Impact of dissolved oxygen and pH on the removal of selenium from water by iron electrocoagulation.

Removing dissolved selenium (i.e., selenate and selenite) from wastewater is a challenging issue for a range of industries. Iron electrocoagulation can produce Fe(II)-containing solids that can adsorb and chemically reduce dissolved Se. In a series of bench-scale experiments we investigated the effects of dissolved oxygen (fully oxic, partially oxic, and strictly anoxic) and pH (6 and 8) on the rate and extent of dissolved selenate and selenite removal by iron electrocoagulation. These studies combined measurements of the aqueous phase with the direct characterization of the resulting solids. Among the conditions studied the rate and extent of dissolved selenium (Se) removal were highest at pH 8 and strictly anoxic conditions. X-ray absorption spectroscopy demonstrated that in the absence of oxygen, Se was primarily transformed to elemental selenium (Se0) and selenide. Green rust that formed in the suspension during electrocoagulation played a key role as a reductant and sorbent of Se. At pH 6 dissolved oxygen did not affect the rates and extents of dissolved Se removal. Under all the conditions studied, dissolved Se removal was more effective with iron electrocoagulation than with the direct addition of pre-synthesized green rust or ferrous hydroxide. The most rapid and substantial dissolved Se removal was achieved by freshly-formed green rust and ferrous hydroxide, which are both Fe(II)-bearing solids. With an improved understanding of the products and mechanisms of the process, iron electrocoagulation can be optimized for removal of Se from wastewater.

Estimation of reactive thiol concentrations in dissolved organic matter and bacterial cell membranes in aquatic systems.

Organic thiols are highly reactive ligands and play an important role in the speciation of several metals and organic pollutants in the environment. Although small thiols can be isolated and their concentrations can be estimated using chromatographic and derivatization techniques, estimating concentrations of thiols associated with biomacromolecules and humic substances has been difficult. Here we present a fluorescence-spectroscopy-based method for estimating thiol concentrations in biomacromolecules and cell membranes using one of the soluble bromobimanes, monobromo(trimethylammonio)bimane (qBBr). The fluorescence of this molecule increases significantly when it binds to a thiol. The change in the sample fluorescence due to thiols reacting with qBBr is used to determine thiol concentration in a sample. Using this method, small thiols such as cysteine and glutathione can be detected in clean solutions down to ~50 nM without their separation and prior concentration. Thiols associated with dissolved organic matter (DOM) can be detected down to low micromolar concentration, depending on the DOM background fluorescence. The charge on qBBr prevents its rapid diffusion across cell membranes, so qBBr is ideal for estimating thiol concentration at the cell membrane-water interface. This method was successfully used to determine the thiol concentration on the cell envelope of intact Bacillus subtilis to nanomolar concentration without any special sample preparation. Among the chemical species tested for potential interferences (other reduced sulfides methionine and cystine, carboxylate, salt (MgCl(2))), carboxylates significantly influenced the absolute fluorescence signal of the thiol-qBBr complex. However, this does not affect the detection of thiols in heterogeneous mixtures using the presented method.