Asteroid impacts on Earth make structurally bizarre diamonds

Diamond grains from the Canyon Diablo meteorite are shown. The tick marks are spaced one-fifth of a millimeter (200 microns) apart. -  Arizona State University/Laurence Garvie
Diamond grains from the Canyon Diablo meteorite are shown. The tick marks are spaced one-fifth of a millimeter (200 microns) apart. – Arizona State University/Laurence Garvie

Scientists have argued for half a century about the existence of a form of diamond called lonsdaleite, which is associated with impacts by meteorites and asteroids. A group of scientists based mostly at Arizona State University now show that what has been called lonsdaleite is in fact a structurally disordered form of ordinary diamond.

The scientists’ report is published in Nature Communications, Nov. 20, by Péter Németh, a former ASU visiting researcher (now with the Research Centre of Natural Sciences of the Hungarian Academy of Sciences), together with ASU’s Laurence Garvie, Toshihiro Aoki and Peter Buseck, plus Natalia Dubrovinskaia and Leonid Dubrovinsky from the University of Bayreuth in Germany. Buseck and Garvie are with ASU’s School of Earth and Space Exploration, while Aoki is with ASU’s LeRoy Eyring Center for Solid State Science.

“So-called lonsdaleite is actually the long-familiar cubic form of diamond, but it’s full of defects,” says Péter Németh. These can occur, he explains, due to shock metamorphism, plastic deformation or unequilibrated crystal growth.

The lonsdaleite story began almost 50 years ago. Scientists reported that a large meteorite, called Canyon Diablo after the crater it formed on impact in northern Arizona, contained a new form of diamond with a hexagonal structure. They described it as an impact-related mineral and called it lonsdaleite, after Dame Kathleen Lonsdale, a famous crystallographer.

Since then, “lonsdaleite” has been widely used by scientists as an indicator of ancient asteroidal impacts on Earth, including those linked to mass extinctions. In addition, it has been thought to have mechanical properties superior to ordinary diamond, giving it high potential industrial significance. All this focused much interest on the mineral, although pure crystals of it, even tiny ones, have never been found or synthesized. That posed a long-standing puzzle.

The ASU scientists approached the question by re-examining Canyon Diablo diamonds and investigating laboratory samples prepared under conditions in which lonsdaleite has been reported.

Using the advanced electron microscopes in ASU’s Center for Solid State Science, the team discovered, both in the Canyon Diablo and the synthetic samples, new types of diamond twins and nanometer-scale structural complexity. These give rise to features attributed to lonsdaleite.

“Most crystals have regular repeating structures, much like the bricks in a well-built wall,” says Peter Buseck. However, interruptions can occur in the regularity, and these are called defects. “Defects are intermixed with the normal diamond structure, just as if the wall had an occasional half-brick or longer brick or row of bricks that’s slightly displaced to one side or another.”

The outcome of the new work is that so-called lonsdaleite is the same as the regular cubic form of diamond, but it has been subjected to shock or pressure that caused defects within the crystal structure.

One consequence of the new work is that many scientific studies based on the presumption that lonsdaleite is a separate type of diamond need to be re-examined. The study implies that both shock and static compression can produce an intensely defective diamond structure.

The new discovery also suggests that the observed structural complexity of the Canyon Diablo diamond results in interesting mechanical properties. It could be a candidate for a product with exceptional hardness.

The School of Earth and Space Exploration is an academic unit of ASU’s College of Liberal Arts and Sciences.

Asteroid impacts on Earth make structurally bizarre diamonds

Diamond grains from the Canyon Diablo meteorite are shown. The tick marks are spaced one-fifth of a millimeter (200 microns) apart. -  Arizona State University/Laurence Garvie
Diamond grains from the Canyon Diablo meteorite are shown. The tick marks are spaced one-fifth of a millimeter (200 microns) apart. – Arizona State University/Laurence Garvie

Scientists have argued for half a century about the existence of a form of diamond called lonsdaleite, which is associated with impacts by meteorites and asteroids. A group of scientists based mostly at Arizona State University now show that what has been called lonsdaleite is in fact a structurally disordered form of ordinary diamond.

The scientists’ report is published in Nature Communications, Nov. 20, by Péter Németh, a former ASU visiting researcher (now with the Research Centre of Natural Sciences of the Hungarian Academy of Sciences), together with ASU’s Laurence Garvie, Toshihiro Aoki and Peter Buseck, plus Natalia Dubrovinskaia and Leonid Dubrovinsky from the University of Bayreuth in Germany. Buseck and Garvie are with ASU’s School of Earth and Space Exploration, while Aoki is with ASU’s LeRoy Eyring Center for Solid State Science.

“So-called lonsdaleite is actually the long-familiar cubic form of diamond, but it’s full of defects,” says Péter Németh. These can occur, he explains, due to shock metamorphism, plastic deformation or unequilibrated crystal growth.

The lonsdaleite story began almost 50 years ago. Scientists reported that a large meteorite, called Canyon Diablo after the crater it formed on impact in northern Arizona, contained a new form of diamond with a hexagonal structure. They described it as an impact-related mineral and called it lonsdaleite, after Dame Kathleen Lonsdale, a famous crystallographer.

Since then, “lonsdaleite” has been widely used by scientists as an indicator of ancient asteroidal impacts on Earth, including those linked to mass extinctions. In addition, it has been thought to have mechanical properties superior to ordinary diamond, giving it high potential industrial significance. All this focused much interest on the mineral, although pure crystals of it, even tiny ones, have never been found or synthesized. That posed a long-standing puzzle.

The ASU scientists approached the question by re-examining Canyon Diablo diamonds and investigating laboratory samples prepared under conditions in which lonsdaleite has been reported.

Using the advanced electron microscopes in ASU’s Center for Solid State Science, the team discovered, both in the Canyon Diablo and the synthetic samples, new types of diamond twins and nanometer-scale structural complexity. These give rise to features attributed to lonsdaleite.

“Most crystals have regular repeating structures, much like the bricks in a well-built wall,” says Peter Buseck. However, interruptions can occur in the regularity, and these are called defects. “Defects are intermixed with the normal diamond structure, just as if the wall had an occasional half-brick or longer brick or row of bricks that’s slightly displaced to one side or another.”

The outcome of the new work is that so-called lonsdaleite is the same as the regular cubic form of diamond, but it has been subjected to shock or pressure that caused defects within the crystal structure.

One consequence of the new work is that many scientific studies based on the presumption that lonsdaleite is a separate type of diamond need to be re-examined. The study implies that both shock and static compression can produce an intensely defective diamond structure.

The new discovery also suggests that the observed structural complexity of the Canyon Diablo diamond results in interesting mechanical properties. It could be a candidate for a product with exceptional hardness.

The School of Earth and Space Exploration is an academic unit of ASU’s College of Liberal Arts and Sciences.

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.

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.

Early Earth less hellish than previously thought

Calvin Miller is shown at the Kerlingarfjoll volcano in central Iceland. Some geologists have proposed that the early Earth may have resembled regions like this. -  Tamara Carley
Calvin Miller is shown at the Kerlingarfjoll volcano in central Iceland. Some geologists have proposed that the early Earth may have resembled regions like this. – Tamara Carley

Conditions on Earth for the first 500 million years after it formed may have been surprisingly similar to the present day, complete with oceans, continents and active crustal plates.

This alternate view of Earth’s first geologic eon, called the Hadean, has gained substantial new support from the first detailed comparison of zircon crystals that formed more than 4 billion years ago with those formed contemporaneously in Iceland, which has been proposed as a possible geological analog for early Earth.

The study was conducted by a team of geologists directed by Calvin Miller, the William R. Kenan Jr. Professor of Earth and Environmental Sciences at Vanderbilt University, and published online this weekend by the journal Earth and Planetary Science Letters in a paper titled, “Iceland is not a magmatic analog for the Hadean: Evidence from the zircon record.”

From the early 20th century up through the 1980’s, geologists generally agreed that conditions during the Hadean period were utterly hostile to life. Inability to find rock formations from the period led them to conclude that early Earth was hellishly hot, either entirely molten or subject to such intense asteroid bombardment that any rocks that formed were rapidly remelted. As a result, they pictured the surface of the Earth as covered by a giant “magma ocean.”

This perception began to change about 30 years ago when geologists discovered zircon crystals (a mineral typically associated with granite) with ages exceeding 4 billion years old preserved in younger sandstones. These ancient zircons opened the door for exploration of the Earth’s earliest crust. In addition to the radiometric dating techniques that revealed the ages of these ancient zircons, geologists used other analytical techniques to extract information about the environment in which the crystals formed, including the temperature and whether water was present.

Since then zircon studies have revealed that the Hadean Earth was not the uniformly hellish place previously imagined, but during some periods possessed an established crust cool enough so that surface water could form – possibly on the scale of oceans.

Accepting that the early Earth had a solid crust and liquid water (at least at times), scientists have continued to debate the nature of that crust and the processes that were active at that time: How similar was the Hadean Earth to what we see today?

Two schools of thought have emerged: One argues that Hadean Earth was surprisingly similar to the present day. The other maintains that, although it was less hostile than formerly believed, early Earth was nonetheless a foreign-seeming and formidable place, similar to the hottest, most extreme, geologic environments of today. A popular analog is Iceland, where substantial amounts of crust are forming from basaltic magma that is much hotter than the magmas that built most of Earth’s current continental crust.

“We reasoned that the only concrete evidence for what the Hadean was like came from the only known survivors: zircon crystals – and yet no one had investigated Icelandic zircon to compare their telltale compositions to those that are more than 4 billion years old, or with zircon from other modern environments,” said Miller.

In 2009, Vanderbilt doctoral student Tamara Carley, who has just accepted the position of assistant professor at Layfayette College, began collecting samples from volcanoes and sands derived from erosion of Icelandic volcanoes. She separated thousands of zircon crystals from the samples, which cover the island’s regional diversity and represent its 18 million year history.

Working with Miller and doctoral student Abraham Padilla at Vanderbilt, Joe Wooden at Stanford University, Axel Schmitt and Rita Economos from UCLA, Ilya Bindeman at the University of Oregon and Brennan Jordan at the University of South Dakota, Carley analyzed about 1,000 zircon crystals for their age and elemental and isotopic compositions. She then searched the literature for all comparable analyses of Hadean zircon and for representative analyses of zircon from other modern environments.

“We discovered that Icelandic zircons are quite distinctive from crystals formed in other locations on modern Earth. We also found that they formed in magmas that are remarkably different from those in which the Hadean zircons grew,” said Carley.

Most importantly, their analysis found that Icelandic zircons grew from much hotter magmas than Hadean zircons. Although surface water played an important role in the generation of both Icelandic and Hadean crystals, in the Icelandic case the water was extremely hot when it interacted with the source rocks while the Hadean water-rock interactions were at significantly lower temperatures.

“Our conclusion is counterintuitive,” said Miller. “Hadean zircons grew from magmas rather similar to those formed in modern subduction zones, but apparently even ‘cooler’ and ‘wetter’ than those being produced today.”

Early Earth less hellish than previously thought

Calvin Miller is shown at the Kerlingarfjoll volcano in central Iceland. Some geologists have proposed that the early Earth may have resembled regions like this. -  Tamara Carley
Calvin Miller is shown at the Kerlingarfjoll volcano in central Iceland. Some geologists have proposed that the early Earth may have resembled regions like this. – Tamara Carley

Conditions on Earth for the first 500 million years after it formed may have been surprisingly similar to the present day, complete with oceans, continents and active crustal plates.

This alternate view of Earth’s first geologic eon, called the Hadean, has gained substantial new support from the first detailed comparison of zircon crystals that formed more than 4 billion years ago with those formed contemporaneously in Iceland, which has been proposed as a possible geological analog for early Earth.

The study was conducted by a team of geologists directed by Calvin Miller, the William R. Kenan Jr. Professor of Earth and Environmental Sciences at Vanderbilt University, and published online this weekend by the journal Earth and Planetary Science Letters in a paper titled, “Iceland is not a magmatic analog for the Hadean: Evidence from the zircon record.”

From the early 20th century up through the 1980’s, geologists generally agreed that conditions during the Hadean period were utterly hostile to life. Inability to find rock formations from the period led them to conclude that early Earth was hellishly hot, either entirely molten or subject to such intense asteroid bombardment that any rocks that formed were rapidly remelted. As a result, they pictured the surface of the Earth as covered by a giant “magma ocean.”

This perception began to change about 30 years ago when geologists discovered zircon crystals (a mineral typically associated with granite) with ages exceeding 4 billion years old preserved in younger sandstones. These ancient zircons opened the door for exploration of the Earth’s earliest crust. In addition to the radiometric dating techniques that revealed the ages of these ancient zircons, geologists used other analytical techniques to extract information about the environment in which the crystals formed, including the temperature and whether water was present.

Since then zircon studies have revealed that the Hadean Earth was not the uniformly hellish place previously imagined, but during some periods possessed an established crust cool enough so that surface water could form – possibly on the scale of oceans.

Accepting that the early Earth had a solid crust and liquid water (at least at times), scientists have continued to debate the nature of that crust and the processes that were active at that time: How similar was the Hadean Earth to what we see today?

Two schools of thought have emerged: One argues that Hadean Earth was surprisingly similar to the present day. The other maintains that, although it was less hostile than formerly believed, early Earth was nonetheless a foreign-seeming and formidable place, similar to the hottest, most extreme, geologic environments of today. A popular analog is Iceland, where substantial amounts of crust are forming from basaltic magma that is much hotter than the magmas that built most of Earth’s current continental crust.

“We reasoned that the only concrete evidence for what the Hadean was like came from the only known survivors: zircon crystals – and yet no one had investigated Icelandic zircon to compare their telltale compositions to those that are more than 4 billion years old, or with zircon from other modern environments,” said Miller.

In 2009, Vanderbilt doctoral student Tamara Carley, who has just accepted the position of assistant professor at Layfayette College, began collecting samples from volcanoes and sands derived from erosion of Icelandic volcanoes. She separated thousands of zircon crystals from the samples, which cover the island’s regional diversity and represent its 18 million year history.

Working with Miller and doctoral student Abraham Padilla at Vanderbilt, Joe Wooden at Stanford University, Axel Schmitt and Rita Economos from UCLA, Ilya Bindeman at the University of Oregon and Brennan Jordan at the University of South Dakota, Carley analyzed about 1,000 zircon crystals for their age and elemental and isotopic compositions. She then searched the literature for all comparable analyses of Hadean zircon and for representative analyses of zircon from other modern environments.

“We discovered that Icelandic zircons are quite distinctive from crystals formed in other locations on modern Earth. We also found that they formed in magmas that are remarkably different from those in which the Hadean zircons grew,” said Carley.

Most importantly, their analysis found that Icelandic zircons grew from much hotter magmas than Hadean zircons. Although surface water played an important role in the generation of both Icelandic and Hadean crystals, in the Icelandic case the water was extremely hot when it interacted with the source rocks while the Hadean water-rock interactions were at significantly lower temperatures.

“Our conclusion is counterintuitive,” said Miller. “Hadean zircons grew from magmas rather similar to those formed in modern subduction zones, but apparently even ‘cooler’ and ‘wetter’ than those being produced today.”

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

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

How much magma is hiding beneath our feet?

Molten rock (or magma) has a strong influence on our planet and its inhabitants, causing destructive volcanic eruptions and generating some of the giant mineral deposits. Our understanding of these phenomena is, however, limited by the fact that most magma cools and solidifies several kilometres beneath our feet, only to be exposed at the surface, millions of years later, by erosion. Scientists have never been able to track the movements of magma at such great depths? that is, until a team from the University of Geneva (UNIGE) discovered an innovative technique, details of which will be published in the next issue of the journal Nature.

It is a story of three scientists: a modelling specialist, an expert in a tiny mineral known as “zircon”, and a volcanologist. Following a casual conversation, the researchers stumbled upon an idea, and eventually a new method to estimate the volume and flow of magma required for the construction of magma chambers was shaped. The technique they developed makes it possible to refine predictions of future volcanic eruptions as well as identifying areas of the planet that are rich in magma-related natural resources.

Zircon: a valuable mineral for scientists

Professor Urs Schaltegger has been studying zircon for more than ten years in his laboratory at UNIGE, one of the world’s few labs in this field. «The zircon crystals that are found in solidified magma hold key information about the injection of molten rock into a magma chamber before it freezes underground,» explains the professor. Zircon contains radioactive elements that enable researchers to determine its age. As part of the study, the team from the Section of Earth and Environmental Sciences of UNIGE paired data collected using natural samples and numerical simulation. As Guy Simpson, a researcher at UNIGE further explains: «Modelling meant that we could establish how the age of crystallised zircon in a cooled magma reservoir depends on the flow rate of injected magma and the size of the reservoir.»

Applications for society and industry


In the Nature article, the researchers propose a model that is capable of determining with unprecedented accuracy the age, volume and injection rate of magma that has accumulated at inaccessible depths. As a result, they have established that the formation of Earth’s crust, volcanic super eruptions and mineral deposits occur under very specific yet different conditions. Professor Luca Caricchi adds: «When we determine the age of a family of zircons from a small sample of solidified magmatic rock, using results from the mathematical model we have developed, we can tell what the size of the entire magma chamber was, as well as how fast the magma reservoir grew». The professor continues: «This information means that we can determine the probability of an explosive volcanic eruption of a certain size to occur. In addition, the model will be of interest to industry because we will be able to identify new areas of our planet that are home to large amounts of natural resources such as copper and gold.»

How much magma is hiding beneath our feet?

Molten rock (or magma) has a strong influence on our planet and its inhabitants, causing destructive volcanic eruptions and generating some of the giant mineral deposits. Our understanding of these phenomena is, however, limited by the fact that most magma cools and solidifies several kilometres beneath our feet, only to be exposed at the surface, millions of years later, by erosion. Scientists have never been able to track the movements of magma at such great depths? that is, until a team from the University of Geneva (UNIGE) discovered an innovative technique, details of which will be published in the next issue of the journal Nature.

It is a story of three scientists: a modelling specialist, an expert in a tiny mineral known as “zircon”, and a volcanologist. Following a casual conversation, the researchers stumbled upon an idea, and eventually a new method to estimate the volume and flow of magma required for the construction of magma chambers was shaped. The technique they developed makes it possible to refine predictions of future volcanic eruptions as well as identifying areas of the planet that are rich in magma-related natural resources.

Zircon: a valuable mineral for scientists

Professor Urs Schaltegger has been studying zircon for more than ten years in his laboratory at UNIGE, one of the world’s few labs in this field. «The zircon crystals that are found in solidified magma hold key information about the injection of molten rock into a magma chamber before it freezes underground,» explains the professor. Zircon contains radioactive elements that enable researchers to determine its age. As part of the study, the team from the Section of Earth and Environmental Sciences of UNIGE paired data collected using natural samples and numerical simulation. As Guy Simpson, a researcher at UNIGE further explains: «Modelling meant that we could establish how the age of crystallised zircon in a cooled magma reservoir depends on the flow rate of injected magma and the size of the reservoir.»

Applications for society and industry


In the Nature article, the researchers propose a model that is capable of determining with unprecedented accuracy the age, volume and injection rate of magma that has accumulated at inaccessible depths. As a result, they have established that the formation of Earth’s crust, volcanic super eruptions and mineral deposits occur under very specific yet different conditions. Professor Luca Caricchi adds: «When we determine the age of a family of zircons from a small sample of solidified magmatic rock, using results from the mathematical model we have developed, we can tell what the size of the entire magma chamber was, as well as how fast the magma reservoir grew». The professor continues: «This information means that we can determine the probability of an explosive volcanic eruption of a certain size to occur. In addition, the model will be of interest to industry because we will be able to identify new areas of our planet that are home to large amounts of natural resources such as copper and gold.»