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In situ contaminant degradation and detoxification mediated by microbes and minerals is an important element of green remediation. Improved understanding of microbe-mineral interactions on the nanoscale offers promising opportunities to further minimize the environmental and energy footprints of site remediation. In this Perspective, we describe new methodologies that take advantage of an array of multidisciplinary toolsâincluding multiomics-based analysis, bioinformatics, machine learning, gene editing, real-time spectroscopic and microscopic analysis, and computational simulationsâto identify the key microbial drivers in the real environments, and to characterize in situ the dynamic interplay between minerals and microbes with high spatiotemporal resolutions. We then reflect on how the knowledge gained can be exploited to modulate the binding, electron transfer, and metabolic activities at the microbe-mineral interfaces, to develop new in situ contaminant degradation and detoxication technologies with combined merits of high efficacy, material longevity, and low environmental impacts. Two main strategies are proposed to maximize the synergy between minerals and microbes, including using mineral nanoparticles to enhance the versatility of microorganisms (e.g., tolerance to environmental stresses, growth and metabolism, directed migration, selectivity, and electron transfer), and using microbes to synthesize and regenerate highly dispersed nanostructures with desired structural/surface properties and reactivity.
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Minerais , Minerais/química , Recuperação e Remediação Ambiental , Biodegradação AmbientalRESUMO
Remediation of large and dilute plumes of groundwater contaminated by oxidized pollutants such as chromate is a common and difficult challenge. Herein, we show that in situ formation of FeS nanoparticles (using dissolved Fe(II), S(-II), and natural organic matter as a nucleating template) results in uniform coating of aquifer material to create a regenerable reactive zone that mitigates Cr(VI) migration. Flow-through columns packed with quartz sand are amended first with an Fe2+ solution and then with a HS- solution to form a nano-FeS coating on the sand, which does not hinder permeability. This nano-FeS coating effectively reduces and immobilizes Cr(VI), forming Fe(III)-Cr(III) coprecipitates with negligible detachment from the sand grains. Preconditioning the sand with humic or fulvic acid (used as model natural organic matter (NOM)) further enhances Cr(VI) sequestration, as NOM provides additional binding sites of Fe2+ and mediates both nucleation and growth of FeS nanoparticles, as verified with spectroscopic and microscopic evidence. Reactivity can be easily replenished by repeating the procedures used to form the reactive coating. These findings demonstrate that such enhancement of attenuation capacity can be an effective option to mitigate Cr(VI) plume migration and exposure, particularly when tackling contaminant rebound post source remediation.
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Cromo , Água Subterrânea , Oxirredução , Poluentes Químicos da Água , Água Subterrânea/química , Cromo/química , Poluentes Químicos da Água/química , Nanopartículas/química , Recuperação e Remediação Ambiental/métodos , Substâncias Húmicas , Compostos Ferrosos/química , Benzopiranos/químicaRESUMO
Salt permeability of polyamide reverse osmosis (RO) membranes has been shown to increase with increasing feed salt concentration. The dependence of salt permeability on salt concentration has been attributed to the variation of salt partitioning with feed salt concentration. However, studies using various analytical techniques revealed that the salt (total ion) partitioning coefficient decreases with increasing salt concentration, in marked contrast to the observed increase in salt permeability. Herein, we thoroughly investigate the dependence of total ion and co-ion partitioning coefficients on salt concentration and solution pH. The salt partitioning is measured using a quartz crystal microbalance (QCM), while the co-ion partitioning is calculated from the measured salt partitioning using a modified Donnan theory. Our results demonstrate that the co-ion and total ion partitioning behave entirely differently with increasing salt concentrations. Specifically, the co-ion partitioning increased fourfold, while total ion partitioning decreased by 60% as the salt (NaCl) concentration increased from 100 to 800 mM. The increase in co-ion partitioning with increasing salt concentration is in accordance with the increasing trend of salt permeability in RO experiments. We further show that the dependence of salt and co-ion partitioning on salt concentration is much more pronounced at a higher solution pH. The good co-ion exclusion (GCE) modelâderived from the solution-friction modelâis used to calculate the salt permeability based on the co-ion partitioning coefficients. Our results show that the GCE model predicts the salt permeabilities in RO experiments relatively well, indicating that co-ion partitioning, not salt partitioning, governs salt transport through RO membranes. Our study provides an in-depth understanding of ion partitioning in polyamide RO membranes and its relationship with salt transport.
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Cloreto de Sódio , Purificação da Água , Osmose , Nylons/química , Membranas Artificiais , Purificação da Água/métodosRESUMO
Inorganic scaling caused by precipitation of sparingly soluble salts at supersaturation is a common but critical issue, limiting the efficiency of membrane-based desalination and brine management technologies as well as other engineered systems. A wide range of minerals including calcium carbonate, calcium sulfate, and silica precipitate during membrane-based desalination, limiting water recovery and reducing process efficiency. The economic impact of scaling on desalination processes requires understanding of its sources, causes, effects, and control methods. In this Critical Review, we first describe nucleation mechanisms and crystal growth theories, which are fundamental to understanding inorganic scale formation during membrane desalination. We, then, discuss the key mechanisms and factors that govern membrane scaling, including membrane properties, such as surface roughness, charge, and functionality, as well as feedwater characteristics, such as pH, temperature, and ionic strength. We follow with a critical review of current characterization techniques for both homogeneous and heterogeneous nucleation, focusing on the strengths and limitations of each technique to elucidate scale-inducing mechanisms, observe actual crystal growth, and analyze the outcome of scaling behaviors of desalination membranes. We conclude with an outlook on research needs and future research directions to provide guidelines for scale mitigation in water treatment and desalination.
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Membranas Artificiais , Purificação da Água , Carbonato de Cálcio , Sulfato de Cálcio , Dióxido de Silício/química , Purificação da Água/métodosRESUMO
Manganese(III/IV) oxide minerals are known to spontaneously degrade organic pollutants in nature. However, the kinetics are too slow to be useful for engineered water treatment processes. Herein, we demonstrate that nanoscale Mn3O4 particles under nanoscale spatial confinement (down to 3-5 nm) can significantly accelerate the kinetics of pollutant degradation, nearly 3 orders of magnitude faster compared to the same reaction in the unconfined bulk phase. We first employed an anodized aluminum oxide scaffold with uniform channel dimensions for experimental and computational studies. We found that the observed kinetic enhancement resulted from the increased surface area of catalysts exposed to the reaction, as well as the increased local proton concentration at the Mn3O4 surface and subsequent acceleration of acid-catalyzed reactions even at neutral pH in bulk. We further demonstrate that a reactive Mn3O4-functionalized ceramic ultrafiltration membrane, a more suitable scaffold for realistic water treatment, achieved nearly complete removal of various phenolic and aniline pollutants, operated under a common ultrafiltration water flux. Our findings mark an important advance toward the development of catalytic membranes that can degrade pollutants in addition to their intrinsic function as a physical separation barrier, especially since they are based on accelerating natural catalytic pathways that do not require any chemical addition.
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Poluentes Químicos da Água , Purificação da Água , Catálise , Manganês , Oxirredução , ÓxidosRESUMO
Understanding the salt-water separation mechanisms of reverse osmosis (RO) membranes is critical for the further development and optimization of RO technology. The solution-diffusion (SD) model is widely used to describe water and salt transport in RO, but it does not describe the intricate transport mechanisms of water molecules and ions through the membrane. In this study, we develop an ion transport model for RO, referred to as the solution-friction model, by rigorously considering the mechanisms of partitioning and the interactions among water, salt ions, and the membrane. Ion transport through the membrane is described by the extended Nernst-Planck equation, with the consideration of frictions between the species (i.e., ion, water, and membrane matrix). Water flow through the membrane is governed by the hydraulic pressure gradient and the friction between the water and membrane matrix as well as the friction between water and ions. The model is validated using experimental measurements of salt rejection and permeate water flux in a lab-scale, cross-flow RO setup. We then investigate the effects of feed salt concentration and hydraulic pressure on salt permeability, demonstrating strong dependence of salt permeability on feed salt concentration and applied pressure, starkly disparate from the SD model. Lastly, we develop a framework to analyze the pressure drop distribution across the membrane, demonstrating that cross-membrane transport dominates the overall pressure drop in RO, in marked contrast to the SD model that assumes no pressure drop across the membrane.
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Membranas Artificiais , Purificação da Água , Filtração , Osmose , ÁguaRESUMO
Experimentally determined heteroaggregation rates between charged and neutral colloidal particles are reported for the first time. Different positively and negatively charged polystyrene latex particles are investigated. The neutral particles are obtained through adsorption of an appropriate amount of oppositely charged additives, such as aliphatic oligoamines, iron cyanide complexes, or alkyl sulfates. Heteroaggregation rates were measured with time-resolved multiangle light scattering. One observes that heteroaggregation between charged and neutral particles is always fast and diffusion controlled. These experimental values are compared with calculations of the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, whereby one finds that this heteroaggregation process is highly sensitive to charge regulation conditions. The comparison with experiments shows unambiguously that the surface of the neutral particles regulates strongly and probably behaves close to a constant potential surface. This observation is in line with direct force measurements on similar systems and further agrees with the fact that for neutral surfaces the capacitance of the diffuse layer is expected to be much smaller than the one of the inner layer.
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It has recently been reported that polystyrene microbeads may be modified to realize plasticizer-free ion-selective optical sensors (optodes) on the basis of solvatochromic dye transducers. We show here that the functionalized microbeads, individually isolated by flow cytometry, exhibit unexpectedly poor fluorescent properties and that the sensor response is instead attributed to the supernatant. A more thorough study reveals that such optical microemulsion sensors can be made operationally functional and chemically selective, seemingly in the absence of any solvent matrix or added surfactant. Instead, it is shown that residual THF used in the fabrication of the emulsified sensors may solubilize the sensing components and give a functional optode response. To evaluate this further, the number of sensing components was stepwise simplified to assess their need. Variation of residual THF levels has no effect on the ion optode response when plasticizer is present, in support of established results. Lipophilic solvatochromic dye transducers are also shown not to require an added surfactant as their nature already endows the emulsified sensors with a stabilizing ionic surface charge. The ionophores are shown to exhibit much larger stability constants in the surfactant-free formulations than surfactant-based ones (valionomycin, log ß > 9.2 compared to 6.1; Na+-ionophore X, 6.7 vs 4.7), which is attributed to a less polar solvent environment for the ionophore. Potassium-, sodium-, and calcium-selective sensors were used as model systems in this study.
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Ion-selective optical microsensors based on surface-modified polystyrene (PS) beads with positively charged lipophilic solvatochromic dye (SD) on the surface were studied with K+ as model ion. Water-soluble SDs are expelled into the aqueous phase by ion exchange with the cationic analyte of interest, resulting in a detectable color change. In contrast, lipophilic SDs are more attractive, as they appear to remain anchored to the surface after expulsion from the sensing phase. This transfers just the ionic chromophore functionality into the aqueous phase and allows the system to act as a reversible, truly self-contained sensor. In this work this mechanism was evaluated with ζ-potential measurements on microsensor suspensions. It indeed provides experimental evidence for the mechanism of SD transfer, as a reversal of the ζ-potential of the PS microsensors was observed for higher potassium concentrations with valinomycin-doped microspheres. For a discriminated ion such as sodium, the ζ-potential change occurs at much higher electrolyte concentrations, in agreement with sensor selectivity. Undoped microspheres showed no apparent dependence of ζ-potential on electrolyte concentration. The study also shows that the effective range of microsensor surface charge is tunable and depends on the concentration of the SD on the coating phase.
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Aqueous suspensions of amidine latex (AL) and sulfate latex (SL) particles containing sodium tetraphenylborate and NaCl are studied with electrokinetic and time-resolved light-scattering techniques. In monovalent salt solutions, AL is positively charged, whereas SL is negatively charged. Electrophoretic mobility measurements demonstrate that adsorption of tetraphenylborate anions leads to a charge reversal of AL particles. At higher concentrations, both types of particles accumulate negative charge. For AL particles, the charge reversal leads to a narrow fast aggregation region and an intermediate regime of slow aggregation. For SL particles, the intermediate slow regime is also observed. These aspects can be explained with classical theory of Derjaguin, Landau, Verwey, and Overbeek (DLVO). Another regime of fast aggregation is observed at intermediate concentrations, and the existence of this regime can be rationalized by an additional attractive non-DLVO force. We suspect that this additional force is caused by surface charge heterogeneities.
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Time-resolved dynamic light scattering is used to measure absolute heteroaggregation rate coefficients and the corresponding stability ratios for heteroaggregation between amidine and sulfate latex particles. These measurements are complemented by the respective quantities for the homoaggregation of the two systems and electrophoresis. Based on the latter measurements, the stability ratios are calculated using Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. In monovalent salt solutions, the two types of particles investigated are oppositely charged. In the presence of multivalent ions, however, one particle type reverses its charge, while the charge of the other particle type is hardly affected. In this region, the heteroaggregation stability ratio goes through a pronounced maximum when plotted versus concentration. This region of slow aggregation is wider than the one observed in the corresponding homoaggregation process. One also finds that the onset of this region sensitively depends on the boundary conditions used to calculate the double layer force. The present results are more in line with constant potential boundary conditions.
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Shifts of the critical coagulation concentration (CCC) in particle suspensions in salt solutions containing multivalent co-ions and monovalent counterions are rationalized. One observes that the CCC is inversely proportional to the valence, and this behavior is referred to as the inverse Schulze-Hardy rule. This dependence is established by means of measurements of the stability ratio for positively and negatively charged latex particles with time-resolved light scattering. The same dependence is equally suggested by calculations of the CCC with the Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory, whereby the full Poisson-Boltzmann equation for the asymmetric electrolytes has to be used. The latter aspect is essential, since in the case of multivalent co-ions the surface charge is principally neutralized by monovalent counterions. This rule complements the classical Schulze-Hardy rule, which applies in the case of multivalent counterions, and states that the CCC is inversely proportional to the sixth power of the valence.
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High concentrations of dissolved silica in saline industrial wastewaters and brines cause silica scale formation, significantly hampering the efficacy of diverse engineered systems. Applying functional polymers as scale inhibitors in process feedwater is a common strategy to mitigate silica scaling. However, feedwater characteristics often vary widely, depending on the specific processes, making the inhibition of silica scaling challenging and complex. In this study, we systematically investigate the role of ionic composition, specifically ionic strength and divalent ions, and solution temperature, in inhibiting silica scaling using molecularly designed amine/amide polymers. The inhibitor demonstrates effective stabilization of silicic acid, with inhibition efficiency of 74 and 55 % in the absence and presence of 20,000 ppm NaCl, respectively. However, further increasing the ionic strength of oversaturated silicic acid solutions significantly diminishes inhibition performance, rendering it ineffective at 180,000 ppm NaCl. Divalent inorganic cations exhibit a stronger impact on reducing inhibition efficiency compared to sodium ions. Molecular dynamics simulations reveal a competition mechanism between anionic silicic acid reactants (i.e., H3SiO4-) and chlorides for binding to ammonium groups within the polymeric inhibitor. Additionally, cations form clusters with H3SiO4- ions, hindering their stabilization with polymeric inhibitor. Notably, at elevated temperatures, the inhibitor achieves near-perfect inhibition for 500 ppm silicic acid solutions. This comprehensive assessment provides important insights into the effectiveness of silica scaling inhibitors under solution conditions relevant to real-world applications, addressing the challenges posed by varying solution parameters in diverse industrial processes.
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Polímeros , Dióxido de Silício , Temperatura , Dióxido de Silício/química , Concentração Osmolar , Polímeros/química , Águas Residuárias/química , Íons , Simulação de Dinâmica MolecularRESUMO
Thin-film composite reverse osmosis membranes have remained the gold standard technology for desalination and water purification for nearly half a century. Polyamide films offer excellent water permeability and salt rejection but also suffer from poor chlorine resistance, high fouling propensity, and low boron rejection. We addressed these issues by molecularly designing a polyester thin-film composite reverse osmosis membrane using co-solvent-assisted interfacial polymerization to react 3,5-dihydroxy-4-methylbenzoic acid with trimesoyl chloride. This polyester membrane exhibits substantial water permeability, high rejection for sodium chloride and boron, and complete resistance toward chlorine. The ultrasmooth, low-energy surface of the membrane also prevents fouling and mineral scaling compared with polyamide membranes. These membranes could increasingly challenge polyamide membranes by further optimizing water-salt selectivity, offering a path to considerably reducing pretreatment steps in desalination.
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Ceramic membranes are a promising alternative to polymeric membranes for selective separations, given their ability to operate under harsh chemical conditions. However, current fabrication technologies fail to construct ceramic membranes suitable for selective molecular separations. Herein, we demonstrate a molecular-level design of ceramic thin-film composite membranes with tunable subnanometer pores for precise molecular sieving. Through burning off the distributed carbonaceous species of varied dimensions within hybrid aluminum oxide films, we created membranes with tunable molecular sieving. Specifically, the membranes created with methanol showed exceptional selectivity toward monovalent and divalent salts. We attribute this observed selectivity to the dehydration of the large divalent ions within the subnanometer pores. As a comparison, smaller monovalent ions can rapidly permeate with an intact hydration shell. Lastly, the flux of neutral solutes through each fabricated aluminum oxide membrane was measured for the demonstration of tunable separation capability. Overall, our work provides the scientific basis for the design of ceramic membranes with subnanometer pores for molecular sieving using atomic layer deposition.
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Gypsum scaling via crystallization is a major obstacle limiting the applications of membrane-based technologies and heat exchangers in engineered systems. Herein, we perform the first comparative investigation on the impacts of natural organic matter (Suwannee River humic acid, SRHA) and colloidal particles on the gypsum crystallization process in terms of induction time and crystal morphology. Results show that the presence of SRHA significantly increases the induction time of gypsum crystallization. Specifically, at a solution saturation index of 4.92, the induction time increases 6.5-fold in the presence of 6 mg/L SRHA, compared to the case without SRHA. SRHA also alters the morphology of the formed calcium sulfate crystals, resulting in a polygon-like shape, differing from the characteristic needle-like shape of gypsum in the absence of additives. These changes in crystal morphology are attributed to the adsorption of SRHA on the gypsum crystal surface, blocking the active sites for gypsum growth. In contrast, in the presence of colloidal particles, the observed induction time of gypsum crystallization either decreases or increases, depending on the competitive interplay between the enhancement effect in the nucleation step and the inhibition effect in the subsequent crystal growth step. Furthermore, the formed gypsum crystals in the presence of colloidal particles exhibit a needle-like morphology similar to the crystals formed in the absence of any additives. Our study provides fundamental understanding of gypsum crystallization in feedwaters containing natural organic matter and colloidal particles, highlighting the importance of feedwater composition in gypsum scaling.
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Sulfato de Cálcio , Substâncias Húmicas , Adsorção , Cristalização , Substâncias Húmicas/análise , Rios/químicaRESUMO
Aggregation kinetics and surface charging properties of rod-like sulfated cellulose nanocrystals (CNCs) have been investigated in aqueous suspensions containing monovalent, divalent, or trivalent inorganic salts. Electrophoresis and time-resolved dynamic light scattering (DLS) were used to characterize the surface charge and colloidal stability of the CNCs, respectively. The surface charge and aggregation kinetics of the sulfated CNCs were found to be independent of solution pH (pH range 2-10). For the monovalent salts (CsCl, KCl, NaCl, and LiCl), the critical coagulation concentration (CCC) followed the order of Cs+ < K+ < Na+ < Li+, which follows the direct Hofmeister series, indicating specific interaction of the cations with the CNCs surface. The experimental aggregation kinetics of CNCs were in very good agreement with predictions based on the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. A Hamaker constant of 3.6 × 10-20 J for the CNCs in aqueous medium was derived, for the first time, from the colloidal stability curves with monovalent salts. This value is consistent with a previous value determined by direct force measurements for cellulose surfaces in aqueous solutions. For the divalent salts (MgCl2, CaCl2, and BaCl2), the CCC values followed the order Mg2+ > Ca2+ > Ba2+, which is in the reverse order of the counterion ionic size. For the trivalent salts (LaCl3, AlCl3, and FeCl3), the CNCs suspension was destabilized much more effectively. The observed complex stability curves with AlCl3 and FeCl3 are attributed to charge neutralization and charge reversal imparted by the adsorption of aluminum and ferric hydrolysis species on the CNC surface. The significant charge reversal induced by the ferric hydrolysis species led to the restabilization of suspensions. Our results on the colloidal stability of CNCs are of central importance to the nanotechnology and materials science communities working on various applications of CNCs.
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Homoaggregation and heteroaggregation involving amidine and sulfate latex particles in the presence of the anionic surfactant octyl sulfate (OS) is studied by light scattering. This surfactant causes a charge reversal of the amidine particles. This reversal induces a rapid homoaggregation near the charge reversal point. In the presence of the same surfactant, the sulfate particles remain negatively charged and stable. The heteroaggregation process is probed in mixed suspensions of amidine and sulfate latex particles with multi-angle time-resolved dynamic light scattering. This technique allows differentiating between the contributions of homoaggregation and heteroaggregation, and permits to measure the heteroaggregation rate. By optimally choosing the sizes of the particles, one can optimize the contrast and extract heteroaggregation stability ratio over a wide range. The heteroaggregation rate is fast at low OS concentrations, where the two particles are oppositely charged. This rate slows down at higher OS concentrations due to double layer repulsion between the negatively charged particles. However, the onset of this slow heteroaggregation occurs at lower OS concentrations than for homoaggregation. The reason for this shift is that the double layer repulsion between two OS-decorated amidine particles is weaker than between one sulfate particle and one OS-decorated amidine particle. These measurements compare favorably with calculations with the theory by Derjaguin, Landau, Verwey, and Overbeek (DLVO). These calculations suggest that constant potential boundary conditions are more appropriate than the ones of constant charge. In the system studied, the present light scattering technique permits to extract heteroaggregation stability ratios over almost three orders of magnitude. This study is the first of its kind, where such a large range is being probed.
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Electrophoretic mobility and time resolved light scattering are used to measure the effect on charging and aggregation of amidine and sulfate latex particles of different oxyanions namely, phosphate, arsenate, sulfate, and selenate. In the case of negatively charged sulfate latex particles oxyanions represent the coions, while they represent counterions in the case of the positively charged amidine latex. Repulsive interaction between the sulfate latex surface and the coions results in weak ion specific effects on the charging and aggregation. On the other hand the interaction of oxyanions with the amidine latex surface is highly specific. The monovalent dihydrogen phosphate ion strongly adsorbs to the positively charged surface and reverses the charge of the particle. This charge reversal leads also to the restabilization of the amidine latex suspension at the intermediate phosphate concentrations. In the case of dihydrogen arsenate the adsorption to amidine latex surface is weaker and no charge reversal and restabilization occurs. Similar differences are seen between the sulfate and selenate analogues, where selenate adsorbs more strongly to the surface as compared to the sulfate ion and invokes charge reversal. The present results indicate that ion specificity is much more pronounced in the case of counterions.