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At least 91 records · Page 5

Chemically Driven Multistep Crystallization in the Synthesis of Sodium Yttrium Fluoride Via a Porous, Electrochemically Active Intermediate

Two-step crystallization mechanisms based on liquid–liquid phase separations followed by crystallization are commonly observed both in the laboratory and in nature. While this pathway quite often occurs as a result of a chemical reaction, the subsequent nucleation and growth are often considered as separate, discrete events from the reaction itself. We show this mechanism in the aqueous synthesis sodium yttrium fluoride, but by using a combination of experimental techniques and computational modeling, we show an additional step of solid-state chemical diffusion that is essential to the nucleation mechanism. In this system, we observe at least four distinct steps in the crystallization process, including (1) the segregation of aqueous ions into a dense liquid phase, (2) the formation of a metastable amorphous aggregate, (3) the continuous, gradual solid-state diffusion of sodium and fluoride ions into the amorphous aggregate toward a NaYF4 stoichiometry, and (4) the crystallization of a stable cubic sodium yttrium fluoride phase. Unlike previous descriptions of nucleation and growth, we find that the stoichiometry of the final solid phase evolves throughout the crystallization process rather than being determined at the time of the initial separation from solution. Further, this emphasizes that the chemical reaction cannot be assumed to be a separate event from the phase separation and growth, especially in compounds with variable stoichiometry. We also find that the amorphous aggregate that forms prior to the ion incorporation step adopts a porous, gel-like structure, which we isolated and showed to be electrochemically active, allowing for its potential use as a battery anode in lithium and sodium ion batteries, among other potential applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exacerbated drought impacts on global ecosystems due to structural overshoot

Vegetation dynamics are affected not only by the concurrent climate but also by memory-induced lagged responses. For example, favourable climate in the past could stimulate vegetation growth to surpass the ecosystem carrying capacity, leaving an ecosystem vulnerable to climate stresses. This phenomenon, known as structural overshoot, could potentially contribute to worldwide drought stress and forest mortality but the magnitude of the impact is poorly known due to the dynamic nature of overshoot and complex influencing timescales. Here, we use a dynamic statistical learning approach to identify and characterize ecosystem structural overshoot globally and quantify the associated drought impacts. We find that structural overshoot contributed to around 11% of drought events during 1981-2015 and is often associated with compound extreme drought and heat, causing faster vegetation declines and greater drought impacts compared to non-overshoot related droughts. The fraction of droughts related to overshoot is strongly related to mean annual temperature, with biodiversity, aridity and land cover as secondary factors. These results highlight the large role vegetation dynamics play in drought development and suggest that soil water depletion due to warming-induced future increases in vegetation could cause more frequent and stronger overshoot droughts.

54 ENVIRONMENTAL SCIENCES↗

The Apollo program and amino acids

Apollo lunar sample analyses designed to detect the presence of organic compounds are reviewed, and the results are discussed from the viewpoint of relevance to laboratory experiments on the synthesis of amino acids and to theoretical models of cosmochemical processes resulting in the formation of organic compounds. Glycine, alanine, glutamic acid, aspartic acid, serine, and threonine have been found repeatedly in the hydrolyzates of hot aqueous extracts of lunar dust. These compounds represent an early step in the sequence of events leading to the rise of living material and were probably deposited by the solar wind. The results of the Apollo program so far suggest that the pathway from cosmic organic matter to life as it evolved on earth could have been pursued on the moon to the stage of amino acid precursors and then may have been terminated for lack of sufficient water.

Fox, S. W.↗

A combustion products analyzer for contingency use during thermodegradation events on spacecraft

The Toxicology Laboratory at JSC and Exidyne Instrumentation Technologies (EIT) have developed a prototype Combustion Products Analyzer (CPA) to monitor, in real time, combustion products from a thermodegradation event on board spacecraft. The CPA monitors the four gases that are the most hazardous compounds (based on the toxicity potential and quantity produced) likely to be released during thermodegradation of synthetic materials: hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen cyanide (HCN), and carbon monoxide (CO). The levels of these compounds serve as markers to assist toxicologists in determining when the cabin atmosphere is safe for the crew to breathe following the contingency event. The CPA is a hand-held, battery-operated instrument containing four electrochemical sensors, one for each target gas, and a pump for drawing air across the sensors. The sensors are unique in their small size and zero-g compatibility. The immobilized electrolytes in each sensor permit the instrument to function in space and eliminate the possibility of electrolye leaks. The sample inlet system is equipped with a particulate filter that prevents clogging from airborne particulate matter. The CPA has a large digital display for gas concentrations and warming signals for low flow and low battery conditions. The CPA has flown on 13 missions beginning with STS 41 in Oct. 1990. Current efforts include the development of a microprocessor, an improved carbon monoxide sensor, and a ground-based test program to evaluate the CPA during actual thermodegradation of selected materials.

Wilson, Steve↗

Wilson Corners SWMU 001 2014 Annual Long Term Monitoring Report Kennedy Space Center, Florida

This document presents the findings of the 2014 Long Term Monitoring (LTM) that was completed at the Wilson Corners site, located at the National Aeronautics and Space Administration (NASA) John F. Kennedy Space Center (KSC), Florida. The goals of the 2014 annual LTM event were to evaluate the groundwater flow direction and gradient and to monitor the vertical and downgradient horizontal extent of the volatile organic compounds (VOCs) in groundwater at the site. The LTM activities consisted of an annual groundwater sampling event in December 2014, which included the collection of water levels from the LTM wells. During the annual groundwater sampling event, depth to groundwater was measured and VOC samples were collected using passive diffusion bags (PDBs) from 30 monitoring wells. In addition to the LTM sampling, additional assessment sampling was performed at the site using low-flow techniques based on previous LTM results and assessment activities. Assessment of monitoring well MW0052DD was performed by collecting VOC samples using low-flow techniques before and after purging 100 gallons from the well. Monitoring well MW0064 was sampled to supplement shallow VOC data north of Hot Spot 2 and east of Hot Spot 4. Monitoring well MW0089 was sampled due to its proximity to MW0090. MW0090 is screened in a deeper interval and had an unexpected detection of trichloroethene (TCE) during the 2013 LTM, which was corroborated during the March 2014 verification sampling. Monitoring well MW0130 was sampled to provide additional VOC data beneath the semi-confining clay layer in the Hot Spot 2 area.

Monitoring↗

The Potential Interactions of Novec 1230 and Its Thermal Degradation Products with Actinide Metals and Oxides

The environmentally friendly and mainly chemically inert fire suppressant, Novec 1230, is being increasingly used worldwide. However, no published study has considered using Novec 1230 with fires involving radioactive material including actinides; here, therefore, this research note focuses on the possible interactions between Novec 1230 and its thermal degradation products (TDPs) with some actinide compounds (e.g., actinide metal and oxides) commonly present in a radiological facility in the event of a fire. Previous studies of halogenated fire suppressants used in actinide metal fires indicate a possibility for Novec 1230 or its TDPs to chemically interact with actinide compounds at elevated temperatures; however, these reactions are highly unlikely to cause either runaway exothermic reactions or gaseous actinide release.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Computational analysis of metal–metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis

Metal–metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal–metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to –2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell “viability zone” bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh 2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M–M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potential safety impacts associated with production of gaseous PuF 6 due to reactions between 3013-compliant PuO 2 with Novec TM 1230 at temperature

A part of the NNSA/SRNS Surplus Plutonium Disposition (SPD) project is a planned expansion of an existing facility with capabilities to handle, process, package, and characterize large amounts of plutonium oxide materials for permanent disposition at WIPP. The facility design for this future processing capability will include glovebox operations, HEPA filters, and exhaust/ventilation systems. An NNSA review of the facility support systems included comments on the potential residual reactivity of previously-stabilized PuO 2 , and on the possibility of chemical interactions between stabilized PuO 2 and a new fire suppressant (Novec TM 1230), a replacement for chlorinated/brominated compounds such as HALON TM , to be employed in the event of a room/glovebox fire where PuO 2 will be processed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Particle Flux Measurements during TRACER (TRACER PFM) (Field Campaign Report)

The purpose of this campaign was to deploy an instrument payload collocated with a suite of in situ and remote-sensing aerosol instruments at the urban site at the La Porte, Texas Municipal Airport during the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Tracking Aerosol Convection Interactions Experiment (TRACER) in Houston, Texas. The payload was designed to characterize the physicochemical properties, mixing state, and size-resolved vertical fluxes of aerosols. Deployed aerosol instruments associated with the flux measurements included three condensation particle counters (CPCs) with different lower cutoff diameters ( D > 2.5 nm, D > 10 nm, and D > 40 nm), a single-particle soot photometer (SP2) measuring refractory black carbon, and a portable optical particle spectrometer (POPS) measuring the optical size distribution (~180 nm < D < ~5000 nm). A 10-m flux tower hosted a sonic anemometer (SONIC) for vertical velocity measurements. In addition, a humidified tandem differential mobility analyzer (HTDMA) was deployed to measure the growth factors and hygroscopicity parameter of 15-50 nm-sized particles in order to constrain the composition of compounds responsible for modal aerosol growth during new particle formation/growth events. Finally, a radial differential mobility analyzer (RDMA) was deployed to extend the size distribution measurement to 5 nm.

54 ENVIRONMENTAL SCIENCES↗

Environmental Health

The Environmental Health activity for the Extended Duration Orbiter Medical Project (EDOMP) was formed to develop an overall strategy for safeguarding crew members from potential airborne hazards anticipated on missions of extended duration. These efforts were necessary because of major modifications to the air revitalization system of the U.S. Space Shuttle and an increased potential for environmental health risks associated with longer space flights. Degradation of air quality in the Shuttle during a space flight mission has the potential to affect the performance of the crew not only during piloting, landing, or egress, but also during space flight. It was anticipated that the risk of significant deterioration in air quality would increase with extended mission lengths and could result from: (1) a major chemical contamination incident, such as a thermodegradation event or toxic leak, (2) continual accumulation of volatile organic compounds to unacceptable levels, (3) excessive levels of airborne particles, (4) excessive levels of microorganisms, or (5) accumulation of airborne pathogens.

Pierson, Duane↗

Method for detection of selected chemicals in an open environment

The present invention relates to a space-invariant independent component analysis and electronic nose for detection of selective chemicals in an unknown environment, and more specifically, an approach to analysis of sensor responses to mixtures of unknown chemicals by an electronic nose in an open and changing environment. It is intended to fill the gap between an alarm, which has little or no ability to distinguish among chemical compounds causing a response, and an analytical instrument, which can distinguish all compounds present but with no real-time or continuous event monitoring ability.

Duong, Tuan↗

Risk Assessment in a Chemical Laboratory Following an Explosive Incident Involving a Novel Diazonium Compound: Retrospective Analysis and Lessons Learned

Diazonium compounds are synthetically useful in the production of dyes and textiles, however they are highly explosive under dry conditions. Explosion prevention becomes more difficult when new diazonium compounds are synthesized, because while some syntheses include a counterion to increase their stability, this is not always a reliable method to prevent an explosive incident. Due to the uncertainty surrounding the explosiveness of different diazonium compounds, it is important to understand how to safely clean up after an incident and how to determine when it is safe to return a laboratory to typical operational use, particularly when the incident involves a novel compound where a standard does not exist for instrument calibration. Here, an explosive event is discussed involving the synthesis of 4-bromo-benzenediazonium-2-carboxylate. Following the explosive incident and 3-step cleanup, which involved a precautionary neutralization step, samples were collected from the fume hood where the incident occurred. Because the incident involved an unstable, novel compound that is not commercially available and was deemed unsafe to resynthesize for instrument calibration, we assessed the risk of further explosion by analyzing for the stable decomposition products. Mass spectrometry analysis confirmed that the residue in the fume hood contained 5-bromosalicylic acid, a decomposition product of 4-bromo-benzenediazonium-2-carboxylate. Samples were taken from multiple points in the fume hood and analyzed to estimate the spatial distribution of the decomposition product. Based on this analysis, we inferred that the primary decomposition product was far more abundant than residual energetic, indicating the energetic had been consumed or neutralized to a trace quantity where the risk of further explosion was low. Furthermore, the steps presented here─specifically, initial neutralization and then analyzing the spatial distribution of expected decomposition products to assess risk when a novel explosive material is detonated in a confined space─were our approach to assess further risk following an explosion due to a novel diazonium compound without the need for any further handling or resynthesis of the energetic. Here, we present our approach and critically analyze these steps by discussing retrospective lessons learned and alternative analytical approaches.

Computer simulations↗

Synthesis and Characterization of Pyridine Dipyrrolide Uranyl Complexes

The first actinide complexes of the pyridine dipyrrolide (PDP) ligand class, ( Mes PDP Ph )UO 2 (THF) and ( Cl2Ph PDP Ph )UO 2 (THF), are reported as the U VI uranyl adducts of the bulky aryl substituted pincers ( Mes PDP Ph ) 2– and ( Cl2Ph PDP Ph ) 2– (derived from 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine (H 2 Mes PDP Ph , Mes = 2,4,6-trimethylphenyl), and 2,6-bis(5-(2,6-dichlorophenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine (H 2 Cl2Ph PDP Ph , Cl 2 Ph = 2,6-dichlorophenyl), respectively). Following the in situ deprotonation of the proligand with lithium hexamethyldisilazide to generate the corresponding dilithium salts (e.g., Li 2 Ar PDP Ph , Ar = Mes of Cl 2 Ph), salt metathesis with [UO 2 Cl 2 (THF) 2 ] 2 afforded both compounds in moderate yields. The characterization of each species has been undertaken by a combination of solid- and solution-state methods, including combustion analysis, infrared, electronic absorption, and NMR spectroscopies. In both complexes, single-crystal X-ray diffraction has revealed a distorted octahedral geometry in the solid state, enforced by the bite angle of the rigid meridional ( Ar PDP Ph ) 2– pincer ligand. The electrochemical analysis of both compounds by cyclic voltammetry in tetrahydrofuran (THF) reveals rich redox profiles, including events assigned as U VI /U V redox couples. Here, a time-dependent density functional theory study has been performed on ( Mes PDP Ph )UO 2 (THF) and provides insight into the nature of the transitions that comprise its electronic absorption spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Launch Complex 34, SWMU CCO542022 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot (HS) 6 Air Sparge (AS) System presents the results of Year 13 operation of the hydraulic containment (HC) Interim Measure (IM), the results of performance monitoring direct-push technology (DPT) sampling and monitoring well sampling conducted in the DSZ, results of the biennial site-wide LTM event, and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. This site has been designated Solid Waste Management Unit (SWMU) CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act (RCRA) Corrective Action Program. For the site-wide biennial LTM event, a total of 55 monitoring wells were sampled for volatile organic compounds (VOCs) in February 2023 and one well was sampled for polychlorinated biphenyls (PCBs) in December 2022. One well planned for VOC sampling was found to be destroyed and could not be sampled (CW0002). The LTM wells are screened in two lithologic zones: Layer 1 (0 to 25 feet below land surface [bls]) and Layer 2 (25 to 30 ft bls), and are located in the outlying areas of LC34 to monitor groundwater conditions within the Low-Concentration Plume (LCP), defined as concentrations exceeding Groundwater Cleanup Target Levels (GCTLs), and the High-Concentration Plume (HCP), defined as concentrations exceeding Natural Attenuation Default Concentrations (NADCs). Results from the biennial sampling event indicated overall plume stability and delineation for the plume, which extends over 300 acres. The operational period for Year 13 of the HCS was from April 1, 2022 to March 31, 2023. Operational runtime for the system was 90 percent during Year 13, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2023, a total of 313,673,241 cumulative gallons of groundwater containing 88,337 pounds of VOCs have been removed by the HCS. Influent concentrations of trichloroethene (TCE) have decreased since startup from approximately 280,000 μg/L (January 2010) to 12,000 μg/L (March 2023). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in December 2022 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2021. Full vertical profile sampling was completed at each DPT from 8 to 98 feet bls, at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 μg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 8 to 98 feet bls. In addition to DPT sampling, groundwater samples were collected from deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2022 to verify vertical delineation. Layer 7/8 monitoring well results were non-detect in December 2022, with exception of three wells (IW0162, IW043D2, and IW044D2), where TCE, cis-1,2-dichloroethene (cDCE), and/or vinyl chloride (VC) were detected above GCTLs. These wells are screened 105 to 115 feet bls, which is below the existing recovery well capture zone. TCE was first detected in IW0162 in December 2021 and has since been sampled at least monthly to monitor TCE concentrations. The maximum TCE concentration during this operational period was 15,000 μg/L at IW0162 in March 2023. Because of the increased TCE concentrations in this well, a new recovery well (RW21D), screened 86 to 106 feet bls, was installed in January 2023 and incorporated into existing HCS operations. The HS 6 AS IM was initiated in 2018 with 160 AS wells, and expanded in 2019 with an additional 140 AS wells. Quarterly performance monitoring was reduced to semi-annual in 2020. The HS 6 AS system remained operational during the reporting period covered under this report. The results of the HS 6 system operation and semi-annual performance monitoring are summarized in this report. Semi-annual monitoring results collected in April and October 2022 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and vinyl chloride) are generally decreasing and not impacting the surface water drainage canal, indicating the HS 6 IM is meeting objectives. A Phase Two Expansion of the HS 6 AS IM was recently completed. As of the date of this report, the expansion became operational in August 2023 and the first quarter of monitoring was conducted in November 2023. Details of the construction, start-up, and performance monitoring will be included in a future Annual PMR. Overall, the tasks associated with Year 13 operation of the HC IM, operation of the HS 6 AS IM, and biennial site-wide sampling were performed in accordance with recommendations included in the previous 2021 LC34 (Year 12) annual report. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives. Results from the site-wide biennial LTM program also show that the overall network of monitoring wells is adequate to continue monitoring plume-wide conditions.

Complex 34↗

The glass transition, crystallization and melting in Au-Pb-Sb alloys

The glass transition, crystallization and melting of Au(55)Pb(22.5)Sb(22.5) alloys have been studied by differential scanning calorimetry DSC. Crystallization on heating above the glass transition temperature Tg (45 C) begins at 64 C. Further crystallization events are observed at 172 C and 205 C. These events were found to correspond to the formation of the intermetallic compounds AuSb2, Au2Pb, and possibly AuPb2, respectively. Isothermal DSC scans of the glassy alloy above Tg were used to monitor the kinetics of crystallization. The solidification behavior and heat capacity in the glass-forming composition range were determined with droplet samples. An undercooling level of 0.3T(L) below the liquidus temperature T(L) was achieved, resulting in crystallization of different stable and metastable phases. The heat capacity C(P) of the undercooled liquid was measured over an undercooling range of 145 C.

Lee, M. C.↗

Development and Performance of the Oxygen Sensor in the CSA-CP Aboard the International Space Station

A combustion products analyzer (CPA) was built for use on Shuttle in response to several thermodegradation incidents that had occurred during early flights. The CPA contained sensors that measured carbon monoxide, hydrogen chloride, hydrogen cyanide, and hydrogen fluoride. These marker compounds, monitored by the CPA, were selected based upon the likely products to be released in a spacecraft fire. When the Toxicology Laboratory group at Johnson Space Center (JSC) began to assess the air quality monitoring needs for the International Space Station (ISS), the CPA was the starting point for design of an instrument to monitor the atmosphere following a thermodegradation event. The final product was significantly different from the CPA and was named the compound specific analyzer-combustion products (CSA-CP). The major change from the CPA that will be the focus of this paper was the replacement of an unreliable hydrogen fluoride (HF) sensor with an oxygen sensor. A reliable HF sensor was not commercially available, but as the toxicology group reviewed the overall monitoring strategy for ISS, it appeared that a portable oxygen sensor to backup the major constituent analyzer was needed. Therefore, an oxygen sensor replaced the HF sensor in the new instrument. This paper will describe the development, deployment, and performance of the CSA-CP oxygen sensor on both Shuttle and ISS. Also, data for CSA-CP oxygen sensor accuracy at nominal and reduced pressures will be presented.

Limero, Thomas↗

Challenges resulting from urban density and climate change for the EU energy transition

Dense urban morphologies further amplify extreme climate events due to the urban heat island phenomenon, rendering cities more vulnerable to extreme climate events. Here we develop a modelling framework using multi-scale climate and energy system models to assess the compound impact of future climate variations and urban densification on renewable energy integration for 18 European cities. We observe a marked change in wind speed and temperature due to the aforementioned compound impact, resulting in a notable increase in both peak and annual energy demand. Therefore, an additional cost of 20–60% will be needed during the energy transition (without technology innovation in building) to guarantee climate resilience. Failure to consider extreme climate events will lower power supply reliability by up to 30%. Here, energy infrastructure in dense urban areas of southern Europe is more vulnerable to the compound impact, necessitating flexibility improvements at the design phase when improving renewable penetration levels.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗