Determination of the most informative chemical elements for discrimination of rice samples according to the producing region.

Several approaches to assess the authenticity of food products have been developed, given that fraudulent products may impact consumers' confidence, affect commercial trades and lead to health risks. This paper proposes an approach to identify the chemical elements that optimally discriminate rice samples according to their producing region in the South of Brazil, the largest rice producer outside Asia. A combinatorial procedure on the concentration of 26 elements determined using inductively coupled mass spectrometry (ICP-MS) and liquid chromatography hyphenated with ICP-MS from 640 rice samples was coupled with Support Vector Machine. The assessed elements included nonmetal and metal elements of 3 types of rice collected from 5 rice-producing regions. The framework selected Mn, Fe, Cu, Zn, Ni, Mo, Cd, Cs, As, Rb, Se, and iAs as the most informative elements for tracking samples' origin. The concentration of such elements is strongly affected by fertilization procedures and soil composition.

Effects of La2O3 nanoparticles and bulk-La2O3 on the development of Pfaffia glomerata (Spreng.) Pedersen and respective nutrient element concentration.

Nanoparticles (NPs) have been progressively applied in the last decades, which may impact the environment. Synthesis of pigments, growing, and nutrient element uptake by plants can also be affected by NPs. The influence of lanthanum oxide nanoparticles (La2O3 NPs) on growth, pigment synthesis, and nutrient element uptake by Pfaffia glomerata (Spreng.) Pedersen, a medicinal plant native in South America, was evaluated in the present study. P. glomerata plantlets were cultivated for 28 days in the absence (control) and presence of 100, 200, and 400 mg L-1 of La2O3 NPs or bulk-La2O3 (b-La2O3) at the same cultivation conditions. Root development, aerial part growth, and pigment concentration in plants were affected by b-La2O3 and La2O3 NPs, mainly by La2O3 NPs. In spite of alteration of nutrient element concentration observed for the 100 and 200 mg L-1 of La2O3 NPs or b-La2O3 treatments, Ca, Cu, Fe, K, La, Mg, Mn, Mo, P, S, and Zn determination in stems and leaves revealed drastically and similar decrease of these elements in plants cultivated in the presence of 400 mg L-1 of La2O3 NPs or b-La2O3. Element distribution (mapping) determined by using laser ablation inductively coupled plasma mass spectrometry in leaves of plants submitted to treatment with 400 mg L-1 of b-La2O3 or La2O3 NPs showed differences in the distribution of elements, indicating distinct effects of b-La2O3 and La2O3 NPs on P. glomerata. As such, this study demonstrated that La2O3 NPs may impact plant growth. However, more investigations are necessary for better understanding of the effect of La2O3 on plants, including a broader range of concentration.

Methodology for elemental analysis of a mineral fertilizer, some of its raw materials and limestone using microwave-induced plasma optical emission spectrometry (MIP OES).

The elemental analysis of complex matrices such as superphosphate-fertilizers and agricultural inputs by means of microwave-induced plasma optical emission has been evaluated in the present study. A commercial single superphosphate-fertilizer and three certified reference materials - CRMs (multi-nutrient, phosphate rock and dolomitic limestone) were analysed. Samples were submitted for three different analyte extraction or decomposition procedures; microwave assisted digestion (MAD), extraction by heating on a metallic plate and ultrasound assisted extraction (US). Analyte recovery tests were carried out to evaluate dilutions of the obtained sample solutions to reduce or avoid matrix effects. Better results were obtained for samples submitted for MAD and the concentration values found agreed with those certified or known for the CRMs. Inductively coupled plasma optical emission spectrometry (ICP OES) was employed as an independent technique for analyte determination in the superphosphate-fertilizer submitted for MAD. The concentrations found by both techniques were in agreement with each other for most of the investigated elements. As such, MIP OES has demonstrated good performance for the determination of 19 elements.

Arsenic speciation analysis in rice milk using LC-ICP-MS.

The consumption of rice milk has increased, mainly by individuals intolerant to lactose or allergic to cow milk. However, rice milk contains As. In this sense, the concentration of As in rice milk should be controlled. In the present study it is proposed a methodology for determination of As(III), dimethylarsenic (DMA), monomethylarsenic (MMA) and As(V) species in rice milk using LC-ICP-MS. The main features of the methodology are fast analysis, easy and simple sample preparation, where the sample is 3-fold diluted in the mobile phase and then filtered. The four arsenic species investigated were detected in the analysed samples, being As(V) the main species. The limit of quantification of the method ranges from 0.25 to 0.43 µg L-1 As. The analyte recovery ranged from 81 to 116% for samples spiked to 1.00 µg L-1 or 5.00 µg L-1 As and the relative standard deviation was better than 5%.

Bioimaging Metallomics.

This chapter focuses on bioimaging in metallomics, which involves metal and metalloids distribution in animal tissues. It starts with laser ablation-inductively coupled plasma-mass spectrometry followed by secondary ion mass spectrometry, synchrotron-based X-ray fluorescence, and electron microscopy, including transmission electron microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The basic principles of these techniques and their application for qualitative and quantitative imaging of elements are presented. Sample preparation for bioimaging is briefly discussed. The usefulness of element bioimaging is demonstrated for cells and several animal tissues, including the brain, liver, hair, eye, teeth, and bone. As such, this chapter addresses the state of the art in bioimaging metallomics.

Toxic and nutrient elements in yerba mate (Ilex paraguariensis).

Toxic and nutrient elements were investigated in yerba mate (Ilex paraguariensis) from South America. Fifty-four brands of commercialised yerba mate from Argentina, Brazil, Paraguay and Uruguay were analysed for Al, Ba, Ca, Cu, Fe, K, Mg, Mn, P, Sr, and Zn, using inductively coupled plasma optical emission spectrometry (ICP-OES), and Li, Be, Ti, V, Cr, Ni, Co, As, Se, Rb, Mo, Ag, Cd, Sb, La, Ce, Pb, Bi and U using inductively coupled plasma mass spectrometry (ICP-MS). Antimony, Se, Ag and Bi were not detected in any sample whereas the limits of detection (LODs) of these elements were 0.19, 0.40, 0.003 and 0.001 µg g(-1), respectively. Analysis of variance (ANOVA) revealed that the concentrations of Cd, Ti, Ni, As, Mo, U, Li and Be in yerba mate were not statistically different with regard to the country of origin, while those of the other investigated elements differed.

Authentication of yerba mate according to the country of origin by using Fourier transform infrared (FTIR) associated with chemometrics.

This study deals with the development of a method for classification of yerba mate (Ilex paraguariensis) using attenuated total-reflectance Fourier transform infrared (ATR-FTIR) and multivariate analysis. Fifty-four brands of yerba mate from southern South America were analysed in order to classify the commercialised yerba mate according to the respective country of yerba mate processing. The yerba mate was ground in a cryogenic mill, and the reflectance was directly measured in the region ranging from 4000 to 650 cm(-1). Different pre-processing algorithms and three methods of multivariate analysis were investigated, including principal component analysis (PCA), partial least square discriminant analysis (PLS-DA) and support vector machine discriminant analysis (SVM-DA). The yerba mate classification was 100% correct when the reflectance spectra were pre-treated (derived at first order, normalised by standard normal variation, smoothed and mean centred) and analysed using the SVM-DA method.

Toxic and micronutrient elements in organic, brown and polished rice in Brazil.

Concentration levels of As, Cd, Hg, Pb, Tl, Sn, Sb Co, Cu, Mn, Se, Zn, Cr, Ni and Mo in different types of rice cultivated in irrigated fields in Brazil were evaluated. Arsenic, Cd, Pb, Zn, Mn and Cu were found in higher concentrations in brown rice samples, suggesting the prevalence of these elements in the bran. Meanwhile, lower concentrations of Pb, Mo, Cr, Se and Co were found in parboiled rice. Organic rice did not differ of cultivated conventionally rice. Thallium, Hg and Sb were not detected in any rice sample whose limits of detection were 0.7 µg kg(-1), 2.5 µg kg(-1) and 8 µg kg(-1), respectively. The concentrations of the investigated elements were compared with those reported for polished rice and brown rice from other countries, unveiling concentrations in general at the same level for rice produced at non-contaminated sites.

Advantages and effects of nitrogen doping into the central channel of plasma in axially viewed-inductively coupled plasma optical emission spectrometry.

The effects and benefits of N2 addition to the central channel of the ICP through the nebulizer gas used in ICP OES with axial view configuration were investigated in the present study. The N2 flow rate, nebulizer gas flow rate, RF power and sample uptake rate were evaluated and compared for two sample introduction systems (pneumatic nebulization/aerosol desolvation and conventional pneumatic nebulization). It was observed that N2 did not affect solution nebulization and aerosol transport but affects the ICP characteristics. The higher thermal conductivity of N2 (in comparison with Ar) changes energy distribution in the ICP, observed by monitoring the signals of Ar emission lines and sodium emission. The ratio Mg(II)-280.270 nm/Mg(I)-285.213 nm was utilized as a diagnostic tool for plasma robustness. The addition of N2 (20 mL min(-1)) increased plasma robustness significantly and mitigated effects caused by Na, K and Ca. For 40 spectral lines evaluated, it was observed that the emission signals of ionic spectral lines were in general more affected by N2 than those of atomic spectral lines. Detection limits, precision, sensitivity and linearity of calibration curves obtained using N2-Ar-ICP were almost similar to those obtained using Ar-ICP. The analysis of 5 different reference materials revealed that accuracy was not degraded by adding N2 to the Ar-ICP.

Lanthanides determination in red wine using ultrasound assisted extraction, flow injection, aerosol desolvation and ICP-MS.

This paper deals with the determination of the fourteen naturally occurring elements of the lanthanide series in red wine. Ultrasound (US) was used for sample preparation prior lanthanides determination using ICP-MS. Flow injection (FI) and pneumatic nebulization/aerosol desolvation were used for nebulization of aliquots of 50 µL of sample and its subsequent transportation to plasma. Sample preparation procedures, matrix interference and time of sonication were evaluated. Better results for lanthanides in red wine were obtained by sonication with US probe for 90 s and sample 10-fold diluted. The limits of detection of La, Ce, Nd, Sm, Gd, Pr, Eu, Tb, Dy, Ho, Er, Tm, Lu and Yb were 6.57, 10.8, 9.97, 9.38, 2.71, 1.29, 1.22, 0.52, 2.35, 0.96, 2.30, 0.45, 0.24 and 1.35 ng L(-1), respectively. Red wines of different varieties from three countries of South America were discriminated according to the country of origin by means of multivariate analysis of lanthanides concentration.

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(+)/(34)S(+) 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.

Metal and hydrocarbon behavior in sediments from Brazilian shallow waters drilling activities using nonaqueous drilling fluids (NAFs).

The impact of drilling oil activities in the Brazilian Bonito Field/Campos Basin (Rio de Janeiro) shell drilling (300 m) using nonaqueous fluids (NAFs) was investigated with respect to Al, Fe, Mn, Ba, Co, Pb, Cu, As, Hg, Cr, Ni, Zn, Cd, V, and aliphatic and polynuclear aromatic hydrocarbons concentrations in the sediment. Sampling took place in three different times during approximately 33 months. For the metals Al, As, Co, Cr, Cu, Cd, Fe, Ni, Mn, V, and Zn, no significant variation was observed after drilling activities in most of the stations. However, an increase was found in Ba concentration--due to the drilling activity--without return to the levels found 22 months after drilling. High Ba contents was already detected prior to well drilling, probably due to drilling activities in other wells nearby. Hydrocarbon contents also suggest previous anthropogenic activities. Aliphatic hydrocarbon contents were in the range usually reported in other drilling sites. The same behavior was observed in the case of polyaromatic hydrocarbons. Nevertheless, the n-alkane concentration increased sharply after drilling, returning almost to predrilling levels 22 months after drilling activities.

Determination of trace elements in paints by direct sampling graphite furnace atomic absorption spectrometry.

A direct sampling graphite furnace atomic absorption spectrometric (DS-GFAAS) method for the determination of Cd, Pb, Cr, Ni, Co and Cu in paints has been developed. Serigraphy, acrylic and tattoo paints were analysed. Approaches like pyrolysis and atomization temperatures, modifiers and sample mass introduced in the atomizer were studied. Quantification was performed using calibration curves measured with aqueous standard solutions pipetted onto the platform. The sample mass introduced in the graphite tube ranged from 0.02 to 8.0 mg. Palladium was used as modifier for Cd, Pb and Cu, while Mg(NO3)2 was used for Co. For Ni determination, the graphite platform was covered with carbon powder. The characteristic masses of Cd, Pb, Cr, Ni, Co and Cu were 1.4, 22.5, 7.9, 11.0, 9.6 and 12.5 pg, while the limits of detection were 0.0004, 0.001, 0.03, 0.22, 0.11 and 0.05 microg g(-1) of Cd, Pb, Cr, Ni, Co and Cu, respectively. The accuracy was determined by comparison of the results with those obtained by inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectrometry (GFAAS), using liquid sampling of digests. For matrix characterization, major and minor elements (Al, Mg, Ba, Ca, Cr, Cu, Pb, Sr, Ti and Mg) were determined by inductively coupled plasma optical emission spectrometry (ICP OES).

Arsenic determination in marine sediment using ultrasound for sample preparation.

This work deals with As determination in marine sediment using ultrasound for sample preparation. It is shown that As can be quantitatively extracted from marine sediment using 20% (v/v) HCl and sonication. The slurry is centrifuged and the analyte is determined in the supernatant by hydride generation atomic absorption spectrometry (HG AAS). A flow injection (FI) system is employed for hydride generation, with 0.5% (m/v) NaBH(4) used as reducdant and a 20% (v/v) HCl used as sample carrier. The limit of quantification is 1.6 microg g(-1) of As, which is based on 800 microl of sample solution and 0.200 g of sample mass in a volume of 50 mL. Certified and non certified marine sediment samples were analyzed; the results were in accordance with the certified or reference values. Speciation analysis by HPLC-ICP-MS showed that As(V) is the only detectable As species present in the supernatant of the centrifuged sample.

Determination of titanium and vanadium in Ziegler-Natta catalysts by inductively coupled plasma atomic emission spectrometry.

A method for the determination of Ti and V using inductively coupled plasma atomic emission spectrometry (ICP OES) in Ziegler-Natta polymerization catalysts is proposed. The concentrations of both Ti and V are efficiently determined after catalyst acid digestion with a mixture of HNO3 + HCl + HF and heating (160 degrees C for 6 h) or with 10% (v/v) H2SO4 and heating (160 degrees C for 6 h) or with 10% (v/v) H2SO4 and sonication (during 2 min). The V and Ti detection limits are 0.002% and 0.08%, respectively, using 0.20 g of catalyst sample in 50 ml. The method is validated by a comparison with the Rutherford backscattering spectrometry (RBS) technique. In this case, catalyst samples are only pressed as pellets before analyte determination. Despite the fact that both the V and Ti concentrations cannot be determined individually by means of RBS, because the atomic numbers of Ti and V are very close, the sum of the V and Ti contents is in accordance with that attained by means of ICP OES. According to scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) it is observed that the Ti distribution on the catalyst grain is not homogenous.