FAY-ates, THAL-ates, or PHAL-ates? Phthalates & EVOO(O)

Posted by ricardo on Jan 27th 2025

[Update Jan 28, 2025 early AM: I forgot to add in our re-calculation of the VK2 MK-4 in EVOO solution drop weights. It is now added at the very end of the post.]

It has recently come to our attention (thanks Mark!) that the EVOO we are using, California Olive Ranch's 100% California EVOO, tested on the high end for phthalates in a study by Defend our Health's Roopa Krithivasan et al. further supplemented by the website Mamavation. We are going to dive into phthalates and circle back into EVOO(O)s later. Hope this flows and you get something out of it (like a goodnight's sleep)!

What are phthalates and where are they found?

The US CDC's Agency for Toxic Substances and Disease Registry (ATSDR) has a brief entry on phthalates, last reviewed on August 14, 2008, listing a cute 4 phthalate substances (highlight mine):

So, phthalates are used in plastics. Plastics need to be "plastic-like" aka flexible. Plastics are everywhere and phthalates "can be released fairly easily from these products" according to the ATSDR. But they don't just make things flexible, they're also used as solvents and fixatives (Tsatsakis, A.M. et al. 2019), meaning they can help dissolve other substances into solution (solvent) or they can help the scent (odor) of perfumes last longer (fixative).

They can also be found in food packaging, inks, adhesives, lubricants, house dust, indoor air, foods, milk, water, flooring, wall coverings, medical devices, lacquers, varnishes, perfumes, lotions, cosmetics, personal care products, nail polish, hair spray timed-release pharmaceuticals, etc (Krithivasan R, et al. 2023; Swan, S.H. 2009).

There are several types of (equally unpronounceable) phthalates, some are listed here:

BBP or BzBP - butyl-benzyl Phthalate
DAP - di-allyl phthalate
DBP - di-n-butyl phthalate (di-butyl phthalate)
DEHA - di-ethylhexyl adipate
DEHP - di(2-ethylhexyl) phthalate
DEHT - bis(2-ethylhexyl) terephthalate
DEP - di-ethyl phthalate
DIBA - di-isobutyl adipate
DiBP - di-isobutyl phthalate
DIDP - di-isodecyl phthalate
DINP - di-isononyl phthalate
DMP: di-methyl phthalate
DnHP - di-n-hexyl phthalate
DOP: di-octyl phthalate
DPP: di-propyl phthalate

What do phthalates do?

There haven't been many studies done on humans. Most of the studies (human or animal models) look at how phthalates may affect male reproductive development or more specifically (get ready for it):

cryptorchidism: testes that fail to descend into the scrotum
hypospadias: urethra opening located on the underside of the penis
anogenital distance (AGD): distance from anus to genitalia

Probably easiest if I quote some studies. Please note that since these studies did NOT give their human test subjects phthalates directly (that's too inhumane), they were mostly measuring downstream phthalate metabolites in the urine as a marker or questionnaires for potential phthalate exposure. It is important to note that these epidemiological studies can only observe statistical patterns or associations (emphasis mine):

Phthalates are often used as excipients in controlled-release capsules and enteric coatings, and patients taking these drugs may be at risk. In both animals and human, phthalates are mainly responsible for testicular dysfunction, ovarian toxicity, reduction in steroidogenesis.

Sree, C.G., et al. (2022) Phthalate toxicity mechanisms: An update (link)

---

In many animal models, exposure to phthalates leads to an adverse effect on reproductive development. This phenomenon derives from the ability of phthalates to inhibit the synthesis of testosterone and disrupt androgen signaling. As a result, higher risks of cryptorchidism and hypospadias, as well as a shorter AGD [anogenital] distance, have been observed in male laboratory animals. It has been speculated that human exposure to phthalates may result in similar effects.

Due to this limited availability of epidemiological data, the results of our meta-analysis were rendered non-significant due to a lack of power.

...Robust evidence has demonstrated that DEHP increases the risks of cryptorchidism and hypospadias, and shortens the AGD. Di-isononyl phthalate (DINP/DiNP) has been introduced to replace DEHP, and consequently, DINP exposure has been rapidly increasing in populations worldwide. While animal data suggest that DINP may have an anti-androgen property that is similar to that of DEHP. Bornehag et al. demonstrated that urinary concentrations of DINP metabolites are also associated with a shorter AGD. Consequently, DINP exposure should be reexamined and safe replacements for harmful phthalates remains a critical need.

...The primary programming period for human genital development is within the first 5–18 weeks of gestation. During this time, phthalate metabolites can cross the placental barrier, thus, making the fetus in early pregnancy one of the most vulnerable groups to the effects of phthalate exposure. In a study conducted by Martino-Andrade et al., exposure to DEHP metabolites only in the first trimester were found to be inversely associated with AGD.

Yu, C., et al. (2022) Maternal phthalate exposure during pregnancy and male reproductive disorders: a systematic review and meta- analysis (link)

---

Certain phthalates, industrial chemicals used as plasticizers of polyvinyl chlorine (PVC) plastics and as additives in a variety of consumer products can inhibit fetal testosterone production during the MPW [masculinization programming window in utero] and, in rats, induce a cluster of reproductive tract abnormalities known as the ‘phthalate syndrome’.

...It is important to mention that inhibition of testosterone production is only one of multiple possible mechanisms by which phthalates and other EDCs [endocrine disrupting chemicals] induce hormonal and reproductive changes. For example, inhibition of prostaglandin synthesis and induction [sic] aromatase enzyme has been reported for several of these compounds.

...In summary, this study demonstrates that maternal exposure to DEHP adversely impacts the genital development of male newborns, but suggests that our study endpoints (PW [penile width] and AGD [anogenital distance]) present different windows of susceptibility. The negative relationship between AGD and maternal DEHP metabolites was restricted to T[rimester]1, whereas PW was inversely associated with DEHP metabolite concentrations in T[rimester]2, which may reflect the increased plasticity of penile development. These results strengthen our previous findings and support the biological plausibility of the associations between maternal exposure to DEHP and anti- androgenic effects in humans.

Martino-Andrade A.J., et al. (2016) Timing of prenatal phthalate exposure in relation to genital endpoints in male newborns (link)

This study was mentioned in other studies, but since it was a self-reported exposure to phthalates, I don't think it has much weight. However, I found an interesting quote again from self-reports:

Analysis of maternal dietary habits showed that eating fruit daily was associated with a lower risk of cryptorchidism, but eating dairy products, meat or fish had no influence.

...We found that daily maternal intake of fruits (but not vegetables) had a protective effect.

Wagner-Mahler, K. et al. (2011) Prospective study on the prevalence and associated risk factors of cryptorchidism in 6246 newborn boys from Nice area, France (link)

What does the agencies say?

US FDA:

October 29, 2024: Allows 9 phthalates for food contact applications, but they're NOT authorized to be directly added to food. (link)
July 21, 2023: FDA denied a reconsideration petition filed by EarthJustice, et al. to "prohibit the use of eight ortho-phthalates in food and revoke the prior-sanctioned uses for five ortho-phthalates in food." (link)
- The FDA is only sanctioned to determine the safety of “the probable consumption of the additive and of any substance formed in or on food because of the use of the additive,” in "the diet of man or animals." In other words, the the Food, Drug and Cosmetic Act of 1938 "does not suggest that FDA must consider exposure from non-dietary sources."
- In response to the petition claiming that its the FDA's responsibility to complete a safety analysis, the FDA responds with (emphasis mine): "This argument ignores that under our regulations, a petitioner bears the burden of justifying the requested action."
May 20, 2022: A petition to the FDA by the Flexible Vinyl Alliance FDA to remove 26 ortho-phthalates from the authorized food additive list was approved. 25 of the ortho-phthalates have been removed because it was shown that these substances have been abandoned by the industry, not for any health reasons. Also notable is this paragraph (emphasis mine):
- "The petitioner [FVA] asserts that the currently authorized uses of the plasticizers identified in tables 2 through 19 have been abandoned. In addition to the uses of the 25 plasticizers that are approved for food additive uses as described in tables 2 through 19, certain plasticizers that are the subject of the petition are also authorized for prior sanctioned uses. Any such prior sanctioned use is beyond the scope of a food additive petition, which applies only to substances that meet the definition of “food additive.” Accordingly, this final rule has no impact on any prior sanctioned uses." (link)
May 19, 2022: Phthalates can be used in fragrances or flavors in cosmetics, however the FDA doesn't require the ingredients of these fragrances and flavors to be listed. Thus "[c]onsumers who nevertheless do not want to purchase cosmetics containing DEP may wish to choose products that do not include "Fragrance" or “Flavor” in the ingredient declaration." (emphasis mine, link)

There isn't much to say here except, to be expected. My assessment could be wrong here, but it seems like most agencies are reactive-based not proactive-based. Shouldn't our FDA be tasked with conducting the necessary research in order to determine what substances are "safe" or not? Maybe that's a stretch and would be mired in revolving doors, but laying the burden of proof on the person or entity who files the petition seems like a perverted version of "innocent until proven guilty" for the corporations who are creating these substances.

US EPA:

The EPA is "actively" evaluating the risks for 6 phthalates (BBP, DEHP, DIBP, DBP, DCHP, DINP) and has already issued a final risk evaluation for DIDP. Not quite sure what this means, as it doesn't seem like any action has been taken and these evaluations have been ongoing since December 2019. (link)

European Food Safety Authority (EFSA):

The EFSA calculated an individual "tolerable daily intake" in mg/kg of body weight per day (TDI) "based on the plausible common mechanism underlying the reproductive effects of DEHP, DBP, and BBP." They tried to "equate" the effects of one type of phthalate to another and for simplicity's sake they established a "group of phthalates" TDI of 50 µg/kg of bodyweight per day. At 100 lbs or 45.36 kg, that's 2.268 mg per day. (link)

What did the Defend our Health's and Mamavation's articles find?

The original 2023 study by Defend our Health's Krithivasan et al. provided a spreadsheet with all the data. I combined this data with the Mamavation article's data and added several columns (olive country of origin, saturated fat %, PUFA %, MUFA %). See table below sorted from lowest to highest total phthalate content:

(note that the original study by Krithivasan et al. listed non-phthalate plasticizers as well, but the Mamavation article did not, so I chose not to list non-phthalate plasticizers here. see the original spreadsheet link for those.):

Yellow rows: are EVOOs made with olives grown in California
Green rows: are EVOOs made from olives grown in Europe, Africa, and unlisted.
Purplish/pink cells: are the highest saturated (SFA) or monounsaturated fat (MUFA) content percentage, or the lowest polyunsaturated fat (PUFA) content percentage, depending on the column.
Red cells: are the highest PUFA or the lowest MUFA, depending on the column.
I only populated fat content data for the EVOOs on the list.

Interestingly, 5 out of the 6 California EVOOs tested on the higher end of phthalate content while the top 14 lowest phthalate oils were seed and soybean oils packed in plastic bottles! The second point is especially interesting because it contradicts what I found in another study that tested EVOOs for phthalate content in Turkey, which showed that plastic (PET) bottled EVOOs had a 3,687% higher amount of phthalates vs EVOOs bottled in glass (Sangur, S. 2015).

Unfortunately, I couldn't find data on the PUFA and MUFA content for the Terra Delyssa EVOOO, but did find a study that allowed me to estimate the values. More on that later.

Calculating how much potential phthalate content there is in each bottle of our ~2 mg/drop VK2 MK-4 in EVOO and at various phthalate levels in ng/g or ppb:

1 bottle of ~2 mg/drop VK2 MK-4 in EVOO
contains: 23.07 g EVOO
each bottle may contain:

@ 500 ppb of phthalates:
= 0.000011535 g
= 0.011535 mg

@ 1,000 ppb:
= 0.000023070 g
= 0.023070 mg

@ 1,500 ppb:
= 0.000034605 g
= 0.034605 mg

@ 2,646 ppb (California Olive Ranch)
= 0.000061043 g
= 0.061043 mg

Regarding the California Olive Ranch EVOO that we were using, if you were use an entire bottle in one day (please don't), it'd be roughly 2.69% of the EFSA's TDI if you weighed ~100 lbs. Put in another way, 10 drops would possibly contain: 0.0007056882 mg of phthalates.

If you think I am trying to belittle the exposure, I'm sorry that's not my intention. I want to make it clear to you the potential quantifiable exposure.

What are you going to do?

I think, we want to be exposed to phthalates as little as possible.

I also think, that we want to be exposed to any harmful substance that we currently know of and do not know of as little as possible.

Years ago it was lead in gas and paints, asbestos and DDT, yesterday it was bisphenol A (BPA), paraffin, and food dyes, today it's bisphenol S (BPS), glyphosate, PFAS/PFOS (teflon) and phthalates. Avoiding phthalates is good, but what's the next plasticizer/substance du jour? Are there other substances that we aren't aware of yet and should be?

People are already working on the next plasticizer and I don't think it'll be much "less bad" for you. We'd still prefer that our plastics retain their plasticity right? Hopefully, we will be able to create materials that are non-toxic by past, present and future standards, but I'm not holding my breath.

Regarding phthalates and other EVOO musings, thoughts going through my mind are:

The Mamavation article was published in May 2024 and the Defend our Health study in September 2023, thus if you were to purchase a bottle now, the phthalate content may vary, as it's from a different batch and time.
100% avoidance of harmful substances is, in my opinion, futile. At the same time, that doesn't mean that we should ignore the available data. We do our best to avoid contamination and oxidation of product once it reaches our hands (more about our process).
What other substances are in the products we use/sell that haven't been tested for? Is there something "worse" than phthalates lurking in there?
We originally chose California Olive Ranch EVOO because it was domestic to us, in a glass bottle and it solidified in the fridge in ~36 hours. We figured it being domestic, the time elapsed since manufacture and time spent in hot summertime logistic chains would be shorter, leading to smaller chances of contamination and oxidation.
We'd prefer to pick an EVOO with a lower percentage of PUFA and a higher percentage of SFA.

Based on the 2 articles/studies and our pondering, we have since purchased different 3 EVOOs. See consolidated table of the 3 new EVOO(O)s and the 1 we originally used:

Did you notice that percentages of fat for the California Ranch EVOO is greater than 100% and Bragg and Séka Hills didn't add up to 100%? Apparently fats are rounded to the nearest half gram increment and fat weights less than 0.5 g are reported as zero. Somewhat understandably, these values are "for reference" only (Appendix H, page 129 link).

As stated earlier, I couldn't find data on the PUFA and MUFA content for the Terra Delyssa EVOOO, but did find a study stating that the MUFA, oleic acid (18:1 n-9), typically makes up at least 70% of the total fats in olive oil (White 2007, Ch.10). Inputting 70% for MUFA (and ignoring any possible palmitoleic acid (16:1 n-7) content), leaves 10.8% of PUFA for the online nutrition label version and 11.1% for the store nutrition label version (I'm not sure why they're different).

Oddly, Bragg took about the same amount of time as the California Olive Ranch EVOO to solidify in the refrigerator even though it supposedly has a higher amount of saturated fat. One reason why the Séka Hills EVOO could have solidified faster than the other brands, it that it's half the volume of the other bottles at 500 vs 1,000 mL and because its in a thin but tall bottle (more surface area to dissipate heat).

Now you maybe wondering, and rightly so, does the EVOO refrigeration test even mean anything? (hat-tip again to Mark!) After looking for papers discussing EVOO's solidification at lower temperatures, it looks like there are 2 distinct crystallization/solidification events, the first event occurs on the more saturated fraction (portion) of fats and a second event, at a lower temperature, for the more unsaturated fraction of fats.

Consequently, EVOO in chilled and frozen foods is frequently present as a mixture of a liquid phase entrapped in a solid made of triglyceride crystals. Due to its fatty acid (FA) composition, the melting range of EVOO is broad and spans from about -20 to 10ºC as determined by DSC analysis.

...EVOO phase transitions occur showing two main consequential thermal events associated with the crystallization/melting of fractions containing different ratios among saturated and unsaturated TAGs [triacylglycerols]

...Two exothermic peaks were detected during cooling. Since saturated TAGs [triacylglycerols] crystallized at higher temperatures than the unsaturated ones, the exothermic peak can be reasonably attributed to the phase transition of an oil fraction containing mainly saturated FAs [fatty acids], such as palmitic (P) (C 16:0) and stearic (S) (C 18:0) acid. The second exothermic peak was observed at -33.5ºC and can be inked to the phase transition of low melting highly unsaturated oil fraction.

...Considering the solid fraction calculated from the partial integration of calorimetric melting curve, it can be assumed that about 17% w/w [weight/weight] of the oil is crystallized under refrigerated storage conditions (4ºC). Only when temperature is reduced below 0ºC, the crystallization of the oil fraction rich in unsaturated FA [fatty acid] could take place.

Barba, L., et al. (2013), Crystallization and melting properties of extra virgin olive oil studied by synchrotron XRD and DSC (emphasis mine, link)

---

Given the study by Barba et al. and our own findings, I think there are two takeaways, the first being something that we probably already knew: that saturated fats solidify at higher temperatures (around refrigerator temperatures) than unsaturated (mono or poly) fats. What I didn't expect, but obviously should have, is that there are 2 distinct fractions of fatty acids, with different saturated-to-unsaturated ratios, that solidify at different temperatures. And when the more-saturated fraction solidifies, it "entraps" the other less-saturated fraction.

This almost invalidates the EVOO refrigerator test, but it does leave questions that maybe we can do a future experiment to test for:

How does the ratio of SFA-to-MUFA-to-PUFA affect how the more-saturated fraction of fatty acids entraps the less-saturated fatty acid fraction at refrigerator temperatures?
How does the ratio of SFA-to-MUFA-to-PUFA affect the speed at which the more-saturated fraction of fatty acids solidifies and entraps the less-saturated fatty acid fraction at refrigerator temperatures?

Let us know if you'd like to see this test.

Ok ok ok, so what EVOO are you picking?

I really wanted to use the Séka Hills EVOO, ok I still want to use them, mainly because I want to support a US farm. But I think I have to rule them out, the biggest reason being that I'm afraid we may not be able to get their product year round when needed. It's also not organic and while I don't want to place too much emphasis on the organic label, I couldn't find anything on their website about their agricultural practices (and now that I look, I can't find anything on California Olive Ranch's site either).

We are going to pick Terra Delyssa EVOOO, because it tested ok for phthalate content, its organic, its in a very dark glass bottle (seems darker than amber), turns solid in the fridge quickly, and mainly because it boasts a (for reference only) 18.9% to 19.2% saturated fat content. The only other EVOOO that tested higher in saturated fats was the Gundry, which is like buying liquid gold at USD$121 per liter (even if you sign up and buy 6 bottles at once). But, the Gundry EVOO also had the highest PUFA (15.38%) and lowest MUFA (61.54%).

Let us know if you agree, disagree, or have any other comments.

[Update 1/28/2025 in the early AM]

Switching to a new EVOO(O) requires us to get another drop weight baseline. We dropped 1,675 drops for a total weight of 48.553 grams, translating to ~0.02897 grams/drop, which is not far off from our drop test made with the EVOO from California Olive Ranch of 0.0287 grams/drop (0.94% bigger). I think it's best to take the overall average of both EVOOs going forward, mainly because the more drop data, the better we can filter out any possible noise. Our calculation is as follows:

Previous drop weight data on California Olive Ranch:
drop count: 3,262
total weight of drops: 93.629 g

Current Terra Delyssa drop weight data:
drop count: 1,675
total weight of drops: 48.533

Combined drop count: 4,937
Combined total weight of drops: 142.162 g
Combined average g/drop: 0.0288

Now, using the new average drop weight of 0.0288, we can calculate the weight of Terra Delyssa EVOOO needed to reach our target VK2 grams/drop:

target VK2 mg/drop: 2.03 (1.5% buffer over 2 mg)
target VK2 g/drop: 0.00203
Avg VK2 EVOO Solution grams/drop: 0.0288

Calc'd Drop Count
  = 1.756 g ÷ 0.00203 g/drop
  = ~865 drops

Calc'd Total Solution grams:
  = 865 drops · 0.0288 g/drop
  = 24.912 g
Calc'd EVOOO grams to add:
  = 24.912 g - 1.756 g
  = 23.156 g

Moving forward, we will update our listing to add 23.156 g of EVOOO instead of the prior 23.070 g.

Sorry, for the long windy road that started out with phthalates and ended up in an EVOO dive leaving more unanswered questions than answers.

Pipeline:

Super Concentrated Vitamin K2 MK-4 in EVOO: ~12 and 14 mg / drop solutions have been stable at room temperature, sadly ~18 and 20 mg / drop precipitates out of solution :(. Will try a 16 mg/drop solution next. ETA Feb 2025
Vitamin D3 in EVOO: All 3 samples of pure VD3 we received tested at 99% purity, and the first sample tested low on heavy metals. We are waiting for the heavy metal results on the last 2 samples. Will test for a couple more things and then will begin bottling! I have made a ~10,000 IU/drop bottle and it has stayed in solution (Hat-tip to John!) ETA Feb 2025
Water filtration testing showdown:on 113 general parameters, 40 PFAS/PFOS parameters and radon for the following filter types:

Straight Well Water vs
Filtered and Softened vs
Reverse Osmosis filtered vs
Distilled water
ETA Late Feb 2025