Determination of total mercury in environmental and biological samples by flow injection cold vapour atomic absorption spectrometry

A simple and accurate method has been developed for the determination of total mercury in environmental and biological samples. The method utilises an off-line microwave digestion stage followed by analysis using a flow injection system with detection by cold vapour atomic absorption spectrometry.

The method has been validated using two certified reference materials (DORM-1 dogfish and MESS-2 estuarine sediment) and the results agreed well with the certified values. A detection limit of 0.2 ng g⁻¹ Hg was obtained and no significant interference was observed. The method was finally applied to the determination of mercury in river sediments and canned tuna fish, and gave results in the range 0.1–3.0 mg kg⁻¹.     

Determination of mercury in environmental and biological samples by cold vapour atomic absorption spectrometry

A continuously operating monitoring method for total mercury at sub-ng/ml level in environmental and biological samples by cold vapour atomic-absorption spectrometry with NaBH₄ as a reductant was developed. The mercury vapour generator and absorption cell closed-end by quartz were used in this study. The detection limit (S/N = 3) and relative standard deviation of 12 determinations of 10 ng/ml Hg(II) were 0.11 ng/ml and 1.1%, respectively. The range of standard calibration curve was 0–50 ng/ml Hg, The proposed method was successfully applied to the completely continuous monitoring of total mercury in waste water, sediments and pork liver.     

Development of a sequential injection system for trace mercury determination by cold vapour atomic absorption spectrometry utilizing an integrated gas-liquid separator/reactor

A simple and robust time-based on-line sequential injection system for trace mercury determination via cold vapour atomic absorption spectrometry (CVAAS), employing a new integrated gas-liquid separator (GLS), which in parallel operates as reactor, was developed. Sample and reductant are sequentially loaded into the GLS while an argon flow delivers the released mercury vapour through the atomic absorption cell. The proposed method is characterized by the ability of successfully managing variable sample volume up to 30 ml in order to achieve high sensitivity. For 20 ml sample volume, the sampling frequency is 25 h⁻¹. The calibration curve is linear over the concentration range 0.05-5.0 μg l⁻¹ of Hg(II), the detection limit is c_L = 0.02 μg l⁻¹, and the relative standard deviation is s_r = 2.6% at 1.0 μg l⁻¹ Hg(II) level. The performance of the proposed method was evaluated by analyzing certified reference material and applied to the analysis of natural waters and biological samples.     

Total and inorganic mercury determination in fish tissue by flow injection cold vapour atomic fluorescence spectrometry

A simple and reliable method for Hg determination in fish samples has been developed. Lyophilised fish tissue samples were extracted in a 25% (w/v) tetramethylammonium hydroxide (TMAH) solution; the extracts were then analysed by FI-CVAFS. This method can be used to determine total and inorganic Hg, using the same FI manifold. For total Hg determination, a 0.1% (w/v) KMnO₄ solution was added to the FI manifold at the sample zone, followed by the addition of a 0.5% (w/v) SnCl₂ solution, whereas inorganic Hg was determined by adding a 0.1% (w/v) L-cysteine solution followed by a 1.0% (w/v) SnCl₂ solution to the FI system. The organic fraction was determined as the difference between total and inorganic Hg. Sample preparation, reagent consumption and parameters that can influence the FI-CVAFS performance were also evaluated. The limit of detection for this method is 3.7 ng g^?1 for total Hg and 4.3 ng g^?1 for inorganic Hg. The relative standard deviation for a 1.0 µg L^?1 CH₃Hg standard solution (n = 20) was 1.1%, and 1.3% for a 1.0 µg L^–1 Hg²⁺ standard solution (n = 20). Accuracy was assessed by the analysis of Certified Reference Material (dogfish: DORM-2, NRCC). Recoveries of 99.1% for total Hg and 93.9% inorganic Hg were obtained. Mercury losses were not observed when sample solutions were re-analysed after a seven day period of storage at 4°C.     

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.     

Calibration by the gradient ratio-standard addition method in flow injection flame atomic absorption spectrometry

A calibration method has been developed which is realised in the flow injection analysis (FIA) by the gradient technique. According to this method two transient peaks, one for a sample and the other for a sample with standard addition, are recorded and compared point by point in the entire defined time range. The analytical result is estimated on the basis of information gained about the local analyte concentrations in the sample zone. The method allows the results to be reliable when both the non-linear calibration dependence and the interference effect occur. As an example, calcium in synthetic samples containing silicon, phosphate, aluminium, vanadium and titanium, and also in iron ore sample, were determined by flame atomic absorption spectrometry (FAAS). It has been proved, that the method can be effective in overcoming even extremely strong interferences, providing analytical results with average accuracy equal to ca. 5% and with precision 2–3 times inferior to that obtained by conventional FI calibration.     

Simple oxidative pretreatment for determination of organomercury by cold vapour atomic fluorescence spectrometry

A simple and rapid method has been developed for the direct determination of organomercury in toluene extracts. The oxidative pretreatment, intended for cold vapour-atomic absorption/fluorescence spectrometry, involves the use of bromide/bromate reagent under strong acid conditions. The pretreatment is performed directly in a volumetric flask and avoids the need for back extraction and phase separation. Recoveries for methyl mercury additions to toluene, at the 2 g/1 level, ranged from 100–106%.On leave Xianjiang Environmental Research Institute, Urumqui, Xianjiang Province, Peoples Republic of China     

An ion-exchange method for speciation of antimony by flow injection electrothermal atomic absorption spectrometry

In this work, a simple preconcentration system, achieved by replacing the sample tip of the autosampler arm by a micro-column packed with Amberlite IRA-910 or silica gel chelating resin functionalised with 1,5-bis(di-2-pyridyl)methylene tbiocarbohydrazide (DPTH-gel), is developed for the determination of Sb(V) and total antimony, respectively. Different factors including pH of sample solution, ionic strength, concentration and volume of eluent, sample flow rate, sample loading time and matrix effects for preconcentration were investigated. The method has been applied to the determination of antimony species in different samples.     

Determination of iron and copper in food samples by flow injection cloud point extraction flame atomic absorption spectrometry

In this study, flow injection-cloud point extraction (FI-CPE) of iron and copper in food samples by flame atomic absorption spectrometric determination was described. Triton X-114 non-ionic surfactant and Eriochrome Cyanine R (ECR) have been used as an extraction medium and a chelating agent, respectively. The amounts of Triton X-114, ECR and the pH value necessary for extraction were carefully optimized. In addition, several parameters of the FI-CPE system, including sample loading rate, column dimension, type of packing material, eluent flow rate were investigated and analytical characteristics of the method were evaluated. Under optimum conditions, detection limits of 0.33 ng/mL and 0.57 ng/mL and quantification limits of 1.1 ng/mL and 1.9 ng/mL for iron and copper along with enrichment factors of 141 and 99 were obtained, respectively. The calibration was linear over the range 1.5-25 ng/mL and 1.0-35 ng/mL for iron and copper, respectively. The proposed CPE technique has been successfully applied for the determination of iron and copper ions in certified reference materials (NCS DC 73349—bush, branches and leaves; and TM-23.2—fortified water), water samples (mineral and sea water) and food samples (vegetables, bread and hazelnut) with high efficiency.     

Direct mercury determination in aqueous slurries of environmental and biological samples by cold vapour generation-electrothermal atomic absorption spectrometry

Direct cold vapour generation from aqueous slurries of environmental (marine sediment, soil, coal) and biological (human hair, seafood) samples have been developed using a batch mode generation system coupled with electrothermal atomic absorption spectroscopy. The effects of several variables affecting the cold vapour generation efficiency from solid particles (hydrochloric acid and sodium tetrahydroborate concentrations, argon flow rate, acid solution volume and mean particle size) have been evaluated using a Plackett-Burman experimental design. In addition, variables affecting cold vapour trapping and atomisation efficiency on Ir-treated graphite tubes (trapping and atomisation temperatures and trapping time) have been also investigated. Atomisation and trapping temperatures, trapping time and hydrochloric acid concentration were the significant variables. The 2²+star and 2³+star central composite designs have been used to obtain optimum values of the variables selected. The accuracy of methods have been verified by using several certified reference materials (PACS-1, GBW-07410, NIST-1632c, CRM-397 and DORM-2). A characteristic mass of 390 pg were achieved. The detection limits of methods were in the range of 40-600 ng g⁻¹. A particle size less than 50 μm is adequate to obtain total cold vapour generation of Hg content in the aqueous slurry particles.     

Determination of methylmercury and inorganic mercury in water samples by slurry sampling cold vapor atomic absorption spectrometry in a flow injection system after preconcentration on silica C18 modified

A novel method for preconcentration of methylmercury and inorganic mercury from water samples was developed involving the determination of ng l⁻¹ levels of analytes retained on the silica C₁₈ solid sorbent, previous complexation with ammonium pyrrolidine dithiocarbamate (APDC), by slurry sampling cold vapor atomic absorption spectrometry (SS-CVAAS) in a flow injection (FI) system. Several variables were optimized affecting either the retention of both mercury species, such as APDC concentration, silica C₁₈ amount, agitation times, or their determination, including hydrochloric acid concentration in the suspension medium, peristaltic pump speed and argon flow-rate. A Plackett-Burman saturated factorial design permitted to differentiate the influential parameters on the preconcentration efficiency, which were after optimized by the sequential simplex method. The contact time between mercury containing solution and APDC, required to reach an efficient sorption, was decreased from 26 to 3 min by the use of sonication stirring instead of magnetic stirring. The use of 1 mol dm⁻³ hydrochloric acid suspension medium and 0.75% (m/v) sodium borohydride reducing agent permitted the selective determination of methylmercury. The combination of 5 mol dm⁻³ hydrochloric acid and 10⁻⁴% (m/v) sodium borohydride was used for the selective determination of inorganic mercury. The detection limits achieved for methylmercury and inorganic mercury determination under optimum conditions were 0.96 and 0.25 ng l⁻¹, respectively. The reliability of the proposed method for the determination of both mercury species in waters was checked by the analysis of samples spiked with known concentrations of methylmercury and inorganic mercury; quantitative recoveries were obtained.     

Preconcentration and determination of trace metals by flow injection micelle-mediated extraction using flame atomic absorption spectrometry

Micelle-mediated extraction/preconcentration is incorporated on-line into a flow injection system used to determine low levels of Cd(II), Co(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) present in various samples. The analyte is complexed with HBDAP (N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2-diaminopropane). Under optimal conditions, a solution of 30% (m/v) NaCl and a sample solution containing 2.5 mL of 1% (m/v) sodium dodecyl sulfate (SDS), 0.5 mL of 1.8 × 10⁻³ M HBDAP and 2.5 mL of pH 8.5 borate buffer solution in 25 mL were pumped through the cotton filled mini-column; onto which the surfactant-rich phase containing the complex is collected. A solution of 0.5 M HNO₃ in 50% acetone is used as the eluent. The limits of detection are (ng mL⁻¹) Cd = 0.39, Cu = 3.2, Co = 7.5, Mn = 3.0, Ni = 3.4, Pb = 17.9 and Zn = 0.89 if the sample is allowed to flow for 30 s, but improved for extended preconcentration periods. Analysis of liquid and solid reference materials showed good agreement with the certified values. Complex formation constants between HBDAP and these metal ions were also determined potentiometrically.     

流动注射在线分离富集-电热原子吸收法测定地球化学样品中的痕量金、铂、钯

建立了流动注射在线同时分离富集，无火焰原子吸收法测定地球化学样品中金、铂、钯的分析方法。研究了联用技术并进行了吸附条件和解脱条件的优化实验。当采样频率为20样/h时，Au、Pt、Pd的富集倍数分别为43、37、41。Au、Pt、Pd的检出限(3σ)分别为5、16、9ng／L。将Au、Pt、Pd质量浓度分别为50、200、100ng／L的混合标准溶液平行测定7次，求得Au、Pt、Pd的相对标准偏差分别为3．6％、5．1％、4．7％。并对国家级标准样品进行了测定，其结果及精密度符合要求。     

Determination of mercury species in gas condensates by on-line coupled high-performance liquid chromatography and cold-vapor atomic absorption spectrometry

A method for the speciation of mercury in gas condensates is reported. Mercury(II) chloride (HgCl₂), methylmercury chloride (MeHgCl), phenylmercury acetate (PhHgAc) and diphenylmercury (Ph₂Hg) are separated by reversed-phase high-performance liquid chromatography (HPLC) using gradient elution. Prior to the determination, the organic ligands and the matrix were destroyed by oxidation with K₂Cr₂O₇. Mercury is detected with cold-vapor atomic absorption spectrometry (CVAA), where the mercury compounds are reduced to metallic mercury by a treatment with NaBH₄. In a continuous-flow system the concentrations of the reagents used are optimized using a modified simplex algorithm. Detection limits for mercury are at the 10 ng ml^?1 level. Analysis of multi-compound mixtures indicates that chemical reactions between HgCl₂ and Ph₂Hg and between MeHgCl and Ph₂Hg take place. The method developed was applied to the speciation of mercury in gas condensates and did not require use of any solvent extraction or chemical derivatization steps. In the gas condensates, mercury(II) compounds were found to be present at the 100 ng ml^?1 level.     

On-line flow injection solvent extraction for electrothermal atomic absorption spectrometry: Determination of nickel in biological samples

A flow injection (FI) on-line solvent extraction system for electrothermal atomic absorption spectrometry (ETAAS) was developed with nickel as a model trace element. The nickel pyrrolidine-dithiocarbamate chelate was extracted on line into isobutyl methyl ketone, which was delivered into the FI system by a peristaltic pump equipped with poly(tetrafluoroethylene) tubing. The organic phase was separated from the aqueous phase by a novel gravity phase separator with a small conical cavity, and stored in a collector tube, from which 50 μl organic concentrate was introduced into the graphite tube by an air flow. ETAAS determination of the analyte was performed in parallel with the extraction process. An enrichment factor of 25 was obtained in comparison with 50 μl direct introduction while achieving a detection limit of 4 ng l⁻¹ (3σ), and a precision of 1.5% relative standard deviation for 1.0 μg l⁻¹ nickel (n = 11). The proposed method was successfully applied to the determination of nickel in body fluids and other biological samples.     

Separation and preconcentration by flow injection coupled to tungsten coil electrothermal atomic absorption spectrometry

A flow injection system coupled to a tungsten coil electrothermal atomizer has been developed for on-line separation and preconcentration, using lead as a model element. The system utilizes three-way solenoid valves for sampling, buffering, washing and reconditioning solution management, and the resin column is inserted in the tip of the autosampler arm of a Varian GTA-96. The solenoid valves and tungsten coil power supply were controlled by a computer program written in Visual Basic, interfaced with the built-in Varian software. The system performance was tested by loading the resin column with the sample flowing at 3 ml min⁻¹ for 60 s. Elution was performed automatically by sampling 20 μl of the eluent from a sample cup of the autosampler, and this aliquot was delivered into a 150 W tungsten coil. With Chelex-100 resin, the separation of concomitants was tested with lead in the presence of as much as 1000 mg l⁻¹ of Ca, Mg, Na or K. The model system presented an enrichment factor of 64 at a sampling rate of 30 samples per hour.     

Methylmercury determination using a hyphenated high performance liquid chromatography ultraviolet cold vapor multipath atomic absorption spectrometry system

The present work investigates the use of a multipath cell atomic absorption mercury detector for mercury speciation analysis in a hyphenated high performance liquid chromatography assembly. The multipath absorption cell multiplies the optical path while energy losses are compensated by a very intense primary source. Zeeman-effect background correction compensates for non-specific absorption. For the separation step, the mobile phase consisted in a 0.010% m/v mercaptoethanol solution in 5% methanol (pH = 5), a C₁₈ column was used as stationary phase, and post column treatment was performed by UV irradiation (60 °C, 13 W). The eluate was then merged with 3 mol L^− 1 HCl, reduction was performed by a NaBH₄ solution, and the Hg vapor formed was separated at the gas–liquid separator and carried through a desiccant membrane to the detector. The detector was easily attached to the system, since an external gas flow to the gas–liquid separator was provided. A multivariate approach was used to optimize the procedure and peak area was used for measurement. Instrumental limits of detection of 0.05 µg L^− 1 were obtained for ionic (Hg²⁺) and HgCH₃⁺, for an injection volume of 200 µL. The multipath atomic absorption spectrometer proved to be a competitive mercury detector in hyphenated systems in relation to the most commonly used atomic fluorescence and inductively coupled plasma mass spectrometric detectors. Preliminary application studies were performed for the determination of methyl mercury in sediments.     

Determination of trace mercury in geological samples by direct slurry sampling cold vapor generation atomic absorption spectrometry

A new method based on ultrasonic slurry sampling atomic absorption spectrometry (AAS) was established for the determination of trace mercury in geological samples by use of recently developed mercury cold vapor generation using formic acid under ultraviolet (UV) irradiation. The generated mercury cold vapor was rapidly separated from the matrix and swept into a T-tube for the measurement of atomic absorbance. Under the optimal experimental conditions, up to 1000-fold of Cu(II), Co(II), Ni(II), Cr(VI), Mn(II), Fe(III), and Zn(II) caused no significant interference with the determination of 50 μg L⁻¹ Hg. The limit of detection at sub-ppb level was obtained for mercury. The method was applied to the determination of mercury in geological samples with satisfactory results. Correspondence: Xiandeng Hou, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China     

Comparative study of copper(II) and cadmium(II) salts as catalytic reagents in the determination of mercury by continuous-microflow cold vapour atomic absorption spectrometry

A continuous-microflow method with cold vapour atomic absorption spectrometric detection was used for the determination of mercury. A comparison of copper(II) and cadmium(II) salts as catalytic reagents is described in detail It was found that in the presence of at least 80 mg 1^?1 of copper(II) salt a similar signal was obtained for both inorganic mercury [mercury(II) chloride]and organic mercury [methylmercury(II) chloride]. With a cadmium(II) salt at least 100 mg 1^?1 were required.     

Coupling of flow injection wetting-film extraction without segmentation and phase separation to flame atomic absorption spectrometry for the determination of trace copper in water samples

A flow injection wetting-film extraction system without segmentor and phase separator has been coupled to flame atomic absorption spectrometry for the determination of trace copper. Isobutyl methyl ketone (MIBK) was selected as coating solvent and 8-hydroxyquinoline (oxine) as the chelating reagent. By switching of a 8-channel valve and alternative initiation of two peristaltic pumps, MIBK, sample solution containing copper chelate of oxine, and air-segment sandwiched eluting solution (1.0 mol l⁻¹ nitric acid) were sequentially aspirated into an extraction coil made of PTFE tubing of 360 cm length and 0.5 mm i.d. The formation of organic film in the wall of the extraction coil, extraction of the copper chelate into the organic film and back-extraction of the analyte into the eluting solution occurred consecutively when these zones aspirated into the extraction coil were propelled down the extraction coil by a carrier solution at a flow rate of 2 ml min⁻¹. After leaving the extraction coil, the concentrated zone was transported to the nebulizer at its free uptake rate for atomization. Under the optimized conditions, an enrichment factor of 43 and a detection limit of 0.2 μg l⁻¹ copper were achieved at a sample throughput rate of 30 h⁻¹. Eleven determinations of a standard copper solution of 60 μg l⁻¹ gave a relative standard deviation of 1.5%. Foreign ions possibly present in tap water and natural water did not interfere with the copper determination. The developed method has been successfully used to the determination of copper content of tap water and river water.