Self absorption

Self-absorption occurs when radiation emitted by the source is absorbed by atoms of the same species in the ground state. Since the probabiUty of re-emission of an absorbed photon is always smaller than unity, self absorption results in a reduction of the radiation produced. The intensity distribution of an emission line is IoPe(v), where Iq stands for the intensity emitted at the line maximum, and P (v) for the profile function. After passage through a layer of absorbing species with a number density of absorbing species, the intensity distribution is  

Where Vq is the intensity in the line centre, Pj (v) the absorption profile function, P Vq) its value at the line centre and p an absorption parameter given by  

When the plasma is sufficiently energetic, atoms may be ionised. The degree of ionisation depends on the temperature of the plasma and the ionisation energy of the considered element. In particular, for easily ionisable species, ionic spectra also contribute to the emission spectra observed in a plasma to a great extent The ionisation of atoms o of a particular element into ions i with liberation of electrons e is an equilibrium reaction. 

Hj and are the concentrations of ions and atoms in the plasma, respectively, and can be expressed as fractions of the total element concentration  

The Saha equation can also be expressed in partial pressures p  

---

Atomic emission line at (a) low concentration of analyte, and (b) high concentration of analyte showing the effect of self-absorption. 

Ema data can be quantitated to provide elemental concentrations, but several corrections are necessary to account for matrix effects adequately. One weU-known method for matrix correction is the 2af method (7,31). This approach is based on calculated corrections for major matrix-dependent effects which alter the intensity of x-rays observed at a particular energy after being emitted from the corresponding atoms. The 2af method corrects for differences between elements in electron stopping power and backscattering (the correction), self-absorption of x-rays by the matrix (the a correction), and the excitation of x-rays from one element by x-rays emitted from a different element, or in other words, secondary fluorescence (the f correction). 

Self-absorption occurs when the path-length is too large [35] and the X-rays emitted have a significant probability of being absorbed by the remainder of the sample before being detected. This has the consequence of reducing the amplitude of the EXAFS oscillations and producing erroneous results. As the sample becomes more dilute this probability decreases. All the atoms in the sample determine the amount of self-absorption hence the need for thin samples. 

The PL spectrum and onset of the absorption spectrum of poly(2,5-dioctyloxy-para-phenylene vinylene) (DOO-PPV) are shown in Figure 7-8b. The PL spectrum exhibits several phonon replica at 1.8, 1.98, and 2.15 eV. The PL spectrum is not corrected for the system spectral response or self-absorption. These corrections would affect the relative intensities of the peaks, but not their positions. The highest energy peak is taken as the zero-phonon (0-0) transition and the two lower peaks correspond to one- and two-phonon transitions (1-0 and 2-0, respectively). The 2-0 transition is significantly broader than the 0-0 transition. This could be explained by the existence of several unresolved phonon modes which couple to electronic transitions. In this section we concentrate on films and dilute solutions of DOO-PPV, though similar measurements have been carried out on MEH-PPV [23]. Fresh DOO-PPV thin films were cast from chloroform solutions of 5% molar concentration onto quartz substrates the films were kept under constant vacuum. 

The deviations of Class I, here called absorption and enhancement effects, are known in the literature also as matrix effects, as self-absorption, and as interelement effects. The authors consider the most important objection to each of the last three names to be as. follows. To matrix effect the element sought (ncrt included in the matrix) contributes to the absorption effect for the sample in the same kind of way as any element (free or combined) in the matrix. To self-absorption the name makes no provision for enhancement effects. To interelement effects it fails to recognize that an absorption effect occurs even when only one element is present (Equation 7-4). The term matrix is useful but requires precise definition. What is the matrix when an internal standard is added, or when a powdered sample is dissolved ... 

Figure 6. Tempcraiure dependence of the fluorescence lifetime of BMPC in 1 1 ethanol-mcihanol. Measurements were carried out at the LENS laboratory of Florence by a picosecond apparatus using as an excitation source (at 380 nm) a dye laser pumped by a frequency-doubled cw Nd-YAG laser and recording the fluorescence time jirofiles by a streak camera. Since the overall insuumental response time was 75-80 ps, decays with t>200 ps, observed at T<130 K, were analyzed without deconvolution. At 177, 178 and 193 K, the lifetimes were roughly estimated as i=(FWHM -77 ), where FWHM was the width at half maximum of the decay. Because of the rather high sample absorbances (An,x=2), self absorption may have reduced the lifetimes to some extent.

The expression is known as the transmission integral in the actual formulation, which is valid for ideal thin sources without self-absorption and homogeneous absorbers assuming equal widths F for source and absorber [9]. The transmission integral describes the experimental Mossbauer spectrum as a convolution of the source emission Une N(E,o) and the absorber response exp —cr( )/abs M - The substitution of N E,d) and cr( ) from (2.19) and (2.20) yields in detail ... 

Concentration At high concentrations fluorescence emission l ecomes non-linear due to self-absorption by the sample itself or complete absorption of the excitation energy before it reaches the cell center. High fluorescence Intensity may overload the photomultiplier tube which returns slowly to its normal operating conditions and misrepresents the actual fluorescence signal until restabilized. 

One of the limitations of the portable field survey instruments in the measurement of americium is that their quantitative accuracy depends on how well the lateral and vertical distribution of americium in the soil compares with the calibration parameters used. These methods can provide a rapid assessment of americium levels on or below surfaces in a particular environment however, laboratory-based analyses of samples procured from these environmental surfaces must be performed in order to ensure accurate quantification of americium (and other radionuclides). This is due, in part, to the strong self absorption of the 59.5 keV gamma-ray by environmental media, such as soil. Consequently, the uncertainty in the depth distribution of americium and the density of the environmental media may contribute to a >30% error in the field survey measurements. Currently, refinements in calibration strategies are being developed to improve both the precision and accuracy (10%) of gamma-ray spectroscopy measurements of americium within contaminated soils (Fong and Alvarez 1997). 

CutshallNH, Larsen IL, Olsen CR. 1983. Direct analysis of 210Pb in sediment samples Self absorption corrections. Nucl Instrum Methods 206 309. 

Self-Absorption—Absorption of radiation (emitted by radioactive atoms) by the material in which the atoms are located in particular, the absorption of radiation within a sample being assayed. 

Houben [256] has compared the determination of flame-retardant elements Br, P, S, K, Cl and F in polycarbonate using commercial (X40 and UniQuant ) software. For the X40 method, a calibration line for each element in PC or PC/ABS blends was mapped for the conversion of intensities to concentrations. With the universal UniQuant method, sensitivity factors (ks) were calibrated with pure standards. The X40 method turned out to be more reliable than UniQuant for the determination of FRs in PC and PC/ABS blends, even in the case of calibration of k values with PC standards. Standard errors of 5 % were achieved for Br, P, S and K, and 20% for Cl and F the latter element could not be determined by means of UniQuant (Table 8.44). GFR PC cannot be quantified with these two methods, because of the heterogeneous nature of the composites. Other difficult matrices for XRF analysis are PBT, PS and PP compounds containing both BFRs and Sb203 (10-30wt %) due to self-absorption of Sb and interelement effects. 

Not previously considered in the above reference is a-particle self-absorption phenomena. However, attempts are at present being made to estimate radon and thoron progeny deposited on the surface of materials by y-spectrometry and gross y-count in order to eliminate self-absorption effects. 

Bulajic D., Corsi M., Cristoforetti G., Legnaioli S., Palleschi V., Salvetti A., Tognoni E., A procedure for correcting self-absorption in calibration-free Laser Induced Breakdown Spectroscopy, Spectrochimica Acta B 2002 57 339-357. 

Self-absorption is a phenomenon whereby emitted radiation is reabsorbed as it passes outwards from the central region of the flame (cf. arc/spark spectrometry). It occurs because of interaction with ground state atoms of the analyte in the cooler outer fringes of the flame and results in attenuation of the intensity of emission. It is particularly noticeable for lines originating from the lowest excited level and increases with the concentration of the analyte solution (Figure 8.24). 

Emission intensity of sodium in the acetylene-oxygen flame at 589 nm showing the effect of self-absorption on calibration curves. 

---