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

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!

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Vibrant Viburnum: the fascinating chemistry of fragrant flowers

There’s a Viburnum carlesii bush (sometimes called Koreanspice) near my front door and, right now, it smells amazing. It only flowers for a relatively short time each year and otherwise isn’t that spectacular – especially in the autumn when it drops its leaves all over the doorstop, and I’m constantly brushing them out of the house.

But it’s all worth it for these few weeks in April, when everyone who has any reason to come anywhere near our door says, ‘ooh, what is that smell? It’s gorgeous!’ We also rear butterflies at this time of year, and they love the flowers once they’ve emerged from their chrysalids. (No, of course this isn’t an excuse to include all my butterfly photos in a post. Painted lady, since you ask.)

But let’s talk chemistry – what is in the Viburnum carlesii’s fragrance? Well, it’s a bit complicated. Fragrances, as you might imagine, often are. We detect smells when volatile (things that vaporise easily) compounds find their way to our noses which are, believe it or not, great chemical detectors.

Well, I say great, many animals have far better smell detection: dogs, of course, are particularly known for it. Their noses have some 300 million scent receptors*, while humans “only” have 5-6 million but, and this is the really fantastic part, by some estimates we’re still able to detect a trillion or so smells. We (and other animals) inhale air that contains odour molecules, and those molecules bind to the receptors in our noses, triggering electrical impulses that our brains interpret as smell.

Most scents aren’t just one molecule, but are actually complex mixtures. Our brains learn to recognise combinations and to associate them with certain, familiar things. It’s not that different from recognising patterns of sound as speech, or patterns of light as images, it’s just that we often don’t think of smell in quite the same way.

Viburnum carlesii flowers have a fragrance often described as sweet and spicy.

So my Viburnum bush – and the flowers I’ve cut and put on my desk – is actually pumping out loads of different molecules right now. After a bit of hunting around, I tracked them down to (brace yourself for a list of chemical names) isoeugenol, eugenol, methyleugenol, 4-allylsyringol, vinyl-guaiacol and methyl nicotinate, plus the old favourites methyl salicylate (this stuff turns up everywhere), methyl benzoate (so does this), indole, cinnamic aldehyde and vanillin, and then some isovaleraldehyde, acetoin, hexanal, (Z)-3-hexen-1-ol and methional.

Phew.

Don’t worry, I’m not going to talk about the chemistry of all of those. But just for a moment consider how wondrous it is that our noses and brains work together to detect all of those molecules, in their relevant quantities, and then send the thought to our conscious mind that oh, hey, the Viburnum is flowering! (It’s also pretty astonishing that, in 2021, I can just plug all those names into a search engine and, with only a couple of exceptions, get all sorts of information about them in seconds – back in the old days when I was studying chemistry, you had to use a book index, and half the time the name you wanted wasn’t there. You kids don’t know how good you’ve got it, I’m telling you.)

Anyway, if you glance at those names, you’ll see eugenol popping up quite a bit, so let’s talk about that. It’s a benzene ring with a few other groups attached, and lots of chemicals like this have distinctive smells. In fact, we refer to molecules with these sorts of ring structures as “aromatic” for this exact, historical reason – when early chemists first isolated them, they noticed their distinctive scents.

Eugenol is an aromatic compound, both in terms of chemistry and fragrance (image source)

In fact there are several groups of molecules in chemistry that we tend to think of as particularly fragrant. There are esters (think nail polish and pear drops), linear terpenes (citrus, floral), cyclic terpenes (minty, woody), amines (fishy, rot) and the aromatics I’ve just mentioned.

But back to eugenol: it’s a yellowish, oily liquid that can be extracted from plants such as nutmeg, cloves, cinnamon, basil and bay leaves. This might give you an idea of its scent, which is usually described as “spicy” and “clove-like”.

Not surprisingly, it turns up in perfumes, and also flavourings, since smell and flavour are closely linked. It’s also a local antiseptic and anaesthetic – you may have used some sort of eugenol-based paste, or perhaps just clove oil, if you’ve ever had a tooth extracted.

Plants, of course, don’t go to the trouble and biological expense of making these chemicals just so that humans can walk past and say, “ooh, that smells nice!” No, the benefit for the plant is in attracting insects, which (hopefully) help with pollination. Which explains why my butterflies like the flowers so much. (Another butterfly pic? Oh well, since you insist.) Eugenol, it turns out, is particularly attractive to various species of orchid bee, which use it to synthesise their own pheromones. Nature’s clever, isn’t she?

By the way, notice I mentioned anaesthetics back there? Eugenol turns out to be too toxic to use for this in large quantities, but the study of it did lead to the development of the widely-used drug propofol which, sadly, is pretty important right now – it’s used to sedate mechanically ventilated patients, such as those with severe COVID-19 symptoms. You may have seen some things in the news earlier this year about anaesthetic supply issues, precisely for this reason.

Isoeugenol has the same “backbone” as eugenol, with just a difference to the position of the C=C bond on the right. (image source)

Back in that list of chemical names, you’ll see “eugenol” forming parts of other names, for example isoeugenol. This points back to a time when chemicals tended to be named based on their origins. Eugenol took its name from the tree from which we get oil of cloves, Eugenia, which was in turn named after Prince Eugene of Savoy – a field marshal in the army of the Holy Roman Empire. And then other molecules with the same “backbone” were given the same name with prefixes and suffixes added on to describe their differences. As I said in my last post, this sort of naming system it was eventually replaced with more consistent rules, but a lot of these older substances have held onto their original names.

Still, regardless of what we call the chemicals, the flowers smell delightful. I’m off to replenish the vase on my desk while I still can. Roll on May, vaccines and (hopefully) lockdown easing!

Take care and stay safe.


*it’s even been suggested dogs’ super-powered sense of smell might be able to detect COVID-19 infections.


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