Ishai Dror

Transport of metal oxide nanoparticles in saturated porous media

The behavior of four types of untreated metal oxide nanoparticles in saturated porous media was studied. The transport of Fe(3)O(4), TiO(2), CuO, and ZnO was measured in a series of column experiments. Vertical columns were packed with uniform, spherical glass beads. The particles were introduced as a pulse suspended in aqueous solutions and breakthrough curves at the outlet were measured using UV-vis spectrometry. Different factors affecting the mobility of the nanoparticles such as ionic strength, addition of organic matter (humic acid), flow rate and pH were investigated. The experiments showed that mobility varies strongly among the nanoparticles, with TiO(2) demonstrating the highest mobility. The mobility is also strongly affected by the experimental conditions. Increasing the ionic strength enhances the deposition of the nanoparticles. On the other hand, addition of humic acid increases the nanoparticle mobility significantly. Lower flow rates again led to reduced mobility, while changes in pH had little effect. Overall, in natural systems, it is expected that the presence of humic acid in soil and aquifer materials, and the ionic strength of the resident water, will be key factors determining nanoparticle mobility.

Transport of silver nanoparticles (AgNPs) in soil.

The effect of soil properties on the transport of silver nanoparticles (AgNPs) was studied in a set of laboratory column experiments, using different combinations of size fractions of a Mediterranean sandy clay soil. The AgNPs with average size of ~30nm yielded a stable suspension in water with zeta potential of -39mV. Early breakthrough of AgNPs in soil was observed in column transport experiments. AgNPs were found to have high mobility in soil with outlet relative concentrations ranging from 30% to 70%, depending on experimental conditions. AgNP mobility through the column decreased when the fraction of smaller soil aggregates was larger. The early breakthrough pattern was not observed for AgNPs in pure quartz columns nor for bromide tracer in soil columns, suggesting that early breakthrough is related to the nature of AgNP transport in natural soils. Micro-CT and image analysis used to investigate structural features of the soil, suggest that soil aggregate size strongly affects AgNP transport in natural soil. The retention of AgNPs in the soil column was reduced when humic acid was added to the leaching solution, while a lower flow rate (Darcy velocity of 0.17cm/min versus 0.66cm/min) resulted in higher retention of AgNPs in the soil. When soil residual chloride was exchanged by nitrate prior to column experiments, significantly improved mobility of AgNPs was observed in the soil column. These findings point to the importance of AgNP-soil chemical interactions as a retention mechanism, and demonstrate the need to employ natural soils rather than glass beads or quartz in representative experimental investigations.

Effects of metal oxide nanoparticles on soil properties.

In recent years the behavior and properties of nanoparticles released to the environment have been studied extensively to better assess the potential consequences of their broad use in commercial products. The fate, transport and mobility of nanoparticles in soil were shown to be strongly dependent on environmental conditions. However, little is known about the possible effects of nanoparticles on soil chemical, physical and biological properties. In this study, two types of metal oxide nanoparticles, CuO and Fe(3)O(4) were mixed into two types of soil and the effects of the nanoparticles on various soil properties were assessed. Metal oxide nanoparticles were shown previously to catalyze the oxidation of organic pollutants in aqueous suspensions, and they were therefore expected to induce changes in the organic material in the soil, especially upon addition of an oxidant. It was found that the nanoparticles did not change the total amount of organic materials in the soil or the total organic carbon in the soil extract; however, three-dimensional fluorescence spectroscopy demonstrated changes in humic substances. The nanoparticles also affected the soil bacterial community composition, based on denaturing gradient gel electrophoresis (DGGE) fingerprinting, but had little impact on the macroscopic properties of the soil.

Effect of Metal Oxide Nanoparticles on Microbial Community Structure and Function in Two Different Soil Types

Increased availability of nanoparticle-based products will, inevitably, expose the environment to these materials. Engineered nanoparticles (ENPs) may thus find their way into the soil environment via wastewater, dumpsters and other anthropogenic sources; metallic oxide nanoparticles comprise one group of ENPs that could potentially be hazardous for the environment. Because the soil bacterial community is a major service provider for the ecosystem and humankind, it is critical to study the effects of ENP exposure on soil bacteria. These effects were evaluated by measuring bacterial community activity, composition and size following exposure to copper oxide (CuO) and magnetite (Fe3O4) nanosized (<50 nm) particles. Two different soil types were examined: a sandy loam (Bet-Dagan) and a sandy clay loam (Yatir), under two ENP concentrations (1%, 0.1%). Results indicate that the bacterial community in Bet-Dagan soil was more susceptible to change due to exposure to these ENPs, relative to Yatir soil. More specifically, CuO had a strong effect on bacterial hydrolytic activity, oxidative potential, community composition and size in Bet-Dagan soil. Few effects were noted in the Yatir soil, although 1% CuO exposure did cause a significant decreased oxidative potential and changes to community composition. Fe3O4 changed the hydrolytic activity and bacterial community composition in Bet-Dagan soil but did not affect the Yatir soil bacterial community. Furthermore, in Bet-Dagan soil, abundance of bacteria annotated to OTUs from the Bacilli class decreased after addition of 0.1% CuO but increased with 1% CuO, while in Yatir soil their abundance was reduced with 1% CuO. Other important soil bacterial groups, including Rhizobiales and Sphingobacteriaceae, were negatively affected by CuO addition to soil. These results indicate that both ENPs are potentially harmful to soil environments. Furthermore, it is suggested that the clay fraction and organic matter in different soils interact with the ENPs and reduce their toxicity.

Catalytic Transformation of Persistent Contaminants Using a New Composite Material Based on Nanosized Zero-Valent Iron

A new composite material based on deposition of nanosized zerovalent iron (nZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented, for catalytic transformation of organic contaminants in water. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with nZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nZVI by preventing agglomeration of iron nanoparticles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material resulting in faster rates of remediation. The composite material rapidly degrades or transforms completely a large spectrum of water contaminants, including halogenated solvents like TCE, PCE, and cis-DCE, pesticides like alachlor, atrazine and bromacyl, and common ions like nitrate, within minutes to hours. A field experiment where contaminated groundwater containing a mixture of industrial and agricultural persistent pollutants was conducted together with a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions.

Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils.

The transport and fate of the pharmaceutical carbamazepine (CBZ) were investigated in the Dan Region Reclamation Project (SHAFDAN), Tel-Aviv, Israel. Soil samples were taken from seven subsections of soil profiles (150 cm) in infiltration basins of a soil aquifer treatment (SAT) system. The transport characteristics were studied from the release dynamics of soil-resident CBZ and, subsequently, from applying a pulse input of wastewater containing CBZ. In addition, a monitoring study was performed to evaluate the fate of CBZ after the SAT. Results of this study indicate adsorption, and consequently retardation, in CBZ transport through the top soil layer (0-5 cm) and to a lesser extent in the second layer (5-25 cm), but not in deeper soil layers (25-150 cm). The soluble and adsorbed fractions of CBZ obtained from the two upper soil layers comprised 45% of the total CBZ content in the entire soil profile. This behavior correlated to the higher organic matter content observed in the upper soil layers (0-25 cm). It is therefore deduced that when accounting for the full flow path of CBZ through the vadose zone to the groundwater region, the overall transport of CBZ in the SAT system is essentially conservative. The monitoring study revealed that the average concentration of CBZ decreased from 1094 ± 166 ng L⁻¹ in the recharged wastewater to 560 ± 175 ng L⁻¹ after the SAT. This reduction is explained by dilution of the recharged wastewater with resident groundwater, which may occur as it flows to active reclamation wells.

Laboratory experiments on dispersive transport across interfaces: The role of flow direction

We present experimental evidence of asymmetrical dispersive transport of a conservative tracer across interfaces between different porous materials. Breakthrough curves are measured for tracer pulses that migrate in a steady state flow field through a column that contains adjacent segments of coarse and fine porous media. The breakthrough curves show significant differences in behavior, with tracers migrating from fine medium to coarse medium arriving significantly faster than those from coarse medium to fine medium. As the flow rate increases, the differences between the breakthrough curves diminish. We argue that this behavior indicates the occurrence of significant, time-dependent tracer accumulation in the resident concentration profile across the heterogeneity interface. Conventional modeling using the advection-dispersion equation is demonstrated to be unable to capture this asymmetric behavior. However, tracer accumulation at the interface has been observed in particle-tracking simulations, which may be related to the asymmetry in the observed breakthrough curves.

Enrofloxacin oxidative degradation facilitated by metal oxide nanoparticles

The activity of copper oxide, titanium carbide and silicon nitride nanoparticles for the oxidative degradation of environmentally relevant concentrations (μg L(-1) range) of enrofloxacin - an important veterinary antibiotic drug - in aqueous solutions was investigated. With hydrogen peroxide as an oxidative agent, both copper oxide and titanium carbide decrease the concentration of enrofloxacin by more than 90% over 12 h. Addition of sodium halide salts strongly increases the reaction rate of copper oxide nanoparticles. The mechanism for the formation of Reactive Oxygen Species (ROS) was investigated by Electron Spin Resonance (ESR).

Experimental and modeling analysis of coupled non-Fickian transport and sorption in natural soils.

We present experimental breakthrough curve (BTC) data and a modeling investigation of conservative and sorbing tracer transport in natural soils. By analyzing the data using the continuous time random walk (CTRW) model, we probe the traditional approach of using conservative tracer model parameters as a basis for quantifying the transport of sorbing solutes in the same domain when non-Fickian transport is present. Many known contaminants in groundwater are sorbed to the host solid porous medium, to varying extents, while being transported; this enhances the long tailing of BTCs which often already occurs because of the inherent non-Fickian nature of the transport. The CTRW framework has been shown to account very well for non-Fickian conservative (nonsorbing) transport. Here, we examine two BTC data sets in laboratory columns packed with natural soils; the first (previously analyzed by Mao and Ren (2004)) comprises transport of (conservative) bromide and (sorbing) atrazine tracers, while the second presents new data with bromide and tribromoneopentyl alcohol (TBNPA), a key flame retardant, as a sorbing solute. TBNPA has received little attention in the past, and is shown to be sorbed onto Bet Dagan soil in a nonlinear manner. We find that the transport behavior of bromide is non-Fickian in all cases, which is caused by the heterogeneity of the soil. Comparative model analysis of the non-Fickian BTCs of the conservative, and sorbing tracers and examination of the fitting parameters, exemplify the coupling between transport and adsorption/desorption processes. The difference in transport parameters used to match the conservative and sorbing data sets shows that conservative tracer parameters (average velocity and dispersion coefficient) are not valid for the transport of reactive tracers.

Effects of air injection on flow through porous media: Observations and analyses of laboratory-scale processes

(1) The effects of air injection on flow through porous media were explored in a series of 1-m and 2-m laboratory flow cells. Our motivation was to examine air barriers as an alternative to hydraulic barriers to inhibit saline intrusion in coastal areas. Steady flow conditions were created in homogeneous and heterogeneous unconsolidated sand systems. Dry air was injected at progressively higher flow rates through a well in the center of each flow cell. Discharge and NaCltracer breakthrough data were measured at the outflow reservoir of each cell. In addition, a dye tracer was used to visualize the flow patterns. In all cases, air injection was found to produce stable, low-conductivity barriers that reduced discharge by an order of magnitude or more. Effective hydraulic conductivity values determined from discharge and hydraulic head data showed exponential declines with increased air-injection rates in all cases. Numerical simulation was used to quantify hydraulic conductivity and effective porosity values in the saturated and aerated regions created by air injection, and to study advective flow behavior. Pore-filling cement formed in the air-injection region and was analyzed to determine its composition, mass, and volume. Approximately 60% of the cement consisted of soluble minerals, and 40% was less soluble carbonates. Evaporation and increase in solution pH due to stripping of CO2 by the injected air were responsible for creating the cement. The cement occupied <10% of the pore space in the sand-cement aggregate. Both the air and mineral pore-fillings dissolved when air injection ceased, indicating that both barriers are temporary. These results serve as a preliminary proof of concept that air-injection barriers might effectively inhibit undesired subsurface flow, such as saline intrusion or contaminated groundwater. INDEX TERMS: 1829 Hydrology: Groundwater hydrology; 1832 Hydrology: Groundwater transport; 1875 Hydrology: Unsaturated zone; KEYWORDS: conductivity reduction, containment, seawater intrusion, subsurface barriers Citation: Dror, I., B. Berkowitz, and S. M. Gorelick (2004), Effects of air injection on flow through porous media: Observations and analyses of laboratory-scale processes, Water Resour. Res., 40, W09203, doi:10.1029/2003WR002960.