Puzzling pool problems?

We’re half way thorough the Rio 2016 Olypics, and it will have escaped no one’s notice that there have been a few little problems with one of the pools.

Maria Lenk Aquatic Enter, Tuesday, Aug. 9, 2016. (AP Photo/Matt Dunham)

Maria Lenk Aquatic Enter, Tuesday, Aug. 9, 2016. (AP Photo/Matt Dunham)

First, the water turned a mysterious green colour. Then there were reports of a ‘sulfurous’ smell, with German diver Stephan Feck reported as saying it smelled like a “fart”.

The diving pool seemed to be the worst affected, but the water-polo pool next to it also suffered problems, and competitors complained of stinging eyes.

So what on earth was happening? An early suggestion was that copper salts were contaminating the water. It’s not unheard of for copper compounds to get into water supplies, and it would certainly explain the colour; copper chloride solutions in particular are famously greeny-blue. But what about that sulfurous smell? Copper chloride doesn’t smell of sulfur.

Was the strange pool colour due to algae bloom?

Was the strange pool colour due to an algae bloom, like this one in Lake Erie?

The most likely culprit was some sort of algae bloom – in other words rapid algae growth – with the smell probably coming from dimethyl sulfide, or DMS. There’s a singled-celled phytoplankton called Emiliania huxleyi which is particularly famous for producing this smelly compound. In fact, it actually has more than one very important role in nature: the smell is thought to alert marine life that there’s food nearby, but it also seeps into the atmosphere and helps with cloud formation, helping to control our planet’s temperature. Without these reactions, Earth might not be nearly so habitable.

But how did algae manage to grow in the pool? The pool chemicals should have prevented it, so what had happened? An Olympic official then went on to make the comment that “chemistry is not an exact science,” which of course led to much hilarity all around. Chemistry is, after all, incredibly exact. What chemistry student doesn’t remember all those calculations, with answers to three significant figures? The endless balancing of equations? The careful addition of one solution to another, drop by drop? How much more ‘exact’ would you like it to be?

But I had a bit of sympathy with the official, because I suspect that what they actually meant – if not said – was that swimming pool chemistry is not an exact science. And while that, too, is hardly accurate, it is true that swimming pool chemistry is very complicated and things can easily go wrong, particularly when you’re trying to work on an extremely tight schedule. They could hardly, after all, close down all the pools and spend several days carrying out extensive testing in the middle of the sixteen-day-long Olympic Games.

Rio 2016 Olympics Aquatics Stadium (Image: Myrtha Pools)

Rio 2016 Olympics Aquatics Stadium (Image: Myrtha Pools)

When a pool is first built and filled, things are, theoretically, simple. You know exactly how many cubic litres of water there are, and you know exactly how much of each chemical needs to be added to keep the water free of bacteria and other nasties. Those chemicals are added, possibly (particularly in a pool this size) via some kind of automated system, and the pH is carefully monitored to ensure the water is neither too alkaline (basic) nor too acidic.

There’s a certain amount of proprietary variation of swimming pool chemicals, but it essentially all comes down to chlorine, which has been used to make water safe now for over 120 years.

Originally, water was treated to make it alkaline and then chlorine gas itself was added. This produced compounds which killed bacteria, in particular sodium hypochlorite, but the practice was risky. Chlorine gas is extremely nasty stuff – it has, after all, been used as a chemical weapon – and storing it, not to mention actually using it, was a dangerous business.

However, hundreds of people swimming in untreated water is a recipe for catching all kinds of water-borne disease, so it wasn’t long before alternatives were developed.

The Chemistry of Swimming Pools (Image: Compound Interest - click for more info)

The Chemistry of Swimming Pools (Image: Compound Interest – click graphic for more info)

Those alternatives made use of the chemistry that was happening anyway in the water, but  allowed the dangerous bit, with the elemental chlorine, to happen somewhere else. And so hypochlorite salts began to be manufactured to be used in swimming pools.

As the lovely graphic from Compound Interest illustrates, sodium hypochlorite reacts with water to form hypochlorous acid, which in turn goes on to form hypochlorite ions. These two substances sit in an equilibrium, and both are oxidants, which is good because oxidants are good at blasting bacteria. The equilibria in question are affected by pH though, which is one reason why, quite apart from the potential effects on swimmers, it’s so important to manage the pH of pool water.

There are a couple of different chemicals which can be added to adjust pH. Sodium bicarbonate, for example, can be used to nudge the pH up if needed. On the other hand, sodium bisulfate can be used to lower pH if the water becomes too alkaline.

Open-air pools have particular problems

UV light breaks down the chemicals that are used to keep swimming pool water clean.

This can all be managed extremely precisely in an unused, enclosed pool. But once you open that pool up, things become less simple. Open-air pools have a particular problem with UV light. Chlorine compounds are often sensitive to UV – this is why CFCs are such a problem for the ozone layer – and hypochlorite is no exception. In the presence of UV it breaks down in a process called photolysis to form chloride ions and oxygen. This means that outdoor pools require more frequent treatments, or the addition of extra chemicals to stabilise the ‘free available chlorine’ (FAC) levels.

Sadly, I haven’t managed to make it over to Rio, but from what I’ve seen the Aquatic Centre has a roof which opens up, which means that the pool water is indeed being exposed to UV light.

So perhaps the chemical levels simply dropped too low, which allowed algae to proliferate? Possibly aggravated by environmental conditions? Indeed, initially this seemed to be the explanation. FINA, the international governing body of aquatics, issued a statement on Wednesday afternoon which said:

“FINA can confirm that the reason for the unusual water color observed during the Rio diving competitions is that the water tanks ran out of some of the chemicals used in the water treatment process. As a result, the pH level of the water was outside the usual range, causing the discoloration. The FINA Sport Medicine Committee conducted tests on the water quality and concluded that there was no risk to the health and safety of the athletes, and no reason for the competition to be affected.”

This prompted people to wonder how on earth chemical levels were allowed to run out in an event as significant as the Olympics – did someone forget to click send on the order? – but still, it seemed to explain what had happened.

FINA issued a new statement

FINA issued a new statement on Sunday

Until today (Sunday), when more information surfaced as Olympic officials announced that they were going to drain at least one of the swimming pools and refill it. This is no small feat and will involve considerable cost: after all, we’re talking about millions of gallons of water. But it seems to be necessary. As Rio 2016’s director of venue management Gustavo Nascimento said:

“On the day of the Opening Ceremonies of the Games, 80 litres of hydrogen peroxide was put in the water. This creates a reaction to the chlorine which neutralises the ability of the chlorine to kill organics. This is not a problem for the health of anyone.”

Whoops. Yes indeed. Hydrogen peroxide reacts with chlorine to produce oxygen and hydrochloric acid. In fact, hydrogen peroxide is actually used to dechlorinate water which contains levels of chlorine that are too high. It might not be the very worst thing you could add to the water (when you think of all the things that could end up swimming pools) but it’s definitely up there.

Why and how this happened doesn’t, at the moment, appear to be clear. Presumably someone is for the high jump, and not just on the athletics field.

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Do you really need to worry about baby wipes?

Never mind ingredients, just give me a packet that's not empty!

Never mind ingredients, just give me a packet that’s not empty!

A little while back I wrote a post about shampoo ingredients, and in passing I mentioned baby wipes. Now, these are one of those products which you’ve probably never bought if you’re not a parent, but as soon as you are you find yourself increasingly interested in them. Yes, I know, reusable ‘wipes’ are a thing. But after dealing with a nappy explosion at 2am in the morning, I’m willing to bet that more than one parent’s environmental conscience has gone in the rubbish bin along with a bag of horror they never want to see again, at least for a little while.

But which wipes to buy? The cheapest ones? The nicest-smelling ones? The fragrance-free ones? The ones with the plastic dispenser on the top that allow you to easily grab one wipe at a time? Or not, because those bulky dispensers produce yet more plastic waste? Or just whichever brand you grabbed first at the all-night supermarket at some unpleasant hour that’s too late to be night yet too early to be morning?

All of the above at one time or another, probably. However, I’m going to suggest that one thing you can stop worrying about right now is whether or not your wipes are labelled ‘chemical-free’.

As I’ve explained before, everything is made up of chemicals. By any sensible definition, water is a chemical, and thus the claim that Water Wipes® (“the world’s purest baby wipe”) are “chemical free” is simply incorrect.

These wipes are not, actually, chemical-free.

These wipes are not, actually, chemical-free.

In fact, Water Wipes® aren’t even, as you might imagine, made of some sort of non-woven fabric impregnated with plain water. No, they contain something else: grapefruit seed extract.

Well, that sounds natural, I hear you say. It does, doesn’t it? Grapefruit, that sounds fresh. Seed, well seeds are healthy, aren’t they? And the word ‘extract’ is very natural-sounding. What’s the problem?

Let’s start with what grapefruit seed extract, also called GSE, actually is. It’s made from the seeds, pulp and white membranes of grapefruit. These ingredients are ground up and a drop of glycerin is added. Glycerin, by the way, is otherwise known as glycerol, or propane-1,2,3-triol. It’s naturally-occurring – it’s one of the molecules you get when you break up fats – and it’s usually made from plants such as soybeans or palm (uh oh…), or sometimes from tallow (oh dear…) or as a byproduct of the petroleum industry (yikes! – I wonder if the manufacturers of Water Wipes® enquired about the nature of the glycerin being added to their product…?)

But anyway, back to GSE. Like all plant extracts, grapefruit seed extract is stuffed full of other chemicals that occur naturally. In particular, flavonoids, ascorbic acid (vitamin C), tocopherols, citric acid, limonoids and sterols.

citric acid synthetic vs natural

Can you tell the difference?

So… in short, not chemical-free at all. Not even a bit. The problem here is that, in marketing, the term ‘chemical-free’ is used to mean something that only contains ingredients from ‘natural’ sources. But this is meaningless. Take citric acid, for example. (E330 by the way – E numbers don’t mean something’s deadly, either. In fact, quite the opposite.) There’s no difference between citric acid extracted from a grapefruit and citric acid prepared in a laboratory. They both have exactly the same atoms and the same molecular formula and structure. They both react in the same way.

They’d both be classified as corrosive in high concentrations, and irritant in low concentrations. This isn’t even “might” cause irritation. This is absolutely, definitely, positively WILL cause irritation.

Wait, hang on a minute! There’s a potentially corrosive chemical in the ‘chemical-free’ baby wipes, and unsuspecting parents are putting it on their baby’s skin?!

Yep.

But before anyone runs off to write the next Daily Mail headline, let’s be clear. It’s really not going to burn, alien acid-style, through a new baby’s skin. It’s not even going to slightly redden a baby’s skin, because the quantity is so miniscule that it quite literally has no corrosive properties at all. It’s the same logic as in the old adage that “the dose makes the poison“.

This is where we, as consumers, ought to stop and think. If a fraction of a drop of citric acid is harmless then…. perhaps that small quantity of PEG 40 hydrogenated castor oil or sodium benzoate in most (considerably less expensive, I’m just saying) other brands of baby wipes isn’t as awful as we thought, either…

Indeed, it’s not. But what sodium benzoate in particular IS, is a very effective preservative.

Grapefruit seed extract is marketed as a natural preservative, but studies haven't backed up this claim.

Grapefruit seed extract is allegedly a natural preservative, but studies haven’t backed up this claim.

Why does this matter? Well, without some sort of preservative baby wipes, which sit in a moist environment for weeks or months or even years, might start to grow mould and other nasties. You simply can’t risk selling packets of water-soaked fabric, at a premium price, without any preservative at all, because one day someone might open one of those packets and find it full of mould. At which point they would, naturally, take a photo and post it all over social media. Dis-as-ter.

This is why Water Wipes® include grapefruit seed extract, because it’s a natural preservative. Except…

When researchers studied GSE and its antimicrobial properties they found that most of their samples were contaminated with benzethonium chloride, a synthetic preservative, and some were contaminated with other preservatives, some of which really weren’t very safe at all. And here’s the kicker, the samples that weren’t contaminated had no antimicrobial properties.

In other words, either your ‘natural’ grapefruit seed extract is a preservative because it’s contaminated with synthetic preservatives, or it’s not a preservative at all.

If you're worried, just use cotton wool pads and water.

You can always use cotton wool pads and water.

If you’re worried that baby wipes may be irritating your baby’s skin – I’m not claiming this never happens – then the best, and cheapest, thing to do would be to simply follow the NHS guidelines and use cotton wool and water. It’s actually easier and less messy than you might imagine – packets of flat, cosmetic cotton wool pads are readily available (and pretty cheap). Simply dip one in some clean water, wipe and throw it away. It’s really no more difficult or messy than wipes.

But if you’re choosing a particular brand of wipes on the basis that they’re “chemical-free”, despite the fact that other types have never actually caused irritation, you can stop. Really. Buy the cheap ones. Or the nicest-smelling ones, or the ones that come out of the packet most easily. Because NONE of them are chemical-free, and it’s really not a problem.


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No element octarine, but Nanny will be pleased…

After lots of speculation over the last few months, the names of the new elements were finally announced by IUPAC yesterday. There will now be a five-month public review, ending on 8 November 2016, but it looks likely that these names will be accepted. They are:

  • 113: Nihonium, Nh, from ‘Nihon’, meaning Japan or ‘The Land of the Rising Sun’, home of RIKEN;
  • 115: Moscovium, Mc, in recognition of the Moscow region, where JINR is based;
  • 117: Tennessine, Ts, for the Tennessee region, home of ORNL;
  • and 118: Oganesson, Og, named after a very important individual*.
New-Element-Names-768x378

New Element Names, by Compound Interest (click image for more info)

As you can see, octarine sadly didn’t make the cut. Perhaps the million to one chance rule just doesn’t work so well on roundworld. Oh well.

But look, they didn’t completely forget about us! They just misspelled ‘Ogg and Son’. It’s easily done. I’m sure Nanny will still be pleased.

nanny_ogg_by_hyaroo-d6mnot6

Nanny Ogg. Image byHyaroo, http://hyaroo.deviantart.com/

*Oganesson actually recognises Professor Yuri Oganessian (born 1933) for his pioneering contributions to transactinoid elements research. But perhaps he’s a distant relative?


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What’s all the fuss about glyphosate?

Glyphosate, the key ingredient in Monsanto’s weedkiller Roundup, has been in the news recently. A few weeks ago it was widely reported that a UN/WHO study had shown it was ‘unlikely to pose a carcinogenic risk to humans‘. But it then emerged that the chairman of the UN’s joint meeting on pesticide residues (who, incidentally, has the fabulous name of Professor Boobis) also runs the International Life Science Institute (ILSI). Which had received a $500,000 donation from Monsanto, and $528,500 from an industry group which represents Monsanto among others.

And then it transpired that there was going to be an EU relicensing vote on glyphosate two days after the (since postponed) UN/WHO report was released, which resulted in another outcry.

Glyphosate molecule

A molecule of glyphosate

So what is glyphosate, and why all the fuss?

It was first synthesized in 1950 by Swiss chemist Henry Martin. It was later, independently, discovered at Monsanto. Chemists there were looking at water-softening agents, and found that some of them also killed certain plants. A chemist called John E. Franz was asked to investigate further, and he went on to discover glyphosate. He famously received $5 for the patent.

Chemically, glyphosate is a fairly simple molecule. It’s similar in structure to amino acids, the building blocks of all proteins, in that it contains a carboxylic acid group (the COOH on the far right) and an amine group (the NH in the middle). In fact, glyphosate is most similar to the smallest of all amino acids, glycine. Where it deviates is the phosphonic group (PO(OH2)) on the left. This makes it a (deep breath) aminophosphonic analogue of glycine. Try saying that when you’ve had a couple of beers.

As is usually the way in chemistry, changing (or indeed adding) a few atoms makes a dramatic difference to the way the molecule interacts with living systems. While glycine is more or less harmless, and is in fact a key component of proteins, glyphosate is a herbicide.

This probably bears stressing. It’s a herbicide. Not an insecticide. A herbicide.

Crop spraying

Glyphosate is a herbicide, not an insecticide.

I say this because people often conflate the two – after all, they’re both chemicals you spray on plants, right? – but they are rather different beasts. Insecticides, as the name suggests, are designed to kill insects. The potential problem being that other things eat those creatures, and if we’re not careful, the insecticide can end up in places it wasn’t expected to end up, and do things it wasn’t expected to do. This famously happened with DDT, a very effective pesticide which unfortunately also had catastrophic effects on certain predatory birds when they ate the animals that had eaten the slightly smaller animals which had eaten the insects that had eaten the other insects (and so on) that had been exposed to the DDT.

Herbicides, on the other hand, kill plants. Specifically, weeds. They’re designed to work on the biological systems in plants, not animals. Often, they have no place to bind in animals and so are simply excreted in urine and faeces, unchanged. Also, since plants aren’t generally known for getting up and wandering away from the field in which they’re growing, herbicide sprays tend to stay more or less where they’re put (unless there’s contamination of waterways, but this can – and should, if the correct procedures are followed – be fairly easily avoided).

Nicotine pesticide

Nicotine is an effective insecticide. It’s also extremely toxic.

Now this is not to say we should be careless with herbicides, or that they’re entirely harmless to humans and other animal species, but we can cautiously say that, in general, they’re rather less harmful than insecticides. In fact, glyphosate in particular is less harmful than a lot of everyday substances. If we simply look at LD50 values (the amount of chemical needed to provide a lethal dose to half of a test population), glyphosate has an LD50 of 4900 mg/kg whereas, for comparison, table salt has an LD50 of 3000. Paracetamol (acetaminophen) has an LD50 of 338, and nicotine (a very effective insecticide, as well as being the active ingredient in cigarettes) has an LD50 of just 9.

Of course, there’s more to toxicity than just killing things, and that’s where it gets tricky. Yes, it might take more than a third of a kilo to kill you outright, but could a smaller amount, particularly over an extended period of time, have more subtle health effects?

But before we go any further down that rabbit hole, let’s take a look at that ‘smaller amount’. Certain campaigners (they always seem to have some sort of stake in the huge business that is organic food, ahem) would have us believe that food crops are ‘drenched’ in glyphosate, and that consumers are eating significant quantities of it every day.

Here’s a great graphic, made by Sarah Shultz of the Nurse Loves Farmer blog (reproduced with her kind permission), that answers this question nice and succinctly:

How much glyphosate?

How much glyphosate is sprayed on crops? (Reproduced with permission of Sarah Shultz)

It’s about 1 can of soda’s worth per acre. Or, if you find an acre hard to visualise, roughly ten drops for every one hundred square feet – the size of a smallish bedroom.

In other words, not a lot. It’s also worth remembering that although there is some pre-harvest spraying – particularly of wheat crops – no farmer is spraying their crops five minutes before harvest. What would be the point of that? Farmers have margins, just like any other business, and chemicals cost money. If you’re going to use them, you use them in the most efficient way you can. The point of spraying pre-harvest is to kill any weeds that might be present so that they don’t get into your harvest. This takes time to happen, so it’s done seven to fourteen days before harvesting takes place. It’s also carefully timed in the growing cycle. Once wheat turns yellow, it’s effectively dead – it’s neither photosynthesising nor transporting nutrients – so if it’s sprayed at this point, glyphosate isn’t moved from the plant into the grain of the wheat. Which means it doesn’t make it into your food.

The long and short of all this is that if there IS any glyphosate in food crops, it’s in the parts per billion range. So is that likely to be harmful?

In March 2015 the International Agency for Research on Cancer (IARC) – the cancer-research arm of the World Health Organisation – announced that glyphosate was ‘probably carcinogenic to humans’, or category 2A. But lots of things fall into this category, for example smoke from wood-burning fires, red meat, and even shift work. The IARC did note that the evidence mainly involved small studies and concerned people that worked with glyphosate, not the general public, and that recommendations were partly influenced by the results of animal studies. The one large-cohort study, following thousands of farmers, found no increased risk.

And by the way, alcohol has been classified as a Group 1 carcinogen, meaning it’s definitely known to cause cancer in humans. If you’re worried about glyphosate in wine and beer, I respectfully suggest you have your priorities the wrong way round.

So, the tiny traces of glyphosate that might be on food definitely aren’t going to poison you or give you cancer. Are there any other health effects?

Gut bacteria

Glyphosate isn’t interfering with your gut bacteria (image: microbeworld.org)

One thing that the health campaigners like to talk about is gut health. Their logic, such as it is, follows that glyphosate passes though our body largely unchanged. Now, you might imagine this would be a good thing, but according to these particular corners of the internet, it’s exactly the opposite. Glyphosate is known to be anti-microbial, and since it’s not changed as it passes through the body, the argument goes that it gets into our guts and starts wiping out the microbes in our digestive system, which have been increasingly linked to a number of important health conditions.

It sort of makes sense, but does it have any basis in fact? Although glyphosate can act as an antimicrobial in fairly large quantities in a petri dish in a laboratory, it doesn’t have a significant effect in the parts per billion quantities that might make their way to your gut from food. Glyphosate prevents bacteria from synthesising certain essential amino acids (it does the same thing to plants; that’s basically how it works) but in the gut these bacteria aren’t generally synthesising those amino acids, because they don’t need to. The amino acids are already there in fairly large quantities; bacteria don’t waste energy making something that’s readily available. In short, glyphosate stops bacteria doing something they weren’t doing anyway. So no, no real basis in fact.

I have so far avoided mentioning GMOs, or genetically-modified organisms. “GMO” often gets muttered in the same breath as glyphosate because certain crops have been modified to resist glyphosate. If they weren’t, it would damage them, too. So the argument goes that more glyphosate is used on those crops, and if you eat them, you’ll be exposed to more of it. But, as I said earlier, farmers don’t throw chemicals around for fun. It costs them money. Plus, not-really-surprisingly-if-you-think-about-it, farmers are usually quite environmentally-conscious. After all their livelihood relies on it! Most of them use multiple, non-chemical methods to control weeds, and then just add the smallest amount of herbicide they can possibly get away with to manage the last few stragglers.

Ah, but even a little bit is too much, you say? Why not eat organic food? Then there will be absolutely no nasty chemicals at all. Well, except for the herbicides that are approved for use in organic farming, and all the other approved chemicals, famously copper sulfate and elemental sulfur, both of which are considerably more toxic than glyphosate by anyone’s measure. And, of course, organic food is much more expensive, and simply not a feasible way of feeding over seven billion people. Perhaps, instead of giving farmers a hard time over ‘intensive’ farming, we should be supporting a mixture of sustainable methods with a little bit of, safe, chemical help where necessary?

In summary, the evidence suggests that glyphosate is pretty safe. Consuming the tiny traces that might be present in food is not going to give you cancer, won’t cause some sort of mysterious ‘leaky gut’ and it’s definitely not to poison you. There is a lot of fuss about glyphosate, but it’s really not warranted. Have another slice of toast.


EDIT 2nd June 2016

After I wrote this post, a very interesting article came my way…

  • Petaluma city suspended use of glyphosate in favour of alternatives. Notable quote:“Having used the alternative herbicides over the past two months, DeNicola said crews have needed to apply the treatments more often to achieve similar results. The plants are also likely to regrow, since the root remains alive underground.The treatments are also said to be extremely pungent during application, with several workers complaining of eye irritation and one experiencing respiratory problems, DeNicola said. Those attributes have required the use of new protective equipment, something that was not required with Roundup.“It’s frustrating being out there using something labeled as organic, but you have to be out there in a bodysuit and a respirator,” he said.”

A classic example of almost-certainly unfounded fear leading to bad decision-making.


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The cold cure that’s 5000 years old

Could we just remove the front of my face? I think it'd be less painful....

Could we just remove the front of my face? I think it’d be less painful….

A couple of days ago I was struck down with a sinus infection. This is something I thought I’d had before, but it turns out that what I’d actually had before was an uncomfortably stuffy nose. Whereas this, on the other hand, was the sensation that someone had put my forehead in a vice and was inflating my eyeballs with a bicycle pump.

I explained this to the doctor. He nodded sympathetically and suggested a drug that’s been used, in one form or another, for five thousand years.

If you’re new to this blog, you might be wondering at this point whether, when I say ‘doctor’ I actually mean ‘naturopath’ (or some other thing that translates as ‘not a doctor’). But, no, this was a properly qualified member of the medical profession. Well, I hope he is. I mean, I haven’t looked him up on the General Medical Council’s list. I assume my surgery did that. I’m sure they did. Anyway….

207px-(+)-Pseudoephedrin

Pseudoephedrine

What was this mysterious, ancient medicine? It was pseudoephedrine, otherwise known (in the UK anyway) by the brand name Sudafed®.

It’s a drug many of us have probably taken to help with cold symptoms, and not given much thought to, but it’s actually got a pretty interesting story.

Pseudoephedrine falls under the class of amphetamines. The ‘amine’ bit of that word refers to the NH group (or it might be NH2, or even just N) and, being one of the fundamental bits in proteins, it turns up in lots of biologically active molecules. It’s in paracetamol (acetaminophen) for example, and antihistamine drugs used to treat allergies, as well as many molecules that occur naturally in the body, such as dopamine and adrenaline (epinephrine).

It’s also there in methamphetamine (commonly known as ‘crystal meth’ or just ‘meth’). In fact, pseudoephedrine and methamphetamine are chemically similar, and the latter can be synthesised from the former (I’m not recommending any of my readers try this; it’s very much frowned upon from a legal point of view). For this reason, the sale of pseudoephedrine is tightly regulated; in the UK you can only buy it over the counter in a licensed pharmacy, and then only in small blister packs. (Cold medications that you can pick up from the shelf usually contain the far less effective phenylephrine.)

800px-Ephedra_sinica_alexlomas

The Ephedra sinica plant

Where does it come from? These days, pseudoephedrine is made in a three-step process, the first of which involves yeast fermentation, but it was first isolated from plants, in particular Ephedra sinica, also known as Chinese ephedra or Ma Huang.

This is where the five thousand years comes in, because these plants have been used in Chinese medicine for millennia. In fact, Ephedra is one of the oldest known medicines. It’s described in the legendary Chinese pharmacopoeia Pen-tsao Kang-mu, and became a common part of Chinese prescriptions to treat cold symptoms, fevers and asthma.

The first substance in Ephedra plants to be used in western medicine was Ephedrine. It was isolated in 1885 by a Japanese chemist called Nagai Nagayoshi, but it was then rather forgotten about until 1920s, when it was rediscovered and became a popular treatment for asthma.

In those days, steroid inhalers had yet to be developed, and the standard treatment for asthma was adrenaline. This was problematic, because adrenaline isn’t orally stable: it had to be injected. Ephedrine, by contrast, would work if swallowed as a pill, making it much easier to use.

Ephedrine_enantiomers

Ephedrine is made up of a mixture of these two mirror-image molecules

Unfortunately, ephedrine had rather unpleasant side-effects. It caused raised blood pressure, and then there were a number of other potential problems such as dizziness, trembling, headache, irregular heartbeat and even, in some cases, heart attack and stroke. Worth the risk perhaps, if you’re in the middle of a life-threatening asthma attack, but not something you’d want to use routinely.

The story goes (although I haven’t been able to verify this by finding, say, a recorded study) that when the use of the whole Ephedra plant as a treatment was compared to the use of pure ephedrine, people noticed that the side-effects were much less severe, even though the whole plant still appeared to be an effective treatment. This caused researchers to wonder whether there was some other substance in Ephedra that had subtly different effects on the body.

Whether this observation was really made or not, it turned out there was another active molecule in the Ephedra plant. It was first separated from ephedrine in in 1927, and was given the name pseudoephedrine, literally ‘false ephedrine’. Ephedrine and pseudoephedrine are structural isomers: they have the same number and type of atoms, ordered slightly differently. This is a common theme in medicinal chemistry: switching just a couple of atoms around can make big differences to the way the human body reacts to drugs.

Like ephedrine, pseudoephedrine was an effective bronchodilator and vasoconstrictor (causing blood vessels to shrink), but its effects were less dramatic, which made it a lot safer. It doesn’t raise blood pressure nearly as much, and is far less likely to cause something really nasty like a heart attack. That said, it’s not side-effect free, and it should go without saying that anyone with an existing medical condition should speak to their doctor before using it. Likewise, don’t go messing about with Ephedra plants.

Vasoconstriction is why pseudoephedrine such a good decongestant. Less fluid leaves the shrunken blood vessels and therefore less fluid enters the throat, nose and sinus linings. This reduces inflammation mucus production, and the incessant pounding of a sinus headache eases up a bit.

Of course, pseudoephedrine doesn’t somehow know to restrict itself to your nose and lungs. Blood vessels throughout the body are affected. This can be useful – for example, pseudoephedrine can help to treat ear infections – but it can also result in other, less desirable effects. In particular, pseudoephedrine suppresses breast-milk production, and for this reason shouldn’t be used by new mothers trying to establish breastfeeding. It might also interfere with mucus membranes in the vagina, potentially causing a small reduction in fertility and, not surprisingly, a substance which is a vasoconstrictor can also aggravate erectile dysfunction. Basically, if you’re trying to make a baby this might be one to avoid, although if you’re stuffed up with a cold you might not feel like it anyway, so perhaps it doesn’t matter.

Anyway, I know what you’re all desperately wondering: But, Chronicle Flask, did it sort out your sinus infection?!

dara

“Science knows it doesn’t know everything; otherwise, it’d stop.”

Well, actually, I’m relieved to report that after taking three doses of pseudoephedrine twice a day for a couple of days the pain has eased up considerably. Of course, there’s nothing antiviral (or antibacterial) in this medicine, but it would appear that my immune system managed to take care of the infection for me, once the inflammation was reduced and the excess fluid which was causing the pressure was able to (yuck) drain away.

To quote the comedian Dara O’Briain:
“‘Oh, herbal medicine’s been around for thousands of years!’ Indeed it has, and then we tested it all, and the stuff that worked became ‘medicine’.”


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Should you be scared of your shampoo?

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

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

273px-Methylchloroisothiazolinone_structure.svg

methylchloroisothiazolinone

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

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

MCl and MI are common preservatives in cosmetic products

MCl and MI are common preservatives in cosmetic products.

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

Yuck.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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Feet of clay? The science of statues

Concept art for the Terry Pratchett statue (c) Paul Kidby

Concept art for the Terry Pratchett statue (c) Paul Kidby

Yesterday we received the exciting news that a statue to commemorate Sir Terry Pratchett and his work has been approved by Salisbury City Council. Hurrah! So, even if we don’t quite manage to get octarine into the periodic table (and thus into every science textbook for ever more), it’s looking very likely that there will still be something permanent to help keep his memory alive.

But this got me thinking about everyday chemistry (who am I kidding, I’m always thinking about everyday chemistry!) and, in particular, bronze – the material from which the statue will be made.

Bronze, I hear you say, what’s that good for apart from, well, statues? And maybe bells? Is it really that interesting?

Well, let’s see. Bronze is an alloy. Alloys are mixtures that contain at least one metal, but they’re stranger than the word ‘mixture’ might perhaps suggest. Imagine combining, say, sand and stones. You still be able to see the sand. You could see the stones. You could, if you could be bothered to do it, separate them out again. And you’d expect the mixture to behave like, well, stony sand.

Alloys aren’t like this. Alloys (other well-known examples include steel, brass and that silver-coloured stuff dentists use for filling teeth) look, on all but the atomic level, like pure metals. They’re bendy and shiny, they make pleasing ringing sounds when you hit them and they’re good electrical conductors. And unlike more simple mixtures, they’re difficult (though not impossible) to separate back into their constituents.

Perhaps the most interesting this about alloys is that their properties are often very different to any of the elements that went into making them. Bronze, in particular, is harder than either tin or copper, and hence The Bronze Age is so historically significant. Copper is one of the few metals that can (just about) be found in its pure form, and so is one of the oldest elements we know, going back at least as far as 9000 BC. But while quite pretty to look at, copper isn’t ideal for making tools, being fairly soft and not great at keeping an edge. Bronze, on the other hand, is much more durable, and was therefore a much better choice for for building materials, armour and, of course, weapons. (War, what is it good for? Er, the development of new materials?)

Hephaestus was the God of fire and metalworking; according to legend he was lame.

Hephaestus was the God of metalworking. According to legend he was lame, could it have been because of exposure to arsenic fumes?

Today we (well, chemists anyway) think of bronze as being an alloy of tin and copper, but the earliest bronzes were made with arsenic, copper ores often being naturally contaminated with this element. Arsenical bronzes can be work-hardened, and the arsenic could, if the quantities were right, also produce a pleasing a silvery sheen on the finished object. Unfortunately, arsenic vaporises at below the melting point of bronze, producing poisonous fumes which attacked eyes, lungs and skin. We know now that it also causes peripheral neuropathy, which might be behind the historical legends of lame smiths, for example Hephaestus, the Greek God of smiths. Interestingly, the Greeks frequently placed small dwarf-like statues of Hephaestus near their hearths, and this is might be where the idea of dwarves as blacksmiths and metalworkers originates.

Tin bronze required a little more know-how (not to mention trade negotiations) than arsenical bronze, since tin very rarely turns up mixed with copper in nature. But it had several advantages. The tin fumes weren’t toxic and, if you knew what you were doing, the alloying process could be more easily controlled. The resulting alloy was also stronger and easier to cast.

teaspoon in mugOf course, as we all know, bronze ultimately gave way to iron. Bronze is actually harder than wrought iron, but iron was considerably easier to find and simpler to process into useful metal. Steel, which came later, ultimately combined superior strength with a relatively lower cost and, in the early 20th century, corrosion resistance. And that’s why the teaspoon sitting in my mug is made of stainless steel and not some other metal.

Bronze has a relatively limited number of uses today, being a heavy and expensive metal, but it is still used to make statues, where heaviness and costliness aren’t necessarily bad things (unless, of course, someone pinches the statue and melts it down – an unfortunately common occurrence with ancient works). It has the advantages of being ductile and extremely corrosion resistant; ideal for something that’s going to sit outside in all weathers. A little black copper oxide will form on its surface over time, and eventually green copper carbonate, but this is superficial and it’s a really long time before any fine details are lost. In addition, bronze’s hardness and ductility means that any pointy bits probably won’t snap off under the weight of the two-millionth pigeon.

So how are bronze statues made? For this I asked Paul Kidby, who designed the concept art for the statue. He told me that he sculpts in Chavant, which is an oil-based clay. It’s lighter than normal clay and, crucially, resists shrinking and cracking. He then sends his finished work away to be cast in bronze at a UK foundry, where they make a mould of his statue and from that, ultimately (skipping over multiple steps), a bronze copy. Bronze has another nifty property, in that it expands slightly just before it sets. This means it fills the finest details of moulds which produces a very precise finish. Conveniently, the metal shrinks again as it cools, making the mould easy to remove.

And just for completeness, Paul also told me that the base of the statue will most likely be polished granite, water jet cut with the design of the Discworld sitting on the back of Great A’Tuin. I can just imagine it – it’s going to be beautiful.

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