Wednesday, November 2, 2016

Citric Acid Derived from Black Mold

Just what is your food made of, anyway? Try industrial synthesis, genetically modified mold secretions, hydrochloric acid, mercury-contaminated caustic soda, ferrocyanide… and, of course, lots of GMO corn.

If common ingredients like “citric acid” and “ascorbic acid (vitamin C)” sound normal and familiar enough that you practically conjure up an image of the flourishing orchard they were grown in – then think again.

Picture instead an industrial factory, carrying out protocols developed in a lab, produced with enough winding nozzles, tanks, valves, pipes and other thinga-ma-jiggers to create a meandering and disorienting Dr. Seuss story. Because, after all, these common –nearly ubiquitous – ingredients don’t come from where you might assume (i.e. simply, citrus fruits).

Instead, mass produced citric acid and ascorbic acid are hidden GMO ingredients that reportedly set off allergenic responses for some sensitive consumers. Further, both are known accomplices to the creation of benzene – a known human carcinogen – inside food and drink products alongside sodium benzoate.

Feel free to peruse these blogs and forums for complaints about citric acid from those allergic or intolerant to citric acid itself, mold & yeast and/or corn. Food intolerance to citric acid, or the components of its production, can trigger such symptoms as: stomach pain, reactions in the mouth, headaches, diarrhea, vomiting, cramping, hives, dark circles under the eye and/or blotchy skin.

Nevertheless, most people are not allergic to citric acid, and have no identifiable negative effects from eating it. But it does serve as a poignant reminder that what we eat comes from food products – constructed as if from tinker toys, with multiple, highly processed ingredients that virtually no one would recognize and few know anything about.

Otto Von Bismarck famously quipped back in the 1800s that “Laws are like sausages, it is better not to see them being made.” But today there is an endless array of foods that would baffle or disgust consumers if they saw them made. Industrial food processes have rendered entire grocery stores filled with food products whose ingredients would be even less recognizable than the contents of sausage.

Citric acid: in practically everything on the shelf


Citric acid is common enough to find in foods of virtually every kind, due to its use as a preservative – extending shelf life and preventing spoilage – as well as to enhance flavor with its acidic and slightly sour taste, which gives all manner of “natural”-ish and completely artificial foods and beverages a “refreshing” kick. Despite being a known hidden GMO, it is even frequently found in certified “organic” foods – and the USDA and FDA allow it to be in there.

Citric acid isn’t becoming a controversial foodie’s food-to-avoid, but instead trending for its ability to bring out the pucker-inducing and tangy tastes in popular foods. It is increasingly celebrated for helping to bring a balance of “all five flavors” to countless restaurant dishes and prepackaged processed foods – indispensable to even celebrity and TV contestant chefs.

Like MSG, the widely used ingredient that enhances ‘savory’ flavors and induces cravings, citric acid is widely used not only as a preservative but as a “fairy dust of flavour amplification” by enhancing and intensifying other flavors present in the recipe.

MSG and citric acid are essentially enablers to modern America’s food frenzy addiction – making even bland foods not just palatable and tasty, but downright delectable and captivating. With so many ingredients raising red flags, piling on sugar, synthetic chemicals and calories while contributing to obesity, diabetes, heart conditions and even cancer – MSG, citric acid and their peers make manufactured food products possible.

Both are used industrially to make even bland foods taste better and last longer on the shelf, regardless of nutritional value. But like many other common food additives, the science behind their production would probably take away from their (artificial) palate appeal.

Manufacturers and distributors of citric acid – as well as the larger food industry who use it as an ingredient in practically everything – benefit from the public’s assumption that citric acid comes from fruit. While this natural appeal is frequently used in food marketing and product imagery (as this chemical manufacturer clearly does), the reality of large scale, mass production of citric acid bears little to no resemblance. Ignorance-based marketing: This chemical company uses the “fresh” image of citrus fruit to market its citric acid – with no mention that it is most likely derived from genetically modified black mold grown on GMO corn syrup.

As the Globe and Mail succinctly puts it:
Citric acid occurs naturally in such fruits as limes, pineapples and gooseberries. The dry, powdered citric acid used as an industrial food additive since the early 19th century, however has a less appetizing source; it is manufactured using a mould that feeds on corn syrup glucose.
Citric acid does in fact occur naturally in citrus fruits like lemons, oranges, grapefruits in significant quantities … in fact, as a product of the Kreb’s Cycle, it is present in most living things. But industry would find it simply too costly and … well, simple to derive their preservative ingredient that way.

Actually, a cornered citrus market was already making this form of citric acid too expensive by the mid-to-late 19th century, making an alternative economically desirable even then. Authors Michael Mattey and Bjorn Kristiansen argue in their introduction to Citric Acid Biotechnology that “the science, though important, is secondary to the economics and politics of production” of citric acid.

Instead, since the early 1900s, the black mold Aspergillus niger has been used to ferment starches to derive citric acid. In 1893, a chemist named C. Wehmer discovered that citric acid could be produced with penicillium mold and sugar. Wartime disruptions in the Italian citric acid market paved the way for full-scale industrial production, after a food chemist named James Currie discovered that Aspergillus niger was even more efficient at producing citric acid. Currie also developed new methods for fermentation, and Pfizer hired him and launched a plant in 1917 to mass produce citric acid grown from mold in a sugar medium. Currie’s methods were also used by Pfizer to drastically increase the production of penicillin, credited with saving countless lives.

Today, it is not only true that nearly all citric acid is made through mold fermentation with GMO corn, but that it is produced by some of the biggest of Big Ag food producers, both in the U.S. and in China.

The three biggest domestic producers of citric acid – Archer Daniels Midland, Cargill and Tate & Lyle Americas (actually a British company) – have been recently involved in suits over import duties and trade turf against Chinese firms, including Shandong TTCA Biochemistry, battling for market share in America.

Think of all the times citric acid shows up on the ingredients label in things that you or those you love eat. We already know it isn’t as simple as squeezing a lemon or lime, but what the hell is it, anyway?

Judge for yourself, with a glance over this “simple” formula:

THE PROCESS: How Citric Acid is Synthesized from Genetically Modified Black Mold

Citric acid production has become a refined and highly prized industrial process. Numerous scientific studies discuss revisions and improvements to the efficiency. But there are definitely some constants to this often competitive and secretive process:
Engineering the mold: Aspergillus niger is a naturally occurring black mold that commonly appears on fruits and vegetables, as pictured on the onion above (source: S.K. Mohan, Creative Commons license). However, significant modification of A. niger has taken place over the past several decades to increase production of citric acid and decrease the production of unwanted byproducts. This has resulted in countless generations of genetically modified mutant variants, now specialized for industrial-scale economics. Two of the main types of modification are:
Further genetic modification and “improvement” of A. niger are an object of ongoing study and industrial practice.

Producing the Sugar Medium: Nearly all industrial citric acid begins with a highly processed glucose corn syrup that is derived from corn wet milling (other parts of the corn residues go to other processes). Other industrial sources include beet sugar and cane molasses, and occasionally also fruit waste.

But it’s hard to beat the economics of subsidized corn – the vast majority of which is the unlabeled, genetically modified, high starch (yellow dent #2) variety – that can synergistically contribute to ingredients like citric acid as well as ingredients like high fructose corn syrup, dextrose (corn sugar), maltodextrin, corn oil, corn meal, ascorbic acid (labeled as vitamin C), MSG and other free glutamates (such as ‘hydrolyzed vegetable protein’), malic acid, baking powder, vanilla, xantham gum and perhaps hundreds of others. Often times, hydrochloric acid is employed in the corn-conversion process.

To transform corn or other plant starches into by-products that can be used to create these ingredients, some serious chemistry must be employed. (click on images to enlarge)



After wet milling corn to separate the starch, the production of many of these ingredients then involves a bath in strong bases, where lyes are used to break down the plant material further. Sometimes this means autolysis, when yeasts or bacteria ferment the material, and other times hydrolysis is used – which vary depending upon the type of additive, and the most efficient and cost effective established processes.

As with other common food ingredients, there is an ongoing issue with mercury cell technology – an outdated model still used in several major chlor-alkali plants – that have a known issue with mercury contamination during the application of caustic soda (to neutralize work with acids). Among hundreds of food ingredients that are potentially contaminated by mercury, studies show the three most common are high fructose corn syrup, sodium benzoate and, yep, citric acid.

A 2009 study published in Environmental Health analyzed the level of mercury contamination from the chlor-alkali process, resulting in numerous grabbing headlines warning about the mercury content in high fructose corn syrup. Although citric acid didn’t make the news, it too is processed in the same way:
Mercury cell chlor-alkali products are used to produce thousands of other products including food ingredients such as citric acid, sodium benzoate, and high fructose corn syrup. High fructose corn syrup is used in food products to enhance shelf life. A pilot study was conducted to determine if high fructose corn syrup contains mercury, a toxic metal historically used as an anti-microbial. High fructose corn syrup samples were collected from three different manufacturers and analyzed for total mercury. The samples were found to contain levels of mercury ranging from below a detection limit of 0.005 to 0.570 micrograms mercury per gram of high fructose corn syrup.
Medium preparation: Various proprietary combinations of acids and heat are used to remove impurities and sterilize the corn syrup or other substrate, including: decationization (to alter the charge of ions), thermodynamic hexacyanoferrate clarification (pertaining to an ion exchange using an iron/cyanide compound) as well as boiling – that’s right, they use cyanide.

Meanwhile, the sugar substrate is diluted in preparation for fermentation.

Inoculation, itself a complicated step: Through a careful process, the spores or cultures of the fermenting agent is introduced, mixed and multiplied. In nearly all current industrial processes, a genetically modified mutant strain of Aspergillus niger (black mold) is then used to ferment the corn sugar syrup into citric acid over the course of several days. (click pictures to enlarge)



Careful control is applied to the pH of the mixture; in various modifications to the process, different types of acids (including hydrochloric acid) are used to increase the productivity of Aspergillus niger and prevent other unwanted products, such as oxalic acid. Subsequent genetically mutated strains of A. niger have been developed to allow the “non-production” of oxalic acid at a higher pH of 5 with the presence of manganese, whereas some production facilities have required a pH as low as 2 to prevent the formation of oxalic acid at the expense of citric acid production. 

Fermentation in the Reactor: The mold-glucose solution is fermented inside in an industrial reactor, generally constructed of stainless steel tanks or towers (to mitigate past manufacturing issues that have occurred in the industry with corrosion and leaching [p. 4 submerged process] and also contain manganese [useful in controlling the production of citric acid]). The reactor includes a sophisticated aeration system that maintains the desirable level of dissolved oxygen, which fluctuates during different stages of the fermentation process.

The process of fermentation leads to the catabolism of glucose sugar by the Aspergillus niger, leading to its secretion of citric acid into the culture broth.

Spore levels, temperature and pH are all tweaked over the course of several hours or days as production of citric acid increases, peaks, then planes off.

Broth separation: After fermentation, the “culture broth” must be separated so the citric acid can be obtained. The processes vary and, again, are closely guarded trade secrets. Some processes cut the fermented broth using a solvent extraction method, while most modern citric acid production utilizes a process known as “calcium citrate precipitation.”

Calcium citrate precipitation: The fermented broth is neutralized by calcium hydroxide, converting/precipitating much of it to calcium citrate. This is then filtered out of the solution, and sulfuric acid is then used to convert the calcium citrate to citric acid and calcium sulfate. The calcium sulfate is filtered out and evaporation for crystallization begins.


Crystallization: Another secretive step is the exact process for converting the final substrate of citric acid into the crystalline white powder that is sold to food manufacturers and consumers. An entry in Volume 17 of Biotechnology and Bioengineering published in 1975 describes the process: “The filtrate is concentrated under vacuum at a low temperature to give crystals of citric acid. Details of both fermentation and crystallization procedures are closely guarded trade secrets.”

The process is likely even more refined, specialized and high tech today. A Wikispaces entry for Citric Acid describes putting the isolated citric acid through additional steps with “activated carbon, cation and anion exchange resins in fixed bed reactors” before evaporation. It then describes both a hot and cold process of crystallization, with the former producing anhydrous citric acid, and the latter producing monohydrate citric acid.

Finishing for Market: The products then can undergo centrifuging, fluidized bed drying and classification (by grain size) before reaching the market.

Sodium Citrate: A related ingredient that is commonly used in foods as an acidulant, as citric acid is, and as an emulsifier in cheese products, is sodium citrate. It is typically created in the same facilities where citric acid is produced, by adding caustic soda (sodium hydroxide, a.k.a. lye) to citric acid, neutralizing it into a weaker citrate salt. Cargill, Archer Daniels Midland and Tate & Lyle are all major producers of sodium citrate.

If the use of caustic soda involves a mercury-cell chlor-alkali plant (see above diagram), further mercury contamination could occur, though membrane-cell technology is replacing it in most plants.

An additional issue with citric acid pertains to its use as a common preservative alongside other ingredients that could cause known carcinogens, like benzene, inside food products:


Citric Acid and Sodium Benzoate “Fizz-ion”: A Carcinogenic Contaminate 
the Soda Companies Have Known About For Decades


Academic studies emerged in the early 1990s about a potent combination of ingredients that was frequently showing up in soft drinks, sports drinks and artificially flavored citrus beverages: the presence of sodium benzoate had the known potential to break down in benzene, a known human carcinogen, when in the presence of heat, or in particular, either citric acid or ascorbic acid. Studies proved that this could happen right inside the drink containers – while in transport, on store shelves or waiting for consumption in consumers’ homes.

Yet nothing was done about it, until the scandal reemerged in 2005 when the FDA was confronted with studies conducted by a private citizen! Numerous European studies in Germany, Belgium and elsewhere backed up the data, and things slowly began to change.

Afterwards, many diet soda brands, sports drinks and citrus-flavored beverages voluntarily removed the troubling ingredient sodium benzoate (though some laughably replaced it only with potassium benzoate, which has the same potential to create benzene).

However, many other brands have done nothing at all, and the FDA allows them to continue using this dangerous mixture of ingredients, despite clear data on the matter. Foods and drinks containing the potentially harmful combination of sodium benzoate and citric acid can STILL be commonly found on store shelves, perhaps especially with generic brands.

Start reading ingredient labels on the brands that you shop for – and those you already know best to avoid – and take note of just how many products contain the hidden GMO ingredient citric acid. We recommend simplifying your diet by eating fresh produce – better if they are grown by someone you know/trust or are “organic” – and foods with as few ingredients as possible.

How many times have you glossed over this seemingly natural ingredient – despite the fact that it is a highly processed and synthetic food additive?

Nevertheless, the FDA has –like practically everything else – “Generally Recognized [it] as Safe” (GRAS). For the record, here is the FDA’s chapter on the oversight of the process of citric acid fermentation by Aspergillus niger:
TITLE 21–FOOD AND DRUGS
CHAPTER I–FOOD AND DRUG ADMINISTRATION
DEPARTMENT OF HEALTH AND HUMAN SERVICES
SUBCHAPTER B–FOOD FOR HUMAN CONSUMPTION (CONTINUED)
PART 173 — SECONDARY DIRECT FOOD ADDITIVES PERMITTED IN FOOD FOR HUMAN CONSUMPTION 
Subpart C–Solvents, Lubricants, Release Agents and Related Substances
Sec. 173.280 Solvent extraction process for citric acid. 
A solvent extraction process for recovery of citric acid from conventional Aspergillus niger fermentation liquor may be safely used to produce food-grade citric acid in accordance with the following conditions: 
  • (a) The solvent used in the process consists of a mixture of n-octyl alcohol meeting the requirements of 172.864 of this chapter, synthetic isoparaffinic petroleum hydrocarbons meeting the requirements of 172.882 of this chapter, and tridodecyl amine.
  • (b) The component substances are used solely as a solvent mixture and in a manner that does not result in formation of products not present in conventionally produced citric acid.
  • (c) The citric acid so produced meets the specifications of the “Food Chemicals Codex,” 3d Ed. (1981), pp. 86-87, which is incorporated by reference (Copies may be obtained from the National Academy Press, 2101 Constitution Ave. NW., Washington, DC 20418, or may be examined at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to: http://www.archives.gov/federal_register/code_of_federal_regulations/ibr_locations.html.), and the polynuclear aromatic hydrocarbon specifications of 173.165.
  • (d) Residues of n-octyl alcohol and synthetic isoparaffinic petroleum hydrocarbons are removed in accordance with good manufacturing practice. Current good manufacturing practice results in residues not exceeding 16 parts per million (ppm)n- octyl alcohol and 0.47 ppm synthetic isoparaffinic petroleum hydrocarbons in citric acid.
  • (e) Tridodecyl amine may be present as a residue in citric acid at a level not to exceed 100 parts per billion.