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bostonapothecary last won the day on July 29 2018

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  1. Recently, I started exploring titration for acids and ester determinations and wrote a primer. Is anyone here currently using titration in their analysis work that is willing to offer some tips? I'd love an automatic titrator, but working affordably so the work can be duplicated by others is important. My goals are to accurately measure titratable esters in a spirit and then subtract the ethyl acetate isolated in the first three birectifier fractions to create a ratio of low value to high value esters. Arroyo worked with a similar ratio in Studies on Rum. I'd also like to be able to create numbers that can bring more of the historic data tables to life. Tracking the development of ethyl acetate is important to understanding maturation. Titratable acidity is key to working with ferments that feature large buffers and significant noble volatile acid production. I'll hopefully add these basic titration results to my birectifier role model case studies. Any tips, tools, suppliers, or calculators you like?
  2. I can only wildly speculate because I do not have enough experience here. From what I've heard, bottles must be rinsed with whatever they are to be filled with. These bottles may have something leftover from their manufacturer. In some of the birectifier analysis I've done of aromatized spirits, stuff with lots of very volatile terpenes appears in the first fraction and I've encountered strange condensation quickly developing in the tasting glass with a watch glass cover. These fraction are dilluted to about 35% ABV. So my theory would be that the manufacturer may have used some kind of citrus based degreaser/cleaning agent on the bottles that contains odd very volatile terpenes. Because this is so common, what I'd like to see is a trade group approach glass manufacturers and convince them to publish a bulletin on the topic for the benefit of the entire industry. Trade groups and the industry used to do tons of stuff like that and it was also often organized by the IRS labs. It doesn't seem too hard to improvise a study to rule out things. I'd hand bottle an array of products at differing proofs with rinsed and unrinsed bottles. Possibly start with neutral spirits and then do your various products. These can live on a shelf with dates on them. Whatever rinses out could also be fractionally distilled to concentrate/isolate it and see if that yielded any quick insights.
  3. I don't really know much about this topic, but I remember a Seagram/Hiram Walker paper from the 1940's mentioning that they reduced a massive amount of losses by instituting an inhouse cooperage repair program to stop leaking. I bet it takes a ton of observational skill and intuition to know what will add up if you don't drag the barrel down and whack the hoops. Are people seeing consistency in stats across barrels or a bunch of outliers?
  4. "How low pH can intensify beta-damascenone and dimethyl trisulfide production through beer aging." This is the paper, I'm going to grab first. One thing that sets rum apart from other spirits, is sometimes have a wildly low pH, like vinegar process rums that Hampden makes, and also the long resting periods where these compounds may form by what the beer industry called "staling". When you maximize the multiple channels of formation, something very special may happen. Tomato brandy has some cool theoretical potential, so does carrot.
  5. I'm hoping that if we finish the birectifier automation kit, we can create case studies for a bunch of distillations with isolated esters to see what happens. Something I'm really curious about is the place of the odder acetals and what they feel like organoleptically. Damascenone has the potential to be everywhere carotene is, but it may not be too important until it is at levels where its radiant sensory properties emerge (to borrow a word the perfumers use). I think the best way to sum up radiance is that it increases the threshold of perception of ethanol, making a spirit feel more mellow while decreasing the threshold of perception of other odorants, like esters, making them seem more intense. It also dramatically increases persistence. Specialty GCMS studies find it everywhere in trace quantities, but if it isn't easily observable with a low resolution tool like the birectifier, it may not be too important.
  6. I'm itching to get reference for all the rose ketones and play with them. I wrote a post called Sensory Sketches for Apprentices where you take fractions and systematically add them to a whole distillate to see how they impact the sensory matrix. It takes a time investment, but you can learn a ton.
  7. Hi all, I started this topic as a catchall for conversations on all the high value congeners chased when producing rum. HVC's includes esters, noble acetals, noble volatile acidity, and what ever rum oil is (rose ketones and goodness knows what else). There is room to talk about harmony, philosophy, and how the fate of everything high value is bound to fusel oil. I thought I would kick off the topic by sharing two French translations I just put up from 1975. The first paper, Qualitative And Quantitative Study Of Volatile Constituents Of Rum, is fascinating. They start inspired by Karl Micko who was the father of the 8 fraction birectifier method: They work their way to a rose ketone connection and give us a rum oil smoking gun: This paper also contains very unique sensory details because they used GC-Olfactometry: What they perform is a bit exotic and startlingly expensive. A lot of the same organoleptic insights can be obtained from the birectifier method. I'm drawn to the comment about Calvados and acetals dominating. I've yet to do a Calvados birectifier case study. The next paper, The Position Of Rhum In The Context Of Spirits In General, is quite unique and raises a lot of questions. They spend quite a bit of time on Damascenone, but also TDN (petrol in reisling) and TTN (not familiar with). What other readers may be most interested in is the unique ester data tables with extraordinary samples: The first question raised by me is don't you think a whiskey would have more ethyl lactate? And then secondly, why do they have a column for isoamyl acetate for rum, but not for the other spirit categories?
  8. The University of Bordeaux was just as aggressive as UC Davis in increasing the quality of European wines. They had storied thinkers like Denis Dubourdieu who just passed recently. They eradicated a lot of very specific flaws through education. A flaw is not a flaw until you attach symbolic concepts like regrets or missed opportunities. A Dubourdieu project was eliminating the bell pepper aroma from certain varietals (Carmenere). Many thought it was site specific terroir, but it was revealed to be removed by pruning techniques. Removal of the character added a lot of value to the grapes. The international style is a whole different story, but related to low risk wine making, and fad flavors. That style doesn't dream enough and no wonder it wore out quick. Even in the center of the terroir scene, a problem is that ordinary wine making flaws have been so significantly eradicated that when they reappear, elite critics are mistaking them for terroir. What is ordinary becomes briefly extraordinary until the regrets and missed opportunities are re-attached. Jamie Goode, who wrote, Authentic Wine: Toward Natural and Sustainable Winemaking, just wrote a book about understanding faults in wine. Mezcal, like so many spirits, are well in the realm of acquired tastes. We have fun looking at the production of eccentric spirits because they seem very risky and yet it mostly works out. Many of them do have flaws and Mezcal is often flinging anything at consumers hoping they will try a single bottle before moving on. We often don't have the language to separate faults from acquired tastes. One cool thing about the flavors in rum, particularly rum oil, is it was absolutely chased. Jamaican rums and Batavia Arracks fetched the highest amount of money in the world for spirits ever. This was leaps and bounds above what other spirits got at the same time. Very certain rums were the pinnacle of luxury consumption so we know something about the value of what we're chasing. It really captivated imaginations.
  9. I think I made some assumptions and chose California's figures at the Judgement of Paris which is an entrepreneurship story which inspires a lot of distillers. Europe having fine wine is a bit messy. It definitely had them, the best, and was no doubt was direct inspiration for California's pioneers, but Europe also had a sea of local wines riddled with faults. The Europe we know today which is a beautiful sea of diverse consistently produced fine wines is probably because of incredible oenology education programs and small scale labs at small properties. Knowledge and awareness of how sulfur acts on wine is not enough, you still need instruments to measure sulfur and wield the knowledge. Old California wine history has some problems which is why the oral history series was created. Tchelistcheff and Amerine gives us really plain looks at the state of the best early California wines (very few and their stories are incredible) while Leon Adams muddies it and gives us another. Adams, running the biggest trade group (the wine institute), was an obsessive propagandist. He admits to fabricating a lot of early wine history to build mythology and erase the notion that wine was a salvage product (table grapes > raisins > wine) drunk by bums on skid roe. His two oral histories are completely insane. I don't think California had any truly extraordinary brandies until the Remy Martin Scramsberg project and there are cool oral histories on it as well as two excellent James Guymon lectures by Eli Skofis and Robert Léauté. The cool thing about analysis is it both reinforces and turbo charges intuition so you know when to invest the time and when to not. It is the key to building a palate and understanding materials. Birectifier analysis is very cool because its most basic form is organoleptic. Working with it constantly builds you palate.
  10. It isn't when you consider California and its transformation under figures like Maynard Amerine and André Tchelistcheff. Wine with with fine ambitions as opposed to commodity existed but was extremely limited before the 1970's. When you read all the memoirs and oral histories, the pattern is that all the players were adept lab guys that spent time working with Tchelistcheff, Mondavi, or sitting in on night classes at UC Davis. That lab work also wasn't too wild. It was a lot of tracking titratable acidity and sulfur dioxide.
  11. I personally favor a lot of the Jamaican ideas over the Arroyo ideas. Arroyo got his ass kicked by numerous factors. He also had numerous successes that are very easy to take for granted. For starters, he died untimely which doesn't help promoting something very complicated. Then his ideas for heavy rum came at a time where the post war economy demanded affordable ubiquitous commodity products. Puerto Rico also had the tax rebate so they focused on that comparative advantage and obliterated everyone else in the commodity sector. There was a super cool talk on "Spanish style rums" in Jamaica this past October. No style was discussed. It was all just startling efficiency and economy. At some point Arroyo's papers were lost and barely referenced again even as others waded into the same territory. Even though no one made heavy rum, the Arroyo victories are everywhere. Continuous stills got filled with encrustations until his molasses pre-treatments were adopted. Many distilleries use centrifuges but Arroyo paved the way. People used simple bakers yeast and paid no attention to pitching quantities that impacted fermentation rate. Yeast nutrient use was a mess. Little attention was also paid to yeast selection even for fast fermenting light rums. Arroyo also taught about record keeping to prove efficiency. Many at the time were running continuous stills inefficiently and losing a ton of alcohol in the stillage with few records to isolate the loss. Arroyo even taught people about even congener composition when before they were just winging it. His stamp is all over fast fermenting economy rum, quite a lot of precedents. Arroyo elaborated the birectifier, but I think no one used it except one guy in Trinidad in 1953 for a PhD dissertation. Rum distilleries really cheaped out on labs until they learned from the Seagram crowd. By that time, chromatography was becoming fashionable. There is significant opportunity today because analysis is faster and much cheaper. Fine wine was born in the lab (Grgich, Stag's Leap, Chateau Montelena) and fine distillates will be the same. Right now people that are frustrated are conducting zero analysis. One of the best things you can do is deconstruct role models to learn the grammar. Back in the day they had a lot of trouble obtaining exemplary samples and now we can go to any corner liquor store. As mostly non formally educated biochemists, we also have the benefit of YouTube University and inter library loan. One of the big complaints in the 20th century was how scattered the literature was, but now it is aggressively being collected and shared. The heavy rum patent may be some kind of weird tease, but is anyone really using 21rst century opportunities in their operations? When I discuss a heavy rum production idea, I've got a comprehensive $3000 analysis solution to examine it. And true, yet another $4000 for a titrator. My goal for 2019 is more case studies and model ferments. Bring it to life backed up by the most basic analysis.
  12. I wrote about Koji's historic use in whiskey as a follow up to some other whiskey documents. It would be awesome to introduce the Noma team to the birectifier. A recent case study shows that it may be a viable way to analyze vinegar. They could also likely take that quince, extract it's aroma with ethanol, then fraction it to gain insights. Reading through the carotene derived aroma literature, there may be spectacular potential in odd substrates if grand arôme ideas are used as opposed to more straight forward fermentation/distillation templates. Arroyo's mold was actually an alt-yeast that metabolized proteins to produce the high value ester, ethyl-tiglate, which smells appley. My microbiologist colleague has isolated it and it's looking like it may be the easiest to work with grand arôme fermentation complication.
  13. I have a bunch of the papers behind paywalls. It is quite the rabbit hole. When you experience these compounds isolated, they are quite extraordinary. I wrote two very funny blog posts where I introduced them from the perfume industry perspective. They very much live up to Arcadi Boix Camps idea that he immediately felt the desire to introduce them to Plato! One of the nice things about them is that targeting them goes hand in hand with targeting esters. Wayne Curtis just wrote an interesting article about the state of tequila rediscovering itself. When they describe character they cannot really pin down through their change in process, even though they have GCMS, a lot of what they are doing may be maximizing these carotene based aromas. The heritage Tahona process (as opposed to diffuser) likely comes with greater time under heat. They also put some shredded agave in the ferment. These compounds are very challenging to look at and only university based labs are sophisticated enough. The birectifier gives a cheap window, but only allows you to do an organoleptic survey. To go to yet another Daily Beast article from Lew Bryson, where I think his argument is flawed, the difference between pot and continuous column stills (beer still) may be their ability to target these hard to reach compounds. A pot still has longer time under heat with increasingly concentrating acidic conditions. If a continuous column has a fusel oil separator, they may be inadvertently trashing these compounds. Two strikes against the continuous column, but if the pot operator doesn't know what they are looking for, how do they know they are maximizing potential? The sour mash process is quite special, just like the dunder process. All that time under heat invested into the stillage can create high value aroma that can be unlocked by the next fermentation. Both articles and the discussion here, show these compounds are going to move to the top of distillation discourse and very much fit in with everyone's pursuit of esters. I hope they present opportunities for smaller producers to really excel and rival large productions.
  14. The birectifier contradicts this somewhat. Ordinary ethyl-acetate appears in the first two fractions, and though quite concentrated, stays perfectly clear. Most extraordinary longer chain, higher molecular weight esters appear in the fifth fraction (while 75% of fusel oil is in the 4th). The turbid cloudiness turns out to be high value esters shocked out of solution. I've experienced aromas I assume to be be iso amyl acetate (banana) in the second fraction. Other esters may lurk in the first fraction but be overshadowed by the cloying noxiousness of the ethyl-acetate. What I just described is highly sorted fractioning by birectifier. On a normal less fractioned run everything would be spread out with significant overlapping. A lot more of what is in fraction 5 (high value) stretches way out into the tails, which you can't capture without risking too much fusel oil. It would be awesome to add titratable acidity. Then we could look at how esters either break and reform or how they stay broken but maybe continue contributing as noble-volatile acidity. This would cost $4000 for the titrator and be pretty low skilled. To bring it around for those reading along, understanding much of this may be key if you plan on adding secondary bacterial ferments.
  15. I wish there was more data on this. The best questions were asked before the GCMS era. We can look at things so easily now which would yield some awesome dissertations. Supposedly, built in water destroys the least esters, but watering high ABV destroys the most. I think it is the final act of getting it to drinking proof that needs to be considered the most. As we all know, challenging economics surrounding building in all that water rather than adding it at the last minute. Isn't ethanol very polor? So what may happen is that higher alcohol esters may break and ethyl esters reform. This would be bad because you're limiting diversity and freeing fusel oil. I don't really understand the higher alcohol esters. Some literature claims they are the weakness of continuous column of stills. Basically higher alcohols get trapped in a zone and increase the chance of ester formation. Problem is that these esters are often plebeian and ordinary, overly diffusive in the top notes, and can make a California brandy or Old Granddad smell cheap like a banana. This problem may assume we are talking about basic ferments that don't have diverse quantities of fatty acids. What do you think of this: many esters formed during distillation are temporary place holders. We hope for ethyl esters to increase the volatility of noble fatty acids even though they will break and not reform. These temporary place holder esters just get them across the cut and in to the hearts defying their typical fate. This may be fine because noble volatile acidity may contribute to quality. However, if a higher alcohol ester breaks this may be very bad. Amyl alcohol is less polar than ethanol so that favors reformation with ethanol and the free amyl alcohol increases fusel oil content. Amyl alcohol is also perceived as the most dissonant of the higher alcohols. But how significant is that number of freed up amyl? Who knows. What I wish we knew more about is, exactly how volatile are all of the higher alcohol esters? The birectifier fractions hint that they are less volatile than fusel oil, but a few are famously more volatile (isoamyl acetate). In many cases, these esters may only function as a temporary place holder for fusel oil, reducing its volatility which is a win and allows you to distill further into the run collecting more of other high value congeners. It is best to reduce fusel oil at fermentation, but to some degree (not well understood), it may be reduced by reactive distillation (mentioned up thread by @Silk City Distillers). Maybe we can't assume all esters are straight forwardly useful?
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