Tag Archives: fungi

Freezing fungal farts: what is hair ice and why does it form?

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Hair ice, in which ice crystals grow in thread-like structures, can be found at northerly latitudes in broadleaf forests [image source]

I’ve written about water before and in particular, if you’ve been paying very close attention, you might remember that November 12th marks the anniversary of the day, in 1783, that Antoine Lavoisier formally declared water to be a compound rather than an element.

Which means that November is always an excellent time to talk about water. But this time, I’m going to focus on its solid state: ice.

A few days ago I stumbled across some beautiful images of hair ice, which prompted me to make a #272sci Twitter post (keep an eye on that hashtag for similar small bits of interesting science). The story behind hair ice is a fascinating one, and not something I could truly cover in 272 characters – so here’s the slightly longer version…

This form of ice is found on dead wood, and it has a few other names, including ice wool or frost beard. Of course, ice naturally forms at 0 ℃ at standard atmospheric pressure, but the form we’re most familiar with looks, to the naked eye at least, rather more random. In fact, it was snowing here just yesterday, which means I have photos!

Ice crystals on a wall in Oxfordshire, UK, in November 2021

As you can (hopefully) see, there’s some regularity to the individual crystals, but they’re sort of growing all over the place. So, how do ice crystals form, and why?

We need to start with the structure of water. Now, you might imagine that a molecule with the formula H2O would have its atoms arranged in a straight line, like this: H–O–H. But it doesn’t, and the reason it doesn’t is that the oxygen atom in the middle has two pairs of electrons which aren’t involved in bonding – which chemists call ‘lone pairs‘.

Imagine, for a moment, that you have a bunch of balloons made up of two sausage-shaped balloons and two round ones, all attached at the neck. What shape would they make, as a whole? Probably, the two long balloons would form a sort of rough V, and the two round ones would stick out, opposite each other.

If you have some balloons to hand, give it a try. It turns out this is actually a pretty good model for water. We end up with a roughly tetrahedral shape, with oxygen in the middle, hydrogen atoms in two of the corners, and the lone pairs in the other two corners.

The H2O atoms in a water molecule adopt a sort of shallow V shape but, if you consider the lone pairs, the molecule actually forms a rough tetrahedron [image source]

This is important because those lone pairs don’t just sit around doing nothing. The element oxygen is very electronegative, which means it likes to attract bonded electrons. Hydrogen, by contrast, is more electropositive, which essentially means it doesn’t.

The result of this is that, although it is very definitely a covalently-bonded molecule (and not made up of ions), the oxygen atom in water has a partially negative charge, while the hydrogens have a partially-positive charge.

Since positive charges attract negative charges, and since molecules don’t exist in isolation. The result is that the hydrogen atoms in one water molecule are attracted to the oxygens in other water molecules. This is called hydrogen bonding.

If your head is spinning as you try to imagine this, take a look at the image below. White is hydrogen, red is oxygen, and the dashed lines represent the attractions between partially-positive hydrogens and partially-negative oxygens.

Do you see the shapes that form? Yes – hexagons!

When water molecules pack together they form hexagonal shapes [image source]

And how many sides does a snowflake have? Yes – six!

It’s not a coincidence: as the temperature drops, molecules that previously had freedom of movement gradually stop moving so much and pack into these hexagonal shapes. Then, water vapour in the air deposits onto this skeleton and, voilà, we end up with six-sided ice crystals.

Now, normally, this happens fairly randomly. Yes, all the snowflakes are hexagonal (and there are images of the different patterns that can form in this graphic from Compound Interest) but, as my photos of ice crystals suggest, they tend to stick out in all directions.

Hair ice is different. The ‘hairs’ appear at what are called wood rays, that is, lines perpendicular to the growth rings of the wood, and it turns out that if a piece of wood forms hair ice once, it will probably keep producing it – which makes things rather easier for the potential photographer!

Each of the hairs is about 0.02 mm thick and, assuming the temperature doesn’t rise above freezing, they can hang around for hours and even days.

Why does hair ice grow in single, curling strands, rather than forming this more typical ‘bushy’ structure?

Which leads to the question: why don’t more ice crystals grow on top of the threads and break up the hair-like structures? After all, if it’s cold enough for ice, it ought to be cold enough for, well, more ice – oughtn’t it?

A quick aside: you’ve probably heard of Alfred Wegener, discoverer of continental drift – an idea that ultimately led to modern tectonic plate theory. These days, those ideas are pretty universally accepted, but when Wegener first proposed continental drift in 1912, he faced a lot of opposition. There was more than one reason for this, but one major one was that Wegener was seen as an outsider to the field of geophysics. His background was in meteorology and polar research. In other words, he spent a lot of time in cold weather conditions.

Which brings me back to the main, ah, thread (sorry). Alfred Wegener described hair ice on wet dead wood in 1918, having observed it the year before, and suggested that mycelium, the thread-like part of a fungal colony, could be involved. He thought this because he could actually see mycelium on the branch surface, which was confirmed by his consultant, Arthur Meyer. Meyer, however, was unable to definitely identify the fungal species at the time.

Some years later, in 1975, scientists named Mühleisen and Lämmle actually managed to grow hair ice on rotten wood in a climate chamber and later still, in 2005, the physicist Gerhart Wagner again suggested that a fungus was involved, although he had no knowledge of Wegener’s observations when he first did so. He went on to carry out experiments with Christian Mätzler in which they were able to reliably grow hair ice on a balcony on nights with freezing conditions.

A photo of hair ice taken in British Columbia, Canada, by Tiarra Friskie

After lots of painstaking (and cold!) observation, they concluded two things: firstly, hair ice forms from water stored in the wood, not atmospheric water – which goes some way to explaining why the structures aren’t more random, as you’d expect if the ice were forming from water vapour in the air.

Secondly, the fungus, as a product of its metabolism, was generating gas pressure, and that was pushing water through the wood rays to the wood surface, where it was fanning out into fine, curling strands.

So, yes, in a way, hair ice is the product of freezing fungal farts. (Yes, yes, very tenuous, but I couldn’t resist ‘freezing fungal farts’, let me have this one.)

There’s a much more scientific explanation in this 2015 paper, the full text of which is freely available online (lots of great photos too!). The culprit turns out to be a fungus called Exidiopsis effusa. Inside the wood, attractions between the water molecules and the wood surface lower the melting point of water slightly, keeping it liquid. Products of wood decomposition left by the fungus also (probably) help to prevent ice forming inside the wood itself.

Once the outside temperature drops, though, the formation of ice crystals on the outer surface of the wood has the effect of drawing out more water, and the result is that the crystals grown in long, thread-like structures – although the fine details of how the fungus does what it does are still a bit of a mystery. Still, it’s nice to find a not-quite-answered science question, isn’t it?

More hair ice in the wild, by Tiarra Friskie

One final thing: just in case you were thinking, oh, come on, is that first picture really real? On the Chronicle Flask Facebook page, a user named Tiarra Friskie commented that they had pictures of this very phenomenon, taken in British Columbia, Canada, and kindly gave me permission to use them. So, here you are: a tiny bit meltier than the picture above, but nevertheless, two guaranteed genuine photographs of hair ice!

If you live somewhere in the vicinity of the latitudes between 45 and 55 °N (which includes most of the UK, by the way), keep an eye out for rotten wood in your local broadleaf forest – if the weather gets cold enough, you might just spot some hair ice yourself.

A little admin note: the chronicle flask blog is now (yikes) almost nine years and 150 posts old. Life is increasingly busy and so, after December 2021, I’m going to stop making monthly updates. But not to worry! You can still follow the Twitter hashtag #272sci for regular tiny pieces of science, and I’ll pop back every now and then. Oh, and please do consider supporting the Great Explanations book project here!

Plus, why not take a look at my fiction blog: the fiction phial? And you can also find me doing various flavours of editor-type-stuff at the horror podcast, PseudoPod.org – so head over there, too!

Content is © Kat Day 2021. You may share or link to anything here, but you must reference this site if you do. You can support my writing my buying a super-handy Pocket Chemist from Genius Lab Gear using the code FLASK15 at checkout (you’ll get a discount, too!) or by buying me a coffee – just hit this button:
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Neem: nice, nasty or… not sure?

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A few days ago it was sunny and slightly breezy outside (yes, it’s August, but I live in the UK – this isn’t as common as you might imagine) and I thought, I should make the most of this and do something about my orchids.

Now, anyone that reads this blog regularly will know that my Dad is a horticulturist. I, however, am not. My fascination with bright colours, interesting smells and complicated naming conventions went down the chemistry route. But I am, oddly, quite good with Phalaenopsis, aka, moth orchids. I don’t really know why, or how, but I seem to have come to some sort of agreement with the ones that live on my kitchen windowsill. It goes along the lines of: I’ll water you once a week, and you make flowers a couple of times a year, and we’ll otherwise leave each other alone, okay?

Scale bugs secrete honeydew, which encourages the growth of sooty moulds

Well, this was fine for years, until we somehow acquired an infestation of scale bugs. These tiny but extremely annoying pests feed by sucking sap from leaves of plants, and they excrete a sticky substance called honeydew. Trust me, it’s not as nice as it sounds. Firstly, it really is sticky, and makes a horrible mess not just of the orchid leaves, but also the area around the plants.

Then it turns out that certain types of mould just love this stuff, so you end up with black spots on the leaves. And, not surprisingly, all this weakens the plant.

So, what’s the answer? Well, there are several. But the one I tend to default to is neem oil.

This stuff is a vegetable oil from the seeds of the Azadirachta indica, or neem, tree. It has a musty, nutty sort of smell, and is fairly easy to buy.

It’s indigenous to the Indian subcontinent and has been historically important in traditional medicine. In fact, The Sanskrit name of this evergreen tree is ‘Arishtha’, which means ‘reliever of sickness’.

So it’s a natural vegetable oil and people have been using it as a remedy for thousands of years – must be totally safe, right? Right?

Well… I’ve said it before, but some of the very best horribly toxic things are entirely natural, and neem is yet another example. Ingestion of significant quantities can cause metabolic acidosis (finally, something that really does have the potential to change blood pH! Er… but not… in a good way), kidney failure, seizures, and brain damage in children. Skin contact can cause contact dermatitis. It’s been shown to work as a contraceptive and, more problematically, it’s a known abortifacient (causes miscarriage).

Neem oil is easy to buy, but it needs to be handled with caution

All this said, as always, the dose make the poison.

One case study in the Journal of The Association of Physicians of India reported on a 36-year-old man who swallowed 30–50 ml (about three tablespoons) of neem oil, in the hope of treating the corns on his feet. As far as I can tell, it didn’t help his corns. It did cause vomiting, drowsiness, a dangerous drop in blood pH and seizures. There’s no specific antidote for neem poisoning, but the hospital managed his symptoms. Luckily, despite the hammering his kidneys undoubtedly took, he didn’t need dialysis, and was discharged from hospital after just over a week.

Now, okay, you’re unlikely to accidentally swallow three tablespoons of any oil, especially not neem which does have quite a strong, not entirely pleasant, smell and (reportedly – I haven’t tried for obvious reasons) a bitter taste. But nevertheless, it’s wise to be cautious, particularly around children who have a smaller body mass and therefore are much more likely to suffer serious effects – up to and including death. In one reported case, a mother gave a 3-month-old child a teaspoon of neem oil in the hope of curing his indigestion – fortunately he survived, but not without some seriously scary symptoms.

Nimbin, a chemical found in neem oil, is reported to have all sorts of beneficial effects [image source]

Okay, so those are the dangers. Let’s talk chemistry. The Pakistani organic chemist Salimuzzaman Siddiqui is thought to be the first scientist to formally investigate the various compounds in neem oil. In 1942 he extracted three compounds, and identified nimbidin as the main antibacterial substance in neem. He was awarded an OBE in 1946 for his discoveries.

I will confess, at this point, to running into a little bit of confusion with the nomenclature. Nimbidin is described, in some places at least, as a mixture of compounds (collectively, tetranortriterpenes) rather than a single molecule. But either way, it has been shown to have anti-inflammatory properties – at least in rats.

Another of the probably-mostly-good substances in neem is nimbin: a triterpenoid which is reported to have a whole range of positive properties, including acting as an anti-inflammatory, an antipyretic, a fungicide, an antiseptic and even as an antihistamine. Interestingly, I went looking for safety data on nimbin, and I couldn’t find much. That could mean it’s safe, or it could mean it just hasn’t been extensively tested.

Azadirachtin, another chemical found in neem, is a known pesticide [image source]

The substance that seems to do most of the pesticide heavy lifting is azadirachtin. This is a limonoid (compounds that are probably best known for their presence in citrus fruits). It’s what’s called an antifeedant – a substance produced by plants to deter predators from munching on them. Well, mostly. Humans have a strange habit of developing a taste for plants that produce such substances. Take, for example, odoriferous garlic, clears-out-your-sinuses horseradish, and of course the daddy of them all: nicotine.

Azadirachtin is known to affect lots of species of insects, both by acting as an antifeedant and as a growth disruptor. Handily, it’s also biodegradable – and breaks down in a few days when exposed to light and water.

That makes it appealing as a potential pesticide, and it’s also generally described as having low toxicity in mammals – its reported LD50 tends to fall into the grams per kilogram range, which makes it “moderately to slightly toxic“. Wikipedia quotes a value (without a source, as I write this) of >3,540 mg/kg in rats.

But… I did find another page quoting 13 mg/kg in mice. That’s quite dramatically different, and would make it extremely/highly toxic. Unfortunately I couldn’t get my hands on the original source, so I haven’t been able to verify it’s not a transposition error.

Let’s assume it isn’t. It would be odd to have such a big difference between mice and rats. Things that poison mice tend to poison rats, too. There might be some confusion over pure azadirachtin vs. “neem extract” – it could be the case that the mixture of chemicals working together in neem create some sort of synergistic (toxic) effect – greater than the sum of all the individual substances. It could be an experimental error, including a contaminated neem sample, or something to do with the way the animals were exposed to the extract.

Neem soap is widely available online, but that may not be a good thing…

It’s difficult to say. Well, it’s difficult for me to say, because I don’t have access to all the primary sources. (Any toxicologists out there, please do feel free to weigh into the comments section!) But either way, as I’ve already mentioned, several case studies have fingered azadirachtin as one of the substances likely to be causing the well-reported nasty side effects.

If you’re asking this chemist? I say be careful with the stuff. If you decide to use it on your plants, keep it out of reach of children, and wear some good-quality disposable gloves while you’re handling it (I put some on after I took that photo back there). If you’re pregnant, or trying to become pregnant, the safest option is to not use it at all.

Which brings me to neem soap.

Yup. It’s sold as a “natural” treatment for skin conditions like acne. I won’t link to a specific brand, but it’s easy to find multiple retailers with a simple Google search. I looked at one selling soap bars for £6.99 a pop, containing 10% (certified organic, because of course) neem oil. Did I mention back there that neem is known to cause contact dermatitis? I’m fairly sure I did. None of the products I saw had obvious safety warnings, and I certainly found nothing about safety (or otherwise) for pregnant women.

Plus – worryingly, not least because children are more likely to get things in their mouth – you can also buy kids and babies versions, again purporting to contain 10% neem oil.

I even found neem toothpaste. Which… given people often swallow toothpaste… yikes.

My moth orchids are looking much healthier now I’ve got rid of all the scale bugs!

Now again, and for the umpteenth time, the dose makes the poison. The case studies I’ve mentioned involved, at a minimum, swallowing a teaspoon of pure neem oil, and you’re not getting that sort of quantity from smears of toothpaste. But, at the same time, when it comes to pregnancy and babies, it’s generally sensible to apply a precautionary principle, especially for things like soap and toothpaste for which alternatives with well-established safety profiles exist.

Bottom line? Would I use these products? I would not.

But I do use neem to treat the scale bugs on my orchids, and they’re doing much better than they were. Fingers crossed for more flowers!

Do you want something non-sciency to distract you from, well, everything? Why not take a look at my fiction blog: the fiction phial? You can also find me doing various flavours of editor-type-stuff at the horror podcast, PseudoPod.org – so head over there, too!

Like the Chronicle Flask’s Facebook page for regular updates, or follow @chronicleflask on Twitter. Content is © Kat Day 2021. You may share or link to anything here, but you must reference this site if you do. You can support my writing my buying a super-handy Pocket Chemist from Genius Lab Gear using the code FLASK15 at checkout (you’ll get a discount, too!) or by buying me a coffee – the button is right here…
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Sunshine, skin chemistry, and vitamin D

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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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Want something non-sciency to distract you from, well, everything? Why not check out my fiction blog: the fiction phial.

Marvellous Mushroom Science

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Glistening ink caps produce a dark, inky substance.

Yesterday I had the fantastic experience of a “fungi forage” with Dave Winnard from Discover the Wild, organised by Incredible Edible Oxford. There are few nicer things than wandering around beautiful Oxfordshire park- and woodland on a sunny October day, but Dave is also an incredibly knowledgeable guide. I’ve always thought mushrooms and fungi were interesting – living organisms that are neither plants nor animals and which we rely on for everything from antibiotics to soy sauce – but I had lots to learn.

Did you know, for example, that fungi form some of the largest living organisms on our planet? And that without them most of our green plants wouldn’t have evolved and probably wouldn’t be here today?

And from a practical point of view, what about the fact that people once used certain fungi to light fires? I’ve always imagined fungi as being quite wet things with a high water content (unless they’re deliberately dried, of course), but some are naturally very dry. Ötzi, the mummified man thought to have lived between 3400and 3100 BCE, was found with two types of fungus on him: birch fungus, which has antiparasitic properties, and a type of tinder fungus which can be ignited with a single spark and will smolder for days.

Coprine causes unpleasant symptoms, including nausea and vomiting, when consumed with alcohol.

Then, of course, there’s all the interesting chemistry. Early on in the day, we came across some glistening ink caps.The gills of these disintegrate to produce a black, inky liquid which contains a form of melanin and can be used as ink. And there’s more to this story: as I’ve already mentioned, fungi are not plants and they can’t photosynthesise, but it seems that some fungi do use melanin to harness gamma rays as energy for growth. Extra mushrooms for the Hulk’s breakfast, then?

Moving away from pigments for a moment, a related species to the glistening ink cap, the common ink cap, contains a chemical called coprine. This causes lots of unpleasant symptoms if it’s consumed with alcohol, similar to Disulfiram, the drug used to treat alcoholism. For this reason one of this mushroom’s other names is tippler’s bane. The coprine in the mushrooms effectively causes an instant hangover by accelerating the formation of acetaldehyde (also known as ethanal) from alcohol. Definitely don’t pair that mushroom omelette with a nice bottle of red and, worse, you’ll need to stay off the booze for a while: apparently the effects can linger for a full three days.

Yellow stainer mushrooms look like field mushrooms, but are poisonous.

We also came across some yellow stainer mushrooms. These look a lot like field mushrooms, but be careful – they aren’t edible. They cause nasty gastric sympoms and are reportedly responsible for most cases of mushroom poisoning in this country, although some people seem to be able to eat them without ill effect. They had a slightly chemically scent that reminded me “new trainer” smell – sort of rubbery and plasticky. It’s often described as phenolic, but I have to say I didn’t detect that myself – although yellow stainers have been shown to contain phenol and this could account for their poisonous nature. Anyway, it was an aroma that wouldn’t be entirely unpleasant if I were opening a new shoebox, but it wasn’t something I’d really want to eat. Apparently the smell gets stronger as you cook them, so don’t ignore what your nose is telling you if you think you have a nice pan of field mushrooms.

4,4′-Dimethoxyazobenzene is an azo dye.

The real giveaway with yellow stainers, though, is their tendency to turn yellow when bruised or scratched, hence the name. This, it seems, is due to 4,4′-dimethoxyazobenzene. The name might not be familiar, but A-level Chemistry students will recognise the structure: it’s an azo-dye. Quite apart from being a very useful word in Scrabble, azo compounds are well-known for their characteristic orange/yellow colours. It’s not really clear whether it forms in the mushroom due to some sort of oxidation reaction, or whether it’s in the cells anyway but only becomes visible when the cells are damaged. Either way, it’s something to look out for if you spot a patch of what look like field mushrooms.

The blushing wood mushroom.

We also came across several species which are safe to eat. One I might look out for in future is the blushing wood mushroom. As is often the way with fungi, the name is literal rather than merely poetic. These mushrooms have a light brown cap, beige gills, and a pale stem, but they turn bright red when cut or scratched due to the formation of an ortho-quinone. It’s quite a dramatic colour-change, and makes them pretty easy to identify. Apparently they’re normally uncommon here, but we found quite a lot of them, which might be something to do with this year’s unusally hot and dry summer.

Red ortho-quinone causes blushing wood mushrooms to literally blush.

I tried to find out the reasons for these colour-changes. In the plant and animal kingdoms pigments are usually there for good reason: camouflage, signalling and communication or, as with chlorophyll, as a way of making other substances. Fruits, for example, often turn bright red as they ripen because it makes them stand out from the green foilage and encourages animals to eat them so that the seeds can be spread. Likewise, they’re green when they’re unripe because it makes them less obvious and less appealing. But what’s the advantage for the mushroom to change colour once it’s already damaged? Perhaps there isn’t one, and it’s just an accident of their biology, but if so it seems strange that it’s a feature of several species. I couldn’t find the answer; if any mycologists are reading this and know, get in touch!

Velvet shank mushrooms.

Other edible species we met were fairy ring champignons, field blewits and jelly ear fungus – which literally looks like a sort of transparent ear. I’ll definitely be looking out for all of these in the future, but it’s important to watch out for dangerous lookalikes. Funeral bell mushrooms, for example, look like the velvet shank mushrooms we found but, once again, the name is quite literal – funeral bells contain amatoxins and eating them can cause kidney and liver failure. As Dave was keen to remind us: never eat anything you can’t confidently name!

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Should you be scared of your shampoo?

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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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