I love my naturally-occurring pesticide

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99.99%, by weight, of all the pesticides we consume are naturally-occurring.

That’s a pretty amazing statement, isn’t it? It comes from a paper about dietary pesticides that was published in 1990, and referred to the American diet, but it’s almost certainly still not far from the truth – pesticide use, despite what some of the crazier corners of the internet will tell you – hasn’t increased significantly in the last 26 years. The authors of the paper concluded that “the comparative hazards of synthetic pesticide residues are insignificant” and it’s a valid point. Many of these natural pesticides – chemicals which plants use to defend themselves – have never been fully tested, and some of them are actually well-known toxins.

Plants have been on this planet for a very long time, 700 million years give or take, which means they’ve had an awful lot of time to evolve defences. Some of these are physical, like thorns or spines, but chemistry plays a key role.

For example, one of the most common toxins is solanine. It turns up in potatoes which, as any good gardener will tell you, are part of the nightshade family. Yep, like deadly nightshade. But don’t panic, it’s mostly in the parts of the plant we don’t eat, namely the leaves and stems, with only very small amounts found in the skin and virtually none in the flesh.

DO NOT EAT!

DO NOT EAT THESE!

Unless, that is, your potatoes are exposed to light. Then the tubers start producing lots of extra solanine (and another alkaloid called chaconine), as a defence to stop the uncovered tuber from being eaten. At the same time, they produce extra chlorophyll, which causes them to turn green. The chlorophyll is harmless, but the solanine most definitely is not. It causes vomiting and diarrhoea, and can even be fatal – although this is really only a risk for people who are undernourished. Still, if your potatoes have turned green its safest to throw them out, since cooking doesn’t break the toxins down. Even if they’re not green, if they have a bitter taste it’s safest to get rid of them if you don’t want to risk an extended visit to the porcelain throne.

But solanine is just the tip of the lettuce. Capsaicin (the stuff in chillies) also evolved as a defence mechanism to repel and kill insects, and there’s evidence that it may be carcinogenic under some circumstances. 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA) is another chemical which is found in corn, wheat, rye and other grasses and which has been shown to cause carcinogenic changes in human cell lines. Then there are all the various substances in herbs and spices, such as tetradecanoic acid in nutmegpulegone in peppermint, carvacrol in oregano and eugenol in cloves, nutmeg and basil.

But not to panic. None of these chemicals are dangerous in the quantities that we usually consume them. And neither, while we’re here, are the really teeny, tiny amounts of synthetic pesticides that we might be exposed to. So just relax and eat your greens. Well, not if they’re potatoes. You know what I mean.

Anyway, there’s one substance I haven’t mentioned yet, and it’s a biggie – it’s something most of us consume on a regular basis. In fact, it might be the source of over a gram of naturally-occurring pesticide a day, and few of us even give it a thought.

What is it? Coffee. Yes, your daily dose of americano is a veritable cocktail of chemicals. As the dietary pesticides paper points out, “13 g of roasted coffee per person per day contains about 765 mg of chlorogenic acid, neochlorogenic acid, caffeic acid, and caffeine.” A single espresso shot uses about 8 grams of ground coffee, so a mere two shots will take you up to best part of a gram of chemically-goodness, and who restrains themselves to two shots a day?

But there’s good news. Some of these substances could actually be beneficial. Chlorogenic acid appears to moderately lower blood pressureNeochlorogenic acid might actually help to prevent certain cancers, as might caffeic acid (although results are mixed in this case).

caffeine

The world’s most widely-consumed psychoactive drug.

And then, of course, there’s caffeine itself – the world’s most widely consumed psychoactive drug. It has umpteen (technical term) effects not the body, both positive and negative, the most famous being its ability to keep us alert and awake. It’s performance-enhancing and its use was at one point restricted for Olympic athletes, until 2004 when officials decided to remove those restrictions – presumably because they were proving impossible to enforce.

But caffeine didn’t evolve for the convenience of humans, although we have, of course, played our part in farming and selectively-breeding plants. No, it originally evolved to paralyse and kill predator insects. Basically, to stop the plant being eaten which, from the plant’s point of view, is quite important. Interestingly, there’s evidence that it evolved separately in coffee, tea and cacao, suggesting it really is a pretty advantageous thing for a plant to make. But in case you’re wondering, it’s broken down by UV light, which explains why it’s not used as an insecticide spray on other plants.

So, if you’re worrying about pesticides with a cup of coffee in your hand, you can stop. You’re probably consuming more pesticide, daily, than you will get from carrots in your lifetime. Drink up!


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Do you love your naturally-occurring pesticide?

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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. It needs to be pointed out that this outcome was controversial, as this post by The Risk Monger explains. But even that controversy aside, lots of things fall into category 2A, 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 (really, go and read that Risk Monger post). 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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Electric daisies: can a flower really give you a shock?

View from National Herb Centre

Sadly, my garden isn’t quite this big.

My Dad was visiting again the other day, making an absolutely lovely job of our garden as usual (our garden is beautiful, despite the fact that my last bit of flora-based input was sowing some grass seed six years ago), and we took a trip to the National Herb Centre.  This is a wonderful place for a day trip if you’re in North Oxfordshire. Never mind the cafe, playground and interesting plants, it’s worth the trip just for the truly spectacular views.

We had lunch and wandered around the many, many rows of medical plants, dye plants and, of course, herbs.  I had no idea there were that that many types of mint.  I plumped for the chocolate one.  Seriously, it’s a plant that smells of chocolate mint.  How brilliant is that?  I’m hoping for fruits in the form of After Eights.  You never know.

But it was on the way out that things got really interesting.  Dad spotted something and called me over to look at some fairly unprepossessing plants with little round, yellow flowers.  A card described them as ‘electric daisies’ and explained that the flowers, when eaten, produce a sensation of an electric shock, or popping candy, and are used as a treatment for toothache and mouth ulcers.

Acmella oleracea, "electric daisy"

Acmella oleracea, the “electric daisy”

Displaying my usual sort of ‘I wonder what will happen if I just mix this with that’ recklessness, I took a tentative nibble from one side of a flower.  At first, it tasted of nothing so much as, well, pretty much how you might expect the middle bit of a daisy to taste: sort of grassy and mushy.

Then the weirdness began.  A mild prickling sensation quickly developed into full-on tingling, but not big pins-and-needles tingling.  It was a more subtle, evenly spread, effect.  The best way I can describe it is like someone pouring lemon juice all over your tongue, having somehow first extracted the flavour of lemons.  The peculiar, but not unpleasant, sensation persisted for a good ten minutes, and was followed by a strange rush of saliva.  It was most odd.

Spilanthol

The spilanthol molecule.

It turns out that these little yellow flowers (technically, inflorescences) are chock full of interesting chemicals, most interestingly spilanthol which acts on the nerves in the mouth and causes saliva production.  It’s also been shown to be antibacterial and anti-inflammatory, so this plant’s traditional use as a cure for toothache is based on a bit more than some in the ‘it might help and it can’t do any harm, can it’ school of plant remedies.

Interestingly, continuing my ongoing obsession of such things, it’s a chemical that actually does permeate skin, causing a local anaesthetic effect.  And it can also, temporarily, stop muscles in your face from contracting – a bit like botox, but conveniently with less of the deadly toxin-ness.  In fact, someone’s even registered a patent for a cosmetic treatment using spilanthol.

But why on earth has a plant evolved something that eases toothache and gets rid of wrinkles in humans?  Perhaps not surprisingly, from the plant’s point of view, these effects are simply happy accidents.  Spilanthol is a form of biological pest control – in other words it kills off critters that might be silly enough to try and make a snack of electric daisies.  It’s particularly good at killing off yellow fever mosquitoes (mosquitoes eat plants when they’re not annoying you), which is good for both the plant and for humans since these little pests spread such delights as yellow fever and dengue fever.

Acmella oleracea flowers may not exactly give you an electric shock, but they can act as a painkiller, insect repellent and anti-ageing cure.  Having learned a bit more about these little wonders I’m starting to think they might just be the most useful plant ever.  Isn’t nature amazing?

You can buy electric daisies, and their seeds, at the National Herb Centre.  I’m quite tempted to go back for another one actually…

After Waco: why are fertilisers so dangerous?

Yesterday there was news of a huge fertiliser explosion in the town of West, near Waco, Texas and as I write the search for survivors is ongoing.  It’s a dreadful tragedy:  the blast all but destroyed a school and a nursing home a few hundred metres away, and dozens of homes were also levelled.  More than 160 people have been injured and so far twelve have been found dead.

ammonium nitrateAt the moment the full details are still unknown.  Fertilisers have long been associated with explosives, and terrorists have been known to use fertiliser bombs (something I shall not be discussing in more detail for fear the men in dark suits might come knocking), although it seems that there’s no indication of malicious intent in this case.  Obviously factories make fertiliser all over the world, and they don’t all blow up on a regular basis, so clearly something went very wrong at 8pm local time on the 17th of April.

So why is fertiliser such potentially dangerous stuff?  Can we make it safer?

First of all, we should probably clarify what we mean by ‘fertiliser‘ (or fertilizer, for our American cousins).  Actually the clue is in the name; it’s something which makes the soil more fertile.  In essence, anything that’s added to the soil to supply one or more of the nutrients that plants need.  In particular, most fertilisers supply nitrogen.  If you were paying attention at school, you’ll remember that most of the solid stuff in plants actually comes from the air in the form of carbon dioxide (see that wooden table over there? A plant made most of that out of air. Air. How cool is that?)

However, just like us, plants also need to make protein for growth, and to do that they need nitrogen.  Unlike us, they can’t (with a few notable exceptions) get that protein from eating animals or other plants, on account of not having teeth, the ability to move and so on.  Except for triffids and that plant in Little Shop of Horrors obviously.  But good old air is about 80% nitrogen, so surely if they can get the carbon from carbon dioxide from air they can get nitrogen too?

Well, there are a few plants that can do that, but most can’t.  The problem is that the nitrogen in air, N2, has one of the strongest bonds between its atoms.  It’s very difficult to break, which means it doesn’t get involved in chemical reactions very easily.  And since growing is basically one big complicated mix of chemical reactions, plants can’t easily use the nitrogen in the air.  Before we started chucking fertiliser on the soil plants managed of course, because useable forms of nitrogen do get into the soil from natural processes.  But if you want to grow large quantities of crops year after year, you need to provide a bit of a helping hand, and that’s what fertiliser does, whether it comes from a factory or, ahem, the back of a cow.

nitrogenBut, and here’s the thing, it’s that strong, triple, bond in N2 that makes fertilisers potentially explosive.  Because if it takes a lot of energy to break those bonds, then exactly the same amount of energy is released when they’re formed.  There is no way around this: energy cannot be created or destroyed, or made to disappear.  (Not in real life, anyway – Harry Potter and co follow different rules.  But they’re not real.  Sorry.)

Why do things explode?  Essentially an explosion occurs when a chemical reaction produces lots of hot gases, very quickly.  If these gases have nowhere to go, because they’re in an enclosed space, they put immense pressure on their immediate surroundings as they rapidly expand.  Ultimately those surrounding are apt to give way, with a bang. (High explosives, like dynamite and TNT, are a little different – but fertilisers aren’t high explosives, so we’ll save that topic for another day.)

ParticleTheoryCompounds that contain nitrogen have the potential to produce nitrogen gas.  Gases take up a lot more space than solids because their particles are further apart and, as I’ve already mentioned, when that hugely strong nitrogen triple bond forms lots of energy is released.  So there you are, hot (that’s the energy bit) gas.  Lots of it.  Surround it with walls – say in a container in a factory – and you have the potential for an explosion.

The fertiliser in this case appears to have been ammonium nitrate.  This is made by reacting ammonia (if you remember, Fritz Haber figured out how to produce that) with nitric acid.  Ammonium nitrate’s chemical formula is NH4NO3 – so plenty of nitrogen there.  In fact when ammonium nitrate decomposes it forms water vapour, nitrogen gas and oxygen gas (via some nitrous oxide, aka laughing gas, along the way).  Lots of gases.  Lots of heat.

The factory also contained lots of anhydrous ammonia.  Not especially surprising this, since you need ammonia to make ammonium nitrate – this was a fertiliser factory.  Anhydrous just means ‘no water’, in other words pure ammonia, NH3.  The boiling point of pure ammonia is -33 oC, so you have a bit of a problem right there if your cooling systems fail; it will quickly turn into vapour at room temperature.  This vapour is pretty nasty.  You know that smell when you use hair dye or perming solution (if you’re still in the 80s)?  That.  Times a hundred.  It’s toxic and corrosive (it poisons you while damaging your lungs), and environmentally damaging.  Oh yes, and flammable.  Not as flammable as say, petrol, but flammable enough.

Reports are that there was a fire at the plant before the explosion, so it looks as though the ammonia might have caught fire.  Ammonium nitrate isn’t easy to ignite, but if the fire is contained and it’s exposed to sustained heat it’ll start reacting.  It decomposes at about 210 oC and once it’s started it’s very difficult to stop, because the reaction gives out a lot of heat which causes the surrounding material to react, and so on in a catastrophic spiral – something chemists call a runaway reaction – ultimately leading to detonation.

So fertilisers are potentially dangerous because they contain nitrogen in a more reactive form, which plants can use.  There’s nothing you can do to make fertilisers explosion-proof.  You can’t say, put additives in to make them less explosive.  It’s in their nature.  Take away their explosiveness and you take away their ability to act as fertilisers.

Factories, though, should be following detailed safety procedures and have numerous protective backup systems to prevent disasters like this.  We don’t yet know what went wrong here, but let’s hope some serious lessons are learned.