Subsurface Flow and Transport Publications

2009

Barry RC, Y Lin, J Wang, G Liu, and C Timchalk. 2009. "Nanotechnology-Based Electrochemical Sensors for Biomonitoring Chemical Exposures ." Journal of Exposure Science and Environmental Epidemiology 19:1-18. doi:10.1038/jes.2008.71 Abstract This manuscript highlights research focused on the development of field-deployable analytical instruments based on EC detection. Background information and a general overview of EC detection methods and integrated use of nanomaterials in the development of these sensors are provided. New developments in EC sensors using various types of screen-printed electrodes, integrated nanomaterials, and immunoassays are discussed. Recent applications of EC sensors for assessing exposure to pesticides or detecting biomarkers of disease are highlighted to demonstrate the ability to monitor chemical metabolites, enzyme activity, or protein biomarkers of disease. In addition, future considerations and opportunities for advancing the use of EC platforms for dosimetric studies are covered.
Wietsma TW, M Oostrom, MA Covert, TE Queen, and MJ Fayer. 2009. "An automated tool for three types of saturated hydraulic conductivity laboratory measurements." Soil Science Society of America Journal 73(2):466-470. Abstract Acquisition of porous medium hydraulic conductivity in the laboratory is usually time-consuming and costly because of the manual labor associated with the currently available techniques. Lately, there has been increased interest in automating hydraulic conductivity laboratory techniques to reduce analysis time and improve data consistency. A new apparatus is presented that is able to determine hydraulic conductivity values with the falling head, constant head, and constant flux methods in an automated fashion. In addition, the columns are designed forcing water to flow in a nominally one-dimensional manner throughout the porous medium. In this paper, hydraulic conductivity data for standard laboratory sands are presented and compared to results obtained using a standard Tempe cell configuration. Hydraulic conductivity values obtained with the new tool for the laboratory sands are consistent with literature data. For highly permeable sands, the newly obtained hydraulic conductivity values are considerable larger then values acquired using a Tempe cell configuration. The lower conductivity values for the Tempe Cell configuration are primarily the result of insufficient spreading of water in the inlet and outlet reservoirs.
Wang H, J Wang, D Choi, Z Tang, H Wu, and Y Lin. 2009. "EQCM Immunoassay for Phosphorylated Acetylcholinesterase as a Biomarker for Organophosphate Exposures Based on Selective Zirconia Adsorption and Enzyme-Catalytic Precipitation ." Biosensors and Bioelectronics 24(8):2377-2383. Abstract A zirconia (ZrO2) adsorption-based immunoassay by electrochemical quartz crystal microbalance (EQCM) has been initially developed, aiming at the detection of phosphorylated acetylcholinesterase (AChE) as a potential biomarker for bio-monitoring exposures to organophosphate (OP) pesticides and chemical warfare agents. Hydroxyl-derivatized monolayer was preferably chosen to modify the crystal serving as the template for directing the electro-deposition of ZrO2 film with uniform nanostructures. The resulting ZrO2 film was utilized to selectively capture phosphorylated AChE from the sample media. Horseradish peroxidase (HRP)-labeled anti-AChE antibodies were further employed to recognize the captured phosphorylated protein. Enzyme-catalytic oxidation of the benzidine substrate resulted in the accumulation of insoluble product on the functionalized crystal. Ultrasensitive EQCM quantification by mass-amplified frequency responses as well as rapid qualification by visual color changes of product could be thus achieved. Moreover, 4-chloro-1-naphthol (CN) was comparably studied as an ideal chromogenic substrate for the enzyme-catalytic precipitation. Experimental results show that the developed EQCM technique can allow for the detection of phosphorylated AChE in human plasma. Such an EQCM immunosensing format opens a new door towards the development of simple, sensitive, and field-applicable biosensor for biologically monitoring low-level OP exposures.
Nellis S, H Yoon, C Werth, M Oostrom, and AJ Valocchi. 2009. "Surface and Interfacial Properties of Nonaqueous-Phase Liquid Mixtures Released to the Subsurface at the Hanford Site ." Vadose Zone Journal 8(2):344-351. Abstract Surface and interfacial tensions that arise at the interface between different phases are key parameters affecting Nonaqueous Phase Liquid (NAPL) movement and redistribution in the vadose zone after spill events. In this study, the impact of major additive components on surface and interfacial tensions for organic mixtures and wastewater was investigated. Organic mixture and wastewater compositions are based upon carbon tetrachloride (CT) mixtures released at the Hanford site, where CT was discharged simultaneously with dibutyl butyl phosphonate (DBBP), tributyl phosphate (TBP), dibutyl phosphate (DBP), and a machining lard oil (LO). A considerable amount of wastewater consisting primarily of nitrates and metal salts was also discharged. The tension values measured in this study revealed that the addition of these additive components caused a significant lowering of the interfacial tension with water or wastewater and the surface tension of the wastewater phase in equilibrium with the organic mixtures, compared to pure CT, but had minimal effect on the surface tension of the NAPL itself. These results lead to large differences in spreading coefficients for several mixtures, where the additives caused both a higher (more spreading) initial spreading coefficient and a lower (less spreading) equilibrium spreading coefficient. This indicates that if these mixtures migrate into uncontaminated areas, they will tend to spread quickly, but form a higher residual NAPL saturation after equilibrium, as compared to pure CT. Over time, CT likely volatilizes more rapidly than other components in the originally disposed mixtures and the lard oil and phosphates would become more concentrated in the remaining NAPL, resulting in a lower interfacial tension for the mixture. Spreading coefficients are expected to increase and perhaps change the equilibrated organic mixtures from nonspreading to spreading in water-wetting porous media. These results show that the behavior of organic chemical mixtures should be accounted for in numerical flow and transport models.
Li J, and Y Lin. 2009. "Nanomaterials for Sensing and Electrocatalysis." Journal of Nanoscience and Nanotechnology 9(4):2173-2174. Abstract This special issue provides an overview of recent advances in nanomaterials for sensing and electrocatalysis. The emergence of nanoscience and nanotechnology has led to great advances in electrochemical science and technology, and these advances may lead to a new branch of electrochemistry research-electrochemical nanotechnology-that combines electrochemical techniques with nanotechnologies to address important issues in energy, electronics, environment, and heath care.

2008

Wu H, J Wang, Z Wang, DR Fisher, and Y Lin. 2008. "Apoferritin-Templated Yttrium Phosphate Nanoparticle Conjugates for Radioimmunotherapy of Cancers." Journal of Nanoscience and Nanotechnology 8(5):2316-2322. doi:10.1166/jnn.2008.177 Abstract We report a templated-synthetic approach based on apoferritin to prepare radionuclide nanoparticle (NP) conjugates. Non-radioactive yttrium (89Y) was used as model target and surrogate for radioyttrium (90Y) to prepare the nanoparticle conjugate. The center cavity and multiple channel structure of apoferritin offer a fast and facile method to precipitate yttrium phosphate by diffusing yttrium and phosphate ions into the cavity of apofrritin, resulting a core-shell nanocomposite. The yttrium phosphate/apoferritin nanoparticle was functionalized with biotin for further application. The synthesized nanoparticle was characterized by transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS). We found that the resulting nanoparticles were uniform in size, with a diameter of around 8 nm. We tested the pre-targeting capability of the biotin-modified yttrium phosphate/apoferritin nanoparticle (yttrium phosphate/apoferritin nanoparticle) conjugate with streptavidin-modified magnetic beads and with aid of biotin-modified fluorecein isothiocyanate (FITC) tracer. This work shows that an yttrium phosphate NP conjugate provides a fast, simple and efficient method to prepare radioactive yttrium conjugate for applications in radioimmunotherapy of cancer.
Wang J, G Liu, H Wu, and Y Lin. 2008. "Quantum-Dot-Based Electrochemical Immunoassay for High-Throughput Screening of the Prostate-Specific Antigen." Small 4(1):82-86. doi:10.1002/smll.200700459 Abstract In this paper, we demonstrate an electrochemical high-throughput sensing platform for simple, sensitive detection of PSA based on QD labels. This sensing platform uses a microplate for immunoreactions and disposable screen-printed electrodes (SPE) for electrochemical stripping analysis of metal ions released from QD labels. With the 96-well microplate, capturing antibodies are conveniently immobilized to the well surface, and the process of immunoreaction is easily controlled. The formed sandwich complexes on the well surface are also easily isolated from reaction solutions. In particular, a microplate-based electrochemical assay can make it feasible to conduct a parallel analysis of several samples or multiple protein markers. This assay offers a number of advantages including (1) simplicity, cost-effectiveness, (2) high sensitivity, (3) capability to sense multiple samples or targets in parallel, and (4) a potentially portable device with an SPE array implanted in the microplate. This PSA assay is sensitive because it uses two amplification processes: (1) QDs as a label for enhancing electrical signal since secondary antibodies are linked to QDs that contain a large number of metal atoms and (2) there is inherent signal amplification for electrochemical stripping analysis—preconcentration of metal ion onto the electrode surface for amplifying electrical signals. Therefore, the high sensitivity of this method, stemming from dual signal amplification via QD labels and pre-concentration, allows low concentration levels to be detected while using small sample volumes. Thus, this QD-based electrochemical detection approach offers a simple, rapid, cost-effective, and high throughput assay of PSA.
Liu G, J Wang, RC Barry, CE Petersen, C Timchalk, PL Gassman, and Y Lin. 2008. "Nanoparticle-Based Electrochemical Immunosensor for the Detection of Phosphorylated Acetylcholinesterase: An Exposure Biomarker of Organophosphate Pesticides and Nerve AgentsOrganophosphate Pesticides and Nerve Agents." Chemistry - a European Journal 14(32):9951-9959. doi:10.1002/chem.200800412 Abstract A nanoparticle-based electrochemical immunosensor has been developed for the detection of phosphorylated acetylcholinesterase (AChE) adducts, which is a potential exposure biomarker for organophosphate pesticides (OP) and chemical warfare nerve agent exposures. Zirconia nanoparticles (ZrO2 NPs) were used as selective sorbents to capture the phosphorylated AChE adduct, and quantum dots (ZnS@CdS, QDs) were used as tags to label monoclonal anti-AChE antibody to track the immunorecognition events. The sandwich-like immunoreactions were performed among the ZrO2 NPs, which were pre-coated on a screen printed electrode (SPE) by electrodeposition, phosphorylated AChE and QD-anti-AChE. The captured QD tags were determined on the SPE by electrochemical stripping analysis of its metallic component (cadmium) after an acid-dissolution step. Paraoxon was used as a model OP insecticide to prepare the phosphorylated AChE adduct to demonstrate the proof of principle for this sensor technology. The paraoxon-AChE adduct was characterized by Fourier Transform Infrared Spectrum, and the binding affinity of anti-AChE to the paraoxon-AChE was validated with an enzyme-linked immunosorbent assay. The parameters (e.g., amount of ZrO2 NP, QD-anti-AChE concentration,) that govern the electrochemical response of immunosensors were optimized. The voltammetric response of the immunosensor is highly linear over the range of 10 pM to 4 nM paraoxon-AChE, and the limit of detection is estimated to be 8 pM. This new nanoparticle-based electrochemical immunosensor thus provides a sensitive and quantitative tool for biomonitoring exposure to OP pesticides and nerve agents.
Liu C, JM Zachara, N Qafoku, and Z Wang. 2008. "Scale-dependent desorption of uranium from contaminated subsurface sediments." Water Resources Research 44:W08413. doi:10.1029/2007WR006478 Abstract Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor, fine-grained (< 2mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter), and from its < 2mm, U(VI)-associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multi-component kinetic model that integrated a distributed rate expression with surface complexation reactions successfully described U(VI) release from the fine-grained, U(VI)-associated materials. The field-textured sediment in the large column displayed dual domain, tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger non-equilibrium behavior than did PFBA and bromide, and required a larger immobile porosity to describe. The dual domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual domain properties over-predicted effluent U(VI) concentrations, while the model based on tritium mass transfer under-predicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained, U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field scale reactive transport models.
Lin YY, J Wang, G Liu, H Wu, CM Wai, and Y Lin. 2008. "A nanoparticle label/immunochromatographic electrochemical biosensor for rapid and sensitive detection of prostate-specific antigen ." Biosensors and Bioelectronics 23(11):1659-1665. Abstract We present a nanoparticle (NP) label/immunochromatographic electrochemical biosensor (IEB) for rapid and sensitive detection of prostate-specific antigen (PSA) in human serum. This IEB integrates the immunochromatographic strip with the electrochemical detector for transducing quantitative signals. The NP label, made of CdSe@ZnS, serves as a signal-amplifier vehicle. A sandwich immunoreaction was performed on the immunochromatographic strip. The captured NP labels in the test zone were determined by highly sensitive stripping voltammetric measurement of the dissolved metallic component (cadmium) with a disposable-screen-printed electrode, which is embedded underneath the membrane of the test zone. Experimental parameters (e.g., immunoreaction time, the amount of anti-PSA-NP conjugations applied) and electrochemical detection conditions (e.g., preconcentration potential and time) were optimized using this biosensor for PSA detection. The analytical performance of this biosensor was evaluated with serum PSA samples according to the “figure-of-merits” (e.g., dynamic range, reproducibility, and detection limit). The results were validated with enzyme-linked immunosorbent assay (ELISA) and show high consistency. It is found that this biosensor is very sensitive with the detection limit of 0.02 ng/mL PSA and is quite reproducible. This method is rapid, clinically accurate, and less expensive than other diagnosis tools for PSA; therefore, this IEB coupled with a portable electrochemical analyzer shows great promise for simple, sensitive, quantitative point-of-care testing of disease-related protein biomarkers.

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