José Neri Gottfried Paniz

Evaluation of sample preparation methods for polymer digestion and trace elements determination by ICPMS and ICPOES

In this work, sample preparation methods for polymer digestion based on microwave-induced combustion (MIC) and microwave-assisted acid digestion (MW-AD) were evaluated for further As, Bi, Cd, Co, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Sr, Ti, V and Zn determination by inductively coupled plasma mass spectrometry (ICPMS) and inductively coupled plasma optical emission spectrometry (ICPOES). Samples of low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET, colorless and green), polyetheretherketone (PEEK) and nylon 6,6 were digested using MIC and MW-AD in closed quartz vessels. The type and concentration of acids used for MIC were investigated and better results were achieved using a 4 mol l−1 HNO3 + 4 mol l−1 HCl solution. Microwave-assisted acid digestion was also evaluated for polymer digestion using concentrated acids. Both sample preparation methods were considered suitable for polymer digestion but MIC was preferable in view of the possibility of using diluted acids as absorbing solution and allowing higher sample mass to be digested and consequently better limits of detection. Residual carbon content in digests of polymers obtained by MIC was lower in comparison with the values obtained after MW-AD. Accuracy for all the analytes determined by ICPOES and ICPMS after MIC digestion was better than 95% (analysis of certified reference materials and by neutron activation analysis). It was possible to digest up to 8 samples by MIC in less time (in 25 min) in comparison with MW-AD (more than 50 min) and also using diluted acids (4 mol l−1 HNO3 and HCl) instead of concentrated acids.

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.

Potentiometric determination of fluoride in geological and biological samples following pyrohydrolytic decomposition

A method for the determination of fluoride in coal, coal fly ash, phosphate rock, limestone, mineral clay, fossilised materials, oyster tissue and vegetation using pyrohydrolysis for sample decomposition is proposed. A specific apparatus was constructed and the influence of vanadium pentoxide (V 2O5) as a catalyst for the pyrohydrolysis reaction was investigated. It was verified that V2O5 does not influence the release of fluoride from the vegetation, oyster tissue, coal and coal fly ash matrices analysed. However, the catalyst was necessary for the phosphate rock, fossil bone, mineral clay and limestone samples. Certified and noncertified samples were analysed using an ion selective electrode (ISE) for the analyte detection. Precise (relative standard deviation—R.S.D .< 7%) and accurate (recovery in accordance to certified values) results were obtained. The limit of quantification (LOQ) of the method was 5.0 gg −1 of fluoride using 20 mg of sample and a final dilution to 10 ml. The sample frequency was five samples per hour.

Determination of Sulfur in Petroleum Coke Combining Closed Vessel Microwave-Induced Combustion and Inductively Coupled Plasma-Optical Emission Spectrometry

Abstract A new procedure based on closed vessel Microwave-Induced Combustion (MIC) technique is proposed for the decomposition of petroleum coke and further determination of sulfur by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES). The procedure is based on sample ignition by microwave radiation using closed quartz vessels pressurized with oxygen and use of NH4NO3 as an ignition aid. The nature and concentration of absorbing/refluxing solution were studied, as well as the operational parameters related to MIC technique. Results were compared with those obtained by conventional wet digestion in closed vessels, certified reference materials (agreement was better than 98%), and also using ion chromatography for S determination.

Determination of fluoride in coal using pyrohydrolysis for analyte separation

E proposto um metodo para a determinacao de fluoreto em carvao mineral. O mesmo e baseado no emprego da pirohidrolise para a separacao do fluoreto da amostra e posterior determinacao do analito por potenciometria direta, com eletrodo ion seletivo. O sistema utilizado para a realizacao da pirohidrolise foi desenvolvido e a influencia do V 2 O 5 como catalisador na reacao de pirohidrolise foi investigada, sendo verificado que o mesmo nao influencia sobre a liberacao do fluoreto presente na amostra. Amostras certificadas e nao certificadas de carvao mineral foram analisadas. Resultados precisos (desvio padrao relativo inferior a 7%) e exatos (recuperacao do fluoreto de acordo com os valores certificados) foram obtidos. O limite de quantificacao (LOQ) do metodo foi de 5,0 µgF/g de amostra, usando 20 mg de amostra e volume final de 10 mL. A frequencia de analise foi de 5 amostras h -1 . A method for the determination of fluoride in coal using pyrohydrolysis for sample decomposition is proposed. An apparatus was constructed, and the influence of vanadium pentoxide (V 2 O 5 ) as a catalyst for the pyrohydrolysis reaction was investigated. It was verified that V 2 O 5 does not influence the release of fluoride from coal. Certified and non-certified samples were analysed using an ion selective electrode (ISE) for analyte detection. Precise (RSD < 7%) and accurate (recovery in accordance with certified values) results were obtained. The limit of quantification (LOQ) of the method was 5.0 µgF/g of sample, using 20 mg of sample and a final dilution to 10 mL. The sample frequency was 5 samples h -1

Minimization of volatile nitrogen oxides interference in the determination of arsenic by hydride generation atomic absorption spectrometry

Abstract In this study emphasis was given to minimize the interference of volatile nitrogen oxides from digestion procedures with nitric acid on the determination of arsenic by hydride generation atomic absorption spectrometry (HG AAS). Sulfamic acid (SA) is proposed to minimize this interference by employing three procedures for the digestion of hair in closed systems: conventional and microwave (MW) heating in polytetrafluorethylene (PTFE) vessels and by MW heating in glass vials. Hair samples were digested with H 2 SO 4 +HNO 3 or HNO 3 +H 2 O 2 mixtures. Concentrated hydrochloric acid was added for the digestion for the procedure in glass vials. The accuracy of the procedures with PTFE vessels was verified by the spike recoveries of organic ( p -aminobenzenearsonic acid and dimethyl arsinic acid, from 92 to 101%) and inorganic (sodium arsenate, from 98 to 102%) arsenic compounds. For the procedure in glass vials the recovery was from 86 to 97% for organic As and from 97 to 102% for inorganic As. The results obtained for a certified hair reference material using the three digestion procedures were well within the 95% confidence interval of the certificate when SA was added to the solutions. However, when SA was not added, recoveries were low and non-reproducible signals and high background levels were observed. Urea, benzoic acid and hydroxylamine hydrochloride were also studied (maximum As recovery of 90% using hydroxylamine hydrochloride) but the best results were obtained with use of SA.

Comparison of advanced processes on the oxidation of acid orange 7 dye.

ABSTRACT The degradation of acid orange 7 dye (AO7) was studied using a 1 L semi-batch tank stirred glass reactor for performing three different photochemical processes (photoperoxidation, Fenton, photo-Fenton). A commercial low pressure lamp was used for irradiation of samples. The advancement of degradation was monitored by measurement of color reduction, UV-spectra, HPLC-UV and COD. The obtained results showed that the photo-Fenton treatment was the most effective for the degradation of AO7.

Determination of bromine, fluorine and iodine in mineral supplements using pyrohydrolysis for sample preparation

Pyrohydrolysis was employed for mineral supplements decomposition prior to F, Br and I determination. Fluoride determination was carried out by potentiometry using a fluoride-ion selective electrode, whereas Br and I were determined by inductively coupled plasma mass spectrometry. The main parameters that influence on pyrohydrolysis were investigated. After evaluation, the following conditions were established: reactor temperature of 1000 oC during 10 min; sample plus accelerator mass ratio of 1 + 5 and carrier gas (air) flow rate of 200 mL min-1. The accuracy of the proposed method was evaluated by analyte recovery tests and analysis of certified reference materials of phosphate rock and soil. Commercial mineral supplement samples were analyzed. The limits of quantification were 16, 0.3 and 0.07 µg g-1 for F, Br and I, respectively. By using a relatively simple and low cost pyrohydrolysis system up to 5 samples can be processed per hour. The developed sample preparation procedure can be routinely employed for F, Br and I determination in mineral supplements.

Mercury speciation in urban landfill leachate by cold vapor generation atomic absorption spectrometry using ion exchange and amalgamation

0 is produced and then measured by cold vapor atomic absorption spectrometry (CV AAS). Hg org does not interact with the resin and is mixed with NaBH 4 at the exit of the column producing volatile species of Hg that are then amalgamated by a gauze of Au/Pt. Mercury is removed from the gauze by heating to 600 °C and subsequently measured by CV AAS. For Hg inorg and Hg org speciation in urban landfill leachate, the samples are centrifuged, filtered and treated with HCl. The detection limits (3 s) of Hg inorg and Hg org are 9 and 12 ng L -1 of Hg, respectively. The analysis frequency is 22 h -1 .

Preparo de amostras de combustíveis fósseis por piroidrólise para a determinação de flúor e cloro

Pyrohydrolysis is proposed for fossil fuels sample preparation for further fluorine and chlorine determination. Samples were heated during 10 min at temperatures up to 1000 °C. Water vapor was passed through the reactor and the volatile products were condensed and collected in NH4OH solution. Fluoride was determined by potentiometry using an ion selective electrode (ISE) and Cl by ICP OES and DRC-ICP-MS. The results are in good agreement with certified values and the precision is better than 10% (n = 4). Sample preparation by means of pyrohydrolysis is relatively simple, whereas chlorine and fluorine can be determined at low concentrations.