Dangerously Sinthetically Natural

A very silly, if not downright dangerous, opinion that I can hear even too often these days is that natural chemicals cannot be that dangerous, and anyway artificial or synthetic ones are worse for us - by definition.

Let's gloss over the moltitude of natural yet noxious, intoxicating if not deadly substances (capsaicin, jellyfish venom, ethanol, morphine, ricin, amatoxins and many more) for pity's sake.

Lately, the group touting this belief that came to my attention is soap/cosmetic homemakers. I personally have nothing against makin this stuff at home, but I'd really like if those who want to spent a bit of time studying basic chemistry first, before reading manuals that perpetuate the misconception.

Instead, I had to develop a product that meets some objective standards of toxicity, and to achieve that I did my research. For example I found a ponderous document prepared by some EU agency, according to which fatty alcohol ethoxylates - a class of non-ionic surfactants - are about as benign as they can be to humans and environment. Yet according to natural detergentmakers, anything ethoxylated is evil.

There is also an issue of effectivness for natural detergents. Sodium and potassium salts of fatty acids - that's what soap is made of, and it is not that natural either because it is manufactured by alkaline hydrolysis of lipids - are not that effective as detergents. Their limits lie in their very chemical structure, and nothing can be done. That's also why more effective chemicals have been developed (by contrast, the iron-based catalyst used for ammonia production has not changed much since it was invented, because it is effective, relatively cheap, strong and durable).

Chemicals approved by natural enthusiasts appear to be alkyl polyglucosides. Which are nice and renewable ones, sure, but still the product of industrial chemistry; they don't come out of plants as they are (at least in significant amounts).

Another website I saw says that caustic soda should not be used for biodegradable formulations, while sodium carbonate is ok. Oh boy... if you're so deficient in basic chemistry, you'd better stay the hell away from preparing stuff that will come in contact with your skin. Well, if the issue is safety during manufacture, then I can agree sodium carbonate is less dangerous. But biodegradability... sodium hydroxide will react very rapidly with a number of chemicals and thus be destroyed. Unless we're talking about an industrial-size spillage of soda, there are no major problems. And sodium carbonate is the same in this regard. Moreover I suspect that often sodium hydroxide is used as part of a buffer system to control pH of the formulation (we're not talking about heavy-duty industrial degreasers here, but personal care products).

And is sodium carbonate truly a deodorizer? Yes, it can be. It can hydrolize ill-smelling compounds, but mostly it will help to bring into solution the ill-smelling chemicals of acid nature - such as rancid oil. Ammonia will do the same, for example. But ammonia is not nice; surely less than most artificial or synthetic surfactants.

And so on and on, I could make many more examples. My take is use as little as possible of the best chemicals for the job, and be careful how you use them.

On the Sinking of Dispersed Oil

Ah, it looks like I have blog! I had kinda forgotten. I may as well write something here.

A very common misconception is that dispersants cause oil to sink to the sea bottom, thus polluting it. I always found it hard to believe, because oils generally are less dense than water and they will naturally tend to resurface rather than sink. Also, the effect of surfactants alone cannot increase the density of oil droplets above that of water.

So, does oil sink in the first place, and what can be the cause? To answer this question, the book "Understanding Oil Spill Dispersants: Efficacy and Effects - Committee on Understanding Oil Spill Dispersants: Efficacy and Effects, National Research Council - ISBN: 0-309-54793-8, 396 pages, 6 x 9, (2005)" comes handy.

First thing: dispersants disperse oil into minute droplets, that can be transported vertically down the water column. In simple terms, this means that while bulk oil remains on the surface, dispersed oil will reach a certain depth. As usual, many factors determine the depth that oil can reach but an indicative value is around 20 meters. The main driver here is waves.

So, at superficial look the effect of dispersants may appear as sinking the oil. But it is not.

But oil droplets have been observed to sink. That happens when denser than water aggregates with mineral particles are formed. In seawater there always is a certain amount of suspended mineral particles, and if they encounter oil droplets they can form aggregates; the buoyancy of these aggregates depends on the type and amount of oil and type and amount of minerals.

Oil droplet size is also important, and it appears that chemically dispersed oil is actually less prone to sinking than naturally (by wave action) dispersed oil. Also the type and amount of surfactants used to disperse oil has an influence.

In fact there are oil-siking agents designed for the purpose; they are made from sand treated with surfactants to make it oleophilic and thus adhere to the oil; the resulting mixture is stable and denser than water. In any case, intentionally sinking oil is a procedure used seldom if ever these days.

There is another plausible mechanisms for oil sinking I would say. Weathering: after light components evaporate and/or dissolve in water, a very dense residual tar may be left behind and sink to the bottom. Mineral particles can also be incorporated in the tar making it even more dense. I am not sure of what effect dispersants may have on this phenomenon. There are reports of accelerated loss of oil light fractions when using dispersants but no comprehensive studies.

So the conclusion is...  not that much is known. But from what it is known. it appears that dispersants do not generally cause sinking of oil although they may have a more important role in some cases.

Cool Vessel

Looking for other things I stumbled upon this story, which I think is pretty cool:

PacX Wave Glider "Papa Mau" arrives in Australia, setting a new world record!

PacX Wave Glider “Papa Mau”, completed his 9,000 nautical mile (16,668 kilometers) scientific journey across the Pacific Ocean to set a new world record for the longest distance traveled by an autonomous vehicle. Throughout his journey, Papa Mau navigated along a prescribed route under autonomous control collecting and transmitting unprecedented amounts of high-resolution ocean data never before available over these vast distances or timeframes.

And there's more details about the kind of vessel that completed the voyage:

The Wave Glider SV Series are the first unmanned autonomous marine robots to use the ocean’s endless supply of wave energy for propulsion (no manpower, no emissions, no refueling). With its ability to stay out at sea for long durations through all weather conditions, and communicate real-time data from the surface of the ocean, the Wave Glider SV Series is helping to advance mankind’s ability to observe and understand the world’s oceans.

Ain't got much to say about it but it seemed interesting and worth sharing.

Fetid Fluids

Chemists often have to deal with chemicals of unpleasant nature, and fouls smells is a common feature of chemicals. On the other end, some truly dangerous ones, like benzene, have a not unpleasant smell.

Luckily these days I do not have to work with the mean amines or the dreadful mercaptans; in fact surfactants have mild, soapy smells for the most part.

But for reasons that shall remain obscure, I am also working with biodiesel. And that has been a surprise, in negative.

I expected biodiesel to have a mild smell like vegetable oil, but I was wrong. Maybe it's just the particular sample I got that has something wrong, maybe others have better aroma.

This one is evil instead. It smells of stale cheese - or more precisely, of the wooden shelves on which cheese is left to age and become impregnated with the oils and fluids exuding from the cheese.
Then the smell proceeds with vegetable oil effluvia - not the mild ones of clean, fresh oil, but potent vapors of not quide rancid, but almost there, oil.
And to top it off there is a note of sweaty feet, not sharp but pervasive. Lovely, eh?

The other unpleasant stuff I am dealing with is crude oil. It comes in many different varieties, but the ones I have are dark brown in color.

The light crude is not bad, it is a thin liquid that looks like very dirty kerosene and has that kind of hydrocarbon smell.
Heavy crude instead is meaner. It is viscous and sticks inexorably to all surfaces; at room temperature it is not smooth but contains a number of tiny lumps (of heavy hydrocarbons, I surmise).
The smell is not so bad at least, like used motor oil, hydrocarbons well cooked at high temperature while coming in contact with some air.

But I wouldn't like to breathe all day long crude oil vapors: as people who respond to oil spills can attest, it's no fun at all.

Oil Where It Belongs

The other day I noticed on Watt's Up With That a couple of articles about the Deepwater Horizon disaster and related issues.

They interested me because now oil spill combat and remediation is my field of work.

But the position expressed by a good number of commenters left me disturbed. At least a bit.

There are people who seem convinced that, because there are natural seeps of crude oil and there are bacteria able to degrade crude, even gigantic spills are no big deal. A few years and the stuff will be gone, so what's to worry about?

Problem is, the big damage comes from the acute, short-term effects of crude oil. Fish and shrimps are killed or tainted becoming inedible; beaches become covered in oil/tar and unaccessible; coastal vegetation such as mangroves can be destroyed and will take many years to regrow.
Last but not least, power plants and chemical/petrochemical factories near a spillage site may have to shut down because oil-polluted water would foul their heat exchangers.

These are well-known effects and occur in a matter of days after a spillage, and after the damage is done the biodegradation time of spilled oil is a secondary concern.

I understand, really, the frustration with dumb alarmism (like that the Macondo oil spill would destroy all marine life in Gulf of Mexico), but science is not served well by swinging back into minimizing the damage.

The Wonderful World of Surfactants

Surfactants are chemicals with a moltitude of uses. The most known ones are detergents and emulsifiers, but they can be used in many other ways.

One curious aspect is, the surfactant know as sodium dioctyl sulfosuccinate, or DSS or sodium docusate is widely used in oil industry as a modifier for drilling muds and as an ingredient of oil spill dispersants.

But it is also used in medicine as stool-softener laxative and to soften impacted cerumen in ears (although the efficacy of these last preparations seems to be scarce). Ah, the knowledge!

News - Life Ends With Death!

So we have this groundbreaking research: if you already present trombosis' risk factors, sitting still for hours on end can cause the aforementioned trombosis!

How does it correlate with the alarmistic title on Yahoo news:

How window seats can harm you

Well, apparently because:

Prolonged sitting, such as in a window seat of a plane, where someone is less likey to get up and move around, can also increase the risk of DVT.

How could we live without these health warnings? Maybe following the flight comfort suggestions given by the airlines, or common sense!

Am I So Good

Really, am I so good that someone from India decided to use my blog for his/her thesis project?

This student from New Delhi is using this blog's archive of Jan - Feb 2007 for a thesis "on flares".

I'm not offended or anything, but if someone wants to use my work for academic purposes, I'd like to be informed by e-mail.

The March of Knowledge

A new experiment at CERN on the role of cosmic rays in cloud formation demonstrates that... well, we don't know so much about cloud formation yet.

It is likely that cosmic rays play a bigger role that previously thought, and the current view that some trace gases (ammonia, sulphuric acid) alone account for all the condensation nuclei is wrong.

Problem - for some - is, cloud cover is very important for Earth's climate, and current models are based on those assumptions that now seem invalid in the light of these experimental results.

Martian Dreaming

High-resolution images from the Mars Reconnaissance Orbiter have finally demonstrated that there is some water on Mars - or just under its surface.

The water, probably very salty, appears only during the hot season, but life is very stubborn and ingenious, so it is possible (this is my speculation, mind you) that some simple organisms can live on Mars.

This minimal presence of water does not seems of any use for eventual colonization plans, but the existence of extraterrestrial life would be of extreme interest for science.

One of the first questions is, how much biochemistry those eventual bacteria share with terrestrial life?

But in fact the Question Zero would be, is it prudent to organize a mission to take samples of martian life back to Earth? Its behaviour and pathogenic capabilities may be surprising, to use an understatement.

Like Snowflake in a Warming World

The Emperor wrote another rant regarding Al Gore:

He said, and we’re not making this up, that the reason for the heavy snowfall was the warmening of the atmosphere causing additional water vapor that then fell as snow.

Yes. Water vapor turns to snow because of warmening. Make a note, children. If you want to make popsicles, you just pick your favorite juice, pour it in a suitable container and heat the everloving fuck out of it. For quicker results use a blowtorch. It will freeze instantly. Hey, the Algore said so, and if one or both of your parents are fiddy2ers, there is no way in hell they’re going to gainsay their cult leader.

Now, Al Gore is very low on my list of Great People, but Misha here is wrong.

Warmer air can carry more water vapor than colder air, this can be verified with any psychrometric chart, and it also the basic principle of dehumidification operations.

So, the atmosphere of a warmer Earth will contain, on average, more water vapor. More water vapor means more intense precipitations when this vapor condensates.

Can this result in heavier snowfall? Yes, it can, because in some locations the temperature will be low enough to cause the water vapor to crystallize and precipitate as snow.

So, it is counterintuitive, but in a warmer world there can be heavier snowfall. Despite Al Gore and the band of climate catastrophists.

About Abiotic Oil

If you're an avid reder of Internet material, probably you have heard it: abiotic oil, the idea that oil is at least in part produced not by the partial decomposition of organic matter trapped in sedimentary rock (no, NOT whole dinosaurs as per caricature version of the biotic oil theory); rather, oil is produced by reactions between carbon and hydrogen (as carbonate and water) in the presence of iron oxide at the temperature and pressure conditions found in the upper part of the mantle, some 100 km under the surface of Earth.

Now, a cursory search will find a lot of people arguing hotly around the issue, but very few talking of it. More in detail, Internet debates rarely touch the science involved: the explantion of how it may happen that those chemical reactions go in the opposite direction of what we can see at STP (standard pressure and temperature).

The "stock" explanation is that high pressure makes the production of abiotic oil possible, but few details are available. What abounds instead is conspiracy and other whacked-out theories about why abiotic oil is kept hidden, and rants against Big Oil and evolution and Obama etc.

Finally, with some more research I was able to obtain some solid science. One of the main figures in the abiotic oil camp is Vladimir Kutcherov (often misspelled as Kutherov) who is currently working at the KTH Royal Institute of Technology in Sweden. The basic work is laid out in the paper The evolution of multicomponent systems at high pressures: VI.The thermodynamic stability of the hydrogen–carbon system: The genesis of hydrocarbons and the origin of petroleum. This contains theoretical modelling of the H-C system (hydrocarbons) and experimental results from a special apparatus built to investigate reactions at high pressure and temperature. According to this paper, at 50 kbar and 1500 °C, starting only from wet calcium carbonate and iron oxide, alkanes up to C10 and alkenes up to C5 were produced.

Another article dealing with the subject, but with only abstract available, is Methane-derived hydrocarbons produced under upper-mantle conditions.

What to say, Kutcherov does not look like a crank, and his work sound, at least under a cursory examination.

There is a point I'd like to stress, tho: even if abiotic oil is real, and plentiful, it does not mean that it is produced at a rate sufficient to cover consumption; moreover the eventual abiotic oil is predicted to exist at considerable depth, making its extraction difficult, expensive and resource-consuming.

Tolerance and True Dedication to Diversity

Those seem to be the governing principles of today's climate science, really:

It doesn’t get much uglier than this. A stasi-esque master list of skeptical scientists and bloggers, with ratings put together by a “scientist” that rants against the very people he rates on his blog.

Well, maybe not. I suppose you know what a list of indesiderables is used for.
To make easier to kick down their doors at dawn.

Gimme Volume

The whole Deepwater Horizon affair (which now seems to be thankfully close to a massive improvement) brought a lof of discussion about flow rates.

Flow rates from the oi leaks were generally expressed in barrels per day (bpd) and sometimes in gallons per day (gpd). So I went and took a look at American volume units, and holy cow, those are a real mess.

A barrel is... well, it depends: oil barrel - 42 gallons; other barrels may vary. But 42 is not basis 12, nor 2, neither 10: it's just a number pulled out of god-knows-where.

And a gallon? Not related to cubic foot, neither inch - 231 cu. in, what is that?

Same for the barrel, no relation to cubic yard.

Not only Americans use units which are more or less closely equivalent to the British ones (before the tidying up of 1824), but apparently every field of technology over there has its own units.

Yes, that may be because they are more free. But the freedom to complicate things unnecessarily is something I can renounce, really.

But Do Not Call Them Scaremongers

A gem of global warming hysteria from WUWT:

WEST LAFAYETTE, Ind. – Reasonable worst-case scenarios for global warming could lead to deadly temperatures for humans in coming centuries, according to research findings from Purdue University and the University of New South Wales, Australia.

Researchers for the first time have calculated the highest tolerable “wet-bulb” temperature and found that this temperature could be exceeded for the first time in human history in future climate scenarios if greenhouse gas emissions continue at their current rate.

Yeah, "reasonable worst-case scenarios" in "coming centuries". I'm so scared right now.

I can't really fault those who are mad at supposed scientist spewing alarmist crap when, well, supposed scientists DO spew alarmist crap.

The Revenge of the Mead

A second batch of mead is now fermenting in a quiet corner of my home.

For this batch I used yeast recovered from an obscure but fine beer known as Tripel Karmeliet. A starter for the fermentation was simply made with 100 g of honey and 300 ml of water boiled together, to which I added 100 ml of the sugary yeast suspension.

Apparently, the wort was too hot the first time, so the yeast died. But after adding another 50 ml, the telltale tiny bubbles of fermentation appeared in a few hours. Baker's yeast appears more resilient than this variety, and it produces a more vigorous fementation: it is not surprising, considering that that baker's yeast is selected for rapid raising of doughs.

The main batch was made of 400 g of honey dissolved in 1,5 l of water and brought to the start of boil with a sprinkle of dry wild fennel - for aroma. I added another liter of cold water (all Brita-filtered) and allowed the wort to cool nearly to room temperature before mixing in the starter (for a total of 3 liters of water) and transferring the wort to a sanitized fermentation bottle through a filtering funnel.

Finally, I capped the bottle with a piece of aluminium foil and placed it in a corner of the living room, at about 20 °C and away from direct sunlight.

My first batch was made using 1 kg of honey and 4 liters of water for a final sugar concentration around 18 °Bx (assuming 90 °Bx for honey). In this case, the sugar concentration in the wort is only 13 °Bx more or less, for which a final alcohol content by volume 0f 6.5 - 7% can be expected: a lighter and possibly drier mead than the first.

We'll have the first impressions in about one month.

What You Measure

It is a undisputable fact - but not one widely discussed out of skeptical circles - that the number of temperature stations over the world has changed with time, going up and down.

Not only the number of stations has changed, but also their geographical distribution - maps of these changes can be found at Climate Audit. As you can see, station coverage is dense in the USA, Europe, Japan and south-east China, but sparse in Central Asia, Africa, South America and of course the oceans.

So what does it matter, it's still a global temperature record, no?

It is in the sense that we do not have anything better. We are stuck with this, like or not.

However, if we wanted to produce a global temperature record over some extended area (for example, the land owned by a farm) what we need to do is to place calibrated thermometers in a regular grid; record metadata for each station and apply standard data recording and processing techniques for all stations. Hot and cold spots are almost sure to appear, and they should be explained properly before being either ignored or mixed with all other data without any adjustement.

What I wonder is if with all station changes and moves the temperature record of this year is the same thing as the record of fifty years ago. Because we have two different sets of stations (different as location and other conditions), which in part overlap, producing the global record.

What can guarantee that the two sets are measuring exactly the same quantity?

Charles and AGW

Charles and his merry band of groupies are at it again. No, thi isn't a particularly notable thread, but just one I bothered to browse.

The LGF community has been a good one only for a brief period of time, but these days it's just dreadful. Suffocating, abusive and intellectually shallow enforced uniformity of views is the best description I can give.

There, anyone dissenting from the Charles' position on AGW is labelled denier, troll, bigot and automatically, even preemtpively, associated with intelligent designers, anti vaccination folks and the like. Even if the commenter has never touched those subjects.

All skeptical arguments are dismissed as canards and talking points, if not outright lies. Then denigrated as not being real science - without any real explanation of why, for example, the data butchery of Mann's Hockey Stick is more scientific than rebuttals to it.

The global level of discussion is generally abysmal, with only a few commenters reaching nothing better than a good level. Critics to the unending support for AGW are generally so bad to look like cartoonish, caricatural versions of what a knowledgeable skeptic would say.

But enough with the Little Green Groupies. It's nice to pile scorn on them, however there's a much bigger world out there.

It's been all around the blogs from some time, Steve McIntyre has found yet another serious flaw in another of the main ingredients of hockey sticks - the famous Yamal series by Briffa. Other people have exposed the whole story better, so go there if you please.

Charles instead thinks that McIntyre's point is disproven by the fact that he had all the data but took a few years to discover the problem. An intellectual giant that man is.

What I want to add is that falsifying the hockey stick has far-reaching implications. It is not just the most famous piece of evidence of AGW, neither a personal obsession.

To exist, the AGW hypothesis requires a rather stable global temperature followed by a sharp increase with rising concentration of CO2 in the atmosphere during the 20th century. A more variable temperature before that time, and even more so no sharp rise mean the death of the AGW hypothesis.

And not just that. No hockey stick temperature pattern also means that CO2 emissions are not the main temperature driver and that there is little need to worry about catastrophic or runaway global warming. No need to happily submit to carbon rationing, either.

The impact of Yamal's implosion on IPCC's own hypothesis is explained in more detail in this other blog post.

I'd like to close my piece with the quote from Lucia, another climate blogger:

One of the issues that gets lost in the whole “should we trust peer review” articles is this: Peer review is a first pass. In the full peer review process, people read articles. Then the ones who can think for themselves form their own opinions about the articles. They, they tell other people what they think.

A Blimp on the Radar

I am writing this piece offline while I wait for the installation of software on some computers to finish. Yes, IT jobs can be that exciting.

Some days ago my blog-friend Wellington asked me a question about blimps, and that made me think. Apparently there are blimp enthusiasts out there who think that those devices can have a much more widespread use than now.

Instead, I think not, because blimps suffer from a basic but serious physical limitation: air density.

In order to provide buoyancy, a blimp must be less dense than the surronding air. But air is already a low-density fluid, roughly only 1 kg/m3 near the sea level (by contrast, the density of water is 1000 times higher). Even if the blimp were "full" of vacuum, and the mass of the shell and other hardware were trascurable, the most lift that can be provided is of one kilogram per cubic meter displaced.

A blimp with any relevant payload must necessarily be huge, and consequentially cumbersome and slow and very susceptible to wind (because the force exerted by wind is a function of the cross-section of the body). Fixed and rotary-wing aircrafts satisfy the needs for speed, payload and manouvrability much better; their only disadvantage is higher fuel consumption.

However, one use where blimps can be the best choice is for semi-mobile (or semi-fixed) observation and surveillance posts. A crew of a few men – or better, automated sensors – does not require a big payload; the blimp can move around in appropriate patterns slow and steady using little fuel and with little noise. Something that airplanes and helicopters do not do as well.

Hooch Success

The experimented I started a little while ago has finally produced fruit.

Yes, not exactly 2 weeks have passed, but who cares.

The drink I produced is fizzy and has a taste that I cannot honestly define excellent, but is bearable. It is not too sweet and it can improve with time.

Even more important, the hooch is definitely alcoholic. I'd put its strength a little above 10 ABV, which is satisfactory.

Onje last thing tho, how do I get rid of that yeast taste?

Update 26/08: After pondering more attently a big glass of my homebrew, I realized the alcohol content is much lower - around the same of a lager beer, 5% or so. A bit of a delusion, yes, but the buzz is here still.