In vivo time-resolved reflectance spectroscopy of the human forehead

We present an in vivo broadband spectroscopic characterization of the human forehead. Absorption and scattering properties are measured on five healthy volunteers at five different interfiber distances, using time-resolved diffuse spectroscopy and interpreting data with a model of the diffusion equation for a homogeneous semi-infinite medium. A wavelength-tunable mode-locked laser and time-correlated single-photon counting detection are employed, enabling fully spectroscopic measurements in the range of 700-1000 nm. The results show a large variation in the absorption and scattering properties of the head depending on the subject, whereas intrasubject variations, assessed at different interfiber distances, appear less relevant, particularly for what concerns the absorption coefficient. The high intersubject variability observed indicates that a unique set of optical properties for modeling the human head cannot be used correctly. To better interpret the results of the analysis of in vivo measurements, we performed a set of four-layer model Monte Carlo simulations based on different data sets for the optical properties of the human head, partially derived from the literature. The analysis indicated that, when simulated time-resolved curves are fitted with a homogeneous model for the photon migration, the retrieved absorption and reduced scattering coefficients are much closer to superficial layer values (i.e., scalp and skull) than to deeper layer ones (white and gray matter). In particular, for the shorter interfiber distances, the recovered values can be assumed as a good estimate of the optical properties of the first layer.     

Diffuse reflectance spectroscopy of particulate systems: a comparative study of discrete models

A comparative study of statistical particle model theory of diffuse reflectance has been made. Theories have been applied to six particulate samples having different optical characteristics and average particle sizes that vary from 42 to 106 mum. We made an overall assessment of each theoretical model by determining the CIELAB color difference using experimentally measured and theoretically predicted diffuse reflectance spectra in the visible spectral range. We discuss the performance ratings of the models of other researchers and discovered numerous typographical errors in Fresnel reflection coefficient expressions. We provide the correct versions for these expressions.     

Noninvasive in vivo measurement of venous blood pH during exercise using near-infrared reflectance spectroscopy

Blood pH is an important indicator of anaerobic metabolism in exercising muscle. This paper demonstrates multivariate calibration techniques that can be used to produce a general pH model that can be applied to spectra from any new subject without significant prediction error. Tissue spectra (725 approximately 880 nm) were acquired through the skin overlying the flexor digitorum profundus muscle on the forearms of eight healthy subjects during repetitive hand-grip exercise and referenced to the pH of venous blood drawn from a catheter placed in a vein close to the muscle. Calibration models were developed using multi-subject partial least squares (PLS) and validated using subject-out cross-validation after the subject-to-subject spectral variations were corrected by mathematical preprocessing methods. A combination of standard normal variate (SNV) scaling and principal component analysis loading correction (PCALC) successfully removed most of the subject-to-subject variations and provided the most accurate prediction results.     

Noninvasive Raman spectroscopy of human tissue in vivo

We report the first transcutaneous Raman spectrum of human bone in vivo obtained at skin-safe laser illumination levels. The spectrum of thumb distal phalanx was obtained using spatially offset Raman spectroscopy (SORS), which provides chemically specific information on deep layers of human tissue, well beyond the reach of existing comparative approaches. The spectroscopy is based on collecting Raman spectra away from the point of laser illumination using concentric rings of optical fibers. As a generic analytical tool this approach paves the way for a range of uses including disease diagnosis, noninvasive probing of pharmaceutical products, biofilms, catalysts, paints, and in dermatological applications.     

Evaluation of physical properties of human hair by diffuse reflectance near-infrared spectroscopy

The objective of the present study is to develop a novel nondestructive, simple, and quick method to evaluate the friction, twist, and gloss of human hair based on near-infrared diffuse reflectance (NIR-DR) spectroscopy and chemometrics. NIR-DR spectra were measured for human hair, which was collected from eleven Japanese women (age 5-44 years), by use of an optical fiber probe. Partial least squares (PLS) regression has been applied to the NIR-DR spectra of human hair after mean centering (MC), standard normal variate (SNV), and first derivative (1d) or second derivative (2d) analysis to develop calibration models that predict the friction, twist, and gloss of human hair. We identified the most suitable wavenumber region for the evaluation of each physical property. Correlation coefficients and standard errors of calibration of the PLS calibration models for the friction, twist, and gloss of hair were calculated to be 0.96 and 0.023, 0.81 and 3.27, and 0.90 and 0.36, respectively. Thus, the calibration models have high accuracy.     

Specular reflection and diffuse reflectance spectroscopy of soils

Studies on the occurrence and effects of specular reflection in midinfrared spectra of soils have shown that distortions due to specular reflection occur for both organic (humic acid) and non-organic fractions (carbonates, silica, ashed fraction of soil). The results explain why the spectra of CaCO(3) in limed soils do not match published spectra and offer an explanation as to why the presence of inorganic C interferes with the development of calibrations for organic C. These results may also have implications for the use of mid-infrared spectra for quantitative and qualitative analysis of soils. For example, libraries of spectra collected by means other than diffuse reflectance would be largely useless for comparing mineral spectra to soil spectra. To obtain the best results with forages and grains, it is necessary to develop separate calibrations for different products, but this has not seemed to be a problem for diverse sets of soil samples with C contents of 0 to 5%. Mid-infrared calibrations have also appeared to be more robust than the corresponding near-infrared calibrations in that fewer outliers are found. However, the results discussed here indicate that at least for some soil types (e. g., large differences in mineralogy or C contents), separate calibrations may be necessary.     

Penetration depth limits of in vivo confocal reflectance imaging

We present experiments to predict the maximum penetration depth atwhich typical biological structures in amelanotic tissue can bedetected with confocal microscopy. The detected signal is examinedas the signal source strength (index of refraction mismatch), thesource depth, and the medium scattering coefficient are varied. Thedetected background produced by scattering outside the focal volume isexamined as the medium scattering coefficient, the depth in the medium, the dimensionless pinhole radius, nu(p), and theshape of the scattering phase function are varied. When the systemapproaches ideal confocal performance (nu(p) ? 3), the penetration depth is limited by the signal-to-noiseratio to approximately 3-4 optical depths (OD's) for a 0.05 indexmismatch. As nu(p) increases to 8, thepenetration depth is limited by the signal-to-background ratio and isdependent on the scattering coefficient. At mu(s) = 100 cm(-1) (l(s) = 100 mum) and an index mismatch of 0.05, the maximum penetrationdepth is approximately 2 OD.     

采用近红外光谱法测定鱼粉的品质

本文比较了用近红外漫反射光谱(NIRS)定量测定和用传统化学方法测定鱼粉中的蛋白质、脂肪和水分含量,结果发现,用近红外漫反射光谱(NIRS)定量测定鱼粉的品质有良好的效果,完全可以替代传统的化学方法。该方法快速、准确且无药品试剂污染,其重现性优于传统化学法。     

A quantitative diffuse reflectance spectroscopy study of chromium-containing zeolites

The diffuse reflectance spectra of chromium-containing zeolites (Y, GaY, X, and mordenite) have been investigated before and after drying, after calcination, after successive CO reduction, and after recalcination. Different methods of Cr zeolites preparation (ion exchange, solid-state ion exchange, and impregnation) were investigated. A method for quantifying Cr(VI) ions was developed. Before and after drying, Cr(III) is octahedrally coordinated, which is almost quantitatively oxidized upon calcination at 550°C to Cr(VI). Cr(VI) is a chromatelike species with two lattice and two extralattice oxygens in the coordination sphere. The Cr dispersion depends on the zeolite type and preparation method. The reducibility of Cr(VI) to Cr(III) and Cr(II) follows the order Cr mordenite > CrY (impregnated) > CrY (ion exchange) > CrX > CrGaY > CrY (solid state). This order can be qualitatively explained in terms of zeolite properties and Cr dispersion.     

Contrast enhancement for in vivo visible reflectance imaging of tissue oxygenation

Results are presented illustrating a straightforward algorithm to be used for real-time monitoring of oxygenation levels in blood cells and tissue based on the visible spectrum of hemoglobin. Absorbance images obtained from the visible reflection of white light through separate red and blue bandpass filters recorded by monochrome charge-coupled devices (CCDs) are combined to create enhanced images that suggest a quantitative correlation between the degree of oxygenated and deoxygenated hemoglobin in red blood cells. The filter bandpass regions are chosen specifically to mimic the color response of commercial 3-CCD cameras, representative of detectors with which the operating room laparoscopic tower systems are equipped. Adaptation of this filter approach is demonstrated for laparoscopic donor nephrectomies in which images are analyzed in terms of real-time in vivo monitoring of tissue oxygenation.     

Measurement of pesticide residues in food based on diffuse reflectance IR spectroscopy

This paper describes nondestructive pesticide measurement of agricultural products based on Fourier transform infrared diffuse reflectance spectroscopy (FT-IR-DRS). Both FT-IR-DRS spectra and the concentration of the pesticide residues are measured for real lettuce samples. Thereafter, the calibration models to estimate the residual concentration of the pesticides are derived by the partial least square regression of the spectra. Cross validations of the calibration models are also carried out. By using this method, it takes two minutes to measure the multi-elements of pesticide residues in a sample lettuce head. Food safety inspection could be enhanced based on FT-IR-DRS.     

Diffuse reflectance of oceanic waters. III. Implication of bidirectionality for the remote-sensing problem

The upwelling radiance field beneath the ocean surface and the emerging radiance field are not generally isotropic. Their bidirectional structure depends on the illumination conditions (the Sun's position in particular) and on the optical properties of the water body. In oceanic case 1 waters, these properties can be related, for each wavelength λ, to the chlorophyll (Chl) concentration. We aim to quantify systematically the variations of spectral radiances that emerge from an ocean with varying Chl when we change the geometric conditions, namely, the zenith-Sun angle, the viewing angle, and the azimuth difference between the solar and observational vertical planes. The consequences of these important variations on the interpretation of marine signals, as detected by a satelliteborne ocean color sensor, are analyzed. In particular, the derivation of radiometric quantities, such as R (λ), the spectral reflectance, or [ L(w)(λ)](N), the normalized water-leaving radiance that is free from directional effects, is examined, as well as the retrieval of Chl. We propose a practical method that is based on the use of precomputed lookup tables to provide values of the f/Q ratio in all the necessary conditions[ f relates (R(λ) to the backscattering and absorption coefficients, whereas Q is the ratio of upwelling irradiance to any upwelling radiance]. The f/Q ratio, besides being dependent on the geometric configuration (the three angles mentioned above), also varies with λ and with the bio-optical state, conveniently depicted by Chl. Because Chl is one of the entries for the lookup table, it has to be derived at the beginning of the process, before the radiometric quantities R(λ) or [L(W)(λ)](N) can be produced. The determination of Chl can be made through an iterative process, computationally fast, using the information at two wavelengths. In this attempt to remove the bidirectional effect, the commonly accepted view relative to the data-processing strategy is somewhat modified, i.e., reversed, as the Chl index becomes a prerequisite parameter that must be identified prior to the derivation of the fundamental radiometric quantities at all wavelengths.     

Diffuse reflectance and transmittance spectra of an interference layer: 1. Model formulation and properties

A model for the calculation of the diffuse reflectance and transmittance of a single interference layer with rough interfaces on a transparent substrate is presented. The model is based on electric field calculations and scalar scattering theory, and it assumes that the interfaces of the layer are totally uncorrelated. Examples are given of calculated spectra in which the parameters of the model are varied systematically to show the influence from different interface roughness and refractive index combinations as well as absorption in the film. A wavelength-dependent effective root-mean-square roughness is introduced. This depends on the nature of the roughness, and the bandwidth limits are given by the experimental conditions. Finally, total integrated scattering spectra are calculated and the importance of taking multiple reflections in the substrate into account is shown.     

Optical diffuse reflectance accessory for measurements of skin tissue by near-infrared spectroscopy

An optimized accessory for measuring the diffuse reflectance spectra of human skin tissue in the near-infrared spectral range is presented. The device includes an on-axis ellipsoidal collecting mirror with efficient illumination optics for small sampling areas of bulky body specimens. The optical design is supported by the results of a Monte Carlo simulation study of the reflectance characteristics of skin tissue. Because the results evolved from efforts to measure blood glucose noninvasively, the main emphasis is placed on the long-wavelength near-infrared range where sufficient penetration depth for radiation into tissue is still available. The accessory is applied for in vivo diffuse reflectance measurements.     

Determination of soil nitrate and water content using attenuated total reflectance spectroscopy

Direct determination of nitrate and soil moisture can significantly improve N-application management and thus reduce N-derived environmental pollution related to agriculture. Several studies have shown that Fourier transform infrared attenuated total reflectance (FT-IR/ATR) spectroscopy could be used to estimate the nitrate content of standardized soil pastes. Paste standardization appeared to be the main obstacle to in situ application of this approach, and the present study shows how FT-IR/ATR can be used to estimate both water content and nitrate concentration of field soil samples. Water content and nitrate concentration are determined sequentially using two subsamples of the initial soil sample. An a priori determined amount of highly concentrated nitrate solution is added to the first subsample and the ATR spectrum of this paste is used to estimate the sample water content. It is then possible to calculate the amount of water that should be added to the second subsample so that the resulting paste is very close to the ideal standard paste. Nitrate concentration, mg [N]/kg [dry soil], is estimated using the FT-IR/ATR spectrum of this second paste. Results are presented for a laboratory experiment with four agricultural soils, as well as for a field trial with a calcareous soil. For water content, the determination errors range from 0.01 to 0.02 g [water]/g [dry soil]. For nitrate concentration, the errors for three of the soils range from 5.9 to 8.4 mg [N]/kg [dry soil], while for the fourth, calcareous clay soil, the determination error is 13.6 mg [N]/kg [dry soil]. The determination errors obtained for the field trial are similar to the ones obtained for a similar soil under laboratory conditions, which shows the potential usefulness of the approach for improving N-application management and reducing environmental pollution.     

Surface chemistry of group IIA and IIIB fluorides in air by diffuse reflectance spectroscopy

The compounds forming on the surface of MgF₂, SrF₂, BaF₂, ScF₃, YF₃, and LaF₃ during storage in air were identified by Fourier-transform IR diffuse reflectance spectroscopy. The adlayer on the surface of MgF₂ was found to contain magnesium hydroxide; on the surface of BaF₂, YF₃, and LaF₃, basic carbonates were present. The mechanisms of the possible surface reactions are discussed, and a procedure is proposed which allows one to replace hydroxide-carbonate surface groups by fluoride groups and to enhance the stability of the fluoride surface to atmospheric attack     

Waveband selection for determination of nitrate in soil using mid-infrared attenuated total reflectance spectroscopy

This paper investigates the possibility of determining nitrate concentration in soil pastes using spectral absorbance at several fixed wavebands. A three-step procedure for determining the most appropriate wavebands, as well as their width, is described. This procedure is applied to a dataset that includes eleven soils with various nitrate concentrations ranging from 0 to approximately 150 mg [N]/kg [dry soil]. The results show that nitrate concentration can be determined quite acceptably using only four 12 cm(-1) wide wavebands, centered at 1280, 1330, 1379, and 1430 cm(-1). The prediction errors range from approximately 1.5 to 14.0 mg [N]/kg [dry soil], depending on soil composition and moisture content, with the lighter and more vulnerable (pollution-wise) soils having errors inferior to 10 mg [N]/kg [dry soil]. These results are similar to results obtained by applying partial least square to the 'continuous' spectrum, and indicate that the development of a soil nitrate attenuated total reflectance (ATR) sensor based on a few fixed mid-infrared (MIR) wavebands could be considered.