Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with gas chromatography–mass spectrometry

A solid-phase extraction (SPE) using multi-walled carbon nanotubes (MWCNTs) as adsorbent coupled with gas chromatography–mass spectrometry (GC–MS) method was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Several condition parameters, such as extraction adsorbents, elution solvents and volumes, and sample loading flow rate and volume were optimized to obtain high SPE recoveries and extraction efficiency. 150 mg MWCNTs as sorbent presented high extraction efficiency of 16 PAHs due to the large specific surface area and high adsorption capacity of MWCNTs compared with the commercial C18 column (250 mg/2 mL). The calibration curves of 16 PAHs extracted were linear in the range of 20–5000 ng L⁻¹, with the correlation coefficients (r²) between 0.9848 and 0.9991. The method attained good precisions (relative standard deviation, RSD) from 1.2% to 12.1% for standard PAHs aqueous solutions; method recoveries ranged in 76.0–125.5%, 74.5–127.0%, and 70.0–122.0% for real spiked samples from river water, tap water and seawater, respectively. Limits of detection (LODs, S/N = 3) of the method were determined from 2.0 to 8.5 ng L⁻¹. The optimized method was successfully applied to the determination of 16 PAHs in real environmental water samples.     

Determination of organic priority pollutants in sewage treatment plant effluents by gas chromatography high-resolution mass spectrometry

In this work, we report the development and validation of an analytical method for the trace level determination of 14 selected (EU-directive) priority organic pollutants (namely, 1,2,3-trichlorobenzene (1,2,3-TCB), 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, hexachloro-1,3-butadiene, pentachlorobenzene, hexachlorobenzene, alachlor, α-hexachloro-cyclohexane (α-HCH), β-HCH, γ-HCH (lindane), δ-HCH, tetra-brominated diphenyl ether (tetra-BDE), penta-brominated diphenyl ether and hepta-brominated diphenyl ether) in wastewater samples from 5 different sewage treatment plants (STPs) located in Spain. The proposed methodology is based on liquid-liquid extraction with n-hexane followed by identification and confirmation of the selected pollutants by gas chromatography high-resolution mass spectrometry in selected ion recording acquisition mode. Recovery studies performed with spiked wastewater samples at two different concentration levels (0.1 and 1 μg L⁻¹) gave mean recoveries in the range 80-120% (except for trichlorobenzenes, ca. with 50%) with RSD values below 10% in most cases, thus confirming the usefulness of the proposed methodology for the analyses of this kind of complex samples. The obtained detection limits in effluent wastewater matrices were in the low nanogram per liter range, with values as low as 0.09 ng L⁻¹ for tetra-BDE and 0.3 ng L⁻¹ for hexachlorobenzene. Finally, the proposed methodology was successfully applied to a monitoring study intended to characterize wastewater effluents of 5 different sewage treatment plants with different major activities (Industrial, Coastal, Urban). Most of the compounds targeted were detected in the ng L⁻¹ range at concentrations ranging from 0.19 ng L⁻¹ to 135 ng L⁻¹ (hexachlorobenzene).     

Quantification of 13 priority polycyclic aromatic hydrocarbons in human urine by headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry

Polycyclic aromatic hydrocarbons (PAHs) are common environmental pollutants in both living and working environments. The aim of this study was the development of a headspace solid-phase microextraction gas chromatography-isotope dilution mass spectrometry (HS-SPME/GC-IDMS) method for the simultaneous quantification of 13 PAHs in urine samples. Different parameters affecting PAHs extraction by HS-SPME were considered and optimized: type/thickness of fiber coatings, extraction temperature/time, desorption temperature/time, ionic strength and sample agitation. The stability of spiked PAHs solutions and of real urine samples stored up to 90 days in containers of different materials was evaluated. In the optimized method, analytes were absorbed for 60 min at 80 °C in the sample headspace with a 100 μm polydimethylsiloxane fiber. The method is very specific, with linear range from the limit of quantification to 8.67 × 10³ ng L⁻¹, a within-run precision of <20% and a between-run precision of <20% for 2-, 3- and 4-ring compounds and of <30% for 5-ring compounds, trueness within 20% of the spiked concentration, and limit of quantification in the 2.28-2.28 × 10¹ ng L⁻¹ range. An application of the proposed method using 15 urine samples from subjects exposed to PAHs at different environmental levels is shown.     

Analysis of chloroacetanilide herbicides in water samples by solid-phase microextraction coupled with gas chromatography-mass spectrometry

A solid-phase microextraction (SPME) method has been developed for the determination of 3 chloroacetanilide herbicides in both fresh and seawater samples. The extracted sample was analyzed by gas chromatography with mass spectrometry detection (GC-MS), and parameters affecting SPME operation including fibre type, sample pH, sample temperature, mixing speed and extraction time have been evaluated and optimized. The amount of dissolved organic matter (DOM) and the salt content both affected SPME extraction efficiency, but the presence of other competitive extractants such as organochlorine pesticides (OCPs) in the matrix showed no insignificance interference. The limit of detection (LOD) for acetochlor, metolachlor and butachlor were 1.2, 1.6 and 2.7 ng L⁻¹, respectively. The recoveries for the herbicides ranged from 79 to 102%, and the linear dynamic range was from 10 to 1000 ng L⁻¹. The developed method has been used to monitor herbicides contaminations in coastal water samples collected around Laizhou bay and Jiaozhou bay in Shandong peninsula, China. The concentrations of acetochlor and metolachlor ranged from undetectable to 78.5 ng L⁻¹ and undetectable to 35.6 ng L⁻¹, respectively. Butachlor was not observed but in only one sample and the concentration is lower than the limit of quantification (LOQ). The concentrations of the three herbicides in this study are low compared to most of the other places reported.     

Determination of total arsenic in seawater by hydride generation atomic fluorescence spectrometry

In this work, the determination of total As in seawater by hydride generation atomic fluorescence spectrometry was studied. The influence of the chemical, flow and instrumental parameters were investigated and optimized. The pre-reduction of As(V) to As(III) was performed using KI plus ascorbic acid in 3.5 mol L^− 1 HCl medium. No multiplicative interference was present and external aqueous calibration could be used. The limit of detection was 36 ng L^− 1, while the repeatability was 2% (n = 10), at a 500 ng L^− 1 concentration level. The sample throughput was 15 h^− 1 if triplicate measurements were made. The accuracy was assessed by the analysis of a seawater certified reference material and excellent agreement between the obtained and certified values was verified. The procedure was used for the analysis of seawater offshore samples collected at the Brazilian coast and results ranging from 860 to 1200 ng L^− 1 were found.     

Leachability and analytical speciation of antimony in coal fly ash

A new procedure was described with multiwalled carbon nanotubes as solid phase extraction packing material for the trace analysis of nicosulfuron, thifensulfuron and metsulfuron-methyl in water samples. The possible parameters influencing the enrichment were optimized and the optimal conditions were as followed: eluent, sample pH, flow rate and sample volume were acetonitrile containing 1% acetic acid, pH 3, 8 mL min⁻¹ and 500 mL, respectively. Under the optimal chromatographic separation and SPE conditions, the linear range, detection limit (S/N = 3) and precision (R.S.D., n = 6) were 0.04-40 ng mL⁻¹, 6.8 ng L⁻¹ and 2.5% for nicosulfuron, 0.04-40 ng mL⁻¹, 11.2 ng L⁻¹ and 5.4% for thifensulfuron, 0.02-20 ng mL⁻¹, 5.9 ng L⁻¹, 2.1% for metsulfuron-methyl, respectively. The established method was well employed to determine nicosulfuron, thifensulfuron and metsulfuron-methyl in tap water, seawater, reservoir water and well water samples, and satisfactory results were obtained, the spiked recoveries in the range of 87.2-100.7%, 96.5-105.6% and 83.7-111.1% for them each, respectively.     

Preparation and characterization of metal-organic framework MIL-101(Cr)-coated solid-phase microextraction fiber

Metal-organic frameworks (MOFs) have received great attention as novel sorbents due to their fascinating structures and intriguing potential applications in various fields. In this work, a MIL-101(Cr)-coated solid-phase microextraction (SPME) fiber was fabricated by a simple direct coating method and applied to the determination of volatile compounds (BTEX, benzene, toluene, ethylbenzene, m-xylene and o-xylene) and semi-volatile compounds (PAHs, polycyclic aromatic hydrocarbons) from water samples. The extraction and desorption conditions of headspace SPME (HS-SPME) were optimized. Under the optimized conditions, the established methods exhibited excellent extraction performance. Good precision (<7.7%) and low detection limits (0.32–1.7 ng L⁻¹ and 0.12–2.1 ng L⁻¹ for BTEX and PAHs, respectively) were achieved. In addition, the MIL-101(Cr)-coated fiber possessed good thermal stability, and the fiber can be reused over 150 times. The fiber was successfully applied to the analysis of BTEX and PAHs in river water by coupling with gas chromatography–mass spectrometry (GC–MS). The analytes at low concentrations (1.7 and 10 ng L⁻¹) were detected, and the recoveries obtained with the spiked river water samples were in the range of 80.0–113% and 84.8–106% for BTEX and PAHs, respectively, which demonstrated the applicability of the self-made fiber.     

Solid phase extractive preconcentration coupled to gas chromatography-atomic emission detection for the determination of chlorophenols in water samples

Solid-phase extraction (SPE) followed by derivatization and gas chromatography-atomic emission detection (GC-AED) was evaluated for the determination of five chlorophenols (CPs) in water samples. The derivatization was based on the esterification of phenolic compounds with ferrocenecarboxylic acid. The determination of the derivatized phenols was performed by GC-AED in the iron selective detection mode at 302 nm. The described method was tested on spiked water samples.The overall method gave detection limits of 1.6-3.7 ng L⁻¹ and recoveries of 90.9-104.5% for the examined mono- to trichlorophenols in 10 mL water samples. The CPs extracted from a 10 mL water sample with SPE were concentrated into 100 μL of organic solvent, a preconcentration factor of 100. The method was applied to lake and tap water samples, and CP contents between 6 and 51 ng L⁻¹ in lake water and between below the detection limit and 8 ng L⁻¹ in tap water were found for different CPs. The method is quick, simple and gives excellent recoveries, limits of detection and standard deviations.     

Highly sensitive and selective fluorescence optosensor to detect and quantify benzo[a]pyrene in water samples

We describe here a method for detecting and quantifying the highly carcinogenic polycyclic aromatic hydrocarbon (PAH) benzo[a]pyrene (BaP) in water, based on a flow-trough optical sensor. The technique is fast (response time of 40 s) and simple and at the same time meets the standards of sensitivity and selectivity required by the European Guidelines on Water for Human Consumption. The optosensor is based on the on-line immobilization of BaP on a non-ionic resin (Amberlite XAD-4) solid support in a continuous-flow system. BaP was analyzed in a 15 mM H₂PO₄⁻/HPO₄²⁻ buffer solution with 25% (v/v) 1,4-dioxane at pH 7. Fluorescence intensity was measured at λ_ex/em=392/406 nm. The experimental conditions (reagent phase, pH, type and concentration of buffer solution and organic solvent) and flow-injection values (flow rate and injection volume) were carefully controlled. Under these conditions the optosensor was sensitive to a linear concentration range of between 3.0 and 250.0 ng l⁻¹ with a detection limit of 3.0 ng l⁻¹ and a standard deviation of 1.5% at 150 ng l⁻¹. The optosensor was applied to the quantification of BaP in drinking and waste water samples (95-105% recovery) in presence of the other 15 EPA PAHs at 1000 ng l⁻¹ concentration level. The influence of other fluorescent polycyclic aromatic hydrocarbons and potential interference from ions usually present in water was also evaluated.     

Determination of copper, cadmium and lead in seawater and mineral water by flame atomic absorption spectrometry after coprecipitation with aluminum hydroxide

An aluminum hydroxide coprecipitation method for the determination of cadmium, copper and lead by flame atomic absorption spectrometry in aqueous solutions, seawater and mineral water samples has been investigated. The coprecipitation conditions, such as the effect of the pH, the amount of carrier element, the effect of possible matrix ions and the time were examined in detail for the studied elements. It was found that cadmium, copper and lead are co-precipitated quantitatively (≥95%) with aluminum hydroxide at pH 7 with low R.S.D. values of around 2 to 3%. Detection limits (38) were 6 ng ml⁻¹ for Cd, 3 ng ml⁻¹ for Cu and 16 ng ml⁻¹ for Pb. The method proposed was validated by the analysis of HPS 312205 seawater standard reference material and spiked mineral water samples.     

Online anion exchange column preconcentration and high performance liquid chromatographic separation with inductively coupled plasma mass spectrometry detection for mercury speciation analysis

A hyphenated method for mercury speciation analysis by the coupling of high performance liquid chromatography and inductively coupled plasma mass spectrometry with the online strong anion exchange column (SAX) preconcentration was developed. The Hg analytes (Hg⁺, MeHg, EtHg and Hg²⁺) were absorbed on the SAX column preconditioned with sodium 3-mercapto-1-propanesulfonate, and then rapidly eluted (less than 16 s) by 5 μL 3% (v/v) 2-mercaptoethanol. The enrichment factors of 1025 for Hg⁺, 1084 for MeHg, 1108 for EtHg and 1046 for Hg²⁺ were obtained using 6 mL sample in a 1.5-min enrichment procedure. Rapid separation of the four mercurial compounds was achieved within 5 min on a 50-mm C₁₈ column using 0.5% (v/v) 2-mercaptoethanol as the mobile phase. The detection limits for Hg⁺, MeHg, EtHg and Hg²⁺ were 0.015, 0.010, 0.009 and 0.016 ng L⁻¹, each, and the relative standard deviations of peak height and peak area (5 ng L⁻¹ for each Hg species) were all below 5%. Mercury speciation in three freshwater, two drinking water and two seawater samples were then analyzed by the proposed method. MeHg and Hg²⁺ concentrations down to 0.14 and 0.56 ng L⁻¹ were detected in the drinking waters.     

Assessing selected estrogens and xenoestrogens in Brazilian surface waters by liquid chromatography-tandem mass spectrometry

A sensitive and specific method was developed and validated for the determination of estrogen and xenoestrogen in surface waters using liquid chromatography followed by tandem mass spectrometry. Chromatographic separation was performed using ammonium hydroxide solutions in water and in methanol as mobile phase. Compounds were determined in a triple quadrupole mass spectrometer equipped with an electrospray ionization interface operating in the negative mode. Multiple reaction monitoring conditions were optimized for estrone, 17β-estradiol, estriol, 17α-ethinylestradiol, bisphenol A, 4-n-octylphenol, and 4-n-nonylphenol. The method was linear from 0.1 ng L^− 1 to 10 µgL^− 1. Limits of quantification varied between 0.1 and 3.1 ng L^− 1 and recoveries for a 50 ng L^− 1 spiked-surface water solution varied between 72 and 140%. The method was successfully used to determine estrogen and xenoestrogen levels in Brazilian water samples collected along the Atibaia River Basin, in the State of São Paulo. Concentrations of estrogens varied from 2.2 to 39 ng L^− 1. Bisphenol A was the most frequently detected compound as well as the only xenoestrogen in the samples with concentrations between 25 and 84 ng L^− 1.     

Supramolecular solvent-based extraction of benzimidazolic fungicides from natural waters prior to their liquid chromatographic/fluorimetric determination

A supramolecular solvent made up of vesicles of decanoic acid in the nano- and microscale regimes dispersed in a continuous aqueous phase is proposed for the extraction/preconcentration of benzimidazolic fungicides (BFs) from river and underground water samples prior to their determination by liquid chromatography (LC)/fluorimetry. The solvent is produced from the coacervation of decanoic acid aqueous vesicles by the action of tetrabutylammonium (Bu₄N⁺). Carbendazim (CB), thiabendazole (TB) and fuberidazole (FB) are extracted on the basis of hydrophobic and π-cation interactions and the formation of hydrogen bonds. The extraction provides high preconcentration factors (160 for CB and 190 for TB and FB), requires a short time (the procedure takes less than 20 min and several samples can be simultaneously processed) and a low sample volume (20 mL), and avoids the use of toxic organic solvents. Because of the absence of matrix interferences and the low viscosity of the extracts, these can be directly injected into the chromatographic system without the need of cleaning-up or diluting them. Recoveries are not influenced by the presence of salt concentrations up to 1 M. The proposed method provides detection limits for the determination of CB, TB and FB in natural waters of 32, 4 and 0.1 ng L⁻¹, respectively, and a precision, expressed as relative standard deviation (n = 11) of 5.5% for CB (100 ng L⁻¹), 4.0% for TB (80 ng L⁻¹) and 2.5% for FB (30 ng L⁻¹). Recoveries obtained by applying this approach to the analysis of river and underground water samples fortified at the ng L⁻¹ level are in the intervals 75–83, 95–102 and 97–101% for CB, TB and FB, respectively.     

New approach to quantitative analysis of benzo[a]pyrene in food supplements by an immunochemical column test

A quantitative immunochemical rapid test for sensitive determination of benzo[a]pyrene (BAP) as a model analyte was developed making use of a handheld reader for results evaluation. The covalent immobilization of antibodies to different Sepharose gels, i.e., CNBr-activated Sepharose 4B and CNBr-activated Sepharose 4 Fast Flow was compared with adsorption to a polyethylene support. The lowest limits of detection (LOD) were 4 ng L⁻¹ and 40 ng L⁻¹, respectively, using optimized assay conditions. The developed test was applied to food supplements (garlic, black radish and maca), including a pretreatment procedure. LOD of 9 ng kg⁻¹ and linear range of 13-80 ng kg⁻¹ were obtained. Results of BAP determination in naturally contaminated samples were confirmed by high-performance liquid chromatography coupled to fluorescence detection and a good correlation was achieved. We suggest that the developed test format can be used to quantitative detection of the low molecular weight analytes, such as mycotoxins, pesticides, other pollutants in food and environmental samples.     

A validated analytical method for the determination of perfluorinated compounds in surface-, sea- and sewagewater using liquid chromatography coupled to time-of-flight mass spectrometry

Perfluorinated compounds (PFCs), which are extensively used in a wide variety of applications because of their specific surfactant properties, have recently appeared as an important new class of global environmental pollutants. Quantitative analysis of PFCs in aqueous matrices remains, however, a challenging task. During this study, a new analytical method for the determination of 14 PFCs in surface-, sewage- and seawater was developed and validated. The target analytes were extracted using solid-phase extraction followed by liquid chromatography coupled to a time-of-flight mass spectrometer (LC–ToF-MS). The use of very narrow mass tolerance windows (<10 ppm) resulted in a highly selective MS-technique for the detection of PFCs in complex aqueous matrices. Validation of this analytical method in surface-, sewage- and seawater resulted in limits of quantification (LOQs) varying from 2 to 200 ng L⁻¹, satisfying recoveries (92–134%), and good linearity (R² = 0.99 for most analytes). Analysis of samples of the North Sea, the Scheldt estuary, and three harbours of the Belgian coastal region led to the detection of four different PFCs. Perfluorooctane sulfonate (PFOS) was found to be the most abundant PFC in levels up to 38.9 ng L⁻¹.     

Single-walled carbon nanotubes as solid-phase microextraction adsorbent for the determination of low-level concentrations of butyltin compounds in seawater

Carbon nanotubes are a kind of new carbon-based nanomaterials, which have drawn great attention in many application fields. The potential of single-walled carbon nanotubes (SWCNTs) as solid-phase microextraction (SPME) adsorbent for the preconcentration of environmental pollutants has been investigated in recent years. In the present study, the feasibility of SWCNTs as SPME adsorbent for the determination of monobutyltin, dibutyltin and tributyltin in seawater samples was studied. To achieve this aim, the potential factors affecting the SPME efficiency, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity were optimized. The developed method showed good performance according to the ICH (International Conference on Harmonization of Technical Requirements for Analytical Methods) criteria. The acquired calibration curves were linear (r ≥ 0.992) over the concentration range from ≤12 to 2000 ng L⁻¹. For all of the analytes, the limit of detection at signal-to-noise ratio of 3 was below 5 ng L⁻¹. Furthermore, in comparison with the commercial carboxen/polydimethylsiloxane fiber, the developed SWCNT fiber showed better thermal stability (over 350 °C) and longer life span (over 150 times). The application of the proposed method in environmental analyses was shown by analyzing seawater samples from the harbors on the Persian Gulf for butyltin residues. Some of the butyltins were detected in the analyzed samples. Results of the present study demonstrate the feasibility of the SWCNTs as SPME adsorbent for the determination of butyltins in seawater samples.     

Application of sulfur microparticles for solid-phase extraction of polycyclic aromatic hydrocarbons from sea water and wastewater samples

The application of sulfur microparticles as efficient adsorbents for the solid-phase extraction (SPE) and determination of trace amounts of 10 polycyclic aromatic hydrocarbons (PAHs) was investigated in sea water and wastewater samples using high performance liquid chromatography coupled with an ultraviolet detector (HPLC–UV). Parameters influencing the preconcentration of PAHs such as the amount of sulfur, solution flow rate and volume, elution solvent, type and concentration of organic modifier, and salt effect were examined. The results showed that at a flow rate of 10 mL min⁻¹ for the sample solutions (100 mL), the PAHs could be adsorbed on the sulfur microparticles and then eluted by 2.0 mL of acetonitrile. For HPLC–UV analysis of extracted PAHs, the calibration curves were linear in the range of 0.05–80.0 μg L⁻¹; the coefficients of determinations (r²) were between 0.9934 and 0.9995. The relative standard deviations (RSDs) for eight replicates at two concentration levels (0.5 and 4.0 μg L⁻¹) of PAHs were lower than 7.3%, under optimized conditions. The limits of detection (LODs, <!-- no-mfc -->S/N<!-- /no-mfc --> = 3) of the proposed method for the studied PAHs were 0.007–0.048 μg L⁻¹. The recoveries of spiked PAHs (0.5 and 4 μg L⁻¹) in the wastewater and sea water samples ranged from 78% to 108%. The simplicity of experimental procedure, high extraction efficiency, short sample analysis, and using of low cost sorbent demonstrate the potential of this approach for routine trace PAH analysis in water and wastewater samples.     

Dispersive liquid-liquid microextraction combined with high performance liquid chromatography-fluorescence detection for the determination of carbendazim and thiabendazole in environmental samples

A rapid and sensitive method for the determination of carbendazim (methyl benzimidazole-2-ylcarbamate, MBC) and thiabendazole (TBZ) in water and soil samples was developed by using dispersive liquid-liquid microextraction (DLLME) coupled with high performance liquid chromatography with fluorescence detection. The water samples were directly used for the DLLME extraction. For soil samples, the target analytes were first extracted by 0.1 mol L⁻¹ HCl. Then, the pH of the extract was adjusted to 7.0 with 2 mol L⁻¹ NaOH before the DLLME extraction. In the DLLME extraction method, chloroform (CHCl₃) was used as extraction solvent and tetrahydrofuran (THF) as dispersive solvent. Under the optimum conditions, the enrichment factors for MBC and TBZ were ranged between 149 and 210, and the extraction recoveries were between 50.8 and 70.9%, respectively. The linearity of the method was obtained in the range of 5-800 ng mL⁻¹ for water sample analysis, and 10-1000 ng g⁻¹ for soil samples, respectively. The correlation coefficients (r) ranged from 0.9987 to 0.9997. The limits of detection were 0.5-1.0 ng mL⁻¹ for water samples, and 1.0-1.6 ng g⁻¹ for soil samples. The relative standard deviations (RSDs) varied from 3.5 to 6.8% (n = 5). The recoveries of the method for MBC and TBZ from water samples at spiking levels of 5 and 20 ng mL⁻¹ were 84.0-94.0% and 86.0-92.5%, respectively. The recoveries for soil samples at spiking levels of 10 and 100 ng g⁻¹ varied between 82.0 and 93.4%.     

A simple method for methylmercury,inorganic mercury and ethylmercury determination in plasma samples by high performance liquid chromatography–cold-vapor-inductively coupled plasma mass spectrometry

A simple and sensitive method with a fast sample preparation procedure is proposed for the determination of mercury species in plasma/serum. The method combines online high-performance liquid chromatography separation, Hg cold-vapor formation and inductively coupled plasma mass spectrometry detection. Prior to analysis, plasma (250 μL) was accurately pipetted into 15 mL conical tubes. Then, an extractant solution containing mercaptoethanol, L-cysteine and HCl was added to the samples following sonication for 10 min. Quantitative mercury extraction was achieved with the proposed procedure. Separation of mercury species was accomplished in less than 8 min on a C8 reverse phase column with a mobile phase containing 3% v/v methanol + 97% v/v (0.5% v/v 2-mercaptoethanol + 0.05% v/v formic acid). The method detection limits were found to be 12 ng L⁻¹, 5 ng L⁻¹ and 4 ng L⁻¹ for inorganic mercury, ethylmercury and methylmercury, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from NIST. Additional validation was provided by the analysis of a secondary reference serum sample from the INSQ-Canada. Finally, the method was successfully applied for the speciation of mercury in plasma samples collected from volunteers exposed to methylmercury through fish consumption. For the first time to our knowledge, levels of different species of Hg in plasma samples from riverside populations exposed to MeHg were determined.     

Method optimization for the determination of four mercury species by micro-liquid chromatography-inductively coupled plasma mass spectrometry coupling in environmental water samples

A method based on the coupling microHPLC-microneb-ICPMS has been developed for Hg(II), MeHg⁺, EtHg⁺ and PhHg⁺ species. Gradient elution using methanol and l-cysteine at pH 3.0 allowed the chromatographic separation of all species in less than 13 min (total analysis time 15 min). The direct coupling of microLC to ICPMS through a Micromist nebulizer permits the analysis of environmental water without sample pretreatment and derivatization steps. Nebulizer type, organic modifier and column length were the main parameters tested. The methanol content and pH of the mobile phase greatly affected the retention time and sensitivity of the method. Key factors to obtain high signal to noise ratio, at concentrations below 1 μg L⁻¹, were found to be the nebulization step and traces of Hg present in the complexing agent. A detailed optimization of carrier and make up gas flow rates have enabled the nebulization of the methanol gradient elution with good mass transport efficiency, low organic solvent loading into the plasma and excellent precision.The performance of the microHPLC-microneb-ICPMS method developed was evaluated on a surface water sample filtered (0.22 μm) and spiked with 0.5 μg L⁻¹ (as Hg) of each species. Precision (R.S.D., n = 6) for all species of Hg varied from 0.5 to 2.1%. Detection limit, defined as three times the standard deviation (n = 6), ranged from 8 ng L⁻¹ for EtHg⁺ to 32 ng L⁻¹ for PhHg⁺ and was noticeably lower than those reported in previous LC-based methods. Accuracy was suitable with recoveries ranging from 85 to 100% when tested at two levels (0.5 and 10 μg L⁻¹) in groundwater samples. Recovery was matrix affected when water samples of high salinity (depurated wastewater and seawater) were used.