Earth’s most abundant mineral finally has a name

An ancient meteorite and high-energy X-rays have helped scientists conclude a half century of effort to find, identify and characterize a mineral that makes up 38 percent of the Earth.

And in doing so, a team of scientists led by Oliver Tschauner, a mineralogist at the University of Las Vegas, clarified the definition of the Earth’s most abundant mineral – a high-density form of magnesium iron silicate, now called Bridgmanite – and defined estimated constraint ranges for its formation. Their research was performed at the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility located at DOE’s Argonne National Laboratory.

The mineral was named after 1964 Nobel laureate and pioneer of high-pressure research Percy Bridgman. The naming does more than fix a vexing gap in scientific lingo; it also will aid our understanding of the deep Earth.

To determine the makeup of the inner layers of the Earth, scientists need to test materials under extreme pressure and temperatures. For decades, scientists have believed a dense perovskite structure makes up 38 percent of the Earth’s volume, and that the chemical and physical properties of Bridgmanite have a large influence on how elements and heat flow through the Earth’s mantle. But since the mineral failed to survive the trip to the surface, no one has been able to test and prove its existence – a requirement for getting a name by the International Mineralogical Association.

Shock-compression that occurs in collisions of asteroid bodies in the solar system create the same hostile conditions of the deep Earth – roughly 2,100 degrees Celsius (3,800 degrees Farenheit) and pressures of about 240,000 times greater than sea-level air pressure. The shock occurs fast enough to inhibit the Bridgmanite breakdown that takes place when it comes under lower pressure, such as the Earth’s surface. Part of the debris from these collisions falls on Earth as meteorites, with the Bridgmanite “frozen” within a shock-melt vein. Previous tests on meteorites using transmission electron microscopy caused radiation damage to the samples and incomplete results.

So the team decided to try a new tactic: non-destructive micro-focused X-rays for diffraction analysis and novel fast-readout area-detector techniques. Tschauner and his colleagues from Caltech and the GeoSoilEnviroCARS, a University of Chicago-operated X-ray beamline at the APS at Argonne National Laboratory, took advantage of the X-rays’ high energy, which gives them the ability to penetrate the meteorite, and their intense brilliance, which leaves little of the radiation behind to cause damage.

The team examined a section of the highly shocked L-chondrite meteorite Tenham, which crashed in Australia in 1879. The GSECARS beamline was optimal for the study because it is one of the nation’s leading locations for conducting high-pressure research.

Bridgmanite grains are rare in the Tenhma meteorite, and they are smaller than 1 micrometer in diameter. Thus the team had to use a strongly focused beam and conduct highly spatially resolved diffraction mapping until an aggregate of Bridgmanite was identified and characterized by structural and compositional analysis.

This first natural specimen of Bridgmanite came with some surprises: It contains an unexpectedly high amount of ferric iron, beyond that of synthetic samples. Natural Bridgmanite also contains much more sodium than most synthetic samples. Thus the crystal chemistry of natural Bridgmanite provides novel crystal chemical insights. This natural sample of Bridgmanite may serve as a complement to experimental studies of deep mantle rocks in the future.

Prior to this study, knowledge about Bridgmanite’s properties has only been based on synthetic samples because it only remains stable below 660 kilometers (410 miles) depth at pressures of above 230 kbar (23 GPa). When it is brought out of the inner Earth, the lower pressures transform it back into less dense minerals. Some scientists believe that some inclusions on diamonds are the marks left by Bridgmanite that changed as the diamonds were unearthed.

The team’s results were published in the November 28 issue of the journal Science as “Discovery of bridgmanite, the most abundant mineral in Earth, in a shocked meteorite,” by O. Tschauner at University of Nevada in Las Vegas, N.V.; C. Ma; J.R. Beckett; G.R. Rossman at California Institute of Technology in Pasadena, Calif.; C. Prescher; V.B. Prakapenka at University of Chicago in Chicago, IL.

This research was funded by the U.S. Department of Energy, NASA, and NSF.

Good vibrations give electrons excitations that rock an insulator to go metallic

Vanadium atoms (blue) have unusually large thermal vibrations that stabilize the metallic state of a vanadium dioxide crystal. Red depicts oxygen atoms. -  ORNL
Vanadium atoms (blue) have unusually large thermal vibrations that stabilize the metallic state of a vanadium dioxide crystal. Red depicts oxygen atoms. – ORNL

For more than 50 years, scientists have debated what turns particular oxide insulators, in which electrons barely move, into metals, in which electrons flow freely. Some scientists sided with Nobel Prize-winning physicist Nevill Mott in thinking direct interactions between electrons were the key. Others believed, as did physicist Rudolf Peierls, that atomic vibrations and distortions trumped all. Now, a team led by the Department of Energy’s Oak Ridge National Laboratory has made an important advancement in understanding a classic transition-metal oxide, vanadium dioxide, by quantifying the thermodynamic forces driving the transformation. The results are published in the Nov. 10 advance online issue of Nature.

“We proved that phonons–the vibrations of the atoms–provide the driving force that stabilizes the metal phase when the material is heated,” said John Budai, who co-led the study with Jiawang Hong, a colleague in ORNL’s Materials Science and Technology Division.

Hong added, “This insight into how lattice vibrations can control phase stability in transition-metal oxides is needed to improve the performance of many multifunctional materials, including colossal magnetoresistors, superconductors and ferroelectrics.”

Today vanadium dioxide improves recording and storage media, strengthens structural alloys, and colors synthetic jewels. Tomorrow it may find its way into nanoscale actuators for switches, optical shutters that turn opaque on satellites to thwart intruding signals, and field-effect transistors to manipulate electronics in semiconductors and spintronics in devices that manipulate magnetic spin.

The next application we see may be energy-efficient “smart windows” coated with vanadium dioxide peppered with an impurity to control the transmission of heat and light. On cool days, windows would be transparent insulators that let in heat. On warm days, they would turn shiny and reflect the outside heat.

Complete thermodynamics


Materials are stabilized by a competition between internal energy and entropy (a measure of disorder that increases with temperature). While Mott and Peierls focused on energy, the ORNL-led team focused on the entropy.

Before the ORNL-led experiments, scientists knew the total amount of heat absorbed during vanadium dioxide’s transition from insulator to metal. But they didn’t know how much entropy was due to electrons and how much was due to atomic vibrations.

“This is the first complete description of thermodynamic forces controlling this archetypical metal-insulator transition,” said Budai.

The team’s current accomplishment was made possible by a novel combination of X-ray and neutron scattering tools, developed within the decade, that enabled lattice dynamics measurements and a calculation technique that Olle Hellman of Linköping University in Sweden recently developed to capture anharmonicity (a measure of nonlinearity in bond forces between atoms). It’s especially important that the calculations, performed by Hong, agree well with experiments because they can now be used to make new predictions for other materials.

The ORNL team came up with the idea to measure “incoherent” neutron scattering (each atom scatters independently) at ORNL’s Spallation Neutron Source (SNS) to determine the phonon spectra at many temperatures, and to measure coherent inelastic and diffuse X-ray scattering at Argonne National Laboratory’s Advanced Photon Source (APS) to probe collective vibrations in pristine crystals. Neutron measurements were enabled by the SNS’s large neutron flux, and X-ray measurements benefited from the high-resolution enabled by the high APS brightness. SNS and APS are DOE Office of Science User Facilities.

Among ORNL collaborators, Robert McQueeney made preliminary X-ray measurements and Lynn Boatner grew crystals for the experiment. Eliot Specht mapped phonon dispersions with diffuse X-ray scattering. Michael Manley and Olivier Delaire determined the phonon spectra using inelastic neutron scattering. Postdoctoral researcher Chen Li helped make experimental measurements and provided neutron expertise. Douglas Abernathy provided expertise with experimental beam lines, as did Argonne’s Ayman Said, Bogdan Leu and Jonathan Tischler.

Their measurements revealed that phonons with unusually large atomic vibrations and strong anharmonicity are responsible for about two-thirds of the total heat that each atom transfers during the lattice’s transition to a metallic phase.

“The entropy of the lattice vibrations competes against and overcomes the electronic energy, and that’s why the metallic phase is stabilized at high temperatures in vanadium dioxide,” Budai summed up. “Using comprehensive measurements and new calculations, we’re the first to close this gap and present convincing arguments for the dominant influence of low-energy, strongly anharmonic phonons.”

Atomic underpinnings


The findings reveal that the vanadium-dioxide lattice is anharmonic in the metal state. Think of atoms connected by bonds in a lattice as masses connected by springs. Pull on a mass and let go; it bounces. If the force is proportional to the distance a mass is pulled, the interaction is harmonic. Vanadium dioxide’s anharmonicity greatly complicates the way the lattice wiggles upon heating.

“A material that only had harmonic connections between atoms would have no thermal expansion; if you heat it up, it would stay the same size,” said Budai. Most materials, it turns out, are somewhat anharmonic. Metals, for example, expand when heated.

When heated to 340 kelvin (just above room temperature), vanadium dioxide turns from insulator to metal. Below 340 K, its lowest-energy lattice configuration is akin to a leaning cardboard box. Above 340 K, where entropy due to phonon vibrations dominates, its preferred state has all bond angles at 90 degrees. The phase change is fully reversible, so cooling a metal below the transition temperature reverts it to an insulator, and heating it past this point turns it metallic.

In metallic vanadium dioxide, each vanadium atom has one electron that is free to roam. In contrast, in insulating vanadium dioxide, that electron gets trapped in a chemical bond that forms vanadium dimers. “For understanding the atomic mechanisms, we needed theory,” Budai said.

That’s where Hong, a theorist at ORNL’s Center for Accelerating Materials Modeling, made critical contributions with quantum molecular dynamics calculations. He ran large-scale simulations at the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility at Lawrence Berkeley National Laboratory, using 1 million computing-core hours to simulate the lattice dynamics of metal and insulator phases of vanadium dioxide. All three types of experiments agreed well with Hong’s simulations. In addition, his calculation further reveals how phonon and electron contributions compete in the different phases.

Predicting new materials


“The theory not only provides us deep understanding of the experimental observations and reveals fundamental principles behind them,” said Hong, “but also gives us predictive modeling, which will accelerate fundamental and technological innovation by giving efficient strategies to design new materials with remarkable properties.”

Many other materials besides vanadium dioxide show a metal-to-insulator transition; however, the detailed role of lattice vibrations in controlling phase stability remains largely unknown. In future studies of other transition metal oxides, the researchers will continue to investigate the impact of anharmonic phonons on physical properties such as electrical conductivity and thermal transport. This fundamental research will help guide the development of improved energy-efficient materials.

Synthetic biology for space exploration

Synthetic biology could be a key to manned space exploration of Mars. -  Photo courtesy of NASA
Synthetic biology could be a key to manned space exploration of Mars. – Photo courtesy of NASA

Does synthetic biology hold the key to manned space exploration of Mars and the Moon? Berkeley Lab researchers have used synthetic biology to produce an inexpensive and reliable microbial-based alternative to the world’s most effective anti-malaria drug, and to develop clean, green and sustainable alternatives to gasoline, diesel and jet fuels. In the future, synthetic biology could also be used to make manned space missions more practical.

“Not only does synthetic biology promise to make the travel to extraterrestrial locations more practical and bearable, it could also be transformative once explorers arrive at their destination,” says Adam Arkin, director of Berkeley Lab’s Physical Biosciences Division (PBD) and a leading authority on synthetic and systems biology.

“During flight, the ability to augment fuel and other energy needs, to provide small amounts of needed materials, plus renewable, nutritional and taste-engineered food, and drugs-on-demand can save costs and increase astronaut health and welfare,” Arkin says. “At an extraterrestrial base, synthetic biology could even make more effective use of the catalytic activities of diverse organisms.”

Arkin is the senior author of a paper in the Journal of the Royal Society Interface that reports on a techno-economic analysis demonstrating “the significant utility of deploying non-traditional biological techniques to harness available volatiles and waste resources on manned long-duration space missions.” The paper is titled “Towards Synthetic Biological Approaches to Resource Utilization on Space Missions.” The lead and corresponding author is Amor Menezes, a postdoctoral scholar in Arkin’s research group at the University of California (UC) Berkeley. Other co-authors are John Cumbers and John Hogan with the NASA Ames Research Center.

One of the biggest challenges to manned space missions is the expense. The NASA rule-of-thumb is that every unit mass of payload launched requires the support of an additional 99 units of mass, with “support” encompassing everything from fuel to oxygen to food and medicine for the astronauts, etc. Most of the current technologies now deployed or under development for providing this support are abiotic, meaning non-biological. Arkin, Menezes and their collaborators have shown that providing this support with technologies based on existing biological processes is a more than viable alternative.

“Because synthetic biology allows us to engineer biological processes to our advantage, we found in our analysis that technologies, when using common space metrics such as mass, power and volume, have the potential to provide substantial cost savings, especially in mass,” Menezes says.

In their study, the authors looked at four target areas: fuel generation, food production, biopolymer synthesis, and pharmaceutical manufacture. They showed that for a 916 day manned mission to Mars, the use of microbial biomanufacturing capabilities could reduce the mass of fuel manufacturing by 56-percent, the mass of food-shipments by 38-percent, and the shipped mass to 3D-print a habitat for six by a whopping 85-percent. In addition, microbes could also completely replenish expired or irradiated stocks of pharmaceuticals, which would provide independence from unmanned re-supply spacecraft that take up to 210 days to arrive.

“Space has always provided a wonderful test of whether technology can meet strict engineering standards for both effect and safety,” Arkin says. “NASA has worked decades to ensure that the specifications that new technologies must meet are rigorous and realistic, which allowed us to perform up-front techno-economic analysis.”

The big advantage biological manufacturing holds over abiotic manufacturing is the remarkable ability of natural and engineered microbes to transform very simple starting substrates, such as carbon dioxide, water biomass or minerals, into materials that astronauts on long-term missions will need. This capability should prove especially useful for future extraterrestrial settlements.

“The mineral and carbon composition of other celestial bodies is different from the bulk of Earth, but the earth is diverse with many extreme environments that have some relationship to those that might be found at possible bases on the Moon or Mars,” Arkin says. “Microbes could be used to greatly augment the materials available at a landing site, enable the biomanufacturing of food and pharmaceuticals, and possibly even modify and enrich local soils for agriculture in controlled environments.”

The authors acknowledge that much of their analysis is speculative and that their calculations show a number of significant challenges to making biomanufacturing a feasible augmentation and replacement for abiotic technologies. However, they argue that the investment to overcome these barriers offers dramatic potential payoff for future space programs.

“We’ve got a long way to go since experimental proof-of-concept work in synthetic biology for space applications is just beginning, but long-duration manned missions are also a ways off,” says Menezes. “Abiotic technologies were developed for many, many decades before they were successfully utilized in space, so of course biological technologies have some catching-up to do. However, this catching-up may not be that much, and in some cases, the biological technologies may already be superior to their abiotic counterparts.”

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This research was supported by the National Aeronautics and Space Administration (NASA) and the University of California, Santa Cruz.

Lawrence Berkeley National Laboratory addresses the world’s most urgent scientific challenges by advancing sustainable energy, protecting human health, creating new materials, and revealing the origin and fate of the universe. Founded in 1931, Berkeley Lab’s scientific expertise has been recognized with 13 Nobel prizes. The University of California manages Berkeley Lab for the U.S. Department of Energy’s Office of Science. For more, visit http://www.lbl.gov.

Microscopic diamonds suggest cosmic impact responsible for major period of climate change

Around 12,800 years ago, a sudden, catastrophic event plunged much of the Earth into a period of cold climatic conditions and drought. This drastic climate change-the Younger Dryas-coincided with the extinction of Pleistocene megafauna, such as the saber-tooth cats and the mastodon, and resulted in major declines in prehistoric human populations, including the termination of the Clovis culture.

With limited evidence, several rival theories have been proposed about the event that sparked this period, such as a collapse of the North American ice sheets, a major volcanic eruption, or a solar flare.


However, in a study published in The Journal of Geology, an international group of scientists analyzing existing and new evidence have determined a cosmic impact event, such as a comet or meteorite, to be the only plausible hypothesis to explain all the unusual occurrences at the onset of the Younger Dryas period.

Researchers from 21 universities in 6 countries believe the key to the mystery of the Big Freeze lies in nanodiamonds scattered across Europe, North America, and portions of South America, in a 50-million-square-kilometer area known as the Younger Dryas Boundary (YDB) field.

Microscopic nanodiamonds, melt-glass, carbon spherules, and other high-temperature materials are found in abundance throughout the YDB field, in a thin layer located only meters from the Earth’s surface. Because these materials formed at temperatures in excess of 2200 degrees Celsius, the fact they are present together so near to the surface suggests they were likely created by a major extraterrestrial impact event.

In addition to providing support for the cosmic impact event hypothesis, the study also offers evidence to reject alternate hypotheses for the formation of the YDB nanodiamonds, such as by wildfires, volcanism, or meteoric flux.

The team’s findings serve to settle the debate about the presence of nanodiamonds in the YDB field and challenge existing paradigms across multiple disciplines, including impact dynamics, archaeology, paleontology, limnology, and palynology.

Birth of a mineral

<IMG SRC="/Images/904289364.jpg" WIDTH="350" HEIGHT="233" BORDER="0" ALT="An aragonite crystal — with its characteristic 'sheaf of wheat' look — consumed a particle of amorphous calcium carbonate as it formed. – Nielsen et al. 2014/Science“>
An aragonite crystal — with its characteristic ‘sheaf of wheat’ look — consumed a particle of amorphous calcium carbonate as it formed. – Nielsen et al. 2014/Science

One of the most important molecules on earth, calcium carbonate crystallizes into chalk, shells and minerals the world over. In a study led by the Department of Energy’s Pacific Northwest National Laboratory, researchers used a powerful microscope that allows them to see the birth of crystals in real time, giving them a peek at how different calcium carbonate crystals form, they report in September 5 issue of Science.

The results might help scientists understand how to lock carbon dioxide out of the atmosphere as well as how to better reconstruct ancient climates.

“Carbonates are most important for what they represent, interactions between biology and Earth,” said lead researcher James De Yoreo, a materials scientist at PNNL. “For a decade, we’ve been studying the formation pathways of carbonates using high-powered microscopes, but we hadn’t had the tools to watch the crystals form in real time. Now we know the pathways are far more complicated than envisioned in the models established in the twentieth century.”

Earth’s Reserve


Calcium carbonate is the largest reservoir of carbon on the planet. It is found in rocks the world over, shells of both land- and water-dwelling creatures, and pearls, coral, marble and limestone. When carbon resides within calcium carbonate, it is not hanging out in the atmosphere as carbon dioxide, warming the world. Understanding how calcium carbonate turns into various minerals could help scientists control its formation to keep carbon dioxide from getting into the atmosphere.

Calcium carbonate deposits also contain a record of Earth’s history. Researchers reconstructing ancient climates delve into the mineral for a record of temperature and atmospheric composition, environmental conditions and the state of the ocean at the time those minerals formed. A better understanding of its formation pathways will likely provide insights into those events.

To get a handle on mineral formation, researchers at PNNL, the University of California, Berkeley, and Lawrence Berkeley National Laboratory examined the earliest step to becoming a mineral, called nucleation. In nucleation, molecules assemble into a tiny crystal that then grows with great speed. Nucleation has been difficult to study because it happens suddenly and unpredictably, so the scientists needed a microscope that could watch the process in real time.

Come to Order


In the 20th century, researchers established a theory that crystals formed in an orderly fashion. Once the ordered nucleus formed, more molecules added to the crystal, growing the mineral but not changing its structure. Recently, however, scientists have wondered if the process might be more complicated, with other things contributing to mineral formation. For example, in previous experiments they’ve seen forms of calcium carbonate that appear to be dense liquids that could be sources for minerals.

Researchers have also wondered if calcite forms from less stable varieties or directly from calcium and carbonate dissolved in the liquid. Aragonite and vaterite are calcium carbonate minerals with slightly different crystal architectures than calcite and could represent a step in calcite’s formation. The fourth form called amorphous calcium carbonate – or ACC, which could be liquid or solid, might also be a reservoir for sprouting minerals.

To find out, the team created a miniature lab under a transmission electron microscope at the Molecular Foundry, a DOE Office of Science User Facility at LBNL. In this miniature lab, they mixed sodium bicarbonate (used to make club soda) and calcium chloride (similar to table salt) in water. At high enough concentrations, crystals grew. Videos of nucleating and growing crystals recorded what happened [URLs to come].

Morphing Minerals


The videos revealed that mineral growth took many pathways. Some crystals formed through a two-step process. For example, droplet-like particles of ACC formed, then crystals of aragonite or vaterite appeared on the surface of the droplets. As the new crystals formed, they consumed the calcium carbonate within the drop on which they nucleated.

Other crystals formed directly from the solution, appearing by themselves far away from any ACC particles. Multiple forms often nucleated in a single experiment — at least one calcite crystal formed on top of an aragonite crystal while vaterite crystals grew nearby.

What the team didn’t see in and among the many options, however, was calcite forming from ACC even though researchers widely expect it to happen. Whether that means it never does, De Yoreo can’t say for certain. But after looking at hundreds of nucleation events, he said it is a very unlikely event.

“This is the first time we have directly visualized the formation process,” said De Yoreo. “We observed many pathways happening simultaneously. And they happened randomly. We were never able to predict what was going to come up next. In order to control the process, we’d need to introduce some kind of template that can direct which crystal forms and where.”

In future work, De Yoreo and colleagues plan to investigate how living organisms control the nucleation process to build their shells and pearls. Biological organisms keep a store of mineral components in their cells and have evolved ways to make nucleation happen when and where needed. The team is curious to know how they use cellular molecules to achieve this control.




Video
Click on this image to view the .mp4 video
Diamond-shaped crystals of calcite form directly from solution. A round particle that could be either amorphous calcium carbonate or vaterite forms nearby. – Nielsen et al. 2014/Science

Mantle plumes crack continents

In some parts of the Earth, material rises upwards like a column from the boundary layer of the Earth’s core and the lower mantel to just below the Earth’s crust hundreds of kilometres above. Halted by the resistance of the hard crust and lithospheric mantle, the flow of material becomes wider, taking on a mushroom-like shape. Specialists call these magma columns “mantle plumes” or simply “plumes”.

Are mantel plumes responsible for the African rift system?


Geologists believe that plumes are not just responsible for creating volcanoes outside of tectonically active areas – they can also break up continents. The scientists offer the Danakil Depression (the lowlands in the Ethiopia-Eritrea-Djibouti triangle) as an example of this. This “triple junction” is extremely tectonically and volcanically active. Geologists believe that the so-called Afar plume is rising up below it and has created a rift system that forks into the Red Sea, the Gulf of Aden and Africa’s Great Rift Valley. However, the sheer length of time required, geologically speaking, for this process to take place, means that nobody is able to confirm or disprove with absolute certainty that the force of a plume causes continental breakup.

Simulations becoming more realistic


Evgueni Burov, a Professor at the University of Paris VI, and Taras Gerya, Professor of Geophysics at ETH Zurich, have now taken a step closer to solving this geological mystery with a new computer model. Their paper has recently been published in the journal Nature. The two researchers conducted numerical experiments to reproduce the Earth’s surface in high-resolution 3D.

These simulations show that the rising flow of material is strong enough to cause continental breakup if the tectonic plate is under (weak) tensile stress. “The force exerted by a plume on a plate is actually too weak to break it up,” says Gerya. In experiments using simple models, the researchers allowed the plumes to hit an unstressed plate, which did not cause it to break, but merely formed a round hump. However, when the geophysicists modelled the same process with a plate under weak tensile stress, it broke apart, forming a crevice and rift system like the ones found around the world.

“The process can be compared to a taut piece of plastic film. Weak, pointed force is enough to tear the film, but if the film is not pulled taut, it is extremely difficult to tear.” This mechanism has already been proposed in the past as a possible model for explaining continental breakup, but had never been outlined in plausible terms before now.

First high-resolution simulations

“We are the first to create such a high-resolution model which demonstrates how a plume interacts with a plate under tensile stress,” says Gerya. Fast and powerful computers and stable algorithms programmed by the scientists themselves were required for the simulations. The researchers benefited from technical advances made and experience accumulated by the ETH professor in this field over the past ten years.

In the model, the deformations are created quickly from a geological point of view. Rift systems several kilometres deep and more than a thousand kilometres long can form after “just” two million years. The processes are therefore up to ten times faster than tectonic processes such as subduction and 50 times faster than the Alpine orogeny, for example.

Disputed idea


The idea of mantel plumes is widely disputed, with some researchers denying that they even exist. “I think it is much more likely that they do exist,” says Gerya. As is often the case in geology, especially when researching the Earth’s interior, such processes and phenomena like the existence of plumes cannot be observed directly. Furthermore, the periods over which geological processes take place are far too long for humans to experience first-hand. “So far, we have only been able to observe the effects that plumes have on the Earth’s surface and on the propagation of seismic waves in the Earth’s interior.”

The scientists are therefore reliant on good, realistic models that show the processes in a geological time lapse. How realistic the calculated simulations are depends on the parameters used. The plume-plate interaction model incorporated physical laws, the characteristics of materials in the Earth’s crust and mantle, and temperature and pressure conditions. “We know the rules, but humans generally lack the intuition to identify how they interact on geological timescales.”

Composition of Earth’s mantle revisited

Research published recently in Science suggested that the makeup of the Earth’s lower mantle, which makes up the largest part of the Earth by volume, is significantly different than previously thought.

Understanding the composition of the mantle is essential to seismology, the study of earthquakes and movement below the Earth’s surface, and should shed light on unexplained seismic phenomena observed there.

Though humans haven’t yet managed to drill further than seven and a half miles into the Earth, we’ve built a comprehensive picture of what’s beneath our feet through calculations and limited observation. We all live atop the crust, the thin outer layer; just beneath is the mantle, outer core and finally inner core. The lower portion of the mantle is the largest layer – stretching from 400 to 1,800 miles below the surface – and gives off the most heat. Until now, the entire lower mantle was thought to be composed of the same mineral throughout: ferromagnesian silicate, arranged in a type of structure called perovskite.

The pressure and heat of the lower mantle is intense – more than 3,500° Fahrenheit. Materials may have very different properties at these conditions; structures may exist there that would collapse at the surface.

To simulate these conditions, researchers use special facilities at the Advanced Photon Source, where they shine high-powered lasers to heat up the sample inside a pressure cell made of a pair of diamonds. Then they aim powerful beams of X-rays at the sample, which hit and scatter in all directions. By gathering the scatter data, scientists can reconstruct how the atoms in the sample were arranged.

The team found that at conditions that exist below about 1,200 miles underground, the ferromagnesian silicate perovskite actually breaks into two separate phases. One contains nearly no iron, while the other is full of iron. The iron-rich phase, called the H-phase, is much more stable under these conditions.

“We still don’t fully understand the chemistry of the H-phase,” said lead author and Carnegie Institution of Washington scientist Li Zhang. “But this finding indicates that all geodynamic models need to be reconsidered to take the H-phase into account. And there could be even more unidentified phases down there in the lower mantle as well, waiting to be identified.”

The facilities at Argonne’s Advanced Photon Source were key to the findings, said Carnegie scientist Yue Meng, also an author on the paper. “Recent technological advances at our beamline allowed us to create the conditions to simulate these intense temperatures and pressures and probe the changes in chemistry and structure of the sample in situ,” she said.

“What distinguished this work was the exceptional attention to detail in every aspect of the research – it demonstrates a new level for high-pressure research,” Meng added.

Team develops a geothermometer for methane formation

John Eiler (left) and Daniel Stolper (right) with the Caltech-led team's prototype mass spectrometer -- the Thermo IRMS 253 Ultra. This instrument is the first equipped to measure abundances of rare isotopic versions of complex molecules, even where combinations of isotopic substitutions result in closely similar masses. This machine enabled the first precise measurements of molecules of methane that contain two heavy isotopes -- 13CH3D, which incorporates both a carbon-13 atom and a deuterium atom, and 12CH2D2, which includes two deuterium atoms. -  Caltech
John Eiler (left) and Daniel Stolper (right) with the Caltech-led team’s prototype mass spectrometer — the Thermo IRMS 253 Ultra. This instrument is the first equipped to measure abundances of rare isotopic versions of complex molecules, even where combinations of isotopic substitutions result in closely similar masses. This machine enabled the first precise measurements of molecules of methane that contain two heavy isotopes — 13CH3D, which incorporates both a carbon-13 atom and a deuterium atom, and 12CH2D2, which includes two deuterium atoms. – Caltech

Methane is a simple molecule consisting of just one carbon atom bound to four hydrogen atoms. But that simplicity belies the complex role the molecule plays on Earth-it is an important greenhouse gas, is chemically active in the atmosphere, is used in many ecosystems as a kind of metabolic currency, and is the main component of natural gas, which is an energy source.

Methane also poses a complex scientific challenge: it forms through a number of different biological and nonbiological processes under a wide range of conditions. For example, microbes that live in cows’ stomachs make it; it forms by thermal breakdown of buried organic matter; and it is released by hot hydrothermal vents on the sea floor. And, unlike many other, more structurally complex molecules, simply knowing its chemical formula does not necessarily reveal how it formed. Therefore, it can be difficult to know where a sample of methane actually came from.

But now a team of scientists led by Caltech geochemist John M. Eiler has developed a new technique that can, for the first time, determine the temperature at which a natural methane sample formed. Since methane produced biologically in nature forms below about 80°C, and methane created through the thermal breakdown of more complex organic matter forms at higher temperatures (reaching 160°C�°C, depending on the depth of formation), this determination can aid in figuring out how and where the gas formed.

A paper describing the new technique and its first applications as a geothermometer appears in a special section about natural gas in the current issue of the journal Science. Former Caltech graduate student Daniel A. Stolper (PhD ’14) is the lead author on the paper.

“Everyone who looks at methane sees problems, sees questions, and all of these will be answered through basic understanding of its formation, its storage, its chemical pathways,” says Eiler, the Robert P. Sharp Professor of Geology and professor of geochemistry at Caltech.

“The issue with many natural gas deposits is that where you find them-where you go into the ground and drill for the methane-is not where the gas was created. Many of the gases we’re dealing with have moved,” says Stolper. “In making these measurements of temperature, we are able to really, for the first time, say in an independent way, ‘We know the temperature, and thus the environment where this methane was formed.'”

Eiler’s group determines the sources and formation conditions of materials by looking at the distribution of heavy isotopes-species of atoms that have extra neutrons in their nuclei and therefore have different chemistry. For example, the most abundant form of carbon is carbon-12, which has six protons and six neutrons in its nucleus. However, about 1 percent of all carbon possesses an extra neutron, which makes carbon-13. Chemicals compete for these heavy isotopes because they slow molecular motions, making molecules more stable. But these isotopes are also very rare, so there is a chemical tug-of-war between molecules, which ends up concentrating the isotopes in the molecules that benefit most from their stabilizing effects. Similarly, the heavy isotopes like to bind, or “clump,” with each other, meaning that there will be an excess of molecules containing two or more of the isotopes compared to molecules containing just one. This clumping effect is strong at low temperatures and diminishes at higher temperatures. Therefore, determining how many of the molecules in a sample contain heavy isotopes clumped together can tell you something about the temperature at which the sample formed.

Eiler’s group has previously used such a “clumped isotope” technique to determine the body temperatures of dinosaurs, ground temperatures in ancient East Africa, and surface temperatures of early Mars. Those analyses looked at the clumping of carbon-13 and oxygen-18 in various minerals. In the new work, Eiler and his colleagues were able to examine the clumping of carbon-13 and deuterium (hydrogen-2).

The key enabling technology was a new mass spectrometer that the team designed in collaboration with Thermo Fisher, mixing and matching existing technologies to piece together a new platform. The prototype spectrometer, the Thermo IRMS 253 Ultra, is equipped to analyze samples in a way that measures the abundances of several rare versions, or isotopologues, of the methane molecule, including two “clumped isotope” species: 13CH3D, which has both a carbon-13 atom and a deuterium atom, and 12CH2D2, which includes two deuterium atoms.

Using the new spectrometer, the researchers first tested gases they made in the laboratory to make sure the method returned the correct formation temperatures.

They then moved on to analyze samples taken from environments where much is known about the conditions under which methane likely formed. For example, sometimes when methane forms in shale, an impermeable rock, it is trapped and stored, so that it cannot migrate from its point of origin. In such cases, detailed knowledge of the temperature history of the rock constrains the possible formation temperature of methane in that rock. Eiler and Stolper analyzed samples of methane from the Haynesville Shale, located in parts of Arkansas, Texas, and Louisiana, where the shale is not thought to have moved much after methane generation. And indeed, the clumped isotope technique returned a range of temperatures (169°C�°C) that correspond well with current reservoir temperatures (163°C�°C). The method was also spot-on for methane collected from gas that formed as a product of oil-eating bugs living on top of oil reserves in the Gulf of Mexico. It returned temperatures of 34°C and 48°C plus or minus 8°C for those samples, and the known temperatures of the sampling locations were 42°C and 48°C, respectively.

To validate further the new technique, the researchers next looked at methane from the Marcellus Shale, a formation beneath much of the Appalachian basin, where the gas-trapping rock is known to have formed at high temperature before being uplifted into a cooler environment. The scientists wanted to be sure that the methane did not reset to the colder temperature after formation. Using their clumped isotope technique, the researchers verified this, returning a high formation temperature.

“It must be that once the methane exists and is stable, it’s a fossil remnant of what its formation environment was like,” Eiler says. “It only remembers where it formed.”

An important application of the technique is suggested by the group’s measurements of methane from the Antrim Shale in Michigan, where groundwater contains both biologically and thermally produced methane. Clumped isotope temperatures returned for samples from the area clearly revealed the different origins of the gases, hitting about 40°C for a biologically produced sample and about 115°C for a sample involving a mix of biologically and thermally produced methane.

“There are many cases where it is unclear whether methane in a sample of groundwater is the product of subsurface biological communities or has leaked from petroleum-forming systems,” says Eiler. “Our results from the Antrim Shale indicate that this clumped isotope technique will be useful for distinguishing between these possible sources.”

One final example, from the Potiguar Basin in Brazil, demonstrates another way the new method will serve geologists. In this case the methane was dissolved in oil and had been free to migrate from its original location. The researchers initially thought there was a problem with their analysis because the temperature they returned was much higher than the known temperature of the oil. However, recent evidence from drill core rocks from the region shows that the deepest parts of the system actually got very hot millions of years ago. This has led to a new interpretation suggesting that the methane gas originated deep in the system at high temperatures and then percolated up and mixed into the oil.

“This shows that our new technique is not just a geothermometer for methane formation,” says Stolper. “It’s also something you can use to think about the geology of the system.”

How productive are the ore factories in the deep sea?

About ten years after the first moon landing, scientists on earth made a discovery that proved that our home planet still holds a lot of surprises in store for us. Looking through the portholes of the submersible ALVIN near the bottom of the Pacific Ocean in 1979, American scientists saw for the first time chimneys, several meters tall, from which black water at about 300 degrees and saturated with minerals shot out. What we have found out since then: These “black smokers”, also called hydrothermal vents, exist in all oceans. They occur along the boundaries of tectonic plates along the submarine volcanic chains. However, to date many details of these systems remain unexplained.

One question that has long and intensively been discussed in research is: Where and how deep does seawater penetrate into the seafloor to take up heat and minerals before it leaves the ocean floor at hydrothermal vents? This is of enormous importance for both, the cooling of the underwater volcanoes as well as for the amount of materials dissolved. Using a complex 3-D computer model, scientists at GEOMAR Helmholtz Centre for Ocean Research Kiel were now able to understand the paths of the water toward the black smokers. The study appears in the current issue of the world-renowned scientific journal “Nature“.

In general, it is well known that seawater penetrates into the Earth’s interior through cracks and crevices along the plate boundaries. The seawater is heated by the magma; the hot water rises again, leaches metals and other elements from the ground and is released as a black colored solution. “However, in detail it is somewhat unclear whether the water enters the ocean floor in the immediate vicinity of the vents and flows upward immediately, or whether it travels long distances underground before venting,” explains Dr. Jörg Hasenclever from GEOMAR.

This question is not only important for the fundamental understanding of processes on our planet. It also has very practical implications. Some of the materials leached from the underground are deposited on the seabed and form ore deposits that may be of economically interest. There is a major debate, however, how large the resource potential of these deposits might be. “When we know which paths the water travels underground, we can better estimate the quantities of materials released by black smokers over thousands of years,” says Hasenclever.

Hasenclever and his colleagues have used for the first time a high-resolution computer model of the seafloor to simulate a six kilometer long and deep, and 16 kilometer wide section of a mid-ocean ridge in the Pacific. Among the data used by the model was the heat distribution in the oceanic crust, which is known from seismic studies. In addition, the model also considered the permeability of the rock and the special physical properties of water.

The simulation required several weeks of computing time. The result: “There are actually two different flow paths – about half the water seeps in near the vents, where the ground is very warm. The other half seeps in at greater distances and migrates for kilometers through the seafloor before exiting years later.” Thus, the current study partially confirmed results from a computer model, which were published in 2008 in the scientific journal “Science”. “However, the colleagues back then were able to simulate only a much smaller region of the ocean floor and therefore identified only the short paths near the black smokers,” says Hasenclever.

The current study is based on fundamental work on the modeling of the seafloor, which was conducted in the group of Professor Lars Rüpke within the framework of the Kiel Cluster of Excellence “The Future Ocean”. It provides scientists worldwide with the basis for further investigations to see how much ore is actually on and in the seabed, and whether or not deep-sea mining on a large scale could ever become worthwhile. “So far, we only know the surface of the ore deposits at hydrothermal vents. Nobody knows exactly how much metal is really deposited there. All the discussions about the pros and cons of deep-sea ore mining are based on a very thin database,” says co-author Prof. Dr. Colin Devey from GEOMAR. “We need to collect a lot more data on hydrothermal systems before we can make reliable statements”.

Vitamin B3 might have been made in space, delivered to Earth by meteorites

Karen Smith crushes meteorites with a mortar and pestle in Goddard's Astrobiology Analytical Laboratory to prepare them for analysis. Vitamin B3 was found in all eight meteorites analyzed in the study. -  Karen Smith
Karen Smith crushes meteorites with a mortar and pestle in Goddard’s Astrobiology Analytical Laboratory to prepare them for analysis. Vitamin B3 was found in all eight meteorites analyzed in the study. – Karen Smith

Ancient Earth might have had an extraterrestrial supply of vitamin B3 delivered by carbon-rich meteorites, according to a new analysis by NASA-funded researchers. The result supports a theory that the origin of life may have been assisted by a supply of key molecules created in space and brought to Earth by comet and meteor impacts.

“It is always difficult to put a value on the connection between meteorites and the origin of life; for example, earlier work has shown that vitamin B3 could have been produced non-biologically on ancient Earth, but it’s possible that an added source of vitamin B3 could have been helpful,” said Karen Smith of Pennsylvania State University in University Park, Pa. “Vitamin B3, also called nicotinic acid or niacin, is a precursor to NAD (nicotinamide adenine dinucleotide), which is essential to metabolism and likely very ancient in origin.” Smith is lead author of a paper on this research, along with co-authors from NASA’s Goddard Space Flight Center in Greenbelt, Md., now available online in the journal Geochimica et Cosmochimica Acta.

This is not the first time vitamin B3 has been found in meteorites. In 2001 a team led by Sandra Pizzarello of Arizona State University, in Tempe discovered it along with related molecules called pyridine carboxylic acids in the Tagish Lake meteorite.

In the new work at Goddard’s Astrobiology Analytical Laboratory, Smith and her team analyzed samples from eight different carbon-rich meteorites, called “CM-2 type carbonaceous chondrites” and found vitamin B3 at levels ranging from about 30 to 600 parts-per-billion. They also found other pyridine carboxylic acids at similar concentrations and, for the first time, found pyridine dicarboxylic acids.

“We discovered a pattern – less vitamin B3 (and other pyridine carboxylic acids) was found in meteorites that came from asteroids that were more altered by liquid water. One possibility may be that these molecules were destroyed during the prolonged contact with liquid water,” said Smith. “We also performed preliminary laboratory experiments simulating conditions in interstellar space and showed that the synthesis of vitamin B3 and other pyridine carboxylic acids might be possible on ice grains.”

Scientists think the solar system formed when a dense cloud of gas, dust, and ice grains collapsed under its own gravity. Clumps of dust and ice aggregated into comets and asteroids, some of which collided together to form moon-sized objects or planetesimals, and some of those eventually merged to become planets.

Space is filled with radiation from nearby stars as well as from violent events in deep space like exploding stars and black holes devouring matter. This radiation could have powered chemical reactions in the cloud (nebula) that formed the solar system, and some of those reactions may have produced biologically important molecules like vitamin B3.

Asteroids and comets are considered more or less pristine remnants from our solar system’s formation, and many meteorites are prized samples from asteroids that happen to be conveniently delivered to Earth. However, some asteroids are less pristine than others. Asteroids can be altered shortly after they form by chemical reactions in liquid water. As they grow, asteroids incorporate radioactive material present in the solar system nebula. If enough radioactive material accumulates in an asteroid, the heat produced as it decays will be sufficient to melt ice inside the asteroid. Researchers can determine how much an asteroid was altered by water by examining chemical and mineralogical signatures of water alteration in meteorites from those asteroids.

When asteroids collide with meteoroids or other asteroids, pieces break off and some of them eventually make their way to Earth as meteorites. Although meteorites are valued samples from asteroids, they are rarely recovered immediately after they fall to Earth. This leaves them vulnerable to contamination from terrestrial chemistry and life.

The team doubts the vitamin B3 and other molecules found in their meteorites came from terrestrial life for two reasons. First, the vitamin B3 was found along with its structural isomers – related molecules that have the same chemical formula but whose atoms are attached in a different order. These other molecules aren’t used by life. Non-biological chemistry tends to produce a wide variety of molecules — basically everything permitted by the materials and conditions present — but life makes only the molecules it needs. If contamination from terrestrial life was the source of the vitamin B3 in the meteorites, then only the vitamin should have been found, not the other, related molecules.

Second, the amount of vitamin B3 found was related to how much the parent asteroids had been altered by water. This correlation with conditions on the asteroids would be unlikely if the vitamin came from contamination on Earth.

The team plans to conduct additional interstellar chemistry experiments under more realistic conditions to better understand how vitamin B3 can form on ice grains in space. “We used pyridine-carbon dioxide ice in the initial experiment,” said Smith. “We want to add water ice (the dominant component of interstellar ices) and start from simpler organic precursors (building-block molecules) of vitamin B3 to help verify our result.”