Bulk Solution Concentration Research Articles

Cloud water composition during HCCT-2010: Scavenging efficiencies, solute concentrations, and droplet size dependence of inorganic ions and dissolved organic carbon

Abstract. Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a three-stage and a five-stage collector were applied and samples were analysed for inorganic ions (SO42−,NO3−, NH4+, Cl−, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 µmol L−1 for ammonium, nitrate, and sulfate respectively, between 4 and 27 µmol L−1 for minor ions, 5.4 µmol L−1 for H2O2 (aq), 1.9 µmol L−1 for S(IV), and 3.9 mgC L−1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC × 1.8) contributed 20–40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60–66 % for solute concentrations and 52–80 % for cloud water loadings (CWLs). The similar variability of solute concentrations and CWLs together with the results of back-trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC), were the main factor controlling bulk solute concentrations for the cloud studied. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CVI) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56–0.94, 0.79–0.99, 0.71–98, and 0.67–0.92 for SO42−, NO3−, NH4+, and DOC respectively when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42−, NO3−, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and “U” shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the three-stage collector and somewhat more pronounced from the five-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the five-stage collector was capable of resolving some features of solute size dependencies not seen in the three-stage data, especially sharp concentration increases (up to a factor of 5–10) in the smallest droplets for many solutes.

Efficacy of a Phosphate-Charged Soil Material in Supplying Phosphate for Plant Growth in Soilless Root Media

A soil material high in crystalline Fe hydrous oxides and noncrystalline Al hydrous oxides collected from the Bw horizon of a Hemcross soil containing allophane from the state of Oregon was charged with phosphate-P at rates of 0, 2.2, and 6.5 mg·g−1, added to a soilless root medium at 5% and 10% by volume, and evaluated for its potential to supply phosphate at a low, stable concentration during 14 weeks of tomato (Solanum esculentumL.) seedling growth. Incorporation of the soil material improved pH stability, whether it was charged with phosphate or not. Bulk solution phosphate-P concentrations in the range of 0.13 to 0.34 mg·dm−3were associated with P deficiency. The only treatment that sustained an adequate bulk solution concentration of phosphate-P above 0.34 mg·dm−3for the 14 weeks of testing contained 10% soil material charged with 6.5 mg·g−1P, but initial dissolved P concentrations were too high (>5 mg·g−1phosphate-P) from the standpoint of phosphate leaching. The treatment amended with 10% soil material charged with 2.2 mg·g−1P maintained phosphate-P within an acceptable range of 0.4 to 2.3 mg·dm−3for 48 d in a medium receiving no postplant phosphate fertilization.

The Scope of Direct Alkylation of Gold Surface with Solutions of C1-C4 n-Alkylstannanes.

Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin oxide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THF solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.

Atomistic simulations of the effect of helium clusters on grain boundary mobility in iron

A series of molecular dynamics simulations was performed in this work to investigate the kinetic interaction between helium clusters and grain boundaries in iron. Helium cluster formation and size distributions were found to be markedly different in the bulk compared to the region of a stationary boundary. Upon reaching a steady-state cluster distribution, the spatial fluctuation of cluster-enriched boundaries was analyzed to determine the grain boundary mobility using the random walk method. Segregated clusters reduced the boundary mobility, the drag effect of clusters increasing as the bulk solute concentration increases. The drag effect was further rationalized by employing Cahn's solute drag model using the effective binding energy of He clusters and the grain boundary diffusivity of a single He atom, their magnitudes having been determined from the segregation level and from monitoring the trajectory of a solute atom in the investigated grain boundaries, respectively. The model is found to provide a satisfactory explanation of the simulation results in the zero velocity limit.

Unquenchable Surface Potential Dramatically Enhances Cu2+ Binding to Phosphatidylserine Lipids

Herein, the apparent equilibrium dissociation constant, K(Dapp), between Cu(2+) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-l-serine (POPS), a negatively charged phospholipid, was measured as a function of PS concentrations in supported lipid bilayers (SLBs). The results indicated that K(Dapp) for Cu(2+) binding to PS-containing SLBs was enhanced by a factor of 17,000 from 110 nM to 6.4 pM as the PS density in the membrane was increased from 1.0 to 20 mol %. Although Cu(2+) bound bivalently to POPS at higher PS concentrations, this was not the dominant factor in increasing the binding affinity. Rather, the higher concentration of Cu(2+) within the double layer above the membrane was largely responsible for the tightening. Unlike the binding of other divalent metal ions such as Ca(2+) and Mg(2+) to PS, Cu(2+) binding does not alter the net negative charge on the membrane as the Cu(PS)2 complex forms. As such, the Cu(2+) concentration within the double layer region was greatly amplified relative to its concentration in bulk solution as the PS density was increased. This created a far larger enhancement to the apparent binding affinity than is observed by standard multivalent effects. These findings should help provide an understanding on the extent of Cu(2+)-PS binding in cell membranes, which may be relevant to biological processes such as amyloid-β peptide toxicity and lipid oxidation.

Incipient mixing by Marangoni effects in slow viscous flow of two immiscible fluid layers

Ignoring inertia, a deformable interface separating two fluid films is considered, subject to non-uniform tension driven by the solutal Marangoni effect in the presence of a scalar concentration field. Detailed description of adsorption kinetics is abrogated by a simple ansatz directly relating interfacial tension and bulk solute concentration. Consequently, the formal mathematical treatment and some of the results share features in common with the Rayleigh–Benard–Marangoni thermocapillary problem. Normal mode perturbation analysis in the limit of small interface deformations establishes the existence of an unstable response for low wavenumber excitation. In the classification of Cross & Hohenberg (1993, Pattern formation outside of equilibrium. Rev. Mod. Phys., 65, 851–1112), both type I and type II behaviour are observed. By considering the zero wavenumber situation exactly, it is proved that all eigenvalues are purely imaginary with non-positive imaginary part; hence, a type III instability is not possible. For characteristic timescales of mass diffusion much shorter than the relaxation time of interfacial fluctuations (infinite crispation number): the response growth rate is obtained explicitly; only a single excitation mode is available, and a complete stability diagram is constructed in terms of the relevant control parameters. Otherwise, from a quiescent base state, an infinite discrete spectrum of modes is observed that exhibit avoided crossing and switching phenomena, as well as exceptional points where stationary state pairs coalesce into a single oscillatory standing wave pattern. A base state plane Poiseuille flow, driven by an external pressure gradient, generally exaggerates the response: growth rates of instabilities are enhanced, and stable decay is further suppressed with increasing base flow speed, but the inherent symmetry breaking destroys stationary and standing wave response. Results are obtained in this most general situation by implementing a numerical Chebyshev collocation scheme. The model was motivated by hydrodynamic processes supposed to be involved in gastric digestion of humans.

A shrinking core model for seeds oil extraction with particularization to Camelina oil separation

The oil extraction from a spherical particle in an adequate solvent is analyzed by a dynamic model. The oil extraction occurs by moving the unsolubilized solid/solute-free phase interface toward the center of the particle. We assume that the transport of solute molecules has three resistances: (1) the resistance due to oil core dissolving; (2) the resistance due to the solute-free portion of the particle; (3) the resistance due to a surface layer near solid–liquid interface. Generally, the equation governing the dynamic behavior of oil extraction is numerically solved. However, sometimes analytical expressions for the time dynamics of the size of the unsolubilized oil portion can be obtained in some special cases. The present analysis on oil process extraction takes into account the effect of variable bulk solute concentration and of seed internal characteristics such as particle porosity, particle tortuosity and core oil dissolving kinetics. Result consists in a general mathematical model whose particularization is given for the case of Camelina seeds oil extraction. For Camelina seeds the oil hexane extraction has been characterized by particularization of the general modified shrinking core model. It has obtained that the particle dimensionless porosity is set to 0.08, while the constant of kinetic process from the shrinking core surface is strongly dependent on core position and on the temperature after relation kd=kd0(t)(rc/R)n with n=4 and kd0(t) in the range 4.3–8.3 10−8m/s.

Water electro-transport with hydrated cations in electrodialysis

Electrodialysis (ED), an efficient, low energy consumption and environmentally friendly separation and desalination technology, has attracted great attentions. Due to a drawback in water transport mechanism from the dilute stream to the concentrate one, its applications are limited, especially on the concentrating or desalinating seawater/brackish water, biological products-contained streams. In this work, the relationship between water transport rate (WTR) and ion species in ED was firstly studied by using ion exchange membranes with different ion exchange capacities (IECs). A mathematical model based on Nernst–Planck equation was established to further associate WTR with IECs, membrane matrix backbone materials, bulk solution concentration, electrolyte type, etc. The results indicate that WTR during ED is a very significant phenomenon and cannot be ignored. To mitigate this effect, attention should be paid to the modification of membrane matrix materials and the selection of suitable IEC or functional groups or the introduction of ligands to obtain a win–win coupling of high desalination ability and low WTR.

Facultative nitrate reduction by electrode-respiring Geobacter metallireducens biofilms as a competitive reaction to electrode reduction in a bioelectrochemical system.

Alternative metabolic options of exoelectrogenic biofilms in bioelectrochemical systems (BESs) are important not only to explain the fundamental ecology and performance of these systems but also to develop reliable integrated nutrient removal strategies in BESs, which potentially involve substrates or intermediates that support/induce those alternative metabolisms. This research focused on dissimilatory nitrate reduction as an alternative metabolism to dissimilatory anode reduction. Using the exoelectrogenic nitrate reducer Geobacter metallireducens, the critical conditions controlling those alternative metabolisms were investigated in two-chamber, potentiostatically controlled BESs at various anode potentials and biofilm thicknesses and challenged over a range of nitrate concentrations. Results showed that anode-reducing biofilms facultatively reduced nitrate at all tested anode potentials (-150 to +900 mV vs Standard Hydrogen Electrode) with a rapid metabolic shift. The critical nitrate concentration that triggered a significant decrease in BES performance was a function of anode biofilm thickness but not anode potential. This indicates that these alternative metabolisms were controlled by the availability of nitrate, which is a function of nitrate concentration in bulk solution and its diffusion into an anode-reducing biofilm. Coulombic recovery decreased as a function of nitrate dose due to electron-acceptor substrate competition, and nitrate-induced suspended biomass growth decreased the effluent quality.

Calcium-mediated polysaccharide gel formation and breakage: Impact on membrane foulant hydraulic properties

The solution phase interaction between the polysaccharide alginate and calcium at various concentrations is examined in this paper. The observed gelation behavior and resulting hydraulic properties of the fouling layer deposited on flat sheet membranes can be directly related to the initial calcium concentration (in bulk solution). Particular attention is given to the effect of calcium concentration, with changes in calcium binding behavior of alginate in bulk solution shown to be closely related to the resistance of the cake layer formed on the membranes. At low calcium concentrations, Ca2+ ions interact strongly with guluronate (G) block functional groups forming a highly interconnected gel assemblage. This resulted in the fouling layer deposited on the membrane surface exhibiting high specific resistance despite being highly porous. Further increase in calcium concentration leads to enhanced calcium binding and significant aggregation of alginate in suspension with concomitant breakdown in the gel structure of the material accumulated on the membrane. The increased calcium concentration resulted in a cake that was characterized by a lower porosity and higher solid fraction and, most importantly, a markedly lower specific resistance to the passage of water. The materials properties of the alginate layers formed on flat sheet membranes were also determined under various pressures, with empirical expressions describing the hydraulic conductivity and compressibility of fouling layers developed as a function of trans-membrane pressure (TMP) for a range of calcium concentrations. The resulting materials properties expressions could be applied for the prediction of the filtration behavior of an alginate-rich solution for a range of calcium concentrations under constant flux (and thus time varying TMP) conditions.

Modeling of Electric Double-Layers Including Chemical Reaction Effects

A physicochemical and numerical model for the transient formation of an electric double-layer between an electrolyte and a chemically-active flat surface is presented, based on a finite elements integration of the nonlinear Nernst-Planck-Poisson model including chemical reactions. The model works for symmetric and asymmetric multi-species electrolytes and is not limited to a range of surface potentials. Numerical simulations are presented, for the case of a CaCO3 electrolyte solution in contact with a surface with rate-controlled protonation/deprotonation reactions. The surface charge and potential are determined by the surface reactions, and therefore they depend on the bulk solution composition and concentration.

Conformation of bovine submaxillary mucin layers on hydrophobic surface as studied by biomolecular probes

In the present study, the conformational changes of bovine submaxillary mucin (BSM) adsorbed on a hydrophobic surface (polystyrene (PS)) as a function of concentration in bulk solution (up to 2mg/mL) have been investigated with biomolecular probe-based approaches, including bicinchoninic acid (BCA), enzyme-linked immunosorbent assay (EIA), and enzyme-linked lectin assay (ELLA). The conformation and hydrodynamic diameter of highly purified BSM molecules, as characterized by circular dichroism (CD) spectroscopy and dynamic light scattering (DLS), respectively, showed a slight, yet gradual coiling and compaction in response to the increase in BSM concentration in bulk solution. Adsorbed masses of BSM onto hydrophobic surface, as probe by BCA, showed a continuously increasing trend up to 2mg/mL. But, the signals from EIA and ELLA, which probe the concentration of available unglycosylated C-terminals and the central glycosylated regions, respectively, showed complicated non-linear responses with increasing surface concentration. The results from this study support the conventional amphiphilic, triblock model of BSM in the adsorption onto hydrophobic surface from aqueous solution. The biomolecular probe-based approaches employed in this study, however, provided further details on the conformational changes of BSM on surface, in particular the accessibility of glycosylated and unglycosylated domains with increasing surface concentration.

Laser-induced fluorescence visualization of ion transport in a pseudo-porous capacitive deionization microstructure

In this paper, a microfluidic experimental set-up is introduced to study the ionic transport in an artificial capacitive deionization (CDI) cell. CDI is a promising desalination technique, which relies on the application of an external electric field and high surface area porous electrodes for ion separation and storage. Photolithography and deep reactive ion etching were used to fabricate a micro-CDI channel with pseudo-porous electrodes on a silicon-on-insulator substrate. Laser-induced fluorescence was performed using cationic Sulforhodamine B (SRB) fluorescent dye to measure ion concentration within the bulk solution and more importantly, within the porous electrodes during the desalination process, with an average normalized root mean square deviation of 8.2 %. Using this set-up, electromigration of ions within the electrode was visualized and the effect of applied electric potential on bulk solution concentration distribution is quantified. In addition, SRB and Fluorescein were used together to visualize anion and cation concentrations simultaneously. The method presented in this study can be used for solution concentrations up to approximately 0.7 mM. The ionic concentration profiles obtained by this approach can be used to test and validate the existing electrosorption models, and pseudo-porous electrodes can be modified to observe the effects of pore size, shape and distribution on electrosorption performance. Furthermore, with proper modifications, the microfabricated structure and experimental set-up can be used for CDI-on-a-chip applications and bio-separation devices.

In Situ Speciation and Distribution of Toxic Selenium in Hydrated Roots of Cowpea

The speciation and spatial distribution of selenium (Se) in hydrated plant tissues is not well understood. Using synchrotron-based x-ray absorption spectroscopy and x-ray fluorescence microscopy (two-dimensional scanning [and associated mathematical model] and computed tomography), the speciation and distribution of toxic Se were examined within hydrated roots of cowpea (Vigna unguiculata) exposed to either 20 µM selenite or selenate. Based upon bulk solution concentrations, selenate was 9-fold more toxic to the roots than selenite, most likely due to increased accumulation of organoselenium (e.g. selenomethionine) in selenate-treated roots. Specifically, uptake of selenate (probably by sulfate transporters) occurred at a much higher rate than for selenite (apparently by both passive diffusion and phosphate transporters), with bulk root tissue Se concentrations approximately 18-fold higher in the selenate treatment. Although the proportion of Se converted to organic forms was higher for selenite (100%) than for selenate (26%), the absolute concentration of organoselenium was actually approximately 5-fold higher for selenate-treated roots. In addition, the longitudinal and radial distribution of Se in roots differed markedly: the highest tissue concentrations were in the endodermis and cortex approximately 4 mm or more behind the apex when exposed to selenate but in the meristem (approximately 1 mm from the apex) when exposed to selenite. The examination of the distribution and speciation of Se in hydrated roots provides valuable data in understanding Se uptake, transport, and toxicity.

Self-patterning induced by a solutal Marangoni effect in a receding drying meniscus

This paper examines through numerical simulations the impact of a solutal Marangoni effect on the deposit obtained from a polymer solution. A hydrodynamical model with lubrication approximation is used to describe the liquid phase in a dip-coating–like configuration. The studied case considers evaporation in stagnant air (diffusion-limited evaporation), which results in a coupling between the liquid and gas phases. Viscosity, surface tension, and saturated vapor pressure depend on the solute concentration. In the evaporative regime, when the surface tension increases with the polymer concentration, the Marangoni effect induces a periodic regime. This results in a self-organized periodic patterning of the dried film in certain control parameter ranges. A morphological phase diagram as well as meniscus and dry-deposit shapes are provided as a function of the substrate velocity and bulk solute concentration.

The effects of the electrical double layer on giant ionic currents through single-walled carbon nanotubes

We developed a computational model for investigating the cause for the high ionic current through a single-walled carbon nanotube nanofluidic device by considering the electrical double layer at a solid–liquid interface. With this model, we were able to examine the influence of the Gouy–Chapman–Stern electrical double layer and the solution concentration on the ionic conductance in the device. Results showed that the conductance–concentration relationship predicted from our model agreed well with experimental observation. Moreover, our model showed that the compact layer thickness increased with the increase of the bulk solution concentration, reducing the internal volume of the nanotube channel available for fluid transport. Fluid within the channel had an enhanced concentration and a net charge which increased the electroosmotic and electrophoretic transport properties of the device, increasing the total ionic conductance of the system.

Crystalline and Osmotic Swelling of an Expansive Clay Inundated with Sodium Chloride Solutions

Compacted expansive clays swell due to crystalline swelling and osmotic/double layer swelling mechanisms. Crystalline swelling is driven by adsorption of water molecules at clay particle surfaces that occurs at inter-layer separations of 10–22 A. Diffuse double layer swelling occurs at inter-layer separations >22 A. The tendency of compacted clay to develop osmotic or double layer swelling reduces with increase in solute concentration in bulk solution. This study examines the consequence of increase in solute concentration in bulk solution on the relative magnitudes of the two swelling modes. The objective is achieved by inundating compacted expansive clay specimens with distilled water and sodium chloride solutions in free-swell oedometer tests and comparing the experimental swell with predictions from Van’t Hoff equation. The results of the study indicate that swell potential of compacted expansive clay specimens wetted with relatively saline (0.4, 1 and 4 M sodium chloride) solutions are satisfied by crystalline swelling alone. Comparatively, compacted clay specimens inundated with less saline solutions (0.005–0.1 M sodium chloride) require both crystalline and osmotic swelling to satiate the swell potential.

Development of a Vero cell DNA reference standard for residual DNA measurement in China

This collaborative study developed a Vero cell DNA reference for standardizing dot blot hybridization, an assay widely employed to measure residual DNA contents of viral vaccines prepared with Vero cells. High purity of Vero cell DNA was extracted and characterized by Hind III enzyme digestion and DNA sequencing. Then, with a cooperative calibration, the concentration of Vero cell DNA reference bulk solution was determined (64.0 ± 1.9 μg/mL, OD260/OD280 = 1.87) and diluted (40 ng/mL) with Tris-EDTA buffer containing bovine serum albumin as freeze-dried excipients. With industrial filling apparatus, the diluted bulk was loaded into ampoules (0.5 mL each) which were heat sealed after nitrogen filling. Finally, a collaborative study showed that the Vero cell DNA reference could reach a sensitivity of 1 to 5 pg/dot and maintained good stability after accelerated destruction test. The successful establishment of the Vero cell DNA quantitative reference will facilitate the standardization of dot blot hybridization for testing residual host cell DNA.

Coordination state probabilities and the solvation free energy of Zn2+ in aqueous methanol solutions

Coordination state probabilities for the [Zn(H(2)O)(n)(CH(3)OH)(m)](2+) complex in aqueous methanol solutions are calculated as a function of the bulk solution concentration, and the number of methanol ligands, m = 0, 1, ..., 6 with n+m = 6. Zinc ion solvation free energies, which serve to normalize these probabilities, also reproduce the methanol concentration dependence of the experimentally derived free energy of zinc ion transfer from water to aqueous methanol solutions. Coordination state probabilities, p(n, m), are derived by extending quasi-chemical theory of ion hydration to solvent mixtures and mixed ligands. Free energy contributions to p(n, m) include the free energy of forming the mixed-ligand complex in the ideal gas, obtained by quantum chemical calculations, and the solvation free energy of the complex, approximated by a dielectric continuum model. We find that replacing water ligands with methanol ligands preferentially stabilizes methanol-rich complexes in the ideal gas. Conversely, water-rich complexes are stabilized by the solvation free energy contribution, such that the [Zn(H(2)O)(6)](2+) complex is the dominant species in solution for all methanol concentrations considered. Stabilization of the methanol-rich complexes is a consequence of the local coordination chemistry, dominated by the delocalization of charge on the zinc ion, while the stabilization of water-rich complexes is a consequence of favorable ion-solvent electrostatic interactions and smaller dielectric cavities for the water-rich complexes at fixed total charge in the dielectric continuum model. Our analysis also highlights an entropic contribution associated with the reversible work required to remove n water and m methanol molecules from bulk solution to form the [Zn(H(2)O)(n)(CH(3)OH)(m)](2+) complex, which captures the methanol concentration dependence of the solvation free energy of the zinc ion.

Photocatalytically driven dissolution of macroscopic metal surfaces. Part 1: Silver

We present the first observation of photocatalytically driven, hydrogen peroxide mediated, dissolution of a macroscopic metal surface. Specifically, we report on the dissolution of silver in the presence of photocatalytically generated H2O2 produced by ultra-band gap illumination of TiO2 at 365 nm in the presence of O2. Direct measurements of photocatalytically generated H2O2 in the TiO2 suspensions studied indicate that peroxide concentration never exceeds 32 μmol dm−3. However, comparison of electrochemical quartz crystal microgravimetrically determined rates of Ag dissolution with rates recorded from solutions spiked with H2O2 indicates that dissolution occurs at a rate equivalent to a bulk solution concentration of ∼100 mmol dm−3 H2O2. This suggests that a local enhancement occurs in the rate of photocatalytically induced metal dissolution on surfaces under direct illumination, which is attributed to two causes: (i) local modification of the TiO2 by deposition of dissolved Ag, so increasing its efficiency for peroxide generation; and (ii) peroxide generation local to the electrode surface mitigating against photolytic loss reactions seen to occur in the solution bulk. The photoinduced dissolution process is found to be both highly controllable/light switchable and spatially specific.