A theoretical exploration of the influencing factors for surface potential

Although it has been widely used to probe the interracial property, dynamics, and reactivity, the surface potential remains intractable for directly being measured, especially for charged particles in aqueous solutions. This paper presents that the surface potential is strongly dependent on the Hofmeister effect, and the theory including ion polarization and ionic correlation shows significant improvement compared with the classical theory. Ion polarization causes a strong Hofmeister effect and further dramatic decrease to surface potential, especially at low concentration; in contrast, ionic correlation that is closely associated with potential decay distance overestimates surface potential and plays an increasing role at higher ionic concentrations. Contributions of ion polarization and ionic correlation are respectively assessed, and a critical point is detected where their contributions can be exactly counteracted. Ionic correlation can be almost neglected at low ionic concentrations, while ion polarization, albeit less important at high concentrations, should be considered across the entire concentration range. The results thus obtained are applicable to other interfacial processes.

Principles of Surface Potential Estimation in Mixed Electrolyte Solutions:Taking into Account Dielectric Saturation

The dielectric properties between in-particle/water interface and bulk solution are significantly different,which are ignored in the theories of surface potential estimation.The analytical expressions of surface potential considering the dielectric saturation were derived in mixed electrolytes based on the nonlinear Poisson-Boltzmann equation.The surface potentials calculated from the approximate analytical and exact numerical solutions agreed with each other for a wide range of surface charge densities and ion concentrations.The effects of dielectric saturation became important for surface charge densities larger than 0.30 C/m^2.The analytical models of surface potential in different mixed electrolytes were valid based on original Poisson-Boltzmann equation for surface charge densities smaller than 0.30 C/m^2.The analytical model of surface potential considering the dielectric saturation for low surface charge density can return to the result of classical Poisson-Boltzmann theory.The obtained surface potential in this study can correctly predict the adsorption selectivity between monovalent and bivalent counterions.

Dynamics of total culturable bacteria and its relationship with methylmercury in the soils of the water level fluctuation zone of the Three Gorges Reservoir

Field investigations were conducted to study the temporal and spatial distribution characteristics of total culturable bacteria(TCB)and its relationship with methylmercury(MeHg)in the soils of the water level fluctuation zone of the Three Gorges Reservoir.Different altitudes(170–180,170–175,165–170 and 160–165 m)in Zhenxi(Site 1),Shibaozhai(Site 2)and Tujing(Site 3),Chongqing,China were chosen as sampling sites.Results indicated that TCB did not have significant difference in the top(0–10 cm)and sub(10–20 cm)soil of the non-inundated area(175–180 m),but showing a significant difference in the water level fluctuation zone(\175 m,suggesting that water level fluctuation had an important effect on TCB.Moreover,TCB in soils of various altitudes of Site 1 and 2had significant difference,while for Site 3,this difference was not significant.And the difference of TCB in Site 2was much greater than that in Site 1.These results suggested that there were significant differences for TCB in soils of mainstream and tributaries.In addition,TCB in soils of 10–20 cm had significant or highly significant positive correlations with MeHg level(r C 0.762,P B 0.048),thus we assumed that there may be some aerobic microorganisms playing dominant roles in mercury methylation.

Observation of specific ion effects in humus aggregation process

Specific ion effects play a vital role in a variety of colloidal and interfacial processes.However,few studies have reported the specific ion effects in the humus aggregation process,which strongly influence the transport and fate of environmental pollutants.In this study,soil humus colloids were prepared and characterized,and the specific ion effects on humus aggregation in electrolyte solutions were investigated at a variety of concentrations and pH values using dynamic light scattering methods.Activation energy(ΔE),which is known to reflect the dynamics and stability of a colloidal system,was used to quantitatively characterize the specific ion effects.The results showed that given ΔE value of 2.48×10^(3) J mol^(-1) at pH 3.0,the electrolyte concentrations were 91.6,58.2,3.8,and 0.8 mmol L^(-1) for Na^(+),K^(+),Mg^(2+),and Ca_(2+),respectively,thus indicating significant specific ion effects in the humus aggregation process.Most importantly,decreasing the electrolyte concentrations increased the differences in the ΔE value between two cation species with the same valence(i.e.,ΔE_(Na)-ΔE_(K) and ΔE_(Mg)-ΔE_(Ca)),while increasing the pH increased the magnitude of ΔE_(Mg)-ΔE_(Ca).However,the classic Derjaguin,Landau,Verwey,and Overbeek(DLVO)theory and the double layer theory,as well as the currently widely used ionic hydration and dispersion effects,failed to predict the experimentally observed increase in the specific ion effects with decreasing electrolyte concentrations in a quantitative sense.These results have implications for the necessity of involving specific ion effects for a better understanding of humus aggregation and interactions in aqueous and soil systems.

Specific ion effect of H^(+) on variably charged soil colloid aggregation

Specific ion effects(Hofmeister effects)have recently attracted the attention of soil scientists,and it has been found that ionic non-classic polarization plays an important role in the specific ion effect in soil.However,this explanation cannot be applied to H+.The aim of this work was to characterize the specific ion effect of H+on variably charged soil(yellow soil)colloid aggregation.The total average aggregation(TAA)rate,critical coagulation concentration(CCC),activation energy,and zeta potential were used to characterize and compare the specific ion effects of H+,K+,and Na+.Results showed that strong specific ion effects of H+,K+,and Na+existed in variably charged soil colloid aggregation.The TAA rate,CCC,and activation energy were sensitive to H+,and the addition of a small amount of H+changed the TAA rate,CCC,and activation energy markedly.The zeta potential results indicated that the specific ion effects of H+,K+,and Na+on soil colloid aggregation were caused by the specific ion effects of H+,K+,and Na+on the soil electric field strength.In addition,the origin of the specific ion effect for H+was its chemical adsorption onto surfaces,while those for alkali cations were non-classic polarization.This study indicated that H+,which occurs naturally in variably charged soils,will dominate variably charged soil colloid aggregation.

A simulation study of mercury release fluxes from soils in wet–dry rotation environment

A simulative mesocosm study was conducted to evaluate the influence of wet-dry rotation on mercury（Hg） flux from soil/water to air and the distribution of Hg species in water as well as Hg chemical fractions in soil. Three types of soil were employed including two kinds of paddy soil, Typic Purpli-Udic Cambosols（TPUC） and Xanthi-Udic Ferralosols（XUF）, as well as the Alluvial Soil（AS） from Three Gorge reservoir area in Chongqing, China. The results showed that Hg fluxes in wetting periods were significantly higher than that in drying periods. It might be due to the formation of a layer of stable air over the water surface in which some redox reactions promote evasion processes over the water surface. This result indicated that more Hg would be evaporated from the Three Gorge reservoir and paddy soil field during the flooding season. Hg fluxes were positively correlated with air temperature and solar irradiation, while negatively correlated with air humidity and the electronic conductivity of water. Hg fluxes from AS and TPUC were significantly higher than that from XUF, which might be due to the higher organic matter（OM） contents in XUF than TPUC and AS. The reduction processes of oxidized Hg were restrained due to the strong binding of Hg to OM, resulting in the decrease in Hg flux from the soil.

Unraveling the size distributions of surface properties for purple soil and yellow soil

Soils contain diverse colloidal particles whose properties are pertinent to ecological and human health, whereas few investigations systematically analyze the surface properties of these particles. The objective of this study was to elucidate the surface properties of particles within targeted size ranges（i.e. 〉 10, 1-10, 0.5-1, 0.2-0.5 and 〈 0.2 μm） for a purple soil（Entisol） and a yellow soil（Ultisol） using the combined determination method. The mineralogy of corresponding particle-size fractions was determined by X-ray diffraction.We found that up to 80% of the specific surface area and 85% of the surface charge of the entire soil came from colloidal-sized particles（〈 1 μm）, and almost half of the specific surface area and surface charge came from the smallest particles（〈 0.2 μm）. Vermiculite,illite, montmorillonite and mica dominated in the colloidal-sized particles, of which the smallest particles had the highest proportion of vermiculite and montmorillonite. For a given size fraction, the purple soil had a larger specific surface area, stronger electrostatic field, and higher surface charge than the yellow soil due to differences in mineralogy.Likewise, the differences in surface properties among the various particle-size fractions can also be ascribed to mineralogy. Our results indicated that soil surface properties were essentially determined by the colloidal-sized particles, and the 〈 0.2 μm nanoparticles made the largest contribution to soil properties. The composition of clay minerals within the diverse particle-size fractions could fully explain the size distributions of surface properties.

Roles of chloride ion in photo-reduction/oxidation of mercury

Photo-reduction of divalent mercury(Hg(II)) in aquatic systems plays a key role in global biogeochemistry cycling of mercury(Hg) in the Earth's surface environment. The mechanisms of this process with various Clconcentrations([Cl-]) under different pH values and irradiation wavelength ranges are still unclear. In this work,photo-reduction and photo-oxidation experiments of Hg with different [Cl-] and pH values under various light conditions were conducted. The results show that photoreduction rate constants of Hg(II) decrease with the increasing of [Cl-] in neutral solution under full light spectrum. Photo-reduction rate constants of Hg(II) with Cl-is highly dependent on Hg(II) species, which is determined by [Cl-] and pH value. Irradiation wavelength ranges have significant effects on reaction processes of photo-reduction of Hg(II) and photo-oxidation of Hg(0) in the presence of Cl-. When cut off ultraviolet(UV) radiation(280–400 nm), the reduction rate constants decrease without Cl-, and increase with higher [Cl-], and the photooxidation rates of Hg(0) decrease with or without Cl-.Except Cl-complexation stabilize the reducible Hg ions in solutions, photo-oxidation is an important reason for Cllowering photo-reduction rate of Hg(II). The results are of great importance for understanding the photo-redox characters of Hg(II) with Cl-.