Presence Of Trifluoroacetic Acid Research Articles

SYNTHESIS OF NEW FRAMEWORK PHOSPHONATES BY THE INTERACTION OF 2-ETHOXYVINYL DICHLOROPHOSPHONATE WITH 4-ETHYLRESORCINOL

A simple, new and promising approach to obtaining previously unknown phosphorus-containing framework compounds by the developed original synthesis method is proposed. The proposed method is based on the condensation reaction of 2-ethoxyvinylphosphonic acid dichloride with resorcinol and its derivatives in toluene in the presence of trifluoroacetic acid. The article presents the results of a study of the reaction of 2-ethoxyvinyl dichlorophosphonate with 4-ethylresorcinol. It was found that this reaction results in the formation of a mixture of two regioisomers. The structure and construction of the obtained regioisomeric framework phosphonates were studied using 31P and 1H NMR. The regioisomeric framework phosphonates obtained as a result of the reaction of vinylphosphonate with 4-ethylresorcinol were separated by acylation of the mixture with acetic anhydride, using as a medium and a reagent. One functionalized regioisomer was isolated as an individual product, which was white crystals with good solubility in acetone-water and DMSO mixtures. The structure and composition of the obtained regioisomer were confirmed by 1H, 31P, 13C NMR, IR spectroscopy, mass spectrometry (MALDI) and elemental analysis. It was found that the reaction of 2-ethoxyvinyl dichlorophosphonate with 4-ethylresorcinol in the presence of an equimolar amount of trifluoroacetic acid in toluene resulted in the formation of a regioisomeric mixture of framework phosphonates in a 4:1 ratio. It was shown that acylation of this regioisomeric mixture with acetic anhydride allowed one of the regioisomers to be isolated individually.

Stability and photophysical study of bright day light fluorescent material and its fabrication in laser patterning and LED application

Developing aggregation-induced emission (AIE) active highly visible fluorescent dyes is of great importance because of its numerous applications. We have successfully developed and synthesized two novel napthalimide based molecules PU1 and PU2, that exhibit bright greenish yellow in day light and vivid green emission when exposed to UV light. Compounds PU1 and PU2 exhibit variable emission behavior at different solvent polarities. Upon raising the solvent polarity from ether to DMF, emission maxima of PU1 and PU2 underwent a bathochromic shift. Additionally, compounds PU1 and PU2 show signs of AIE, which cause a restriction in intramolecular mobility. A distinct self-assembled structure was generated at 30 % aqueous DMF solution following aggregation, as demonstrated by experiments using dynamic light scattering and field emission scanning electron microscopy. Compounds PU1 and PU2 have been blended with poly(urethane) to develop a polymeric film. Tensile strain studies, and TGA, DSC analyses were used to examine the thermal/mechanical stability of PU films. The photostability of PU1 and PU2 in both solution and polymeric film was examined using a 5-h UV-beam irradiation. Furthermore, in the presence of trifluoroacetic acid, the blended polymeric film and 365 nm LED light coated material exhibits distinct colorimetric and fluorimetric transformations. Finally, laser-induced periodic surface structure (LIPSS) pattern processing on PU1 coated substrates can be extended for optical applications.

Mitigation of Dendrite Growth in Zinc-iodide Flow Battery with Tröger’s Base Anion Exchange Membrane

Tröger’s base anion exchange membrane (TB-AEM) was readily prepared by condensation polymerization of biphenyl diamine and dimethoxymethane in the presence of trifluoroacetic acid followed by quaternization with methyl iodide. The film cast from N-Methyl-2-Pyrrolidone (NMP) solvent displayed good mechanical strength, a tensile modulus of 1.18 GPa with elongation at break of 17%, and a glass transition temperature (Tg) at 248 °C. It exhibited OH− ion conductivity of 108 mS cm−1 by impedance measurement at 80 °C in 1M KOH. The membrane exhibited good affinity toward I2, resulting in the formation of I2Br− ions in the membrane matrix. Over 300 charge/discharge cycles at a 50 mA cm−2 current density, the battery exhibited 95.5% Coulombic efficiency (CE), 76.4% voltage efficiency (VE), and 74.0% energy efficiency (EE) and delivered a capacity of 24.8 Ah L−1. Over a span of 60 h, the open-circuit voltage (OCV) of the cell remained constant at 1.2 V. Collectively, our findings suggest that the anion exchange membrane's charge and porosity tuning are key factors in the design of new generation separators for zinc-iodide flow batteries.

Acid-Mediated Modulation of the Conductance of Diazapentalene Molecular Junctions.

We report an acid-mediated regulation of single-molecule junction conductance achieved using an electron-deficient unit, diazapentalene, functionalized with thiophene extending units and thiomethyl aurophilic terminal groups. This diazapentalene derivative exhibits a protonation reaction in the presence of trifluoroacetic acid, as characterized by UV-vis absorption spectroscopy, and the protonated species shows a voltage-dependent single-molecule conductance, which is not observed for the pristine molecules. Specifically, under a high bias voltage of 850 mV, we observe a conductance value for the protonated molecule larger than that for the deprotonated one by a factor of 4. Density functional theory-based transport calculations show a slight broadening of the HOMO and LUMO frontier orbitals, as well as a reduced HOMO-LUMO gap when the molecule becomes protonated; this implies an increased conductance under protonation that is consistent with the experimental conductance data. Our work demonstrates a new molecular design for versatile control of molecular conductance through the use of acid in the solvent environment.

Thin layer chromatography of methylated derivatives of sodium alkylbenzenesulfonates in water analysis by GC-MS

Sodium alkylbenzene sulfonates or linear alkyl benzene sulfonates (LAS) are the most common synthetic anionic surfactants and water pollutants. They can cause both acute and chronic toxic effects on water organisms. Selective determination of sodium alkylbenzene sulfonates as a separate class of anionic surfactants is possible using gas chromatography coupled with mass spectrometry (GC-MS) in the form of linear alkylbenzenesulfonic acid methyl esters (LABSA ME). In order to purify the extracts and concentrate the analytes, we studied the behaviour of these compounds by ascending high-performance thin-layer chromatography using Kieselgel 60 F254 and Sorbfil plates. A mixture of n-hexane and methanol solvents in a ratio of 23:1 (by volume) was used as the mobile phase. Under these conditions, sodium alkylbenzenesulphonates remain on the start line, while their derivatives (ME ABSC), obtained by methylation with trimethyl orthoformate in the presence of trifluoroacetic acid (with a yield of η=98%), form zones characterised by retention coefficient values of Rf = 0.62 and Rf = 0.71 on Kieselgel 60 F254 and Sorbfil plates, respectively. The repeatability of the Rf values was characterised by a standard deviation of 6.1 and 5.9 %, respectively (n=16). The completeness of extraction (95.0–100.0 %) of analytes from the plates by descending TLC with acetonitrile was noted. The applicability of the TLC method for the concentration of analytes and pretreatment of extracts on the example of real water samples was shown. Using GC-MS with electron impact ionisation, we determined the concentrations of sodium alkylbenzenesulphonates in water sampled in the southern basin of Lake Baikal from a depth of 400 m (0.24±0.02 µg/dm3) and in snowmelt water from the ice of the Krestovka River where it flows into Lake Baikal near the village of Listvyanka (31.1 ± 1.0 µg/dm3).

Catalytic reduction of oxygen to water by non-heme iron complexes: exploring the effect of the secondary coordination sphere proton exchanging site.

In this study, we prepared non-heme FeIII complexes (1, 2, and 3) of an N4 donor set of ligands (H2L, Me2L, and BPh2L). 1 is supported by a monoanionic bispyridine-dioxime ligand (HL). In 2 and 3, the primary coordination sphere of Fe remained similar to that in 1, except that the oxime protons of the ligand were replaced with two methyl groups and a bridging -BPh2 moiety, respectively. X-ray structures of the FeII complexes (1a and 3a) revealed similar Fe-N distances; however, they were slightly elongated in 2a. The FeIII/FeII potential of 1, 2, and 3 appeared at -0.31 V, -0.25 V, and 0.07 V vs. Fc+/Fc, respectively, implying that HL and Me2L have comparable donor properties. However, BPh2L is more electron deficient than HL or Me2L. 1 showed electrocatalytic oxygen reduction reaction (ORR) activity in acetonitrile in the presence of trifluoroacetic acid (TFAH) as the proton source at Ecat/2 = -0.45 V and revealed selective 4e-/4H+ reduction of O2 to H2O. 1 showed an effective overpotential (ηeff) of 0.98 V and turnover frequency (TOFmax) of 1.02 × 103 s-1. Kinetic studies revealed a kcat of 2.7 × 107 M-2 s-1. Strikingly, 2 and 3 remained inactive for electrocatalytic ORR, which established the essential role of the oxime scaffolds in the electrocatalytic ORR of 1. Furthermore, a chemical ORR of 1 has been investigated using decamethylferrocene as the electron source. For 1, a similar rate equation was noted to that of the electrocatalytic pathway. A kcat of 6.07 × 104 M-2 s-1 was found chemically. Complex 2, however, underwent a very slow chemical ORR. Complex 3 chemically enhances the 4e-/4H+ reduction of O2 and exhibits a TOF of 0.24 s-1 and a kcat value of 2.47 × 102 M-1 s-1. Based on the experimental observations, we demonstrate that the oxime backbone of the ligand in 1 works as a proton exchanging site in the 4e-/4H+ reduction of O2. The study describes how the ORR is affected by the tuning of the ligand scaffold in a family of non-heme Fe complexes.

Hydrogen evolution driven by heteroatoms of bidentate N-heterocyclic ligands in iron(II) complexes.

While Pt is considered the best catalyst for the electrocatalytic hydrogen evolution reaction (HER), it is evident that non-noble metal alternatives must be explored. In this regard, it is well known that the binding sites for non-noble metals play a pivotal role in facilitating efficient catalysis. Herein, we studied Fe(II) complexes with bidentate 2-(2'-pyridyl)benzoxazole (LO), 2-(2'-pyridyl)benzthiazole (LS), 2-(2'-pyridyl)benzimidazole (LNH), and 2-2'-bipyridyl (Lpy) ligands - by adding trifluoroacetic acid (TFA) to their acetonitrile solution - in order to examine how their reactivity towards protons under reductive conditions could be impacted by the non-coordinating heteroatoms (S, O, N, or none). By applying this ligand series, we found that the reduction potentials relevant for HER correlate with ligand basicity in the presence of TFA. Moreover, DFT calculations underlined the importance of charge distribution in the ligand-based LUMO and LUMO+1 orbitals of the complexes, dependent on the heterocycle. Kinetic studies and controlled potential electrolysis - using TFA as a proton source - revealed HER activities for the complexes with LNH, LO, and LS of kobs = 0.03, 1.1, and 10.8 s-1 at overpotentials of 0.81, 0.76, and 0.79 V, respectively, and pointed towards a correlation between the kinetics of the reaction and the non-coordinating heteroatoms of the ligands. In particular, the activity was associated with the [Fe(LS/O/NH)2(S)2]2+ form (S = solvent or substrate molecule), and the rate-determining step involved the formation of [Fe(H-H)]+, during the weakening of Fe-H and CF3CO2-H bonds, according to the experimental and DFT results.

A mild and convenient protocol for the synthesis of quinoxalin-2(1H)-ones and benzimidazoles.

We present a mild and simple method for the cyclization of N-protected o-phenylenediamines with carbonyl compounds in the presence of trifluoroacetic acid. This method reliably provides various substrates of benzimidazoles and quinoxalin-2(1H)-ones, with all reactions conducted at room temperature, demonstrating excellent substrate adaptability and a broad substrate scope.

Highly Stable Amide-Functionalized Zirconium-Organic Frameworks: Synthesis, Structure, and Methane Storage Capacity.

With the development of crystalline porous materials toward methane storage, the stability issue of metal-organic framework (MOF) materials has caused great concern despite high working capacity. Considering the high stability of zirconium-based MOFs and effective functions of amide groups toward gas adsorption, herein, a series of UiO-66 type of Zr-MOFs, namely, Zr-fcu-H/F/CH3/OH, were successfully designed and synthesized by virtue of amide-functionalized dicarboxylate ligands bearing distinct side groups (i.e., -H, -F, -CH3, and -OH) and ZrCl4 in the presence of trifluoroacetic acid as the modulator. Single-crystal X-ray diffraction and topology analyses reveal that these compounds are archetypal fcu MOFs encompassing octahedral and tetrahedral cages, respectively. The N2 sorption isotherms and acid-base stability tests demonstrate that the materials possess not only relatively high surface areas, pore volumes, and appropriate pore sizes but also great hydrolytic stabilities ranging pH = 3-11. Furthermore, the volumetric methane storage working capacities of Zr-fcu-H, Zr-fcu-F, Zr-fcu-CH3, and Zr-fcu-OH at 298/273 K and 80 bar are 187/217, 175/193, 167/187, and 154/171 cm3 (STP) cm-3, respectively, which indicate that the zirconium-based crystalline porous materials are capable of storing relatively high amounts of methane.

Palladium-Catalyzed Stereocontrolled Synthesis of Aryl-C-Glycosides from Arylboronic Acids and Glycal Enones Through 1,4-Conjugate Addition Reactions

Abstract1,4-Conjugate addition of arylboronic acids to the glycal enones delivered 2-deoxy-α-aryl-C-glycosides in good yields. The reaction was catalyzed by palladium acetate in the presence of trifluoroacetic acid and 1,10-phenanthroline. A wide range of glycal enones derived from d-glucal, d-galactal, and d-rhamnal participated in the coupling reaction with different arylboronic acids smoothly. Different protecting groups including benzyl, acetyl, pivaloyl, and benzoyl were compatible under optimized conditions.

Isolation and Purification of Harpagogenin as an Nrf2-ARE Activator from the Tubers of Chinese Artichoke (Stachys sieboldii).

Chinese artichoke tuber (Stachys sieboldii Miq.) is used as an herbal medicine as well as edible food. This study examined the effect of the Chinese artichoke extracts on the nuclear factor erythroid 2-related factor 2 (Nrf2)-antioxidant response element (ARE) pathway that induces the expression of antioxidant enzymes to explore its novel characteristics. Hot water extracts exhibited relatively high ARE activity. ARE activity was observed in two fractions when the hot water extracts were separated in the presence of trifluoroacetic acid using HPLC. Conversely, the highly active fraction disappeared when the hot water extracts were separated in the absence of trifluoroacetic acid. These results indicate that acidic degradation produces active ingredients. The structural analysis of the two active fractions identified harpagide, which is an iridoid glucoside, and harpagogenin. In vitro experiments revealed that harpagide was converted into harpagogenin under acidic conditions and that harpagogenin, but not harpagide, had potent ARE activity. Therefore, this study identified harpagogenin, which is an acid hydrolysate of harpagide, as an ARE activator and suggests that Nrf2-ARE pathway activation by Chinese artichoke contributes to the antioxidative effect.

Excited-State Dynamics in 4-[4'(Dimethylamino)styryl]pyridine, a Photobase: Role of Photoinitiated Proton-Coupled Electron Transfer.

The photoinitiated proton-coupled electron transfer (PCET) process in photoacid-based adducts is predominantly governed by the evolution of the electron-proton transfer state. However, such a process is underexplored in the case of photobases as the excited states evolve through multiple competitive channels. Here, we elucidate the excited-state dynamics of a photobase, 4-[4'-(dimethylamino)styryl]pyridine (DMASP), in the presence of hexafluoroisopropanol (HFIP) that enables PCET. Transient absorption measurements show the evolution of a protonated species in the excited state with a time constant of ∼2.5 ps. Fluorescence upconversion measurements reveal the signatures of an emissive intramolecular charge transfer state and a protonated state. The role of such states is further confirmed by time-resolved measurements in the presence of trifluoroacetic acid and computational analysis. Furthermore, the proton-abstraction dynamics of DMASP is analyzed in bulk methanol and butanol solvents. The extent of proton abstraction by DMASP is found to be higher in the presence of HFIP when compared with the normal alcohols over a time period of a few picoseconds.

Synthesis and Crystal Structures of (HL)2[B10Cl10]·3CH3CN (L = Bipy, Phen)

Reactions of (Et3NH)2[B10Cl10] and organic ligands 2,2'-bipyridyl (Bipy) and 1,10-phenanthroline (Phen) in the acetonitrile–trifluoroacetic acid system have yielded compounds of composition (HL)2[B10Cl10]·3CH3CN (L = Bipy, Phen). The compounds have been characterized by IR spectroscopy, elemental analysis, and X-ray diffraction (CCDC nos. 2224377 and 2224378). It has been shown that in the presence of trifluoroacetic acid, protonation of organic ligands occurs with the formation of bipyridylium and phenanthrolinium salts, which are stabilized by the decachloro-closo-decaborate anion. It has been found that the cations participate in the formation of hydrogen bonds with the solvate molecules of acetonitrile, while only weak C–H…Cl and B–Cl…π interactions are observed for boron cluster anions.

1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic Acid

Here, we first report the 2′-acyloxy-1,3-dicarbonyl compound construction in a three-component oxidative reaction of alkyl ketene dimer with cyclic diacyl peroxide and trimethyl orthoformate. The discovered synthesis allows us to form 2′-functionalized 1,3-dicarbonyl compounds instead of the common 2-functionalized moiety. The reaction between 4-butylidene-3-propyloxetan-2-one and cyclopropyl malonoyl peroxide proceeds in the presence of trifluoroacetic acid and trimethyl orthoformate at 120 °C for 1 h. The synthesized compound was characterized by NMR spectroscopy, mass spectrometry, and IR spectroscopy.

Biologically inspired 3Fe4S cluster as structural mimics of FeMoco M‐cluster

AbstractA 3Fe4S cluster related to M‐cluster of Mo‐nitrogenase is reported. [K(THF)5][Fe3(μ‐bdt)2(μ‐PPh2)(CO)5] (1) is synthesized from photo‐assisted structural rearrangement of [K(THF)2][(μ,κ2‐bdt)Fe2(μ‐PPh2)(CO)5] under visible light irradiation. The molecular structure of 1 consists of a Fe3 core bearing one dithiolate bridge and the second dithiolate group capping onto the metallic plane. The structural motif of 1 is analogous to that of Mo‐participated 3Fe4S unit in M‐cluster of Mo‐nitrogenase, with the similar Fe‐Fe and Fe‐S bond distances. Upon protonation in 193 K, a Fe‐hydride species (1H) is generated and characterized to possess the bridging hydride group (δ = −12.57 ppm) by 1H‐NMR spectroscopy and DFT calculation. In CH3CN solution, complex 1 exhibits a reversible reduction and oxidation process at = −1.94 V and = −0.18 V, respectively, at 273 K. The reduction behavior of 1 in CH2Cl2 solution at 243 K displays a slight modification in the presence of trifluoroacetic acid, revealing a moderate anodic potential shift (~50 mV). The current amplitude of the reduction wave is linearly increased with the increasement of acid added, indicative of the catalytic event.

Synthesis of novel tetrahydropyrimidines via the reaction of sodium [1-(3,3-diethoxypropyl)ureido]methansulfonates with <i>C</i>-nucleophiles

A series of new substituted tetrahydropyrimidines was obtained by the reaction of sodium [1-(3,3-diethoxypropyl)ureido]methansulfonates with various C -nucleophiles (4-chlororesorcinol, sesamol, 2,4-dihydroxybenzoic acid, 4-hydroxy-6-methyl-2 H -pyran-2-one) in chloroform in the presence of trifluoroacetic acid.

Characterization of paramagnetic states in an organometallic nickel hydrogen evolution electrocatalyst

Significant progress has been made in the bioinorganic modeling of the paramagnetic states believed to be involved in the hydrogen redox chemistry catalyzed by [NiFe] hydrogenase. However, the characterization and isolation of intermediates involved in mononuclear Ni electrocatalysts which are reported to operate through a NiI/III cycle have largely remained elusive. Herein, we report a NiII complex (NCHS2)Ni(OTf)2, where NCHS2 is 3,7-dithia-1(2,6)-pyridina-5(1,3)-benzenacyclooctaphane, that is an efficient electrocatalyst for the hydrogen evolution reaction (HER) with turnover frequencies of ~3,000 s−1 and a overpotential of 670 mV in the presence of trifluoroacetic acid. This electrocatalyst follows a hitherto unobserved HER mechanism involving C-H activation, which manifests as an inverse kinetic isotope effect for the overall hydrogen evolution reaction, and NiI/NiIII intermediates, which have been characterized by EPR spectroscopy. We further validate the possibility of the involvement of NiIII intermediates by the independent synthesis and characterization of organometallic NiIII complexes.

Kinetic and mechanistic investigations of dioxygen reduction by a molecular Cu(II) catalyst bearing a pentadentate amidate ligand.

A pentadentate Cu(II) complex, [CuII(dpaq)](ClO4) (1), featuring a redox active ligand, H-dpaq (H-dpaq = 2-[bis(pyridine-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), catalyses four-electron reduction of dioxygen by decamethylferrocene (Fc*) in the presence of trifluoroacetic acid (CF3COOH) in acetone at 298 K. No catalytic oxygen reduction was observed in the presence of stronger Brønsted acids than CF3COOH, such as perchloric acid (HClO4) or trifluoromethanesulphonic acid (HOTf). In contrast, facile catalytic reduction of O2 occurs by Fc* with 1 and HClO4 or HOTf in dimethylformamide (DMF). The use of CF3COOH as the proton source in DMF results in the suppression of O2 reduction under otherwise identical reaction conditions. While the O2 reduction reactions in DMF are linearly dependent on the pKa of Brønsted acids, the acid dependence on catalytic O2-reduction reactivity by 1 in acetone showed complete reversal. Cyclic voltammetry studies using p-chloranil as the probe substrates in the presence of acids in the solvents reveal that the strengths of the protonic acids increase significantly in acetone compared to that in DMF. The amidate-N in [CuII(dpaq)](ClO4) (1) undergoes protonation in the presence of HClO4 or HOTf in DMF to form [CuII(H-dpaq)]2+ (1-H+), but not in the presence of CF3COOH. Enhanced acid strength of CF3COOH in acetone, however, effectively protonates 1 and triggers O2 reduction. Protonation of 1 with HClO4 or HOTf in acetone results in the change of its coordination environment, and this protonated species does not trigger O2 reduction. Detailed kinetic studies indicate that 1-H+ undergoes reduction by two-electrons and the reduced species binds O2 to form a Cu(II)-superoxo intermediate. This is followed by a rate-determining proton-coupled electron-transfer (PCET) reduction to generate the Cu(II)-hydroperoxo intermediate. While catalytic O2 reduction in acetone occurs predominantly via a 4e-/4H+ pathway, product selectivity (H2O vs. H2O2) in DMF depends upon the concentration of the reductant (Fc*). While dioxygen reduction to H2O2 is favoured at low [Fc*], mechanistic studies suggest that O2 reduction with high [Fc*] proceeds via a [2e- + 2e-] mechanism, where the released H2O2 during catalysis is further reduced to water.

A safety-catch protecting group strategy compatible with Boc-chemistry for the synthesis of peptide nucleic acids (PNAs).

Peptide Nucleic Acids (PNAs) are an intriguing class of synthetic biomolecules with great potential in medicine. Although PNAs could be considered analogs of oligonucleotides, their synthesis is more like that of peptides. In both cases, a Solid-Phase Synthesis (SPS) approach is used. Herein, the advantage using Boc as a temporal protecting group has been demonstrated to be more favored than Fmoc. In this context, a new PNA SPS strategy has been developed based on a safety-catch protecting group scheme for the exocyclic nitrogen of the side-chain bases and the linker. Sulfinyl (sulfoxide)-containing moieties are fully stable to the trifluoroacetic acid (TFA) used to remove the Boc group, but they can be reduced to the corresponding sulfide derivatives, which are labile in the presence of TFA. The efficiency of this novel synthetic strategy has been demonstrated in the synthesis of the PNA pentamer H-PNA(TATCT)-βAla-OH.

An Inventory of Fluorspar Production, Industrial Use, and Emissions of Trifluoroacetic Acid (TFA) in the Period 1930 to 1999

There is a generally accepted conclusion that trifluoroacetic acid (TFA) does occur naturally, in part based on the large quantities of TFA in the oceans (61 - 205 million tonnes, measured in 1998-2002). However, the recent review paper “Insufficient evidence for the existence of natural trifluoroacetic acid” concludes that “the presence of TFA in the deep ocean and lack of closed TFA budget is not sufficient evidence that TFA occurs naturally, especially without a reasonable mechanism of formation”. Industrial sources of TFA can only result from the use of fluoride minerals in industrial processes. Major industrial uses of fluorspar started significant expansion from about the same time (1930s). Over 190 million tonnes of fluorspar have been mined in the period 1930 to 1999. An inventory has been developed (1930-1999), accounting for most of the fluorspar production (86%) and estimating emissions of TFA. Industrial emissions of TFA are estimated as 230,000 to 470,000 tonnes. Significant other industrial uses of fluorides have not been identified that could account for the large burden of TFA in the oceans. This inventory provides complementary evidence that the quantity of TFA in the oceans must include a large natural burden.