Chromium removal from aqueous solutions using new silica gel conjugates of desferrioxamine or diethylenetriaminepentaacetic acid.

Desferrioxamine (DFO) and diethylenetriaminepentaacetic acid (DTPA) conjugated with silica gel (IDFOSG and IDTPASG, respectively) were evaluated as adsorbents for chromium in aqueous solutions. Different parameters affecting adsorption such as pH, sorbent dosage, contact time, sample volume and potential of interfering ions have been optimized. The optimum pH for chromium binding was 4 for 100 mg of adsorbents at 5 min of table shaking with 5 mL sample volume of chromium solutions. Langmuir adsorption model described the removal of chromium ions. The adsorption capacity for chromium was 90% for IDFOSG and 83% for IDTPASG in single solutions, and at least 75% in multielemental solutions. Considering the removal efficacy, regeneration and stability, DFO-grafted silica gel was generally superior to its DTPA counterpart and may be applied to the removal of traces of chromium species from natural waters.

Direct determination of the nutrient profile in plant materials by femtosecond laser-induced breakdown spectroscopy.

Femtosecond laser-induced breakdown spectroscopy (fs-LIBS) has been used for the first time for quantitative determination of nutrients in plant materials from different crops. A highly heterogeneous population of 31 samples, previously analyzed by inductively coupled plasma optical emission spectroscopy, covering a wide range of matrices was interrogated. To tackle the analysis, laser-induced plasmas under argon atmosphere of pellets prepared from sieved cryogenically ground leaves were studied. Predictive functions based on univariate and multivariate modeling of optical emissions associated to macro- (Ca, Mg, and P) and micronutrients (Cu, Fe, Mn and Zn) were designed. Hierarchical cluster analysis was performed to select representative calibration (n(cal)=17) and validation (n(val)=14) datasets. The predictive performance of calibration functions over fs-LIBS data was compared with that attained on spectral information from nanosecond LIBS (ns-LIBS) operating at different wavelengths (1064 nm, 532 nm, and 266 nm). Findings established higher accuracy and less uncertainty on mass fractions quantification from fs-LIBS, whatever the modeling approach. Quality coefficients below 20% for the accuracy error on mass fractions' prediction in unknown samples, and residual predictive deviations in general above 5, were obtained. In contrast, only multivariate modeling satisfactorily handled the non-linear variations of emissions in ns-LIBS, leading to 2-fold decrease in the root mean square error of prediction (RMSEP) of Ca, Mg, P, Cu, Fe, Mn and Zn in comparison with the univariate approach. But still, an averaged quality coefficient about 35% and residual predictive deviations below 3 were found. Similar predictive capabilities were observed when changing the laser wavelength. Although predicted values by ns-LIBS multivariate modeling exhibit better agreement with reference mass fractions as compared to univariate functions, fs-LIBS conducts better quantification of nutrients in plant materials since it is less dependent on the chemical composition of the matrices.

Assessment of total and organic mercury levels in blue sharks (Prionace glauca) from the south and southeastern Brazilian coast.

Mercury occurrence was evaluated in samples of edible muscle tissue of 27 blue sharks (Prionace glauca) caught in the Atlantic Ocean, adjacent to the south and southeastern Brazilian coast, indicating a slight increase in comparison with previous data obtained for the same studied area and being higher than those fish caught at different sites of the Atlantic Ocean. Total Hg concentrations ranged from 0.46 to 2.40 mg kg(-1) with the organic Hg fraction ranging between 0.44 and 2.37 mg kg(-1). A negative correlation between total Hg concentration in muscle tissue and blue shark size was obtained, and 40% of samples analyzed had Hg concentrations higher than 1.0 mg kg(-1) Hg, the maximum concentration permitted in Brazilian predator fish. Data obtained showed that total Hg can be used as a reliable predictor of organic Hg in blue shark muscle because 95 to 98% of the total Hg measured was found to be organic mercury. The wide range of Hg concentrations obtained for our set of samples can be explained by the heterogeneity of sampled population and the large size of the studied area. Given the adverse toxicological effects of Hg on animals and humans, a regular monitoring program of Hg contamination in Brazilian marine ecosystem can be recommended.

Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry.

It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25J cm(-2)). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 µs, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 µm. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity.