Ricardo N.M.J. Páscoa

A Review on the Applications of Portable Near-Infrared Spectrometers in the Agro-Food Industry

Industry has created the need for a cost-effective and nondestructive quality-control analysis system. This requirement has increased interest in near-infrared (NIR) spectroscopy, leading to the development and marketing of handheld devices that enable new applications that can be implemented in situ. Portable NIR spectrometers are powerful instruments offering several advantages for nondestructive, online, or in situ analysis: small size, low cost, robustness, simplicity of analysis, sample user interface, portability, and ergonomic design. Several studies of on-site NIR applications are presented: characterization of internal and external parameters of fruits and vegetables; conservation state and fat content of meat and fish; distinguishing among and quality evaluation of beverages and dairy products; protein content of cereals; evaluation of grape ripeness in vineyards; and soil analysis. Chemometrics is an essential part of NIR spectroscopy manipulation because wavelength-dependent scattering effects, instrumental noise, ambient effects, and other sources of variability may complicate the spectra. As a consequence, it is difficult to assign specific absorption bands to specific functional groups. To achieve useful and meaningful results, multivariate statistical techniques (essentially involving regression techniques coupled with spectral preprocessing) are therefore required to extract the information hidden in the spectra. This work reviews the evolution of the use of portable near-infrared spectrometers in the agro-food industry.

Review on recent applications of the liquid waveguide capillary cell in flow based analysis techniques to enhance the sensitivity of spectroscopic detection methods

Incorporation of long path length liquid waveguide capillary cell (LWCC or LCW) into spectrometric detection systems can increase the sensitivity of these by orders of magnitude (up to 500 times), and consequently can reduce the detection limits. The combination of the long path length spectrophotometry with flow methodologies can provide analytical solutions for various challenges in the field of environmental, biochemical and food chemistry. In this present work, the analytical applications of the long capillary cells are summarised and critically discussed. A historical overview of the cell development is given; applications in different areas are presented and grouped by analyte type. Major improvements achieved based on the use of the LWCC in the analytical characteristics (like sensitivity and detection limit) are emphasised while some of the limitations are also discussed.

Rapid assessment of bioactive phenolics and methylxanthines in spent coffee grounds by FT-NIR spectroscopy

Spent coffee grounds (SCGs) are a great source of bioactive compounds with interest to pharmaceutical and cosmetic industries. Phenolics and methylxanthines are the main health related compounds present in SCG samples. Content estimation of these compounds in SCGs is of upmost importance in what concerns their profitable use by waste recovery industries. In the present work, near-infrared spectroscopy (NIRS) was proposed as a rapid and non-destructive technique to assess the content of three main phenolics (caffeic acid, (+)-catechin and chlorogenic acid) and three methylxanthines (caffeine, theobromine and theophylline) in SCG samples obtained from different coffee brands and diverse coffee machines. The content of these compounds was determined for 61 SCG samples by HPLC coupled with diode-array detection. Partial least squares (PLS) regression based models were calibrated to correlate diffuse reflectance NIR spectra against the reference data for the six parameters obtained by HPLC. Spectral wavelength selection and number of latent variables were optimized by minimizing the cross-validation error. PLS models showed good linearity with a coefficient of determination for the prediction set (Rp(2)) of 0.95, 0.92, 0.88, 071 and 0.84 for caffeine, caffeic acid, (+)-catechin, chlorogenic acid and theophylline, respectively. The range error ratio (RER) was higher for caffeine (17.8) when compared to other compounds (12.0, 10.1, 7.6 and 9.2, respectively for caffeic acid, (+)-catechin, chlorogenic acid and theophylline). Moreover, the content of caffeine could be used to predict the antioxidant properties of SCG samples (R=0.808, n=61), despite not presenting this property itself. The results obtained confirmed that NIRS is a suitable technique to screen SCG samples unveiling those with high content of bioactive compounds, which are interesting for subsequent extraction procedures.

In situ near infrared monitoring of activated dairy sludge wastewater treatment processes

A sequential batch reactor (SBR) for aerobic treatment of dairy residues (activated sludge process) was monitored on-line by near infrared (NIR) spectroscopy. NIR spectra in the wavelength range of 900–1700 nm were acquired in situ with a transflectance probe. Measured in situ NIR spectra allowed the development of multivariate statistical process control models for supervision of the SBR process. The directly acquired spectra permitted characterisation of the different SBR operation stages and the detection of process disturbances. Calibration models based on partial least squares regression were developed for three process parameters: total solids (TS), total suspended solids (TSS) and chemical oxygen demand (COD). Model errors were estimated as root mean squared errors of cross-validation. The cross-validation errors obtained were 0.066 g TS L−1, 0.075 g TSS L−1 and 86.6 mg O2 L−1 respectively. Results demonstrated the viability of NIR spectroscopy as an alternative method for monitoring and control of activated sludge wastewater treatment processes having advantages both in terms of efficient determination of process parameters (fast, in situ and requiring no toxic reagents) and in terms of process monitoring.

In-line monitoring of the coffee roasting process with near infrared spectroscopy: Measurement of sucrose and colour.

In this work, a real-time and in-situ analytical tool based on near infrared spectroscopy is proposed to predict two of the most relevant coffee parameters during the roasting process, sucrose and colour. The methodology was developed taking in consideration different coffee varieties (Arabica and Robusta), coffee origins (Brazil, East-Timor, India and Uganda) and roasting process procedures (slow and fast). All near infrared spectroscopy-based calibrations were developed resorting to partial least squares regression. The results proved the suitability of this methodology as demonstrated by range-error-ratio and coefficient of determination higher than 10 and 0.85 respectively, for all modelled parameters. The relationship between sucrose and colour development during the roasting process is further discussed, in light of designing in real-time coffee products with similar visual appearance and distinct organoleptic profile.

Spectrophotometric determination of zinc and copper in a multi-syringe flow injection analysis system using a liquid waveguide capillary cell: Application to natural waters

This work exploits a multi-syringe injection analysis (MSFIA) system coupled with a long liquid waveguide capillary cell for the spectrophotometric determination of zinc and copper in waters. A liquid waveguide capillary cell (1.0m pathlength, 550 μm i.d. and 250 μL internal volume) was used to enhance the sensitivity of the detection. The determination for both ions is based on a colorimetric reaction with zincon at different pH values. The developed methodology compares favourably with other previously described procedures, as it allows to reach low detection limits for both cations (LODs of 0.1 and 2 μg L(-1), for copper and zinc, respectively), without the need for any pre-concentration step. The system also provided a linear response up to 100 μg L(-1) with a high throughput (43 h(-1)) and low reagent consumption and effluent production. The developed work was applied to natural waters and three certified reference water samples.

A Non-invasive Real-Time Methodology for the Quantification of Antioxidant Properties in Coffee During the Roasting Process Based on Near-Infrared Spectroscopy

This paper describes the development of a real-time method based on near-infrared spectroscopy (NIRS) for determination of total antioxidant capacity (TAC) and total phenolic content (TPC) in coffee during the roasting process. The real-time non-invasive monitoring procedure involved pointing a diffuse reflectance probe directly at the roasting chamber through a glass window in order to monitor the roasting process. The figures of merit of the chemometric models to estimate TAC and TPC showed selectivity values higher than 12% and determination coefficients (R2P) above 0.90. The TAC and TPC profiles during the roasting procedure are discussed in terms of the antioxidant compounds likely to be present in green and roasted coffee. NIRS was found to be a satisfactory real-time tool for monitoring the content of antioxidant compounds in coffee during the roasting process, complementing other established procedures.

Exploratory study on vineyards soil mapping by visible/near-infrared spectroscopy of grapevine leaves

Vineyards soils discrimination based on Vis/NIR spectral analysis of leaves.High-throughput method for scanning soils in vineyards for precision agriculture.In-situ analysis with hand-held spectrometer.Fast and high-precision mapping of vineyard soils. This work demonstrates the possibility of discriminating vineyard soils through the non-destructive and in-situ visible/near infrared monitoring of leaves. A portable Vis/NIR spectrometer was applied for monitoring in-situ Vitis vinifera leaves in vineyards of two wine regions in Portugal in the maturation period. Leaves reflectance spectra of different grapevine varieties planted in different vineyard locations (distinct soil taxonomic types) were analyzed by principal component analysis and partial least squares discriminant analysis. Soil discriminant models based on leaves Vis/NIR spectra yielded for both vineyards approximately 95% correct soil taxonomic predictions. This methodology was then applied to monitor all plants within a 0.3ha vineyard block in the Dao vineyard resulting in a highly detailed soil taxonomic map built exclusively from leaves Vis/NIR spectra. A comparison with the existing soil map proved that the NIR spectroscopy based estimation was very similar. Even though further studies are needed, namely in different maturation stages and other geographical regions, to ensure reliability of this technique, results in this work showed that it can be used as an additional auxiliary tool for obtaining vineyard soil maps. Its main advantages over pedological reference procedures are speed and cost efficiency analysis.

Real-time monitoring of a coffee roasting process with near infrared spectroscopy using multivariate statistical analysis: a feasibility study

This work proposes the use of near infrared (NIR) spectroscopy in diffuse reflectance mode and multivariate statistical process control (MSPC) based on principal component analysis (PCA) for real-time monitoring of the coffee roasting process. The main objective was the development of a MSPC methodology able to early detect disturbances to the roasting process resourcing to real-time acquisition of NIR spectra. A total of fifteen roasting batches were defined according to an experimental design to develop the MSPC models. This methodology was tested on a set of five batches where disturbances of different nature were imposed to simulate real faulty situations. Some of these batches were used to optimize the model while the remaining was used to test the methodology. A modelling strategy based on a time sliding window provided the best results in terms of distinguishing batches with and without disturbances, resourcing to typical MSPC charts: Hotellings T2 and squared predicted error statistics. A PCA model encompassing a time window of four minutes with three principal components was able to efficiently detect all disturbances assayed. NIR spectroscopy combined with the MSPC approach proved to be an adequate auxiliary tool for coffee roasters to detect faults in a conventional roasting process in real-time.

Varietal discrimination of hop pellets by near and mid infrared spectroscopy

Hop is one of the most important ingredients of beer production and several varieties are commercialized. Therefore, it is important to find an eco-real-time-friendly-low-cost technique to distinguish and discriminate hop varieties. This paper describes the development of a method based on vibrational spectroscopy techniques, namely near- and mid-infrared spectroscopy, for the discrimination of 33 commercial hop varieties. A total of 165 samples (five for each hop variety) were analysed by both techniques. Principal component analysis, hierarchical cluster analysis and partial least squares discrimination analysis were the chemometric tools used to discriminate positively the hop varieties. After optimizing the spectral regions and pre-processing methods a total of 94.2% and 96.6% correct hop varieties discrimination were obtained for near- and mid-infrared spectroscopy, respectively. The results obtained demonstrate the suitability of these vibrational spectroscopy techniques to discriminate different hop varieties and consequently their potential to be used as an authenticity tool. Compared with the reference procedures normally used for hops variety discrimination these techniques are quicker, cost-effective, non-destructive and eco-friendly.