Evaluation of the Hydrophilic Complexant N,N,N’,N’-tetraethyldiglycolamide (TEDGA) and its Methyl-substituted Analogues in the Selective Am(III) Separation

ABSTRACT

N,N,N’,N’-tetraethyldiglycolamide (TEDGA) is used in the French EXAm (extraction of americium) process to separate Am(III) from Cm(III) and Ln(III). In this study, the complexation behavior of TEDGA towards actinides(III) and lanthanides(III) was compared to its methyl-substituted derivatives Me-TEDGA and Me₂-TEDGA under experimental conditions applying to the EXAm process. Using the EXAm solvent, 0.6 mol/L N,N’-dimethyl-N,N’-dioctyl-hexylethoxymalonamide (DMDOHEMA) and 0.45 mol/L bis(2-ethylhexyl)-phosphoric acid (HDEHP), An(III) and Ln(III) distribution ratios increase in the order TEDGA < Me-TEDGA < Me₂-TEDGA. This is explained by differences in the strength of complexation in the aqueous phase: Conditional stability constants for the formation of [Cm(DGA)_x]³⁺ complexes decrease in the order TEDGA > Me-TEDGA > Me₂-TEDGA, as shown by time-resolved laser fluorescence spectroscopy (TRLFS). TRLFS measurements verified the exclusive existence of [Cm(DGA)₃]³⁺ complexes in the aqueous phase. Both the homoleptic [Cm(DMDOHEMA)_n]³⁺ and the heteroleptic [Cm(DGA)_x(DMDOHEMA)_y]³⁺ complexes were detected in the organic phase, as postulated in the literature.^[14]     

Radiation chemistry of the branched-chain monoamide di-2-ethylhexyl-isobutyramide

The radiolytic degradation of di-2-ethylhexyl-isobutyramide (DEHiBA) was examined by subjecting the compound to gamma irradiation, measuring the remaining concentration of the intact compound, identifying the degradation products, and measuring uranium distribution ratios. The combined effects of radiation dose, contact with aqueous solutions of HNO₃, and aeration were also examined. The DEHiBA displayed significant stability at doses up to 1000 kGy, undergoing a slow exponential concentration decrease that was accompanied by the appearance of multiple degradation products. The most abundant compounds that were formed by radiolysis resulted from cleavage of the C_carbonyl–N and C_ethylhexyl–N bonds, generating di-ethylhexylamine and mono-ethylhexyl-isobutyramide. Acid contact did alter the radiolytic pathways, with acid favoring cleavage of the C_carbonyl-N bond, while a more diverse array of compounds was formed in the absence of acid. Pulsed radiolysis experiments were also conducted, in which picosecond bursts of energetic electrons were used to irradiate solutions of dodecane containing DEHiBA; formation of the dodecane radical cation was implicated, which serially reacted with DEHiBA to form a radical or radical cation species intermediate in the formation of the observed products. The slow degradation kinetics suggests that DEHiBA possesses good potential for selective extraction of uranium in fuel cycle extraction operations.     

A Comparison of the γ-Radiolysis of TODGA and T(EH)DGA Using UHPLC-ESI-MS Analysis

Solutions of TODGA and T(EH)DGA in n-dodecane were subjected to γ-irradiation in the presence and absence of an aqueous nitric acid phase and analyzed using UHPLC-ESI-MS to determine the rates of radiolytic decay of the two extractants, as well as to identify radiolysis products. The DGA concentrations decreased exponentially with increasing dose, and the measured degradation rate constants were uninfluenced by the presence or absence of an acidic aqueous phase, or by chemical variations in the alkyl side-chains. The DGA degradation was attributed to reactions of the dodecane radical cation, whose kinetics were measured for TODGA using picosecond electron pulse radiolysis to be k₂ = (9.72 ± 1.10) × 10⁹ M^?1 s^?1. The identified radiolysis products suggest that the bonds most vulnerable to radiolytic attack are those in the diglycolamide center of these molecules and not on the side-chains.     

Synthesis,thermal degradation and dielectric properties of poly[2-hydroxy,3-(1-naphthyloxy)propyl methacrylate]

2-Hydroxy-3-(1-naphthyloxy)propyl methacrylate (NOPMA) monomer was synthesized from reaction of 2-[(2-naphthyloxy)methyl]oxirane with methacrylic acid in the presence of pyridine. The polymerization of NOPMA was carried out by free radical polymerization method in the presence of AIBN at 60 °C. The structure of monomer and polymer was characterized by ¹H-NMR, ¹³C-NMR and FT-IR spectroscopy techniques. The glass transition temperature and average-molecular weights of poly(NOPMA) were measured using differential scanning calorimetry and gel permeation chromatography, respectively. The thermal degradation behavior of poly(NOPMA) has been investigated by FT-IR studies of the partially degraded polymer and thermogravimetry. The cold ring fractions (CRFs) were collected at two different temperatures, initially fraction-1 (CRF₁) is from room temperature to 320 °C, and the other fraction-2 (CRF₂) is from 320 to 500 °C. The volatile products of the degradation were trapped at ?195 °C (in liquid nitrogen). All the fractions were characterized by FT-IR, ¹H and ¹³C-NMR spectroscopic techniques, and the cold ring fractions (CRFs) were also characterized by GC–MS. For the degradation of polymer, the major compound between products of CRFs is α-naphthol. The GC–MS, FT-IR and NMR data showed that depolymerization corresponding to monomer was not prominent below 320 °C in the thermal degradation of poly(NOPMA). The mode of thermal degradation containing formation of the major products was identified. The dielectric permittivity (ε′), the loss factor (ε″) and conductivity (σ_ac) were measured using a dielectric analyzer in the frequency range of 50 Hz to 20 kHz.     

Radiolysis of Tributyl Phosphate by Particles of High Linear Energy Transfer

Tributyl Phosphate (TBP), used in chemical separation processes for used nuclear fuel, is susceptible to radiolysis causing losses in process performance. We have studied its degradation by exposing dry 1M TBP/n-dodecane solutions to gamma radiation from a cesium-137 source and in a mix of low and high linear energy transfer (LET) radiation by irradiating samples in the UC Irvine TRIGA^® reactor and utilizing the ¹⁰B(n,α)⁷Li reaction. In a 1 M solution of TBP in n-dodecane the degradation of TBP (G^?_TBP) was found to be 0.36 and 0.14 μmol/J for low and high LET radiation, respectively. The formation of dibutyl phosphoric acid, DBP, (G⁺_DBP) in this solution was found to be 0.18 and 0.047 μmol/J for low and high LET radiation, respectively. In samples exposed to low LET as well as a mix of low and high LET a variety of TBP degradation products containing phosphorus were observed indicating that other degradation products than DBP and the monobutyl diacid (MBP) were formed. Our results for both low and high LET radiation compare well with previous studies on these systems indicating that high LET degrades TBP to a lesser extent than gamma radiation. Available data for high LET is not as abundant as for low LET making such comparisons challenging. Nevertheless, our method yields a value for G⁺_DBP that agrees well with previous alpha radiolysis studies indicating that our method shows promise for studying high LET radiolysis in liquid-liquid extraction systems.     

Studies on the use of N,N,N′,N′-Tetra(2-Ethylhexyl) Diglycolamide (TEHDGA) for Actinide Partitioning II: Investigation on Radiolytic Stability

Abstract

N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (TEHDGA) was found to be a promising extractant for actinide partitioning from high-level waste (HLW) (Part I). In order to evaluate the applicability of TEHDGA to the HLW partitioning process, investigations on its radiolytic stability were carried out. The present work deals with the studies on the uptake of americium by γ-irradiated 0.2 M TEHDGA/n-dodecane in the absence and presence of phase modifiers—di(n-hexyl)octanamide (DHOA), isodecanol and n-decanol—against the absorbed dose up to 1 × 10⁶ Gy in the presence of nitric acid at varying concentrations. The addition of phase modifiers suppressed the radiolysis of TEHDGA in n-dodecane and DHOA was found to be the most effective radiolysis suppressor. Investigations were also carried out on the degradation of neat TEHDGA by γ-irradiation, and it was attempted to isolate and identify its degradation products by instrumental analysis. The radiolysis study showed that the degradation products were formed by the cleavage of the –C-N bond, to eliminate an ethylhexyl group, and the bond adjacent to the ether bond. The results obtained for TEHDGA radiolysis were compared with that of its straight-chain isomer TODGA, and TEHDGA was observed to be more resistant to radiation than TODGA. The changes in the physico-chemical properties of γ-irradiated TEHDGA against the absorbed dose were also investigated.     

γ‐Radiation Effects on the Performance of HCCD‐PEG for Cs and Sr Extraction

Abstract

Cobalt dicarbollide and polyethylene glycol in phenyltrifluoromethyl sulfone (HCCD/PEG in FS‐13) is currently under consideration for use in the process‐scale selective extraction of fission product cesium and strontium from acidic radioactive solutions. While the Cs and Sr solvent extraction efficiency of this formulation has been previously characterized, this solvent will be exposed to high radiation doses during use, and has not been adequately investigated for radiation stability. Here, HCCD/PEG was γ‐irradiated to various absorbed doses, to a maximum of 432 kGy, using ⁶⁰Co. Irradiations were performed for the neat organic phase, and also for the organic phase in contact with 1 M‐nitric acid mixed by air sparging. Post‐irradiation solvent extraction measurements showed that Cs distribution ratios were unaffected; however, strontium distribution ratios decreased with the absorbed dose under both conditions. The decrease in the extraction efficiency for strontium was greater when in contact with the aqueous phase. The stripping performance was not affected. A mechanism, based on reaction with the products of direct diluent radiolysis, is proposed to explain the decreases in the strontium extraction efficiency.     

2,6-Bis-benzimidazolylpyridines as new catalyst in copper-based ATRP

The ligands, 2,6-bis(NH-benzimidazol-2-yl)pyridine (L1) and 2,6-bis(N-methyl-benzimidazol-2-yl)pyridine (L2), were synthesized by a one-step reaction of 2,6-pyridinedicarboxylic acid with a diamine (o-phenylenediamine or N-methyl-1,2-phenylenediamine), respectively, in syrupy phosphoric acid at ca. 200 °C. Their efficiency as a catalyst in Cu-based atom transfer radical polymerizations (ATRP) of methylmethacrylate (MMA) was investigated. The linear first-order kinetic plots were observed; indicating that the number of active species is constant during the polymerization and termination reactions are limited. The apparent rate constant values of ATRP of MMA with CuCl/L1 catalyst system at 90 °C in acetonitrile were found to be between 3.83 × 10^?5 and 1.33 × 10^?4 s^?1, while they were between 1.86 × 10^?4 and 4.40 × 10^?4 s^?1 in the case of CuCl/L2 catalyst, indicating the presence of lower radical concentration throughout the polymerization of MMA using CuCl/L1 catalyst system. In both the cases, low apparent rate constant values are obtained. This indicates that ATRP proceeded at reasonable rates and a good control over ATRP in general. Apparent rate constant vs [ligand]/[catalyst] ratio plots showed a maximum at the [ligand]/[catalyst] ratio of two. M _n,GPC values increased slightly linearly with conversion and molecular weight values were closer to M _n,th in the case of ATRP of MMA using CuCl/L2 catalyst complex. Cyclic voltammetry measurements confirmed that CuCl/L1 and CuCl/L2 complexes in acetonitrile give reversible redox couples and copper(I) centers in CuCl/L1 and CuCl/L2 catalyst complexes that are readily oxidized and they potentially suit to facile ATRP.     

Preparation of SnO2 Nanoparticles from a New Tin(IV) Complex: Spectroscopic and Photoluminescence Studies

A new dimethyltin(IV) complex, {[Me₂Sn(O₂CNC₉H₆)]₂O}₂ (1), was prepared by reaction of dimethyltin(IV) dichloride with the quinoline-2-carboxylic acid and characterized by elemental analysis, IR, ¹H-, ¹³C-, ¹¹⁹Sn-NMR spectroscopes. The structure of 1 was determined by single-crystal X-ray diffraction. The results showed that 1 is a tetranuclear, centrosymmetric dimeric, and contains two endo-cyclic five-coordinated and two exo-cyclic six-coordinated tin atoms and a N-atom of the 2-quinaldic carboxylate ligand coordinated to exo-cyclic tin. Complex 1 was utilized as a precursor for SnO₂ nanoparticles by direct thermal decomposition at 500 °C in air. The nano-structure of SnO₂ was characterized by scanning electron microscopy and X-ray powder diffraction. The SnO₂ core showed a band gap of ~4 eV determined from the UV/visible absorption spectrum. The SnO₂ nanoparticles show stable photoluminescence (PL) with an emission centered at 557 nm.     

New Insight into the Americium/Curium Separation by Solvent Extraction using Diglycolamides

The liquid–liquid extraction process called EXAm was developed by the CEA to allow the recovery of Americium alone from a PUREX raffinate. Americium is extracted from a highly acidic feed solution (HNO₃ 4–6 M) by a mixture of two extractants: DMDOHEMA and HDEHP. The Am/Cm selectivity is improved using a specific diglycolamide (TEDGA) as a selective aqueous complexing agent which retains preferentially Cm and heavier lanthanides in the aqueous phase. In this study, the impact of the lipophilicity and steric hindrance of several diglycolamides on the Am/Cm selectivity was investigated in order to understand the enhancement brought by TEDGA. For this purpose, liquid–liquid extraction and partitioning experiments were performed under various conditions.     

A Study of the γ-Radiolysis of N,N-Didodecyl-N′,N′-Dioctyldiglycolamide Using UHPLC-ESI-MS Analysis

Solutions of N,N-didodecyl-N′,N′-dioctyldiglycolamide in n-dodecane were subjected to γ-irradiation in the presence and absence of both an aqueous nitric acid phase and air sparging. The solutions were analyzed using ultra-high-performance liquid chromatography-electrospray ionization-mass spectrometry (UHPLC-ESI-MS) to determine the rates of radiolytic decay of the extractant as well as to identify radiolysis products. The DGA concentration decreased exponentially with increasing dose, and the measured degradation rate constants were uninfluenced by the presence or absence of acidic aqueous phase, or by air sparging. The identified radiolysis products suggest that the bonds most vulnerable to radiolytic attack are those in the diglycolamide center of these molecules and not in the side chains.     

Reaction of dipyridamole with the hydroxyl radical

Dipyridamole [2,6-bis-diethanolamino-4,8-dipiperidinopyrimido-(5,4-d) pyrimidine], a well known platelet aggregation inhibitor, shows powerful hydroxyl radical scavenging activity by inhibiting OH-dependent salicylate and deoxyribose degradation. Steady-state competition kinetics experiments with deoxyribose were carried out to evaluate the second-order rateconstant for the reaction between hydroxyl radical and dipyridamole. OH· radicals were generated either by a Fenton-type reaction or by X-ray irradiation of water solutions. A second-order rate constant k_{(Dipyridamole+OH·)} of 1.72±0.11×10¹⁰M⁻¹ s⁻¹ and of 1.54±0.15×10¹⁰ M⁻¹ s⁻¹ was measured by Fenton chemistry and by radiation chemistry, respectively. Mannitol was used as an internal standard for hydroxyl radicals in steady-state competition experiments with deoxyribose. A rate constant k_{(Mannitol+OH·)} of 1.58±0.13×10⁹ M⁻¹ s⁻¹ and 1.88±0.14×10⁹ M⁻¹ s⁻¹ was measured in the Fenton model and in the water radiolysis system, respectively. Both these rate constants are in good agreement with the published data obtained by the “deoxyribose assay” and by pulse radiolysis.     

Extraction of some Hexavalent Actinide Ions from Nitric Acid Medium using Several Substituted Diglycolamides

Several substituted diglycolamides, namely TPDGA, THDGA, TODGA, and TDDGA, were evaluated in a comparative study on the extraction of hexavalent actinide ions such as UO₂²⁺, NpO₂²⁺, and PuO₂²⁺ from nitric acid medium. The acid extraction constants (K_H) for the diglycolamides were determined to be 3.8 ± 0.6, 1.6 ± 0.1, 4.1 ± 0.4, and 1.4 ± 0.2 for TPDGA, THDGA, TODGA, and TDDGA, respectively. Though metal ion extraction generally increased with increasing the feed acid concentration, the nature of the extracted species changed with aqueous-phase acidity. While complexes of the type MO₂(NO₃)₂·nL (where L is the diglycolamide extractant and n is 1 and 2) were found to be extracted at 1 M HNO₃, the average number of ligand molecules associated with the complex decreased to ?1 when the nitric acid concentration increased to 3 M. These results have great significance from the actinide separation point of view, as the actinides ions can be made virtually inextractable by adjusting their oxidation state. The thermodynamic parameters were also calculated, which indicated spontaneous reactions with large exothermicities.     

Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst

An economical method was proposed to develop an efficient alumina-supported manganese (Mn) and copper (Cu) oxides (Mn-Cu-O/Al₂O₃) catalyst with a high surface area, 184.06 cm² g^?1. The catalyst was utilized for degradation refinery wastewater by heterogeneous catalytic ozonation. The effects of various operating variables including pH, ozone and catalyst dosages, and temperature were systematically investigated in detail to obtain the optimized conditions for accelerated degradation of refinery wastewater. The optimum values were as follows: ozone dose 50.0 mg L^?1, catalyst dose 3.0 g L^?1, initial pH = 6.8, T = 17 °C. Refinery wastewater samples were analyzed by chemical oxygen demand (COD) and the results indicated that kinetics of COD followed a pseudo–first-order degradation. Moreover, hydroxyl radical mechanism rather than absorption was proposed, indicating that the surface hydroxyl groups were the active sites that played a significant role in catalytic ozonation.     

Mechanistic studies of ruthenium(III)-catalyzed oxidation of DL-methionine by hexacyanoferrate(III) in an alkaline medium

The kinetics and mechanism of ruthenium(III) catalyzed oxidation of dl-methionine by alkaline hexacyanoferrate(III) (HCF(III)) in an alkaline medium were studied spectrophotometrically at 30±0.1°C. The reaction was first-order-dependent each on [HCF(III)] and [ruthenium(III)] and fractional-order-dependent on [alkali]. The rate of the reaction was found to be decreased with the increase in [methionine]. The main product of oxidation was methionine sulfone nitrile (3-(methylsulfonyl)propanenitrile) and it was identified and confirmed by FT-IR and mass spectral studies. Further, no effect of added reaction product was observed. A plausible mechanism was proposed involving complexation between methionine and ruthenium(III) species, [Ru(H₂O)₅OH]²⁺. Thermodynamic parameters for the reaction, E _a and Δ S ^#, were computed using linear least squares method and are found to be 65.83±1.03 kJ/mol and?249.58±3.35 J/K mol, respectively.

     

Esterification of stearic acid with methanol over mesoporous ordered sulfated ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> mixed oxide aerogel catalyst

Aerogel sulfated ZrO₂–SiO₂ mixed oxide solid acid catalyst was prepared by sol–gel method followed by supercritical drying (SCD) in n-propanol solvent, which resulted into higher surface area (170 m²/g), pore volume (0.31 cm³/g) and pore diameter (7.2 nm) having ordered mesoporous structure as well as more number of Brönsted and Lewis acid sites available on larger surface area. The catalyst exhibited 91 % yield of methyl stearate at 60 °C in 7 h, which increased from 71 to 91 % with an increase in the Zr to Si ratio from 1:2 to 2:1 due to increase in acid site concentration. The reaction followed pseudo-first order kinetics under the optimized reaction conditions with a reaction rate of 1.15 mmol h^?1, rate constant of 2.7 × 10^?1 h^?1 and turn over frequency of 9.68 h^?1. The catalyst displayed higher activity (91 %) compared to ion exchange resins (44–68 %), Nafion (58 %), acid clay (61 %) and pure sulfated zirconia (78 %), and was slightly lower as compared to H₂SO₄ (97 %). The study clearly reveals the improved structural, textural and acidic properties of ZrO₂–SiO₂ mixed oxide aerogel prepared via SCD technique.     

Infrared Studies on Polymethyl Methacrylate Doped with a Sulphur-Containing Ligand and Its Cobalt (II) Complex During Gamma Radiolysis

ABSTRACT

Infrared spectroscopic studies were performed for poly(methyl methacrylate) samples doped with an organic ligand (N,N-dioxaloyl benzenesulphonyl-N,N-dioxaloylthiocarbazide) and its cobalt (II) complex during gamma radiolysis after extraction of the dopant. There are no drastic changes in the IR-absorption band positions, but noticeable changes in the intensities are found. The relative transmission of IR-absorption bands such as bands at 750, 840, 1065, and 1388 cm^?1 were measured relative to the transmission of the carbonyl group band at 1717 cm^?1. The degradation and recombination mechanism of different groups in the polymeric chain or backbone during radiolysis are suggested by the behavior of the relative transmission data for each group with increasing exposure dose. The tacticity of the PMMA sample was unchanged during radiolysis and was found to be syndiotactic. This fact is confirmed by measuring the IR J-values for different PMMA samples before and after irradiation. The protection efficiency of the organic ligand and its cobalt (II) complex were also investigated and the organic ligand is a more protective material than the cobalt (II) complex     

Osmium(VIII) catalyzed oxidation of a sulfur containing amino acid—a kinetics and mechanistic approach

The kinetics of osmium (VIII) catalyzed oxidation of DL-methionine by hexacyanoferrate(III) (HCF) in aqueous alkaline medium at a constant ionic strength of 0.50 mol dm^?3 was studied spectrophoto-metrically. The reaction between hexacyanoferrate(III) and DL-methionine in alkaline medium exhibits 2:1 stoichiometry (2HCF:DL-methionine). The reaction is of first order each in [HCF] and [Os(VIII)], less than unit order in [alkali] and zero order for [DL-methionine]. The decrease in dielectric constant of the medium increases the rate of the reaction. The added products have no effect on the rate of reaction. The main products were identified by spot test. A free radical mechanism has been proposed. In a prior equilibrium step Os(VIII) binds to OH^? species to form a hydroxide species and reacts with [Fe(CN)₆]^3? in slow step to form an intermediate species(C₁). This reacts with a molecule of DL-methionine in a fast step to give the sulfur radical cation of methionine and yields the sulfoxide product by reacting with another molecule of [Fe(CN)₆]^3?. The rate constant of the slow step of the mechanism is calculated. The activation parameters with respect to slow step of the mechanism are evaluated and discussed.     

Degradation Effect and Mechanism of Dinitrotoluene Wastewater by Magnetic Nano-Fe3O4/H2O2 Fenton-like

The characteristics and influencing factors for dinitrotoluene degradation by nano-Fe₃O₄-H₂O₂ were studied, and the nano-scale Fe₃O₄ catalyst was prepared by the coprecipitation method, with dinitrotoluene wastewater as the degradation object. The results showed that the catalytic reaction system within the pH value range of 1 to 9 could effectively degrade dinitrotoluene, and the optimal pH value was 3; with the increase of catalyst dosage, the degradation efficiency and the catalytic reaction rate of dinitrotoluene grew as well. The optimal catalyst dosage was 1.0 g/L when the H₂O₂ dosage was within the range of 0 to 0.8 mL/L; the degradation efficiency and reaction rate grew with the increase of H₂O₂ dosage. With further increase of H₂O₂ dosage, degradation efficiency and reaction rate decreased; under the best conditions with the H₂O₂ dosage of 0.8 mL/L, the catalyst concentration of 1 g/L and the pH value of 3 at room temperature (25 °C), the degradation rate of the 100-mg/L dinitrotoluene in 120 min reached 97.6%. Through the use of the probe compounds n-butyl alcohol and benzoquinone, it was proved that the oxidation activity species in the nano-Fe₃O₄-H₂O₂ catalytic system were mainly hydroxyl radical (?OH) and superoxide radicals (HO2 ?), based on which, the reaction mechanism was hypothesized.     

Reaction Kinetics of Ozone with Selected Pharmaceuticals and Their Removal Potential from a Secondary Treated Municipal Wastewater Effluent in the Great Lakes Basin

Oxidation kinetics of selected pharmaceutical compounds and their degradation during ozonation of secondary treated municipal wastewater effluent (MWWE) was investigated. The apparent second-order rate constants for the reaction between chlorotetracycline (CTC), enrofloxacin (ENR), gemfibrozil (GEM) and ozone ranged between 6.82 – 52.7 × 10⁴ M^?1s^?1. The measured second-order hydroxyl radical rate constants were several orders of magnitude higher at 8.4 × 10⁹ – 13.1 × 10⁹ M^?1s^?1 with a reactivity sequence of GEM > CTC > ENR. Overall degradation of CTC, ENR and GEM in secondary treated municipal wastewater effluent was >76 % at ozone doses of 0.33 mg O₃/mg DOC or higher.