<h1>foreword: Particles and Droplets</h1>

<p>Commonly, atmospheric particles can be considered as wet particles. E.g. when we talk about sulfate particles ($SO_4^{2-}$), these particles are actually droplets with dissolved sulfuric acid (or with a dissolved sulfate-cation compound).</p>

<h1>Mechanism involving $SO_2$</h1>

<p>$SO_2$ is released as gas and it reacts to $SO_4^{2-}$ (sulfate). Basically, there are different reaction pathways for the formation of sulfate from $SO_2$:</p>

<ul>
<li>$SO_{2,g}$ --(gas phase reaction)--> $H_2SO_{4,g}$ --($H_2O$ accumulates)--> "sulfate particle"</li>
<li>$SO_{2,(g)}$ --(goes into solution)--> $SO_{2,solution}$ --(formation)--> $H_2SO_{4,solution}$ (deprotonizes directly)</li>
</ul>

<p>Commonly, the second pathway is dominant. <strong>The relevant aspect is that it leads to the formation of ultra fine sulfate particles (sulfate droplets).</strong> </p>

<p>Sulfate particles are cloud condensation nuclei. That means that they support the formation of clouds. There are satellite pictures available, in which you can identify shipping lanes by lines of clouds. These clouds were formed because ships emit large amounts of $SO_2$ (at least outside of <a href="https://en.wikipedia.org/wiki/Sulphur_Emission_Control_Area" rel="nofollow noreferrer">sulfur emission control areas</a>). </p>

<p>Most clouds above the ocean reflect more solar radiation than the sea surface. In general, clouds above the ocean are considered as "good clouds" with respect to cooling the Earth. Since a large proportion of the Earth is covered by sea surface, one might wonder to generate clouds above it - e.g. by releasing $SO_2$. However, as far as I know, this process is relevant in the troposphere.</p>

<p>Releasing $SO_2$ into the stratosphere (as proposed in the linked article) is not meant to support cloud formation (correct me, if I am wrong). Nevertheless, the released $SO_2$ leads to ultra-fine sulfate particles. These sulfate particles themselves effectively scatter solar radiation and, thus, prevent it from reaching the Earth's surface. There is also a Wikipedia article available <a href="https://en.wikipedia.org/wiki/Stratospheric_sulfate_aerosols_(geoengineering)" rel="nofollow noreferrer">here</a>.</p>

<p>Unfortunately, sulfate indirectly degrades the ozone layer: sulfate leads to the release of radicals that (and their successors) catalytically destroy ozone. See <a href="http://dx.doi.org/10.1073/pnas.1615572113" rel="nofollow noreferrer">Keith et al. (2016)</a> for a more detailed overview.</p>

<h1>Why $CaCO_3$?</h1>

<p>The basic idea is to add salts of alkali metals that neutralize sulfuric acid and nitric acid (generated in the presence of sulfuric acid) when we emit $SO_2$. This will reduce the negative impact on the ozone layer. $CaCO_3$ is such a salt <a href="http://dx.doi.org/10.1073/pnas.1615572113" rel="nofollow noreferrer">(Keith et al., 2016)</a>. </p>

<h2>Why $Al_2O_3$?</h2>

<p><strong><em>Foreword:</strong> I am not expert on this and just read some articles on this topic.</em></p>

<p>According to <a href="http://dx.doi.org/10.5194/acp-15-11835-2015" rel="nofollow noreferrer">Weisenstein et al. (2015)</a>, fine aluminum particles (as well as diamonds) are an alternative to sulfate particles. According to them, aluminum is favourable. However, as studies on emissions from missiles and space crafts indicate, $Al_2O_3$ also has negative impacts on the ozone layer (<a href="https://books.google.de/books?id=a2YrAAAAYAAJ&amp;pg=PA166&amp;lpg=PA166&amp;dq=Al2O3%20stratosphere&amp;source=bl&amp;ots=xnPx9BMx_5&amp;sig=JqqaiIlc2nfSG-fZEBSfGwBHr_A&amp;hl=de&amp;sa=X&amp;ved=0ahUKEwiSlY2m__3SAhWLvhQKHQb_CbgQ6AEIRzAD#v=onepage&amp;q=Al2O3%20stratosphere&amp;f=false" rel="nofollow noreferrer">SomeReport</a>; <a href="https://books.google.de/books?id=lRQ0AQAAMAAJ&amp;pg=SA4-PA37&amp;lpg=SA4-PA37&amp;dq=Al2O3%20stratosphere&amp;source=bl&amp;ots=CA6b2ssqcP&amp;sig=7vCBpBjykk0m5wtu42sRzuGpI1U&amp;hl=de&amp;sa=X&amp;ved=0ahUKEwiSlY2m__3SAhWLvhQKHQb_CbgQ6AEIOTAB#v=onepage&amp;q=Al2O3%20stratosphere&amp;f=false" rel="nofollow noreferrer">DoD, 2004</a>): $Cl$ radicals are released that degrade ozone. $CaCO_3$ also counteracts here, too.</p>

CC BY-SA 3.0
2017-03-29T23:56:57.663Z
This is really helpful! My impression was that the CaCO3 and Al2O3 were alternate type of particles to be tested independently and their reflectivity compared to that of the sulfate particles. It could be that the carbonate is to chemically mitigate problems caused by sulfate, but alumina is extremely stable. It might provide some catalysis perhaps?
uhoh
CC BY-SA 3.0
2017-03-30T10:19:51.967Z
In the press/news release it actually sounds as when there were three (possibly exclusive) alternatives (SO2/SO4--, CaCO3 and Al2O3) but the linked articles describes the interaction. I am not sure about Al2O3 but it seems to be an alternative to sulfate particles. I will update my answer in a few minutes.
daniel.heydebreck
CC BY-SA 3.0
2017-07-12T04:33:37.057Z
This is a great answer! I'm not sure why I hadn't clicked accept a few months ago. Just to double check, does *alternative to sulfate particles* means in this case that the result would be aerosols; condensed water droplets? And the possible use of CaCO3 would not be for enhanced reflectivity directly, but to potentially reduce some "side effects" of releasing additional SO2?
uhoh
CC BY-SA 3.0
2017-07-12T08:26:49.540Z
@uhoh Thanks for accepting :-) . Second question: Yes. First question: What exactly do you mean with 'condensed water droplets'? The SO2 leads to the formation of sulfate particles. The Al2O3 is directly emitted as particles. With 'alternative to' I mean that we can use Al2O3 or SO2->Sulfate for the modification of atmospheric reflectivity. I am not sure whether Sulfate and Al2O3 are equally 'attractive' for water condensatioin. I would guess that the Al2O3 particle is not dissolved (solid core, liquid hull) whereas sulfate is when water condenses (liquid sulfuric acid droplet).
daniel.heydebreck
CC BY-SA 3.0
2017-07-12T09:19:09.790Z
Actually I realize that I don't know what a 'sulphate particle' really is. So rather than ask here, I've asked a [follow-up question](https://earthscience.stackexchange.com/q/10806/6031).
uhoh
CC BY-SA 3.0
2017-03-29T23:40:43.953Z
2017-03-30T10:34:35.150Z
2017-03-30T10:34:35.150Z
daniel.heydebreck
<p>The MIT Technology Review news item <a href="https://www.technologyreview.com/s/603974/harvard-scientists-moving-ahead-on-plans-for-atmospheric-geoengineering-experiments/" rel="nofollow noreferrer">Harvard Scientists Moving Ahead on Plans for Atmospheric Geoengineering Experiments</a> discusses a proposed experiment to study in a carefully controlled way the reflectivity induced by various kinds of particles released into the stratosphere. The underlying idea being explored is that increased atmospheric reflectance could partially offset warming effects due to greenhouse gases.</p>
<blockquote>
<p>Sometime next year, Harvard professors <a href="https://www.technologyreview.com/s/603974/harvard-scientists-moving-ahead-on-plans-for-atmospheric-geoengineering-experiments/" rel="nofollow noreferrer">David Keith</a> and Frank Keutsch hope to launch a high-altitude balloon, tethered to a gondola equipped with propellers and sensors, from a site in Tucson, Arizona. After initial engineering tests, the “StratoCruiser” would spray a fine mist of materials such as <strong>sulfur dioxide, alumina, or calcium carbonate</strong> into the stratosphere. The sensors would then measure the reflectivity of the particles, the degree to which they disperse or coalesce, and the way they interact with other compounds in the atmosphere.</p>
<p>The researchers first proposed these balloon experiments in a <a href="http://rsta.royalsocietypublishing.org/content/372/2031/20140059" rel="nofollow noreferrer">2014 paper</a>. But at a geoengineering conference in Washington, D.C., on Friday, Keith said they have begun engineering design work with Arizona test balloon company World View Enterprises. They’ve also started discussions about the appropriate governance structure for such an experiment, and they plan to set up an independent body to review their proposals.</p>
</blockquote>
<p>This is an effort to explore how best to do a small, controlled test and how to establish proper guidelines. This type of atmospheric experiment is very different than the long established practice of <a href="https://en.wikipedia.org/wiki/Cloud_seeding" rel="nofollow noreferrer">cloud seeding</a> for rain, so this thoughtful approach is taken.</p>
<p>A short review of the background concept and associated issues can be found in the <a href="http://www.theverge.com/2017/3/24/15053204/ice-balloon-geoengineering-climate-change-world-view-david-keith" rel="nofollow noreferrer">video shown in this article</a>, after the first minute or so it gets more serious.</p>
<p>While Alumina (Al2O3) and calcium carbonate (CaCO3) might be in the form of solid particles for such an experiment, and particle size can be engineered to various controlled size distributions ahead of time, sulfur dioxide (SO2) is a gas at STP. At one atmosphere of pressure, it would become a liquid <a href="https://en.wikipedia.org/wiki/Sulfur_dioxide" rel="nofollow noreferrer">at about -10C</a>. Would the plan be to spray or atomize liquid SO2 at the low ambient temperature at altitude?</p>
<p>If I understand correctly, SO2's mechanism would be to 'chemically scavenge'  water vapor from the air, forming reflective droplets of sulfuric acid. Would the alumina and calcium carbonate also seed water droplet formation as their reflective mechanism, or would only the particles themselves be reflective?</p>

CC BY-SA 3.0
2017-03-28T03:37:36.537Z
Is a `climate modification` tag warranted?
uhoh
CC BY-SA 3.0
2017-03-28T19:52:32.243Z
SO2 can form fine particualte matter, which also increases the reflectivity.
BarocliniCplusplus
<climate-change><atmospheric-chemistry><atmospheric-radiation><upper-atmosphere>
How would this experiment's different particle types produce atmospheric reflectivity?
uhoh
# How would this experiment's different particle types produce atmospheric reflectivity?

(Asked by: username_0 on 2017-03-28)

The MIT Technology Review news item [Harvard Scientists Moving Ahead on Plans for Atmospheric Geoengineering Experiments](https://www.technologyreview.com/s/603974/harvard-scientists-moving-ahead-on-plans-for-atmospheric-geoengineering-experiments/) discusses a proposed experiment to study in a carefully controlled way the reflectivity induced by various kinds of particles released into the stratosphere. The underlying idea being explored is that increased atmospheric reflectance could partially offset warming effects due to greenhouse gases.

> Sometime next year, Harvard professors [David Keith](https://www.technologyreview.com/s/603974/harvard-scientists-moving-ahead-on-plans-for-atmospheric-geoengineering-experiments/) and Frank Keutsch hope to launch a high-altitude balloon, tethered to a gondola equipped with propellers and sensors, from a site in Tucson, Arizona. After initial engineering tests, the “StratoCruiser” would spray a fine mist of materials such as **sulfur dioxide, alumina, or calcium carbonate** into the stratosphere. The sensors would then measure the reflectivity of the particles, the degree to which they disperse or coalesce, and the way they interact with other compounds in the atmosphere.
>
> The researchers first proposed these balloon experiments in a [2014 paper](http://rsta.royalsocietypublishing.org/content/372/2031/20140059). But at a geoengineering conference in Washington, D.C., on Friday, Keith said they have begun engineering design work with Arizona test balloon company World View Enterprises. They’ve also started discussions about the appropriate governance structure for such an experiment, and they plan to set up an independent body to review their proposals.

This is an effort to explore how best to do a small, controlled test and how to establish proper guidelines. This type of atmospheric experiment is very different than the long established practice of [cloud seeding](https://en.wikipedia.org/wiki/Cloud_seeding) for rain, so this thoughtful approach is taken.

A short review of the background concept and associated issues can be found in the [video shown in this article](http://www.theverge.com/2017/3/24/15053204/ice-balloon-geoengineering-climate-change-world-view-david-keith), after the first minute or so it gets more serious.

While Alumina (Al2O3) and calcium carbonate (CaCO3) might be in the form of solid particles for such an experiment, and particle size can be engineered to various controlled size distributions ahead of time, sulfur dioxide (SO2) is a gas at STP. At one atmosphere of pressure, it would become a liquid [at about -10C](https://en.wikipedia.org/wiki/Sulfur_dioxide). Would the plan be to spray or atomize liquid SO2 at the low ambient temperature at altitude?

If I understand correctly, SO2's mechanism would be to 'chemically scavenge' water vapor from the air, forming reflective droplets of sulfuric acid. Would the alumina and calcium carbonate also seed water droplet formation as their reflective mechanism, or would only the particles themselves be reflective?

**Tags:** climate-change, atmospheric-chemistry, atmospheric-radiation, upper-atmosphere

> **Comments:**
> **username_0**: Is a `climate modification` tag warranted?  
> **username_1**: SO2 can form fine particualte matter, which also increases the reflectivity.  

---

## 1 answers

### Answer by username_2 on 2017-03-29. Score: 2 | Accepted answer

# foreword: Particles and Droplets

Commonly, atmospheric particles can be considered as wet particles. E.g. when we talk about sulfate particles ($SO\_4^{2-}$), these particles are actually droplets with dissolved sulfuric acid (or with a dissolved sulfate-cation compound).

# Mechanism involving $SO\_2$

$SO\_2$ is released as gas and it reacts to $SO\_4^{2-}$ (sulfate). Basically, there are different reaction pathways for the formation of sulfate from $SO\_2$:

* $SO\_{2,g}$ --(gas phase reaction)--> $H\_2SO\_{4,g}$ --($H\_2O$ accumulates)--> "sulfate particle"
* $SO\_{2,(g)}$ --(goes into solution)--> $SO\_{2,solution}$ --(formation)--> $H\_2SO\_{4,solution}$ (deprotonizes directly)

Commonly, the second pathway is dominant. **The relevant aspect is that it leads to the formation of ultra fine sulfate particles (sulfate droplets).**

Sulfate particles are cloud condensation nuclei. That means that they support the formation of clouds. There are satellite pictures available, in which you can identify shipping lanes by lines of clouds. These clouds were formed because ships emit large amounts of $SO\_2$ (at least outside of [sulfur emission control areas](https://en.wikipedia.org/wiki/Sulphur_Emission_Control_Area)).

Most clouds above the ocean reflect more solar radiation than the sea surface. In general, clouds above the ocean are considered as "good clouds" with respect to cooling the Earth. Since a large proportion of the Earth is covered by sea surface, one might wonder to generate clouds above it - e.g. by releasing $SO\_2$. However, as far as I know, this process is relevant in the troposphere.

Releasing $SO\_2$ into the stratosphere (as proposed in the linked article) is not meant to support cloud formation (correct me, if I am wrong). Nevertheless, the released $SO\_2$ leads to ultra-fine sulfate particles. These sulfate particles themselves effectively scatter solar radiation and, thus, prevent it from reaching the Earth's surface. There is also a Wikipedia article available [here](https://en.wikipedia.org/wiki/Stratospheric_sulfate_aerosols_(geoengineering)).

Unfortunately, sulfate indirectly degrades the ozone layer: sulfate leads to the release of radicals that (and their successors) catalytically destroy ozone. See [Keith et al. (2016)](http://dx.doi.org/10.1073/pnas.1615572113) for a more detailed overview.

# Why $CaCO\_3$?

The basic idea is to add salts of alkali metals that neutralize sulfuric acid and nitric acid (generated in the presence of sulfuric acid) when we emit $SO\_2$. This will reduce the negative impact on the ozone layer. $CaCO\_3$ is such a salt [(Keith et al., 2016)](http://dx.doi.org/10.1073/pnas.1615572113).

## Why $Al\_2O\_3$?

***Foreword:*** I am not expert on this and just read some articles on this topic.

According to [Weisenstein et al. (2015)](http://dx.doi.org/10.5194/acp-15-11835-2015), fine aluminum particles (as well as diamonds) are an alternative to sulfate particles. According to them, aluminum is favourable. However, as studies on emissions from missiles and space crafts indicate, $Al\_2O\_3$ also has negative impacts on the ozone layer ([SomeReport](https://books.google.de/books?id=a2YrAAAAYAAJ&pg=PA166&lpg=PA166&dq=Al2O3%20stratosphere&source=bl&ots=xnPx9BMx_5&sig=JqqaiIlc2nfSG-fZEBSfGwBHr_A&hl=de&sa=X&ved=0ahUKEwiSlY2m__3SAhWLvhQKHQb_CbgQ6AEIRzAD#v=onepage&q=Al2O3%20stratosphere&f=false); [DoD, 2004](https://books.google.de/books?id=lRQ0AQAAMAAJ&pg=SA4-PA37&lpg=SA4-PA37&dq=Al2O3%20stratosphere&source=bl&ots=CA6b2ssqcP&sig=7vCBpBjykk0m5wtu42sRzuGpI1U&hl=de&sa=X&ved=0ahUKEwiSlY2m__3SAhWLvhQKHQb_CbgQ6AEIOTAB#v=onepage&q=Al2O3%20stratosphere&f=false)): $Cl$ radicals are released that degrade ozone. $CaCO\_3$ also counteracts here, too.

> **Comments:**
> **username_0**: This is really helpful! My impression was that the CaCO3 and Al2O3 were alternate type of particles to be tested independently and their reflectivity compared to that of the sulfate particles. It could be that the carbonate is to chemically mitigate problems caused by sulfate, but alumina is extremely stable. It might provide some catalysis perhaps?  
> **username_2**: In the press/news release it actually sounds as when there were three (possibly exclusive) alternatives (SO2/SO4--, CaCO3 and Al2O3) but the linked articles describes the interaction. I am not sure about Al2O3 but it seems to be an alternative to sulfate particles. I will update my answer in a few minutes.  
> **username_0**: This is a great answer! I'm not sure why I hadn't clicked accept a few months ago. Just to double check, does *alternative to sulfate particles* means in this case that the result would be aerosols; condensed water droplets? And the possible use of CaCO3 would not be for enhanced reflectivity directly, but to potentially reduce some "side effects" of releasing additional SO2?  
> **username_2**: @username_0 Thanks for accepting :-) . Second question: Yes. First question: What exactly do you mean with 'condensed water droplets'? The SO2 leads to the formation of sulfate particles. The Al2O3 is directly emitted as particles. With 'alternative to' I mean that we can use Al2O3 or SO2->Sulfate for the modification of atmospheric reflectivity. I am not sure whether Sulfate and Al2O3 are equally 'attractive' for water condensatioin. I would guess that the Al2O3 particle is not dissolved (solid core, liquid hull) whereas sulfate is when water condenses (liquid sulfuric acid droplet).  
> **username_0**: Actually I realize that I don't know what a 'sulphate particle' really is. So rather than ask here, I've asked a [follow-up question](https://earthscience.stackexchange.com/q/10806/6031).  

---

