Rochele S. Picoloto

Microwave-assisted digestion in closed vessels: effect of pressurization with oxygen on digestion process with diluted nitric acid

The efficiency of diluted nitric acid solutions under oxygen pressure for decomposition of bovine liver was evaluated using microwave-assisted wet digestion. Calcium, Cu, Fe, Mg, Mn and Zn were determined by inductively coupled plasma optical emission spectrometry (ICP OES). Efficiency was evaluated by determining the residual carbon content (RCC) by ICP OES and residual acidity in digests. Samples (up to 500 mg) were digested using nitric acid solutions (0.1, 0.5, 1, 2, 3, 7, and 14 mol L−1 HNO3) and the effect of oxygen pressure was evaluated using pressures of 0.5, 1, 1.5 and 2 MPa. It was demonstrated that 2 and 0.5 mol L−1 nitric acid solutions may be used for efficient digestion of 500 and 100 mg of bovine liver, respectively, with oxygen pressures ranging from 0.5 to 2 MPa. Using these conditions, less than 0.86 and 0.21 mL of concentrated nitric acid were necessary to digest 500 and 100 mg of sample, respectively. Similar digestion efficiencies for both conditions were obtained under pressures of O2 ranging from 0.5 to 2 MPa. The residual acidities in final digests were lower than 24% when compared to the initial amount of acid used for digestion. The accuracy of the proposed procedure was evaluated using certified reference materials of bovine liver and bovine muscle. Using a solution of 2 mol L−1 with oxygen pressure of 0.5 MPa for 500 mg of sample, the agreement with certified values ranged from 96 to 105% (n = 5). Using the proposed procedure with diluted nitric acid it was possible to obtain RCC values lower than 15% that is important for minimizing the generation of laboratory residues and improving limits of detection.

Effects of Hg(II) Exposure on MAPK Phosphorylation and Antioxidant System in D. melanogaster

The heavy metal mercury is a known toxin, but while the mechanisms involved in mercury toxicity have been well demonstrated in vertebrates, little is known about toxicological effects of this metal in invertebrates. Here, we present the results of our study investigating the effects associated with exposure of fruit fly Drosophila melanogaster to inorganic mercury (HgCl2). We quantify survival and locomotor performance as well as a variety of biochemical parameters including antioxidant status, MAPK phosphorylation and gene expression following mercury treatment. Our results demonstrate that exposure to Hg(II) through diet induced mortality and affected locomotor performance as evaluated by negative geotaxis, in D. melanogaster. We also saw a significant impact on the antioxidant system including an inhibition of acetylcholinesterase (Ache), glutathione S‐transferase (GST) and superoxide dismutase (SOD) activities. We found no significant alteration in the levels of mRNA of antioxidant enzymes or NRF‐2 transcriptional factor, but did detect a significant up regulation of the HSP83 gene. Mercury exposure also induced the phosphorylation of JNK and ERK, without altering p38MAPK and the concentration of these kinases. In parallel, Hg(II) induced PARP cleavage in a 89 kDa fragment, suggesting the triggering of apoptotic cell death in response to the treatment. Taken together, this data clarifies and extends our understanding of the molecular mechanisms mediating Hg(II) toxicity in an invertebrate model.

Total sulfur determination in residues of crude oil distillation using FT-IR/ATR and variable selection methods.

Total sulfur concentration was determined in atmospheric residue (AR) and vacuum residue (VR) samples obtained from petroleum distillation process by Fourier transform infrared spectroscopy with attenuated total reflectance (FT-IR/ATR) in association with chemometric methods. Calibration and prediction set consisted of 40 and 20 samples, respectively. Calibration models were developed using two variable selection models: interval partial least squares (iPLS) and synergy interval partial least squares (siPLS). Different treatments and pre-processing steps were also evaluated for the development of models. The pre-treatment based on multiplicative scatter correction (MSC) and the mean centered data were selected for models construction. The use of siPLS as variable selection method provided a model with root mean square error of prediction (RMSEP) values significantly better than those obtained by PLS model using all variables. The best model was obtained using siPLS algorithm with spectra divided in 20 intervals and combinations of 3 intervals (911-824, 823-736 and 737-650 cm(-1)). This model produced a RMSECV of 400 mg kg(-1) S and RMSEP of 420 mg kg(-1) S, showing a correlation coefficient of 0.990.

Mercury determination in soil by CVG-ICP-MS after volatilization using microwave-induced combustion

Microwave-induced combustion (MIC) was applied for mercury volatilization from soil with subsequent determination by cold vapor generation coupled with inductively coupled plasma mass spectrometry (CVG-ICP-MS). Samples of soil were mixed with microcrystalline cellulose (300 mg), pressed as pellets and combusted in closed quartz vessels pressurized with 20 bar of oxygen. Mercury was volatilized from the sample matrix during combustion and quantitatively absorbed in a suitable solution. The type and concentration of absorbing solution (diluted or concentrated nitric or hydrochloric acids, or even water) as well as the use of a reflux step after combustion were studied. Accuracy was evaluated using soil certified reference materials. Using 0.25 mol L−1 HNO3 as absorbing solution with a reflux step of 5 min the agreement with reference values was better than 95%. The limit of detection was 0.006 μg g−1 Hg (using 300 mg of sample mass) and the residual carbon content for MIC digests was always below 1%. The main advantage of the proposed method is related to the complete separation of the analyte from the sample matrix. Up to eight samples could be simultaneously combusted in only 25 min. Taking into account that only 6 ml of very diluted nitric acid solution (0.25 mol L−1) were used, the proposed MIC method coupled with CVG-ICP-MS can be considered in good agreement with green analytical chemistry recommendations.

Halogen determination in food and biological materials using plasma-based techniques: challenges and trends of sample preparation

Halogens are a group of reactive elements, which are capable of making stable bonds with metals and nonmetals. Due to their properties, they play an important biochemical role in living organisms; some, such as F, Cl and I, are essential for humans, whereas others, such as Br, are non-essential and can cause key toxicological effects. This is probably the main reason why this group of elements has been extensively studied in food and biological materials, especially in recent years. The determination of halogens at trace levels requires suitable instrumentation, and plasma-based techniques, such as inductively coupled plasma optical emission spectrometry (ICP-OES) and especially inductively coupled plasma mass spectrometry (ICP-MS), are particularly well suited for this purpose. Although they are very versatile for performing multielemental determination, halogens present high ionization potentials and low wavelength emission lines, and they are prone to interferences due to matrix effects. Such drawbacks are difficult to overcome without changing instrumental features, such as mass or optical resolution. On the other hand, some interferences due to the presence of dissolved carbon in solution, enhancement or suppression of ionization, and related matrix effects can be minimized by applying an appropriate sample preparation step. In this sense, the present review covers the main sample preparation methods applied for halogen determination in food and biological materials by using ICP-OES and ICP-MS. Methods based on dilution, solubilization, extraction or those involving matrix decomposition (e.g., acid digestion and combustion) are discussed based on key applications selected in the last 20 years.

Ultraviolet radiation combined with microwave-assisted wet digestion of Antarctic seaweeds for further determination of toxic elements by ICP-MS

In this work, the use of ultraviolet radiation combined with microwave-assisted wet digestion (MW-UV) was applied for digestion of seaweed samples and further determination of As, Cd and Pb by inductively coupled plasma mass spectrometry (ICP-MS). In the proposed method, UV radiation was generated in situ by electrodeless Cd discharge lamps inserted into digestion quartz vessels. This approach increased the digestion efficiency allowing lower consumption of acids. The feasibility of using diluted acid solution (0.5 to 7 mol L−1 HNO3) was evaluated for relatively higher sample masses (up to 800 mg). The efficiency of digestion was evaluated taking into account the residual carbon content and residual acidity in digests. Under the selected conditions, it was possible to digest up to 700 mg of sample using a nitric acid solution as diluted as 2 mol L−1 HNO3 allowing an efficiency of digestion higher than 77% (considering the total C content in the sample) and acidity as low as 0.19 mol L−1 that is convenient for ICP-MS measurements. The accuracy of the proposed MW-UV method was evaluated by the digestion of two certified reference materials of aquatic plant (BCR 060 and BCR 670) and by comparison with the results obtained after digestion by microwave-assisted wet digestion in a high pressure system using concentrated HNO3 (MW-AD). The results obtained by the proposed method did not present difference (t-test, 95% confidence level) with the certified values and with results obtained after seaweed sample digestion using the MW-AD method. Using 700 mg of sample, the limit of detection was 0.005, 0.001, and 0.012 μg g−1 for As, Cd, and Pb, respectively. A clear advantage of the proposed method over classical approaches is that only diluted solution was necessary and it is possible to digest a relatively high sample mass, that is important to minimize the generation of laboratory residues and to improve the limits of detection, respectively.

Determination of toxic elements in tricyclic active pharmaceutical ingredients by ICP-MS: a critical study of digestion methods

The determination of As, Cd, Hg and Pb in tricyclic active pharmaceutical ingredients (APIs) was performed by ICP-MS after digestion by both combustion and wet digestion methods. Carbamazepine was digested using the dry ashing method recommended in United States Pharmacopeia 35th edition and significant losses of analytes were observed in recovery tests (38.0 ± 8.9, 99.5 ± 7.1, and 89.4 ± 6.3% of recovery for As, Cd and Pb, respectively). Mercury was completely lost by volatilization during digestion. The digestion of carbamazepine, amitriptyline hydrochloride and imipramine hydrochloride by microwave-assisted wet digestion in closed vessels (MW-AD) was not effective and a yellow-orange solid residue was observed for all substances. 1H NMR of the carbamazepine residue indicated the nitration of carbamazepine aromatic rings forming stable nitro compounds. High pressure asher digestion systems were also used and solid residues were observed for carbamazepine and amitriptyline hydrochloride even under drastic digestion conditions (280 °C, 120 min). A complete digestion of all substances was obtained only by the use of high temperature and long time of digestion and reduction of sample mass to 0.08 g (320 °C, 180 min). The microwave-induced combustion (MIC) method for digestion of tricyclic APIs allowed the digestion of 0.5 g of all substances with high efficiency (RCC lower than 1%) using diluted nitric acid as absorbing solution (7 mol l−1). The recoveries using this method were between 94 and 103% for the evaluated elements. The low RCC and acidity of digests obtained using MIC allowed the compatibility with ICP-MS and makes MIC a promising alternative as a sample preparation method for subsequent determination of toxic elements in APIs by ICP-MS.

Microwave-assisted ultraviolet digestion of petroleum coke for the simultaneous determination of nickel, vanadium and sulfur by ICP-OES.

A method for the simultaneous determination of Ni, V and S in petroleum coke by inductively coupled plasma optical emission spectrometry (ICP-OES) after microwave-assisted ultraviolet digestion (MW-UV) in closed vessels was proposed. Digestion was performed using electrodeless discharge lamps positioned inside quartz vessels and turned on by microwave radiation. The following parameters were evaluated: HNO3 concentration (15 mL of 1, 4, 7, 10 or 14.4 mol L(-1)), volume of H2O2 (30%, 1 or 3 mL), sample mass (100, 250 or 500 mg) and heating time (40 or 60 min) with or without the use of UV lamps. Digestion efficiency was evaluated by the determination of the residual carbon content (RCC) in digests. Using UV lamps lower RCC was obtained and the combination of 4 mol L(-1) HNO3 with 3 mL of H2O2 and 60 min of heating allowed a suitable digestion of up to 500 mg of petroleum coke (RCC< 21%). The agreement with the reference values for Ni, V and S (obtained by digestion of petroleum coke by microwave-induced combustion) and with a certified reference material of petroleum coke was between 96 and 101%. The proposed method was considered as advantageous when compared to American Society for Testing and Materials method because it allowed the simultaneous determination of Ni, V and S with lower limit of detection (0.22, 0.12 and 8.7 µg g(-1) for Ni, V and S, respectively) avoiding the use of concentrated nitric acid and providing digests suitable for routine analysis by ICP-OES.

Determination of bromine and iodine in shrimp and its parts by ICP-MS after decomposition using microwave-induced combustion

A digestion method based on microwave-induced combustion (MIC) was developed for bromine and iodine determination in shrimp and its parts (shells and head, and tissue) by inductively coupled plasma mass spectrometry (ICP-MS). Ammonium nitrate solution was used as an igniter for combustion and vessels were pressurized with O2 at 20 bar. Solutions of (NH4)2CO3 (50 or 100 mmol L−1) and NH4OH (25, 50, 75 or 100 mmol L−1) were evaluated as absorbing media for Br and I. Better results were obtained for Br and I determination using 50 mmol L−1 NH4OH as absorbing medium. Using this solution, blanks were always negligible and memory effects were virtually absent. The accuracy of the proposed MIC method was evaluated using a reference material (NIST 8414) with agreement better than 99% for both analytes. The limits of detection by MIC and further ICP-MS determination (Br: 0.12 μg g−1; I: 0.001 μg g−1) were better than those obtained when the extraction procedure was used. Additionally, a microwave-assisted alkaline extraction method was also evaluated using 0.11 mol L−1 TMAH as extractant solution. However, alkaline extraction was only feasible for shrimp tissue and not for whole shrimp or shells. Decomposition using MIC allowed the determination of Br and I by ICP-MS in shrimp and the respective distribution of these elements in shells and head, and in tissue avoiding the use of concentrated digestion or extraction solutions.

Evaluation of bromine and iodine content of milk whey proteins combining digestion by microwave-induced combustion and ICP-MS determination.

The bromine and iodine content of whey protein concentrate (WPC), hydrolysate (WPH), and isolate (WPI) was evaluated combining microwave-induced combustion (MIC) digestion with inductively coupled plasma mass spectrometry (ICP-MS) determination. MIC digestion allowed the decomposition of up to 500 mg of samples using diluted NH4OH solution (25 mmol L(-1)) for absorption of analytes, assuring the compatibility with ICP-MS determination. Accuracy was evaluated using milk powder certified reference material (NIST 8435) with good agreements for Br and I (102% and 105%, respectively). For Br and I, the limit of quantification obtained by ICP-MS was 7 and 281 times lower in comparison with ion chromatography determination, respectively. Iodine could be enriched in whey protein production and up to 70% of the tolerable upper intake level was found, thus revealing the need to monitor it in whey proteins. On the other hand, the concentration of Br was below its acceptable daily intake.