Laser-induced breakdown spectroscopy and chemometrics for classification of toys relying on toxic elements

Quality control of toys for avoiding children exposure to potentially toxic elements is of utmost relevance and it is a common requirement in national and/or international norms for health and safety reasons. Laser-induced breakdown spectroscopy (LIBS) was recently evaluated at authors` laboratory for direct analysis of plastic toys and one of the main difficulties for the determination of Cd. Cr and Pb was the variety of mixtures and types of polymers. As most norms rely on migration (lixiviation) protocols, chemometric classification models from LIBS spectra were tested for sampling toys that present potential risk of Cd, Cr and Pb contamination. The classification models were generated from the emission spectra of 51 polymeric toys and by using Partial Least Squares - Discriminant Analysis (PLS-DA), Soft Independent Modeling of Class Analogy (SIMCA) and K-Nearest Neighbor (KNN). The classification models and validations were carried out with 40 and 11 test samples, respectively. Best results were obtained when KNN was used, with corrected predictions varying from 95% for Cd to 100% for Cr and Pb. (C) 2011 Elsevier B.V. All rights reserved.

Dispersion of natural arsenic in the Malcantone watershed, Southern Switzerland: field evidence for repeated sorption-desorption and oxidation-reduction processes

In recent years, elevated arsenic concentrations have been found in waters and soils of many, countries, often resulting in a health threat for the local population. Switzerland is not an exception and this paper deals with the release and subsequent fate of arsenic in a 200-km(2) mountainous watershed, characterized by crystalline silicate rocks (gneisses, schists, amphibolites) that contain abundant As-bearing sulfide ore deposits, some of which have been mined for iron and gold in the past. Using analytical methods common for mineralogical, ground water and soil studies (XRD, XRF, XAS-XANES and -EXAFS, electron microprobe, extraction, ICP, AAS with hydride generator, ion chromatography), seven different field situations and related dispersion processes of natural arsenic have been studied: (1) release by rock weathering, (2) transport and deposition by water and ice; (3) release of As to the ground and surface water due to increasing pH; (4) accumulation in humic soil horizons; (5) remobilization by reduction in water-saturated soils and stagnant ground waters; (6) remobilization by using P-rich fertilizers or dung and (7) oxidation, precipitation and dilution in surface waters. Comparison of the results with experimental adsorption studies and speciation diagrams from the literature allows us to reconstruct and identify the typical behavior of arsenic in a natural environment under temperate climatic conditions. The main parameters identified are: (a) once liberated from the primary minerals, sorption processes on Fe-oxy-hydroxides dominate over Al-phases, such as Al-hydroxides or clay minerals and limit the As concentrations in the spring and well waters between 20 and 300 mug/l. (b) Precipitation as secondary minerals is limited to the weathering domain, where the As concentrations are still high and not yet too diluted by rain and soils waters. (c) Although neutral and alkaline pH conditions clearly increase the mobility of As, the main factor to mobilize As is a low redox potential (Eh close or below 0 mV), which favors the dissolution of the Fe-oxy-hydroxides on which the As is sorbed. (d) X-ray absorption spectroscopy (XAS) of As in water-logged humic forest soils indicates that the reduction to As III only occurs at the solid-water interface and that the solid contains As as As V (e) A and Bh horizons of humic cambisols can effectively capture As when As-rich waters flow through them. Complex spatial and temporal variation of the various parameters in a watershed results in repeated mobilization and immobilization of As, which continuously transports As from the upper to the lower part of a watershed and ultimately to the ocean. (C) 2004 Elsevier B.V. All rights reserved.

Method development using ICP-MS and LA-ICP-MS and their application in environmental and material science

Within this PhD thesis several methods were developed and validated which can find applicationare suitable for environmental sample and material science and should be applicable for monitoring of particular radionuclides and the analysis of the chemical composition of construction materials in the frame of ESS project. The study demonstrated that ICP-MS is a powerful analytical technique for ultrasensitive determination of 129I, 90Sr and lanthanides in both artificial and environmental samples such as water and soil. In particular ICP-MS with collision cell allows measuring extremely low isotope ratios of iodine. It was demonstrated that isotope ratios of 129I/127I as low as 10-7 can be measured with an accuracy and precision suitable for distinguishing sample origins. ICP-MS with collision cell, in particular in combination with cool plasma conditions, reduces the influence of isobaric interferences on m/z = 90 and is therefore well-suited for 90Sr analysis in water samples. However, the applied ICP-CC-QMS in this work is limited for the measurement of 90Sr due to the tailing of 88Sr+ and in particular Daly detector noise. Hyphenation of capillary electrophoresis with ICP-MS was shown to resolve atomic ions of all lanthanides and polyatomic interferences. The elimination of polyatomic and isobaric ICP-MS interferences was accomplished without compromising the sensitivity by the use of a high resolution mode as available on ICP-SFMS. Combination of laser ablation with ICP-MS allowed direct micro and local uranium isotope ratio measurements at the ultratrace concentrations on the surface of biological samples. In particular, the application of a cooled laser ablation chamber improves the precision and accuracy of uranium isotopic ratios measurements in comparison to the non-cooled laser ablation chamber by up to one order of magnitude. In order to reduce the quantification problem, a mono gas on-line solution-based calibration was built based on the insertion of a microflow nebulizer DS-5 directly into the laser ablation chamber. A micro local method to determine the lateral element distribution on NiCrAlY-based alloy and coating after oxidation in air was tested and validated. Calibration procedures involving external calibration, quantification by relative sensitivity coefficients (RSCs) and solution-based calibration were investigated. The analytical method was validated by comparison of the LA-ICP-MS results with data acquired by EDX.

Chemical properties and mineralogy of soils with plinthite and petroplinthite in Iranduba (AM), Brazil

Large areas of Plinthosols with ferruginous materials such as plinthite and/or petroplinthite are fairly common in the Brazilian Amazon basin. This work was carried out to investigate the chemical behavior, mineralogical composition and weathering stage of four representative soil profiles with plinthite and petroplinthite, in Iranduba, AM (Central Amazon). Three well-drained soil profiles at high elevations were studied (P1, Plinthic Vetic Ferralsol; P2 and P3, Vetic Endopetric Plinthosol) and a contrasting poorly drained soil (P4 Haplic Plinthosol), located at low elevation. After profile descriptions, soil samples were collected from each horizon, air-dried, sieved (2 mm), and analyzed for particle-size distribution, pH, exchangeable cations (Al3+, Ca2+, Mg2+, K+, and Na+), as well as available P and total organic carbon (TOC) content. The minerals present in the clay and sand fractions, as well as in the ferruginous materials were identified by X-ray Diffraction (XRD). The weathering stage of these soils was assessed by means of Ki and Kr indexes, and the amounts of free and amorphous Fe and Al oxides by using dithionite citrate bicarbonate (DBC) and ammonium oxalate dissolution procedures, respectively. The results showed that all soils were extremely unfertile, with pH levels ranging between strong and moderate acidity, very low sum of bases and organic matter content, and of available P. The mineralogy of the soil profiles was very similar, mainly of the well-drained soils, with predominance of kaolinite and quartz in the clay and sand fractions, respectively. In the poorly-drained P4, 2:1 clay particles were also observed. These profiles can be considered highly developed according to the Ki index, however, the Ki value of P4 was higher, indicating that this soil was less developed than the others. In summary, these profiles with plinthite and petroplinthite can be characterized as highly developed and infertile soils and are, with exception of P4, well-drained.

Mordenite from Spain and its application as pozzolana

In Spain, natural zeolites have been only found in the volcanic areas of Canary Islands (San Gil, M.M., 1959). However, several years ago the study of the South Eastern region of continental Spain (Cabo de Gata) revealed the presence of a deposit of mordenite being industrially commercialized as bentonite. The deposit San José-Los Escullos is located in the concession registered as Los Murcianos, managed by Bentonitas Especiales, S.A. (BENESA) who was extracting bentonite while ignoring the presence of the zeolite. The name San José-Los Escullos refers to the discovery of mordenite in this deposit. The deposit is located in a volcanic area, constituted by pyroxenic andesites, breccias, tuffs, pyroclasts with andesitic and dacitic composition, largely altered by the hydrothermal solutions. The recent discovery of this zeolite with mordenite content up to 97%, has changed the initial vision about that deposit, and new possible uses of this mineral in the pozzolanic cement industry are foreseen. This work intends to give preliminary data on the characterization of this zeolite according to X-ray diffraction (XRD), ICP analyses, and scanning electron microscopy (SEM), as well as to emphasize the pozzolanic properties of this material, using both chemical and mechanical tests.

Efficient removal of paracetamol using LaCu1-xMxO3 (M=Mn, Ti) perovskites as heterogeneous Fenton-like catalysts

A series of perovskite-like oxides LaCu1-xMxO3 (M=Mn, Ti; 0.0 ⩽ x ⩽ 0.8) was prepared by amorphous citrate decomposition and characterized by XRD, ICP-OES and XPS techniques. The catalysts were tested in the Fenton-like degradation of paracetamol with H2O2, under mild reaction conditions, 25 °C and nearly neutral pH. Values of decomposition of paracetamol between 80 and 97% at 300 min were achieved for most of samples. The presence of the Cu2+/Cu+ pair at the surface of the catalysts is necessary to carry out the reaction and the catalysts containing higher amount of copper at the surface, resulted to be more active. The leaching of metals was less than 1%, which discards the contribution of the homogenous Fenton-like reaction and remarks the high stability of the metals into the mixed oxide network. The catalytic activity of LaCu0.8Mn0.2O3 was maintained after three cycles of reaction, which proves the stability and reusability of the catalyst.

Exploring the emission intensities of ICP OES aided by chemometrics in the geographical discrimination of mineral waters

A rapid method for classification of mineral waters is proposed. The discrimination power was evaluated by a novel combination of chemometric data analysis and qualitative multi-elemental fingerprints of mineral water samples acquired from different regions of the Brazilian territory. The classification of mineral waters was assessed using only the wavelength emission intensities obtained by inductively coupled plasma optical emission spectrometry (ICP OES), monitoring different lines of Al, B, Ba, Ca, Cl, Cu, Co, Cr, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Si, Sr, Ti, V, and Zn, and Be, Dy, Gd, In, La, Sc and Y as internal standards. Data acquisition was done under robust (RC) and non-robust (NRC) conditions. Also, the combination of signal intensities of two or more emission lines for each element were evaluated instead of the individual lines. The performance of two classification-k-nearest neighbor (kNN) and soft independent modeling of class analogy (SIMCA)-and preprocessing algorithms, autoscaling and Pareto scaling, were evaluated for the ability to differentiate between the various samples in each approach tested (combination of robust or non-robust conditions with use of individual lines or sum of the intensities of emission lines). It was shown that qualitative ICP OES fingerprinting in combination with multivariate analysis is a promising analytical tool that has potential to become a recognized procedure for rapid authenticity and adulteration testing of mineral water samples or other material whose physicochemical properties (or origin) are directly related to mineral content.

Soil mineral genesis and distribution in a saline lake landscape of the Pantanal Wetland, Brazil

The origin of the saline lakes in the Pantanal wetland has been classically attributed to processes occurring in past periods. However, recent studies have suggested that saline water is currently forming from evaporative concentration of fresh water, which is provided annually by seasonal floods. Major elements (Ca, Mg, K) and alkalinity appear to be geochemically controlled during the concentration of waters and may be involved in the formation of carbonates and clay minerals around the saline lakes. The mineralogy of soils associated with a representative saline lake was investigated using XRD, TEM-EDS, and ICP-MS in order to identify the composition and genesis of the secondary minerals suspected to be involved in the control of major elements. The results showed that Ca, Mg, and K effectively undergo oversaturation and precipitation as the waters become more saline. These elements are incorporated in the authigenically formed carbonates, smectites, and micas surrounding the saline lake. The control of Ca occurs by precipitation of calcite and dolomite in nodules while Mg and K are mainly involved in the neoformation of Mg-smectites (stevensitic and saponitic minerals) and, probably, iron-enriched micas (ferric-illite) in surface and subsurface horizons. Therefore, our study confirms that the salinity of Pantanal, historically attributed to inheritance from former regimes, has a contribution of current processes. (C) 2009 Elsevier B.V. All rights reserved.

VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

Use of Metals and Anion Species with Chemometrics Tools for Classification of Unprocessed and Processed Coconut Waters

Coconut water is a natural isotonic, nutritive, and low-caloric drink. Preservation process is necessary to increase its shelf life outside the fruit and to improve commercialization. However, the influence of the conservation processes, antioxidant addition, maturation time, and soil where coconut is cultivated on the chemical composition of coconut water has had few arguments and studies. For these reasons, an evaluation of coconut waters (unprocessed and processed) was carried out using Ca, Cu, Fe, K, Mg, Mn, Na, Zn, chloride, sulfate, phosphate, malate, and ascorbate concentrations and chemometric tools. The quantitative determinations were performed by electrothermal atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and capillary electrophoresis. The results showed that Ca, K, and Zn concentrations did not present significant alterations between the samples. The ranges of Cu, Fe, Mg, Mn, PO (4) (3-) , and SO (4) (2-) concentrations were as follows: Cu (3.1-120 A mu g L(-1)), Fe (60-330 A mu g L(-1)), Mg (48-123 mg L(-1)), Mn (0.4-4.0 mg L(-1)), PO (4) (3-) (55-212 mg L(-1)), and SO (4) (2-) (19-136 mg L(-1)). The principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to differentiate unprocessed and processed samples. Multivariated analysis (PCA and HCA) were compared through one-way analysis of variance with Tukey-Kramer multiple comparisons test, and p values less than 0.05 were considered to be significant.

Classificação de água de coco processada e natural por meio de HCA, PCA e teores de íons metálicos determinados por ICP OES

Inductively Coupled Plasma Optical Emission Spectrometry was used to determine Ca, Mg, Mn, Fe, Zn and Cu in samples of processed and natural coconut water. The sample preparation consisted in a filtration step followed by a dilution. The analysis was made employing optimized instrumental parameters and the results were evaluated using methods of Pattern Recognition. The data showed common concentration values for the analytes present in processed and natural samples. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) indicated that the samples of different kinds were statistically different when the concentrations of all the analytes were considered simultaneously.

Cement stabilization of runoff residuals: A study of stabilization/solidification of urban rainfall-runoff residuals in type 1 Portland cement by XRD and Si-29 NMR analysis

Urban rainfall-runoff residuals contain metals such as Cr, Zn, Cu, As, Pb and Cd and are thus reasonable candidates for treatment using Portland cement-based solidification-stabilization (S/S). This research is a study of S/S of urban storm water runoff solid residuals in Portland cement with quicklime and sodium bentonite additives. The solidified residuals were analyzed after 28 days of hydration time using X-ray powder diffraction (XRD) and solid-state Si-29 nuclear magnetic resonance (NMR) spectroscopy. X-ray diffraction (XRD) results indicate that the main cement hydration products are ettringite, calcium hydroxide and hydrated calcium silicates. Zinc hydroxide and lead and zinc silicates are also present due to the reactions of the waste compounds with the cement and its hydration products. Si-29 NMR analysis shows that the coarse fraction of the waste apparently does not interfere with cement hydration, but the fine fraction retards silica polymerization.

Characterization and application of the solid waste generated in the production of calcium carbonate precipitate as a corrective for the soil acidity

The calcium carbonate industry generates solid waste products which, because of their high alkaline content (CaO, CaCO(3) and Ca (OH)(2)), have a substantial impact on the environment. The objectives of this study are to characterize and classify the solid waste products, which are generated during the hydration process of the calcium carbonate industry, according to ABNT`s NBR 10.000 series, and to determine the potential and efficiency of using these solid residues to correct soil acidity. Initially, the studied residue was submitted to gross mass, leaching, solubility, pH. X-ray Diffractometry, Inductive Coupled Plasma - Atomic Emission Spectrometry (ICP-AES), granularity and humidity analyses. The potential and efficiency of the residue for correcting soil acidity was determined by analysis of the quality attributes for soil correctives (PN, PRNT, Ca and Mg contents, granularity). Consequently, the results show that the studied residue may be used as a soil acidity corrective, considering that a typical corrective compound is recommended for each different type of soil. Additionally, the product must be further treated (dried and ground) to suit the specific requirements of the consumer market.

Spatial Modeling of a Soil Fertility Index using Visible-Near-Infrared Spectra and Terrain Attributes

Our objective was to develop a methodology to predict soil fertility using visible near-infrared (vis-NIR) diffuse reflectance spectra and terrain attributes derived from a digital elevation model (DEM). Specifically, our aims were to: (i) assemble a minimum data set to develop a soil fertility index for sugarcane (Sarcharum officinarum L.) (SFI-SC) for biofuel production in tropical soils; (ii) construct a model to predict the SFI-SC using soil vis-NIR spectra and terrain attributes; and (iii) produce a soil fertility map for our study area and assess it by comparing it with a green vegetation index (GVI). The study area was 185 ha located in sao Paulo State, Brazil. In total, 184 soil samples were collected and analyzed for a range of soil chemical and physical properties. Their vis-NIR spectra were collected from 400 to 2500 nm. The Shuttle Radar Topographic Mission 3-arcsec (90-m resolution) DEM of the area was used to derive 17 terrain attributes. A minimum data set of soil properties was selected to develop the SFI-SC. The SFI-SC consisted of three classes: Class 1, the highly fertile soils; Class 2, the fertile soils; and Class 3, the least fertile soils. It was derived heuristically with conditionals and using expert knowledge. The index was modeled with the spectra and terrain data using cross-validated decision trees. The cross-validation of the model correctly predicted Class 1 in 75% of cases, Class 2 in 61%, and Class 3 in 65%. A fertility map was derived for the study area and compared with a map of the GVI. Our approach offers a methodology that incorporates expert knowledge to derive the SFI-SC and uses a versatile spectro-spatial methodology that may be implemented for rapid and accurate determination of soil fertility and better exploration of areas suitable for production.

Soil mineralogy of mangrove forests from the state of Sao Paulo, Southeastern Brazil

The minerals of the clay fraction in estuarine plains are mainly detrital being a mixture of marine and continental sediments, but can also be authigenic. Because of the importance of mangrove ecosystems in tropical estuarine areas and the relatively few existing studies of the mineralogical composition of soils in these environments, the aim of this study was to determine the mineralogical assemblage and identify potential contrasts along the coast of the State of Sao Paulo. Soils from I I mangroves distributed along the coastal plain of the State of Sao Paulo were sampled at depths of 0 to 20 and 60 to 80 cm, and samples of suspended sediments from the Ribeira do Iguape River were collected for analysis. Mineralogical analyses were performed on the clay and silt fractions by x-ray diffraction (XRD) and transmission electron microscopy, and fresh soil samples were analyzed by scanning electron microscopy-energy dispersive spectrometry and suspended sediments by XRD. The silt fraction contained quartz, feldspars, gibbsite, kaolinite, illite, and vermiculite, and the clay fraction contained smectite, kaolinite, illite, gibbsite, quartz, and feldspars. Locally, vermiculite, biotite, anatase, halloysite, and goethite may occur because of recent transport of sediments to the system. Pyrite was identified in fresh samples. The allochthonous minerals found either were terrestrial and transported by rivers or had originated from the continental platform by past transgressive events. We suggest that the neoformation of smectite and kaolinite occurs in mangrove soils. Different geomorphological settings along the Sao Paulo coast appear to regulate mineral distribution in mangrove soils.