ABSTRACT: Much research has been published regarding the relation between major gas hydrate accumulations and the global carbon cycle. In this context, the determination of the sulfate/methane interface (SMI) depth is of primary importance in order to understand the dynamics of methane flux in the shallow section. This paper identifies the depth of the SMI in sediments based on sulfate and methane concentration profiles in cores recovered in the Rio Grande Cone Gas Hydrate Province, Pelotas Basin, southern Brazil. The shape of methane and sulfate concentration profiles in the sediments can be linked to the local methane flux rate as follows: (i) near linear, high upward-diffusing methane flux coupled with high sulfate diffusion from seawater; (ii) irregular, variable methane flux rates; and (iii) kink-type profile, which is indicative of variable rather than strictly high upward methane flux. The areas in which a high methane flux was identified are spatially associated with gas chimneys in sediments within pockmarks, whereas profiles with low methane flux are present in adjacent areas. These chimneys appear as acoustic blankings in seismic records and can therefore be mapped in subsurface. The wavy-like seismic reflection following the SMI coincides with the occurrence of authigenic carbonate nodules and concretions. In addition, high methane fluxes and the occurrence of concretions and nodules carbonates were correlated by stratigraphic position of the concretions bearing intervals and sulfate profiles.

Trace impurities of Cd, Cu and Pb were determined in alumina-based catalysts using direct solid sampling graphite furnace atomic absorption spectrometry (DSS-GF AAS). The analyzed catalysts are widely used in petrochemical industry. Major elements were determined by inductively coupled plasma optical emission spectrometry (ICP OES) for matrix characterization. The following analytical parameters were evaluated: pyrolysis and atomization temperatures, feasibility of calibration with aqueous solutions, the use of palladium as chemical modifier, influence of sample mass introduced into the atomizer. Test samples between 0.05 and 30 mg were used and palladium was considered unnecessary for all elements. The obtained results were compared to those obtained by ICP OES, inductively coupled plasma mass spectrometry (ICP-MS) and by graphite furnace atomic absorption spectrometry (GF AAS). By using DSS-GF AAS the relative standard deviation was less than 10%, good agreement with results by ICP-MS and GF AAS, while characteristic masses were 1.3, 8.9 and 22 pg, for Cd, Cu and Pb, respectively. Calibration by means of aqueous solutions showed good linearity along the calibration range, being the correlation coefficient typically better than R2 = 0.997. Limits of detection (3σ, n =10) for Cd, Cu and Pb using the DSS-GF AAS proposed procedure were 0.2, 22, and 1.2 ng g-1, respectively.

Polymeric diphenylmethane diisocyanate (PMDI) and diphenylthane dianiline (MDA) are importante raw materials in the manufacture of polyurethanes. These products have wide application in various fields such as medicine, catalysis and electronics. Actually, considerable interest has been given for the presence of metal contaminants in raw materials for the production of polymers, because metals influence the process and modifies the thermal properties of the products. Thus, this paper proposes a procedure for the determination of Cr, Fe, Mg, Mn, Na and Ni using the direct sampling by atomic absorption spectrometry with graphite furnace (DS-GF AAS). Initially, it was obtained pyrolysis and atomization curves for PMDI, MDA samples and reference solutions. It was possible to analytes quantification using calibration using aqueous reference solutions. In addition, it was used a Zeemaneffect background correction system with variable magnetic field for construction curves with higher concentration range, allowing the analysis of samples with higher concentrations. Sample masses between 0.5 and 35 mg were using depending of the analyte concentration. It was obtained good linearity (R> 0.99), relatively good precision (RSD <15%) and detection limit between 0.1 ng g-1 for Fe and 3 ng g-1 for Ni. Samples of PMDI and MDA were decomposed using different digestionprocedures: Wet decomposition in open systems with conventional heating, microwave and microwave-induced combustion for subsequent determination by ICP OES and ICP-MS. The results were compared with those obtained by wet decomposition (microwave heating and combustion initiated by microwave). There was no significant difference (confidence level 95%) for the results obtained for Cr, Fe, Mg, Mn, Na and Ni when compared with wet procedures and DS-GF AAS.

Metal impurities (Al, Cd, Co, Cr, Cu, Mg, Mn and Pb) were determined in carbon nanotubes (CNTs) by direct solid sampling electrothermal atomic absorption spectrometry (DSS-ET AAS, deuterium lamp background corrector). Parameters as pyrolysis and atomization temperatures, use of Pd as chemical modifier, feasibility of calibration using aqueous standard solutions and maximum sample mass were investigated. Results obtained by the proposed method were compared with those obtained by neutron activation analysis (NAA) and also by inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP OES) after high-pressure microwave assisted wet digestion and microwave-induced combustion methods. No significant differences were observed between the results obtained by DSS-ET AAS, ICP-MS and ICP OES after both digestion methods and also by NAA. Calibration was performed using aqueous standards. Background signals were always lower than 0.02 (peak height) and no chemical modifier was used. The proposed method allowed the determination of all elements in CNTs with lower limits of detection in comparison with other techniques.

This study evaluates the properties of chitosan (CS) membranes modified with different percentages (0.5%, 3%, and 5% w/w) of a graphene-based material. Graphene oxide (GO) and reduced graphene oxide (RGO) were obtained by the chemical exfoliation of graphite and thermal reduction. Then, they were characterized by electrical conductivity measurements, FESEM, XRD, AFM, and Raman spectroscopy. The composites’ morphology was evaluated by FESEM. The degree of swelling over a 48 h period and mass loss behavior in phosphate-buffered saline solution for up to 70 days were also studied. The hydrophilicity of the CS and CS/graphene nanocomposites was examined by water contact angle. The graphene materials showed small stacks (6-8 sheets) with low defect density and nanoscale thickness (1.3-5.9 nm). The dispersion of the graphene material in the CS matrix significantly decreased the degree of swelling (460%) but did not modify the hydrolytic degradation process and the hydrophilicity of membranes.

This study evaluates the properties of chitosan (CS) membranes modified with different percentages (0.5%, 3%, and 5% w/w) of a graphene-based material. Graphene oxide (GO) and reduced graphene oxide (RGO) were obtained by the chemical exfoliation of graphite and thermal reduction. Then, they were characterized by electrical conductivity measurements, FESEM, XRD, AFM, and Raman spectroscopy. The composites’ morphology was evaluated by FESEM. The degree of swelling over a 48 h period and mass loss behavior in phosphate-buffered saline solution for up to 70 days were also studied. The hydrophilicity of the CS and CS/graphene nanocomposites was examined by water contact angle. The graphene materials showed small stacks (6–8 sheets) with low defect density and nanoscale thickness (1.3–5.9 nm). The dispersion of the graphene material in the CS matrix significantly decreased the degree of swelling (460%) but did not modify the hydrolytic degradation process and the hydrophilicity of membranes.