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Hydrogen sulfide: Difference between revisions
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[[Category:off flavors]][[Category: | [[Category:off flavors]] [[Category:brewing chemistry]] | ||
[[File:1024px-Tavurvur volcano edit.jpg|thumb|Volcanic gas]] | [[File:1024px-Tavurvur volcano edit.jpg|thumb|Volcanic gas]] | ||
Hydrogen sulfide (H<sub>2</sub>S), or just "sulfide" is a microbe-derived off flavor. It is the most common of a group of fermentation products known as volatile sulfur compounds (VSCs). Sulfide aroma and flavor is often described as sulfurous like rotten eggs, "rhino farts", sewer, or volcanic gas. It is also sometimes called a "[[reductive]]" aroma because it is more likely to accumulate under low-oxygen conditions.<ref name="Jastrzembski"/> | Hydrogen sulfide (H<sub>2</sub>S), or just "sulfide" is a microbe-derived off flavor. It is the most common of a group of fermentation products known as volatile sulfur compounds (VSCs). Sulfide aroma and flavor is often described as sulfurous like rotten eggs, "rhino farts", sewer, or volcanic gas. It is also sometimes called a "[[reductive]]" aroma because it is more likely to accumulate under low-oxygen conditions.<ref name="Jastrzembski"/> | ||
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For wine and beer: | For wine and beer: | ||
* '''Sulfite''' - | * '''Sulfite''' - The presence of [[sulfite]] at the beginning of fermentation has been shown to cause formation of H<sub>2</sub>S.<ref name=Hallinan/><ref name=Jiranek/><ref name=Jiranek2002/><ref>[https://brewbrothers.freeforums.net/thread/682/biab-deoxygenated-strike-water BIAB and deoxygenated strike water.] The Biergarten website. April 2022. Accessed April 5, 2022.</ref> Brewers that use sulfite in the wort (i.e. [[low oxygen brewing|low oxygen brewers]]) need to adequately aerate/oxygenate the wort to neutralize the residual sulfite when pitching. For wine stabilization, it is recommended to wait at least two weeks before adding sulfite after fermentation ends, particularly when the yeast is still present.<ref name=Enartis>[https://www.enartis.com/wp-content/uploads/2019/12/Prevention-and-Treatment-of-Reductive-Aromas.pdf Prevention and treatment of reductive aromas.] Enartis News. Accessed March 2020.</ref> Because there is such a high risk of H<sub>2</sub>S production when adding sulfite soon after fermentation completes, we do not recommend adding sulfite to beer. | ||
* '''Aeration''' - Adding oxygen before pitching yeast is especially important in affecting nitrogen utilization and fermentation vigor, which increases the amount of sulfide stripping from the wine or beer.<ref name= | * '''Aeration''' - Adding oxygen before pitching yeast is especially important in affecting nitrogen utilization and fermentation vigor, which increases the amount of sulfide stripping from the wine or beer.<ref name=Jiranek/><ref name=Jiranek2002/> In wine production, aerating during fermentation is also helpful.<ref>Bekker MZ, Day MP, Holt H, Wilkes E, Smith PA. [https://onlinelibrary.wiley.com/doi/abs/10.1111/ajgw.12172 Effect of oxygen exposure during fermentation on volatile sulfur compounds in Shiraz wine and a comparison of strategies for remediation of reductive character.] ''Aust J Grape Wine Res.'' 2016;22(1):24–35.</ref> (See [[Aeration]]) | ||
* '''Vitamins''' - Vitamins should be supplemented | * '''Vitamins''' - Vitamins should be supplemented in wine. Supplementation is not strictly necessary in beer production since [[wort]] typically contains adequate vitamins,<ref>Briggs DE, Hough JS, Stevens R, Young TW. [https://books.google.com/books?id=bHuCdG5VSmUC&pg=PA92&lpg=PA92&source=bl&ots=8c_VpU3Fs4&sig=ACfU3U1fgQ3aPJpEANWLRXjbv580IWc1Zw&hl=en&sa=X&ved=2ahUKEwiq96Ouqp_oAhUGVa0KHf3bDJoQ6AEwA3oECAcQAQ#v=onepage&f=false ''Malting and Brewing Science: Malt and Sweet Wort.''] 2nd ed. Kluwer Academic Plenum Publishers; 1981:92.</ref><ref name=fix/><ref name=bsp>Briggs DE, Boulton CA, Brookes PA, Stevens R. [[Library|''Brewing Science and Practice.'']] Woodhead Publishing Limited and CRC Press LLC; 2004.</ref> although it is potentially helpful. Deficiencies of [[pantothenic acid]] and [[pyridoxine]] (co-factors to SRS enzymes) may cause overproduction of H<sub>2</sub>S — even when adequate [[nitrogen]] is present.<ref name=Jiranek/><ref name=Jiranek2002/><ref name=Wang>Wang XD, Bohlscheid JC, Edwards CG. [https://sfamjournals.onlinelibrary.wiley.com/doi/pdf/10.1046/j.1365-2672.2003.01827.x Fermentative activity and production of volatile compounds by ''Saccharomyces'' grown in synthetic grape juice media deficient in assimilable nitrogen and/or pantothenic acid.] ''J Appl Microbiol.'' 2003;94(3):349–359.</ref><ref name="Tokuyama">Tokuyama T, Kuraishi H, Aida K, Uemura T. [https://www.jstage.jst.go.jp/article/jgam1955/19/6/19_6_439/_pdf Hydrogen sulfide evolution due to pantothenic acid deficiency in the yeast requiring this vitamin, with special reference to the effect of adenosine triphosphate on yeast cysteine desulfhydrase.] ''J Gen Appl Microbiol.'' 1973;19:439–466.</ref><ref name="Bohlscheid"/> (See [[yeast#Nutrition|Yeast Nutrition]]) | ||
* '''Nitrogen''' - Supplementing [[yeast-assimilable nitrogen]] (YAN) can help lower sulfide production, but only when there are also adequate co-factors (vitamins) present for the SRS.<ref name="Jiranek"/><ref name="Park">Park SK, Boulton RB, Noble AC. [https://www.ajevonline.org/content/51/2/91.short Formation of hydrogen sulfide and glutathione during fermentation of white grape musts.] ''Am J Enol Vitic.'' 2000;51(2):91–97.</ref> Otherwise nitrogen supplementation may ''increase'' sulfide production.<ref name="Bohlscheid"/><ref name="Wang"/><ref>Kumar GR, Ramakrishnan V, Bisson LF. [https://www.ajevonline.org/content/61/3/365.short Survey of hydrogen sulfide production in wine strains of ''Saccharomyces cerevisiae''.] ''Am J Enol Vitic.'' 2010;61(3):365–371.</ref><ref name="Butzke"/><ref name="Ugliano">Ugliano M, Kolouchova R, Henschke PA. [https://link.springer.com/article/10.1007/s10295-010-0786-6 Occurrence of hydrogen sulfide in wine and in fermentation: influence of yeast strain and supplementation of yeast available nitrogen.] ''J Ind Microbiol Biotechnol.'' 2011;38:423–429.</ref><ref name="UglianoM"/> There may also be some variability among yeast strains or species with regard to whether increasing nitrogen decreases sulfide formation.<ref name="UglianoM"/><ref>Mendes-Ferreira A, Mendes-Faia A, Leão C. [https://www.researchgate.net/publication/11282471_Survey_of_Hydrogen_Sulphide_Production_by_Wine_Yeasts Survey of hydrogen sulphide production by wine yeasts.] ''J Food Prot.'' 2002;65(6):1033–1037.</ref> Similar to vitamins, nitrogen supplementation in [[wort]] or beer is not always required, but still may be helpful under certain conditions.<ref name="Duan">Duan WD, Roddick FA, Higgins VJ, Rogers PJ. [https://www.researchgate.net/publication/281600914_A_Parallel_Analysis_of_H2S_and_SO2_Formation_by_Brewing_Yeast_in_Response_to_Sulfur-Containing_Amino_Acids_and_Ammonium_Ions A parallel analysis of H2S and SO2 formation by brewing yeast in response to sulfur-containing amino acids and ammonium ions.] ''J Am Soc Brew Chem.'' 2004;62(1):35–41.</ref><ref name="Ferreira">Ferreira IM, Guido LF. [https://www.mdpi.com/2311-5637/4/2/23/pdf Impact of wort amino acids on beer flavour: a review.] ''Fermentation (Basel).'' 2018;4(23).</ref> (See [[yeast#Nutrition|Yeast]]) | * '''Nitrogen''' - Supplementing [[yeast-assimilable nitrogen]] (YAN) can help lower sulfide production, but only when there are also adequate co-factors (vitamins) present for the SRS.<ref name="Jiranek"/><ref name="Park">Park SK, Boulton RB, Noble AC. [https://www.ajevonline.org/content/51/2/91.short Formation of hydrogen sulfide and glutathione during fermentation of white grape musts.] ''Am J Enol Vitic.'' 2000;51(2):91–97.</ref> Otherwise nitrogen supplementation may ''increase'' sulfide production.<ref name="Bohlscheid"/><ref name="Wang"/><ref>Kumar GR, Ramakrishnan V, Bisson LF. [https://www.ajevonline.org/content/61/3/365.short Survey of hydrogen sulfide production in wine strains of ''Saccharomyces cerevisiae''.] ''Am J Enol Vitic.'' 2010;61(3):365–371.</ref><ref name="Butzke"/><ref name="Ugliano">Ugliano M, Kolouchova R, Henschke PA. [https://link.springer.com/article/10.1007/s10295-010-0786-6 Occurrence of hydrogen sulfide in wine and in fermentation: influence of yeast strain and supplementation of yeast available nitrogen.] ''J Ind Microbiol Biotechnol.'' 2011;38:423–429.</ref><ref name="UglianoM"/> There may also be some variability among yeast strains or species with regard to whether increasing nitrogen decreases sulfide formation.<ref name="UglianoM"/><ref>Mendes-Ferreira A, Mendes-Faia A, Leão C. [https://www.researchgate.net/publication/11282471_Survey_of_Hydrogen_Sulphide_Production_by_Wine_Yeasts Survey of hydrogen sulphide production by wine yeasts.] ''J Food Prot.'' 2002;65(6):1033–1037.</ref> Similar to vitamins, nitrogen supplementation in [[wort]] or beer is not always required, but still may be helpful under certain conditions.<ref name="Duan">Duan WD, Roddick FA, Higgins VJ, Rogers PJ. [https://www.researchgate.net/publication/281600914_A_Parallel_Analysis_of_H2S_and_SO2_Formation_by_Brewing_Yeast_in_Response_to_Sulfur-Containing_Amino_Acids_and_Ammonium_Ions A parallel analysis of H2S and SO2 formation by brewing yeast in response to sulfur-containing amino acids and ammonium ions.] ''J Am Soc Brew Chem.'' 2004;62(1):35–41.</ref><ref name="Ferreira">Ferreira IM, Guido LF. [https://www.mdpi.com/2311-5637/4/2/23/pdf Impact of wort amino acids on beer flavour: a review.] ''Fermentation (Basel).'' 2018;4(23).</ref> (See [[yeast#Nutrition|Yeast]]) | ||
* '''Yeast strain''' - Low sulfide-producing and/or low nitrogen-requirement yeast strains may be considered.<ref name="Jiranek2002"/> | * '''Yeast strain''' - Low sulfide-producing and/or low nitrogen-requirement yeast strains may be considered.<ref name="Jiranek2002"/> Unfortunately it is not very well known which strains are high or low producers of H<sub>2</sub>S. Scott Labs and Renaissance Yeast have both bred some wine yeast strains specifically to reduce sulfide production.<ref>[https://scottlab.com/h2s-production Understanding the production of hydrogen sulfide (H<sub>2</sub>S) during fermentation.] Scott Laboratories. Accessed March 2020.</ref><ref>[https://www.thebeveragepeople.com/products/yeast/10-g-fresco-cider-wine-yeast.html 10 g fresco cider yeast - H2S preventing.] The Beverage People. Accessed March 2020.</ref> | ||
* '''Pitch rate and yeast health''' - Pitch healthy yeast at a good pitch rate to decrease nutrient demand.<ref name="Ferreira"/><ref name="Zoecklein"/> "Shocking" the yeast (rapid changes in growth conditions like temperature or [[pH]]) should be avoided.<ref name="Jiranek2002"/><ref name="OsborneJ">Osborne JP. [https://owri.oregonstate.edu/sites/agsci/files/owri/05_vitnewsletteroct07webversion.pdf Sulfides and mercaptans in wine.] Oregon State University Wine and Grape Research and Extension Newsletter. Published October 2007.</ref> Significant over-pitching may also cause excessive sulfide.<ref name="fart"/><ref name=fix/> Even re-pitching yeast may cause increased production of sulfide.<ref>Thorne RSW. [https://onlinelibrary.wiley.com/doi/pdf/10.1002/j.2050-0416.1968.tb03167.x Some observations on yeast mutation during continuous fermentation.] ''J Inst Brew.'' 1968;74:516–524.</ref> (See [[Yeast]]) | * '''Pitch rate and yeast health''' - Pitch healthy yeast at a good pitch rate to decrease nutrient demand.<ref name="Ferreira"/><ref name="Zoecklein"/> "Shocking" the yeast (rapid changes in growth conditions like temperature or [[pH]]) should be avoided.<ref name="Jiranek2002"/><ref name="OsborneJ">Osborne JP. [https://owri.oregonstate.edu/sites/agsci/files/owri/05_vitnewsletteroct07webversion.pdf Sulfides and mercaptans in wine.] Oregon State University Wine and Grape Research and Extension Newsletter. Published October 2007.</ref> Significant over-pitching may also cause excessive sulfide.<ref name="fart"/><ref name=fix/> Even re-pitching yeast may cause increased production of sulfide.<ref>Thorne RSW. [https://onlinelibrary.wiley.com/doi/pdf/10.1002/j.2050-0416.1968.tb03167.x Some observations on yeast mutation during continuous fermentation.] ''J Inst Brew.'' 1968;74:516–524.</ref> (See [[Yeast]]) | ||
* '''Fermentation temperature''' - Generally lower temperatures decrease sulfide liberation, although not necessarily because of decreased production.<ref name="Bohlscheid">Bohlscheid JC, Osborne JP, Ross CF, Edwards CG. [https://onlinelibrary.wiley.com/doi/pdf/10.1111/j.1745-4557.2010.00365.x Interactive effects of selected nutrients and fermentation temperature on H<sub>2</sub>S production by wine strains of ''Saccharomyces''.] ''J Food Qual.'' 2011;34:51–55.</ref> However each strain has an optimum fermentation temperature to minimize its production, so lower temperature doesn't always mean lower sulfide production.<ref name="Kim">Kim YR, Moon ST, Park SK. [http://ocean.kisti.re.kr/downfile/volume/ksfst1/SPGHB5/2008/v40n2/SPGHB5_2008_v40n2_238.pdf Effects of yeast strains and fermentation temperatures in production of hydrogen sulfide during beer fermentation.] ''Korean J Food Sci Technol.'' 2008;40(2):238–242.</ref> The fermentation temperature should be controlled within the suggested range of the yeast. (See [[Temperature control]]) | * '''Fermentation temperature''' - Generally lower temperatures decrease sulfide liberation, although not necessarily because of decreased production.<ref name="Bohlscheid">Bohlscheid JC, Osborne JP, Ross CF, Edwards CG. [https://onlinelibrary.wiley.com/doi/pdf/10.1111/j.1745-4557.2010.00365.x Interactive effects of selected nutrients and fermentation temperature on H<sub>2</sub>S production by wine strains of ''Saccharomyces''.] ''J Food Qual.'' 2011;34:51–55.</ref> However each strain has an optimum fermentation temperature to minimize its production, so lower temperature doesn't always mean lower sulfide production.<ref name="Kim">Kim YR, Moon ST, Park SK. [http://ocean.kisti.re.kr/downfile/volume/ksfst1/SPGHB5/2008/v40n2/SPGHB5_2008_v40n2_238.pdf Effects of yeast strains and fermentation temperatures in production of hydrogen sulfide during beer fermentation.] ''Korean J Food Sci Technol.'' 2008;40(2):238–242.</ref> The fermentation temperature should be controlled within the suggested range of the yeast. (See [[Temperature control]]) | ||
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* A small syringe or pipette to measure 1 mL volumes | * A small syringe or pipette to measure 1 mL volumes | ||
* Plastic wrap or watch glasses | * Plastic wrap or watch glasses | ||
* 1% [[Copper sulfate]] (CuSO<sub>4</sub>) solution (If you can't obtain copper sulfate, you can clean several pennies in an acid solution like lemon juice or vinegar.<ref name="Kaiser"/>) | * 1% [[Copper sulfate]] (CuSO<sub>4</sub>) solution (If you can't obtain copper sulfate, you can clean several U.S. pennies in an acid solution like lemon juice or vinegar.<ref name="Kaiser"/>) | ||
* Optional: [[Ascorbic acid]] and distilled water to make a 5% ascorbic acid solution. Mix 2.5 g ascorbic acid into 50 mL water. | * Optional: [[Ascorbic acid]] and distilled water to make a 5% ascorbic acid solution. Mix 2.5 g ascorbic acid into 50 mL water. | ||
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'''Biology and sulfide formation'''<br /> | '''Biology and sulfide formation'''<br /> | ||
For a review of the biological production pathways, see these articles: | For a review of the biological production pathways, see these articles: | ||
* Wang, | * Wang XD, Bohlscheid JC, Edwards CG. [https://sfamjournals.onlinelibrary.wiley.com/doi/pdf/10.1046/j.1365-2672.2003.01827.x Fermentative activity and production of volatile compounds by Saccharomyces grown in synthetic grape juice media deficient in assimilable nitrogen and/or pantothenic acid.] ''J Appl Microbiol.'' 2003;94(3):349–359. | ||
* Huang, | * Huang CW, Walker ME, Fedrizzi B, Gardner RC, Jiranek V. [https://academic.oup.com/femsyr/article/17/6/fox058/4056150 Hydrogen sulfide and its roles in Saccharomyces cerevisiae in a winemaking context.] ''FEMS Yeast Res.'' 2017;17(6). | ||
'''Sulfite'''<br /> | '''Sulfite'''<br /> | ||
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'''Cysteine'''<br /> | '''Cysteine'''<br /> | ||
The amino acid cysteine is commonly referenced as contributing to increased formation of hydrogen sulfide, but in practice its effect is negligible since cysteine concentration in must is typically very low.<ref name=thesis>Jiranek V. [https://digital.library.adelaide.edu.au/dspace/bitstream/2440/21637/2/02whole.pdf Hydrogen sulfide formation in ''Saccharomyces cerevisiae'' and its regulation by assimilable nitrogen.] Doctoral thesis for University of Adelaide. | The amino acid cysteine is commonly referenced as contributing to increased formation of hydrogen sulfide, but in practice its effect is negligible since cysteine concentration in must is typically very low.<ref name=thesis>Jiranek V. [https://digital.library.adelaide.edu.au/dspace/bitstream/2440/21637/2/02whole.pdf Hydrogen sulfide formation in ''Saccharomyces cerevisiae'' and its regulation by assimilable nitrogen.] Doctoral thesis for University of Adelaide. Published August 1992.</ref><ref name="Osborne"/><ref name="Giudici"/><ref name="Moreira"/><ref name="Huang"/><ref name="Jiranek"/><ref name="Huang"/><ref name="Jiranek2002"/> It's believed that aspartate aminotransferase deaminates cysteine to give mercaptopyruvate, which in a subsequent step catalyzed by MST liberates H<sub>2</sub>S and pyruvate.<ref>Kabil O, Banerjee R. [https://www.jbc.org/content/285/29/21903.full.pdf Redox biochemistry of hydrogen sulfide.] ''J Biol Chem.'' 2010;285(29):21903–21907.</ref> However, that hasn't been fully confirmed by other sources.<ref name="Huang"/> | ||
'''Methionine'''<br /> | '''Methionine'''<br /> | ||
Methionine addition has a variable effect on hydrogen sulfide (and sulfite) production, and the effect also varies by yeast strain.<ref>Boudreau TF IV, Peck GM, Ma S, et al. [https://onlinelibrary.wiley.com/doi/full/10.1002/jib.449 Hydrogen sulphide production during cider fermentation is moderated by pre-fermentation methionine addition.] ''J Inst Brew.'' 2017;123;553–561.</ref><ref name="Giudici"/><ref name="Moreira"/><ref name="Duan"/><ref name="Spiropoulos"/> | Methionine addition has a variable effect on hydrogen sulfide (and sulfite) production, and the effect also varies by yeast strain.<ref>Boudreau TF IV, Peck GM, Ma S, et al. [https://onlinelibrary.wiley.com/doi/full/10.1002/jib.449 Hydrogen sulphide production during cider fermentation is moderated by pre-fermentation methionine addition.] ''J Inst Brew.'' 2017;123(4);553–561.</ref><ref name="Giudici"/><ref name="Moreira"/><ref name="Duan"/><ref name="Spiropoulos"/> | ||
==See | ==See also== | ||
* [http://allaboutbeer.com/article/sulfur-in-beer/ Article about VSCs in beer] by Randy Mosher. | * [http://allaboutbeer.com/article/sulfur-in-beer/ Article about VSCs in beer] by Randy Mosher. | ||
* [https://wineserver.ucdavis.edu/industry-info/enology/fermentation-management-guides/wine-fermentation/characters Scientific discussion of the variety of VSCs and their formation] from UC Davis. | * [https://wineserver.ucdavis.edu/industry-info/enology/fermentation-management-guides/wine-fermentation/characters Scientific discussion of the variety of VSCs and their formation] from UC Davis. | ||