Effectiveness of ionizing radiation in reducing furan and acrylamide levels in foods

Furan and acrylamide are two possible carcinogens commonly found in many thermally processed foods. The possibility of using ionizing radiation to reduce the levels of thermally induced furan and acrylamide in water and selected foods was investigated. Aqueous furan solutions, and foods (frankfurters, sausages, infant sweet potatoes) that contained furan were irradiated to various doses of gamma-rays. Water and oil spiked with acrylamide and potato chips (a known acrylamide-containing food) were also irradiated. In addition, possible irradiation-induced formation of acrylamide in glucose and asparagine solutions was analyzed. Results showed that irradiation at 1.0 kGy destroyed almost all furan in water. In frankfurters, sausages, and infant sweet potatoes, the rate of irradiation-induced destruction of furan was much lower than the rate in water, although significant reductions in furan levels were observed in all foods. Irradiation at 2.5-3.5 kGy, doses that can inactivate 5-log of most common pathogens, reduced furan levels in the food samples by 25-40%. Similarly to furan, acrylamide in water was also sensitive to irradiation. After 1.5 kGy of irradiation, most of the acrylamide was degraded. Irradiation, however, had a very limited effect on acrylamide levels in oil and in potato chips, even at a dose of 10 kGy. No detectable acrylamide was formed in the mixture of asparagine and glucose upon irradiation. These results suggest that a low dose of irradiation easily destroys furan and acrylamide in water. In real foods, however, the reduction of furan was less effective than in water, whereas the reduction in acrylamide was minimal.     

Ionizing radiation induces formation of malondialdehyde, formaldehyde, and acetaldehyde from carbohydrates and organic acid

A study was conducted to investigate irradiation-induced formation of malondialdehyde (MDA), formaldehyde (FA), and acetaldehyde (ACT) from fructose, sucrose, glucose, and malic acid solutions. MDA and FA were generated from the carbohydrate solutions upon irradiation while little was formed from malic acid solution. On the other hand, a much higher amount of ACT was formed from malic acid than from the carbohydrate solutions. The G values (number of molecules formed per 100 eV radiation) for MDA were 0.042, 0.0066, and 0.0026 from 0.9 mg mL(-1) fructose, sucrose, and glucose solutions at pH 3.5, respectively. The G values for FA formation were 0.134, 0.233, and 0.0081 from the fructose, sucrose, and glucose solutions, respectively. As concentration of sugars in solutions increased from 0 to 90 mg mL(-1), the formation of these compounds increased rapidly. A further increase in sugar concentration from 90 to 900 mg mL(-1) resulted in a lower rate of increase in MDA and FA formation. pH had a profound effect on the irradiation-induced formation of these compounds from carbohydrates, especially on MDA formation. The minimum amount of MDA from fructose and glucose solutions was observed at pH 5 while formation of MDA from sucrose solution decreased as pH decreased from 7 to 2. The results can be used by the food industry to optimize food formulation in order to minimize formation of these compounds.     

Formation of a seed germination promoter from carbohydrates and amino acids

The ability of plant-derived smoke to act as a germination cue in many species has led to widespread interest in this aspect of seed biology. Recently, 3-methyl-2H-furo[2,3-c]pyran-2-one was identified as the main germination cue from smoke. Here, we report on the formation of this compound from reactions of sugars with amino acids. Heating proteins or amino acids with sugars at 180 degrees C for 30 min produces water soluble extracts that promote germination. High-performance liquid chromatography indicated that the active compound(s) derived from these reactions coeluted with the active fraction from a smoke solution. Gas chromatography-mass spectroscopy showed that the active constituent is identical to the germination cue from plant-derived smoke. The results presented in this paper provide evidence for the formation of the major germination cue found in smoke from ubiquitously occurring organic compounds.     

Bioaccessibility of tocopherols, carotenoids, and ascorbic acid from milk- and soy-based fruit beverages: influence of food matrix and processing

A study was made of the effect of high-pressure processing (HPP) and thermal treatment (TT) on plant bioactive compounds (tocopherols, carotenoids, and ascorbic acid) in 12 fruit juice-milk beverages and of how the food matrix [whole milk (JW), skimmed milk (JS), and soy milk (JSy)] modulates their bioaccessibility (%). HPP (400 MPa/40 °C/5 min) produced a significant decrease in carotenoid and ascorbic acid bioaccessibility in all three beverages and maintained the bioaccessibility of tocopherols in JW and JS while decreasing it in JSy. TT (90 °C/30 s) produced a significant decrease in tocopherol and carotenoid bioaccessibility in all three beverages and increased the bioaccessibility of ascorbic acid. With regard to the food matrix, α-tocopherol and ascorbic acid bioaccessibility was greatest in JW beverages and lowest in JSy beverages, whereas no significant differences were found among the three beverages in terms of carotenoid bioaccessibility. HPP-treated samples showed higher tocopherol and carotenoid bioaccessibility than TT-treated samples, thus indicating that HPP combined with a milk matrix positively modulates the bioaccessibility of certain types of bioactive components of food, mainly those of a lipophilic nature.     

Changes in carotenoid and ascorbic acid contents in fruits of different tomato genotypes related to the depletion of UV-B radiation

The aim of the present study was to investigate if the depletion of UV-B radiation affected the most representative carotenoids as well as the ascorbic acid content in tomato fruits, harvested at both breaker and firm red stages. To do this, three tomato genotypes, DRW 5981, HP 1, and Esperanza, were grown inside a greenhouse either covered with polyethylene transparent to UV-B or depleted of UV-B by a special covering film. The antioxidant properties of the fruits were evaluated on the water-insoluble fractions according to the ABTS method. UV-B effect on antioxidant activity was negligible in DRW and HP 1 genotypes, whereas it was detrimental in Esperanza at both ripening stages. This genotype seems to have a negligible capability of accumulating carotenoids and a great susceptibility to detrimental effects of UV-B; conversely, the DRW genotype shows high carotenoid levels under sunlight conditions and a further promotion by UV-B. On the other hand, the HP 1 mutant displays an intermediate behavior and represents the only genotype favored by UV-B with respect to ascorbic acid accumulation.     

Meat and ascorbic acid can promote Fe availability from Fe-phytate but not from Fe-tannic acid complexes

This study utilized an in vitro digestion/Caco-2 cell model to determine the levels of ascorbic acid (AA) and "meat factor" needed to promote Fe absorption from Fe complexed with phytic acid (PA) or tannic acid (TA). AA reversed the inhibition of Fe absorption by PA beginning at a molar ratio of 1:20:1 (Fe:PA:AA) but essentially had no effect on the Fe complexed with TA. Fish also reversed the inhibition of Fe uptake by PA but not by TA. TA and fish decreased total Fe solubility. Iron in the presence of PA was highly soluble. AA, but not fish, increased the percentage of soluble Fe as Fe2+ in the presence of both inhibitors. The results indicate that monoferric phytate is a form of Fe that can be available for absorption in the presence of uptake promoters. In contrast, a TA-Fe complex is much less soluble and unavailable in the presence of promoters.     

Identification and thermal degradation kinetics of chlorophyll pigments and ascorbic acid from ditax nectar (Detarium senegalense J.F. Gmel)

Detarium senegalense J.F. Gmel (ditax) is a forest tree found in Senegal the fruits of which are characterized by an attractive green flesh with a high amount in ascorbic acid. It is generally consumed as a nectar in Senegal. In this study, the main pigments of ditax pulp were identified and quantified by HPLC-DAD. Pheophytin a (128 mg/kg), which represents 58% of the total pigments, followed by hydroxypheophytin a' (33 mg/kg), chlorophyll b (24 mg/kg), and chlorophyll a (20 mg/kg) was the major pigment of ditax pulp. Lutein and β-carotene were present in lower amounts (4.6 and 3.6 mg/kg, respectively). The thermal degradation kinetics of pheophytin a, hydroxypheophytin a', and ascorbic acid were determined at temperatures ranging from 60 to 95 °C in ditax nectar. Pheophytin a was the most heat sensitive. Thermal processing induced the formation of degradation products such as pyropheophytin a and pyropheophytin b. The kinetics parameters have been calculated according to the models of Arrhenius, Eyring, and Ball. Following the Arrhenius relation, activation energies of pheophytin a, hydroxypheophytin a', and ascorbic acid were, respectively, 79, 74, and 46 kJ mol(-1). Losses calculated during isothermal treatments were close to experimental losses in pheophytin a, hydroxypheophytin a', and ascorbic acid. The Eyring model can then be used to predict chlorophyll pigments and vitamin C losses during pasteurization of the nectar (<10%).     

Formation of tetracycline degradation products in chicken and pig meat under different thermal processing conditions

Tetracycline (TC) and 4-epitetracycline (4eTC) degradation, as well as anhydrotetracycline (ATC) and 4-epianhydrotetracycline (4eATC) formation, has been evaluated in thermally treated chicken breast, pig loin, and pig loin with added back-fat. Samples containing TC and 4eTC residues were submitted to microwave or boiling heating, extracted with a mixture of McIlvaine buffer/methanol (75:25), and analyzed by high-performance liquid chromatography-diode array detection on a phenyl-hexyl reverse phase chromatographic column. The formation of ATC and 4eATC, as well as of two unidentified compounds, was described for the first time in edible meat samples submitted to mild thermal treatments, similar to those applied at home to cook foods. Degradation of TC and 4eTC and formation of ATC and 4eATC versus time of treatment fitted satisfactorily a first-order kinetic. Even if the potential toxic effects of these breakdown compounds should be further investigated, their formation in cooked meat should be taken into account when maximum residue limits are established.     

Formation of furan and methylfuran by maillard-type reactions in model systems and food

The formation of furan and 2-methylfuran was studied in model systems based on sugars and selected amino acids. Both compounds were preferably formed under roasting conditions in closed systems yielding up to 330 micromol of furan and 260 micromol of 2-methylfuran per mol of precursor. The amounts obtained under pressure cooking conditions were much lower, usually below 20 micromol/mol, except for 2-furaldehyde, which yielded 70-100 micromol/mol of furan. Labeling studies indicated two major formation pathways for both furans: (i) from the intact sugar skeleton and (ii) by recombination of reactive C(2) and/or C(3) fragments. Under roasting conditions in the absence of amino acids, furan was mainly formed from the intact sugar skeleton. Formic and acetic acid were identified as byproducts of sugar degradation, indicating the split off of C(1) and/or C(2) units from hexoses. The presence of alanine, threonine, or serine promoted furan formation by the recombination of C(2) fragments, such as acetaldehyde and glycolaldehyde, which may originate from both sugars and amino acids. In aqueous solution, about half of furan was generated by the recombination of sugar fragments. 2-Methylfuran was preferably formed in the presence of amino acids by aldol-type reactions of C(2) and C(3) fragments with lactaldehyde as a key intermediate, the Strecker aldehyde of threonine. The total furan levels in cooked vegetables were increased by spiking with hexoses. However, in pumpkin puree, only about 20% of furan was formed from sugars, preferably from the intact carbon skeleton.     

Golfer exposure to chlorpyrifos and carbaryl following application to turfgrass

Exposure of golfers to pesticides following their application to turfgrass is of concern to regulators, turfgrass professionals, and consumers. Multipathway exposures were evaluated for golfers on turfgrass treated with chlorpyrifos and carbaryl. Air concentrations and transferable foliar residues (TFRs) were measured to assess potential respiratory and dermal exposures, respectively. At the same time, exposure to individuals simulating the play of golf was determined by dosimetry and urinary biomonitoring. Individual golfer exposure was determined in 76 rounds of golf following eight applications of chlorpyrifos and two applications of carbaryl. Estimated exposures to golfers following full course and full rate applications of chlorpyrifos and carbaryl were 19-68 times below current U.S. EPA acute reference dose (Rfd) values, indicating safe exposures under U.S. EPA hazard quotient criteria. Dermal exposure was determined to be the dominant exposure pathway to golfers, accounting for approximately 60% of the chlorpyrifos absorbed dose and 100% of the carbaryl absorbed dose. This study also provides a set of transfer factors (TFs) that may be used to determine dermal exposure of golfers to pesticides using transferable residue data.     

Thermal stability of ascorbic acid and ascorbic acid oxidase in african cowpea leaves ( Vigna unguiculata ) of different maturities

Cowpea, an African leafy vegetable ( Vigna unguiculata ), contains a high level of vitamin C. The leaves harvested at 4-9 weeks are highly prone to vitamin C losses during handling and processing. Therefore, the purpose of this research was to study the effect of thermal treatment on the stability of ascorbic acid oxidase (AAO), total vitamin C content (l-ascorbic acid, l-AA), and dehydroascorbic acid (DHAA) and l-AA/DHAA ratio in cowpea leaves harvested at different maturities (4, 6, and 8 weeks old). The results showed that AAO activity, total vitamin C content, and l-AA/DHAA ratio in cowpea leaves increased with increasing maturity (up to 8 weeks). Eight-week-old leaves were the best source of total vitamin C and showed a high ratio of l-AA/DHAA (4:1). Thermal inactivation of AAO followed first-order reaction kinetics. Heating at temperatures above 90 °C for short times resulted in a complete AAO inactivation, resulting in a protective effect of l-AA toward enzyme-catalyzed oxidation. Total vitamin C in young leaves (harvested at 4 and 6 weeks) was predominantly in the form of DHAA, and therefore temperature treatment at 30-90 °C for 10 min decreased the total vitamin C content, whereas total vitamin C in 8-week-old cowpea leaves was more than 80% in the form of l-AA, so that a high retention of the total vitamin C can be obtained even after heating and/or reheating (30-90 °C for 10 min) before consumption. The results indicated that the stability of total vitamin C in situ was strongly dependent on the plant maturity stage and the processing conditions applied.     

Stabilizing effect of ascorbic acid on flavan-3-ols and dimeric procyanidins from cocoa

Cocoa flavanols and procyanidins have numerous biological activities. It is known that (-)-epicatechin, (+)-catechin, epicatechin-(4beta-8)-epicatechin (dimer B2), and epicatechin-(4beta-6)-epicatechin (dimer B5) are unstable at physiologic pH, degrading almost completely within several hours, whereas they are relatively stable at pH 5.0. The present study investigated the effects of ascorbic and citric acid on the stability of monomers and dimers in simulated intestinal juice (pH 8.5) and in sodium phosphate buffer (pH 7.4). The addition of ascorbic acid to the incubation mixture significantly increased the stability of the monomers and dimers, whereas the addition of citric acid provided no protective effects. LC-MS showed that with the degradation of dimer B2 and dimer B5, doubly linked A-type dimers were formed. The present results, although not directly transferable to in vivo conditions, suggest that ascorbic acid may stabilize cocoa flavanols and procyanidins in the intestine where the pH is neutral, or alkaline, before absorption.     

One-step production of a biologically active novel furan fatty acid from 7,10-dihydroxy-8(E)-octadecenoic acid

Furan fatty acids (F-acids) gain special attention because they are known to play important roles in biological systems including humans. Specifically, F-acids are known to have strong antioxidant activitis such as radical scavenging activity. Although widely distributed in most biological systems, F-acids are trace components and their biosynthesis is complicated and quite different by sources. On the basis of biochemical study, they are considered to be an essential nutritional factor for mammals and should be provided through the diet. Hence, several studies reported the chemical synthesis of F-acids using chemical catalysts. However, chemical synthesis required complicated multiple steps. In this study was developed a simple one-step synthesis of a novel F-acid, 7,10-epoxyoctadeca-7,9-dienoic acid (EODA), from a dihydroxyl fatty acid, 7,10-dihydroxy-8(E)-octadecenoic acid (DOD), by heat treatment. The structure of EODA was confirmed by GC-MS, NMR, and FTIR analyses, and maximum production yield under the reaction conditions of 90 °C and 24 h reached 80%.     

Elevated UV-B radiation modifies the extractability of carbohydrates from leaf litter of Quercus robur

We examined the influence of elevated UV-B radiation on the extractability of carbohydrates from leaf litter of Quercus robur. Saplings were exposed to a 30% elevation above the ambient level of erythemally weighted UV-B (280-315 nm) radiation for eight months at an outdoor facility. UV-B radiation was applied under arrays of fluorescent lamps filtered with cellulose diacetate, which transmitted both UV-B and UV-A (315-400 nm) radiation. Saplings were also exposed to elevated UV-A radiation under arrays of polyester-filtered lamps and to ambient radiation under arrays of non-energised lamps. Abscised leaves were collected, ground and sequentially treated with seven solvents in order to fractionate extractable carbohydrates based on the way in which they are held in the cell wall. Elevated UV-B radiation reduced the extractability of carbohydrates from cell walls of Q. robur. Sodium phosphate buffer at pH 7 extracted 10% less total carbohydrate from leaf material exposed during growth to elevated UV-B radiation under cellulose diacetate-filtered lamps than from leaf material grown under polyester-filtered and non-energised lamps. The cumulative amount of carbohydrate released by sequential extraction with phosphate buffer, CDTA, urea and sodium carbonate was between 5.1% and 7.8% lower from leaf material grown under cellulose diacetate-filtered lamps relative to that from leaves grown under non-energised lamps. Abscised leaves were also digested with Driselase, an enzyme mixture extracted from a basidiomycete fungus. No effects of elevated UV radiation were recorded on the amount of carbohydrate released by Driselase digestion. Regression analyses, using data from a previous field decomposition study, suggested that reduced availability of carbohydrates enhanced the colonisation of Q. robur litter by basidiomycete fungi, which then accelerated the decomposition rate of the litter in soil. We recommend that future studies into the effects of UV-B radiation on plant litter decomposition measure not only the concentrations of chemical constituents of litter, but also determine the availability of litter carbon sources to soil microbes, using methods similar to those used here.     

Browning in ethanolic solutions of ascorbic acid and catechin

Nonenzymatic browning occurs readily in alcoholic beverages and degrades their color quality. Ascorbic acid degradation in the presence of phenolic compounds is a major browning pathway in alcoholic beverages with fruit or fruit juice as the raw material or an ingredient. In the present study ethanolic solutions of ascorbic acid and catechin were prepared to simulate the alcoholic beverages. Ascorbic acid degradation and browning in these model solutions were investigated. Glycerol solutions with the same water activity (A(w)) values as those of the ethanolic model solutions were used as controls in the evaluation of browning rate. Results showed that the aerobic degradation of ascorbic acid dominates over the anaerobic one in ethanolic solutions, that the browning rate decreases as the ethanol concentration increases, that the compound 3-hydroxy-2-pyrone may not be a good indicator of browning in ethanolic ascorbic acid-catechin solutions, and that A(w) is a major factor responsible for the difference in the browning rate among ascorbic acid-catechin solutions with different ethanol concentrations.     

Evolution of composition and content of soil carbohydrates following forest wildfires

The time evolution of the content and composition of carbohydrates was studied in the surface layer of forest soils non-affected and affected by wildfires. The low- and high-severity fires caused an immediate reduction of the C present as carbohydrates of 34% and 47–55%, respectively, which was due to the decrease of both hexoses and pentoses in two hydrolysis fractions (hydrolysate-A, non-cellulosic polysaccharides; hydrolysate-B, cellulosic polysaccharides). Carbohydrates tended to recover with time; however, values had still not reached the amounts found in the corresponding unburnt samples after 12–15 months. No difference between the unburnt and burnt samples was observed in the distribution of the neutral sugars in the hydrolysates over time. On a percentage basis, 72–92% of the total neutral sugars was extracted in hydrolysate-A (59 ± 7% hexoses; 24 ± 7% pentoses) and the rest, 8–28%, in hydrolysate-B (15 ± 5% hexoses; 2 ± 1% pentoses). The contribution of hexoses and pentoses to the neutral sugar pool was different between the two hydrolysis fractions being the hexoses/pentoses ratio higher for hydrolysate-B than for hydrolysate-A. The results also showed that the proportion of soil C present as carbohydrates-C rather than the total carbohydrates content should be used for monitoring short- and medium-term changes induced by fire in soil organic matter quality.     

Defining the ascorbic acid crossover from anti-oxidant to pro-oxidant in a model wine matrix containing (+)-catechin

An examination of the ascorbic acid-induced oxidation of (+)-catechin was carried out. Using varying concentrations of ascorbic acid in a model white winebase, it was observed that there are at least two distinct steps in its oxidation process. The first step involves the formation of species that absorb in the visible region of the spectrum, while the second step generates species of less or no absorbance in the visible region. The first step reaches an absorbance maximum when ascorbic acid is completely oxidized. In winebase solutions containing both ascorbic acid and (+)-catechin, the lag period prior to the onset of (+)-catechin oxidation was dependent on the concentration of ascorbic acid. It was also observed that the end of the lag period corresponds to the complete oxidation of ascorbic acid. Xanthylium cations were identified as a species responsible for the increase in absorbance at 440 nm post lag period. The implication of the results, for establishing a chemical basis to the ascorbic acid crossover from antioxidant to pro-oxidant, is discussed.     

Formation of amines and aldehydes from parent amino acids during thermal processing of cocoa and model systems: new insights into pathways of the strecker reaction

A method based on a derivatization with dansyl chloride and LC-MS-MS determination was developed for the quantitation of 2-methylbutyl-, 3-methylbutyl-, 2-phenylethyl-, 3-(methylthio)propyl-, and 2-methylpropylamine. Its application on unfermented, fermented, and roasted cocoas from Ghana and Sulawesi revealed an increase of all amines, except the 3-(methylthio)propylamine, during cocoa fermentation, suggesting an enzymic formation from the parent amino acids isoleucine, leucine, phenylalanine, and valine. However, a much more pronounced formation of most of the amines was measured after roasting of the cocoa, leading to concentrations in the milligrams per kilogram range. This result suggested a new "thermogenic" formation pathway of "biogenic amines". A comparison of the amounts of the amines and the aldehydes in roasted cocoa revealed similar concentrations, for example, for 2- and 3-methylbutanal and the respective amines, whereas the amounts of 2-phenylethylamine were much higher as compared to the amounts of phenylacetaldehyde. Strecker-type model systems, in which each parent amino acid was reacted with 2-oxopropanal, revealed the formation of both the amine and the aldehyde; however, in contrast to cocoa, the concentrations of the aldehydes were always much higher as compared to the amines. The results showed for the first time the thermally induced generation of "biogenic amines" from amino acids. Possible reasons for the different ratios of amines versus aldehydes formed during the roasting of cocoa or the model systems, respectively, are discussed.     

Formation of metal-humic acid complexes by titration and their characterization by differential thermal analysis and infrared spectroscopy

Humic acid (HA) extracted from a Eustis loamy sand (Psammentic Paleudult, Red Yellow Podzolic soil) was flocculated by titration with Al³⁺-, Fe³⁺-, Cu²⁺-, Zn²⁺-, Mn²⁺-, Ba²⁺-, Ca²⁺-, and Mn²⁺-chloride solutions, respectively, to determine possible development of metal-HA complexes, as reported by Flaig et al. (1975), and Tiurin and Kononova (1962). Titration was conducted with HA solutions with an initial pH 11.5 or 7.0. The results indicated that the cations used, except Mg²⁺, yielded insoluble complexes with HA, irrespective of initial pH. After titration, the pH of the metal-HA flocs was 6.0–7.0, which was expected in view of the presence of cation exchange and buffering capacity of HA compounds. More complex formation through electrovalent and covalent bonding by COO^? and phenolic OH groups of the HA molecule was only attained by the use of HA solutions with pH 11.5. On the other hand, less complex formation occurred by the use of HA solutions with an initial pH 7.0, through electrovalent bonding by COO^? groups. Differential thermal analysis (d.t.a.) curves of HA showed shifts in temperatures of the main decomposition peak as a result of flocculation with the different metals. Based on the type of the cations involved, the metal-humic acid flocs could be listed in the following decreasing order of thermal stability: Al³⁺ = Zn²⁺ = Mg²⁺ ≥ HA > Ca²⁺ > Ba²⁺ > Fe³⁺ > Cu²⁺ > Mn²⁺. A systematic relationship could not be found indicating that trivalent ions resulted in the formation of thermally less stable metal-humic acid flocs than divalent ions, as has been reported for HA-metal complexes. Physical mixtures of HA and metal hydroxides exhibited d.t.a. features resembling those of original (nontreated) HA, but not those of the HA-metal flocs.Infrared spectroscopy revealed increased absorption for COO^? vibrations at 1620 and 1400cm^?1 in spectrograms of metal-HA flocs compared to that of original humic acid, a phenomenon explained by many authors to be caused by bonding of the metal ions in hydrated form to the carboxyl or phenolic hydroxyl groups or both of the humic acid molecule. HA-flocs formed from solutions with an initial pH 11.5 had identical i.r. spectra compared with those formed from solutions with an initial pH 7.0.