Cannot overcome my Hazy IPA oxidation problem!!

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https://www.researchgate.net/profil...Lager_Beer/links/585cfe6608ae6eb8719fc4c5.pdf

I just stumbled across this paper. Summary as far as is pertinent to this thread: Malt contains significant iron, lighter malt contains less, munich contains 200% more than pilsner. Iron is the primary source of free-radical oxidative staling agents in beer. Alpha acids in hops are an antioxidant and can remove/complex with free iron (which is probably the cause of your color changes).

So a good strategy for more stable NEIPA's might be to confine your grain bill to pale malts (<6 SRM), add more bittering hops, and first wort hops in addition to your massive whirlpool additions as an antioxidant. Adding hops directly to your mash was also suggested.
 
https://www.researchgate.net/profil...Lager_Beer/links/585cfe6608ae6eb8719fc4c5.pdf

I just stumbled across this paper. Summary as far as is pertinent to this thread: Malt contains significant iron, lighter malt contains less, munich contains 200% more than pilsner. Iron is the primary source of free-radical oxidative staling agents in beer. Alpha acids in hops are an antioxidant and can remove/complex with free iron (which is probably the cause of your color changes).

So a good strategy for more stable NEIPA's might be to confine your grain bill to pale malts (<6 SRM), add more bittering hops, and first wort hops in addition to your massive whirlpool additions as an antioxidant. Adding hops directly to your mash was also suggested.

Do the authors suggest a mechanism by which more iron gets into the darker malts? I always thought that color came from degree of kilning/roasting. There is no way that heat treatment creates iron.

Brew on :mug:
 
Do the authors suggest a mechanism by which more iron gets into the darker malts? I always thought that color came from degree of kilning/roasting. There is no way that heat treatment creates iron.

Brew on :mug:

Agreed, they did not mention the mechanism that I saw, but I suspect that it is more a matter of malt variety than actual kilning, and they only compared pilsner and munich. They merely stated their findings that munich contains 200% more iron than pilsner malt and made vague links to malt color. I would need to re-read the article more thoroughly to understand the link they are implying there. I don't think the authors intended for malt roast to equate to iron content though.
 
Do the authors suggest a mechanism by which more iron gets into the darker malts? I always thought that color came from degree of kilning/roasting. There is no way that heat treatment creates iron.

Brew on :mug:

I mis-read the article, here's the passage I was thinking of. They don't link color and iron content directly:

Table 5 depicts the extracts, pH-values, and colors of the individual wort samples without hops added. While wort extracts were not in&#64258;uenced by initial malt bill used, the color increased when us-ing higher proportions of Munich malt and the pH dropped which may be explained by the acidifying properties of certain Maillard reaction products [50].As demonstrated in &#64257;gure 3, the initial malt bill had a signi&#64257;cant effect on the initial iron concentrations of the worts and increased with higher proportions of Munich malt (50 % Munich malt, 84 % increase; 100 % Munich malt, 202 % increase)
 
Since the typical NEIPA recipe has 0% munich malt, this seems to be totally unrelated to the issue at hand.
 
Since the typical NEIPA recipe has 0% munich malt, this seems to be totally unrelated to the issue at hand.


Please read the article or my first post. Doug was correcting an improper correlation that I made. Munich malt has nothing to do with the overall premise that isomerization of hops acids acts as an antioxidant and will help preserve your beer and that iron is the better element to reduce in order to minimize staling reactions since complete elimination of oxygen is not actually possible.
 
Yeah I read it. Did you get to the conclusion? "Taking all these data together, clearly, the modi&#64257;ed hop dosages were superior in suppressing staling as compared to a beer produced with hops dosed solely at the beginning of wort boil-ing. "

According to that study, all the the IPA style hopping techniques lead to greater beer stability. That's the exact opposite of what is being discussed. Brewers have known for hundreds of years that increased hop rates/dry hopping etc improve stability. There is something different happening in the NEIPA techniques that is making the beer highly subject to oxidation issues.
 
Yeah I read it. Did you get to the conclusion? "Taking all these data together, clearly, the modi&#64257;ed hop dosages were superior in suppressing staling as compared to a beer produced with hops dosed solely at the beginning of wort boil-ing. "

According to that study, all the the IPA style hopping techniques lead to greater beer stability. That's the exact opposite of what is being discussed. Brewers have known for hundreds of years that increased hop rates/dry hopping etc improve stability. There is something different happening in the NEIPA techniques that is making the beer highly subject to oxidation issues.

Could it be that reduced isomerization of alpha acids in favor of very large late additions, in combination with the increased suspension of vegetative matter and increased polyphenols due to this "bio-transformation" effect from early dry hopping leaves sufficient iron complexes unbound to oxidize the hop compounds in suspension and change their color?

You can't answer that, and neither can I.

I was merely presenting a paper discussing one oxidative process that has not been considered as far as I know in this thread, and it is highly relevant to the discussion at hand, especially in combination with the information on the oxidation of polyphenolic hop compounds I posted earlier.

There's no reason/cause/evidence to wholly dismiss this effect as non-relevant.
 
I was merely presenting a paper discussing one oxidative process that has not been considered as far as I know in this thread, and it is highly relevant to the discussion at hand, especially in combination with the information on the oxidation of polyphenolic hop compounds I posted earlier.

There's no reason/cause/evidence to wholly dismiss this effect as non-relevant.

It was new info to me. I learned something. Thanks.
 
My latest bottled NEIPA is my best attempt so far and it was hopped in the more traditional way 60 15 10 5 etc plus larger dry hops than I usually do. There are several possible explanations (I bottled preFG, used 1318), but maybe hopping during the boil helps.
 
Could it be that reduced isomerization of alpha acids in favor of very large late additions, in combination with the increased suspension of vegetative matter and increased polyphenols due to this "bio-transformation" effect from early dry hopping leaves sufficient iron complexes unbound to oxidize the hop compounds in suspension and change their color?

You can't answer that, and neither can I.

I was merely presenting a paper discussing one oxidative process that has not been considered as far as I know in this thread, and it is highly relevant to the discussion at hand, especially in combination with the information on the oxidation of polyphenolic hop compounds I posted earlier.

There's no reason/cause/evidence to wholly dismiss this effect as non-relevant.

The problem is that there ISN'T " reduced isomerization of alpha acids " in more NEIPA. As a style, it's got relatively high levels of isomerize alpha acids present. And really, the paper shows that late hop additions are benifitial in preventing oxidation in their testing. ie increasing the percentage of non-isomerized acids increases stability, not decreases. It's a perfectly interesting paper, but it's conclusions are all pointing in the opposite direction of the effect people are experiencing.
 
The problem is that there ISN'T " reduced isomerization of alpha acids " in more NEIPA. As a style, it's got relatively high levels of isomerize alpha acids present. And really, the paper shows that late hop additions are benifitial in preventing oxidation in their testing. ie increasing the percentage of non-isomerized acids increases stability, not decreases. It's a perfectly interesting paper, but it's conclusions are all pointing in the opposite direction of the effect people are experiencing.


Yes it is high relative to a dunkel or a porter, but compared to a west coast IPA, the IBU's are low, and many recipes call for no hop additions until 5 minutes then massive amounts of whirlpool and dryhopping. That leads to minimal isomerization.

I agree that this should result in some anti-oxidant properties, as the study shows. But it also showed that the isomerized alpha acids were the most effective chelating agent, and that adding hops even to the mash can add benefit because of its antioxidant properties.

If you look at the amount of isomerized alpha acids relative the total amount of hops added to this beer, it is VERY low. This may be the problem.

My point is that the massive additions of whirlpool and dryhops may be adding something (polyphenols, some organic compound from the yeast/hops interaction, etc) that requires a certain proportional amount of isomerized hop acids in order to prevent it from being oxidized (or to stabilize it against some other reaction taking place). It could be that this style requires a careful balance of boiled hops along with the dry hops in order to ensure that all oxidative reaction catalysts (metal ions) are complexed.

That would explain why some people are seeing this happen and others are not. It would all come down to recipe and hop additions.

This should be easily tested by those who have had issues. Increase your early boil hops and see if the problem persists.
 
A recent batch I brewed mostly oxidized after a couple weeks in bottle. Ironically almost all of the last few bottles I had (6 out of the last 7 bottles) did not oxidize. Which makes me believe a slight tweek in my process could be improved to prevent the oxidation. I however don't know what that would be at the moment.

Also reading up on PPO it appears that potassium metabisulfite or campden tablets is an inhibitor. I don't use them when brewing but to those who do, are you still getting the oxidation?
 
A recent batch I brewed mostly oxidized after a couple weeks in bottle. Ironically almost all of the last few bottles I had (6 out of the last 7 bottles) did not oxidize. Which makes me believe a slight tweek in my process could be improved to prevent the oxidation. I however don't know what that would be at the moment.

Also reading up on PPO it appears that potassium metabisulfite or campden tablets is an inhibitor. I don't use them when brewing but to those who do, are you still getting the oxidation?

Short answer: Best NEIPA's I've made have been by using campden tablets and minimizing oxygen ingress on the hot and cold side. Lasting hop flavor, no darkening of the beer.

Long answer (warning, your eyes may glaze over and/or you may need a beer):

I'm using sodium metabisulfite in the mash & sparge water and I've also used a bit at kegging. Using campden tablets alone though won't take care of oxidation, you need to employ other means to minimize oxygen uptake on both hot side and cold side. Lots of little changes in the brewing process add up to big changes in the final product. My NEIPA's that started out great and became muted (and sometimes eventually darkened) just a few weeks later now are staying fresh for a couple of months now with just a few changes in my process.

I'm talking about just adjusting your process, not even buying anything new, other than campden tablets. I could go on but I don't need to as the whole check list can be found on ******************** and besides, I'm not an expert at it. I will say that my beers are much better as a result of implementing as many of the process changes as I can manage. It's nice not to have my beers lose their lovely hop nose and turn into a muted caramel beer. I will say I'm not a fan of bottling conditioning NEIPA's and I know that's what the concern is on this thread. Strictly my opinion but I do believe there is oxygen being introduced somewhere (or several places) along the brewing process that then comes out like a monster in the bottle conditioned NEIPA's turning them brown and muted.

It's very easy to introduce oxygen all along the brewing process and not even know it. Really. Unless you're doing dissolved oxygen readings along the whole process, you really don't know. Like 'knowing' the temperature of something without a thermometer, you can guess and estimate but if you can't measure, you don't know. I'm not saying that anyone needs a DO meter, just pointing out that you can't 'know' and so sometimes having a 'what if' attitude helps with looking at your process and thinking about what changes you could make to prevent the oxidation through the whole process. Oxygen introduced on the hot side doesn't go away so even if you take care of introducing no oxygen on the cold side (other than oxygenating wort for the yeast of course), that will come out when you bottle, it might be minimal, it might be horrible.

So campden tablets are one more tool along with looking at adjusting your whole brewing process in the quest make better and more stable beer. Just my opinion of course.
 
I totally agree with Brewstergal, but I'm still curious if there is something genetic about Conan that causes browning. A local brewery, that's not that good, started canning some one off neipas. They were browning over the course of a week. They were not muted, but I didn't keep them around any longer than 10 days. Last week I asked the rep if they were using Conan, and he came back this week and confirmed they were.
 
Does whirlpooling is considered as introducing Oxygen on the hot Side?
I say yes, you can certainly be introducing oxygen during whirlpooling. How much? Who knows as there are many variables (batch size, system, technique, etc.). What to do? First remember it's just beer. Then do your best to not whirlpool for longer than necessary, keep from splashing too much, cool ASAP, pitch and then oxygenate. Just my opinion.
 
Thanks for the fedback brewstergal. I would not expect any one thing to be a magic bullet for oxidation as beer is incredibly complex. But as you say it is another tool.

I found this paper the other day that I have been slowly reading through.

http://www.sciencedirect.com/science/article/pii/S0308814605000865?via%3Dihub

Section 4.2 addresses the role of iron and cooper in oxidation. I will limit my wort chiller time in my boil to see if that helps.

Section 4.3.5 addresses the degradation of hop bitter acids.
 
The pdf is 3 KB to large. When I have more time I will see what I can do, maybe just copy paste the more relavant parts.
 
Basically the take home for me is if you can limit your iron and cooper you should be able to reduce the amount of oxidation as well. I have since noticed that both wheat and oats are higher in iron than barley. Is it a meaningful amount, I don't know. I will also decrease or eliminate the amount of time I put my wort chiller into the boil for sanitation. I may try putting it a separate pot of boiling water. Here is one section of the article.


4.2. Reactive oxygen species in stored beer

Oxygen, in particular, causes a rapid deterioration of beer flavour, meaning that oxygen must initiate some very important aging reactions. The importance of reactive oxygen species (ROS) in beer staling was first indicated by Bamforth and Parsons (1985). In recent years, studies using electron spin resonance (ESR) with spin trapping reagents (Andersen & Skibsted, 1998; Kaneda, Kano, Koshino, & Ohyanishiguchi, 1992; Kaneda et al., 1988; Uchida & Ono, 1996; Uchida & Ono, 1999) and chemiluminescence (CL) (Kaneda, Kano, Osawa, Kawakishi, & Koshino, 1991) analysis made it possible to unravel the initial oxygen-dependent reactions (Fig. 2) see below.


Oxygen in the ground state (3O2) is quite stable and will not easily react with organic molecules. In the presence of ferrous iron (Fe2+) in beer, oxygen can capture an electron and form the superoxide anion
and Fe3+. Copper ions probably have the same behaviour and Cu+ is oxidized to Cu2+ (Kaneda, Kobayashi, Takashio, Tamaki, & Shinotsuka, 1999). It is believed that Cu+/Cu2+ and Fe2+/Fe3+ ions are part of a mixed function oxidation system in which polyphenols, sugars, isohumulones and alcohols might act as electron donors (Kaneda et al., 1992). The superoxide anion can be protonated to form the perhydroxyl radical (OOH ), which has much higher reactivity. The pKa of this reaction is 4.8, which means that, at the pH of beer, the majority of the superoxide will be in the perhydroxyl form. The superoxide anion can also be reduced by Fe2+ or Cu+ to the peroxide anion. In beer, this anion is readily protonated to hydrogen peroxide (H2O2). Hydroxyl radicals (OH ) can then be produced from H2O2 or the superoxide anion O2&#8722; by metal-induced reactions, such as the Fenton and the Haber–Weiss reaction.

The reactivity of the oxygen species increases with their reduction status (superoxide anion < perhydroxyl radical < hydroxyl radical). The concentration of free radicals during the aging of beer increases with increasing iron/copper ion concentrations, with increasing oxygen concentrations or with higher storage temperatures (Kaneda et al., 1992; Kaneda, Kano, Osawa, Kawakishi, & Kamada, 1989). Furthermore, the free radicals are not always generated just after the start of the aging process, but can be formed after a definite time period, called the “lag time” of free-radical generation (Uchida & Ono, 1996; Uchida, Suga, & Ono, 1996). The “lag-time” seems related to the endogenous antioxidant activity of beer and can be used as an objective tool for its evaluation.

Hydroxyl radicals are one of the most reactive species that have been identified. Therefore, it was suggested that they non-selectively react with ethanol in beer because it is the second most abundant compound of beer and a good radical scavenger. The findings of Andersen and Skibsted (1998), which revealed the 1-hydroxyethyl radical as quantitatively the most important radical in beer, support this. The 1-hydroxyethyl radical arises in the reaction of ethanol with the hydroxyl radical. Generally, the reactive oxygen species (HOO , H2O2 and HO ) react with all kinds of organic molecules in beer, such as polyphenols, isohumulones and alcohols, resulting in various changes in the sensory profile of beer.

Fenton and Haber-Weiss.jpg
 
I coincidentally got an interesting comparison on the effect of head space when bottling NEIPA (auto siphon to bottling bucket with priming solution). The two pictures below are from two bottles of the very same batch, 4 weeks after bottling. The first one had about 1" of head space, and the second was filled almost to the top (a few millimeters space maybe). The first one tasted stale, bitter, and lacked hop aroma. It seems that reducing head space can have a big impact. The recipe was from the Melcher Street clone thread on here, using yeast harvested from Trillium cans. Next time I will try with 1318 to see if it that makes a difference.

DSC_0012.jpg


DSC_0013.jpg
 
I coincidentally got an interesting comparison on the effect of head space when bottling NEIPA (auto siphon to bottling bucket with priming solution). The two pictures below are from two bottles of the very same batch, 4 weeks after bottling. The first one had about 1" of head space, and the second was filled almost to the top (a few millimeters space maybe). The first one tasted stale, bitter, and lacked hop aroma. It seems that reducing head space can have a big impact. The recipe was from the Melcher Street clone thread on here, using yeast harvested from Trillium cans. Next time I will try with 1318 to see if it that makes a difference.
Can you bottle carb without headspace?
 
Can you bottle carb without headspace?

Both bottles had pretty much the same level of carbonation. It's probably difficult to really have zero head space. Without spending too much though on it, I don't see why it wouldn't work. In the end it's just an equilibrium between CO2 gas and dissolved CO2. If you have less head space with the same amount (mass/mole) of CO2, it should just mean higher pressure and more dissolved CO2 (more carbonation) at the equilibrium.
 
Basically the take home for me is if you can limit your iron and cooper you should be able to reduce the amount of oxidation as well. I have since noticed that both wheat and oats are higher in iron than barley. Is it a meaningful amount, I don't know. I will also decrease or eliminate the amount of time I put my wort chiller into the boil for sanitation. I may try putting it a separate pot of boiling water. Here is one section of the article.


4.2. Reactive oxygen species in stored beer

Oxygen, in particular, causes a rapid deterioration of beer flavour, meaning that oxygen must initiate some very important aging reactions. The importance of reactive oxygen species (ROS) in beer staling was first indicated by Bamforth and Parsons (1985). In recent years, studies using electron spin resonance (ESR) with spin trapping reagents (Andersen & Skibsted, 1998; Kaneda, Kano, Koshino, & Ohyanishiguchi, 1992; Kaneda et al., 1988; Uchida & Ono, 1996; Uchida & Ono, 1999) and chemiluminescence (CL) (Kaneda, Kano, Osawa, Kawakishi, & Koshino, 1991) analysis made it possible to unravel the initial oxygen-dependent reactions (Fig. 2) see below.


Oxygen in the ground state (3O2) is quite stable and will not easily react with organic molecules. In the presence of ferrous iron (Fe2+) in beer, oxygen can capture an electron and form the superoxide anion
and Fe3+. Copper ions probably have the same behaviour and Cu+ is oxidized to Cu2+ (Kaneda, Kobayashi, Takashio, Tamaki, & Shinotsuka, 1999). It is believed that Cu+/Cu2+ and Fe2+/Fe3+ ions are part of a mixed function oxidation system in which polyphenols, sugars, isohumulones and alcohols might act as electron donors (Kaneda et al., 1992). The superoxide anion can be protonated to form the perhydroxyl radical (OOH ), which has much higher reactivity. The pKa of this reaction is 4.8, which means that, at the pH of beer, the majority of the superoxide will be in the perhydroxyl form. The superoxide anion can also be reduced by Fe2+ or Cu+ to the peroxide anion. In beer, this anion is readily protonated to hydrogen peroxide (H2O2). Hydroxyl radicals (OH ) can then be produced from H2O2 or the superoxide anion O2&#8722; by metal-induced reactions, such as the Fenton and the Haber–Weiss reaction.

The reactivity of the oxygen species increases with their reduction status (superoxide anion < perhydroxyl radical < hydroxyl radical). The concentration of free radicals during the aging of beer increases with increasing iron/copper ion concentrations, with increasing oxygen concentrations or with higher storage temperatures (Kaneda et al., 1992; Kaneda, Kano, Osawa, Kawakishi, & Kamada, 1989). Furthermore, the free radicals are not always generated just after the start of the aging process, but can be formed after a definite time period, called the “lag time” of free-radical generation (Uchida & Ono, 1996; Uchida, Suga, & Ono, 1996). The “lag-time” seems related to the endogenous antioxidant activity of beer and can be used as an objective tool for its evaluation.

Hydroxyl radicals are one of the most reactive species that have been identified. Therefore, it was suggested that they non-selectively react with ethanol in beer because it is the second most abundant compound of beer and a good radical scavenger. The findings of Andersen and Skibsted (1998), which revealed the 1-hydroxyethyl radical as quantitatively the most important radical in beer, support this. The 1-hydroxyethyl radical arises in the reaction of ethanol with the hydroxyl radical. Generally, the reactive oxygen species (HOO , H2O2 and HO ) react with all kinds of organic molecules in beer, such as polyphenols, isohumulones and alcohols, resulting in various changes in the sensory profile of beer.

Which is what I was posting about a few days ago. The solution I was proposing to test was that early boil hops and first wort hops can be used as a chelant to bind free iron and copper, since isomerized alpha acids bind iron ions. So upping your IBU's a few points with a 60 minute hop addition might benefit the shelf-life of this style.

The reason it's important to have the 60 minute addition is because you then boil for 45+ minutes with free iron ions in solution. Due to the many reactions that take place during boiling, those iron ions might form radicals that can no longer be bound by hop alpha acids, so your late boil and whirlpool hop additions don't complex them. The earlier in the process you add hops, the simpler the structure of the iron ions should be, and the higher the probability of binding them with the hop acids instead of creating staling compounds.

I'm tempted to brew a side by side batch and use a 60 minute addition +whirlpool, and a 5 minute + whirlpool and see which one has better shelf-life.
 
Could you, in theory, use a very mild/low AA hop and still gain the benefit with minimal impact on IBU?
 
Could you, in theory, use a very mild/low AA hop and still gain the benefit with minimal impact on IBU?
Like a first wort hopping?
That's what I did with my latest brew (still fermenting). I'll report back when all is done.
 
Could you, in theory, use a very mild/low AA hop and still gain the benefit with minimal impact on IBU?

According to the paper I posted earlier, its the alpha acids themselves that act as a chelant to bind the iron. So a lower alpha acid hop should be less effective than a high alpha acid hop ounce for ounce.
 
Another data point for you guys...Two photos of the same batch of beer, bottle differently.

The first photo was bottled in a bottle only 1/2 full. I did not do any CO2 sparging, just filled the bottle half way and threw a cap on it.

The second photo of "normal" looking beer was bottled correctly, with maybe 1/2" or so of headspace at the top of the bottle.

Both beers were bottle conditioned for 3 weeks, at ~76F in the same closet.

Oxidized.jpg


Non Ox.jpg
 
Also, what yeast.
And, for science, woul put 2-3 in the fridge, compare color when you are half way through the batch, and again near the last bottle
Curios if and how much difference temperature has long term storage and srm.
 
Another data point. I brewed my latest NEIPA 5 1/2 weeks ago and Keg conditioned it at 2 weeks. At 3 weeks I bottled a few when I thought it was peaking. I bottled it by using BierMuncher's method, overflowing each bottle with foam, and a little beer. 2 1/2 weeks later I'm checking whether any oxidation has begun. It was looking and tasting the same.
QGVu1kP.jpg

So it looks like this method seems to help prevent oxidation.
 
Another data point. I brewed my latest NEIPA 5 1/2 weeks ago and Keg conditioned it at 2 weeks. At 3 weeks I bottled a few when I thought it was peaking. I bottled it by using BierMuncher's method, overflowing each bottle with foam, and a little beer. 2 1/2 weeks later I'm checking whether any oxidation has begun. It was looking and tasting the same.
QGVu1kP.jpg

So it looks like this method seems to help prevent oxidation.

Cold storage the entire time, I assume?
 
Have a couple bottles left?
If able and willing, could you put one at room temp for 10-15 days and compare with one kept cold?


I suppose so, what are you thinking? Fermentation hasn't completed?

Edit: will post results
 
Curious about browning or change in flavor from biotransformation.
Could help rule out if bottling or yeast/hops interaction causes alteration in SRM/flavor.
If it changes significantly, it likely due to interaction of yeast and hops.
If not, would be a strike against bottle conditioning.
 
Here are the results to my bottle test. It's been 13 days, I left the bottle on the left in the cooler the entire time. I left the bottle on the right on a shelf at temp range of 65 - 83F.

After opening and tasting, I did not notice any significant difference in color, aroma, or taste between the two. The only noticeable difference was the bottle left on a shelf had thicker and better head retention. So this may have actually improved the beer.
au3UmfJ.jpg
 
Scturo thanks for posting these results. What yeast was this?


S-04 yeast was used. This batch was made in June, so the overall hop aroma and flavor has subsided some for both, and I would say equally.

These beers were bottled using BierMuncher's method, filling all the way to the top, with no head space. Kegging and using this bottling method seems to have help resolved my oxidation issues when bottling.
 

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