Nitrite Reduction to Nitrous Oxide and Ammonia by TiO2 Electrons in a Colloid Solution via Consecutive One-Electron Transfer Reactions.

The mechanism of nitrite reduction by excess electrons on TiO2 nanoparticles (eTiO2(-)) was studied under anaerobic conditions. TiO2 was loaded with up to 75 electrons per particle, induced by γ-irradiation of acidic TiO2 colloid solutions containing 2-propanol. Time-resolved kinetics and material analysis were performed, mostly at 1.66 g L(-1) TiO2. At relatively low nitrite concentrations (R = [eTiO2(-)]o/[nitrite]o > 1.5), eTiO2(-) decays via two consecutive processes; at higher concentrations, only one decay step is observed. The stoichiometric ratio Δ[eTiO2(-)]/[nitrite]o of the faster process is about 2. This process involves the one-electron reduction of nitrite, forming the nitrite radical (k1 = (2.0 ± 0.2) × 10(6) M(-1) s(-1)), which further reacts with eTiO2(-) (k2) in competition with its dehydration to nitric oxide (NO) (k3). The ratios k2/k3 = (3.0 ± 0.5) × 10(3) M(-1) and k2 > 1 × 10(6) M(-1) s(-1) were derived from kinetic simulations and product analysis. The major product of this process is NO. The slower stage of the kinetics involves the reduction of NO by eTiO2(-), and the detailed mechanism of this process has been discussed in our earlier publication. The results reported in this study suggest that several intermediates, including NO and NH2OH, are adsorbed on the titanium nanoparticles and give rise to inverse dependency of the respective reaction rates on the TiO2 concentration. It is demonstrated that the reduction of nitrite by eTiO2(-) yields mainly N2O and NH3 via consecutive one-electron transfer reactions.

Nitric oxide reduction to ammonia by TiO2 electrons in colloid solution via consecutive one-electron transfer steps.

The reaction mechanism of nitric oxide (NO) reduction by excess electrons on TiO2 nanoparticles (e(TiO2)(-)) has been studied under anaerobic conditions. TiO2 was loaded with 10-130 electrons per particle using γ-irradiation of acidic TiO2 colloid solutions containing 2-propanol. The study is based on time-resolved kinetics and reactants and products analysis. The reduction of NO by e(TiO2)(-) is interpreted in terms of competition between a reaction path leading to formation of NH3 and a path leading to N2O and N2. The proposed mechanism involves consecutive one-electron transfers of NO, and its reduction intermediates HNO, NH2O(•), and NH2OH. The results show that e(TiO2)(-) does not reduce N2O and N2. Second-order rate constants of e(TiO2)(-) reactions with NO (740 ± 30 M(-1) s(-1)) and NH2OH (270 ± 30 M(-1) s(-1)) have been determined employing the rapid-mixing stopped-flow technique and that with HNO (>1.3 × 10(6) M(-1) s(-1)) was derived from fitting the kinetic traces to the suggested reaction mechanism, which is discussed in detail.

Global survey shows planners use widely varying sea-level rise projections for coastal adaptation.

Including sea-level rise (SLR) projections in planning and implementing coastal adaptation is crucial. Here we analyze the first global survey on the use of SLR projections for 2050 and 2100. Two-hundred and fifty-three coastal practitioners engaged in adaptation/planning from 49 countries provided complete answers to the survey which was distributed in nine languages - Arabic, Chinese, English, French, Hebrew, Japanese, Korean, Portuguese and Spanish. While recognition of the threat of SLR is almost universal, only 72% of respondents currently utilize SLR projections. Generally, developing countries have lower levels of utilization. There is no global standard in the use of SLR projections: for locations using a standard data structure, 53% are planning using a single projection, while the remainder are using multiple projections, with 13% considering a low-probability high-end scenario. Countries with histories of adaptation and consistent national support show greater assimilation of SLR projections into adaptation decisions. This research provides new insights about current planning practices and can inform important ongoing efforts on the application of the science that is essential to the promotion of effective adaptation.

Influencing beach littering behaviors through infrastructure design: An in situ experimentation case study.

Marine litter is one of the most pressing problems of our time and a major threat to ocean health; much of it comes from land-based sources, including from beachgoer activities. This study investigates how product design could influence littering behaviors of beachgoers when applied to beach trash cans (TCs). Over the course of six weeks three differently designed TCs were placed on a Mediterranean Sea tourist beach in Israel while observers tracked the behavior of 536 nearby groups ("entities") of beachgoers. Researchers analyzed: a) entities' locational choices; b) materials discarded in the TCs; and c) littering behaviors around the TCs. Based on the data collected, a "motivating" TC design performed best, encouraging the highest level of beachgoer interaction. Further research is needed in more and varied beach contexts, but this type of initial interdisciplinary research suggests how the design discipline could contribute to preventing marine litter from land-based sources.

Beachgoer participation in prevention of marine litter: Using design for behavior change.

Much marine litter comes from land-based sources, with a significant amount coming from activities on bathing beaches. Thus, the overall focus of this exploratory research is to identify elements important for the design of beach infrastructure (i.e., trash cans (TCs)) to reduce littering behaviors. We base our investigation on principles of a relatively new approach, called Design for Sustainable Behavior. In doing so, we consider design for two user groups: bathing beachgoers and beach managers. We examined these users' perceptions of beach TCs through the use of an on-line survey of beachgoers, in-depth interviews with Israeli beach managers, a survey of international Blue Flag beach managers and a design 'ideation' workshop. Most importantly, we found that there is interest on the part of beach managers and other stakeholders in applying design principles to improve TCs. The findings of this study have implications for further interdisciplinary - and multidisciplinary - research on this topic.

Kinetics of hydrogen production upon reduction of aqueous TiO2 nanoparticles catalyzed by Pd(0), Pt(0), or Au(0) coatings and an unusual hydrogen abstraction; steady state and pulse radiolysis study.

Reduction of H(+) by TiO(2) electrons (e(TiO)(2)(-)) in aqueous colloidal solution takes place in the presence of surface metal catalysts. The catalytic reduction gives rise to adsorbed hydrogen atoms. In the presence of Pd(0) or Pt(0), material balance shows that most of the adsorbed H atoms combine to molecular hydrogen. When the TiO(2) nanoparticles are partially coated with Au(0) instead of Pd(0) or Pt(0), a higher than expected molecular hydrogen level is observed, attributed to a short chain reaction involving hydrogen abstraction from 2-propanol. This unusual hydrogen abstraction reaction has not been reported before. The mechanism and energy balance are discussed. The surface modification of TiO(2) nanoparticles was carried out by reduction of K(2)PdCl(4), H(2)PtCl(6), or HAuCl(4) with e(TiO)(2)(-). The latter had been generated through electron injection from hydrated electrons, hydrogen atoms, or 2-propanol radicals, produced by gamma or pulse radiolysis prior to the addition of the metal compounds. Upon addition of the metal compounds, immediate reactions take place producing metals clusters (M(0)) by multistep reductions reactions on the TiO(2) surface. The chemical kinetics involving the different metals and the reaction rate constant of e(aq)(-) and e(TiO)(2)(-) with AuCl(4)(-) is also reported.