Chemical du jour: how bad is BPA, really?

BPA is an additive in many plastics

When I was writing my summary of 2017 I said that there would, very probably, be some sort of food health scare at the start of 2018. It’s the natural order of things: first we eat and drink the calorie requirement of a small blue whale over Christmas and New Year, and then, lo, we must be made to suffer the guilt in January. By Easter, of course, it’s all forgotten and we can cheerfully stuff ourselves with chocolate eggs.

Last year it was crispy potatoes, and the year before that it was something ridiculous about sugar in ketchup causing cancer (it’s the same sugar that’s in everything, why ketchup? Why?). This year, though, it seems that the nasty chemical of the day is not something that’s in our food so much as around it.

Because this year the villain of the piece appears to be BPA, otherwise known as Bisphenol A or, to give it its IUPAC name, 4,4′-(propane-2,2-diyl)diphenol.

BPA is an additive in plastics. At the end of last year an excellent documentary aired on the BBC called Blue Planet II, all about our planet’s oceans. It featured amazing, jaw-dropping footage of wildlife. It also featured some extremely shocking images of plastic waste, and the harm it causes.

Plastic waste is a serious problem

Plastic waste, particularly plastic waste which is improperly disposed of and consequently ends up in the wrong place, is indisputably something that needs to be addressed. But this highlighting of the plastic waste problem had an unintended consequence: where was the story going to go? Everyone is writing about how plastic is bad, went (I imagine) editorial meetings in offices around the country – find me a story showing that plastic is even WORSE than we thought!

Really, it was inevitable that a ‘not only is plastic bad for the environment, but it’s bad for you, too!’ theme was going to emerge. It started, sort of, with a headline in The Sun newspaper: “Shopping receipts could ‘increase your cancer risk’ – as 93% contain dangerous chemicals also linked to infertility. Shopping receipts are, of course, not made of plastic – but the article’s sub-heading stated that “BPA is used to make plastics”, so the implication was clear enough.

Then the rather confusing: “Plastic chemical linked to male infertility in majority of teenagers, study suggests” appeared in The Telegraph (more on this in a bit), and the whole thing exploded. Search for BPA in Google News now and there is everything from “5 Ways to Reduce Your Exposure to Toxic BPA” to “gender-bending chemicals found in plastic and linked to breast and prostate cancer are found in 86% of teenagers”.

Yikes. It’s all quite scary. It’s true that right now you can’t really avoid plastic. Look around you and it’s likely that you’ll immediately see lots of plastic objects, and that’s before you even try to consider all the everyday things which have plastic coatings that aren’t immediately obvious. If you have young children, you’re probably drowning in plastic toys, cups, plates and bottles. We’re pretty much touching plastic continually throughout our day. How concerned should we be?

As the Hitchiker’s Guide to the Galaxy says, Don’t Panic. Plastic (like planet Earth in the Guide) can probably be summed up as mostly harmless, at least from a BPA point of view if not an environmental one.

BPA is a rather pleasingly symmetrical molecule with two phenol groups. (A big model of this would make a wonderfully ironic pair of sunglasses, wouldn’t it?) It was first synthesized by the Russian chemist Alexander Dianin in the late 19th century. It’s made by reacting acetone – which is where the “A” in the name comes from – with two phenol molecules. It’s actually a very simple reaction, although the product does need to be carefully purified, since large amounts of phenol are used to ensure a good yield.

It’s been used commercially since the fifties, and millions of tonnes of BPA are now produced worldwide each year. BPA is used to make plastics which are clear and tough – two characteristics which are often valued, especially for things like waterproof coatings, bottles and food containers.

The concern is that BPA is an endocrine disruptor, meaning that it interferes with hormone systems. In particular, it’s a known xenoestrogen, in other words it mimics the female hormone estrogen. Animal studies have suggested possible links to certain cancers, infertility, neurological problems and other diseases. A lot of the work is fairly small-scale and, as I’ve mentioned, focused on animal studies (rather than looking directly at effects in humans). Where humans have been studied it’s usually been populations that are exposed to especially high BPA levels (epoxy resin painters, for example). Still, it builds up into quite a damning picture.

BPA has been banned from baby bottles in many countries, including the USA and Europe

Of course, we don’t normally eat plastic, but BPA can leach from the plastic into the food or drink that’s in the plastic, and much more so if the plastic is heated. Because of these concerns, BPA has been banned from baby bottles (which tend to be heated, both for sterilisation and to warm the milk) in several countries, including the whole of Europe, for some years now. “BPA free” labels are a fairly common sight on baby products these days. BPA might also get onto our skin from, for example, those thermal paper receipts The Sun article mentioned, and then into our mouths when we eat. Our bodies break down and excrete the chemical fairly quickly, in as little as 6 hours, but because it’s so common in our environment most of us are continually meeting new sources of it.

How much are we getting, though? This is a critical question, because as I’m forever saying, the dose makes the poison. Arsenic is a deadly poison at high levels, but most of us – were we to undergo some sort of very sensitive test – would probably find we have traces of it in our systems, because it’s a naturally-occuring mineral. It’s nothing to worry about, unless for some reason the levels become too high.

When it comes to BPA, different countries have different guidelines. The European Food Safety Authority recommended in January 2015 that the TDI (tolerable daily intake) should be reduced from 50 to 4 µg/kg body weight/day (there are plans for a new assessment in 2018, so it might change again). For a 75 kg adult, that translates to about 0.0003 g per day. A USA Federal Drug and Administration document from 2014 suggests a NOAEL (no-observed-adverse-effect-level) of 5 mg/kg bw/day, which translates to 0.375 g per day for the same 75 kg adult. NOAEL values are usually much higher than TDIs, so these two figures aren’t as incompatible as they might appear. Tolerable daily intake values tend to have a lot of additional “just in case” tossed into them – being rather more guidance than science.

The European Food Standards Authority published a detailed review of the evidence in 2015 (click for a summary)

So, how much BPA are we exposed to? I’m going to stick to Europe, because that’s where I’m based (for now…), and trying to look at all the different countries is horribly complicated. Besides, EFSA produced a really helpful executive summary of their findings in 2015, which makes it much easier to find the pertinent information.

The key points are these: most of our exposure comes from food. Infants, children and adolescents have the highest dietary exposures to BPA, probably because they eat and drink more per kilogram of body weight. The estimated average was 0.375 µg/kg bw per day.  For adult women the estimated average was 0.132 µg/kg bw per day, and for men it was 0.126 µg/kg bw per day.

When it came to thermal paper and other non-dietary exposure (mostly from dust, toys and cosmetics), the numbers were smaller, but the panel admitted there was a fair bit of uncertainty here. The total exposure from all sources was somewhere in the region of 1 µg/kg bw per day for all the age groups, with adolescents and young children edging more toward values of 1.5 µg/kg bw per day (this will be important in a minute).

Note that all of these numbers are significantly less than the, conservative, tolerable daily intake value of 4 µg/kg bw per day recommended by EFSA.

Here’s the important bit: the panel concluded that there is “no health concern for BPA at the estimated levels of exposure” as far as diet goes. They also said that this applied “to prenatally exposed children” (in other words, one less thing for pregnant women to worry about).

When it came to total exposure, i.e. diet and exposure from other sources such as thermal paper they concluded that “the health concern for BPA is low at the estimated levels of exposure”.

The factsheet that was published alongside the full document summarises the results as follows: “BPA poses no health risk to consumers because current exposure to the chemical is too low to cause harm.”

Like I said: Don’t Panic.

What about those frankly quite terrifying headlines? Well, firstly The Sun article was based on some work conducted on a grand total of 208 receipts collected in Southeast Michigan in the USA from only 39 unique business locations. That’s a pretty small sample and not, I’d suggest, perhaps terribly relevant to the readership of a British newspaper. Worse, the actual levels of BPA weren’t measured in the large majority of samples – they only tested to see if it was there, not how much was there. There was nothing conclusive at all to suggest that the levels in the receipts might be enough to “increase your cancer risk”. All in all, it was pretty meaningless. We already knew there was BPA in thermal receipt paper – no one was hiding that information (it’s literally in the second paragraph of the Wikipedia page on BPA).

The Telegraph article, and the many others it appeared to spawn, also weren’t based on especially rigorous work and, worse, totally misrepresented the findings in any case. Firstly, let’s consider that headline: “Plastic chemical linked to male infertility in majority of teenagers, study suggests”. What does that mean? Are they suggesting that teenagers are displaying infertility? No, of course not. They didn’t want to put “BPA” in the headline because that, apparently, would be too confusing for their readers. So instead they’ve replaced “BPA” with “plastic chemical linked to male infertility”, which is so much more straightforward, isn’t it?

And they don’t mean it’s linked to infertility in the majority of teenagers, they mean it’s linked to infertility and it’s in the majority of teenager’s bodies. I do appreciate that journalists rarely write headlines – this isn’t a criticism of the poor writer who turned in perfectly good copy – but that is confusing and misleading headline-writing of the highest order. Ugh.

Plus, as I commented back there, that wasn’t even the conclusion of the study, which was actually an experiment carried out by students under the supervision of a local university. The key finding was not that, horror, teenagers have BPA in their bodies. The researchers assumed that almost all of the teenagers would have BPA in their bodies – as the EFSA report showed, most people do. No, the conclusion was actually that the teenagers – 94 of them – had been unable to significantly reduce their levels of BPA by changing their diet and lifestyle. Although the paper admits the conditions weren’t well-controlled. Basically, they asked a group of 17-19 year-olds to avoid plastic, and worked on the basis that their account of doing so was accurate.

And how much did the teenagers have in their samples? The average was 1.22 ng/ml, in urine samples (ng = nanogram). Now, even if we assume that these levels apply to all human tissue (which they almost certainly don’t) and that therefore the students had roughly 1.22 ng per gram of body weight, that only translates to, very approximately, 1.22 micrograms (µg) per kilogram of body weight.

Wait a second… what did EFSA say again…. ah yes, they estimated total exposures of 1.449 µg/kg bw per day for adolescents.

Sooooo basically a very similar value, then? And the EFSA, after looking at multiple studies in painstaking detail, concluded that “BPA poses no health risk to consumers”.

Is this grounds for multiple hysterical, fear-mongering headlines? I really don’t think it is.

It is interesting that the teenagers were unable to reduce their BPA levels. Because it’s broken down and excreted quite quickly by the body, you might expect that reducing exposure would have a bigger effect – but really all we can say here is that this needs to be repeated with far more tightly-controlled conditions. Who knows what the students did, and didn’t, actually handle and eat. Perhaps their school environment contains high levels of BPA in dust for some reason (new buildings or equipment, maybe?), and so it was virtually impossible to avoid. Who knows.

In summary, despite the scary headlines there really is no need to worry too much about BPA from plastics or receipts. It may be worth avoiding heating plastic, since we know that increases the amound of BPA that makes its way into food – although it’s important to stress that there’s no evidence that microwaving plastic containers causes levels to be above safe limits. Still, if you wanted to be cautious you could choose to put food into a ceramic or glass bowl, covered with a plate rather than clingfilm. It’ll save you money on your clingfilm bills anyway, and it means less plastic waste, which is no bad thing.

Roll on Easter…

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The Chronicles of the Chronicle Flask: 2017

We’ve made it! Not only to 2018 (which was starting to look doubtful earlier in the year), but also to the Chronicle Flask’s 100th post. Which doesn’t seem that many, really, but since posts on here frequently run to 1500 words, that adds up to a rather more impressive-sounding 150,000 words or so. I mean, that’s like… half a Brandon Sanderson novel. Oh.

Anyway, it’s time for a yearly round-up. Here goes!

Last January I began with a post about acrylamide. We’d all been enjoying lots of lovely crispy food over Christmas; it was time to tell us about the terrible dangers of such reckless indulgence. The newspapers were covered with pictures of delicious-looking chips, toast and roast potatoes alongside scary headlines such as:  “Crunchy toast could give you cancer, FSA warns”. The truth was not quite so dramatic. Acrylamide does form when foods are cooked to crispiness, and it is potentially harmful, but the quantities which form in food are tiny, and very unlikely to cause you any serious harm unless you literally live on nothing but burnt toast. The FSA (Food Standards Agency) hadn’t significantly revised their guidelines, it turned out, but were in fact only suggesting that the food industry should be mindful of acrylamide levels in food and seek to reduce them as much as possible. That wouldn’t have made for quite such a good “your food is going to killllll you!” story though, I suppose.

In February the spikey topic of vaccination came up. Again. Vaccines are awesome. They protect us from deadly diseases. No, I don’t want to hear any nonsense about “Big Pharma“, and I definitely don’t want to hear how “natural immunity” is better. It’s not. At best, it might provide a similar level of protection (but not in every case), but it comes with having to suffer through a horrible, dangerous disease, whereas vaccination doesn’t. It ought to be a no-brainer. Just vaccinate your kids. And yourself.

It was Red Nose Day in the UK in March, which brought some chemistry jokes. Turns out all the best ones aren’t gone, after all. Did you hear about the PhD student who accidentally cooled herself to absolute zero? She’s 0K now.

April brought a post which ought to have been an April Fool’s joke, but wasn’t. Sceptics often point out that homeopathy is just sugar and water, but the trouble is, sometimes, it’s not. There’s virtually no regulation of homeopathy. As far as I’ve been able to establish, no one tests homeopathic products; no one checks the dilutions. Since a lot of the starting materials are dangerously toxic substances such as arsenic, belladona, lead and hemlock, this ought to worry people more than it does. There has been more than one accidental poisoning (perhaps most shockingly, one involving baby teething products). It really is time this stuff was banned, maybe 2018 will be the year.

In May I turned to something which was to become a bit of a theme for 2017: alkaline water. It’s not so much that it doesn’t do anything (although it really doesn’t), more the fact that someone is charging a premium for a product which you could literally make yourself for pennies. It’s only a matter of dissolving a pinch of baking soda (sodium bicarbonate) in some water.

June brought a selection of periodic tables because, well, why not? This is a chemistry blog, after all! And now we’ve finally filled up period seven they do have a rather elegant completness. 2019, by the way, has just been announced as the International Year of the Periodic Table of Chemical Elements, to coincide with IUPAC’s 100th anniversary and the 150th anniversary of Mendeelev’s discovery of periodicity (his presentation, The Dependence Between the Properties of of the Atomic Weights of the Elements, was made on 6th March 1869). Looks like 2019 will be an exciting year for chemists!

In July it was back to the nonsense of alkaline diets again, when Robert O. Young was finally sentenced to 3 years, 8 months in custody for conning vulnerable cancer patients into giving him large sums of money for ineffective and dangerous treatments. Good. Moving on.

August brought me back to a post that I’d actually started earlier in the year when I went to a March for Science event in April. It was all about slime, and August seemed like a good time to finally finish it, with the school holidays in full swing – what could be more fun on a rainy day at home than making slime? Slime was a bit of a 2017 craze, and there have been a few stories featuring children with severely irritated skin. But is this likely to be caused by borax? Not really. Turns out it’s actually very safe. Laundry detergents in general, not so much. In short, if you want to make slime the traditional way with PVA glue and borax, fill your boots. (Not really – your parents will be uninpressed.)

In September it was back to quackery: black salve. A nasty, corrosive concoction which is sold as a cancer cure. It won’t cure your cancer. It will burn a nasty great big hole in your skin. Do not mess with this stuff.

October carried on in a similar vein, literally. This time with a piece about naturopaths recommending hydrogen peroxide IVs as a treatment for lots of things, not least – you guessed it – cancer. Yes, hydrogen peroxide. The stuff you used to bleach hair. Intraveneously. Argh.

The puking pumpkin!

The end of the month featured a far better use for hydrogen peroxide, that of the puking pumpkin. Definitely one to roll out if, for any reason, you ever find yourself having to demonstrate catalysis.

November brought us, somewhat unseasonally, to tomatoes. Where is the best place to store them? Fridge or windowsill? Turns out the answer involves more chemistry than you might have imagined.

And then, finally, December. Looking for a last-minute Christmas gift? Why not buy a case of blk water? I mean, other than it’s an exorbitantly priced bottle of mysterious black stuff which doesn’t do any of the things it claims to do, and might actually get its colour from coal deposits, that is.

And that, dear friends and followers, is it for 2017! Happy New Year! Remember to be sceptical when the inevitable “deadly food” story appears in a few weeks….

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In the fridge or on the windowsill: where’s the best place to keep tomatoes?

Fresh fruit and vegetables are great, but where’s the best place to store them?

I’ve mentioned before that my Dad is a professional plant-wrangler (if you’ve never read the electric daisies post, do go and have a look – it’s a little-read favourite) and he often brings me home-grown fruit and vegetables.

What follows is an inevitable disagreement about storage, specifically, my habit of putting everything in the fridge.

In my defence, modern houses rarely have pantries (boo) and we don’t even have a garage. We do have a shed, but it’s at the bottom of our poorly-lit, somewhat muddy garden. Do I want to traipse out there on a cold, dark, autumn evening? No, I do not. So the fabled “cool, dark place” is a bit of problem. My fridge is cool and dark, I have argued, but here’s the thing – turns out, it’s too cool. And quite probably too dark.

This I have learned from the botanist James Wong (@botanygeek on Twitter), whose talk I attended on Monday this week at the Mathematical Institute in Oxford. James, it turns out, had a rather similar argument with his Mum, particularly regarding tomatoes.

We should’ve listened to out parents, because they were right. A lot of fruit and vegetables really are better stored outside of the fridge, and for tomatoes in particular “better” actually means “more nutritious”.

Lycopene is a very long molecule with lots of double C=C bonds.

Tomatoes, James explained, contain a lot of a chemical called lycopene. It’s a carotene pigment, and it’s what gives tomatoes their red colour.

Lycopene has lots of double bonds between its carbon atoms which form something chemists call a conjugated system. This has some rather cool properties, one of which is an ability to absorb certain wavelengths of light. Lycopene is especially good at absorbing blue and green wavelengths, leaving our eyes to detect the red light that’s left.

Lycopene absorbs blue and green light, which is why tomatoes appear red.

Tomatoes and lycopene also seem to have a lot of health benefits. There’s some evidence that lycopene might reduce the risk of prostate and other cancers. It also appears to reduce the risk of stroke, and eating tomato concentrate might even help to protect your skin from sun damage (don’t get any ideas, you still need sunblock). Admittedly the evidence is currently a bit shaky – it’s a case of “more research is needed” – but even if it turns out to that the causative relationship isn’t terribly strong, tomatoes are still a really good source of fibre and vitamins A, C and E. Plus, you know, they taste yummy!

But back to the fridge. Surely they will keep longer in the fridge, and the low temperatures will help to preserve the nutrients? Isn’t that how it works?

Well, no. As James explained, once tomatoes are severed from the plant they have exactly one purpose: to get eaten. The reason, from the plant’s point of view, is that the critter which eats them will hopefully wander off and – ahem – eliminate the tomato seeds at a later time, somewhere away from the parent plant. This spreads the seeds far and wide, allowing little baby tomato plants to grow in a nice, open space with lots of water and sun.

For this reason once the tomato fruit falls, or is cut, from the tomato plant it doesn’t just sit there doing nothing. No, it carries on producing lycopene. Or rather, it does if the temperature is above about 10 oC. Below that temperature (as in a fridge), everything more or less stops. But, leave a tomato at room temperature and lycopene levels increase significantly. Plus, the tomato pumps out extra volatile compounds – both as an insect repellant and to attract animals which might usefully eat it – which means… yes: room temperature tomatoes really do smell better. As if that weren’t enough, chilling tomatoes can damage cell membranes, which can actually cause them to spoil more quickly.

In summary, not only will tomatoes last longer out of the fridge, they will actually contain more healthy lycopene!

Anecdotally, once I got over my scepticism and actually started leaving my tomatoes on my windowsill (after years of refrigeration) I discovered that it’s true. My windowsill tomatoes really do seem to last longer than they used to in the fridge, and they almost never go mouldy. Of course, it’s possible that I might not be comparing like for like (who knows what variety of tomato I bought last year compared to this week), but I urge you to try it for yourself.

James mentioned lots of other interesting bits and pieces in his talk. Did you know that sun-dried shiitake mushrooms are much higher in vitamin D? Or that you can double the amount of flavonoid you absorb from your blueberries by cooking them? (Take that, raw food people!) Storing apples on your windowsill is likely to increase the amount of healthy polyphenols in their skin, red peppers are better for you than green ones, adding mustard to cooked broccoli makes it more nutritious, and it would be much better if we bought our butternut squash in the autumn and saved it for Christmas – it becomes sweeter and more flavoursome over time.

In short, fascinating. Who wants to listen to some “clean eater” making it up as they go along when you can listen to a fully-qualified botanist who really knows what he’s talking about? Do check out the book, How to Eat Better, by James Wong – it’s packed full of brilliant tidbits like this and has loads of recipes.

And yes, Dad: you were right.

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Hydrogen peroxide: another deadly alternative?

I’m sure most people have heard of hydrogen peroxide. It’s used as a disinfectant and, even if you’ve never used it for that, you probably at least know that it’s used to bleach hair. It’s where the phrase “peroxide blonde” comes from, after all. Hydrogen peroxide, and its formula, is so famous that there’s an old chemistry joke about it:

(I have no idea who to credit for the original drawing – if it’s you, leave me a message.)

To save you squinting at the text, it goes like this:
Two men walk into a bar. The first man says, “I’ll have some H2O.”
The second man says, “I’ll have some H2O, too.”
The barman brings the drinks. The second man dies horribly.

Now I think about it, it’s not a terribly funny joke.

Hydrogen peroxide has an extra oxygen atom in the middle.

Never mind. You get the idea. H2O2 (“H2O, too”) is the formula for hydrogen peroxide. Very similar to water’s formula, except with an extra oxygen atom in the middle. In fact, naturopaths – purveyors of alternative therapies – often refer to hydrogen peroxide as “water with extra oxygen”. But this is really misleading because, to torture a metaphor, that extra oxygen makes hydrogen peroxide the piranha to water’s goldfish.

Water, as we know, is pretty innocuous. You should try not to inhale it obviously, or drink more than about six litres in one go, but otherwise, its pretty harmless. Hydrogen peroxide, on the other hand, not so much. The molecule breaks apart easily, releasing oxygen. That makes it a strong oxidising agent. It works as a disinfectant because it basically blasts cells to pieces. It bleaches hair because it breaks down pigments in the hair shaft. And, as medical students will tell you, it’s also really good at cleaning up blood stains – because it oxidises the iron in haemoglobin to Fe3+, which is a pale yellow colour*.

Dilute hydrogen peroxide is readily available.

In its dilute form, hydrogen peroxide is a mild antiseptic. Three percent and even slightly more concentrated solutions are still readily available in high-street pharmacies. However, even these very dilute solutions can cause skin and eye irritation, and prolonged skin contact is not recommended. The trouble is, while it does destroy microbes, it also destroys healthy cells. There’s been a move away from using hydrogen peroxide for this reason, although it is still a popular “home” remedy.

More concentrated** solutions are potentially very dangerous, causing severe skin burns. Hydrogen peroxide is also well-known for its tendency to react violently with other chemicals, meaning that it must be stored, and handled, very carefully.

All of which makes the idea of injecting into someone’s veins particularly horrific.

But this is exactly what some naturopaths are recommending, and even doing. The idea seems to have arisen because hydrogen peroxide is known to damage cancer cells. But so will a lot of other dangerous substances – it doesn’t mean it’s a good idea to inject them. Hydrogen peroxide is produced by certain immune cells in the body, but only in a very controlled and contained way. This is definitely a case where more isn’t necessarily better.

The use of intravenous hydrogen peroxide appears to have begun in America, but it may be spreading to the UK. The website, which claims to empower people with cancer to “make informed decisions”, states “The most common form of hydrogen peroxide therapy used by doctors calls for small amounts of 30% reagent grade hydrogen peroxide added to purified water and administered as an intravenous drip.”

30% hydrogen peroxide is really hazardous stuff. It’s terrifying that this is being recommended to vulnerable patients.

Other sites recommend inhaling or swallowing hydrogen peroxide solutions, both of which are also potentially extremely dangerous.

If anyone ever suggests a hydrogen peroxide IV, run very fast in the other direction.

In 2004 a woman called Katherine Bibeau died after receiving intravenous hydrogen peroxide treatment from James Shortt, a man from South Carolina who called himself a “longevity physician”. According to the autopsy report she died from systemic shock and DIC – the formation of blood clots in blood vessels throughout the body. When her body arrived at the morgue, she was covered in purple-black bruises.

Do I need to state the obvious? If anyone suggests injecting this stuff, run. Run very fast, in the other direction. Likewise if they suggest drinking it. It’s a really stupid idea, one that could quite literally kill you.

* As anyone who’s ever studied chemistry anywhere in my vicinity will tell you, “iron three is yellow, like wee.”

** The concentration of hydrogen peroxide is usually described in one of two ways: percentage and “vol”. Percentage works as you might expect, but vol is a little different. It came about for practical, historical reasons. As Prof. Poliakoff comments in this video, hydrogen peroxide is prone to going “flat” – leave it in the bottle for long enough and it gradually decomposes until what you actually have is a bottle of ordinary water. Particularly in the days before refrigeration (keeping it cold slows down the decomposition) a bottle might be labelled 20%, but actually contain considerably less hydrogen peroxide.

What to do? The answer was quite simple: take, say, 1 ml of hydrogen peroxide, add something which causes it to decompose really, really fast (lots of things will do this: potassium permanganate, potassium iodide, yeast, even liver) and measure the volume of oxygen given off. If your 1 ml of hydrogen peroxide produces 10 ml of oxygen, it’s 10 vol. If it produces 20, it’s 20 vol. And so on. Simple. 3% hydrogen peroxide, for the record, is about 10 vol***. Do not mix up these numbers.

*** Naturally, there are mole calculations to go with this. Of course there are. For A-level Chemists, here’s the maths (everyone else can tune out; I’m adding this little footnote because I found this information strangely hard to find):

Hydrogen peroxide decomposes as shown in this equation:
2H2O2 –> 2H2O + O2

Let’s imagine we decompose 1 ml of hydrogen peroxide and obtain 10 mls of oxygen.

Assuming the oxygen gas occupies 24 dm3 (litres), or 24000 mls, at standard temperature and pressure, 10 mls of oxygen is 10 / 24000 = 0.0004167 moles. But, according to the equation, we need two molecules of hydrogen peroxide to make one molecule of oxygen, so we need to multiply this number by two, giving us 0.0008333 moles.

To get the concentration of the hydrogen peroxide in the more familar (to chemists, anyway) mol dm-3, just divide that number of moles by the volume of hydrogen peroxide. In other words:

0.0008333 mols / 0.001 dm3 = 0.833 mol dm-3

If you really want to convert this into a percentage by mass (you can see why people stick with “vol” now, right?), then:

0.833 mol (in the litre of water) x 34 g mol-1 (the molecular mass of H2O2)
= 28.32 g (in 1000 g of water)

Finally, (28.32 / 1000) x 100 = 2.8% or, rounding up, 3%

In summary (phew):
10 vol hydrogen peroxide = 0.83 mol dm-3 = 3%

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Black Salve BS

Historically, people weren’t always careful in the sun.

Summer is fast disappearing in the Northern hemisphere and with it, the sunshine. Which is sad, as we all love a bit of sun, don’t we? Even if it doesn’t always love us, particularly those of us with fairer skin. Sunburn is no fun, but these days we also understand that it’s worse than a couple of days of painfully peeling skin: too much sun exposure can cause cancer.

Unfortunately there’s a whole generation – indeed more than one – who didn’t grow up with parents constantly slathering on the factor 50 (easy-to-use transparent sunscreens with very high SPFs didn’t appear on the market until the 1990s). For some sunburn was a regular part of summer, and those people need to be particularly vigilant for changes which might signify something nasty is going on.

On the plus side, these types of cancer are very treatable, and the outlook is hopeful. Often, the growth can be removed by surgery or even cryotherapy with very little scarring. Even the most dangerous kind of skin cancer, malignant melanoma, has a ten-year survival rate of around 90% with appropriate treatment.

But there’s the key: appropriate treatment. If you notice changes in your skin, especially a mole which is changing in colour or shape, you must see a qualified doctor as soon as you can.

What you should absolutely not do is visit the Black Salve page on Facebook (which I am not linking to for reasons which will be come obvious). This page, so Facebook tells me, is followed by nearly 17,000 users. It features a cheery cover photo of a family holding a canoe over their heads, and its profile picture is a pretty white and yellow flower.

Sanguinarine is a toxic salt extracted from the bloodroot plant. It’s infamous for its ability to destroy animal cells.

It’s all very suggestive of a homely, traditional remedy. The sort of thing your grandma had in her medicine cabinet. Very safe and “natural“. But while black salve might be a traditional remedy, it is anything but safe. Most preparations contain bloodroot, a source of the toxin sanguinarine, which kills animal cells.

Applying bloodroot to the skin destroys tissues and causes the formation of a large, black lump of dead flesh. Eventually this mass, called an eschar, falls off, leaving varying degrees of damage behind (internal use is also not recommended: consuming bloodroot can cause vomiting and loss of consciousness).

Bloodroot is easy to buy. Back in May this year the Good Thinking Society reported that eBay had removed “listings for dangerous cancer ‘cure’” following an investigation. Those listings were for black salve, and this was, of course, very positive news. Except for one thing: whilst listings for black salve were removed (and remain absent), listings for bloodroot were not. At the time of writing, a quick search reveals several bloodroot preparations still for sale.

At the time of writing, bloodroot is easy to find on eBay. The listing confirms that this is prepared from the “rhizome of certified organically grown Sanguinaria conadensis plants”.

Why is this such a bad thing? Because it’s easy to find recipes for making homemade black salve with bloodroot online, and using such mixtures can have truly horrific consequences. Last year the story of a woman who applied it to a basal cell carcinoma on her nose was widely reported. The black salve paste she used did so much damage that she ended up with a large hole in her nose through which she could actually draw air. Photos and video are available online (be warned: it’s gruesome).

Many patients turn to black salve as an alternative to what they imagine will be disfiguring surgery to treat their cancer. But, as in this woman’s case, the paste can do so much damage that far more extensive, reconstructive, surgery is ultimately needed.

Black Salve usually contains bloodroot and, sometimes, zinc chloride – another skin irritant.

It won’t surprise anyone to learn that dermatologists don’t recommend black salve. It can do enormous damage to the surface of the skin, resulting in scarring and a high risk of infection, and it does kill cancer cells along the way. But there is no guarantee that all of the cancerous cells deep within the skin will be destroyed. As a result, patients who’ve attempted to cure themselves may end up with cancerous tissue hidden, and growing, beneath a scar.

In fact, exactly this happened to an otherwise healthy 76 year-old woman in 2006. Her case is described in detail in the journal Dermatology Practical Conceptual – in summary, she refused surgery on a small melanoma on her leg. Instead, she bought black salve on the internet and applied it. A few years later the cancer had spread to her lungs, liver and lymph nodes.

Some people even recommend using black salve on breast cancers but this is, if possible, even worse. It’s highly unlikely that the salve will reach the entirety of a tumour which is beneath the skin. It is likely to do some horribly painful and disfiguring damage along the way, though.

Black salve is particularly popular in Australia, which of course has some of the highest rates of skin cancer in the world. But it’s available in the UK too. One online “herbal medicine” site is openly selling various formulations at prices ranging from £25-£100. Ironically, they describe their “Herbactive” product as “chemical free” (it isn’t, nothing is) and then go onto boast that it “now has a stronger concentration of bloodroot”. Fantastic.

They also sell a product which contains zinc chloride along with bloodroot. They claim zinc chloride is safe. It isn’t. It’s well-known to be a skin irritant, and should never be left in contact with skin.

The Black Salve Facebook page is full of anecdotes and testimonials, but light on evidence.

The Black Salve Facebook page is packed full of anecdotes and testimonials from people who claim to have used these mixtures safely. It’s all interspersed, of course, with the usual “Big Pharma” conspiracy theories. Namely, that the “truth” is being suppressed because there’s “no money in it for the pharmaceutical [industry].”

The irony is that reconstructive surgery is incredibly expensive, and the antibiotics, painkillers and other drugs that are inevitably needed to treat black salve victims aren’t free, either.

Given that Facebook’s community standards page states that: “We remove content, disable accounts and work with law enforcement when we believe that there is a genuine risk of physical harm or direct threats to public safety.” one has to wonder why the Black Salve page is still there. People are actually posting pictures of physical harm. What more does Facebook need?

Please, don’t be tempted to use black salve, or anything containing bloodroot. If you think you have a skin tumour see a properly qualified doctor and follow his or her advice.

It might literally save your life.

Like the Chronicle Flask’s Facebook page for regular updates, or follow @chronicleflask on Twitter. All content is © Kat Day 2017. You may share or link to anything here, but you must reference this site if you do.

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Alkaline water: if you like it, why not make your own?

Me* reading the comments section on the Amazing Alkaline Lemons post (*not actually me)

Alkaline water seems to be a trend at the moment. Not quite so much in the UK, yet, but more so in the US where it appears you can buy nicely-packaged bottles with the numbers like 8 and 9.5 printed in large, blue letters on their sides.

It’s rather inexplicable, because drinking slightly alkaline water does literally NOTHING for your health. You have a stomach full of approximately 1 M hydrochloric acid (and some other stuff) which has an acidic pH of somewhere between 1.5 and 3.5. This is entirely natural and normal – it’s there to kill any bugs that might be present in your food.

Chugging expensive water with an alkaline pH of around 9 will neutralise a bit of that stomach acid (bringing the pH closer to a neutral value of 7), and that’s all it will do. A stronger effect could be achieved with an antacid tablet (why isn’t it antiacid? I’ve never understood that) costing around 5p. Either way, the effect is temporary: your stomach wall contains special cells which secrete hydrochloric acid. All you’re doing by drinking or eating alkaline substances is keeping them busy.

(By the way, I’m not recommending popping antacids like sweeties – it could make you ill with something called milk-alkali syndrome, which can lead to kidney failure.)

Recently, a video did the rounds of a woman testing various bottled waters, declaring the ones with slightly acidic pHs to be “trash” and expressing surprise that several brands, including Evian, were pH neutral. The horror. (For anyone unsure, we EXPECT water to have a neutral pH.)

Such tests are ridiculous for lots of reasons, not least because she had tiny amounts of water in little iddy-biddy cups. Who knows how long they’d been sitting around, but if it was any length of time they could well have absorbed some atmospheric carbon dioxide. Carbon dioxide is very soluble, and it forms carbonic acid when it dissolves in water which, yes, would lower the pH.

Anyway, there’s absolutely nothing harmful about drinking water containing traces of acid. It doesn’t mean the water is bad. In fact, if you use an ion exchange filter (as found in, say, Brita filter jugs) it actually replaces calcium ions in the water with hydrogen ions. For any non-chemists reading this: calcium ions are the little sods that cause your kettle to become covered in white scale (I’m simplifying a bit). Hydrogen ions make things acidic. In short, less calcium ions means less descaling, but the slight increase in hydrogen ions means a lower pH.

So, filtered water from such jugs tends to be slightly acidic. Brita don’t advertise this fact heavily, funnily enough, but it’s true. As it happens, I own such a filter, because I live in an area where the water is so hard you can practically use it to write on blackboards. After I bought my third kettle, second coffee machine and bazillionth bottle of descaler, I decided it would be cheaper to use filtered water.

I also have universal indicator strips, because the internet is awesome (when I was a kid you couldn’t, easily, get this stuff without buying a full chemistry set or, ahem, knowing someone who knew someone – now three clicks and it’s yours in under 48 hours).

The pH of water that’s been through a (modern) ion-exchange filter tends to be slightly acidic.

The water in the glass was filtered using my Brita water filter and tested immediately. You can see it has a pH of about 5. The water straight from the tap, for reference, has a pH of about 7 (see the image below, left-hand glass).

The woman in the YouTube video would be throwing her Brita in the trash right now and jumping up and down on it.

So, alkaline water is pretty pointless from a health point of view (and don’t even start on the whole alkaline diet thing) but, what if you LIKE it?

Stranger things have happened. People acquire tastes for things. I’m happy to accept that some people might actually like the taste of water with a slightly alkaline pH. And if that’s you, do you need to spend many pounds/dollars/insert-currency-of-choice-here on expensive bottled water with an alkaline pH?

Even more outlandishly, is it worth spending £1799.00 on an “AlkaViva Vesta H2 Water Ionizer” to produce water with a pH of 9.5? (This gizmo also claims to somehow put “molecular hydrogen” into your water, and I suppose it might, but only very temporarily: unlike carbon dioxide, hydrogen is very insoluble. Also, I’m a bit worried that machine might explode.)

Fear not, I am here to save your pennies! You do not need to buy special bottled water, and you DEFINITELY don’t need a machine costing £1.8k (I mean, really?) No, all you need is a tub of….

… baking soda!

Yep, good old sodium bicarbonate, also known as sodium hydrogencarbonate, bicarb, or NaHCO3. You can buy a 200 g tub for a pound or so, and that will make you litres and litres and litres of alkaline water. Best of all, it’s MADE for baking, so you know it’s food grade and therefore safe to eat (within reason, don’t eat the entire tub in one go).

All you need to do is add about a quarter of a teaspoon of aforementioned baking soda to a large glass of water and stir. It dissolves fairly easily. And that’s it – alkaline water for pennies!

Me* unconvinced by the flavour of alkaline water (*actually me).

Fair warning, if you drink a lot of this it might give you a bit of gas: once the bicarb hits your stomach acid it will react to form carbon dioxide – but it’s unlikely to be worse than drinking a fizzy drink. It also contains sodium, so if you’ve been told to watch your sodium intake, don’t do this.

If I had fewer scruples I’d set up shop selling “dehydrated alkaline water, just add water”.

Sigh. I’ll never be rich.

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Hazardous homeopathy: ‘ingredients’ that ought to make you think twice

Would you take a medicine made with arsenic? Or deadly nightshade? Lead? Poison ivy?

You’d ask some serious questions first, at least, wouldn’t you? Is it definitely safe? Or, more accurately, are the odds better than even that it will make me better without causing horrible side-effects? Or, you know, killing me?

There ARE medicines that are legitimately made from highly toxic compounds. For example, the poison beloved of crime writers such as Agatha Christie, arsenic trioxide, is used to treat acute promyelocytic leukemia in patients who haven’t responded to other treatments. Unsurprisingly, it’s not without risks. Side-effects are unpleasant and common, affecting about a third of patients who take it. On the other hand, acute promyelocytic leukemia is fatal if untreated. A good doctor would talk this through with a patient, explain both sides, and leave the final choice in his or her properly-informed hands. As always in medicine, it’s a question of balancing risks and benefits.

Would you trust something with no proven benefit and a lot of potential risk? There are, it turns out, a swathe of entirely unregulated mixtures currently being sold in shops and online which clearly feature the substances I listed at the beginning. And more. Because they are all, supposedly, the starting materials in certain homeopathic remedies.

Homeopaths like to use unfamiliar, usually Latin-based, names which somewhat disguise the true nature of their ingredients. Here’s a short, but by no means comprehensive, list. (You might find remedies labelled differently but these are, as far as I can tell, the most common names given to these substances.)

If you haven’t heard of some of these, I do urge you to follow the links above, which will largely take you pages detailing their toxicology. Spoiler: the words “poison”, “deadly” and “fatal” feature heavily. These are nasty substances.

There are some big ironies here, and I’m not referring to the metal. For example, a common cry of anti-vaccinationists is that vaccines contain animal tissues – anything and everything from monkey DNA to dog livers. But many also seem to be keen to recommend homeopaths and courses of homeoprophylaxis – so-called “homeopathic vaccines” – which use bodily fluids such as pus and blood as starting materials.

Now, at this point I’m sure some of you are thinking, hang on a minute: aren’t you always telling us that “the dose makes the poison“? And aren’t homeopathic remedies diluted so much that none of the original substance remains, so they’re just placebos?

Yes, I am, and yes, they are.

Does anyone test homeopathic remedies to make sure there’s nothing in them….?

In THEORY. But here’s the problem: who’s testing these mixtures to make sure that the dilutions are done properly? And how exactly are they doing that (if they are)?

One technique that chemists use to identify tiny quantities of substance is gas chromatography (GC). This is essentially a high-tech version of that experiment you did at school, where you put some dots of different coloured ink on a piece of filter paper and watched them spread up the paper when you put it in some water.

GC analysis is brilliant at identifying tiny quantities of stuff. 10 parts per million is no problem for most detectors, and the most sensitive equipment can detect substances in the parts per billion range. Homeopathy dilutions are many orders of magnitude higher than this (30c, for example, means a dilution factor of 1060), but this doesn’t matter – once you get past 12c (a factor of 1024) you pass the Avogadro limit.

This is because Avogadro’s number, which describes the number of molecules in what chemists call a “mole” of a substance, is 6×1023. For example, if you had 18 ml of water in a glass, you’d have 6×1023 molecules of H2O. So you can see, if you’ve diluted a small sample by a factor of 1024 – more than the total number of molecules of water you had in the first place – the chances are very good that all you have is water. There will be none of the original substance left. (This, by the way, is of no concern to most homeopaths, who believe that larger dilutions magically produce a stronger healing effect.)

What if the sample ISN’T pure water after it’s been diluted?

If you carried out GC analysis of such a sample, you should find just pure water. Indeed, if you DIDN’T find pure water, it should be cause for concern. Potassium cyanide, for example, is toxic at very low levels. The lethal dose is is only 0.2-0.3 grams, and you’d suffer unpleasant symptoms long before you were exposed to that much.

So what if the dilutions somehow go wrong? What if some sample gets stuck in the bottle? Or on the pipette? Or a few dilution steps get skipped for some reason?

Are these largely unregulated companies rigorously quality-checking their remedies?

Well, maybe. It’s possible some producers are testing their raw materials for purity (ah yes, another question: they CLAIM they’re starting with, say, arsenic, but can we be certain?), and perhaps testing the “stability” of their products after certain periods of time (i.e. checking for bacterial growth), but are they running tests on the final product and checking that, well, there’s nothing in it?

And actually, isn’t this a bit of a conflict? If the water somehow “remembers” the chemical that was added and acquires some sort of “vibrational energy”, shouldn’t that show up somehow in GC analysis or other tests? If your tests prove it’s pure water, indistinguishable from any other sample of pure water, then… (at this point homeopaths will fall back on arguments such as “you can’t test homeopathy” and “it doesn’t work like that”. The name for this is special pleading.)

A warning was issued in the U.S. after several children became ill.

Am I scaremongering? Not really. There’s at least one published case study describing patients who suffered from arsenic poisoning after using homeopathic preparations. In January this year the U.S. Food and Drug Administration issued a warning about elevated levels of belladonna (aka deadly nightshade) in some homeopathic teething products. Yes, teething products. For babies. This warning was issued following several reports of children becoming ill after using the products. The FDA said that its “laboratory analysis found inconsistent amounts of belladonna, a toxic substance, in certain homeopathic teething tablets, sometimes far exceeding the amount claimed on the label.”

Now, admittedly, I’m based in the U.K. and these particular teething remedies were never readily available here. But let’s just type “homeopathy” into the (the British high-street pharmacy) website and see what pops up… ah yes. Aconite Pillules, 30c, £6.25 for 84.

What happens if you search for “homeopathy” on the website?

Have you been paying attention lovely readers? Aconite is…. yes! Monkshood! One of the most poisonous plants in the garden. Large doses cause instant death. Smaller doses cause nausea and diarrhea, followed by a burning and tingling sensation in the mouth and abdomen, possibly muscle weakness, low blood pressure and irregular heartbeat.

I must stress at this point that there is no suggestion, absolutely none whatsoever, that any of the products for sale at has ever caused such symptoms. I’m sure the manufacturers check their preparations extremely carefully to ensure that there’s absolutely NO aconite left and that they really are just very small, very expensive, sugar pills.

Well, fairly sure.

In summary, we seem to be in a situation where people who proclaim that rigorously-tested and quality-controlled pharmaceuticals are “toxic” also seem to be happy to use unregulated homeopathic remedies made with ACTUALLY toxic starting materials.

I wonder if the new “documentary” about homeopathy, Just One Drop, which is being screened in London on the 6th of April will clarify this awkward little issue? Somehow, I doubt it. Having watched the trailer, I think it’s quite clear which way this particular piece of film is going to lean.

One last thing. Some homeopathic mixtures include large quantities of alcohol. For example, the Bach Original Flower Remedies are diluted with brandy and contain approximately 27% alcohol (in the interests of fairness, they do also make alcohol-free versions of some of their products and, as I’ve recently learned, they may not be technically homeopathic). Alcohol is a proven carcinogen. Yes, I know, lots of adults drink moderate quantities of alcohol regularly and are perfectly healthy, and the dose from a flower remedy is minuscule, but still, toxins and hypocrisy and all that.

There are cheaper ways to buy brandy than Bach Flower Remedies.

Amusingly, the alcohol in these remedies is described an “inactive” ingredient. It’s more likely to be the only ACTIVE ingredient. And since Flower Remedies retail for about £7 for 20 ml (a mighty £350 a litre, and they’re not even pure brandy) may I suggest that if you’re looking for that particular “medicine” you might more wisely spend your money on a decent bottle of Rémy Martin?

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