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Why blog posts warning people of coloured vitamin C serums annoy me and other stories….

September 12, 2017

I’m a little bit angry today, in fact, I’ve been a little bit angry for a while now as there seems to be a thing going on that is not entirely helpful. That thing is this idea that for a vitamin C serum to be good it has to be colourless. I want to talk to you all about that.

The scientific hook.

Vitamin C is a powerful antioxidant but it is also pretty unstable, especially in its cheapest, water-soluble form – Ascorbic Acid.  This just happens to be the biologically active form too so it is quite attractive to brand owners wanting to make a high Vitamin C content claim.

When vitamin C oxidises (goes off) it changes colour from clear to yellowy then orange finally turning to dark brown when it is all gone to hell.  So yes, there is some logic to this idea of wanting your vitamin C serums and creams to be crystal clear – makes it easier for you to know if it is active or not.

Now I know that I’m mad today but turns out some of you are too, some people are angry because they think their vitamin C serums are not doing anything, that they are shonky- possibly because of ‘bad’ formulating and possibly because of something else but the net result is that people aren’t entirely happy.  I think that’s fair enough.

So can crystal clear formulations solve this problem?

Maybe but maybe not.

See as a formulator I deal with lots of materials every day and many of them are colourful – browns, greens, oranges, yellow, red even.  I don’t want some half-baked idea whizzing around the internet and putting a stop to both mine and my customers creativity.  More than that, some of these colourful ingredients might just have a positive role to play in making these vitamin C products work well.

Here are some examples of coloured ingredients that might make it into a vitamin C product:

  • Rosehip Oil (natural source of carotinoids which are natures vitamin A)
  • Vitamin A (retinol, Retinyl palmitate – useful in an A, C and E product)
  • Coenzyme Q10 (very, very yellow)
  • Vitamin E (can be quite browny orange and may affect the colour of a formula when used at 0.5-2%)
  • Honey (honey coloured – can be anything from light yellow through to brown)
  • Seaweed (Different chlorophyls make this anything from greeny blue through to brown)
  • Folic Acid (very, very yellow)
  • Green Tea (brownish)
  • Calendula Oil (very yellow through to orange)
  • Turmeric Infused Oil (bright yellow)
  • Spirulina (very bluish-green)
  • Hemp Seed Oil (very green)
  • Some grape extracts (brown to purple)
  • Activated Charcoal (black/ grey)
  • Alpha Lipoic Acid (yellow)
  • Dragons Blood (from orange through to brown)
  • Sodium Phytate (A useful chelating agent to help stabilise the vitamin C – brown)
  • Various fruit and veg extracts including Melon, Olive Leaf, Quinoa- usually from pink to yellow to brown.
  • Many blended actives from manufacturers
  • Many essential oils
  • Vanilla Oleoresin.
  • Benzoin Tincture.

So what’s going on here.

What I think is happening here is that a couple of brands who make pretty bland (and there’s nothing wrong with bland BTW) Vitamin C serums that focus on just being vitamin C serums – nothing else- are trying to set themselves up as being somehow better (or best).  I think that’s disingenuous really given that these guys give no evidence that their products are indeed better than anything else and worthy of this elevated status.   As a formulator I am well aware of how hard it is to make a stable vitamin C serum or cream but I’m also aware of how some of the above ingredients and many more besides can potentially add to the efficacy of a formula and can bring other, supportive benefits to the product, thus turning a single-purpose product into something that can do so much more.  That said, I am also aware that some of these other ingredients can also add to the chaos of the formula and make it even harder to stabilise.  In short, it is all too complex to just brush off with a ‘if it has a colour it’s crap’ one-liner.  I hate that kind of marketing, it always makes me wonder what the writer is trying to hide…..

Is colour and colour change a guarantee the product is a) crap to start with and b) oxidising out of vitamin C?

So hopefully we can see that a coloured vitamin C product does not have to mean that the formulator is trying to pull the wool over your eyes and ‘hide’ oxidation because they can’t figure out how to stop it so that leaves us with a colour change.  Sure a change in colour from crystal clear to dark brown is a worry but what about a change from a light yellow to an orange or an orange to a brown?  What about a product that starts off a colour because of the above? What do we do then?

While all colour changes mean that something is going on, that is not the same as saying that it’s a guarantee that the vitamin C has all gone. Colour changes can be a fairly standard part of ageing of a natural and especially an organic formula and while that does mean some chemical changes have happened it only matters if those changes mean the product will no longer work, will be irritating or will no longer meet its label promise.  Let’s have a closer look at that.

A common non-critical colour changes typical in organic and natural products.

Plant extracts including many vegetable oils contain chlorophyl pigments that can break down over a product’s life span. Being chlorophyl it is a no-brainer that these pigments will be light reactive and so UV radiation will change their colour – but UV also breaks down vitamin C so most vitamin C products are protected from UV by their packaging.   The most common way chlorophyl pigments break down in vitamin C formulations is by interaction with the acidity in the formula.  There is more than one type of chlorophyl and some break down to become colourless and others become brown.  So your vitamin C serum browning marker may potentially be skewed by little old chlorophyl. Now if chlorophyl breaks down it may increase the likelihood of the whole formula going to crap but it also may not, it depends on how much is in there and how quickly it breaks down but suffice to say the visual effect may give rise to false alarm!  From a formulators perspective it may well be a good idea to avoid chlorophyl containing actives in a vitamin C serum or cream but as chlorophyll is usually present as part and parcel of a natural plant extract or active virgin quality oil that can be easier said than done.   Being non-biologically active whether a cosmetic product contains chlorophyll or not is not important and will not usually affect the performance of a product. So it is possible that a product be quite brown but still contain the specified amount of vitamin C.  This discussion here is quite useful.  

So what can we do?

The main thing we can do is test.  Sure, very few people are going to go out and buy heaps of different serums and get them assayed to see how much vitamin C is left vs what the formula says but if you REALLY REALLY want to know (i.e: you are a brand who wants to know what’s real rather than what’s just in your imagination so you can run a factually correct marketing campaign/ educational blog) then it might be worth doing.

A Vitamin C assay costs between $200-$300 each (plus GST – prices are a guide only and are dependent on provider and method used and are in AUD).  The testing takes a day or so and only a few grams of product are needed.   This is the sort of testing I recommend and do on my formulations and for my brands that want to make a specific claim based on a specific active being present.  Not all vitamin C serum / creams are sold on a percentage of C basis, some just claim to contain Vitamin C and don’t specify the amount.

OK so we test a few products, find they fall short of their Vitamin C concentrations and get mad, but is there anything more than that to worry about?

Vitamin C WILL break down over time no matter how good the formulator is so there will be some oxidation happening eventually.  In a decent formulation this breakdown of Vitamin C will be annoying but will not be much more than that.  It is also worth remembering that oxidation happens over time and bit by bit, it isn’t like the vitamin C is all there one minute and not there the next.   To work out whether a bit of vitamin C oxidation is going to make the product more irritating or not we have to have a look at what the vitamin C turns into.

Vitamin C degradation.

Ascorbic Acid can react with various different things to give different results.  One of the most dramatic reaction pathways in terms of fast colour change is the Maillard pathway of degradation – this is the reaction that happens on an apple when you cut it then leave it – it goes brown quite fast.  Ascorbic Acid is a reducing carbohydrate that reacts with amino acids, peptides and proteins in a reaction that turns brown.  This means that it is a good idea to not have peptides, amino acids or proteins in your vitamin C serum – and most vitamin C serums don’t have these so this most dramatic of pathways is rarely enacted to be honest.  That’s not to say that a vitamin C serum can’t go brown – I’ve had products of my own go brown before their first birthday is up – but that the pictures you often see of vitamin C turning dark brown very quickly indeed will most likely be using this Maillard pathway reaction as it looks the most dramatic.

But that isn’t the only pathway.

Oxygen can also cause a breakdown of the vitamin C but in low pH environments (typical for vitamin C products) this can be relatively slow unless there is a catalyst – some metal ions are catalysts and these may be present as contaminants in the formula (Lead>Zinc>Cobalt>Iron> Manganese>Nickel> Calcium> Magnesium).  It is important to note that these contaminants may even be present in the Ascorbic Acid – it’s hard to get 100% pure anything.

Oxygen catalysed breakdown of vitamin C proceeds somewhat like this:  Ascorbic Acid > Dehydroascorbic Acid (still biologically active) > Diketogulonic Acid (BROWN and not an active form of Vitamin C > HydroxyFural (BROWN and not an active form of vitamin C).  So from that you can see that there can be a chemical change in the vitamin C without it changing the colour of the product immediately – Dehydroascorbic Acid is less likely to brown than Ascorbic Acid according to a 1996 study into this.

But eliminating oxygen doesn’t eliminate all of your problems as vitamin C can also break down anerobically (without oxygen).  In an oxygen free environment Vitamin C can break down to form Furfural, 2-Furoic Acid and 3 hydroxy-2Pyrone.   Furfural is a colourless oily liquid but it does darken very quickly when exposed to air but as we are talking about anaerobic breakdown here it may well be possible to have a critical breakdown in active vitamin C to Furfural in an airless product without seeing that reflected as a colour change. I say might because I am not sure of all the other reactions and changes that go on around this reaction – it is also possible that this reaction critically destabilises the formula. I don’t know.

On top of that UV can also break down vitamin C but again most vitamin C serums know this and are protected by their packaging and in any case, in the grand scheme of things UV is the least of our worries (according to Vitamin manufacturers DSM who rank light way below Alkalinity and oxidising agents as a potential source of degradation and put heat and humidity somewhere in the middle.

 

The bottom line is that colour change is just one thing that can indicate a chemical reaction in your vitamin C product. Sure it is quite dramatic and yep it might well happen but it is not really fair to say that it is the only or even main way to always tell if your product has shat its self.

As an aside you may be interested to know that your vitamin C product might release a bit of gas, change pH or start to smell different as other signs that something chemical is going on.

So what should we all do then?

What I’d like people to understand is that stabilising vitamin C into a usable and cosmetically acceptable formula is not easy and you really are trying to hold back the tide, especially if you are trying to achieve a natural or organically certified product.  I’d like people to remember that colour change is not always a cause for major alarm, that a coloured product is not a sign that you are being duped and that a reduction in vitamin C potency over a products shelf life is not necessarily a show stopper.  In the food world it is widely accepted that vitamin C levels will drop over time and often the stated value on the pack is the end point value (at the end of the shelf life) rather than the starting point. I found data showing ranges of between 75-97% retention after 12 months room temperature to be acceptable – it might be that this is also acceptable in a cosmetic product.   The problem with cosmetics is that we have tended towards marketing what we put in (20% Vitamin C, 10% or 5% for example) rather than what we are left with.  Alternatively we have brands who have chosen to limit their formulation complexity as a way of (hopefully) increasing stability. While this is totally rational and even sensible, I can’t stand by and let that hamper creativity and experimentation – we don’t know everything about vitamin C yet and it would be a shame for brands to give up just because the market has only been groomed for simplicity.

I believe it is best to market our products based on evidence gained on what the product actually does and how it actually performs rather than just opt for a simple numbers game or ‘talk down the opposition’ positioning.   A simple assay or two can validate the Vitamin C content, a stability test can check for pH stability, pack compatibility and general form and function and then a patch test can do the final check to make sure any oxidation hasn’t made the formula more irritating.  These simple steps will ensure that we can keep pushing the envelope with regards to vitamin C formulations while meeting consumers expectations of a good and safe product.  So let’s get on with it shall we and if you want to make and/or sell an orange, pink, green or brown vitamin C product please feel free to do it!

 

20 Comments leave one →
  1. halrac permalink
    September 13, 2017 5:16 am

    Fantastic article!

    • RealizeBeautyEd permalink*
      September 13, 2017 10:40 am

      Thank you 🙂

  2. Alif permalink
    September 13, 2017 6:40 pm

    thank you so much Amanda for this article! it’s all been too worrying now that most lay people claim to be experts in skincare and felt the need to attack cosmetic chemists and manufacturers without knowing the reasoning behind the chemical composition of certain products. it’s all good to be well-informed on one hand, but on the other we have to realize that it is more complicating than we wanted it NOT to be.

    • RealizeBeautyEd permalink*
      September 13, 2017 7:14 pm

      I too have noticed an uprising in people who have lots of opinions and questions but very little idea of why (when you drill down a bit). While it is not a bad thing to be interested and ask questions it is rather tiresome when people do so with such pre-formed bias and closed mindedness – not many people ask to understand any more (in this industry), most just ask as if you are being accused of something dreadful. It is quite sad but it does push me on with my blogging which, I figure helps me figure stuff out even if nobody else thinks they can benefit from it.

      • Alif permalink
        September 19, 2017 7:32 pm

        I can personally guarantee you that your blog has made me extremely informed and it has helped a lot to me. thank you so much for your effort and the hard work you put into this blog with all the information and expertise that you have provided!

      • RealizeBeautyEd permalink*
        September 19, 2017 11:41 pm

        Oh that is so sweet Alif 🙂 thank you x It is something that I’m compelled to do as I think best when I write and it then helps guide my lab work. It helps me to unravel my brain – following the logic

  3. Peter permalink
    September 17, 2017 9:51 am

    “Ascorbic Acid is a reducing carbohydrate that reacts with amino acids, peptides and proteins in a reaction that turns brown. This means that it is a good idea to not have peptides, amino acids or proteins in your vitamin C serum”

    I used a vitamin C serum over a Matrixyl serum and the next morning my hands smelled like self tanner and were stained brown. So possibly the ascorbic acid reacted with the peptides, and I shouldn’t use these products together?

    Although I think you have written a very good article, I think it’s not strange the regular consumer would like to have a clear vitamin C formula. It’s very difficult to determine the percentage of actives in a formula, so also difficult to know to what extend the color is caused by other ingredients than Vitamin C. Since the regular consumer also won’t do expensive assays to test for stability or receive any stability data from the cosmetic companies, the only information they have is to look at the color of the serum and determine the stability based on that. You say people these days are closed minded and have pre-formed bias on subjects, but to be honest I think that is a standpoint we could have expected to happen. The skincare industry has bombarded us with so many claims about wrinkle reduction and lifting effects, while we later learned from experts this is mainly about visible reduction and most cosmetics contain negligible amounts of actives, most likely not doing anything. Now it is quite easy to search for some articles on ncbi. but as you noted skincare companies are still bombarding us with different theories about stability of actives, the way products should be formulated, and it seems like a new trend, critizing the competitors. Looking at (self claimed) experts like Paula Begoun, Hannah Sivak, Stephen Alain Ko, Jetske Ultee, Brandon Truaxe, they all seem to have different opinions on some subjects. How can we as consumers without a scientific background in cosmetics realistically learn then? Reading a few scientific studies won’t help to get a full understanding on a specific subject, but companies not wanting to share any stability data or not helping us with the right information (if they even have that knowledge) makes it almost impossible as a consumer to know what is the right decision and who to believe. I think Ascorbic Acid can be beneficial for skin, and I would so badly want to find a good product with it, but if you believe the persons I mentioned it seems you can never choose the right product.

    • Peter permalink
      September 17, 2017 10:28 am

      If Ascorbic Acid can react with metal ions, amino acids and peptides for example. I also wonder if other products you use can affect the Ascorbic Acid on skin. So if you use a peptide serum, powder or a foundation, can for example iron oxides influence the stability of ascorbic acid? And considering this, can iron oxides and titanium dioxide in foundations also cause free radical formation and photocatalytic activity? Colipa reports noted that it is not clearly known how stable coatings for titanium dioxide are, and if over very long term usage small amounts could penetrate skin (a recent study did find penetration of titanium dioxide particles (https://www.ncbi.nlm.nih.gov/pubmed/26913928)), so if that’s correct I also wonder if the free radical formation could be true for foundations since they use pigment grade titanium dioxide (150-200nm).

      • RealizeBeautyEd permalink*
        September 18, 2017 12:36 pm

        Hello again, OK so this is very interesting and theoretically possible that the iron from iron oxides could interact with ascorbic acid to destabilise it, potentially causing more free radicals than it quenches. However, to know if this is the case and then to quantify the impact is much trickier. Ingredients in a formula have much more time to react than ingredients applied onto the skin. A serum might have existed for 6-12 months before you apply it but a serum would last no more than 12 hours or so before being washed off the skin I expect. That isn’t to say that I don’t think this is a scenario worth modelling. It absolutely is. More, I feel that the reaction conditions on the skin might not be so ‘optimal’ and so an interaction might not be fast enough to cause an issue. Putting vitamin C (Ascorbic Acid) into a foundation would be a clear problem due to the contact time and the fact that the two ingredients would be swimming in a catalytic soup so to speak. With regards to sunscreen and titanium dioxide, sunscreen manufacturers are aware of the photocatalytic nature of titanium dioxide and zinc oxide and as such go to great lengths to either coat or dope them (to quench any reaction). You are right that titanium dioxide used in colour cosmetics is not a sunscreen grade usually and as such could be more photo reactive, however, it is also present in a formula at relatively low levels and again may be devoid of a mechanism of action when worn – sub-optimal conditions for a chain reaction possibly. Still, there is a potential for a problem that should be looked into. It certainly is the case that pigmented formulations can oxidise and change colour on the skin and in the packaging when exposed to air / water. As for nano particles penetrating the skin, there are several things to keep in mind here – penetrating the skin can mean different things – pooling in the epidermis, sinking into the dermis, gathering at the dermal-epidermal layer or being taken up into the bloodstream. There are many pathways and many different nanoparticles. It would be important to map what impact a particular nanoparticle might have on the body should it be absorbed and whether the body could excrete it or not. Again, all very complicated and interesting but not necessarily alarming. Your questions and thoughts are very probing and are the types of questions that the scientific community are investigating so hopefully over time we will have more and more knowledge to share. The only trouble is that when this knowledge is applied into a cosmetic setting anything can happen and the end-product still has to be tested. It is important to remember that again, if a product is used and widely sold safely (with little to no negative feedback over time) then it is not likely to be causing any catastrophic problems to people during use. If the worst thing that happens is that it does nothing much and is disappointing then market forces usually sort that out and the product gets discontinued and customers get their money back.

    • RealizeBeautyEd permalink*
      September 18, 2017 12:17 pm

      Dear Peter, I don’t think it is strange at all that people want a clear vitamin C serum given the information that is being pushed by some brands and the knowledge (and fact) that some vitamin C degradation gives rise to a discolouration. What I aimed to do in this article is broaden the understanding of the issue – that vitamin C serums can be coloured for good reasons and not just to further dupe consumers (as some brands are currently suggesting). Also I don’t expect consumers to pay for assays of products, that would be really unlikely, but I do expect brand owners (whom my blog is primarily aimed at) will spend that money and test and then make those test results available to their public along with explanations of why they have the formulation they do, what it can actually do, how and why. When I say that people are closed minded or bias etc I mean that people don’t know what to think so they tend to err on the side of caution based by fear – the industry is always ripping us off, there is no way of trusting them so I have to have a clear product so I can see (take back control) what is going on……. I am not dismissive of this, I’m sad about it. I hear your frustrations Peter and I don’t really know what to say other than that I am trying to promote the sharing of real information and honesty – concepts that are not well liked in marketing but that ultimately have to come out at some point or another. Cosmetics are not pharmaceuticals and they will, for the most part just focus on visible improvements and topical impacts but that doesn’t mean they do nothing. More often than not modern cosmetic formulations are designed to do no harm and to act as a prevention against harm so in that regard they might help us to look and feel better for longer. It is a complicated world that’s for sure and the best advice I’d give is to form your opinions by trying rather than by what other people say. If something works for you and you can afford it then that’s good enough. Everyone has different skin, diets and lifestyles so it is all pretty individual anyway. Back to vitamin C (Ascorbic acid) it is a good ingredient to use and as it is readily water soluble if you totally give up on brands you could always pop some into your own serum base and use it fresh each day if you were really worried. That’s what a few salons do and it works for them.

    • Alif permalink
      September 19, 2017 7:41 pm

      i personally think you have to go with how your skin feels and reacts to specific products and how they interact with other products. i do believe the reason why some people say “don’t combine this or that” is probably because they want to avoid irritation in people’s skin as much as they can. no one wants to be held accountable if someone’s face flares up into a red balloon or God forbid, an acute dermatitis. the fact that most of the time there’s not one consensus makes it, personally, an interesting fact for me. the world is complex, the chemicals and other things that come into contact with us and our bodies are complex. it is a double edge sword, but thank goodness there’s no one solution to everything. either way, take what you can from the ‘self-proclaimed’ experts you’ve referred to (i also look into them as well), or experts for that matter (Amanda, the Beauty Brains, labmuffin), learn some stuff for yourself, make your own judgements and formulate your own opinions from all the information that you’ve gathered!

      • RealizeBeautyEd permalink*
        September 19, 2017 11:42 pm

        Good advice.

  4. Janine permalink
    September 19, 2017 10:27 am

    Would Tetrahexyldecyl Ascorbate (an oil soluble Vitamin C ester ) perform better? I understand that it does not degrade like ascorbic acid does. Comments and opinions?

    • RealizeBeautyEd permalink*
      September 19, 2017 11:51 am

      Hi there, yes it would be more stable but performance wise it would have to be tested. This version is not exactly the same molecule as Ascorbyl Tetraisopalmitate which has quite a bit of data on it and does have quite good efficacy with regards to skin lightening and antioxidant activity. So I guess there are two main things to consider – stability and efficacy. Just because something is more stable doesn’t mean it will work better and vice versa 🙂

      • Peter permalink
        September 20, 2017 7:25 am

        The strange this is that Deciem claims that Tetrahexyldecyl Ascorbate is the same molecule as Ascorbyl Tetraisopalmitate: “We have confirmed with our lab that Tetrahexyldecyl Ascorbate is the term used to refer to Ascorbyl Tetraisopalmitate in an ingredients listing.”

  5. peanut permalink
    September 23, 2017 9:07 pm

    Hi Amanda, this is off topic but i need your help on sunscreens. Do you have any inside information about what is going on with tinosorb susncreens? I use Cetaphil Suntivity Liposomal lotion SPF 50 which has really good UVA Tinosorb protection. Earlier this year they stopped making more of it, so i emailed them and they just said they were “repackaging it” and should be available later on the year. Anyway, i went to Chemist Warehouse and Priceline, and gasp horror, it’s repackaged as “Cetaphil Sun” and only 2 products in the range- the Ultra Light SPF 50 and the Kids Liposomal one. So i emailed Cetaphil Galderma back and they now telling me that they decided to stop selling Cetaphil Suntivity Liposomal Lotion. Even Actinica Lotion is sold out everywhere. And the Cetaphil UVA/UVB Defence SPF 50 with Mexoryl technology is discontinued too which would be my next best thing. I don’t like La Roche Posay- don’t like the texture and they seem to have the monopoly in the market. So i’m wondering what’s going on, are they trying to reformulate to Tinosorb A2B or something better???

    • RealizeBeautyEd permalink*
      September 24, 2017 11:10 am

      Hi there,
      I actually have no idea but if there is something going on with the active it shouldn’t take me long to find out. I’ll look into it during the week and report back 🙂

  6. peanut permalink
    September 25, 2017 9:10 pm

    They replied back to me, Cetaphil. They said they are having “supply issues” with Actinica sunscreen and is out of stock for 6 months approx. It explains everything- Actinica and Cetaphil Suntivity Lipsomal are same thing and makes sense. Explains why there’s only 2 products from the relaunched Cetaphil Sun range. 6 months is long time, wonder what’s happening? Yes i have eagle eyes when it comes to sunscreens. I see a lot of changes at the shops, everyone is launching new sunscreens. Neutrogena released a whole bunch of zinc oxide sunscreens which i’m not really interested in and seemed to have discontinued the popular Ultra Sheer SPF 50 one.

    • RealizeBeautyEd permalink*
      September 26, 2017 7:30 am

      OK I see. I haven’t had a chance to follow up on the ingredient side yet but I will. The sunscreen market globally is quite tightly knit (well, the big end anyway) so if one changes something, they all want to but I would like to find out more.

  7. peanut permalink
    October 11, 2017 11:59 pm

    Sunscreen update: I think the “supply issues” Galderma is having is due to them closing down the factory in Switzerland…can’t read German, translate does a lousy job. If you know more about it let me know. It’s a shame, Galderma brands sunscreen aren’t that popular but they use the best ingredients. Everyone favours ultra light matte sunscreens so no one buys Cetaphil sunscreens. I went and purchased a few more sunscreen to experiment. The Cetaphil Sun Ultra Light SPF 50 is close enough to the liposomal one, it uses Univual A Plus. I guess I will have to wait till next year to see what happens.

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