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NASA NTRS2002

Internet Technology for Future Space Missions

Ongoing work at National Aeronautics and Space Administration Goddard Space Flight Center (NASA/GSFC), seeks to apply standard Internet applications and protocols to meet the technology challenge of future satellite missions. Internet protocols and technologies are under study as a future means to provide seamless dynamic communication among heterogeneous instruments, spacecraft, ground stations, constellations of spacecraft, and science investigators. The primary objective is to design and demonstrate in the laboratory the automated end-to-end transport of files in a simulated dynamic space environment using off-the-shelf, low-cost, commodity-level standard applications and protocols. The demonstrated functions and capabilities will become increasingly significant in the years to come as both earth and space science missions fly more sensors and the present labor-intensive, mission-specific techniques for processing and routing data become prohibitively. This paper describes how an IP-based communication architecture can support all existing operations concepts and how it will enable some new and complex communication and science concepts. The authors identify specific end-to-end data flows from the instruments to the control centers and scientists, and then describe how each data flow can be supported using standard Internet protocols and applications. The scenarios include normal data downlink and command uplink as well as recovery scenarios for both onboard and ground failures. The scenarios are based on an Earth orbiting spacecraft with downlink data rates from 300 Kbps to 4 Mbps. Included examples are based on designs currently being investigated for potential use by the Global Precipitation Measurement (GPM) mission.

Hennessy, Joseph F.↗

DOE OSTI2016

Development of Kinetics and Mathematical Models for High Pressure Gasification of Lignite-Switchgrass Blends

The overall objective of the current project was to investigate the high pressure gasification characteristics of a feed containing both coal and biomass. The two feed types differ in their ash contents and ash composition, particularly the alkali content. Gasification of a combined feed of coal and biomass has the potential for considerable synergies that might lead to a dramatic improvement in process economics and flexibility. The proposed study aimed to develop a detailed understanding of the chemistry, kinetics, and transport effects during high pressure gasification of coal-biomass blend feed. Specifically, we studied to develop: (a) an understanding of the catalytic effect of alkali and other inorganic species present in the biomass and coal, (b) an understanding of processing conditions under which synergistic effects of the blending of coal and biomass might be observed. This included the role of particle size, residence time, and proximity of the two feed types, (c) kinetics of high pressure gasification of individual feeds as well as the blends, and (d) development of mathematical models that incorporate kinetics and transport models to enable prediction of gasification rate at a given set of operating conditions, and (e) protocols to extend the results to other feed resources. The goal was to provide a fundamental understanding of the gasification process and guide in optimizing the configurations and design of the next generation of gasifiers. The approach undertaken was centered on two basic premises: (1) the gasification for small particles without internal mass transfer limitations can be treated as the sum of two processes in series (pyrolysis and char gasification) , and (2) the reactivity of the char generated during pyrolysis not only depends on the pressure and temperature but is also affected by the heating rates. Thus low heating rates (10-50 °C/min) typical of PTGA fail to produce char that would typically be formed at high heating rates (~10 4 °C/sec), encountered in entrained flow gasifiers. The char morphology, also a function of the heating rate, would influence the transport rates during the char gasification phase. Thus, heating rate plays a critical role through which both, pyrolysis and char gasification, are interconnected. We utilized two complementary gasification experiments: PEFR (pressurized entrained flow gasifier) and PTGA (pressurized thermo-gravimetric analyzer). The PEFR allowed us to study gasification at pressures, temperatures, and heating rates relevant for coal-biomass gasifiers. The PTGA work was useful in understanding the basic chemistry of the evolution of various gaseous species during pyrolysis. These results helped improved our understanding of the chemistry and chemical changes during pyrolysis. The role alkali metals and other inorganics in char gasification using steam and/or CO 2 was investigated. Finally, the mathematical models for char gasification without the transport effects were developed at commercial operating conditions.

09 BIOMASS FUELS↗

NASA NTRS2002

ISS and STS Commercial Off-the-Shelf Router Testing

This report documents the results of testing performed with commercial off-the-shelf (COTS) routers and Internet Protocols (IPs) to determine if COTS equipment and IP could be utilized to upgrade NASA's current Space Transportation System (STS), the Shuttle, and the International Space Station communication infrastructure. Testing was performed by NASA Glenn Research Center (GRC) personnel within the Electronic Systems Test Laboratory (ESTE) with cooperation from the Mission Operations Directorate (MOD) Qualification and Utilization of Electronic System Technology (QUEST) personnel. The ESTE testing occurred between November 1 and 9, 2000. Additional testing was performed at NASA Glenn Research Center in a laboratory environment with equipment configured to emulate the STS. This report documents those tests and includes detailed test procedures, equipment interface requirements, test configurations and test results. The tests showed that a COTS router and standard Transmission Control Protocols and Internet Protocols (TCP/IP) could be used for both the Shuttle and the Space Station if near-error-free radio links are provided.

Ivancie, William D.↗

DOE OSTI2024

A Blockchain and PKI-Based Secure Vehicle-to-Vehicle Energy-Trading Protocol

With the increasing awareness for sustainable future and green energy, the demand for electric vehicles (EVs) is growing rapidly, thus placing immense pressure on the energy grid. To alleviate this, local trading between EVs should be encouraged. In this paper, we propose a blockchain and public key infrastructure (PKI)-based secure vehicle-to-vehicle (V2V) energy-trading protocol. A permissioned blockchain utilizing the proof of authority (PoA) consensus and smart contracts is used to securely store data. Encrypted communication is ensured through transport layer security (TLS), with PKI managing the necessary digital certificates and keys. A multi-leader, multi-follower Stackelberg game-based trade algorithm is formulated to determine the optimal energy demands, supplies, and prices. Finally, we propose a detailed communication protocol that ties all the components together, enabling smooth interaction between them. Key findings, such as system behavior and performance, scalability of the trade algorithm and the blockchain, smart contract execution costs, etc., are presented through numerical results by implementing and simulating the protocol in various scenarios. This work not only enhances local energy trading among EVs, encouraging efficient energy usage and reducing burden on the power grid, but also paves a way for future research in sustainable energy management.

Stackelberg game↗

DOE OSTI2015

P type porous silicon resistivity and carrier transport

The resistivity of p type porous silicon (PS) is reported on a wide range of PS physical properties. Al/PS/Si/Al structures were used and a rigorous experimental protocol was followed. The PS porosity (P{sub %}) was found to be the major contributor to the PS resistivity (ρ{sub PS}). ρ{sub PS} increases exponentially with P{sub %}. Values of ρ{sub PS} as high as 1 × 10{sup 9} Ω cm at room temperature were obtained once P{sub %} exceeds 60%. ρ{sub PS} was found to be thermally activated, in particular, when the temperature increases from 30 to 200 °C, a decrease of three decades is observed on ρ{sub PS}. Based on these results, it was also possible to deduce the carrier transport mechanisms in PS. For P{sub %} lower than 45%, the conduction occurs through band tails and deep levels in the tissue surrounding the crystallites. When P{sub %} overpasses 45%, electrons at energy levels close to the Fermi level allow a hopping conduction from crystallite to crystallite to appear. This study confirms the potential of PS as an insulating material for applications such as power electronic devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Measurement of ion transport properties in ion exchange membranes for photoelectrochemical water splitting

Photoelectrochemical (PEC) water-splitting systems have the unique ability to produce renewable hydrogen directly from sunlight, independent of the electrical grid. These systems are therefore appealing technological options for resilient long-term energy storage. Ion selective membranes, such as monopolar and bipolar membranes, are a vital component of PEC water-splitting systems. These membranes allow for ionic conduction between the cathode and anode chambers, separation of products, and improved catalyst environments for reactions. In order to measure key properties and to study the performance of these ion exchange membranes, it is imperative to develop a robust testing protocol that can be used across the field. This paper introduces two standard electrochemical cells designed to directly measure ion transport properties in monopolar and bipolar membranes. The first electrochemical cell uses commercially available Pt disk electrodes to preform electrochemical impedance spectroscopy (EIS) and reliably measure through-plane conductivity of monopolar membranes. The second electrochemical cell uses four-point measurements with Luggin capillaries and a series of membrane configurations to perform current density-voltage and Faradaic efficiency (FE) measurements for water dissociation (WD) reactions on bipolar membranes. The cell designs and techniques laid out below allow for accurate measurement of ion transport parameters in ion exchange membranes, direct comparison of membranes being developed across the field, and in turn, greater advancements in ion exchange membranes and PEC water-splitting systems.

cation exchange membrane↗

DOE OSTI2019

Elucidating the Dynamic Nature of Fuel Cell Electrodes as a Function of Conditioning: An ex Situ Material Characterization and in Situ Electrochemical Diagnostic Study

To increase the commercialization of fuel cell electric vehicles, it is imperative to improve the activity and performance of electrocatalysts through combined efforts focused on material characterization and device-level integration. Obtaining fundamental insights into the ongoing structural and compositional changes of electrocatalysts is crucial for not only transitioning an electrode from its as-prepared to functional state, also known as 'conditioning', but also for establishing intrinsic electrochemical performances. Here, we investigated several oxygen reduction reaction (ORR) electrocatalysts via in situ and ex situ characterization techniques to provide fundamental insights into the interfacial phenomena that enable peak ORR mass activity and high current density performance. A mechanistic understanding of a fuel cell conditioning procedure is described, which encompasses voltage cycling and subsequent voltage recovery (VR) steps at low potential. In particular, ex situ membrane electrode assembly characterization using transmission electron microscopy and ultra-small angle X-ray scattering were performed to determine changes in carbon and Pt particle size and morphology, while in situ electrochemical diagnostics were performed either during or after specific points in the testing protocol to determine the electrochemical and interfacial changes occurring on the catalyst surface responsible for oxygen transport resistances through ionomer films. The results demonstrate that the voltage cycling (break-in) step aids in the removal of sulfate and fluoride and concomitantly reduces non-Fickian oxygen transport resistances, especially for catalysts where Pt is located within the pores of the carbon support. Subsequent low voltage holds at low temperature and oversaturated conditions, i.e., VR cycles, serve to improve mass activities by a factor of two to three, through a combined removal of contaminants, surface-blocking species (e.g., oxides), and rearrangement of the catalyst atomic structure (e.g., Pt-Pt and Pt-Co coordination).

30 DIRECT ENERGY CONVERSION↗

NASA NTRSDate not supplied

NASA’s Secured Airspace for Urban Air Mobility (UAM)

The Urban Air Mobility (UAM) architecture is leveraged from the Unmanned Traffic Management (UTM) concept of operations. Within the UAM environment, UAM operators work collaboratively to manage aerial vehicles in the urban environment. Providers of Services for UAM (PSU), UAM operators, and Supplemental Data Service Providers (SDSP) provide services to support flight operations within that environment. As a recognized need, various views of UAM flight information are provided to the public and public safety entities. To accomplish this, among other goals, the Federal Aviation Administration (FAA) can coordinate flight information between the FAA controlled National Airspace System (NAS) and the UAM environments through the FAA-Industry Data Exchange Protocol (FIDXP). This concept of UAM proposes to develop short-range, point-to-point transportation systems in metropolitan areas using vertical take-off and landing (VTOL) or short take-off and landing (STOL) aircraft to overcome increasing surface congestion. To garner the support of UAM and to realize its potential, an assurance of cybersecurity is critical for public acceptance. Understanding the various components communicating with one-another cybersecurity, like in other industries, has come to the forefront highlighting the need to protect these networks and systems from cyberattacks. With the planned growth and reach of UAM systems, it’s clear that the associated data exchange and service interactions will be at risk due to numerous types of cybersecurity attacks. Consequently, as these threats evolve, the UAM cybersecurity capabilities must adapt to these changes as well. While learning is always the goal, the overall intent of this workshop is to make recommendations on the following: (1) how future UAM environments can be protected against cyber-attacks, and (2) what mechanisms should be put in place to detect attacks against UAM environments.

UAM↗

NASA NTRS1991

Analysis of NASA communications (Nascom) II network protocols and performance

The NASA Communications (Nascom) Division of the Mission Operations and Data Systems Directorate is to undertake a major initiative to develop the Nascom II (NII) network to achieve its long-range service objectives for operational data transport to support the Space Station Freedom Program, the Earth Observing System, and other projects. NII is the Nascom ground communications network being developed to accommodate the operational traffic of the mid-1990s and beyond. The authors describe various baseline protocol architectures based on current and evolving technologies. They address the internetworking issues suggested for reliable transfer of data over heterogeneous segments. They also describe the NII architecture, topology, system components, and services. A comparative evaluation of the current and evolving technologies was made, and suggestions for further study are described. It is shown that the direction of the NII configuration and the subsystem component design will clearly depend on the advances made in the area of broadband integrated services.

Omidyar, Guy C.↗

NASA NTRSDate not supplied

The Stratospheric Aerosol and Gas Experiment IV

Atmospheric composition continues to be a key Earth science focus for international space agencies and research organizations. The target constituent varies depending upon the topic area of interest such as monitoring the ozone layer and the efficacy of the Montreal Protocol, assessing the influence of volcanic eruptions and large wildfires on the atmosphere, improving our knowledge of transport processes, or evaluating the impacts of greenhouse gases on climate. Additionally, there is a growing need for measurement continuity of many trace gases both from an inability to properly assess long-term trends without it as well as the reliance of reanalyses and chemistry climate models on observational input. To this end, proper continuity requires continuous and overlapping multi-instrument data records of which spaceborne measurements are a critical component. However, most current satellite systems are well beyond their expected lifetimes, and so we look toward the future to develop the Stratospheric Aerosol and Gas Experiment (SAGE) IV as a future mission concept. Enabled by the NASA Earth Science Technology Office’s (ESTO) Instrument Incubator Program, the SAGE IV Pathfinder project has developed and validated a prototype demonstration that paves the way for a future SAGE IV spaceflight mission. Utilizing solar occultation imaging, SAGE IV will be capable of measuring key species in the stratosphere and upper troposphere with the same quality as previous SAGE instruments but with greatly improved pointing knowledge and extensibility to new science targets. Furthermore, current technological advancements allow SAGE IV to fit within a CubeSat framework and make use of commercial hardware, significantly reducing the size and cost when compared with traditional missions and enabling sustainability of future measurements.

Robert Damadeo↗

NASA NTRSDate not supplied

The Stratospheric Aerosol and Gas Experiment (SAGE) IV

Atmospheric composition continues to be a key Earth science focus for international space agencies and research organizations. The target constituent varies depending upon the topic area of interest such as monitoring the ozone layer and the efficacy of the Montreal Protocol, assessing the influence of volcanic eruptions and large wildfires on the atmosphere, improving our knowledge of transport processes, or evaluating the impacts of greenhouse gases on climate. Additionally, there is a growing need for measurement continuity of many trace gases both from an inability to properly assess long-term trends without it as well as the reliance of reanalyses and chemistry climate models on observational input. To this end, proper continuity requires continuous and overlapping multi-instrument data records of which spaceborne measurements are a critical component. However, most current satellite systems are well beyond their expected lifetimes, and so we look toward the future to develop the Stratospheric Aerosol and Gas Experiment (SAGE) IV as a future mission concept. Enabled by the NASA Earth Science Technology Office’s (ESTO) Instrument Incubator Program, the SAGE IV Pathfinder project developed and validated a prototype demonstration that paves the way for a future SAGE IV spaceflight mission. Utilizing solar occultation imaging, SAGE IV will be capable of measuring key species in the stratosphere and upper troposphere with the same quality as previous SAGE instruments but with greatly improved pointing knowledge and extensibility to new science targets. The precision and stability of a well-designed occultation instrument can act as a calibration reference standard for other spaceborne instruments, ensuring proper continuity of the desired science targets. Furthermore, current technological advancements allow SAGE IV to fit within a CubeSat framework and make use of commercial hardware, significantly reducing the size and cost when compared with traditional missions and enabling sustainability of future measurements.

Robert Damadeo↗

NASA NTRS1998

MPEG-2 Over Asynchronous Transfer Mode (ATM) Over Satellite Quality of Service (QoS) Experiments: Laboratory Tests

Asynchronous transfer mode (ATM) quality of service (QoS) experiments were performed using MPEG-2 (ATM application layer 5, AAL5) over ATM over an emulated satellite link. The purpose of these experiments was to determine the free-space link quality necessary to transmit high-quality multimedia information by using the ATM protocol. The detailed test plan and test configuration are described herein as are the test results. MPEG-2 transport streams were baselined in an errored environment, followed by a series of tests using, MPEG-2 over ATM. Errors were created both digitally as well as in an IF link by using a satellite modem and commercial gaussian noise test set for two different MPEG-2 decoder implementations. The results show that ITU-T Recommendation 1.356 Class 1, stringent ATM applications will require better link quality than currently specified; in particular, cell loss ratios of better than 1.0 x 10(exp -8) and cell error ratios of better than 1.0 x 10(exp -7) are needed. These tests were conducted at the NASA Lewis Research Center in support of satellite-ATM interoperability research.

Ivancic, William D.↗

DOE OSTI2019

Authentication Protocol for ICS without Encryption

Industrial control systems (ICS) describes the different types of control systems and associated instrumentation, which includes the devices, systems, networks, and controls used to operate and/or automate industrial processes. Depending on the industry, each ICS functions differently and are built to electronically manage tasks efficiently. Historically, industrial plants have included networking, and changes have been made over time without consideration for security. Many ICS devices currently have inadequate security features. Adding encryption in ICS is undesirable because many of the new detection method involves deep packet inspection. Therefore, we propose to develop a method of providing authentication between devices without encrypting the data. This testbed design will allow rapid development and experimentation with Cyber Physical Systems. Modbus connects to a supervisory computer with a Remote Terminal Unit (RTU) in Supervisory Control and Data Acquisition (SCADA) systems. Our project seeks to enhance security in the ICS environment by adding device authentication to the lower levels of the plant floor. This approach was selected as it allows verification of the sender of data from level 1/level 0 devices up to supervisory systems. This addition is desirable as it adds enhanced verification to the integrity of system data without obscuring (via encryption) the data being transmitted across the network. This is important because many ICS systems are real time critical (decryption adds to latency) and many other good security options require deep packet inspection (which encryption completely defeats). To accomplish this, a proof of concept of adding an authentication scheme was designed and will be tested with a common ICS protocol. The setup includes a single serial cable connecting the serial ports on two devices, a Master and a Minion. Authentication will occur in the following methods: - Data layer involving Transport Layer Security/Secure Socket Layer (TLS/SSL); - TCP/IP route implementation; - Key exchange algorithm; - Raspberry Pi programming for authentication. A portion of the setup includes adding Raspberry Pi into the system as the device is handling the authentication for the network traffic. Modbus is the chosen ICS protocol. It is used to transmit signals from instrumentation and control devices back to a main controller or data gathering system. Typically, the device identity is assumed but not verified. For verifying device identity, we constructed a digital signature architecture with TLS. A novel adaptation of this is to use only the digital signature that is provided and not the encryption capability. This allows ICS traffic to flow unobscured while still providing verification for the integrity of the data. Verification of this process will involve adding additional I/O level network devices with spoofed IP addresses and detecting the authenticated versus unauthenticated traffic. Our TLS implementation will have encryption disabled but should still allow for digital signing of data. This will enable our system to distinguish between real end devices and spoofed end devices. This experiment is presently building the test setup. It is focusing on a small setting to identify authenticated and unauthenticated devices on the network. This should allow for scaling to a larger network size after the initial proof of concept. One concern with this scheme is a certificate deployment has a large scale key management. Network size will thus increase the key management task for security. In addition, we believe that further research should be done on exploring the use of this method to defeat man-in-the-middle attacks.

42 ENGINEERING↗

NASA NTRS2006

Transferring Files Between the Deep Impact Spacecrafts and the Ground Data System Using the CCSDS File Delivery Protocol (CFDP): A Case Study

The CCSDS File Delivery Protocol (CFDP) Standard could reshape ground support architectures by enabling applications to communicate over the space link using reliable-symmetric transport services. JPL utilized the CFDP standard to support the Deep Impact Mission. The architecture was based on layering the CFDP applications on top of the CCSDS Space Link Extension Services for data transport from the mission control centers to the ground stations. On July 4, 2005 at 1:52 A.M. EDT, the Deep Impact impactor successfully collided with comet Tempel 1. During the final 48 hours prior to impact, over 300 files were uplinked to the spacecraft, while over 6 thousand files were downlinked from the spacecraft using the CFDP. This paper uses the Deep Impact Mission as a case study in a discussion of the CFDP architecture, Deep Impact Mission requirements, and design for integrating the CFDP into the JPL deep space support services. Issues and recommendations for future missions using CFDP are also provided.

CCSDS File Delivery Protocol (CFDP)↗

NASA NTRS2015

Nearly a Decade of CALIPSO Observations of Asian and Saharan Dust Properties Near Source and Transport Regions

The lidar on the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) mission, makes robust measurements of dust and has generated a length of record that is significant both seasonally and inter-annually. We exploit this record to determine a multi-year climatology of the properties of Asian and Saharan dust, in particular seasonal optical depths, layer frequencies, and layer heights of dust gridded in accordance with the Level 3 data products protocol, between 2006-2015. The data are screened using standard CALIPSO quality assurance flags, cloud aerosol discrimination (CAD) scores, overlying features and layer properties. To evaluate the effects of transport on the morphology, vertical extent and size of the dust layers, we compare probability distribution functions of the layer integrated volume depolarization ratios, geometric depths and integrated attenuated color ratios near the source to the same distributions in the far field or transport region. CALIPSO is collaboration between NASA and Centre National D'études Spatiales (CNES), was launched in April 2006 to provide vertically resolved measurements of cloud and aerosol distributions. The primary instrument on the CALIPSO satellite is the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP), a near-nadir viewing two-wavelength polarization-sensitive instrument. The unique nature of CALIOP measurements make it quite challenging to validate backscatter profiles, aerosol type, and cloud phase, all of which are used to retrieve extinction and optical depth. To evaluate the uncertainty in the lidar ratios, we compare the values computed from dust layers overlying opaque water clouds, considered nominal, with the constant lidar ratio value used in the CALIOP algorithms for dust. We also explore the effects of noise on the CALIOP retrievals at daytime by comparing the distributions of the properties at daytime to the nighttime distributions.

Omar, Ali H.↗

DOE OSTI2014

Review of Quantitative Monitoring Methodologies for Emissions Verification and Accounting for Carbon Dioxide Capture and Storage for California’s Greenhouse Gas Cap-and-Trade and Low-Carbon Fuel Standard Programs

The Cap-and-Trade and Low Carbon Fuel Standard (LCFS) programs being administered by the California Air Resources Board (CARB) include Carbon Dioxide Capture and Storage (CCS) as a potential means to reduce greenhouse gas (GHG) emissions. However, there is currently no universal standard approach that quantifies GHG emissions reductions for CCS and that is suitable for the quantitative needs of the Cap-and-Trade and LCFS programs. CCS involves emissions related to the capture (e.g., arising from increased energy needed to separate carbon dioxide (CO 2 ) from a flue gas and compress it for transport), transport (e.g., by pipeline), and storage of CO 2 (e.g., due to leakage to the atmosphere from geologic CO 2 storage sites). In this project, we reviewed and compared monitoring, verification, and accounting (MVA) protocols for CCS from around the world by focusing on protocols specific to the geologic storage part of CCS. In addition to presenting the review of these protocols, we highlight in this report those storage-related MVA protocols that we believe are particularly appropriate for CCS in California. We find that none of the existing protocols is completely appropriate for California, but various elements of all of them could be adopted and/or augmented to develop a rigorous, defensible, and practical surface leakage MVA protocol for California. The key features of a suitable surface leakage MVA plan for California are that it: (1) informs and validates the leakage risk assessment, (2) specifies use of the most effective monitoring strategies while still being flexible enough to accommodate special or site-specific conditions, (3) quantifies stored CO 2 , and (4) offers defensible estimates of uncertainty in monitored properties. California’s surface leakage MVA protocol needs to be applicable to the main CO 2 storage opportunities (in California and in other states with entities participating in California’s Cap-and-Trade or LCFS programs), specifically CO 2 -enhanced oil recovery (CO 2 -EOR), CO 2 injection into depleted gas reservoirs (with or without CO 2 -enhanced gas recovery (CO 2 -EGR)), as well as deep saline storage. Regarding the elements of an effective surface leakage MVA protocol, our recommendations for California are that: (1) both CO 2 and methane (CH 4 ) surface leakage should be monitored, especially for enhanced recovery scenarios, (2) emissions from all sources not directly related to injection and geologic storage (e.g., from capture, or pipeline transport) should be monitored and reported under a plan separate from the surface leakage MVA plan that is included as another component of the quantification methodology (QM), (3) the primary objective of the surface leakage MVA plan should be to quantify surface leakage of CO 2 and CH 4 and its uncertainty, with consideration of best-practices and state-of-the-art approaches to monitoring including attribution assessment, (4) effort should be made to monitor CO 2 storage and migration in the subsurface to anticipate future surface leakage monitoring needs, (5) detailed descriptions of specific monitoring technologies and approaches should be provided in the MVA plan, (6) the main purpose of the CO 2 injection project (CO 2 -EOR, CO 2 -EGR, or pure geologic carbon sequestration (GCS)) needs to be stated up front, (7) approaches to dealing with missing data and quantifying uncertainty need to be described, and (8) post-injection monitoring should go on for a period consistent with or longer than that prescribed by the U.S. EPA.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films

Two-dimensional coordination polymers (2DCPs) have been predicted to exhibit exotic properties such as superconductivity, topological insulating behavior, catalytic activity, and superior ion transport for energy applications; experimentally, these materials have fallen short of their expectation due to the lack of synthesis protocols that yield continuous, large crystallite domains, and highly ordered thin films with controllable physical and chemical properties. Herein, the fabrication of large-area, highly ordered 2DCP thin films with large crystallite domains using chemical vapor deposition (CVD) approaches is described. It is demonstrated that defects and the packing motifs of 2DCP thin films may be controlled by adjusting the vapor–vapor and vapor–solid interactions of the metal and organic linker precursors during the CVD fabrication process. Such control allows for the fabrication of defects-controlled 2DCP thin films that show either semiconducting or metallic behavior. The findings provide the first demonstration of tuning the electrical properties of sub 100 nm-thick continuous 2DCP thin films by controlling their electronic landscape through defect engineering. As such, it is determined that large-area, highly ordered 2DCP thin films may undergo a semiconducting to metallic transition that is correlated to changes in morphology, crystalline domain sizes, crystallite orientation, defect interactions, and electronic structure.

2D coordination polymers↗

DOE OSTI2015

Current limitations and challenges in nanowaste detection, characterisation and monitoring

Highlights: • First review on detection of nanomaterials in complex waste samples. • Focus on nanoparticles in solid, liquid and gaseous waste samples. • Summary of current applicable methods for nanowaste detection and characterisation. • Limitations and challenges of characterisation of nanoparticles in waste. - Abstract: Engineered nanomaterials (ENMs) are already extensively used in diverse consumer products. Along the life cycle of a nano-enabled product, ENMs can be released and subsequently accumulate in the environment. Material flow models also indicate that a variety of ENMs may accumulate in waste streams. Therefore, a new type of waste, so-called nanowaste, is generated when end-of-life ENMs and nano-enabled products are disposed of. In terms of the precautionary principle, environmental monitoring of end-of-life ENMs is crucial to allow assessment of the potential impact of nanowaste on our ecosystem. Trace analysis and quantification of nanoparticulate species is very challenging because of the variety of ENM types that are used in products and low concentrations of nanowaste expected in complex environmental media. In the framework of this paper, challenges in nanowaste characterisation and appropriate analytical techniques which can be applied to nanowaste analysis are summarised. Recent case studies focussing on the characterisation of ENMs in waste streams are discussed. Most studies aim to investigate the fate of nanowaste during incineration, particularly considering aerosol measurements; whereas, detailed studies focusing on the potential release of nanowaste during waste recycling processes are currently not available. In terms of suitable analytical methods, separation techniques coupled to spectrometry-based methods are promising tools to detect nanowaste and determine particle size distribution in liquid waste samples. Standardised leaching protocols can be applied to generate soluble fractions stemming from solid wastes, while micro- and ultrafiltration can be used to enrich nanoparticulate species. Imaging techniques combined with X-ray-based methods are powerful tools for determining particle size, morphology and screening elemental composition. However, quantification of nanowaste is currently hampered due to the problem to differentiate engineered from naturally-occurring nanoparticles. A promising approach to face these challenges in nanowaste characterisation might be the application of nanotracers with unique optical properties, elemental or isotopic fingerprints. At present, there is also a need to develop and standardise analytical protocols regarding nanowaste sampling, separation and quantification. In general, more experimental studies are needed to examine the fate and transport of ENMs in waste streams and to deduce transfer coefficients, respectively to develop reliable material flow models.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗