Sunshine, skin chemistry, and vitamin D

The UK is on the same latitude as Northern Canada (Image Source: Wiki Commons)

As I write this it’s the last day of September in the U.K., which means we’re well into meteorological autumn and summer is, at least here, a distant memory. The weather is cooler and the days are getting shorter. Soon, the clocks will go back an hour, and we’ll shift from BST (British Summer Time) to GMT (Greenwich Mean Time).

Seasons in the U.K. are particularly marked because of our northerly latitude. British weather tends to be fairly mild (thanks, Gulf Stream), and it’s easy to forget just how far north we are – but a quick look at a globe makes it clear: London is actually further north than most of the major Canadian cities, while the Polar Bear Provincial Park in Ontario is roughly on the same latitude as Scotland’s capital city, Edinburgh.

Yes, I hear you say, but what on Earth (hoho) does this have to do with chemistry?

Well, a clever little piece of chemistry happens in human skin, and, if you live in the U.K., it’s about to stop. At least, until next spring.

Some clever chemistry happens in human skin.

There’s a substance in your skin called 7-dehydrocholesterol (7-DHC). It is, as the name suggests, something to do with cholesterol (which, despite its bad press, is an essential component of animal cell membranes). In fact, 7-DHC is converted to cholesterol in the body, but it’s also converted to something else.

You will have heard of vitamin D. It helps us to absorb calcium and other minerals, and if children, in particular, don’t get enough it can lead to rickets – which leads to weak bones, bowed legs and stunted growth. Vitamin D deficiency has also been linked to lots of other health problems, including increased risk of certain cancers, heart disease, arthritis and even type one diabetes.

More recently, vitamin D has been linked to COVID-19. It’s estimated that around 80-85% of people who contract COVID-19 experience mild or no symptoms, while the rest develop severe symptoms and, even if they recover, may suffer life-altering after-effects for many months. Early data suggest that patients with low vitamin D levels are much more likely to experience those severe symptoms. There’s a plausible mechanism for this: vitamin D helps to regulate the immune system and, in particular, helps to reduce the production of cytokines.

It’s possible that having inadequate levels of vitamin D may increase your chances of a severe response to COVID-19.

Cytokines are small proteins which are important in cell signalling, but if the body starts to produce too many in response to a virus it can cause something called a cytokine storm, which can lead to organ failure and death.

It’s proposed that having the right levels of vitamin D might help to prevent such cytokine storms, and therefore help to prevent a severe COVID-19 response. This is all early stages, because everyone is still learning about COVID-19, and it may turn out to be correlation without causation, but so far it looks promising.

One thing you many not know is that vitamin D is, technically, misnamed. Vitamins are, by definition, substances which are required in small quantities in the diet, because they can’t be synthesised in the body.

But vitamin D, which is actually a group of fat soluble molecules rather than a single substance, can be synthesised in the body, in our skin. The most important two in the group are ergocalciferol (vitamin D2) and cholecalciferol (vitamin D3), sometimes known collectively as calciferol.

Shiitake mushrooms are a good source of vitamin D2.

Vitamin D2 is found in fungi, but it’s cleared more quickly from the body than D3, so needs to be consumed in some form daily. Mushrooms are a good source (especially if they’ve been exposed to UV light), so if you like mushrooms, that’s one way to go. Vitamin D3 is hard to obtain from diet – the only really good source is oily fish, although other foods are fortified – but that’s okay because, most of the time, we don’t need to eat it.

Which brings us back to 7-DHC. It’s found in large quantities in the skin, although exactly how it gets there has been the subject of some debate. It used to be thought it was formed from cholesterol via an enzymatic reaction in the intestine wall and then transported to the skin via the bloodstream. But the trouble with this idea is that the blood would pass through the liver, and 7-DHC would be reconverted to cholesterol, never having a chance to build up in skin. A more robust theory is it’s actually synthesised in the skin in the first place, particularly since higher levels are found in a layer closer to the surface (the stratum spinosum) than in the deeper dermis.

We make vitamin D in our skin when we’re exposed to UVB light from the sun.

Anyway, the important thing is that 7-DHC absorbs UV light, particularly wavelengths between 290 and 320 nm, that is, in the UVB range, sometimes called “intermediate” UV (in contrast with “soft” UVA, and “hard” UVC). When exposed to UVB light, one of the rings in the 7-DHC molecule breaks apart, forming something known pre-D3, that then converts (isomerises) to vitamin D3 in a heat-sensitive process.

In short, we make vitamin D3 in our skin when we’re in the sunshine. Obviously we need to avoid skin damage from UV light, but the process doesn’t take long: 10-15 minutes of midday sunlight three times a week, in the U.K. in the summer, is enough to keep our levels up.

Sun exposure is by far the quickest, and certainly the cheapest, way to get your vitamin D. If you live somewhere where that’s possible.

Here’s the thing, though, if you live in the U.K., for a chunk of the year, it’s just not. I’ve pinched the graph here from my husband, whose work involves solar panels, because it makes a nice visual point.

The amount of sunlight we’re exposed to in the U.K. drops sharply in autumn and winter.

From April – September, there’s plenty of energy available from sunlight. But look at what happens from October – March. The numbers drop drastically. And here’s the thing: it turns out that vitamin D production in human skin only occurs when UV radiation exceeds a certain level. Below this threshold? Well, no photocoversion takes place.

In short: if you live in the U.K. you can’t make vitamin D in your skin for a few months of the year. And those few months are starting… round about now.

The NILU has a web page where you can calculate how much vitamin D you can synthesise in your skin on a given day.

If you want to experiment, there’s a website here, published by the Norwegian Institute for Air Research (NILU), where you can enter various parameters – month, longitude, cloudiness etc – and it will tell you how many hours during a given a day it’s possible to synthesise vitamin D in your skin.

Have a play and you’ll see that, for London, vitamin D synthesis drops off to zero somewhere around the end of November, and doesn’t restart until sometime after the 20th of January. In Edinburgh, the difference is even more marked, running from the first week or so of November to the first week of February.

It’s important to realise that it tails off, too, so during the days either side of these periods there’s only a brief period during midday when you can synthesise vitamin D. And all this assumes a cloudless sky which in this country… is unlikely.

The skin pigment, melanin, absorbs UVB. (Image Source: Wiki Commons)

The situation is worse still if you have darker skin because the skin pigment, melanin, absorbs UVB. On the one hand, this is a good thing, since it protects skin cells from sun-related damage. But it also reduces the ability to synthesise vitamin D. In short, wimpy autumn and winter sunshine just isn’t going to cut it.

Likewise, to state the obvious, anyone who covers their skin (with clothing or sunblock), also won’t be able to synthesise vitamin D in their skin.

Fortunately, there’s a simple answer: supplements. The evidence is fairly solid that vitamin D supplements increase blood serum levels as well as, if not better than, sunshine – which, for the reasons mentioned above, can be difficult to obtain consistently.

Now, as I’ve said many times before, I’m not a medical doctor. However, I’m on fairly safe ground here, because Public Health England do actually recommend everyone take a vitamin D supplement from October to May. That is, from now. Yes, now.

I do need to stress one point here: DO NOT OVERDO IT. There always seems to be someone whose reasoning goes along the lines of, “if one tablet is good, then ten will be even better!” and, no. No. Excessive doses of vitamin D can cause vomiting and digestive problems, and can lead to hypercalcemia which results in weakness, joint pain confusion and other unpleasant symptoms.

If you live in the U.K. you should be taking a vitamin D supplement from October-May.

Public Health England recommend everyone in the U.K. take 10 micrograms per day in autumn and winter. Babies under one year should also be given 8.5–10 micrograms of vitamin D in the form of vitamin drops, unless they’re drinking more than 500 ml of infant formula a day (because that’s already fortified).

Amounts can get a little confusing, because there are different ways to measure vitamin D doses, and in particular you may see IU, or “international units“. However, if you buy a simple D3 supplement, like this one that I picked up at the supermarket, and follow the dose instructions on the label, you won’t go far wrong.

So, should you (and everyone else in your family) be taking a simple vitamin D supplement right around now? If you live in the U.K., or somewhere else very northerly, then yes. Well, unless you’re really keen to eat mushrooms pretty much every day. At worst, it won’t make much difference, and at best, well, there’s a chance it might help you to avoid a really unpleasant time with COVID-19, and that’s got to be a good thing.

But, look, it’s not toilet roll. Don’t go and bulk buy vitamin D, for goodness sake.

Until next time, take care, and stay safe.


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Should you be scared of your shampoo?

I was doing some grocery shopping online recently (I have small children, I’ve started to view traditional supermarket shopping in the same way as beating my carpets with a stick and washing clothes in a stream) when I came across some reviews for a particular brand of shampoo.

Most of the reviews were positive, but some were not. In particular, there were a few one star ones complaining about ingredients called methylchloroisothiazolinone and methylisothiazolinone.

273px-Methylchloroisothiazolinone_structure.svg

methylchloroisothiazolinone

What, you may be wondering, are these monstrosities? Surely with names that long they must be huge great big molecules? Actually no, they’re quite small. Methylchloroisothiazolinone (shown in the graphic) has a mere four carbon atoms and an interesting assortment of other elements. They’re part of a group of compounds called isothiazolinones, which are heterocyclic molecules that include a five-membered ring which contains nitrogen, sulfur and a C=O group.

Not surprisingly considering the unwieldy name, methylchloroisothiazolinone is often shortened to MCI. Likewise, the chemically-similar methylisothiazolinone (imagine the molecule above without the -Cl bit) goes by the moniker MI, or sometimes MIT.

MCl and MI are common preservatives in cosmetic products

MCl and MI are common preservatives in cosmetic products.

Why are these things in shampoo? Well, they are very effective preservatives. They’re antibacterial and antifungal, and work against both gram-positive and gram-negative bacteria, as well as yeast and fungi. This is a good thing, because some of these microbes are pretty nasty. The bacteria, for example, include such lovelies as Nocardia (associated with a particular type of respiratory disease), Staphylococcus (associated with various infections) and Listeria (most famous for causing gastrointestinal distress). It may be a small risk, but showers are warm, moist environments – basically the perfect breeding ground for these sorts of things. If these microbes start growing in your shampoo, shower gel and so on, they would then end up on your hair and skin, possibly be inhaled, and might even make their way into your bloodstream if you had a small cut somewhere.

Yuck.

So, that’s why these chemicals are there. That all sounds good, right? Why are people complaining?

The dose makes the poison is an important principle in toxicology (image credit: Lindsay Labahn, click for link)

The dose makes the poison is an important principle in toxicology (image credit: Lindsay Labahn, click for link)

Well, because they also have their hazards. Now, before I go any further, we should remember a very important principle of toxicology, which is that “the dose makes the poison“. Everything, I really mean EVERYTHING, is dangerous if you’re exposed to too much of it. Oxygen is quite crucial if you want to carry on living, for example, but breathe in too much of it for too long and you’re at risk of developing visual disturbances, tinnitus, nausea and muscle spasms. Too much could even be lethal. Similarly, a pinch of salt is quite nice on chips, but try and drink say, seawater, and you’ll soon regret it. Even plain water can be dangerous if you consume too much in too short a time, particularly if you’re also exercising hard.

Many chemicals that are used industrially have scary lists of associated hazards, but it’s important to remember that these warnings are usually aimed at people who use said chemical in an industrial setting. In other words, they might be handling kilograms or even tonnes of the stuff, all day every day, as opposed to the teeny tiny quantity you’re likely to meet a few times a week.

I could pick literally any ingredient in that shampoo bottle and proclaim that it’s dangerous. This would be perfectly true, but also meaningless. A more pertinent question is: is it dangerous in the quantity that you usually use?

Are methylchloroisothiazolinone and methylisothiazolinone in shampoo dangerous? There’s no evidence that they bioaccumulate (build up in the body) or that they’re linked to any kind of cancer (phew). In 2002, there was an in vitro (i.e. outside of living organisms) study of the neurotoxicity of MI which showed that mature neurons in tissue culture could be killed by 4-12 ppm solutions of the chemical. But these experiments were performed on rat brain cells in culture. Lots of things will damage cells in a petri dish: it doesn’t mean that we necessarily have to worry about them in every day life. A shampoo solution pouring straight into your brain might well be harmful, but I suggest that if that’s happening in the shower you have bigger problems. Namely, major head trauma.

However, in high concentrations, MI and MCl are definitely skin and membrane irritants, which can cause chemical burns. They’re known chemical ‘sensitisers‘. This means that exposure to them, even at fairly low levels, might cause an allergic reaction.

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A patient who presented to a medical centre following a severe reaction to methylisothiazolinone in a wipe (SA Government – click image for source).

This is where we get into difficult territory, because exactly how a particular individual is going to respond to something like this can be hard to predict. For example, I’ve never had a nasty reaction to methylchloroisothiazolinone. Give me an aspirin, on the other hand, and I’m likely to be in trouble. Allergies are specific to individuals. But there is no doubt that some people do have nasty reactions to MCI and MI; some sources have suggested it might be as many as 15% of the population (and that this number might, worryingly, have increased in recent years).

These chemicals are, or at least have been, also used as preservatives in other products such as sunscreens, moisturisers and wipes (baby wipes, facial wipes and moist toilet tissue, for example), which is a particular concern because you don’t wash off the the residue from these products – that generally being the point of using them – so it lingers on the skin.

A 2014 report from the International Journal of Toxicology concluded that although MI and MCI are sensitisers at concentrations of 50 ppm and above, they weren’t at concentrations of 15 ppm (and below). And therefore they, “may be safely used in ‘rinse-off’ products at a concentration not to exceed 15 ppm and in ‘leave-on’ cosmetic products at a concentration not to exceed 7.5 ppm”.

However, also in 2014, the European Commission Scientific Committee on Consumer Safety argued that: “For leave-on cosmetic products (including ‘wet wipes’), no safe concentrations of MI for induction of contact allergy or elicitation have been adequately demonstrated.”

People have been particularly worried about children, especially with respect to baby wipes. This is not unreasonable, since not only is the contact dermatitis that can occur painful and unpleasant, but once sensitisation has occurred it can’t be reversed: anyone affected will have to read labels extremely carefully for ever after. As a result, consumer groups have campaigned to have MI and MCI removed from any product that’s left on the skin over the last few years.

I happen to have three different brands of baby wipes in my house at the moment (small children you see), and a quick glance at the ingredients tells me that MI and MCI aren’t in any of them, and nor are they ingredients in the packet of flushable moist toilet tissue in the bathroom. This is hardly a comprehensive survey of course, but it suggests that these substances might be falling out of favour. Big companies aren’t really out to get us: pictures of people with nasty skin lesions after using their products doesn’t do them any favours.

Some consumers have complained about the use of MI and MCl in products.

Some consumers have complained about the inclusion of MI and MCl in products.

Do you really need to worry? Were these consumers right to highlight the fact that the shampoo contains MI and MCI in their reviews? Well, if you know you have sensitive skin then these substances probably are best avoided. But is shampoo likely to cause sensitisation if you’re fortunate enough to be blessed with the sort of skin that generally doesn’t erupt into a rash if the wind so much as changes? No one can say for certain, but it seems unlikely because you wash it off: these substances are only in contact with your skin for a few seconds.

So, whilst it doesn’t hurt to be aware of such things, there’s probably no need to panic and throw out all your shampoo just in case. On the other hand, if you’ve been wondering why your skin seems to be permanently irritated, it might be worth checking a few ingredients labels.

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