Determination of Na, K, Ca and Mg in biodiesel samples by flame atomic absorption spectrometry (F AAS) using microemulsion as sample preparation

This study proposes a procedure for determining sodium, potassium, calcium and magnesium in biodiesel samples by flame atomic absorption spectrometry (F AAS). The sample was prepared as a microemulsion without surfactant. The optimized composition of the microemulsion was 10% (w/v) biodiesel, 75% (v/v) n-propanol, 1% (v/v) concentrated nitric acid and 14% (v/v) of aqueous solution formed by 0.2% (v/v) of nitric acid and 0.5% (v/v) of ionization suppressor. Analyte signals in the samples as microemulsion were found to be stable for a period of 15 days. Analytical curves were obtained using organometallic standard solutions. The limits of detection (LOD) found for the proposed procedure were 0.1 µg g^− 1, 0.01 µg g^− 1, 0.04 µg g^− 1, and 0.004 µg g^− 1 for Na, K, Ca and Mg, respectively. The reference method established by ABNT (Brazilian Association of Technical Norms) NBR 15556:2008 was used to verify the accuracy of the proposed procedure. No significant statistical difference was found between the results obtained with the proposed and the chosen reference procedure. The proposed procedure showed no matrix influence when recovery tests were performed (89%-103%). The results found in this study show that the proposed procedure is a good alternative for determining Na, K, Ca, and Mg by F AAS in biodiesel samples.     

Utilization of W/Mg(NO3)2 modifiers for the direct determination of As and Sb in soils,sewage sludge and sediments by solid sampling electrothermal atomic absorption spectrometry

A simple method has been developed for the determination of arsenic and antimony in environmental samples by solid sampling electrothermal atomic absorption spectrometry, which was validated using certified reference materials of soils (S-VM — Soil Eutric Cambisol; S-MS — Soil Orthic Luvisols; S-SP — Soil Rendzina), sewage sludge (WT-L; WT-M) and sediments (NIES2; GBW07906). The analytical procedure combines solid sampling with utilization of a matrix modifier admixture containing 5 µg of W and 5 µg of Mg. The tungsten in the admixture serves to stabilize the solid matrix during atomisation, which results in dramatically reduced non-specific absorption compared with the conventional palladium modifier. Magnesium was efficient in reducing the accumulation of the matrix residue on the platform. An alternative resonance line of 197.2 nm for arsenic and 206.8 nm for Sb was used in order to eliminate the spectral interferences caused by aluminum compounds, and silicon and iron compounds, respectively. Under optimized experimental conditions, the effective in situ analyte/matrix separation was achieved so that the use of aqueous standards for calibration became possible. With the modifier, a 3 SD detection limit of 0.5 µg g⁻¹ As and 0.1 µg g⁻¹ Sb and 10 SD quantification limit of 1.7 µg g⁻¹As and 0.3 µg g⁻¹ Sb and a characteristic mass of 65 pg As and 53 pg Sb were obtained. For all the matrices under scrutiny, a good agreement with certified values was achieved with RSD values less than 10%.     

Solid-phase spectrophotometric determination of nickel in water and vegetable samples at sub-mug l(-1) level with o-carboxylphenyldiazoaminoazobenzene loaded XAD-4

A highly sensitive and selective solid-phase spectrophotometric method for the determination of sub-μg l⁻¹ level nickel(II) is described. Nickel(II) was sorbed on a styrene-divinylbenzene-type resin Amberlite XAD-4 as a Ni(II)-o-carboxylphenyldiazoaminoazobenzene (o-CDAA) complex. At pH 9.0, resin phase absorbances at 588 and 800 nm were measured directly with an apparent molar absorptivity of 2.95×10⁷ g mol⁻¹ cm⁻¹. The linear range of the determination was 1.2-41 μg g⁻¹ resin. The detection limit and the quantification limit were found to be 0.24 and 0.76 μg g⁻¹ resin, respectively. The relative standard deviation of 10 replicate determinations of 1.0 μg nickel(II) in 100 ml sample was of 1.5%. The tolerance limit of coexistent ions was also investigated. Most of them are in tolerable amount. For practical analyses, 1 ml acetylacetone used can eliminate the interferences caused by Cu and Fe. The procedure was validated by analysis a certified water reference material (GBW 08618 Beijing, China) and a tomato leaf certified reference material (GBW 08402 Beijing, China) with the results in agreement with the certified values. The method was applied to the determination of nickel(II) in water and vegetable samples with satisfactory results.     

Determination of trace amounts of sodium and lithium in zirconium dioxide (ZrO2) using liquid electrode plasma optical emission spectrometry

This paper describes a quantitative measurement of trace elements (Na, Li) in high purity zirconium dioxide powder using liquid electrode plasma optical emission spectrometry (LEP-OES). Conventionally, for such type of measurements, inductively coupled plasma optical emission spectrometry (ICP-OES) is frequently employed. The detection limits of elements in zirconium by ICP-OES are degraded due to the spectra interference between the trace elements and zirconium of the matrix, because zirconium is a line rich element in spectra obtained by ICP-OES. LEP-OES is an elemental analysis method developed by the authors. The measurement principle is simple, as follows. Sample solution is put into a narrow channel on a small cuvette and voltage pulse is applied from both ends of the channel. At the center of the channel which is made narrower, the voltage and current are concentrated there, and plasma is generated. From the emission of the plasma, the quantitative analysis of the elements in the solution is achieved. The LEP-OES has the property that the emission of zirconium is relatively weak, so that highly sensitive measurement of trace elements in zirconium matrix can be conducted without interference. Sample solution is prepared by dissolving high purity zirconium dioxide powder and trace amounts of Na or Li with sulfuric acid. The voltage dependence and the pulse width dependence of optical emission spectra are also investigated. With increase of the voltage or the pulse width, the ratio of emission intensities of Na to those of hydrogen increases. This suggests that the ratio of sensitivity of two elements is variable, that means the element selectivity is controllable to some extent by the measurement conditions in LEP-OES. In the case of Na and H, the ratio can be controlled from 7.4 to 21.6%. Finally, the detection limits (3S.D.) of the trace elements, Na and Li, in 4000 μg g⁻¹ zirconium dioxide aqueous solution are found to be 0.02 and 0.133 μg g⁻¹, respectively. These values correspond to 5 μg g⁻¹ for Na, 33.25 μg g⁻¹ for Li in original high purity zirconium dioxide powder. The correlation coefficient of calibration curve was 0.995 for Na, 0.985 for Li. Those are comparable to the literature values of detection limits using ICP-OES.     

A new and direct method for the trace element determination in cauliflower by differential pulse polarography

Using the DPP polarograms of wet digested cauliflower sample in acetate buffer at pH values of 2, 4 and 6, Fe, Zn, Mo, Se, Cr, Cd, Pb, Ti and Cu quantities were determined. The best separation and determination conditions for Zn, Se and Mo was pH 2; for Cr, Zn, Mo and As was pH 4; for Pb pH 6, for Ti, Cu and Fe was pH 6-7 EDTA, for Cd pH 2 EDTA and for lead pH 6, all in acetate buffer. The trace element ranges for cauliflowers from two different seasons were (first figure for winter, the second for summer) for Se 120-250 μg g⁻¹, Fe 70-85 μg g⁻¹, Cu 320-150 μg g⁻¹, Ti 90-120 μg g⁻¹, Cr 130-630 μg g⁻¹, Zn 90-550 μg g⁻¹, Mo 170-230 μg g⁻¹, Cd 20 μg g⁻¹ (in winter) and Pb 130-300 μg g⁻¹ in dry sample. Cd was under the detection limit in summer. The length of digestion time had no effect on the recovery of copper, iron, molybdenum and zinc between 15 and 3 h of digestion.     

Analysis of metals and phosphorus in biodiesel B100 from different feedstock using a Flow Blurring multinebulizer in inductively coupled plasma-optical emission spectrometry

A simple and fast method for determining the content of Na, K, Ca, Mg, P, and 20 heavy metals in biodiesel samples with inductively coupled plasma optical emission spectrometry (ICP OES) using a two-nozzle Flow Blurring^® multinebulizer prototype and on-line internal standard calibration, are proposed. The biodiesel samples were produced from different feedstock such as sunflower, corn, soybean and grape seed oils, via a base catalyst transesterification. The analysis was carried out without any sample pretreatment. The standards and samples were introduced through one of the multinebulizer nozzles, while the aqueous solution containing yttrium as an internal standard was introduced through the second nozzle. Thus, the spectral interferences were compensated and the formation of carbon deposits on the ICP torch was prevented. The determination coefficients (R²) were greater than 0.99 for the studied analytes, in the range 0.21–14.75 mg kg⁻¹. Short-term and long-term precisions were estimated as relative standard deviation. These were acceptable, their values being lower than 10%. The LOQ for major components such as Ca, K, Mg, Na, and P, were within a range between 4.9 ng g⁻¹ for Mg (279.553 nm) and 531.1 ng g⁻¹ for Na (588.995 nm), and for the other 20 minor components they were within a range between 1.1 ng g⁻¹ for Ba (455.403 nm) and 2913.9 ng g⁻¹ for Pb (220.353 nm). Recovery values ranged between 95% and 106%.     

A study of the direct determination of Cd, Cr, Cu, Pb and Zn in certified reference materials of soils by solid sampling electrothermal atomic absorption spectrometry

A simple and rapid method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil was developed. The method was developed using three certified reference materials of soil: Eutric Cambisol, Orthic Luvisols and Rendzina, which differed in their matrix composition. Chemical modifiers were essential to achieve reproducible and interference-free signals for the analytes studied. The best results were obtained with a Pd/Mg(NO₃)₂ admixture for the determination of Cd, Pb and Zn and NH₄F for Cu. The combination of W (as a permanent modifier) and Mg(NO₃)₂ provided well-defined signal profiles for Cr. The following spectral lines were used: Cd 228.8 nm, Cr 520.6 nm, Cu 218.2 nm, Pb 205.3 nm and Zn 307.6 nm. The limit of detection was 4.2 ng g^− 1 for Cd, 1.1 μg g^− 1 for Cr, 0.5 μg g^− 1 for Cu, 1.3 μg g^− 1 for Pb and 8.6 μg g^− 1 for Zn for the maximum sample mass used. Under optimized conditions, the analyte and matrix were separated effectively in situ, and aqueous standards could be used for calibration.     

Characterization and determination of 28 elements in fly ashes collected in a thermal power plant in Argentina using different instrumental techniques

Different techniques were selected for comprehensive characterization of seven samples of fly ashes collected from the electrostatic precipitator of the San Nicolás thermal power plant (Buenos Aires, Argentina). Particle size was measured using laser based particle size analyzer. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the mineral phase present in the matrix consisting basically of aluminosilicates and large amounts of amorphous material. The predominant crystalline phases were mullite and quartz. Major and minors elements (Al, Ca, Cl, Fe, K, Mg, Na, S, Si and Ti) were detected by energy dispersive X-ray analysis (EDAX). Trace elements (As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Se, V and Zn) content was quantified by inductively coupled plasma optical emission spectrometry (ICP OES). Different acid mixtures and digestion procedures were compared for subsequent ICP OES measurements of the dissolved samples. The digestion procedures used were: i) a mixture of FH + HNO₃ + HClO₄ (open system digestion); ii) a mixture of FH + HNO₃ (MW-assisted digestion); iii) a mixture of HF and aqua regia (MW-assisted digestion). Instrumental neutron activation analysis (INAA) was employed for the determination of As, Ba, Co, Cr, Ce, Cs, Eu, Fe, Gd, Hf, La, Lu, Rb, Sb, Sc, Sm, Ta, Tb, Th, U and Yb. The validation of the procedure was performed by the analysis of two certified materials namely, i) NIST 1633b, coal fly ash and ii) GBW07105, rock. Mean elements content spanned from 41870 μg g^− 1 for Fe to 1.14 μg g^− 1 for Lu. The study showed that Fe (41870 μg g^− 1) ? V (1137 μg g^− 1) > Ni (269 μg g^− 1) > Mn (169 μg g^− 1) are the main components. An enrichment, with respect to crustal average, in many elements was observed especially for As, V and Sb that deserve particular interest from the environmental and human health point of view.     

Application of multivariate techniques in the optimization of a procedure for the determination of bioavailable concentrations of Se and As in estuarine sediments by ICP OES using a concomitant metals analyzer as a hydride generator

A procedure has been developed for the determination of bioavailable concentrations of selenium and arsenic in estuarine sediments employing inductively coupled plasma optical emission spectrometry (ICP OES) using a concomitant metals analyzer device to perform hydride generation. The optimization of hydride generation was done in two steps: using a two-level factorial design for preliminary evaluation of studied factors and a Doehlert design to assess the optimal experimental conditions for analysis. Interferences of transition metallic ions (Cd²⁺, Co²⁺, Cu²⁺, Fe³⁺ and Ni²⁺) to selenium and arsenic signals were minimized by using higher hydrochloric acid concentrations. In this way, the procedure allowed the determination of selenium and arsenic in sediments with a detection limit of 25 and 30 μg kg⁻¹, respectively, assuming a 50-fold sample dilution (0.5 g sample extraction to 25 mL sample final volume). The precision, expressed as a relative standard deviation (% RSD, n = 10), was 0.2% for both selenium and arsenic in 200 μg L⁻¹ solutions, which corresponds to 10 μg g⁻¹ in sediment samples after acid extraction. Applying the proposed procedure, a linear range of 0.08-10 and 0.10-10 μg g⁻¹ was obtained for selenium and arsenic, respectively. The developed procedure was validated by the analysis of two certified reference materials: industrial sludge (NIST 2782) and river sediment (NIST 8704). The results were in agreement with the certified values. The developed procedure was applied to evaluate the bioavailability of both elements in four sediment certified reference materials, in which there are not certified values for bioavailable fractions, and also in estuarine sediment samples collected in several sites of Guanabara Bay, an impacted environment in Rio de Janeiro, Brazil.     

Method development for the determination of cadmium in fertilizer samples using high-resolution continuum source graphite furnace atomic absorption spectrometry and slurry sampling

The determination of cadmium (Cd) in fertilizers is of major interest, as this element can cause growth problems in plants, and also affect animals and humans. High-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) with charge-coupled device (CCD) array detection overcomes several of the limitations encountered with conventional line source AAS, especially the problem of accurate background measurement and correction. In this work an analytical method has been developed to determine Cd in fertilizer samples by HR-CS GF AAS using slurry sampling. Both a mixture of 10 μg Pd + 6 μg Mg in solution and 400 μg of iridium as permanent modifier have been investigated and aqueous standards were used for calibration. Pyrolysis and atomization temperatures were 600 °C and 1600 °C for the Pd-Mg modifier, and 500 °C and 1600 °C for Ir, respectively. The results obtained for Cd in the certified reference material NIST SRM 695 (Trace Elements in Multi-Nutrient Fertilizer) of 16.7 ± 1.3 μg g⁻¹ and 16.4 ± 0.75 μg g⁻¹ for the Pd-Mg and Ir modifier, respectively, were statistically not different from the certified value of 16.9 ± 0.2 μg g⁻¹ on a 95% confidence level; however, the results obtained with the Ir modifier were significantly lower than those for the Pd-Mg modifier for most of the samples. The characteristic mass was 1.0 pg for the Pd-Mg modifier and 1.1 pg Cd for the Ir modifier, and the correlation coefficients (R²) of the calibration were > 0.99. The instrumental limits of detection were 7.5 and 7.9 ng g⁻¹, and the limits of quantification were 25 and 27 ng g⁻¹ for Pd-Mg and Ir, respectively, based on a sample mass of 5 mg. The cadmium concentration in the investigated samples was between 0.07 and 5.5 μg g⁻¹ Cd, and hence below the maximum value of 20 μg g⁻¹ Cd permitted by Brazilian legislation.     

Direct determination of major elements in solid plant materials by electrothermal vaporization inductively coupled plasma atomic emission spectrometry

The present work demonstrates the capability of electrothermal vaporization (ETV) to become an important tool of solid sample introduction in ICP-AES for plant sample analysis. Direct determination of Al, Ca, Fe, K, Mg, Mn, Na and Zn was investigated in powdered plant samples. Obtaining good results for major elements in plant samples was governed by some special operating conditions. The sensitivity of the method necessitated the use of ICP in radial view configuration. The behavior of elements during vaporization was studied between 500 and 2600 °C. External calibration was carried out using solid external (cellulose) spiked with aqueous standard solutions. However, performances of the analytical method were found dependent of argon flow rates. Analytical accuracy of the method was tested in three reference materials. Analytical results agreed with certified values when cellulose was used in calibration. However, K could not be determined because of excessive sensitivity. Without cellulose, it was found that Fe results were underestimated and Zn results overestimated. Relative standard deviations varied from 3 to 23%. Limits of detection varied from 1 to 80 ng g⁻¹ from one element to the other for a typical mass sample of 2 mg.     

Optimization and comparison of chemical and electrochemical hydride generation for optical emission spectrometric determination of arsenic and antimony using a novel miniaturized microwave induced argon plasma exiting the microstrip wafer

Continuous flow (CF) chemical hydride generation (CHG) and electrochemical hydride generation (ECHG) directly coupled to a novel 40 W, atmospheric pressure, 2.45 GHz microwave microstrip Ar plasma exiting a microstrip wafer has been developed for the emission spectrometric determination of As and Sb using a miniaturized optical fiber spectrometer and a CCD-array detector. The experimental conditions for both procedures were optimized with respect to the relative net intensities of the As I 228.8 nm and Sb I 252.8 nm lines and their signal-to-background intensity ratios. Additionally, the susceptibility to interferences from Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn and other hydride-forming elements in the determination of As and Sb using the CHG and ECHG techniques was investigated in detail. Under the optimized conditions, it was found that ECHG is more prone to interferences compared to CHG. The detection limits (3σ) of As (6 ng mL⁻¹) and Sb (7 ng mL⁻¹) obtained for the ECHG-MSP-OES method are about three times lower than in the case of the CHG-MSP-OES method due to a two-fold lower amount of H₂ introduced into the MSP in case of the ECHG, resulting in a better plasma stability and reduced background level. The linearity ranges for both calibration curves to a concentration of up to 5 μg mL⁻¹ and a precision between 2% and 7% (2 μg mL⁻¹ and 0.050 μg mL⁻¹ of As and Sb, respectively) were found for both methods. The developed ECHG-MSP-OES method was validated for As through the analysis of a certified coal fly ash standard reference material (NIST SRM 1633a) after sample dissolution. The derived concentration (140 ± 8 μg g⁻¹) was found to agree well with the certified data (145 ± 15 μg g⁻¹). The method was also successfully applied to the analysis of both a galvanic bath sample, which contained Sb and was spiked with As, and a tap water sample spiked with both analytes. Recovery rates of 99-101% and a Sb concentration of 6.6 μg mL⁻¹ in the galvanic bath sample were revealed. The latter value showed a good agreement with the data obtained from ICP-OES analysis, which was also used for validation purpose.     

Determination of cadmium and lead in cetacean Dolphinidae tissue from the coast of Bahia state in Brazil by GFAAS

In the present study, cadmium and lead in the muscle, lung, liver and kidney of dolphins (Sotalia guianensis and Stenella clymene) of the Bahia coast in the northwest of Brazil were determined by graphite furnace atomic absorption spectrometry. Samples were digested using a diluted oxidant mixture (HNO₃ + H₂O₂) with a microwave heating program performed in five steps. The optimized temperatures and chemical modifier for the pyrolysis and atomization were 700 °C, 1400 °C and Pd plus Mg for Cd, and 900 °C, 1800 °C and NH₄H₂PO₄ for Pb, respectively. Characteristic masses and limits of detections (n = 20, 3σ) for Cd and Pb were 1.6 and 9.0 pg and 0.82 ng g^− 1 and 0.50 ng g^− 1, respectively. Repeatability ranged from 0.87 to 8.22% for Cd and 4.31 to 8.09% for Pb. The found concentrations presented no statistical differences at the 95% confidence level when compared with the ICP OES methods. Addition and recovery tests were also performed and the results ranged between 87 and 112% for both elements. Samples of cetacean Dolphinidae (S.guianensis and S.clymene) were analyzed, and the higher concentrations ranged from 0.09 to 46.2 µg g^− 1 for Cd and 0.04 to 0.47 µg g^− 1 for Pb in liver, and from 0.133 to 277 µg g^− 1 for Cd in the kidney.     

Simultaneous determination of Cd and Fe in grain products using direct solid sampling and high-resolution continuum source electrothermal atomic absorption spectrometry

Cadmium and iron are antagonistic elements in the sense that they produce different effects in the human body. Both elements have to be determined routinely in grain products, cadmium because of its toxicity, and iron because all grain products, according to Brazilian law, have to contain a minimum of 42 mg kg⁻¹ Fe to combat anemia. A routine screening method has been developed for the quasi simultaneous determination of cadmium and iron using high-resolution continuum source electrothermal atomic absorption spectrometry and direct solid sampling. The primary absorption line at 228.802 nm has been used for Cd, and an adjacent secondary line at 228.726 nm for the determination of Fe. Various chemical modifiers have been investigated, and a mixture of tungsten and iridium, applied as a permanent modifier, showed the best performance; it stabilized Cd up to a pyrolysis temperature of 700 °C and did not over-stabilize Fe. Two atomization temperatures were used sequentially, 1700 °C for Cd and 2600 °C for Fe, because of their significantly different volatilities. The characteristic masses obtained were 0.9 pg for Cd and 1.2 ng for Fe. The limits of detection (3σ, n = 10) were 0.6 μg kg⁻¹ for Cd and 0.5 mg kg⁻¹ for Fe. The relative standard deviation ranged from 3 to 7% for Cd and from 4 to 13% for Fe, which is satisfactory for the purpose. The accuracy of the method was confirmed by the analysis of three certified reference materials; the results were in agreement with the certified values at a 95% confidence interval. The Cd content in the investigated grain products was between 0.9 and 10.5 μg kg⁻¹, but most of them did not contain the required minimum amount of iron.     

Measurement of methyl mercury (I) and mercury (II) in fish tissues and sediments by HPLC-ICPMS and HPLC-HGAAS

A procedure for the extraction and determination of methyl mercury and mercury (II) in fish muscle tissues and sediment samples is presented. The procedure involves extraction with 5% (v/v) 2-mercaptoethanol, separation and determination of mercury species by HPLC-ICPMS using a Perkin-Elmer 3 μm C8 (33 mm × 3 mm) column and a mobile phase 3 containing 0.5% (v/v) 2-mercaptoethanol and 5% (v/v) CH₃OH (pH 5.5) at a flow rate 1.5 ml min⁻¹ and a temperature of 25 °C. Calibration curves for methyl mercury (I) and mercury (II) standards were linear in the range of 0-100 μg l⁻¹ (r² = 0.9990 and r² = 0.9995 respectively). The lowest measurable mercury was 0.4 μg l⁻¹ which corresponds to 0.01 μg g⁻¹ in fish tissues and sediments. Methyl mercury concentrations measured in biological certified reference materials, NRCC DORM - 2 Dogfish muscle (4.4 ± 0.8 μg g⁻¹), NRCC Dolt - 3 Dogfish liver (1.55 ± 0.09 μg g⁻¹), NIST RM 50 Albacore Tuna (0.89 ± 0.08 μg g⁻¹) and IRMM IMEP-20 Tuna fish (3.6 ± 0.6 μg g⁻¹) were in agreement with the certified value (4.47 ± 0.32 μg g⁻¹, 1.59 ± 0.12 μg g⁻¹, 0.87 ± 0.03 μg g⁻¹, 4.24 ± 0.27 μg g⁻¹ respectively). For the sediment reference material ERM CC 580, a methyl mercury concentration of 0.070 ± 0.002 μg g⁻¹ was measured which corresponds to an extraction efficiency of 92 ± 3% of certified values (0.076 ± 0.04 μg g⁻¹) but within the range of published values (0.040-0.084 μg g⁻¹; mean ± s.d.: 0.073 ± 0.05 μg g⁻¹, n = 40) for this material. The extraction procedure for the fish tissues was also compared against an enzymatic extraction using Protease type XIV that has been previously published and similar results were obtained. The use of HPLC-HGAAS with a Phenomenox 5 μm Luna C18 (250 mm × 4.6 mm) column and a mobile phase containing 0.06 mol l⁻¹ ammonium acetate (Merck Pty Limited, Australia) in 5% (v/v) methanol and 0.1% (w/v) l-cysteine at 25 °C was evaluated as a complementary alternative to HPLC-ICPMS for the measurement of mercury species in fish tissues. The lowest measurable mercury concentration was 2 μg l⁻¹ and this corresponds to 0.1 μg g⁻¹ in fish tissues. Analysis of enzymatic extracts analysed by HPLC-HGAAS and HPLC-ICPMS gave equivalent results.     

Direct and simultaneous determination of arsenic, manganese, cobalt and nickel in urine with a multielement graphite furnace atomic absorption spectrometer

A simple method was developed for the direct and simultaneous determination of arsenic (As), manganese (Mn), cobalt (Co), and nickel (Ni) in urine by a multi-element graphite furnace atomic absorption spectrometer (Perkin-Elmer SIMAA 6000) equipped with the transversely heated graphite atomizer and longitudinal Zeeman-effect background correction. Pd was used as the chemical modifier along with either the internal furnace gas or a internal furnace gas containing hydrogen and a double stage pyrolysis process. A standard reference material (SRM) of Seronorm™ Trace Elements in urine was used to confirm the accuracy of the method. The optimum conditions for the analysis of urine samples are pyrolysis at 1350 °C (using 5% H₂ v/v in Ar as the inter furnace gas during the first pyrolysis stage and pure Ar during the second pyrolysis stage) and atomization at 2100 °C. The use of Ar and matrix-free standards resulted in concentrations for all the analytes within 85% (As) to 110% (Ni) of the certified values. The recovery for As was improved when mixture of 5% H₂ and 95% Ar (v/v) internal furnace gas was applied during the first step of a two-stage pyrolysis at 1350 °C, and the found values of the analytes were within 91-110% of the certified value. The recoveries for real urine samples were in the range 88-95% for these four elements. The detection limits were 0.78 μg l⁻¹ for As, 0.054 μg l⁻¹ for Mn, 0.22 μg l⁻¹ for Co, and 0.35 μg l⁻¹ for Ni. The upper limits of the linear calibration curve are 60 μg l⁻¹ (As); 12 μg l⁻¹ (Mn); 12 μg l⁻¹ (Co) and 25 μg l⁻¹ (Ni), respectively. The relative standard deviations (R.S.D.s) for the analysis of SRM were 2% or less. The R.S.D.s of a real urine sample are 1.6% (As), 6.3% (Mn), 7.0% (Ni) and 8.0% (Co), respectively.     

Speciation of dissolved Fe(II) and Fe(III) in environmental water samples by micro-column packed with N-benzoyl-N-phenylhydroxylamine loaded on microcrystalline naphthalene and determination by electrothermal vaporization inductively coupled plasma-optical emission spectrometry

A novel solid phase extraction technique for the speciation of trace dissolved Fe(II) and Fe(III) in environmental water samples was developed by coupling micro-column packed with N-benzoyl-N-phenylhydroxylamine (BPHA) loaded on microcrystalline naphthalene to electrothermal vaporization inductively coupled plasma-optical emission spectrometry (ETV-ICP-OES). Various influencing factors on the separation and preconcentration of Fe(II) and Fe(III), such as the acidity of the aqueous solution, sample flow rate and volume, have been investigated systematically, and the optimized operation conditions were established. At pH 3.0 Fe(III) could be selectively retained by micro-column (20 mm × 1.4 mm, i.d.) packed with BPHA immobilized on microcrystalline naphthalene, and Fe(II) passed through the micro-column. Both Fe(II) and Fe(III) could be adsorbed by the micro-column at pH 6.5. Thus, the total Fe could be determined without the need for preoxidation of Fe(II) to Fe(III). The retained Fe(III) or the Fe(II) and Fe(III) was subsequently eluted by 0.1 ml of 1 mol l⁻¹ HCl. The adsorption capacity of the solid phase adsorption material was found to be 45.0 mg g⁻¹ for Fe(III) at pH 3.0 and 65.3 mg g⁻¹ for Fe(II) at pH 6.5, respectively. The detection limit (3σ) of 0.053 μg l⁻¹ was obtained with a practical enrichment factor of 156 at a sample volume of 17 ml. The relative standard deviations of 4.2% and 4.6% (C_Fe(III) = C_Fe(II) = 10 μg l⁻¹, n = 7) for Fe(III) and total iron were found, respectively. The method was successfully applied to the determination of trace Fe(II) and Fe(III) in environmental water samples (East Lake water, local tap water and mineral water). In order to validate the method, the developed method was applied to the determination of total iron in certified materials of NIES NO.10-b rice flour and GBW07605 tea leaves, and the results obtained were in good agreement with the certified values.     

Simultaneous determination of hydride forming (As, Bi, Ge, Sb, Se, Sn) and Hg and non-hydride forming (Ca, Fe, Mg, Mn, Zn) elements in sonicate slurries of analytical samples by microwave induced plasma optical emission spectrometry with dual-mode sample introduction system

A slurry sampling method for the simultaneous determination of hydride forming (As, Bi, Ge, Sb, Se, Sn) and Hg and non-hydride forming (Ca, Fe, Mg, Mn, Zn) elements, without total sample digestion has been developed using the commercial dual-mode sample introduction system (MSIS) coupled with microwave induced plasma optical emission spectrometry (MIP-OES) from biological and environmental reference materials and real samples. The main advantage of this system is its simultaneous determination of elements that form volatile vapor species and elements that do not, without any instrumental changes. Optimization of reaction, nebulization and instrumental conditions was performed to characterize the new system. Slurry concentration up to 4% m/v (particles < 100 μm) prepared in 10% HNO₃ containing 100 μL of decanol, by application of ultrasonic agitation, was used with calibration by the standard addition technique. An ultrasonic probe was used to homogenize the slurry in the quartz cup just before its introduction into the reaction/nebulization system; the multimode sample introduction system (MSIS) combines the benefits of nebulization and vapor generation in a single device. Detection limits (LOD, 3σ_blank, peak area) of 0.07, 0.29, 0.25, 0.10, 0.12, 0.14, 0.11, 0.28, 0.42, 0.02, 0.21 and 0.34 μg g^− 1 were obtained for As, Bi, Ge, Sb, Se, Sn, Hg, Ca, Fe, Mg, Mn and Zn, respectively. The relative standard deviations were ca. 10%, adequate for slurry analysis. To test the accuracy, six certified reference materials were analyzed with the analyte concentrations mostly in the μg g^− 1 level. Measured concentrations are in satisfactory agreement with certified values for the biological reference materials (LUTS-1, DOLT-2) and environmental reference materials (PACS-1, GWB 07302, NIST 2710, NBS 1633b), all adequate for slurry sampling. The method was successfully applied to the determination of the elements in real samples (coal fly ash, lake sediment, sewage). The method requires small amounts of reagents and reduces contamination and losses.     

Determination of traces of palladium in stream sediment and auto catalyst by FI-ICP-OES using on-line separation and preconcentration with QuadraSil TA

A flow injection analysis (FIA) method using on-line separation and preconcentration with a novel metal scavenger beads, QuadraSil™ TA, has been developed for the ICP-OES determination of traces of palladium. QuadraSil TA contains diethylenetriamine as a functional group on spherical silica beads and shows the highest selectivity for Pd(II) at pH 1 (0.1 mol l⁻¹ hydrochloric acid) solution. An aliquot of the sample solution prepared as 0.1 mol l⁻¹ in hydrochloric acid was passed through the QuadraSil TA column. After washing the column with the carrier solution, the Pd(II) retained on the column was eluted with 0.05 mol l⁻¹ thiourea solution and the eluate was directly introduced into an ICP-OES. The proposed method was successfully applied to the determination of traces of palladium in JSd-2 stream sediment certified reference material [0.019 ± 0.001 μg g⁻¹ (n = 3); provisional value: 0.0212 μg g⁻¹] and SRM 2556 used auto catalyst certified reference material [315 ± 4 μg g⁻¹ (n = 4); certified value: 326 μg g⁻¹]. The detection limit (3σ) of 0.28 ng ml⁻¹ was obtained for 5 ml of sample solution. The sample throughputs for 5 ml and 100 μl of the sample solutions were 10 and 15 h⁻¹, respectively.     

Fast on-line ultrasound-assisted extraction coupled to a flow injection-atomic absorption spectrometric system for zinc determination in meat samples

A continuous ultrasound-assisted extraction system connected to a flow injection manifold has been used for the on-line determination of zinc in meat samples by flame atomic absorption spectrometry. An experimental design was used for the optimisation of the continuous manifold. This flow injection methodology allowed a sampling frequency of ca. 80 samples per hour with a relative standard deviation for the whole procedure of 0.3% (for a sample containing 163.6 μg g⁻¹ Zn). The detection limit was 0.6 μg g⁻¹ for a sample amount of 5 mg. Accurate results were obtained by measuring certified reference materials (BCR-186 (pig kidney) and BCR-184 (bovine muscle)). The analytical procedure was applied to different real meat samples with satisfactory results.