Experimental and numerical iInvestigations of effects of silica colloids on transport of strontium in saturated sand columns

Transport experiments with strontium were conducted using saturated sand columns in the presence and absence of silica colloids, and numerical modeling was performed with modeling results compared to experimental data. The experiments were aimed at testing the hypothesis that under certain chemical conditions colloids act as movement-retarding agents and yield a larger effective retardation factor for the migrating contaminant. Four individual experiments were conducted to identify conditions where the mobility of silica colloids is increased or decreased, and a similar set was conducted for strontium transport in the absence of colloids. Mobility of colloids was found to increase with decreasing ionic strength and increasing pH, with the ionic strength having the more significant impact. The reverse effect was obtained for strontium. Based on these results, two additional experiments were conducted where both colloids and strontium were injected at the column inlet. Results showed that under certain conditions of ionic strength and pH (I = 3.0 x 10(-2) M and pH = 4-5.4) colloids retarded the movement of strontium. The retardation effect was obtained in two experiments under slightly modified conditions, which confirms the role of colloids as retarding agents. Afinite difference numerical model was used to (a) simulate mobile breakthrough curves and compare to experimental data and (b) estimate the model parameters describing cotransport of strontium and colloids. The model accurately predicted arrival time and the overall shape of the breakthrough curves.     

Enhanced transport of colloidal oil droplets in saturated and unsaturated sand columns

Colloidal-sized triacylglycerol droplets demonstrated enhanced transport compared to ideal latex colloid spheres in both saturated and unsaturated quartz sand columns. Oil droplets (mean diameter 0.74 ± 0.03 μm, density 0.92 g cm(-3), ζ-potential -34 ± 1 mV) were injected simultaneously with latex microsphere colloids (FluoSpheres; density 1.055 g cm(-3), diameters 0.02, 0.2, and 1.0 μm, ζ-potentials -16 ± 1, -30 ± 2, and -49 ± 1, respectively) and bromide into natural quartz sand (ζ-potential -63 ± 2 mV) via short-pulse column breakthrough experiments. Tests were conducted under both saturated and unsaturated conditions. Breakthrough of oil droplets preceded bromide and FluoSpheres. Recovery of oil droplets was 20% greater than similarly sized FluoSpheres in the saturated column, and 16% greater in the 0.18 ± 0.01 volumetric water content (VWC) unsaturated column. Higher variability was observed in the 0.14 ± 0.01 VWC column experiments with oil droplet recovery only slightly greater than similarly sized FluoSpheres. The research presents for the first time the direct comparison of colloidal oil droplet transport in porous media with that of other colloids, and demonstrates transport under unsaturated conditions. Based on experimental results and theoretical analyses, we discuss possible mechanisms that lead to the observed enhanced mobility of oil droplets compared to FluoSpheres with similar size and electrostatic properties.     

Humic acid facilitates the transport of ARS-labeled hydroxyapatite nanoparticles in iron oxyhydroxide-coated sand

Hydroxyapatite nanoparticles (nHAP) have been widely used to remediate soil and wastewater contaminated with metals and radionuclides. However, our understanding of nHAP transport and fate is limited in natural environments that exhibit significant variability in solid and solution chemistry. The transport and retention kinetics of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated packed columns that encompassed a range of humic acid concentrations (HA, 0-10 mg L(-1)), fractional surface coverage of iron oxyhydroxide coatings on sand grains (λ, 0-0.75), and pH (6.0-10.5). HA was found to have a marked effect on the electrokinetic properties of ARS-nHAP, and on the transport and retention of ARS-nHAP in granular media. The transport of ARS-nHAP was found to increase with increasing HA concentration because of enhanced colloidal stability and the reduced aggregate size. When HA = 10 mg L(-1), greater ARS-nHAP attachment occurred with increasing λ because of increased electrostatic attraction between negatively charged nanoparticles and positively charged iron oxyhydroxides, although alkaline conditions (pH 8.0 and 10.5) reversed the surface charge of the iron oxyhydroxides and therefore decreased deposition. The retention profiles of ARS-nHAP exhibited a hyperexponential shape for all test conditions, suggesting some unfavorable attachment conditions. Retarded breakthrough curves occurred in sands with iron oxyhydroxide coatings because of time-dependent occupation of favorable deposition sites. Consideration of the above effects is necessary to improve remediation efficiency of nHAP for metals and actinides in soils and subsurface environments.     

TiO2/PAN碳化纳米纤维膜的制备及其对腐殖酸的降解效果

以丙烯腈为原料自制聚丙烯腈(PAN)粉末,静电纺丝法制备PAN纳米纤维,采用溶胶-凝胶法负载TiO2,制备TiO2/PAN碳化纳米纤维膜.通过SEM、DG-DTG及元素分析等方法对纳米纤维进行表征.研究结果表明,用PAN质量分数为3%的纺丝液进行静电纺丝,在预氧化温度280℃及碳化温度550℃条件下可制得直径100～1...     

Optimization of nano- and microiron transport through sand columns using polyelectrolyte mixtures

Sand-packed columns were used to study the transport of micro- and nanoiron particle suspensions modified with anionic polyelectrolytes. With microscale carbonyl iron powder (CIP), the profiles of initial and eluted particle diameters were compared with simulations based on classical filtration theory (CFT), using both the Tufenkji-Elimelech (TE) and Rajagopalan-Tien (RT) models. With particle size distributions that peaked in the submicron range, there was reasonable agreement between both models and the eluted distributions. With distributions that peaked in the 1.5 mirom range, however, the eluted distributions were narrower and shifted to a smaller particle size than predicted by CFT. Apparent sticking coefficients depended on column length and flow rate, and the profile of retained iron in the columns did not follow the log-linearform expected from CFT. These observations could be rationalized in terms of the secondary energy minimum model recently proposed by Tufenkji and Elimelech (Langmuir 2005, 21, 841). For microiron, sticking coefficients correlated well with particle zeta potentials and polyacrylate (PAA) concentration. With nanoscale iron particles, there was no apparent correlation between filtration length and total electrolyte concentration. However, mixtures of PAA with poly (4-styrenesulfonate) and bentonite clay significantly enhanced nanoiron transport, possibly by affecting the aggregation of the particles.     

Role of the air-water interface in the retention of TiO2 nanoparticles in porous media during primary drainage

The increasing use of nanomaterials in commercial products has resulted in increased concerns about their potential environmental impacts. The overall mobility of nanomaterials in the environment may depend in part on their mobility in the unsaturated zone of the subsurface, which may provide a sink for nanomaterials, preventing their spread, or a long-term contaminant source. The objective of this work was to study the dynamic unsaturated transport of titanium dioxide (TiO2) during primary drainage to examine the role of air-water interface formation on nanomaterial retention. A specialized automated system was used to track depletion of TiO2 in the pore solution of a porous medium during dynamic drainage, while simultaneously measuring capillary pressure (Pc) and saturation (S). A continuous mass balance was used to calculate the mass of retained TiO2 nanoparticles. Experiments were specifically designed to minimize TiO2 interactions with solid surfaces to allow direct assessment of the role of the air-water interface. Results indicate that the mass of retained TiO2 increases as saturation decreases at all drainage rates, with slower drainage rates corresponding to greater retention at a given saturation. Normalizing the retained mass (M) bythe measured air-water interfacial area (A) shows near-constant M/A values at high saturations (S > 0.4) and increasing M/A values with decreasing saturation as saturation drops below 0.4. This result may indicate air-water interfacial adsorption at high saturations, with increasing contributions from film straining at lower saturations.     

Ionic strength and composition affect the mobility of surface-modified Fe0 nanoparticles in water-saturated sand columns

The surfaces of nanoscale zerovalent iron (NZVI) used for groundwater remediation must be modified to be mobile in the subsurface for emplacement. Adsorbed polymers and surfactants can electrostatically, sterically, or electrosterically stabilize nanoparticle suspensions in water, but their efficacy will depend on groundwater ionic strength and cation type as well as physical and chemical heterogeneities of the aquifer material. Here, the effect of ionic strength and cation type on the mobility of bare, polymer-, and surfactant-modified NZVI is evaluated in water-saturated sand columns at low particle concentrations where filtration theory is applicable. NZVI surface modifiers include a high molecular weight (MW) (125 kg/mol) poly(methacrylic acid)-b-(methyl methacrylate)-b-(styrene sulfonate) triblock copolymer (PMAA-PMMA-PSS), polyaspartate which is a low MW (2-3 kg/mol) biopolymer, and the surfactant sodium dodecyl benzene sulfonate (SDBS, MW = 348.5 g/mol). Bare NZVI with an apparent zeta-potential of -30 +/- 3 mV was immobile. Polyaspartate-modified nanoiron (MRNIP) with an apparent zeta-potential of -39 +/- 1 mV was mobile at low ionic strengths (< 40 mM for Na+ and < 0.5 mM for Ca2+), and had a critical deposition concentration (CDC) of approximately 770 mM Na+ and approximately 4 mM for Ca2+. SDBS-modified NZVI with a similar apparent zeta-potential (-38.3 +/- 0.9 mV) showed similar behavior (CDC approximately 350 mM for Na+ and approximately 3.5 mM for Ca2+). Triblock copolymer-modified NZVI had the highest apparent zeta-potential (-50 +/- 1.2 mV), the greatest mobility in porous media, and a CDC of approximately 4 M for Na+ and approximately 100s of mM for Ca2+. The high mobility and CDC is attributed to the electrosteric stabilization afforded by the triblock copolymer but not the other modifiers which provide primarily electrostatic stabilization. Thus, electrosteric stabilization provides the best resistance to changing electrolyte conditions likely to be encountered in real groundwater aquifers, and may provide transport distances of 10s to 100s of meters in unconsolidated sandy aquifers at injection velocities used for emplacement.     

Virus retention and transport in chemically heterogeneous porous media under saturated and unsaturated flow conditions

Retention and transport of colloids and microorganisms are complex processes, especially in the vadose zone due to the more complicated water flow regime and additional interfacial reactions involved. In this study, we examined the retention and transport behavior of two bacteriophages, MS-2 and phiX174, in homogeneous and chemically heterogeneous media under variably saturated conditions. Column experiments with glass beads (treated to have either hydrophilic or hydrophobic surface properties) were conducted using a phosphate-buffered saline solution at different pore water ionic strengths ranging from 0.025 to 0.163 M. In columns packed with 100% hydrophilic glass beads, retention of the viruses increased with decreasing water content and increasing ionic strength, a result similar to those reported in the literature. However, greater retention of both MS-2 and phiX174 was observed in saturated columns than in unsaturated columns packed with a 1:1 mixture of hydrophilic and hydrophobic glass beads, especially at high ionic strengths. This result contradicts the common belief that viruses (and colloids in general) are subject to greater removal in unsaturated media. Our study suggests that while the mechanisms controlling colloid interfacial interactions (i.e., attachment on solid-water and air-water interfaces and film straining) on the pore scale are relevant, nonuniform wetting conditions due to heterogeneous grain surface hydrophobicity can strongly influence water flow and phase interconnection. Under these conditions, hydrodynamic effects on the mesopore scale will dominate pore-scale interfacial reactions in controlling the extent of colloid retention and movement in unsaturated media.     

Solubility and batch retention of CeO2 nanoparticles in soils

There is a paucity of information on the environmental fate of cerium oxide nanoparticles (CeO2 NPs) for terrestrial systems that may be exposed to CeO2 NPs by the application of biosolids derived from wastewater treatment systems. Using ultrafiltration (UF), dissolution, and nonequilibrium retention (Kr) values of citrate-coated (8 nm diameter) CeO2 NPs and partitioning (Kd) values of dissolved Ce(III) and Ce(IV) were obtained in suspensions of 16 soils with a diversity of physicochemical properties. Dissolution of CeO2 NPs studied in solutions was only significant at pH 4 and was less than 3.1%, whereas no dissolved Ce was detected in soils spiked with CeO2 NPs. Kr values of CeO2 NP were low (median Kr=9.6 L kg(-1)) relative to Kd values of dissolved CeIII and CeIV (median Kd=3763 and 1808 L kg(-1), respectively), suggesting low CeO2 NP retention in soils. Surface adsorption of phosphate to CeO2 NP caused a negative zeta potential, which may explain the negative correlation of log Kr values with dissolved phosphate concentrations and the significant reduction of Kr values upon addition of phosphate to soils. The positive correlation of Kr values with clay content suggested heterocoagulation of CeO2 NPs with natural colloids in soils. Co-addition of CeO2 NPs with biosolids, on the other hand, did not affect retention.     

Effects of phosphate on the transport of Escherichia coli O157:H7 in saturated quartz sand

Consumption of groundwater contaminated with E. coli O157:H7 has led to several waterborne disease outbreaks over the past decade. A thorough understanding of the transport of E. coli O157:H7 within the soil-groundwater system is critical to the protection of public health. Although phosphate is ubiquitous in the natural environment, the influence of phosphate on the transport of E. coli O157:H7 in the groundwater system remains unknown. In this research, we performed column transport experiments to evaluate the effect of phosphate on the transport of E. coli O157:H7 cells within saturated sand. The pH of the solutions was maintained at 7.2, the ionic strength varied from 10 to 100 mM, and the phosphate concentration ranged from 0 to 1 mM. Our results show that (1) phosphate could enhance the transport of E. coli O157:H7 cells under both ionic strength conditions; (2) E. coli O157:H7 displayed lower retention in sand under higher ionic strength conditions; (3) increased phosphate in the mobile aqueous phase led to the release of previously immobilized E. coli O157:H7 cells. The response of E. coli O157:H7 cells to variations in phosphate concentrations and ionic strength conditions are explained using the extended DLVO (XDLVO) theory and the steric repulsion caused by extracellular macromolecules. In summary, our results suggest that phosphate could widen the spread of E. coli O157:H7 cells, and potentially other types of bacterial cells, within the soil-groundwater system.     

Transport of fullerene nanoparticles (nC60) in saturated sand and sandy soil: controlling factors and modeling

Understanding subsurface transport of fullerene nanoparticles (nC(60)) is of critical importance for the benign use and risk management of C(60). We examined the effects of several important environmental factors on nC(60) transport in saturated porous media. Decreasing flow velocity from approximately 10 to 1 m/d had little effect on nC(60) transport in Ottawa sand (mainly pure quartz), but significantly inhibited the transport in Lula soil (a sandy, low-organic-matter soil). The difference was attributable to the smaller grain size, more irregular and rougher shape, and greater heterogeneity of Lula soil. Increasing ionic strength and switching background solution from NaCl to CaCl(2) enhanced the deposition of nC(60) in both sand and soil columns, but the effects were more significant for soil. This was likely because the clay minerals (and possibly soil organic matter) in soil responded to changes of ionic strength and species differently than quartz. Anions in the mobile phase had little effect on nC(60) transport, and fulvic acid in the mobile phase (5.0 mg/L) had a small effect in the presence of 0.5 mM Ca(2+). A two-site transport model that takes into account both the blocking-affected attachment process and straining effects can effectively model the breakthrough of nC(60).     

Retention and transport of silica nanoparticles in saturated porous media: effect of concentration and particle size

Investigations on factors that affect the fate and transport of nanoparticles (NPs) remain incomplete to date. In the present study, we conducted column experiments using 8 and 52 nm silica NPs to examine the effects of NPs' concentration and size on their retention and transport in saturated porous media. Results showed that higher particle number concentration led to lower relative retention and greater surface coverage. Smaller NPs resulted in higher relative retention and lower surface coverage. Meanwhile, evaluation of size effect based on mass concentration (mg/L) vs particle number concentration (particles/mL) led to different conclusions. A set of equations for surface coverage calculation was developed and applied to explain the different results related to the size effects when a given mass concentration (mg/L) and a given particle number concentration were used. In addition, we found that the retained 8 nm NPs were released upon lowered solution ionic strength, contrary to the prediction by the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The study herein highlights the importance of NPs' concentration and size on their behavior in porous media. To the best of our knowledge, it is the first report of an improved equation for surface coverage calculation using column breakthrough data.     

Specific UV absorbance of Aldrich humic acid: changes during transport in aquifer sediment

This study examined the transport behavior of Aldrich humic acid (AHA) in low natural organic carbon content sediment contaminated with tetrachloroethene (PCE), for comparison to a nonionic surfactant mixture previously examined in the same system. Tracking of individual molecular weight (MW) fractions of AHA was attempted by UV absorbance, followed by conversion to mass of carbon using specific ultraviolet absorbance (SUVA) (UV absorbance per mass of carbon) measurements. The analysis required determination of variations of SUVA with MW, which showed a maximum at 10 000 Daltons. Furthermore, SUVAs of AHA MW fractions greater than about 10 000 Daltons increased following AHA interaction with sediment in batch experiments, and this was associated with AHA-driven leaching of cations from the sediment. AHA transport was examined in a series of three columns representing the up-gradient, residual-zone, and down-gradient portions of a DNAPL contaminated site. SUVAs of larger MW AHA fractions cycled through decreased, increased, and eventual return to influent values during the early, intermediate, and final stages of breakthrough, respectively. These variations were attributable to a combination of preferential adsorption of low MW fractions of the AHA during early breakthrough and AHA-driven leaching of sediment cations during intermediate breakthrough, with eventual exhaustion of sediment cation complexation during the final stage of breakthrough. The complex variations in SUVA precluded accurate conversion of measured UV absorbance to carbon mass. However, the effect of AHA loss to sediment on the solubilizing capacity of the AHA solution was indicated by the breakthrough behavior of AHA-solubilized PCE, which showed that AHA loss from the aqueous phase during transport in this system did not decrease the solubilizing capacity of the AHA mixture.     

Disaggregation kinetics of a peat humic acid: mechanism and pH effects

Fluorescence correlation spectroscopy was used to study the disaggregation kinetics of a peat humic acid (PPHA) at several pH. FCS measures diffusion coefficients of fluorescent molecules and aggregates, thus allowing for the determination of disaggregation rates with a temporal resolution of seconds to minutes. Disaggregation was initiated by dilution of a peat concentrate consisting of a mixture containing 80% large aggregates (average hydrodynamic radius, rH, of about 300 nm) and free monomers (average rH of about 1 nm). Upon dilution at different pH values, aggregate size decreased, and the proportion of free monomers in solution increased until complete disaggregation occurred. The mechanism appeared to involve the release of monomers from the surface of the aggregates. The pH markedly affected the disaggregation rate. Complete disaggregation took 1 month at pH 3.6, took less than 1 h at pH 5.6, and was extremely rapid in alkaline solutions. The results suggested that at least two processes were operating in parallel with the overall rate being the sum of both processes. At pH higher than 4.5, the disaggregation rate increased more than 3 orders of magnitude per pH unit increase. For concentrations lower than 30 mg L(-1), the equilibrium condition for the PPHA was complete disaggregation even for a pH as low as 3.6.     

Mobility of functionalized quantum dots and a model polystyrene nanoparticle in saturated quartz sand and loamy sand

Quantum dots (QDs) are one example of engineered nanoparticles (ENPs) with demonstrated toxic effects. Yet, little is known about the behavior of QDs in the natural environment. This study assessed the transport of two commercial carboxylated QDs (CdTe and CdSe) and carboxylated polystyrene latex (nPL) as a model nanoparticle using saturated laboratory-scale columns. The influence of solution ionic strength (IS) and cation type (K(+) or Ca(2+)) on the transport potential of these ENPs was examined in two granular matrices - quartz sand and loamy sand. The retention of all three particles was generally low in the quartz sand columns within the range of studied IS (0.1-100 mM) for the monovalent salt (KCl). In contrast, the retention of the three ENPs in the quartz sand was significant in the presence of 10 mM Ca(2+). Moreover, ENP attachment efficiencies (α) were enhanced by at least 1 order of magnitude in columns packed with loamy sand (for IS between 0.1-10 mM KCl). Although all three ENPs used here are carboxylated, they differ in the type of surface coating (e.g., choice of polymers or polyelectrolytes). Regardless of the surface coatings, the three ENPs exhibit comparable mobility in the quartz sand. However, the ENPs demonstrate variable transport potential in loamy sand suggesting that differences in the binding affinities of surface-modified ENPs for specific soil constituents can play a key role in the fate of ENPs in soils.     

Study on the effects of humic and fulvic acids on quantum dot nanoparticles using capillary electrophoresis with laser-induced fluorescence detection

The increasing production and use of quantum dot (QD) nanoparticles have caused concerns on the possibility of contaminating the aquatic and terrestrial ecosystems with wastes that may contain QDs. Therefore, studies on the behavior of QDs upon interaction with components of the natural environment have become of interest. This study investigated the fluorescence and electrophoretic mobility of carboxylic or amine polyethylene glycol (PEG)-functionalized CdSe/ZnS QDs in the presence of two aquatic humic substances (HS), Suwannee River humic and fulvic acids, using capillary electrophoresis with laser-induced fluorescence detection. Results showed initial enhancement in fluorescence of QDs at the onset of the interaction with HS, followed by fluorescence quenching at longer exposure with HS (>30 min). It was also observed that the electrophoretic mobility of QDs increases with increasing concentration of HS, suggesting an increase in the ratio in charge to hydrodynamic size of the nanoparticles. To determine if the QDs degraded upon interaction with HS, the QD-HS mixtures were dialyzed to separate free Cd2+ from intact QDs, followed by analysis of the solutions using inductively coupled plasma-mass spectrometry. Results suggested that degradation of QDs in the presence of HS did not occur within the period of incubation.     

Effects of humic substances on precipitation and aggregation of zinc sulfide nanoparticles

Nanoparticulate metal sulfides such as ZnS can influence the transport and bioavailability of pollutant metals in anaerobic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences the stability of zinc sulfide nanoparticles as they nucleate and aggregate in water with dissolved NOM. We compared NOM fractions that were isolated from several surface waters and represented a range of characteristics including molecular weight, type of carbon, and ligand density. Dynamic light scattering was employed to monitor the growth and aggregation of Zn-S-NOM nanoparticles in supersaturated solutions containing dissolved aquatic humic substances. The NOM was observed to reduce particle growth rates, depending on solution variables such as type and concentration of NOM, monovalent electrolyte concentration, and pH. The rates of growth increased with increasing ionic strength, indicating that observed growth rates primarily represented aggregation of charged Zn-S-NOM particles. Furthermore, the observed rates decreased with increasing molecular weight and aromatic content of the NOM fractions, while carboxylate and reduced sulfur content had little effect. Differences between NOM were likely due to properties that increased electrosteric hindrances for aggregation. Overall, results of this study suggest that the composition and source of NOM are key factors that contribute to the stabilization and persistence of zinc sulfide nanoparticles in the aquatic environment.     

用壳聚糖/纳米TiO2对毛针织物进行功能性整理

文章应用壳聚糖/纳米TiO2和固化剂形成的溶液对羊毛针织物进行功能性整理,对壳聚糖和纳米TiO2在羊毛上的吸附率、染色性能、织物上染率和固色率以及抗菌性等进行了测试.经过整理的羊毛织物,既可达到防缩可机洗的效果,又具有抗菌性能,其染色性能也得到了提高.