Studies on acrylamide levels in roasting, storage and brewing of coffee

The content of acrylamide in coffee reaches a peak early in the roasting process, reflecting occurrence of both formation and destruction of acrylamide during roasting. Levels of acrylamide in the fully roasted product are a small fraction of the peak reached earlier. Glucose and moisture in green coffee do not show a significant correlation with acrylamide in roasted coffee. Pre-roasting levels of asparagine show a correlation only in Arabica coffee. The main factors affecting the level of acrylamide in roasted coffee appear to be the Arabica/Robusta ratio, with Robusta giving higher levels; time and degree of roast, with both shorter and lighter roasting at the edges of the normal roasting range giving higher levels; storage condition and time, with clear reduction at ambient storage. This storage reduction of acrylamide followed second order reaction kinetics with an activation energy of 73 KJ/mole. The acrylamide in roasted coffee is largely extracted into the brew and stable within usual time of consumption. As these four main factors also substantially affect the sensorial characteristics of the brew, and as modifications of the process have to comply with the consumer-accepted boundaries of taste profiles, only small effects on the acrylamide level are expected to be achievable.     

The effects of phytic acid on the Maillard reaction and the formation of acrylamide

Phytic acid, myo-inositol hexaphosphoric acid, exists in substantial (1–5%) amounts in edible plant seeds. In this study the effects of phytic acid on the Maillard reaction and the formation of acrylamide were investigated. Both phytic acid and phosphate enhanced browning in glucose/β-alanine system, but phytic acid was less effective than phosphate. Higher pH favoured the catalytic activities for both of them. The influence of the types of sugar and amino acid on the reaction was also examined. Browning was suppressed by the addition of calcium and magnesium ions, but an additive effect was observed for ferrous ions and phytic acid in glucose/β-alanine solution at pH 8.0. Both phytic acid and phosphate promoted the polymerisation of the reaction intermediates. The kinetics of Maillard reaction was first-ordered reaction in the presence of phytic acid. Phytic acid was less effective than phosphate in the formation of acrylamide. When potato slices were treated with sodium phytate and calcium chloride successively, the formation of acrylamide was greatly suppressed.     

Study of acrylamide in coffee using an improved liquid chromatography mass spectrometry method: Investigation of colour changes and acrylamide formation in coffee during roasting

An improved analytical method for the determination of acrylamide in coffee is described using liquid chromatography coupled to mass spectrometric detection (LC-MS). A variety of instant, ground and laboratory roasted coffee samples were analysed using this method. The sample preparation entails extraction of acrylamide with methanol, purification with Carrez I and II solutions, evaporation and solvent change to water, and clean-up with an Oasis HLB solid-phase extraction (SPE) cartridge. The chromatographic conditions allowed separation of acrylamide and the remaining matrix co-extractives with accurate and precise quantification of acrylamide during MS detection in SIM mode. Recoveries for the spiking levels of 50, 100, 250 and 500 µg/kg ranged between 99 and 100% with relative standard deviations of less than 2%. The effects of roasting on the formation of acrylamide and colour development were also investigated at 150, 200 and 225°C. Change in the CIE (Commission Internationale de l'Eclairage) a* colour value was found to show a good correlation with the change in acrylamide. CIE a* and acrylamide data was fitted to a non-linear logarithmic function for the estimation of acrylamide level in coffee. Measured acrylamide levels in commercial roasted coffees compared well with the predicted acrylamide levels from the CIE a* values.     

Acrylamide in espresso coffee: Influence of species,roast degree and brew length

Espresso coffees were analysed for acrylamide contents by matrix solid-phase dispersion and GC–MS. The influence of coffee species, roast degree, and brew length were ascertained. Mean acrylamide contents of medium roasted espressos (30 mL) were 1.16 ± 0.25 and 2.31 ± 0.43 μg for pure arabica and robusta samples, respectively. Espressos prepared from commercial blends contained an average acrylamide level of 1.26 ± 0.28 μg. A 25% decrease was observed when comparing espressos prepared with medium and dark roasted coffee. The extraction efficacy of acrylamide for standard espressos of 30 mL was near 80%, being only affected by brew volume, with long espressos (70 mL) containing practically all acrylamide of the coffee cake (99%), almost double that of short ones (20 mL). When compared with other common coffee beverages, espresso acrylamide concentration (μg/L) was higher. However, due to the small volume per cup, it may contribute less to acrylamide ingestion.     

The impact of roasting on the ochratoxin A content of coffee

Roasting coffee led to a drop in the ochratoxin A (OTA) concentration, as measured by the reference method, especially for dark type roasts. The way the beverage was prepared also affected the OTA content, which could paradoxically be higher than that of the initial roasted coffee. Assays on the thermal stability of pure OTA showed that it ought to be found in larger quantities in roasted coffee. This suggested that OTA was masked by reactions with the substrate during roasting. The absence of OTA in green coffee is therefore the best guarantee of safety.     

Confirmation that the Maillard reaction is the principle contributor to the antioxidant capacity of coffee brews

Chemical characteristics related to the antioxidant activity of roasted coffee (RC) were evaluated, using non-roasted coffee beans (NRC) and model Maillard reaction products (MRPs) as controls. The formation of MRPs and the degradation of phenolics in RC were characterized by employing a battery of fluorescence, UV-vis spectra and tri-stimulus color parameters measured on NRC, RC and the model MRPs. Total chlorogenic acid (CGA) and caffeine contents in NRC and RC extracts were also quantified using HPLC. Both RC and controls showed high antioxidant activity in three chemical based assays irrespective of caffeine content. Data from this study suggested that natural phenolics present in NRC had higher antioxidant activity compared to MRPs derived from coffee and model MR systems. However, MRPs were the prevailing antioxidants in RC as free CGA was lost (> 90%). The mechanisms of the antioxidant action associated with coffee MRPs involved hydrogen atom transfer and single electron transfer mechanisms.     

ABTS radical scavenging capacity in green and roasted coffee extracts

The impact of two parameters (temperature and duration) on the radical scavenging capacity of individual compounds, and total extracts found in coffee was investigated. Phenolic coffee extracts of light (200 °C), medium (225 °C) and dark (235 °C) roasted coffees in a range of 0–30 min were analyzed by an on-line RP-HLPC-ABTS^•+ decolourization assay. This study revealed a general decrease of radical scavenging capacity related to native phenolic compounds. Processing coffee beans leads to generation of up to 10 new radical scavengers. The roasting process influences not only color and taste in coffees, but also the radical scavenging capacity of coffee as well. Phenolic content in roasted coffee and green coffee is very different. Six compounds identified as caffeoylquinic acids and dicaffeoylquinic acids, endowed with radical scavenging capacity were found in green coffee, whereas depending on the roasting process, roasted coffees can present up to 16 different radical scavengers. The compounds formed during the roast are most likely chlorogenic acids derivatives, of which 4 could be clearly identified as two feruloylquinic acids and two caffeoylquinides. In longer roasting durations, these molecules are subjected to auto-degradation, thus total radical scavenging capacity in coffee decline along with roasting (duration and temperature).     

Effect of different extraction methods on the recovery of chlorogenic acids,caffeine and Maillard reaction products in coffee beans

Water and ethanolic extracts were obtained from green and roasted (3 different roast degrees) Arabica and Robusta coffee beans. Three types of water extracts were prepared from the examined, finely ground material through: (a) brewing with boiling water, (b) boiling in water, and (c) boiling in water under elevated pressure. All these extracts were lyophilized. Two types of ethanolic extracts were derived from the examined material through (a) extraction of the finely ground coffee beans and (b) extraction of the solid residue that remained after boiling the coffee beans in water under elevated pressure. These ethanolic extracts were dried. Both water and ethanolic extracts were analyzed for concentration of potential antioxidants such as chlorogenic acids and caffeine (by HPLC) and Maillard reaction products (measurements of absorbance at 420 nm). Concentration of chlorogenic acids in Robusta extracts varied between 0.4 and 36.0 g × 100 g⁻¹ dry extract weight (db.), while in Arabica extracts it ranged from 0.1 to 22.4 g × 100 g⁻¹ db. Extracts of dark roasted Arabica contained more chlorogenic acids than those of Robusta. Concentration of caffeine, which in green and roasted coffee beans is maintained at the similar level, tended to increase in Robusta extracts with the roast degree and temperature of extraction with water, while in case of Arabica extracts there was no noticeable tendency. Caffeine concentrations varied between 0.12 and 8.41 g × 100 g⁻¹ db. and between 0.03 and 6.53 g × 100 g⁻¹ db. in Robusta and Arabica extracts, respectively. Ethanolic extracts were characterized by relatively higher caffeine concentrations and lower contents of brown pigments and chlorogenic acids as compared to water extracts. The richest in antioxidants were extracts of green Robusta coffee beans derived through boiling in water under elevated pressure.     

Impact of the reducing sugars on the relationship between acrylamide and Maillard browning in French fries

The relationship between acrylamide content and Maillard browning in French fries was studied as a function of different glucose/fructose ratios in the raw product using several colour measurement methods. An exponential correlation was found between acrylamide formation and surface colour, as evaluated by the parameters a*, delta E and Agtron. As a consequence, small differences in product colour could result in more pronounced differences in acrylamide contamination. This relationship however appeared to be dependant upon the glucose/fructose ratio of the raw material. An excess of fructose compared to glucose stimulated acrylamide formation to a higher extent than Maillard browning. The opposite effect was established with an excess of glucose. In addition, a linear relationship was found between the absorbance of aqueous French fries extracts and acrylamide content, which moreover appeared to be less affected by the addition of extra reducing sugars prior to frying. To predict acrylamide formation, sugar analysis however remains an important instrument and is complementary to surface colour measurement.     

Effects of dough formula and baking conditions on acrylamide and hydroxymethylfurfural formation in cookies

The effects of dough formula and baking conditions on the formations of acrylamide and hydroxymethylfurfural (HMF) were studied in a cookie model system. Increasing the sugar concentration in the dough formula increased acrylamide formation during baking at 205 °C for 11 min. The effect of sugar on acrylamide formation was more pronounced for glucose than for sucrose, expectedly. Addition of citric acid into dough formula comprising sucrose increased the susceptibility of acrylamide formation, while it decreased acrylamide formation in the dough formula comprising glucose. Decreasing the pH of dough formula increased the tendency to surface browning and the formation of hydroxymethylfurfural in cookies during baking. The results suggest that a cookie with acceptable texture and colour, but having less than 150 ng/g of acrylamide, can be manufactured by lowering the baking temperature and avoiding reducing sugars in the recipe.     

Supercritical fluid extraction as a potential mitigation strategy for the reduction of acrylamide level in coffee

The removal of acrylamide from coffee through supercritical CO₂ extraction has been investigated for the first time. Two steps were performed: a pre-roasting treatment and a supercritical extraction process. The main aim of this first work was to investigate the feasibility of the process more than the impact of the treatment on the organoleptic properties of coffee. The efficiency of acrylamide removal was checked by measuring its content in the coffee beans before and after the supercritical treatment. The role of temperature, pressure, extraction time and the addition of a modifier (ethanol) was examined.     

Effect of roasting conditions and grinding on free radical contents of coffee beans stored in air

The influence of roasting and storage conditions on free radical contents of individual Arabica coffee beans was examined during storage of whole, half and ground beans in air over a 1-month period. Free radical contents increased with increasing roasting time (roasting degree), but the atmosphere (air vs. N₂) used in the roasting and cooling process had little effect. There was a progressive increase in free radical contents with storage time, but the rate was much lower in whole beans than with half and fully ground beans, for which the rate was similar. These results suggest that exposure to O₂, rather than physical grinding is the main mechanism for storage-related free radical generation, and strongly indicate that roasted coffee is best kept as whole beans in order to minimise changes during prolonged periods of aerobic storage. Furthermore, they demonstrate that EPR measurements can contribute to understanding the process and storage related changes in coffee.     

The effect of frying on browning,acrylamide and 5-hydroxymethylfurfural formation on Malaysian curry puff skin treated with l-asparaginase

Food Science and Biotechnology - Acrylamide and 5-hydroxymethylfurfural (HMF) is the product of the Maillard reaction and its accumulation may lead to adverse health effects. Hence, this paper aims...     

Positive interaction between amino and sulfhydryl groups for acrylamide removal

The reaction of acrylamide with glutamic acid (Glu), N-acetylcysteine (AcCys), glutamic acid/N-acetylcysteine mixture, glutathione (GSH), and cysteine was studied to analyze the combined action of amino and sulfhydryl groups on acrylamide reduction. Their reactivities for decreasing acrylamide content were inversely correlated (r = − 0.975, p = 0.025) to the E_a of the reaction and acrylamide disappearance decreased in the following order: Cys > GSH > AcCys >> Glu. In addition, E_a of acrylamide/nucleophile reactions seemed to be determined not only by the simultaneous presence of amino and sulfhydryl groups but also by the distance among them. Thus, when both groups were present in different molecules, an interaction between the protective effects of amino and sulfhydryl groups was only observed when small concentrations of AcCys and Glu were employed. However, this interaction was always positive when amino and sulfhydryl groups were simultaneously present in the same molecule and the closer the position of both groups, the higher the positive interaction observed. All these results suggest that, in the search of potential acrylamide-mitigating substances, nucleophiles should have both amino and sulfhydryl groups and these groups should be as close as possible in the molecule.     

Unravelling the kinetics of the formation of acrylamide in the Maillard reaction of fructose and asparagine by multiresponse modelling

A kinetic model for the formation of acrylamide in a fructose–asparagine reaction system at initial pH 5.5 is proposed, based on an approach called multiresponse kinetic modelling. The formation of acetic acid and formic acid from the degradation of fructose and its isomer glucose was included in the proposed kinetic model. The kinetic model suggests that the effect of temperature on acrylamide formation with fructose is more due to the preceding steps with the formation of the Schiff base. The use of fructose and lower pH resulted in a higher yield of acrylamide (3%), suggesting that both can play an important role in acrylamide mitigation. Furthermore, these models have shown that, at high temperatures (120–200 °C), the Maillard reaction rapidly goes into the advanced stages, forming high amounts of organic acids and high molecular weight melanoidins. Overall, these mechanistic models provide more insight of the formation of acrylamide in a quantitative way.     

Influence of torrefacto roast on antioxidant and pro-oxidant activity of coffee

The addition of sugar at the end of the torrefacto roasting process may influence the antioxidant and pro-oxidant properties of coffee because sugar is one of the main precursors the Maillard reaction. The aim of the work was to study and to compare the antioxidant and pro-oxidant properties of some commercial roasted coffees which are selected to represent conventional roasted arabica coffee and arabica/robusta blends, and torrefacto roasted blends. Higher antioxidant activity was observed in Colombian coffees than in conventional roasted coffee blends. On the other hand, when the percentage of torrefacto coffee was increased, an increase of the antioxidant activity and a slight tendency to decrease the pro-oxidant activity were observed. Moreover, principal component analysis allowed separation of: (a) brands by PC1 (46.9%), characterised by colour parameters defined by roasting degree and (b) torrefacto roasted blends by PC2 (33.7%), characterised by antioxidant/pro-oxidant activity.     

Model studies on the role of 5-hydroxymethyl-2-furfural in acrylamide formation from asparagine

This study aimed to investigate the mechanism of acrylamide formation during heating asparagine (ASN) at elevated temperatures with glucose (GLC), and 5-hydroxymethyl-2-furfural (HMF). The results revealed that HMF rapidly reacted with ASN, leading to acrylamide formation. The ASN-HMF model system generated acrylamide more efficiently than the ASN-GLC model system during heating at 180 °C. A significantly higher amount of 3-aminopropionamide (3-APA) was formed in the ASN-HMF model system than in the ASN-GLC model system within 5 min at 180 °C. The amount of 3-APA decreased after 5 min of heating in both model systems while the amount of acrylamide continued to increase in the ASN-HMF model system. In-depth high resolution mass spectrometry analyses of reaction products formed in the model systems together with the kinetic data suggested that HMF is a potent carbonyl accelerating acrylamide formation during heating. 3-APA was found as one of the key intermediates leading to acrylamide formation.     

Effect of flour type on Maillard reaction and acrylamide formation during toasting of bread crisp model systems and mitigation strategies

Maillard reaction along with caramelisation are the main chemical reactions occurring in bakery products. They are referred to as non enzymatic browning. In this work, the effect of flour type (wheat, rye and whole-wheat flours) and process conditions were investigated by using a bread crisp model system made up of flour, water and yeast. The bread was toasted at different temperature for different times. In a second set of experiments several additives (glycine, 0.1% on flour; asparaginase, 2000 U kg⁻¹ of flour and an antioxidant extract from green tea) were added to the basic formulations in order to test their ability in reducing the formation of potentially harmful Maillard reaction compounds such as HMF and acrylamide. Browning development and water content along with antioxidant activity were also monitored.Rye model systems produced more HMF and acrylamide at all temperature tested, while wholewheat systems produced less HMF, but more acrylamide than wheat one. The addition of glycine was effective in reducing acrylamide formation, and it increased browning development, antioxidant activity and HMF formation. Asparaginase reduced acrylamide formation up to 88% and had no effect on browning development and antioxidant activity. The addition of exogenous antioxidant compounds from green tea did not produce clear effect on acrylamide formation, thus it was not useful as mitigation strategy in bakery products, likely because of the low fat content.     

Influence of sodium chloride on colour,residual volatiles and acrylamide formation in model systems and breakfast cereals

To elucidate the salt action in breakfast cereals to decrease its amount without a quality loss, a model system was developed. This model, composed of native maize starch, glucose and a mixture of five amino acids (glucose/amino acids molar ratio = 1/1) generated similar colour and volatiles (m/z = 45, 59, 69, 73, 87 and 103 g mol^?1) after heating compared to commercial breakfast cereals. A designed experiment used this model to study the influence of salt concentration (0–5.44%), heating time (0–25 min) and temperature (180–230 °C) on colour, residual volatiles and acrylamide formation. The higher the salt concentration, heating time and temperature, the darker were the products (P < 0.05). The L* values of the model systems containing 5 % salt and heated for 25 min at 230 °C were twelve points lower than the same systems without salt heated in the same conditions. Presence of salt significantly decreased acrylamide formation in the model systems (up to 50 % decrease when 2.5 % salt is added). However, salt did not have a significant impact on volatile levels. These findings were confirmed by observations made on four types of commercial breakfast cereals.     

Impact of extraction conditions on the content of acrylamide in model systems and food

It has recently been suggested that the analytical methods that have been developed to date for the determination of acrylamide (AA) may underestimate the concentration of AA in certain foods, because significantly higher results were obtained upon extraction of the food matrix under alkaline conditions. The present study employs food (potato, rye) and chemical model systems to better understand the tentative release of AA under high pH extraction conditions. The experimental design is based on the generation of AA in an environment containing an AA-isotopomer, and by comparing the ratio of AA, respectively the AA-isotopomer, after extraction at pHs 7 and 12. The results show that the additional AA released is not due to improved extractability of AA from the food matrix, and should therefore be regarded as an extraction artefact. Strongly alkaline conditions seem to induce net formation of AA from water-soluble precursors formed during thermolysis.