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Authors: Steve Ettlinger

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Vanilla extract is precisely defined. The FDA requires a minimum of 13.35 ounces of vanilla beans per gallon, made up with a minimum of 35 percent alcohol (and 65 percent water). Some of the better beans are extracted with more alcohol to bring out the flavor, and some brands add sugar or corn syrup to take the edge off the alcohol or to act as a stabilizer. The alcohol, which is bitter to taste, evaporates during baking. Contrary to what some enthusiastic vanilla ice cream lovers may wish to believe, Nielsen confirms that the tiny bits of vanilla bean in some high-end brands of ice cream are there for impression only—they are
not
the flavorful seeds that we might think they are, but ground-up pods that were used to make the extract that actually flavors the ice cream.

O
IL
R
EFINERIES
, N
OT
O
RCHID
G
ROVES

The name 4-hydroxy-3-methoxybenzaldehyde is not very elegant for the synthetic equivalent to the fruit of a beautiful tropical orchid. This is vanillin, and rather than hailing from exotic islands, just about all of it is made in two major petrochemical plants in China and one in Baton Rouge, Louisiana (the only place it is made in the United States). And most of
that
is made by one company, Rhodia, a French-owned, $6 billion-a-year, global chemical company with more than twenty thousand employees. (Rhodia owns the Louisiana plant and just in 2005 bought one of the two Chinese plants, in Zhejiang province, just west of Shanghai.) Besides being the backbone of the most popular ice cream flavor, vanillin is the most common aroma chemical in the world. For well over a hundred years, we haven’t been able to live without it.

Vanillin was first synthesized in 1875, only about twenty years after it was first isolated and identified in the natural world. Originally, vanillin was painstakingly cooked (in Germany) from coniferin, those sugary crystals on pinecones that give off a slight vanilla smell. In the 1890s, a French chemist (not a chef, mind you) found a way to make vanillin from clove oil. (If you
really
smell it you can see how they are related.) For years vanillin was extracted in the form of lignin from wood as a by-product of papermaking, but now less than 10 percent, and maybe only 5 percent, of food-grade lignin comes from wood pulp these days. It is actually cleaner and easier to make it from hydrocarbons (petroleum) because of all the sulfuric acid and energy needed to process pulp.

As noted, most flavor companies won’t talk, but fortunately, some are more accommodating, including Firmenich, the third largest of the flavor companies (founded in 1895). Mike Cadwell, senior flavorist in its Anaheim, California, office, is glad to help explain how these flavors are made.

Chemically, vanillin is an oxidized alcohol, a (luckily distant) cousin of formaldehyde. Economically, its popularity is a nobrainer: it costs about one-two-hundredth of its natural counterpart because it is about two hundred times as strong, depending on what strength natural vanilla you compare it to (less than an ounce to a gallon is a common but inaccurate measure). Aesthetically, most food scientists agree, the artificial version never quite develops the full flavor of its natural counterpart, though it does survive the high heat of baking better than the natural version does. But since Madagascar became to vanilla what Saudi Arabia is to oil some time around the 1960s, the price difference is too profound for the big food companies to ignore, and the use of artificial vanilla flavoring has since taken off.

Artificial vanilla manufacturing starts a long way from the flower fields, with crude oil and one of its basic components, benzene, a colorless, sweet-smelling, flammable liquid solvent, one of the so-called aromatic compounds found in flowers, fruits, and vegetables as well as in crude oil (the major source), natural gas, and coal tar. Cadwell says of these delicate scents, “Most are straight from the dinosaurs.” Benzene is the source of feedstocks for thousands of products including vanilla flavoring, artificial colors, gasoline, and that symbol of clean chemistry, aspirin. But as straightforward as this may sound, it’s important to note that making benzene is a bit dangerous: not only is it a known carcinogen, but in March 2005, a benzene tank at a refinery in Texas City, Texas, exploded, killing fifteen and injuring 170.

Whether in Baton Rouge or just west of Zhejiang, making vanillin is complex and not at all appetizing. In fact, it is almost impossible to view as a food process. At the refinery, benzene is oxidized at the steam cracker and reacted with propylene (also from petroleum) to get cumene, an important industrial chemical, which is then further reacted to get phenol, a clear, sweetish-tarry-smelling liquid that used to be sold under its common name, carbolic acid, as a sore throat remedy (it was the first surgical antiseptic used by Sir Joseph Lister, who invented the mouthwash that still bears his name). Phenol is still used in antiseptic products; it was reacted with formaldehyde to make the first plastic, Bakelite, too, but is now mostly used to make plywood glue, with leftovers going into artificial vanilla.

The chemical reactions in the name of food continue in the same refinery-like plant. The phenol is condensed into white crystals called catechol, an oily methyl ester used in photographic developers, which is liquefied and catalyzed into guaiacol, a yellowish semisolid, light-sensitive alcohol that has a slight smoky/woody/spicy vanilla scent. This is dried into off-white crystals or liquefied and sold by the major chemical companies to the major flavor companies for further processing into vanillin. Guaiacol is a popular chemical with the pharmaceutical companies, too, who make it into guaifenesin, which you might recognize as a popular decongestant used in the cough and cold elixirs that line the shelves in your local drugstore. It might work for cough syrup, but not for Twinkies, not yet.

Next, the guaiacol is reacted under high temperature and pressure with a dash of the corrosive, solid glyoxylic acid so a sweet cherry hint (or “note”) develops in addition to the almost delicate, sweet benzene odor. And bingo: bright, white, aromatic vanilla-smelling crystals drop out of the liquid. Pure vanillin, if you can call something synthetic pure.

A scientist at one of the big firms who insisted upon anonymity explains this oil-refining/chemical process in almost artisanal terms: “You go from medicinal to woody notes to sweet woody notes to smoky sweet and then vanilla, which is a combination of all these things. It’s a nice progression.” Except that instead of mixing little test tubes in a lab or aging wine in oak barrels, this is done in giant, off-limits chemical plants with towers and tanks and railcars coming and going—not to mention the ever-present risk of detonation.

Building a Flavor

The pure artificial vanillin can’t quite fully substitute for natural vanilla, not yet. First, it must be mixed or cut with other flavors to become more palatable and to more closely resemble real vanilla, with its hundreds of subtle components. Evidence of this can be found on the labels of imitation vanilla sold in grocery stores: every producer blends it a bit differently to please each of its big customers in terms of price, performance, and aroma.

My favorite ingredient on the label of bottles of artificial flavor such as vanilla is the seemingly redundant term “artificial flavor.” This begs a philosophical (or perhaps grammatical) question, implying that if the second artificial flavor was
not
added to the first artificial flavor, then perhaps the first artificial flavor might not be artificial, or might not even exist.

In an example of chemical incestuousness, what’s added tends to be some of the very same intermediate or precursor chemicals used to make vanillin in the first place, put back in to round it out: guaiacol; ethyl maltol, a powdered, white sweetener that smells like caramel, jam, strawberries, and burnt toast (some say cotton candy) made from an oily, aromatic chemical with the energy-packed name furfural, which is itself distilled from oat hulls, corncobs, sugarcane stalks, or wood that has been treated with sulfuric acid; or heliotropine, another white, crystalline refinery product similar to vanillin, an aldehyde with a cherry and floral scent that suggests heliotropes, a popular kind of garden plant, as well as the distinctive smell of Tahitian vanilla (it is also popular in perfumery). These flavor chemists go deep not into tropical jungles but into organic chemistry to make their products sing.

Artificial vanilla also needs to be mixed with some additive to smooth it out, thicken it, and keep it moist. McCormick
®
Pure Vanilla Extract, along with supermarket brands like Stop & Shop’s, uses corn syrup. Some add caramel color. Many other brands use the decidedly unfoodlike-sounding additive propylene glycol (also found in artificial colors). Colorless, odorless, and oily, it’s a great additive, a solvent (an alcohol based on glycerin) that is so safe it’s used in cosmetics and medicines as a moisturizer, as well as in personal or sexual lubricants. It’s also the primary ingredient in the “paint” inside a paintball and the fuel for theatrical smoke machines, among other industrial applications (not to be confused with its sister, ethylene glycol, the main ingredient in automobile antifreeze). And it comes from a rather industrial source: oil refineries.

Propylene glycol is made by Equistar and Dow Chemical, the biggest producer in the world (worldwide annual capacity: more than a billion pounds), in half a dozen Gulf Coast petrochemical plants in Texas and Louisiana. Like most everything else in this flavor, it is made from petroleum at a refinery in a violent and unfoodlike process that varies from place to place and time to time. One common way is to “crack” natural gas under a flash of high heat and crack it again to separate out propylene gas, which is then reacted with chlorine and lye (or sometimes hydrochloric acid—all are chemicals made from salt, another useful Twinkie ingredient) to become a liquid, propylene oxide. The PO is then reacted with that old chemical standby, water, to make propylene glycol—alcohol from oil.

But vanilla is only half of the flavor added to Twinkies. It takes butter to complete the taste, no matter that there is no real butter in a Twinkie at all.

G
AS AND
B
UTTER

Twinkies’ buttery flavor provides the richness we expect from cake and likely also helps to mask their oiliness. Since due to cost and rancidity issues there’s no room in a packaged cake like Twinkies for fresh butter, artificial butter is the answer—the same “butter flavor” used on movie popcorn (what many theaters accurately and nonsensically refer to as “golden-flavored topping”) as well as in French vanilla ice cream. The most surprising thing about it is that it really stinks.

One of the most desirable artificial flavors due to its taste and versatility, artificial butter, like many flavor chemicals, smells positively awful in its concentrated state. “Terrible, revolting” is what one expert called it, not an auspicious start. Diacetyl—the “di” in the name refers to its molecular structure, and the “acetyl” part shows that it is related to acetic acid and acetylene welding gas—is so powerfully bad-smelling that some companies that deal with it do so in a dedicated, separate building. But diacetyl is a very common, smooth, slippery, butter/butterscotch flavor, and it occurs naturally quite often in spoiled fruit juice and over-fermented beer. A mere touch of it—it is detectable in concentrations as low as fifty parts per
billion
—gives Chardonnay wine its smoothness; higher concentrations are what make butter smell like butter, but even higher concentrations are what make butter smell rancid.

Diacetyl could also be extracted from butter, but that is extremely difficult and expensive. It can be fermented from yeast, and sometimes is, but luckily, the same exact molecule is more inexpensively created from natural gas by a few obscure Chinese chemical companies and a well-known German multinational corporation. And once it’s baked into a cake, unlike butter, it doesn’t need refrigeration. All it takes is the biggest chemical plants in the world, a major dose of petroleum, a little hydrochloric acid, plus some very unexotic and inexpensive water and air.

BASF makes diacetyl and tens of thousands of other chemicals at its headquarters in Ludwigshafen, Germany, smack on the Rhine, a bit south of Frankfurt. Though it is almost a commodity, the actual process used is kept secret, but given the company’s massive network of interconnected petrochemical production facilities, BASF probably takes butane, a natural gas component, and processes it with ultrahot steam into a clear, very volatile, flammable liquid called methyl ethyl ketone (MEK), technically the main aroma in blue cheese (try telling that to a French cheesemaker). In fact, it actually smells more like a sweet hospital antiseptic.

You can also buy a can of MEK at hardware stores, in case you want to make diacetyl at home (kids, don’t do this!) or, more likely, thin some epoxy resin when repairing your boat or car (kids, don’t do this, either). In the final step, when the MEK is passed over a rare metal catalyst like vanadium oxide and then mixed with a little of the basic, common hydrochloric acid, it changes to diacetyl, a volatile liquid that is such a bright, intense, fluorescent yellow that you can easily see where real butter gets its color. Packed carefully into twenty-five-kilogram drums and sealed with a layer of nitrogen to protect it from moisture and fire (it is so highly flammable that a vapor mixture can actually explode) it must be stored under refrigeration. On top of that, due to the strength of its apparently awful (but nontoxic) smell, diacetyl must be kept separate from other chemicals and treated carefully to guard against leaks. The containers are labeled “harmful if swallowed,” both ironic and ominous for a food ingredient.

When the flavor houses are finished with diacetyl, it is usually no longer pure. Much as is done with artificial vanilla extract, they buy the pure stuff from one of the big chemical companies and then blend it for a rounder, more useful flavor profile to sell to the food companies. Instead of a dash of salt or a touch of wine, though, they usually add more petroleum products: butyric acid, deltadodecalactone, and propylene glycol (as was used with vanillin). They also might even add vanilla, which is kind of odd when you consider that they’re using vanilla to round out a flavor that is used to round out vanilla.

BOOK: Twinkie, Deconstructed
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