This report details some proof-of-principle experiments we conducted under a small, one year ($100K) grant from the Strategic Environmental Research and Development Program (SERDP) under the SERDP Exploratory Development (SEED) effort. Our chemiresistor technology had been developed over the last few years for detecting volatile organic compounds (VOCs) in the air, but these sensors had never been used to detect VOCs in water. In this project we tried several different configurations of the chemiresistors to find the best method for water detection. To test the effect of direct immersion of the (non-water soluble) chemiresistors in contaminated water, we constructed a fixture that allowed liquid water to pass over the chemiresistor polymer without touching the electrical leads used to measure the electrical resistance of the chemiresistor. In subsequent experiments we designed and fabricated probes that protected the chemiresistor and electronics behind GORE-TEX{reg_sign} membranes that allowed the vapor from the VOCs and the water to reach a submerged chemiresistor without allowing the liquids to touch the chemiresistor. We also designed a vapor flow-through system that allowed the headspace vapor from contaminated water to be forced past a dry chemiresistor array. All the methods demonstrated that VOCs in a high enough concentration in water can be detected by chemiresistors, but the last method of vapor phase exposure to a dry chemiresistor gave the fastest and most repeatable measurements of contamination. Answers to questions posed by SERDP reviewers subsequent to a presentation of this material are contained in the appendix.
Waste characterization is probably the most costly part of radioactive waste management. An important part of this characterization is the measurements of headspace gas in waste containers in order to demonstrate the compliance with Resource Conservation and Recovery Act (RCRA) or transportation requirements. The traditional chemical analysis methods, which include all steps of gas sampling, sample shipment and laboratory analysis, are expensive and time-consuming as well as increasing worker's exposure to hazardous environments. Therefore, an alternative technique that can provide quick, in-situ, and real-time detections of headspace gas compositions is highly desirable. This report summarizes the results obtained from a Laboratory Directed Research & Development (LDRD) project entitled 'Potential Application of Microsensor Technology in Radioactive Waste Management with Emphasis on Headspace Gas Detection'. The objective of this project is to bridge the technical gap between the current status of microsensor development and the intended applications of these sensors in nuclear waste management. The major results are summarized below: {sm_bullet} A literature review was conducted on the regulatory requirements for headspace gas sampling/analysis in waste characterization and monitoring. The most relevant gaseous species and the related physiochemical environments were identified. It was found that preconcentrators might be needed in order for chemiresistor sensors to meet desired detection {sm_bullet} A long-term stability test was conducted for a polymer-based chemresistor sensor array. Significant drifts were observed over the time duration of one month. Such drifts should be taken into account for long-term in-situ monitoring. {sm_bullet} Several techniques were explored to improve the performance of sensor polymers. It has been demonstrated that freeze deposition of black carbon (CB)-polymer composite can effectively eliminate the so-called 'coffee ring' effect and lead to a desirable uniform distribution of CB particles in sensing polymer films. The optimal ratio of CB/polymer has been determined. UV irradiation has been shown to improve sensor sensitivity. {sm_bullet} From a large set of commercially available polymers, five polymers were selected to form a sensor array that was able to provide optimal responses to six target-volatile organic compounds (VOCs). A series of tests on the response of sensor array to various VOC concentrations have been performed. Linear sensor responses have been observed over the tested concentration ranges, although the responses over a whole concentration range are generally nonlinear. {sm_bullet} Inverse models have been developed for identifying individual VOCs based on sensor array responses. A linear solvation energy model is particularly promising for identifying an unknown VOC in a single-component system. It has been demonstrated that a sensor array as such we developed is able to discriminate waste containers for their total VOC concentrations and therefore can be used as screening tool for reducing the existing headspace gas sampling rate. {sm_bullet} Various VOC preconcentrators have been fabricated using Carboxen 1000 as an absorbent. Extensive tests have been conducted in order to obtain optimal configurations and parameter ranges for preconcentrator performance. It has been shown that use of preconcentrators can reduce the detection limits of chemiresistors by two orders of magnitude. The life span of preconcentrators under various physiochemical conditions has also been evaluated. {sm_bullet} The performance of Pd film-based H2 sensors in the presence of VOCs has been evaluated. The interference of sensor readings by VOC has been observed, which can be attributed to the interference of VOC with the H2-O2 reaction on the Pd alloy surface. This interference can be eliminated by coating a layer of silicon dioxide on sensing film surface. Our work has demonstrated a wide range of applications of gas microsensors in radioactive waste management. Such applications can potentially lead to a significant cost saving and risk reduction for waste characterization.
This report summarizes the work performed as part of a Laboratory Directed Research and Development project focused on evaluating and mitigating risk associated with biological dual use research of concern. The academic and scientific community has identified the funding stage as the appropriate place to intervene and mitigate risk, so the framework developed here uses a portfolio-level approach and balances biosafety and biosecurity risks, anticipated project benefits, and available mitigations to identify the best available investment strategies subject to cost constraints. The modeling toolkit was designed for decision analysis for dual use research of concern, but is flexible enough to support a wide variety of portfolio-level funding decisions where risk/benefit tradeoffs are involved. Two mathematical optimization models with two solution methods are included to accommodate stakeholders with varying levels of certainty about priorities between metrics. An example case study is presented.
The potential effects on wildlife of the implementation of thermal mitigation alternatives for C and K reactors were evaluated using Habitat Evaluation Procedures (HEP) developed by the US Fish and Wildlife Service (FWS) and modified by the Savannah River Laboratory (SRL) for the Savannah River Plant (SRP) environment. These procedures allow for the relative ranking of project alternatives and/or mitigation with respect to representative wildlife species over the life of the project or for selected time periods in the future. The Department of Energy-Savannah River was requested by the FWS to provide a HEP analysis for the cooling water alternatives for C and K reactors during the comment period on the Draft Thermal Mitigation Environment Impact Statement, Alternative Cooling Water Systems (DOE, 1986). For C and K reactors the potential wildlife impacts and/or benefits of once-through and recirculating cooling towers were evaluated for both near-term (30-year) and long-term (100-year) time periods.
This report provides a summary of the three-year LDRD (Laboratory Directed Research and Development) project aimed at developing microchemical sensors for continuous, in-situ monitoring of volatile organic compounds. A chemiresistor sensor array was integrated with a unique, waterproof housing that allows the sensors to be operated in a variety of media including air, soil, and water. Numerous tests were performed to evaluate and improve the sensitivity, stability, and discriminatory capabilities of the chemiresistors. Field tests were conducted in California, Nevada, and New Mexico to further test and develop the sensors in actual environments within integrated monitoring systems. The field tests addressed issues regarding data acquisition, telemetry, power requirements, data processing, and other engineering requirements. Significant advances were made in the areas of polymer optimization, packaging, data analysis, discrimination, design, and information dissemination (e.g., real-time web posting of data; see www.sandia.gov/sensor). This project has stimulated significant interest among commercial and academic institutions. A CRADA (Cooperative Research and Development Agreement) was initiated in FY03 to investigate manufacturing methods, and a Work for Others contract was established between Sandia and Edwards Air Force Base for FY02-FY04. Funding was also obtained from DOE as part of their Advanced Monitoring Systems Initiative program from FY01 to FY03, and a DOE EMSP contract was awarded jointly to Sandia and INEEL for FY04-FY06. Contracts were also established for collaborative research with Brigham Young University to further evaluate, understand, and improve the performance of the chemiresistor sensors.
