Sandra Maria Maia

Determination of Cd, Hg, Pb and Tl in coal and coal fly ash slurries using electrothermal vaporization inductively coupled plasma mass spectrometry and isotopic dilution

A method has been investigated for the determination of Cd, Hg, Pb and Tl in coal and in coal fly ash, using slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry and isotope dilution. The slurry, 25 mg ml−1, was prepared by mixing the powdered sample (≤36–45 µm) with acid solutions (nitric acid for coal and nitric and hydrofluoric acids for coal fly ash) and submitting the mixture to an ultrasonic agitation, letting it stand afterwards in a water bath at 60 °C for 2 h. An ultrasonic probe was used to homogenize the slurry in the autosampler cup just before its introduction into the graphite tube. The best conditions were determined regarding analyte sensitivity, furnace temperature program, amount of modifier, acid concentration, gas flow rate and particle size. For Hg, the pyrolysis stage was omitted and a low vaporization temperature was used (450–1000 °C); the residual matrix was eliminated in the first step of the following cycle. The modifiers used were: Pd for Cd and Tl; Au, Ir or Pd for Hg; Ir or Pd for Pb. The accuracy of the method was checked by analyzing six certified coal reference materials (SARM 20, SARM 19, BCR No. 40, BCR No. 180, BCR No. 181 and NIST 1630a) and one certified coal fly ash (NIST 1633b). With one exception (Hg in BCR No. 180), the found concentrations were typically within 95% confidence interval of the certified values, or close enough to the recommended values, as long as the samples were ground to a small enough particle size. The limits of detection were typically around 0.08 µg g−1, 0.03 µg g−1, 1 µg g−1 and 0.02 µg g−1 for Cd, Hg, Pb and Tl, respectively. The precision was also adequate with relative standard deviations of usually <5%.

Feasibility of eliminating interferences in graphite furnace atomic absorption spectrometry using analyte transfer to the permanently modified graphite tube surface

Abstract A procedure is proposed to avoid spectral and/or non-spectral interferences in graphite furnace atomic absorption spectrometry (GF AAS) by transferring the analyte during the pyrolysis stage from a solid sampling platform to the graphite tube wall that has been coated with a permanent modifier, e.g. by electrodeposition of a platinum-group metal. The direct determination of mercury in solid coal samples was chosen as a model to investigate the feasibility of this idea. The graphite tube surface was coated with palladium and the analyte was transferred from the solid sampling platform to the tube wall at a temperature of 500±50 °C. A characteristic mass of m 0 =64 pg Hg was obtained for an atomization temperature of 1300 °C, proposing a quantitative transfer of the analyte to the tube wall. Calibration against aqueous mercury standards was not feasible as this element was lost in part already during the drying stage and could not be trapped quantitatively on the modified graphite tube surface. However, the results for all except one of the coal reference materials were within the 95% confidence interval of the certificate when the slope of a correlation curve between the integrated absorbance, normalized for 1 mg of sample, and the certified value for mercury was used for calibration. A detection limit of 0.025–0.05 μg g −1 Hg in coal, calculated from three times the standard deviation of the investigated coal samples, could be obtained with the proposed method. The spectral interference due to excessive background absorption in the direct determination of mercury in coal could be eliminated completely. It is expected that this analyte transfer can be used in a similar way to eliminate other spectral and/or non-spectral interferences in the GF AAS determination of other volatile analytes.

Decontamination of CCA-treated eucalyptus wood waste by acid leaching

Preservatives such as chromated copper arsenate (CCA) are used to increase the resistance of wood to deterioration. The components of CCA are highly toxic, resulting in growing concern over the disposal of the waste generated. The aim of this study was to investigate the removal of Cu, Cr and As present in CCA-treated eucalyptus wood from utility poles removed from service in southern Brazil, in order to render them non-hazardous waste. The removal was carried out by acid leaching in bench-scale and applying optimal extractor concentration, total solid content, reactor volume, temperature and reaction time obtained by factorial experiments. The best working conditions were achieved using three extraction steps with 0.1 mol L(-1) H2SO4 at 75°C for 2h each (total solid content of 15%), and 3 additional 1h-long washing steps using water at ambient temperature. Under these conditions, removal of 97%, 85% and 98% were obtained for Cu, Cr and As, respectively, rendering the decontaminated wood non-hazardous waste. The wastewater produced by extraction showed acid pH, high organic loading as well as high concentrations of the elements, needing prior treatment to be discarded. However, rinsing water can be recycled in the extraction process without compromising its efficiency. The acid extraction is a promising alternative for CCA removal from eucalyptus wood waste in industrial scale.

CLASSIFICAÇÃO DE RESÍDUOS DE MADEIRA TRATADA COM PRESERVATIVOS À BASE DE ARSENIATO DE COBRE CROMATADO E DE BORO/FLÚOR

Classification of waste wood treated with chromated copper arsenate (CCA) and boron/fluorine preservatives, according to NBR 10004, was investigated. The leaching test (ABNT NBR 10005) for As and Cr, and solubilization test (ABNT NBR 10006) for F, were applied to out-of-service wooden poles. Concentrations of As and Cr in leachates were determined by ICP-MS and of F by ESI. Values for As were higher than 1 mg L-1 classifying the waste as hazardous material (Class I) whereas values for F (> 1.5 mg L-1) were non-hazardous but indicated non-inert material (Class IIA).