Oxygen and carbon isotope composition of structural carbonate in weathering apatites from laterites, southern Brazil and western Senegal

The oxygen (δ¹⁸O_c) and carbon (δ¹³C_c) isotope compositions of the structural carbonate group (CO₃) in apatites from lateritic profiles were investigated. The weathering profiles, located in southern Brazil and in western Senegal, are developed on three different types of apatite-rich parent rock: carbonatite, metamorphosed marine phosphorite and sedimentary marine phosphorite. The parent rock apatites are of magmatic, hydrothermal, metamorphic and sedimentary origins. The in situ formation of apatite of weathering origin in the profiles is well documented petrographically and geochemically.The overall range of measured δ¹⁸O_c and δ¹³C_c values of apatites of weathering origin (22 to 27 SMOW for δ¹⁸O_c and −15 to −10 PDB for δ¹³C_c) is much smaller than the range of measured and/or published isotope compositions of parent rock apatites (4–35 for δ¹⁸O_c and −11 to +1 for δ¹³C_c). In any profile, the apatites of weathering origin can exhibit lower, similar or higher δ¹⁸O_c values than parent rock apatites. In contrast, their δ¹³C_c values are systematically and significantly lower than those of the parent rock apatites. Apatites formed as a result of weathering in laterites can therefore be readily distinguished from apatites of other origin on the basis of their isotope composition.Assuming that apatite CO₃ fractionates O in a way similar to calcite CO₃, the structural carbonate group of the apatites of weathering origin appears to form in approximate isotopic equilibrium with the weathering solutions. The very low δ¹³C_c values exhibited by these apatites indicate that the dominant sources of dissolved CO₂ in the soil water are organic. The isotope composition of structural carbonate in apatite of weathering origin in lateritic profiles may provide useful information for paleoenvironmental studies.     

Geochemistry of Apatite from the Apatite-rich Iron Deposits in the Ningwu Region, East Central China

Four types of apatite have been identified in the Ningwu region.The first type of apatite is widely distributed in the middle dark colored zones(i.e.iron ores) of individual deposits.The assemblage includes magnetite,apatite and actinolite(or diopside).The second type occurs within magnetite-apatite veins in the iron ores.The third type is seen in magnetite-apatite veins and (or) nodules in host rocks(i.e.gabbro-diorite porphyry or gabbro-diorite or pyroxene diorite).The fourth type occurs within apatite-pyrite-quartz veins filling fractures in the Xiangshan Group.Rare earth elements (REE) geochemistry of apatite of the four occurrences in porphyry iron deposits is presented.The REE distribution patterns of apatite are generally similar to those of apatites in the Kiruna-type iron ores,nelsonites.They are enriched in light REE,with pronounced negative Eu anomalies.The similarity of REE distribution patterns in apatites from various deposits in different locations in the world indicates a common process of formation for various ore types,e.g. immiscibility.Early magmatic apatites contain 3031.48-12080×10~(-6) REE.Later hydrothermal apatite contains 1958×10~(-6) REE,indicating that the later hydrothermal ore-forming solution contains lower REE.Although gabbro-diorite porphyry and apatite show similar REE patterns,gabbro-diorite porphyries have no europium anomalies or feeble positive or feeble negative europium anomalies, caused both by reduction environment of mantle source region and by fractionation and crystallization(immiscibility) under a high oxygen fugacity condition.Negative Eu anomalies of apatites were formed possibly due to acquisition of Eu~(2+) by earlier diopsite during ore magma cooling. The apatites in the Aoshan and Taishan iron deposits yield a narrow variation range of ~(87)Sr/~(86)Sr values from 0.7071 to 0.7073,similar to those of the volcanic and subvolcanic rocks,indicating that apatites were formed by liquid immiscibility and differentiation of intermediate and basic magmas.     

宁芜玢岩铁矿磷灰石的稀土元素特征

文章分析了宁芜玢岩铁矿 4种产状磷灰石的稀土元素组成 ,并与Kiruna型铁矿和斜长岩、苏长岩及钛铁霞辉岩中磷灰石的稀土元素组成进行了对比。结果表明产地和母岩不同的矿床中 ,它们的磷灰石稀土元素分布型式一致 ,以轻稀土富集和Eu负异常明显为特征 ,属陆相岩浆成因。前 3种产状磷灰石的ΣREE变化于 30 31.48×10 -6～ 12 0 80× 10 -6,第 4种产状磷灰石的ΣREE仅为 195 8× 10 -6,反映岩浆演化到热液的晚期阶段成矿溶液稀土元素含量较低。尽管辉长闪长玢岩与磷灰石的稀土元素分布型式一致 ,但辉长闪长玢岩无Eu异常或有弱Eu正异常 ,代表它们的地幔源区低氧逸度的还原环境 ,或反映氧逸度较高情况下的分离结晶作用。不混溶作用形成的矿浆在冷凝过程中 ,Eu2 + 优先被透辉石捕获 ,使得稍晚结晶的磷灰石产生负Eu异常     

Apatite as an indicator mineral for mineral exploration: trace-element compositions and their relationship to host rock type

Over 700 apatite grains from a range of rock types have been analysed by laser-ablation microprobe ICPMS for 28 trace elements, to investigate the potential usefulness of apatite as an indicator mineral in mineral exploration. Apatites derived from different rock types have distinctive absolute and relative abundances of many trace elements (including rare-earth elements (REE), Sr, Y, Mn, Th), and chondrite-normalised trace-element patterns. The slope of chondrite-normalised REE patterns varies systematically from ultramafic through mafic/intermediate to highly fractionated granitoid rock types. (Ce/Yb)_cn is very high in apatites from carbonatites and mantle-derived lherzolites (over 100 and over 200, respectively), while (Ce/Yb)_cn values in apatites from granitic pegmatites are generally less than 1, reflecting both HREE enrichment and LREE depletion. Within a large suite of apatites from granitoid rocks, chemical composition is closely related to both the degree of fractionation and the oxidation state of the magma, two important parameters in determining the mineral potential of the magmatic system. Apatite can accept high levels of transition and chalcophile elements and As, making it feasible to recognise apatite associated with specific types of mineralisation. Multivariate statistical analysis has provided a user-friendly scheme to distinguish apatites from different rock types, based on contents of Sr, Y, Mn and total REE, the degree of LREE enrichment and the size of the Eu anomaly. The scheme can be used for the recognition of apatites from specific rock types or styles of mineralisation, so that the provenance of apatite grains in heavy mineral concentrates can be determined and used in geochemical exploration.     

Oxygen isotope evolution of biogenic calcite and apatite during the Middle and Late Devonian

Oxygen isotope ratios of well-preserved brachiopod calcite and conodont apatite were used to reconstruct the palaeotemperature history of the Middle and Late Devonian. By assuming an oxygen isotopic composition of –1 V-SMOW for Devonian seawater, the oxygen isotope values of Eifelian and early Givetian brachiopods and conodonts give average palaeotemperatures ranging from 22 to 25 °C. Late Givetian and Frasnian palaeotemperatures calculated from ¹⁸O values of conodont apatite are close to 25 °C in the early Frasnian and increase to 32 °C in the latest Frasnian and early Famennian. Oxygen isotope ratios of late Givetian and Frasnian brachiopods are significantly lower than equilibrium values calculated from conodont apatite ¹⁸O values and give unrealistically warm temperatures ranging from 30 to 40 °C. Diagenetic recrystallization of shell calcite, different habitats of conodonts and brachiopods, as well as non-equilibrium fractionation processes during the precipitation of brachiopod calcite cannot explain the ¹⁸O depletion of brachiopod calcite. Moreover, the ¹⁸O depletion of brachiopod calcite with respect to equilibrium ¹⁸O values calculated from conodont apatite is too large to be explained by a change in seawater pH that might have influenced the oxygen isotopic composition of brachiopod calcite. The realistic palaeotemperatures derived from ¹⁸O _apatite may suggest that biogenic apatite records the oxygen isotopic composition and palaeotemperature of Palaeozoic oceans more faithfully than brachiopod calcite, and do not support the hypothesis that the ¹⁸O/¹⁶O ratio of Devonian seawater was significantly different from that of the modern ocean.     

沉积磷灰石形成中的生物有机质因素

本文研究了黔中磷块岩中磷灰石的化学成分、红外光谱、碳和硫同位素组成以及伴生微量元素和稀土元素地球化学特征,获得了若干生物有机质成因的证据.磷灰石红外光谱特征表明CO₃^2-和SO₄^2-以类质同象部分替代PO₄^2-而进入磷灰石晶格,而碳、硫同位素特征表明,这CO₃^2-及SO₄^2-的相当部分是由生物有机质分解演化而来;叠层石磷灰石的P₂O₅含量与亲生物微量元素关系非常密切,而非叠层石者关系不甚密切;稀土元素地球化学特征表明,磷灰石的形成具有两种既有联系又各不相同的作用机制,即直接的生物作用和间接的有机质作用.     

Trace element and Nd isotope analyses of apatite in granitoids and metamorphosed granitoids from the eastern Central Asian Orogenic Belt: Implications for petrogenesis and post-magmatic alteration

We present in situ trace element and Nd isotopic data of apatites from metamorphosed and metasomatized (i.e., altered) and unaltered granitoids in the Songnen and Jiamusi massifs in the eastern Central Asian Orogenic Belt, with the aim of fingerprinting granitoid petrogenesis, including both the magmatic and post-magmatic evolution processes. Apatites from altered granitoids (AG) and unaltered granitoids (UG) are characterized by distinct textures and geochemical compositions. Apatites from AG have irregular rim overgrowths and complex internal textures, along with low contents of rare earth elements (REEs), suggesting the re-precipitation of apatite during epidote crystallization and/or leaching of REEs from apatite by metasomatic fluids. ε_Nd(t) values of the these apatites are decoupled from zircon ε_Hf(t) values for most samples, which can be attributed to the higher mobility of Nd as compared to Sm in certain fluids. Apatites from UG are of igneous origin based on their homogeneous or concentric zoned textures and coupled Nd-Hf isotopic compositions. Trace element variations in igneous apatite are controlled primarily by the geochemical composition of the parental melt, fractional crystallization of other REE-bearing minerals, and changes in partition coefficients. Sr contents and Eu/Eu* values of apatites from UG correlate with whole-rock Sr and SiO₂ contents, highlighting the effects of plagioclase fractionation during magma evolution. Apatites from UG can be subdivided into four groups based on REE contents. Group 1 apatites have REE patterns similar to the host granitoids, but are slightly enriched in middle REEs, reflecting the influence of the parental melt composition and REE partitioning. Group 2 apatites exhibit strong light REE depletions, whereas Group 3 apatites are depleted in middle and heavy REEs, indicative of the crystallization of epidote-group minerals and hornblende before and/or during apatite crystallization, respectively. Group 4 apatites are depleted in heavy REEs, but enriched in Sr, which are features of adakites. Some unusual geochemical features of the apatites, including the REE patterns, Sr contents, Eu anomalies, and Nd isotopic compositions, indicate that inherited apatites are likely to retain the geochemical features of their parental magmas, and thus provide a record of small-scale crustal assimilation during magma evolution that is not evident from the whole-rock geochemistry.     

Artificial neural networks approach for zeta potential of Montmorillonite in the presence of different cations

In this study, the zeta potential of montmorillonite in the presence of different chemical solutions was modeled by means of artificial neural networks (ANNs). Zeta potential of the montmorillonite was measured in the presence of salt cations, Na⁺, Li⁺ and Ca²⁺ and metals Zn²⁺, Pb²⁺, Cu²⁺, and Al³⁺ at different pH values, and observed values pointed to a different behavior for this mineral in the presence of salt and heavy metal cations. Artificial neural networks were successfully developed for the prediction of the zeta potential of montmorillonite in the presence of salt and heavy metal cations at different pH values and ionic strengths. Resulting zeta potential of montmorillonite shows different behavior in the presence of salt and heavy metal cations, and two ANN models were developed in order to be compared with experimental results. The ANNs results were found to be close to experimentally measured zeta potential values. The performance indices such as coefficient of determination, root mean square error, mean absolute error, and variance account for were used to control the performance of the prediction capacity of the models developed in this study. These indices obtained make it clear that the predictive models constructed are quite powerful. The constructed ANN models exhibited a high performance according to the performance indices. This performance has also shown that the ANNs seem to be a useful tool to minimize the uncertainties encountered during the soil engineering projects. For this reason, the use of ANNs may provide new approaches and methodologies.     

A study of factors affecting on the zeta potential of kaolinite and quartz powder

The purpose of this study was to determine the effects of pH, ion type (salt and metal cations), ionic strength, cation valence, hydrated ionic radius, and solid concentration on the zeta potential of kaolinite and quartz powder in the presence of NaCl, KCl, CaCl₂, CuCl₂, BaCl₂, and AlCl₃ solutions. The kaolinite and quartz powder have no isoelectric point (iep) within the entire pH range (3 < pH < 11). In the presence of hydrolysable metal ions, kaolinite and quartz powder have two ieps. As the cationic valence increases, the zeta potential of kaolinite and quartz powder becomes less negative. Monovalent cation, K⁺, yields more negative zeta potential values than the divalent cation Ba²⁺. As concentration of solid increases, the zeta potential of the minerals becomes more positive under acidic conditions; however, under alkaline conditions as solid concentration increases the zeta potential becomes more negative. Hydrated ionic radius also affects the zeta potential; the larger the ion, the thicker the layer and the more negative zeta potential for both kaolinite and quartz powder.     

Laser-induced time-resolved luminescence as a tool for rare-earth element identification in minerals

 We have determined and distinguished a number of rare-earth elements in several minerals by use of laser-induced time-resolved luminescence spectroscopy. Unlike the conventional measurement of steady-state luminescence, the method allows discrimination between ions that emit in the same spectral range but have different decay times. The main new results are the following: decay time data for all REE luminescence centers; Tm³⁺, Pr³⁺, Er³⁺, Ho³⁺ luminescence in apatite, scheelite, zircon, calcite, and fluorite; Eu³⁺ luminescence in apatite, zircon, fluorite, calcite, danburite, and datolite. Received: 17 April 2000 / Accepted: 4 January 2001     

On the cathodic reaction coupled with the oxidation of xanthates at the pyrite/aqueous solution interface

The adsorption of ethyl, propyl and butyl xanthates on pyrite has been studied through electrokinetics, batch adsorption tests, and quantification of Fe²⁺ ions in solution. Adsorption isotherms for the three alkyl xanthates indicate that their adsorption to dixanthogen produces Fe²⁺ ions in solution and decreases the pyrite zeta potential negatively. It seems that the oxidation reaction of xanthates to dixanthogen on pyrite is coupled with the reduction reaction of surface-ferric hydroxide to ferrous ions, leading to the dissolution of hydrophilic ferric hydroxide and growth of hydrophobic dixanthogen on the surface of pyrite. Flotation of pyrite is presented as a function of pH using various ethyl xanthate concentrations. The floatability results are explained in terms of the surface coverage relationship between ferric hydroxide and dixanthogen, which is pH dependent.     

Study of the surface properties of enargite as a function of pH

The surface properties of enargite as a function of pH were investigated. The zeta potential values increased from − 10 mV (pH = 3) to − 45 mV (pH = 12) and no isoelectric point (iep) was detected. The zeta potential of enargite was highly sensitive to pH and interesting peaks/valleys, unusual in common sulfide minerals, were observed. In the present study, these results were interpreted on the basis of the chemistry of enargite, which is a tetra-thioasenate of Cu(I). A thermodynamic approach, including the Eh–pH diagram for enargite, and the hydrolysis diagrams for arsenic, thioarsenic, and oxo-thioarsenic acids was employed. An interpretation based on the simultaneous ionization and dissociation reactions of the hydrolysis products of arsenic and thioarsenic acids on the enargite surface was discussed. On the other hand, covellite (CuS), under low concentrations of arsenate ions, showed similar zeta potential peaks. Additionally, enargite's zeta potential showed sign reversal for a certain pH range, with the addition of low concentrations of Cu(I) and Cu(II) ions, suggesting that other hydrolysis and precipitation reactions may also be involved.     

The influence of artificial radiation damage and thermal annealing on helium diffusion kinetics in apatite

Recent work [Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249(3-4), 148-161] revealing a correlation between radiogenic ⁴He concentration and He diffusivity in natural apatites suggests that helium migration is retarded by radiation-induced damage to the crystal structure. If so, the He diffusion kinetics of an apatite is an evolving function of time and the effective uranium concentration in a cooling sample, a fact which must be considered when interpreting apatite (U-Th)/He ages. Here we report the results of experiments designed to investigate and quantify this phenomenon by determining He diffusivities in apatites after systematically adding or removing radiation damage.Radiation damage was added to a suite of synthetic and natural apatites by exposure to between 1 and 100 h of neutron irradiation in a nuclear reactor. The samples were then irradiated with a 220 MeV proton beam and the resulting spallogenic ³He used as a diffusant in step-heating diffusion experiments. In every sample, irradiation increased the activation energy (E_a) and the frequency factor (D_o/a²) of diffusion and yielded a higher He closure temperature (T_c) than the starting material. For example, 100 h in the reactor caused the He closure temperature to increase by as much as 36 °C. For a given neutron fluence the magnitude of increase in closure temperature scales negatively with the initial closure temperature. This is consistent with a logarithmic response in which the neutron damage is additive to the initial damage present. In detail, the irradiations introduce correlated increases in E_a and ln(D_o/a²) that lie on the same array as found in natural apatites. This strongly suggests that neutron-induced damage mimics the damage produced by U and Th decay in natural apatites.To investigate the potential consequences of annealing of radiation damage, samples of Durango apatite were heated in vacuum to temperatures up to 550 °C for between 1 and 350 h. After this treatment the samples were step-heated using the remaining natural ⁴He as the diffusant. At temperatures above 290 °C a systematic change in T_c was observed, with values becoming lower with increasing temperature and time. For example, reduction of T_c from the starting value of 71 to ∼52 °C occurred in 1 h at 375 °C or 10 h at 330 °C. The observed variations in T_c are strongly correlated with the fission track length reduction predicted from the initial holding time and temperature. Furthermore, like the neutron irradiated apatites, these samples plot on the same E_a − ln(D_o/a²) array as natural samples, suggesting that damage annealing is simply undoing the consequences of damage accumulation in terms of He diffusivity.Taken together these data provide unequivocal evidence that at these levels, radiation damage acts to retard He diffusion in apatite, and that thermal annealing reverses the process. The data provide support for the previously described radiation damage trapping kinetic model of Shuster et al. (2006) and can be used to define a model which fully accommodates damage production and annealing.     

Hallimond tube flotation of scheelite and calcite with amines

Hallimond tube flotation experiments have been carried out on the two calcium minerals scheelite and calcite using dodecylammonium chloride as collector. The main variables studied were the calcium ion concentration and the pH.In the case of scheelite, addition of calcium chloride markedly lowered the flotation recovery. Recovery was also lowered when the pH was reduced below about 10. Since it is known that the zeta potential of scheelite is almost independent of pH this confirms that co-adsorption of un-ionized amine is necessary for good flotation. Other un-ionized long-chain molecules can replace the amine; thus it was shown that excellent flotation can be obtained event at about pH 7 by adding dodecanol together with dodecylammonium chloride. With the completely ionic trimethyldodecylammonium chloride recoveries were poor and were independent of pH.In the case of calcite, calcium chloride had no immediate effect on flotation recovery, but at low collector concentrations marked depression occurred after many hours standing in the presence of calcium ions. The effect of pH on flotation of calcite was anomalous and there appear to be two pH regions in which recoveries are high.The results are discussed and attention is drawn to the need for more thorough studies of the calcium carbonate/water interface.     

Electrokinetic properties and flotation behaviour of apatite and calcite in the presence of sodium oleate and sodium metasilicate

Calcite is generally associated with apatite minerals in phosphate deposits. To explore the possibility of separating these minerals by a soap flotation technique, their electrokinetic properties and flotation behaviour were studied in the presence of sodium oleate.Microelectrophoresis data indicate oleate adsorption on these minerals, and from Hallimond-tube flotation tests it has been noted that in a controlled pH environment and for a certain sodium oleate concentration range, separation of these minerals is possible.The study of apatite/calcite-sodium metasilicate-sodium oleate systems indicates the preferential adsorption of silicate at the calcite surface. This suggests the potential use of sodium metasilicate as the modifying agent for the separation of apatite from calcite by depressing calcite when using sodium oleate as collector.     

Major and Trace Element Characteristics of Apatites in Granitoids from Central Kazakhstan: Implications for Petrogenesis and Mineralization

This paper presents abundances of major and trace elements of apatites in granitic rocks associated with different types of ore deposits in Central Kazakhstan on the basis of electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. Our results demonstrate that the concentrations and ratios of elements in apatites from different granitoid rocks show distinct features, and are sensitive to magma evolution, petrogenetic and metallogenetic processes. Apatites in the rocks associated with Mo‐W deposits have high content of F and MnO, low content of Cl, which may be indicative of sedimentary sources, while apatites from a Pb‐Zn deposit show relatively high content of Cl and low F content, which possibly suggest a high water content. In these apatites, Sr contents decrease, while Mn and Y contents increase with magma evolution. This relationship reflects that these elements in apatites are related with the degree of magmatic differentiation. Four types of REE patterns in apatites are identified. Type 1 character of highest (La/Yb)_N in apatites of Aktogai porphyry Cu‐Mo deposit, Sayak‐I skarn Cu deposit and Akzhal skarn Pb‐Zn depposit is likely produced by the crystallization of heavy REE‐enriched minerals. Type 2 character of upward‐convex light REE in apatite of Aktogai porphyries likely results from La‐enriched mineral crystallization. Type 3 feature of Nd depletion in apatites of East Kounrad and Zhanet deposits both from Mo‐W deposits primarily inherits the character of host‐rock. Type 4 apatites of Aktogai deposit and Akshatau W‐Mo deposit with wide range of REE contents may suggest that apatites crystallize under a wide temperature range. Three types of apatite with distinct redox states are identified based on Eu anomaly. The Aktogai apatite with slight negative Eu anomaly displays the most oxidized state of the magma, and the apatites of other samples at Aktogai, East Kounrad and Akzhal with moderate negative Eu anomaly show moderate oxidizing condition of these rocks, while the remaining apatites with strong En anomaly indicate a moderate reductive state of these rocks.     

Flotation of calcareous Mussorie phosphate ore

Separation of Mussorie rock phosphate (P₂O₅ = 20%) from Uttar Pradesh, India, containing pyrite, calcite and other carbonaceous impurities by flotation has been successfully attempted to upgrade the phosphate values. Based on Hallimond cell flotation results of single and synthetic mineral mixtures of calcite and apatite using oleic acid and potassium phosphate, conditions were obtained for the separation of calcite from apatite which is considered to be the most difficult step in the beneficiation of calcareous phosphates. Further studies using 250 g of the mineral (?60 +150 and ?150 mesh fractions, deslimed) in laboratory size Fagergren subaeration machine employed a stagewise flotation viz. carbonaceous materials using terpineol, pyrite using potassium-ethyl xanthate and calcite using oleic acid respectively. Separation was, however, found to be unsatisfactory in the absence of a depressant.Among starch, hydrofluosilicic acid and dipotassium hydrogen phosphate, which were tried as depressants for apatite in the final flotation stage, dipotassium hydrogen phosphate proved to be superior to others. However, the tests with the above fractions did not yield the required grade. This was possibly due to insufficient liberation of the phosphate mineral from the ore body and different experimental conditions due to scale up operations. Experiments conducted using ?200 mesh deslimed fractions has yielded an acceptable grade of 27.6% P₂O₅ with a recovery of about 60%. The results have been explained in terms of the specific adsorption characteristics of phosphate ions on apatite and the liberation size of the mineral.     

Geochemie des Apatits in Tiefengesteinen am Beispiel des Odenwaldes

Summary The apatite in various igneous rocks (from quartzmonzonitic to gabbroic composition) in one and the same area of differentiation was geochemically examined. The samples were taken from 24 different localities in the Odenwald (Germany) and the thin sections were determined petrographically with a point counter. 25 kg of each sample were dressed and the apatite separated from the heavy mineral concentrates. The pure apatite was analysed quantitative chemically. The variable components of the apatite are represented diagrammatically as functions of the rockchemistry, the physical- and the X-ray constants and their relationships are discussed. The following relations were established: The F-content of magmatic apatites increases in the acidic rocks without showing a stringent lawfulness to the rockchemistry. F remains in all apatites, compared with Cl, OR and 0, alwavs in predominance.With increase in the content of F the refractive index, as well as the lattice constants of the apatites, decrease.The Cl-content of magmatic apatites increases towards the basic rocks, but here too it remains much less than the amount of F. Further more all other statements refering to F can be applied to Cl, but with opposite meaning.A comparison of the chemical analyses of apatites from the newer literature and these of the author reveals in all probability that there is only a limited miscibility between F- and Cl-apatites. The limit being 20 atom per cent Cl. The relation of F : Cl as 1:1 in some apatites might be attributed to an orderly arranged state of the F- and Cl-apatites.OH behaves in a similar manner as Cl, except that the results have wider dispersion effect.According to the chemical equivalence calculations there is generally a small excess of cations. This means that Oxygen must fill up free halogen-places in the lattice.The content of SiO₂ of the apatites shows an increasing tendency towards in the basic rocks and the content of P₂O₅ a decreasing one.The contents of the rare earths of magmatic apatites increase in acidic rocks and only those ones with even numbers (with the exception of La) appear.Only apatites from rocks with metamorphic characteristics had an amount of SO₃.By means of a comparison between the exploit of apatite and P₂O₅-contents of the rocks can be supposed with probability that the principal quantity of the P₂O₅ in the magmatic rocks is not bound to the apatite but to the silicates. This supposition will shortly be further examined.The relative increasing of the intensity of the line (0002) and (0004) in the X-ray-graphs (X-ray-goniometer) in the F-rich apatites suggests a better (0001)-cleavage as in the Cl-rich apatites. This observation can be explained easily with the different structures of the F- and the Cl-apatites.     

Luminescence properties of Pr3+ and Sm3+ ions in natural apatites

The luminescence spectra of Pr³⁺ and Sm³⁺ ions in apatite Ca₅[F∣(PO₄)₃] crystals from Spain and Russia have been compared with those for phosphate glasses doped with Pr³⁺, Sm³⁺ and Pr³⁺, Sm³⁺ ions. Time-resolved spectra measurements confirm that, in apatites, samarium ions occupy two non-equivalent crystal sites; the same is assumed for praseodymium ions. For the first time in minerals, the Stark splitting energy levels ΔE for ³H₆ and ¹D₂ of Pr³⁺ ion and ⁶H_7/2 of Sm³⁺ ion were determined. Some small differences in ΔE values for the Spanish and Russian apatite are discussed. The decay times of the excited levels of Pr³⁺, Sm³⁺ and Pr³⁺, Sm³⁺ doped in phosphate glass were measured at room temperature and at 77 K. The energy transfer process between samarium and praseodymium ions was observed and the energy transfer rate was calculated.     

Flüssige Phasen im migmatitisehen Lauterbrunner-Kristallin (Aarmassiv,Alpen)

During boudinage of competent, amphibolitic layers in the Lauterbrunner Crystalline Complex a pegmatitic liquid phase filled the cross-fractures and other areas of reduced pressure (“hetero-kinetic” spaces according toSander, 1950, p. 306) between the boudins. The mobile components were derived from the adjacent incompetent rocks as well as the apatite rich boudins. The habit of the stubby apatite within the amphibolitic boudins is markedly different from the slender apatite needles which grew in the pegmatitic liquid between the boudins. Various authors, on the basis of microscopic observations and experimental work, propose that acicular apatite crystals cannot be used as a criterion for crystallization from a high temperature magmatic phase. Investigations in the Lauterbrunner Crystalline Complex suggest that acicular apatites have grown in a low temperature liquid phase.