Chemical contamination in coastal areas alters shape, resistance and composition of carnivorous gastropod shells.

Morphological, structural and compositional alterations in shells of molluscs have been proposed as putative biomarkers of chemical contamination in coastal zones. Despite this, few studies were carried out using top predator gastropods which tend to be more susceptible to contamination exposure. Thus, the present study assessed disturbances on shells of Stramonita brasiliensis considering compression resistance and organic and mineralogical matrix composition, related to morphometric alterations. Results showed reductions in compression resistance and organic matrix content associated with higher contaminated sites. In addition, a predominance of calcite polymorphs was seen in shells obtained in polluted areas. Such outputs were consistent with local contamination levels which may have induced the observed alterations. Thus, changes in mollusc shells showed good performance as potential biomarkers of coastal contamination, being probably observed in other species of carnivorous gastropods around the world.

Expanding information on the bioaccessibility and bioavailability of iron and zinc in biofortified cowpea seeds.

This work presents new findings on the nutritional quality of recently introduced biofortified and non-biofortified cowpea cultivars as well as some common beans. ICP-MS was used for the measurements. Biofortified cowpea cultivars showed high levels of Fe and Zn, greater than 60 and 40 mg kg-1 dry weight, respectively. The in vitro digestion protocol enabled simultaneous evaluation of bioaccessibility and bioavailability. Fe levels in cowpea cultivars were ca. 2.5-fold higher than in common beans. Cowpea seeds also had higher Zn levels, reaching 50.1% bioaccessibility and 44.2% bioavailability. Cooking improved the availability of micronutrients in bean seeds. The cooked biofortified Aracê cowpea showed a high Zn bioavailability above 60%. Consumption of 50 g of Aracê would contribute 27% and 48% of the Fe and Zn DRI for 1-3-year-old children. The new cowpea cultivars biofortified are a potential vehicle for improving the Fe and Zn status in groups in which the micronutrient deficiency is prevalent.

Southern-Brazilian geopropolis: A potential source of polyphenolic compounds and assessment of mineral composition.

Geopropolis is a stingless bee product compose mainly by soil, presenting complex composition geopropolis has bioactive compounds that will depend on geographical characteristics as well bee species, changing their chemical and biological properties. Thus the study aims to evaluate the solubility and chemical stability of geopropolis extracts, through radical capture capacity and reducing capacity. Besides, analysis of free and bonded phenolic compounds, and mineral composition. Geopropolis samples of Melipona mondury, Melipona quadrifasciata, Melipona scutellaris, Melipona seminigra and Tetragonisca angustula were analyzed. Both reducing compounds with a maximum of 2.96% GAE and free radical scavenging potential with a maximum of 5.84% AAE and 8.58% TE increases over 30 days of storage time. Also, methanolic extracts released at least 51% more reducing compounds and exhibited at least 27% more free radical scavenging potential in comparison to ethanolic extracts. The polyphenolic profile shows 31 compounds after acid and alkaline hydrolysis as cinnamic acid, ferulic acid, p-coumaric acid, aromadendrin, vanillin. For the mineral composition, sixteen minerals were found among essential and non-essential, differentiating each sample by chemometric PCA and HCA analysis according to geographic region. Geopropolis is a potential source of natural compounds that could enhance food quality, increasing the bioactive content and preventing oxygen damages in foods, likewise for pharmacological application for healthcare.

Lead, Cadmium, and Arsenic Bioaccessibility of 24 h Duplicate Diet Ingested by Preschool Children Attending Day Care Centers in Brazil.

Lead, known as a metal with high neurotoxicity to children, cadmium, which is a carcinogenic and bioaccumulative contaminant, and arsenic, a class 1 carcinogenic according to the International Agency for Research on Cancer, are toxic elements (TEs) whose relevant route of exposure may be diet. We determined the bio-accessible fraction of lead, cadmium, and arsenic from the diet of preschool children from two day care centers (DCC). A cross-sectional study was conducted with 64 one⁻four-year-old children from two DCCs where the 24-h duplicate diet samples were collected. The diet samples were analyzed by ICP-MS for lead, cadmium, and arsenic total concentrations (n = 64) and their bio-accessibility were analyzed for a subsample (n = 10). The dietary intake (DI) mean for lead, cadmium, and arsenic were 0.18 ± 0.11 µg kg-1 bw, 0.08 ± 0.04 µg kg-1 bw, and 0.61 ± 0.41 µg kg-1 bw, respectively. All DI calculated for TEs, considering total intake, were found lower than the tolerable limits (TL) (European Union, or World Health Organization, WHO, when applicable) except for one child's Pb intake. Bio-accessibilities ranged between 0% to 93%, 0% to 103%, and 0% to 69%, for lead, cadmium, and arsenic, respectively. Although DI for TEs has been found lower than TL, these reference values have been recently decreased or withdrawn since it was for lead and arsenic whose TL were withdrawn by WHO.

Fast determination of cations in honey by capillary electrophoresis: a possible method for geographic origin discrimination.

This study reports the development and validation of a fast capillary electrophoresis method for cation determination in honey samples and the classification of honey by geographical origin using Principal Components Analysis (PCA). The background electrolyte (BGE) was optimized using the Peakmaster(®) software, which evaluates the tendency of the analytes to undergo electromigration dispersion and the BGE buffer capacity and conductivity. The final BGE composition was defined as 30 mmol L(-1) imidazole, 300 mmol L(-1) acetic acid and 140 mmol L(-1) Lactic acid, at pH 3,0, and the separation of K(+), Na(+), Ca(2+), Mg(2+) and Mn(2+) using Ba(2+) as the internal standard was achieved in less than 2 min. The method showed satisfactory results in terms of linearity (R(2)>0.999), the detection limits ranged from 0.27-3.17 mg L(-1) and the quantification limits ranged from 0.91-10.55 mg L(-1). Precision measurements within 0.55 and 4.64%RSD were achieved and recovery values for the analytes in the honey samples ranged from 93.6%-108.6%. Forty honey samples were analyzed to test the proposed method. These samples were dissolved in deionized water and filtered before injection. The CE-UV reliability in the cation analysis in the real sample was compared statistically with ICP-MS methodology. No significant differences were found, with a 95% confidence interval between the methodologies. The PCA showed that the cumulative variance for the first two principal components explain more than 85% of the variability of the data. The analytical data suggest a significant influence of the geographical origin on the mineral composition.

Metal-metallothioneins like proteins investigation by heteroatom-tagged proteomics in two different snails as possible sentinel organisms of metal contamination in freshwater ecosystems.

Metal speciation analysis in MLPs was carried out in two snails, Marisa cornuarietis and Pomacea bridgesi, in order to investigate them as possible sentinel organisms of heavy metal contamination. To carry out this study snails born in a non-contaminated environment were divided into two groups: a control group and a contaminated one with cadmium administered for 40 days. Subsequently, we investigated the speciation of the induced MLPs in exposed animals in relation to controls. In order to obtain the MLP fraction, cytosols from both snail species where subjected to size-exclusion fractionation, monitoring on-line the metal signal (Cd, Cu and Zn) by ICP-MS while protein elution was followed by on-line UV detection. MLP fraction was then separated by anion-exchange (AE)-FPLC using optimal chromatographic conditions for the separation of the different MLP isoforms in both snail species. Specific detection of separated metalloforms was carried out again by the hyphenation of the AE chromatographic system with ICP-MS. The determination of the amount of metal bound to MLPs was carried out by post-column isotope dilution analysis ICP-MS, finding that the snail M. cornuarietis accumulated higher concentrations of cadmium than P. bridgesi. Thus this first snail could therefore be a better candidate sentinel organism of pollution in natural waters. Identification and characterization of the isoforms separated in M. cornuarietis was carried out for the entire or intact isoforms by MALDI-TOF and then conventional triptic digestion was also carried out to identify the nature of the formed peptides. The presence identification of a MLP isoform of relatively low molecular weight in M. cornuarietis is reported.

Speciation of Cr(III) and Cr(VI) in environmental samples determined by selective separation and preconcentration on silica gel chemically modified with niobium(V) oxide.

In this study a new method for chromium speciation in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The adsorption behavior of Cr(III) and Cr(VI) on Nb2O5-SiO2 allowed the selective separation of Cr(III) from Cr(VI) in the pH range of 6-9. Thus, a method for Cr(III) preconcentration and extraction using Nb2O5-SiO2 was developed. Total chromium was determined after the reduction of Cr(VI) to Cr(III) using sodium sulfite in acidic medium. The operational variables of the preconcentration and reduction procedures were optimized through full factorial and Doehlert designs. The limit of detection for Cr(III) was 0.34microgL(-1) and the precision was below 4.6%. Results for recovery tests using different environmental samples were between 90 and 105%. Certified reference materials (NIST 1640 and NIST 1643e) were analyzed in order to check the accuracy of the proposed method, and the results were in agreement with the certified values.

Simultaneous on-line pre-concentration and determination of trace metals in environmental samples by flow injection combined with inductively coupled plasma mass spectrometry using silica gel modified with niobium(V) oxide.

This work presents the development of an on-line pre-concentration system for simultaneous determination of Cd, Cu, Ni, V, Zn, Co and Pb in aqueous environmental samples and detection by inductively coupled plasma mass spectrometry. The system is based on cationic retention of the analytes onto a mini-column filled with silica gel modified with niobium(V) oxide. The effects of chemicals and flow variables have been investigated. The optimized operating conditions, selected as a compromise between sensitivity and analytical frequency were: sample pH 7.0, sample flow rate of 6.0mL min(-1), eluent flow rate of 2.0mL min(-1), and eluent (HNO(3)) concentration of 2.5mol L(-1). The relative standard deviation (n=7), enrichment factor and linear working range were 0.8-4.5%, 23.3-37.2 and 0.05-25.0microg L(-1), respectively. Limits of detection were between 0.01 and 0.03microg L(-1). The accuracy of the proposed method was checked with certified materials (NASS-4, NASS-5, CASS-4 and SRM 1643e). Values obtained were in accordance with those reported for the certified materials. Recovery was found to be in the range of 90-110% for a suit of water samples with variable matrices (seawater, tap water and ground water) collected in Florianopolis, Brazil.

Single drop micro-extraction with O,O-diethyl dithiophosphate for the determination of lead by electrothermal atomic absorption spectrometry.

Lead was extracted as the O,O-diethyldithiophosphate (DDTP) complex from aqueous solution into a drop of CHCl(3) immersed in the solution. Unlike previously reported procedures using single drop micro-extraction (SDME) for the extraction of inorganic analytes, the complexation reaction was conducted in the aqueous phase, as the ammonium salt of DDTP is soluble in water. The concentration of DDTP was optimized as 0.01% (m/v). Experimental parameters such as extraction time (7min) and organic drop volume (3microL) were optimized and selected as a compromise between sensitivity and stability of the organic drop in the aqueous solution. The sensitivity with electrothermal atomic absorption spectrometry (ET AAS) was low, probably due to infiltration of the organic drop into the totally pyrolytic graphite platform. To overcome this problem, tungsten (400microg) was thermally deposited onto the platform surface. A short pyrolysis stage at 700 degrees C was included to reduce background absorption. Under these conditions, five certified reference materials with different characteristics were analyzed using calibration against aqueous standards submitted to the SDME procedure, resulting in good agreement between certified and found concentration values at a 95% confidence level. Two real water samples have also been analyzed, with recoveries ranging from 85 to 92% after enrichment with Pb. An enhancement factor of 52 allowed a detection limit of 0.2microg L(-1) or 0.04microg g(-1), demonstrating the high detection capability of the proposed procedure, with a relative standard deviation typically below 4%.

Application of factorial design and Doehlert matrix for determination of trace lead in environmental samples by on-line column preconcentration FAAS using silica gel chemically modified with niobium(V) oxide.

In this study a new method for Pb determination in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The sorbent used for Pb preconcentration and extraction was silica gel chemically modified with niobium(V) oxide. Flow and chemical variables of the system were optimized through a multivariate procedure. The factors selected were buffer type, eluent concentration, and sample and eluent flow rates. It was verified that the aforementioned factors as well as their interactions were statistically significant at the 95% confidence level. The effect of foreign ions was evaluated using a fractionary factorial experimental design. The detection limit was 0.35 microg L(-1) and the precision was 1.6%. Results for recovery tests using different environmental samples were between 90 and 104%. Certified reference materials were analyzed in order to check the accuracy of the proposed method.

Use of 8-hydroxyquinoline-chitosan chelating resin in an automated on-line preconcentration system for determination of zinc(II) by F AAS.

This study presents the development of an on-line preconcentration system for zinc(II) determination in aqueous samples. The analyte was trapped in a mini-column filled with a chelating resin based on a chitosan biopolymer modified with 8-hydroxyquinoline obtained by the diazotization reaction. Flow and chemical variables of the system, as well as the potential interference ions, were optimized through a multivariate procedure. The factors selected were sample pH, eluent concentration (HNO(3)), and sample and eluent flow rates. It was verified through a full factorial design that the sample pH and eluent flow rate factors were statistically significant at the 95% confidence level. A final optimization of the significant factors was carried out using a Doehlert matrix. The preconcentration system was linear between 2.5 and 75 microgL(-1), with a regression coefficient of 0.9995. The enrichment factor was 17.6. The limits of detection and quantification were 0.8 and 2.5 microgL(-1), respectively. The repeatability and the analytical frequency were, respectively, 2.7 (25.0 microgL(-1), n=8) and 18 samples per hour. Results for recovery tests using mineral water samples were between 85 and 93%. Certified reference materials were analyzed in order to check the accuracy of the proposed method.

Chromium speciation and preconcentration using zirconium(IV) and zirconium(IV) phosphate chemically immobilized onto silica gel surface using a flow system and F AAS.

A procedure for chromium speciation by F AAS using a flow system has been proposed. In this system, Cr(III) and Cr(VI) ions were adsorbed sequentially onto a mini-column packed with silica gel modified with zirconium phosphate and a mini-column packed with silica gel modified with zirconium oxide, respectively. The elution of Cr(III) and Cr(VI) was made with, respectively, nitric acid solution and tris(hydroxymethyl)methylamine (THAM) solution in reverse mode and determination by flame atomic absorption spectrometry without interference of the matrix. Chemical and flow variables as well as concomitant ions were studied in the developed procedure. The enrichment factor for Cr(III) and Cr(VI) was 20.8 and 24.9, respectively, using a preconcentration time of 3.75min. The limit of detection for Cr(III) and Cr(VI) was 1.9, and 2.3mugl(-1), respectively. The precision of the method, evaluated as the relative standard deviation in solutions containing 100mugl(-1) of chromium species, by analyzing a series of seven replicates, was lower than 3.0%. The accuracy was assessed through recovery experiments of water samples and using another methodology.