Characterization of aquatic particles by direct FTIR analysis of filters and quantification of elemental and molecular compositions.

This paper presents the first characterization of aquatic particles and particulate organic matter (POM) by attenuated total reflectance infrared spectroscopy (ATR-FTIR) using particles deposited on filters. Particles from 30 water samples from the St. Lawrence System (Canada) were analyzed. ATR-FTIR spectra revealed changes in numerous organic and inorganic functional group contents. Particles from marine waters contained POM enriched in amide, N-H, and aliphatic groups, while terrigenous POM had more COO(-)/COOH and aromatic groups. The spectra showed the selective degradation of amide, N-H, aliphatic, and carbohydrate-like structures during the sinking of the particles. Partial least-squares (PLS) regression of the ATR-FTIR spectra was used to quantify 12 important elemental and molecular parameters, such as amino acids, bacterial biomarkers, and degradation indices. Most parameters were quantified with good accuracy compared to conventional methods (<15% error). The spectral regions leading to the best quantifications and the PLS loadings revealed that aromatic cycles, other unsaturated structures, and COO(-)/COOH groups were degraded at a much slower rate than N-molecules, such as amino acids, and carbohydrates. Marine POM was enriched in CH(3) groups. CH(3) groups appeared highly labile and abundant in bacterial POM. ATR-FTIR represents a new and powerful method for a rapid, inexpensive, and nondestructive characterization of particles collected by filtration revealing important biogeochemical processes involving POM.

Qualitative analysis using Raman spectroscopy and chemometrics: a comprehensive model system for narcotics analysis.

The rapid, on-site identification of illicit narcotics, such as cocaine, is hindered by the diverse nature of the samples, which can contain a large variety of materials in a wide concentration range. This sample variance has a very strong influence on the analytical methodologies that can be utilized and in general prevents the widespread use of quantitative analysis of illicit narcotics on a routine basis. Raman spectroscopy, coupled with chemometric methods, can be used for in situ qualitative and quantitative analysis of illicit narcotics; however, careful consideration must be given to dealing with the extensive variety of sample types. To assess the efficacy of combining Raman spectroscopy and chemometrics for the identification of a target analyte under real-world conditions, a large-scale model sample system (633 samples) using a target (acetaminophen) mixed with a wide variety of excipients was created. Materials that exhibit problematic factors such as fluorescence, variable Raman scattering intensities, and extensive peak overlap were included to challenge the efficacy of chemometric data preprocessing and classification methods. In contrast to spectral matching analyte identification approaches, we have taken a chemometric classification model-based approach to account for the wide variances in spectral data. The first derivative of the Raman spectra from the fingerprint region (750-1900 cm(-1)) yielded the best classifications. Using a robust segmented cross-validation method, correct classification rates of better than ∼90% could be attained with regression-based classification, compared to ∼35% for SIMCA. This study demonstrates that even with very high degrees of sample variance, as evidenced by dramatic changes in Raman spectra, it is possible to obtain reasonably reliable identification using a combination of Raman spectroscopy and chemometrics. The model sample set can now be used to validate more advanced chemometric or machine learning algorithms being developed for the identification of analytes such as illicit narcotics.

Alleviating the effects of light scattering in multivariate calibration of near-infrared spectra by path length distribution correction.

Near-infrared (NIR) spectroscopy has been used for noninvasive measurements of solid and liquid samples, through highly scattering media such as colloids, food, and tissue. It has seen many applications in agriculture, medicine, and petroleum industries, mainly due to the minimal sample preparation that is required. This minimal sample preparation does come at a cost to the analyst, since the high signal-to-noise ratio of a typical NIR instrument can be riddled with effects stemming from heterogeneity and the scattering of light. This work proposes a novel preprocessing method, the path length distribution correction (PDC) method, to correct spectral nonlinearities in samples of highly scattering media. These nonlinearities stem from the distribution of path lengths of the incident light, which are a result of the scattering of light in the sample. Recent developments in time-of-flight (TOF) spectroscopy have allowed for the acquisition of the distribution of times that photons travel within a sample simultaneous with the collection of the NIR spectrum. The TOF distribution is used to estimate a path length distribution within a sample, which is then used to fix the measurement spectra, giving each spectrum an apparent path length of unity. The PDC-corrected spectra can then be used with traditional multivariate calibration methods such as principal component regression (PCR) and partial least squares (PLS). Another discussion looks at the viability of using a lognormal distribution as a simple approximation of the TOF distribution. This would be very useful in circumstances in which experimental TOF distributions are not collected. PDC is shown to significantly improve prediction errors in experimental data sets, while diagnostic plots indicate that the corrected spectra do appear to have a path length of unity, thus alleviating effects of the distribution of path lengths.

Comparison of derivative preprocessing and automated polynomial baseline correction method for classification and quantification of narcotics in solid mixtures.

This work offers a real-world comparison of derivative preprocessing and a new polynomial method described by Lieber and Mahadevan-Jansen (LMJ) for baseline correction of Raman spectra with widely varying backgrounds. This comparison is based on their outcomes in factor analysis, analyte discrimination, and quantification. Both correction methods are applied to a Raman spectra data set taken from 85 solid samples of illegal narcotics diluted with various materials. It is found that neither approach outperforms the other, as they give similar principal component analysis (PCA) models and quantification errors: cocaine and heroin show cross-validation errors of approximately 8%, while MDMA is quantified to a cross-validation error of approximately 3-4%. The LMJ method does offer several other advantages, the most significant being the retention of original peak shapes after the correction, which simplifies the interpretation of the preprocessed spectra. The LMJ method is therefore recommended for use as a baseline correction method in future research with Raman spectroscopy.

Maximum likelihood principal components regression on wavelet-compressed data.

Maximum likelihood principal component regression (MLPCR) is an errors-in-variables method used to accommodate measurement error information when building multivariate calibration models. A hindrance of MLPCR has been the substantial demand on computational resources sometimes made by the algorithm, especially for certain types of error structures. Operations on these large matrices are memory intensive and time consuming, especially when techniques such as cross-validation are used. This work describes the use of wavelet transforms (WT) as a data compression method for MLPCR. It is shown that the error covariance matrix in the wavelet and spectral domains are related through a two-dimensional WT. This allows the user to account for any effects of the wavelet transform on spectral and error structures. The wavelet transform can be applied to MLPCR when using either the full error covariance matrix or the smaller pooled error covariance matrix. Simulated and experimental near-infrared data sets are used to demonstrate the benefits of using wavelets with the MLPCR algorithm. In all cases, significant compression can be obtained while maintaining favorable predictive ability. Considerable time savings were also attained, with improvements ranging from a factor of 2 to a factor of 720. Using the WT-compressed data in MLPCR gave a reduction in prediction errors compared to using the raw data in MLPCR. An analogous reduction in prediction errors was not always seen when using PCR.