) employing atomic fluorescence spectrometry (AFS) as detection technique was developed. Mercury species showed a particular behavior in the presence of several reagents. In a first stage SnCl₂ was employed for Hg²⁺ determination; in a second step, [Hg²⁺ + PhHg⁺] concentration was determined using SnCl₂ and UV radiation. MeHg⁺ decomposition was prevented adding 2-mercaptoethanol. In a third stage, [Hg²⁺ + PhHg⁺ + MeHg⁺] concentration was determined using K₂S₂O₈. Finally, the four species were determined employing NaBH₄. Reagents concentration and flow rates were optimized. The extraction technique of mercury species involved the use of 2-mercaptoethanol as ion-pair reagent. The limits of detection for Hg²⁺, PhHg⁺, MeHg⁺, and Me₂Hg were 1, 40, 68, and 99 ng L⁻¹ with a relative standard deviation of 1.5, 3.1, 4.7 and 5.8%, respectively. Calibration curve was linear with a correlation factor equal to 0.9995. The method was successfully applied to the determination of the mercury species in two Antarctic materials: IRMM 813 (Adamussium colbecki) and MURST-ISS-A2 (Antarctic Krill).     

Production of artifact methylmercury during the analysis of certified reference sediments: use of ionic exchange in the sample treatment step to minimise the problem

Production of artifact methylmercury (MeHg⁺) during the analysis of two certified reference sediments, CRM-580 and IAEA-405, was investigated. Leaching of the analyte from the solid sample was achieved by ultrasound assisted acidic extraction. The aqueous leachate was either ethylated (NaBEt₄) or phenylated (NaBPh₄) using acetic/acetate or citric/citrate to buffer the solution. Preconcentration of the volatile compounds was carried out by extraction with an organic solvent (n-hexane) or solid phase microextraction (SPME). MeHg⁺ was finally separated and detected by gas chromatography with atomic emission or mass spectrometry detection (GC-MIP-AED or GC-MS). In all the cases the concentrations obtained for MeHg⁺ in the CRM-580 were significantly higher than the certified value. For the IAEA-405, however, the MeHg⁺ concentration found was always statistically indistinguishable from the certified value. Experiments were also conducted with synthetic samples, such as aqueous mixtures of MeHg⁺ and inorganic mercury (Hg²⁺) or silica-gel spiked with both compounds. The methylation rates found (defined as the percentage of Hg²⁺ present in the sample which methylates to give artifact MeHg⁺) ranged from not observable (in certain synthetic aqueous mixtures) to 0.57% (analysis of CRM-580 under certain conditions). As the amount of Hg²⁺ available in the sample seems to be the main factor controlling the magnitude of the artifact, several experiments were conducted using an ionic exchange resin (Dowex M-41) in order to minimise the concentration of this chemical in the reaction medium. First, a hydrochloric leachate of the sample was passed through a microcolumn packed with the exchanger. Second, the resin was mixed with the sample prior to extraction with HCl. In both cases, the predominant Hg²⁺ species, HgCl₄²⁻, was adsorbed on the resin, whereas MeHg⁺, mainly as MeHgCl, remained in solution. Following the second option, a new method to analyse MeHg⁺ in conflictive matrices like certain sediments was proposed. This approach produced better results for the CRM-580, but a MeHg⁺ concentration slightly, but statistically significant, higher than the reference value was still obtained.     

Exploiting the κ2-Fashioned Coordination of [Se2]-Donor Ligand L3Se for Facile Hg−C Bond Cleavage of Mercury Alkyls and Cytoprotection against Methylmercury-Induced Toxicity

The Hg−C bond of MeHgCl, a ubiquitous environmental toxicant, is notoriously inert and exceedingly difficult to cleave. The cleavage of the Hg−C bond of MeHgCl at low temperature, therefore, is of significant importance for human health. Among various bis(imidazole)-2-selones L_nSe (n=1–4, or 6), the three-spacer L₃Se shows extraordinarily high reactivity in the degradation of various mercury alkyls including MeHgCl because of its unique ability to coordinate through κ²-fashion, in which both the Se atoms simultaneously attack the Hg center of mercury alkyls for facile Hg−C bond cleavage. It has the highest softness (σ) parameter and the lowest HOMO(L_nSe)-LUMO(MeHgX) energy gap and, thus, L₃Se is the most reactive among L_nSe towards MeHgX (X=Cl or I). L₃Se is highly efficient, more than L₁Se, in restoring the activity of antioxidant enzyme glutathione reductase (GR) that is completely inhibited by MeHgCl; 80 % GR activity is recovered by L₃Se relative to 50 % by L₁Se. It shows an excellent cytoprotective effect in liver cells against MeHgCl-induced oxidative stress by protecting vital antioxidant enzymes from inhibition caused by MeHgCl and, thus, does not allow to increase the intracellular reactive oxygen species (ROS) levels. Furthermore, it protects the mitochondrial membrane potential (ΔΨ_m) from perturbation by MeHgCl. Major Hg-responsive genes analyses demonstrate that L₃Se plays a significant role in MeHg⁺ detoxification in liver cells.     

Mercury speciation in thawed out and refrozen fish samples by gas chromatography coupled to inductively coupled plasma mass spectrometry and atomic fluorescence spectroscopy

Different sub-sampling procedures were applied for the determination of mercury species (as total mercury Hg, methylmercury MeHg⁺ and inorganic mercury Hg²⁺) in frozen fish meat. Analyses were carried out by two different techniques. After the sample material was pre-treated by microwave digestion, atomic fluorescence spectroscopy (AFS) was used for the determination of total Hg. Speciation analysis was performed according to the following procedure: dissolution of sample material in tetramethylammonium hydroxide (TMAH), derivatisation with sodium tetraethylborate (NaBEt₄), extraction into isooctane and measurement with gas chromatography inductively coupled plasma mass spectrometry (GC-ICPMS) for the identification and quantification of methylmercury (MeHg⁺) and inorganic mercury (Hg²⁺). The concentration range of total Hg measured in the shark fillets is between 0.9 and 3.6 g g^–1 thawed out shark fillet. Speciation analysis leads to 94% Hg present as MeHg⁺. Homogeneity, storage conditions and stability of analytical species and sample materials have great influence on analytical results. Sub-sampling of half-frozen/partly thawed out fish and analysis lead to significantly different concentrations, which are on average a factor of two lower.     

Speciation of mercury in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry

The dispersive liquid-liquid microextraction (DLLME) combined with high performance liquid chromatography-inductively coupled plasma mass spectrometry for the speciation of mercury in water samples was described. Firstly methylmercury (MeHg⁺) and mercury (Hg²⁺) were complexed with sodium diethyldithiocarbamate, and then the complexes were extracted into carbon tetrachloride by using DLLME. Under the optimized conditions, the enrichment factors of 138 and 350 for MeHg⁺ and Hg²⁺ were obtained from only 5.00 mL sample solution. The detection limits of the analytes (as Hg) were 0.0076 ng mL⁻¹ for MeHg⁺ and 0.0014 ng mL⁻¹ for Hg²⁺, respectively. The relative standard deviations for ten replicate measurements of 0.5 ng mL⁻¹ MeHg⁺ and Hg²⁺ were 6.9% and 4.4%, respectively. Standard reference material of seawater (GBW(E)080042) was analyzed to verify the accuracy of the method and the results were in good agreement with the certified values. Finally, the developed method was successfully applied for the speciation of mercury in three environmental water samples.     

Improvement of analytical performances for mercury speciation by on-line derivatization, cryofocussing and atomic fluorescence spectrometry

A modified automated on-line hyphenated system for simultaneous inorganic ionic mercury (Hg²⁺) and monomethylmercury (MeHg⁺) analysis by hydride generation (HG) or ethylation (Eth), cryofocussing, gas chromatography (GC) separation and atomic fluorescence spectrometry (AFS) detection has been improved. Both derivatization methods are investigated with respect to the chromatographic and analytical performances. They can be both affected by interferences when the AFS detection system is used. Water vapor removal using a soda lime moisture trap improves significantly the chromatographic performances, the reproducibility and the detection limits for Hg²⁺ and MeHg⁺ analyzed with both methods. For ethylation (Eth) derivatization, a scattering interference generated from low-quality ethylation reagent has also been eliminated. For HG, improved detection limits are 0.13 ng l⁻¹ and 0.01 ng l⁻¹ for Hg²⁺ and MeHg⁺, respectively (0.1 l water sample), and reproducibility are 5% for Hg²⁺ (20 ng l⁻¹) and MeHg⁺ (5 ng l⁻¹). Improved detection limits for Eth are 0.22 ng g⁻¹ for Hg²⁺ and 0.02 ng g⁻¹ for MeHg⁺ (1 g dry sediment sample) and the reproducibility are 5-6% for Hg²⁺ and MeHg⁺ (1-2 ng g⁻¹).     

Multicapillary gas chromatography coupled to inductively coupled plasma-time-of-flight mass spectrometry for rapid mercury speciation analysis

A simple, rapid and accurate method on the basis of multicapillary gas chromatography (MCGC) combined with inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS) was developed for speciation analysis of methylmercury (MeHg⁺) and inorganic mercury (Hg²⁺). The potential of the ICP-TOFMS for transient multi-isotope detection of very short signals (peak width of 0.4 s at half peak height) was evaluated. Two injection systems (purge-and-trap (PTI) and split (SI) injections) were compared in terms of species separation resolution and transient signal profile. Using purge-and-trap injection, after in situ derivatization of the ionic mercury species with sodium tetraethylborate, a baseline separation of MeHg⁺ and Hg²⁺ was achieved within a chromatographic run of <35 s. To correct for matrix-induced ion signal variation and instrumental drift, propylmercury (PrHg⁺) was used as internal standard. Detection limits of 16 and 257 fg g⁻¹ for MeHg⁺ (as Hg) and Hg²⁺, respectively, were achieved. The analytical precision (R.S.D. (%)) for 10 successive injections of a standard mixture containing 10 pg MeHg⁺ (as Hg) and Hg²⁺ was 1.2% for MeHg⁺ and 4.1% for Hg²⁺. The method was validated by analysis of two biological certified reference materials (CRM): a dogfish muscle (DORM-2) and a freeze-dried tuna fish (CRM 464).     

Sequential cloud point extraction for the speciation of mercury in seafood by inductively coupled plasma optical emission spectrometry

A novel nonchromatographic speciation technique for the speciation of mercury by sequential cloud point extraction (CPE) combined with inductively coupled plasma optical emission spectrometry (ICP-OES) was developed. The method based on Hg²⁺ was complexed with I⁻ to form HgI₄²⁻, and the HgI₄²⁻ reacted with the methyl green (MG) cation to form hydrophobic ion-associated complex, and the ion-associated complex was then extracted into the surfactant-rich phase of the non-ionic surfactant octylphenoxypolyethoxyethanol (Triton X-114), which are subsequently separated from methylmercury (MeHg⁺) in the initial solution by centrifugation. The surfactant-rich phase containing Hg(II) was diluted with 0.5 mol L^− 1 HNO₃ for ICP-OES determination. The supernatant is also subjected to the similar CPE procedure for the preconcentration of MeHg⁺ by the addition of a chelating agent, ammonium pyrrolidine dithiocarbamate (APDC), in order to form water-insolvable complex with MeHg⁺. The MeHg⁺ in the micelles was directly analyzed after disposal as describe above. Under the optimized conditions, the extraction efficiency was 93.5% for Hg(II) and 51.5% for MeHg⁺ with the enrichment factor of 18.7 for Hg(II) and 10.3 for MeHg⁺, respectively. The limits of detection (LODs) were 56.3 ng L^− 1 for Hg(II) and 94.6 ng L^− 1 for MeHg⁺ (as Hg) with the relative standard deviations (RSDs) of 3.6% for Hg(II) and 4.5% for MeHg⁺ (C = 10 μg L⁻¹, n = 7), respectively. The developed technique was applied to the speciation of mercury in real seafood samples and the recoveries for spiked samples were found to be in the range of 93.2–108.7%. For validation, a certified reference material of DORM-2 (dogfish muscle) was analyzed and the determined values are in good agreement with the certified values.     

Robust microwave-assisted extraction protocol for determination of total mercury and methylmercury in fish tissues

A rapid and efficient closed vessel microwave-assisted extraction (MAE) method based on acidic leaching was developed and optimized for the extraction of total mercury (Hg), inorganic mercury (Hg²⁺) and methylmercury (CH₃Hg⁺) from fish tissues. The quantitative extraction of total Hg and mercury species from biological samples was achieved by using 5 mol L⁻¹ HCl and 0.25 mol L⁻¹ NaCl during 10 min at 60 °C. Total Hg content was determined using inductively coupled plasma mass spectrometry (ICP-MS). Mercury species were measured by liquid chromatography hyphenated with inductively coupled plasma mass spectrometry (LC-ICP-MS). The method was validated using biological certified reference materials ERM-CE464, DOLT-3, and NIST SRM-1946. The analytical results were in good agreement with the certified reference values of total Hg and CH₃Hg⁺ at a 95% confidence level. Further, accuracy validation using speciated isotope-dilution mass spectrometry (SIDMS, as described in the EPA Method 6800) was carried out. SIDMS was also applied to study and correct for unwanted species transformation reactions during and/or after sample preparation steps. For the studied reference materials, no statistically significant transformation between mercury species was observed during the extraction and determination procedures. The proposed method was successfully applied to fish tissues with good agreement between SIDMS results and external calibration (EC) results. Interspecies transformations in fish tissues were slightly higher than certified reference materials due to differences in matrix composition. Depending on the type of fish tissue, up to 10.24% of Hg²⁺ was methylated and up to 1.75% of CH₃Hg⁺ was demethylated to Hg²⁺.     

Novel methodology for the study of mercury methylation and reduction in sediments and water using <Superscript>197</Superscript>Hg radiotracer

Mercury tracers are powerful tools that can be used to study mercury transformations in environmental systems, particularly mercury methylation, demethylation and reduction in sediments and water. However, mercury transformation studies using tracers can be subject to error, especially when used to assess methylation potential. The organic mercury extracted can be as low as 0.01% of the endogenous labeled mercury, and artefacts and contamination present during methylmercury (MeHg) extraction processes can cause interference. Solvent extraction methods based on the use of either KBr/H₂SO₄ or HCl were evaluated in freshwater sediments using ¹⁹⁷Hg radiotracer. Values obtained for the ¹⁹⁷Hg tracer in the organic phase were up to 25-fold higher when HCl was used, which is due to the coextraction of ¹⁹⁷Hg²⁺ into the organic phase during MeHg extraction. Evaluations of the production of MeHg gave similar results with both MeHg extraction procedures, but due to the higher Hg²⁺ contamination of the controls, the uncertainty in the determination was higher when HCl was used. The Hg²⁺ contamination of controls in the HCl extraction method showed a nonlinear correlation with the humic acid content of sediment pore water. Therefore, use of the KBr/H₂SO₄ method is recommended, since it is free from these interferences. ¹⁹⁷Hg radiotracer (T _1/2 = 2.673 d) has a production rate that is about 50 times higher than that of ²⁰³Hg (T _1/2 = 46.595 d), the most frequently used mercury radiotracer. Hence it is possible to obtain a similar level of performance to ²⁰³Hg when it is used it in short-term experiments and produced by the irradiation of ¹⁹⁶Hg with thermal neutrons, using mercury targets with the natural isotopic composition. However, if the 0.15% natural abundance of the ¹⁹⁶Hg isotope is increased, the specific activity of the ¹⁹⁷Hg tracer can be significantly improved. In the present work, ¹⁹⁷Hg tracer was produced from mercury 51.58% enriched in the ¹⁹⁶Hg isotope, and a 340-fold increase in specific activity with respect to natural mercury targets was obtained. When this high specific activity tracer is employed, mercury methylation and reduction experiments with minimum mercury additions are feasible. Tracer recovery in methylation experiments (associated with Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spike, but also with Hg²⁺ contamination and Me¹⁹⁷Hg artefacts) with marine sediments was about 0.005% g⁻¹ WS (WS: wet sediment) after 20 h incubation with mercury additions of 0.05 ng g⁻¹ WS, which is far below natural mercury levels. In this case, the amount of Hg²⁺ reduced to Hg⁰ (expressed as the percent ¹⁹⁷Hg⁰ recovered with respect to the ¹⁹⁷Hg²⁺ added) varied from 0.13 to 1.6% g⁻¹ WS. Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spike after 20 h of incubation of freshwater sediment ranged from 0.02 to 0.13% g⁻¹ WS with mercury additions of 2.5 ng g⁻¹ WS, which is also far below natural levels. ¹⁹⁷Hg⁰ recoveries were low, 0.0058 ± 0.0013% g⁻¹ WS, but showed good reproducibility in five replicates. Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spiked in freshwater samples ranged from 0.1 to 0.3% over a period of three days with mercury additions of 10 ng L⁻¹. A detection limit of 0.05% for Me¹⁹⁷Hg production from ¹⁹⁷Hg²⁺ spike was obtained in seawater in a 25 h incubation experiment with mercury additions of 12 ng L⁻¹.     

Determination of ultra-trace amount methyl-, phenyl- and inorganic mercury in environmental and biological samples by liquid chromatography with inductively coupled plasma mass spectrometry after cloud point extraction preconcentration

The cloud point extraction (CPE) preconcentration of ultra-trace amount of mercury species prior to reverse-phase high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP-MS) detection was studied. Mercury species including methyl-, ethyl-, phenyl- and inorganic mercury were transformed into hydrophobic chelates by reaction with sodium diethyldithiocarbamate, and the hydrophobic chelates were extracted into a surfactant-rich phase of Triton X-114 upon heating in a water bath at 40 °C. Ethylmercury was found partially decomposed during the CPE process, and was not included in the developed method. Various experimental conditions affecting the CPE preconcentration, HPLC separation, and ICP-MS determination were optimized. Under the optimized conditions, detection limits of 13, 8 and 6 ng l⁻¹ (as Hg) were achieved for MeHg⁺, PhHg⁺ and Hg²⁺, respectively. Seven determinations of a standard solution containing the three mercury species each at 0.5 ng ml⁻¹ level produced relative standard deviations of 5.3, 2.3 and 4.4% for MeHg⁺, PhHg⁺ and Hg²⁺, respectively. The developed method was successfully applied for the determination of the three mercury species in environmental water samples and biological samples of human hair and ocean fish.     

Speciation analysis of mercury in water samples by cold vapor atomic absorption spectrometry after preconcentration with dithizone immobilized on microcrystalline naphthalene

Trace amounts of inorganic mercury (Hg²⁺) and methylmercury cations (MeHg²⁺) were adsorbed quantitatively from acidic aqueous solution onto a column packed with immobilized dithizone on microcrystalline naphthalene. The trapped mercury was eluted with 10 ml of 7 mol L^–1 hydrochloric acid solution. The Hg²⁺ was then directly reduced with tin (II) chloride, and volatilized mercury was determined by cold vapor atomic absorption spectrometry (CVAAS). Total mercury (Hgt) was determined after decomposition of MeHg⁺ into Hg²⁺. Hg²⁺ and MeHg⁺ cations were completely recovered from the water with a preconcentration factor of 200. The relative standard deviation obtained for eight replicate determinations at a concentration of 0.3 g L^–1 was 1.8%. The procedure was applied to analysis of water samples, and the accuracy was assessed via recovery experiment.     

Ionic liquids dispersive liquid–liquid microextraction and HPLC‐atomic fluorescence spectrometric determination of mercury species in environmental waters

An ionic liquid (IL) based dispersive liquid–liquid microextraction combined with HPLC hydride generation atomic fluorescence spectrometry method for the preconcentration and determination of mercury species in environmental water samples is described. Four mercury species (MeHg⁺, EtHg⁺, PhHg⁺, and Hg²⁺) were complexed with dithionate and the neutral chelates were extracted into IL drops using dispersive liquid–liquid microextraction. Variables affecting the formation and extraction of mercury dithizonates were optimized. The optimum conditions found were as follows: IL‐type and amount, 0.05 g of 1‐octyl‐3‐methylimidazolium hexafluorophosphate; dispersive solvents type and amount, 500 μL of acetone; pH, 6; extraction time, 2 min; centrifugation time, 12 min; and no sodium chloride addition. Under the optimized conditions, the detection limits of the analytes were 0.031 μg/L for Hg²⁺, 0.016 μg/L for MeHg⁺, 0.024 μg/L for EtHg⁺, and 0.092 μg/L for PhHg⁺, respectively. The repeatability of the method, expressed as RSD, was between 1.4 and 5.2% (n = 10), and the average recoveries for spiked test were 96.9% for Hg²⁺, 90.9% for MeHg⁺, 90.5% for EtHg⁺, 92.3% for PhHg⁺, respectively. The developed method was successfully applied for the speciation of mercury in environmental water samples.     

Detoxification of mercury species—an in vitro study with antidotes in human whole blood

To investigate the effects of mercury species intoxication and to test the efficiency of different commonly applied antidotes, human whole blood and plasma surrogate samples were spiked with inorganic mercury (Hg²⁺) and methylmercury (MeHg⁺, CH₃Hg⁺) prior to treatment with the antidotes 2,3-dimercaptopropan-1-ol (British Anti Lewisite), 2,3-dimercaptosuccinic acid (DMSA), and N-acetylcysteine (NAC). For mercury speciation analysis in these samples, liquid chromatography was coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionisation time-of-flight mass spectrometry (ESI-TOF-MS). Adduct formation between mercury species and physiological thiols (cysteine and glutathione) was observed as well as the release of glutathione under treatment with the antidotes DMSA and NAC.     

Ultrasound-assisted vapor generation of mercury

Cold vapor generation arising from reduction of both Hg²⁺ and CH₃Hg⁺ occurs using ultrasonic (US) fields of sufficient density to achieve both localized heating as well as radical-based attack in solutions of formic and acetic acids and tetramethylammonium hydroxide (TMAH). A batch sonoreactor utilizing an ultrasonic probe as an energy source and a flow through system based on a US bath were optimized for this purpose. Reduction of CH₃Hg⁺ to Hg⁰ occurs only at relatively high US field density (>10 W cm⁻³ of sample solution) and is thus not observed when a conventional US bath is used for cold vapor generation. Speciation of mercury is thus possible by altering the power density during the measurement process. Thermal reduction of Hg²⁺ is efficient in formic acid and TMAH at 70 °C and occurs in the absence of the US field. Room temperature studies with the batch sonoreactor reveal a slow reduction process, producing temporally broad signals having an efficiency of approximately 68% of that arising from use of a conventional SnCl₂ reduction system. Molecular species of mercury are generated at high concentrations of formic and acetic acid. Factors affecting the generation of Hg⁰ were optimized and the batch sonoreactor used for the determination of total mercury in SLRS-4 river water reference material.     

Inorganic mercury and methylmercury determination in polluted waters by HPLC coupled to cold vapour atomic fluorescence spectroscopy

A systematic study of Hg²⁺ and CH₃Hg⁺ (MeHg⁺) speciation using hyphenated techniques, was performed for high-performance liquid chromatography coupled to on-line UV irradiation and cold-vapour atomic fluorescence spectroscopy (HPLC-UV-CV-AFS). First, a comparative study of the behaviour of three mobile phase compositions (using tetrabutylammonium bromide (TBAB), L-cysteine and ammonium pyrrolidinedithiocarbamate (APDC)) is presented. The separation and detection system was optimised by considering factors that modify fluorescence signal and the separation such as, the addition of different percentages of an organic modifier (methanol (MeOH) and acetonitrile (ACN)) to the mobile phase, the type of reducing agent used (SnCl₂ and NaBH₄) and the potential memory effects of the material of which the injection system is made (stainless steel, PEEK). The mobile phase selected for its sensitivity was a mixture 80?:?20 MeOH?:?0.0015?mol?l^–1 APDC and 0.01?mol?l^–1 NH₄CH₃COO (pH 5.5). The detection and quantification limits were close to 1.5 and 5?µg?l^?1 for both species (as Hg), respectively. Recoveries obtained using fortified water samples of distinct origin (soft mineral, tap, river, seawater, and wastewater), ranged from 90 to 115% for concentrations about 2 and 20 times over quantification limits. Good repeatability was obtained (about 5%) independently of the concentrations, with reproducibility values about 20% at low concentrations and 5–10% at higher concentrations. Our proposed method proved to be straightforward for use by environmental laboratories for routine Hg²⁺ and MeHg⁺ determinations in polluted water samples.     

Determination of methylmercury and inorganic mercury by coupling short-column ion chromatographic separation,on-line photocatalyst-assisted vapor generation,and inductively coupled plasma mass spectrometry

We have combined short-column ion chromatographic separation and on-line photocatalyst-assisted vapor generation (VG) techniques with inductively coupled plasma mass spectrometry to develop a simple and sensitive hyphenated method for the determination of aqueous Hg²⁺ and MeHg⁺ species. The separation of Hg²⁺ and MeHg⁺ was accomplished on a cation-exchange guard column using a glutathione (GSH)-containing eluent. To achieve optimal chromatographic separation and signal intensities, we investigated the influence of several of the operating parameters of the chromatographic and photocatalyst-assisted VG systems. Under the optimized conditions of VG process, the shortcomings of conventional SnCl₂-based VG techniques for the vaporization of MeHg⁺ was overcome; comparing to the concentric nebulizer-ICP-MS system, the analytical sensitivity of ICP-MS toward the detection of Hg²⁺ and MeHg⁺ were also improved to 25- and 7-fold, respectively. With the use of our established HPLC–UV/nano-TiO₂–ICP-MS system, the precision for each analyte, based on three replicate injections of 2 ng/mL samples of each species, was better than 15% RSD. This hyphenated method also provided excellent detection limits—0.1 and 0.03 ng/mL for Hg²⁺ and MeHg⁺, respectively. A series of validation experiments—analysis of the NIST 2672a Standard Urine Reference Material and other urine samples—confirmed further that our proposed method could be applied satisfactorily to the determination of inorganic Hg²⁺ and MeHg⁺ species in real samples.     

Determination of organic and inorganic mercury species in water and sediment samples by HPLC on-line coupled with ICP-MS

This paper describes a preconcentration method for Hg²⁺ and MeHg⁺ in water samples using sodium diethyldithiocarbamate immobilized in polyurethane foam (PU-NaDDC) and an extraction method for several mercury species in sediment samples, including MeHg⁺, EtHg⁺ and PhHg⁺, which is simple, rapid, and uses a single organic solvent. Separation and measurement were done by high-performance liquid chromatography on-line with inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Initially, the test of recovery was applied using procedures compatible with HPLC. Under the optimum extraction conditions, recoveries of 96.7, 96.3 and 97.3% were obtained for MeHg⁺, EtHg⁺, and PhHg⁺, respectively, from n = 4 spiked sediment samples. This study also demonstrates that the combination of solid-phase extraction on PU-NaDDC with HPLC separation and ICP-MS detection is an effective preconcentration procedure for simultaneous measurement of Hg²⁺ and MeHg⁺ at ultra-trace levels in water samples. The application of the proposed procedure to the determination of mercury species in drinking water sample was investigated. The proposed method clearly gave satisfactory average recoveries between 93.7 and 101.5%.     

Liquid-phase microextraction with in-drop derivatization combined with microvolume fluorospectrometry for free and hydrolyzed formaldehyde determination in textile samples

A novel approach for preconcentration and speciation analysis of trace amount of mercury from water samples was proposed by dispersive liquid–liquid microextraction (DLLME) coupled to high performance liquid chromatography with diode array detection (HPLC-DAD). Mercury species (Hg²⁺, methylmercury (MeHg⁺) and phenylmercury (PhHg⁺)) were complexed with dithizone (DZ) to form hydrophobic chelates and then extracted into the fine drops of extraction solvent dispersed in the aqueous sample by dispersive solvent. After extraction, the sedimented phase was analyzed by HPLC-DAD. Some important parameters affecting the DLLME such as extraction solvent and dispersive solvent type and volume, concentration of dithizone solution, sample pH, extraction time and salt effect were investigated. Ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM][PF₆]) was found to be a suitable extractant for the chelates. Under the optimized conditions (extraction solvent: 70 μL of ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM][PF₆]); dispersive solvent: 0.75 mL of methanol containing dithizone (0.02%, m/v); pH: 4; extraction time: 5 min; and without salt addition), the limits of detection for Hg²⁺, MeHg⁺ and PhHg⁺ were 0.32, 0.96 and 1.91 μg L⁻¹ (S N⁻¹ = 3) respectively, and the relative standard deviation (RSD) was between 4.1 and 7.3% (n = 5). Three real water samples (tap water, river water and lake water) spiked with mercury species were detected by the developed method, and the relative recoveries obtained for Hg²⁺, MeHg⁺ and PhHg⁺ were 89.6–101.3%, 85.6–102.0% and 81.3–97.6%, respectively.