Galligu and assorted niceties...

Googling for some thermochemical data on calcium sulfide (CaS) I came across a story that illustrates the kind of progress that's been made in terms of protecting the environment (as well as humans and other life forms that inhabit it) from wasteful activities by industrial scale chemistry. The story's main protagonist is a waste product that was generated in large quantities around the turn of the 19^th century, called galligu (a neologism that reflects the black, gooey and stinky nature of that hitherto unknown waste product), in which calcium sulfide features as a prime component. Ironically, my backyard process for producing titanium by means of sulfate boosted thermite reactions generates some calcium sulfide by-product too, albeit in much smaller concentrations and in a dry, fused and much less smelly form (hence my interest in CaS...) Britain has numerous former industrial sites that contain massive deposits of this seriously soil-contaminating waste product (galligu) and we're in a sense still dealing with the legacy of the 'alkali wars'.

The account is that of one of the first industrial chemical processes for the production of a chemical that still today is much sought after: soda ash, aka soda, washing soda, chemically sodium carbonate (Na₂CO₃). Soluble alkali carbonates had previously for centuries been produced only on a medium scale with more artisan methods, in particular the extraction (leaching with water in designated pots) of potash (potassium carbonate or K₂CO₃, from which the English word potassium is derived) from wood, plant or kelp ashes (these ashes are quite literally the calcined remains of plant metabolisms).

But demand for soluble alkali (sodium or potassium) carbonates grew exponentially and fueled the need for an industrial conversion of more readily available soluble sodium sources like sodium chloride (sea salt or kitchen salt) to carbonates.

And so in 1791, the Frenchman Nicholas Leblanc patented a process that could accomplish just that: converting abundantly available sea salt, combined with equally cheap-as-chips limestone, coal and sulfuric acid with some creative chemistry into that prized commodity: soda.

The Leblanc process must go down in history as one of the most polluting and wasteful industrial processes ever to have been put to massive use: this source here claims totally plausibly that:

In 1862, 1,834,000 tonnes of raw material were used to produce just 280,000 tonnes of saleable product, a ratio of more than 6:1. For every tonne of salt used in the process, three tonnes of coal were burned. It is estimated that one million tonnes of coal were burned annually at the height of Leblanc production. Furthermore, it is known that for every tonne of soda ash produced, two tonnes of waste material (galligu) were generated [...]

It's wastefulness would have been more of an economic problem than anything else, if it hadn't been for the extreme smelliness, indeed toxicity of its waste streams, which in those days were quite unceremoniously dumped, mostly where the factories stood.

The galligu itself contains large quantities of calcium sulfide, which due to hydrolysis in the presence of water (galligu is in fact a watery slurry!) generates hydrogen sulfide (H₂S), aka rotten eggs or stink bomb gas. Apart from the repulsive odour, perceptible even in trace amounts, H₂S is also toxic, more toxic in fact than hydrogen cyanide... In today's terms, Leblanc plants and environs must have been some of the smelliest and toxic places in this green and pleasant land! An 1839 suit against soda works alleged:

"the gas from these manufactories is of such a deleterious nature as to blight everything within its influence, and is alike baneful to health and property. The herbage of the fields in their vicinity is scorched, the gardens neither yield fruit nor vegetables; many flourishing trees have lately become rotten naked sticks. Cattle and poultry droop and pine away. It tarnishes the furniture in our houses, and when we are exposed to it, which is of frequent occurrence, we are afflicted with coughs and pains in the head ... all of which we attribute to the Alkali works."

But there's more. Another, this time gaseous waste product of the Leblanc process is hydrogen chloride (HCl), aka hydrochloric acid, spirit of salt or muriatic acid. Incredibly, back then HCl had no real residual value and Leblanc operators gaily pumped this highly corrosive, pungent smelling and toxic gas through smoke stacks straight into the free atmosphere!

Under pressure from legislators, to this problem a rather hasty and half-hearted solution was found by using primitive gas scrubbers which absorbed the HCl into water, thereby obtaining a dilute solution of hydrochloric acid... which was then simply allowed to flow into nearby water streams with predictably deleterious effects on the water's fauna and flora...

And upstream from the Leblanc process lay an equally polluting process: the production of one of Leblanc's feedstocks: sulfuric acid, back then produced mainly by burning pyrite ores (aka fool's gold, FeS₂) that often contained dangerously high levels of heavy metals, among others arsenic, nickel, zinc and chromium...

Not so much later, the Belgian chemist and founder of the Solvay chemical empire, Ernest Solvay, developed a sulfurless means of soda production (the Solvay process) which was overall almost squeaky clean and fairly quickly replaced all Leblanc capacity.

Those who today still believe that G-d's green Earth has an infinite capacity for healing and that it's therefore OK to pollute to one's heart's content should accepts that careless and wasteful (albeit also highly useful) industrial activity can lay waste to large areas of the human environment for decades...

Ferrofluids, Anne Marie Helmenstine and plagiarism...

Upon my many Internet travels I was recently reminded of those strangely behaving paramagnetic fluids, known as ferrofluids or ferroliquids (see a demo below). Easy to make at home, they provide an ideal party trick and something that will enchant young and old. Unfortunately my surfing also lead me to a case of plagiarism so blatant, I haven't seen one like it in a long time...

Google searching a little for ferrofluid, I came across this little hub on home made magnetic fluids, written by a Anne Marie Helmenstine, Ph D, who provides About.com's guide to Chemistry since 2001. The author's 5 page article on ferroliquids is well written and provides a step-by-step approach to safely making your own.

Except, Mizz Anne Marie Helmenstine's method and much of her text isn't really her own. Scrolling down just a little in Google's search results I found another detailed web page describing the home production of such ferrofluids, at Sci-Spot.com and which clearly provided the inspiration, to put things very, very mildly, for Helmenstine's piece.

Anne Marie Helmenstine, "Ph D", has lifted entire passages from Sci-Spot.com's original text, almost verbatim. Read both texts in parallel and see for yourself. You'll also conclude that Anne Marie has probably never ever actually conducted a ferrofluid experiment in her life: the only photo of a ferrofluid in action is a photo lifted from Wiki (but with credit at least). For someone making a living from writing a science column, that's truly appalling and amounts to intellectual property theft, nothing less.

Please don't also forget that About.com generates web content, in this case provided by a paid writer, because said web content provides advertising space and revenue for About.com... that, and that alone, is their raison d'être.

What's more, she could have avoided all this simply by proving proper credit to Sci-Spot.com, she chose not too. Of course being a purely commercial resource, About.com would rather be seen dead than sporting a non-paid external link, so screw Sci-Spot.com, who, after all, are they? Something somewhat similar happened to me sometime ago and I didn't feel happy about it either...

Edit: Lauren Leonardi (Manager, Guide Operations, About.com - see comment section of this blog post) claims Hemelstine does link to Sci-Spot.com. Well, I'll take her word for it but cannot find this link.

Mizz Helmenstine's condescending defense of her actions, presented at Sci-Spot.com as a reply to one of their emails, is also worth noting:

"Yes, your article is one I read when I wrote that tutorial. It was not, however, the only one, and I haven't copied you...

You haven't been plagiarized. You have a one-page recipe for a ferrofluid. I have a 5-page resource, with background information and information on what to do with a fluid. I think it's obvious I didn't lift your text.

Best wishes,
Anne Helmenstine, Ph.D.
About Chemistry"

A 5-page resource... as opposed to a measly 1 page recipe... I challenge anyone to tell me what exactly About.com has added to Sci-Spot.com's original content that isn't simply advertising space and some irrelevant fluff. No, Anne Marie Helmenstine, the lifting is so obvious it's blinding and you're the empress with no clothes on (perish the thought...) Helmenstine strikes me as one of these people that, when faced with personal and genuine criticism, would retort: "Do you know who I am?"

I wonder if About.com has a page about plagiarism...

Sci-Spot.com's response to all this, to invite readers of their web page to contact Anne Marie, is of course a plaster on a wooden leg. They should sue About.com, period.

Update:

The plot thickens somewhat. Because I want to make some ferrofluid too but having no OTC source of oleic acid, one of the vital ingredients in the mix, I decided to make oleic acid by extracting it from its source material, olive oil, via alkaline route. I envisaged a purification step that involves converting the oleic acid to ammonium oleate and decided to Google a bit to see if I could find some more information on this substance.

On page 3 of Google.co.uk's search results for ammonium oleate I found in positions #23, #24 and #25 (at the time of writing) three texts that all share entire sections with Helmenstine's About.com piece and Sci-Spot.com ferrofluid page:

This one cites Helmenstine's piece, but in a strange twist uses the same format as Sci-Spot.com:

Mentoring Advanced Placement

This text here is basically identical to Helmenstine's piece but doesn't cite it:

How to Make Liquid magnets - Introduction

And this one lifts selectively, without citation:

ferroliquid (liquid magnet) (scroll down a bit from top).

This now really begs the question: which is the actual source text? Mentoring Advanced Placement can be excluded as they have at least the courtesy of citing their source (Helmenstine). But whether Sci-Spot.com's claim that Helmenstine's piece lifted theirs holds up to scrutiny isn't clear because it's impossible to establish whether they really were the trailblazers here or whether the phy.hr web page really provided the original information and Sci-Spot.com failed to cite that text. The phy.hr pdf version makes no claims to originality but cites no source at all.

The pdf version of the AP Mentoring web page however is quite revealing: part of the pdf document is simply Sci-Spot.com's web page converted into the pdf format. And in the middle of page 2 of the AP Mentoring pdf there's a bizarre link that compounds Helmenstine's About.com page with Sci-Spot.com's page...

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On a lighter note, watch this highly arty demo with sophisticated use of a ferrofluid (turn on the audio). Art, electromagnetism and fluid mechanics all rolled into one. Creepy, isn't it?