How are amber teething necklaces supposed to work?

Do amber beads have medicinal properties?

Amber, as anyone that was paying attention during Jurassic Park will tell you, is fossilised resin from trees that lived at least twenty million years ago (although some scientists have speculated it could be older). It takes the form of clear yellow through to dark brown stones, seemingly warm to the touch, smooth and surprisingly hard. It is certainly beautiful. But does it also have medicinal properties? And if it does, are they risk-free?

In 2016 a one year-old boy was found dead at his daycare centre in Florida. The cause of death was a necklace, which had become tangled and tightened to the point that he was unable to breathe.

Why was he wearing a necklace? Surely everyone knows that babies shouldn’t wear jewellery around their necks where it could so easily cause a terrible tragedy like this? No one needs a necklace, after all – it’s purely a decorative thing. Isn’t it?

Yes. Yes, it is. However, this particular type of jewellery was specifically sold for use by babies. Sold as a product that parents should give their children to wear, despite all the advice from medical professionals. Why? Because this jewellery was made from amber, and that’s supposed to help with teething pains.

Teething is a literal pain.

Anyone whose ever had children will tell you that teeth are basically a non-stop, literal pain from about 4 months onward. Even once your child appears to have a full set, you’re not done. The first lot start falling out somewhere around age five, resulting in teeth that can be wobbly for weeks. And then there are larger molars that come through at the back somewhere around age seven. Teenagers often find themselves suffering through braces and, even when all that’s done, there’s the joy of wisdom teeth still to come.

It’s particularly difficult with babies, who can’t tell you what hurts and who probably have inconsistent sleep habits at the best of times. Twenty sharp teeth poking through swollen gums at different times has to be unpleasant. Who could blame any parent for trying, well, pretty much anything to soothe the discomfort?

Enter amber teething necklaces. They’re sold as a “natural” way to soothe teething pain. They look nice, too, which I’m sure is part of their appeal. A chewed plastic teething ring isn’t the sort of thing to keep in baby’s keepsake box, but a pretty necklace, well, I’m sure many parents have imagined getting that out, running their fingers over the beads and having a sentimental moment years in the future.

Amber is fossilised tree resin.

So-called amber teething necklaces are made from “Baltic amber,” that is, amber from the Baltic region: the largest known deposit of amber. It is found in other geographical locations, but it seems that the conditions – and tree species – were just right in the Baltic region to produce large deposits.

Chemically, it’s also known as succinite, and its structure is complicated. It’s what chemists would call a supramolecule: a complex of two or more (often large) molecules that aren’t covalently bonded. There are cross-links within its structure, which make it much denser than you might imagine something that started as tree resin to be. Baltic amber, in particular, also contains something else: between 3-8% succinic acid.

Succinic acid is a dicarboxylic acid.

Succinic acid is a much simpler molecule with the IUPAC name of butanedioic acid. It contains two carboxylic acid groups, a group of atoms we’re all familiar with whether we realise it or not – because we’ve all met vinegar, which contains the carboxylic acid also known as ethanoic acid. If you imagine chopping succinic acid right down the middle (and adding a few extra hydrogen atoms), you’d end up with two ethanoic acid molecules.

Succinic acid (the name comes from the Latin, succinum, meaning amber) is produced naturally in the body where it is (or, rather, succinate ions are) an important intermediate in lots of chemical reactions. Exposure-wise it’s generally considered pretty safe at low levels and it’s a permitted food additive, used as an acidity regulator. In European countries, you might see it on labels listed as E363. It also turns up in a number of pharmaceutical products, where it’s used as an excipient – something that helps to stabilise or enhance the action of the main active ingredient. Often, again, it’s there to regulate acidity.

Basically, it’s mostly harmless. And therefore, an ideal candidate for the alternative medicine crowd, who make a number of claims about its properties. I found one site claiming that it could “improve cellular respiration” which… well, if you’ve got problem with cellular respiration, you’re less in need of succinic acid and more in need of a coffin. Supposedly it also relives stress and prevents colds, because doesn’t everything? And, of course, it allegedly relieves teething pains in babies, either thanks to its general soothing effect or because it’s supposed to reduce inflammation, or both.

Purporters claim succinic acid is absorbed through the skin.

The reasoning is usually presented like this: succinic acid is released from the amber when the baby wears the necklace or bracelet and is absorbed through the baby’s skin into their body, where it works its magical, soothing effects.

Now. Hold on, one minute. Whether this is true or not – and getting substances to absorb through skin is far less simple than many people imagine, after all, skin evolved as a barrier – do you really, really, want your baby’s skin exposed to a random quantity of an acidic compound? Succinic acid may be pretty harmless but, as always, the dose makes the poison. Concentrated exposure causes skin and eye irritation. Okay, you might say, it’s unlikely that an amber necklace is going to produce anywhere near the quantities to cause that sort of effect, but if that’s your logic, then how can it also produce enough to pass through skin and have any sort of biological effect on the body?

The answer, perhaps predictably, is that it doesn’t. In a paper published in 2019, a group of scientists actually went to the trouble of powdering Baltic amber beads and dissolving the powder in sulfuric acid to measure how much succinic acid they actually contained. They then compared those results with what happened when undamaged beads from the same batches were submerged in solvents, with the aim of working out how much succinic acid beads might conceivably release into human skin. The answer? They couldn’t measure any. No succinic acid was released into the solvents, at all. None.

Scientists submerged Baltic amber beads in solvents to see how much succinic acid they released.

They concluded that there was “no evidence to suggest that the purported active ingredient succinic acid could be released from the beads into human skin” and also added that they found no evidence to suggest that succinic acid even had anti-inflammatory properties in the first place.

So amber necklaces don’t work to relieve teething pains. They can’t. Of course, there could be a sort of placebo effect – teething pain is very much one of those comes-and-goes things. It’s very easy to make connections that just aren’t there in this kind of situation, and imagine that the baby is more settled because of the necklace, when in fact they might have calmed down over the next few hours anyway. Or maybe they’re just distracted by the pretty beads.

And, fine. If wearing the jewellery was really risk-free, then why not? But as the story at the start of this post proves, it is not. Any kind of string around a baby’s neck can become twisted, interfering with their breathing. Most necklaces claim to have some sort of “emergency release” mechanism so that they come apart when pulled, but this doesn’t always work.

Don’t fall for the marketing.

Ah, goes the argument. But it’s okay, because we only sell bracelets and anklets for babies. They don’t go around the baby’s neck. It’s completely safe!

No. Because I don’t care how carefully you make it: the string or cord could still break (especially if it’s been chewed), leaving loose beads to pose a serious choking hazard. Not to mention get jammed in ears or nostrils. Even if you’re with the baby, watching them, these sorts of accidents can happen frighteningly quickly. Letting a baby sleep with such an item is nothing short of asking for disaster, and no matter how good anyone’s intentions, babies do have a habit of dozing off at odd times. Will you really wake the child up to take off their bracelet? Every time?

In summary, don’t fall for the marketing. Amber necklaces may be pretty, but they’re not suitable for babies. The claims about succinic acid are completely baseless, and the risks are very real.


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A natural remedy that’s full of chemicals?

Blossoms

The summer holidays are here! A time when parents of small children find themselves exploring every park in their local vicinity, quite probably several times (whilst hoping against hope that it doesn’t rain). On just such a quest myself, I recently visited one particular park that was filled with a gorgeous smell.

What was it? A bit of sniffing around quickly identified this tree. Now, I am not a botanist (or even much of a gardener), so I immediately resorted to the rather wonderful Seek app by iNaturalist, which uses some very clever image recognition software to identify plants and animals (disclaimer: accuracy is not guaranteed — don’t eat anything based on this app!)

Seek told me that this was a lime tree, or a linden (genus Tilia). A bit of cross-referencing (thanks Dad!) suggested that it had identified the tree correctly. It’s not an uncommon plant: you’ll probably come across it yourself if you go looking (or smelling).

The name ‘linden’ was more familiar to me. The wood is soft and easily worked, and is used to make musical instruments because it has good acoustic properties. It’s also used to make wooden blinds and other pieces of furniture because it’s lightweight, stable, and holds stains and finishes well.

Linden blossoms can be used to make tea.

But let’s go back to the flowers and their delicious scent. The tree blooms during July and August in the Northern hemisphere. The flowers are sometimes described as mucilaginous — which is a fabulous word meaning, basically, thick and sticky. More specifically: “containing a polysaccharide substance that is extracted as a viscous or gelatinous solution and used in medicines and adhesives.”

Linden flowers are a ‘natural remedy’ with a list of applications in herbal medicine as long as your arm. They contain lots of different substances. One that comes up a lot is farnesol, which is actually a type of alcohol. Of course, it’s nothing like the alcohol we’re familiar with from drinks, which is the much simpler ethanol — but it’s important to remember that ‘alcohol’ actually refers to a class of compounds (which, in simple terms, contain an -OH group like the one in the image here) and not a single substance.

The chemical structure of farnesol

Farnesol turns up in lots of essential oils, such as citronella, rose and lemon grass. It’s used in perfumes to enhance floral scents. But plants don’t make substances just to please humans (well, it’s complicated…). It acts as a pheromone for several insects. Sometimes this doesn’t work out so well for the insects, as it confuses their mating behaviour and effectively acts as a natural pesticide. On the other hand, it actively encourages others: bumblebees release farnesol when they return to the hive to spur other bees into action. It’s the bee equivalent of shouting, ‘oi! Move it you lot, pollen this way!’

Farnesol acts as a pheromone for bumblebees.

Linden flowers also contain one of my all-time favourite chemicals, benzaldehyde. That’s the one that smells of almonds and isn’t a deadly cyanide salt. Its delicious almondy-ness is the reason it’s used as a flavouring and scent, but it’s also a starting material for loads of different chemicals, for example the dye malachite green, which is used to give a green colour to leather, fabric and paper. A form of this dye called ‘brilliant green‘ is mixed with a second, violet, dye to make ‘Bonney’s blue,’ a disinfectant dye used to mark skin for surgeries. Benzaldehyde is also used to make styrene, which is of course used to make the well-known packing material, polystyrene.

And these are just a couple of the substances found in those yummy-smelling flowers. They also contain arabinogalactans, uronic acid, tannins, rutin, hyperoside, quercitrin, isoquercitrin, astragalin and others. In short, a veritable cocktail of different chemicals.

So next time you smell the scent of a lovely flower, just think about all the amazing chemical substances the plant is making. All natural, of course!


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What is Water? The Element that Became a Compound

November 2018 marks the 235th anniversary of the day when Antoine Lavoisier proved water to be a compound, rather than an element.

I’m a few days late at the time of writing, but November 12th 2018 was the 235th anniversary of an important discovery. It was the day, in 1783, that Antoine Lavoisier formally declared water to be a compound, not an element.

235 years seems like an awfully long time, probably so long ago that no one knew anything very much. Practically still eye of newt, tongue of bat and leeches for everyone, right? Well, not quite. In fact, there was some nifty science and engineering going on at the time. It was the year that Jean-François Pilâtre de Rozier and François Laurent made the first untethered hot air balloon flight, for example. And chemistry was moving on swiftly: lots of elements had been isolated, including oxygen (1771, by Carl Wilhelm Scheele) and hydrogen (officially by Henry Cavendish in 1766, although others had observed it before he did).

Cavendish had reported that hydrogen produced water when it reacted with oxygen (known then as inflammable air and dephlogisticated air, respectively), and others had carried out similar experiments. However, at the time most chemists favoured phlogiston theory (hence the names) and tried to interpret and explain their results accordingly. Phlogiston theory was the idea that anything which burned contained a fire-like element called phlogiston, which was then “lost” when the substance burned and became “dephlogisticated”.

Cavendish, in particular, explained the fact that inflammable air (hydrogen) left droplets of “dew” behind when it burned in “common air” (the stuff in the room) in terms of phlogiston, by suggesting that water was present in each of the two airs before ignition.

Antoine-Laurent Lavoisier proved that water was a compound. (Line engraving by Louis Jean Desire Delaistre, after a design by Julien Leopold Boilly.)

Lavoisier was very much against phlogiston theory. He carried out experiments in closed vessels with enormous precision, going to great lengths to prove that many substances actually became heavier when they burned and not, as phlogiston theory would have it, lighter. In fact, it’s Lavoisier we have to thank for the names “hydrogen” and “oxygen”. Hydrogen is Greek for “water-former”, whilst oxygen means “acid former”.

When, in June 1783, Lavoisier found out about Cavendish’s experiment he immediately reacted oxygen with hydrogen to produce “water in a very pure state” and prove that the mass of the water which formed was equal to the combined masses of the hydrogen and oxygen he started with.

He then went on to decompose water into oxygen and hydrogen by heating a mixture of water and iron filings. The oxygen that formed combined with the iron to form iron oxide, and he collected the hydrogen gas over mercury. Thanks to his careful measurements, Lavoisier was able to demonstrate that the increased mass of the iron filings plus the mass of the collected gas was, again, equal to the mass of the water he had started with.

Water is a compound of hydrogen and oxygen, with the formula H2O.

There were still arguments, of course (there always are), but phlogiston theory was essentially doomed. Water was a compound, made of two elements, and the process of combustion was nothing more mysterious than elements combining in different ways.

As an aside, Scottish chemist Elizabeth Fulhame deserves a mention at this point. Just a few years after Lavoisier she went on to demonstrate through experiment that many oxidation reactions occur only in the presence of water, but the water is regenerated at the end of the reaction. She is credited today as the chemist who invented the concept of catalysis. (Which is a pretty important concept in chemistry, and yet her name never seems to come up…)

Anyway, proving water’s composition becomes a lot simpler when you have a ready supply of electricity. The first scientist to formally demonstrate this was William Nicholson, in 1800. He discovered that when leads from a battery are placed in water, the water breaks up to form hydrogen and oxygen bubbles, which can be collected separately at the submerged ends of the wires. This is the process we now know as electrolysis.

You can easily carry out the electrolysis of water at home.

In fact, this is a really easy (and safe, I promise!) experiment to do yourself, at home. I did it myself, using an empty TicTac box, two drawing pins, a 9V battery and a bit of baking soda (sodium hydrogencarbonate) dissolved in water – you need this because water on its own is a poor conductor.

The drawing pins are pushed through the bottom of the plastic box, the box is filled with the solution, and then it’s balanced on the terminals of the battery. I’ve used some small test tubes here to collect the gases, but you’ll be able to see the bubbles without them.

Bubbles start to appear immediately. I left mine for about an hour and a half, at which point the test tube on the negative terminal (the cathode) was completely full of gas, which produced a very satisfying squeaky pop when I placed it over a flame.

The positive electrode (the anode) ended up completely covered in what I’m pretty sure is a precipitate of iron hydroxide (the drawing pins presumably being plated steel), which meant that very little oxygen was produced after the first couple of minutes. This is why in proper electrolysis experiments inert graphite or, even better, platinum, electrodes are used. If you do that, you’ll get a 1:2 ratio by volume of oxygen to hydrogen, thus proving water’s formula (H2O) as well.

So there we have it: water is a compound, and not an element. And if you’d like to amuse everyone around the Christmas dinner table, you can prove it with a 9V battery and some drawing pins. Just don’t nick the battery out of your little brother’s favourite toy, okay? (Or, if you do, don’t tell him it was my idea.)


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Carbon dioxide: the good, the bad, and the future

Carbon dioxide is a small molecule with the structure O=C=O

Carbon dioxide has been in and out of the news this summer for one reason or another, but why? Is this stuff helpful, or heinous?

It’s certainly a significant part of our history. Let’s take that history to its literal limits and start at the very beginning. To quote the great Terry Pratchett: “In the beginning, there was nothing, which exploded.”

(Probably.) This happened around 13.8 billion years ago. Afterwards, stuff flew around for a while (forgive me, cosmologists). Then, about 4.5 billion years ago, the Earth formed out of debris that had collected around our Sun. Temperatures on this early Earth were extremely hot, there was a lot of volcanic activity, and there might have been some liquid water. The atmosphere was mostly hydrogen and helium.

The early Earth was bashed about by other space stuff, and one big collision almost certainly resulted in the formation of the Moon. A lot of other debris vaporised on impact releasing gases, and substances trapped within the Earth started to escape from its crust. The result was Earth’s so-called second atmosphere.

An artist’s concept of the early Earth. Image credit: NASA. (Click image for more.)

This is where carbon dioxide enters stage left… er… stage under? Anyway, it was there, right at this early point, along with water vapor, nitrogen, and smaller amounts of other gases. (Note, no oxygen, that is, O2 – significant amounts of that didn’t turn up for another 1.7 billion years, or 2.8 billion years ago.) In fact, carbon dioxide wasn’t just there, it made up most of Earth’s atmosphere, probably not so different from Mars’s atmosphere today.

The point being that carbon dioxide is not a new phenomenon. It is, in fact, the very definition of an old phenomenon. It’s been around, well, pretty much forever. And so has the greenhouse effect. The early Earth was hot. Really hot. Possibly 200 oC or so, because these atmospheric gases trapped the Sun’s heat. Over time, lots and lots of time, the carbon dioxide levels reduced as it became trapped in carbonate rocks, dissolved in the oceans and was utilised by lifeforms for photosynthesis.

Fast-forward a few billion years to the beginning of the twentieth century and atmospheric carbon dioxide levels were about 300 ppm (0.03%), tiny compared to oxygen (about 20%) and nitrogen (about 78%).

Chemists and carbon dioxide

Flemish chemist Jan Baptist van Helmont carried out an experiment which eventually led to the discovery of carbon dioxide gas.

Let’s pause there for a moment and have a little look at some human endeavours. In about 1640 Flemish chemist Jan Baptist van Helmont discovered that if he burned charcoal in a closed vessel, the mass of the resulting ash was much less than that of the original charcoal. He had no way of knowing, then, that he had formed and collected carbon dioxide gas, but he speculated that some of the charcoal had been transmuted into spiritus sylvestris, or “wild spirit”.

In 1754 Scottish chemist Joseph Black noticed that heating calcium carbonate, aka limestone, produced a gas which was heavier than air and which could “not sustain fire or animal life”. He called it “fixed air”, and he’s often credited with carbon dioxide’s discovery, although arguably van Helmont got there first. Black was also the first person to come up with the “limewater test“, where carbon dioxide is bubbled through a solution of calcium hydroxide. He used the test to demonstrate that carbon dioxide was produced by respiration, an experiment still carried out in schools more than 250 years later to show that the air we breathe out contains more carbon dioxide than the air we breathe in.

In 1772 that most famous of English chemists, Joseph Priestley, experimented with dripping sulfuric acid (or vitriolic acid, as he knew it) on chalk to produce a gas which could be dissolved in water. Priestley is often credited with the invention of soda water as a result (more on this in a bit), although physician Dr William Brownrigg probably discovered carbonated water earlier – but he never published his work.

In the late 1700s carbon dioxide became more widely known as “carbonic acid gas”, as seen in this article dated 1853. In 1823 Humphry Davy and Michael Faraday manged to produce liquified carbon dioxide at high pressures. Adrien-Jean-Pierre Thilorier was the first to describe solid carbon dioxide, in 1835. The name carbon dioxide was first used around 1869, when the term “dioxide” came into use.

A diagram from “Impregnating Water with Fixed Air”, printed for J. Johnson, No. 72, in St. Pauls Church-Yard, 1772.

Back to Priestley for a moment. In the late 1800s, a glass of volcanic spring water was a common treatment for digestive problems and general ailments. But what if you didn’t happen to live near a volcanic spring? Joseph Black, you’ll remember, had established that CO2 was produced by living organisms, so it occurred to Priestly that perhaps he could hang a vessel of water over a fermentation vat at a brewery and collect the gas that way.

But it wasn’t very efficient. As Priestly himself said, “the surface of the fixed air is exposed to the common air, and is considerably mixed with it, [and] water will not imbibe so much of it by the process above described.”

It was then that he tried his experiment with vitriolic acid, which allowed for much greater control over the carbonation process. Priestly proposed that the resulting “water impregnated with fixed air” might have a number of medical applications. In particular, perhaps because the water had an acidic taste in a similar way that lemon-infused water does, he thought it might be an effective treatment for scurvy. Legend has it that he gave the method to Captain Cook for his second voyage to the Pacific for this reason. It wouldn’t have helped of course, but it does mean that Cook and his crew were some of the first people to produce carbonated water for the express purpose of drinking a fizzy drink.

Refreshing fizz

You will have noticed that, despite all his work, there is no fizzy drink brand named Priestly (at least, not that I know of).

Joseph Priestley is credited with developing the first method for making carbonated water.

But there is one called Schweppes. That’s because a German watchmaker named Johann Jacob Schweppe spotted Priestley’s paper and worked out a simpler, more efficient process, using sodium bicarbonate and tartaric acid. He went on to found the Schweppes Company in Geneva in 1783.

Today, carbonated drinks are made a little differently. You may have heard about carbon dioxide shortages this summer in the U.K. These arose because these days carbon dioxide is actually collected as a by-product of other processes. In fact, after several bits of quite simple chemistry that add up to a really elegant sequence.

From fertiliser to fizzy drinks

It all begins, or more accurately ends, with ammonia fertiliser. As any GCSE science student who’s been even half paying attention can tell you, ammonia is made by reacting hydrogen with nitrogen during the Haber process. Nitrogen is easy to get hold of – as I’ve already said it makes up nearly 80% of our atmosphere – but hydrogen has to be made from hydrocarbons. Usually natural gas, or methane.

This involves another well-known process, called steam reforming, in which steam is reacted with methane at high temperatures in the presence of a nickel catalyst. This produces carbon monoxide, a highly toxic gas. But no problem! React that carbon monoxide with more water in the presence of a slightly different catalyst and you get even more hydrogen. And some carbon dioxide.

Fear not, nothing is wasted here! The CO2 is captured and liquified for all sorts of food-related and industrial uses, not least of which is fizzy drinks. This works well for all concerned because steam reforming produces large amounts of pure carbon dioxide. If you’re going to add it to food and drinks after all, you wouldn’t want a product contaminated with other gases.

Carbon dioxide is a by-product of fertiliser manufacture.

We ended up with a problem this summer in the U.K. because ammonia production plants operate on a schedule which is linked to the planting season. Farmers don’t usually apply fertiliser in the summer – when they’re either harvesting or about to harvest crops – so many ammonia plants shut down for maintenance in April, May, and June. This naturally leads to reduction in the amount of available carbon dioxide, but it’s not normally a problem because the downtime is relatively short and enough is produced the rest of year to keep manufacturers supplied.

This year, though, natural-gas prices were higher, while the price of ammonia stayed roughly the same. This meant that ammonia plants were in no great hurry to reopen, and that meant many didn’t start supplying carbon dioxide in July, just when a huge heatwave hit the UK, coinciding with the World Cup football (which tends to generate a big demand for fizzy pop, for some reason).

Which brings us back to our atmosphere…

Carbon dioxide calamity?

Isn’t there, you may be thinking, too much carbon dioxide in our atmosphere? In fact, that heatwave you just mentioned, wasn’t that a global warming thing?  Can’t we just… extract carbon dioxide from our air and solve everyone’s problems? Well, yes and no. Remember earlier when I said that at the beginning of the twentieth century and atmospheric carbon dioxide levels were about 300 ppm (0.03%)?

Over the last hundred years atmospheric carbon dioxide levels have increased from 0.03% to 0.04%

Today, a little over 100 years later, levels are about 0.04%. This is a significant increase in a relatively short period of time, but it’s still only a tiny fraction of our atmosphere (an important tiny fraction nonetheless – we’ll get to that in a minute).

It is possible to distill gases from our air by cooling air down until it liquefies and then separating the different components by their boiling points. For example nitrogen, N2, boils at a chilly -196 oC whereas oxygen, O2, boils at a mere -183 oC.

But there’s a problem: CO2 doesn’t have a liquid state at standard pressures. It forms a solid, which sublimes directly into a gas. For this reason carbon dioxide is usually removed from cryogenic distillation mixtures, because it would freeze solid and plug up the equipment. There are other ways to extract carbon dioxide from air but although they have important applications (keep reading) they’re not practical ways to produce large volumes of the gas for the food and drink industries.

Back to the environment for a moment: why is that teeny 0.04% causing us such headaches? How can a mere 400 CO2 molecules bouncing around with a million other molecules cause such huge problems?

For that, I need to take a little diversion to talk about infrared radiation, or IR.

Infrared radiation was first discovered by the astronomer William Herschel in 1800. He was trying to observe sun spots when he noticed that his red filter seemed to get particularly hot. In what I’ve always thought was a rather amazing intuitive leap, he then passed sunlight through a prism to split it, held a thermometer just beyond the red light that he could see with his eyes, and discovered that the thermometer showed a higher temperature than when placed in the visible spectrum.

He concluded that there must be an invisible form of light beyond the visible spectrum, and indeed there is: infrared light. It turns out that slightly more than half of the total energy from the Sun arrives on Earth in the form of infrared radiation.

What has this got to do with carbon dioxide? It turns out that carbon dioxide, or rather the double bonds O=C=O, absorb a lot of infrared radiation. By contrast, oxygen and nitrogen, which make up well over 90% of Earth’s atmosphere, don’t absorb infrared.

CO2 molecules also re-emit IR but, having bounced around a bit, not necessarily in the same direction and – and this is the reason that tiny amounts of carbon dioxide cause not so tiny problems – they transfer energy to other molecules in the atmosphere in the process. Think of each CO2 molecule as a drunkard stumbling through a pub, knocking over people’s pints and causing a huge bar brawl. A single disruptive individual can, indirectly, cause a lot of others to find themselves bruised and bleeding and wondering what the hell just happened.

Like carbon dioxide, water vapour also absorbs infrared, but it has a relatively short lifetime in our atmosphere.

Water vapor becomes important here too, because while O2 and N2 don’t absorb infrared, water vapour does. Water vapour has a relatively short lifetime in our atmosphere (about ten days compared to a decade for carbon dioxide) so its overall warming effect is less. Except that once carbon dioxide is thrown into the mix it transfers extra heat to the water, keeping it vapour (rather than, say, precipitating as rain) for longer and pushing up the temperature of the system even more.

Basically, carbon dioxide molecules trap heat near the planet’s surface. This is why carbon dioxide is described as a greenhouse gas and increasing levels are causing global warming. There are people who are still arguing this isn’t the case, but truly, they’ve got the wrong end of the (hockey) stick.

It’s not even a new concept. Over 100 years ago, in 1912, a short piece was published in the Rodney and Otamatea Times which said: “The furnaces of the world are now burning about 2,000,000,000 tons of coal a year. When this is burned, uniting with oxygen, it adds about  7,000,000,000 tons of carbon dioxide to the atmosphere yearly. This tends to make the air a more effective blanket for the earth and to raise its temperature.”

This summer has seen record high temperatures and some scientists have been warning of a “Hothouse Earth” scenario.

This 1912 piece suggested we might start to see effects in “centuries”. In fact, we’re seeing the results now. As I mentioned earlier, this summer has seen record high temperatures and some scientists have been warning of “Hothouse Earth” scenario, where rising temperatures cause serious disruptions to ecosystems, society, and economies. The authors stressed it’s not inevitable, but preventing it will require a collective effort. They even published a companion document which included several possible solutions which, oddly enough, garnered rather fewer column inches than the “we’re all going to die” angle.

Don’t despair, DO something…

But I’m going to mention it, because it brings us back to CO2. There’s too much of it in our atmosphere. How can we deal with that? It’s simple really: first, stop adding more, i.e. stop burning fossil fuels. We have other technologies for producing energy. The reason we’re still stuck on fossil fuels at this stage is politics and money, and even the most obese of the fat cats are starting to realise that money isn’t much use if you don’t have a habitable planet. Well, most of them. (There’s probably no hope for some people, but we can at least hope that their damage-doing days are limited.)

There are some other, perhaps less obvious, sources of carbon dioxide and other greenhouse gases that might also be reduced, such as livestock, cement for building materials and general waste.

Forests trap carbon dioxide in land carbon sinks. More biodiverse systems generally store more carbon.

And then, we’re back to taking the CO2 out of the atmosphere. How? Halting deforestation would allow more CO2 to be trapped in so-called land carbon sinks. Likewise, good agricultural soil management helps to trap carbon underground. More biodiverse systems generally store more carbon, so if we could try to stop wiping out land and coastal systems, that would be groovy too. Finally, there’s the technological solution: carbon capture and storage, or CSS.

This, in essence, involves removing CO2 from the atmosphere and storing it in geological formations. The same thing the Earth has done for millenia, but more quickly. It can also be linked to bio-energy production in a process known as BECCS. It sounds like the perfect solution, but right now it’s energy intensive and expensive, and there are concerns that BECCS projects could end up competing with agriculture and damaging conservation efforts.

A new answer from an ancient substance?

Forming magnesite, or magnesium carbonate, may be one way to trap carbon dioxide.

Some brand new research might offer yet another solution. It’s another carbon-capture technology which involves magnesium carbonate, or magnesite (MgCO3). Magnesite forms slowly on the Earth’s surface, over hundreds of thousands of years, trapping carbon dioxide in its structure as it does.

It can easily be made quickly at high temperatures, but of course if you have to heat things up, you need energy, which might end up putting as much CO2 back in as you’re managing to take out. Recently a team of researchers at Trent University in Canada have found a way to form magnesite quickly at room temperature using polystyrene microspheres.

This isn’t something which would make much difference if, say, you covered the roof of everyone’s house with the microspheres, but it could be used in fuel-burning power generators (which could be burning renewables or even waste materials) to effectively scrub the carbon dioxide from their emissions. That technology on its own would make a huge difference.

And so here we are. Carbon dioxide is one of the oldest substances there is, as “natural” as they come. From breathing to fizzy drinks to our climate, it’s entwined in every aspect of our everyday existence. It is both friend and foe. Will we work out ways to save ourselves from too much of it in our atmosphere? Personally, I’m optimistic, so long as we support scientists and engineers rather than fight them…


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No need for slime panic: it’s not going to poison anyone

This is one of my favourite photos, so I’m using it again.

The school summer holidays are fast approaching and, for some reason, this always seems to get people talking about slime. Whether it’s because it’s a fun end-of-term activity, or it’s an easy bit of science for kids to do at home, or a bit of both, the summer months seem to love slimy stories. In fact, I wrote a piece about it myself in August 2017.

Which (hoho) brings me to the consumer group Which? because, on 17th July this year, they posted an article with the headline: “Children’s toy slime on sale with up to four times EU safety limit of potentially unsafe chemical” and the sub-heading: “Eight out of 11 popular children’s slimes we tested failed safety testing.”

The article is illustrated with lots of pots of colourful commercial slime pots with equally colourful names like Jupiter Juice. It says that, “exposure to excessive levels of boron could cause irritation, diarrhoea, vomiting and cramps in the short term,” and goes on to talk about possible risks of birth defects and developmental delays. Yikes. Apparently the retailer Amazon has removed several slime toys from sale since Which? got on the case.

The piece was, as you might expect, picked up by practically every news outlet there is, and within hours the internet was full of headlines warning of the dire consequences of handling multicoloured gloopy stuff.

Before I go any further, here’s a quick reminder: most slime is made by taking polyvinyl alcohol (PVA – the white glue stuff) and adding a borax solution, aka sodium tetraborate, which contains the element boron. The sodium tetraborate forms cross-links between the PVA polymer chains, and as a result you get viscous, slimy slime in place of runny, gluey stuff. Check out this lovely graphic created by @compoundchem for c&en’s Periodic Graphics:

The Chemistry of Slime from cen.acs.org (click image for link), created by Andy Brunning of @compoundchem

And so, back to the Which? article. Is the alarm justified? Should you ban your child from ever going near slime ever again?

Nah. Followers will remember that back in August last year, after I posted my own slime piece, I had a chat with boron-specialist David Schubert. He said at the time: “Borax has been repeated[ly] shown to be safe for skin contact. Absorption through intact skin is lower than the B consumed in a healthy diet” (B is the chemical symbol for the element boron). And then he directed me to a research paper backing up his comments.

Borax is a fine white powder, Mixed with water it can be used to make slime.

This, by the way, is all referring to the chemical borax – which you might use if you’re making slime. In pre-made slime the borax has chemically bonded with the PVA, and that very probably makes it even safer – because it’s then even more difficult for any boron to be absorbed through skin.

Of course, and this really falls under the category of “things no one should have to say,” don’t eat slime. Don’t let your kids eat slime. Although even if they did, the risks are really small. As David said when we asked this time: “Borates have low acute toxicity. Consumption of the amount of borax present in a handful of slime would make one sick to their stomach and possibly cause vomiting, but no other harm would result. The only way [they] could harm themselves is by eating that amount daily.”

It is true that borax comes with a “reproductive hazard” warning label. Which? pointed out in their article that there is EU guidance on safe boron levels, and the permitted level in children’s’ toys has been set at 300 mg/kg for liquids and sticky substances (Edited 18th July, see * in Notes section below).

EU safety limits are always very cautious – an additional factor of at least 100 is usually incorporated. In other words, for example, if 1 g/kg exposure of a substance is considered safe, the EU limit is likely to be set at 0.01 g/kg – so as to make sure that even someone who’s really going to town with a thing would be unlikely to suffer negative consequences as a result.

The boron limit is particularly cautious and is based on animal studies (and it has been challenged). The chemists I spoke to told me it’s not representative of the actual hazards. Boron chemist Beth Bosley pointed out that while it is true that boric acid exposure has been shown to cause fetal abnormalities when it’s fed to pregnant rats, this finding hasn’t been reproduced in humans. Workers handling large quantities of borate in China and Turkey have been studied and no reproductive effects have been seen.

Rat studies, she said, aren’t wholly comparable because rats are unable to vomit, which is significant because it means a rat can be fed a large quantity of a boron-containing substance and it’ll stay in their system. Whereas a human who accidentally ingested a similar dose would almost certainly throw up. Plus, again, this is all based on consuming substances such as borax, not slime where the boron is tied up in polymer chains. There really is no way anyone could conceivably eat enough slime to absorb these sorts of amounts.

These arguments aside, we all let our children handle things that might be harmful if they ate them. Swallowing a whole tube of toothpaste would probably give your child an upset stomach, and it could even be dangerous if they did it on a regular basis, but we haven’t banned toothpaste “just in case”. We keep it out of reach when they’re not supposed to be brushing their teeth, and we teach them not to do silly things like eating an entire tube of Oral-B. Same basic principle applies to slime, even if it does turn out to contain more boron than the EU guidelines permit.

In conclusion: pots of pre-made slime are safe, certainly from a borax/boron point of view, so long as you don’t eat them. The tiny amounts of boron that might be absorbed through skin are smaller than the amounts you’d get from eating nuts and pulses, and not at all hazardous.

Making slime at home can also be safe, if you follow some sensible guidelines like, say, these ones:

Stay safe with slime by following this guidance

Slime on, my chemistry-loving friends!


Notes:
* When I looked for boron safety limits the first time, the only number I could find was the rather higher 1200 mg/kg. So I asked Twitter if anyone could direct me to the value Which? were using. I was sent a couple of links, one of which contained a lot of technical documentation, but I think the most useful is probably a “guide to international toy safety” pamphlet which includes a “Soluble Element Migration Requirements” table. In the row for boron, under “Category II: Liquid or sticky materials”, the value is indeed given as 300 mg/kg.

BUT, there is also ” Category I: Dry, brittle, powder like or pliable materials” and the value there is the much higher 1,200 mg/kg. Which begs the question: does slime count as “pliable” or “sticky”? It suggests to me that, say, a modelling clay product (pliable) would have the 4x higher limit. But surely the risk of exposure would be essentially the same? If 1,200 mg/kg is okay for modelling clay, I can’t see why it shouldn’t be for slime. In the Which? testing, only the Jupiter Juice product exceeded the Category I limit, and then not by that much (1,400 mg/kg).

Also (the notes are going to end up being longer than the post if I’m not careful), these values are migration limits, not limits on the amount allowed in the substance in total. Can anyone show that more than 300 mg/kg is able to migrate from the slime to the person handling it? Very unlikey. But again, don’t eat slime.

This is not an invitation to try and prove me wrong.

I suppose it’s possible that someone could sell slime that’s contaminated with some other toxic thing. But that could happen with anything. The general advice to “wash your/their hands and don’t eat it” will take you a long way.


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Spectacular Strawberry Science!

Garden strawberries

Yay! It’s June! Do you know what that means, Chronicle Flask readers? Football? What do you mean, football? Who cares about that? (I jest – check out this excellent post from Compound Interest).

No, I mean it’s strawberry season in the U.K.! That means there will be much strawberry eating, because the supermarkets are full of very reasonably-priced punnets. There will also be strawberry picking, as we tramp along rows selecting the very juiciest fruits (and eating… well, just a few – it’s part of the fun, right?).

Is there any nicer fruit than these little bundles of red deliciousness? Surely not. (Although I do also appreciate a ripe blackberry.)

And as if their lovely taste weren’t enough, there’s loads of brilliant strawberry science, too!

This is mainly (well, sort of, mostly, some of the time) a chemistry blog, but the botany and history aspects of strawberries are really interesting too. The woodland strawberry (Fragaria vesca) was the first to be cultivated in the early 17th century, although strawberries have of course been around a lot longer than that. The word strawberry is thought to come from ‘streabariye’ – a term used by the Benedictine monk Aelfric in CE 995.

Woodland strawberries

Woodland strawberries, though, are small and round: very different from the large, tapering, fruits we tend to see in shops today (their botanical name is Fragaria × ananassa – the ‘ananassa’ bit meaning pineapple, referring to their sweet scent and flavour.

The strawberries we’re most familiar with were actually bred from two other varieties. That means that modern strawberries are, technically, a genetically modified organism. But no need to worry: practically every plant we eat today is.

Of course, almost everyone’s heard that strawberries are not, strictly, a berry. It’s true; technically strawberries are what’s known as an “aggregate accessory” fruit, which means that they’re formed from the receptacle (the thick bit of the stem where flowers emerge) that holds the ovaries, rather than from the ovaries themselves. But it gets weirder. Those things on the outside that look like seeds? Not seeds. No, each one is actually an ovary, with a seed inside it. Basically strawberries are plant genitalia. There’s something to share with Grandma over a nice cup of tea and a scone.

Anyway, that’s enough botany. Bring on the chemistry! Let’s start with the bright red colour. As with most fruits, that colour comes from anthocyanins – water-soluble molecules which are odourless, moderately astringent, and brightly-coloured. They’re formed from the reaction of, similar-sounding, molecules called anthocyanidins with sugars. The main anthocyanin in strawberries is callistephin, otherwise known as pelargonidin-3-O-glucoside. It’s also found in the skin of certain grapes.

Anthocyanins are fun for chemists because they change colour with pH. It’s these molecules which are behind the famous red-cabbage indicator. Which means, yes, you can make strawberry indicator! I had a go myself, the results are below…

Strawberry juice acts as an indicator: pinky-purplish in an alkaline solution, bright orange in an acid.

As you can see, the strawberry juice is pinky-purplish in the alkaline solution (sodium hydrogen carbonate, aka baking soda, about pH 9), and bright orange in the acid (vinegar, aka acetic acid, about pH 3). Next time you find a couple of mushy strawberries that don’t look so tasty, don’t throw them away – try some kitchen chemistry instead!

Peonidin-3-O-glucoside is the anthocyanin which gives strawberries their red colour. This is the form found at acidic pHs

The reason we see this colour-changing behaviour is that the anthocyanin pigment gains an -OH group at alkaline pHs, and loses it at acidic pHs (as in the diagram here).

This small change is enough to alter the wavelengths of light absorbed by the compound, so we see different colours. The more green light that’s absorbed, the more pink/purple the solution appears. The more blue light that’s absorbed, the more orange/yellow we see.

Interestingly, anthocyanins behave slightly differently to most other pH indicators, which usually acquire a proton (H+) at low pH, and lose one at high pH.

Moving on from colour, what about the famous strawberry smell and flavour? That comes from furaneol, which is sometimes called strawberry furanone or, less romantically, DMHF. It’s the same compound which gives pineapples their scent (hence that whole Latin ananassa thing I mentioned earlier). The concentration of furaneol increases as the strawberry ripens, which is why they smell stronger.

Along with menthol and vanillin, furaneol is one of the most widely-used compounds in the flavour industry. Pure furaneol is added to strawberry-scented beauty products to give them their scent, but only in small amounts – at high concentrations it has a strong caramel-like odour which, I’m told, can actually smell quite unpleasant.

As strawberries ripen their sugar content increases, they get redder, and they produce more scent

As strawberries ripen their sugar content (a mixture of fructose, glucose and sucrose) also changes, increasing from about 5% to 9% by weight. This change is driven by auxin hormones such as indole-3-acetic acid. At the same time, acidity – largely from citric acid – decreases.

Those who’ve been paying attention might be putting a few things together at this point: as the strawberry ripens, it becomes less acidic, which helps to shift its colour from more green-yellow-orange towards those delicious-looking purpleish-reds. It’s also producing more furaneol, making it smell yummy, and its sugar content is increasing, making it lovely and sweet. Why is all this happening? Because the strawberry wants (as much as a plant can want) to be eaten, but only once it’s ripe – because that’s how its seeds get dispersed. Ripening is all about making the fruit more appealing – redder, sweeter, and nicer-smelling – to things that will eat it. Nature’s clever, eh?

There we have it: some spectacular strawberry science! As a final note, as soon as I started writing this I (naturally) found lots of other blogs about strawberries and summer berries in general. They’re all fascinating. If you want to read more, check out…


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Where did our love of dairy come from?

The popularity of the soya latte seems to be on the rise.

A little while ago botanist James Wong tweeted about the myriad types of plant ‘milk’ that are increasingly being offered in coffee shops, none of which are truly milk (in the biological sense).

This generated a huge response, probably rather larger than he was expecting from an off-hand tweet. Now, I’m not going to get into the ethics of milk production because it’s beyond the scope of this blog (and let’s keep it out of the comments? — kthxbye) but I do want to consider one fairly long thread of responses which ran the gamut from ‘humans are the only species to drink the milk of another animal’ (actually, no) to ‘there’s no benefit to dairy’ (bear with me) and ending with, in essence, ‘dairy is slowly killing us‘ (complicated, but essentially there’s very little evidence of any harm).

Humans have been consuming dairy products for thousands of years.

But wait. If dairy is so terrible for humans, and if there are no advantages to it, why do we consume it at all? Dairy is not a new thing. Humans have been consuming foods made from one type of animal milk or another for 10,000 years, give or take. That’s really quite a long time. More to the point (I don’t want to be accused of appealing to antiquity, after all), keeping animals and milking them is quite resource intensive. You have to feed them, look after them and ensure they don’t wander off or get eaten by predators, not to mention actually milk them on a daily basis. All that takes time, energy and probably currency of some sort. Why would anyone bother, if dairy were truly detrimental to our well-being?

In fact, some cultures don’t bother. The ability to digest lactose (the main sugar in milk) beyond infancy is quite low in some parts of the world, specifically Asia and most of Africa. In those areas dairy is, or at least has been historically, not a significant part of people’s diet.

But it is in European diets. Particularly northern European diets. Northern Europeans are, generally, extremely tolerant of lactose into adulthood and beyond.

Which is interesting because it suggests, if you weren’t suspicious already, that there IS some advantage to consuming dairy. The ability to digest lactose seems to be a genetic trait. And it seems it’s something to do, really quite specifically, with your geographic location.

Which brings us to vitamin D. This vitamin, which is more accurately described as a hormone, is a crucial nutrient for humans. It increases absorption of calcium, magnesium and phosphate, which are all necessary for healthy bones (not to mention lots of other processes in the body). It’s well-known that a lack of vitamin D leads to weakened bones, and specifically causes rickets in children. More recently we’ve come to understand that vitamin D also supports our immune system; deficiency has been meaningfully linked to increased risk of certain viral infections.

What’s the connection between vitamin D and geographic location? Well, humans can make vitamin D in their skin, but we need a bit of help. In particular, and this is where the chemistry comes in, we need ultraviolet light. Specifically, UVB – light with wavelengths between 280 nm to 315 nm. When our skin is exposed to UVB, a substance called 7-dehydrocholesterol (7-DHC to its friends) is converted into previtamin D3, which is then changed by our body heat to vitamin D3, or cholecalciferol – which is the really good stuff. (There’s another form, vitamin D2, but this is slightly less biologically active.) At this point the liver and kidneys take over and activate the chloecalciferol via the magic of enzymes.

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

How much UVB you’re exposed to depends on where you live. If you live anywhere near the equator, no problem. You get UVB all year round. Possibly too much, in fact – it’s also linked with skin cancers. But if you live in northerly latitudes (or very southerly), you might have a problem. In the summer months, a few minutes in the sun without sunscreen (literally a few minutes, not hours!) will produce more than enough vitamin D. But people living in UK, for example, get no UVB exposure for 6 months of the year. Icelanders go without for 7, and inhabitants of Tromsø, in Norway, have to get by for a full 8 months. Since we can only store vitamin D in our bodies for something like 2-4 months (I’ve struggled to find a consistent number for this, but everyone seems to agree it’s in this ballpark), that potentially means several months with no vitamin D at all, which could lead to deficiency.

In the winter northern Europeans don’t receive enough UVB light from the sun to produce vitamin D in their skin.

In the winter, northern Europeans simply can’t make vitamin D3 in their skin (and for anyone thinking about sunbeds, that’s a bad idea for several reasons). In 2018, this is easily fixed – you just take a supplement. For example, Public Health England recommends that Brits take a daily dose of 10 mcg (400 IU) of vitamin D in autumn and winter, i.e. between about October and March. It’s worth pointing out at this point that a lot of supplements you can buy contain much more than this, and more isn’t necessarily better. Vitamin D is fat-soluble and so it will build up in the body, potentially reaching toxic levels if you really overdo things. Check your labels.

Oily fish is an excellent source of vitamin D.

But what about a few thousand years ago, before you just could pop to the supermarket and buy a bottle of small tablets? What did northern Europeans do then? The answer is simple: they had to get vitamin D from their food. Even if it’s not particularly well-absorbed, it’s better than nothing.

Of couse it helps if you have access to lots of foods which are sources of vitamin D. Which would be…  fatty fish (tuna, mackerel, salmon, etc) – suddenly that northern European love of herring makes so much more sense – red meat, certain types of liver, egg yolks and, yep, dairy products. Dairy products, in truth, contain relatively low levels of vitamin D (cheese and butter are better than plain milk), but every little helps. Plus, they’re also a good source of calcium, which works alongside vitamin D and is, of course, really important for good bone health.

A side note for vegans and vegetarians: most dietry sources of vitamin D come from animals. Certain mushrooms grown under UV can be a good source of vitamin D2, but unless you’re super-careful a plant-based diet won’t provide enough of this nutrient. So if you live in the north somewhere or you don’t, or can’t, expose your skin to the sun very often, you need a supplement (vegan supplements are available).

Fair skin likely emerged because it allows for better vitamin D production when UVB levels are lower.

One thing I haven’t mentioned of course is skin-colour. Northern Europeans are generally fair-skinned, and this is vitamin D-related, too. The paler your skin, the better UVB penetrates it. Fair-skinned people living in the north had an advantage over those with darker skin in the winter, spring and autumn months: they could produce more vitamin D. In fact, this was probably a significant factor in the evolution of fair skin (although, as Ed Yong explains in this excellent article, that’s complicated).

In summary, consuming dairy does have advantages, at least historically. There’s a good reason Europeans love their cheeses. But these days, if you want to eat a vegan or vegetarian diet for any reason (once again, let’s not get into those reasons in comments, kay?) you really should take a vitamin D supplement. In fact, Public Health England recommends that everyone in the UK take a vitamin D supplement in the autumn and winter, but only a small amount – check your dose.

By the way, if you spot any ‘diary’s let me know. I really had to battle to keep them from sneaking in…

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