Quite likely it is even more complicated.  The bubbles return light to the 
surface, but this could cause a surface layer to see more intense light than 
normally.  (Rather than vanishing at depth, light that makes it through the 
first thin layer, returns from below and passes through the same layer a second 
time.  So it is darker a few feet down and brighter higher up. How this affects 
the eco-system is anybody’s guess.  The problem with many of these options is 
that they locally look just fine.  They only have impact because they operate 
on a large scale.  But they typically will have more impacts than just the one 
which is desired.

From: <[email protected]> on behalf of Franz Dietrich Oeste 
<[email protected]>
Reply-To: "[email protected]" <[email protected]>
Date: Monday, April 3, 2017 at 7:04 AM
To: "[email protected]" <[email protected]>, geoengineering 
<[email protected]>
Subject: Re: [geo] Low intensity geoengineering – microbubbles and microspheres

Dear All,

Microbubbles and microspheres to brighten the oceans surfaces - brilliant idea?

My answer is No. This idea will not work because the bubbles reflect sunlight. 
Just this sunlight phytoplankton needs to fix CO2 by assimilation. What is the 
consequence of this? At least a faster increase of the CO2 concentration in the 
atmosphere. Additional severe consequences to the oceanic ecosystems. For 
instance: because phytoplankton is the basis of the oceanic food chain any 
reduction of phytoplankton mass will have negative consequences on the oceanic 
food web; coral reefs might die away because they need sunlight to live.

All best,
Franz

------ Originalnachricht ------
Von: "Andrew Lockley" 
<[email protected]<mailto:[email protected]>>
An: "geoengineering" 
<[email protected]<mailto:[email protected]>>
Gesendet: 03.04.2017 15:03:46
Betreff: [geo] Low intensity geoengineering – microbubbles and microspheres

Old but brilliant - A

https://www.google.com.au/amp/s/bravenewclimate.com/2011/10/08/low-intensity-geoengineering-microbubbles-and-microspheres/amp/

Low intensity geoengineering – microbubbles and microspheres
[https://secure-gravatar-com.cdn.ampproject.org/ii/w82/s/secure.gravatar.com/avatar/66d42919adcf3f34221f7a7c94745cfe?s=24&d=identicon]
 Barry Brook
5 years ago

[https://bravenewclimate-files-wordpress-com.cdn.ampproject.org/i/s/bravenewclimate.files.wordpress.com/2011/10/jm.jpg?w=354&h=244]<https://bravenewclimate.files.wordpress.com/2011/10/jm.jpg>Guest
 post by John 
Morgan<http://en.search.wordpress.com/?q=%22John+Morgan%22+site:bravenewclimate.com&t=comment>.
 John runs R&D programmes at a Sydney startup company. He has a PhD in physical 
chemistry, and research experience in chemical engineering in the US and at 
CSIRO. He is a regular commenter on BNC.

A 9-page printable PDF version of this post can be downloaded 
here<https://bravenewclimate.files.wordpress.com/2011/10/jm-low-intensity-geoengineering.pdf>.

———————————–

Crazy talk

Geoengineering is crazy. The sheer scale of the aspiration speaks of hubris. 
Terraforming the planet by pulling down billions of tonnes of carbon dioxide, 
or pushing millions of tonnes of plastic up into orbit is absurd. The material 
intensities and costs are ridiculous.

And yet, with no deep cuts in emissions in evidence, with atmospheric CO2 at 
390 parts per million<http://co2now.org/> and climbing at a rate of about 2 ppm 
a year, our “safe” working level of 350 ppm is rapidly disappearing in the rear 
view mirror even as we’re pushing the pedal harder to the floor. We do a lot of 
crazy things.

But what if there was a geoengineering approach that used no materials, almost 
no energy, works at sea level, with cheap technology we could start deploying 
at scale today?

That’s exactly what Russell Seitz at Harvard is proposing. In this post I want 
to look at his idea of increasing the reflectivity of the oceans with tiny 
microbubbles, It’s a fascinating, low impact concept, though not without some 
challenges. So I’ll also propose a different means to the same end that 
addresses these issues, and of course has some of its own. Then we can talk 
about how crazy it all is.

Bright Water

In a remarkable 
paper<http://dash.harvard.edu/bitstream/handle/1/4737323/Seitz_BrightWater.pdf?sequence=1>
 published just over a year ago – which I highly recommend reading – Seitz 
proposed injecting microbubbles of air into seawater, effectively creating an 
“inverse cloud”. Sunlight is scattered back into space from these bubbles. This 
concept has no material inputs, bubble sparging equipment is cheap and low 
power, and could be installed on ships already travelling the worlds waterways.

We don’t need to launch giant lenses into 
space<http://en.wikipedia.org/wiki/Space_sunshade> or build giant balloon 
tethered pipelines to the 
stratosphere<http://en.wikipedia.org/wiki/Stratospheric_sulfur_aerosols_%28geoengineering%29>.
 We have a much more down to earth delivery system already in place, in the 
form of more than 10 000 ships at sea, 1300 working oil rigs and many thousands 
of retired platforms (3500 in the Gulf of Mexico alone) not to mention islands 
and suitable coastlines.

[https://bravenewclimate-files-wordpress-com.cdn.ampproject.org/i/s/bravenewclimate.files.wordpress.com/2011/10/jmf11.png]<https://bravenewclimate.files.wordpress.com/2011/10/jmf11.png>
It’s the little bubbles of nothing that make it really something

The appeal of this technique comes from the fact that you only need very small 
bubbles to scatter light. Leveraging the cube law relationship for volume gives 
you a lot of scattering power if you can make really small bubbles. The air 
from a single 1 cm bubble, could fill a trillion 1 μm bubbles.

Seawater naturally contains up to 1 ppm by volume of air as larger bubbles – in 
the 10-100 μm range. Their reflectance can be measured, but is so small as to 
be irrelevant to the Earth’s energy balance. But if this quantity of air were 
broken down to 1 μm bubbles, there would be a million more of them, and Seitz 
estimates the backscattered light would amount to several watts per square 
metre. That’s some serious power.

Light scattering from small spherical particles is calculated using Mie 
theory<http://en.wikipedia.org/wiki/Mie_theory>, a fairly horrendous piece of 
mathematical machinery. Seitz reports Mie theory scattering results 1 μm radius 
bubbles at various concentrations. At 0.2 ppm of air in water as 1 μm radius 
bubbles, the albedo (reflectivity) increase is 1%, equal to the current CO2 
forcing (Figure 2).

This is an astonishing result: global warming is fully offset by 0.2 parts per 
million of 1 μm bubbles! Using the IPCC mid-range climate sensitivity of 0.7 K 
per Wm-2 the global average temperature would decrease by about 1 degree, more 
than the 0.74 K warming seen in the 20th century.

The NCAR CAM3.1 climate model was used to look at the effect of 1 ppm of 1 μm 
bubbles in a 780 ppm CO2 scenario – double our current CO2 level. Under this 
extravagant CO22 burden the model nevertheless indicated a cooling of 2.7 K 
[Seitz 2010; Figure 5]. So microbubbles really could be a powerful engineered 
response to climate change, if we can deploy them.

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Not so fast

But won’t these bubbles just bubble up to the surface and burst? Not the small 
ones, it turns out. The velocity of a rising bubble is readily calculated (from 
the Stokes equation<http://en.wikipedia.org/wiki/Stokes%27_law>), and a one 
micron radius bubble takes about 5 days to rise a metre. With near-surface 
mixing they’ll be there for a while.

No, the real problem is that the bubbles want to dissolve. The air inside a 
bubble is at a higher pressure than the water it floats in, because surface 
tension is trying to pull the surface inwards, and the air is compressed. The 
pressure increase (given by the Young-LaPlace 
equation<http://en.wikipedia.org/wiki/Young-Laplace_equation>) is greater the 
smaller the bubble, and can be surprisingly large. For a 1 mm diameter bubble 
in seawater, the internal pressure is almost 3 atmospheres greater than the 
water outside.

At these high pressures the air bubble will rapidly dissolve, even in water 
that is saturated with air at sea level. Unstabilized 10 μm bubbles in seawater 
are observed to dissolve in about 10 seconds. However, as Seitz describes, some 
seawater bubbles are much more durable, being stabilized by adsorption of 
natural surfactants and small particles on their surfaces. These materials form 
incompressible surface films that balance the pull of surface tension, and 
stabilized bubbles in the micron size range have been 
observed<http://www.sciencemag.org/content/213/4504/209.full.pdf> to last for 
20-30 hours.

So the key to the bright water concept is increasing the lifetime of these 
bubbles by ensuring that they are stabilized somehow. I’ll discuss some 
possible strategies for this below.

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I’m forever blowing bubbles

– Doris Day, On Moonlight Bay

Another problem is generation of microbubbles. Making large bubbles is easy. 
Making small bubbles is hard. To make 1 micron bubbles requires we pressurize 
air to three atmospheres. We could try to do this by pushing high pressure air 
through one micron holes. But in practice surface tension effects cause bubbles 
to stick to the hole and continue to inflate to much larger sizes.

Seitz presents an image of a tank filled with micron scale bubbles generated by 
a commercial bubbler system (Figure 1). However, I harbour a degree of 
scepticism for manufacturer claims of bubble sizes especially below 10 μm, and 
from the images presented it appears the lower 10 cm has cleared in 120 s, 
suggesting (from the Stokes equation) that the bubbles are of the order 20 μm, 
consistent with my expectations for this kind of technology.

We could instead inject air into a high shear mixer and break large bubbles 
down to smaller ones, like shaking up a bottle of soapy water. Here we are 
relying on turbulence to transiently generate 3 atmospheres of pressure 
throughout the mix. To do this by, say, shaking a drink bottle, you’d need to 
generate ~150 g acceleration as you shake. Vortex mixers can do this, but it is 
obviously an energy intensive process. Seitz calculates the energy cost of 1 
micron bubble production to be ~1 kW hr m-3 of air, a theoretical limit which 
is unlikely to be obtained in practice.

Seitz estimates that to sustain a bubble concentration of 0.5 ppm bubbles (1 mg 
m-3) in the top 10 m of the ocean would require the injection of 50 million 
tonne of air a year, if bubble stabilization for 20 hours could be achieved. 
Ignoring fixed structures and coastline, 10 000 ships would have to disperse 
about 11 000 m3 of air a day. Each ship would need to generate 11 MW hr a day 
for bubble generation, requiring 0.5 MW of dedicated generation.

This is obviously a big ask. We can reduce the scale of the task by being more 
targeted about where and when we generate bubbles – by restricting deployment 
to the tropics where the sun is nearly overhead, rather than the high latitudes 
where the sun is low in the sky, and by timing bubble generation for daylight 
hours only.

Armwrestling thermodynamics

The biggest purely technical problem with the bright water idea is that bubbles 
are thermodynamically unstable due to their high internal pressure, with quite 
short lifetimes. An air bubble with 3 atmospheres internal pressure will 
dissolve in water saturated with air at only 1 atmosphere. And the smaller the 
bubble gets, the faster it dissolves. As observed above, a 10 μm bubble in 
seawater lasted 10 
seconds<http://www.sciencemag.org/content/213/4504/209.full.pdf>. A 1 μm bubble 
would presumably last a fraction of a second.

How can we fight this? Well, I can think of a few different ways. We could try 
to make the bubble surface impermeable to air. Surfactants can improve the 
barrier properties of surfaces to some kinds of molecular species. Phospholipid 
bilayers, for instance, are impermeable to water. Unfortunately, they do not 
present a significant barrier to nitrogen or oxygen molecules, which are 
soluble in these surfactant layers. I don’t believe targeting the barrier 
properties of bubbles will be successful.

A second approach is to load the bubble surface with a raft of fine particles 
or proteins, which can support the two dimensional compressive load from 
surface tension, taking the pressure off the air, rather like a microscopic 
diving bell. This behaviour is observed in seawater bubbles. The long lived 
small bubbles reported by Johnson and Cooke were observed to be stabilized by a 
shell of adsorbed matter (Figure 3).

Could this be a viable strategy for bubble stabilization? I don’t think so. 
Johnson and Cooke report only “some” of the seawater bubbles they observed 
behaving this way, so we know the yield of stabilized bubbles in natural 
seawater is small. Stabilizing agents such as surfactants, and surface active 
proteins – could be added to the water, but the material input would be 
enormous and capture by low bubble concentrations hopelessly inefficient. And 
the observed lifetimes are still only about 20 hours.

A third strategy is to apply a bit of thermodynamic jujitsu by adding a trace 
of an insoluble gas to the air, and use the bubble shrinkage against itself. As 
the bubble shrinks, the insoluble gas remains, and the partial pressure of the 
soluble gasses drops faster than the internal pressure rises. The bubble 
eventually stabilizes at a smaller size.

Hydrogen is not very soluble in water. If 1% hydrogen were added to the air of 
a 5 μm bubble, air leakage would be nearly arrested before it got to 1 μm.

This approach is actually used in medical ultrasound imaging, where stabilized 
microbubbles are employed as acoustic contrast agents. The insoluble gases 
favoured are perfluoroalkanes. These are more insoluble than hydrogen, and we 
have performance data for this system.

The lifetime of these bubbles in blood is short – a half life of 1.3 minutes 
for one lipid stabilized perfluoroctane bubble 
product<http://www.fda.gov/downloads/AdvisoryCommittees/CommitteesMeetingMaterials/Drugs/CardiovascularandRenalDrugsAdvisoryCommittee/UCM254502.pdf>.
 This does not bode well for bubble geoengineering. These ultrasound contrast 
agents represent the best that we can do now, under ideal conditions – a small 
volume, high value cost-no-object pharmaceutical product that can bear the 
expense of exotic very insoluble gasses and sophisticated lipid encapsulation 
stabilization strategies – and they still dissolve after a few minutes (Figure 
4).

In the end, thermodynamics always wins.

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Watercolours

Is there another way to look at this? The Achilles heel of the hydrosol 
approach is the short bubble lifetime. But are there other ways to brighten 
water? Are there any other micron sized light scattering particles cheaply 
available in prodigious quantities, which float in water and don’t dissolve?

It turns out the answer is yes. Synthetic latex is produced on a huge scale – 
1010kg in 
2005<http://books.google.com.au/books?id=3CdgNiBrHfIC&pg=PA43&lpg=PA43&dq=cost+of+bulk+synthetic+latex&source=bl&ots=X5hv6DcDeR&sig=48ZERM5d3UWtW2yZ4NDtjhiKriU&hl=en&ei=5iGITuPBHayUiQeAwe2jDw&sa=X&oi=book_result&ct=result&resnum=5&ved=0CDoQ6AEwBA#v=onepage&q&f=false>.
 A latex is a dispersion of polymer microspheres in water (Figure 5). The 
particle size is typically around 0.1 – 0.5 μm. The polymer content is high – 
about 50% by weight. And its cheap – a bit over a dollar per kilo 
wet<http://books.google.com.au/books?id=3CdgNiBrHfIC&pg=PA43&lpg=PA43&dq=cost+of+bulk+synthetic+latex&source=bl&ots=X5hv6DcDeR&sig=48ZERM5d3UWtW2yZ4NDtjhiKriU&hl=en&ei=5iGITuPBHayUiQeAwe2jDw&sa=X&oi=book_result&ct=result&resnum=5&ved=0CDoQ6AEwBA#v=onepage&q&f=false>.
 It looks like a bright white opaque liquid, like wood glue, which is a 
polyvinylacetate latex. Its a bulk commodity used in adhesives, paper coatings, 
paint and many other applications.

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The common polymers are acrylates, polystyrene and its copolymers, PVA, and 
others. These polymers themselves are inert and non toxic. Whether they present 
any physical risk to the biota needs to be determined but given the small 
particle size and low concentration in a milieu already loaded with natural 
micro- and nanoparticles it seems low risk. The main safety concern in my 
opinion would be any residual monomers, which are toxic. But these can be 
eliminated, certainly to the point where these materials can be safely 
unleashed on the public as paints and glues.

The chief virtues of latex particles over bubbles is they don’t dissolve, they 
don’t coalesce, they are durable, and they can be made much smaller. They have 
a density of just over 1 g cm-3 so they sink, but at 0.2 micron the 
sedimentation velocity is too slow to matter. This presents a different problem 
– the chief loss mechanism now is not dissolution but loss by convection to 
deeper waters. Is there some way to keep these particles afloat?

I think there is. Most of these latex polymers, polystyrene, for example, are 
hydrophobic – they’re water repellent. To keep the particles in suspension 
requires added surfactants, or putting electrically charged groups on the 
surface. But when diluted with salt water, both these stabilization mechanisms 
fail. Without stabilization a polystyrene sphere will attach to the water 
surface. Breaking waves will drive them under, but rising bubbles will scavenge 
them back to the surface again. This mechanism is well known and extensively 
studied in the mineral separation process of flotation, where particles of 
mineral ores are recovered from slurries by attachment to rising bubbles. The 
natural bubble population from breaking waves could keep even submicron 
particles concentrated at and near the ocean surface (Figure 6).

The use of latex technology opens other doors for engineering particle 
properties. For instance, rather than producing a particle composed of a single 
polymer, its possible to construct a particle with two different polymers in a 
core-shell morphology, or even hollow particles. Such particles can have much 
higher scattering power than simple spheres, and are also made in bulk at 
commodity prices. Indeed, they are used as opacifiers in paint.

We could paint the oceans white.
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Figure 6. Latex particles adsorbed on the surface of an oil droplet. Similar 
behaviour would be observed at the air-water interface.

Painting by numbers

Lets run the numbers on this and ask, what would it take to reverse current 
warming? First we need to know how much light these particles scatter back to 
space. I used Mie theory<http://omlc.ogi.edu/calc/mie_calc.html> to analyse 
scattering of 500 nm wavelength light (roughly the solar peak) from 0.1 μm 
diameter polystyrene spheres, as if the sun were overhead. The back scattering 
from these very small particles is intense – 42% of overhead light returns to 
space. And this is just direct scattering. Some of the light that scatters 
forward will scatter off a second particle, and a third. Multiple scattering 
will see more than 42% of light returned to space.

[https://bravenewclimate-files-wordpress-com.cdn.ampproject.org/i/s/bravenewclimate.files.wordpress.com/2011/10/jmf7.png]<https://bravenewclimate.files.wordpress.com/2011/10/jmf7.png>

Since these particles attach to the surface, lets consider, for the moment, a 
monolayer on the water surface. This requires 1014 particles per square metre, 
with a volume of 5.2×10-8 m3 per m2 (or 5 parts per billion of the top 10 m, 
for comparison with Seitz’ figures). Polystyrene has a density of 1050 kg m-3, 
so that’s a mass of 55 mg m-2. Over 3.16×1014 m2 of ocean that’s 1.7×1010 kg 
polymer.

What would this do to the earth’s energy balance? Average insolation 
(accounting for cloud cover [Jin et al. 2002, cited by Seitz]) is 239 Wm-2. The 
monolayer cross sectional area fraction is pi/4. So the energy returned by 
direct overhead scattering is about 78 W. That’s huge compared to the current 
CO2 forcing of about 2.25 Wm-2.

Modelling reported by Seitz indicates an increase of ocean albedo of 0.05 
translates to an increase of planetary albedo by 0.031 [Seitz 2010; Figure 5]. 
So I’ll assume planetary albedo increase is 60% of the ocean albedo increase, 
which means we need ocean backscattering of 3.75 Wm-2. We would only need 4.8% 
of a monolayer to offset current CO2 forcing (ignoring the contribution from 
multiple scattering).

4.8% of a whole ocean monolayer is 8.3×108 kg of dry polymer, or about 1.7×109 
kg wet latex. At say $1.20 per kg, this would cost $2.0 billion and account for 
17% of 2005 global production capacity.

This is, surprisingly, well within reach. $2.0b to reverse global warming is 
cheap. Restricting dispersal to the mid latitudes where the greatest effect is 
achieved, using core-shell latex technology, and properly accounting for 
multiple scattering would see this cost drop even further. Annual growth in 
latex production grew organically by 4.5% per 
annum<http://books.google.com.au/books?id=3CdgNiBrHfIC&pg=PA43&lpg=PA43&dq=cost+of+bulk+synthetic+latex&source=bl&ots=X5hv6DcDeR&sig=48ZERM5d3UWtW2yZ4NDtjhiKriU&hl=en&ei=5iGITuPBHayUiQeAwe2jDw&sa=X&oi=book_result&ct=result&resnum=5&ved=0CDoQ6AEwBA#v=onepage&q&f=false>
 between 2000-2005. Ramping production by 17% would be completely feasible.

The ongoing cost depends on the residence time of the particles at the ocean 
surface. Equatorial currents run at about 1 
ms-1<http://oceanmotion.org/html/resources/oscar.htm>, which would imply a 
traversal time of about 1 year for the Pacific ocean. Mid latitude the currents 
are much slower. The latex particles themselves will degrade in the 
environment, and there will be losses by association and entrainment in a 
complex marine environment.
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Figure 8. Major ocean surface currents.

But let’s provisionally estimate a cost of $2b per year. This is significantly 
cheaper than, say, stratospheric sulfur aerosol injection which is estimated at 
$25-50b per year, let alone space sunshades. And it doesn’t require exotic 
engineering, enabling R&D, or orbital launches – it uses existing materials at 
a rate well inside existing production capacity.

Conclusion

So consider this final elaboration of Russell Seitz’ bright idea: 0.1 μm 
diameter latex particles, possibly hollow, or of core-shell morphology, bearing 
a conventional stabilization system that is inactivated in salt water ensuring 
that the particles are retained at and near the surface, are produced in bulk 
using about 17% of existing production capacity and using commercial recipes, 
and are sprayed onto the sea from tanks aboard ships or crop dusting aircraft, 
oil rigs, and other structures, in the mid latitudes.

For a cost in the order of a mere $2b per year we could offset current global 
warming, subject to the many disclaimers and qualifications discussed above, 
and many others not mentioned. More limited, local applications, such as the 
direct cooling of coral reefs as envisaged by Seitz for the microbubble 
concept, are also possible.

As they say on Top Gear, what could possibly go wrong
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