A Tale of Chemistry and Poison Photo by Sam Johnson from Pexels During the American Prohibition, moonshine was responsible for over 750 deaths and more than a hundred thousand cases of blindness or paralysis in New York City alone. Over eighty years later, in early 2019, several outbreaks of toxic alcohol poisoning lead to hundreds of deaths and injuries in northeast India.
- The culprit in both these cases was methanol contamination.
- Chemically, the only difference between methanol and ethanol is the number of carbons (two in ethanol and one in methanol).
- Methanol and ethanol taste about the same and produce about the same initial intoxicating effect.
- The only difference is that methanol, once ingested, is metabolized by the liver into formaldehyde and formic acid, chemicals that can damage the optic nerve, leading to blindness, and eventually resulting in death.
Methanol is a common contaminant of moonshine, which is typically made from fermenting a “mash” of corn, sugar, and yeast for a few days and then distilling the mixture. During the fermentation process, the enzymes in the yeast convert the sugar into energy for the cell.
A byproduct of this reaction is ethanol, the main ingredient of alcohol. Methanol is not a direct byproduct of fermentation, but instead forms from the breakdown of pectin in corn. After fermentation, the slurry is distilled by boiling it and running the gas through a still. The first element of the still is a long upward shaft through which the gas rises.
The length of this shaft prevents anything that is not gas from escaping to the next stage. Next, the gas travels downwards through another shaft that’s kept ice cold. On the other side of this shaft, the gas is cool enough to condense into liquid again. Photo by Davide Baraldi from Pexels Methanol is easily removed in regulated alcohol production, and extensive testing is required by the U.S. Food and Drug Administration (FDA) to ensure that very little methanol makes it into the final batch. In the case of alcohol that is used for industrial or scientific purposes, methanol is often added back into the batch after distillation to make it toxic and thus not subject to alcoholic beverage tax.
- Bootleggers can use this cheaper methanol-tainted alcohol to turn a considerable profit.
- During Prohibition, the government doubled the amount of methanol in industrial alcohol to make it more toxic and discourage bootleggers from stealing and redistributing it.
- Bootleggers put significant effort into overcoming these measures, hiring chemists to distill the toxic chemicals out of their alcohol.
But the government only doubled down their efforts, adding up to 10% methanol and a whole slew of other poisons including chloroform, gasoline, and mercury salts. The only thing these measures accomplished, however, was to poison and kill an estimated 10,000 Americans by the time the Prohibition ended.
These days, epidemics of toxic alcohol poisoning still occur around the world in poor areas, like the tea plantations in India, where unscrupulous bootleggers sell cheap alcohol laced with methanol or lead. Lead can be leached from truck radiators, which are frequently used in crude distillation setups.
Drinkers discern very little difference between clean alcohol and alcohol laced with methanol, and the body’s immediate reaction to the alcohol is the same. It’s only hours later, once the methanol has been digested and converted to formic acid, that the poison presents itself with convulsions, blindness, and death.
- 1 How is methanol made in alcohol?
- 2 How does distilling create methanol?
- 3 Why we Cannot drink methanol?
- 4 Why is methanol not drinkable?
- 5 Which is more toxic ethanol or methanol?
- 6 What is the risk of methanol in moonshine?
How does moonshine get methanol?
How is Methanol Produced in Moonshine? – via GIPHY Methanol is a by-product produced during the fermentation process of making moonshine. During fermentation the enzymes in the yeast are responsible for converting the fermentable sugars into energy for the cell.
How is methanol made in alcohol?
Methanol is produced during fermentation by the hydrolysis of naturally occurring pectin in the wort (Nakagawa et al.2000; Mendonca et al.2011). PME de-esterify pectin to low—methoxyl pectins resulting in the production of methanol (Chaiyasut et al.
How does distilling create methanol?
During fruit sugar fermentation to ethanol by yeast, methanol is formed primarily through degradation of pectin by pectin-methylesterase (PME). Methanol can be quantified also with compact and multiuse liquid or gas sensors.
Why we Cannot drink methanol?
Nineteen people in Costa Rica have died after consuming alcohol tainted with harmful levels of methanol. The Costa Rican Ministry of Health has confirmed that out of these fatalities, 14 were men and five were women, all were between the ages of 32 and 72, and occurred across various cities in Costa Rica,
The U.S. Department of State confirmed that no U.S. citizen’s illness or death has been related to the consumption of adulterated alcohol in Costa Rica. All victims identified so far have been Costa Rican, and did not consume the alcohol at hotels. The health ministry has confiscated about 30,000 containers of alcohol labeled as Guaro Montano, Guaro Gran Apache, Star Welsh and Aguardiente Molotov, after identifying toxic levels of methanol in them.
They have advised the general public to avoid consuming these alcoholic beverages until further investigations are completed and the sources of counterfeit products have been found. Costa Rica President Carlos Alvarado Quesada tweeted out last Friday that he has instructed authorities to continue gathering data in order to identify the sources responsible for these deaths.
- While Costa Rica is now making headlines, in recent years there have been numerous outbreaks related to tainted alcohol in Cambodia, Czech Republic and Ecuador, among other countries.
- Some outbreaks have affected as many as 800 victims with mortality rates greater than 30%, according to the World Health Organization,
In India, 154 people died and over 200 were hospitalized this year alone after drinking unregulated moonshine. Methanol poisoning typically occurs due to the consumption of “adulterated counterfeit or informally produced spirit drinks,” according to the World Health Organization,
- Here’s what you need to know about tainted alcohol and how to avoid being a victim of methanol poisoning.
- Methanol is a widely available chemical that is used in everyday household products.
- Methanol, otherwise known as methyl alcohol, has many industrial applications and can be found in household items such as varnishes, antifreeze, and windscreen wash.
Methanol is also found in things we consume – trace amounts are found naturally in fruit juices, fermented alcoholic and non-alcoholic beverages at non-toxic levels. Low concentrations of naturally present methanol are not harmful, but higher concentrations may be toxic.
- Since methanol is a product of fermentation, low levels of methanol are detected in all beer and spirits, but these low concentrations are not toxic when consumed.
- Harm can be incurred when distillation processes are ill managed, or more commonly, methanol is deliberately added to alcoholic beverages and methanol levels exceed 10-220 mg/L.
When ingested, the body metabolizes methanol into formaldehyde and formic acid, which in large amounts are toxic and even fatal. Methanol levels in the blood exceeding approximately 500 mg/L is toxic if left untreated. The onset of methanol poisoning symptoms do not appear immediately after alcohol consumption.
Methanol poisoning symptoms take a while to surface. The consumed methanol must be metabolized, and toxic levels of formic acid must accumulate in the body. In the first few hours, a person will experience drowsiness, feel unsteady and disinhibited. Eventually these symptoms will escalate into a headache, vomiting, abdominal pain and vertigo.
Patients may also hyperventilate or feel out of breath, and even experience convulsions, and permanent visual impairment. Most victims seek medical care after a significant delay, which contributes to the high level of morbidity and mortality. Misleading bottle design, labeling, and cheaper prices often cause consumers to unknowingly purchase and consume tainted beverages.
- Unregulated, illegal production and distribution of alcoholic drinks takes place worldwide.
- Cheaper alcohol is particularly attractive to low-income consumers and people who are alcohol dependent.
- Tourists visiting foreign bars, shops and vacation spots with high alcohol consumption are also at a higher risk.
The main objective of treatment is to prevent further metabolism of methanol. If you suspect someone is a victim of methanol poisoning seek immediate medical help. Ethanol or fomepizole administration, intubation, or mechanical ventilation are the primary forms of treatment.
These are meant to prevent further metabolism of methanol and rapidly remove methanol from the body. You can protect yourself from methanol poisoning. Avoid purchasing or producing illegal alcoholic drinks and be cautious when purchasing alcoholic beverages at informal settings or from vendors who are not licensed to sell alcohol, especially if it is being sold at suspiciously cheap prices.
Avoid all unlabeled alcoholic beverages or labels that are poorly printed with broken seals. These are likely counterfeit and potentially toxic Eden David is a rising senior at Columbia University majoring in neuroscience, matriculating into medical school in 2020 and working for ABC News’ Medical Unit.
Why is methanol not drinkable?
Pearls and Other Issues –
Methanol is metabolized to its toxic metabolite, formic acid/formate. Formic acid is responsible for metabolic acidosis and end-organ toxicity. End-organ toxicity includes primarily retinal damage, and possibly basal ganglia damage. Methanol is osmotically active. An osmolar gap cannot be relied upon to rule out toxic alcohol poisoning. A normal osmolar gap is not reassuring and should be expected in the presence of an anion gap acidosis believed to be related to toxic alcohol poisoning. The mainstay of treatment is fomepizole, supportive care and resuscitation, and dialysis. Dialysis indications include the presence of end-organ toxicity. In the absence of end-organ toxicity, methanol toxicity often benefits from dialysis, unlike ethylene glycol toxicity, due to its very long elimination rate once alcohol dehydrogenase is blocked with fomepizole.
Can you run moonshine twice?
If you are wanting to double distil the spirit you have collected from your Air Still, we recommend topping up to the 4 L (1.1 US Gal) max line with water. Put the 700 ml (23.7 US fl oz) of alcohol you’ve collected from the first run, back into the boiler and top up to the 4 L (1.1 US Gal) max line with water.
Why is methanol so much worse than ethanol?
Methanol is an alcohol similar in structure to ethanol. An enzyme in the body, alcohol dehydrogenase, breaks down either one. With ethanol, the product is acetaldehyde, which is toxic but readily broken down even further. With methanol, the enzyme breaks it down into formaldehyde, which is highly toxic.
Which is more toxic ethanol or methanol?
Methanol, sometimes called wood alcohol, is the simplest of the class of chemicals chemists call alcohols. Ethanol, the spirit many enjoy in beer, wine, and cocktails, is closely related. Both can be made naturally when yeast ferment the natural chemicals in grains and fruits.
- And like all chemicals, both can be toxic when you are exposed to too much.
- But, when you consume methanol, the way your body metabolizes it makes it much more toxic than ethanol.
- Methanol poisonings were common during the Prohibition Era of the 1920’s and 30’s because methanol was intentionally added to industrially produced ethanol.
This was to prevent bootleggers from using it for alcoholic beverages. Ethanol treated to prevent it from being consumed is called “denatured” alcohol (so never drink denatured alcohol!). Because of concerns over possible toxicity, ethanol denatured with methanol is not allowed for use in things we apply to our skin, like cosmetics.
- Methanol in hand sanitizers used to combat COVID-19 has recently been in the news with the US FDA warning the public and recalling a number of ethanol based hand sanitizers contaminated with methanol.
- Why is Methanol Toxic, and How is it Different From Ethanol Toxicity? The answer to this question lies in the differences in what your body does to these two chemicals, often referred to as metabolism.
In the case of ethanol your liver first metabolizes it to something called acetaldehyde. Acetaldehyde is rapidly metabolized to something called acetate, a far less toxic molecule that is readily eliminated from the body. For the average person there is no significant build-up of metabolic products.
- We hasten to note however that you can certainly poison yourself with ethanol if you drink too much too fast and overwhelm your body’s ability to get rid of it.
- Moderation in drinking is wise! Methanol on the other hand is converted first into formaldehyde and then into formic acid.
- High levels of formic acid cause a range of different effects including something called acidosis, where the acidity of your blood gets too high and a number of organs (like the kidney) begin to malfunction.
Formic acid is also a primary cause for damage to the nervous system (what toxicologists call neurotoxicity). Damage to the optic nerve and subsequent permanent blindness is a hallmark for non-lethal methanol toxicity. Methanol is a great example of how your body can actually make a chemical more toxic.
- How Much Methanol is Toxic? The lethal human dose of pure methanol is estimated to be about 2.5 ounces.
- This is the median lethal dose, meaning about 50% of people that consume this much may die.
- Consuming about half an ounce of pure methanol could cause blindness.
- By comparison, the lethal human dose of ethanol is estimated to be about 6 ounces for an average sized person.
Since alcoholic drinks are usually 45% ethanol or less, 6 ounces of pure ethanol is equal to about 14 drinks (assuming a drink with a 1 oz shot of a typical liquor). If a typical bottle of liquor was all methanol instead of ethanol it would only take about 1 drink to cause permanent blindness.
- Please note that these are estimates for comparative purposes.
- Bottom Line Methanol is much more toxic than its close cousin ethanol and is a great example of how differences in the way our bodies handle different chemicals has an influence on both the nature and the extent of toxic effects.
- But, as always, the dose makes the poison and just because something may contain methanol (e.g.
many natural foods) does not mean ingesting it, or being exposed to it through air or skin, will cause harm. https://www.cdc.gov/niosh/ershdb/emergencyresponsecard_29750029.html https://emedicine.medscape.com/article/1174890-overview https://cfpub.epa.gov/ncea/iris/iris_documents/documents/toxreviews/0305tr.pdf http://prohibition.themobmuseum.org/the-history/the-prohibition-underworld/alcohol-as-medicine-and-poison/ https://www.fda.gov/drugs/drug-safety-and-availability/fda-updates-hand-sanitizers-methanol
Can you drink 95% ethanol?
3) Denatured Ethanol – Denatured ethanol (either 95% or absolute) contains additives (such as methanol and isopropanol) that render it unsafe to drink and therefore exempt from certain beverage taxes. This makes it cheaper than pure ethanol. Of all the ethanol grades, this is the one you’re most likely to use for disinfection in your lab.
How much methanol is in vodka?
The Analysis of Vodka: A Review Paper Vodka is the most popular alcoholic beverage in Poland, Russia and other Eastern European countries, made from ethyl alcohol of agricultural origin that has been produced via fermentation of potatoes, grains or other agricultural products.
Despite distillation and multiple filtering, it is not possible to produce 100 % ethanol. The solution with a minimum ethanol content of 96 %, which is used to produce vodkas, also contains trace amounts of other compounds such as, esters, aldehydes, higher alcohols, methanol, acetates, acetic acid and fusel oil.
Regarding that fact, it is very important to carry on research on the analysis of the composition and verifying the authenticity of the produced vodkas. This paper summarizes the studies of vodka composition and verifying the authenticity and detection of falsified products.
It also includes the methods for analysing vodkas, such as: using gas, ion and liquid chromatography coupled with different types of detectors, electronic nose, electronic tongue, conductivity measurements, isotope analysis, atomic absorption spectroscopy, near infrared spectroscopy, spectrofluorometry and mass spectrometry.
In some cases, the use of chemometric methods and preparation techniques were also described. Vodka is the most popular alcoholic beverage in Poland, Russia and other Eastern European countries. In Russia, vodka is mostly produced from wheat; while in Poland, a rye mash is most frequently used.
Vodka is made from ethyl alcohol of agricultural origin that has been produced via fermentation of potatoes, grains or other agricultural products. The obtained ethanol-containing solution is distilled or rectified to selectively reduce the intensity of taste and smell of the raw materials and the by-products of fermentation (Act of 13 September on the spirit drinks).
The distillation process takes place in a distillation column. Vodka owes its neutral character to the separation of the heads fraction (higher alcohols) from the tails fraction (the least volatile esters). The soft taste of vodka is achieved by multiple filtering of alcohol through activated charcoal, followed by dilution with water, the latter being distilled, demineralized or treated with Permutit or water softeners (Regulation, E.C.N.110/; Christoph and Bauer-Christoph ; Ng et al.).
The minimum strength of vodka is 37.5 % by volume. Besides pure vodkas, there are flavoured vodkas, which are characterized by a dominant flavour different than the taste of raw materials used in their production. Flavoured vodka can be artificially sweetened, blended, flavoured, matured or coloured. It can be sold under the name of any dominant taste, which is added to the name “vodka” (Regulation, E.C.N.110/).
Despite distillation and multiple filtering, it is not possible to produce 100 % ethanol. The obtained solution with a minimum ethanol content of 96 % also contains trace amounts of other compounds such as esters, aldehydes, higher alcohols, methanol, acetates, acetic acid and fusel oil (Regulation, E.C.N.110/; Hu et al.).
- The chemical and sensory analyses of flavoured spirit-based beverages concern the three main components of the product, i.e.
- Alcohol, water and flavourants.
- Both analyses are used for assessing the raw materials, production type, quality control, authentication and the detection of possible falsification.
The analysis of alcohol used in vodka production encompasses a sensory evaluation, the measurement of alcohol content, and a detailed chemical composition analysis. The sensory evaluation is usually conducted by the group of trained persons on the approved sample.
- The alcohol content measurement is traditionally performed by using the hydrometric or pycnometric method.
- The chemical composition analysis is commonly conducted by means of one-dimensional gas chromatography (GC).
- Due to the requirements imposed on alcohol used in vodka production, mainly the content of methanol, acetaldehyde, ethyl acetate and higher alcohols is measured via direct sample injection into the gas chromatograph equipped with a flame ionization detector (FID).
Such content analysis is useful for comparing different alcohols and confirming the compliance with the imposed requirements (Aylott ). Presently, besides the aforementioned analyses, studies on alcohol samples are conducted by using ion chromatography (IC), liquid chromatography (LC), mass spectrometry (MS), spectrophotometry, electronic nose, electronic tongue, isotope analysis and others.
Due to the low concentration of the analysed compounds, the techniques aimed at increasing the analyte concentration prior to analysis are often used, such as solid-phase microextraction (SPME) and solid-phase extraction (SPE) (Siříšťová et al.). In this review paper, we describe research conducted by means of various analytical techniques whose aim was to determine more details of vodka composition, to detect falsified vodkas and to identify different vodka types, which are placed in Table,
Table 1 Examples of analysis of vodkas As previously mentioned, vodkas are produced from various raw materials of agricultural origin such as grains and potatoes. Due to diversity of raw materials, the final products are also highly diversified. At present, numerous brands of vodka are offered on the market, including pure and flavoured vodkas produced from one or more raw materials.
The types of vodka production also differ, which influences the final composition of the product. Due to the ever increasing number of vodka products and the client’s interest in new products, it is necessary to precisely determine their composition. Low concentrations of the compounds present in vodkas pose a big challenge for chemical analysts.
The majority of studies are conducted by means of one-dimensional gas chromatography because this technique has many advantages such as high resolution and high sensitivity. This allows the identification of a large number of analytes. Moreover, the possibility of coupling GC with different detectors makes this technique applicable to a wide spectrum of alcohol-based products.
- Flame ionization detector (FID) is most commonly used because of its relatively low price and universal application.
- A GC-FID system was used, among others, to determine methanol content in commercial and illegally produced vodkas.
- The obtained results differed depending on the vodka type, and ranged from 17 to 376 mg/l (Chłobowska et al.).
The admissible concentration of methanol in pure vodka is 100 mg/l of vodka; while in case of flavoured vodkas, the admissible concentration of methanol is 2 g/l of vodka. All the investigated samples were within these limits. A GC-FID system was also applied to analyse the volatile fraction of vodkas originating from Brazil (Pereira et al.) and Vietnam (Lachenmeier et al.).
In the case of Brazilian vodkas, 32 brands were analysed with regard to the content of higher alcohols, acetaldehyde, ethyl acetate and methanol. Both methanol and acetaldehyde were present in these vodkas at the concentrations below the limit of quantification. For most samples, the content of higher alcohols and ethyl acetate did not meet the EU standards although the total content of contaminants was definitely lower than the values prescribed by the Brazilian regulations (Pereira et al.).
Lachenmeier et al. () analysed 11 samples of alcoholic beverages available in local stores in Hanoi, which included three vodkas, one whiskey, one brandy, one rum and others. The collected samples were analysed with regard to the content of ethanol, methanol, acetaldehyde, 1-propanol, 1-butanol, 2-butanol, isobutanol, amyl alcohols, 1-hexanol, 2-phenylethanol, ethyl acetate, ethyl lactate and ethyl octanoate.
- None of the analysed vodkas contained 1-butanol, 2-butanol, 1-hexanol, 2-phenylethanol, ethyl acetate, ethyl lactate and ethyl octanoate (Lachenmeier et al.).
- The GC-FID technique was also used to determine diethyl phthalate in vodka, ethanol and illegal alcoholic products (Savchuk et al.) as well as for assessing changes in the composition of vodka before and after filtration through activated charcoal (Siříšťová et al.).
In both cases, besides GC-FID analysis, the analysis by means of gas chromatography coupled with mass spectrometry (GC-MS) was performed as it gives better results compared to GC-FID analysis. A gas chromatograph coupled with a mass spectrometer is a configuration often used in the analysis of alcoholic beverages.
- In comparison to FID, the MS detector is more sensitive and allows easier identification of the analysed compound.
- As previously mentioned, the GC-MS system was used to determine selected compounds in vodkas, ethanol and illegal alcoholic products (Savchuk et al.).
- A total of 13 samples were analysed, which included three samples purchased at the grocery stores in Stavropol, one reference sample purchased legally in the store in the city, and nine samples bought from individual home owners by the agents from the Kryzyl distillery.
All samples were analysed with regard to the content of ethanol, ethyl acetate, methanol, 2-propanol, n-propanol, n-butanol, ethylene glycol and diethyl phthalate. The composition of all analysed samples differed from the composition of reference sample (Savchuk et al.).
The content of diethyl phthalate was also the object of investigation in the article on the risk of consuming this compound via intake of various alcoholic beverages, among others, vodkas. Phthalates are highly durable esters of phthalic acid commonly utilized in the chemical industry. They are used as plasticizers in many products such as furniture, car air fresheners, medical devices, toys for children or food packages.
Phthalates are not chemically bound to plastic materials, which means they can migrate into the environment. Thus, people are exposed to phthalates via swallowing, inhalation or skin contact. Diethyl phthalate is applied as ethyl alcohol denaturing agent.
Acute toxicity of phthalates is LD50 1–30 g/kg. Moreover, chronic toxicity is observed, too. Aforementioned diethyl phthalate is also considered a potential carcinogenic and teratogenic agent. Due to this fact, it is of utmost importance to test spirit-based beverages for diethyl phthalate presence, especially in case of the products sold in Eastern Europe where alcohol is frequently denatured with phthalate in many production processes.
Leitz et al. () conducted the study by means of GC-MS, while the sample preparation involved the use of liquid-liquid extraction (LLE). Vodka was used as a blind sample because it did not contain diethyl phthalate (Leitz et al.). Due to the presence of sulphur compounds (including dimethyl sulphide, DMS) in some spirit-based beverages, Cardoso et al.
() analysed selected products for the presence of DMS; alcohols popular in Brazil such as cachaça, whiskey, rum, brandy, grappa, tiquira, tequila and vodka were among the investigated samples. The application of GC-MS was described however this technique did not detect DMS in the samples of vodka, tequila and rum (Cardoso et al.).
GC-MS was used to determine fatty acids and esters in some alcoholic beverages and tobacco. Vodka was also among the analysed alcohols. Samples were pretreated by solid-phase microextraction (SPME). This allowed for detecting the compounds present at low concentrations such as, ethyl dodecanoate, ethyl tetradecanoate, ethyl hexadecanoate, ethyl hexadecenoate, ethyl oleate, ethyl stearate and ethyl linoleate (Ng ).
Siříšťová et al. () described changes in the vodka composition after filtering through activated charcoal; the GC-MS system was used to create a list of volatile organic compounds that had been detected in the analysed vodka samples. As in the previous case, the head space (HS)-SPME technique was applied to preconcentrate the analytes.
A total of 29 compounds were detected, including acetaldehyde, limonene, dodecane, hexyl acetate and 2-methylfuran, which were identified based on their retention times and mass spectra (Siříšťová et al.). Studies on the presence of ethyl carbamate (EC) in spirit-based beverages are frequently conducted.
- Ethyl carbamate occurs naturally in fermented foods and alcoholic beverages such as, bread, yoghurt, soy sauce, wine, beer and particularly in spirits made from stone fruits and the stone fruit pomace obtained from cherries, prunes, mirabelle plums and apricots.
- The conducted animal studies proved that ethyl carbamate is a carcinogen.
The International Agency for Research on Cancer has classified this compound as probably carcinogenic to humans (Balcerek and Szopa ; Commission recommendation 133/). The content of EC in Brazilian vodkas (Pereira et al.) and various spirit-based beverages, including vodkas purchased in Ontario (Clegg et al.), was determined by using GC-MS.
The gas chromatography coupled with tandem mass spectrometry (GC-MS/MS) was used to detect EC in Vietnamese vodkas (Nordon et al.). In all these studies, ethyl carbamate has not been detected. Besides the above-mentioned detectors, the electron capture detector (ECD) and flame photometric detector (FPD) have been used for analysing vodkas.
The ECD is a nondestructive detector which allows the determination of the concentrations of halogenated compounds at ppb-ppt level. The articles describing the development and application of the method for determining carbonyl compounds in alcoholic beverages can serve as an example here.
In both studies, the samples were subjected to derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) in order to separate the investigated compounds (Wardencki et al. ; Sowiński et al.). Wardencki et al. () employed the HS-SPME technique for this purpose, while Sowiński et al.
() compared the results obtained by headspace injection with those obtained by SPME. In both studies, the analysis included methanal, ethanal, propanal, propenal, butanal, isopentanol, 2-butenal, pentanal and hexanal. Additionally, dimethyl ketone was determined by Wardencki et al.
- And isobutanal by Sowiński et al. ().
- Most carbonyl compounds have a negative impact on the aroma and taste of spirit-based beverages.
- Some of them, for instance propenal (acrylaldehyde), are highly carcinogenic substances and irritating to the eyes and respiratory tract.
- That is why it is important to conduct research aimed at their control.
Both techniques described in the aforementioned papers proved to be effective in the analysis of carbonyl compounds. HS-GC-ECD analysis revealed higher concentration of some investigated compounds compared to SPME-GC-ECD. This technique allows faster analysis than in the case of using SPME, thanks to the exclusion of preliminary preparation of the samples via solid-phase microextraction technique.
- With this method, the HS-GC-ECD technique occurred to be better compared to SPME-GC-ECD for most of the investigated carbonyl compounds.
- The FPD registers the intensity of light emitted by analyte particles returning to the ground state after excitation in the hydrogen flame.
- This detector is mainly used to determine the concentrations of compounds that contain sulphur (spectral line at 393 nm) and phosphorus (spectral line at 526 nm).
The FPD was used by Leppänen et al. () to determine volatile sulphur compounds present in alcoholic beverages at low concentrations. Even small amounts of sulphur compounds can have a negative effect on the quality of consumed alcoholic beverages. The samples of wine, beer, cognac, brandy, whiskey, rum and vodka were analysed.
- The vodka brands originating from Finland, Russia and Poland were among the analysed samples.
- The analysed substances included dimethyl sulphide, diethyl sulphide, dimethyl disulphide and dimethyl trisulfide.
- The application of FPD allowed the detection of only dimethyl disulphide in vodkas originating from Poland and Russia (Leppänen et al.).
Dimethyl sulphide was present in vodkas at very low concentration so its influence on the aroma and taste of the vodkas was insignificant. Besides one-dimensional gas chromatography, it is also possible to employ two-dimensional chromatography (GC × GC) (Fig.) for analysing spirit-based beverages.
- Despite its many advantages (e.g.
- Improved resolution, better sensitivity and structured chromatograms), two-dimensional chromatography is not used often.
- This is due to the fact that these techniques require qualified personnel and expensive equipment, the latter definitely more expensive than a one-dimensional chromatograph.
In the case of GC × GC, time-of-flight mass spectrometer (TOFMS) is the most frequently used detector. This technique was employed for analysing the volatile organic compounds in selected spirit-based beverages such as, cachaça, rum, vodka, whiskey, tequila, gin and some liqueurs (melon, banana, strawberry and Tia Maria) (Cardeal and Marriott ).
- The lowest number of compounds was detected in vodkas which demonstrate their poor aroma profile compared to other analysed alcoholic beverages.
- Among the detected groups of compounds were alcohols, aldehydes, ketones, esters, terpenes and aromatic compounds.
- Fig.1 Schematic diagram of the GC × GC.1 injector, 2 first column, 3 modulator, 4 second column, 5 detector, 6 first oven 7 second oven Although the vodka composition is mainly analysed by means of gas chromatography, there are studies in which spectrophotometry, atomic absorption and high-performance liquid chromatography (HPLC) have been applied.
The aforementioned techniques are used to determine specific compounds which cannot be determined or are difficult to determine by GC. In the case of spirit-based beverages, HPLC is used rather rarely. This is due to the composition of such beverages which contain many volatile organic compounds therefore their analysis is easier by using gas chromatography.
Coumarin is one of the vodka components which is analysed by means of HPLC. It belongs to lactones and can be found in some plants. Coumarin is present, among others, in Polish vodka Żubrówka which is made from rye and flavoured with the grass species Hierochloe odorata growing in Białowieża Forest in Poland.
The HPLC analysis of Żubrówka showed that coumarin concentration was at the level admissible by norms, i.e., below 10 mg/kg (Sproll et al.). In the case of flavoured vodkas, studies aimed at detection of calcium and citrate was also conducted by means of UV–VIS spectrophotometry and artificial neural networks (ANN).
The aim of this research was the evaluation of aforementioned techniques in comparison to NMR technique (McCleskey et al.). Near infrared (NIR) spectroscopy and Raman spectroscopy were used to determine the ethanol content in vodkas (Nordon et al.). NIR spectroscopy is a nondestructive technique characterized by fast and precise measurements, low costs and the possibility of concurrent determination of multiple components.
The technique uses radiation in the range of 750–2500 nm (Chodak ). In Raman spectroscopy, the mechanism of operation is based on the scattering of radiation by a sample. Both these techniques allowed the ethanol content determination with only a slight deviation from the true value (Nordon et al.).
The aforementioned techniques possess some important advantages as compared to the standard techniques utilized for determination of alcohol content. These are non-invasive techniques that can be applied to the already bottled alcohols without the need to open them. Analysis takes a short time, which makes it suitable for online techniques.
NIR and Raman spectroscopies can be employed to determine falsification without destroying the sample. Unfortunately, it is extremely important to verify additional parameters such as bottle glass thickness or the bottle movement on the production belt.
- These elements limit the applicability of the above techniques on the production lines.
- Mid infrared (MIR) spectroscopy in attenuated total reflectance (ATR) mode was utilized to analyse ethanol, sugar and tartaric acid content in selected alcohol-based beverages including vodka.
- This technique was employed as an alternative to chemical analyses.
The results were comparable with the ones obtained using the classical chemical analyses. ATR method is fast, precise and easy to operate, which can contribute to its broader implementation for analysis of alcohol-based beverages in future (Nagarajan et al.).
Spirit-based beverages, e.g. vodkas were analysed by means of atomic emission spectroscopy and atomic absorption spectroscopy. Atomic absorption spectroscopy (AAS) is characterized by high selectivity, the detection limit at ppb level, and a possibility to analyse ca.70 elements. Because of that, AAS was used to determine the content of lead and copper in Brazilian vodkas for which the measurements were below the detection limit (Pereira et al.).
Atomic emission spectroscopy allows for the concurrent detection or determination of many elements even when they are present in infinitesimal amounts. Both techniques were employed to determine selected metal ions, e.g. sodium, magnesium, aluminium, iron and calcium in spirit-based beverages including vodkas (Nascimento et al.).
- Unfortunately, the detailed results have been published for cachaça only.
- Spectrofluorometry was used to determine formaldehyde in vodka samples (De Andrade et al.
- Tsuchiya et al.).
- This technique is characterized by high sensitivity and good selectivity.
- Formaldehyde is an irritating and carcinogenic substance so investigation of its content in spirit-based beverages is very important.
Spectrofluorometry is the technique suitable for determination of substances, which upon light absorption, emits the radiation of different wavelengths. In the case of aldehydes, it is necessary to conduct derivatization into the radiation-emitting products.
Due to this fact, spectrofluorometry is not a common approach to determine other aldehydes. The measured concentrations of formaldehyde in Russian (De Andrade et al.) and Japanese (Tsuchiya et al.) vodkas were 0.33–0.65 mg/l and 18.4 nmol/ml, respectively. Formaldehyde was determined in alcohol-based beverages including two vodka samples using flow injection analysis.
A method based on the reaction between Fluoral-P and formaldehyde was used, which yields DDl compound that reveals fluorescence at λ ex = 410 nm and λ em = 510 nm. Formaldehyde was not detected in one sample, while in the other one, it was at the lowest level with respect to the other investigated alcohols (De Oliveira et al.).
- Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine metals in vodkas (Lachenmeier et al.).
- ICP-MS is a very sensitive technique with high precision, which can be employed to make concurrent determinations of multiple elements and selective determinations of specific isotopes of the same element in complex matrices.
It also has low detection limit (at the level of pg/L in solutions) due to highly efficient plasma ionization, and a wide linear range of calibration curves, which allows for determining trace and macro elements by a single measurement (Szpunar and Łobiński ; Vanhaecke and Moens ).
ICP-MS enabled detection of alkaline earth metals, e.g. sodium, potassium, calcium and magnesium at the level of milligrams per liter in vodkas originating from Vietnam (Lachenmeier et al.). This technique supplemented with photochemical vapour generation (PVG) was also utilized for determination of cobalt, nickel and tellurium in three cachaça samples, one vodka sample and one sweet vermouth sample.
It occurred to be superior to traditional ICP-MS due to lower limit of detection. The highest content of tellurium was detected in vodka, whereas nickel and cobalt content values are higher than the case of two out of three cachaça samples and lower than the case of vermouth and the third cachaça sample analysis (De Quadros and Borges ).
Moreover, studies aimed at assessing the influence of water hardness on the transparency of vodka were also conducted. The samples of tap water, artesian well water and commercial bottled water were analysed. The hardness of water was determined by titration with Na 2 H 2 EDTA. Based on the study results, it can be concluded that the transparency of vodka depends, to a large degree, on the type of water used in vodka production (Krosnijs and Kuka ).
The important stage of studies on vodkas involves distinguishing vodkas from other spirit-based beverages. These studies allowed the determination of the unique composition of vodka which, in turn, enabled its appropriate identification. Distinguishing among alcohol-based beverages by means of an electronic nose can serve as an example of such investigations (Ragazzo-Sanchez et al.).
- The electronic nose is an analytical device for the fast detection and identification of odorant mixtures; its mode of operation mimics the human sense of smell.
- The electronic nose usually employs specific chemical sensors which generate a characteristic aroma profile, a so-called fingerprint, in response to being exposed to the investigated gaseous mixture.
The identification of mixture components is based on the comparison with reference profiles. Considering the mode of operation, the electronic nose is similar to the human nose. Conductometric sensors are the most frequently utilized. Metal oxide semiconductor (MOS) type sensors are the most characteristic ones within this group.
They are relatively inexpensive, stable, easy to operate and reveal high sensitivity (ppb v/v ). Electronic nose instruments based on sensors are not selective with respect to particular compounds. Each MOS-type sensor utilized in the electronic nose is selective with respect to a particular compound group, which yields a summary aroma profile characteristic for a given mixture.
Hence, the electronic nose instruments of this type are suitable for distinguishing the samples, which differ in aroma profile in a significant way. Application of the chemometric methods, which allow identification of the most important data allowing distinguishing the samples, increases the distinguishing abilities of the electronic nose instruments.
Ragazzo-Sanchez et al. () analysed the alcoholic beverages such as, tequila, vodka, whiskey, beer and red wine. It was demonstrated that vodkas are characterized by the poorest aroma profile, which translates into the lowest content of volatile substances. Based on the principal component analysis (PCA), it was possible to divide the alcohols into groups.
Only tequila and whiskey partially overlapped, while vodka formed a separate, easily distinguishable group (Ragazzo-Sanchez et al.). It can be seen that the electronic nose based on MOS-type sensors enabled distinguishing the alcohol samples, which differ significantly between each other, especially in ethanol concentration.
However, there were difficulties in distinguishing the samples exhibiting similar aroma profile. Electronic nose instrument was utilized for distinguishing 21 different alcohol-based beverages (wine, beer, vodka, whisky and tequila). Data analysis was performed with PCA and discriminant factorial analysis (DFA).
Both DFA and PCA made it possible to distinguish the spirit-based beverages from wine and beer products. In the case of investigation of only spirit-based beverages, both methods allowed distinguishing particular types of alcohol; however, DFA occurred to be better in this field.
In both cases, vodkas were distinguished in the best way, whereas whisky and tequila products were very close to each other on the plots (Ragazzo-Sanchez et al.). Similar research was conducted on vodka, gin, whiskey and brandy by applying sensory evaluation and spectral analysis (Sujka et al.). All samples were purchased in the stores in Warsaw.
Sample preparation consisted of lyophilization which resulted in the removal of water and, consequently, in analyte enrichment. The sensory evaluation was performed by profiling with the use of unipolar scale of categories (evaluation of taste and smell), namely, a 7-point scale in which the highest value had been assigned to the highest intensity of the investigated quality.
- The team conducting the evaluation consisted of five trained persons.
- The vodkas were analysed with regard to the taste categories (sweet, bitter and grassy) as well as smell categories (sharp, sweet and pear).
- In comparison to gins, vodkas had a more intense taste and smell; sharp smell and grassy taste were best detected.
Samples after lyophilization were analysed by means of Fourier transform infrared spectroscopy (FT-IR). The obtained results were processed by using discriminant analysis which enables the identification or quality evaluation of an unknown sample. The best results were obtained from the model describing vodka because it correctly classified all vodka samples and rejected all samples of brandy, 73 % of whiskey samples, and 97 % of gin samples (Sujka et al.).
- The task of distinguishing among the different types of alcohols was performed via ICP spectroscopy (Kokkinofta et al.).
- A total of 68 alcoholic beverages were analysed, which mainly consisted of different types of zivania and included only four samples of vodka from Russia and Sweden.
- The obtained data were grouped by using canonical discriminant analysis (CDA) or classification binary trees (CBT) depending on the content of metals in samples.
Thanks to the application of the aforementioned statistical methods, it was possible to distinguish between vodkas and other investigated beverages. Vodkas are produced on a very large scale by various manufacturers, by different production methods and from diverse raw materials.
- All the aforementioned factors influence the quality of products and, as a consequence, their price.
- Both the manufacturers and the clients expect that a given product will fulfil specific requirements which are important to them.
- Due to the costs of alcohol production and prospective revenue from alcohol sales, the cases of falsification of alcohol-based products are frequent.
It happens that higher-quality alcohols are substituted with cheaper and lower-quality ones, or raw materials other than the required ones are used in the production of high-quality alcohols. Such types of falsification have become the subject of research for many analytical chemists who employ various analytical techniques, e.g.
Gas and ion chromatography to authenticate the alcohols and detect falsified products. In order to determine the authenticity of a given product, it is often necessary to check the raw materials used in the production. Flow injection analysis–isotope ratio mass spectrometry (FIA-IRMS) was employed for the investigation of authenticity of 81 selected alcohol-based beverages including vodkas.
Botanic origin of the investigated samples was verified with this method. Eight out of 10 samples were classified as the vodkas produced from potatoes or from crops such as rye and wheat. The remaining two samples were classified as the ones produced from molasses, which is a by-product of sugar cane processing (Jochmann et al.).
- This method is effective in investigation of botanic origin of the samples, which can be especially useful in the case of vodka, the producers of which provide its composition on labels.
- FIA-IRMS makes it possible to detect falsification of vodkas via distillate produced from molasses.
- Reshetnikova et al.
() analysed different vodkas available on the Russian market with regard to the quality of spirit from which they had been made. The study employed gas chromatography (GC-FID), while the data were processed by using fuzzy logic. The investigated vodkas were made from the two types of spirit, i.e.
- Pure spirit of best quality, Extra and Lux; and Pure spirit of best quality and Extra.
- Among 12 analysed vodka types, only 1 was incorrectly classified into a better quality group (Reshetnikova et al.).
- Similar research on the quality of ethanol used in vodka production was conducted by means of an electronic tongue (Legin et al.).
The electronic tongue (Fig.), also known as artificial tongue or taste sensor, is an analytical device mainly used for classifying tastes of various chemical substances in liquid samples. Its mode of operation is based on the human sense of taste. The electronic tongue can be applied to identify, classify and quantitatively and qualitatively analyse multicomponent mixtures by comparing the reference profiles with the profiles of investigated substances (so-called fingerprint method).
- Potentiometric sensors, especially ion-selective electrodes, are the most frequently applied sensors in the electronic tongue instruments.
- The advantages of the potentiometric sensors engulf well-established principle of operation, low cost, ease of production, possibility of obtaining selective sensors and closest similarity to the natural mechanism of molecular recognition (Ciosek and Wróblewski ).
Fig.2 Comparison of the principles of natural and artificial sense of taste Legin et al. () analysed the samples of spirit from three quality categories (Lux, Extra and High Purity) in triplicates. The data analysis was conducted by using partial least squares (PLS) regression, which allowed for distinguishing among the samples.
Fourteen samples of vodka were analysed with regard to the prescribed quality standards. Four vodkas fulfilling the standards and nine vodkas departing from the standards were selected. As in the case of analysed spirits, PLS regression enabled the identification of the investigated vodka types. Besides this analysis, a study aimed at distinguishing among vodka brands was also conducted.
Ten brands produced from ethanol of different quality, diluted with various water types and containing defined additives, e.g. sugar, had been compared. The collected data were processed by PCA. Most of the vodkas were very well distinguished in the plotted graph, while some were too close to each other which had made the identification difficult.
- Nevertheless, this study demonstrated that the electronic tongue can be successfully used for identifying vodka brands (Legin et al.).
- The application of conductivity measurements to distinguish vodka brands was described by Lachenmeier et al. ().
- According to the authors, each type of vodka displays a specific conductivity due to the raw materials and methods used in the production process.
The authors also mentioned that the use of flavourings do not have a significant effect on the conductivity; therefore, the method can be used to distinguish among the vodka brands. In this study, vodkas originating from Russia, Poland, and Sweden and vodkas without the country of origin, but purchased in Germany were investigated.
- Conductivity measurements allowed the identification of the analysed samples (Lachenmeier et al.).
- Research on vodka identification also employs chromatography, for example, the study of commercial vodkas from the USA and Canada (Ng et al.).
- The samples were prepared by SPME technique, while the determinations were performed by GC-MS.
The analysed vodkas were produced from various raw materials. The authors distinguished between Canadian and American vodkas by using ethyl esters profiles and checking for the presence of compounds such as, 5-hydroxymethyl-2-furaldehyde (5-HMF) and triethyl citrate (TEC).
Besides gas chromatography, ion chromatography was also applied to identify vodkas. In this case, the concentrations of sodium, potassium, magnesium, calcium, chloride, nitrate and sulphate ions were determined in vodkas of Russian origin. In order to supplement the obtained results, GC-FID was used, which allowed for distinguishing among different vodka brands (Arbuzov and Savchuk ).
Ion chromatography was also employed to detect falsified rum and vodka based on the analysis of chloride, nitrate and sulphate ions, and the sum of anions. This allowed for discriminating between Russian and German vodkas (Lachenmeier et al.). Near infrared (NIR) spectroscopy was used for distinguishing the vodkas made in Russia from those produced in other countries.
- A total of 109 samples were investigated; 67 originated from Russia and 42 from Western European countries.
- The following chemometric methods were employed to data analysis: soft independent modelling of class analogy (SIMCA) and linear discriminant analysis (LDA).
- None of the statistical methods allowed ideal distinguishing of the investigated samples (Kolomiets et al.).
Despite such results, it can be stated that the technique employed could be useful while coupled with other chemometric methods. Besides authentication of vodka brands, scientists also check vodkas for possible falsification. Ethanol content different from the one stated on the vodka label can be an example of falsification.
- The study on this subject was conducted on 17 samples of commercial vodka purchased in Poland by using FT-IR spectrometry and two models, and by applying the alcoholometric method described in the Polish standard PN-A-79529-4:2005.
- In nine cases, the alcoholometric method gave different results than those stated on the labels of the analysed vodkas.
For all samples, the values obtained from experimental models differed from those stated by the vodka manufacturers. This study demonstrated that the true values often depart from the values on the labels, which points to, either conscious or accidental, product falsification.
- Despite the observed discrepancies, all vodkas fulfilled the EU norm according to which the minimum ethanol content in vodka should be 37.5 % (Sujka and Koczoń ).
- Another possible falsification of vodka concerns the use of synthetic ethanol instead of ethanol from natural fermentation.
- Studies on this subject were conducted by using GC-MS; three compounds characteristic for synthetic ethanol, i.e.2-butanol, acetone and crotonaldehyde were determined.
All these compounds are present in synthetic ethanol, while 2-butanol does not occur in ethanol from natural fermentation. The samples of whiskey, vodka, cognac and synthetic alcohols were analysed (Savchuk and Kolesov ). Vodkas are the most frequently consumed spirit-based beverages, particularly in Eastern Europe (Hollensen ).
Vodkas are not commonly analysed because of their matrix, which mainly consists of ethanol and water, and includes numerous organic and inorganic substances at low concentration levels. In general, gas chromatography is used to analyse the vodka composition; however, there were some reports on the use of other techniques for determining specific analytes.
The largest number of compounds comprising the matrix was detected by employing two-dimensional gas chromatography because this technique is characterized by high sensitivity and high peak capacity. Studies conducted my means of HPLC were the rarest due to the fact that the volatile substances present in vodkas are best analysed via GC.
Until now, the chemicals belonging to alcohols, aldehydes, ketones, esters, terpenes, aromatic compounds and volatile sulphur compounds have been detected in vodkas. The product authentication and detection of falsified products are of utmost importance in relation to the quality of alcohol consumed.
In comparison to other spirit-based beverages, vodka has the poorest aroma profile; therefore, it is easy to distinguish it from other alcohols. Such studies were conducted thanks to the use of electronic nose, infrared spectroscopy and sensory evaluation.
- The task of identifying different vodka types seems more difficult.
- Until now, vodkas have been identified based on the quality of ethanol used in their production, which was assessed via electronic tongue or gas chromatography.
- In addition, vodka brands were also identified because it was necessary for maintaining the high quality of a given brand (by making comparisons with other brands) and for avoiding the attempts of falsifying a given brand.
To this end, vodkas were analysed by means of conductivity measurements, gas chromatography, ion chromatography and FT-IR spectroscopy. This review paper shows that despite many years of research and using numerous techniques, vodka still remains an interesting object of investigations.
Act of 13 September 2002 on the spirit drinks, “USTAWA z dnia 13 września 2002 r. o napojach spirytusowych „ No 1362/166 J. Laws, 10582–10589. Arbuzov VN, Savchuk SA (2002) Identification of vodkas by ion chromatography and gas chromatography. J Anal Chem 57:428–433 Aylott RI (2003) Vodka, gin and other flavored spirits. In Fermented beverage production Springer, US, pp.289–308. Balcerek M, Szopa JS (2006) Zawartość karbaminianu etylu w destylatach owocowych. Żywność Nauka Technol Jakość 1:91–101 Cardeal ZL, Marriott PJ (2009) Comprehensive two-dimensional gas chromatography–mass spectrometry analysis and comparison of volatile organic compounds in Brazilian cachaca and selected spirits. Food Chem 112:747–755 Cardoso DR, Andrade Sobrinho LG, Lima-Neto BS, Franco DW (2004) A rapid and sensitive method for dimethyl sulphide analysis in Brazilian sugar cane sugar spirits and other distilled beverages. J Braz Chem Soc 15:277–281 Chłobowska Z, Chudzikiewicz E, Świegoda C (2000) Analysis of alcoholic products at the Institute of Forensic Research. Z Zagadnień Nauk Sądowych 41:52–61 Chodak M (2005) Zastosowanie spektroskopii w bliskiej podczerwieni (NIR) do oznaczania zawartości C, N, S, P i kationów metali w materii organicznej gleb leśnych. Inżynieria Środowiska 10:213–222 Christoph N, Bauer-Christoph C (2006) Vodka. In: Berger RG (ed) Flavours and fragrances chemistry, bioprocessing and sustainability. Springer, Berlin, p 341 Ciosek P, Wróblewski W (2007) Sensor arrays for liquid sensing–electronic tongue systems. Analyst 132:963–978 Clegg BS, Frank R, Ripley BD, Chapman ND, Braun HE, Sobolov M, Wright SA (1988) Contamination of alcoholic products by trace quantities of ethyl carbamate (urethane). Bull Environ Contam Toxicol 41:832–837 Commission recommendation 133/2010 of 2 March 2010 on the prevention and reduction of ethyl carbamate contamination in stone fruit spirits and stone fruit marc spirits and on the monitoring of ethyl carbamate levels in these beverages. Off J Eur Uni, 53–57 De Andrade JB, Bispo MS, Rebouças MV, Carvalho MLSM, Pinheiro HLC (1996) Spectrofluorimetric determination of formaldehyde in liquid samples. Am Lab 28:56–59 De Oliveira FS, Sousa ET, De Andrade JB (2007) A sensitive flow analysis system for the fluorimetric determination of low levels of formaldehyde in alcoholic beverages. Talanta 73:561–566 De Quadros DPC, Borges DLG (2014) Direct analysis of alcoholic beverages for the determination of cobalt, nickel and tellurium by inductively coupled plasma mass spectrometry following photochemical vapor generation. Microchem J 116:244–248 Hollensen S (2007) Designing the global marketing programme. In Global marketing: a decision-oriented approach. Pearson education, UK, pp.588–589 Hu N, Wu D, Cross K, Burikov S, Dolenko T, Patsaeva S, Schaefer DW (2010) Structurability: a collective measure of the structural differences in vodkas. Agric Food Chem 58:7394–7401 Jochmann MA, Steinmann D, Stephan M, Schmidt TC (2009) Flow injection analysis–isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages. J Agric Food Chem 57:10489–10496 Kokkinofta R, Petrakis PV, Mavromoustakos T, Theocharis CR (2003) Authenticity of the traditional cypriot spirit “Zivania” on the basis of metal content using a combination of coupled plasma spectroscopy and statistical analysis. J Agric Food Chem 51:6233–6239 Kolomiets OA, Lachenmeier DW, Hoffmann U, Siesler HW (2010) Quantitative determination of quality parameters and authentication of vodka using near infrared spectroscopy. J Near Infrared Spectrosc 18:59–67 Krosnijs I, Kuka P (2003) Influence of water hardness on the clearness and stability of vodka. Pol J Food Nutr Sci 12:58–60 Lachenmeier DW, Attig R, Frank W, Athanasakis C (2003) The use of ion chromatography to detect adulteration of vodka and rum. Eur Food Res Technol 218:105–110 Lachenmeier DW, Schmidt B, Bretschneider T (2008) Rapid and mobile brand authentication of vodka using conductivity measurement. Microchim Acta 160:283–289 Lachenmeier DW, Anh PTH, Popova S, Rehm J (2009) The quality of alcohol products in Vietnam and its implications for public health. Int.J. Environ. Res. Public Health 6:2090–2101 Legin A, Rudnitskaya A, Seleznev B, Vlasov Y (2005) Electronic tongue for quality assessment of ethanol, vodka and eau-de-vie. Anal Chim Acta 534:129–135 Leitz J, Kuballa T, Rehm J, Lachenmeier DW (2009) Chemical analysis and risk assessment of diethyl phthalate in alcoholic beverages with special regard to unrecorded alcohol. PLoS ONE 4:1–7 Leppänen O, Denslow J, Ronkainen P (1979) A gas chromatographic method for the accurate determination of low concentrations of volatile sulphur compounds in alcoholic beverages. J Inst Brew 85:350–353 McCleskey SC, Floriano PN, Wiskur SL, Anslyn EV, McDevitt JT (2003) Citrate and calcium determination in flavored vodkas using artificial neural networks. Tetrahedron 59:10089–10092 Nagarajan R, Gupta A, Mehrotra R, Bajaj MM (2006) Quantitative analysis of alcohol, sugar, and tartaric acid in alcoholic beverages using attenuated total reflectance spectroscopy. J Autom Methods Manage Chem 1–5 Nascimento RF, Bezerra CW, Furuya S, Schultz MS, Polastro LR, Lima Neto BS, Franco DW (1999) Mineral profile of Brazilian cachacas and other international spirits. J Food Compos Anal 12:17–25 Ng LK (2002) Analysis by gas chromatography/mass spectrometry of fatty acids and esters in alcoholic beverages and tobaccos. Anal Chim Acta 465:309–318 Ng L-K, Hupe M, Harnois J, Moccia D (1996) Characterisation of commercial vodkas by solid-phase microextraction and gas chromatography/mass spectrometry analysis. Sci Food Agric 70:380–388 Nordon A, Mills A, Burn RT, Cusick FM, Littlejohn D (2005) Comparison of non-invasive NIR and Raman spectrometries for determination of alcohol content of spirits. Anal Chim Acta 548:148–158 Pereira EV, Oliveira S, Nóbrega IC, Lachenmeier DW, Araújo AC, Telles DL, Silva M (2013) Brazilian vodkas have undetectable levels of ethyl carbamate. Quim Nova 36:822–825 Ragazzo-Sanchez JA, Chalier P, Chevalier D, Ghommidh C (2006) Electronic nose discrimination of aroma compounds in alcoholised solutions. Sensors Actuators B 114:665–673 Ragazzo-Sanchez JA, Chalier P, Chevalier D, Calderon-Santoyo M, Ghommidh C (2008) Identification of different alcoholic beverages by electronic nose coupled to GC. Sensors Actuators B 134:43–48 Regulation, E.C.N.110/2008 of the European parliament and of the council of 15 January 2008 on the definition, description, presentation, labelling and the protection of geographical indications of spirit drinks and repealing Council Regulation (EEC) No 1576/89 Off.J. Eur. Commun. L, 16–54 Reshetnikova VN, Filatova EA, Kuznetsov VV (2007) Identification of raw materials for the production of vodkas based on the results of gas–liquid chromatographic analysis with the use of fuzzy logic. J Anal Chem 62:1013–1016 Savchuk SA, Kolesov GM (2005) Markers of the nature of ethyl alcohol: chromatographic techniques for their detection. J Anal Chem 60:1102–1113 Savchuk SA, Nuzhnyi VP, Kolesov GM (2006) Factors affecting the accuracy of the determination of diethyl phthalate in vodka, ethanol, and samples of illegal alcoholic products. J Anal Chem 61:1198–1203 Siříšťová L, Přinosilová Š, Riddellová K, Hajšlová J, Melzoch K (2012) Changes in quality parameters of vodka filtered through activated charcoal. Czech J Food Sci 30:474–482 Sowiński P, Wardencki W, Partyka M (2005) Development and evaluation of headspace gas chromatography method for the analysis of carbonyl compounds in spirits and vodkas. Anal Chim Acta 539:17–22 Sproll C, Ruge W, Andlauer C, Godelmann R, Lachenmeier DW (2008) HPLC analysis and safety assessment of coumarin in foods. Food Chem 109:462–469 Sujka K, Koczoń P (2012) Zastosowanie spektroskopii FT-IR do oceny zawartości alkoholu etylowego w komercyjnych wódkach. Zesz Probl Postep Nauk Rol 571:107–114 Sujka K, Koczoń P, Gorska A, Wirkowska M, Reder M (2013) Sensoryczne i spektralne cechy wybranych wyrobów spirytusowych poddanych procesowi liofilizacji. Żywność Nauka Technol Jakość 4:184–194 Szpunar J, Łobiński R (1999) Spektrometria masowa z jonizacją w plazmie sprzężonej indukcyjnie (ICP MS) In Zastosowanie metod spektrometrii atomowej w przemyśle i ochronie środowiska. IChF PAN, Warszawa, pp 34–36 Tsuchiya H, Ohtani S, Yamada K, Akagiri M, Takagi N, Sato M (1994) Determination of formaldehyde in reagents and beverages using flow injection. Analyst 119:1413–1416 Vanhaecke F, Moens L (1999) Recent trends in trace element determination and speciation using inductively coupled plasma mass spectrometry. Fresenius J Anal Chem 364:440–451 Wardencki W, Sowiński P, Curyło J (2003) Evaluation of headspace solid-phase microextraction for the analysis of volatile carbonyl compounds in spirits and alcoholic beverages. J Chromatogr A 984:89–96
The authors acknowledge the financial support for this study by the Grant No.2012/05/B/ST4/01984 from the National Science Centre of Poland.
Why would someone drink methanol?
Why would people add methanol to alcoholic beverages? Methanol is often deliberately and illegally added to alcoholic beverages as a cheaper alternative to ethanol (normal alcohol that can be consumed) in countries where taxes on legitimate alcohol or the cost of legitimate alcohol might be perceived as too high.
What is the risk of methanol in moonshine?
Methanol Risks – While the flammability of the moonshine distillation process is dangerous in and of itself, the health effects of moonshine-methanol consumption pose an even bigger threat. More people have died from drinking moonshine than by any explosions at stills, despite the few old and handmade stills that are left.
- A major risk of drinking moonshine is methanol blindness.
- Detecting methanol upon the first step is impossible, and consuming more of it will simply get the person drunker.
- However, it’s eventually metabolized as its toxic metabolite, formic acid, in the body, which can have an extremely harmful effect.
Just 10 milliliters (ml) of methanol is all it takes to cause permanent optic and partial nerve damage, if not complete blindness. As little as 30 ml of methanol is lethal, and, for reference, a standard shot glass in the U.S. holds 40 ml. Old stills use car radiators during the distilling process, which often contain lead soldering and remnants of antifreeze glycol products that could contaminate and add toxins to the moonshine.
Larger batches of moonshine are more likely to contain methanol. Because methanol is vaporized or evaporated at a lower temperature than alcohol, the first liquid produced by the distillation process usually contains methanol. While moonshiners have adopted new ways to discard methanol, some moonshiners will actually add it back into the batch to make the drink more potent.
However, because these processes aren’t regulated, there’s no way of knowing whether the illicit alcohol actually contains any methanol.