Ultrasound-assisted extraction of chromium from tanned leather shavings: A promising continuous flow technology for the treatment of solid waste.

In this work, a continuous flow extraction system assisted by ultrasound (US) was developed for the extraction of Cr(III) from residual tanned leather shavings. US energy was delivered into the system by a tubular applicator (clamp-on tube US applicator). The effect of the US energy was investigated at 20 kHz of frequency and electrical input power of 75, 150, 300 and 600 W. Residence time and temperature profile were also evaluated. It was observed that the internal temperature profile was affected by the presence of US and inverted in comparison with the conditions without US. In this way, the temperature profile generated by the US was reproduced by using electrical resistances in order to compare the obtained results. The US intensity was measured using a hydrophone connected to a sound pressure meter. The use of the US did not alter the dynamic behavior of the system but increased the extraction efficiency when compared to the silent condition. US power above 75 W did not lead to increased extraction efficiency, when the residence time was 30 min. However, when 60 min of residence time were employed, the optimized US power was 150 W, resulting in an extraction efficiency of 71.7 ± 0.7 %, about 28 % higher when compared to the silent condition in the same temperature and other conditions. The US energy allowed a reduction in processing time and operational temperature when compared to the silent condition with the same temperature profile. The overall energy consumption with US was similar or lower than that observed without US, showing the feasibility of the proposed extraction system.

Development of an eco-friendly sample preparation protocol for metal determination in food samples: an oxygen pressurized single reaction chamber using diluted nitric acid.

Many efforts have been recently made to improve the digestion efficiency by using powerful equipment or by using an auxiliary reagent. In this work, an alternative method is reported, which explores a digestion system based on a single reaction chamber (SRC) technology pressurized with O2 for reducing the amount of acid, without impairing the digestion efficiency. Before digestion, the system was pressurized with compressed air (20 bar, 20% O2) while the temperature was evaluated from 180 up to 270 °C. The procedure was also carried out under O2 pressure (20 bar). For each temperature several acid concentrations were evaluated (0.1 to 3 mol L-1 HNO3), being possible to correlate the effectiveness of each acid concentration with temperature. The proposed method was applied to the simultaneous digestion of several organic matrices with variable content of fat, protein, and carbohydrate (whole milk powder, bovine liver, parsley, and linseed). The residual carbon content was lower than 4% (C lower than 200 mg L-1 in digests), showing the high digestion efficiency of the proposed approach. Up to 250 mg of all food matrices were digested using a sub-stoichiometric amount of HNO3 (1 mol L-1 solution), which was only achieved due to the use of O2 as an auxiliary reagent. Barium, Ca, Cu, Fe, K, Mg, Mn, Na, Sr, and Zn were determined by ICP-OES, and the accuracy was better than 95% for standard reference materials of corn bran, whole milk powder, and bovine liver. It is an important feature, being in agreement with green chemistry recommendations because very low amounts of reagents are required for sample digestion, as well as low amounts of residues are generated.

Ultrasound-assisted biomass valorization to industrial interesting products: state-of-the-art, perspectives and challenges.

Nowadays, the application of ultrasound (US) energy for assisting the lignocellulosic biomass and waste materials conversion into value-added products has dramatically increased. In this sense, this review covers theoretical aspects, promising applications, challenges and perspectives about US and its use for biomass treatment. The combination of US energy with a suitable reaction time, temperature and solvent contributes to the destruction of recalcitrant lignin structure, allowing the products to be used in thermochemical and biological process. The main mechanisms related to US propagation and impact on the fragmentation of lignocellulosic materials, selectivity, and yield of conversion treatments are discussed. Moreover, the synergistic effects between US and alternative green solvents with the perspective of industrial applications are investigated. The present survey analysed the last ten years of literature, studying challenges and perspectives of US application in biorefinery. We were aiming to highlight value-added products and some new areas of research.

A single step ultrasound-assisted nitrocellulose synthesis from microcrystalline cellulose.

Nitrocellulose is a nitrated cellulose polymer with a broad application in industry. Depending on the nitrogen content, this polymer can be used for manufacturing explosives, varnishes, clothes, and films, being considered a product of high value-added. In this work, the use of ultrasound was investigated for the intensification of nitrocellulose synthesis from microcrystalline cellulose. The ultrasound-assisted nitrocellulose synthesis (UANS) was carried out using several ultrasound systems, such as baths and cup horns, allowing the evaluation of the frequency (from 20 to 130 kHz) and delivered power (from 23 to 134 W dm-3) to the reaction medium. The following parameters were evaluated: acid mixture (H2SO4, H3PO4, CH2O2 or CH3COOH with HNO3, 2 to 14.4 mol L-1), ultrasound amplitude (10 to 70%) and reaction time (5 to 50 min). Better nitrocellulose yield (nitrogen content of 12.5% was obtained from 1 g of microcrystalline cellulose employing a cup horn system operating at 20 kHz, 750 W of nominal power with 60% of amplitude, 25 mL of acid solution (13.6 mL of 18.4 mol L-1 H2SO4 + 9.2 mL of 14.4 mol L-1 HNO3 + 2.2 mL H2O), at 30 °C for 30 min. At silent conditions (mechanical stirring ranging from 100 to 500 rpm), the nitrogen content was lower than 11.8% which demonstrate the ultrasound effects for nitrocellulose synthesis.

Ultrasound-assisted conversion of tannic acid to gallic acid as a strategy to obtain value-added products.

In this work, ultrasound was applied for the conversion of tannic acid into gallic acid using only diluted H2O2 as reagent. Experiments were carried out using several types of ultrasonic horns operating at 20 kHz (VC750W processor). The following experimental conditions were evaluated: H2O2 concentration (0.2 to 8.5 mol L-1), horn type (10 to 25 mm of diameter), ultrasound amplitude (20 to 70%), sonication time (10 to 45 min), tannic acid concentration (170 to 1360 mg L-1), and reaction temperature (50 to 90 °C). Gallic acid production was monitored with ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS). The isolated gallic acid was confirmed with nuclear magnetic resonance (1H and 13C NMR). It is important to emphasize that this study was developed as a proof of concept to demonstrate the potential of ultrasound for tannic acid conversion into gallic acid using just diluted H2O2. Under selected conditions gallic acid production yield was 128 ± 4 mg g-1 of initial tannic acid (using 170 mg L-1 of tannic acid as starting material). Reaction time was set as 30 min, which was carried out using 1 mol L-1 H2O2 and ultrasound amplitude of 50% at 90 °C. At silent conditions (mechanical stirring, from 100 to 1000 rpm), gallic acid production was halved (less than 78 ± 4 mg g-1 of initial tannic acid).

Determination of microplastic content in seafood: An integrated approach combined with the determination of elemental contaminants.

A method for the determination of microplastic (MP) content in seafood is proposed based on the selective digestion of seafood without the degradation of MP. A simple approach was developed using diluted acid with microwave-assisted wet digestion. The following parameters were evaluated: nitric acid concentration (0.5 to 14.4 mol L-1), digestion temperature (180 to 220 °C), irradiation program holding time (10 to 30 min), MP particle size (0.3 to 5 mm), and the seafood mass (0.5 to 2 g). To develop a reliable method for the determination of MP amount, up to 2 g of an in natura seafood sample were spiked with a known amount of MP (100 mg of mixed MP). Suitable conditions were obtained using 1 mol L-1 HNO3 at 200 °C (10 min holding time). Digests were filtered and the plastic content was gravimetrically determined. The heating program was 20 min, which represents a significant reduction in the time normally reported in the literature for MP analysis (from few hours up to 3 days). The proposed method allowed gravimetric determination of eight plastic types (polyethylene terephthalate, polystyrene, expanded polystyrene, polypropylene, high and low density polyethylene, polycarbonate and polyvinyl chloride) with particle size ≥0.3 mm. Up to 2 g of an in natura seafood sample (shark species, acoupa weakfish, tuna fish, trahira, and pink shrimp) were efficiently digested, which opened the possibility of using the proposed digestion method for determining elemental contaminants (Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, La, Mg, Mn, Mo, Ni, Pb, and Zn). Thus, as the main feature of the proposed digestion method is the possibility of determining MP and elemental contaminants using the same digestion protocol, saves time and reagents and provides accurate and precise information about different classes of marine pollutants (MP and elemental contaminants).

Consequences of oxidative damage on the fatty acid profile in muscle of Cichlasoma amazonarum acutely exposed to copper.

Rapid industrialization results in the production of large quantities of waste that are commonly discharged into water bodies, leading to the damage of the aquatic ecosystem and freshwater organisms. Copper (Cu) can induce oxidative damage in fish muscle, the main fish portion that is consumed by humans. However, the responses of the Amazon fish Cichlasoma amazonarum and its capacity to withstand acute Cu concentrations found in Amazon water around mines remain unknown. Thus, the aim of this study was to evaluate whether exposure to Cu causes muscle oxidative stress and/or oxidative damage and impairs the fillet fatty acid profile of C. amazonarum acutely exposed to Cu found in Amazon waters around mines. Muscle reactive oxygen species and protein carbonylation levels were significantly higher in fish exposed to 1500 µg/L Cu compared with the control group, while muscle lipid peroxidation levels were significantly higher in fish exposed to 500, 750, and 1500 µg/L Cu compared with control group. Muscle antioxidant capacity against peroxyl radical's levels and glutathione peroxidase activity were significantly lower in fish exposed to 1500 µg/L Cu compared with the control group, while muscle superoxide dismutase activity was significantly lower in fish exposed to 750 and 1500 µg/L Cu compared with control group. The total content of saturated fatty acids was significantly higher in fish exposed to 1500 µg/L Cu compared with the control group, while the total content of monounsaturated fatty acids and sum of n3 fatty acids were significantly lower in fish exposed to 1500 µg/L Cu compared with control group. No significant difference was observed regarding muscle catalase, glutathione S-transferase, and glutathione reductase activities. Based on these lines of evidence, the results of this comprehensive study agree with the initial hypothesis that the exposure to Cu found in Amazon water around mines induces oxidative damage and inhibits enzymatic and non-enzymatic antioxidant response in the muscle of C. amazonarum exposed to high Cu levels. Moreover, the impairment of the fillet fatty acid profile appears to be mediated by oxidative damage, representing a negative impact on fish health.

Ultrasound-assisted extraction of chromium from residual tanned leather: An innovative strategy for the reuse of waste in tanning industry.

The tannery industry generates huge amount of waste with high Cr concentration, being classified as a dangerous waste. The development of alternative treatments for these residues aiming environmental friendly protocols are important topics of research. In this work, the use of ultrasound (US) energy for Cr removal from residual tanned leather was investigated. Ultrasound-assisted extraction (UAE) experiments were carried out in several systems as ultrasonic baths, cup horns, and probes, allowing to evaluate several frequencies (20-130 kHz) and power delivered to the extraction system. The following experimental conditions were evaluated: extraction solution (HCl, HNO3, H2SO4, CH2O2 and C2H2O4), temperature (10-90 °C), time (1-40 min), US amplitude (10-90%), feedstock amount (50-450 mg), and concentration of extraction solution (0.1-4 mol L-1). A multivariate factorial design with 10 axial points and 3 central points was applied. After UAE optimization an efficiency of 92% was achieved for Cr removal using 150 mg of feedstock, 3 mol L-1 HNO3, at 30 °C, 90% of amplitude, and 30 min. The same efficiency was not observed using mechanical stirring (100-500 rpm), which was lower than 65%. To prove the applicability of the proposed process some experiments for scaling up were performed using several reactor loads (1-9 L). Moreover, using the proposed UAE process Cr was efficiently removed at lower reaction time and at room temperature only by using US and diluted acid solution, representing energy and reagents saving.

Furfural production from lignocellulosic biomass by ultrasound-assisted acid hydrolysis.

Furanic platforms (e.g. furfural, furfuryl alcohol and hydroxymethylfurfural) can be obtained from biomass, being considered as a green alternative to petrochemical products such as fuels, and solvents. In this work, the use of ultrasound energy was investigated for the conversion of several lignocellulosic materials into furfural. The following parameters were evaluated: reaction time (30 to 120 min), ultrasound amplitude (20 to 70%) and feedstock amount (100 to 500 mg). The ultrasound-assisted acid hydrolysis (UAAH) process was applied to several lignocellulosic materials (sugar cane straw, rice husk, yerba-mate waste, grass and wood waste) aiming an investigation about the effects when working with real and complex feedstock. Better furfural yields (72.4 ±â€¯4.3 mg g-1) were obtained from 0.1 g of grass, employing an ultrasound cup horn system operating at 20 kHz, 20 mL of 4 mol L-1 HNO3, at 30 °C, 50% amplitude, and 60 min of sonication. Under the same reaction conditions, the results were compared with those obtained at silent condition (mechanical stirring, 100 to 500 rpm), which demonstrate the ultrasound effects for furfural synthesis. Therefore, the proposed UAAH process can be considered as a suitable alternative for biomass conversion to furfural, because it does not need previous step of lignin removal and might be performed in a single step.

Determination of toxic elements in yerba mate by ICP-MS after diluted acid digestion under O2 pressure.

In this work, a procedure allowing effective digestion of a high mass of yerba mate (up to 1500 mg) using diluted HNO3, in a system pressurized with oxygen, is proposed. Digests were suitable for direct analysis by ICP-MS, virtually free of interferences. Digestion was performed using 7 mol l-1 HNO3 and 8 bar O2. The digestion efficiency was better than 92% and digests presented a relatively low acidity (<10 mmol HNO3). The limit of quantification was 4.0, 1.0 and 1.0 ng g-1 for As, Cd and Pb, respectively. Under optimized conditions up to 1500 mg of sample were digested and no interferences were observed during analyses by ICP-MS, making this approach suitable for routine determination of As, Cd and Pb in yerba mate and also in agreement with the quality control requirements.

Maxwell-Wagner Effect Applied to Microwave-Induced Self-Ignition: A Novel Approach for Carbon-Based Materials.

A new method for analytical applications based on the Maxwell-Wagner effect is proposed. Considering the interaction of carbonaceous materials with an electromagnetic field in the microwave frequency range, a very fast heating is observed due to interfacial polarization that results in localized microplasma formation. Such effect was evaluated in this work using a monomode microwave system, and temperature was recorded using an infrared camera. For analytical applications, a closed reactor under oxygen pressure was evaluated. The combination of high temperature and oxidant atmosphere resulted in a very effective self-ignition reaction of sample, allowing its use as sample preparation procedure for further elemental analysis. After optimization, a high sample mass (up to 600 mg of coal and graphite) was efficiently digested using only 4 mol L-1 HNO3 as absorbing solution. Several elements (Ba, Ca, Fe, K, Li, Mg, Na, and Zn) were determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Accuracy was evaluated by using a certified reference material (NIST 1632b). Blanks were negligible, and only a diluted solution was required for analytes absorption preventing residue generation and making the proposed method in agreement with green chemistry recommendations. The feasibility of the proposed method for hard-to-digest materials, the minimization of reagent consumption, and the possibility of multi elemental analysis with lower blanks and better limits of detection can be considered as the main advantages of this method.

Ultrasound-assisted acid hydrolysis of cellulose to chemical building blocks: Application to furfural synthesis.

In this work, the use of ultrasound energy for the production of furanic platforms from cellulose was investigated and the synthesis of furfural was demonstrated. Several systems were evaluated, as ultrasound bath, cup horn and probe, in order to investigate microcrystalline cellulose conversion using simply a diluted acid solution and ultrasound. Several acid mixtures were evaluated for hydrolysis, as diluted solutions of HNO3, H2SO4, HCl and H2C2O4. The influence of the following parameters in the ultrasound-assisted acid hydrolysis (UAAH) were studied: sonication temperature (30 to 70°C) and ultrasound amplitude (30 to 70% for a cup horn system) for 4 to 8molL-1 HNO3 solutions. For each evaluated condition, the products were identified by ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS), which provide accurate information regarding the products obtained from biomass conversion. The furfural structure was confirmed by nuclear magnetic resonance (1H and 13C NMR) spectroscopy. In addition, cellulosic residues from hydrolysis reaction were characterized using scanning electron microscopy (SEM), which contributed for a better understanding of physical-chemical effects caused by ultrasound. After process optimization, a 4molL-1 HNO3 solution, sonicated for 60min at 30°C in a cup horn system at 50% of amplitude, lead to 78% of conversion to furfural. This mild temperature condition combined to the use of a diluted acid solution represents an important contribution for the selective production of chemical building blocks using ultrasound energy.

Intensification of ultrasonic-assisted crude oil demulsification based on acoustic field distribution data.

Water removal is an essential step during crude oil production due to several problems such as increased transportation costs and high corrosion rate due to dissolved salts. Indirect low frequency ultrasonic energy (US), using baths, has been recently proposed as an effective alternative for crude oil demulsification. However, the reactor position during sonication and its influence on the demulsification efficiency for crude oil has not been evaluated. In this sense, the aim of this study was to develop an automated system based on an open source hardware for mapping the acoustic field distribution in an US bath operating at 35kHz using a hydrophone. Data acquired with this system provided information to evaluate the demulsification efficiency in the different positions of the US bath and correlate it with the acoustic intensity distribution. The automated 3D-mapping system revealed a higher acoustic intensity in the regions immediately above the transducers (ca. 0.6Wcm-2), while the other regions presented a relatively lower intensity (ca. 0.1Wcm-2). Experimental data demonstrated that reactors positioned in the most intense acoustic regions provided a much higher efficiency of demulsification in comparison with the ones positioned in the less intense acoustic field regions. Demulsification efficiency up to 93% was obtained with 15min of sonication (100% amplitude) using few amount of chemical demulsifier. Hence, this work demonstrated that the information acquired with the developed mapping system could be used for inducing a higher efficiency of demulsification only by finding the more suitable position of reactor in the US bath, which certainly will help development of appropriate reactors design when looking for such approach.

Microwave-induced combustion: Thermal and morphological aspects for understanding the mechanism of ignition process for analytical applications.

In the present work, for the first time a systematic study was performed using an infrared camera and scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectrometry (EDS) to evaluate the mechanisms involved in microwave-induced combustion method, which has been extensively used for sample preparation. Cellulose and glass fiber discs, wetted with the igniter solution (6molL-1 NH4NO3), were evaluated under microwave field in a monomode system. The temperature of the discs surface was recorded during microwave irradiation and the effect of NH4NO3 concentration and irradiation time on cellulose oxidation was evaluated. The morphology of the discs surface was characterized by SEM before and after irradiation in an inert atmosphere. According to the results, the surface temperature of the discs increased near to 100°C and remained in this temperature for few seconds while water evaporate. After that, temperature increased over 200°C due to the thermal decomposition of NH4NO3 salt, releasing a large amount of energy that accelerates cellulose oxidation. The higher the igniter concentration, the shorter was the microwave irradiation time for cellulose oxidation. The SEM images revealed that cellulose disc was more porous after microwave irradiation, enhancing oxygen diffusion within the paper and making easier its ignition. The EDS spectrum of cellulose and glass fiber discs showed that signal intensity for nitrogen decreased after microwave irradiation, showing that NH4NO3 was consumed during this process. Therefore, it was demonstrated that the ignition process is the result of synergic interaction of NH4NO3 thermal decomposition and organic matter oxidation (cellulose) releasing heat and feeding the chain reaction.

Microwave-assisted wet digestion with H2O2 at high temperature and pressure using single reaction chamber for elemental determination in milk powder by ICP-OES and ICP-MS.

In this work a green digestion method which only used H2O2 as an oxidant and high temperature and pressure in the single reaction chamber system (SRC-UltraWave™) was applied for subsequent elemental determination by inductively coupled plasma-based techniques. Milk powder was chosen to demonstrate the feasibility and advantages of the proposed method. Samples masses up to 500mg were efficiently digested, and the determination of Ca, Fe, K, Mg and Na was performed by inductively coupled plasma optical emission spectrometry (ICP-OES), while trace elements (B, Ba, Cd, Cu, Mn, Mo, Pb, Sr and Zn) were determined by inductively coupled plasma mass spectrometry (ICP-MS). Residual carbon (RC) lower than 918mgL(-1) of C was obtained for digests which contributed to minimizing interferences in determination by ICP-OES and ICP-MS. Accuracy was evaluated using certified reference materials NIST 1549 (non-fat milk powder certified reference material) and NIST 8435 (whole milk powder reference material). The results obtained by the proposed method were in agreement with the certified reference values (t-test, 95% confidence level). In addition, no significant difference was observed between results obtained by the proposed method and conventional wet digestion using concentrated HNO3. As digestion was performed without using any kind of acid, the characteristics of final digests were in agreement with green chemistry principles when compared to digests obtained using conventional wet digestion method with concentrated HNO3. Additionally, H2O2 digests were more suitable for subsequent analysis by ICP-based techniques due to of water being the main product of organic matrix oxidation. The proposed method was suitable for quality control of major components and trace elements present in milk powder in consonance with green sample preparation.

Bromine and Iodine Contents in Raw and Cooked Shrimp and Its Parts.

The concentration of bromine and iodine was determined in shrimp and its parts (tissue and shells), and changes in the analyte concentration were evaluated after the cooking procedure. Bromine and iodine concentrations were determined by a method recently developed by our research group based on microwave-induced combustion for sample preparation and inductively coupled plasma mass spectrometry for analyte determination. The accuracy was evaluated using a reference material (NIST 8414) that was digested using the proposed method. No statistical difference was observed between certified and determined values (Student's t test, 95% confidence level). Suitable limits of detection (Br, 0.02 µg g(-1) and I, 0.01 µg g(-1)) were obtained for both analytes. Higher concentrations of both analytes were observed in shrimp shells in comparison to shrimp tissue for raw and cooked samples. Moreover, losses of Br and I (between 24 and 43%) were observed after cooking.

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.

Simple and fast method for iron determination in white and red wines using dispersive liquid-liquid microextraction and ultraviolet-visible spectrophotometry.

This work reports the development of a method for Fe extraction in white and red wines using dispersive liquid-liquid microextraction (DLLME) and determination by ultraviolet-visible spectrophotometry. For optimization of the DLLME method, the following parameters were evaluated: type and volume of dispersive (1300 µL of acetonitrile) and extraction (80 µL of C(2)Cl(4)) solvents, pH (3.0), concentration of ammonium pyrrolidinedithiocarbamate (APDC, 500 µL of 1% m/v APDC solution), NaCl concentration (not added), and extraction time. The calibration curve was performed using the analyte addition method, and the limit of detection and relative standard deviation were 0.2 mg L(-1) and below 7%, respectively. The accuracy was evaluated by comparison of results obtained after Fe determination by graphite furnace atomic absorption spectrometry, with agreement ranging from 94 to 105%. The proposed method was applied for Fe determination in white and red wines with concentrations ranging from 1.3 to 4.7 mg L(-1).

Effect of simultaneous cooling on microwave-assisted wet digestion of biological samples with diluted nitric acid and O2 pressure.

The present work evaluates the influence of vessel cooling simultaneously to microwave-assisted digestion performed in a closed system with diluted HNO3 under O2 pressure. The effect of outside air flow-rates (60-190 m(3) h(-1)) used for cooling of digestion vessels was evaluated. An improvement in digestion efficiency caused by the reduction of HNO3 partial pressure was observed when using higher air flow-rate (190 m(3) h(-1)), decreasing the residual carbon content for whole milk powder from 21.7 to 9.3% (lowest and highest air flow-rate, respectively). The use of high air flow-rate outside the digestion vessel resulted in a higher temperature gradient between liquid and gas phases inside the digestion vessel and improved the efficiency of sample digestion. Since a more pronounced temperature gradient was obtained, it contributed for increasing the condensation rate and thus allowed a reduction in the HNO3 partial pressure of the digestion vessel, which improved the regeneration of HNO3. An air flow-rate of 190 m(3) h(-1) was selected for digestion of animal fat, bovine liver, ground soybean, non fat milk powder, oregano leaves, potato starch and whole milk powder samples, and a standard reference material of apple leaves (NIST 1515), bovine liver (NIST 1577) and whole milk powder (NIST 8435) for further metals determination by inductively coupled plasma atomic emission spectroscopy (ICP-OES). Results were in agreement with certified values and no interferences caused by matrix effects during the determination step were observed.

Analytical methods for the determination of halogens in bioanalytical sciences: a review.

Fluorine, chlorine, bromine, and iodine have been studied in biological samples and other related matrices owing to the need to understand the biochemical effects in living organisms. In this review, the works published in last 20 years are covered, and the main topics related to sample preparation methods and analytical techniques commonly used for fluorine, chlorine, bromine, and iodine determination in biological samples, food, drugs, and plants used as food or with medical applications are discussed. The commonest sample preparation methods, as extraction and decomposition using combustion and pyrohydrolysis, are reviewed, as well as spectrometric and electroanalytical techniques, spectrophotometry, total reflection X-ray fluorescence, neutron activation analysis, and separation systems using chromatography and electrophoresis. On this aspect, the main analytical challenges and drawbacks are highlighted. A discussion related to the availability of certified reference materials for evaluation of accuracy is also included, as well as a discussion of the official methods used as references for the determination of halogens in the samples covered in this review.