Kinetics of phase separation and aging dynamics of segregating fluid mixtures in the presence of quenched disorder.

Quenched or frozen-in structural disorder is ubiquitous in real experimental systems. Much of the progress is achieved in understanding the phase separation of such systems using the diffusion-driven coarsening in an Ising model with quenched disorder. But there is a paucity of research on the phase-separation kinetics in fluids with quenched disorder. In this paper, we present results from a detailed molecular dynamics simulation, showing the effects of randomly placed localized impurities on the phase separation kinetics of binary fluid mixtures. Two different models are offered for representing the impurities. We observe a dramatic slowing down in the pattern formation with increasing impurity concentration. This sluggish domain growth kinetics follows a power-law with a disorder-dependent exponent. The correlation function and structure factor show a non-Porod behavior, indicating the roughening of the domain interfaces. We have also studied the effect of quenched disorder on the aging dynamics by calculating the two-time order parameter auto correlation function and find that the Fisher and Huse scaling law holds good in the presence of quenched disorder.

Integrating multiple spheres to identify the provenance and risk of urban dust and potentially toxic elements: Case study from central Mexico.

This study aims to improve the current method of studying potentially toxic elements (PTEs) in urban dust using direct chemical evidence (from dust, rock, and emission source samples) and robust geochemical methods. The provenance of urban dust was determined using rare earth elements (REEs) and geochemical diagrams (V-Ni-Th*10, TiO2 vs. Zr, and Zr/Ti vs. Nb/Y). The geogenic or anthropogenic source of PTEs was determined using the enrichment factor (EF) and compositional data analysis (CoDA), while a PTE's point emission source was identified using a 3.1*La-1.54*Ce-Zn diagram, mineralogy, and morphology analyses. The spatiotemporal distribution of PTEs was determined using a geographic information system, and their health risk (by inhalation) was estimated using a lung bioaccessibility test and particle size distribution. We collected urban dust (n = 38), rock (n = 4), and zinc concentrate (n = 2) samples and determined PTEs and REEs in a city of 1.25 million inhabitants in central Mexico. Results showed that urban dust derived from the San Miguelito Range. REEs, Sc, and Zr were geogenic, while Mn, Cu, Zn, As, and Pb were anthropogenic. Due to the presente of sphalerite particles, a zinc refinery was identified as the point emission source of Zn, As, and Pb. High concentrations of Zn (5000-20,008 mg/kg), As (120-284 mg/kg), and Pb (350-776 mg/kg) were found in urban dust near the zinc refinery. Additionally, particles of PM2.5 (66-84%), PM5.0 (13-27%), PM10 (3-8%), and PM20 (0-2%) and lung bioaccessibility of Sr (48.5-72.4%), Zn (9.6-28.4%), Cu (10.5-27.0%), Fe (4.5-8.6%), Mn (2.9-9.2%), Cr (38.3%) and Pb (30.6%) demonstrated a latent risk to human health. These approaches improve our understanding of the provenance of urban dust and its PTE emission sources in urban areas.

Characteristics and correlations of nonaffine particle displacements in the plastic deformation of athermal amorphous materials.

When an amorphous solid is deformed homogeneously, it exhibits heterogeneous plastic instabilities with a localized cooperative rearrangement of a cluster of particles in response. The heterogeneous behavior plays an important role in deciding the mechanical properties of amorphous solids. In this paper, we employ computer simulations to study the characteristics and the spatial correlations of these clusters characterized by their non-affine displacements in amorphous solids under simple shear deformation in the athermal quasistatic limit. The clusters with large displacements are found to be homogeneously distributed in space in the elastic regime, followed by a localization within a system-spanning shear band after yielding. The distributions of the displacement field exhibit a power-law nature in the elastic regime with an exponential cutoff post yielding. The non-affine displacements show strong spatial correlations, which become long-ranged with increasing strain. From our results, it is evident that the decay of the correlation functions is exponential in nature in the elastic regime. The yielding transition is marked by an abrupt change in the decay after which it is well described by a power-law with an exponential cutoff. These results demonstrate a scale-free character of non-affine correlations in the steady flow regime. These results are found to be robust and independent of the strain window over which the total non-affine displacement is calculated.

Mechanical properties and pore size distribution in athermal porous glasses.

We study the mechanical properties and pore structure in a three-dimensional molecular dynamics model of porous glass under athermal quasistatic shear. The vitreous samples are prepared by rapid thermal quenching from a high-temperature molten state. The pore structures form via solid-gas phase separation. The quiescent samples exhibit a wide range of pore topography, from inter-connected pore networks to randomly distributed compact pores depending on the material density. We find that the shear modulus strongly depends on the density and porosity. Under mechanical loading, the pore structure rearranges which is reflected in the pore size distribution function. Our results show that with increase in strain the distribution widens as the adjacent pores coalesce and form larger pores. We also propose a universal scaling law for the pore size distribution function which offers excellent data collapse for highly porous materials in the undeformed case. From the data scaling, we identify a critical density that can be attributed to the transition point from a porous-type to bulk-type material. The validity of the scaling law under finite deformation is also analyzed.

Alluvial and gypsum karst geological transition favors spreading arsenic contamination in Matehuala, Mexico.

Arsenic transport in alluvial aquifers is usually constrained due to arsenic adsorption on iron oxides. In karstic aquifers, however, arsenic contamination may spread to further extensions mainly due to favorable hydrogeochemical conditions. In this study, we i) determined the spatial and temporal behavior of arsenic in water in an alluvial-karstic geological setting using field and literature data, ii) established whether a contaminated aquifer exists using field and literature piezometric data and geophysical analysis, iii) studied the local geology and associated arsenic contaminated water sources to specific aquifers, iv) revealed and modeled subsoil stratigraphy, and v) established the extent of arsenic exposure to the population. We found arsenic contamination (up to 91.51 mg/l) in surface and shallow groundwater (<15 m), where water flows from west to east through a shallow aquifer, paleochannels and a qanat within an alluvial-karst transition that favors the spreading and transport of arsenic along 8 km as well as the increase of arsenic exposure to the population (up to 3.6 mgAs/kghair). Results from this study contribute to understanding arsenic transport in semi-arid, mining-metallurgical, and urban environments, where the presence of karst could favor arsenic transport to remote places and exacerbate arsenic exposure and impact in the future.

Characterization and Adsorption Behavior of Strontium from Aqueous Solutions onto Chitosan-Fuller's Earth Beads.

Fuller's earth spherical beads using chitosan as a binder were prepared for the removal of strontium ions from aqueous solution. The adsorbents were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which revealed the porous nature of the beads. The Brunauer⁻Emmett⁻Teller (BET) surface area of the beads was found to be 48.5 m²/g. The adsorption capacities of the beads were evaluated under both batch and dynamic conditions. The adsorption capacity was found to be ~29 mg/g of adsorbent at 298 K when the equilibrium concentration of strontium in the solution was 925 mg/L at pH 6.5. The X-ray photoelectron spectroscopy (XPS) data suggest that strontium uptake by the beads occurs mainly through an ion-exchange process. Kinetic data indicate that the sorption of strontium onto the beads follows anomalous diffusion. Thermodynamic data suggest that the ion-exchange of Sr2+ on the bead surface was feasible, spontaneous and endothermic in nature.

Distribution of Arsenic and Risk Assessment of Activities on Soccer Pitches Irrigated with Arsenic-Contaminated Water.

The aim of this research was to estimate the risk of human exposure to arsenic due to sporting activities in a private soccer club in Mexico, where arsenic-contaminated water was regularly used for irrigation. For this purpose, the total concentration in the topsoil was considered for risk assessment. This was accomplished through three main objectives: (1) measuring arsenic concentrations in irrigation water and irrigated soils, (2) determining arsenic spatial distribution in shallow soils with Geographical Information Systems (GIS) using geostatistical analysis, and (3) collecting field and survey data to develop a risk assessment calculation for soccer activities in the soccer club. The results showed that the average arsenic concentrations in shallow soils (138.1 mg/kg) were 6.2 times higher than the Mexican threshold for domestic soils (22 mg/kg). Furthermore, dermal contact between exposed users and contaminated soils accounted for a maximum carcinogenic risk value of 1.8 × 10−5, which is one order of magnitude higher than the recommended risk value, while arsenic concentrations in the irrigation water were higher (6 mg/L) than the WHO’s permissible threshold in drinking water, explaining the contamination of soils after irrigation. To the best of our knowledge, this is the first risk study regarding dermal contact with arsenic following regular grass irrigation with contaminated water in soccer pitches.

Arsenic and fluoride removal from contaminated drinking water with Haix-Fe-Zr and Haix-Zr resin beads.

The objective of the study was to carry-out batch tests to examine the effectiveness of Haix-Fe-Zr and Haix-Zr resin beads in the removal of As(III), As(V) and F- from groundwater with a similar geochemistry to a site where a community-based drinking water plant has been installed in West Bengal, India. The groundwater was spiked separately with ∼200 µg/L As(III) and As(V) and 5 mg/L F-. Haix-Zr resin beads were more effective than Haix-Fe-Zr resin beads in removing As(III) and As(V). Haix-Zr resin beads showed higher removal of As(V) compared to As(III). Haix-Zr resin beads removed As(V) below the WHO (10 µg/L) drinking water standards at 8.79 µg/L after 4 h of shaking, while As(III) was reduced to 7.72 µg/L after 8 h of shaking. Haix-Fe-Zr resin beads were more effective in removing F- from the spiked groundwater compared to Haix-Zr resin beads. Concentrations of F- decreased from 6.27 mg/L to 1.26 mg/L, which is below the WHO drinking water standards (1.5 mg/L) for F-, after 15 min of shaking with Haix-Fe-Zr resin beads. After 20 min of shaking in groundwater treated with Haix-Zr resin beads, F- concentrations decreased from 6.27 mg/L to 1.43 mg/L. In the removal of As(III), As(V), and F- from the groundwater, Haix-Fe-Zr and Haix-Zr resin beads fit the parabolic diffusion equation (PDE) suggesting that adsorption of these contaminants was consistent with inter-particle diffusion.

Remediation of Arsenic Contaminated Soil Using Phosphate and Colloidal Gas Aphron Suspensions Produced from Sapindus mukorossi.

Phosphate and colloidal gas aphrons (CGAs) generated from saponin extracted from Sapindus mukorossi fruit, were evaluated for washing low levels of arsenic from an iron rich soil. Phosphate is one of the most commonly dispersed chemicals that increases arsenic mobility in soil due to their structural similarities, making it an important factor in arsenic removal process. Column washing experiments were performed with CGAs in down flow and up flow modes on soil of pH 5 and 6. Soapnut CGAs, when paired with phosphate removed up to 95 % arsenic while soapnut CGAs alone could only remove up to 70 % arsenic. The presence of phosphate improved efficiency of soapnut solution by up to 35 %. SEM image of washed soil revealed minor corrosion of soil surface while using phosphate with soapnut. Therefore, the addition of phosphates would have positive impact on soil washing using soapnut saponin.

Enhanced removal of lead from contaminated soil by polyol-based deep eutectic solvents and saponin.

Deep eutectic solvents (DESs) are a class of green solvents analogous to ionic liquids, but less costly and easier to prepare. The objective of this study is to remove lead (Pb) from a contaminated soil by using polyol based DESs mixed with a natural surfactant saponin for the first time. The DESs used in this study were prepared by mixing a quaternary ammonium salt choline chloride with polyols e.g. glycerol and ethylene glycol. A natural surfactant saponin obtained from soapnut fruit pericarp, was mixed with DESs to boost their efficiency. The DESs on their own did not perform satisfactory due to higher pH; however, they improved the performance of soapnut by up to 100%. Pb removal from contaminated soil using mixture of 40% DES-Gly and 1% saponin and mixture of 10% DES-Gly and 2% saponin were above 72% XRD and SEM studies did not detect any major corrosion in the soil texture. The environmental friendliness of both DESs and saponin and their affordable costs merit thorough investigation of their potential as soil washing agents.

Remediation of Pb/Cr co-contaminated soil using electrokinetic process and approaching electrode technique.

Electrokinetic process has emerged as an important tool for remediating heavy metal-contaminated soil. The process can concentrate heavy metals into smaller soil volume even in the absence of hydraulic flow. This makes it an attractive soil pre-treatment method before other remediation techniques are applied such that the chemical consumption in the latter stage can be reduced. The present study evaluates the feasibility of electrokinetic process in concentrating lead (Pb) and chromium (Cr) in a co-contaminated soil using different types of wetting agents, namely 0.01 M NaNO3, 0.1 M citric acid and 0.1 M EDTA. The data obtained showed that NaNO3 and citric acid resulted in poor Pb electromigration in this study. As for Cr migration, these agents were also found to give lower electromigration rate especially at low pH region as a result of Cr(VI) adsorption and possible reduction into Cr(III). In contrast, EDTA emerged as the best wetting agent in this study as it formed water-soluble anionic complexes with both Pb and Cr. This provided effective one-way electromigration towards the anode for both ions, and they were accumulated into smaller soil volume with an enrichment ratio of 1.55-1.82. A further study on the application of approaching cathode in EDTA test showed that soil alkalisation was achieved, but this did not provide significant enhancement on electromigration for Pb and Cr. Nevertheless, the power consumption for electrokinetic process was decreased by 22.5%.

Application of colloidal gas aphron suspensions produced from Sapindus mukorossi for arsenic removal from contaminated soil.

Colloidal gas aphron dispersions (CGAs) can be described as a system of microbubbles suspended homogenously in a liquid matrix. This work examines the performance of CGAs in comparison to surfactant solutions for washing low levels of arsenic from an iron rich soil. Sodium Dodecyl Sulfate (SDS) and saponin, a biodegradable surfactant, obtained from Sapindus mukorossi or soapnut fruit were used for generating CGAs and solutions for soil washing. Column washing experiments were performed in down-flow and up flow modes at a soil pH of 5 and 6 using varying concentration of SDS and soapnut solutions as well as CGAs. Soapnut CGAs removed more than 70% arsenic while SDS CGAs removed up to 55% arsenic from the soil columns in the soil pH range of 5-6. CGAs and solutions showed comparable performances in all the cases. CGAs were more economical since it contains 35% of air by volume, thereby requiring less surfactant. Micellar solubilization and low pH of soapnut facilitated arsenic desorption from soil column. FT-IR analysis of effluent suggested that soapnut solution did not interact chemically with arsenic thereby facilitating the recovery of soapnut solution by precipitating the arsenic. Damage to soil was minimal arsenic confirmed by metal dissolution from soil surface and SEM micrograph.

A comparative study of biopolymers and alum in the separation and recovery of pulp fibres from paper mill effluent by flocculation.

Recovery of cellulose fibres from paper mill effluent has been studied using common polysaccharides or biopolymers such as Guar gum, Xanthan gum and Locust bean gum as flocculent. Guar gum is commonly used in sizing paper and routinely used in paper making. The results have been compared with the performance of alum, which is a common coagulant and a key ingredient of the paper industry. Guar gum recovered about 3.86mg/L of fibre and was most effective among the biopolymers. Settling velocity distribution curves demonstrated that Guar gum was able to settle the fibres faster than the other biopolymers; however, alum displayed the highest particle removal rate than all the biopolymers at any of the settling velocities. Alum, Guar gum, Xanthan gum and Locust bean gum removed 97.46%, 94.68%, 92.39% and 92.46% turbidity of raw effluent at a settling velocity of 0.5cm/min, respectively. The conditions for obtaining the lowest sludge volume index such as pH, dose and mixing speed were optimised for guar gum which was the most effective among the biopolymers. Response surface methodology was used to design all experiments, and an optimum operational setting was proposed. The test results indicate similar performance of alum and Guar gum in terms of floc settling velocities and sludge volume index. Since Guar gum is a plant derived natural substance, it is environmentally benign and offers a green treatment option to the paper mills for pulp recycling.

Nonequilibrium dynamics of four-point correlations of collective density fluctuations in a supercooled liquid.

In this paper we study the four-point correlation function χ(4) of collective density fluctuations in a nonequilibrium liquid. The equilibration is controlled by a modified stretched exponential behavior (exp[-(t(w)/τ)(ß)]) having the relaxation time τ dependent on the aging time t(w). Similar aging behavior has been seen experimentally in supercooled liquids. The basic equations of fluctuating nonlinear hydrodynamics are solved here numerically to obtain χ(4) for equilibrium and non equilibrium states. We also identify a dynamic length scale ξ from the equilibrated function. ξ(T) grows with fall of temperature T. From a broader perspective, we demonstrate here that the characteristic signatures of dynamical heterogeneities in a supercooled liquid, observed previously in computer simulations of the dynamics of a small number of particles, are also present in the coarse grained equations of generalized hydrodynamics.

Comparison of a plant based natural surfactant with SDS for washing of As(V) from Fe rich soil.

This study explores the possible application of a biodegradable plant based surfactant, obtained from Sapindus mukorossi, for washing low levels of arsenic (As) from an iron (Fe) rich soil. Natural association of As(V) with Fe(III) makes the process difficult. Soapnut solution was compared to anionic surfactant sodium dodecyl sulfate (SDS) in down-flow and a newly introduced suction mode for soil column washing. It was observed that soapnut attained up to 86% efficiency with respect to SDS in removing As. Full factorial design of experiment revealed a very good fit of data. The suction mode generated up to 83 kPa pressure inside column whilst down-flow mode generated a much higher pressure of 214 kPa, thus making the suction mode more efficient. Micellar solubilisation was found to be responsible for As desorption from the soil and it followed 1st order kinetics. Desorption rate coefficient of suction mode was found to be in the range of 0.005 to 0.01, much higher than down-flow mode values. Analysis of the FT-IR data suggested that the soapnut solution did not interact chemically with As, offering an option for reusing the surfactant. Soapnut can be considered as a soil washing agent for removing As even from soil with high Fe content.

Metastable-state dynamics of a liquid: a free-energy landscape study.

Using the time dependence of density fluctuations in a supercooled liquid obtained from the solutions of the equations of nonlinear fluctuating hydrodynamics (NFH), the evolution of the system in the free energy landscape is studied. A crossover from a continuous fluid type dynamics to that of hopping between different free energy minima is observed as the liquid is increasingly supercooled. We demonstrate that our results are also in agreement with equilibrium density functional analysis of the same system. The density field obtained in the numerical solution of the NFH equations are further analyzed to introduce complimentary density of voids in the supercooled liquid state and its static and dynamic correlations are computed. The nature of the relaxation of vacancy correlations are observed to be similar to that of the density fluctuations.

Time dependent stretching of aging dynamics in a generalized hydrodynamic model for supercooled liquids.

The nonequilibrium dynamics and aging behavior of a supercooled liquid is investigated from an analysis of the correlation of density fluctuations at two different times. The dynamic correlation functions are computed by solving numerically the equations of nonlinear fluctuating hydrodynamics. The aging time dependence follows a modified stretched exponential form with a relaxation time which is dependent on the aging time. This is similar to the behavior seen in the aging data of dielectric response functions of a typical glass forming liquid.

Glassy aging with modified Kohlrausch-Williams-Watts form.

In this paper, we address the question of whether aging in the nonequilibrium glassy state is controlled by the equilibrium alpha-relaxation process, which occurs at temperatures above T(g) . Recently, Lunkenheimer [Phys. Rev. Lett. 95, 055702 (2005)] proposed a model for the glassy aging data of dielectric relaxation using a modified Kohlrausch-Williams-Watts form exp[-(t(age)/tau(age)(beta(age))] . The aging time t(age) dependence of the relaxation time tau(age) is defined by these authors through a functional relation involving the corresponding frequency nu(t(age))=1/(2pi tau(age)) , but the stretching exponent beta(age) is the same as beta(alpha), the alpha-relaxation stretching exponent. We present here an alternative functional form for tau(age)(t(age)) directly involving the relaxation time itself. The proposed model fits the data of Lunkenheimer perfectly with a stretching exponent beta(age) different from beta(alpha) .