Tag Archives: co2

AOCS Highlights Cannabis Lab Standards, Extraction Technology

By Aaron G. Biros
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The American Oil Chemists’ Society (AOCS) held its annual conference in Salt Lake City this week, with a track focused on cannabis testing and technology. Cynthia Ludwig, director of technical services at AOCS and member of the advisory panel to The Emerald Test, hosted the two-day event dedicated to all things extraction technology and analytical testing of cannabis.

Highlights in the discussion surrounding extraction technologies for the production of cannabis concentrates included the diversity of concentrate products, solvent selection for different extraction techniques and the need for cleaning validation in extraction equipment. Jerry King, Ph.D., research professor at the University of Arkansas, began the event with a brief history of cannabis processing, describing the physical morphologies in different types of extraction processes.

J. Michael McCutcheon presents a history of cannabis in medicine
J. Michael McCutcheon presents a history of cannabis in medicine

Michael McCutcheon, research scientist at Eden Labs, laid out a broad comparison of different extraction techniques and solvents in use currently. “Butane is a great solvent; it’s extremely effective at extracting active compounds from cannabis, but it poses considerable health, safety and environmental concerns largely due to its flammability,” says McCutcheon. He noted it is also very difficult to get USP-grade butane solvents so the quality can be lacking. “As a solvent, supercritical carbon dioxide can be better because it is nontoxic, nonflammable, readily available, inexpensive and much safer.” The major benefit of using supercritical carbon dioxide, according to McCutcheon, is its ability for fine-tuning, allowing the extractor to be more selective and produce a wider range of product types. “By changing the temperature or pressure, we can change the density of the solvent and thus the solubility of the many different compounds in cannabis.” He also noted that, supercritical carbon dioxide exerts tremendous pressure, as compared to hydrocarbon solvents, so the extraction equipment needs to be rated to a higher working pressure and is generally more expensive.

John A. Mackay, Ph.D., left at the podium and Jerry King, Ph.D., on the right
John A. Mackay, Ph.D., left at the podium and Jerry King, Ph.D., on the right

John A. Mackay, Ph.D., senior director of strategic technologies at Waters Corporation, believes that cannabis processors using extraction equipment need to implement cleaning SOPs to prevent contamination. “There is currently nothing in the cannabis industry like the FDA CMC draft for the botanical industry,” says Mackay. “If you are giving a child a high-CBD extract and it was produced in equipment that was previously used for another strain that contains other compounds, such as CBG, CBD or even traces of THC extract, there is a high probability that it will still contain these compounds as well as possibly other contaminants unless it was properly cleaned.” Mackay’s discussion highlighted the importance of safety and health for workers throughout the workflow as well as the end consumer.

Jeffrey Raber, Ph.D., chief executive officer of The Werc Shop, examined different testing methodologies for different applications, including potency analyses with liquid chromatography. His presentation was markedly unique in proposing a solution to the currently inconsistent classification system for cannabis strains. “We really do not know what strains cause what physiological responses,” says Raber. “We need a better classification system based on chemical fingerprints, not on baseless names.” Raber suggests using a chemotaxonomic system to identify physiological responses in strains, noting that terpenes could be the key to these responses.

Cynthia Ludwig welcomes attendees to the event.
Cynthia Ludwig welcomes attendees to the event.

Dylan Wilks, chief scientific officer at Orange Photonics, discussed the various needs in sample preparation for a wide range of products. He focused on sample prep and variation for on-site potency analysis, which could give edibles manufacturers crucial quality assurance tools in process control. Susan Audino, Ph.D., chemist and A2LA assessor, echoed Wilks’ concerns over sample collection methods. “Sampling can be the most critical part of the analysis and the sample size needs to be representative of the batch, which is currently a major issue in the cannabis industry,” says Audino. “I believe that the consumer has a right to know that what they are ingesting is safe.” Many seemed to share her sentiment about the current state of the cannabis testing industry. “Inadequate testing is worse than no testing at all and we need to educate the legislators about the importance of consumer safety.”

46 cannabis laboratories participated in The Emerald Test’s latest round of proficiency testing for potency and residual solvents. Cynthia Ludwig sits on the advisory panel to give direction and industry insights, addressing specific needs for cannabis laboratories. Kirsten Blake, director of sales at Emerald Scientific, believes that proficiency testing is the first step in bringing consistency to cannabis analytics. “The goal is to create some level of industry standards for testing,” says Blake. Participants in the program will be given data sets, judged by a consensus mean, so labs can see their score compared to the rest of the cannabis testing industry. Proficiency tests like The Emerald Test give labs the ability to view how consistent their results are compared to the industry’s results overall. According to Ludwig, the results were pleasantly surprising. “The results were better than expected across the board; the vast majority of labs were within the acceptable range,” says Ludwig. The test is anonymous so individual labs can participate freely.

The AOCS cannabis working groups and expert panels are collaborating with Emerald Scientific to provide data analytics reports compliant with ISO 13528. “In the absence of a federal program, we are trying to provide consistency in cannabis testing to protect consumer safety,” says Ludwig. At the AOCS annual meeting, many echoed those concerns of consumer safety, proposing solutions to the current inconsistencies in testing standards.

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BEST Extractions

Busting the Myth: Examining CO2 versus Butane Extraction

By John A. Mackay, Ph. D.
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The basis of anecdotal controversy continues about the use of hydrocarbons versus carbon dioxide. It is important to note that hydrocarbons span a range of phases on the planet earth.

It is important to eliminate the cost of the instruments and the cost of the facilities from this comparison to keep the discussion on specifically the extraction principles.

Source: (https://en.wikipedia.org/wiki/Butane#Isomers)
Source: (https://en.wikipedia.org/wiki/Butane#Isomers)

Butane is a gaseous hydrocarbon. As you add more carbons to hydrocarbons, they move from gaseous to liquid.

It is also important to note that the same is true of carbon dioxide in its natural form on the earth’s atmosphere, it is a gas. It is nonflammable and used in fire extinguishers.

At typical conditions, carbon dioxide in the supercritical range is similar to hexane (C6H14) and ethyl acetate in its solubility characteristics. Propane (C3H8) and butane (C4H10) are gases at normal atmospheric conditions. Both must be manipulated for the extraction of CBDA and CBD. For example, both CO2 and C4H10 must be placed under pressure and then passed through the material to extract the lipophilic terpenes and cannabinoids.

For this short discussion, let’s remove the concern about the different volatilities of the compounds. Hydrocarbons with a spark will be significantly more powerful of an explosion than carbon dioxide (note it could be used to put out the butane fire). The hydrocarbons can be in more configurations and therefore the getting the correct form initially is critical. For example, butane can have all the carbons in a row like a train, or branched like a tree. Those are very different and have different characteristics too. Getting pharmaceutical grade butane is essential to ensure safety. The concern that people have expressed with butane is what is in the other 0.1% for 99.9%. Checking for residual butane is less of a concern than the polyaromatic hydrocarbons in the untested cylinder. Furthermore, in the wrong hands it can be more volatile.

Source: (https://en.wikipedia.org/wiki/Carbon_dioxide)
Source: (https://en.wikipedia.org/wiki/Carbon_dioxide)

The critical premise that needs to be considered is the final formulation. Is one solvent significantly more applicable than the other? No. They have different characteristics.

Propane is a common solvent in the spices, flavors and fragrances industry. For example, the extraction of lipids and oils from vegetables and the fatty oils from seeds, it would be an advantage to have a solvent that is totally miscible, i.e. will be totally soluble in a fluid. This is similar to the idea of sugar in hot water versus in water in ice. If an example of cardamom were used comparing CO2 and propane (which is similar to butane), the pressure needed for CO2 would be 100 bar, while propane would be only 20 bar. However the increasing the pressure of the propane from 20 to 50 bar at a constant 25 C, also increases the chlorophyll from 3.4 g/g oil to 10.8 g/g oil. Meanwhile with the more finely tunable CO2 from 80 to 100 to 200 the amount of chlorophyll is negligible (0.36 g/g oil) but at 300 bar it dramatically increases to 4.53 g/g oil.

Additionally the CO2 is a better extraction for the terpenes in the cardamom. The beta-pinine, Cineole, linalool, alpha-terpinol and bornelole. The increase in the propane pressure will allow us to increase the yield of the CO2 (Illes, V, et. al. Proceedings of the Fifth Meeting of Supercritical Fluids, Nice, France, Tome 2, 555-560).

This example is the same with the butane and cannabis. Butane is a stronger solvent and if left too long will continue to pull out more and more polar compounds like chlorophyll. With the fine-tuning of CO2, you can eliminate or you can pull out the chlorophyll if you choose the wrong conditions.

So fast extractions are possible with butane but little control of all the material, while CO2 can be tunable and therefore is able to collect all of the same material, just through a segmented process.

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BEST Extractions

Defining BEST Extraction

By John A. Mackay, Ph. D.
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Over the next few months, I would like to walk through a series of articles to cover the number of ways to extract potentially pharmaceutically active compounds from cannabis plants. However, in the first article I would like to review concerns being addressed in state regulations: contamination in concentrates with pesticides, mycotoxins, and residual solvents. The next article will cover the most common extraction with two different modes: CO2 versus hydrocarbons.

Currently, there is a lot of focus on the cannabis strain of hemp. This is defined as having less than 0.3% of THC, (the psychoactive compound). To be clear, the science of extraction is eons old, but the current revitalization is due to new scientific inquiry regarding the applications of the cannabis plant.

I am often asked, “What is the ‘best’ extraction for a natural product?” The BEST extraction? The key to this answer is that you must assume unintended consequences until you can prove that they are at least minimized compared to the intended consequences.

I have a suggestion for you to consider and I look forward to your response to it. I also assume the right to adapt and revise it.

Botanical integrity from seed to shelf

Efficacy of the process beyond efficiency, economics, effectiveness

Safety of people and product

Testing for confirmation at each step of process

The hemp industry has changed significantly over the past few years. Just casually flipping through the channels on television, reading a newspaper or magazine, (on any topic – news, business, sports, food and science) and there is some facet of hemp’s value being examined. The reduction of traditional pulmonary intake (smoking) in the legal marketplace can be tracked by sales of these products in the states where it is legal. The balance of ingestion is drastically tipping toward what might still be considered smoking with vaporizer products as well as toward edible consumables. The ingredients in these products come not from just adding the plant to the formulation, but rather a concentrated mixture. This is the difference between adding a raw vanilla and a teaspoon of vanilla extract. The compound getting the most coverage is cannabidiol (CBD), which is the compound derived from cannabidiolic acid (CBDA). The effects of the other compounds in the plant are being studied as well.

Unintended consequences from the concentration – extraction – are something we need to consider seriously as consumers. The labeled use of “natural” is one that is critical, but can be totally nullified by the unintended contamination in the extraction workflow. Years of making sure the hemp adheres to strict growing environment can be destroyed in seconds with the addition of polycyclic aromatic hydrocarbons (PAH’s) by the use of solvent that has these toxic chemicals in them. These come not through intended consequences, but not knowing the stabilizers and other additives in material being added to these previously pure plants.

What if I pour sour milk on a natural granola for breakfast? What if I use water with high lead or contaminated water to pour over natural coffee grind? Not a great way to start the day, but it is no different than using the most premium hemp and unknowingly adding low grade solvents or adding components from cleaning the surfaces of instruments that come in contact with hemp.

Note that, by definition, we are concentrating the material from the hemp plant. From 4,000 grams, we are getting 400 grams of CBDA if it is 10% by weight (and later converted to CBD). That compound is 10 times more concentrated in a solution. What other compounds are now also 10 times or 5 times or 100 times more concentrated? Maybe no “bad” ones, but how do you know that something else is not also in the mixture?

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Figure 1. With each step of concentration of the green balls, so it could be with other components in the mixture.

This is illustrated in the filtering of green balls in Figure 1. As the green balls become a greater and greater percentage of the solution, it is possible that other compounds like pesticides are also increasing in percentage of the extraction solution. The solution is more concentrated and “simpler” versus all of the other things in the original mixture.

The simple answer is in the testing of the components. The labeling of major compounds is only the beginning of what is on the label that you read. Heavy metals? PAH’s? Residual solvents? Pesticides? Molds? And a long list of other material that could come into the process after the plant left its pristine organic farm. Many studies can be read about slip agents in bags, contamination from workers in the workflow, and other sources of inconsistency.

There are a significant number of companies that I have seen that take this very seriously. New companies are being formed that have safety of product at the top of the list of importance. They are building facilities that are sterile and putting standard operating procedures in place that continually test the product along every step to ensure that they are in compliance.

ecxtractionfig2
Figure 2. Science and economics merge when considering all the possible uses of concentrated compounds to final product formulations

Supercritical fluid extraction is GRAS (generally regarded as safe). It is, only as long as the solvent specifications are known, the vendor meets those standards, and the instrument surfaces meet any necessary standards.

Supercritical carbon dioxide is used to clean surfaces of electronics and bones for skin grafts. It is used for the decaffeination of coffee as well as pulling trace amounts of pesticides from soil. It is used to extract antioxidants from krill and the active ingredients from algae as well as oil from core samples deep below the earth. It also extracts the terpenes and CBDA from hemp – as well as possibly anything that has been added to it.

The key take away from this article is to know the BEST extraction.

Botanical integrity from seed to shelf

Efficacy of the process beyond efficiency, economics, effectiveness

Safety of people and product

Testing for confirmation

Taking each of these into consideration will bring the best results for concentrations of hemp products. I hope you can extract the best from your day.