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After a really, really long nap…Science and the State Department

One of the great things about being in DC now is that I really am in the heart of where public policy is made! But the downside is that I feel that I have left chemistry except for when I flip through C&EN and scroll through my twitter feed. #ChemCoach! Therefore, I feel like I am still trying to find where chemistry fits in to public policy.

Nonetheless, being in DC allows for me to attend a large number of talks and events centered around science policy. Early October, I attended a talk by Dr. Kerri-Ann Jones, the Assistant Secretary of State for Oceans and International Environmental and Scientific Affairs. It was a great overview of where science fits into diplomacy at the State Department. For example, I did not realize that Wildlife Trafficking is not just a trade concern, but also a public health issue due to diseases being transmitted through unconventional pathways.  Dr. Jones mentioned a lab in Ashland, Oregon that is taking the basic science of understanding the baseline animal migration patterns to better distinguish where a pelt could have originated and the path it took as a result of humans.

The State Department also participates in partnerships that can help countries like Indonesia lower their greenhouse gas emissions.  Along the lines of environmental diplomacy, Dr. Jones spoke of talks within the UN to develop a Mercury Treaty to reduce the use of mercury globally. I wished that Dr. Jones would have talked more about the process for the development of a practical guide of non-mercury alternatives for the mining of artisanal gold. The mining of artisanal gold employs 12 to 15 million people in 70 countries. [1] How are the guides being distributed? Are these alternatives as economically viable? However, it was great to hear about policy solutions that science can help solve to ensure the safety and health of these miners and their economic livelihood.


Ammonia, you Toxic Chemical…

This blog post is written for Sciencegeist’s #ToxicCarnival

Ah Nitrogen (N2), thank you for helping me run my oxygen-sensitive reactions, you are 78% of the earth’s atmosphere, and when fixed you provide us with food. The last example that I am talking about is the Haber-Bosch process of taking inert N2 and converting it into reactive ammonia (NH3) that we put into fertilizer.

Fritz Haber and his synthetic process of fixing nitrogen is very relevant to our discussion of “toxic chemicals” because ultimately his process was discovered because Germany needed nitrates for making explosives during WWI.  Here is a great example of how a chemical and the ability to mass produce a chemical can be for good and bad. When asked about the duality of his discovery Haber said this:

“The interest of a wider circle has its source in the recognition that ammonia synthesis on a large scale represents a useful…way to satisfy an economic need. This practical usefulness was not the preconceived goal of my experiments. I was not in doubt that my laboratory work could furnish no more than a scientific statement of the foundations and a knowledge of the experimental equipment, and that much had to be added to this result in order to attain economic success on an industrial scale.”

Ammonia in fertilizer is one of the most important chemicals used today. The hydrogenation of nitrogen is catalyzed by a heterogeneous iron oxide catalyst at over 300 C and around 15 – 20 MPa.  This is a very energy intensive process using about 1.2% of the world’s energy. Yet, the massive production of ammonia through the Haber-Bosch process allows for the global food supply to keep up with the demands of human population growth. And in general, reactive forms of nitrogen not only provides the necessary nutrients for feeding the world, it is also responsible for providing us with the precursors for industrial goods such as cleaners, antiseptics, and nylon.

However we are beginning to see the detrimental effects to our environment such as ozone depletion in our excessive use of these reactive nitrogen reagents in fertilizer and the burning of fossil fuels. Yet, it is slightly more complicated than making overarching regulatory decisions to decrease reactive nitrogen use.  For example nitrogen that has leached into the ecosystem has enhanced plant growth in wetlands and riparian restoration and in turn account for substantial carbon sequestration and slowing of global warming. Another compounding factor of nitrogen management is that N2O slows decomposition and the release of CH4, but itself also contributes to the breakdown of the ozone. (reference)

So how can we better manage the nitrogen cycle? Nitrogen played a significant role during Haber’s lifetime and it is again an important element to understanding how we have changed its ecosystem, and make better decisions on how to manage it and take advantage of its benefits.

Further reading:
Great plot of the production of ammonia over the last decade:

Carbon Dioxide as a Feedstock for Acrylic Acid Production

Fun with Dry Ice (4 of 9)One of the largest sources of carbon, CO2, is emitted as a pollutant and is attributing to the rising climate temperatures. So then why are we not using CO2 as a feedstock? Well, for one thing is it very very difficult. CO2 is incredibly stable as it is a thermodynamic sink. Therefore, It requires even more energy to convert it into something else, and where does all of energy come from? Fossil fuels. Thereby generating even more CO2 to convert CO2 into something useful. But if we can find a means for converting or reducing CO2 into a commodity through a less energy intensive pathway, then there is potential to generate revenue from “waste” and reduce emissions.

Currently, the US generates 5,500 million metric tons/yr of CO2. Industries are currently capturing and using CO2, approximately 200 million metric tons/yr in the food industry and oil and gas industry, but a majority of this is released back into the atmosphere. Only about 0.5% of the CO2 that is captured is sequestered and not released.

We can think about carbon/CO2 utilization in two categories, 1.) carbon sequestration (burying in deep geological formations) and 2.) carbon as a useful feedstock. I am focusing on the second categories because investigations into into using CO2 as a freely available and abundant feedstock to develop commercial chemicals, plastics, and building materials has the potential to be an economically viable industry. Additionally, carbon sequestration has its limitations, and although it is being heavily federally funded, it’s large scale deployment has estimates in the range of $30-70/ton attributed to the new CO2 transmission lines that will need to be built. There are instances where CO2 cannot be transported to sequestration sites.

One of my favorite examples being investigated for CO2 utilization to generate commercial chemicals is the oxidative coupling of CO2 with ethylene to generate acrylic acid with molybdenum catalysts.  This is work done at Brown University in the lab of Dr. Bernskoetter.

Acrylic Acid

Acrylic acid is used heavily as the raw material for polymers, coatings and adhesives. Global production of acrylic acid is 3.4 million metric tons/yr and with 60% by weight CO2, that is over 2 million metric tons/yr of CO2 that could be resold and prevented from entering the atmosphere. The production of acrylic acid through a more economically viable method would be advantageous, so much so that Dow has begun similar efforts to generate acrylic acid through the generation of 3-hydroxypropionic acid with the use of a biocatalyst.  They claim that their process is 25% cheaper and 75% less greenhouse gas intensive.

The current process for acrylic acid production is the oxidation of propene and is incredibly energy intensive because it not only requires reaction temperatures of 200 – 300 C but also multiple distillations to remove impurities. Dr. Bernskoetter’s catalysts can oxidatively add CO2 and ethylene slightly above, if not close to, room temperature.  However, at the moment, the biggest challenge is the reductive elimination of the hydroxide to release acrylic acid from the metal.  But once that can be done, unlike the use of catalytic microbes, organometallic catalysts can more easily (and usually cheaply) be modified to improve upon turnover rates and efficiency.  I am especially excited and looking forward to Dr. Bernskoetter’s next publication on this catalyst.

Science Outlook – If Newt won the White House

What would science look like if Republicans won the White House in 2012? (Part 1 of 2)After hearing Former Speaker Gingrich’s promise that there will be colonies on the moon by 2020, and then the subsequent parodies by various comedians and Romney, I want to ask: what did you find yourself thinking?

Although I don’t believe that we should go back to the moon to settle colonies, Former Speaker Gingrich’s pandering to the space coast got me thinking about the foundation I had for the stress that with a republican in the White House we would lose all of the momentum in R&D we worked so hard to gain these last 3-4 years.  Where did I get this feeling? Because public debates rarely go into how candidates think about science and research and development.

Now a disclaimer: this post is all speculation based on limited research. I have merely looked into the past decisions, votes, and bills introduced by Gringrich (during the 104th Congress) and cherry picked the legislation that might hint at a passion and interest in science. This post is in no way guaranteeing that this will be the agenda that he will take.  I am only looking for patterns to help guide thinking about the candidates that are bombarding the news cycles.

And of course, the candidate will not be the only one who makes decisions on science, as if he does win the White House, it will also depend on who he will appoint to his cabinet positions and other key science positions. But again, this is just a small list to begin to think about the candidates from the viewpoint of what they can do for science, because R&D is not often talked about in national debates.

Gingrich perhaps was not just pandering to the space coast, but has always found an interest in space policy, since growing up during the space race. In an interview with The Space Review in 2006, he sees a lot of potential in large monetary prizes and tax incentives to encourage businesses and the private sector to be involved. Although many of these partnerships with the private sector are already happening and have been the efforts of the current (Obama) administration.

Energy and the Environment:
This is a bit difficult to tease out as there are instances where Newt has been a proponent of climate change going as far as doing a commercial with Former Speaker Nancy Pelosi in support of Al Gore’s Alliance for Climate Protection and even authoring A Contract with the Earth, a book on green conservatism. However in recent months in during his campaign for the presidency he is on the same side of nearly every other republican candidate, expressing that the commercial was the “dumbest single thing I’ve done in the last few years”.

In addition, his quote about changing the EPA to the Environmental Solutions Agency (ESA) is a bit convoluted as he expresses the need for this agency to work with industry to build incentives rather than punishments. One specific example to keep an eye on is his proposal to incentivize “flex-fuel” vehicles.  However, these types of vehicles would need to broaden beyond just ethanol to not be seen as choosing ethanol as the “winner”.

Former Speaker Gingrich has a very strong commitment to education. He knows that prosperity and national security are tied into education. Although he does rely heavily on the charter school system, but as does Secretary Duncan (interview with Meet the Press).

As an additional disclaimer, this post in no way endorses Newt Gingrich. I just wanted to have a discussion about the speculations on the consequence of science if republicans were to win the White House. Did you catch any other articles I should take a look at? Tomorrow: Mitt Romney, what is the outlook for science if he wins the White House?

Oil from Plastic Waste

One of my many interests is to read about alternative processes that turn waste into meaningful/reusable materials. For example: dog poop into methane to light a lamp. or turning plastic into fuel. In an earlier post I outlined a few attributes as to why perhaps we cannot completely do away with plastic. But what we can do is to find a means to have it not sit in landfills forever. Therefore, naturally, this article in the NYTimes about Reaping Oil From Discarded Plastic caught my attention. An Oregon-based start-up, Agilyx, has a system that can turn plastic into crude oil. They only have a small prototype system at the moment and are looking to start selling commercial systems soon.  From the descriptions of the article, we figured that polyethylene was undergoing an incomplete combustion, then the resulting vapor (H2 and CO) is converted into hydrocarbons that can then be converted to diesel, jet fuel or other forms of oil. Pretty cool, right?! Well, we did some calculations with the numbers that were in the article and although a very good idea, it only about 64% efficient by weight. Which is comparable to other processes and actually might work, considering the input source is, in essence, free, if it is in fact coming from the local waste management. This process could perhaps be a way for municipal waste to fuel their own fleet. If they had the $5 million upfront to invest in the system.

* Special thanks to my labmate for the helpful discussion and unit conversion reminder. (thanks to article for not having easily interchangeable units.)

yeah, yeah, i know, too many sig figs. (I was taught to carry more than enough through the calculations then round) so technically, since the article only gave me 1 SF, it should be 60% efficiency

The Things They Carried

“Mobility is freedom and progress.” – Bill Ford, TED talk, TED2011

This post is to shed a bit of light on the extent of our fuel dependency that you might not hear about everyday. Until recently, I also did not realize how the energy needs of our vehicles, communication devices, GPS, computers, and robots impacted our military. Plus, the other reason for discussing this issue and the strategies that the Army and Marines are doing to decrease their energy demand is that we are in the throws of another budget/debt ceiling debate in Congress. And what are we spending a majority of tax payer money on besides Medicare and Social Security? Defense. And that, as I hope to outline, is also an energy and environment matter.

The Department of Defense (DOD) R&D budget proposal for the FY 2012 is $77.8 billion. The DOD knows what it should be working on with this funding: Energy. And they are doing so for two reasons: 1.) to lighten the load in which our troops carry, a minimum of 20 pounds of which are the seven types of batteries being carried in addition to their gear and 2.) to save the resources and personnel required to protect convoys that transport fuel.  There are a number of reasons why our energy demands are detrimental to our military. Cost: the Government Accountability Office has the DOD spending at least $2.1 billion on power sources between 2006 and 2010. Danger: the weight of the batteries cause physical harm to the soldiers, perhaps even long-term, not to mention decreasing the effectiveness of these soldiers in combat. Strategic: Where does the fuel come from? It is transported, like many other supplies, through hazardous, mine-infested roads. You can see how maintaining the upper hand on our adversaries while gaining the necessary energy to have that advantage is a logistical nightmare.

An important start is to get better data on the DOD energy use. There is information about how much was purchased, but not information about where it is used. In the works are more automated energy-measurement systems to collect better data and be able to analyze where the most energy use is taking place.

Second is to develop centralized and standardized power that is reliably distributed. This can decrease the reliance on batteries as well as decrease the number of different batteries in which soldiers carry. One of the problems with rechargeable gadgets (and we all experience this with our devices at home) is that each requires specific chargers and batteries. Standardized power would also be much more adaptive and establish legacy systems. A majority of the DOD’s equipment like tanks and aircrafts are quite old. There needs to be considerations about the reliability and legacy of the new vehicles. What energy source are we going to use? And the vehicles that we build, will they use the same source 50 years from now? 70 years from now?

Many of the efforts that the DOD is deploying for decreasing its energy demand can also be done at the national level. Perhaps the problems do not seem has immediate as that of the military (protecting the lives of our troops and not placing them in unnecessarily in harms way); however still urgent. 1.) data acquisition: where can we decrease our energy use? The need for real time data. This is one of the most important things that we can do. Last week the White House hosted an event unveiling the policy for modernizing our grid system. At the event, they had two high school students who had sysytems installed that monitored the energy use of their school. They were able to decrease the schools energy use by 13 percent and a 250 percent return on investment! If two high school students can do this! Surely the rest of the Nation can too!  2.) Standardization: finding the systems that are competitive so that the convenience, efficiency, and confidence we have in disposable batteries doesn’t win. 3.) Entire life-cycle cost considerations: thinking about legacy systems in the context of the environmental implications involved in the energy systems that we employ.

The TED talk I linked at the start of this post is great example of thinking about sustainability through out the entire network or system. It is not enough to just have energy efficiency vehicles but to also have our energy using gadgets with the ability to anticipate and communicate with each other so that we are not expending energy when we are idle.

More Reading:

National Defense Magazine May 2011

Looking at Sea Salt from Space

Here is an introductory chemistry mantra: freezing point depression, boiling point elevation.

Tomorrow, NASA’s JPL will launch Aquarius, a satellite outfitted to collect sea surface salinity data. The salinity data will allow for us to gain a better understanding of the global water cycle, ocean circulation and the effects of these on our climate. Even with all of the routine ship and buoy observations, there is only salinity data for 24% of the ocean’s surface. This is a significant gap in our understanding of the ocean and the current models for ocean circulation. Recently, for World Ocean’s Day, there was a great guest blog post in Scientific American mentioning that perhaps the “Ocean Conveyor Belt”  picture for our understanding of heat flow in the ocean is an oversimplification. This concept has dominated the field of oceanography and what is exciting is that Aquarius has the potential to help researchers track processes such as precipitation, evaporation, ice melting, and river runoff that influence the global water cycle in order to develop better models.  Aquarius will provide sea salinity surface data for the entire Earth’s surface every 7 days. 

Salinity of the ocean may seem like a simple and obvious concept for many of us who have experienced the coast. But knowing salt concentrations to 0.2 g/kg (about 1 ppt) can reveal what salinity changes can disrupt ocean circulations. Drastic changes in salinity (ocean circulations) has the potential to lead to changes in the Earth’s climate. The dry regions of the ocean (more evaporation, less precipitation) are the regions of highest salinity. Creating and understadning patterns for future climate/precipitation conditions will be important for agriculture or the stability of ocean fronts for fisheries.

It is all connected. Oceanographer Josh Willis uses balloons to show how water in ... on Twitpic Pictured is an excellent demonstration done by Josh Willis at the JPLtweetup June 7, wherein he illustrates water’s ability to store heat. This ability to store heat effects the temperature of our oceans, which has a direct effect on salinity. And what happens in places with strong variations in salinity? Drastic changes in evaporation and precipitation from season-to-season. Which in turn impacts the global water cycle and ocean circulation.

Global warming is perhaps changing the way in which the ocean is adapting. And isn’t it fascinating that a simple compound like NaCl, with the help of a satellite can help us understand the connection between our climate and the ocean better?

My work here has only begun....*Edit (06/10/2011) Aquarius is about to launch (t-minus 15 min.) How exactly is Aquarius able to measure salt from space? Through microwave emissions! From an interview with Gary Lagerloef, Principle Investigator, just before the launch: Aquarius will measure the electrical conductivity (directly correlated to the salt concentration – greater the salt concentration, higher the electrical conductivity) which modulate the microwave emissions off the surface of the ocean.

**Edit (06/10/2011. 10:4o am) successful launch of Aquarius/SAC-D!

Aquarius SAC-D Launch (201106100016HQ)

Plastic is not evil

We have all seen the pictures of coastlines littered with plastics bottles and bags and we also cringe at the thought that these materials will persist for many years after they are disposed.  However, it is also not reasonable to do away with plastics completely as their inexpensive production and ease of disposal are a staple to sterile environments such as hospitals.  Yet, these fleeting applications for polymers are not appropriate for their persistence in our environment. In the last decade the chemical community has been working on the development of biodegradable polymers that can degrade through chemical hydrolysis or enzymatic processes. The applications for such polymers are when they are soiled by food or other biological substances and cannot be recycled. The benefits of these polymers are that they are generated from renewable resources and then degrade into CO2, CH4, water, biomass, and other natural substances in a short amount of time.

This bag will self desctruct in 18 months ..

Last week, a study, published in Environmental Science and Technology, carefully modeled the methane release of rapidly degrading polymers in landfills to gauge the benefits of biodegradable polymers. The researchers conclude that the polymer that they looked at (poly(3-hydroxybutyrate-co-3-hydroxyoctanoate (PHBO)) degraded and released a significant amount of methane too fast to be sufficiently captured by landfills with gas collection systems. Methane is a concern because like CO2 it is a greenhouse gas but is over 20 times more effective in trapping heat in the atmosphere. Their suggestion therefore were to develop biodegradable polymers that degraded slower to account for the delay in the gas collection systems to reach a critical concentration of GHG emissions to operate.

There are a couple of questions concerning this conclusion, as the authors only analyzed a single biodegradable polymer. There are other more common biodegradable polymers like poly(-e-caprolactone) PCL or poly(lactic acid) (PLA). PCL, in landfill reactors, degrades at a much slower rate than PHBO. Also there have been studies that have shown that biodegradable characteristics depend on the type of polymer and degradation conditions.

Although the authors of the paper do have a good point to have manufacturers of these types of polymers to consider the environmental impact of their products even after disposal. They put it best at the conclusion of their paper, I am paraphrasing: If the emissions for producing a biodegradable material is comparable to that of producing a material from petroleum-based feedstocks, and yet the disposal emissions is higher for the biodegradable materials, is it then a viable alternative?

But also this paper is a reminder for the need to create an infrastructure for biodegradable polymer disposal. Now that worldwide consumption of these types of polymers perhaps exceeds 68 million kg, we should worry about its disposal emissions. A possibility that was not considered in the paper was to analyze composting conditions for biodegradable polymers. A recent study in Korea compared the aerobic and anaerobic environments of poly(caprolactone) and poly(butylene succinate). They concluded that pretreatment technologies coupled with composting would be a means to decrease the waste of biodegradable polymers. This is important for them as the Korean government recently encouraged substituting biodegradable polymers for non-biodegradable polymers.

In addition to considering the disposal emissions of our materials, we should consider an infrastructure for disposal of biodegradable materials that would reduce or mitigate the emissions from these materials as they are an advantage because that do not persist in our environment and are made from non-petroleum-based (renewable) feedstocks.