Alanine Formation in a Zero-Gap Flow Cell and the Role of TiO2/Ti Electrocatalysts.

The electrochemical synthesis of α ${\alpha }$ -amino acids at room temperature and pressure is a sustainable alternative to conventional methods like microbial fermentation and Strecker synthesis. A custom-built zero-gap flow electrolyzer was used to study the electrosynthesis of alanine via the electrocatalytic reductive amination (ERA) of the corresponding biomass-derivable α ${\alpha }$ -keto acid precursor - pyruvic acid (PA), and hydroxylamine (NH2OH) at very low pH. Non-toxic, abundant, and easy to prepare TiO2/Ti electrocatalysts were utilized as the cathode. Three TiO2/Ti felt electrodes with different oxide thicknesses were prepared and their characterization results were correlated with their respective electrochemical performance in terms of Faradaic efficiency η ${\eta }$ , and partial current density j ‾ ${\left|\overline{j}\right|}$ . Cyclic voltammetry indicated a different electrocatalytic reduction process on hydrothermally treated electrodes, compared to thermally oxidized ones. Hydrothermally treated electrodes were also found to have the thickest porous anatase layer and achieved 50-75 % alanine conversion efficiencies. Optimization showed that the cell potential, reactant flow rate and the PA: NH2OH ratio were crucial parameters in determining the conversion efficiency. η ${\eta }$ and j ‾ ${\left|\overline{j}\right|}$ were found to significantly decrease when an excess of is used and, an optimal alanine η ${\eta }$ of 75 % was achieved at 2.0 V applied cell potential and 10 mL/h reactant flow rate.

Concentration of contaminants in breeding bird eggs from the Colorado River Delta, Mexico.

Organic contaminants (organochlorine [OC], organophosphorus [OP] pesticides and polychlorinated biphenyls [PCBs]), and metals (As, Cd, Hg, Pb, and Se) are a concern to avian health in the Colorado River delta, Mexico. We determined concentrations of contaminants in eggs of three breeding species of birds from the delta (mourning doves [Zenaida macroura], burrowing owls [Athene cunicularia], and marsh wrens [Cistothorus palustris]). We collected 27 eggs of mourning doves, eight eggs of burrowing owls, and 18 eggs of marsh wrens for analyses. Polychlorinated biphenyls, OC, and OP pesticides were analyzed by gas chromatography equipped with an electron capture detector, and metals were analyzed by inductively coupled plasma mass spectrometry. The non-ortho PCB congeners (PCB 77 and 126) were found in mourning dove and burrowing owl eggs at concentrations in which hatchability can be affected. Mean selenium concentration found in marsh wren eggs (5.6 microg/g dry wt) exceeded the level of concern. Arsenic and Cd were found at higher than normal concentrations, Hg concentrations did not exceed the level of concern in any of the species, and Pb concentrations were higher in eggs of species subject to hunting. With the exception of lead, marsh wren eggs contained the highest metal concentrations.