Decline of pesticide residues from barley to malt.

The fate of dinitroaniline herbicides (pendimethalin and trifluralin), organophosphous insecticides (fenitrothion and malathion), and pyrimidine (nuarimol) and triazole (myclobutanil and propiconazole) fungicides from barley to malt was determined. Several samples for residue analysis were taken after each stage of malting (steeping, germination and kilning). Pesticide residue analysis was carried out by GC/ITMS in selected ion monitoring mode. Pesticides decline along the process, although in different proportions. The carryover of residues after steeping was 45-85%. A good correlation (r > 0.92) was observed between percentages removed after steeping and the P(OW) values of pesticides. The amount remaining after malting ranged from 13 to 51% for fenitrothion and nuarimol, respectively. Steeping was the most important stage in the removal of pesticide residues (52%) followed by germination (25%), and kilning (drying and curing, 23%). During malt storage (3 months) the fall in pesticide residues was not significant. Applying the standard first-order kinetics equation (r > 0.95), the half-lives obtained for the pesticides during malt storage varied from 244 to 1533 days for myclobutanil and nuarimol, respectively.     

Decay of dinitroaniline herbicides and organophosphorus insecticides during brewing of lager beer

This article examines the fate of four pesticides that can be present during the brewing of lager beer. For this purpose, malted barley was spiked at 2 mg/kg with pendimethalin and trifluralin (dinitroaniline herbicides) and fenitrothion and malathion (organophosphorus insecticides). Analyses of pesticide residues were carried out by a gas chromatograph with an electron capture detector, and their identity was confirmed by gas chromatography-mass spectrometry. Cleanup was necessary for the malt and spent grain samples. Beginning with mashing and ending with the final product 4 months later, various samples (spent grain, sweet wort, brewer wort, and beer) were taken to determine the concentration of the targeted residual pesticides during the various beer making phases. In all cases, the residual levels recorded in sweet wort sampled after the mashing phase were below the respective maximum residue limits established by Spanish legislation for barley. Significant proportions of pesticide residues (17 to 40%) were retained on the spent grain. Applying the standard first-order kinetics equation (r > 0.91), the half-lives obtained for the four compounds during the storage of the spent grain (3.5 months) varied from 138 days (fenitrothion) to 192 days (malathion and pendimethalin). Herbicide residues practically disappeared (<0.3%) after wort boiling, whereas the percentages of the remaining insecticides, fenitrothion and malathion, ranged from 3.5 to 4.3%, respectively, at this time. No residues of dinitroaniline compounds were detected in young beer, whereas there was a significant reduction in fenitrothion (58%) and malathion (71%) residues during fermentation. Lagering and filtering processes also reduced the content of the organophosphorus insecticides (33 to 37%). Finally, after the storage period (3 months), the content of fenitrothion was reduced by 75%, with malathion residues being below its detection limit.     

Dissipation of organophosphorus pesticides in wheat during pasta processing

For investigating the carryover of some organophosphorus pesticide residues in the cereal food chain from grain to consumer, a study was set up on durum wheat, semolina and pasta. Pesticide-free durum wheat was placed into a small-scale model of a commercial storage vessel and treated with pesticides (malathion, fenitrothion, chlorpyrifos methyl, and pirimiphos methyl) according to the raw material legislation of Turkey. The residue levels of insecticides were determined in wheat, semolina, and spaghetti produced from stored wheat at various time intervals during five months of storage. A multiresidue analysis was performed using GC equipped with an NPD. The confirmation was performed by GC–MS. The residue levels of insecticides in wheat exceeded the maximum residue limits (MRLs) for wheat. The storage period was generally not effective enough to reduce the residues in wheat to levels below the MRLs. Although a considerable amount of the insecticides remained in the semolina, spaghetti processing significantly reduced residue concentrations in general. Pirimiphos methyl was the most persistent of the insecticides and comparatively less substantial loss occurred during milling and spaghetti processing due to its physicochemical properties.     

Degradation of organophosphorus pesticides in wheat during cookie processing

For investigating carryover of some organophosphorus pesticide residues in the cereal food chain from grain to consumer, a study was set up on wheat bran, flour and cookies, with and without bran. Special emphasis was given to malathion and chlorpyrifos-methyl residues in cookies for better protection of consumers. Pesticide-free wheat was placed in a small-scale model of a commercial storage vessel and treated with these pesticides. The residue levels of insecticides were determined in wheat, as well as in bran, flour and cookies produced from stored wheat at various time intervals during storage. A multiresidue analysis was performed using GC–NPD and GC–MS. Malathion and chlorpyrifos-methyl residue levels were higher than the maximum residue limits (MRLs) in wheat after 240 days of storage. MRLs established by the EC for malathion and chlorpyrifos-methyl in wheat are 8 and 3 mg kg⁻¹, respectively. The residue levels of insecticides in flour samples also exceeded the MRL (2 mg kg⁻¹ for both insecticides). Eight months of storage were not effective for reducing the residues in wheat to the levels below MRLs. Although, considerable amounts of the insecticides remained in the bran and flour, the cookie processing significantly reduced the concentrations in general. Chlorpyrifos-methyl was more persistent than was malathion and comparatively less degradation occurred during milling and cookie processing due to its physicochemical properties.     

The Influence of Barley Storage on Respiration and Glucose‐6‐Phosphate Dehydrogenase During Malting

Malt is produced by the controlled, but limited germination of barley. To produce good quality malt, the barley employed must be able to germinate rapidly and synchronously. Dormancy is a seed characteristic that can interfere with the rapid and uniform germination of barley, thereby reducing the resultant malt quality. Various studies have shown that post harvest storage can be used to remove dormancy and enhance barley germination characteristics and malt quality. Because of its complexity, the fundamental basis of dormancy induction, maintenance and termination remain unknown. Glucose‐6‐phosphate dehydrogenase (G6PDH) is the rate limiting enzyme of the pentose phosphate pathway and has been associated with dormancy decay and increased seed vigor of a variety of different seeds. The aim of this study was to determine if changes in barley germination vigour were associated with respiration and/or G6PDH changes during malting. Commercially grown barley (cv. Gairdner) was obtained from various states of Australia and stored at room temperature for up to 7 months. At 1, 3 and 7 months, samples were taken and stored at ?18°C. The germinative energy (GE) and germinative index (GI) of these samples were measured. Samples were micro‐malted and the α‐amylase activity, respiration rate, and G6PDH activity of the germinating grains were measured at various stages of malting. It was found that storage of barley for up to seven months significantly improved the germination characteristics and increased the α‐amylase activity during malting. However, these improvements were not associated with concomitant changes in respiration rate or G6PDH activity during malting.     

Changes in Germination and Malting Quality During Storage of Barley

To increase brewing yield and efficiency, malts with high extract values, high enzymic activities and good modification are essential. To produce malt that meets these requirements, the barley employed must have minimal post‐harvest dormancy and be able to germinate vigorously. The aims of this study were to determine the extent to which some Australian barley varieties changed during post‐harvest storage, how these changes influenced germination characteristics, enzyme production and malt quality, and, of the germination tests examined, which gave the best indication of a barley's malting potential. Four commercially grown barley samples were obtained, one from Tasmania and three from Victoria. Each sample was stored at room temperature for one year. At monthly intervals, samples were taken and placed at ?18°C. The germinative energy (GE) and germinative index (GI) of these samples were measured. Samples were also micro‐malted and the quality of the malt was assessed using standard EBC methodology. Storage at room temperature positively influenced the germination characteristics of all samples, with concomitant improvements in hydrolytic enzyme production during malting and in a number of malt quality parameters. It was found that, of the germination tests examined, the GI consistently correlated with enzyme activities during malting and with various malt quality parameters thus indicating that the GI is a good indicator of malting potential.     

The effect of boiling on the removal of persistent malathion residues from stored grains

This study aimed at finding the fate of malathion in maize grains and beans stored in a tropical laboratory for 12 months at temperatures of 20-24°C, relative humidity of 42-80% and grain moisture contents of 11.7-12.5% in maize grains and 14.1-15.3% in beans. Malathion and its degradation products malaoxon, malathion α-monocarboxylic acid and β-monocarboxylic acid were found in stored maize grains and beans treated with a mixture of pure radiolabelled malathion and 2% malathion dust after 12 months of storage. A significant percentage of these residues were removed from the grains by cooking in boiling water. Though malathion and its polar metabolites, malathion α- and malathion β-monocarboxylic acids were completely eliminated by boiling, malaoxon was still detected in quite high quantities in the solvent extracts of cooked beans and maize. Addition of NaCl to the grains increased the rate of removal of the residues from both maize grains and beans by boiling water. The data obtained clearly showed a distinction in persistence, distribution and metabolism of malathion between the two types of crop, indicating also that more adverse windy, humid and hot tropical conditions contributed to higher rates of metabolism and loss of the pesticide from the grains. The accuracy and ease of using radiolabelled malathion in investigating its fate and behaviour in the two matrices is shown in this study.     

Efficiency of some technological processes on reducing the residues of malathion and pirimiphos methyl in mature broad bean seeds

Residue study was performed on several insecticides which could contaminate local Egyptian beans. The effect of storage periods and various processing steps on lowering the residues of malathion and pirimiphos methyl in treated seeds and their processed products were investigated. The data indicated that malathion and pirimiphos methyl persisted for more than 90 days on and in stored mature dry broad beans after postharvest treatment. However, stored broad beans could be safely used for human consumption after 90 days when the insecticide residues reached safe levels. Washing removed 69 and 75% of malathion and pirimiphos methyl residues of treated broad beans, respectively. Malathion residue was not detected in various processed products. More than 89 and 99% of malathion residues were absent in dehulled and heated dehulled broad beans. In addition, pirimiphos methyl residues were reduced to 92, 97, 87, 99, 99, and 95% from the initial levels in treated beans following dehulling, cooking of dehulled beans, germination, cooking of germinated beans and cooking of the beans by the common method and under pressure, respectively.     

THE FATE OF THE SULPHUR CONTENT OF MALATHION WHEN APPLIED TO BARLEY USED TO PRODUCE MALT WHISKY

The use of malathion to protect malting barley from infestation by insects led to fears that malt whisky could be tainted by odorous sulphur compounds such as mercaptans derived from the malathion. Laboratory scale experiments in which barley was treated with sulphur-35 radio-labelled malathion, showed that the majority of the sulphur from the malathion was lost in the early stages of processing and that none penetrated to the final distilled spirit. Treatment of malt with the radio-labelled malathion showed that although the majority of the sulphur from the malathion was lost after the infusion and fermentation stages, a small percentage was found in the distilled spirit. However, re-use of the final infusion liquor as the first liquor on the next batch of malt as is common practice, could lead to a slight risk of an accumulation of sulphur compounds until equilibrium is reached.     

Changes in β-glucan and other carbohydrate components of barley during malting

Changes in total (1→3), (1→4)-β-glucan content were followed during the micro-malting of nine varieties of barley with a wide range of malting qualities. These changes were related to estimates of endosperm modification based upon staining with Calcofluor. β-Glucan content declined from an average of 3.54% in the barley to 0.75% in the malt. Pentosan and total starch (including starch-derived oligosaccharides) levels showed comparatively little change during malting. β-Glucan composition of the barley was a poor indicator of malting performance. However, the β-glucan, starch and xylose contents of the malt all showed significant correlations with malt extract. Estimation of malt β-glucan content gave the best indication of malt quality. Direct determination of β-glucan may be of more value in assessing malt quality than indirect techniques based upon assessing modification of stained grains.     

Effect of electron-beam irradiation on the safety and quality of Fusarium-infected malting barley

Utilization of Fusarium-infected barley for malting may lead to mycotoxin production during malting and decreased malt quality. Electron-beam irradiation may prevent safety and quality defects and allow use of otherwise good quality barley. We evaluated electron-beam irradiation for preventing Fusarium growth and mycotoxin production while maintaining barley-malt quality characteristics. Four barley lots with varying deoxynivalenol (DON) concentrations were irradiated at 0, 2, 4, 6, 8, and 10 kGy. Treated barley was malted in a pilot-scale malting unit. Barley and malt were analyzed for Fusarium infection (FI), germinative energy (GE), aerobic plate counts (APC), mold and yeast counts (MYC), and DON. Malt quality parameters included malt extract, soluble protein, wort color, wort viscosity, free amino nitrogen, alpha-amylase, and diastatic power. FI, APC, and MYC decreased in barley with an increase in dosage. The APC and MYC for malts from barley exposed to 8–10 kGy were slightly higher than in other malted samples indicating that irradiation-resistant microflora could flourish during malting. Barley GE significantly decreased (3–15%) at 8–10 kGy. Although irradiation had no effect on DON in raw barley, DON decreased significantly (60–100%) in finished malts prepared from treated barley (6–10 kGy). Malt quality parameters were slightly affected by electron-beam radiation. The results suggest 6–8 kGy may be effective for reducing FI in barley and DON in malt with minimal effects on malt quality.     

The effectiveness of fenitrothion and malathion as grain protectants under bulk storage conditions in New South Wales, Australia

Fenitrothion at 2.5, 5.0 and 6.0 ppm was compared with malathion at 12.0 and 18.0 ppm for the protection of bulk wheat in vertical bin silos, and 10 ppm fenitrothion was compared to 18.0 ppm malathion in horizontal bulk depots. In both types of storage the persistence of the insecticides could be correlated with the temperature and moisture content of the grain. Under the conditions of silo storage, both protectants remained effective against Rhyzopertha dominica, Sitophilus granarius and secondary pests for as long as 19 months. Under the more severe conditions of horizontal bulk storage the higher applications were effective for only 6–7 months. Fenitrothion at one half the application rate of malathion appears to give equivalent protection against the deterioration of stored wheat caused by attack from stored product insect pests.     

Fundamental study on the influence of Fusarium infection on quality and ultrastructure of barley malt

Barley infection with Fusarium species has been a long standing problem for the malting and brewing industries. In this study, we evaluate the impact of Fusarium culmorum infected raw barley on the final malt quality. Barley grains were infected for 5 days at optimum fungal growth conditions. Grains were fully characterized and compared to standard barley grains. Due to fungal infection, germinative energy of infected barley grains decreased by 45%; its water sensitivity increased dramatically, and grains accumulated 199 μg/kg of deoxynivalenol (DON). Barley grains were subsequently malted for 8 days, fully characterized and compared to standard malt grains. Fungal growth behavior was evaluated during malting using a PCR-based assay and mycotoxins were measured using HPLC. Fungal biomass increased in grains, during all stages of malting. Infected malt accumulated 8-times its DON concentration during malting. Kernel ultrastructure was evaluated using scanning electron and confocal laser scanning microscopy. Infected malt grains were characterized by extreme structural proteolytic, (hemi)-cellulolytic and starch deterioration with increased friability and fragmentation. Infected grains had higher protease and β-glucanase activities, lower amylase activity, a greater proportion of free amino and soluble nitrogen, and a lower β-glucan content. Malt loss was over 27% higher in infected malt in comparison to the control. The results of this study revealed that 20% F. culmorum infected barley kernels lead to a significant reduction in malt quality as well as mycotoxin formation.     

Analysis of pesticide residues in bananas harvested in the Canary Islands (Spain)

In this work, 11 pesticides (ethoprofos, dimethoate, diazinon, malaoxon, chlorpyrifos-methyl, fenitrothion, malathion, chlorpyrifos, fenamiphos, buprofezin and phosmet) were analysed in 57 banana samples taken from the local markets of the Canary Islands (Spain). Analyses were carried out by the QuEChERS approach developed for pesticide residue analysis in food, using gas chromatography (GC) with nitrogen–phosphorus detection (NPD). Triphenylphosphate (TPP) was used as internal standard. Recoveries ranged between 67% and 118% with RSD values below 16%. Typical limits of quantification (LOQs) of the method were 0.01–0.14 mg/kg, which are below the EU maximum residue limits (MRLs) established for these compounds in bananas. Chlorpyrifos was detected in 50 samples (88%) in the concentration range 0.03–0.65 mg/kg, malathion in five samples (8.8%) in the concentration range 0.16–0.17 mg/kg, fenitrothion in four samples (7.0%) in the concentration range 0.02–0.10 mg/kg and buprofezin in one sample (1.8%) at 0.15 mg/kg. All these values are below the MRLs established for these compounds except for two samples containing fenitrothion. Among the studied pesticides only chlorpyrifos has a high occurrence in the samples. However, the levels of these residues cannot be considered a serious public health problem according to EU regulations. Because of the high occurrence of chlorpyrifos, its distribution between the pulp and the peel was also investigated. Results show that most of the pesticide remains in the peel and that only amounts between 0.07 and 0.12 mg/kg occur in the pulp even at concentrations in the peel as high as 0.87 mg/kg.     

高压电场低温等离子体对马拉硫磷的降解效能及降解途径

为探索高压电场低温等离子体对水中马拉硫磷的降解效能特性,以电压、作用时间及农药初始浓度为试验因素,采用气相色谱测定马拉硫磷的残留并建立降解动力学模型,利用气相串联质谱分析鉴定马拉硫磷降解产物,并结合傅里叶红外光谱研究低温等离子体对马拉硫磷的降解效能,解析其降解途径。结果表明:马拉硫磷在水中的降解效率随着低温等离子体电压强度及作用时间的延长显著增加(P<0.05);在初始浓度为0.1 μg/mL,50 Hz、80 kV处理180 s后,马拉硫磷降解效率达到79.62%±2.97%。马拉硫磷降解趋势符合一级动力学模型,产生的主要中间降解产物为马拉氧磷、磷酸三乙酯、顺-丁烯二酸二乙酯、反-丁烯二酸二乙酯、O,O,S-三甲基二硫代磷酸酯及2-二甲氧基膦硫酰磺基-4-乙氧基-4-氧丁酸。其中毒性较高的马拉氧磷可进一步降解为毒性较低的磷酸三乙酯。马拉硫磷降解过程中中间产物的形成主要经历了P=S键的氧化及C-S键的断裂两种途径。研究为降解水中农药残留研究提供了新的方法参考。     

Effects of Malting on Phase Transition Behaviour of Starch in Barley Cultivars with Varying Amylose Content

The effect of malting on the phase transition behaviour of starch in barley cultivars with varying amylose content was studied using differential scanning calorimetry (DSC). A slight elevation in the melting transition temperature of amylopectin of malt starch and a pronounced decrease in gelatinisation enthalpy for both malt flour and starch were observed for all samples. Evidence was provided from the calorimetric data and the ¹³C CP/MAS NMR spectra that starch-lipid interactions in the form of complexes are enhanced as a result of malting. There was also a large reduction in the melting transition temperature of the amylose-lipid complexes of malt flours, presumably due to partial degradation of amylose in malt, whereas the transition enthalpies of the complexes increased for both malt flours and starches. The DSC transition characteristics of the three good malting barley cultivars grown in different locations and of their respective malts showed that environmental conditions during starch synthesis have a great influence on starch granule organization, and thereby affect the thermal stability of amylopectin crystallites.     

Effects of temperature and duration of storage on the degradation of malathion residues in dry rapeseed

Rapeseed containing up to 1 ppm malathion and ≤ 10% moisture was stored for up to 32 weeks at 10, 20 and 30°C to determine the time required to reach residue levels of 0.1 ppm. Malathion levels < 0.1 ppm were found only in seed at 20°C, 7.7% moisture content by 32 weeks and at 30°C, 7.1% moisture content by 16 weeks. The malathion degradation rates were related to calculated safe storage times to determine acceptable storage conditions. An improved analytical method of malathion extraction from rapeseed was developed. Manipulation of temperature ≤ 60°C for short periods was ineffective in lowering malathion residues to 0.1 ppm.     

Carbohydrate content and structure during malting and brewing: a mass balance study

A holistic view of the fate of barley starch, arabinoxylan and β-glucan throughout malting and brewing is largely missing. Here, an industrial scale malting trial and pilot brewing trial were performed, and the concentration and structural characteristics of carbohydrates were analysed at 28 key points in the process. The barley starch content decreased during malting from 75.0% to 69.7%. During mashing, malt starch was converted to fermentable sugars (75.3%), dextrin (22.8%) or was retained in spent grains (1.8%). Arabinoxylan was partially hydrolysed during malting. Despite mashing-in at 45°C, no further solubilisation of arabinoxylan was observed during mashing. However, the average degree of polymerisation of the soluble arabinoxylan fraction decreased slightly. During fermentation, the arabinoxylan content decreased to 2.5 g/L. The amount of barley β-glucan decreased gradually in time during malting. Of the solubilised β-glucan, 31% was retained in the spent grains during wort filtration, slightly lowering the β-glucan content in the wort. The β-glucan content remained at 0.5 g/L during fermentation. Sucrose was hydrolysed during mashing, probably by barley invertases. From the total amount of malt used, 41.0% was converted to fermentable sugars. This mashing yield could have been improved by the full hydrolysis to fermentable sugars of the present β-glucan (to 41.1%), the remaining starch in spent grains (to 42.0%) and dextrin in wort (to 50.3%). These results provide more insight into the carbohydrate conversions during malting and brewing and can act as a baseline measurement for future work. © 2020 The Institute of Brewing & Distilling     

Effect of Malting on Protein Metabolism in Two Varieties of Sorghum

The metabolism of albumin, globulin, glutelin and prolamin in two varieties of sorghum recommended as alternatives to barley malt for brewing in Nigeria has been studied. There was a continuous degradation of prolamin and glutelin (storage proteins) with a concomitant rise in albumin and globulin (enzyme proteins) resulting in a synchronous rise in free amino nitrogen (FAN) during malting of SK 5912. On the other hand, all the major proteins in farafara increased at the peak of malting without a synchronous increase in FAN. When compared to the unmalted sorghum digested with external enzymes, only a quarter to half of the groups of amino acids required for yeast nutrition were obtained with malted sorghum. The production of FAN in SK 5912 malt is higher than farafara malt. FAN produced in SK 5912 malt is high enough for lager beer production therefore its recommendation as a local substitute is supported, in part, by this study. © 1997 SCI.     

LIPOLYTIC AND OXIDATIVE CHANGES OF BARLEY LIPIDS DURING MALTING AND MASHING

Lipolytic and oxidative changes of barley lipids were studied during malting and mashing. The amount of lipid decreased by 23% during malting and changes in the composition of lipid classes were minor. On the other hand, during mashing the amount of free fatty acids (FFA) increased which indicated, that lipid hydrolysis had occurred. The same phenomenon was seen when malt flour was soaked in water at 23°C. The triglyceride (TG) and polar lipid (PL) contents were reduced and the proportion of FFA in total lipids was increased. Following similar soaking of barley flour, TG and PL were reduced but the accumulation of FFA and especially linoleic acid (LA) was slight. The results were consistent with the data on lipoxygenase activity (LOX) during malting. During steeping LOX decreased and was 15–20% of the activity of raw barley at the beginning of germination. The activity remained low during germination but rose sharply in the middle of kilning only to decrease again to a very low level at the end of kilning (5%). This in combination with the fact that the proportion of FFA remained high in the soaked malt samples suggests that the oxidation by LOX is negligible in the malt samples. However, the data suggest that mashing of barley, but not that of malt, includes the potential for the formation of highly polar lipid oxidation products.