Magnetic properties of sheet silicates; 2:1 layer minerals

Susceptibility, magnetisation and Mössbauer measurements are reported for a representative selection of 2:1 layer phyllosilicates. Eight samples from the mica, vermiculite and smectite groups include examples diluted in iron which are paramagnetic at all temperatures, as well as iron-rich silicates which order magnetically below 10 K. Anisotropic susceptibility of crystals of muscovite, biotite and vermiculite is quantitatively explained with a model where the Fe²⁺ ions lie in sites of effective trigonal symmetry, the trigonal axis lying normal to the sheets. The ferrous ground state is an orbital singlet. Ferric iron gives an isotropic contribution to the susceptibility. Fe²⁺-Fe²⁺ exchange interactions are ferromagnetic with y ～ 2 K, whereas Fe³⁺-Fe³⁺ coupling is antiferromagnetic in the purely ferric minerals. A positive paramagnetic Curie temperature for glauconite may be attributable to Fe²⁺ → Fe³⁺ charge transfer. Magnetic order was found to set in inhomogeneously for glauconite at 1–7 K. One biotite sample showed an antiferromagnetic transition at T _N =7 K marked by a well-defined susceptibility maximum. Its magnetic structure, consisting of ferromagnetic sheets with moments in their planes coupled antiferromagnetically by other, weak interactions, resembles that found earlier for the 1:1 mineral greenalite.     

Magnetic properties of sheet silicates; 1:1 layer minerals

Three iron-rich 1:1 clay minerals, greenalite [Si₂]{Fe ₃ ²⁺ }O₅(OH)₄, berthiérine [Si, Al]₂{Fe², Mg, Fe³⁺, Al}₃ O₅(OH)₄ and cronstedtite [Si, Fe³⁺]₂{Fe²⁺, Fe³⁺}₃O₅(OH)₄ have been studied by Mössbauer spectroscopy, magnetization measurements and neutron diffraction to determine their magneticproperties. The predominant magnetic coupling is ferromagnetic for pairs of ferrous ions in the octahedral sheet, but antiferromagnetic for ferric pairs. The crystal field at Fe²⁺ sites in greenalite and berthiérine is effectively trigonal with an orbital singlet l _z=0 as ground state. These mainly ferrous minerals order magnetically at 17K and 9K respectively. The magnetic structure of greenalite consists of ferromagnetic octahedral sheets, with the moments lying in the plane, coupled antiferromagnetically by much weaker interplane interactions. The ratio of intraplane to interplane coupling is of order 50, so the silicate has a two-dimensional aspect, both structurally and magnetically. Although the overall magnetic order is established as antiferromagnetic by neutron diffraction, the magnetization curves resemble those of a ferromagnet because of the very weak interplane coupling. Cronstedtite orders antiferromagnetically around 10K. Moments within the planes are antiferromagnetically coupled. The magnetism has no particular two-dimensional character because exchange paths between the layers are provided by the ferric cations present in the tetrahedral sheets.     

An57Fe mössbauer effect study of ankerite

A natural sample of ankerite has been characterized by chemical analysis, X-ray diffraction and differential thermal analysis. The composition was found to be (Ca_1.11Mg_0.50Fe_0.33Mn_0.09) [Co₃]_1.99.⁵⁷Fe Mössbauer effect measurements were performed at temperatures between 4.2 and 400 K. At low temperatures (T < 25 K) relaxation effects are clearly dominant. The temperature dependence of the center shift is remarkably well reproduced by a model based on the Debije approximation of the lattice vibrations. In contrast, the temperature dependence of the quadrupole splitting cannot be described by any reasonable crystal field model. It is argued that an orbit-lattice coupling might explain the observed quadrupole splittings. A spectrum recorded in an applied field of 6 T reveals a positive electric field gradient from which an orbital doublet ground state is concluded. Highly anisotropic field reductions are derived but cannot be quantitatively explained due to a lack of knowledge concerning the magnetic structure of ankerite. The line widths decrease significantly with increasing temperature which is only partly due to the decreasing Mössbauer fraction.     

Magnetic properties of the clinopyroxenes aegirine and hedenbergite: a magnetic susceptibility study on single crystals

Two natural clinopyroxene single crystals were investigated, an aegirine-augite (AEG) and a magnesian hedenbergite (HED). Both samples were carefully characterized by electron microprobe, X-ray diffraction, and Mössbauer spectroscopy. Magnetic susceptibility measurements of powdered samples reveal low temperature antiferromagnetic coupling and Curie-Weiss behaviour with T _N =7.5(5)?K, Θ _P =?19(1)?K for AEG, and T _N =31(1)?K, Θ _P =+21(1)?K for HED, respectively. Low temperature Mössbauer spectra exhibit relaxation phenomena. Magnetic susceptibility measurements of the single crystals show the direction of the magnetic moments to be lying within the a/c plane for both samples: 50(±2)° from a and 57(±2)° from c in AEG, and 45(±2)° from a and 60(±2)° from c in HED, respectively. The antiferromagnetic interchain interaction competes with the ferromagnetic intrachain interaction in both pyroxenes. In the magnesian hedenbergite a field induced magnetic transition is found. Its dependence on temperature, magnetic field and crystallographic direction is investigated and described.     

Structure and Mössbauer spectroscopy of barbosalite Fe2+Fe3+ 2 (PO4)2(OH)2 between 80 K and 300 K

Natural barbosalite Fe²⁺Fe³⁺ ₂ (PO₄)₂(OH)₂ from Bull Moose Mine, South Dakota, U.S.A., having ideal composition, was investigated with single crystal X-ray diffraction techniques, Mössbauer spectroscopy and SQUID magnetometry to redetermine crystal structure, valence state of iron and evolution of ⁵⁷Fe Mössbauer parameter and to propose the magnetic structure at low temperatures. At 298?K the title compound is monoclinic, space group P2₁/n, a _o ?= 7.3294(16)?Å, b _o ?=?7.4921(17)?Å, c _o ?=?7.4148 (18)?Å, β?=?118.43(3)°, Z?=?2. No crystallographic phase transition was observed between 298?K and 110?K. Slight discontinuities in the temperature dependence of lattice parameters and bond angles in the range between 150?K and 180?K are ascribed to the magnetic phase transition of the title compound. At 298?K the Mössbauer spectrum of the barbosalite shows two paramagnetic components, typical for Fe²⁺ and Fe³⁺ in octahedral coordination; the area ratio Fe³⁺/Fe²⁺ is exactly two, corresponding to the ideal value. Both the Fe²⁺ and the Fe³⁺ sublattice order magnetically below 173?K and exhibit a fully developed magnetic pattern at 160?K. The electric field gradient at the Fe²⁺ site is distorted from axial symmetry with the direction of the magnetic field nearly perpendicular to V_zz, the main component of the electric field gradient. The temperature dependent magnetic susceptibility exhibits strong antiferromagnetic ordering within the corner-sharing Fe³⁺-chains parallel to [101], whereas ferromagnetic coupling is assumed within the face-sharing [1?1?0] and [?1?1?0] Fe³⁺-Fe²⁺-Fe³⁺ trimer, connecting the Fe³⁺-chains to each other.     

Mössbauer spectra and magnetic features of ilvaites

Ilvaite samples from six different localities in Japan are found to be members of a solid-solution series varying from Ca(Fe²⁺,Fe³⁺)₂Fe²⁺(OH)O Si₂O₇ to approaximately Ca(Fe²⁺,Fe³⁺)₂Fe _0.5 ²⁺ Mn _0.5 ²⁺ (OH)O Si₂O₇, and have been studied by Mössbauer spectrometry and magnetic measurements. The variation in intensity of Mössbauer doublets confirms that Mn substitutes for Fe²⁺ in the M(B) cation site. An temperatures decreasing from 300 K to 4K, an abrupt change in the reciprocal mass magnetic susceptibility, 1/x _g, occurs about 120 K; 1/x _g depends linearly upon temperature above 120 K. This change, which is characterized by an unusual mode of decrease in 1/x _g, has been interpreted based on Mössbauer spectra at 80 K: the spectra of Fe²⁺ and Fe³⁺ in the M(A) site show Zeeman splitting, whereas those of Fe²⁺ in the M(B) site do not show the effect. This Mössbauer evidence suggests that magnetic spins of Fe in M(A) are in an ordered state, very likely of antiparallel coupling, whereas those of Fe in M(B) are randomly oriented, showing that below 120 K ilvaite has two different magnetic states for Fe ions. As there is a line of evidence that the spins of Fe in M(B) would take an ordered state at extremely low temperatures, ilvaite magnetism may be regarded as basically antiferromagnetic. The magnetic spins of Fe in M(A) and M(B) undergo magnetic transitions at different specific temperatures, thus giving as a whole unusual features of magnetism.     

Field-induced ferromagnetism in minnesotaite

Minnesotaite, a 2:1 layer sheet silicate, is antifer-romagnetic below 30 K. A spin flop or metamagnetic transition occurs in a small applied magnetic field. Neutron diffraction and Mössbauer spectroscopy, in an external magnetic field of 4.0 T, show that the magnetic structure consists of Fe²⁺ spins coupled ferromagnetically in the c plane with alternate ferromagnetic planes coupled antiferromagnetically.     

Magnetization,mössbauer spectroscopy and structural studies of a ferrimagnetic Fe-Oxide formed by heating nontronite in air

On heating the paramagnetic clay mineral nontronite for ≈ 30 h at 970 °C in air, a new ferrimagnetic phase forms which was studied by magnetic techniques, microprobe analysis, x-ray diffraction and Mössbauer spectroscopy. The new phase has a Curie temperature T _c ≈ 240°C and high magnetic anisotropy at room temperature with a spontaneous magnetization >12 Am²/kg. Semiquantitative microprobe analyses show Fe to be the dominating consistuent. X-ray analysis points to a lattice which may be similar to that of ?-Fe₂O₃ but differs from it in detail. ⁵⁷Fe Mössbauer spectra, taken between 78 K and 295 °C, can be deconvoluted into three sextet subpatterns in the ferrimagnetic region which are well resolved at room temperature and exhibit a rather small line width. Above T _c, a doublet is visible which is typical for Fe³⁺ ions.     

Distribution of Fe2+ and Fe3+ and next-nearest neighbour effects in natural chromites: comparison between results of QSD and Lorentzian doublet analysis

The Mössbauer spectra of one chromite at 298 K and one chromite at 298, 200, 170, 140 and 90 K have been analyzed in this study. A Voigt-based quadrupole splitting distribution (QSD) method was used to analyze the spectra. The tetrahedral site Fe²⁺ and the octahedral site Fe³⁺ quadrupole splitting distributions (QSDs) were obtained from the Mössbauer spectra of chromites, and the multiple tetrahedral site Fe²⁺ Gaussian QSD components and the large widths σ _Δ of the Gaussian QSD components of the tetrahedral site Fe²⁺ QSDs for chromites were attributed to next-nearest neighbor effects. In addition, temperature dependences of the isomer shift and the quadrupole splitting were presented and discussed. Comparisons between the Mössbauer parameters for thickness-corrected folded spectra and raw-folded spectra of chromites were made, and the results show that the two sets of the Mössbauer parameters and ratios of ferric to total iron as well as χ² are very close to each other. This is because of the small absorber thickness of chromites in this study. Comparisons between the Mössbauer parameters of chromites obtained using the Voigt-based QSD method and a Lorentzian doublet method were also made. The results show that there are some differences between the two sets of the Mössbauer parameters and ratios of ferric to total iron, but not significant. However, much larger χ² were obtained when the Lorentzian doublet method was used to fit the spectra of chromites. This indicates that the Voigt-based QSD method is more adequate to analyze the Mössbauer spectra of chromites from the point of view of statistics.     

Ferric iron in tourmaline

Red Fe³⁺-rich and black Fe³⁺, Fe²⁺-rich tourmalines have been studied by optical and Mössbauer spectroscopies to determine the optical characteristics of Fe³⁺ in tourmaline. Prominent optical absorption features at 485 and 540 nm are assigned to transitions of multiple exchange-coupled Fe³⁺ pairs in several site combinations. These transitions are more intense than those of isolated Fe³⁺ and are polarized along the vector between the interacting ions, thus permitting site assignments. The 485 nm band occurs at an unusually low energy for Fe³⁺ in silicate minerals. Similar behavior has been observed in the spectrum of coalingite, Mg₁₀Fe ₂ ³⁺ (OH)₂₄CO₃·2H₂O, in which Fe³⁺ occurs in related pairs in edge-shared sheets. These lower energies are proposed to result from magnetic exchange in edge-shared geometries. Antiferromagnetic exchange has been confirmed by a variable temperature magnetic susceptibility study of a Kenyan dravite with 3.36 wt percent Fe. The Mössbauer spectrum of this sample is unusual in that it shows a pronounced decrease in width of component peaks from 298 K to 5 K.     

Magnetic properties of natural and synthetic wolframites Fe x Mn1−x WO4

We report in the present paper the main results concerning the evolution of the structural, magnetic and hyperfine properties of natural and synthetic wolframites Fe _x Mn_1?x WO₄ in the composition range 0.16<x<1. The iron and the manganese content of the samples are obtained by atomic absorption spectrophotometry. The lattice parameters are determined from least-squares fits of the X-ray diffraction data. Mössbauer experiments have been carried out between 200 and 4.2 K. Their parameters can be attributed to a high spin ferrous ion in a quite distorted octahedral symmetry. From the magnetic spectra, we deduce a very weak value for the magnetic hyperfine field (?50 kG), a negative sign for the quadrupole interaction and an asymmetry parameter η different from zero for x>0.3 ( \(\bar \eta\) ?0.7). In addition we discuss the variation of the magnitude of H _hf and of the angle ? between the H _hf direction and the principal axis of the electric field gradient (EFG) V _zz with the iron content. A single crystal Mössbauer study has also been performed to determine the orientation of the principal axis of the EFG and of the H _hf direction relative to the crystallographic axes. Mössbauer spectroscopy and magnetic susceptibility techniques have been used to obtain the magnetic ordering temperature T _N. One finds a linear variation of T _N with x for 0.4<x<1 and a deviation from the linear behavior for 0.16<x<0.3. These results are discussed in terms of the contributions of the different Fe-Fe, Fe-Mn and Mn-Mn exchange interactions.     

Electronic and magnetic structure of pyroxenes I. Hedenbergite

The electronic and magnetic structure of the chain silicate hedenbergite (CaFe²⁺Si₂O₆) has been investigated by a number of experimental methods (neutron diffraction, Mössbauer spectroscopy, low temperature magnetic measurements), as well as by electronic structure calculations for clusters of different size in the local spin density approximation. The calculated size-converged spectroscopic data (d-d excitation energies, hyperfine parameters) are in quantitative agreement with the respective experimental values. The calculated magnetic coupling constants are about +25 cm^?1 and ?4 cm^?1 for intra-chain and inter-chain coupling, respectively. The latter value shows that weak superexchange via edges of silicon tetrahedra is well reproduced by the calculations, and it is in qualitative agreement with an observed metamagnetic transition at 4.2 K in an external magnetic field with an onset around 4 T but saturation is not achieved in fields up to 14.5 T. The large ferromagnetic intra-chain coupling is attributed to a nearly degenerate ground state. The ratio between the two magnetic coupling constants agrees with earlier estimates on similar compounds. Finally, it is demonstrated how the detailed discussion of the various exchange pathways contributes to an improved understanding of the connection between magnetic properties and the geometrical structure.     

Electrical and magnetic properties of cronstedtite

Two samples of cronstedtite, a mixed valence serpentine with ideal formula {Fe ₂ ²⁺ ,Fe³⁺}[Si,Fe³⁺]O₅(OH)₄, have been examined by X-ray and neutron diffraction, thermopiezic analysis, magnetization and susceptibility measurements and Mössbauer spectroscopy. The conductivity is thermally activated, with activation energies of 0.25 eV in the basal plane and 0.37 eV in the perpendicular direction. The shape of paramagnetic Mössbauer spectra above 200 K is influenced by charge fluctuations in octahedral sites and fits of spectra at temperatures up to 410 K with a stochastic relaxation model give an activation energy of 0.19 eV. Static charge ordering sets in progressively below about 100 K. Cronstedtite orders antiferromagnetically below 12 K in a structure with antiferromagnetic octahedral sheets and moments perpendicular to the a-axis. Magnetic and charge-ordered structures are proposed for the ideal composition.     

Chemical and physical characterization of iron-intercalated vermiculite compounds

Herein we report on synthetic iron-intercalated vermiculites prepared from a Mg-vermiculite mineral from Santa Olalla, Huelva, Spain, by means of an ion exchange process from aqueous solutions of FeCl₂ and FeCl₃. Thermogravimetric, X-ray diffraction, magnetic susceptibility and Mössbauer spectral studies have been used to characterize the synthetic iron-intercalated vermiculites. The results suggest that the intercalation process employed induces modifications in both the interlayer spacing and in the octahedral sheet; the disordered structure of the Mg-vermiculite mineral is not altered. The presence of solvated Fe(H₂O) _n ²⁺ ions has been shown by the Mössbauer spectroscopy. No magnetic order has been observed between 2 and 300 K neither in the Mg-vermiculite mineral nor in the two synthetic iron-intercalated vermiculites.     

Activation energy of annealed metamict gadolinite from 57Fe Mössbauer spectroscopy

Gadolinite, REE₂FeBe₂Si₂O₁₀, is commonly metamict. ⁵⁷Fe Mössbauer annealing studies of fully metamict gadolinite from Ytterby, Sweden, have been completed in argon atmosphere from 873 to 1473 K. This technique has rarely been employed in studies of metamict minerals. Changes in the experimental parameters of Mössbauer spectra are sensitive indicators of the thermal recrystallization process of metamict gadolinite and revealed two stages of the structural recovery: a major stage from 873 to 1073 K and a slower recovery stage from 1133 to 1473 K. These observations are confirmed by X-ray powder diffraction. In relation to the first stage, the exponential behaviour of the changes in the Mössbauer parameters can be used for deriving the activation energy E _a of the recrystallization process. The calculated value E _a =1.97 eV in argon atmosphere explains the common occurrence of gadolinite in the fully or partially metamict state. Results of Mössbauer spectroscopy suggest that the recrystallization of metamict gadolinite is a displacive transition that involves rotation and translation of SiO₄ and BeO₄ to their normal positions associated with removal of OH groups from the structure.     

Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2 · 4H2O, and of its oxidation products

Mössbauer spectra (MS) of anapaite (Ca₂ Fe²⁺(PO₄)₂?·?4H₂O) and of a sample after being immersed in a 4% H₂O₂ solution at room temperature (RT) over 12 days (hereafter an4ox) were collected at temperatures in the range 4.2 to 420?K and 11 to 300?K respectively. All MS consist of symmetrical doublets, hence magnetic ordering was not observed. The temperature dependencies of the Fe²⁺ centre shifts of anapaite and an4ox were analysed with the Debye model for the lattice vibrations. The characteristic Mössbauer temperatures were found as 370?K?±?25?K and 340?K?±?25?K, and the intrinsic isomer shifts as 1.427?±?0.005?mm/s and 1.418?±?0.005?mm/s respectively. From the external-field (60?kOe) MS recorded at 4.2 and 189?K for the non-treated sample, the principal component V _zz of the electric field gradient (EFG) is determined to be positive and the asymmetry parameter η?≈?0.2 and 0.4 respectively. The temperature variations of the quadrupole splittings, ΔE _Q(T), cannot be interpreted on the basis of the thermal population of the ⁵ D electronic levels resulting from the tetragonal compression of the O₆ co-ordination. The low-temperature linear behaviour of ΔE _Q(T) is attributed to a strong orbit-lattice coupling. A field of 60 kOe applied to anapaite at 4.2?K produces magnetic hyperfine splitting with effective hyperfine fields of ?136, ?254 and ?171?kOe along the principal axes Ox, Oy and Oz of the EFG tensor respectively. Additional oxidation treatments in solutions with various H₂O₂ concentrations up to 20% and subsequent Mössbauer experiments at room temperature, have revealed that the anapaite structure is not sensitive to oxidation since eventually only a small amount of Fe²⁺ (～6.5%) is converted into Fe³⁺.     

Electron delocalization and magnetic behavior in a single crystal of ilvaite,a mixed valence iron silicate

Ilvaite, Ca(Fe²⁺, Fe³⁺)Fe²⁺Si₂O₈(OH), a black mixed valence iron silicate shows considerable Fe²⁺?Fe³⁺ electron delocalization above 400 K, reminiscent of magnetite. A crystallographic phase transition from orthorhombic (Pnam) to monoclinic (P2 ₁/a) symmetry takes place on cooling at 343 K induced by electron ordering. In both phases, Fe²⁺ and Fe³⁺ occur in double octahedral chains parallel to the c axis. The thermal characteristics of the magnetic susceptibilities and their anisotropies in different crystallographic planes have been measured in the temperature range 400?21 K. Below 343±1K, a continuous rotation of the molar susceptibility K _∥ in the ab plane down to 90±2 K is observed, where the symmetry of the magnetic ellipsoid remains unchanged. X _a, X _b and X _c increase abruptly below 123±0.5 K, although antiferromagnetic ordering of Fe²⁺ and Fe³⁺ spins on A sites was suggested in previous Mössbauer and neutron powder diffraction studies. In addition, 1/X _a shows an antiferromagnetic maximum at 50±3 K, whereas 1/X _b and 1/X _c at first increase sharply below 123 K, followed by antiferromagnetic curvatures in the lowest temperature region. This behavior is consistent with the antiferromagnetic ordering of Fe²⁺ spins in the B sites. The observed magnetic phenomena suggest charge delocatization effects between adjacent Fe²⁺(A)-Fe³⁺(A) pairs not only along c, but also along a and b directions. The negative sign of the molar anisotropy (K _∥-K_⊥) suggests a singlet ground State ⁵A₁ for the Fe²⁺ ions, in agreement with previous Mössbauer studies.     

Mössbauer study of natural wolframites

The first Mössbauer results obtained with powdered samples of natural wolframites Fe _x Mn_1?x WO₄ from some famous Portuguese and Peruvian mines are reported here. The Mössbauer experiments have been carried out at 300, 77 and 4.2 K with four natural and one synthetic powdered samples of different compositions. The Mössbauer parameter values can be attributed to a high spin ferrous ion in a quite distorted octahedral symmetry. From the 4.2 K spectra, one deduces a weak value for the hyperfine magnetic field (H _hf?45 kOe), a negative sign for the quadrupole interaction, and an approximate value for the asymmetry parameter (η?0.7). X-ray diffractometry experiments developed to determine the lattice constants have shown a linear behaviour of the most sensitive parameter a as a function of the iron content x. In parallel, a linear behaviour of the Néel temperature T _N with x observed between x=0.5 and x=1.     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.     

Single crystal Mössbauer spectroscopy on the three principal sections of a synthetic fayalite sample in the antiferromagnetic state

The present work reports Mössbauer investigations for several temperatures below T _N on fayalite single crystal sections cut perpendicularly to the crystallographic a and b-axis (Pnma). The previously detected correspondence between the c-component of the magnetic moment on M1 from neutron diffraction and our own Mössbauer measurements published elsewhere are confirmed for the other principal sections to a large extent. Small humps in the angular dependence of two components of the internal magnetic field H(0) on T below T=23 K are in good agreement with magnetometric and calorimetric data published elsewhere; a reinterpretation of single reflection neutron data has been possible by our results. Moreover, the axes of the electric field gradient (efg) are oriented within the crystallographic axes for the M1-site at low temperatures. The violation of symmetry on the M2 position as a result of our previous investigations could be confirmed for the section ⊥ a, but not with respect to b. A possible explanation in terms of saturation effects of large line intensities at the expense of the small ones is given in the context.