The wide presence of fluorinated compounds in common chemical products and the environment: a review.

The C-F bonds, due to their many unique features, have been incorporated into numerous compounds in countless products and applications. These fluorinated compounds eventually are disposed of and released into the environment through different pathways. In this review, we analyzed the occurrence of these fluorinated compounds in seven types of products (i.e., refrigerants/propellants, aqueous film-forming foam, cosmetics, food packaging, agrochemicals, pharmaceuticals, coating materials) and discussed their fate in the environment. This is followed by describing the quantity of fluorinated compounds from each source based on available data. Total on- and off-site disposal or other releases of 536 fluorinated compounds in 2021 were analyzed using the data sourced from the U.S. EPA Toxics Release Inventory (TRI). Among the chemicals examined, chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) were the primary contributors in terms of total mass. Upon examining the seven sources of fluorinated compounds, it became evident that additional contributors are also responsible for the presence of organofluorine compounds in the environment. Although various toxic degradation products of fluorinated compounds could form in the environment, trifluoroacetic acid (TFA) was specifically highlighted in this review given the fact that it is a common dead-end degradation product of > 1 million chemicals. This paper ended with a discussion of several questions raised from this study. The path forward was elaborated as well for the purpose of protecting the environment and human health.

Tunable Mechanical and Electrical Properties of Coaxial Electrospun Composite Nanofibers of P(VDF-TrFE) and P(VDF-TrFE-CTFE).

The coaxial core/shell composite electrospun nanofibers consisting of relaxor ferroelectric P(VDF-TrFE-CTFE) and ferroelectric P(VDF-TrFE) polymers are successfully tailored towards superior structural, mechanical, and electrical properties over the individual polymers. The core/shell-TrFE/CTFE membrane discloses a more prominent mechanical anisotropy between the revolving direction (RD) and cross direction (CD) associated with a higher tensile modulus of 26.9 MPa and good strength-ductility balance, beneficial from a better degree of nanofiber alignment, the increased density, and C-F bonding. The interfacial coupling between the terpolymer P(VDF-TrFE-CTFE) and copolymer P(VDF-TrFE) is responsible for comparable full-frequency dielectric responses between the core/shell-TrFE/CTFE and pristine terpolymer. Moreover, an impressive piezoelectric coefficient up to 50.5 pm/V is achieved in the core/shell-TrFE/CTFE composite structure. Our findings corroborate the promising approach of coaxial electrospinning in efficiently tuning mechanical and electrical performances of the electrospun core/shell composite nanofiber membranes-based electroactive polymers (EAPs) actuators as artificial muscle implants.

Pharmacokinetic Study of Epinephrine Hydrofluoroalkane (Primatene MIST) Metered-Dose Inhaler.

Background: Primatene® MIST CFC, an epinephrine metered-dose inhaler (MDI), was discontinued from the market owing to environmental concerns from its use of chlorofluorocarbon (CFC) propellant. As a result, a new epinephrine MDI was developed using hydrofluoroalkane (HFA) propellant. This article reports the pharmacokinetic (PK) profile of the newly Food and Drug Administration-approved epinephrine HFA MDI. Methods: A randomized, evaluator-blinded, active-controlled, single-dose, two-arm crossover study was conducted to evaluate the PK profile of epinephrine HFA (Primatene® MIST) and epinephrine CFC (Primatene® MIST CFC) in 23 healthy volunteers to characterize the epinephrine absorption extent and rate. The study was performed at a high dose of five times the normal dose to obtain measurable plasma epinephrine levels. Plasma epinephrine levels were measured and safety was assessed by adverse events (AEs), vital signs, clinical laboratory tests, and physical examinations. Results: Epinephrine HFA demonstrated a greater systemic drug exposure (greater area under the curve) than that of epinephrine CFC (∼37% higher). The Cmax occurred at ∼2 minutes and was significantly higher in the epinephrine HFA group (0.18 ng/mL) compared with the CFC version (0.046 ng/mL) at normal dose. Within 20 minutes, both groups demonstrated comparable plasma epinephrine levels. No clinically significant adverse effects were found to be associated with epinephrine HFA, even after an ultrahigh dose (i.e., 10 inhalations). Conclusions: The systemic exposure of epinephrine HFA was found to be higher for the first 20 minutes, and then comparable with epinephrine CFC. Minimal AEs were found in this study despite the very high 1250-2200 µg inhaled doses (i.e., 10 inhalations) used for PK characterization.

Reliable and Robust Fabrication Rules for Springtail-Inspired Superomniphobic Surfaces.

We report a reliable and robust method for the fabrication of bioinspired superomniphobic surfaces with precise concave-cap-shaped micropillar arrays. This method includes silicon-based conventional microelectromechanical systems (MEMS) and polymer replication processes. We have elucidated two critical cases of fabrication rules for precise micromachining of a negative-shaped bioinspired silicon master. The fabricated polymeric structure replicated from the semipermanent silicon master based on the design rules exhibited high structural fidelity and robustness. Finally, we validated the superomniphobic properties, structural durability, and long-term stability of the fabricated bioinspired surfaces.

NEW DEVELOPMENTS AND APPLICATIONS OF SUPERHEATED EMULSIONS: WARHEAD VERIFICATION AND SPECIAL NUCLEAR MATERIAL INTERDICTION.

In recent years, neutron detection with superheated emulsions has received renewed attention thanks to improved detector manufacturing and read-out techniques, and thanks to successful applications in warhead verification and special nuclear material (SNM) interdiction. Detectors are currently manufactured with methods allowing high uniformity of the drop sizes, which in turn allows the use of optical read-out techniques based on dynamic light scattering. Small detector cartridges arranged in 2D matrices are developed for the verification of a declared warhead without revealing its design. For this application, the enabling features of the emulsions are that bubbles formed at different times cannot be distinguished from each other, while the passive nature of the detectors avoids the susceptibility to electronic snooping and tampering. Large modules of emulsions are developed to detect the presence of shielded special nuclear materials hidden in cargo containers 'interrogated' with high energy X-rays. In this case, the enabling features of the emulsions are photon discrimination, a neutron detection threshold close to 3 MeV and a rate-insensitive read-out.

Synthesis and Characterization of Waterborne Fluoropolymers Prepared by the One-Step Semi-Continuous Emulsion Polymerization of Chlorotrifluoroethylene, Vinyl Acetate, Butyl Acrylate, Veova 10 and Acrylic Acid.

Waterborne fluoropolymer emulsions were synthesized using the one-step semi-continuous seed emulsion polymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), n-butyl acrylate (BA), Veova 10, and acrylic acid (AA). The main physical parameters of the polymer emulsions were tested and analyzed. Characteristics of the polymer films such as thermal stability, glass transition temperature, film-forming properties, and IR spectrum were studied. Meanwhile, the weatherability of fluoride coatings formulated by the waterborne fluoropolymer and other coatings were evaluated by the quick ultraviolet (QUV) accelerated weathering test, and the results showed that the fluoropolymer with more than 12% fluoride content possessed outstanding weather resistance. Moreover, scale-up and industrial-scale experiments of waterborne fluoropolymer emulsions were also performed and investigated.

Electroreductive Remediation of Halogenated Environmental Pollutants.

Electrochemical reduction of halogenated organic compounds is gaining increasing attention as a strategy for the remediation of environmental pollutants. We begin this review by discussing key components (cells, electrodes, solvents, and electrolytes) in the design of a procedure for degrading a targeted pollutant, and we describe and contrast some experimental techniques used to explore and characterize the electrochemical behavior of that pollutant. Then, we describe how to probe various mechanistic features of the pertinent electrochemistry (including stepwise versus concerted carbon-halogen bond cleavage, identification of reaction intermediates, and elucidation of mechanisms). Knowing this information is vital to the successful development of a remediation procedure. Next, we outline techniques, instrumentation, and cell designs involved in scaling up a benchtop experiment to an industrial-scale system. Finally, the last and major part of this review is directed toward surveying electrochemical studies of various categories of halogenated pollutants (chlorofluorocarbons; disinfection byproducts; pesticides, fungicides, and bactericides; and flame retardants) and looking forward to future developments.

Effect of non-solvent additives on the morphology, pore structure, and direct contact membrane distillation performance of PVDF-CTFE hydrophobic membranes.

Four common types of additives for polymer membrane preparation including organic macromolecule and micromolecule additives, inorganic salts and acids, and the strong non-solvent H2O were used to prepare poly (vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) hydrophobic flat-sheet membranes. Membrane properties including morphology, porosity, hydrophobicity, pore size and pore distribution were investigated, and the permeability was evaluated via direct contact membrane distillation (DCMD) of 3.5g/L NaCl solution in a DCMD configuration. Both inorganic and organic micromolecule additives were found to slightly influence membrane hydrophobicity. Polyethylene glycol (PEG), organic acids, LiCl, MgCl2, and LiCl/H2O mixtures were proved to be effective additives to PVDF-CTFE membranes due to their pore-controlling effects and the capacity to improve the properties and performance of the resultant membranes. The occurrence of a pre-gelation process showed that when organic and inorganic micromolecules were added to PVDF-CTFE solution, the resultant membranes presented a high interconnectivity structure. The membrane prepared with dibutyl phthalate (DBP) showed a nonporous surface and symmetrical cross-section. When H2O and LiCl/H2O mixtures were also used as additives, they were beneficial for solid-liquid demixing, especially when LiCl/H2O mixed additives were used. The membrane prepared with 5% LiCl+2% H2O achieved a flux of 24.53kg/(m(2)·hr) with 99.98% salt rejection. This study is expected to offer a reference not only for PVDF-CTFE membrane preparation but also for other polymer membranes.

Emergence of healing in the Antarctic ozone layer.

Industrial chlorofluorocarbons that cause ozone depletion have been phased out under the Montreal Protocol. A chemically driven increase in polar ozone (or "healing") is expected in response to this historic agreement. Observations and model calculations together indicate that healing of the Antarctic ozone layer has now begun to occur during the month of September. Fingerprints of September healing since 2000 include (i) increases in ozone column amounts, (ii) changes in the vertical profile of ozone concentration, and (iii) decreases in the areal extent of the ozone hole. Along with chemistry, dynamical and temperature changes have contributed to the healing but could represent feedbacks to chemistry. Volcanic eruptions have episodically interfered with healing, particularly during 2015, when a record October ozone hole occurred after the Calbuco eruption.

Controlled droplet transport on a gradient adhesion surface.

A surface with continuously changed adhesion from ultrahigh to ultralow is fabricated by an integrated method of anodic oxidation combined with octafluorocyclobutane (C4F8) plasma. The control of droplet transport along the direction of the adhesion gradient in length is achieved, as the surface is submitted to either tilted angle or vibration frequency.

A cryospectroscopic infrared and Raman study of the CX⋯π halogen bonding motif: complexes of the CF3Cl, CF3Br, and CF3I with ethyne, propyne and 2-butyne.

Experimental information on the C-X⋯π halogen bonding motif was obtained by studying the formation of molecular complexes of CF3Cl, CF3Br and CF3I with ethyne, propyne and 2-butyne in liquid krypton, using FTIR and Raman spectroscopy. For CF3Br, experimental evidence was found for the formation of 1:1 complexes with propyne and 2-butyne only, while for CF3I spectroscopic features confirming the existence of the halogen bonded complexes were observed for ethyne, propyne and 2-butyne. In addition, at higher concentrations of CF3I and 2-butyne, weak absorptions due to a 2:1 complex were also observed. The experimental complexation enthalpies, obtained by using spectra recorded at temperatures between 120 K and 140 K, are -5.9(3) kJ mol(-1) for CF3I.ethyne, -5.6(3) kJ mol(-1) for CF3Br.propyne, -8.1(2) kJ mol(-1) for CF3I.propyne, -7.3(2) kJ mol(-1) for CF3Br.2-butyne, -10.9(2) kJ mol(-1) for CF3I.2-butyne and -20.9(7) kJ mol(-1) for (CF3I)2.2-butyne. The experimental study is supported by theoretical data obtained from ab initio calculations at the MP2/aug-cc-pVDZ(-PP) and MP2/aug-cc-pVTZ(-PP) levels, and Monte Carlo Free Energy Perturbation (MC-FEP) simulations. The experimental and theoretical values on the C-X⋯π halogen-bonding motifs studied are compared with previously reported data for the complexes with ethene and propene and with preliminary results obtained for benzene and toluene.

The dynamical behavior of the s-trioxane radical cation-A low-temperature EPR and theoretical study.

The radical cation of s-trioxane, radiolytically generated in a freon (CF3CCl3) matrix, was studied in the 10-140 K temperature region. Reversible changes of the EPR spectra were observed, arising from both ring puckering and ring inversion through the molecular plane. The ESREXN program based on the Liouville density matrix equation, allowing the treatment of dynamical exchange, has been used to analyze the experimental results. Two limiting conformer structures of the s-trioxane radical cation were taken into account, namely "rigid" half-boat and averaged planar ones, differing strongly in their electron distribution. The spectrum due to the "rigid" half-boat conformer can be observed only at very low (<60 K) temperatures, when the exchange of conformers is very slow. Two transition states for interconversion by puckering and ring-inversion were identified, close in activation energy (2.3 and 3.0 kJ/mol calculated). Since the energy difference is very small, both processes set on at a comparable temperature. In the case of nearly complete equilibration (fast exchange) between six energetically equivalent structures at T > 120 K in CF3CCl3, a septet due to six equivalent protons (hfs splitting constant 5.9 mT) is observed, characteristic of the dynamically averaged planar geometry of the radical cation. DFT quantum chemical calculations and spectral simulation including intramolecular dynamical exchange support the interpretation.

Developing an in vitro understanding of patient experience with hydrofluoroalkane-metered dose inhalers.

As a result of the Montreal Protocol on Substances that Deplete the Ozone Layer, manufacturers of metered dose inhalers began reformulating their products to use hydrofluoroalkanes (HFAs) as propellants in place of chlorofluorocarbons (CFCs). Although the new products are considered safe and efficacious by the US Food and Drug Administration (FDA), a large number of complaints have been registered via the FDA's Adverse Events Reporting System (FAERS)-more than 7000 as of May 2013. To develop a better understanding of the measurable parameters that may, in part, determine in vitro performance and thus patient compliance, we compared several CFC- and HFA-based products with respect to their aerodynamic performance in response to changes in actuator cleaning interval and interactuation delay interval. Comparison metrics examined in this study were: total drug delivered ex-actuator, fine particle dose (<5 µm), mass median aerodynamic diameter, plume width, plume temperature, plume impaction force, and actuator orifice diameter. Overall, no single metric or test condition distinguishes HFA products from CFC products, but, for individual products tested, there were a combination of metrics that differentiated one from another.

Mechanism of OH-initiated atmospheric oxidation of E/Z-CF3CF=CFCF3: a quantum mechanical study.

A detailed theoretical investigation was performed on the mechanisms for the reactions of E/Z-CF3CF= CFCF3 with OH radicals by means of density functional theory (DFT). The geometries and frequencies of all the stationary points and the minimum energy path (MEP) are calculated at the M06-2X/aug-cc-pVDZ level. To obtain more reliable energy information, the high-level single-point energies are further refined at the MCG3/3 level. Possible reaction pathways including the addition-elimination and the OH-initiated oxidation pathways are considered. A complete description of the possible degradation mechanisms of E/Z-CF3CF = CFCF3 in the absence and presence of O2/NO has been presented. The calculated results demonstrate that the most accessible products are CF3, CF(OH)= CFCF3, CF(O)CHFCF3, CF3C(O)F, and CHFCF3 via the dissociation reactions starting from the addition intermediates IM1E/IM1Z in the absence of O2/NO. While in the atmosphere, IM1E/IM1Z can further react with O2/NO to form the likely products CF3C(O)F and HO2. The calculated results are consistent with the experimental results.

Degradation of chlorofluorocarbons using granular iron and bimetallic irons.

Degradation of trichlorofluoromethane (CFC11) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC113) by granular iron and bimetallic (nickel- or palladium-enhanced) irons was studied in flow-through column tests. Both compounds were rapidly degraded, following pseudo-first-order kinetics with respect to the parent compounds. The average pseudo-first-order rate constants for CFC11 were similar among different materials, except for palladium-enhanced iron (PdFe), in which the rate of degradation was about two times faster than for the other materials. In the case of CFC113, the rate constants for bimetallic irons were about two to three times greater than for the regular iron material. The smaller than expected differences in degradation rate constants of chlorofluorocarbons (CFCs) between regular iron and bimetallic irons suggested little, if any, catalytic effect of the bimetallic materials in the initial degradation step. Subsequent degradation steps involved catalytic hydrogenation, however, playing a significant role in further degradation of reaction intermediates. The degradation intermediates and final products of CFC11 and CFC113 suggested that degradation proceeded through hydrogenolysis and α/ß-elimination in the presence of regular iron (Fe) and nickel-enhanced iron (NiFe). Even though there is only minor benefit in the use of bimetallic iron in terms of degradation kinetics of the parent CFCs, enhanced degradation rates of intermediates such as chlorotriflouroethene (CTFE) in subsequent reaction steps could be beneficial.

Mechanism, kinetics and atmospheric fate of CF3CH=CH2, CF3CF=CH2, and CF3CF=CF2 by its reaction with OH-radicals: CVT/SCT/ISPE and hybrid meta-DFT methods.

The dual level direct dynamic study is carried out for the reactions of CF3CH=CH2, CF3CF=CH2 and CF3CF=CF2 with hydroxyl radicals. The dynamic calculations are performed using the variational transition state theory (VTST) with interpolated single-point energies (ISPE) method at M06-2X/MG3S//M06-2X/6-31+G(d,p) level of theory. All the possible reactions such as abstraction and addition-elimination pathways are explored for the title reactions. The temperature dependent rate coefficients using canonical variational transition state theory with small curvature tunneling for the reaction of OH radicals with test molecules over the temperature range of 200-3000 K are computed. The predicted rate coefficients (in 10⁻¹² cm³ molecule⁻¹ s⁻¹) using CVT/SCT/ISPE methodology for the reaction of CF3CH=CH2, CF3CF=CH2 and CF3CF=CF2 with OH radicals are 1.48, 1.02 and 1.77, respectively, are in good agreement with reported ones at 298 K. The atmospheric lifetimes for the test molecules CF3CH=CH2, CF3CF=CH2 and CF3CF=CF2 are calculated at 277 K to be 8, 11 and 6 days, respectively. Global warming potentials are also reported for the different time horizon of 20, 100 and 500 years.

Comprehensive theoretical studies on the reaction of 1-bromo-3,3,3-trifluoropropene with OH free radicals.

The potential energy surfaces (PES) for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals is probed theoretically at the CCSD/aug-cc-pVDZ//B3LYP/6-311++G(d,p) level of theory. All the possible stationary and first-order saddle points along the reaction paths were verified by the vibrational analysis. The calculations account for all the product channels. Based on the calculated CCSD/aug-cc-pVDZ potential energy surface, the possible reaction mechanism is discussed. Six distinct reaction pathways of 1-bromo-3,3,3-trifluoropropene (BTP) with OH are investigated. The geometries, reaction enthalpies and energy barriers are determined. Canonical transition-state theory with Wigner tunneling correction was used to predict the rate constants for the temperature range of 290-3,000 K without any artificial adjustment, and the computed rate constants for elementary channels can be accurately fitted with three-parameter Arrhenius expressions. OH addition reaction channel and the H atom abstraction channels related to the carbon-carbon double bond are found to be the main reaction channels for the reaction of 1-bromo-3,3,3-trifluoropropene (CF3CHCBrH) with hydroxyl (OH) free radicals while the products leading to CF3CHCH + BrOH and COHF2CHCBrH + F play a negligible role.

Italian WEEE management system and treatment of end-of-life cooling and freezing equipments for CFCs removal.

This study presents and analyzes the data of the Italian system for take-back and recovery of waste electrical and electronic equipments (WEEEs) in the start-up period 2008-2010. The analysis was focused particularly on the data about the treatment of end-of-life cooling and freezing equipments. In fact, the wastes of cooling and freezing equipments have a high environmental impact. Indeed, in their compressor oil and insulation polyurethane (PU) foams chlorofluorocarbon (CFC) ozone-depleting gases are still present. In the period 2001-2004 Northern Italy resulted the main source in Europe of CFCs. The European Directive on WEEE management was enacted in 2002, but in Italy it was implemented by the legislative Decree in 2005 and it became operational in 2008. Actually, in 2008 the national WEEE Coordination Centre was founded in order to organize the WEEE pick-up process and to control collection, recovery and recycling targets. As a result, in 2010 the average WEEE collection per capita exceeded the threshold of more than 4 kg per inhabitant, as well as cooling and freezing appliances represented more than one fourth of the Italian WEEE collection stream. During the treatment of end-of-life cooling and freezing equipments, CFCs were recovered and disposed principally by burner methods. The analyses of defined specimens collected in the treatment facilities were standardized to reliably determine the amount of recovered CFCs. Samples of alkaline solid salt, alkaline saline solution, polyurethane matrix and compressor oil collected during the audit assessment procedure were analyzed and the results were discussed. In particular, the analysis of PU samples after the shredding and the warm pressing procedures measured a residual CFCs content around 500-1300 mg/kg of CFCs within the foam matrix.