Impacts of Combustion Conditions and Photochemical Processing on the Light Absorption of Biomass Combustion Aerosol.

The aim was to identify relationships between combustion conditions, particle characteristics, and optical properties of fresh and photochemically processed emissions from biomass combustion. The combustion conditions included nominal and high burn rate operation and individual combustion phases from a conventional wood stove. Low temperature pyrolysis upon fuel addition resulted in "tar-ball" type particles dominated by organic aerosol with an absorption Ångström exponent (AAE) of 2.5-2.7 and estimated Brown Carbon contributions of 50-70% to absorption at the climate relevant aethalometer-wavelength (520 nm). High temperature combustion during the intermediate (flaming) phase was dominated by soot agglomerates with AAE 1.0-1.2 and 85-100% of absorption at 520 nm attributed to Black Carbon. Intense photochemical processing of high burn rate flaming combustion emissions in an oxidation flow reactor led to strong formation of Secondary Organic Aerosol, with no or weak absorption. PM1 mass emission factors (mg/kg) of fresh emissions were about an order of magnitude higher for low temperature pyrolysis compared to high temperature combustion. However, emission factors describing the absorption cross section emitted per kg of fuel consumed (m(2)/kg) were of similar magnitude at 520 nm for the diverse combustion conditions investigated in this study. These results provide a link between biomass combustion conditions, emitted particle types, and their optical properties in fresh and processed plumes which can be of value for source apportionment and balanced mitigation of biomass combustion emissions from a climate and health perspective.

Electrocatalytic oxygen evolution from water on a Mn(III-V) dimer model catalyst--a DFT perspective.

A complete water oxidation and oxygen evolution reaction (OER) cycle is monitored by means of density functional theory (DFT). A biomimetic model catalyst, comprising a µ-OH bridged Mn(III-V) dimer truncated by acetylacetonate ligand analogs and hydroxides is employed. The reaction cycle is divided into four electrochemical hydrogen abstraction steps followed by a series of chemical steps. The former employ the tyrosine/tyrosyl redox couple acting as electron and proton sink, thus determining the reference potential. Stripping hydrogen from water leads to the formation of two highly unstable Mn(V)=O/Mn(IV)-O˙ moieties, which subsequently combine to form a µ-peroxy O-O bond. O(2) evolution results from subsequent consecutive replacement of the remaining Mn-O bonds by water. A Zener "spintronic" type mechanism for virtually barrierless O(2) evolution is found. The applicability of DFT is discussed and extended to include the rate-limiting steps in the OER. Rather than attempting to compute transition states where KS-DFT is unreliable, an upper bound for the activation barrier of the O-O bond formation step is estimated from the hessians of the relevant intermediates.

Hydroxide oxidation and peroxide formation at embedded binuclear transition metal sites; TM = Cr, Mn, Fe, Co.

Key steps in electro-catalytic water oxidation on binuclear Transition Metal (TM) sites are addressed. These comprise (a) two one-electron oxidation steps of TM-OH moieties to form the corresponding two TM=O oxy-groups, and (b) a chemical step whereby the two oxy-species form a TM-O-O-TM peroxy-bridge. A test rig representing a generic low crystal field oxide support is described and employed. The energetics for homo-nuclear Cr(III-V), Mn(III-V), Fe(II-IV) and Co(II-IV) sites are compared. The uniqueness of the tyrosine/tyrosyl-radical (TyrOH/TyrO˙) reference potential for driving the oxidation steps is demonstrated. The oxidation of adsorbed TM-OH moieties on binuclear Mn and Co candidates requires an overpotential of approximately 0.5 V relative to the chosen reference potential. Correspondingly, the subsequent O-O bond formation becomes strongly exothermic, of the order of 1 eV. The hydroxide oxidation steps on binuclear CrCr and FeFe systems are, in total, exothermic by 1.21 and 0.61 eV, respectively, relative to the TyrOH/TyrO˙ reference potential. Consequently, the chemical step for transforming the TM=O moieties to the peroxo species is found to be endothermic by the order of 0.7 eV. Based on these findings, a catalyst containing one TM from each class is suggested. The validity of this concept is demonstrated for the FeCo binuclear site. The results are discussed in the context of experimental observations, which display a preference for mixed oxide systems.

Sorption Studies of Cobalt(II) on Colloidal Hematite Using Potentiometry and Radioactive Tracer Technique.

The sorption of Co(II) on colloidal hematite was studied as a function of pH, ionic strength, and Co(II) concentration. Two different techniques were used, yielding two different sets of information: (i) potentiometric titrations that provide information on the number of protons released as a function of pH owing to the sorption of Co(II) and (ii) measurement of the amount of cobalt sorbed on the surface as a function of pH using a radioactive tracer, (60)Co. At low Co(II) concentrations (10(-8) M), the sorption was found to be independent of ionic strength but there seems to be a weak ionic strength dependence at higher Co(II) concentrations (10(-4) M). The adsorption edge moved to higher pH with increasing Co(II) concentration. For the high Co(II) concentration, the number of protons released per cobalt sorbed increased from zero to approximately 1.5. The basic charging properties of hematite were modeled with four different surface complexation models. The 1-pK Basic Stern Model (BSM), with binding of electrolyte ions to the Stern plane, seems to be the most reasonable model if the ambition is to describe experimental data at different ionic strengths. The sorption of cobalt was modeled with the 1-pK BSM. By introducing a low concentration of high affinity surface sites for cobalt sorption it was possible to model the sorption in very wide cobalt concentrations, ranging from 10(-8) M to 10(-4) M. Copyright 2000 Academic Press.

Competitive Metal Ion Adsorption in Goethite Systems Using In Situ Voltammetric Methods and Potentiometry.

Competitive complexation with respect to the binary-metal ion combinations Cu(II)-Zn(II), Cu(II)-Pb(II), and Pb(II)-Zn(II) were studied at the goethite (alpha-FeOOH)-water interface (25 degrees C, I = 0.1 M NaNO(3)). In addition to potentiometric titrations and batch adsorption experiments, an in situ voltammetric technique was utilized. Sorption studies were performed within the ranges 3.5

In Situ Voltammetric Determinations of Metal Ions in Goethite Suspensions: Single Metal Ion Systems.

In the present paper voltammetric techniques have been used to study the sorption of Pb(II), Cd(II), Zn(II), and Cu(II) at low concentrations ( approximately 10(-6) M) in goethite (alpha-FeOOH) suspensions with varying solid concentrations as a function of pH. Metal ion adsorption on the cell walls was minimized by using a Teflon cell. Measurements in the absence of goethite showed the applicability of the voltammetric techniques for trace analysis in a wide pH range. The analysis seems to be limited mainly by the onset of metal ion hydrolysis at high pH values, where neutral and negatively charged species are formed. The results obtained in the presence of goethite were compared with previously determined surface complexation models, evaluated from relatively high metal ion ( approximately 10(-3) M) and solid concentrations ( approximately 10 g/L). Application of these models to more dilute conditions could thus be questioned. The results obtained indicated that no "high-affinity" sites are present on the surface of alpha-FeOOH. The voltammetric measurements showed good agreement for the Zn(II) and Cu(II) goethite systems. In the case of Pb(II), deviations between calculated and experimentally determined metal ion concentrations were detected at pH >7 and a molar ratio of Pb(II) to the surface concentration of goethite of 0.17. These deviations may be explained by assuming either formation of polymeric species or surface precipitates at high total concentrations (instead of the previously suggested surface complex identical withFeOPbOH) or slow adsorption kinetics at low concentrations. Also in the Cd(II) goethite system, a corresponding weaker adsorption than predicted was found. These observations strongly emphasize the importance of evaluating surface complexation models from data within concentration ranges as wide as possible. This holds for all components including the solid concentration. Copyright 1997 Academic Press.