Noninvasive method for monitoring ethanol in fermentation processes using fiber-optic near-infrared spectroscopy

Short-wavelength near-infrared (SW-near-IR) spectroscopy (700-1100 nm) is used for the determination of ethanol during the time course of a fermentation. Measurements are performed noninvasively by means of a photodiode array spectrometer equipped with a fiber-optic probe placed on the outside of the glass-wall fermentation vessel. Pure ethanol/water and ethanol/yeast/water mixtures are studied to establish the spectral features that characterize ethanol and to show that determination of ethanol is independent of the yeast concentration. Analysis of the second-derivative data is accomplished with multilinear regression (MLR). The standard error of prediction (SEP) of ethanol in ethanol/water solutions is approximately 0.2% over a range of 0-15%; the SEP of ethanol in ethanol/yeast/water solutions is 0.27% (w/w). Results from the mixture experiments are then applied to actual yeast fermentations of glucose to ethanol. By use of a gas chromatographic method for validation, a good correlation is found between the intensity of backscattered light at 905 nm and the actual ethanol. Additional experiments show that a calibration model created for one fermentation can be used to predict ethanol production during the time course of others with a prediction error of 0.4%.     

Development of a rapid on-line acetylene sensor for industrial hydrogenation reactor optimization using off-axis integrated cavity output spectroscopy

A spectroscopic analyzer has been developed for rapid, accurate quantification of acetylene and methyl acetylene in hydrocarbon cracked gas processing plants. The system utilizes off-axis integrated output cavity spectroscopy to measure the near-infrared, cavity-enhanced absorption spectrum of ethylene, methyl acetylene, and acetylene and employs a chemometric data analysis strategy to quantify the respective constituents. Initial tests verified that the instrument is capable of measuring, <0.050 ppmv of acetylene, has a precision of +/-0.025 ppmv, and can accurately determine acetylene concentrations with comparable accuracy to a gas chromatograph (+/-0.1 ppmv) in an actual process stream composition matrix under plant operating conditions. Subsequently, the prototype analyzer was installed in a hydrocarbon facility for field-trials, where its rapid response (< or =30 seconds or better) allowed it to measure transient acetylene and methyl acetylene fluctuations that were too fast for conventional methodologies. Moreover, the analyzer showed an extended dynamic range that enabled measurement of very high acetylene levels (0-1000 ppmv) during abnormal plant operations. Finally, two commercial acetylene analyzer systems with stream-switching capabilities were implemented in an industrial facility and initial results are presented.     

Comparison of methods for transfer of calibration models in near-infared spectroscopy: a case study based on correcting path length differences using fiber-optic transmittance probes in in-line near-infrared spectroscopy

This article addresses problems related to transfer of calibration models due to variations in distance between the transmittance fiber-optic probes. The data have been generated using a mixture design and measured at five different probe distances. A number of techniques reported in the literature have been compared. These include multiplicative scatter correction (MSC), path length correction (PLC), finite impulse response (FIR), orthogonal signal correction (OSC), piecewise direct standardization (PDS), and robust calibration. The quality of the predictions was expressed in terms of root mean square error of prediction (RMSEP). Robust calibration gave good calibration transfer results, while the other methods did not give acceptable results.     

Kinetics of the removal of mono-chlorobenzene vapour from waste gases using a trickle bed air biofilter

The performance of a trickle bed air biofilter (TBAB) in the removal of mono-chlorobenzene (MCB) was evaluated in concentrations varying from 0.133 to 7.187 g m(-3) and at empty bed residence time (EBRT) varying from 37.7 to 188.52 s. More than 90% removal efficiency in the trickle bed air biofilter was achieved for the inlet MCB concentration up to 1.069 g m(-3) and EBRT less than 94.26 s. The trickle bed air biofilter was constructed with coal packing material, inoculated with a mixed consortium of activated sludge obtained from sewage treatment plant. The continuous performance of the removal of MCB in the trickle bed air biofilter was monitored for various gas concentrations, gas flow rates, and empty bed residence time. The experiment was conducted for a period of 75 days. The trickle bed air biofilter degrading MCB with an average elimination capacity of 80 g m(-3) h(-1) was obtained. The effect of starvation was also studied. After starvation period of 8 days, the degradation was low but recovered within a short period of time. Using macrokinetic determination method, the Michaelis-Menten kinetic constant K(m) and maximum reaction rate, r(max) evaluated as 0.121 g m(-3) s(-1) and 7.45 g m(-3), respectively.     

Proportional control of moisture content of granules by adjusting inlet air temperature in fluidized bed granulation using near-infrared spectroscopy

For process control of fluidized bed granulation process, we investigated proportional (P) moisture content control via adjustment of inlet air temperature in proportion to the difference between measured and target moisture content of granules. Here, we first validated P moisture content control by comparison with bed temperature control. We then confirmed that P moisture content control is effective in maintaining the moisture content, and in minimizing the variance of the particle size of granules following granulation. Furthermore, we observed that when the target temperature was higher than the measured value of inlet air temperature the P moisture content control response was accelerated. In contrast, when the target temperature was less than the measured value of inlet air temperature (<50 °C) the response was delayed. In summary, P moisture content control has good scalability and can be introduced without changing granulation conditions in the development of orally administered pharmaceutical products.     

Fatty acid profiling of soybean cotyledons by near-infrared spectroscopy

Genetically improved soybean grain often contains altered fatty acid profiles. Such alterations can have deleterious effects on seed germination and seedling development, making it necessary to monitor fatty acid profiles in follow-up physiological studies. The objective of this research was to quantify the five fatty acids in soybean (Glycine max) cotyledons using near-infrared (NIR) spectroscopy. Soybean cotyledon samples were dried, ground, and scanned with visible and NIR radiation from 400 to 2500 nm, and reflectance was recorded. Samples were also analyzed by gas chromatography (GC) for palmitic, stearic, oleic, linoleic, and linolenic acids and total oil; GC data, expressed as actual concentration and proportion of total oil, were regressed against spectral data to develop calibration equations. Equation statistics indicated that four of the five fatty acids could be predicted accurately by NIR spectroscopy; the fifth fatty acid could be determined by subtraction. Principal component analysis revealed that most of the spectral variation in this population was due to chlorophyll absorbance in the visible region. Therefore, the spectra were trimmed to include the NIR region only (1100-2500 nm), and a second set of equations was developed. Equations based exclusively on NIR spectra had equal or greater precision than equations based on visible and NIR spectra. Principal component analysis and partial least squares analysis revealed that even after trimming, at least 90% of the spectral variation was unrelated to fatty acid, though variation from fatty acid was identified in the second and third principal components. This research provides an NIR method for complete fatty acid profiling of soybean cotyledons. Equations were achieved with NIR spectra only, so spectrophotometers that analyze both the visible and NIR regions are not needed for this analysis. In addition, equations were possible with a 250 mg sample, which is one-tenth the normal sample size for this analysis.     

Biodegradation of diesel fuel-contaminated wastewater using a three-phase fluidized bed reactor

Aerobic biodegradation of diesel fuel (DF)-contaminated wastewater is carried out in a three-phase fluidized bed reactor under unsteady and steady state conditions. The solid phase lava rock particles, which act as the support for the biomass, are fluidized by the upward flows of influent wastewater, and air. The results show that the reactor under unsteady state operation achieved 100% DF removal from synthetic wastewater loaded with 0.43-1.03 kg/m3 day of DF. An average of over 97% of the influent chemical oxygen demand (COD) was also removed from the wastewater with COD concentrations in the range, 547-4025 mg/L. For influent COD concentrations up to 1345 mg/L, the removal is greater than 90%. Under steady state operation, the reactor was able to remove 100% of the DF, and an average of 96% of the COD from the wastewater. It had approximately 200 mg/L of DF, and 1237 mg/L of COD at a low hydraulic residence time of 4 h. In general, the results demonstrate that the reactor is very efficient, and requires short residence times to remove both DF and COD from heavily contaminated wastewater.     

Open-loop operation experiments in a resonator fiber-optic gyro using the phase modulation spectroscopy technique

A detection system in the resonator fiber-optic gyro is set up by the phase modulation (PM) spectroscopy technique. The slope of the demodulated curve near the resonant point is found to affect the ultimate sensitivity of the gyro. To maximize the demodulated signal slope, the modulation frequency and index are optimized by the expansion of the Bessel function and optical field overlapping method. Using different PM frequencies for the light waves, the open-loop gyro output signal is observed. The modulation frequency in this PM technique is limited only by the cutoff frequency of the LiNbO3 phase modulators, which can reach several gigahertz. This detection technique and system can be applied to the resonator micro-optic gyro with a less than 10 cm long integrated optical ring.     

Detection of apple juice adulteration using near-infrared transflectance spectroscopy

Near-infrared transflectance spectroscopy was used to detect adulteration of apple juice samples. A total of 150 apple samples from 19 different varieties were collected in two consecutive years from orchards throughout the main cultivation areas in Ireland. Adulterant samples at 10, 20, 30, and 40% w/w were prepared using two types of adulterants: a high fructose corn syrup (HFCS) with 45% fructose and 55% glucose, and a sugars solution (SUGARS) made with 60% fructose, 25% glucose, and 15% sucrose (the average content of these sugars in apple juice). The results show that NIR analysis can be used to predict adulteration of apple juices by added sugars with a detection limit of 9.5% for samples adulterated with HFCS, 18.5% for samples adulterated with SUGARS, and 17% for the combined (HFCS + SUGARS) adulterants. Discriminant partial least squares (PLS) regression can detect authentic apple juice with an accuracy of 86-100% and adulterant apple juice with an accuracy of 91-100% depending on the adulterant type and level of adulteration considered. This method could provide a rapid screening technique for the detection of this type of apple juice adulteration, although further work is required to demonstrate model robustness.     

Main inorganic component measurement of seawater using near-infrared spectroscopy

The potential of near-infrared (NIR) spectroscopy to measure the main inorganic components of seawater as salt-manufacturing materials was investigated. A total of 72 seawater samples collected from six locations was used, and spectra (1100-1800 nm) were acquired by a NIR spectrophotometer with a 1-mm path length. Principal component analysis (PCA), canonical correlation analysis (CCA), and partial least-squares (PLS) regression were performed based on the reference inorganic components. As a result, the principal component analysis and canonical correlation analysis showed that the near-infrared spectra could be related to the inorganic components of seawater. The partial least-squares regression analysis showed that the inorganic components (ion concentration of Cl, Na+, K+, SO4(2-), and Ca2+) could be predicted with good accuracy using NIR spectra and their second derivatives. For Cl ion and K+ ion concentrations, the accuracy was high.     

Nondestructive assessment of engineered cartilage constructs using near-infrared spectroscopy

Noninvasive assessment of engineered cartilage properties would enable better control of the developing tissue towards the desired structural and compositional endpoints through optimization of the biochemical environment in real time. The objective of this study is to assess the matrix constituents of cartilage using near-infrared spectroscopy (NIRS), a technique that permits full-depth assessment of developing engineered tissue constructs. Mid-infrared (mid-IR) and NIR data were acquired from full-thickness cartilage constructs that were grown up to 4 weeks with and without mechanical stimulation. Correlations were assessed between established mid-IR peak areas that reflect the relative amount of collagen (amide I, amide II, and 1338 cm(-1)) and proteoglycan (PG), (850 cm(-1)), and the integrated area of the NIR water absorbance at 5190 cm(-1). This analysis was performed to evaluate whether simple assessment of the NIR water absorbance could yield information about matrix development. It was found that an increase in the mid-IR PG absorbance at 850 cm(-1) correlated with the area of the NIR water peak (Spearman's rho = 0.95, p < 0.0001). In the second analysis, a partial least squares method (PLS1) was used to assess whether an extended NIR spectral range (5400-3800 cm(-1)) could be utilized to predict collagen and proteoglycan content of the constructs based on mid-IR absorbances. A subset of spectra was randomly selected as an independent prediction set in this analysis. Average of the normalized root mean square errors of prediction of first-derivative NIR spectral models were 7% for 850 cm(-1) (PG), 11% for 1338 cm(-1) (collagen), 8% for amide II (collagen), and 8% for amide I (collagen). These results demonstrate the ability of NIRS to monitor macromolecular content of cartilage constructs and is the first step towards employing NIR to assess engineered cartilage in situ.     

Quantifying ethanol content of beer using interpretive near-infrared spectroscopy

On the basis of absorption measurements in the near-infrared (NIR) spectral range, a new method for the quantification of the ethanol content of beer is presented. Instead of the multivariate calibration models most commonly employed in NIR spectroscopic works, we use interpretive difference spectroscopy: Two wavelengths are selected according to the assignment of the absorption bands of the main substances of content of beer in the NIR region, and the difference between the absorbances at these wavelengths is used for ethanol quantification. Absorption spectra of the dominating beer ingredients are discussed and the calibration procedure with ethanol/water mixtures is shown. Robustness against the carbohydrate content of beer samples was demonstrated by analyzing solutions of ethanol and maltose in water. Validation of the method was performed with various beer samples with an ethanol concentration range between 0.5 and 7.7 vol %. The pertinent advantage of the procedure developed in this work is the indication that the results are independent from seasonal variations of the ingredients, which is of high interest for products with natural ingredients such as beer.     

Temperature measurements of turbid aqueous solutions using near-infrared spectroscopy

We report a method that uses near-infrared spectroscopy and multivariate analysis to measure the temperature of turbid aqueous solutions. The measurement principle is based on the fact that the peak wavelength of the water absorption band, with its center near 1440 nm, shifts with changes in temperature. This principle was used to measure the temperatures of 1 mm thick samples of aqueous solutions containing Intralipid (2%), which are often used as optical phantoms for biological tissues due to similar scattering characteristics. Temperatures of pure water and aqueous solutions containing glucose (100 mg/ml and 200 mg/ml) were also measured for comparison. For the turbid Intralipid solutions, the absorbance spectrum varied irregularly with time due to the change in scattering characteristics. However, by making use of the difference between the absorbance at 1412 nm and the temperature-independent absorbance at 1440 nm, we obtained SEPs (standard error of prediction) of 0.3 degrees C and 0.2 degrees C by univariate linear regression and partial least squares regression, respectively. These accuracies were almost the same as those for the transparent samples (pure water and glucose solution).     

Multivariate analysis and classification of the chemical quality of 7-aminocephalosporanic acid using near-infrared reflectance spectroscopy

The capability of near-infrared (NIR) spectroscopy in comparison to conventional chemical testing to control the chemical quality of a pharmaceutical intermediate has been investigated. Multivariate projection methods including principal component analysis, partial least-squares discriminant analysis and soft independent modeling of class analogy have been evaluated. 7-Aminocephalosporanic acid has been chosen as an example providing a large variation of quality due to its relative chemical instability. Three sets of production lots have been selected to study the extent of quality information extractable from NIR spectra. The first set of 91 lots covers a very broad range of chemical quality assessed by 8 parameters with a partially extended characterization by physical properties. The general congruence of spectral, chemical, and physical information has been investigated. The second set of 110 lots covers a very narrow range of chemical quality assessed by 11 parameters. With extended quality information, the intrinsic selectivity within the spectral data structure has been studied. The third set of 228 lots characterized by 8 parameters is a selection out of more than 1000 lots over a production period of two years. The ruggedness of the multivariate approach has been confirmed by a cross validation of the classification test.     

Autofluorescence and diffuse reflectance spectroscopy of oral epithelial tissue using a depth-sensitive fiber-optic probe

Optical spectroscopy can provide useful diagnostic information about the morphological and biochemical changes related to the progression of precancer in epithelial tissue. As precancerous lesions develop, the optical properties of both the superficial epithelium and underlying stroma are altered; measuring spectral data as a function of depth has the potential to improve diagnostic performance. We describe a clinical spectroscopy system with a depth-sensitive, ball lens coupled fiber-optic probe for noninvasive in vivo measurement of oral autofluorescence and diffuse reflectance spectra. We report results of spectroscopic measurements from oral sites in normal volunteers and in patients with neoplastic lesions of the oral mucosa; results indicate that the addition of depth selectivity can enhance the detection of optical changes associated with precancer.     

Boriding of nickel in a fluidized bed reactor

Heat treatments of alloys in fluidized bed reactors have been carried out for more than 25 years. Recently, this technology has been used for surface engineering applications in the deposition of hard and/or corrosion resistant layers. In the present paper we used FBT to deposit boride coatings on nickel metal. The coatings were examined by means of optical microscopy, X-rays diffraction and Vickers microhardness in terms of the coating’s morphology, thickness, hardness and phase formation. The coating’s tribological properties were evaluated under dry wear. The as-produced coatings are characterized by good uniformity and it was found that only Ni₃B (space group Pnma) was formed during the treatment. Furthermore, the boride layer improved the tribological properties of nickel.     

Phase modulation spectroscopy using an all-fiber piezoelectric transducer modulator for a resonator fiber-optic gyroscope

The theoretical analysis and experimental demonstration of phase modulation spectroscopy employing an all-fiber piezoelectric transducer modulator for a fiber ring resonator fiber-optic gyroscope is presented for the first time as far as we know. The results support the feasibility of such a technique as a rotation detection scheme for a resonator fiber-optic gyroscope.     

Control of acid gases using a fluidized bed adsorber

During incineration, secondary pollutants such as acid gases, organic compounds, heavy metals and particulates are generated. Among these pollutants, the acid gases, including sulfur oxides (SO(x)) and hydrogen chloride (HCl), can cause corrosion of the incinerator piping and can generate acid rain after being emitted to the atmosphere. To address this problem, the present study used a novel combination of air pollution control devices (APCDs), composed of a fluidized bed adsorber integrated with a fabric filter. The major objective of the work is to demonstrate the performance of a fluidized bed adsorber for removal of acid gases from flue gas of an incinerator. The adsorbents added in the fluidized bed adsorber were mainly granular activated carbon (AC; with or without chemical treatment) and with calcium oxide used as an additive. The advantages of a fluidized bed reactor for high mass transfer and high gas-solid contact can enhance the removal of acid gases when using a dry method.On the other hand, because the fluidized bed can filter particles, fine particles prior to and after passing through the fluidized bed adsorber were investigated. The competing adsorption on activated carbon between different characteristics of pollutants was also given preliminary discussion. The results indicate that the removal efficiencies of the investigated acid gases, SO(2) and HCl, are higher than 94 and 87%, respectively. Thus, a fluidized bed adsorber integrated with a fabric filter has the potential to replace conventional APCDs, even when there are other pollutants at the same time.     

Fast identification of Echinacea purpurea dried roots using near-infrared spectroscopy

Near-infrared (NIR) reflectance spectroscopy was used to develop a fast identification method for Echinacea purpurea dried milled roots. Method development was carried out using a PLS (partial least-squares) algorithm and pretreatment options. The aim of this qualitative analysis was to confirm the identity of E. purpurea and to detect the presence of fraud, i.e., samples adulterated or substituted by Echinacea angustifolia, Echinacea pallida, or Parthenium integrifolium. Specificity was demonstrated by testing a validation set against the method. A total of 10% of the E. purpurea batches (true samples) and 0% of the false samples from that validation set were misidentified by the method. The misidentification was due to the difference in particle size distribution of one E. purpurea batch compared to that of the other samples. Adulterated E. purpurea samples can be detected at a minimum of 10% of adulteration. This study demonstrates that NIR spectroscopy is a good tool for the fast identification of E. purpurea roots if the samples are milled using the same procedure as for the calibration samples. The method is robust with respect to the origin of the samples and can be used routinely by the pharmaceutical industry or herbal suppliers to avoid mislabeling errors or adulteration.