Dimethyl Sulfide

From Milk The Funk Wiki
Revision as of 15:29, 12 July 2018 by DanABA (talk | contribs)
Jump to: navigation, search

Dimethyl sulfide (DMS), sometimes spelled "dimethyl sulphide" [1], is the simplest type of thioether [2], which are sulfur-containing oils that are generally considered off-putting in beer [3][4]. The flavor and aroma of DMS have been characterized as being like cooked sweetcorn, tomato sauce, celery, or sauerkraut. In beer, it is sometimes confused with methyl thiocetate, ethanethiol, and dimethyl trisulphide. DMS in beer originates from malt-derived precursors, S-methyl methionine (SMM) and dimethyl sulphoxide (DMSO), and to a lesser extent can be formed during fermentation by certain microbes [5]. Small amounts of DMS have also been found in hops, which is volatilized during boiling [6]. The flavor threshold of DMS is 30-50 µg/liter. Low levels above threshold between 30-100 µg/liter are considered acceptable and even beneficial to some lagers in the United Kingdom (but not in Germany) [7] (~25 minutes in), and maybe some traditional farmhouse ales that are not boiled (see Considerations for Historical Examples of Raw Ale). However, amounts above 100 µg/liter are generally considered offensive for any beer. Ales typically have below the flavor threshold of DMS [4]. The basis of the understanding of DMS and it's creation in beer was uncovered in the late 70's and early 80's. DMS is a common compound found throughout nature, including having an importance in cycling sulfur in ecosystems involving algae and other microbes, helping the navigation of seabirds, and is found in many foods such as corn, cabbage, parsley, asparagus, potatoes, beef, Camembert cheese, fish (carp), tea, cocoa, milk, wine, rum, beetroot, black truffles, and seafood [2][8].

Production From Malt

While malted barley contains small but not insignificant amounts of DMS (more than 10 ppm) [2], the primary source of DMS are the precursors S-methyl methionine (SMM) and dimethyl sulphoxide (DMSO), both of which are present in malted barley [4]. When listed on malt analysis sheets they are usually listed as a combined value as "DMS-P" or "DMSP". This value should be between 5-15 ppm for pilsner malts, and less for fully modified malt [9]. DMSP is rarely included on modern malt analysis sheets because it is viewed as much less important than the brewing process [10].

SMM Precursor

The primary source for DMS in beer (as well as cooked vegetables) is caused by the decomposition of SMM into DMS. This decomposition is caused by heat above ~80°C. Levels of SMM in raw barley are initially low, but as the barley is malted the SMM precursor is formed inside the malt. Many factors influence the amount of SMM found in malted barley. SMM amounts are correlated with nitrogen amounts. The longer the barley is stored before malting, the more SMM will be produced. The majority of SMM in malted barley, however, is determined by how the malt is kilned. During kilning temperatures above 70°C the SMM is partially broken down into DMS and homoserine (isothreonine). Some of the DMS is driven off by the high temperatures of kilning due to its high volatility, but the DMS present during kilning can also be oxidized into DMSO. The lower the temperatures are during kilning (such as for pilsner malt), the more the SMM precursor is retained in the malted barley [4][2].

Mashing and Boiling

During mashing, small spikes of DMS have been reported. This has been proposed to be due to the volatility of DMS existing in the malt rather than being converted from SMM (mash infusion temperatures are too low to convert significant amounts of SMM into DMS). When mashing in a closed system, evaporated DMS condenses and falls back into the mash. The small amount of DMS that is produced during the mash is volatilized by the early stages of boiling. Decoction mashing also introduces DMS due to the boiling of the mash and the resulting conversion of SMM into DMS. SMM from the malt is easily dissolved into the wort during mashing [11][4].

Boiling and cooling have the most impact on levels of DMS in beer. At boiling temperatures, SMM is decomposed into DMS. Wilson & Booer showed that SMM's half-life is about 35 minutes at a pH of 5.4, meaning that it takes ~35 minutes to reduce half of the SMM present into DMS [4]. pH plays a role in the reduction of SMM to DMS, with a higher pH reducing the half-life of SMM. Dickenson showed that at a wort pH of 5.2, SMM had a half-life of 38 minutes, but at a pH of 5.5 the SMM has a half-life of 32.5 minutes [12]. It has long been reported that the half-life of SMM doubles for every 6°C cooler, meaning that at 95°C the half-life is ~70 minutes (see the table below) [8]. If the wort is held at a perfectly uniform temperature (which may not reflect real brewery conditions) then the half-life doubles more quickly as the wort cools [6]. During the boil, the converted DMS is evaporated off due to its low boiling temperature of 37.3°C [1] and the convection currents of the boil. Unhomogenized boiling of the wort can be a cause of DMS (e.g. dead-spots where the wort doesn't mix throughout the boil kettle). Calculations have been proposed to determine if this is a problem for a given kettle (see reference) [13].

The largest contribution of DMS from SMM is after boiling the wort and during the chilling process. SMM continues to break down into DMS after boiling and before the wort is completely chilled. DMS formed during this time is mostly retained in the wort due to the wort being still, especially in a closed cooling system where evaporation is prevented completely. Once the wort reaches a temperature of 80-85°C, the decomposition of SMM into DMS is greatly reduced [4]. It has been shown that a longer boil will help decompose the SMM and drive off DMS [14], however if the level of SMM in the malt is high (3-8 µg DMS equivalents/g malt) and more than 50 µg DMS equivalents/liter of SMM survives the boil, then reducing the time in the whirlpool where the wort sits above 80°C can help reduce the amount of DMS in the finished beer. SMM that is not decomposed into DMS during the boil/whirlpool and survives going into the fermenter is not metabolized by yeast, but is also not decomposed into DMS (typical brewing conditions result in little SMM going into the fermenter) [4][8].

Temp°C SMM half-life at ph 5.2 (min) SMM half-life at ph 5.5 (min) [8]
100 38 32.5
94 76 65
88 152 130
82 304 260
76 608 520
70 1,216 1,040

DMSO Precursor

Dimethyl Sulphoxide (DMSO) is the second precursor to DMS and is also present in malted barley. Conversion of DMSO to DMS in beer is a function of microbial activity. DMSO is formed in malted barley during kilning at temperatures above 60°C (ale wort can contain more DMSO than lager wort because of this [8]). Drying the green malt before kilning also increases DMSO (and SMM). DMSO is readily dissolved into water during mashing, and with a boiling point of 189°C, it survives mashing and boiling temperatures. Wort generally contains 200-400 µg of DMSO per liter, with wort made from higher kilned malts containing more DMSO [4][8].

Saccharomyces species convert less than 25% of DMSO into DMS as a side effect of an enzyme whose primary function is to reduce methionine sulfoxide to methionine [8]. In a lab setting with simple glucose-salts and DMSO added, ~13% of DMSO is converted to DMS. However, in wort only ~5% of DMSO is converted to DMS [8], which generally equates to about 5-10 µg/L of DMS [15]. The percentage of DMSO that is converted to DMS does not change as DMSO levels increase, so although low percentages are converted, high amounts of DMSO can still contribute significant DMS. With high levels of DMSO in the wort, a slight increase in DMS from DMSO precursor can be observed towards the end of fermentation from yeast metabolism. This increase in DMS from yeast metabolism has been observed during the conditioning of fermented beer and surprisingly under cold temperatures (0°C in one report), so if yeast is left in the beer then it can convert DMSO to DMS in the packaged beer [4].

Yeast species/strain, temperature, pH, wort composition, and open/closed fermentation vessels contribute to how much DMSO gets converted into DMS. For example, S. uvarum (potentially reclassified to S. bayanus) produces less DMS than S. cerevisiae, as does S. pastorianus [8]. DMSO is converted to DMS by yeast more readily at lower temperatures than warmer temperatures with five times as much at 8°C than at 25°C. Higher gravity worts (1.033 vs 1.060 in the linked reference) also produce more DMS from DMSO during fermentation. A higher pH of wort also leads to more DMS production; for example, lager wort pH is typically 5.4-5.7, while ale wort pH is typically ~5.1. This might explain why DMS is present more in lager beers [4].

Spoilage Organisms and Spontaneous Fermentation

Many types of microbes are capable of producing DMS from DMSO as a secondary metabolite of fermentation. Microbes that can produce high amounts of DMS include gram-negative, facultative anaerobes in the Enterobacteriaceae family, which includes species of Klebsiella, Citrobacter, Enterobacter, Obesumbacterium, Proteus, Salmonella, and Escherichia, as well as gram-negative aerobic bacteria such as Pseudomonas aeruginosa [16][17]. Gram-positive bacteria can also produce high amounts of DMS, such as Bacillus subtilis [17]. These bacteria species can convert 17-37% of DMSO into DMS, whereas S. cerevisiae converts around 5% of DMSO into DMS. Many other bacteria such as species of Clostridium, Streptococcus, and Staphylococcus produce only small amounts of DMS (less than 1% of DMSO converted into DMS) [17]. All bacteria that can produce DMS from DMSO do so with a different enzyme than yeast, which might account for the ability of some bacteria to convert a higher percentage of DMSO to DMS than S. cerevisiae. The DMS production by facultative anaerobic bacteria is encouraged by the lack of oxygen [4].

In lambic production where the pH of the wort is not lowered to less than 4.5 before entering the coolship for spontaneous fermentation, Enterobacteriaceae are responsible for high amounts of DMS production. No DMS was found in the referenced study before the wort was cooled in the coolship, which might be due to the long boil of the wort due to the turbid mash. After two weeks of fermentation, 450 ppb of DMS was found, far more than the 30 ppb taste threshold, and the vegetal aroma of DMS could be detected during the fermentation at this time. After two weeks the fermentation of Saccharomyces begins, and the DMS levels decline due to the formation and blow-off of CO2. At 6 months the DMS was down to 100 ppb, and a range of 25-75 ppb of DMS found in bottles of lambic (and at 16+ months), which is a typical amount for regular ales and lagers [18].

Production From Hops

DMS, as well as the related compounds dimethyl disulfide (DMSD) and dimethyl trisulfide (DMST), can be found in hops in small amounts. The amounts are generally considered so small that they volatilize off during the beer brewing process, however dry hopping has been shown to increase DMS in beer. One study found that lager beer that was dry hopped had 15 ppb more DMS on average. DMST can have a cooked vegetable, or onion-like aroma [19]. DMSD is said to have a garlic-like aroma and flavor [20].

Volatility of DMS

DMS is a very volatile compound. Scheuren et al. (2016) determined that there is not a significant difference in DMS evaporation in water versus wort, and came up with equations for determining the evaporation of DMS in water using the laws of thermodynamics. They presented a somewhat counterintuitive result that DMS actually volatilizes more readily as temperatures drop, until about 50°C (volatilization of DMS drops significantly under 50°C). Their calculations state that 3.2% of the total wort volume needs to be evaporated for 90% of the DMS to volatilize at 100°C, whereas only 1.3% of the total wort volume needs to be evaporated for 90% of the DMS to volatilize at 80°C (keep in mind that the rate of evaporation at 80°C is much slower, and thus it takes more time to reach 1.3% evaporation). This indicates that some amount of DMS is evaporating off at temperatures below boiling until 50°C is reached [21][2]. Therefore, a very vigorous boil is not necessary for boiling off DMS.

They also established that the volatility of DMS is the same regardless of the gravity of the wort and that it is instead affected by temperature, atmospheric pressure, and the concentration of DMS (higher concentration of DMS slightly raises the volatility of DMS). For non-wort solutions, 10% sucrose in water greatly increased the volatility of DMS, possibly due to a salting-out effect of sucrose which leads to a higher evaporation rate for DMS molecules [21]. A larger top surface area will allow for faster evaporation of the total DMS present in the wort, but the total DMS present in the wort would eventually be evaporated off regardless of what the top surface area of the kettle is [2]. In order to limit DMS in the end product, it is advised to allow no more than 100 µg/L of DMS into the fermenter [21].

Much of the DMS in wort that is formed during the wort production process is volatilized off during fermentation due to off-gassing of CO2. However, if high amounts of DMS survive the boil, then the off-gassing from fermentation may not be enough to volatilize all of the DMS. The shape and type of the fermenter also play a role in how much DMS is volatilized during fermentation, for example, Anderson et al. and Booer & Wilson showed that open fermentation leads to less DMS compared to closed fermentation [4]. Higher fermentation temperatures (18°C versus 9-12°C, for example) can lead to higher rates of DMS volatilization [15]. DMS can spike towards the end of fermentation from yeast metabolizing DMSO into DMS (see DMSO Precursor) [4].

Short Boils and Raw Ale

Raw ale, also referred to as "no-boil", is a method of wort production that involves not boiling the wort, or perhaps by some definitions, very short boils [22]. Although mainly a historical method of brewing, this style of brewing has recently become popular in the production of Berliner Weissbier and other styles of beer using wort souring or kettle souring methods. Many recipes for these styles of beer call for pilsner malts to be used, which can contain higher amounts of SMM precursor. An often asked question about no-boil/raw ales and wort boiled for 15 minutes or less is: are there concerns about DMS production?

Anecdotal reports of no issues with DMS in these types of beers seem to far outweigh the reports of DMS problems [23][24][25][22]. The specific nature of (or lack of) DMS detection in no-boil/raw ale has not been widely explored by science. There are, however, some explanations that have been proposed. For example, when boiling smaller volumes of wort such as on the homebrew scale there is a larger surface area to volume ratio. This larger surface area to volume ratio allows for more evaporation and volatilization of DMS to occur [7] (~30 minutes in). Smaller fermenters would also benefit from a larger surface area to volume ratio since CO2 from fermentation volatilize DMS. This may account for the general lack of DMS reported in homebrewed and small-scale farmhouse beer.

Commercial brewers performing no-boil beers have also often reported a lack of DMS issues in their beer [26][27]. There are likely other factors at play that limit the amount of DMS produced. Specifically, the conversion of SMM to DMS happens extremely slowly at temperatures under 95°C, which would result in less DMS being produced during no-boil brewing. DMS is also very volatile in the temperature range of 50-100°C. See DMS Volatility and DMS Prediction Models for more information on why DMS is probably not an issue with no-boil beers.

In sour beer, there might be other compounds that make the detection of DMS more difficult. For example, 2-phenylethanol and phenethyl acetate mask the perception of DMS in beer [8]. Additionally, some tasters might be genetically predisposed to perceive the flavor of DMS more easily than others.

Considerations for Historical Examples of Raw Ale

In the case of raw ale, and particularly Norwegian/Latvian/Lithuanian traditional farmhouse ales, Finish "sahti", and Estonian "koduõlu", there is some debate as to whether or not DMS should always be considered an off-flavor. Traditionally these beers were made with lightly kilned malts that were malted by the brewers themselves (up until about 20 years ago), and these malts may have had high levels of SMM precursor. Lars Marius Garshol offers his philosophy on off-flavors in beer in general, which is inspired by writings of Michael Jackson, and makes an argument that DMS may have been considered desirable or acceptable in farmhouse raw ales brewed in certain regions of Europe, especially considering that the flavor of DMS is desirable in other foods [28].

Additionally, it has been suggested that small amounts of DMS in wine can give the wine a pleasant "jammy" character. High amounts still lead to vegetal off-flavors in wine. This may or may not have a similar effect for sour beers with fruit [29].

Avoiding DMS

If the brewer is experiencing unwanted DMS in no-boil/raw ale/short boiled beers:

  • With the lid on the boil kettle ("closed system"), avoid allowing wort to stand between 80-100°C/176-212°F (or between 80°C and your area's boiling point). If the lid is off, DMS will continue to evaporate even at lower than boiling temperatures due to its thermodynamic properties, and less will be retained. Note that homebrewers using the Australian "No-Chill" brewing method have reported DMS as not being a problem [30][31]; however, at least one example of reporting DMS in side by side comparisons of No-Chill versus immersion/counter-flow chilling when using pilsner malt exists [32] (36:05 minutes).
  • If the wort is allowed to stand in the above mentioned temperature range in a closed system (especially when brewed with a low modified malt), boil the wort for a few minutes afterward, and then quickly cool it below 80°C (176°F).
  • Keep the lid off while the wort is chilling, until it reaches around 60°C/140°F, and then cover it. This temperature is still hot enough to keep the wort pasteurized [33], and DMS will continue to volatilize off (see the DMS Volatilization Model below).
  • If getting DMS in a 15 minute boil, try pasteurizing the wort at 82°C/180°F for 15 minute and not boiling at all.
  • Use open and/or shallow fermenters [8].
  • Increase fermentation temperature [8].
  • Allow the beer to age longer, particularly if it contains Brettanomyces. Studies in lambic brewing have shown that DMS will volatilize over time if left in the fermenter.
  • Use more highly kilned malts such as 2 row instead of pilsner malt.
  • If the pH must be lowered, for example when pre-acidifying the wort before kettle souring, lower the pH near the end of the boil but before the cooling or whirlpooling process. A higher pH will increase the rate that SMM converts to DMS during the boil, and lowering the pH after the boil but before cooling will slow the rate at which SMM converts to DMS [34].

DMS Prediction Models

Equations have been established for estimating how much DMS will be converted from SMM during boiling, and how much SMM will be converted to DMS during cooling the wort after the boil. These equations are well explained in "Principles of Brewing Science: A Study of Serious Brewing Issues", by George Fix, 1999, Pgs 89-93. One thing to keep in mind is that the equations assume "typical" brewing practices, which include boiling the wort at some point at a pH of 5.2 - 5.5. Because of this, the equation for how much SMM is converted to DMS during cooling may not reflect no-boil or kettle sour wort accurately. Let's look at some examples of the equations from "Principles of Brewing Science: A Study of Serious Brewing Issues":

George Fix Model

First let's look at an example that should accurately predict how much SMM is in a given batch of wort, and how much of that SMM is converted during an 82°C no-boil pasteurization rest at 15 minutes. Assuming a given pilsner malt has 5 µg of SMM per gram, and the malt concentration (weight of malt per liter of water) is 200 g/L, the total SMM content of the malt can be calculated:

Total SMM = 5 µg/g x 200 g/L = 1,000 µg/L

The half-life of SMM at 100°C is ~40 minutes, but since we are not boiling then the half-life of SMM at 82°C is ~300 [8]. Time also has to be considered, but since the heating up time period would make the equation unwieldy, it is suggested to add the heating up time to the "boil" time (or for us, "pasteurization" time) [17]. If it takes 20 minutes to heat up the wort, and it is held at 82°C for 15 minutes, then that gives us 35 minutes. With the time and half-life values, we can predict how much SMM will survive the heat pasteurization and how much will be converted to DMS:

SMM left over = 1,000 µg/L x 2-(35 min/300 min)> = 1,000 x 2-0.12> = 1,000 x 0.92 = 920 µg/L

and

DMS created = 1,000 µg/L - 920 µg/L = 80 µg/L

As expected, a high amount of SMM survives (920 µg/L) the 82°C heat pasteurization, and a relatively low amount of DMS is created (80 µg/L). The example in "Principles of Brewing Science: A Study of Serious Brewing Issues" uses the same total SMM value for the malt, but with a 90 minute boil 210 µg/L of SMM is left over after the boil, and 790 µg/L of DMS is created during the boil. During boiling the created DMS is evaporated off, but during heat pasteurization, the DMS is retained in the wort.

The next equation determines how much SMM is converted to DMS during cooling, and this amount is considered more important because it is mostly not evaporated off (especially in a closed cooling system). This equation, however, uses an average between the boiling temperature and the final chilling temperature. This model has proven to work well assuming normal brewing procedures which assume the wort is boiled, but cannot be used for wort that is not boiled. This is because the half-life of SSM is doubled for every 6°C cooler (see the SMM half-life table above).

An example will help demonstrate this issue. Suppose the wort cools from 82°C to 20°C over 60 minutes. Using the accepted set of equations that predict how much SMM is converted to DMS during cooling, first an average between the starting temperature and the final temperature is computed:

Average temperature = (82°C + 20°C)/2 = 51°C

then, using 4,000 as a constant used in the equation, a time-dependent differential equation is used:

Time differential = (60 min x 51°C)/4000 min) = 0.765

and finally the 0.765 number is used to determine how much SMM is left over:

SMM left over after cooling = 920 µg/L x 2-0.765> = 920 µg/L x 0.588 = 541 µg/L

and the amount of DMS created in the wort during cooling:

DMS created during cooling = 920 µg/L - 541 µg/L = 379 µg/L

now add the DMS created during the heating and 82°C pasteurization to get the total calculated DMS:

Total DMS = 80 µg/L + 379 µg/L = 459 µg/L

Using the exact same wort composition but with a 60 minute boil, this example in "Principles of Brewing Science: A Study of Serious Brewing Issues" computes only 92 µg/L of DMS, mostly because a lot more of the SMM is converted to DMS during boiling, which is then volatilized during the boiling, and leaving less SMM to convert to DMS during cooling. Even with the higher SMM during cooling in our heat pasteurized wort example, that hardly seems fair considering that the half-life of SMM is ~300 minutes at the pasteurization temperature of 82°C.

Numerical Modeling Using Updated DMS Volatility Data

Mark Hammond from MTF used a computer program to model the conversion of SMM to DMS taking into account the SMM half-life at different times and temperatures during various methods of the "no boil" process. Rather than using Fix's average half-life approach, numerical modeling divides the heating, boiling and cooling times into very small time steps (for the work below, a time step of 0.6 seconds was used), during which the temperature is approximated to be constant. The computer program calculates the amount of SMM converted to DMS during the time step, the amount of DMS volatilized during the time step, then plots the total DMS and SMM in the wort at the end of the time step. Finally, the program calculates a new temperature, which depends on whether the wort is heating up, being held at a constant temperature, or cooling. The program then loops through all the calculations at this new temperature, calculating all the same quantities for the next time step.

The new equations from "Scheuren, Baldus, Methner and Dillenburge (2016): Evaporation behaviour of DMS in an aqueous solution at infinite dilution – a review" were used to determine the evaporation of DMS during heating, boiling, and cooling. The evaporation of DMS during cooling assumes an open cooling system in order to demonstrate the volatilization of DMS at temperatures below 100°C. The DMS value will be retained in the wort at the point at which the wort is closed to open cooling (for example, the cooling wort can remain open so as to volatilize DMS during cooling until the wort temperature drops below the pasteurization temperature of 60°C). Hammond assumed a linear heating rate and used Newton's Law of Cooling with constants based on empirical data taken from his own homebrewing equipment. The volume graphs were determined by evaporation rates from the heat of vaporization for water coupled with empirical evaporation rates of Hammond's homebrewing equipment. By observing these estimations, it can be seen that no-boil or "raw ale", and wort boiled for short durations, Hammond predicts less DMS than what is predicted using the traditional model.

For the DMS amounts in the following graphs, Hammond calculated the mass of DMS to be 62/164 of a gram of DMS for every gram of SMM decomposed. Since we get one molecule of DMS (62 g/mole) from each molecule of SMM (164 g/mole), we don't get one for one mass of DMS for SMM. Keep that in mind when comparing the decline in the SMM concentration graph to the DMS concentration graph [35].

 
SMM conversion to DMS during a 20 minute heat up, 15 minute pasteurization at 82°C, and 60 minute cooldown to 20°C. Graph created and provided by Mark Hammond.

In the above computer generated graph based on the half-life rates of SMM, only ~60 µg/L of SMM is converted into very little DMS. Even if a closed cooling system were to be used, only ~6 µg/L of DMS would be retained. This demonstrates the very slow decomposition of SMM into DMS at below boiling temperatures.

Hammond also generated graphs for a 15 minute boil and a "0 minute" boil (wort heated to 100°C, then immediately cooled). These graphs are seen below:

 
SMM conversion to DMS during a 20 minute heat up, 15 minute boil at 100°C, and 60 minute cooldown to 20°C. Graph created and provided by Mark Hammond.
 
SMM conversion to DMS during a 20 minute heat up to boiling temperature (100°C), then immediate cooling for 60 minutes to 20°C ("0 minute" boil). Graph created and provided by Mark Hammond.

In the case of the 15 minute boil, approximately 350 µg/L of SMM is converted into about 40 µg/L of DMS. 15 minutes of boiling appears not to be long enough to efficiently boil off the created DMS, however in an open cooling system much of the DMS will still be evaporated during cooling (see DMS Volatility). Even if the wort was cooled in a closed system and this amount of DMS was retained in the wort, 40 µg/L of DMS is still below the recommended threshold of 100 µg/L of DMS that should be allowed to enter the fermenter [21].

In the case of the "0 minute" boil, approximately 175 µg/L of SMM is converted into approximately 20 µg/L of DMS. Just as in the other examples, the DMS continues to volatilize below boiling temperatures in an open cooling system (see DMS Volatility). Even if the wort was cooled in a closed system and this amount of DMS was retained in the wort, 20 µg/L of DMS is still below the recommended threshold of 100 µg/L of DMS that should be allowed to enter the fermenter [21].

For comparison sake, a graph of a 60 minute boil is shown below, again with an "open cooling" system that allows continued evaporation of DMS during the cooling period:

 
SMM conversion to DMS during a 20 minute heat up, 60 minute boil at 100°C, and 60 minute cooldown to 20°C. Graph created and provided by Mark Hammond.

In an open cooling system, which the graphs assume, DMS continues to volatilize off. In a closed cooling system, the points on the graphs where the boiling/heating stops and the cooling begins, are the points where DMS amounts will remain. If the cooling rate is slow to begin and the wort is held within the 90-100°C range for an extended period of time (for example in the case of whirlpooling), more DMS will continue to accumulate. Assuming the wort is quickly chilled, the table below shows a summary of the predicted DMS from the above charts:

Boil Type µg/L DMS into Fermenter (closed cooling) µg/L DMS into Fermenter (open cooling)
15 Min Pasteurzation at 82°C/180°F ~5 ~2
15 Min Boil ~35 ~5
"0 Minute" Boil ~25 ~5
60 Minute Boil ~25 ~0

In summary, the new model predicts that the 15 minute pasteurization rest produces the least amount of DMS (~5 µg/L), while the 15 minute boil produces the most DMS (~35 µg/L). Note that 35 µg/L of DMS is still below the recommended 100 µg/L of DMS that should be allowed to go into the fermenter [21].

Kettle Souring and Impacts of pH

The normal procedure for kettle souring techniques is to boil the wort a second time after the pH has been lowered in order to kill the Lactobacillus souring culture. The lactic acid fermentation by the Lactobacillus generally results in a wort pH of around 3.0 - 3.6, at which time the wort is boiled to kill the Lactobacillus. In this case, yet another consideration is the impact of low pH on the decomposition of SMM into DMS. The half-life table above demonstrates that a decrease of -0.3 pH increases the half-life by 5.5 minutes at 100°C. Unfortunately, we do not have data to show how the much lower pH values that are achieved after souring wort will affect the half-life of SMM [6], but assuming the impact is linear then the conversion of SMM into DMS during the second boil would be greatly reduced. Assuming the effect of pH on SMM half-life is linear, and that every -0.3 pH increases the half-life by 5.5 minutes at 100°C, the half-life table could hypothetically be updated to include data that looks something like what we present in the first column below. This indicates that wort boiled after souring probably does not create significant amounts of DMS from SMM.

Temp°C SMM half-life at ph 3.4 (minutes; may not reflect reality) SMM half-life at ph 5.2 (minutes) SMM half-life at ph 5.5 (minutes) [8]
100 71 38 32.5
94 142 76 65
88 284 152 130
82 568 304 260
76 1,136 608 520
70 2,272 1,216 1,040

Updated Prediction Models

Updated DMS prediction models have been proposed in the scientific literature. These are largely based on thermodynamic laws.

See Also

References

  1. ↑ 1.0 1.1 Dimethyl Sulfide. PubChem. Retrieved 03/02/2016.
  2. ↑ 2.0 2.1 2.2 2.3 2.4 2.5 Evaporation behaviour of DMS in an aqueous solution at infinite dilution – a review. H. Scheuren, M. Baldus, F.-J. Methner and M. Dillenburger. 2016
  3. ↑ Wikipedia. Thioether. Retrieved 03/01/2016.
  4. ↑ 4.00 4.01 4.02 4.03 4.04 4.05 4.06 4.07 4.08 4.09 4.10 4.11 4.12 4.13 DIMETHYL SULPHIDE—A REVIEW. B. J. Anness and C. W. Bamforth. 1982.
  5. ↑ Aroxa. Dimethyl sulphide. Retrieved 03/01/2016.
  6. ↑ 6.0 6.1 6.2 Decomposition kinetics of dimethyl sulfide. H. Scheuren, J. Tippmann, F.-J. Methner, and, K. Sommer. 2014.
  7. ↑ 7.0 7.1 Boiling Home Brewed Beer with Dr Charlie Bamforth - BeerSmith Podcast #121.
  8. ↑ 8.00 8.01 8.02 8.03 8.04 8.05 8.06 8.07 8.08 8.09 8.10 8.11 8.12 8.13 Dimethyl Sulfide – Significance, Origins, and Control. Charles W. Bamforth. 2014.
  9. ↑ Understanding Malt Analysis Sheets -- How to Become Fluent in Malt Analysis Interpretation. Greg Noonan. Retrieved 03/02/2016.
  10. ↑ "Unraveling the Malt Puzzle." Joseph Hertrich. Michigan Brewers Guild MBAA – District Michigan Winter Conference. 01/13/2012. Retrieved 08/04/2016.
  11. ↑ Explanation for the increase in free dimethyl sulphide during mashing. H. Scheuren, K. Sommer and, Dillenburger. 2015.
  12. ↑ THE RELATIONSHIP OF DIMETHYL SULPHIDE LEVELS IN MALT, WORT AND BEER. C. J. Dickenson. 1979.
  13. ↑ Quantification of Wort Homogeneity for Projecting the Evaporation of Dimethyl Sulfide in an Open, Discontinuous Boiling Process by Means of Direct Heating of the Wort Kettle. Benjamin Kloos and Hans Scheuren. 2016.
  14. ↑ CONTROL OF THE DIMETHYL SULPHIDE CONTENT OF BEER BY REGULATION OF THE COPPER BOIL. R. J. H. Wilson and C. D. Booer. 1979.
  15. ↑ 15.0 15.1 Die Bierbrauerei: Band 2: Die Technologie der Würzebereitung, 8 Auflage. Ludwig Narziss. 2008. Section 5.6.4.3.
  16. ↑ The Microbiology of Malting and Brewing. Nicholas A. Bokulicha and Charles W. Bamforth. 2013.
  17. ↑ 17.0 17.1 17.2 17.3 Dimethyl sulphoxide reduction by micro-organisms. Zinder S.H., Brock T.D. 1978.
  18. ↑ ORIGIN AND EVOLUTION OF DIMETHYL SULFIDE AND VICINAL DIKETONESDURING THE SPONTANEOUS FERMENTATION OF LAMBIC AND GUEUZE. D. Van Oevelen, P. Timmermans, L. Geens and H. Verachtert. 1978.
  19. ↑ VOLATILE ORGANOSULPHUR COMPOUNDS IN HOPS AND HOP OILS: A REVIEW. T.L. Peppard. 1981.
  20. ↑ Dimethyl disulfide. Wikipedia. Retrieved 12/28/2016.
  21. ↑ 21.0 21.1 21.2 21.3 21.4 21.5 Influence of Extract on Volatility of Flavor Components in Wort During Open and Closed Boil. Hans Scheuren Roland Feilner, Frank-Jürgen Methner, and Michael Dillenburger. MBAA website. 2016.
  22. ↑ 22.0 22.1 Raw ale. Lars Marius Garshol. Larsblog. 06/05/2016. Retrieved 03/02/2016.
  23. ↑ "Update: Lab Data on Pils Malt Boil Length Exbeeriment" on Brulosophy. Retrieved 03/08/2016.
  24. ↑ "All Grain Pale Ale 30-Minute Boil Experiments" by James Spencer on Beer & Wine Journal. 06/24/2015. Retrieved 03/08/2016.
  25. ↑ Discussion on MTF regarding DMS in raw ale/no boil/short boils. 03/01/2016.
  26. ↑ Poll to commercial brewers on MTF on getting DMS in no-boil beers. 08/04/2016.
  27. ↑ Conversation with Jeff Crane from Council Brewing Co on no-boil and DMS. 03/12/2016.
  28. ↑ Private correspondence with Lars Marius Garshol by Dan Pixley regarding whether DMS should be considered an off-flavor in farmhouse raw ales. 03/10/2016.
  29. ↑ Conversation with John Frederick on MTF. 02/25/2016.
  30. ↑ "A Year of No Chill | Lessons From A Secret xBmt". Aaron Collier. Brulosophy website. Retrieved 07/04/2018.
  31. ↑ "Australian NO CHILL Brewing Technique TESTED". Brewer's Friend website. 06/06/2009. Retrieved 07/04/2018.
  32. ↑ "November 8, 2012 - ANHC Chilling Experiment". BasicBrewing Podcast. Australian National Homebrew Conference 2012. Retrieved 07/04/2018.
  33. ↑ A suitable model of microbial survival curves for beer pasteurization. Sencer Buzrul. 2006.
  34. ↑ 125th Anniversary Review: Bacteria in brewing: The good, the bad and the ugly. Frank Vriesekoop, Moritz Krahl, Barry Hucker and Garry Menz. 2013.
  35. ↑ Private correspondence between Mark Hammond and Dan Pixley. 03/15/2016 - 03/23/2016.
Retrieved from "http://www.milkthefunk.com/w/index.php?title=Dimethyl_Sulfide&oldid=10286"