Dongye Zhao

Field assessment of carboxymethyl cellulose stabilized iron nanoparticles for in situ destruction of chlorinated solvents in source zones.

This study pilot-tested carboxymethyl cellulose (CMC) stabilized zero-valent iron (ZVI) nanoparticles (with a trace amount of Pd catalyst) for in situ destruction of chlorinated ethenes such as perchloroethylene (PCE) and trichloroethylene (TCE) and polychlorinated biphenyls (PCBs) that had been in groundwater for decades. The test site was located in a well-characterized secondary source zone of PCBs and chlorinated ethenes. Four test wells were installed along the groundwater flow direction (spaced 5 ft apart), including one injection well (IW), one up-gradient monitoring well (MW-3) and two down-gradient monitoring wells (MW-1 and MW-2). Stabilized nanoparticle suspension was prepared on-site and injected into the 50-ft deep, unconfined aquifer. Approximately 150 gallons of 0.2 g/L Fe-Pd (CMC = 0.1 wt%, Pd/Fe = 0.1 wt%) was gravity-fed through IW-1 over a 4-h period (Injection #1). One month later, another 150 gallons of 1.0 g/L Fe-Pd (CMC = 0.6 wt%, Pd/Fe = 0.1 wt%) was injected into IW-1 at an injection pressure <5 psi (Injection #2). When benchmarked against the tracer, approximately 37.4% and 70.0% of the injected Fe was detected in MW-1 during injection #1 and #2, respectively, confirming the soil mobility of the nanoparticles through the aquifer, and higher mobility of the particles was observed when the injection was performed under higher pressure. Rapid degradation of PCE and TCE was observed in both MW-1 and MW-2 following each injection, with the maximum degradation being observed during the first week of the injections. The chlorinated ethenes concentrations gradually returned to their pre-injection levels after approximately 2 weeks, indicating exhaustion of the ZVIs reducing power. However, the injection of CMC-stabilized nanoparticle and the abiotic reductive dechlorination process appeared to have boosted a long-term in situ biological dechlorination thereafter, which was evidenced by the fact that PCE and TCE concentrations showed further reduction after two weeks. After 596 days from the first injection, the total chlorinated ethenes concentration decreased by about 40% and 61% in MW-1 and MW-2, respectively. No significant long-term reduction of PCB 1242 was observed in MW-1, but a reduction of 87% was evident in MW-2. During the 596 days of testing, the total concentrations of cis-DCE (dichloroethylene) and VC (vinyl chloride) decreased by 20% and 38% in MW-1 and MW-2, respectively. However, the combined fraction of cis-DCE and VC in the total chlorinated ethenes (PCE, TCE, cis-DCE and VC) increased from 73% to 98% and from 62% to 98%, respectively, which supports the notion that biological dechlorination of PCE and TCE was active. It is proposed that CMC-stabilized ZVI-Pd nanoparticles facilitated the early stage rapid abiotic degradation. Over the long run, the existing biological degradation process was boosted with CMC as the carbon source and hydrogen from the abiotic/biotic processes as the electron donor, resulting in the sustained enhanced destruction of the chlorinated organic chlorinated ethenes in the subsurface.

Ultimate removal of phosphate from wastewater using a new class of polymeric ion exchangers

Abstract The presence of trace concentrations of dissolved phosphate is often responsible for causing eutrophication problems in lakes, reservoirs, other confined water bodies and coastal waters. In this regard, both biological and physico–chemical treatment processes have been studied extensively to remove phosphate from contaminated water/wastewater. There, however, remains a major need to identify/develop a viable fixed-bed process which can essentially eliminate phosphate from contaminated water/wastewater. Previous investigators have shown the advantages as well as shortcomings of the fixed-bed process when strong-base anion exchangers, activated alumina and zirconium oxides are used as sorbents. The present study reports the results of a detailed investigation pertaining to selective phosphate removal by a new class of sorbent, referred to as polymeric ligand exchanger (PLE). Laboratory studies show strong evidence that the PLE is very selective toward phosphate, chemically stable, and also amenable to efficient regeneration. Anion exchange accompanied by Lewis acid–base interaction is the underlying reason for PLEs enhanced affinity toward phosphate. In several ways, this new ion exchanger (PLE) overcomes the shortcomings of previously used inorganic and polymeric sorbents.

Transport of carboxymethyl cellulose stabilized iron nanoparticles in porous media: Column experiments and modeling

Carboxymethyl cellulose (CMC) can facilitate in situ delivery of zero-valent iron (ZVI) nanoparticles in contaminated aquifer. This work investigated transport of CMC-stabilized ZVI nanoparticles (CMC-Fe) using column breakthrough experiments and model simulations. The nanoparticles (18.1+/-2.5 nm) were transportable through four saturated model porous media: coarse and fine glass beads, clean sand, and sandy soil. The transport data were interpreted using both classical filtration theory and a modified convection-dispersion equation with a first-order removal rate law. At full breakthrough, a constant concentration plateau (Ce/C0) was reached, ranging from 0.99 for the glass beads to 0.69 for the soil. While Brownian diffusion was the predominant mechanism for particle removal in all cases, gravitational sedimentation also played an important role, accounting for 30% of the overall single-collector contact efficiency for the coarse glass beads and 6.7% for the soil. The attachment efficiency for CMC-Fe was found to be 1-2 orders of magnitude lower than reported for ZVI nanoparticles stabilized with other commercial polymers. The particle removal and travel distance are strongly dependent on interstitial flow velocity, but only modestly affected by up to 40 mM of calcium. Simulation results indicate that once delivered, 99% of the nanoparticles will be removed by the soil matrix within 16 cm at a groundwater flow velocity of 0.1 m/day, but may travel over 146 m at flow velocity of 61 m/day.

Heavy metals in surface sediments of the Jialu River, China: Their relations to environmental factors

This work investigated heavy metal pollution in surface sediments of the Jialu River, China. Sediment samples were collected at 19 sites along the river in connection with field surveys and the total concentrations were determined using atomic fluorescence spectrometer and inductively coupled plasma optical emission spectrometer. Sediment samples with higher metal concentrations were collected from the upper reach of the river, while sediments in the middle and lower reaches had relatively lower metal concentrations. Multivariate techniques including Pearson correlation, hierarchical cluster and principal components analysis were used to evaluate the metal sources. The ecological risk associated with the heavy metals in sediments was rated as moderate based on the assessments using methods of consensus-based Sediment Quality Guidelines, Potential Ecological Risk Index and Geo-accumulation Index. The relations between heavy metals and various environmental factors (i.e., chemical properties of sediments, water quality indices and aquatic organism indices) were also studied. Nitrate nitrogen, total nitrogen, and total polycyclic aromatic hydrocarbons concentrations in sediments showed a co-release behavior with heavy metals. Ammonia nitrogen, total nitrogen, orthophosphate, total phosphate and permanganate index in water were found to be related to metal sedimentation. Heavy metals in sediments posed a potential impact on the benthos community.

A review of oil, dispersed oil and sediment interactions in the aquatic environment: Influence on the fate, transport and remediation of oil spills

The 2010 Deepwater Horizon oil spill has spurred significant amounts of researches on fate, transport, and environmental impacts of oil and oil dispersants. This review critically summarizes what is understood to date about the interactions between oil, oil dispersants and sediments, their roles in developing oil spill countermeasures, and how these interactions may change in deepwater environments. Effects of controlling parameters, such as sediment particle size and concentration, organic matter content, oil properties, and salinity on oil-sediment interactions are described in detail. Special attention is placed to the application and effects of oil dispersants on the rate and extent of the interactions between oil and sediment or suspended particulate materials. Various analytical methods are discussed for characterization of oil-sediment interactions. Current knowledge gaps are identified and further research needs are proposed to facilitate sounder assessment of fate and impacts of oil spills in the marine environment.

Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: Effects of sorption, surfactants, and natural organic matter

Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼ 44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼ 82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1 × cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼ 10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5 × cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.

Effect of cationic and anionic surfactants on the sorption and desorption of perfluorooctane sulfonate (PFOS) on natural sediments

Sorption and desorption of PFOS at water-sediment interfaces were investigated in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), and an anionic surfactant, sodium dodecylbenzene sulfonate (SDBS). CTAB remarkably enhanced the sorption of PFOS on the sediment. In contrast, the influence of SDBS to the sorption of PFOS was concentration dependent. Two contrasting factors were responsible for the phenomenon. One was the sorption of the surfactant itself to the sediment, which enhanced the sorption of PFOS. The other was the increase in solubility of PFOS caused by the adding of surfactants, which decreased the sorption of PFOS. SDBS had a much lower sorption capacity, but rather strong ability to increase the solubility of PFOS. High levels of SDBS remarkably reduced the sorption of PFOS on the sediment. These results imply that cationic and anionic surfactants may have contrast impacts on the distribution and transport of PFOS in the environment.

Immobilization of mercury in sediment using stabilized iron sulfide nanoparticles.

Mercury (Hg) immobilization using stabilized iron sulfide (FeS) nanoparticles was investigated through a series of batch and column experiments. The nanoparticles were prepared using a low-cost, food-grade cellulose (sodium carboxymethyl cellulose, CMC) as the stabilizer. The hydrodynamic diameter of fresh FeS-CMC nanoparticles was measured to be 38.5+/-5.4nm. Batch tests showed that the nanoparticles can effectively immobilize Hg in a clay loam sediment. The Hg distribution coefficient for the nanoparticles was determined to be 8930+/-1480L/g, which is >4 orders of magnitude greater than for the sediment. When the Hg-laden sediment was treated at an FeS-to-Hg molar ratio of 26.5, the Hg concentration leached into water was reduced by 97% and the TCLP (toxicity characteristic leaching procedure) leachability of Hg was reduced by 99%. Column tests showed that water-leachable mercury from the sediment containing 3120mg/L Hg was reduced by 67% and the TCLP leachability by >77% when the sediment was treated with 67 pore volumes (PVs) of a 0.5g/L FeS nanoparticle suspension. Column tests proved that the stabilized nanoparticles were highly mobile in the sediment and full breakthrough of the nanoparticles occurred at approximately 18 PVs.

An overview of preparation and applications of stabilized zero-valent iron nanoparticles for soil and groundwater remediation.

Nano-scale zero-valent iron (nZVI) is one of the most intensively studied materials for environmental cleanup uses over the past 20 years or so. Freshly prepared nZVI is highly reactive due to its high specific surface area and strong reducing power. Over years, the classic borohydride reduction method for preparing nZVI has been modified by use of various stabilizers or surface modifiers to acquire more stable and soil deliverable nZVI for treatment of different organic and inorganic contaminants in water and soil. While most studies have been focused on testing nZVI for water treatment, the greater potential or advantage of nZVI appears to be for in situ remediation of contaminated soil and groundwater by directly delivering stabilized nZVI into the contaminated subsurface as it was proposed from the beginning. Compared to conventional remediation practices, the in situ remediation technique using stabilized nZVI offers some unique advantages. This work provides an update on the latest development of stabilized nZVI for various environmental cleanup uses, and overviews the evolution and environmental applications of stabilized nZVI. Commonly used stabilizers are compared and the stabilizing mechanisms are discussed. The effectiveness and constraints of the nZVI-based in situ remediation technology are summarized. This review also reveals some critical knowledge gaps and research needs, such as interactions between delivered nZVI and the local biogeochemical conditions.

Immobilization of Mercury by Carboxymethyl Cellulose Stabilized Iron Sulfide Nanoparticles: Reaction Mechanisms and Effects of Stabilizer and Water Chemistry

Iron sulfide (FeS) nanoparticles were prepared with sodium carboxymethyl cellulose (CMC) as a stabilizer, and tested for enhanced removal of aqueous mercury (Hg(2+)). CMC at ≥0.03 wt % fully stabilized 0.5 g/L of FeS (i.e., CMC-to-FeS molar ratio ≥0.0006). FTIR spectra suggested that CMC molecules were attached to the nanoparticles through bidentate bridging and hydrogen bonding. Increasing the CMC-to-FeS molar ratio from 0 to 0.0006 enhanced mercury sorption capacity by 20%; yet, increasing the ratio from 0.0010 to 0.0025 diminished the sorption by 14%. FTIR and XRD analyses suggested that precipitation (formation of cinnabar and metacinnabar), ion exchange (formation of Hg0.89Fe0.11S), and surface complexation were important mechanisms for mercury removal. A pseudo-second-order kinetic model was able to interpret the sorption kinetics, whereas a dual-mode isotherm model was proposed to simulate the isotherms, which considers precipitation and adsorption. High mercury uptake was observed over the pH range of 6.5-10.5, whereas significant capacity loss was observed at pH < 6. High concentrations of Cl(-) (>106 mg/L) and organic matter (5 mg/L as TOC) modestly inhibited mercury uptake. The immobilized mercury remained stable when preserved for 2.5 years at pH above neutral.