DATEM stands for “diacetyl tartaric acid esters of monoglycerides”.
In the above figure, the general formula for forming esters is depicted. The R and R’ symbols are hydrated carbon chains of any length. In diagrams of chemical species like above, any place where two straight lines intersect that does not have elemental symbols from the periodic table, it is assumed a carbon atom (C) is present with the maximum number of bonds assumed to be four; all the remaining bonds on that carbon atom is assumed to be hydrogen (H) unless otherwise noted by the diagram.
The above figure is the chemical structure for drinking alcohol, ethanol. Alcohols are chemicals with a hydrated carbon chain with a hydroxyl functional group (-OH) fixed to it. The two hydrated carbons preceding the hydroxyl group can be represented by the symbol (-R). Esters are formed by condensation reactions of carboxylic acid (-COOH). The functional group has the symbol for elemental oxygen twice (O) because it appears in two separate bonds in the same chemical species as opposed to with a subscript as seen in carbon dioxide (CO2) which indicates a different bonding context not relevant. Carboxylic acid is characterized by a carbon being fixed to a hydroxyl (-OH), a double bond with an oxygen atom (O), and the rest of the carbon chain (-R).
Esters are formed via condensation reactions between species of carboxylic acids and species of alcohols. The reaction is called a condensation reaction because it releases a molecule of water (H2O) when the hydroxyl group (-OH) from the alcohol interacts with the hydrogen (H) in the hydroxyl group of the carboxylic acid species. The hydrated carbon chain of the alcohol species then becomes linked to the remaining oxygen in the carboxylic acid species.
Esters for food, are generally manufactured to impart specific aromas. DATEM is manufactured as an emulsifier. It is found in salad dressings, infant formula, and bread products. In infant formula, DATEM is used to keep the mixture well blended and palatable. In bread this is to improve the strength and volume of the dough. Typically, DATEM is 0.375 to 0.5 percent of the total flour weight in most commercial baking or mass produced bread products. It can be found as an emulsifier in ice cream and salad dressing. DATEM is composed of esterified fatty acids and/or glycerin. DATEM is typically manufactured through the reaction of diacetyl tartaric anhydride (DTA) with monoglycerides and diglycerides.
DTA can be manufactured from tartaric acid, tartaric acid salts, or tartaric acid analogues. Tartaric acid can be found in various plants but it is especially present in grapes, particularly in the skins and seeds. As a result, the primary manufacturer of tartaric acid is winemakers who extract it from residues left behind following the fermentation of grape juice. During the winemaking process, tartaric acid can crystallize and form sediment, which is often referred to as wine diamonds or potassium bitartrate. Tartaric acid in its pure form is typically not used for baking, rather its potassium salt, potassium bitartrate, is used commonly known as “cream of tartar.”
In wine, the chemical reaction that forms wine diamonds is depicted above. It does not involve ethanol. The numbers in the tartaric acid structure indicate the sequence of carbon atoms for chemistry purposes but do not contribute to anything significant in the figure.
The extraction of the tartaric acid can generally be described in five general steps:
1/ During wine production wine diamonds and wine lees are two byproducts formed as sediments that are physically separated from liquid wine usually by filtration. The composition of the sediments is not homogenous. Wine lees contain tartaric acid. Wine diamonds are composed of potassium bitartrate. The wine diamonds crystalize out of the wine whereas the wine lees are the solid remains to include dead yeast and grape solids. Both of these byproducts will be used.
2/ To separate tartaric acid from the wine lees, acidification is used to lower pH. Typically by adding sulfuric acid (though any significantly acidic species can be potentially used), the tartaric acid is displaced in the solution and crystalizes out. At this point there are two relevant chemical species present as crystals: tartaric acid and potassium bitartrate.
3/ The crystals are removed from their respective solutions. For the potassium bitartrate, also known as wine diamonds or as cream of tartar, the solution is the wine. For the tartaric acid crystals, they are separated from the acidified solution used to isolate them. Some mechanical filtering may be used if there are other solids present if they did not dissolve in the acidification solution.
4/ Centrifugation may be used to further separate the tartaric acid crystals from any remaining liquid. This can vary from manufacturer to manufacturer. And, generally speaking, the crystals are then dried in some way. This is likely accomplished by applying heat but vacuuming may be employed. The specifics would also vary from manufacturer to manufacturer.
5/ Finally purification of the crystals must occur prior. While the purification of the crystals technically started with the filtration from their respective solutions however that is not accepted as sufficiently pure. The purification step refers to washing the crystals, typically with water. Alcohols, particularly ethanol, is miscible with water. It dissolves completely. Tartaric acid is dissolves significantly less readily in water. Potassium bitartrate is less soluble in water than tartaric acid. Certain manufactures will dissolve and recrystallize washed tartaric acid crystals, sometimes more than once to further purify the crystals. This can be for several reasons. If they have reason to believe there are sediments trapped in the crystals then they may employ further recrystallization. Or they may do so to achieve a more concentrated final product.
As stated earlier, DATEM is typically manufactured through the reaction of diacetyl tartaric anhydride (DTA) with monoglycerides and diglycerides. DTA is produced by acetylation reactions. The acetyl group (CH3CO) is provided by acetic anhydride; the isolated and purified tartaric acid and potassium bitartrate (in their crystalized forms) react with acetic anhydride. The two reactions are as follows:
C4H6O6 (tartaric acid) + (CH3CO)2O (acetic anhydride) → C8H10O7 (DTA) + 2CH3COOH (acetic acid) + H2O
KHC4H4O6 (potassium bitartrate) + (CH3CO)2O (acetic anhydride) → C8H10O7(DTA) + KC4H5O6 (potassium acetate) +H2O
Monoglycerides and diglycerides are sourced from fats and oils. While the source of the fats or oils are typically vegetable oils, typically soybean oil or palm oil, there are many market considerations and ultimately it will be whatever is cheapest to procure to include the cost of logistics. The fats are considered chemically transformed into a different chemical species, DATEM, in the context of secular chemistry. Even if it happens to be considered chemically transformed in the context of fiq, chemical reactions do not occur with the minimum number of molecules or compounds needed for a reaction; even if the glycerin or fatty acids used were the limiting reagent, if there is too much present than the DATEM would have to be purified and isolated from them. This is another potential vector of haram contamination. Further, the process is not standardized so any one manufacturer would not be using the same protocols as another. After the reaction, the mixture may contain DATEM along with other components such as unreacted fats, fatty acids, and glycerin. The isolation of DATEM from these components is up to the manufacturer dependent not only on cost but the instruments and methods available to them. It is also dependent on the form it is sold in. DATEM can be found in both liquid and solid forms on the market (ex: https://no.chinaimprover.com/emulsifiers/food-emulsifiers/bakery-emulsifier-datem-e472e.html), though it is much more frequently found packaged as a solid. Usually, the solid is in the form of a powder or crystal though beads and flakes can be found.
Based on the chemical properties of DATEM there are several viable methods for purification available to manufactures to isolate DATEM from its reaction mixture. They aren’t all necessary employed, nor are they the exclusive set of techniques. The combination of techniques used would be dependent on the conditions of the reaction environment and the desired concentration of the final product for sale. The techniques may be improved by first performing a neutralization or acidification to adjust pH to facilitate separation. Due to the lipid presence in the structure of DATEM, it has solubility in nonpolar organic solvents. Some options include hexane, acetone, and chloroform. Physical separation via filtration followed by centrifuging can be used to remove and solid by products from the solution of selective solvent and DATEM. Centrifuging is a powerful technique that can even separate plasma and serum from the cellular components of whole blood. However, the solution could still contain other impurities such as unreacted glycerin, glyceride, or fatty acids still present. Crystallization of DATEM can be induced if the solvent was first heated and the amount was controlled to create a supersaturated solution. As the solution cools, the excess DATEM solute would precipitate and crystallize out of solution. The trace amounts of reactants or any fatty byproducts that may still be present in the solution would not constitute an amount enough to be considered supersaturated though they may still be present in some trace amount in the precipitate proportional to how similar they are to DATEM. If the concentration or purity of the crystals is not to the desired standard of the manufacturer, crystals can be dissolved and recrystallized. The crystals are usually washed and dried prior to packaging for sale. DATEM is amphiphilic, meaning it has both polar and nonpolar functional groups imparting both polar and nonpolar qualities to it. Polar contaminants are easily removed with polar solvents; since DATEM is relatively nonpolar, it does not dissolve as readily in polar solvents. Due to the hydrophobic nature of the reactants a nonpolar, organic solvent is also used for washing. Hexane is a typically employed nonpolar solvent and good for removing nonpolar contaminants, in particular any unreacted monoglycerides and diglycerides since they are more nonpolar than DATEM. Ultimately the choice of solvent is up to the manufacturer. Other options include but are not limited to isopropyl alcohol, ethyl acetate, or acetone. The crystals are dried after washing to ensure they are safe for use in consumable goods.
Without access to industry reports, market research studies, or directly contact DATEM manufacturers or suppliers for the purpose of cross referencing and generating the necessary data, it is hard to tell what percentage of the market is using vegetable derived glycerides with certainty. In the United States of America, the FDA guidelines and regulations for the use of food additives in general and the standards they are held to can be found in the Code of Federal Regulations (CFR), Title 21 part 172.842 [https://www.ecfr.gov/current/title-21/chapter-I/subchapter-B/part-172]. DATEM is specifically mentioned in CFR Title 21 part 184 [https://www.ecfr.gov/current/title-21/chapter-I/subchapter-B/part-184/subpart-B/section-184.1101]. Neither of these documents mention a standard for purity.
To sidestep this issue, bread without any such additives can be purchased.
The above is a picture of the ingredients label of the bread consumed in my home. As halal certification becomes more mainstream, the general population is becoming more aware of ingredients and practices that may be haram or mushbooh. From a health perspective, I always encourage buying foods that do not have ingredients labels that are not easily understood by the general public. But especially for the consumer worried about consuming exclusively halal with absolute certainty, by definition this cannot be accomplished if you are uncertain about how the ingredients are manufactured or synthesized. I am only able to report on the superficial chemistry and manufacturing of DATEM.
If anyone knows a mufti who is qualified in the ilm and fiq of chemistry and is willing to publically provide a fatwa with his name, contact me or drop it in the comments so the ummah has an answer that is not hearsay. Or if anyone knows of a source for a whitelist or a blacklist of vedors of products made with or manufacturers of DATEM produced from esterification of glycerides of animal fats please leave it in the comments below. If anyone has a connect or has done the necessary labor to compile the data to determine how much of the market is using glycerides from animal fats for esterification for the manufacturing of DATEM please contact me or drop it in the comments below. If I made any mistakes regarding the chemistry or manufacturing, please point them out in the comments below.