Cd(II) determination in the presence of aqueous micellar solutions.

The equilibrium constants and molar absorptivities for the fast formation of a 1:3 complex between cadmium(II) (Cd(II)) and dithizonate anion, in the presence of cationic and non-ionic surfactants, allowed a simple and fast spectrophotometric determination of total cadmium. Indeed, the molar absorptivities of the Cd(II)-dithizone (Dz) complex formed in the presence of the neutral Triton X-100 and cationic cetyltrimethylammonium bromide (CTAB) surfactants are almost twice the value observed in the standard method and the maxima of absorption are shifted by about 40nm when compared with the standard method. Clearly, the use of neutral and cationic surfactants promotes a higher value of the molar absorptivities of the complex, resulting in an increase in the sensitivity of the method. Application of the method to the desorption of Cd(II) ions from clays is illustrated.

Theoretical framework for the distribution of trace metals among the operationally defined speciation phases of a sediment.

The use of a model based on Langmuir's isotherm to evaluate the metal associated with separate geochemical phases of a sediment is proposed and its validity tested with sediments of certified composition. The model takes into account a standard procedure for a certified reference material (CRM601), which defines, experimentally, a set of sequential extractions that divide the sediment into four operational fractions. The derived equations allow the treatment of data from sediment of Flumendosa Lake, Italy, and certified material CRM601 and also allow the computation of corrected concentrations, i.e., the metal affinities for each fraction. Experimental values for Ni show its low sensitivity and an equal distribution among different phases, which suggests a similar adsorption mechanism in all cases. In the case of Cd, the corrected concentration in the Fe/Mn oxide phase is nine times higher than for the residual fraction. For sediment of the Bèsos River, Spain, results show the percentage distribution of Ni over different fractions. Affinity values for Ni on a Flumendosa Lake sediment have also been calculated. The present model is simple to apply and shows satisfactory agreement with experimental data.

Acid volatile sulfide determination in sediments using elemental analyzer with thermal conductivity detector.

A method for the determination of acid volatile sulfides (AVS) in sediments, using a common elemental analyzer with thermal conductivity detector, is proposed. The method uses a mixture of Sn and V(2)O(5) for pyrolysis and combustion to determine total sulfur (TS), and non volatile sulfur (NVS), after an acidic attack. AVS is calculated as the difference between TS and NVS. The method for TS is validated by analyzing a certified reference material. The recovery in the determination of acid volatile sulfide is determined by spiking a river sediment with ZnS. The method is accurate and gives a good reproducibility, recovering 97.7-99.6% of the sulfur in the 0-3% total sulfur content, with SD of approximately 0.015%.