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General : Columns : The Elements Last Updated: 12, Nov 2008 - 10:20


Phosphorus - a piddling little element
By Bowser
24, Apr 2004 - 20:29

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It is probably no accident that the scientific symbol for the element Phosphorus is 'P'. This glow-in-the-dark stuff was originally obtained by boiling down enormously large quantities of human urine. That was back in 1675 when an alchemist guy called Brandt made a valuable discovery. Very valuable to him at least - and he did make a lot of money – and not piddling amounts either you might say. At that stage phosphorus was just a novelty item that was toured around to entertain royalty and the masses all over Europe. People came to shows to watch phosphorus glow in the dark. A precursor if you like of the phosphorescent screens that keep people entertained today.

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Safety matches

More useful perhaps was the discovery of how to make matches based on phosphorus. Money drove this too of course and large fortunes were made on the back of the workers who assembled matches in factories that were hellish and dangerous. Phosphorus isn’t called the Devil’s element for nothing. Apart from the obvious dangers of fire and explosion, many workers suffered from a wasting disease that caused their jaws in particular to literally disintegrate. Today’s safety matches are a sure-fire thing though – much safer due to some clever chemical modifications to the original match formula.

Having said that though, I remember as a child experimenting with matches and caps – scraping the heads off matches into a jam jar. A group of wanna-be-explosives-experts – we were gathered inside a small pup tent beheading the phosphor-tips from the matches and scraping cowboy-gun caps into a jam jar. The agreed aim was to make a big bang by gathering together enough explosive material first and then to ignite it with a fuse and watch from a safe distance in the hope of seeing a monstrous explosion, a loud bang and a satisfying puff of smoke and flame. We had failed to obtain any real gunpowder – our fathers had their guns and ammo under lock and key and our plan to dismantle bullets and remove the gunpowder was foiled before it began due to lack of bullets. Luckily we were reduced to mere matches and caps. As we were only eight or nine years old at the time the fact that we were using metal knives to scrape the caps didn’t strike us as being any way dangerous.
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With a 'whoosh' rather than a bang!

The ensuing explosion inside the small tent only had the combined TNT equivalent of two boxes of matches and three rolls of caps. But it caught my young next door neighbour pal full in the face as he bent over the jar scraping vigorously and unfortunately creating some sparks that ignited the mix. It was more of a ‘whoosh!’ sound than a bang. He was an asthmatic kid and, while there was a bit of singeing around the eyebrows and his fringe, the main effect of the mini-explosion was to give him a very serious asthma attack. He ended up in an oxygen tent and later he was sent away to stay with relatives near the sea to assist his recovery. We didn’t see him for weeks afterwards.

The devil’s element it’s called and while the little incident above gives you an idea of its dangerous side it’s a trivial example compared with the phosphorus bombing of Hamburg or Dresden. During the Second World War 37,000 civilians were killed in Hamburg in just one week and another 10,000 missing presumed dead. The idea that one nation could inflict such mass civilian killings on another nation was a relatively new concept at the time. Dropping hundreds of thousands of 30lb phosphorus bombs on a city during calm hot weather had the effect of creating a firestorm. The hot spot at the middle of the city acted like a chimney, creating a partial vacuum due to the hot air rising at the centre. This caused air to be sucked in from the surrounding area at speeds up to hurricane force, literally bowling people along sucking them into the fire too. Molten burning phosphorus dripped from the buildings sticking to anyone it landed on helping to up the death rate quite efficiently. Difficult to imagine scientists sitting around and discussing the efficiency of such weapons of mass destruction as we fondly refer to them today. But call me a bleeding heart if you like – but I don’t like the smell of napalm in the morning.

The name O-Isopropyl methylphosphonofluoridate won’t mean much to you if you’re not a chemist – nor will the chemical formula (C3H7O)P(O)(CH3)F. This is a compound, a colourless liquid, that boils at 147°C with just one phosphorus atom in the middle. It was discovered by scientists researching organo-phosphorus pesticides. But call it sarinand you know what I am talking about. Saddam Hussein used sarin most infamously in 1988 to kill at least 5000 Kurdish villagers of Halabja in Iraq, 250km to the north of Bagdad. This happened near the end of the Iran-Iraq war, when ironically Saddam Hussein was still regarded as an important ally by the US Government. He had been very heavily supported by the USA during this war against Iran – a war in which one million people died - they are still unearthing the bones of victims today. Famous of course was Donald Rumsfeld who shook hands with Saddam Hussein as an ally in 1983. (Incidentally according to a US Senate report, even after the sarin attack, the U.S. Department of Commerce approved shipment of weapons grade anthrax and botulinumto Iraq as late as September 1988! That joke "We know Iraq has WMD because we have the receipts" is not so funny when you see the list of approvals for the shipments.)
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The chemical formula for sarin the notorious phosphorus-based nerve toxin

Rachel Carson’s book Silent Spring announced the real beginning of the environmental movement in the early 1960s. Her eerie description of the silence – the "Silent Spring" of the title – is compelling. She describes a mass wipe-out of birds because of the overuse of agricultural pesticides. Her description of the silence that descended on these rural areas effectively kick-started the environmental movement. The insecticide DDT was the main culprit at the time – not an organo-phosphorus one – but it illustrated some of the dangers of pesticides especially the tendency to be concentrated in the tissues of those of us who live higher up the food chain – birds of prey and humans, for example. Phosphorus in pesticides adds a certain kick. Organo-phosphorus pesticides, like Sarin gas, are nerve toxins. Sheep farmers especially have suffered from exposure to organo-phosphorus pesticides used for dipping their sheep. Some individuals have become super-sensitised to a wide range of chemicals such as perfumes and hygiene products and suffer severe allergic reactions. They have to live almost like ‘the boy in the bubble’ posting notices on their front doors warning that anyone wearing perfume or using deodorants is not welcome to cross the threshold. More recently there has been a switch away from phosphorus-based pesticides to insecticides based on chrysanthemum extracts that are much kinder to humans - but as always there’s a sting in the tail and in this case these pyrethrin insecticides are more deadly to fish and insect life.

The discovery of phosphate detergents also made some people very rich and gave the world really white shirts – a bit like the one that Enda Kenny wore on his election billboards in the run up to the June 2004 election. Something that seemed so motherhood-and-apple-pie-ish– clean clothes and white shirts –– unfortunately also had an environmental sting in the tail. Cleanliness is next to godliness they say, but unfortunately in this case the outpouring of phosphate from our washing machines and dishwashers into the world’s rivers and lakes ended up turning them a distinctly ungodly putrid green. And ‘being green’ in this case was not at all environmentally friendly.

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Colas contain a lot of phosphorus helping to create algal blooms just like this one!
The phosphate pollution problem has been well understood since the early 1970s but even today only a fraction of water treatment works remove phosphorus from their effluent. Needless to say no septic tank system removes phosphorus so – flush and pollute – if you are living the rural idyll, hooked up to that cesspool down the back garden! In Castlebar town though the sewage treatment plant does actually remove the phosphates from the final effluent before discharging it into the river. So we are being nice to the fish. In some countries phosphate detergents are banned altogether. As a consequence the slightly off-colour greyish shirt is a symbol of environmental friendliness, - something akin to using paper bag rather than plastic bags or bringing your shopping bags to the supermarket. So change your mindset about whiter-than-white shirts. A white shirt equals environmental pollution because you have been using phosphate detergents.

Of course the fact that phosphorus was first extracted from Pee – urine is rich in ‘P’ - means that even without detergents we contribute quite a bit of phosphorus to the local sewage works. We’ll say nothing about the ‘number twos’ but suffice to say there’s plenty of P there too. Of course cattle are big P producers – at least 10 times as much as a human and remember there are twice as many cows in Ireland as people so that’s a factor of 20 or more. Tens of thousands of tonnes of phosphorus are ‘produced’ every year by our eight million grass-eating friends – cows, bulls, bullocks, heifers and calves. And they don’t use sewage works either. It’s just plopped straight onto the grass in summer. Or in the winter it’s all stored up in big tanks and spread back out onto the land. You can tell it’s going to rain in rural Ireland by the rattling of slurry tankers up and down the roads. Farmers have a definite preference for spreading slurry when it’s raining – this is because nearby neighbours are more likely to have their windows closed and therefore are less likely to notice the smell and ring up complaining! But the corollary of spreading in the rain is that the slurry is washed off into the nearest stream or river very quickly causing even more pollution.

Because slurry has a lot of phosphorus and nitrogen in it, it is valuable as a fertiliser. But it is very smelly stuff and farmers see it more as a nuisance to be dumped rather than a valuable fertiliser. They have more faith in that nice clean, chemical, no-smell stuff from the 50kg plastic bags. So it’s as if no slurry had ever been spread - and many fields get fertilised twice - once with slurry and once with chemical fertiliser. According to Teagasc and the EPA this has caused a huge build-up of phosphorus in Irish fields. They are now saturated with phosphorus in many of the more intensively farmed parts of the country. As a result ordinary fields are leaking phosphorus out into our rivers and lakes at a fierce rate. So even well away from town sewage, river beds are becoming covered with thick blankets of algae and lakes produce nice harvests of green algae or blue-green bacteria. In an ironic twist sometimes these phosphorus-driven algae and bacteria can themselves turn into toxic substances giving off nerve toxins that are not too far off Saddam Hussein’s sarin in terms of their ability to poison. Dogs lapping around the lake edge are particularly at risk and there are a number of Irish cases of dogs being poisoned by eating algae accumulated along the water’s edge.

Of course there is some good news about phosphorus - you can't live without it. Phosphorus is crucially important in the form of the phosphate compounds that store energy in our bodies – and in pretty much every other living organism too come to that. Every time you take a breath you store energy in phosphate compounds which keep your vital internal organs chugging along. Phosphorus is also very important in the chemical composition of your DNA. And what could be more important than your DNA? So forget the fact that it was first extracted from pee and forget that it's implicated in nerve gases and other weapons of mass destruction, pesticides, poison algae and pollution - you really we can’t live without the ‘devil’s element’ – phosphorus.

Next up: Sulphur – more fire and brimstone

Previous element: Sending up Silicon



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