Jose E. Herrera

Enhanced stability and dechlorination activity of pre-synthesis stabilized nanoscale FePd particles

Nanoscale zero-valent iron (NZVI) particles are promising materials for the in-situ remediation of a wide variety of source zone contaminants. This study presents the results of a systematic investigation of the stability of bimetallic FePd nanoparticle suspensions in water and their capability to degrade trichloroethylene (TCE) synthesized in the presence of various stabilizers (i.e., carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), and guar gum). Results indicate a dramatic improvement in FePd suspension stability when the stabilizer is present in the matrix during the nanoparticle synthesis step. Stability enhancement is controlled by iron nanoparticle/stabilizer electrostatic and steric interactions, which are a function of the molecular structure of the stabilizer. Stabilization mechanisms differed for each stabilizer with CMC and guar gum exhibiting the best nanoparticle suspension stability improvement. Results suggest that the complexation of iron precursors with the stabilizer, during synthesis, plays a key role in nZVI stability improvement. In case of guar gum, gelation during synthesis significantly increased suspension viscosity, enhancing suspension stability. The capability of these materials to degrade TCE was also investigated. Results demonstrated that when stabilizers were present in the matrix dechlorination rates increased significantly. FePd nanoparticles in CMC had the highest observed rate constant; however the highest surface area-normalized rate constant was obtained from FePd stabilized in PVP360K. Results from this study can be used to aid in the selection of appropriate iron nanoparticle stabilizers. Stabilizer selection should be assessed on a case by case basis as no stabilizer will meet the needs of all in-situ remediation applications.

Characteristics of Lead Corrosion Scales Formed during Drinking Water Distribution and Their Potential Influence on the Release of Lead and Other Contaminants

Destabilization of the corrosion scale present in lead pipes used in drinking water distribution systems is currently considered a major problem for municipalities serviced in part by lead pipes. Although several lead corrosion strategies have been deployed with success, a clear understanding of the chemistry of corrosion products present in the scale is needed for an effective lead control. This contribution focuses on a comprehensive characterization of the layers present in the corrosion scale formed on the inner surfaces of lead pipes used in the drinking water distribution system of the City on London, ON, Canada. Solid corrosion products were characterized using X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Toxic elements accumulated in the corrosion scale were also identified using inductively coupled plasma (ICP) spectrometry after acid digestion. Based on the XRD results, hydrocerussite was identified as the major lead crystalline corrosion phase in most of the pipes sampled, while cerussite was observed as the main crystalline component only in a few cases. Lead oxides including PbO(2) and Pb(3)O(4) were also observed in the inner layers of the corrosion scale. The presence of these highly oxidized lead species is rationalized in terms of the lead(II) carbonate phase transforming into lead(IV) oxide through an intermediate Pb(3)O(4) (2Pb(II)O x Pb(IV)O(2)) phase. In addition to lead corrosion products, an amorphous aluminosilicate phase was also identified in the corrosion scale. Its concentration is particularly high at the outer surface layers. Accumulation of toxic contaminants such as As, V, Sb, Cu, and Cr was observed in the corrosion scales, together with a strong correlation between arsenic accumulation and aluminum concentration.

Effect of pH on the concentrations of lead and trace contaminants in drinking water: A combined batch, pipe loop and sentinel home study

High lead levels in drinking water are still a concern for households serviced by lead pipes in many parts of North America and Europe. This contribution focuses on the effect of pH on lead concentrations in drinking water delivered through lead pipes. Though this has been addressed in the past, we have conducted a combined batch, pipe loop and sentinel study aiming at filling some of the gaps present in the literature. Exhumed lead pipes and water quality data from the City of Londons water distribution system were used in this study. As expected, the lead solubility of corrosion scale generally decreased as pH increased; whereas dissolution of other accumulated metals present in the corrosion scale followed a variety of trends. Moreover, dissolved arsenic and aluminum concentrations showed a strong correlation, indicating that the aluminosilicate phase present in the scale accumulates arsenic. A significant fraction of the total lead concentration in water was traced to particulate lead. Our results indicate that particulate lead is the primary contributor to total lead concentration in flowing systems, whereas particulate lead contribution to total lead concentrations for stagnated systems becomes significant only at high water pH values.

Role of Pb(II) Defects in the Mechanism of Dissolution of Plattnerite (β-PbO2) in Water under Depleting Chlorine Conditions

Destabilization of lead corrosion scales present in plumbing materials used in water distribution systems results in elevated lead concentrations in drinking water. Soluble lead release caused by changes in water chemistry has been linked to dissolution of lead carbonate and/or lead oxide solid phases. Although prior studies have examined the effects of varying water chemistry on the dissolution of plattnerite (β-PbO2), β-PbO2 dissolution under depleting chlorine conditions is poorly understood. This paper reports results obtained for long-term batch dissolution experiments for solid phase β-PbO2 under depleting chlorine conditions. Results indicate that the initial availability of free chlorine effectively depresses dissolved lead concentrations released from β-PbO2. However, the dissolved lead levels remained low (∼4 μg/L) even after free chlorine was depleted. Detailed spectroscopic characterization of solid samples collected during the β-PbO2 experiments indicates that changes in the electronic structure of PbO2 occurred during the dissolution. This further points out that Pb2+ defects present in crystalline β-PbO2 play a dominant role in the dissolution of this solid phase.

The Reducibility and Cluster Size of Vanadium Oxide as Potential Descriptors of Its Catalytic Activity in the Partial Oxidation of Ethanol

Abstract A series of vanadium oxide (VOx) catalysts prepared using three different supports were tested for the partial oxidation of ethanol to acetaldehyde. Optical absorption spectroscopy and Temperature Programmed reductions experiments indicate that the reducibility and average domain size of the vanadia clusters anchored on the supports are very sensitive to vanadia loading. The catalytic activity results were modeled using a pseudo steady state approximation using the ethanol hydrogen abstraction step as rate limiting. The results obtained strongly suggest that catalytic activity can be correlated to both average vanadia cluster size and the ability of vanadia to uptake hydrogen during TPR experiments.

Supported vanadium oxide clusters in partial oxidation processes: Catalytic consequences of size and electronic structure.

The catalytic activity for ethanol partial oxidation of vanadium oxide (VOx) anchored on titanium oxide was correlated to their electronic structure. In situ Raman spectroscopy and temperature‐programmed desorption (TPD) experiments indicate that the presence of catalytically active VOx moieties is very sensitive to vanadia loading: highly dispersed VOx predominantly exists at low VOx contents whereas larger vanadia clusters coexist at higher VOx loadings. In situ UV/Vis spectroscopy revealed that a significant fraction of these larger clusters remain reduced during catalysis, and thus do not fully participate in catalytic turnovers. The electronic structures of model VOx nanoclusters of different sizes (monomer, dimer, trimer, and one‐dimensional polymers) were investigated by using periodic density functional theoretical calculations. Results indicate that their electronic structures are significantly affected by their size. Our analysis also revealed that the formation of reduced VOx species (V4+) during catalysis is concomitant to the reduction of adjacent Ti cations (Ti3+). Theoretically calculated optical absorption spectra matched the experimental spectroscopic results obtained under in situ reaction conditions. Furthermore, the determination of defect formation enthalpies reported previously as the main descriptor for catalytic activity of vanadia nanoclusters, predicted that isolated monomeric VOx clusters predominantly take part in catalytic turnovers.