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DOE OSTI2023

A life cycle and product type based estimator for quantifying the carbon stored in wood products

Background: Timber harvesting and industrial wood processing laterally transfer the carbon stored in forest sectors to wood products creating a wood products carbon pool. The carbon stored in wood products is allocated to end-use wood products (e.g., paper, furniture), landfill, and charcoal. Wood products can store substantial amounts of carbon and contribute to the mitigation of greenhouse effects. Therefore, accurate accounts for the size of wood products carbon pools for different regions are essential to estimating the land-atmosphere carbon exchange by using the bottom-up approach of carbon stock change. Results: To quantify the carbon stored in wood products, we developed a state-of-the-art estimator (Wood Products Carbon Storage Estimator, WPsCS Estimator) that includes the wood products disposal, recycling, and waste wood decomposition processes. The wood products carbon pool in this estimator has three subpools: (1) end-use wood products, (2) landfill, and (3) charcoal carbon. In addition, it has a user-friendly interface, which can be used to easily parameterize and calibrate an estimation. To evaluate its performance, we applied this estimator to account for the carbon stored in wood products made from the timber harvested in Maine, USA, and the carbon storage of wood products consumed in the United States. Conclusion: The WPsCS Estimator can efficiently and easily quantify the carbon stored in harvested wood products for a given region over a specific period, which was demonstrated with two illustrative examples. In addition, WPsCS Estimator has a user-friendly interface, and all parameters can be easily modified.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Thermal Integration of Advanced Nuclear Reactors with a Reference Refinery, Methanol Synthesis, and a Wood Pulp Plant (Rev.1)

The present report is intended to provide process flow diagrams (PFDs) and energy and mass balance data sheets for a U.S. industrial sector subset with which nuclear heat and power could be integrated—a subset that includes the oil refining, methanol and pulp and paper industries. Coupling options for integrating nuclear energy into these industries are quantitatively outlined for reference systems, and future work will extend this analysis in greater detail. Opportunities for integrating small modular nuclear reactors (SMNRs) were investigated for each of the industrial process configurations. Aspen HYSYS and Cycle-Tempo models for a high-temperature gas-cooled reactor were developed to evaluate the proposed integration. This introductory evaluation provides a general description and assessment of the operating principles, reactor coolant core outlet temperature, and reactor size to be integrated with industry. The industrial processes of oil refining and the production of methanol, pulp and paper were simulated by using Aspen HYSYS, Aspen Plus, and the PRELIM (Petroleum Refinery Life Cycle Inventory Model) tool to develop process details. Cycle-Tempo models then extend the process modeling results to obtain net energy demands (e.g., heat, steam, and electricity) when accounting for process steam and waste heat recovery. This information is intended to foster the analysis of integrating an SMNR to decarbonize industrial facilities. The SMNR would provide reliable, competitive, and sustainable clean energy while reducing carbon emissions and other environmental impacts, such as water withdrawals, consumption, and contamination. The refining industry, exhibited in Figure ES1, is a leading consumer of fossil -fuel-based heat, power, and hydrogen in the U.S. industrial sector, generating over 164 million metric tons (MMT) of CO 2 emissions in 2023. The overall mass and energy pertaining to a generalized complex refinery in the United States is reflected in Figure ES1, along with energy metrics regarding integration with a nuclear power plant (NPP). Data sheets were developed to indicate the energy requirements for the overall refinery and each refinery process. The data sheet for the overall refinery is shown in Table ES2.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

NASA NTRS2005

Itegrated Test and Evaluation of a 4-Bed Molecular Sieve (4BMS) Carbon Dioxide Removtal System (CDRA), Mechanical Compressor Engineering Development Unit (EDU), and Sabitier Engineering Development Unit (EDU)

Currently on the International Space Station s (ISS) U.S. Segment, carbon dioxide (CO2) scrubbed from the cabin by a 4-Bed Molecular Sieve (4BMS) Carbon Dioxide Removal Assembly (CDRA) is vented overboard as a waste product. Likewise, the product hydrogen (H2) that will be generated by the Oxygen Generation Assembly (OGA) planned for installation will also be vented. A flight experiment has been proposed that will take the waste CO2 removed from the cabin, and via the catalytic Sabatier process, reduce it with waste H2 to generate water and methane. The water produced may provide cost and logistics savings for ISS by reducing the amount of water periodically re-supplied to orbit. To make this concept viable, a mechanical piston compressor and accumulator were developed for collecting and storing the CO2 from the CDRA. The compressor, accumulator and Sabatier system would be packaged together as one unit and referred to as the Carbon Dioxide Reduction Assembly (CRA). Testing was required to evaluate the performance of a 4BMS CDRA, compressor, accumulator, and Sabatier performance along with their operating rules when integrated together. This had been numerically modeled and simulated; however, testing was necessary to verify the results from the engineering analyses. Testing also allowed a better understanding of the practical inefficiencies and control issues involved in a fully integrated system versus the theoretical ideals in the model. This paper presents and discusses the results of an integrated engineering development unit test.

Knox, James C.↗

DOE OSTI2026

High waste loading glass formulation development for high-P HLW

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2026

Glass Formulation Development for Al, Fe, and Na Phosphate HLW

The primary objective of the work described herein was to develop and identify HLW glass compositions and glass forming additive blends that achieve high waste loadings and processing rates for high phosphorus HLW streams while maintaining acceptable glass properties. Another objective was to determine the effect of phosphate form (aluminum, iron, sodium) on feed processing properties, glass production rates, and product quality while vitrifying a high phosphorus HLW stream. This was accomplished through a combination of crucible-scale tests, vertical gradient furnace tests, and confirmation tests on a DM100 melter system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2026

Technoeconomic and Life Cycle Analysis of an Integrated Fermentation and Microbial Electrochemical Process for Volatile Fatty Acid Production from Food Waste

Techno-economic analysis (TEA) and life cycle assessment (LCA) were conducted for an integrated system designed for the production of volatile fatty acid (VFA) from food waste. The TEA estimated a production cost of $\$$3.12/kg VFA, and the LCA predicted negative greenhouse gas (GHG) emissions of -0.4 kg CO 2 e/kg VFA, driven primarily by diverting organic waste from landfills and avoiding methane emissions while producing valuable chemical products. Hotspot analysis showed arrested methanogenesis (AM) fermentation as the largest contributor to costs (37%) and environmental burden (47%), driven by high sodium hydroxide (NaOH) consumption. Distillation and microbial electrosynthesis (MES) units were the next-largest environmental contributors (28% and 18%). Major cost drivers also included residuals management (biosolids and wastewater) and the equipment and operating costs for AM, MES, and sonication pretreatment units. Although the new integrated system is environmentally benign, its costs and environmental impacts can be further reduced by integrating alternative energy sources, minimizing chemical and energy inputs through process optimization, and improving efficiency. In conclusion, this work highlighted the viability of waste-derived VFA production and provided a clear, data-driven strategy to accelerate the commercialization of waste valorization technology.

Carboxylic Acid Production↗

DOE OSTI2026

High waste loading glass formulation development for High-Mn HLW

One of the primary objectives of the work described herein was to develop and identify HLW glass compositions and glass forming additive blends that achieve high waste loadings and processing rates for high manganese HLW streams while maintaining acceptable glass properties. Another objective was to determine the effect of the form of manganese (MnO, MnO2, MnCO3) on feed processing properties, glass production rates, and product quality while vitrifying a high manganese HLW stream. This was accomplished through a combination of crucible-scale tests, vertical gradient furnace tests, and confirmation tests on a DM100 melter system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Investigation into Reductive Separation of Tc-99 from Low Activity Waste Off-Gas Condensate by Zero Valent Iron Materials - 20311

This study is investigating the potential for reductive separation of technetium-99 (Tc) from off-gas condensate generated from vitrification of legacy tank waste at the Hanford Tank Waste Treatment and Immobilization Plant. Management of Tc is a high-priority activity for the U.S. Department of Energy (DOE) Office of Environmental Management (EM) complex, which must be addressed based on knowledge gaps and technology development needs outlined in the DOE-EM Technetium Management Program Plan [1]. Technetium is one of the main risk drivers in the permanent disposal of low activity waste (LAW) by vitrification at the Hanford Site due to its high volatility and only fractional incorporation into borosilicate glass. Volatilized Tc will be captured by an off-gas treatment system, and the current plan is to continuously recycle generated condensate back to the LAW glass melter feed. Off-gas recycling is effective at increasing Tc loading in the LAW glass, but it also disproportionately increases concentrations of sulfate, halides, and other volatile compounds impeding overall LAW processing leading to significantly greater waste glass volume requirements. Removal of Tc from secondary liquid waste offers an alternative disposal route to continuous off-gas recycling which may result in significant reduction of the volumes of LAW waste glass and substantial cost savings. The objective of this research funded by the DOE-EM Minority Serving Institutions Partnership Program (MSIPP) is to determine the suitability of zero valent iron (ZVI) as a separation technology to remove Tc from the off-gas condensate stream to minimize its recycle. While ZVI has been proposed for various remediation applications with Tc, it has not been studied for its suitability for removing Tc from the LAW off-gas condensate. The goal is to identify the optimal conditions for which Tc{sup (VII)} will be reduced to Tc{sup (IV)} species and incorporated into an iron matrix. This paper presents a programmatic overview of our evaluation of commercial ZVI materials for their efficiency towards Tc{sup (VII)} reductive removal from simplified off-gas simulant solutions under aerobic conditions. Tc concentrations in solutions were monitored for up to 30 days to determine efficiency and kinetics of reductive removal of Tc. The best performing candidate materials were selected for further experiments evaluating the effects of (1) variable ionic strength, (2) the presence of chromium and corrosive anions, and (3) ZVI aging on Tc{sup (VII)} reductive removal in batch experiments. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

FY2020 Rotating Bed Reactor for Iodine Removal from WTP Melter Effluent to Support DFLAW Start-Up

In Performance Assessment (PA) of the Hanford Integrated Disposal Facility (IDF), 129 I is a significant contributor to the risk. The 2017 IDF PA accounted for 0.22% of the total 129 I inventory in Hanford tank waste as residing in the solidified liquid waste from the Effluent Treatment Facility (ETF). However, recent estimates suggest that higher percentages of the iodine processed at the Hanford Waste Treatment and Immobilization Plant (WTP) may be present in the liquid waste routed to the Liquid Effluent Retention Facility (LERF) for eventual treatment at the ETF. In addition, a recent integrated melter test performed at the Vitreous State Laboratory (VSL) at The Catholic University of America (CUA) showed the possibility that a significant fraction (>50%) of the total iodine in the melter feed could be present in the aqueous waste stream destined for the ETF. This stream represents a combination of the Effluent Management Facility (EMF) evaporator overhead condensate and the liquid waste from the WTP off-gas caustic scrubber. Higher levels of 129 I in this stream could affect the LERF and ETF Hazard Categorizations as well as the acceptability of the solidified ETF liquid secondary waste brine for disposal at the IDF. Accordingly, there is a need to investigate and develop potential methods and processes to mitigate this risk. Washington River Protection Solutions, LLC (WRPS) tasked Atkins and VSL to perform development and testing work to evaluate potential methods for removal of iodine species from the waste stream routed to the LERF. In particular, the testing investigated the use of an Atkins-SpinIonic™ Rotating Bed Reactor (RBR) system as a potential alternative to conventional column-based ion exchange or absorption processes. The present report provides results obtained from testing with an RBR system for the removal of iodine from simulants of the projected WTP waste stream that discharges to the LERF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Planning for Material Control and Accountancy at Liquid Fueled Molten Salt Reactors

The purpose of this report is to provide molten salt reactor (MSR) developers and future US Nuclear Regulatory Commission (NRC) license applicants with recommendations for developing an effective and practical material control and accounting (MC&A) plan, focused primarily on MSR designs that use circulating liquid fuel. Because of the breadth of MSR designs, there is no single, generic, detailed MC&A plan that will work for every design. The wide variation of fresh fuel salts, the method and frequency of loading fresh fuel, the reactor system design components (e.g., tanks, filtration systems, chemical processing streams), and waste streams will determine the specific measurement locations and instrumentation that can best meet MC&A objectives throughout an MSR facility. Additionally, MSR designs are rapidly evolving, and new design features and deployment scenarios that will affect MC&A are being explored and pursued. This report defines a generic MC&A approach that was developed for terrestrial (as opposed to maritime) deployments to meet the intent of NRC domestic safeguards and MC&A. MSR license applicants should consider nuclear safeguards (both domestic and international) and security throughout the design, as early as the preconceptual design phase. MC&A of special nuclear material (SNM) is an aspect of the NRC’s domestic safeguards program, alongside physical protection. Because liquid-fueled MSRs are reactors with SNM in nondiscrete (or item) form, it is likely that the NRC may require liquid-fueled MSR license applicants to submit a formal MC&A plan as a part of their license application. Currently, the NRC licensing protocol presents a challenge because the NRC MC&A regulations have not been updated to accommodate advanced reactors, including types of MSRs. Because no liquid-fueled MSR has been licensed for operation at the time of this report, no template or precedence for a successfully licensed MSR MC&A plan exists. However, the MSR license applicant can take advantage of the NRC’s published commitments to performance-based regulations. The authors recommend that the license applicant, or MSR designers, develop an MC&A plan throughout the design lifecycle and plan to submit a detailed MC&A program description, or MC&A plan, to the NRC as a part of a license application. No MC&A plan template or guidance exists that is specific to liquid-fueled MSRs. The authors recommend that license applicants discuss the topic of MC&A during preapplication engagement. Because of the uniqueness of MC&A for liquid fueled MSRs, the authors recommend that liquid fueled MSR developers engage with the NRC on the topic of MC&A in the early phases of its design development and follow up any time there are significant modifications in design plans that would affect MC&A. For example, topics like modifications in fuel handling processes, changes in uranium enrichment, or additional chemical processing streams added to the design could be discussed with the NRC specifically on the topic of MC&A.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS2018

A Two-Stage Biological Reactor for Treatment of Space Based Waste Waters

Previous works on Membrane Aerobic Biological Reactors (MABR) CoMANDR 1.0, CoMANDR 2.0, and R-CoMANDAR have demonstrated their ability to stabilize various space based waste streams over operating periods of ~1 year. Biological pretreatment by MABR systems can stabilize space based waste streams. Biological stabilization includes reducing the pH, conversion of organic N to NOx- and oxidation of dissolved organic matter to CO2. These processes produce a more stable waste product (brine), facilitate the distillation processes, and enable evaporative or membrane based systems. An alternative to aerobic operation would be to include anoxic operation to promote denitrification and production of N2 gas. This results in a reduced O2 demand and increases ammonia oxidation efficiency. Denitrifictaion can be accomplished in either a single reactor (Simultaneous Nitrification Denitrification) or in a two-stage system with separate aerobic and anoxic reactors. We evaluated the performance of both architectures in pilot scale systems (1-2 crew/d). Each system was continuously operated for over 2 years during which they processed a variety of habitation waste streams (ISS, Transit, and EPB) in both a continuous and on production feed mode. Here we report the results of the two stage system. Results indicate that the two stage system can successfully remove organic carbon, lower pH and convert organic N to N2 gas. Organic carbon and organic N oxidation reaction rates for the two stage system are similar to past studies for single stage aerobic systems. The two stage system is more complex and requires an additional pump. While no maintenance was required on the system during the nearly two year period of operation, the packed bed did produce N2 gas for many operational test points. The performance and comparison of operational conditions are detailed below

Water↗

DOE OSTI2023

Kinetics of the Temperature-Dependent e aq - and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions

The reactivity of chromium(III) species with the major oxidizing and reducing radiolysis products of water was investigated in aqueous solutions at temperatures up to 150 °C. The reaction between the hydrated electron (e aq - ) and Cr(III) species showed a positive temperature dependence over this temperature range. The reaction was also studied in pH 2.5 and 3.5 solutions for the first time. This work also studied the reaction between acidic Cr(III) species and the hydroxyl radical (·OH). It was found that Cr 3+ did not react significantly with the ·OH radical, but the first hydrolysis species, Cr(OH) 2+ , did with a rate coefficient of k= (7.2±0.3)×10 8 M -1 s -1 at 25 °C. The oxidation of Cr(OH) 2+ by the ·OH radical formed an absorbing product species that ultimately oxidized to give Cr(VI). In conclusion, these newly measured reaction rates allow for the development of improved models of aqueous chromium speciation for the effective remediation of liquid high-level nuclear waste via vitrification processes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Mechanistic insights into the pyrolysis of poly (vinyl chloride)

The accumulation of unmanaged plastic waste in the environment has a devastating impact upon marine life and human health. Catalytic and thermal pyrolysis are promising technologies toward the efficient utilization of plastic waste. Yet, the processing of polymers, such as polyvinyl chloride (PVC), that decompose into corrosive compounds remains a major challenge. In this work, we employ density functional theory (DFT) and thermogravimetric analysis (TGA) to explore the elementary chemical steps that underpin the thermal decomposition of PVC. We determine that the dehydrochlorination reaction (i.e., 1 st stage of thermal decomposition) begins in tertiary chloride defects and propagates via HCl–mediated autocatalysis of internal allylic (IA) chloride groups. The latter groups, when in the vicinity of π–conjugated polymer segments, release HCl in a facile manner. We predict that other compounds, including hydrogen halides and H 2 O could also catalyze PVC’s dehydrochlorination. We suggest that hydrogen halides are the most efficient catalysts for this process, while other compounds like H 2 O may slow down the dehydrochlorination compared to purely HCl-catalyzed process, because of the dilution of the produced HCl. This result is corroborated by TGA experiments. Additionally, we study the thermochemistry and kinetics of polyene chain crosslinking and the formation of aromatics. The former reaction proceeds in parallel with the dehydrochlorination process (i.e., during the 1st stage of thermal decomposition), whilst the latter may occur at high temperatures (i.e., during the 2 nd stage of thermal decomposition). Furthermore, this work contributes to the fundamental understanding of molecular scale phenomena that take place during PVC pyrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Time dependent zero valent iron oxidation and the reductive removal of pertechnetate at variable pH

Elemental iron Fe 0 is a promising reductant for removal of radioactive technetium-99 (Tc) from complex aqueous waste streams that contain sulfate, halides, and other inorganic anions generated during processing of legacy radioactive waste. The impact of sulfate on the kinetics of oxidation and reduction capacity of Fe 0 in the presence of Tc has not been examined. We investigated the oxidative transformation of Fe 0 and reductive removal of TcO 4 - in 0.1 M Na 2 SO 4 as a function of initial pH (i.e., pH i 4, 7, and 10) under aerobic conditions up to 30 days. Tc reduction was the fastest at pH i 7 and slowest at pHi 10 (Tc reduction rate pHi 7 > 4 > 10). Aqueous fraction of Tc was measured at 0.4% at pH i 7 within 6 h, whereas ≥ 97% of Tc was removed from solutions at pH i of 4 and 10 within 24 h. Solid phase characterization showed that magnetite was the only oxidized crystalline phase for the first 6 h regardless of initial pH. Lepidocrocite was the most abundant oxidized product for pH i 10 after 5 days, but was not observed at pH of 4 or 7.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Upcycling and urban mining for nanomaterial synthesis

Responsible processing of complex waste streams, especially through resource recovery and upgrading, is essential to lessen the environmental and societal impacts of materials production and disposal. Upcycling waste into materials that have higher value than their original form, and urban mining, the recovery of metals from electronic waste, are two recent strategies in waste management. Sustainable cradle-to-grave manufacturing means recovering resources that would otherwise contaminate the planet. Here, we discuss upcycling of plastic, rubber, and related carbon waste streams into graphene, as well as the recovery of precious metals and rare earth elements, while removing toxic heavy metals, all using flash Joule heating. Furthermore, this article provides a brief overview of the current state of upcycling and urban mining as it applies to materials conversion, recovery, or nanomaterial synthesis, with a concluding perspective highlighting the considerations, opportunities, and challenges that accompany upcycling and urban mining research.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2021

Joint influence of γ–irradiation and high temperature shear grinding on the IR spectra and surface–energy properties of polyethylene

The optical and surface-energy properties of polyethylene (PE) subjected to γ-irradiation and post-radiation, high temperature, shear grinding are presented. Comparison of the IR spectra of the initial and γ-irradiated PE shows that oxygen-containing groups and unsaturated bonds in the polymer macromolecules are formed and accumulate during their radiolysis in air, increasing with γ-irradiation dose. A redistribution of the products of radiation-chemical conversion on the surface of the polymer granules throughout the entire volume of the powder occurs after high-temperature shear milling to a powder as observed in the IR spectrum. Polar functional groups due to oxidation reactions are observed on the surface layer of the sample after post-radiation grinding. Furthermore, the initial polymer surface is weakly basic with an acidity parameter of -0.34. The value of the acidity parameter of the sample made of ground irradiated PE has an acidic surface with an acidity parameter of 0.65. γ irradiation of the secondary processing of PE waste with high-temperature shear grinding is a promising approach to obtain a secondary PE powder with specified parameters and different degrees of functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Mechanisms of Al3+ dimerization in alkaline solutions

The molecular speciation of aluminum (Al3+) in alkaline solutions is fundamental to its precipitation chemistry within a number of industrial applications that include ore renement and industrial processing of Al wastes. Under these conditions, Al3+ is predominantly Al(OH) {4 , while at high [Al] dimeric species also known to form. To date, the mechanism of dimer formation remains unclear and it is likely infuenced by complex ion ion interactions. In the present work, we investigate the role of ion pairing and a suite of potential dimerization pathways using a three-pronged approach that consists of density functional theory-based molecular dynamics (DFTMD), static DFT calculations (sDFT) and semi-empirical density functional tight binding molecular dynamics (SEMD). Specic cation eects imparted by the background electrolyte cations Na+, Li+ and K+ have been examined. Our simulations predict that when the Al species are ion paired with either cation the formation of the oxo-bridged Al2O(OH) 2{6 is favored with respect to the dihydroxo-bridged Al2(OH) 2{8 , in agreement with previousspectroscopic work. The formation of both dimers rst proceeds by bridging of two monomeric units via one hydroxo ligand, leading to a labile Al2(OH) 2{8 isomer. The eect of contact ion pairing of Li+ and K+ on the dimerization energetics is distinctly more favorable than that of Na+, which may have an impact on further ligomerization.

Pouvreau, Maxime↗

DOE OSTI2020

Selective Lanthanide Sensing with Gold Nanoparticles and Hydroxypyridinone Chelators

The octadentate hydroxypyridinone chelator 3,4,3-LI(1,2-HOPO) is a promising therapeutic agent because of its high affinity for f-block elements and noncytotoxicity at medical dosages. The interaction between 3,4,3-LI(1,2-HOPO) and other biomedically relevant metals such as gold, however, has not been explored. Gold nanoparticles functionalized with chelators have demonstrated great potential in theranostics, yet thus far, no protocol that combines 3,4,3-LI(1,2-HOPO) and colloidal gold has been developed. Here, we characterize the solution thermodynamic properties of the complexes formed between 3,4,3-LI(1,2-HOPO) and Au 3+ ions and demonstrate how under specific pH conditions the chelator promotes the growth of gold nanoparticles, acting as both reducing and stabilizing agent. 3,4,3-LI(1,2-HOPO) ligands on the nanoparticle surface remain active and selective toward f-block elements, as evidenced by gold nanoparticle selective aggregation. Finally, a new colorimetric assay capable of reaching the detection levels necessary for the quantification of lanthanides in waste from industrial processes is developed based on the inhibition of particle growth by lanthanides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗