Contaminant mobilization from the vadose zone to groundwater during experimental river flooding events.

Natural river flooding events can mobilize contaminants from the vadose zone and lead to increased concentrations in groundwater. Characterizing the mass and transport mechanisms of contaminants released from the vadose zone to groundwater during these recharge events is particularly challenging. Therefore, conducting highly-controlled in-situ experiments that simulate natural flooding events can help increase the knowledge of where contaminants can be stored and how they can move between hydrological compartments. This study specifically targets uranium pollution, which is accompanied by high sulfate levels in the vadose zone and groundwater. Two novel experimental river flooding events were conducted that utilized added non-reactive halides (bromide and iodide) and 2,6-difluorobenzoate tracers. In both experiments, about 8 m3 of traced water from a nearby contaminant-poor river was flooded in a 3-m diameter basin and infiltrated through the vadose zone and into a contaminant-rich unconfined aquifer for an average of 10 days. The aquifer contained 13 temporary wells that were monitored for solute concentration for up to 40 days. The groundwater analysis was conducted for changes in contaminant mass using the Theissen polygon method and for transport mechanisms using temporal moments. The results indicated an increase in uranium (21 and 24%), and sulfate (24 and 25%) contaminant mass transport to groundwater from the vadose zone during both experiments. These findings confirmed that the vadose zone can store and release substantial amounts of contaminants to groundwater during flooding events. Additionally, contaminants were detected earlier than the added tracers, along with higher concentrations. These results suggested that contaminant-rich pore water in the vadose zone was transported ahead of the traced flood waters and into groundwater. During the first flooding event, elevated concentrations of contaminants were sustained, and that chloride behaved similarly. The findings implied that contaminant- and chloride-rich evaporites in the vadose zone were dissolved during the first flooding event. For the second flooding event, the data suggested that the contaminant-rich evaporites continued to dissolve whereas chloride-rich evaporites were previously flushed. Overall, these findings indicated that contaminant-rich pore water and evaporites in the vadose zone can play a significant role in contaminant transport during flooding events.

Comparison of Zn-Al and Mg-Al layered double hydroxides for adsorption of perfluorooctanoic acid.

Per-and polyfluoroalkyl substances (PFAS), a large class of synthesized chemicals, are persistent in nature and generally recalcitrant to conventional chemical and biological treatment. Adsorption is considered an economical and practical method for PFAS treatment. Layered double hydroxides (LDHs) represent a promising class of mineral-based adsorbents for PFAS removal because of the highly positive charge of their structural layers. In this research, the performance of two representative LDHs with varied cation compositions, namely Zn-Al and Mg-Al LDHs, were investigated and compared for the removal of perfluorinated carboxylic acids (PFCAs) with an emphasis on perfluorooctanoic acid (PFOA). Zn-Al LDH showed high efficiency for the removal of medium- and long-chain PFCAs (i.e., C ≥ 7), and performed consistently better than Mg-Al LDH. Based on detailed adsorption kinetics and isotherm studies toward PFOA, Zn-Al LDH showed higher adsorption capacity, stronger adsorption affinity, and faster kinetics than Mg-Al LDH. Presence of natural organic matter had minimal impact on PFOA removal by Zn-Al LDH, but sulfate severely inhibited PFOA adsorption. Combined results of aqueous adsorption experiments and sorbent characterization suggested that electrostatic interactions may be the primary mechanism for PFOA adsorption onto LDHs. Our results suggested that cation composition of LDHs can have significant effect on the performance for PFCA removal.

Removal of Arsenate and Chromate by Lanthanum-modified Granular Ceramic Material: The Critical Role of Coating Temperature.

The development of economical, low-maintenance, environmentally friendly and effective water filtration techniques can have far-reaching public health, social and economic benefits. In this research, a cost-effective La-modified granular ceramic material made of red art clay and recycled paper fiber was developed for the removal of two major anionic contaminants, As(V) (arsenate) and Cr(VI) (chromate). La modification temperature significantly impacted the resulting composition and properties of the adsorbents, and thus played a crucial role in the adsorbent performance. The La-modified ceramic materials were extensively characterized through scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area measurement, thermal gravimetric analysis (TGA), zeta potential measurements, and Fourier-transform infrared spectroscopy (FTIR) analysis. The characterization results suggested that surface coating by LaONO3-related compounds was critical for As(V) and Cr(VI) adsorption. At the modification temperature of 385 °C, the adsorption of As(V) and Cr(VI) reached maximum, which were 23 mg/g and 13 mg/g, respectively, under circumneutral conditions that are relevant to various aquatic systems. The adsorption kinetics and isotherm, the influence of pH, ionic strength and coexisting anions on As(V) and Cr(VI) adsorption were investigated to further understand both As(V) and Cr(VI) adsorption behavior. Findings from this research showed that La-modified ceramic material made of recycled paper waste represents a cost-effective adsorbent for anionic contaminant removal under environmentally relevant conditions.

Comparison of the transport of Bacteroides fragilis and Escherichia coli within saturated sand packs.

Pathogens in groundwater accounted for ∼50% of waterborne disease outbreaks in the United States between 1971 and 2006. The fast and reliable detection of groundwater microbial contamination and the identification of the contamination sources are of critical importance to the protection of public health. Recent studies suggested that fecal anaerobe Bacteriodes spp. could be employed as an effective tool for surface water microbial source tracking (MST). The usefulness of Bacteroides spp. for groundwater MST depends strongly on its mobility within the subsurface system. This research provides laboratory results comparing transport and attachment of E. coli K12 and B. fragilis within packed quartz sands. The results indicate that at low ionic strengths both E. coli K12 and B. fragilis are readily transported through saturated sand packs. At higher ionic strengths such as may be found near concentrated sources of fecal contamination, B. fragilis displayed significantly higher mobility than E. coli K12. Analysis of the extended Derjaguin-Landau-Verweu-Overbeek (XDLVO) energy interactions for both types of bacteria showed a significant repulsive energy barrier exists between the sand surface and the bacteria, precluding attachment directly to the sand surface. However a secondary minimum energy level exists under higher ionic strength conditions. The depth of this energy low is greater for E. coli K12, which results in greater attachment of E. coli K12 than of B. fragilis. The high mobility of B. fragilis suggests that it represents a promising tool for the detection of groundwater fecal contamination as well as the identification of the microbial sources.

Modification of a Ca-montmorillonite with ionic liquids and its application for chromate removal.

Ionic liquids (ILs), due to their low vapor pressure, have been explored as green solvents for organic synthesis. In this study, the uptake of ILs on a high charge Ca-montmorillonite (MMT) and the use of the IL-modified MMT for the removal of anionic contaminants from water were systematically studied. Uptake of ILs by MMT was exclusively resulted from a cation exchange mechanism when the initial IL concentrations were less than the critical micelle concentration (CMC) and the sorbed ILs formed a monolayer conformation on the surface of MMT. When the initial IL concentrations were greater than the CMC, both cation exchange and hydrophobic interactions were responsible for the IL uptake. The IL molecules formed admicelles and the surface charge was reversed to positive balanced by counterion Cl(-) when the IL loading was higher than the cation exchange capacity of the mineral. The modified MMT could remove chromate from water instantaneously, with an adsorption capacity of 190 mmol/kg and a 99.5% removal efficiency at an initial chromate concentration of 2.6 mmol/L. These features could further expand the application of ILs and enable IL-modified MMT to be used as inexpensive sorbents for the removal of chromate and other oxyanions from water.

Impact of the exopolysaccharides Pel and Psl on the initial adhesion of Pseudomonas aeruginosa to sand.

In this study, the impact of the exopolysaccharides Pel and Psl on the cell surface electron donor-electron acceptor (acid-base) properties and adhesion to quartz sand was investigated by using Pseudomonas aeruginosa PAO1 and its isogenic EPS-mutant strains Δpel, Δpsl and Δpel/Δpsl. The microbial adhesion to hydrocarbon (MATH) test and titration results showed that both Pel and Psl contribute to the surface hydrophobicity of the cell. The results of contact angle measurement, however, showed no correlation with the cell surface hydrophobicity measured by the MATH test and the titration method. Packed-bed column experiments indicated that the exopolysaccharides Pel and Psl are involved in the initial cell attachment to the sand surface and the extent of their impact is dependent on the ionic strength (IS) of the solution. Overall, the Δpel/Δpsl double mutant had the lowest adhesion coefficient to sand compared with the wild-type PAO1, the Δpel mutant and the Δpsl mutant. It is hypothesized that in addition to bacterial surface hydrophobicity and DLVO forces, other factors, eg steric repulsion caused by extracellular macromolecules, and cell surface appendages (flagella and pili) also contribute significantly to the interaction between the cell surface and a sand grain.

Effects of outer membrane protein TolC on the transport of Escherichia coli within saturated quartz sands.

The outer membrane protein (OMP) TolC is the cell surface component of several drug efflux pumps that are responsible for bacterial resistance against a variety of antibiotics. In this research, we investigated the effects of OMP TolC on E. coli transport within saturated sands through column experiments using a wild-type E. coli K12 strain (with OMP TolC), as well as the corresponding transposon mutant (tolC::kan) and the markerless deletion mutant (ΔtolC). Our results showed OMP TolC could significantly enhance the transport of E. coli when the ionic strength was 20 mM NaCl or higher. The deposition rate coefficients for the wild-type E. coli strain (with OMP TolC) was usually >50% lower than those of the tolC-negative mutants. The measurements of contact angles using three probe liquids suggested that TolC altered the surface tension components of E. coli cells and lead to lower Hamaker constants for the cell-water-sand system. The interaction energy calculations using the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory suggested that the deposition of the E. coli cell primarily occurred at the secondary energy minimum. The depth of the secondary energy minimum increased with ionic strength, and was greater for the TolC-deletion strains under high ionic strength conditions. Overall, the transport behavior of three E. coli strains within saturated sands could be explained by the XDLVO calculations. Results from this research suggested that antibiotic resistant bacteria expressing OMP TolC could spread more widely within sandy aquifers.

Deposition and remobilization of graphene oxide within saturated sand packs.

In this research, we examined the deposition kinetics of graphene oxide (GO) particles within saturated sand packs as a function of ionic strength as well as the remobilization of previously retained GO particles due to chemical perturbation. The retention of GO particles within saturated quartz sand was found to be strongly dependent on ionic strength. At low ionic strength (e.g., 1 mM of NaCl), little retention of GO particles occurred. When the ionic strength was increased to 100 mM of NaCl, the retention of GO particles increased significantly but would be limited by its retention capacity. The reduction of ionic strength from 100 mM (NaCl) to 1 mM (NaCl) released ~100% of previously retained GO particles. The transport behavior of GO particles within saturated sand packs could be described by the Langmuir-type of transport model. The extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory, which considers Lifshitz-van der Waals (LW) interaction, the electrostatic double layer (EDL) interaction as well as the Lewis acid-base (AB) (i.e., hydrophobic) interaction between GO plates and the surface of quartz sand, could explain the observed trend of GO retention under various ionic strength conditions.

Influence of enterococcal surface protein (esp) on the transport of Enterococcus faecium within saturated quartz sands.

Enterococcus was selected by US EPA as a Gram-positive indicator microorganism for groundwater fecal contamination. It was recently reported that enterococcal surface protein (esp) was more prevalent in Enterococcus from human sources than in Enterococcus from nonhuman sources and esp could potentially be used as a source tracking tool for fecal contamination (Scott et al., 2005). In this research, we performed laboratory column transport experiments to investigate the transport of Enterococcus faecium within saturated quartz sands. Particularly, we used a wild type strain (E1162) and a mutant (E1162Δesp) to examine the influence of esp on the transport behavior of E. faecium. Our results showed that esp could significantly enhance the attachment of E. faecium cells onto the surface of silica sands and thus lower the mobility of E. faecium within sand packs. Cell surface properties (e.g., zeta potential) were determined and the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory was applied to explain the effects of esp on the retention of E. faecium. Overall, our results suggested that E. faecium strains with esp could display lower mobility within saturated sand packs than E. faecium strains without esp. The disparity in the transport behavior of E. faecium with and without esp could limit the effectiveness of esp as a source tracking tool within the groundwater system.

The effects of starvation on the transport of Escherichia coli in saturated porous media are dependent on pH and ionic strength.

In this research, we investigate the effects of starvation on the transport of Escherichia coli K12 in saturated porous media. Particularly, we examine the relationship between the starvation effects and the pH and ionic strength of the electrolyte solutions used for cell starvation. E. coli K12 was cultured using either Luria-Bertani Miller (LB-Miller) broth, which contained 10 g/L of NaCl, or LB-Luria broth, which contained 0.5 g/L of NaCl. As both types of broths had similar pH (~7.2) they differed in ionic strengths. The bacterial cells were harvested at late-exponential phase and resuspended in buffered (pH=7.2) and non-buffered (pH=5.7) electrolyte solutions that had ionic strengths of 8.4mM or 168 mM, respectively. Column transport experiments were performed following 4, 25 and 52 h of cell starvation to evaluate the temporal changes in cell mobility. Our results showed that starvation led to a significant increase in the mobility of E. coli K12, particularly between 4 and 25 h, when both pH and ionic strength of the electrolyte solution were different from those of the growth media. The size, viability and surface properties (e.g., zeta potential, hydrophobicity, LPS sugar content, outer membrane protein profiles) of the bacterial cells were determined and related to the observed temporal variation patterns of cell mobility. We found that starvation in electrolyte solutions that had different pH and ionic strength from the growth media significantly lowered cell viability, which may be related to the temporal change in cell mobility under these specific conditions.

Comparison of the Transport of Tetracycline-Resistant and Tetracycline-Susceptible Escherichia coli Isolated from Lake Michigan.

It was recently reported that tetracycline could enhance the mobility of manure-derived Escherichia coli within saturated porous media (Walczak et al. (Water Research 45:1681-1690, 2011)). It was also shown, however, that E. coli from various sources could display marked variation in their mobility (Bolster et al. (Journal of Environmental Quality 35:1018-1025, 2009)). The focus of this research was to examine if the observed difference in the mobility of manure-derived tetracycline-resistant (tet(R)) and tetracycline-susceptible (tet(S)) E. coli strains was source-dependent. Specifically, E. coli were isolated from Lake Michigan, and the influence of tetracycline resistance on Lake Michigan-derived E. coli was investigated through column transport experiments. Additionally, a variety of cell morphology and surface properties were determined and related to the observed bacterial transport behavior. Our experimental results showed that, consistent with previous observations, the deposition rate coefficients of the tet(R)E. coli strain was ~20-100% higher than those of the tet(S)E. coli strain. The zeta potential of the tet(R)E. coli cells was ~25 mV more negative than the tet(S)E. coli cells. Because the surfaces of the E. coli cells and the quartz sands were negatively charged, the repulsive electrostatic double-layer interaction between the tet(R)E. coli cells and the quartz sands was stronger, and the mobility of the tet(R)E. coli cells in the sand packs was thus higher. The tet(R)E. coli cells were also more hydrophilic than the tet(S)E. coli cells. Results from migration to hydrocarbon phase (MATH) tests showed that about ~35% more tet(S)E. coli cells partitioned to the hydrocarbon phase. As it was previously shown that cell hydrophobicity could enhance the attachment of bacterial cells to quartz sand, the difference in cell hydrophobicity could also have contributed to the observed higher mobility of the tet(R)E. coli cells. The size of the tet(R) and tet(S)E. coli cells were similar, suggesting that the observed difference in their mobility was not size-related. Characterization of cell surface properties also showed that tet(R) and tetS E. coli cells differed slightly in cell-bound lipopolysaccharide contents and had distinct outer membrane protein profiles. Such difference could alter cell surface properties which in turn led to changes in cell mobility.

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.

Influence of tetracycline resistance on the transport of manure-derived Escherichia coli in saturated porous media.

In this research, tetracycline resistant (tet(R)) and tetracycline susceptible (tet(S)) Escherichia coli isolates were retrieved from dairy manure and the influence of tetracycline resistance on the transport of E. coli in saturated porous media was investigated through laboratory column transport experiments. Experimental results showed that tet(R)E. coli strains had higher mobility than the tet(S) strains in saturated porous media. Measurements of cell surface properties suggested that tet(R)E. coli strains exhibited lower zeta potentials than the tet(S) strains. Because the surface of clean quartz sands is negatively charged, the repulsive electrostatic double layer (EDL) interaction between the tet(R) cells and the surface of sands was stronger and thus facilitated the transport of the tet(R) cells. Although no difference was observed in surface acidity, cell size, lipopolysaccharides (LPS) sugar content and cell-bound protein levels between the tet(R) and tet(S) strains, they displayed distinct outer membrane protein (OMP) profiles. It was likely that the difference in OMPs, some potentially related to drug efflux pumps, between the tet(R) and tet(S) strains led to alteration in cell surface properties which in turn affected cell transport in saturated porous media. Findings from this research suggested that manure-derived tet(R)E. coli could spread more widely in the groundwater system and pose serious public health risks.

Colloid straining within saturated heterogeneous porous media.

The transport of 0.46 µm, 2.94 µm, 5.1 µm and 6.06 µm latex particles in heterogeneous porous media prepared from the mixing of 0.78 mm, 0.46 mm and 0.23 mm quartz sands was investigated through column transport experiments. It was observed that the 0.46 µm particles traveled conservatively within the heterogeneous porous media, suggesting that under the experimental conditions employed in this research the strong repulsive interactions between the negatively charged latex particles and the clean quartz sands led to minimal colloid immobilization due to physicochemical filtration. The immobilization of the 2.94 µm, 5.1 µm and 6.06 µm latex particles was thus attributed to colloid straining. Experimental results showed that the straining of colloidal particles within heterogeneous sand mixtures increased when the fraction of finer sands increased. The mathematical model that was developed and tested based on results obtained using uniform sands (Xu et al., 2006) was found to be able to describe colloid straining within heterogeneous porous media. Examination of the relationship between the best-fit values of the clean-bed straining rate coefficients (k(0)) and the ratio of colloid diameter (d(p)) and sand grain size (d(g)) indicated that when number-average sizes were used to represent the size of the heterogeneous porous media, there existed a consistent relationship for both uniform sands and heterogeneous sand mixtures. Similarly, the use of the number-averaged sizes for the heterogeneous porous media produced a uniform relationship between the colloid straining capacity term (λ) and the ratio of d(p)/d(g) for all the sand treatments.

Straining of nonspherical colloids in saturated porous media.

We explore the effects of colloid shape on straining kinetics by measuring the filtration of spherical and nonspherical colloids within saturated columns packed with quartz sand. Our observations demonstrate that the transport of peanut-shaped colloids matches the transport of spherical colloids with diameters equal to the minor-axis length of the peanut-shaped colloids. The straining rates of the spherical colloids vary linearly with the ratio of colloid diameter (d(p)) to sand-grain diameter (d(g)) for 0.0083 < d(p)/d(g) < 0.06. This linear relationship also quantifies the straining rates of the peanut-shaped particles provided that the particle's minor axis length is used for d(p). Results of pore-scale simulations reveal that a peanut-shaped particle adopts a preferred orientation as it approaches a pore-space constriction such that its major axis tends to align with the local flow direction. The extent of this reorientation increases with the particle's aspect ratio. Findings from this research suggest that straining is sensitive to changes in colloid shape and thatthe kinetics of this process can be approximated on the basis of measurable properties of the nonspherical colloids and porous media.

Effects of plants on the removal of hexavalent chromium in wetland sediments.

The effect of two wetland plants, Typha latifolia L. (cattail) and Phragmites australis (Cav.) Trin. ex Steud (common reed), on the fate of Cr(VI) in wetland sediments was investigated using greenhouse bench-scale microcosm experiments. The removal of Cr(VI) was monitored based on the vertical profiles of aqueous Cr(VI) in the sediments. The Cr(VI) removal rates were estimated taking into account plant transpiration, which was found to significantly concentrate dissolved species in the sediments. After correcting for evapotranspiration, the actual Cr(VI) removal rates were significantly higher than would be inferred from uncorrected profiles. On average, the Cr(VI) removal rates were 0.005 to 0.017 mg L(-1) d(-1), 0.0003 to 0.08 mg L(-1) d(-1), and 0.004 to 0.13 mg L(-1) d(-1) for the control, T. latifolia, and P. australis microcosms, respectively. The fate of the removed Cr(VI) was examined by determining the quantity and chemical speciation of the Cr in the sediment and plant materials. Chromium(III) was the dominant form of Cr in both the sediment and plants, and precipitation of Cr(III) in the sediment was the major pathway responsible for the disappearance of aqueous Cr(VI) from the pore water. Incubation results showed that abiotic reduction was the primary mechanism underlying Cr(VI) removal in the microcosm sediments. Organic compounds produced by plants, including root exudates and mineralization products of dead roots, are thought to be the factor that is either directly or indirectly responsible for the gap between Cr(VI) removal efficiencies in the sediments of the vegetated and unvegetated microcosms.

Uptake of bromide by two wetland plants (Typha latifolia L. and Phragmites australis (Cav.) Trin. ex Steud).

The successful use of bromide (Br-) as a conservative tracer for hydrological tests in wetland systems requires minimal Br- loss due to plant uptake. The uptake of Br- by two wetland plants, cattail (Typha latifolia L.) and reed grass (Phragmites australis (Cav.) Trin. ex Steud), was investigated in greenhouse flow-through microcosms. Concentrations of Br- and other pertinent constituents in sediment pore water were measured at 2 cm depth increments in the sediment column. The vertical Br- concentration profiles in the sediments clearly revealed Br- uptake by T. latifolia and by P. australis. X-ray spectroscopy studies of bromine in plant samples revealed the accumulation of Br- in root and leaf tissues. Plant transpiration was found to significantly concentrate dissolved species in sediments and was accounted for in the calculations of Br uptake rates. Michaelis-Menten kinetics satisfactorily describe Br- uptake by T. latifolia. The uptake of Br- by P. australis, however, showed unique features that could not be described using Michaelis-Menten kinetics. The addition of chloride (Cl-) effectively inhibited Br- uptake, and the uptake of Cl- and Br- by T. latifolia was shown to follow dual-substrate Michaelis-Menten kinetics. Results of this study indicate that the use of Br- for tracer experiments in vegetated wetland systems should be evaluated with great caution.