Q-band esr studies of fossil teeth: Consequences for esr dating

At least 14 axial-symmetry ESR lines in Plio-Quaternary enamel fibres were observed by Q-band technique. Some lines follow a law e.g. the main anisotropic A-line whose g = 2.0018 and g = 1.9977 are close to g_eff = 2.0020 and g_eff = 1.9975 respectively of the isotropic doublets B- and E-lines. The other lines are blocked below 220K e.g. one isotropic hyperfine (g = 2.0033, a = 21.6 Gauss) M-septet and one isotropic singlet (g = 2.0007) D-line. By heating, the M-septet intensity increases up to 250°C and is lost at 280°C; B- and E-lines decrease while a new isotropic (g = 2.0056) C-line appears. At 300°C, only the two C- and A-lines usually remain and hold up to 400°C.The natural dose rate of fossil enamel is calculated from U-, Th-, K-content and disequilibrium measured both in enamel and dentine, bones and sediments in contact, by methods of low-background γ-spectrometry, isotopic dilution and fission-tracks mapping.ESR dating of quaternary Proboscidae, Bovidae, Equidae and Cervidae has been attempted by a new comparative method: the A-line intensity, normalized for the same dose rate and weight, of various fossil dental enamels varies quasi-linearly with the age of the geological sites from which they are issued.     

Electron spin resonance of stabilized free radicals in sedimentary organic matter

Electron spin resonance (ESR) is evaluated as a method to study the thermal degradation of sedimentary organic matter which consists mainly of kerogen. Whole rock and separated kerogen samples were pyrolysed stepwise (ambient to 700°C at 50°C increments), extracted and analysed for elemental composition and ESR spectra at each step. Whole rock samples give rise to complex spectra which include those of paramagnetic metals and are therefore unsuitable in most cases for this purpose.The ESR parameters g value, ΔH and N_g differ for different types of immature organic matter. An increase in N_g,shift of g value to 2.0026–2.0028 and reduction in h are the main trends during pyrolysis and in natural heating of sedimentary organic matter.The peak generations of liquid and gaseous hydrocarbons coincide with maxima of free radical density. ESR spectroscopy in combination with complementary geochemical characterization of the sedimentary organic matter can serve to indicate maturity with respect to peak oil-gas generation.     

The Correlation Bias for Two-Dimensional Simulations by Turning Bands

The turning bands method (TBM) generates realizations of isotropic Gaussian random fields by summing contributions from line processes. We consider two-dimensional simulations and study the correlation bias attributable to the use of only a finite number L of lines. Our analytical and numerical results confirm that the maximal bias is of order 1/L, and that L = 64 lines suffice for excellent covariance reproduction. The notorious banding observed in simulations with an insufficient number of lines is a related but different phenomenon and depends strongly on the choice of the line simulation technique. Clear-cut recommendations for the number of lines necessary to avoid the effect can only be based on practical experience with the specific code at hand.     

An intercomparison of ESR and uranium series ages for quaternary speleothem calcites

Equivalent dose (ED) estimates for speleothem calcite derived by ESR measurements of the g = 2.0005 signal have a typical precision of ±7% (minimum ±2%), and depend on the signal strength, radiation sensitivity and the presence of interfering signals. Underestimation of ED will occur if the crushing signal at g = 2.0001 is not removed by acid etching, while overestimation may be caused if the short-lived radiation induced interfering signal at g = 2.0020 is not removed by annealing. Quoted errors for ESR ages are rarely better than ±10% and are typically ±15% because of uncertainties in ED, calibration of dosimeters and gamma source, and in the a-value. Serial analyses along the growth axis of single speleothems, and between speleothems interbedded in a sequence demonstrate excellent stratigraphic concordance. Intercomparison of ESR and uranium series ages for samples derived from 11 geographically diverse sites show good agreement with no indication of systematic error. Although validation is more difficult for samples beyond the limit of dating, the results appear encouraging, but recrystallisation and changes in the external radiation dose may cause problems.     

Interferences encountered in the determination of AD of mollusc samples

Inflexion points interfere with the radiation growth curve of the dating signal at g = 2.0014 for mollusc samples. Several experiments give evidence that the definition of the dating signal at g = 2.0014 has to be reconsidered. A reliable AD determination very often seems questionable for ESR dating of mollusc samples.     

The effects of deviations from LTE in sulphur lines for late-type stars

We analyze the formation of lines of neutral sulfur in the spectra of F-K stars taking into account the effects of deviations from local thermodynamical equilibrium (LTE). Our calculations were carried out for Kurucz model atmospheres with T _eff = 5000–6500 K, log g = 2?4 and [Fe/H] = ?4?0, using a 65-level model of the SI atom. Deviations from LTE affect lines of different multiplets of the sulfur atom differently. Non-LTE corrections, which are relatively small (to ?0.10 dex) for the 6543–6557 Å lines, increase to ?0.26 dex for the 8694 Å line, and reach ?1.1 dex for the 9212–9237 Å IR triplet. The model of the atom was verified by modeling the sulfur lines of the studied multiplets in the spectra of the Sun, two main sequence stars, and two supergiants. Good consistency with the observed line profiles was obtained. Failure to take into account strong non-LTE-effects may explain the large sulfur excesses detected in stars with very low metal abundances.     

Identification and valuation of paramagnetic radicals in natural dolomites as an indicator of geological events

 Geological sedimentary dolomite samples from the Superior Proterozoic are studied using electron paramagnetic resonance (EPR) spectroscopy. The complex spectra in the g=2.0 region is composed of Mn²⁺ lines and signals due to crystallization and radiation-induced defects. Measurements in microwave frequencies of 9.5 GHz (X-band) and 35 GHz (Q-band), and thermal and/or radiation treatments allowed identification of seven paramagnetic radicals in the g=2.0 region: (1) isotropic organic radical; (2) axial SO₂ ⁻; (3) axial PO₂ ⁰ or PO₂ ²⁻; (4) isotropic CO₂ ⁻; (5) axial CO₂ ⁻; (6) axial CO₃ ³⁻; (7) isotropic unknown line. The use of these paramagnetic centres as indicators of geological events is discussed. Received: 18 March 2002 / Accepted: 3 October 2002     

Color centers in topaz: comparison between neutron and gamma irradiation

Neutron- and gamma irradiation-induced paramagnetic centers in natural colorless topaz from four different Brazilian localities were studied by electron paramagnetic resonance (EPR) and optical absorption as a function of irradiation dose and thermal treatment. Gamma irradiation doses were applied up to 1,000 kGy with a dose rate of 15 kGy h⁻¹. For the neutron irradiation experiments, a neutron flux of 4 × 10¹² cm⁻² s⁻¹ was used with an integrated flux of up to 1 × 10¹⁸ cm⁻². From the experiments, it is concluded that brownish colors are induced by gamma-rays and may be associated with a single broad isotropic EPR line with g = 2.015(2). Both the EPR line and the related optical absorption band at 460 nm (2.7 eV) are lost during thermal treatments between 150 and 200°C. Fast neutrons create the paramagnetic peroxyl radicals O₂ ⁻ and the paramagnetic O⁻ hole centers. The O⁻ centers have the same thermal stability as the optical absorption band at 620 nm (2.0 eV). It is confirmed that the absorption due to the O⁻ center is responsible for the blue color in topaz. Both color centers and their absorption bands are discussed in the context of O⁻ bound small polarons.     

ESR dating and trapped electrons lifetime of quartz grains in loess of China

This paper reports the preliminary application of ESR dating to loess strata. The samples were collected from the 7th palaeosol layer (S7) of the Luochuan section, Shaanxi province in China. The ESR age of S7 is 736 ka (total dose 2945 Gy, annual dose 4 mGy/year). This age represents the original eolian accumulation age. The result is consistent with the palaeomagnetic data (730 ka). We have also carried out thermal annealing experiments on quartz grains from the S7 sample. ESR intensities (g = 2.0005) increase from 25°C to 320°C. It may be that trapped electrons transfer into the E′ centre site. ESR intensities decrease from 340°C to 460°C due to thermal annealing. We obtained a mean-life of E′ centre electrons at 20°C of 6.66 × 10⁸ years. The activation energy is 1.35 eV and frequency factor is 3.7 × 10⁸ min⁻¹.     

Electron spin resonance spectra of marine and fresh-water manganese nodules

Eighty ferromanganese nodules from a wide variety of marine and fresh-water environments have been analyzed by electron spin resonance spectroscopy. The purpose has been to gain information on the forms in which the major constituents of manganese nodules are present. Contributions to ESR spectra of the nodules come mainly from Mn²⁺ and Fe³⁺. Deep-sea samples generally showed only broad resonance lines, and those with larger peaks close to g = 2.0 are believed to contain more Mn²⁺ than others. Some Antarctic and fresh-water nodules lack a strong Mn²⁺ resonance and have a peak around g = 4.0 which is most likely tetrahedral Fe³⁺. A number of smaller peaks in several samples could not be readily interpreted in terms of contributions from individual ionic species because of fundamental problems in preparing standards having the ion of interest in the same micro-environment as it experiences in the nodules.     

Native and artificial radiation-induced defects in montmorillonite. An EPR study

A natural montmorillonite containing radiation-induced defects was studied with Electron Paramagnetic Resonance (EPR) spectroscopy (X- and Q-band). A first dominant native defect, namely native defect 1, is identified. It gives rise to an orthorhombic spectrum with g_x= 2.004 ± 0.005 g_y= 2.010 ± 0.003, g_z= 2.065 ± 0.002. Simulation of the EPR spectrum at X- and Q-band reveals a second native defect with isotropic spectrum at g= 2.019 ± 0.005. Both are electron holes trapped on oxygen atoms of the structure. The native defect 1 is located on an oxygen-silicon bond or a non-bonding orbital parallel to the c* axis. These defects are annealed at 500°C and the half-life determined for native defect 1 is circa 3,000 years. Irradiations with beta rays produced two additional hole centers of lower stability and distinct EPR parameters. Artificial irradiations show that montmorillonite can be used as a dosimeter in a large dose range.     

Closed Form Solutions of the Two-Dimensional Turning Bands Equation

The turning bands method generates realizations of isotropic Gaussian random fields by means of appropriately summed line processes. For two-dimensional simulations the relation between the isotropic correlation function of the random field and the correlation function to be simulated along the lines is given by an integral equation of Abel type. We present closed form solutions of this integral equation for almost all two-dimensional correlation models encountered in practice and discuss their numerical implementation. As an additional benefit, our tables and illustrations serve as a concise guide to correlation models useful in geostatistics.     

Magnetic phases in lunar fines: metallic Fe or ferric oxides?

The ferromagnetic resonance (g = 2.08 ± 0.03) observed for the Apollo 11 and 12 lunar fines is characterized by an asymmetric lineshape with a narrower appearance on the high field side. This asymmetry together with an anisotropy energy which varies from + 640 to + 500 G over the temperature range of 80 to 298 K indicates that the ferromagnetic resonance arises from metallic Pe having the body-centered cubic structure and not from hematite, magnetite or other Fe³⁺ ions in magnetite-like phases. The g-value, the lineshape asymmetry, and the temperature dependence of the linewidth for the Apollo 14 and 15 fines as reported by other workers are found to be essentially similar to those observed for the Apollo 11 and 12 fines, except a narrower linewidth is observed in the case of the Apollo 14 fines (600–650 G vs 700–800 G, at X-band and room temperature). This difference in linewidth is found to be correlated with the Ni and/or Co content in these samples. The ESR signal for the so-called ‘unknown ferric oxide’ phase of Griscom and Marquardt is also shown to have frequency and temperature dependences significantly different from those for the lunar fines.     

Measurements of iron concentration in kaolinites considering disorder broadening of EPR lines

Only one part of the EPR lines of a kaolinite spectrum of structural Fe³⁺ is clearly observable because of the overlapping of other lines with other spectra. For this reason, to determine the structural Fe³⁺ concentration we used the line near g=9, although it is not intense. A standard is needed: powders of ZnS containing given concentrations of Mn²⁺ (isoelectronic to Fe³⁺) were used for this purpose. Using the simulations of the EPR spectra, the concentration (number of Fe³⁺ per Al³⁺) is determined; it is in the range 10^?5 to 10^?4 for our samples. Considering that the crystal-field disorder around Fe³⁺ is responsible for line broadening, we looked for a possible effect of the broadening on the intensity of the EPR spectra. This effect is taken as a distribution of the parameter λ=B₂²/B₂⁰. The influence of the parameter λ and its statistical distribution on the position, shape, width and intensity of the EPR line has been calculated using simulation procedures. The correction due to the disorder on the calculated concentration is of the same order of magnitude as the precision measurement. This method can be applied for other kaolinites by comparing the area of their g=9 lines with known ones.     

Long-living free radicals study of stepwise pyrolyzed melanoidins and humic substances

ESR measurements of stepwise-pyrolyzed melanoidins and humic substances (at various temperatures, mesh size, and pH values) furnished the following information: the melanoidin structure stabilizes the long-living free radicals in a manner similar to humic substances; the g and Ng values of melanoidins are similar to those of the humic substances, the cleavage of CC and CX (X = heteroatom) bonds increases the Ng value. Thermogravimetric curves, weight loss by stepwise pyrolysis, and ¹³C-CP/MAS NMR were found to be in good correlation with ESR data regarding the structural features of melanoidins and humic substances.     

Influence of particle shape and angularity on the behaviour of granular materials: a numerical analysis

This paper analyses the influence of grain shape and angularity on the behaviour of granular materials from a two‐dimensional analysis by means of a discrete element method (Contact Dynamics). Different shapes of grains have been studied (circular, isotropic polygonal and elongated polygonal shapes) as well as different initial states (density) and directions of loading with respect to the initial fabric. Simulations of biaxial tests clearly show that the behaviour of samples with isotropic particles can be dissociated from that of samples with anisotropic particles. Indeed, for isotropic particles, angularity just tends to strengthen the behaviour of samples and slow down either local or global phenomena. One of the main results concerns the existence of a critical state for isotropic grains characterized by an angle of friction at the critical state, a critical void ratio and also a critical anisotropy. This critical state seems meaningless for elongated grains and the behaviour of samples generated with such particles is highly dependent on the direction of loading with respect to the initial fabric. The study of local variables related to fabric and particle orientation gives more information. In particular, the coincidence of the principal axes of the fabric tensor with those of the stress tensor is sudden for isotropic particles. On the contrary, this process is gradually initiated for elongated particles. Copyright © 2003 John Wiley & Sons, Ltd.     

Yielding and shear behaviour of cement-treated dredged materials

The mechanical behaviour of three cement-treated dredged materials (DM) was studied in the laboratory by isotropic compression and undrained triaxial tests. The intrinsic properties of the untreated and reconstituted soil were used as a reference framework to interpret the effect of cementation on the mechanical behaviour of the cement-treated DM. The isotropic compression line of the reconstituted soil is termed the intrinsic normal compression line (INCL). It is found that the isotropic compression lines of the cement-treated DM lie above the INCL, i.e. the void ratio of the cement-treated soil is higher than that of the reconstituted soil for a given confining pressure. The yield stress measured from the isotropic compression tests increases with increasing cement content and curing time. The pre-yield and post-yield shear responses of the cement-treated DM are different. Pre-yield soil specimens show a tendency to dilate, but post-yield soil specimens show a tendency to contract. Failure envelopes of the cement treated DM lie above that of the reconstituted DM. Linear Mohr–Coulomb failure envelopes were observed for the range of applied stress used in the study. The cohesion intercept increases with increasing cement content and curing time. The strength enhancement of the cement-treated DM is the result of the structures developed during cementation process. Based on a recently proposed soil water transfer model, the change in normalised bound water content, (Δm_bw)_N, is used to evaluate the combined effects of cement content and curing period on the mechanical behaviour of the cement-treated DM. It is found that there exists a threshold value of (Δm_bw)_N, beyond which the yield stress and cohesion intercept increases nonlinearly with increasing (Δm_bw)_N. The threshold value is equal to 0.37 for the three DM used in the study.     

Organic geochemistry of Deep Sea Drilling Project sediments from the Gulf of Calofornia—hydrothermal effects on unconsolidated diatom ooze

The effects of intrusive thermal stress have been studied on a number of Pleistocene sediment samples obtained from Leg 64 of the DSDP-IPOD program in the Gulf of California. Samples were selected from Sites 477, 478 and 481 where the organic matter was subjected to thermal stress from sill intrusions. For comparison purposes, samples from Sites 474 and 479 were selected as representative of unaltered material.The GC and GC-MS data show that lipids of the thermally unaltered samples were derived from microbial and terrestrial higher-plant detritus. Samples from sill proximities were found to contain thermally-derived distillates and those adjacent to sills contained essentially no lipids. Curie point pyrolysis combined with GC and GC-MS was used to show that kerogens from the unaltered samples reflected their predominantly autochthonous microbial origin. Pyrograms of the altered kerogens were much less complex than the unaltered samples, reflecting the thermal effects. The kerogens adjacent to the sills produce little or no pyrolysis products since these intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter.Examination of the kerogens by ESR showed that spin density and line width pass through a maximum during the course of alteration but ESR g-values show no correlation with maturity. Stable carbon isotope (δ¹³C) values of kerogens decrease by 1–1.5‰ near the sills at Sites 477 and 481 and the atomic N/C decreases slightly with proximity to a smaller sill at Site 478. Differences in maturation behavior between Site 477 and 481 and Site 478 are attributed to dissimilarities in thermal stress and to chemical and isotopic heterogeneity of Guaymas Basin protokerogen.     

Effective stress concept in unsaturated soils: Clarification and validation of a unified framework

The effective stress principle, conventionally applied in saturated soils, is reviewed for constitutive modelling purposes. The assumptions for the applicability of Terzaghi's single effective stress are recalled and its advantages are inventoried. The possible stress frameworks applicable to unsaturated soil modelling are reassessed in a comparative manner, specifically the Bishop's single effective stress, the independent stress variables approach and the generalized stress framework. The latter considerations lead to the definition of a unified stress context, suitable for modelling soils under different saturation states. In order to qualify the implications brought by the proposed stress framework, several experimental data sets are re‐examined in the light of the generalized effective stress. The critical state lines (CSLs) at different saturation states tend to converge remarkably towards a unique saturated line in the deviatoric stress versus mean effective stress plane. The effective stress interpretation is also applied to isotropic paths and compared with conventional net stress conception. The accent is finally laid on a second key feature for constitutive frameworks based on a unified stress, namely the sufficiency of a unique mechanical yield surface besides the unique CSL. Copyright © 2007 John Wiley & Sons, Ltd.     

Resonance potassium and sodium lines in the spectra of ultracool dwarfs

We discuss the methodological problems and results of computations of the spectral energy distributions (SEDs) of L dwarfs. Over a wide wavelength interval (λλ4000–10 000 Å), the spectra of these stars are determined to a considerable extent by absorption in resonance lines of potassium (7666.961, 7701.031 Å) and sodium (5891.518, 5897.489 Å). We compute the extended wings of these lines using the theory of quasi-stationary broadening. We compute the cores and nearby wings (up to Δλ = 40 Å from the line center) of the KI and NaI lines in a collisional approximation (van der Waals theory). In our modeling of the SED of the ultracool dwarf 2MASS J15232263+3014562 (L8), we find that the observations agree best with the COND atmospheric models of Allard et al. with T _eff = 2200 K and log g = 6.0.