Identification of a stale-beer-like odorant in extracts of naturally aged beer

For a long time, beer staling has been a prime concern in brewery research. Yet, to improve flavor stability, better knowledge of all chemicals involved is still needed. From our aroma extract dilu-tion analyses (AEDA) applied to naturally aged lager beers emerged an old-beer-like odorant at RICP-SIL 5 CB = 1532 and RIFFAP = 2809, with a FD value close to that of trans-2-nonenal (the well-known cardboard off-flavor found in aged beers). Specific phenol extraction, GC cold trapping, and mass spectrometry (electron impact and chemical ionization) enabled us to identify it as 4-vinylsyringol. Although already mentioned in some fresh beers, this compound had never been highlighted as involved in the aging process of lager beers.     

Involvement of flavanoids in beer color instability during storage

Besides Maillard reactions, structural rearrangements of flavan-3-ol monomers cause color changes in beer during storage. Acetone/water-soluble fractions (70/30, v/v) of three lager beers of the same batch, differently stabilized before bottling in glass or poly(ethylene terephthalate) (PET) bottles, were monitored by normal-phase HPLC-ESI(-)-MS/MS over a 1-year period of storage at 20 degrees C. In parallel, beer color was monitored by the European Brewery Convention assay. The evolution of color was similar in the silica gel-filtered beer to that in identically bottled and stored poly(vinylpolypyrrolidone)-treated samples, despite the high flavanoid dimers content of the former. On the other hand, color evolved more rapidly in the PET bottle, suggesting a key role of oxygen. The kinetics was still increased in model media containing (+)-catechin, while no color was detected when normal-phase HPLC-fractionated dimers or trimers were investigated. (+)-Catechin emerged as the precursor of less polar products, characterized by a yellow-brown color. MS/MS enabled us to identify these products as issued from the oxidation and intramolecular additions of dehydrodicatechin B4. Similar structures were found in aged beers spiked with (+)-catechin. Beer storage in the absence of oxygen and at low temperature is recommended so as to minimize the synthesis of such pigments.     

Effects of weathering on metal releases from an engineered deposit for alum shale leaching residues

A pile of ca 15,000 t of crushed alum shale leaching residues from uranium refining was deposited in Ranstad, Sweden, in 1972 as a part of a pilot study of various waste storage concepts. A field study has been performed in order to evaluate the efficiency of the engineered barriers (bentoniteltill or crushed limestone) for the prevention of weathering of the leaching residues and subsequent release of metal rich leachates. The concentration levels of Fe (from pyrite in the alum shale) as well as metals associated with the pyrite (e.g. Cu and Ni) indicate that the weathering of leaching residues underneath the cover has progressed to less than 4 cm in 15 yr. No breakthrough of precipitation is indicated from the composition of the percolation water coming from the deposit. Thus, the weathering rate is reduced by ca 3 orders of magnitude in comparison with leaching residues freely exposed to air and precipitation.     

Combinatorial synthesis and sensorial properties of polyfunctional thiols.

Over the past few years, polyfunctional thiols present as trace components have been found to play a major role in many food flavors, due to their exceptionally low odor thresholds. Unfortunately, their presence in minute concentration (in ng/kg to a few microg/kg) and their high reactivity make it very difficult to extract and identify them. Furthermore, most of them are not yet commercially available. The aim of this work was to characterize the chromatographic and sensorial properties of 10 synthetic mercaptoketones and mercaptoalcohols. Combinatorial chemistry proved to be a very useful way to synthesize them rapidly. Sulfur-selective sulfur chemiluminescence detection chromatograms coupled with mass spectroscopy enabled the target compounds to be identified. Flavor profiles and best estimate gas chromatography lowest amount detected by sniffing (BE-GC-LOADS) values were further determined by GC-olfactometry. As expected, new, exceptionally odorant molecules (BE-GC-LOADS < 0.1 ng) were revealed by this unusual approach.     

Release of deuterated (E)-2-nonenal during beer aging from labeled precursors synthesized before boiling

Although lipid autoxidation in the boiling kettle is a key determinant of the cardboard flavor of aged beers, recent results show that mashing is another significant source of wort nonenal potential, the well-known indicator of how a beer will release (E)-2-nonenal during storage. Although unstable, deuterated (E)-2-nonenal nitrogen adducts created during mashing can in some cases partially persist in the pitching wort, to release deuterated (E)-2-nonenal during beer aging. In the experiment described here, the relative contributions of mashing and boiling were estimated at 30 and 70%, respectively. The presence of oxygen during mashing and, to a lesser extent, high lipoxygenase activity can intensify the stale cardboard flavor.     

Evidence of Strecker aldehyde excretion by yeast in cold contact fermentations

A medium containing labeled leucine-d(10) has been used to show that Saccharomyces cerevisiae was able to produce deuterated 3-methylbutanal in a cold contact fermentation. Whereas residual unreduced Strecker aldehydes bound to polyphenols were considered until now as the main defect of alcohol-free beers, yeast emerges from this work as an additional source of worty flavor. When the same experiment was conducted without leucine, 3-methylbutanal excretion also occurred, indicating that valine could be used by yeast as precursor.     

3-methylthiopropionaldehyde as precursor of dimethyl trisulfide in aged beers

Hop S-methylcysteine sulfoxide has previously been postulated as the precursor of dimethyl trisulfide (DMTS) in beers. The present data point to 3-methylthiopropionaldehyde, the Strecker aldehyde issued from methionine, as another potential precursor in aged beers. Spiking either fresh beer or wort before boiling leads in all cases to higher levels of DMTS after storage. Moreover, special malts with a high level of 3-methylthiopropionaldehyde also favor polysulfide synthesis. A higher pH should increase this onion-like off-flavor, whereas a low pH is unfortunately known to enhance the cardboard flavor of aged beers. 3-methylthiopropanol, issued from yeast reducing activity, can be considered as an additional DMTS source during aging.