João Rodrigo Santos

Evaluation of green coffee beans quality using near infrared spectroscopy: A quantitative approach

Characterisation of coffee quality based on bean quality assessment is associated with the relative amount of defective beans among non-defective beans. It is therefore important to develop a methodology capable of identifying the presence of defective beans that enables a fast assessment of coffee grade and that can become an analytical tool to standardise coffee quality. In this work, a methodology for quality assessment of green coffee based on near infrared spectroscopy (NIRS) is proposed. NIRS is a green chemistry, low cost, fast response technique without the need of sample processing. The applicability of NIRS was evaluated for Arabica and Robusta varieties from different geographical locations. Partial least squares regression was used to relate the NIR spectrum to the mass fraction of defective and non-defective beans. Relative errors around 5% show that NIRS can be a valuable analytical tool to be used by coffee roasters, enabling a simple and quantitative evaluation of green coffee quality in a fast way.

Determination of E-2-nonenal by high-performance liquid chromatography with UV detection: Assay for the evaluation of beer ageing

The analysis of E-2-nonenal is of considerable interest for the brewery industry as this compound is claimed to be responsible for a paper/cardboard unpleasant flavour. Usually, the presence of E-2-nonenal can be noticed in aged beers at levels higher than 0.1 microg/l. In this work, an analytical method was developed to determine E-2-nonenal in beer involving steam distillation of beer followed by an extraction/concentration step using solid-phase extraction and determination of E-2-nonenal by HPLC with UV detection. Fastness and simplicity are the main advantages of the proposed method, when compared with other existing methodologies for the determination of E-2-nonenal in beer. Using the developed conditions, the interference of E-2-nonenal formed by degradation of its precursors during steam distillation is almost negligible. The presence of sulphur dioxide at legal levels does not interfere with the assay. The method was used in a comparative study of fresh and either naturally or forced aged beers. A much larger chromatographic peak was found near the peak of E-2-nonenal that correlates well with the peak of E-2-nonenal. Identification of the corresponding compound is currently under investigation, considering its future application on the evaluation of beer ageing.

Development of a chromatographic low pressure flow injection system: application to the analysis of methylxanthines in coffee.

In this work, the coupling of a commercial monolithic column to a traditional low pressure FIA system is proposed for the analysis of theobromine, theophylline and caffeine in coffee brewed samples using UV detection. The parameters mobile phase composition, flow rate and loop volume were evaluated and discussed considering the various chromatographic parameters in order to enable resolution of the methylxanthines studied within the coffee brewed sample matrix. The analyses of methylxanthines in coffee brewed samples by the proposed methodology were in good agreement with those obtained by the reference procedure based on HPLC. Relative errors were below 6% for all samples analyzed. Detection limits in the selected experimental conditions were within 10(-6)M range for theobromine and theophylline, and 10(-5) M for caffeine. The determination rate of the three methylxanthines for coffee brewed samples was ca of 10 h(-1). The main advantage of the proposed flow system was the possibility to perform chromatographic separations in low pressure flow systems. This substantial improvement was achieved due to the compatibility of monolithic columns within the flow injection system surpassing in this way one of the main handicaps of traditional flow analysis systems. Additional features of the strategy presented were low cost, efficiency, high versatility and low reagent consumption comparing to HPLC methodologies usually followed in the case study herein presented.

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.

Standard addition flow method for potentiometric measurements at low concentration levels: application to the determination of fluoride in food samples.

A standard addition method was implemented by using a flow manifold able to perform automatically multiple standard additions and in-line sample treatment. This analytical strategy was based on the in-line mixing of sample and standard addition solutions, using a merging zone approach. The flow system aimed to exploit the standard addition method to quantify the target analyte particularly in cases where the analyte concentration in the matrix is below the lower limit of linear response of the detector. The feasibility of the proposed flow configuration was assessed through the potentiometric determination of fluoride in sea salts of different origins and different types of coffee infusions. The limit of quantification of the proposed manifold was 5×10(-6) mol L(-1), 10-fold lower than the lower limit of linear response of the potentiometric detector used. A determination rate of 8 samples h(-1) was achieved considering an experimental procedure based on three standard additions per sample. The main advantage of the proposed strategy is the simple approach to perform multiple standard additions, which can be implemented with other ion selective electrodes, especially in cases when the primary ion is below the lower limit of linear response of the detector.

Development of a chromatographic low pressure flow injection system using amperometric detection: Application to the analysis of niacin in coffee.

In this work, an analytical flow system able to perform low pressure chromatography with amperometric detection is presented. As case study, the determination of niacin (vitamin B3) in coffee brewed samples was selected. The manifold comprised a 1.0 cm length monolithic column coated with didecyldimethylammonium bromide, a laboratory-made boron doped diamond electrode, and featured in-line ionic strength adjustment of the mobile phase. The figures of merit concerning the selected case study namely, detection limit, 7.90 × 10(-7) M, determination rate, ca. 10 samplesh(-1), mobile phase and ISA solution consumption, ca. 2.6 mL per analysis, and CV, below 5% for retention time and peak height, showed the competitiveness of this analytical strategy comparing to the described HPLC methods for niacin determination. The strategy displays a simple configuration, low cost, fast and easy assembling, foreseeing its use to general purpose applications.

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.

Single interface flow system with potentiometric detection for the determination of nitrate in water and vegetables

In this work a single interface flow system (SIFA) with potentiometric detection was for the first time implemented and applied to the determination of nitrate in waters and plant extracts. The analytical potential of the SIFA system was exploited not only to transport the sample towards detection but also to carry out, in a reproducible and automated way, the tasks associated with sample pre-treatment, namely ionic strength, pH adjustment and interfering species suppression. The advantageous aspects of combining a SIFA system with potentiometry with enhanced simplicity, ease of implementation and automation were further discussed and emphasised. The obtained results showed relative deviations lower than 5%, for both types of samples, with sampling rates of about 40h(-1). In addition, an innovative and straightforward process for constructing plastic membrane ion selective electrodes with a tubular configuration able to be coupled to flow-based analytical systems is also proposed. The developed approach, consisting of assembling the electrode inside a flow tubing connector is very simple to implement, robust, particularly adequate to be combined with flow methodologies and maintains all dynamic and analytical characteristics exhibited by previous assembling processes.

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.

Determination of Caffeine in Coffee Using Low-Pressure Chromatography

Coffee is probably the main source of caffeine in human diet and, because of legal requirements and organoleptic properties, this alkaloid in this beverage is frequently quantified. This chapter presents the approaches recently developed toward this aim, focusing on different coffee sample pretreatment before detection. Main advantages and disadvantages of the described methods are briefly discussed. A new approach using low-pressure flow systems with monolithic columns has been followed in the development of new analytical methodologies. The main feature of this strategy is the compatibility of monolithic columns to traditional low-pressure flow systems, enabling chromatographic separations to be performed using current small-sized flow manifold equipment. In this context, we recently proposed a method focusing on the determination of caffeine in coffee, which is illustrated here. The experimental conditions studied and the main figures of merit obtained are presented.