Ultra-trace monitoring of copper in environmental and biological samples by inductively coupled plasma atomic emission spectrometry after separation and preconcentration by using octadecyl silica membrane disks modified by a new schiff's base

Ultra-trace amounts of Cu(II) were separated and preconcentrated by solid phase extraction on octadecyl-bonded silica membrane disks modified with a new Schiff,s base (Bis- (2-Hydroxyacetophenone) -2,2-dimethyl-1,3-propanediimine) (SBTD) followed by elution and inductively coupled plasma atomic emission spectrometric detection. The method was applied as a separation and detection method for copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The concentration factor and detection limit of the proposed method are 500 and 12.5 pg mL-1, respectively.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Quantification of the uranium concentration in human urine by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS)

In this study, the validation of a method for analyzing the uranium (U) concentration in human urine samples by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) was conducted. PROCORAD (the Association for the Promotion of Quality Control in Radiotoxicological Analysis) provided two urine samples spiked with unknown contents of U (Sample A = 33.6 ± 1.0 µg/L and Sample B = 3.3 ± 0.1 µg/L) and one unspiked sample as a blank. The analyses were directly performed on the diluted urine samples (dilution factor = 1:20) in 5% v/v HNO3. The results obtained by ICP-SFMS corresponded well with the reference values, and the limits of detection were 235U = 0.049 × 10-3 µg/L and 238U = 7.37 × 10-3 µg/L. The ICP-SFMS technique has been shown to be successful in the analysis of the U concentration in human urine samples and for the quantification of isotopic ratios.

Determinações multi-elementares de metais, Sulfato e Cloreto em amostras de águas por espectrometria de massas com fonte de plasma (ICP-MS)

The multi-element determination of Al, Cr, Mn, Ni, Cu, Zn, Cd, Ba, Pb, SO4= and Cl- in riverine water samples was accomplished by inductively coupled plasma mass spectrometry (ICP-MS). The sample passed through a column containing the anionic resin AG1-X8 and the metals were determined directly. The retained anionic species were eluted and SO4= and Cl- were determined at m/z 48 and 35 correspondent to the ions SO+ and Cl+ formed at the plasma. Accuracy for metals was assessed by analysing the certified reference TM-26 (National Water Research Institute of Canada). Results for SO4= and Cl- were in agreement with those obtained by turbidimetry and spectrophotometry. LOD's of 0.1 µg l-1 for Cd, Ba and Pb; 0.2 µg l-1 for Al, Mn and Cu; 0.5 µg l-1 for Cr; 0.9 for Zn; 2.0 µg l-1for Ni , 60 µg l-1 for S and 200 µg l-1 Cl were attained.

Determinação de Cd, Ni e Zn por espectrometria de emissão atômica com plasma indutivamente acoplado, após separação e pré-concentração em coluna contendo p-dimetilaminobenzilidenorodanina adsorvida sobre sílica gel

A column packed with 5-(4-dimethylaminobenzylidene)rhodanine adsorbed on silica gel was used for the preconcentration of Cd, Ni and Zn at different spiked solutions prior to their determination by inductively coupled plasma atomic emission spectrometry. This column allowed recoveries over than 98% for the above elements and accurate analyses of coastal sea-water certified reference material were also achieved.

Análise de suspensões de argilas por espectrometria de emissão óptica com plasma induzido com configuração axial

The goal of this study was to evaluate the feasibility of direct introduction of clay slurries in an inductively coupled plasma optical emission spectrometer with axial view configuration. Calibration was performed using a certified reference material with a mean particle size of 13 µm (IPT-42) and the analytical curve was applied for quantification of two others reference materials (IPT-28 and IPT-32) and four samples. It was demonstrated that the analytical curve thus obtained was not completely suitable for IPT-28 and samples due to different mineralogical phases determined by X-ray diffraction. After considering this effect, it was possible for most elements to obtain results in agreement with certified values or with values obtained by a conventional technique at a 95% confidence level. It was demonstrated that the ICP-OES with axial view configuration did not present any incompatibility with the direct introduction of a complex inorganic suspension.

Eletroforese capilar acoplada à espectrometria com plasma: uma ferramenta eficiente para a especiação

The most important features of the CE-ICP hyphenation, as well as its advantages and drawbacks as a tool for speciation are discussed. The fundamental principles of capillary electrophoresis and inductively coupled plasma mass spectrometry are also presented. Some applications involving different designs proposed in the literature to couple CE and ICP system for elemental speciation are reviewed.

Identificação de resíduos de disparos de armas de fogo por meio da técnica de espectrometria de massas de alta resolução com fonte de plasma indutivo

The violence derived from crimes involving firearms represents one of the main concerns of society. For this reason modern techniques have emerged in forensic science to identify suspects at crime scenes. This work describes a methodology to identify residues present in the hands of suspect by using a high resolution inductively coupled plasma mass spectrometry and collection procedure based on ethylenediaminetetraacetic acid (EDTA) solution as a complexing agent in moistened swabs. In order to distinguish real gunshot residues from others types of residues present in the hand of suspect, ternary ratio per cent diagrams were developed for antimony (Sb), barium (Ba) and lead (Pb) detected on the hands of volunteers, before and immediately after shooting tests, revealing a remarkable difference in both situations.

Decomposição de argilas em forno de microondas e determinação simultânea dos seus constituintes principais por espectrometria de emissão óptica em plasma indutivamente acoplado

In this work a closed-vessel microwave-assisted acid decomposition procedure for clays was developed. Aluminum, Ca, Fe, K, Mg, Na, Si, and Ti were determined in clay digestates by inductively coupled plasma optical emission spectrometry. The most critical parameter for total decomposition of clays was the composition of the reagent mixture. The applied power and the heating time exerted a less critical influence. Best decomposition conditions were attained using a reagent mixture containing 4 mL aqua regia plus 3 mL HF and the heating program was implemented in 12 min. The accuracy of the results was demonstrated using two standard reference materials and a paired t-test showed a good agreement between determined and certified values at a 95% confidence level.

EXTRAÇÃO ASSISTIDA POR ULTRASSOM PARA DETERMINAÇÃO COLORIMÉTRICA DE FERRO EM SOLO: UMA COMPARAÇÃO COM ESPECTROMETRIA DE MASSA COM PLASMA INDUTIVAMENTE ACOPLADO

A simple procedure for ultrasound-assisted extraction and colorimetric determination of iron in soil samples was developed. The iron concentration in the analyzed samples was determined by the colorimetric method and the results compared with inductively coupled plasma mass spectrometry (ICP-MS). Fifteen soil samples were analyzed and the iron concentration results compared with those obtained by ICP-MS using microwave-assisted sample digestion. The proposed procedure showed good efficiency for iron extraction and the results obtained by colorimetric determination exhibited good agreement with ICP-MS. Moreover, ultrasound-assisted extraction and colorimetric determination is a simple, fast and low-cost procedure for application in routine analysis.

Association of dental enamel lead levels with risk factors for environmental exposure

OBJECTIVE: To analyze household risk factors associated with high lead levels in surface dental enamel. METHODS: A cross-sectional study was conducted with 160 Brazilian adolescents aged 14-18 years living in poor neighborhoods in the city of Bauru, southeastern Brazil, from August to December 2008. Body lead concentrations were assessed in surface dental enamel acid-etch microbiopsies. Dental enamel lead levels were measured by graphite furnace atomic absorption spectrometry and phosphorus levels were measured by inductively coupled plasma optical emission spectrometry. The parents answered a questionnaire about their children's potential early (05 years old) exposure to well-known lead sources. Logistic regression was used to identify associations between dental enamel lead levels and each environmental risk factor studied. Social and familial covariables were included in the models. RESULTS: The results suggest that the adolescents studied were exposed to lead sources during their first years of life. Risk factors associated with high dental enamel lead levels were living in or close to a contaminated area (OR = 4.49; 95% CI: 1.69;11.97); and member of the household worked in the manufacturing of paints, paint pigments, ceramics or batteries (OR = 3.43; 95% CI: 1.31;9.00). Home-based use of lead-glazed ceramics, low-quality pirated toys, anticorrosive paint on gates and/or sale of used car batteries (OR = 1.31; 95% CI: 0.56;3.03) and smoking (OR = 1.66; 95% CI: 0.52;5.28) were not found to be associated with high dental enamel lead levels. CONCLUSIONS: Surface dental enamel can be used as a marker of past environmental exposure to lead and lead concentrations detected are associated to well-known sources of lead contamination.

Analysis of the chemical components of hydatid fluid from Echinococcus granulosus

Introduction The aim of this study was to explore the environment of Echinococcus granulosus (E. granulosus) protoscolices and their relationship with their host. Methods Proteins from the hydatid-cyst fluid (HCF) from E. granulosus were identified by proteomics. An inductively coupled plasma atomic emission spectrometer (ICP-AES) was used to determine the elements, an automatic biochemical analyzer was used to detect the types and levels of biochemical indices, and an automatic amino acid analyzer was used to detect the types and levels of amino acids in the E. granulosus HCF. Results I) Approximately 30 protein spots and 21 peptide mass fingerprints (PMF) were acquired in the two-dimensional gel electrophoresis (2-DE) pattern of hydatid fluid; II) We detected 10 chemical elements in the cyst fluid, including sodium, potassium, calcium, magnesium, copper, and zinc; III) We measured 19 biochemical metabolites in the cyst fluid, and the amount of most of these metabolites was lower than that in normal human serum; IV) We detected 17 free amino acids and measured some of these, including alanine, glycine, and valine. Conclusions We identified and measured many chemical components of the cyst fluid, providing a theoretical basis for developing new drugs to prevent and treat hydatid disease by inhibiting or blocking nutrition, metabolism, and other functions of the pathogen.

Brazil nuts: determination of natural elements and aflatoxin

A study was carried out to evaluate the association of levels of radioactivity, selenium and aflatoxin in shelled Brazil nuts, which were classified in different sizes, for export. The selenium determinations were performed by inductively coupled plasma optical emission spectrometry (LOQ = 3.0 µg g-1), and aflatoxins were detected by Liquid chromatography-mass spectrometry (LOQ = 0.85 µg kg-1), recovery rates were between 92 and 100%. Radioactivity was measured by high-resolution gamma spectrometry. The selenium mean concentration was (22.7 ± 7.4) µg g-1. (n = 30). Mean activities determined for the following radium isotopes were: 15.77 Bq kg-1 for 224Ra, 104.8 Bq kg-1 for 226Ra and 99.48 Bq kg-1 for 228Ra. For 226Ra, the levels did not vary significantly with nut sizes, although such differences were observed for 224Ra and 228Ra. There was no statistically significant association between the level of selenium and the activity of radionuclides, however, there was correlation between the radionuclides. Aflatoxins above the quantification limit were not found.

Chemical composition of phytoplankton from the estuaries of Eastern Amazonia

Phytoplankton is important bioindicator of chemical and biological modifications of natural ecosystems. The objective of this study was to determine the total chemical composition of the phytoplankton of the Pará and Mocajuba estuaries on the eastern coast of the Amazon region in the Brazilian state of Pará. The chemical composition of the surface water, bottom sediments (total sample and bioavailable fraction), and the phytoplankton were determined by inductively coupled plasma optical emission spectrometry. Phytoplankton contained high concentrations of Ca, P, Mn, Fe, Zn, Al, Ba, and Pb. The phytoplankton of the Mocajuba estuary is rich in Fe (2,967-84,750 µg g-1), while those from the Pará is rich in Al (1,216-15,389 µgg-1), probably reflecting divergent anthropogenic inputs. Both samples indicated a high bioconcentration factor derived from both the water and the bioavailable fraction, reflecting the efficiency of these organisms in the concentration of metals.

Speciation of antimony (III) and antimony (V) using hydride generation for meglumine antimoniate pharmaceutical formulationsquality control

The pentavalent antimonies, mainly the meglumine antimoniate, are recommends as first-choice medicines for leishmaniasis therapy. In this work we described the development of formulations of meglumine antimoniate injectable medication, as well as the analytical methodology used in the selective determination of Sb(III) and Sb(Total) by hydride generation - inductively coupled plasma atomic emission spectrometry (HG-ICP-AES) and ICP-AES, respectively. On that purpose the analytical methodology was developed focusing on the HG-ICP-AES technique. The formulations using propylene glycol/water as vehicles in a 20:80 proportion were more appropriate for subsequent use in industrial scale. These formulations also showed a lower variation on Sb(III) percentage, no need of buffer solution to stabilize the formulation and no influence of the autoclaving in the quality of the product. The results of the development of the analytical methodology point out the proposed method as an efficient alternative for the determination of Sb(III) in the presence of large quantities of Sb(V) in injectable solutions of meglumine antimoniate, in a selective, linear, accurate and precise manner. In addition, the method showed a low limit of quantification, less interference of the matrix, and more resilience than batch techniques proposed in the Brazilian Pharmacopeia.