External calibration strategy for trace element quantification in botanical samples by LA-ICP-MS using filter paper

The use of reference solutions dispersed on filter paper discs is proposed for the first time as an external calibration strategy for matrix matching and determination of As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr, V and Zn in plants by laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS). The procedure is based on the use of filter paper discs as support for aqueous reference solutions, which are further evaporated, resulting in solid standards with concentrations up to 250 μg g⁻¹ of each element. The use of filter paper for calibration is proposed as matrix matched standards due to the similarities of this material with botanical samples, regarding to carbon concentration and its distribution through both matrices. These characteristics allowed the use of ¹³C as internal standard (IS) during the analysis by LA-ICP-MS. In this way, parameters as analyte signal normalization with ¹³C, carrier gas flow rate, laser energy, spot size, and calibration range were monitored. The calibration procedure using solution deposition on filter paper discs resulted in precision improvement when ¹³C was used as IS. The method precision was calculated by the analysis of a certified reference material (CRM) of botanical matrix, considering the RSD obtained for 5 line scans and was lower than 20%. Accuracy of LA-ICP-MS determinations were evaluated by analysis of four CRM pellets of botanical composition, as well as by comparison with results obtained by ICP-MS using solution nebulization after microwave assisted digestion. Plant samples of unknown elemental composition were analyzed by the proposed LA method and good agreement were obtained with results of solution analysis. Limits of detection (LOD) established for LA-ICP-MS were obtained by the ablation of 10 lines on the filter paper disc containing 40 μL of 5% HNO₃ (v v⁻¹) as calibration blank. Values ranged from 0.05 to 0.81  μg g⁻¹. Overall, the use of filter paper as support for dried aqueous standards showed to be a useful strategy for calibration and plant analysis by LA-ICP-MS.     

Biomonitoring of essential and toxic metals in single hair using on-line solution-based calibration in laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has been established as a powerful and sensitive surface analytical technique for the determination of concentration and distribution of trace metals within biological systems at micrometer spatial resolution. LA-ICP-MS allows easy quantification procedures if suitable standard references materials (SRM) are available. In this work a new SRM-free approach of solution-based calibration method in LA-ICP-MS for element quantification in hair is described. A dual argon flow of the carrier gas and nebulizer gas is used. A dry aerosol produced by laser ablation (LA) of biological sample and a desolvated aerosol generated by pneumatic nebulization (PN) of standard solutions are carried by two different flows of argon as carrier or nebulizer gas, respectively and introduced separately in the injector tube of a special ICP torch, through two separated apertures. Both argon flows are mixed directly in the ICP torch. External calibration via defined standard solutions before analysis of single hair was employed as calibration strategy. A correction factor, calculated using hair with known analyte concentration (measured by ICP-MS), is applied to correct the different elemental sensitivities of ICP-MS and LA-ICP-MS. Calibration curves are obtained by plotting the ratio of analyte ion M⁺/³⁴S⁺ ion intensities measured using LA-ICP-MS in dependence of analyte concentration in calibration solutions. Matrix-matched on-line calibration in LA-ICP-MS is carried out by ablating of human hair strands (mounted on a sticky tape in the LA chamber) using a focused laser beam in parallel with conventional nebulization of calibration solutions. Calibrations curves of Li, Na, Mg, Al, K, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Sr, Mo, Ag, Cd, I, Hg, Pb, Tl, Bi and U are presented. The linear correlation coefficients (R) of calibration curves for analytes were typically between 0.97 and 0.999. The limits of detection (LODs) of Li, V, Mn, Ni, Co, Cu, Sr, Mo, Ag, Ba, Cd, I, Hg, Pb, Bi and U in a single hair strand were in the range of 0.001-0.90 μg g⁻¹, whereas those of Cr and Zn were 3.4 and 5.1 μg g⁻¹, respectively. The proposed quantification strategy using on-line solution-based calibration in LA-ICP-MS was applied for biomonitoring (the spatial resolved distribution analysis) of essential and toxic metals and iodine in human hair and mouse hair.     

Comparison of laser ablation-inductively coupled plasma-mass spectrometry and micro-X-ray fluorescence spectrometry for elemental imaging in Daphnia magna

Visualization of elemental distributions in thin sections of biological tissue is gaining importance in many disciplines of biological and medical research. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and scanning micro-X-ray fluorescence spectrometry (micro-XRF) are two widely used microanalytical techniques for elemental mapping. This article compares the capabilities of the two techniques for imaging the distribution of selected elements in the model organism Daphnia magna in terms of detection power and spatial resolution. Sections with a thickness of 10 and 20 μm of the fresh water crustacean Daphnia magna were subjected to LA-ICP-MS and micro-XRF analysis. The elemental distributions obtained for Ca, P, S and Zn allow element-to-tissue correlation. LA-ICP-MS and micro-XRF offer similar limits of detection for the elements Ca and P and thus, allow a cross-validation of the imaging results. LA-ICP-MS was particularly sensitive for determining Zn (LOD 20 μg g⁻¹, 15 μm spot size) in Daphnia magna, while the detection power of micro-XRF was insufficient in this context. However, LA-ICP-MS was inadequate for the measurement of the S distributions, which could be better visualized with micro-XRF (LOD 160 μg g⁻¹, 5 s live time). Both techniques are thus complementary in providing an exhaustive chemical profiling of tissue samples.     

Biomonitoring of metal contamination in a marine prosobranch snail (Nassarius reticulatus) by imaging laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

An imaging mass spectrometric method using laser ablation inductively coupled plasma spectrometry (LA-ICP-MS) was developed to determine Cu, Zn, Cd, Hg and Pb and metal distribution in longitudinal tissue sections of the marine snail Nassarius reticulatus (Gastropoda, Prosobranchia). Snails were sampled in northern Brittany (France) at three stations with different contamination levels.The quantification of metal distribution (imaging or mapping) in a thin slice of the snail tissue was carried out using different strategies: by one-point calibration and via matrix-matched laboratory standards using different biological materials (BCR 278, snail tissue, and rat brain). Together with the imaging of metals the distribution of two non-metals (carbon and sulfur) was analyzed. The imaging LA-ICP-MS analysis yielded an inhomogeneous distribution for all elements investigated. The detection limits for the distribution analysis of Cu, Zn, Cd, Hg and Pb measured by LA-ICP-MS were in the low μg g⁻¹ range.     

Comparative imaging of P,S, Fe,Cu, Zn and C in thin sections of rat brain tumor as well as control tissues by laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for quantitative imaging of selected elements (P, S, Fe, Cu, Zn and C) in thin sections of rat brain samples (thickness 20 μm). The sample surface was scanned (raster area ~ 2 cm²) with a focused laser beam (wavelength 266 nm, diameter of laser crater 50 μm, and irradiance 1 × 10⁹ W cm^− 2). The laser ablation system was coupled to a double-focusing sector field. The possibility was evaluated of using carbon (via measurement of ¹³C⁺) as an internal standard element for imaging element distribution as part of this method. The LA-ICP-MS images obtained for P, S, Fe Cu and Zn were quantified using synthetically prepared matrix-matched laboratory standards. Depending on the sample analyzed, concentrations of Cu and Zn in the control tissue were found to be in the range of 8–10 μg g^− 1 and 10–12 μg g^− 1, while in the tumor tissue these concentrations were in the range of 12–15 μg g^− 1 and 15–17 μg g^− 1, respectively. The measurements of P, S and Fe distribution revealed the depletion of these elements in tumor tissue. In all the samples, the shape of the tumor could be clearly distinguished from the surrounding healthy tissue by the depletion in carbon. Additional experiments were performed in order to study the influence of the water content of the analyzed tissue on the intensity signal of the analyte. The results of these measurements show the linear correlation (R² = 0.9604) between the intensity of analyte and amount of water in the sample. The growth of a brain tumor was thus studied for the first time by imaging mass spectrometry.     

A methodology for the determination of reductive sulphur in optical and technical glass

This paper describes an analytical method for the determination of reductive sulphur (S(IV), S(-II)) in glass. The glass sample is dissolved in hydrofluoric/hydrochloric acid mixture and the sulphur is separated via distillation in an apparatus made of polyfluoralkoxyethylene (PFA). The distilled hydrogen sulphide is trapped in buffered boric acid-zinc acetate solution and subsequently determined after conversion to an ethylene blue dye. The range of the method lies within a range of 2-1200 μg g⁻¹ reductive sulphur. The quantification limit for reductive sulphur is 2 μg g⁻¹.Different analysed glass types show either no detectable reductive sulphur or up to 30% of the total sulphur content reductive sulphur. The inter-laboratory standard deviation shown by a round robin test performed is excellent (±4 μg g⁻¹; average 59 μg g⁻¹). Sources of error of the methodology are discussed.     

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L⁻¹ of mercury. Standard addition calibration curves using standards between 0 and 20 μg L⁻¹ gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L⁻¹, and from 1.1 to 1.3 μg L⁻¹, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L⁻¹). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L⁻¹ as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).     

Imaging of nutrient elements in the leaves of Elsholtzia splendens by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of nutrient elements (such as K, Mg, Mn, Cu, P, S and B) in the leaves of Elsholtzia splendens. The plant leaves were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based ICP-MS (ICP-QMS), and the ion intensities of ³⁹K⁺, ²⁴Mg⁺, ⁵⁵Mn⁺, ⁶³Cu⁺, ³¹P⁺, ³⁴S⁺ and ¹¹B⁺ were measured by ICP-QMS to study the distribution of the elements of interest. The imaging technique using LA-ICP-MS on plant leaves does not require any sample preparation. Carbon (¹³C⁺) was used as an internal standard element to compensate for the difference in the amount of material ablated. Additional experiments were performed in order to study the influence of the water content of the analyzed leaves on the intensity signal of the analyte. For quantification purposes, standard reference material (NIST SRM 1515 Apple Leaves) was selected and doped with standard solutions of the analytes within the concentration range of 0.1-2000 mg L⁻¹. The synthetic laboratory standards together with the samples were measured by LA-ICP-MS. The shape and structure of the leaves was clearly given by LA-ICP-MS imaging of all the elements measured. The elemental distribution varied according to the element, but with a high content in the veins for all the elements investigated. Specifically, Cu was located uniformly in the mesophyll with a slightly higher concentration in the main vein. High ion intensity was measured for S with a high amount of this element in the veins similar to the images of the metals, whereas most of the B was detected at the tip of the leaf. With synthetic laboratory standard calibration, the concentrations of elements in the leaves measured by LA-ICP-MS were between 20 μg g⁻¹ for Cu and 14,000 μg g⁻¹ for K.     

Simultaneous determination of dimethoate and its metabolite omethoate in curry leaf using LC-MS/MS and risk assessment

This study presents the method development, validation, and simultaneous determination of dimethoate and its metabolite omethoate in curry leaf. Samples were extracted following modified quick, easy, cheap, effective, rugged, and safe extraction protocol and analyzed using liquid chromatography-tandem mass spectrometry. The limit of quantification in the matrix was 0.005 μg g⁻¹ for dimethoate and omethoate. Extraction using acetonitrile recorded the average recoveries in the range of 82.25 to 112.97% for dimethoate and 85.57 to 107.22% for omethoate at 0.005, 0.025 and 0.050 μg g⁻¹ fortification levels and relative standard deviation less than 5%. Similarly, the relative standard deviation values for intraday (Repeatability) and interday (Reproducibility) tests were less than 15%. Dissipation kinetics of dimethoate 30% emulsifiable concentrate at 200 and 400 g a.i h⁻¹ recorded initial deposits of 5.20 and 10.05 μg g⁻¹ and 0.33 and 0.48 μg g⁻¹ for dimethoate and omethoate, respectively, and half-life of 3.07 and 3.34 days. The estimated hazard index value found more than one at a day after dimethoate application. It is not safe for consumer health to use curry leaves in the initial days after application.     

Accurate determination of trace amounts of phosphorus in geological samples by inductively coupled plasma atomic emission spectrometry with ion-exchange separation

In order to determine trace amounts of phosphorus in geological and cosmochemical rock samples, simple as well as reliable analytical schemes using an ICP-AES instrument were investigated. A (conventional) ICP-AES procedure could determine phosphorus contents at the level of several 100 μg g⁻¹ with a reasonable reproducibility (<10% for 200 μg g⁻¹; 1σ). An ICP-AES procedure coupled with matrix-separation using cation and anion exchange resins could lower the quantification level down to 1 μg g⁻¹ or even lower under the present experimental conditions. The matrix-separation ICP-AES procedure developed in this study was applied to twenty-one geological reference samples issued by Geological Survey of Japan. Obtained values vary from 1250 μg g⁻¹ for JB-3 (basalt) to 2.07 μg g⁻¹ for JCt-1 (carbonate). Matrix-separation ICP-AES yielded reasonable reproducibility (less than 8.3%; 1σ) of three replicate analyses for all the samples analyzed. In comparison of our data with certificate values as well as literature or reported values, there appear to be an apparent (and large) discrepancy between our values and certificate/reported values regardless of phosphorus contents. Based on the reproducibility of our data and the analytical capability of the matrix-separation ICP-AES procedure developed in this study (in terms of quantification limit, recovery, selectivity of an analyte through pre-concentration process, etc.), it is concluded that certified values for several reference standard rocks should be reevaluated and revised accordingly. It may be further pointed that some phosphorus data reported in literatures should be critically evaluated when they are to be referred in later publications.     

Simultaneous determination of bromine and chlorine in coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis

A new method for the direct analysis of coal using electrothermal vaporization inductively coupled plasma mass spectrometry and direct solid sample analysis was developed, aiming at the determination of Br and Cl. The procedure does not require any significant sample pretreatment and allows simultaneous determination of both elements to be carried out, requiring small mass aliquots of sample (about 0.5 mg). All operating parameters, including carrier gas flow-rate and RF power, were optimized for maximum sensitivity. The use of modifiers/aerosol carriers (Pd, Pd + Al and Pd + Ca) was evaluated, and the mixture of Pd and Ca was chosen, allowing pyrolysis and vaporization temperatures of 700 °C and 1900 °C, respectively. Chlorine was accurately determined using calibration against solid standards, whereas Br could also be determined using calibration against aqueous standard solutions. The limits of quantification were 0.03 μg g⁻¹ for Br and 7 μg g⁻¹ for Cl, and no spectral interferences were observed.     

Determination of acrylamide in food by solid-phase microextraction coupled to gas chromatography-positive chemical ionization tandem mass spectrometry

A method has been developed to determine acrylamide in aqueous matrices by using direct immersion solid-phase microextraction (SPME) coupled to gas chromatography-positive chemical ionization tandem mass spectrometry (GC-PCI-MS-MS) in the selected reaction monitoring (SRM) mode. The optimized SPME experimental procedures to extract acrylamide in water solutions were: use of a carbowax/divinylbenzene (CW/DVB)-coated fiber at pH 7, extraction time of 20 min and analyte desorption at 210 °C for 3 min. A detection limit of 0.1 μg L⁻¹ was obtained. The linear range was 1-1000 μg L⁻¹. The relative standard deviation was 10.64% (n = 7). The proposed analytical method was successfully used for the quantification of trace acrylamide in foodstuffs such as French fries (1.2 μg g⁻¹) and potato crisps (2.2 μg g⁻¹).     

Determination of aminoglycosides in honey by capillary electrophoresis tandem mass spectrometry and extraction with molecularly imprinted polymers

A new analytical method based on capillary zone electrophoresis-tandem mass spectrometry is proposed and validated for the identification and simultaneous quantification of nine aminoglycosides in honey samples. Detection using an ion trap mass analyzer operating in the multiple reaction monitoring mode was used. Different parameters were optimized in order to obtain an adequate separation combined with the highest sensitivity. In order to achieve high selectivity in the sample treatment, a commercially-available molecularly imprinted polymer has been used for the solid phase extraction of the analytes. Under optimum conditions, recoveries for fortified samples ranged from 88.2 to 99.8%, with relative standard deviations lower than 8%. The limits of detection ranged from 0.4 to 28.5 μg kg⁻¹. Furthermore, the decision limit and the detection capability were evaluated, ranging from 3.5 to 60.5 μg kg⁻¹ and from 6.0 to 103.1 μg kg⁻¹, respectively, demonstrating the sensitivity and applicability of this fast and simple method.     

Fluorescent determination of graphene quantum dots in water samples

This work presents a simple, fast and sensitive method for the preconcentration and quantification of graphene quantum dots (GQDs) in aqueous samples. GQDs are considered an object of analysis (analyte) not an analytical tool which is the most frequent situation in Analytical Nanoscience and Nanotechnology. This approach is based on the preconcentration of graphene quantum dots on an anion exchange sorbent by solid phase extraction and their subsequent elution prior fluorimetric analysis of the solution containing graphene quantum dots. Parameters of the extraction procedure such as sample volume, type of solvent, sample pH, sample flow rate and elution conditions were investigated in order to achieve extraction efficiency. The limits of detection and quantification were 7.5 μg L⁻¹ and 25 μg L⁻¹, respectively. The precision for 200 μg L⁻¹, expressed as %RSD, was 2.8%. Recoveries percentages between 86.9 and 103.9% were obtained for two different concentration levels. Interferences from other nanoparticles were studied and no significant changes were observed at the concentration levels tested. Consequently, the optimized procedure has great potential to be applied to the determination of graphene quantum dots at trace levels in drinking and environmental waters.     

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.     

Determination of calcium, magnesium and zinc in lubricating oils by flame atomic absorption spectrometry using a three-component solution

Lubricating oils are used to decrease wear and friction of movable parts of engines and turbines, being in that way essential for the performance and the increase of that equipment lifespan. The presence of some metals shows the addition of specific additives such as detergents, dispersals and antioxidants that improve the performance of these lubricants. In this work, a method for determination of calcium, magnesium and zinc in lubricating oil by flame atomic absorption spectrometry (F AAS) was developed. The samples were diluted with a small quantity of aviation kerosene (AVK), n-propanol and water to form a three-component solution before its introduction in the F AAS. Aqueous inorganic standards diluted in the same way have been used for calibration. To assess the accuracy of the new method, it was compared with ABNT NBR 14066 standard method, which consists in diluting the sample with AVK and in quantification by F AAS. Two other validating methods have also been used: the acid digestion and the certified reference material NIST (SRM 1084a). The proposed method provides the following advantages in relation to the standard method: significant reduction of the use of AVK, higher stability of the analytes in the medium and application of aqueous inorganic standards for calibration. The limits of detection for calcium, magnesium and zinc were 1.3 μg g⁻¹, 0.052 μg g⁻¹ and 0.41 μg g⁻¹, respectively. Concentrations of calcium, magnesium and zinc in six different samples obtained by the developed method did not differ significantly from the results obtained by the reference methods at the 95% confidence level (Student's t-test and ANOVA). Therefore, the proposed method becomes an efficient alternative for determination of metals in lubricating oil.     

Optimal design of experiments applied to headspace solid phase microextraction for the quantification of vicinal diketones in beer through gas chromatography-mass spectrometric detection

Vicinal diketones, namely diacetyl (DC) and pentanedione (PN), are compounds naturally found in beer that play a key role in the definition of its aroma. In lager beer, they are responsible for off-flavors (buttery flavor) and therefore their presence and quantification is of paramount importance to beer producers. Aiming at developing an accurate quantitative monitoring scheme to follow these off-flavor compounds during beer production and in the final product, the head space solid-phase microextraction (HS-SPME) analytical procedure was tuned through experiments planned in an optimal way and the final settings were fully validated. Optimal design of experiments (O-DOE) is a computational, statistically-oriented approach for designing experiences that are most informative according to a well-defined criterion. This methodology was applied for HS-SPME optimization, leading to the following optimal extraction conditions for the quantification of VDK: use a CAR/PDMS fiber, 5 ml of samples in 20 ml vial, 5 min of pre-incubation time followed by 25 min of extraction at 30 °C, with agitation. The validation of the final analytical methodology was performed using a matrix-matched calibration, in order to minimize matrix effects. The following key features were obtained: linearity (R² > 0.999, both for diacetyl and 2,3-pentanedione), high sensitivity (LOD of 0.92 μg L⁻¹ and 2.80 μg L⁻¹, and LOQ of 3.30 μg L⁻¹ and 10.01 μg L⁻¹, for diacetyl and 2,3-pentanedione, respectively), recoveries of approximately 100% and suitable precision (repeatability and reproducibility lower than 3% and 7.5%, respectively). The applicability of the methodology was fully confirmed through an independent analysis of several beer samples, with analyte concentrations ranging from 4 to 200 g L⁻¹.     

Total microcystins analysis in water using laser diode thermal desorption-atmospheric pressure chemical ionization-tandem mass spectrometry

A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (<15 s sample⁻¹). Several oxidation and LDTD parameters were optimized to improve recoveries and signal intensity. MCs oxidation recovery yield was 103%, showing a complete reaction. Internal calibration with standard addition was achieved with the use of 4-phenylbutyric acid (4-PB) as internal standard and showed good linearity (R² > 0.999). Limits of detection and quantification were 0.2 and 0.9 μg L⁻¹, respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 μg L⁻¹ for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices.     

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.     

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.