Diffuse reflectance near infrared spectroscopy can distinguish normal from enzymatically digested cartilage

A non-destructive, diffuse reflectance near infrared spectroscopy (DR-NIRS)approach is considered as a potential tool for determining the component-level structural properties of articular cartilage. To this end, DR-NIRS was applied in vitro to detect structural changes, using principal component analysis as the statistical basis for characterization. The results show that this technique, particularly with first-derivative pretreatment, can distinguish normal, intact cartilage from enzymatically digested cartilage. Further, this paper establishes that the use of DR-NIRS enables the probing of the full depth of the uncalcified cartilage matrix, potentially allowing the assessment of degenerative changes in joint tissue, independent of the site of initiation of the osteoarthritic process.

Motivation, development and validation of a new spectral greenness index : a spectral dimension related to foliage projective cover

A method is presented for the development of a regional Landsat-5 Thematic Mapper (TM) and Landsat-7 Enhanced Thematic Mapper plus (ETM+) spectral greenness index, coherent with a six-dimensional index set, based on a single ETM+ spectral image of a reference landscape. The first three indices of the set are determined by a polar transformation of the first three principal components of the reference image and relate to scene brightness, percent foliage projective cover (FPC) and water related features. The remaining three principal components, of diminishing significance with respect to the reference image, complete the set. The reference landscape, a 2200 km2 area containing a mix of cattle pasture, native woodland and forest, is located near Injune in South East Queensland, Australia. The indices developed from the reference image were tested using TM spectral images from 19 regionally dispersed areas in Queensland, representative of dissimilar landscapes containing woody vegetation ranging from tall closed forest to low open woodland. Examples of image transformations and two-dimensional feature space plots are used to demonstrate image interpretations related to the first three indices. Coherent, sensible, interpretations of landscape features in images composed of the first three indices can be made in terms of brightness (red), foliage cover (green) and water (blue). A limited comparison is made with similar existing indices. The proposed greenness index was found to be very strongly related to FPC and insensitive to smoke. A novel Bayesian, bounded space, modelling method, was used to validate the greenness index as a good predictor of FPC. Airborne LiDAR (Light Detection and Ranging) estimates of FPC along transects of the 19 sites provided the training and validation data. Other spectral indices from the set were found to be useful as model covariates that could improve FPC predictions. They act to adjust the greenness/FPC relationship to suit different spectral backgrounds. The inclusion of an external meteorological covariate showed that further improvements to regional-scale predictions of FPC could be gained over those based on spectral indices alone.

Characterisation of soils with the use of instrumental techniques : a multivariate forensic study

The value of soil evidence in the forensic discipline is well known. However, it would be advantageous if an in-situ method was available that could record responses from tyre or shoe impressions in ground soil at the crime scene. The development of optical fibres and emerging portable NIR instruments has unveiled a potential methodology which could permit such a proposal. The NIR spectral region contains rich chemical information in the form of overtone and combination bands of the fundamental infrared absorptions and low-energy electronic transitions. This region has in the past, been perceived as being too complex for interpretation and consequently was scarcely utilized. The application of NIR in the forensic discipline is virtually non-existent creating a vacancy for research in this area. NIR spectroscopy has great potential in the forensic discipline as it is simple, nondestructive and capable of rapidly providing information relating to chemical composition. The objective of this study is to investigate the ability of NIR spectroscopy combined with Chemometrics to discriminate between individual soils. A further objective is to apply the NIR process to a simulated forensic scenario where soil transfer occurs. NIR spectra were recorded from twenty-seven soils sampled from the Logan region in South-East Queensland, Australia. A series of three high quartz soils were mixed with three different kaolinites in varying ratios and NIR spectra collected. Spectra were also collected from six soils as the temperature of the soils was ramped from room temperature up to 6000C. Finally, a forensic scenario was simulated where the transferral of ground soil to shoe soles was investigated. Chemometrics methods such as the commonly known Principal Component Analysis (PCA), the less well known fuzzy clustering (FC) and ranking by means of multicriteria decision making (MCDM) methodology were employed to interpret the spectral results. All soils were characterised using Inductively Coupled Plasma Optical Emission Spectroscopy and X-Ray Diffractometry. Results were promising revealing NIR combined with Chemometrics is capable of discriminating between the various soils. Peak assignments were established by comparing the spectra of known minerals with the spectra collected from the soil samples. The temperature dependent NIR analysis confirmed the assignments of the absorptions due to adsorbed and molecular bound water. The relative intensities of the identified NIR absorptions reflected the quantitative XRD and ICP characterisation results. PCA and FC analysis of the raw soils in the initial NIR investigation revealed that the soils were primarily distinguished on the basis of their relative quartz and kaolinte contents, and to a lesser extent on the horizon from which they originated. Furthermore, PCA could distinguish between the three kaolinites used in the study, suggesting that the NIR spectral region was sensitive enough to contain information describing variation within kaolinite itself. The forensic scenario simulation PCA successfully discriminated between the ‘Backyard Soil’ and ‘Melcann® Sand’, as well as the two sampling methods employed. Further PCA exploration revealed that it was possible to distinguish between the various shoes used in the simulation. In addition, it was possible to establish association between specific sampling sites on the shoe with the corresponding site remaining in the impression. The forensic application revealed some limitations of the process relating to moisture content and homogeneity of the soil. These limitations can both be overcome by simple sampling practices and maintaining the original integrity of the soil. The results from the forensic scenario simulation proved that the concept shows great promise in the forensic discipline.

The structure of selected magnesium carbonate minerals : a near infrared and mid-infrared spectroscopic study

The approach to remove green house gases by pumping liquid CO2 several kilometres below the ground implies that many carbonate containing minerals will be formed. Among these minerals the formation of dypingite and artinite are possible; thus necessitating a study of such minerals. Two carbonate bearing minerals dypingite and artinite with a hydrotalcite related formulae have been characterised by a combination of infrared and near-infrared spectroscopy. The infrared spectra of both minerals are characterised by OH and water stretching vibrations. Both the first and second fundamental overtones of these bands are observed in the NIR spectra in the 7030 to 7235 cm-1 and 10490 to 10570 cm-1. Intense (CO3)2- symmetric and antisymmetric stretching vibrations confirm the distortion of the carbonate anion. The position of the water bending vibration indicates water is strongly hydrogen bonded to the carbonate anion in the mineral structure. Split NIR bands at around 8675 and 11100 cm-1 indicates that some replacement of magnesium ions by ferrous ions in the mineral structure has occurred.

Near infrared spectroscopy of stearic acid adsorbed on montmorillonite

The adsorption of stearic acid on both sodium montmorillonites and calcium montmorillonites has been studied by near infrared spectroscopy complimented with infrared spectroscopy. Upon adsorption of stearic acid on Ca-Mt additional near infrared bands are observed at 8236 cm-1 and is assigned to an interaction of stearic acid with the water of hydration. Upon adsorption of the stearic acid on Na-Mt, the NIR bands are now observed at 5671, 5778, 5848 and 5912 cm-1 and are assigned to the overtone and combination bands of the CH fundamentals. Additional bands at 4177, 4250, 4324, 4337, 4689 and 4809 cm-1 are attributed to CH combination bands resulting from the adsorption of the stearic acid. Stearic acid is used as a model molecule for adsorption studies. The application of near infrared spectroscopy to the study of this adsorption proved most useful.

Multi-sensor tracking using a scalable condensation filter

Surveillance and tracking systems typically use a single colour modality for their input. These systems work well in controlled conditions but often fail with low lighting, shadowing, smoke, dust, unstable backgrounds or when the foreground object is of similar colouring to the background. With advances in technology and manufacturing techniques, sensors that allow us to see into the thermal infrared spectrum are becoming more affordable. By using modalities from both the visible and thermal infrared spectra, we are able to obtain more information from a scene and overcome the problems associated with using visible light only for surveillance and tracking. Thermal images are not affected by lighting or shadowing and are not overtly affected by smoke, dust or unstable backgrounds. We propose and evaluate three approaches for fusing visual and thermal images for person tracking. We also propose a modified condensation filter to track and aid in the fusion of the modalities. We compare the proposed fusion schemes with using the visual and thermal domains on their own, and demonstrate that significant improvements can be achieved by using multiple modalities.

Raman spectroscopic study of the antimony containing mineral partzite Cu2Sb2(O,OH)7

Raman spectroscopy of the mineral partzite Cu2Sb2(O,OH)7 complimented with infrared spectroscopy were studied and related to the structure of the mineral. The Raman spectrum shows some considerable complexity with a number of overlapping bands observed at 479, 520, 594, 607 and 620 cm-1 with additional low intensity bands found at 675, 730, 777 and 837 cm-1. Raman bands of partzite in the spectral region 590 to 675 cm-1 are attributable the ν1 symmetric stretching modes. The Raman bands at 479 and 520 cm-1 are assigned to the ν3 antisymmetric stretching modes. Raman bands at 1396 and 1455 cm-1 are attributed to SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and OH units is found. Raman bands are observed at 3266, 3376, 3407, 3563, 3586 and 3622 cm-1. The first three bands are assigned to water stretching vibrations. The three higher wavenumber bands are assigned to the stretching vibrations of the OH units. It is proposed that based upon observation of the Raman spectra that water is involved in the structure of partzite. Thus the formula Cu2Sb2(O,OH)7 may be better written as Cu2Sb2(O,OH)7 •xH2O

Near infrared spectroscopy of benzoic acid adsorbed on montmorillonite

The adsorption of benzoic acid on both sodium and calcium montmorillonites has been studied by near infrared spectroscopy complimented with infrared spectroscopy. Upon adsorption of benzoic acid additional near infrared bands are observed at 8665 cm-1 and assigned to an interaction of benzoic acid with the water of hydration. Upon adsorption of the benzoic acid on Na-Mt, the NIR bands are now observed at 5877, 5951, 6028 and 6128 cm-1 and are assigned to the overtone and combination bands of the CH fundamentals. Additional bands at 4074, 4205, 4654 and 4678 cm-1 are attributed to CH combination bands resulting from the adsorption of the benzoic acid. Benzoic acid is used as a model molecule for adsorption studies. The application of near infrared spectroscopy to the study of adsorption has the potential for the removal of acids from polluted aqueous systems.

Optical absorption near infrared and EPR studies of mottramite

Mottramite mineral originated from Tsumeb Corporation Mine, Tsumeb, Otavi, Namibia, is used in the present work. The mineral contains of vanadium and copper to the extent of 22.73% and 16.84% by weight respectively as V2O5 and CuO. An EPR study of sample confirms the presence of Cu(II) with g = 2.2. Optical absorption spectrum of mottramite indicates that Cu(II) is present in rhombic environment. NIR results are due to water fundamentals.

EPR and optical absorption spectral studies on voglite mineral

A voglite mineral sample of Volrite Canyon #1 mine, Frey Point, White Canyon Mine District, San Juan County, Utah, USA is used in the present study. An EPR study on powdered sample confirms the presence of Mn(II) and Cu(II). Optical absorption spectral results are due to Cu(II) which is in distorted octahedron. NIR results are indicating the presence of water fundamentals.

Raman and infrared study of phyllosilicates containing heavy metals (Sb, Bi) : bismutoferrite and chapmanite.

The kaolinite-like phyllosilicate minerals bismutoferrite BiFe3+2Si2O8(OH) and chapmanite SbFe3+2Si2O8(OH) have been studied by Raman spectroscopy and complemented with infrared spectra. Tentatively interpreted spectra were related to their molecular structure. The antisymmetric and symmetric stretching vibrations of the Si-O-Si bridges,  SiOSi and  OSiO bending vibrations,  (Si-Oterminal)- stretching vibrations,  OH stretching vibrations of hydroxyl ions, and  OH bending vibrations were attributed to observed bands. Infrared bands 3289-3470 cm-1 and Raman bands 1590-1667 cm-1 were assigned to adsorbed water. O-H...O hydrogen bond lengths were calculated from the Raman and infrared spectra.

An application of near-infrared and mid-infrared spectroscopy to the study of natural halotrichites : halotrichite, apjohnite and wupatkiite

Near-infrared (NIR) and Fourier transform infrared (FTIR) spectroscopy have been used to determine the mineralogical character of isomorphic substitutions for Mg2+ by divalent transition metals Fe, Mn, Co and Ni in natural halotrichite series. The minerals are characterised by d-d transitions in NIR region 12000-7500 cm-1. NIR spectrum of halotrichite reveals broad feature from 12000 to 7500 cm-1 with a splitting of two bands resulting from ferrous ion transition 5T2g ® 5Eg. The presence of overtones of OH- fundamentals near 7000 cm-1 confirms molecular water in the mineral structure of the halotrichite series. The appearance of the most intense peak at around 5132 cm-1 is a common feature in the three minerals and is derived from combination of OH- vibrations of water molecules and 2 water bending modes. The influence of cations like Mg2+, Fe2+, Mn2+, Co2+, Ni2+ shows on the spectra of halotrichites. Especially wupatkiite-OH stretching vibrations in which bands are distorted conspicuously to low wave numbers at 3270, 2904 and 2454 cm-1. The observation of high frequency 2 mode in the infrared spectrum at 1640 cm-1 indicates coordination of water molecules is strongly hydrogen bonded in natural halotrichites. The splittings of bands in 3 and 4 (SO4)2- stretching regions may be attributed to the reduction of symmetry from Td to C2v for sulphate ion. This work has shown the usefulness of NIR spectroscopy for the rapid identification and classification of the halotrichite minerals.

Chemical functionalities of high and low sulfur Australian coals : a case study using micro attenuated total reflectance–fourier transform infrared (ATR–FTIR) spectrometry

The macerals in bituminous coals with varying organic sulfur content from the Early Permian Greta Coal Measures at three locations (Southland Colliery, Drayton Colliery and the Cranky Corner Basin), in and around the Sydney Basin (Australia), have been studied using light-element electron microprobe (EMP) analysis and micro-ATR–FTIR. Electron microprobe analysis of individual macerals reveals that the vitrinite in both the Cranky Corner Basin and Drayton Colliery (Puxtrees seam) samples have similar carbon contents (ca. 78% C in telocollinite), suggesting that they are of equivalent rank. However, the Cranky Corner coals have anomalously low vitrinite reflectance (down to 0.45%) vs. the Drayton materials (ca. 0.7%). They also have very high organic S content (3–6.5%) and lower O content (ca. 10%) than the equivalent macerals in the Drayton sample (0.7% S and 15.6% O). A study was carried out to investigate the impacts of the high organic S on the functional groups of the macerals in these two otherwise iso-rank, stratigraphically-equivalent seams. An iso-rank low-S coal from the overlying Wittingham Coal Measures near Muswellbrook and coals of slightly higher rank from the Greta Coal Measures at Southland Colliery near Cessnock were also evaluated using the same techniques to extend the data set. Although the telocollinite in the Drayton and Cranky Corner coals have very similar carbon content (ca.78% C), the ATR–FTIR spectra of the vitrinite and inertinite macerals in these respectively low S and high S coals show some distinct differences in IR absorbance from various aliphatic and aromatic functional groups. The differences in absorbance of the aliphatic stretching bands (2800–3000 cm−1) and the aromatic carbon (CC) peak at 1606 cm−1 are very obvious. Compared to that of the Drayton sample (0.7% S and 15% O), the telocollinite of the Cranky Corner coal (6% S and 10% O) clearly shows: (i) less absorbance from OH groups, represented by a broad region around 3553 cm−1, (ii) much stronger aliphatic C–H absorbance (stretching modes around 3000–2800 cm−1 and bending modes around 1442 cm−1) and (iii) less absorbance from aromatic carbon functional groups (peaking at 1606 cm−1). Evaluation of the iso-rank Drayton and Cranky Corner coals shows that: (i) the aliphatic C–H absorbances decrease with increasing oxygen content but increase with increasing organic S content and (ii) the aromatic H to aliphatic H ratio (Har/Hali) for the telocollinite increases with (organic) O%, but decreases progressively with increasing organic S. The high organic S content in the maceral appears to be accompanied by a greater proportion of aliphatic functional groups, possibly as a result of some of the O within maceral ring structures in the high S coal samples being replaced.

Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.