Routine analysis of mercury species using commercially available instrumentation: chemometric optimisation of the instrumental variables

Mercury speciation analysis (inorganic mercury, Hg²⁺, methylmercury, CH₃Hg⁺ and dimethylmercury, (CH₃)₂Hg) by gas chromatography (GC) coupled to atomic emission spectroscopy with microwave induced plasma as excitation source (MIP-AES), after ethylation of the sample and extraction of the derivatised species into an organic phase, has been optimised using factorial design, analysis of variance and MultiSimplex techniques. Standard conditions were used in the derivatisation step with sodium tetraethylborate (NaB(C₂H₅)₄) and in the extraction step into hexane. Good separation of the species investigated and maximum sensitivity was achieved using an OV-1701 capillary column. The sensitivity was found to be maximum with an helium flow rate (make-up flow) of 100 ml min⁻¹. Procedures for a correct cleaning of glass and plastic ware, as well as for the purification of reagents used throughout the analytical process, are also suggested in order to avoid unacceptably high blank signals. The effect that ageing of stock solutions used in calibrations has on the artefact formation of CH₃Hg⁺ has been also investigated. Using the optimum conditions found, good quality calibration curves (R²>0.995) for the three mercury species were obtained. Absolute detection limits of 0.5, 3 and 15 pg of (CH₃)₂Hg, CH₃Hg⁺ and Hg²⁺, respectively, were estimated. The repeatability of the analysis was found to be better than 5% (n=5) in relative standard deviation (R.S.D.) units. The optimised procedure for the speciation of mercury in standard samples is the first step in the development of a method for routine analysis of mercury species in aquatic environmental samples.     

Selective detection of mercury(II) and methylmercury(II) via coordination-induced emission of a small-molecule probe

Mercury is one of the major toxic pollutants and has many adverse effects on human health. The main mercury species in the environment or in living organisms are inorganic mercuric ion (Hg²⁺) and organic methylmercury (CH3Hg+). Detection of the two mercury ions is a particularly active topic in the molecular sensing field during the past decade. However, efficient sensors that can sensitively detect and discriminate the two species are rare. In this work, we adopt the concept of restriction of intramolecular rotations which is the basis of aggregation induced emission, and design a molecular probe with pyridyl group as the chelating unit and 1,8-naphthalimide as the fluorescent unit for the detection of both Hg²⁺ and CH₃Hg⁺. When the probe is free in solution, it exhibits weak fluorescence because free intramolecular rotations of the 1,8-naphthalimide moieties non-radiatively annihilate its excited state. However, upon coordination with Hg²⁺ or CH₃Hg⁺, the rotation of 1,8-naphthalimide moieties would be restricted due to the chelation between 1,8-naphthalimide and Hg²⁺ or CH₃Hg⁺, leading to significantly enhanced fluorescent emission. The response induced by Hg²⁺ is much stronger than CH₃Hg⁺; but for specific detection of CH₃Hg⁺, we introduced a T-rich DNA fragment which could completely mask Hg²⁺ in solution. Furthermore, we have employed the sensor for confocal imaging of Hg²⁺ and CH₃Hg⁺in immobilized cells. We expect the probe design tactics can be generally useful for sensing many other analytes.     

Determination of inorganic and total mercury by vapor generation atomic absorption spectrometry using different temperatures of the measurement cell

A simple and inexpensive laboratory-built flow injection vapor generation system coupled to atomic absorption spectrometry (FI-VG AAS) for inorganic and total mercury determination has been developed. It is based on the vapor generation of total mercury and a selective detection of Hg^2 + or total mercury by varying the temperature of the measurement cell. Only the inorganic mercury is measured when the quartz cell is at room temperature, and when the cell is heated to 650 °C or higher the total Hg concentration is measured. The organic Hg concentration in the sample is calculated from the difference between the total Hg and Hg^2 + concentrations. Parameters such as the type of acid (HCl or HNO₃) and its concentration, reductant (NaBH₄) concentration, carrier solution (HCl) flow rate, carrier gas flow rate, sample volume and quartz cell temperature, which influence FI-VG AAS system performance, were systematically investigated. The optimized conditions for Hg^2 + and total Hg determinations were: 1.0 mol l^− 1 HCl as carrier solution, carrier flow rate of 3.5 ml min^− 1, 0.1% (m/v) NaBH₄, reductant flow rate of 1.0 ml min^− 1 and carrier gas flow rate of 200 ml min^− 1. The relative standard deviation (RSD) is lower than 5.0% for a 1.0 μg l^− 1 Hg solution and the limit of quantification (LOQ, 10 s) is 55 ng g^− 1. Certified samples of dogfish muscle (DORM-1 and DORM-2) and non-certified fish samples were analyzed, using a 6.0 mol l^− 1 HCl solution for analyte extraction. The Hg^2 + and CH₃Hg⁺ concentrations found were in agreement with certified ones.     

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⁺.     

Cationic and Anionic Effects on the Glass Transition Temperature for Aqueous Electrolyte Solutions

Glass-forming composition regions of aqueous CH₃COOM (M = Li, Na, K, Rb, Cs, and Tl), CF₃COOM (M = Li, Na, K, Rb, and Cs), and Et₄NX (Et₄ = C₂H₅, X = OH, CH₃COO, Cl, Br, NO₃, and SCN) solutions are reported as a function of water concentration R (R = moles of water per moles of salt). Glass transition temperatures (T _g) were measured by a simple differential thermal analysis (DTA) method with a cooling rate of about 600 K-min^–1. The T _g of all solutions decrease with increasing R (decreasing salt concentration). It is found that T _g at the same R value decrease in the order Na⁺ > Li⁺ > K⁺ > Rb⁺ > Cs⁺ in all glass-forming composition regions of the alkali acetate salt and alkali trifluoroacetate salt solutions. T _g for Et₄NX solutions decrease in the order CH₃COO^– ~OH^– > Cl^– > Br^– > NO ₃ ^– > SCN^–. The effects of the cation and anion on the glass-forming behavior in these aqueous solutions are discussed.     

Assessment of dispersive liquid–liquid microextraction for the simultaneous extraction,preconcentration, and derivatization of Hg2+ and CH3Hg+ for further determination by GC–MS

This work reports the development of a dispersive liquid – liquid microextraction method for the simultaneous extraction, preconcentration, and derivatization of Hg²⁺ and CH₃Hg⁺ species from water samples for further determination by GC – MS. Some parameters of the proposed method, such as volume and type of disperser and extraction solvent, and Na[B(C₆H₅)₄] concentration were investigated using response surface methodology. Suitable recoveries were obtained using 80 μL C₂Cl₄ (as extraction solvent), 1000 μL ethanol (as disperser solvent), and 300 μL 2.1 mmol/L Na[B(C₆H₅)₄] (as derivatizing agent). Accuracy was evaluated in terms of recovery and ranged from 87 to 99% with RSD values <7%. In addition, a certified reference material of water (NIST 1641d) was analyzed and agreed with the certified value about 107% (for Hg²⁺), with RSD values <8.5%. LODs were 0.3 and 0.2 μg/L, with enrichment factors of 112 and 115 for Hg²⁺ and CH₃Hg⁺, respectively. The optimized method was applied for the determination of Hg²⁺ and CH₃Hg⁺ in tap, well, and lake water samples.     

Chelate Complexes with Methylmercury and Phenylmercury Cations

The complex formation of Hg²⁺, CH₃Hg⁺ and C₆H₅Hg⁺ with eight substituted quinolines, α,α′-bipyridyl and 1, 10-phenanthroline has been investigated in water and 75(v)% dioxane by pH and pHg methods. Hg²⁺ forms mercurated products with 8-hydroxyquinolines, if the 5- or 7-positions are unsubstituted. The formation of chelates by CH₃Hg⁺ and C₆H₅Hg⁺ is postulated.     

Copper,nickel, and vanadium in the Western Galician Shelf in early spring after the <Emphasis Type="Italic">Prestige</Emphasis> catastrophe: is there seawater contamination?

A simple and efficient extraction method based on acidic leaching has been developed for measurement of methylmercury (MeHg) in benthic organisms and plant material. Methylmercury was measured by speciated isotope-dilution mass spectrometry (SIDMS), using gas chromatography interfaced with inductively coupled plasma mass spectrometry (GC–ICP–MS). Reagent concentration and digestion temperature were optimized for several alkaline and acidic extractants. Recovery was evaluated by addition of MeHg enriched with CH₃²⁰¹Hg⁺. Certified reference materials (CRM) were used to evaluate the efficiency of the procedure. The final digestion method used 5 mL of 4 mol L^–1 HNO₃ at 55°C to leach MeHg from tissue and plant material. The digest was further processed by aqueous phase ethylation, without interference with the ethylation step, resulting in 96±7% recovery of CH₃²⁰¹Hg⁺ from oyster tissue and 93±7% from pine needles. Methylmercury was stable in this solution for at least 1 week and measured concentrations of MeHg in CRM were statistically not different from certified values. The method was applied to real samples of benthic invertebrates and inter-laboratory comparisons were conducted using lyophilized zooplankton, chironomidae, and notonectidae samples.Contribution No. 15 of the Mercury Experiment to Assess Atmospheric Loadings in Canada and the US (METAALICUS).     

Distribution studies of metal ions on arsenophosphates of Sn(IV) and Cr(III) and on amine Sn(II) hexacyanoferrates (II) using radio tracers: Separation of Sr2+−Cs+, Hg2+−Ag+ and Hg2+−Zn2+

Summary Distribution studies of some metal ions have been made on Sn(IV) and Cr(III) arsenophosphates and on some samples of Sn(II) amine hexacyanoferrates(II), using radiotracers. The K_d values of Cs⁺ and Rb⁺ have been followed at varying HNO₃ concentrations also. As a result 3 useful binary separations have been achieved on Sn(IV) and Cr(III) arsenophosphates, such as Sr²⁺–Cs⁺, Hg²⁺–Ag⁺ and Hg²⁺–Zn²⁺.     

The interaction of water with sulfonium ions and the effects of hydration on the energetics of methyl group transfer: An ab initio molecular orbital study of the hydration of (CH3)3S+ and (CH3)2S+CH2CO2 −

The interactions of the sulfonium ions (CH₃)₃S⁺, (CH₃)₂S⁺CH₂CO₂ ^–, and (CH₃)₂S⁺-CH₂CH₂CO₂ ^– with up to four water molecules have been studied by ab initio molecular orbital methods. Complexes of (CH₃)₃S⁺ with one to three water molecules involve strong electrostatic sulfur-oxygen interactions; in contrast, the sulfide (CH₃)₂S interacts with water molecules via weak S-H hydrogen bonds, suggesting that methyl-group transfer from (CH₃)₃S⁺ in aqueous solution involves a significant alteration of the hydration pattern around the sulfur atom. Two conformers of (CH₃)₂S⁺CH₂CO₂ ^– were found that display sulfur-oxygen distances which are approximately 0.3 å less than the sum of the sulfur and oxygen van der Waals radii, indicating a strong intramolecular electrostatic interaction. For the complexes (CH₃)₂S⁺CH₂CO₂ ^–·nH₂O(n =1–4), water interacts primarily with the carboxylate group via hydrogen bonds, rather than electrostatically with the sulfur atom, although in complexes with the three- and four-water complexes, the proximity of the positively charged sulfur atom to the carboxylate group significantly alters the hydration pattern compared to that in the corresponding of complexes CH₃SCH₂CO₂ ^–· Thus, methyl transfer from (CH₃)₂S⁺CH₂CO₂ ^– to an acceptor in aqueous solution also involves substantial changes in the hydration pattern around the carboxylate group.     

Analytical speciation of mercury in fish tissues by reversed phase liquid chromatography-inductively coupled plasma mass spectrometry with Bi as internal standard

In this work, the quantification of two mercury species (Hg²⁺ and CH₃Hg⁺) in fish tissues has been revisited. The originality of our approach relies on the use of Bi³⁺ as internal standard (IS) and on the modification of typical extraction conditions. The IS (125 μl, 1000 μg l⁻¹ Bi³⁺) was added to the aliquot of fresh fish tissue (400-500 mg). A high-speed blender and ultrasound-assisted homogenization/extraction was carried out in the presence of perchloric acid (1.5 ml, 0.6 mol l⁻¹), l-cysteine (500 μl, 0.75 mol l⁻¹) and 500 μl toluene:methanol (1:1). Perchloric acid was used for protein denaturation and precipitation, toluene helped to destroy lipid structures potentially sequestering CH₃Hg⁺, l-cysteine was used to form water-soluble complexes with Bi³⁺, Hg²⁺ and CH₃Hg⁺. The excess of perchloric acid was eliminated by addition of potassium hydroxide (pH 5 with acetic acid). The obtained extract, was diluted with the mobile phase (1:1) and introduced (20 μl) to the reversed phase HPLC-ICP-MS system. The separation was achieved by isocratic elution (2.5 mmol l⁻¹ cysteine, 12.5 mmol l⁻¹ (NH₄)₂HPO₄, 0.05% triethylamine, pH 7.0:methanol (96:4)) at a flow rate 0.6 ml min⁻¹. Column effluent was on-line introduced to ICP-MS for specific detection of ²⁰²Hg, ²⁰⁰Hg and ²⁰⁹Bi. Analytical signal was defined as the ratio between ²⁰²Hg/²⁰⁹Bi peak areas. The detection limits evaluated for Hg²⁺ and CH₃Hg⁺ were 0.8 and 0.7 μg l⁻¹. Recovery of the procedure, calculated as the sum of species concentrations found in the sample with respect to total ICP-MS-determined Hg was 91.9% for king mackerel muscle and 89.5% for red snapper liver. In the standard addition experiments, the recovery results were 98.9% for Hg²⁺ and 100.6% for CH₃Hg⁺. It should be stressed that the use of Bi³⁺ as IS enabled to improve analytical performance by compensating for incomplete extraction and for imprecision of sample handling during relatively non-rigorous protocol.     

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.     

Abtrennung von toxischen Schwermetallen aus L?sungen mit chelatbildenden Celluloseaustauschern

Zusammenfassung Die Abtrennung von Spurenelementen (Hg, Cd, As, Mo, Cr) an drei Celluloseaustauschern mit chelatbildenden Ankergruppen wird beschrieben. An den Austauschern mit den Ankergruppen o-Aminothiophenol und Glyoxal-bis(2-mercaptoanil) werden hohe Verteilungskoeffizienten für Hg²⁺, Hg ₂ ²⁺ , CH₃Hg⁺ und Cd²⁺ gefunden, niedrigere für Arsenit und Arsenat; (CH₃)₂Hg wird nicht gebunden. Der mit Fe³⁺ beladene Hyphan-Austauscher weist hohe Verteilungskoeffizienten für Arsenat auf, etwas niedrigere für Arsenit, Chromat und Molybdat. In Trennsäulen werden die Kationen Hg²⁺ und Cd²⁺ und die Anionen Arsenat und Molybdat voneinander getrennt.

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Separation of toxic heavy metals from solutions by means of chelating cellulose exchanges

Summary The separation of trace elements (Hg, Cd, As, Mo, Cr) on three cellulose exchangers with chelating anchor groups is described. On exchangers with the anchor groups o-aminothiophenol and glyoxal-bis(2-mercaptoanil) high distribution coefficients are found for Hg²⁺, Hg ₂ ²⁺ , CH₃Hg⁺ and Cd²⁺, lower ones for arsenite and arsenate; (CH₃)₂Hg is not bound. The exchanger Hyphan loaded with Fe³⁺ shows high distribution coefficients for arsenate, somewhat lower ones for arsenite, chromate and molybdate. In separation columns the cations Hg²⁺ and Cd²⁺ and the anions arsenate and molybdate are separated from each other.

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Herrn Prof. Dr. H. Weisz zum 60. Geburtstag gewidmet     

Application of stable isotopes in environmental tracer studies – Measurement of monomethylmercury (CH3Hg+) by isotope dilution ICP-MS and detection of species transformation

The monovalent cation monomethylmercury (CH₃Hg⁺) was determined in certified reference materials by isotope dilution GC/ICP-MS and good agreement between measured and certified values has been found. The use of enriched stable isotopes with subsequent detection by ICP-MS is a powerful tracer technique to study dynamic environmental processes. For the first time, it was possible to monitor opposite processes like Hg²⁺ methylation and CH₃Hg⁺ demethylation at ambient tracer levels simultaneously in the same sample. A scheme for calculating the formation of new species from stable tracers used in environmental studies is presented. The sensitivity of stable tracer methods is superior to traditional tracer or radiotracer techniques. In case of mercury methylation, where the generation of a new compound is monitored, the limit of detection depends only on the precision of the isotope ratio measurements and the concentration of the ambient CH₃Hg⁺ already present in the sample, not on the absolute detection limit of the GC/ICP-MS technique used for analyzing CH₃Hg⁺. A 0.25% change in concentration of CH₃Hg⁺ is detectable. In the case of CH₃Hg⁺ demethylation, where the decrease of the added tracer is monitored, the detection limit again depends on the precision of the isotope ratio measurement and the ambient CH₃Hg⁺ concentration but additionally on the amount of the added tracer as well. A decrease in the CH₃Hg⁺ level of 2% of the added tracer is detectable. The validity of the calculation scheme was tested and no difference was found between individually measured isotope concentrations and calculated concentrations from solutions with multiple stable tracers.     

Preconcentration and speciation of inorganic and methyl mercury in waters using polyaniline and gold trap-CVAAS

Applicability of polyaniline (PANI) has been investigated for the preconcentration and speciation of inorganic mercury (Hg²⁺) and methyl mercury (CH₃Hg⁺) in various waters (ground, lake and sea waters). Preliminary experiments (batch) with powdered PANI for the quantitative removal of both Hg²⁺ and CH₃Hg⁺ showed that the retention of Hg²⁺ was almost independent of pH while a pH dependent trend from pH 1 to 12 was seen for CH₃Hg⁺ with maximum retention at pH > 5. Time dependence batch studies showed that a contact time of 10 min was sufficient to reach equilibrium. The K_d values were found to be ∼8 × 10⁴ and ∼7 × 10³ for Hg²⁺ and CH₃Hg⁺, respectively.Subsequently column experiments were carried out with PANI and the separation of the species was carried out by selective and sequential elution with 0.3% HCl for CH₃Hg⁺ and 0.3% HCl-0.02% thiourea for Hg²⁺. This was then followed by further pre-concentration of mercury on a gold trap and its determination by CVAAS. The uptake efficiency studies showed that the PANI column was able to accumulate up to 100 mg Hg²⁺/g and 2.5 mg CH₃Hg⁺/g. This method allows both preconcentration and speciation of mercury with preconcentration factors around 120 and 60 for Hg²⁺ and CH₃Hg⁺, respectively. The interfering effects of various foreign substances on the retention of mercury were investigated.     

Exchange of mercury between mercuric ions and methylmercuric nitrate

The rate constant for the exchange between Hg²⁺ and CH₃Hg⁺ ions in a Cl-free 1NH₂SO₄ solution at 25°C was measured with²⁰³Hg as a radiotracer and separation of the two compounds by liquid extraction of the organic species into benzene from a NaCl- or NaI-solution.     

Novel properties of molecular assemblies of isoprenoid surfactants

Unlike micelles of straight hydrocarbon chain-surfactants, isoprenoid surfactants, CH₃ [CH(CH₃)CH₂CH₂CH₂]₃ CH(CH₃)CH₂–R (R=CH₂N⁺ (CH₃)₃ Br^–, CH₂OPO₃H^– Na⁺, CH₂OSO ₃ ^– Na⁺, CO ₂ ^– Na⁺), gave large globular and cellular assemblies in water which could be observed directly by transmission electron microscopy; critical micelle concentration of 0.31.4×10^–3 M at 20°C, aggregation number of 215×10⁴, and diameter of 200–2000 Å. A basic structure of the assemblies was a thin layer with a thickness (about 30 Å) which was close to the molecular length of the surfactants. The assemblies were decomposed during gel column chromatography; viz., they were not as stable as the liposomes of lecithins. The morphology was discussed in conjunction with a steric effect of the isoprenoid chain.     

Effect of selenium on the Hg,Zn, Fe and Co content of yeast cells

The yeast cells, Saccharomyces cerevisiae, were exposed to Hg²⁺ ions (10^–4M) and SeO₂ (2·10^–4–10^–2M) or Se- methionine (2·10^–4M). Instrumental neutron activation analysis (INAA) was used to analyze changes in the Hg, Zn, Fe and Co levels in these cells. When the yeast was incubated in a medium containing 10^–3M and 10^–2M SeO₂, the Hg content of the yeast markedly increased. It was also found that the uptake of Se and Hg influenced the levels of Zn, Fe and Co found in the cells. While the presence of Se-methionine (Se-Met), SeO₂ or Hg²⁺ ions caused increases in the intracellular Zn levels, the combined presence of Hg²⁺ and SeO₂ and their assumed interaction, reduced the efficiency of Se for increasing the Zn content of yeast.     

Analysis of inorganic mercury species associated with airborne particulate matter/aerosols: method development

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP–MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg⁰, HgCl₂, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50° min^–1, different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg⁰, HgCl₂, HgO, and HgS species from these samples were detected.     

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.