Evaluation of sample preparation methods for cereal digestion for subsequent As, Cd, Hg and Pb determination by AAS-based techniques.

Sample preparation methodsforcereal digestion were evaluated for the first time for subsequent As, Cd, Hg, and Pb determination by atomic absorption spectroscopy techniques. Microwave-assisted digestion (MW-AD) under high and medium pressure and microwave-induced combustion (MIC) were evaluated. The use of MIC made it possible to digest 700 mg of samples, and agreements of 97, 96, 100 and 92% were obtained for As, Cd, Hg and Pb, respectively, when 7 mol L-1 HNO3 was used as the absorbing solution. It was not necessary to dilute the digests obtained to avoid interferences in the quantification of As, Cd, Hg, and Pb. Although high pressure MW-AD was efficient for cereal digestion, interferences were observed on analyte determination. Limits of quantification obtained by MIC were 0.034 (As), 0.015 (Cd), 0.021 (Hg) and 0.105 (Pb) µg g-1, which are suitable to attain the maximum levels recommended by international agencies in cereal samples.

Effect of ultrasonic frequency on separation of water from heavy crude oil emulsion using ultrasonic baths.

In this work, a comprehensive study was performed for the evaluation of ultrasound (US) frequency for demulsification of crude oil emulsions. Experiments were performed using ultrasonic baths operating at the following frequencies: 25, 35, 45, 130, 582, 862 and 1146kHz. Synthetic water-in-oil emulsions with 12%, 35% and 50% of water and medians of droplet size distribution (DSD, D(0.5)) of 5, 10 and 25µm were prepared using a heavy crude oil (API density of 19). Crude oil demulsification was achieved at frequencies in the range of 25-45kHz for all tested emulsions. When frequencies higher than 45kHz were applied, no changes in the characteristics of the crude oil emulsions were observed. Demulsification efficiencies of about 65% were achieved at a frequency of 45kHz after 15min of US application (emulsions with original water content of 50% and D(0.5)=10µm). An important aspect is that no addition of chemical demulsifiers was performed, and the demulsification efficiency was considered high, taking into account that the results were obtained using a non-conventional crude oil. Contrary to the normal application of low-frequency US that has been used for emulsification, the proposed approach seems to be a promising technology for water removal from crude oil emulsions.

Determination of elemental impurities in poly(vinyl chloride) by inductively coupled plasma optical emission spectrometry.

In this work, a method for poly(vinyl chloride) (PVC) analysis by inductively coupled plasma optical emission spectrometry (ICP-OES) was developed. Samples were digested by microwave-induced combustion (MIC) and thirteen elements (Ba, Cd, Co, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sr, V and Zn) were determined by ICP-OES. Operational conditions of MIC were investigated allowing quantitative determination of all the analytes and suitable results were achieved using a 3 mol L(-1) HNO3 solution. Microwave-assisted wet digestion (MAWD) using closed quartz vessels and a single reaction chamber microwave digestion system (MAWD-SRC), were also evaluated for PVC digestion for results comparison. All the evaluated sample preparation methods were considered suitable for PVC digestion but MIC was preferable due to the possibility of using diluted HNO3 instead of concentrated reagents and due to the better digestion efficiency. The residual carbon content (RCC) in digests obtained by MIC was significantly lower in comparison with the values obtained after MAWD and by MAWD-SRC. Accuracy for the proposed method was better than 94% for all analytes by comparison of results with those obtained by neutron activation analysis (NAA). Using MIC, it was possible to digest a relatively high sample mass (500 mg) and up to 8 samples in less time (25 min) in comparison with MAWD and MAWD-SRC (about 60 min for both methods). The efficiency of digestion by MIC was higher 99% and lower limits of detection (as low as 0.1 µg g(-1)) were obtained avoiding the use of concentrated acids that is of great concern according to the current green chemistry recommendations.

Feasibility of low frequency ultrasound for water removal from crude oil emulsions.

The feasibility of indirect application of low frequency ultrasound for demulsification of crude oil was investigated without using chemical demulsifiers. Experiments were performed in an ultrasonic bath with frequency of 35 kHz. Synthetic emulsions with water content of 12%, 35% and 50% and median of droplet size distribution (DSD), median D(0.5), of 5, 10 and 25 µm were prepared from crude oil with API density of 19 (heavy crude oil) and submitted to the proposed ultrasound-assisted demulsification procedure. Experimental conditions as temperature, time of exposition to ultrasound and ultrasonic power were evaluated. Separation of water from crude oil emulsion was observed for all emulsions investigated. Demulsification efficiency up to 65% was obtained for emulsion with 50% of water content and DSD of 10 µm. Higher efficiency of demulsification was achieved using US temperature of 45 °C and ultrasound power of 160 W by 15 min. Results obtained in this study showed that ultrasound could be considered a promising technology for industrial crude oil treatment and respective water removal.

Lactating and nonlactating rats differ to renal toxicity induced by mercuric chloride: the preventive effect of zinc chloride.

This study evaluated the effects of HgCl2 on renal parameters in nonlactating and lactating rats and their pups, as well as the preventive role of ZnCl2 . Rats received 27 mg kg(-1) ZnCl2 for five consecutive days and 5 mg kg(-1) HgCl2 for five subsequent days (s.c.). A decrease in δ-aminolevulinic acid dehydratase (δ-ALA-D) activity in the blood and an increase in urine protein content in renal weight as well as in blood and urine Hg levels were observed in lactating and nonlactating rats from Sal-Hg and Zn-Hg groups. ZnCl2 prevented partially the δ-ALA-D inhibition and the proteinuria in nonlactating rats. Renal Hg levels were increased in all HgCl2 groups, and the ZnCl2 exposure potentiated this effect in lactating rats. Nonlactating rats exposed to HgCl2 exhibited an increase in plasma urea and creatinine levels, δ-ALA-D activity inhibition and histopathological alterations (necrosis, atrophic tubules and collagen deposition) in the kidneys. ZnCl2 exposure prevented the biochemical alterations. Hg-exposed pups showed lower body and renal weight and an increase in the renal Hg levels. In conclusion, mercury-induced nephrotoxicity differs considerably between lactating and nonlactating rats. Moreover, prior exposure with ZnCl2 may provide protection to individuals who get exposed to mercury occupationally or accidentally.

Sample preparation methods for subsequent determination of metals and non-metals in crude oil--a review.

In this review sample preparation strategies used for crude oil digestion in last ten years are discussed focusing on further metals and non-metals determination. One of the main challenges of proposed methods has been to overcome the difficulty to bring crude oil samples into solution, which should be compatible with analytical techniques used for element determination. On this aspect, this review summarizes the sample preparation methods for metals and non metals determination in crude oil including those based on wet digestion, combustion, emulsification, extraction, sample dilution with organic solvents, among others. Conventional methods related to wet digestion with concentrated acids or combustion are also covered, with special emphasis to closed systems. Trends in sample digestion, such as microwave-assisted digestion using diluted acids combined with high-efficiency decomposition systems are discussed. On the other hand, strategies based on sample dilution in organic solvents and procedures recommended for speciation analysis are reported as well as the use of direct analysis in view of the recent importance for crude oil field. A compilation concerning sample preparation for crude oil provided by official methods as well as certified reference materials available for accuracy evaluation is also presented and discussed.

Behavior and brain enzymatic changes after long-term intoxication with cadmium salt or contaminated potatoes.

This study investigated the cadmium (Cd) intoxication on cognitive, motor and anxiety performance of rats subjected to long-term exposure to diet with Cd salt or with Cd from contaminated potato tubers. Potato plantlets were micropropagated in MS medium and transplanted to plastic trays containing sand. Tubers were collected, planted in sand boxes and cultivated with 0 or 10 µM Cd and, after were oven-dried, powder processed and used for diet. Rats were divided into six groups and fed different diets for 5 months: control, potato, potato+Cd, 1, 5 or 25 mg/kg CdCl2. Cd exposure increased Cd concentration in brain regions. There was a significant decrease in the step-down latency in Cd-intoxicated rats and, elevated plus maze task revealed an anxiolytic effect in rats fed potato diet per se, and an anxiogenic effect in rats fed 25 mg/kg Cd. The brain structures of rats exposed to Cd salt or Cd from tubers showed an increased AChE activity, but Na+,K+-ATPase decreased in cortex, hypothalamus, and cerebellum. Therefore, we suggest an association between the long-term diet of potato tuber and a clear anxiolytic effect. Moreover, we observed an impaired cognition and enhanced anxiety-like behavior displayed by Cd-intoxicated rats coupled with a marked increase of brain Cd concentration, and increase and decrease of AChE and Na+,K+-ATPase activities, respectively.

Determination of total organic halogen (TOX) in humic acids after microwave-induced combustion.

Chemically chlorinated organic matter as well as natural background humic acids contain significant amounts of organically bound halogens that must be determined for assessment of environmental pollution. In this work the use of ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) is proposed for the determination of total organic Cl, Br and I concentration in humic acids extracted from various forest soil horizons after a single digestion by microwave-induced combustion (MIC). Samples were pressed as pellets and combusted using 20 bar of oxygen and ammonium nitrate solution as igniter. Analytes were absorbed in diluted alkaline solution (50mM (NH(4))(2)CO(3)) and a reflux step was applied after combustion to improve analyte recoveries (5 min, microwave power of 1400W). The accuracy was evaluated using certified reference materials (CRM) and spiked samples. Using MIC the agreement with CRM values and spike recoveries was higher than 97% for all analytes. As an advantage over conventional procedures, using MIC it was possible to digest up to eight samples in only 25 min, obtaining a single solution suitable for all halogens determination in humic acids samples by different techniques (IC and ICP-MS). The limit of detection (3σ) for Cl, Br and I obtained by IC was 1.2, 2.5 and 4.3µgg(-1) and by ICP-MS it was 1.4, 0.03 and 0.002µgg(-1), respectively.

Evaluation of sample preparation methods for elastomer digestion for further halogens determination.

In this work, three sample preparation methods were evaluated for further halogen determination in elastomers containing high concentrations of carbon black. Samples of nitrile-butadiene rubber, styrene-butadiene rubber, and ethylene-propylene-diene monomer elastomers were decomposed using oxygen flask combustion and microwave-induced combustion (MIC) for further Br and Cl determination by ion chromatography (IC), inductively coupled plasma optical emission spectrometry (ICP OES), and inductively coupled plasma mass spectrometry (ICP-MS). Extraction assisted by microwave radiation in closed vessels was also evaluated using water or alkaline solution. Digestion by MIC was carried out using 50 mmol l(-1) (NH(4))(2)CO(3) as the absorbing solution. The effect of the reflux step was also evaluated. Accuracy was evaluated using certified reference materials with polymeric matrix composition and by comparison of results using neutron activation analysis. Agreement for Br and Cl was better than 95% by MIC using 5 min of reflux, and no statistical difference was found using IC, ICP OES, and ICP-MS for determination of both analytes. For MIC, the relative standard deviation (RSD) was lower than 5%. Using extraction in closed vessels, a high amount of residues was observed, and recoveries were lower than 45% for both analytes. For oxygen flask combustion, the agreement was similar using MIC but RSD was higher (20%). The residual carbon content, an important parameter used to evaluate the digestion efficiency, was always below 1% for MIC. Using MIC, it was possible to digest elastomers with high efficiency, resulting in a single solution suitable for halogen determination by different techniques.

Focused microwave-induced combustion: a new technique for sample digestion.

A procedure for sample digestion based on focused microwave-induced combustion (FMIC) is proposed. This system was developed using a commercial focused microwave oven with a lab-made quartz sample holder and a modified glass vessel. Oxygen flow was used to start and support the combustion. A botanical sample was used to evaluate the operational conditions for further Al, Ba, Ca, Fe, Mg, Mn, Sr, and Zn determination by inductively coupled plasma optical emission spectrometry. Pelletized samples were positioned on the quartz holder, and 50 microL of 6 mol L(-1) NH(4)NO(3) solution was added as igniter. Combustion was completed in less than 2 min, and the temperature was higher than 950 degrees C. The use of a reflux step, the position of sample holder inside the vessel, sample mass, ignition and combustion time, oxygen flow rate, and condenser type were evaluated. Results were compared with those obtained by focused microwave-assisted wet digestion and by high pressure microwave-assisted wet digestion. Agreement of 95-103% was obtained for certified reference materials digested by FMIC (reflux step with 10 mL of 4 mol L(-1) HNO(3)). With the proposed procedure, a complete sample decomposition (residual carbon content lower than 0.5%) was achieved with low consumption of reagents as only 10 mL of diluted nitric acid was necessary. Low relative standard deviation (lower than 3.8%) was observed and high amount of sample (up to 1500 mg) could be digested that allowed lower limits of detection.

Chloride determination by ion chromatography in petroleum coke after digestion by microwave-induced combustion.

Microwave-induced combustion was applied to petroleum coke digestion in closed vessels for further chloride determination by ion chromatography. Samples were pressed as pellets and placed on a quartz holder. Combustion was performed using oxygen pressure of 2 MPa and 50 microl of 6 moll(-1) NH(4)NO(3) as aid for ignition. Recoveries from 97 to 102% were obtained for all studied absorbing solutions (water, H(2)O(2), Na(2)CO(3) or (NH(4))(2)CO(3)). Accuracy was evaluated using certified reference materials with agreement better than 98% using water as absorbing solution with reflux step. The limit of quantification was 3.8 microg g(-1).

Determination of halogens in coal after digestion using the microwave-induced combustion technique.

The microwave-induced combustion (MIC) technique was applied for coal digestion and further determination of bromide, chloride, fluoride, and iodide by ion chromatography (IC). Samples (up to 500 mg) were combusted at 2 MPa of oxygen. Combustion was complete in less than 50 s, and analytes were absorbed in water or (NH(4))(2)CO(3) solution. A reflux step was applied to improve analyte absorption. Accuracy was evaluated for Br, Cl, and F using certified reference coal and spiked samples for I. For Br, Cl, and F, the agreement was between 96 and 103% using 50 mmol L(-1) (NH(4))(2)CO(3) as the absorbing solution and 5 min of reflux. With the use of the same conditions, the recoveries for I were better than 97%. Br, Cl, and I were also determined in MIC digests by inductively coupled plasma mass spectrometry, inductively coupled plasma optical emission spectrometry, and F was determined by an ion-selective electrode with agreement better than 95% to the values obtained using IC. Temperature during combustion was higher than 1350 degrees C, and the residual carbon content was lower than 1%. With the use of the MIC technique, up to eight samples could be processed simultaneously, and a single absorbing solution was suitable for all analytes and determination techniques (limit of detection by IC was better than 3 microg g(-1) for all halogens).