In-situ Diffusive Gradients in thin-films passive sampling coupled with ex-situ small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry as green and white method for the simultaneous determination of labile species of toxic elements in surface water.

This study presents for the first time the coupling between in-situ Diffusive Gradient in Thin-film (DGT) passive sampling technique and ex-situ small-sized instrumentation based on electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry (SSETV-µCCP-OES) for the simultaneous determination of Cd, Pb, Cu, Zn and Hg in surface water. Unique features of the DGT-SSETV-µCCP-OES are low power and low Ar consumption for plasma generation (15 W, 150 mL min-1) and significant improvement of the detection limits following DGT passive sampling. The new method was validated in terms of river water analysis in comparison with graphite furnace atomic absorption spectrometry and thermal decomposition atomic absorption spectrometry. Combining the abilities of preconcentration by in-situ Chelex-DGT passive sampling with plasma microtorch equipped with a low resolution microspectrometer provided multielemental simultaneous determination with detection limits of (µg L-1) 0.01 (Cd, Zn and Hg), 0.02 (Cu) and 0.07 (Pb) in water, at least one order of magnitude better than using grab sampling without preconcentration. It was possible the quantification of labile fraction of priority hazardous metals (Cd, Pb) in river water below the instrumental limits of detection (µg L-1) of 0.12 and 0.80 obtained in SSETV-µCCP-OES without DGT sampling. The precision of the method was in the range 15.3-22.4% (combined uncertainty), while the accuracy was 95-103% and trueness of 27-33% (expanded uncertainty, k = 2). The DGT-SSETV-µCCP-OES coupling proved to be an ideal and powerful tool for surface water analysis in compliance with green and white analytical chemistry concepts. The application of the RGB-12 algorithm provided very good red/green (AGREEprep)/blue/white scores (%) of 100/80/98/93, determined primarily by in-situ DGT passive sampling, very good detection limits and cost-effective SSETV-µCCP-OES instrumentation.

Ionization of elements in medium power capacitively coupled argon plasma torch with single and double ring electrodes.

A medium power, low Ar consumption capacitively coupled plasma torch (275 W, 0.4 L min-1) with molybdenum tubular electrode and single or two ring electrodes in non-local thermodynamic equilibrium (LTE) was characterized with respect to its ability to achieve element ionization. Ionization degrees of Ca, Mg, Mn and Cd were determined from ionic-to-atomic emission ratio and ionization equilibrium according to Saha's equation. The ionization degrees resulted from the Saha equation were higher by 9-32% than those obtained from spectral lines intensity in LTE regime and closer to reality. A linear decrease of ionization with increase of ionization energy of elements was observed. Plasma torch with two ring electrodes provided higher ionization degrees (85 ± 7% Ca, 79 ± 7% Mn, 80 ± 7% Mg and 73 ± 8% Cd) than those in single ring arrangement (70 ± 6% Ca, 57 ± 7% Mn, 57 ± 8% Mg and 42 ± 9% Cd). The Ca ionization decreased linearly by up to 79 ± 4% and 53 ± 6% in plasma with two ring electrodes and single ring respectively in the presence of up to 400 µg mL-1 Na as interferent. The studied plasma was effective in element ionization and could be a potential ion source in mass spectrometry.

Discharge characteristics and non-spectral interferences on the emission of ca species in a medium power radiofrequency capacitively coupled plasma source.

Non-spectral interference of easily ionized elements (EIEs) as chlorides and Al as AlCl3 and Al(NO3)3 on the emission of Ca II 393.367 nm, Ca I 422.673 nm, CaOH 554 nm and 622 nm were studied in a medium power radiofrequency capacitively coupled Ar plasma (275 W, 27.12 MHz) with single (SRTrfCCP) and double ring electrode (DRTrfCCP). The mechanisms of interferences were explained based on the matrix energy demand (MED) supposing the local thermal equilibrium (LTE) in plasma, emphasizing also processes contrasting with this model. Matrix effects were found to be dependent on the coupling geometry of the rf power to the torch, observation height, emitting Ca species and EIEs matrix nature but independent from Al as regards its salt origin. The magnitude of the matrix effects was correlated with the electron number density and the discharge temperature. The optimization of the observation height and use of the DRT geometry allowed the reduction of EIEs and Al matrix effects on the emission of Ca species compared to SRT. The best Ca detection limits in SRTrfCCP were at CaOH 622 nm (106-450 ng ml-1), while in DRTrfCCP at Ca I 422.673 nm (92-145 ng ml-1).

Interference-free, green microanalytical method for total mercury and methylmercury determination in biological and environmental samples using small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry.

An analytical method for the quantification of total Hg and CH3Hg+ in biological tissues (fish, mushroom) and water sediment was developed based on small-sized electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry using a low-resolution microspectrometer as detector. Sample preparation was carried out according to the procedure recommended by JRC Technical Report of European Commission for the determination of CH3Hg+ in seafood and adapted by us for lower consumption of reagents. Amounts of 0.1 - 0.5 g sample were subjected to extraction in 5 ml of 47% HBr then CH3Hg+ was extracted in 2 × 1 ml toluene and back-extracted in 2 ml aqueous solution of 1% l-cysteine. Total Hg/CH3Hg+ were quantified in 10 µl of acidic extract/l-cysteine solution after electrothermal vaporization and measurement of 253.652 nm Hg signal in the episodic emission spectra. Under the optimal working conditions of system (70 °C sample drying, 1300 °C sample vaporization, 10 W plasma power and 150 ml min-1 Ar flow) the limits of detection were 7.0 µg kg-1 total Hg and 3.5 µg kg-1 CH3Hg+. Comparison of slopes in external calibration and standard addition procedure revealed the lack of non-spectral interferences of multimineral matrix, so that the calibration against Hg2+ standards was adopted. Pooled recovery of total mercury/methylmercury was 101 ± 7%/100 ± 7%, while precision assessed from measurements of real samples was in the range 1.6-9.6%/2.7-12.8%. The proposed method validated according to Eurachem Guide 2014 is selective and complies with demands in European legislation (Decisions 657/2002; 333/2007; 836/2011) and Association of Official Analytical Chemists Guide in terms of performances for food control. The method displays a high degree of greenness by circumventing cold vapor generation, use of small amounts of reagents and full-miniaturized instrumentation resulting in low analytical costs without reducing results quality. Besides, the method is simple and rapid, since it uses external calibration curves prepared from Hg2+standard solutions both for total Hg and CH3Hg+ determination.

Methylmercury determination in seafood by photochemical vapor generation capacitively coupled plasma microtorch optical emission spectrometry.

A non-chromatographic method based on double liquid-liquid extraction and measurements by UV photochemical vapor generation capacitively coupled plasma microtorch optical emission spectrometry was developed and characterized for methylmercury determination in seafood. Samples were prepared following the procedure recommended in JRC Technical Report of European Commission formerly proposed for the determination of methylmercury in seafood by thermal decomposition atomic absorption spectrometry, namely confinement of Hg species in 47% HBr solution, extraction of CH3Hg+ in toluene and back-extraction in 1% l-cysteine aqueous solution. Mercury cold vapor was generated by flow injection UV photo-reduction from CH3Hg+ in 0.6molL-1 HCOOH, while quantification was performed against external Hg2+ aqueous standards and measuring Hg 253.652nm emission using a low power/Ar consumption plasma microtorch (15W, 100mLmin-1) and a low resolution microspectrometer (Ocean Optics). The figures of merit and analytical capability were assessed by analyzing certified reference materials and test samples of fish fillet and discussed in relation with requirements for Hg determination in seafood in European legislation (Decisions 2007/333/EC and 2002/657/EC) as well as compared to performances achieved in thermal decomposition atomic absorption spectrometry. The limit of detection and quantification of 2µgkg-1 and 6µgkg-1 respectively, precision of 2.7-9.4% and accuracy of 99±8% of the proposed method for the determination of CH3Hg+ fulfill the demands of European legislation for Hg quantification. The limit of detection and quantification were better than those in the used reference method or other non-/chromatographic methods taken for comparison. The analysis of certified reference materials and the Bland and Altman test performed on 12 test samples confirmed trueness of the proposed method and its reliability for the determination of traces of CH3Hg+ with 95% confidence level. The proposed method fulfills several demands of the eco-scale concept, is sensitive, simple and safe related to sample preparation through elimination of classical, harmful reductants and attractive by using economical miniaturized instrumentation incorporating a low power and low Ar consumption plasma.

A miniaturized capacitively coupled plasma microtorch optical emission spectrometer and a Rh coiled-filament as small-sized electrothermal vaporization device for simultaneous determination of volatile elements from liquid microsamples: spectral and analytical characterization.

A low power and low argon consumption (13.56 MHz, 15 W, 150 ml min(-1)) capacitively coupled plasma microtorch interfaced with a low-resolution microspectrometer and a small-sized electrothermal vaporization Rh coiled-filament as liquid microsample introduction device into the plasma was investigated for the simultaneous determination of several volatile elements of interest for environment. Constructive details, spectral and analytical characteristics, and optimum operating conditions of the laboratory equipment for the simultaneous determination of Ag, Cd, Cu, Pb and Zn requiring low vaporization power are provided. The method involves drying of 10 µl sample at 100°C, vaporization at 1500°C and emission measurement by capture of 20 successive spectral episodes each at an integration time of 500 ms. Experiments showed that emission of elements and plasma background were disturbed by the presence of complex matrix and hot Ar flow transporting the microsample into plasma. The emission spectrum of elements is simple, dominated by the resonance lines. The analytical system provided detection limits in the ng ml(-1) range: 0.5(Ag); 1.5(Cd); 5.6(Cu); 20(Pb) and 3(Zn) and absolute detection limits of the order of pg: 5(Ag); 15(Cd); 56(Cu); 200(Pb) and 30(Zn). It was demonstrated the utility and capability of the miniaturized analytical system in the simultaneous determination of elements in soil and water sediment using the standard addition method to compensate for the non-spectral effects of alkali and earth alkaline elements. The analysis of eight certified reference materials exhibited reliable results with recovery in the range of 95-108% and precision of 0.5-9.0% for the five examined elements. The proposed miniaturized analytical system is attractive due to the simple construction of the electrothermal vaporization device and microtorch, low costs associated to plasma generation, high analytical sensitivity and easy-to-run for simultaneous multielemental analysis of liquid microsamples.

Arsenic and antimony determination in non- and biodegradable materials by hydride generation capacitively coupled plasma microtorch optical emission spectrometry.

A sensitive method using a miniature analytical system with a capacitively coupled plasma microtorch (25 W, 13.56 MHz, 0.4 l min(-1) Ar) was developed and evaluated for the determination of As and Sb in recyclable plastics and biodegradable materials by hydride generation optical emission spectrometry. Given their toxicity, As and Sb should be subject to monitoring in such materials despite not being included within the scope of Restriction of Hazardous Substances Directive. The advantages of the proposed approach are better detection limits and lower analysis cost relative to conventional systems based on inductively coupled plasma optical emission and flame atomic absorption spectrometry with/without derivatization. Samples were subjected to acidic microwave-assisted digestion in a nitric-sulfuric acid mixture. Chemical hydride generation with 0.5% NaBH4 after the prereduction of As(V) and Sb(V) with 0.3% L-cysteine in 0.01 mol l(-1) HCl (10 min contact time at 90±5°C) was used. Under the optimal hydride generation conditions and analytical system operation the detection limits (mg kg(-1)) were 0.5 (As) and 0.1 (Sb), whereas the precision was 0.4-7.1% for 10.2-46.2 mg kg(-1) As and 0.4-3.2% for 7.1-156 mg kg(-1) Sb. Analysis of two polyethylene CRMs revealed recoveries of 101±2% As and 100±1% Sb.

Simple and robust method for lithium traces determination in drinking water by atomic emission using low-power capacitively coupled plasma microtorch and microspectrometer.

A method for Li determination in drinking water using atomic emission spectrometry in a new low-power Ar capacitively coupled plasma microtorch (15 W, 0.6 L min(-1)) with a detection limit of 0.013 µg L(-1) was developed. The method is based on external calibration in the presence of a buffering solution containing 5 mg L(-1) Na, K, Ca, Mg added both to calibration standards and water samples. The statistical validation on 31 bottled drinking water samples (0.4-2140 µg L(-1) Li) using the Bland and Altman test and regression analysis has shown results similar to those obtained by the standard additions method. The buffering solution approach is simpler than the standard additions and has demonstrated good intra- and interday precision, accuracy and robustness. It was successfully applied over a wide concentration range of Li and multimineral matrix with a pooled precision of 2.5-3.5% and 99±9% accuracy.

Determination, speciation and distribution of mercury in soil in the surroundings of a former chlor-alkali plant: assessment of sequential extraction procedure and analytical technique.

BACKGROUND: The paper presents the evaluation of soil contamination with total, water-available, mobile, semi-mobile and non-mobile Hg fractions in the surroundings of a former chlor-alkali plant in connection with several chemical soil characteristics. Principal Component Analysis and Cluster Analysis were used to evaluate the chemical composition variability of soil and factors influencing the fate of Hg in such areas. The sequential extraction EPA 3200-Method and the determination technique based on capacitively coupled microplasma optical emission spectrometry were checked. RESULTS: A case study was conducted in the Turda town, Romania. The results revealed a high contamination with Hg in the area of the former chlor-alkali plant and waste landfills, where soils were categorized as hazardous waste. The weight of the Hg fractions decreased in the order semi-mobile > non-mobile > mobile > water leachable. Principal Component Analysis revealed 7 factors describing chemical composition variability of soil, of which 3 attributed to Hg species. Total Hg, semi-mobile, non-mobile and mobile fractions were observed to have a strong influence, while the water leachable fraction a weak influence. The two-dimensional plot of PCs highlighted 3 groups of sites according to the Hg contamination factor. The statistical approach has shown that the Hg fate in soil is dependent on pH, content of organic matter, Ca, Fe, Mn, Cu and SO42- rather than natural components, such as aluminosilicates. Cluster analysis of soil characteristics revealed 3 clusters, one of which including Hg species. Soil contamination with Cu as sulfate and Zn as nitrate was also observed. CONCLUSIONS: The approach based on speciation and statistical interpretation of data developed in this study could be useful in the investigation of other chlor-alkali contaminated areas. According to the Bland and Altman test the 3-step sequential extraction scheme is suitable for Hg speciation in soil, while the used determination method of Hg is appropriate.

Analytical capability of a medium power capacitively coupled plasma for the multielemental determination in multimineral/multivitamin preparations by atomic emission spectrometry.

A method for multielemental (Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P and Zn) determination in multimineral/multivitamins by atomic emission spectrometry in a medium power radiofrequency capacitively coupled plasma (275 W) and low Ar consumption (0.4 L min(-1)) is proposed. Determinations were performed on commercially available tablets and a standard reference material after acidic high-pressure microwave assisted digestion and using the standard additions procedure. The detection limits (mg g(-1)) were in the range 0.003 (Na)-1.5 (P) and were not depreciated by the non-spectral interference of mineral matrices of K, Ca, Mg and Na excepting Zn and P. Found concentrations corresponded generally to the labelled contents with recovery in the range of 90-107% and 1.0-13.0% repeatability. The proposed technique could be an advantageous alternative to the more expensive inductively coupled plasma atomic emission spectrometry in the quality control of multimineral/multivitamin preparations.

Mercury determination in non- and biodegradable materials by cold vapor capacitively coupled plasma microtorch atomic emission spectrometry.

A new analytical system consisting of a low power capacitively coupled plasma microtorch (20 W, 13.56 MHz, 150 ml min(-1) Ar) and a microspectrometer was investigated for the Hg determination in non- and biodegradable materials by cold-vapor generation, using SnCl(2) reductant, and atomic emission spectrometry. The investigated miniaturized system was used for Hg determination in recyclable plastics from electronic equipments and biodegradable materials (shopping bags of 98% biodegradable polyethylene and corn starch) with the advantages of easy operation and low analysis costs. Samples were mineralized in HNO(3)-H(2)SO(4) mixture in a high-pressure microwave system. The detection limits of 0.05 ng ml(-1) or 0.08 µg g(-1) in solid sample were compared with those reported for other analytical systems. The method precision was 1.5-9.4% for Hg levels of 1.37-13.9 mg kg(-1), while recovery in two polyethylene certified reference materials in the range 98.7 ± 4.5% (95% confidence level).