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Researchers demonstrate complete solar-powered hydrocarbon production

Enlarge / Either of two reaction chambers (bottom) can be targeted by concentrated sunlight.

ETH Zurich

Carbon capture. Hydrogen production. Synthetic fuels. All of these technologies have been proposed as potential resources for dealing with the crises created by our carbon dioxide emissions. While they have worked in small pilot demonstrations, most of them haven’t demonstrated that they can scale to provide the economical solutions we need.

In the meantime, a group of European researchers sees the methods as part of a single coherent production platform, one that goes from sunlight and air to kerosene. Thanks to a small installation on the roof of a lab in Zurich, the team has been producing small amounts of different fuels using some mirrors and a handful of reaction chambers. While the full production process would also need to demonstrate that it can scale, the researchers calculate that the platform could fuel the entire commercial aircraft industry using a small fraction of the land in the Sahara.

The process

There are only three steps involved in the process of turning air into fuels. The first is separating out the raw ingredients, specifically carbon dioxide and water. This is done using a small commercial unit from a spinoff of ETH Zurich; the device uses a heating/cooling cycle and amines that absorb both CO2 and H2O at environmental temperatures, releasing them when they are heated. Critically, the supplied water is highly pure and doesn’t compete with the many other uses we have for clean water.

From there, the materials are sent to another unit that converts them to carbon monoxide and hydrogen, again using a heating/cooling cycle. The process uses cerium oxide, which partially decomposes and releases oxygen at high temperatures. Upon returning to environmental temperatures, the cerium will strip oxygen from whatever source (water or carbon dioxide) happens to be present. The high heat needed to drive this process is provided by a set of mirrors that concentrate incoming sunlight, with the reaction chamber peaking at over 5,000 suns while heating. The heating is sufficient to run two of these reaction chambers at the same time—one for water and one for carbon dioxide—by switching the mirrors’ focus back and forth.

The resulting carbon monoxide and hydrogen are sent to a second reaction chamber, where a commercial copper-based catalyst can convert them to fuels like methanol or kerosene, with the reaction product being determined by the precise mix of materials put in place. This step requires high pressures and elevated temperatures.

The system is not entirely self-contained. Valves need opening and closing, and gasses need to be pressurized. But it would be relatively trivial to attach a photovoltaic panel and battery to handle these tasks. The heat used for the first and final steps could also be provided through the extraction of waste heat from the high temperatures used during the middle step.

At the very small scales used here, the process was pretty slow. Over the course of a day, with seven hours of useful sunlight, the setup produced 32 milliliters of methanol, which was mixed in with water as a major contaminant. Switching the reaction mix allowed for the production of kerosene, which is much easier to separate. Compared to the contaminants present in kerosene derived from fossil fuels, the results here were good. The synthetic kerosene lacked the sulfur- and nitrogen-containing chemicals that tend to result in soot and other pollutants.

Will it scale?

Overall, the results are clear: The process can work, but it’s not productive enough to matter in its current state, so a large portion of the paper considers optimization and scale. Optimization is mostly a matter of many little improvements, like the better use of waste heat to ensure all the necessary heat is provided by the solar reflectors. Other targets include better catalysts and more efficient means of storing the gasses between steps.

Then there’s a matter of scale. To fuel a daily round-trip flight between New York City and London, the researchers estimate, it would take 10 mirror farms directing sunlight at reaction chambers in an area that gets strong and consistent sunlight. That translates to covering around 3.8 square kilometers of the desert with mirrors. (For context, that’s about a quarter of the size of California’s Ivanpah solar facility.)

Providing for all of commercial aviation’s fuel needs would require taking over half of one percent of the surface of the Sahara Desert. And that means a lot of mirrors.

The researchers suggest we will likely see the sort of dramatic cost reductions seen in other renewable resources, including technologies like concentrating solar power. That mirror-based tech saw prices drop by 60 percent over a recent 15-year period. But it’s questionable whether the sorts of price drops we’ve seen with photovoltaics are possible, given the large material costs of all those mirrors and their associated hardware, plus the maintenance costs of keeping them clean.

The flipside is that concentrating solar power costs have continued to come down, and a lot of those savings could probably be applied to heat-driven chemistry like this. And it’s possible that this basic concept—solar-powered green chemistry—could be adapted to produce fuels with a higher value than kerosene.

Nature, 2021. DOI: 10.1038/s41586-021-04174-y  (About DOIs).

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Scientists Discover an Immense, Unknown Hydrocarbon Cycle Hiding in The Oceans

In the awful wake of an oil spill, it’s typically the smallest of organisms who do most of the cleaning up. Surprisingly, scientists know very little about the tools these tiny clean-up crews have at their disposal.

 

But now, thanks to a new study, researchers have uncovered a whole new cycle of natural hydrocarbon emissions and recycling facilitated by a diverse range of tiny organisms – which could help us better understand how some microbes have the power to clean up the mess an oil spill leaves in the ocean.

“Just two types of marine cyanobacteria are adding up to 500 times more hydrocarbons to the ocean per year than the sum of all other types of petroleum inputs to the ocean, including natural oil seeps, oil spills, fuel dumping and run-off from land,” said Earth scientist Connor Love from the University of California, Santa Barbara (UCSB).

But unlike more familiar human contributions of hydrocarbons into our ocean, this isn’t a one-way, local dump.

These hydrocarbons, primarily in the form of pentadecane (nC15), are spread across 40 percent of Earth’s surface, and other microbes feast on them. They’re constantly being cycled in such a way that Love and colleagues estimate only around 2 million metric tonnes are present in the water at any one time.

“Every two days you produce and consume all the pentadecane in the ocean,” Love explained.

(Luke Thompson, Chisholm Lab/Nikki Watson, MIT)

Above: A species of the globally distributed marine cyanobacteria, Prochlorococcus.

Today, humanity’s hydrocarbon footprints can be found in most aspects of our surroundings. We emit these molecules composed of only carbon and hydrogen atoms in many ways – the bulk through extraction and use of fossil fuels, but also from plastics, cooking, candles, painting, and the list goes on.

 

So it probably shouldn’t be a huge surprise that traces of our own emissions drowned out our ability to see the immense hydrocarbon cycle that naturally occurs in our oceans.

It took Love and colleagues some effort to clearly identify this global cycle for the first time.

Far from most human sources of hydrocarbons, in the nutrient-poor North Atlantic subtropical waters, the team had to position the ship they sampled from to face the wind, so the diesel fuel that also contains pentadecane did not contaminate the seven study sites. No one was permitted to cook, smoke or paint on deck during collections.

“I don’t know if you’ve ever been on a ship for an extended period of time, but you paint every day,” explained Earth scientist David Valentine from UCSB. “It’s like the Golden Gate Bridge: You start at one end and by the time you get to the other end it’s time to start over.”

Back on land, the researchers were able to confirm the pentadecane in their seawater samples were of biological origin, by using a gas chromatograph.

 

Analysing their data, they found concentrations of pentadecane increased with greater abundance of cyanobacteria cells, and the hydrocarbon’s geographic and vertical distribution were consistent with these microbe’s ecology.

Cyanobacteria Prochlorococcus and Synechococcus are responsible for around a quarter of the global ocean’s conversion of sunlight energy into organic matter (primary production) and previous laboratory cultivation revealed they produce pentadecane in the process.

Valentine explains the cyanobacteria likely use pentadecane as a stronger component for highly curved cellular membranes, like those found in chloroplasts (the organelle that photosynthesise). 

The cycle of pentadecane in the ocean also follows the diel cycling of these cyanobacteria – their vertical migration in the water in response to changes of light intensity throughout a day.

Together, these findings suggest the cyanobacteria are indeed the source of the biological pentadecane, which is then consumed by other microorganisms that produce the carbon dioxide the cyanobacteria then use to continue the cycle.

Earth’s natural hydrocarbon cycle. (David Valentine/UCSB)

Love’s team identified dozens of bacteria and surface-dwelling archaea that bloomed in response to the addition of pentadecane in their samples.

So they then tested to see if the hydrocarbon-consuming microbes could also break down petroleum. The researchers added a petroleum hydrocarbon to samples increasingly closer to areas with active oil seepage, in the Gulf of Mexico.

 

Unfortunately, only the sea samples from areas already exposed to non-biological hydrocarbons contained microbes that bloomed in response to consuming these molecules.

DNA tests showed genes thought to encode proteins that can degrade these hydrocarbons differed between the microbes, with a contrast evident between those that ate biological hydrocarbons and those that devoured the petroleum-sourced ones.

“We demonstrated that there is a massive and rapid hydrocarbon cycle that occurs in the ocean, and that it is distinct from the ocean’s capacity to respond to petroleum input,” said Valentine.

The researchers have begun sequencing the genomes of the microbes in their sample to further understand the ecology and physiology of the creatures involved in Earth’s natural hydrocarbon cycle.

“I think [these findings reveal] just how much we don’t know about the ecology of a lot of hydrocarbon-consuming organisms,” said Love.

This research was published in Nature Microbiology.

 

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Researchers discover an immense hydrocarbon cycle in the world’s ocean

Researchers retrieve water samples from the Sargasso Sea. Credit: David Valentine

Hydrocarbons and petroleum are almost synonymous in environmental science. After all, oil reserves account for nearly all the hydrocarbons we encounter. But the few hydrocarbons that trace their origin to biological sources may play a larger ecological role than scientists originally suspected.

A team of researchers at UC Santa Barbara and Woods Hole Oceanographic Institution investigated this previously neglected area of oceanography for signs of an overlooked global cycle. They also tested how its existence might impact the ocean’s response to oil spills.

“We demonstrated that there is a massive and rapid hydrocarbon cycle that occurs in the ocean, and that it is distinct from the ocean’s capacity to respond to petroleum input,” said Professor David Valentine, who holds the Norris Presidential Chair in the Department of Earth Science at UCSB. The research, led by his graduate students Eleanor Arrington and Connor Love, appears in Nature Microbiology.

In 2015, an international team led by scientists at the University of Cambridge published a study demonstrating that the hydrocarbon pentadecane was produced by marine cyanobacteria in laboratory cultures. The researchers extrapolated that this compound might be important in the ocean. The molecule appears to relieve stress in curved membranes, so it’s found in things like chloroplasts, wherein tightly packed membranes require extreme curvature, Valentine explained. Certain cyanobacteria still synthesize the compound, while other ocean microbes readily consume it for energy.

Valentine authored a two-page commentary on the paper, along with Chris Reddy from Woods Hole, and decided to pursue the topic further with Arrington and Love. They visited the Gulf of Mexico in 2015, then the west Atlantic in 2017, to collect samples and run experiments.

The team sampled seawater from a nutrient-poor region of the Atlantic known as the Sargasso Sea, named for the floating sargassum seaweed swept in from the Gulf of Mexico. This is beautiful, clear, blue water with Bermuda smack in the middle, Valentine said.

Obtaining the samples was apparently a rather tricky endeavor. Because pentadecane is a common hydrocarbon in diesel fuel, the team had to take extra precautions to avoid contamination from the ship itself. They had the captain turn the ship into the wind so the exhaust wouldn’t taint the samples and they analyzed the chemical signature of the diesel to ensure it wasn’t the source of any pentadecane they found.

Extensive quantities of pentadecane are produced and consumed in the upper layers of the ocean. Credit: David Valentine

What’s more, no one could smoke, cook or paint on deck while the researchers were collecting seawater. “That was a big deal,” Valentine said, “I don’t know if you’ve ever been on a ship for an extended period of time, but you paint every day. It’s like the Golden Gate Bridge: You start at one end and by the time you get to the other end it’s time to start over.”

The precautions worked, and the team recovered pristine seawater samples. “Standing in front of the gas chromatograph in Woods Hole after the 2017 expedition, it was clear the samples were clean with no sign of diesel,” said co-lead author Love. “Pentadecane was unmistakable and was already showing clear oceanographic patterns even in the first couple of samples that [we] ran.”

Due to their vast numbers in the world’s ocean, Love continued, “just two types of marine cyanobacteria are adding up to 500 times more hydrocarbons to the ocean per year than the sum of all other types of petroleum inputs to the ocean, including natural oil seeps, oil spills, fuel dumping and run-off from land.” These microbes collectively produce 300-600 million metric tons of pentadecane per year, an amount that dwarfs the 1.3 million metric tons of hydrocarbons released from all other sources.

While these quantities are impressive, they’re a bit misleading. The authors point out that the pentadecane cycle spans 40% or more of the Earth’s surface, and more than one trillion quadrillion pentadecane-laden cyanobacterial cells are suspended in the sunlit region of the world’s ocean. However, the life cycle of those cells is typically less than two days. As a result, the researchers estimate that the ocean contains only around 2 million metric tons of pentadecane at any given time.

It’s a fast spinning wheel, Valentine explained, so the actual amount present at any point in time is not particularly large. “Every two days you produce and consume all the pentadecane in the ocean,” he said.

In the future, the researchers hope to link microbes’ genomics to their physiology and ecology. The team already has genome sequences for dozens of organisms that multiplied to consume the pentadecane in their samples. “The amount of information that’s there is incredible,” said Valentine, “and I think reveals just how much we don’t know about the ecology of a lot of hydrocarbon-consuming organisms.”

Having confirmed the existence and magnitude of this biohydrocarbon cycle, the team sought to tackle the question of whether its presence might prime the ocean to break down spilled petroleum. The key question, Arrington explained, is whether these abundant pentadecane-consuming microorganisms serve as an asset during oil spill cleanups. To investigate this, they added pentane—a petroleum hydrocarbon similar to pentadecane—to seawater sampled at various distances from natural oil seeps in the Gulf of Mexico.

The amount of pentadecane cycling through the oceans dwarfs the input of hydrocarbons from oil. However, the microbes involved in the pentadecane cycle are unlikely to be able to handle the chemical complexity of hydrocarbons from oil. Credit: David Valentine

They measured the overall respiration in each sample to see how long it took pentane-eating microbes to multiply. The researchers hypothesized that, if the pentadecane cycle truly primed microbes to consume other hydrocarbons as well, then all the samples should develop blooms at similar rates.

But this was not the case. Samples from near the oil seeps quickly developed blooms. “Within about a week of adding pentane, we saw an abundant population develop,” Valentine said. “And that gets slower and slower the further away you get, until, when you’re out in the North Atlantic, you can wait months and never see a bloom.” In fact, Arrington had to stay behind after the expedition at the facility in Woods Hole, Massachusetts to continue the experiment on the samples from the Atlantic because those blooms took so long to appear.

Interestingly, the team also found evidence that microbes belonging to another domain of life, Archaea, may also play a role in the pentadecane cycle. “We learned that a group of mysterious, globally abundant microbes—which have yet to be domesticated in the laboratory—may be fueled by pentadecane in the surface ocean,” said co-lead author Arrington.

The results beg the question why the presence of an enormous pentadecane cycle appeared to have no effect on the breakdown of the petrochemical pentane. “Oil is different from pentadecane,” Valentine said, “and you need to understand what the differences are, and what compounds actually make up oil, to understand how the ocean’s microbes are going to respond to it.”

Ultimately, the genes commonly used by microbes to consume the pentane are different than those used for pentadecane. “A microbe living in the clear waters offshore Bermuda is much less likely to encounter the petrochemical pentane compared to pentadecane produced by cyanobacteria, and therefore is less likely to carry the genes for pentane consumption,” said Arrington.

Loads of different microbial species can consume pentadecane, but this doesn’t imply that they can also consume other hydrocarbons, Valentine continued, especially given the diversity of hydrocarbon structures that exist in petroleum. There are less than a dozen common hydrocarbons that marine organisms produce, including pentadecane and methane. Meanwhile, petroleum comprises tens of thousands of different hydrocarbons. What’s more, we are now seeing that organisms able to break down complex petroleum products tend to live in greater abundance near natural oil seeps.

Valentine calls this phenomenon “biogeographic priming”—when the ocean’s microbial population is conditioned to a particular energy source in a specific geographic area. “And what we see with this work is a distinction between pentadecane and petroleum,” he said, “that is important for understanding how different ocean regions will respond to oil spills.”

Nutrient-poor gyres like the Sargasso Sea account for an impressive 40% of the Earth’s surface. But, ignoring the land, that still leaves 30% of the planet to explore for other biohydrocarbon cycles. Valentine thinks the processes in regions of higher productivity will be more complex, and perhaps will provide more priming for oil consumption. He also pointed out that nature’s blueprint for biological hydrocarbon production holds promise for efforts to develop the next generation of green energy.


Window to another world: Life is bubbling up to seafloor with petroleum from deep below


More information:
Connor R. Love et al. Microbial production and consumption of hydrocarbons in the global ocean, Nature Microbiology (2021). DOI: 10.1038/s41564-020-00859-8
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University of California – Santa Barbara

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Researchers discover an immense hydrocarbon cycle in the world’s ocean (2021, February 2)
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