THE PRESENCE OF TWO DIMETHYL SULPHIDE PRECURSORS IN MALT,THEIR CONTROL BY MALT KILNING CONDITIONS,AND THEIR EFFECT ON BEER DMS LEVELS

The precursor of dimethyl sulphide (DMS) which is formed during barley germination and is present in green malt differs from that present in malt kilned at high (> ～75°C) temperatures in that it cannot be metabolized to DMS by yeast. It is therefore termed ‘inactive’ precursor to distinguish it from the ‘active’ precursor present in kilned malt, which is metabolized to DMS by yeast. During malt kilning, inactive precursor is changed into the active form, but only at temperatures at which destruction of both precursors is also taking place. Therefore, for any kiln there is an optimum temperature range over which maximum conversion of inactive to active precursor can be combined with minimum destruction of both precursors. The DMS in beers brewed from green malt or malts kilned only at low (< ～70°C) temperatures is almost entirely the result of precursor destruction during wort boiling, final levels being governed not only by the conditions of boiling, but also by the extent of losses during fermentation and subsequent processing. In contrast, the DMS in beers brewed from malts kilned at higher temperatures is mostly formed during fermentation, and since beer DMS levels can be related to wort and beer DMS precursor levels, they can be better predicted and controlled. The method used for the measurement of total DMS precursor levels in malts is described in detail.     

THE RELATIONSHIP OF DIMETHYL SULPHIDE LEVELS IN MALT,WORT AND BEER

The half-life for the conversion of malt dimethyl sulphide (DMS) precursor to free DMS has been determined at various temperatures and pH values. At pH 5·2 the half-life of the precursor in wort (S.G. 1·060) at its boiling point is 38 min, and is doubled for each 6°C fall in temperature. At pH 5·5 the half-life at the boiling point is 32·5 min. Knowing the stability of the precursor at the various temperatures in the brewing process, the extent of conversion to free DMS in wort at pitching can be predicted for malt of a given precursor content and for a given set of process conditions. The results of DMS analyses of samples taken during brewery trials are in reasonable agreement with the predicted values. This work involved infusion mashing only, but the same principles apply to decoction mashing. The fate of precursor and free DMS during fermentation and conditioning has been followed on a production scale. With some brews, where high levels of free DMS were present at pitching, much free DMS was lost during fermentation. Also, precursor DMS reappeared in the beer after a few days and there was some increase in the level of free DMS. The DMS precursor in green malt has been isolated by ion-exchange and gel-filtration chromatography. A preparation has been obtained which has 0·6 mol potential DMS per mol amino nitrogen. Thin layer chromatography showed that the preparation and its hydrolysis product had the same R_f values as S-methylmethionine and homoserine respectively.     

ISOLATION AND PARTIAL CHARACTERIZATION OF THE DIMETHYL SULPHIDE PRECURSOR IN GREEN MALT,AND ITS EFFECT ON BEER DIMETHYL SULPHIDE LEVELS

The component from which dimethyl sulphide (DMS) is produced when green malt worts are heated has been purified and its effects on wort and beer DMS levels studied. The green malt precursor can be split into S-methylmethionine and an as-yet uncharacterized ninhydrin-positive component. When the purified precursor is added to worts derived from kilned malts, it is rapidly taken up by yeast, but there is no resulting increase in DMS production. DMS production during fermentation occurs with worts made from kilned malts but not with worts from green malt; however, this difference is not due to an inhibitor being present in green malt worts. The evidence suggests that malt kilning affects the nature as well as the amount of DMS precursor in malts.     

IDENTIFICATION OF THE DIMETHYL SULPHIDE PRECURSOR IN MALT

The heat-labile dimethyl sulphide (DMS) precursor in green malt has been isolated using ion exchange chromatography and gel-filtration under mild conditions. The final preparation had ～0.7 mol potential DMS per mol amino groups. Thin layer chromatography of this preparation, and the gel-filtration behaviour of both crude and purified preparations, showed that the precursor had identical properties to S-methylmethionine (SMM). The DMS precursor in a continental lager malt was also examined. The malt had been kilned under conditions which were expected to lead to a significant content of ‘active’ DMS precursor (reported to be metabolized to free DMS by suitable yeast strains, and contrasting with the ‘inactive’ green malt precursor). The DMS precursor in an extract of this kilned malt had the same elution volume on Sephadex G15 as SMM. There was no evidence for any difference from the DMS precursor in green malt. It is concluded that SMM is the only heat-labile DMS precursor in malt.     

Low temperature brewing using cells immobilized on brewer’s spent grains

A biocatalyst, prepared by immobilization of the psychrotolerant yeast strain Saccharomyces cerevisiae AXAZ-1 on delignified brewer’s spent grains, was used for brewing at very low temperatures, resulting in beers with fine clarity, excellent quality and mature character after the end of primary fermentation. Fermentation times were low (only 20 days at 0 °C), while ethanol and beer productivities were high, showing suitability of the biocatalyst for very low temperature brewing. Diacetyl (61–167 ppb), 2,3-pentadione (32–109 ppb) and DMS (11–37 ppb) concentrations in all the green beers were low (the lowest values being those found in beers produced at 0–5 °C). GC/GC–MS analysis showed significant quantitative differences in the composition of aroma volatiles, revealing an impact of fermentation temperature on organoleptic qualities. The increased productivities and fine quality of the products, with low vicinal diketone, DMS and amyl alcohol concentrations, may allow elimination of maturation time, resulting in reduction of production and investment costs.     

CONTROL OF THE DIMETHYL SULPHIDE CONTENT OF BEER BY REGULATION OF THE COPPER BOIL

In pilot brewing trials where wort boil time was varied from 15 min up to 2 hours the DMS contents of the resultant beers were greatly altered without substantial effect on many other aspects of beer quality. The worts were separately fermented by two yeast strains and a consistent difference between DMS levels of the pairs of beers was found which was almost independent of the boil time. The breakdown of the malt-derived DMS precursor in boiling wort was found to be a first order reaction having a rate constant of about 0.02 min^?1, implying a half life of about 35 min. The breakdown rate of S-methylmethionine in a boiling sucrose solution at pH 5.3 was similar. Free DMS was found to leave this wort substitute rapidly, again as a first order process, but with a rate constant of 0.18 min^?1 (t_1/2 ～ 4 min) when the evaporation rate was 17%/h.     

二甲基硫的形成与控制

啤酒中过高的二甲基硫（DMS）含量会影响啤酒的风味。简术DMS的形成途径和影响DMS其前驱物质形成的因素,并提出控制啤酒中DMS含量的措施。     

啤酒酿造中二甲基硫、甲基蛋氨酸、二甲基亚砜含量的变化与控制

为控制啤酒风味物质二甲基硫（dimethyl sulfide,DMS）的含量,实验运用气相色谱-氢火焰离子化检测器测定了15 种国内市售啤酒样品DMS的含量,并研究了啤酒酿造中DMS、甲基蛋氨酸（S-methylmethionine,SMM）、二甲基亚砜（dimethyl sulfoxide,DMSO）的含量变化。结果表明,抽取的国内市售啤酒样品中有47%的样品DMS含量超出60 μg/kg,特别是爱尔啤酒（Ale）中71%的样品DMS含量超出60 μg/kg,最高值达到105 μg/kg;实验抽检10 种国内市售麦芽DMS、SMM、DMSO含量,不同麦芽间DMS与二甲基硫前驱体（dimethyl sulfide precursor,DMSP）差异较大,差异最高达160%,且多数小麦芽的DMS与DMSP含量低于澳麦芽。实验研究了麦汁煮沸、发酵过程中的DMS及DMSP含量的变化,在100 ℃、pH 5.6时,麦汁煮沸40 min后DMS含量比初始含量降低92%,SMM的半衰期为31 min。发酵过程中DMS含量在发酵旺盛期时有明显的下降,最高下降41%。     

Enzyme inhibition and enzyme-linked immunosorbent assay methods for carbamate pesticide residue analysis in fresh produce

An acetylcholinesterase inhibition method was employed for detection of 21 carbamate pesticides in bananas, peaches, strawberries, and tomatoes. Each of these four agricultural commodities was spiked with 0.1 to 10 ppm of each of the 21 carbamates and individual detection levels were determined. Similar responses and detection limits were observed for all four produce when tested for a given carbamate. The detection levels ranged from 0.1 ppm for carbofuran and 3-hydroxycarbofuran to 6 ppm for promecarb and aldicarb sulfoxide. These results are generally at or below the tolerances established by the Environmental Protection Agency for these commodities. Positive samples from the enzyme inhibition screening were also analyzed with the carbaryl-specific enzyme-linked immunosorbent assay (ELISA) kit. The detection limits for carbaryl and carbofuran were 2.0 ppb and 8.0 ppb, respectively. The other carbamates did not exhibit cross-reactivity even at high ppb levels. Thus, the enzyme inhibition assay and ELISA are simple and fast screening procedures for the detection of carbamate pesticide residues in food commodities.     

Some insights into the gas chromatographic determination of reduced sulfur compounds (RSCs) in air

The analytical properties of four reduced sulfur compounds (RSCs), including hydrogen sulfide (H2S), methyl mercaptan (CH3SH), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS), were investigated to improve the techniques for their measurements at sub-part-per-billion (sub-ppb) concentration levels. Forthis purpose, a gas chromatographic (GC) system with a pulsed-flame photometric detector (PFPD) was interfaced with a thermal desorption (TD) unit for the collection and analysis of RSCs in ambient air. The calibration results obtained by working standards of equimolar concentrations (prepared at five different concentrations of 5, 10, 20, 50, and 100 ppb) were evaluated to properly describe the detection characteristics of the GC/ PFPD setting and of different RSCs. It was observed that the absolute magnitude of calibration slopes changed among different S compounds in a consistent manner (e.g., enhanced sensitivity toward the compound of heavy molecular weight and/or high sulfur contents), while their full scales of linearity range varied in an opposite pattern. The absolute magnitude of the H2S calibration slope values was remarkably sensitive to the initial standard concentrations, while such effects were not so evident from other RSCs. The overall results of this study suggest that the GC detection of H2S by means of the bag sampling technique can suffer from the strongest variability due to the dynamic change of its calibration in accord with its initial concentration.     

Moisture content,insect pest infestation and mycotoxin levels of maize in markets in the northern region of Ghana

Reliable quantitative data on maize post-harvest losses and factors that cause them in northern Ghana are limited. In this study we assessed maize at six markets in the Northern Region of Ghana, in and around Tamale, during the harvest and storage period of October 2015–June 2016. Across all the markets and sampling periods grain temperature was 32.6 ± 0.2 °C and equilibrium moisture content (EMC) was 9.5 ± 0.2%. EMC tended to decrease to a low in January and February and then increased again, while mean maize temperature was above 30 °C in all months. The primary stored product insects collected from the samples were Tribolium castaneum (Herbst), Sitophilus spp., Rhyzopertha dominica (Fauvel), and Cryptolestes ferrugineus (Stephens). Using all the market and sampling month data, there was a significant correlation between EMC and total number of insects recovered, but not between total number of insects and temperature. The average percentage of insect-damaged kernels (IDK) in the maize sampled across all the markets and sampling periods was 2.7 ± 0.2%, with a range between 0 and 21.4%. Using all the market and sampling month data, levels of insect damage tended to be positively correlated with maize moisture, but not temperature, and levels of insect damage increased with number of stored product insects recovered. The action threshold for aflatoxin in maize in Ghana is 15 ppb, but overall mean aflatoxin level was 19.8 ± 1.5 ppb and aflatoxin levels ranged from 0.3 to 132.2 ppb, with 53% of the samples having levels above 15 ppb. The mean fumonisin level was 1.2 ± 0.0 ppm, which is below the 4.0 ppm action threshold for Ghana. Our results show that aflatoxin levels were high in the market maize in Northern Region of Ghana and insects were prevalent, even though grain moisture tended to be relatively low, especially compared to the Middle Belt of Ghana.     

Ozone-initiated chemistry in an occupied simulated aircraft cabin

We have used multiple analytical methods to characterize the gas-phase products formed when ozone was added to cabin air during simulated 4-hour flights that were conducted in a reconstructed section of a B-767 aircraft containing human occupants. Two separate groups of 16 females were each exposed to four conditions: low air exchange (4.4 (h-1)), <2 ppb ozone; low air exchange, 61-64 ppb ozone; high air exchange (8.8 h(-1)), <2 ppb ozone; and high air exchange, 73-77 ppb ozone. The addition of ozone to the cabin air increased the levels of identified byproducts from approximately 70 to 130 ppb at the lower air exchange rate and from approximately 30 to 70 ppb at the higher air exchange rate. Most of the increase was attributable to acetone, nonanal, decanal, 4-oxopentanal (4-OPA), 6-methyl-5-hepten-2-one (6-MHO), formic acid, and acetic acid, with 0.25-0.30 mol of quantified product volatilized per mol of ozone consumed. Several of these compounds reached levels above their reported odor thresholds. Most byproducts were derived from surface reactions with occupants and their clothing, consistent with the inference that occupants were responsible for the removal of >55% of the ozone in the cabin. The observations made in this study have implications for other indoor settings. Whenever human beings and ozone are simultaneously present, one anticipates production of acetone, nonanal, decanal, 6-MHO, geranyl acetone, and 4-OPA.     

CAMBRIDGE PRIZE LECTURE DIMETHYL SULPHIDE—ITS ORIGIN AND CONTROL IN BREWING

The fate of dimethyl sulphide (DMS) and its precursors, S-methylmethionine (SMM) and dimethyl sulphoxide (DMSO), in the malting and brewing processes, has been studied on both a laboratory and a production scale. The information gained has been used to show how the level of DMS in beer may be controlled. The principal determinant of the beer DMS level was the SMM present in malt. DMSO was not a significant precursor of DMS in normal lager production.     

Enhanced production of oceanic dimethylsulfide resulting from CO₂-induced grazing activity in a high CO₂ world

Oceanic dimethylsulfide (DMS) released to the atmosphere affects the Earth's radiation budget through the production and growth of cloud condensation nuclei over the oceans. However, it is not yet known whether this negative climate feedback mechanism will intensify or weaken in oceans characterized by high CO(2) levels and warm temperatures. To investigate the effects of two emerging environmental threats (ocean acidification and warming) on marine DMS production, we performed a perturbation experiment in a coastal environment. Two sets of CO(2) and temperature conditions (a pCO(2) of ～900 ppmv at ambient temperature conditions, and a pCO(2) of ～900 ppmv at a temperature ～3 °C warmer than ambient) significantly stimulated the grazing rate and the growth rate of heterotrophic dinoflagellates (ubiquitous marine microzooplankton). The increased grazing rate resulted in considerable DMS production. Our results indicate that increased grazing-induced DMS production may occur in high CO(2) oceans in the future.     

Mycoflora and Aflatoxin Content of Hazelnuts,Walnuts, Peanuts,Almonds and Roasted Chickpeas (LEBLEBI) Sold in Turkey

In this study, 28 hazelnuts, 24 walnuts, 18 peanuts, 13 almonds, and 11 roasted chickpeas (leblebi) were analyzed for aflatoxin contamination using thin layer chromatography (TLC). Aflatoxin was found in 26 of 94 samples (27.66%) at concentrations ranging from 1 to 113 ppb. Detectable levels of aflatoxin were 33.4 ppb in hazelnuts, 22.1 ppb in walnuts, 43.0 ppb in peanuts, 7.4 ppb in almonds, and 1.7 ppb in roasted chickpeas. The highest level of aflatoxin was 113 ppb in a single hazelnut sample. Aspergillus and Penicillium species were frequently determined in all the samples.     

Dimethyl sulfoxide (DMSO) waste residues and municipal waste water odor by dimethyl sulfide (DMS): the north-east WPCP plant of Philadelphia

This study shows for the first time that overlooked mg/L concentrations of industrial dimethyl sulfoxide (DMSO) waste residues in sewage can cause "rotten cabbage" odor problems bydimethyl sulfide (DMS) in conventional municipal wastewater treatment. In laboratory studies, incubation of activated sludge with 1-10 mg/L DMSO in bottles produced dimethyl sulfide (DMS) at concentrations that exceeded the odor threshold by approximately 4 orders of magnitude in the headspace gas. Aeration at a rate of 6 m3 air/m3 sludge resulted in emission of the DMS into the exhaust air in a manner analogous to that of an activated sludge aeration tank. A field study atthe NEWPCP sewage treatment plant in Philadelphia found DMSO levels intermittently peaking as high as 2400 mg/L in sewage near an industrial discharger. After 3 h, the DMSO concentration in the influent to the aeration tank rose from a baseline level of less than 0.01 mg/L to a level of 5.6 mg/L and the DMS concentration in the mixed liquor rose from less than 0.01 to 0.2 mg/L. Finding this link between the intermittent occurrence of DMSO residues in influent of the treatment plant and the odorant DMS in the aeration tank was the keyto understanding and eliminating the intermittent "canned corn" or "rotten cabbage" odor emissions from the aeration tank that had randomly plagued this plant and its city neighborhood for two decades. Sewage authorities should consider having wastewater samples analyzed for DMSO and DMS to check for this possible odor problem and to determine whether DMSO emission thresholds should be established to limit odor generation at sewage treatment plants.     

Aflatoxins, patulin and ergosterol contents of dried figs in Turkey.

Dried figs of three different categories, palatable, fluorescent, and cull, were investigated for their contents of aflatoxins (B(1), B(2), G(1) and G(2)), patulin, and ergosterol. Samples were obtained from four fig processing plants located in a major fig producing area in the Aegean Region in Turkey. Affinity column clean-up methods were employed for aflatoxins. All aflatoxins, patulin, and ergosterol were determined using high performance liquid chromatography. Palatable figs contaminated with trace amounts of aflatoxins, patulin, and ergosterol, so they posed no risk for the consumer when national and/or international regulatory limits were considered. Fluorescent figs were contaminated with high (117.9-471.9 ppb) aflatoxin levels and cull figs with high patulin (39.3-151.6 ppb) and ergosterol (4.5-18 ppm) levels. The total aflatoxins content was significantly correlated with the patulin content (r(2) = 0.813, p < 0.002) and the ergosterol content (r(2) = 0.920, p < 0.002) only in fluorescent figs. However there was no significant correlation between patulin and ergosterol contents of fluorescent figs. Furthermore, there were no significant correlations between the contents of any two of the three substances in cull figs. This is the first report on the presence of patulin and its co-occurrence with aflatoxin in dried figs.     

Contaminants and levels of occurrence in washed and shredded poly(ethylene terephthalate) from curbside collection. Part 1: Extraction conditions

The aim was to determine which contaminants were present in washed and dried shredded poly(ethylene terephthalate) (PET, flake) obtained from curbside collection and whether the concentrations were above the US FDA threshold of 215 ppb. Thirty-two semi-volatile contaminants were extracted from the treated flake by Soxhlet extraction using dichloromethane as a PET swelling solvent and gas chromatography-mass spectrometry (GC-MS) was used for identification and quantification. Soxhlet extraction of flake ground to 0-300 pm was effectively completed in 24 h, whereas sonication reduced the extraction time to 3 h. In contrast, Soxhlet extractions of flake ground to a larger particle size range (300-425 pm) were completed in 4 h, possibly due to less aggregation in the extraction thimble. The levels of 26 contaminants were below 215 ppb, but six were not. Dodecanoic acid was present at about 1200 ppb, 2-butoxyethanol was approximately 1000 ppb, limonene, benzophenone and methyl salicylate were above 800 ppb, and 2-methyl-naphthalene near 215 ppb.     

Carry-Over of Aflatoxins to Fig Molasses from Contaminated Dried Figs

The carry-over of aflatoxins to fig molasses produced by using two different processing techniques from contaminated dried figs (> 1000 ppb of total aflatoxins) were examined by using a HPLC technique. The effects of extraction, bleaching and concentration steps on the reduction of aflatoxin levels were also investigated. The reductions in total aflatoxin levels in fig molasses produced by using the two techniques were detected to be 62 and 38%, respectively. Extraction, bleaching and concentration steps were observed to cause 22% reduction in total aflatoxin levels.     

Rapid determination of tetracycline in milk by FT-MIR and FT-NIR spectroscopy

The feasibility of measuring tetracycline at the ppb levels in milk was investigated by Fourier transform mid-infrared (FT-MIR) and Fourier transform near-infrared (FT-NIR) spectroscopic techniques. Milk samples spiked with different concentrations of tetracycline were scanned using FT-MIR and FT-NIR spectroscopy. Suitable spectral wave number regions were selected for principal least square (PLS) regression models development. Prediction errors were high when the calibration model was developed using the wide range of tetracycline concentrations (4 to 2000 ppb) in milk. Maximum correlation coefficient (R2) value of about 0.89 was obtained for the validation models developed using different concentration ranges. Prediction errors were high for FT-NIR method. Results indicated that FT-MIR spectroscopy could be used for rapid detection of tetracycline hydrochloride residues in milk.