Fluorine abundance

Abstract. The astrophysical origins of the element fluorine remain uncertain due in part to the availability of just a small number of abundance results for this element, that has readily observable transitions only in the infrared via vibration-rotation lines of HF. In this paper, we discuss all the available Galactic fluorine abundances to date, and add results for field stars with metallicities between [Fe/H] = -0.5 and -1.0, plus two stars that are members of the Orion association. The fluorine abundances obtained for the young Orion members are found to be in agreement with the trend of [F/O] versus O observed for the disk and they are a good representation of the present day value in the Galactic disk. 

Recent observations of the HF (1-0) R9 line at 2.3 /tm with the Phoenix spectrograph on the Gemini-South telescope has opened a new window that sheds light on understanding the chemical evolution of fluorine and the nuclear processes that produce this element. Until recently, only a small number of observations of fluorine were available and the trend of fluorine abundances with metallicity had yet to be probed in the Galaxy. 

Fig. 1. The Galactic fluorine abundances obtained to date. Three samples are represented the disk of the Milky Way (crosses), including the two young Orion pre-main-sequence stars (open circles), and u> Centauri giants (filled circles).

Fig. 24. Comparison of fluorine abundances observed by [130] and model predictions for the 3Mq, 7 = 0.008 model. The predictions are normalized such that the initial 19F abundance corresponds to the average F abundance observed in K and M stars. Each symbol on the prediction lines represents a TDU episode. Solid lines represent calculations performed using no 18F(q, p)21 Ne reaction, which are equivalent to using the current lower limit, recommended value and Brussels library rate. Dotted lines are calculations performed using the current upper limit of the rate. Figure provided by Maria Lugaro...

Although continuous wave NMR is sufficient for naturally abundant nuclei with strong magnetic moments such as hydrogen, fluorine and phosphorous, the study of low abundance nuclei and/or weak magnetic moments such as carbon 13 or silicon 29 requires pulse NMR. 

McFeely F R, Morar J F, Shinn N D, Landgren G and Himpsel F J 1984 Synchrotron photoemission investigation of the initial stages of fluorine attack on Si surfaces relative abundance of fluorosilyl species Phys. Rev. B 30 764-70... 

We also developed a number of other useful new fluorinating reagents. They ineluded a convenient in situ form of sulfur tetrafluoride in pyridinium polyhydrogen fluoride, selenium tetrafluoride, and ey-anurie fluoride. We introdueed uranium hexafluoride (UFg), depleted from the U-235 isotope, which is an abundant by-product of enrichment plants, as an effective fluorinating agent. 

The upper part of the figure illustrates why the small difference in mass between an ion and its neutral molecule is ignored for the purposes of mass spectrometry. In mass measurement, has been assigned arbitrarily to have a mass of 12.00000, All other atomic masses are referred to this standard. In the lower part of the figure, there is a small selection of elements with their naturally occurring isotopes and their natural abundances. At one extreme, xenon has nine naturally occurring isotopes, whereas, at the other, some elements such as fluorine have only one. 

For any one element, the abundances (relative amounts) of isotopes can be described in percentage terms. Thus, fluorine is monoisotopic viz., it contains only nuclei of atomic mass 19, and phosphorus has 100% abundance of atoms with atomic mass 31. For carbon, the first two isotopes occur in the proportions of 98.882 to 1.108. 

The earth s cmst consists of 0.09% fluoiine. Among the elements fluorine ranks about thirteenth ia terrestrial abundance. 

On average, fluorine is about as abundant as chlorine in the accessible surface of the earth including oceans. The continental cmst averages about 650 ppm fluorine. Igneous, metamorphic, and sedimentary rocks all show abundances in the range of 200 to 1000 ppm. As of 1993, fluorspar was still the principal source of fluorine for industry. 

Oxygen is by far the most abundant element in cmstal rocks, composing 46.6% of the Hthosphere (4). In rock mineral stmctures, the predominant anion is, and water (H2O) itself is almost 90% oxygen by weight. The nonmetaUic elements fluorine, sulfur, carbon, nitrogen, chlorine, and phosphoms are present in lesser amounts in the Hthosphere. These elements aU play essential roles in life processes of plants and animals, and except for phosphoms and fluorine, they commonly occur in earth surface environments in gaseous form or as dissolved anions. 

Synthetic cryolite solved the supply problem, but synthetic cryolite requires fluorine which is actually more abundant in the Earth s crust than chlorine, but dispersed in small concentrations in rocks. Until the 1960s, fluorspar (CaFj) a mineral long known and used as a flux in various metallurgical operations was the source. A source is phosphate rock that contains fluorine i.s 3% quantity,... 

The enamines, enol ethers and enol acetates of A -3-keto steroids provide important substrates for fluorination with FCIO3. Reaction of such A -enol ethers and acetates (6) with perchloryl fluoride results in 6a- and 6jff-fluoro-A -3-ketones (7) and (8), the latter representing the more abundant isomer. Tetrahydrofuran or dioxane-water mixtures appear to be particu-... 

The simplest method for obtaining selective fluonnation is to conduct reactions under conditions that invigorate the electrophilicity of fluorine In practice this method entails the creation of anionic or strongly nucleophilic reactive centers on substrate molecules while suppressing or reducing the tendency toward radical attack Numerous examples of seleetive fluorine attack on carbanionic, amido and carboxylato species are documented Especially abundant is alpha fluonnation of nitroalkanes in polar solvents [42 43, 44, 45 46] (equations 10-14)... 

Abundances of lUPAC (the International Union of Pure and Applied Chemistry). Their most recent recommendations are tabulated on the inside front fly sheet. From this it is clear that there is still a wide variation in the reliability of the data. The most accurately quoted value is that for fluorine which is known to better than I part in 38 million the least accurate is for boron (1 part in 1500, i.e. 7 parts in [O ). Apart from boron all values are reliable to better than 5 parts in [O and the majority arc reliable to better than I part in 10. For some elements (such as boron) the rather large uncertainty arises not because of experimental error, since the use of mass-spcctrometric measurements has yielded results of very high precision, but because the natural variation in the relative abundance of the 2 isotopes °B and "B results in a range of values of at least 0.003 about the quoted value of 10.811. By contrast, there is no known variation in isotopic abundances for elements such as selenium and osmium, but calibrated mass-spcctrometric data are not available, and the existence of 6 and 7 stable isotopes respectively for these elements makes high precision difficult to obtain they are thus prime candidates for improvement. 

Fluorine is the thirteenth element in order of abundance in crustal rocks of the earth, occurring to the extent of 544 ppm (cf. twelfth Mn, 1060 ppm fourteenth Ba, 390 ppm fifteenth Sr, 384 ppm). The three most important minerals are... 

Bromine is substantially less abundant in crustal rocks than either fluorine or chlorine at 2.5 ppm it is forty-sixth in order of abundance being similar to Hf 2.8, Cs 2.6, U 2.3, Eu 2.1 and Sn 2.1 ppm. Like chlorine, the largest natural source of bromine is the oceans, which contain 6.5 x 10 %, i.e. 65 ppm or 65mg/l. The mass ratio Cl Br is 300 1 in the oceans, corresponding to an atomic ratio... 

As it happens, naturally occurring fluorine consists of a single isotope, ijF. It ibllows that the atomic mass of the element fluorine must be the same as that of F-19,19.00 amu. The situation with most elements is more complex, because they occur in nature as a mixture of two or more isotopes. To determine the atomic mass of such an element, it is necessary to know not only the masses of the individual isotopes but also their atom percents (isotopic abundances) in nature. 

Many of the metals used by ancient man— coppei (cuprum, Cu), silver (argentum, Ag), gold (aurum, Au), tin (stannum, Sn), and lead (plumbum, Pb)—are in relatively short supply. Ancient man found deposits of the first three occurring as the elementary metals. These three may also be separated from their ores by relatively simple chemical processes. On the othei hand, aluminum and titanium, though abundant, are much more difficult to prepare from their ores. Fluorine is more abundant in the earth than chlorine but chlorine and its compounds are much more common—they are easier to prepare and easier to handle. However, as the best sources of the elements now common to us become depleted, we will have to turn to the elements that are now little used. 

The molecular ions of perfluorinated olefins are usually observed. The m/z 31 ion is frequently more abundant in fluorinated olefins than in fluorinated saturated compounds. 

Because the fluoride ion is so small, the lattice enthalpies of its ionic compounds tend to be high (see Table 6.6). As a result, fluorides are less soluble than other halides. This difference in solubility is one of the reasons why the oceans are salty with chlorides rather than fluorides, even though fluorine is more abundant than chlorine in the Earth s crust. Chlorides are more readily dissolved and washed out to sea. There are some exceptions to this trend in solubilities, including AgF, which is soluble the other silver halides are insoluble. The exception arises because the covalent character of the silver halides increases from AgCl to Agl as the anion becomes larger and more polarizable. Silver fluoride, which contains the small and almost unpolarizable fluoride ion, is freely soluble in water because it is predominantly ionic. 

Fluorine-19, like phosphorus-31, is a spin-Vi nucleus with 100% natural abundance. The signals it produces are almost as strong as those of the proton, and the resonance frequency at a given field is also relatively close to that of the proton. Although for many years it was in fact necessary to have a special probehead for fluorine-19, those days have gone and fluorine has become a completely normal nucleus. 

Fluoride ions may be relatively abundant in groundwater at one location and practically absent in that at another site hence the rate of fluoridation of the bone (the rate of increase in the relative amount of fluorine in the bone) varies from site to site. For instance, bones buried for a short time at a site in which the groundwater is rich in fluoride may acquire much more fluorine than bones buried for a very long time at a place where there is little fluoride in the groundwater. Therefore, fluorine analysis does not provide a tool for estimating the absolute age of buried bone, but only for dating bones at the same site, comparative to each other. The relative amount of fluoride in buried bone at a particular site thus provides a clue as to the length of time the bone has been buried. 

---