Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. ...Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5–11 nm, and the height increased by 6–12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10–550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.
Dissolution of copper-based nanoparticles (NPs) can control their environmental persistence and toxicity. Previous research has generally reported limited dissolution of Cu-based NPs at circumneutral ...pH, but the environmentally important case of dissolution in solutions that are undersaturated with respect to copper mineral phases has not been investigated thoroughly. In this study, immobilized Cu-based NPs were fabricated on solid supports. Metallic copper (Cu), cupric oxide/hydroxide (Cuox), and copper sulfide (Cu x S) NPs were investigated. Dissolution rate constants were measured in situ by an atomic force microscope equipped with a flow-through cell. A mass-balance model indicated that the flowing solution was consistently undersaturated with respect to cupric solid phases. Based on the measured rate constants, Cuox NPs are expected to dissolve completely in these undersaturated conditions within a matter of hours, even at neutral to basic pH. The expected persistence of metallic Cu NPs ranges from a few hours to days, whereas Cu x S NPs showed no significant dissolution over the time scales studied. Field deployment of Cu-based NP samples in a freshwater stream confirmed these conclusions for a natural aquatic system. These results suggest that Cu and Cuox NPs will be short-lived in the environment unless dissolution is hindered by a competing process, such as sulfidation.
Sulfidation of silver nanoparticles (AgNPs), which is known to alter AgNP toxicity, occurs during transport through wastewater treatment plants. In this study, arrays of immobilized AgNPs fabricated ...by nanosphere lithography (NSL) were used to study AgNP sulfidation in a full-scale wastewater treatment plant (WWTP). A detailed laboratory study preceded field deployment. The characteristic NSL pattern remained discernible by atomic force microscopy and transmission electron microscopy after both lab and field exposures. Growth of AgNPs due to an increase in density upon sulfidation permitted the study of sulfidation kinetics in the WWTP. Sulfidation occurred almost exclusively in anaerobic zones of the WWTP, where the initial sulfidation rate was 11–14 nm of Ag converted to Ag2S per day. Measurements of the chemical composition and crystallinity of AgNPs exposed to primary influent for ∼10 d confirmed that they had been converted almost entirely to Ag2S. Laboratory experiments revealed that the sulfidation process is not uniform and that partially sulfidized AgNPs retain the potential to release toxic Ag+ ions. The results indicate that primary AgNPs are sulfidized directly without dissolving and forming secondary precipitates. This study demonstrates the utility of immobilized AgNPs for detailed, in situ investigations of nanomaterial tranformations.
Nanotoxicity studies are greatly needed to advance nanomedical technologies into clinical practice. We assessed the toxic effects of a single intravenous exposure to commercially available gold ...nanoparticles (GNPs) in mice and rats. Fifteen-nm GNPs were purchased and independently characterized. Animals were exposed to either 1,000 mg GNPs/kg body weight (GNP group) or phosphate-buffered saline. Subsets of animals were euthanized and samples collected at 1, 7, 14, 21, and 28 days postexposure. Independent characterization demonstrated that the physicochemical properties of the purchased GNPs were in good agreement with the information provided by the supplier. Mice exposed to GNPs developed granulomas in the liver and transiently increased serum levels of the pro-inflammatory cytokine interleukin-18. No such alterations were found in rats. While there was no fatality in mice post-GNP exposure, a number of the rats died within hours of GNP administration. Differences in GNP biodistribution and excretion were also detected between the two species, with rats having a higher relative accumulation of GNPs in spleen and greater fecal excretion. In conclusion, GNPs have the ability to incite a robust macrophage response in mice, and there are important species-specific differences in their biodistribution, excretion, and potential for toxicity.
The U.S. Department of Energy Office of Legacy Management is responsible for the long-term care and maintenance of former uranium mill sites in the United States. Prior predictions of site flushing ...times (monitored natural attenuation) are not being met due to the presence of secondary contaminant sources associated with uranium-rich sediments in the vadose zone and organic-rich sediments near the water table below and near former mill tailings (tailings have been moved to a separate disposal site). Updated sitewide modeling for future releases of contaminants (including uranium) from these secondary sources to the groundwater need appropriate input parameters. To test field techniques, two cross-hole tracer tests and one infiltration tracer test were completed at a former uranium mill site in Grand Junction, Colorado. Reactive transport modeling was completed to derive physical and geochemical parameters. The observed data from saturated zone cross-hole tracer testing was adequately simulated using PHT-USG (reactive transport model) and PEST++ (calibration routine) with reasonable estimates of hydraulic conductivity, dispersion, effective porosity, cation exchange, calcite saturation index, and uranium sorption potential. The use of multiple layering in one cross-hole model was able to capture hydraulic conductivity variations with depth, which produced a double hump in the tracer concentrations. Estimated parameter values were very similar to prior estimates from column testing and single-well push–pull testing, except for a lower uranium sorption potential in one cross-hole test. This difference is likely due to the larger scale of the cross-hole testing including pathways with a lower uranium sorption potential. The infiltration testing released constituents from the vadose zone that can contribute to ongoing groundwater contamination. Modeling simulated the immediate release of these constituents to the water table similar to downward displacement of the existing residual porewater. Delayed drainage of the infiltration water was more difficult to simulate. However, the overall contaminant release concentrations from the vadose-zone secondary sources and ongoing groundwater contamination are adequately simulated for current site purposes. Additional details on vadose-zone processes may be needed if various remedial fluids are evaluated.
Groundwater contamination at legacy uranium processing sites is an ongoing global challenge. Plumes at many uranium-contaminated sites are more persistent than originally predicted by groundwater ...modeling. Previous investigations of uranium plume persistence identified residual and secondary sources that contribute to plume longevity, but there is a remaining need to revise forecasted cleanup times using information about these ongoing sources. The purpose of this study is to investigate the quantitative impact of residual vadose zone sources of uranium on groundwater remediation time frame. This objective was approached by applying numerical uranium transport simulations and uncertainty analysis to a former uranium mill site in the southwestern United States. Information from recent site investigations provided details about the distribution and release characteristics of uranium accumulations in the vadose zone. The residual uranium characteristics were incorporated as decaying source terms in the transport model. A stochastic approach using an iterative ensemble smoother was applied for history matching, and the transport model was used to assess the impact of multiple remedial alternatives on forecasted time frame. The forecasted time frame to achieve the groundwater remediation goal for uranium by monitored natural attenuation is on the order of thousands of years, and treatment of the dissolved plume does not reduce the projected time frame. The large proportion of residual uranium mass remaining in the vadose zone and the gradual leaching rate due to the site's semiarid climate create a long-lived source that can sustain a dissolved plume for thousands of years despite an estimated 99% mass removal achieved during mill tailings disposal. Residual uranium in vadose zone sediments beneath former tailings impoundments could present comparable uranium plume persistence and remediation challenges at other legacy uranium mill sites in semiarid climates. Other remaining uranium-impacted sites are similarly complex, and forecasted remedial time frames are needed to effectively achieve compliance, manage risk, assess the benefits of additional treatment, manage and project costs, and support beneficial site reuse.
•Significant residual uranium mass can remain after uranium mill tailings removal.•Residual uranium leaches slowly in semiarid climates, creating long-term sources.•Residual vadose zone sources can sustain a uranium plume for thousands of years.•Dissolved plume treatment is ineffective while the residual sources are active.
2017 AAHA Canine Vaccination Guidelines Ford, Richard B; Larson, Laurie J; McClure, Kent D ...
The Journal of the American Animal Hospital Association,
2017 Sep/Oct, Letnik:
53, Številka:
5
Journal Article
At a former uranium mill site where tailings have been removed, prior work has determined several potential ongoing secondary uranium sources. These include locations with uranium sorbed to organic ...carbon, uranium in the unsaturated zone, and uranium associated with the presence of gypsum. To better understand uranium mobility controls at the site, four single-well push–pull tests (with a drift phase) were completed with the goal of deriving aquifer flow and contaminant transport parameters for inclusion in a future sitewide reactive transport model. This goes beyond the traditional use of a constant sorption distribution coefficient (Kd) and allows for the evaluation of alternative remedial injection fluids, which can produce variable Kd values. Dispersion was first removed from the resulting data to determine possible reactions before conducting reactive transport simulations. These initial analyses indicated the potential need to include cation exchange, uranium sorption, and gypsum dissolution. A reactive transport model using multiple layers to account for partially penetrating wells was completed using the PHT-USG reactive transport modeling code and calibrated using PEST. The model results quantify the hydraulic conductivity and dispersion parameters using the injected tracer concentrations. Uranium sorption, cation exchange, and gypsum dissolution parameters were quantified by comparing the simulated versus observed geochemistry. All simulations required some cation exchange and calcite equilibrium, and one simulation required gypsum dissolution to improve the model fit for calcium and sulfate. Uranium sorption parameters were not strongly influenced by the other parameter values but were highly influenced by uranium concentrations during the drift phase, with possible kinetic rate limitations. Thus, a future recommendation for such push–pull tests is to collect more geochemical data during the drift phase. The final uranium sorption parameters were within the range of values determined from prior column testing. The flow and transport parameters derived from these single-well push–pull tests will provide initial parameters for any future sitewide reactive transport model.
Flip-chip heterogeneously integrated n-p-n InGaP/GaAs heterojunction bipolar transistors (HBTs) with integrated thermal management on wide-bandgap AlN substrates followed by GaAs substrate removal ...are demonstrated. Without thermal management, substrate removal after integration significantly aggravates self-heating effects, causing poor I - V characteristics due to excessive device self-heating. An electrothermal codesign scheme is demonstrated that involves simulation (design), thermal characterization, fabrication, and evaluation. Thermoreflectance thermal imaging, electrical-temperature sensitive parameter-based thermometry, and infrared thermography were utilized to assess the junction temperature rise in HBTs under diverse configurations. In order to reduce the thermal resistance of integrated devices, passive cooling schemes assisted by structural modification, i.e., positioning indium bump heat sinks between the devices and the carrier, were employed. By implementing thermal heat sinks in close proximity to the active region of flip-chip integrated HBTs, the junction-to-baseplate thermal resistance was reduced over a factor of two, as revealed by junction temperature measurements and improvement of electrical performance. The suggested heterogeneous integration method accounts for not only electrical but also thermal requirements providing insight into realization of advanced and robust III-V/Si heterogeneously integrated electronics.
2011 AAHA canine vaccination guidelines Welborn, Link V; DeVries, John G; Ford, Richard ...
The Journal of the American Animal Hospital Association,
2011 Sep-Oct, Letnik:
47, Številka:
5
Journal Article
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