Determination of arsenic,selenium and mercury in an estuarine sediment standard reference material using flow injection and atomic absorption spectrometry

A flow-injection analysis atomic absorption spectrometric (FIA-AAS) method was developed for the determination of trace amounts of arsenic, selenium and mercury in a proposed estuarine sediment standard reference material (SRM 1646a). The samples were prepared in two manners: a) A wet digestion procedure with HNO₃, H₂SO₄, and HClO₄ using a reflux column and b) A microwave-oven digestion procedure utilizing HNO₃, H₂SO₄, and HCl for As and Se, and HNO₃ for Hg. Microwave-oven digestion provides results comparable to those found by reflux column digestion and reduces the sample preparation time by a factor of 10. The proposed method employing the microwave-oven digestion procedure coupled with FIA-AAS for As and Se, and FIA-CVAAS for Hg, has detection limits of 0.15 ng As/ml, O.17 ng Se/ml and 0.15 ng Hg/ml.On leave from the Defense Metallurgical Research Laboratory, Hyderabad, India     

荧光粉表面吸附汞的检测

在荧光灯的燃点过程中，荧光粉表面沉积吸附的汞对光衰有重要的影响。本文提出用冷原子吸收方法（CVAAS）直接检测荧光粉表面吸附汞量的变化，利用室温下原子汞对254nm共振线的吸收，且其吸收与汞原子蒸气浓度成正比进行汞量测试，测得方法的标准曲线回归方程为Y＝0.4455X 0.2000，试样的加标回收率为92.3-99.8%，满足荧光粉含汞量测定的要求。对燃点不同时间后的铝酸盐蓝色荧光粉（BAM）进行测定，结果表明：荧光粉表面沉积吸附的汞量随点灯时间的延长而增加，与灯的光衰增大趋向一致，汞的吸附沉积确实是造成荧光灯光衰的主要原因之一。检测结果还表明，将未作表面包膜处理的BAM粉与经过表面包覆纳米Al2O3膜层处理的BAM粉作对照，前者的含汞量比后者的含汞量明显要高。可见：对荧光粉进行表面包膜处理，能够保护粉体、减少汞的沉积吸附，从而降低点灯过程中的光衰。     

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.     

Comparison of open and closed focussed microwave digestions in view of total mercury determination by cold vapour atomic absorption spectrometry

Food samples digestion, in view to quantify total mercury, is the first step to perform before measuring mercury by cold vapour atomic absorption spectrometry (CVAAS).We have compared two microwave digestion systems, one working at atmospheric pressure (open system) and the other one under pressure (closed system). Results obtained for fish muscle samples by the two methods are in good agreement. However, fat is not digested in the open system, whereas in the closed system no more fat remains in the final solution. During the quantification step, applying the CVAAS technique, we have noticed that the choice and the concentration of the reductant solution is very important to obtain good results. Elaborated methods have been validated using certified reference materials.     

Determination of total mercury in biological samples using flow injection CVAAS following tissue solubilization in formic acid

Total mercury in biological samples was determined by flow injection (FI) cold vapour atomic absorption spectrometry (CVAAS) following tissue solubilization with formic acid. A mixture of potassium bromide and potassium bromate was used to decompose organomercury compounds prior to their reduction with sodium borohydride. A gold amalgam system was used to achieve lower detection limits when required. National Research Council Canada certified reference materials dogfish liver (DOLT-3), dogfish flesh (DORM-2) and lobster hepatopancreas (TORT-2), as well as oyster tissue (NIST SRM 1566b) and mussel tissue (NIST SRM 2976) were used to assess the accuracy of the method. The method of standard additions provided the most accurate results. Limit of detection (LOD) for Hg in the solid sample of 0.001 and 0.01 μg g⁻¹ were achieved with and without amalgamation, respectively. The precision of measurement for 1.6 ng ml⁻¹ methylmercury was 2.7% using the amalgam system.     

Estimation of uncertainty for the determination of mercury in food by CVAAS

This paper is aimed at reporting a full validation of a Cold Vapour Atomic Absorption Spectrometry (CVAAS) method for mercury determination in fishery products. Method precision, trueness, limit of detection and limit of quantification are evaluated. The uncertainty of measurement is estimated following the bottom-up approach in conjunction with the validation data as suggested for complex analysis. The precision is evaluated using a pooled relative standard deviation and the recovery is added to the measurement uncertainty budget. Uncertainties of weight of sample, dilution factor, calibration, work solution and analyte amount are also assessed. The most relevant uncertainty sources result those associated to amount of mercury determined in the final sample solution, to method precision and to recovery. The relative contributions have different weights according to the analyst decision regarding recovery correction of results. In conclusion, the adopted CVAAS method fully complies with EU requirements. Presented at AOAC Europe/Eurachem Symposium March 2005, Brussels, Belgium     

Development of a novel and robust microprecipitation approach using cetyltrimethyl ammonium bromide (CTAB) for preconcentration and speciation of mercury in waters prior to CVAAS determination

A novel and simple microprecipitation method was developed for the preconcentration of ultra-trace quantities of inorganic and methyl mercury species (iHg and MeHg) prior to their determination by cold vapour atomic absorption spectrometry (CVAAS). This method is based on the formation of anionic complexes of Hg²⁺ with KI followed by ion-associate complex with cetyltrimethyl ammonium bromide (CTAB) that forms a fluffy precipitate in perchloric acid medium. As a result, a fluffy coagulated mass separates and collects at the top of the liquid surface with clear phase separation without need of cooling or heating or centrifugation. The ion-association complex of iHg was then extracted into surfactant-rich phase (top layer) of CTAB-perchlorate precipitate while the uncomplexed MeHg remained in the aqueous phase (bottom layer). This condition also facilitates the removal of aqueous phase by simply draining out. The fluffy mass formed was dissolved in a mixture of HNO₃ and HCl which was subsequently treated with chloroform to separate the surfactant from the mixture. Then the aqueous phase containing the preconcentrated iHg was analysed for mercury by CVAAS. Key factors such as sample pH, concentration of KI and CTAB that affect the performance of the proposed microprecipitation method were thoroughly investigated. For the determination of total mercury, another fresh aliquot of water was initially adjusted to pH ~ 3.5 with perchloric acid and subjected to oxidation by using modified UV-irradiation set-up and then taken through the microprecipitation procedure. This method allows speciation of mercury with a preconcentration factor of 200 and the limits of detection (LOD) of mercury obtained for CVAAS in conjunction with the present preconcentration method was found to be 2.4 ng L^?1. Average recoveries obtained with the proposed approach were found to be in the range of 96–104% with RSD values < 5%. The interfering effects of various cations and anions were also investigated. The method was successfully applied for the determination of ultra-trace quantities of mercury species in real samples such as bottled water, tap water, lake water and ground waters.     

Multi-Elemental Analysis of Wine Samples in Relation to Their Type,Origin, and Grape Variety

Wine is one of the most popular alcoholic beverages. Therefore, the control of the elemental composition is necessary throughout the entire production process from the grapes to the final product. The content of some elements in wine is very important from the organoleptic and nutritional points of view. Nowadays, wine studies have also been undertaken in order to perform wine categorization and/or to verify the authenticity of products. The main objective of this research was to evaluate the influence of the chosen factors (type of wine, producer, origin) on the levels of 28 elements in 180 wine samples. The concentration of studied elements was determined by ICP-MS (Ag, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Sn, Sr, Te, Tl, U, Zn), ICP-OES (Ca, Fe, K, Mg, Ti), and CVAAS (Hg) techniques in 79 red, 75 white, and 26 rose wine samples. In general, red wines contained higher values of mean and median of B, Ba, Cr, Cu, Mn, Sr and Zn in contrast to other wine types (white and rose). In white wines (when compared to red and rose wines) higher levels of elements such as Ag, Be, Bi, Cd, Co, Li, K and Ti were determined. In contrast, rose wines were characterized by a higher concentration of Fe and U. The study also revealed that in the case of 18 samples, the maximum levels of some metals (Cd—8 samples, Pb—9 samples, Cu—1 sample) were slightly exceeded according to the OIV standards, while for Zn and Ti in any wine sample the measured concentrations of these metals were above the permissible levels. Thus, it can be stated that the studied wines contained, in general, lower levels of heavy metals, suggesting that they should have no effect on the safety of consumption. The results also showed higher pH level for red wines as a consequence of the second fermentation process which is typically carried out for this type of wine (malolactic fermentation). The highest median value of pH was reported for Merlot-based wines, while the lowest was for Riesling. It is assumed that dry Riesling has a higher content of tartaric and malic acid than dry Chardonnay grown in the same climate. From all of the studied countries, wines from Poland seemed to present one of the most characteristic elemental fingerprints since for many elements relatively low levels were recorded. Moreover, this study revealed that also wine samples from USA and Australia can be potentially discriminated from the rest of studied wines. For USA the most characteristic metal for positive identification of the country of origin seems to be uranium, whereases for Australia – strontium and manganese. Based on the highly reduced set of samples, it was not possible to differentiate the studied wine products according to the grape variety other than Syrah, and partially Chardonnay. Since all the Syrah-based samples originated from the same country (Australia) thus, the observed grouping should be more related with the country of origin than the grape variety.     

A rapid ultrasound-assisted thiourea extraction method for the determination of inorganic and methyl mercury in biological and environmental samples by CVAAS

A rapid ultrasound-assisted extraction procedure for the determination of total mercury, inorganic and methyl mercury (MM) in various environmental matrices (animal tissues, samples of plant origin and coal fly ash) has been developed. The mercury contents were estimated by cold vapour atomic absorption spectrometry (CVAAS). Inorganic mercury (IM) was determined using SnCl₂ as reducing agent whereas total mercury was determined after oxidation of methyl mercury through UV irradiation. Operational parameters such as extractant composition (HNO₃ and thiourea), sonication time and sonication amplitude found to be different for different matrices and were optimized using IAEA-350 (Fish homogenate), IM and MM loaded moss and NIST-1633b (Coal fly ash) to get quantitative extraction of total mercury. The method was further validated through the analysis of additional certified reference materials (RM): NRCC-DORM2 (Dogfish muscle), NRCC-DOLT1 (Dogfish liver) and IAEA-336 (Lichen). Quantitative recovery of total Hg was achieved using mixtures of 5% HNO₃ and 0.02% thiourea, 10% HNO₃ and 0.02% thiourea, 20% HNO₃ and 0.2% thiourea for fish tissues, plant matrices and coal fly ash samples, respectively. The results obtained were in close agreement with certified values with an overall precision in the range of 5-15%. The proposed ultrasound-assisted extraction procedure significantly reduces the time required for sample treatment for the extraction of Hg species. The extracted mercury species are very stable even after 24 h of sonication. Closed microwave digestion was also used for comparison purposes. The proposed method was applied for the determination of Hg in field samples of lichens, mosses, coal fly ash and coal samples