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.

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.

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.

New study finds oceans arrived early to Earth

In this illustration of the early solar system, the dashed white line represents the snow line -- the transition from the hotter inner solar system, where water ice is not stable (brown) to the outer Solar system, where water ice is stable (blue). Two possible ways that the inner solar system received water are: water molecules sticking to dust grains inside the 'snow line' (as shown in the inset) and carbonaceous chondrite material flung into the inner solar system by the effect of gravity from protoJupiter. With either scenario, water must accrete to the inner planets within the first ca. 10 million years of solar system formation. -  Illustration by Jack Cook, Woods Hole Oceanographic Institution
In this illustration of the early solar system, the dashed white line represents the snow line — the transition from the hotter inner solar system, where water ice is not stable (brown) to the outer Solar system, where water ice is stable (blue). Two possible ways that the inner solar system received water are: water molecules sticking to dust grains inside the ‘snow line’ (as shown in the inset) and carbonaceous chondrite material flung into the inner solar system by the effect of gravity from protoJupiter. With either scenario, water must accrete to the inner planets within the first ca. 10 million years of solar system formation. – Illustration by Jack Cook, Woods Hole Oceanographic Institution

Earth is known as the Blue Planet because of its oceans, which cover more than 70 percent of the planet’s surface and are home to the world’s greatest diversity of life. While water is essential for life on the planet, the answers to two key questions have eluded us: where did Earth’s water come from and when?

While some hypothesize that water came late to Earth, well after the planet had formed, findings from a new study led by scientists at the Woods Hole Oceanographic Institution (WHOI) significantly move back the clock for the first evidence of water on Earth and in the inner solar system.

“The answer to one of the basic questions is that our oceans were always here. We didn’t get them from a late process, as was previously thought,” said Adam Sarafian, the lead author of the paper published Oct. 31, 2014, in the journal Science and a MIT/WHOI Joint Program student in the Geology and Geophysics Department.

One school of thought was that planets originally formed dry, due to the high-energy, high-impact process of planet formation, and that the water came later from sources such as comets or “wet” asteroids, which are largely composed of ices and gases.

“With giant asteroids and meteors colliding, there’s a lot of destruction,” said Horst Marschall, a geologist at WHOI and coauthor of the paper. “Some people have argued that any water molecules that were present as the planets were forming would have evaporated or been blown off into space, and that surface water as it exists on our planet today, must have come much, much later—hundreds of millions of years later.”

The study’s authors turned to another potential source of Earth’s water— carbonaceous chondrites. The most primitive known meteorites, carbonaceous chondrites, were formed in the same swirl of dust, grit, ice and gasses that gave rise to the sun some 4.6 billion years ago, well before the planets were formed.

“These primitive meteorites resemble the bulk solar system composition,” said WHOI geologist and coauthor Sune Nielsen. “They have quite a lot of water in them, and have been thought of before as candidates for the origin of Earth’s water.

In order to determine the source of water in planetary bodies, scientists measure the ratio between the two stable isotopes of hydrogen: deuterium and hydrogen. Different regions of the solar system are characterized by highly variable ratios of these isotopes. The study’s authors knew the ratio for carbonaceous chondrites and reasoned that if they could compare that to an object that was known to crystallize while Earth was actively accreting then they could gauge when water appeared on Earth.

To test this hypothesis, the research team, which also includes Francis McCubbin from the Institute of Meteoritics at the University of New Mexico and Brian Monteleone of WHOI, utilized meteorite samples provided by NASA from the asteroid 4-Vesta. The asteroid 4-Vesta, which formed in the same region of the solar system as Earth, has a surface of basaltic rock—frozen lava. These basaltic meteorites from 4-Vesta are known as eucrites and carry a unique signature of one of the oldest hydrogen reservoirs in the solar system. Their age—approximately 14 million years after the solar system formed—makes them ideal for determining the source of water in the inner solar system at a time when Earth was in its main building phase. The researchers analyzed five different samples at the Northeast National Ion Microprobe Facility—a state-of-the-art national facility housed at WHOI that utilizes secondary ion mass spectrometers. This is the first time hydrogen isotopes have been measured in eucrite meteorites.

The measurements show that 4-Vesta contains the same hydrogen isotopic composition as carbonaceous chondrites, which is also that of Earth. That, combined with nitrogen isotope data, points to carbonaceous chondrites as the most likely common source of water.

“The study shows that Earth’s water most likely accreted at the same time as the rock. The planet formed as a wet planet with water on the surface,” Marschall said.

While the findings don’t preclude a late addition of water on Earth, it shows that it wasn’t necessary since the right amount and composition of water was present at a very early stage.

“An implication of that is that life on our planet could have started to begin very early,” added Nielsen. “Knowing that water came early to the inner solar system also means that the other inner planets could have been wet early and evolved life before they became the harsh environments they are today.

New study finds oceans arrived early to Earth

In this illustration of the early solar system, the dashed white line represents the snow line -- the transition from the hotter inner solar system, where water ice is not stable (brown) to the outer Solar system, where water ice is stable (blue). Two possible ways that the inner solar system received water are: water molecules sticking to dust grains inside the 'snow line' (as shown in the inset) and carbonaceous chondrite material flung into the inner solar system by the effect of gravity from protoJupiter. With either scenario, water must accrete to the inner planets within the first ca. 10 million years of solar system formation. -  Illustration by Jack Cook, Woods Hole Oceanographic Institution
In this illustration of the early solar system, the dashed white line represents the snow line — the transition from the hotter inner solar system, where water ice is not stable (brown) to the outer Solar system, where water ice is stable (blue). Two possible ways that the inner solar system received water are: water molecules sticking to dust grains inside the ‘snow line’ (as shown in the inset) and carbonaceous chondrite material flung into the inner solar system by the effect of gravity from protoJupiter. With either scenario, water must accrete to the inner planets within the first ca. 10 million years of solar system formation. – Illustration by Jack Cook, Woods Hole Oceanographic Institution

Earth is known as the Blue Planet because of its oceans, which cover more than 70 percent of the planet’s surface and are home to the world’s greatest diversity of life. While water is essential for life on the planet, the answers to two key questions have eluded us: where did Earth’s water come from and when?

While some hypothesize that water came late to Earth, well after the planet had formed, findings from a new study led by scientists at the Woods Hole Oceanographic Institution (WHOI) significantly move back the clock for the first evidence of water on Earth and in the inner solar system.

“The answer to one of the basic questions is that our oceans were always here. We didn’t get them from a late process, as was previously thought,” said Adam Sarafian, the lead author of the paper published Oct. 31, 2014, in the journal Science and a MIT/WHOI Joint Program student in the Geology and Geophysics Department.

One school of thought was that planets originally formed dry, due to the high-energy, high-impact process of planet formation, and that the water came later from sources such as comets or “wet” asteroids, which are largely composed of ices and gases.

“With giant asteroids and meteors colliding, there’s a lot of destruction,” said Horst Marschall, a geologist at WHOI and coauthor of the paper. “Some people have argued that any water molecules that were present as the planets were forming would have evaporated or been blown off into space, and that surface water as it exists on our planet today, must have come much, much later—hundreds of millions of years later.”

The study’s authors turned to another potential source of Earth’s water— carbonaceous chondrites. The most primitive known meteorites, carbonaceous chondrites, were formed in the same swirl of dust, grit, ice and gasses that gave rise to the sun some 4.6 billion years ago, well before the planets were formed.

“These primitive meteorites resemble the bulk solar system composition,” said WHOI geologist and coauthor Sune Nielsen. “They have quite a lot of water in them, and have been thought of before as candidates for the origin of Earth’s water.

In order to determine the source of water in planetary bodies, scientists measure the ratio between the two stable isotopes of hydrogen: deuterium and hydrogen. Different regions of the solar system are characterized by highly variable ratios of these isotopes. The study’s authors knew the ratio for carbonaceous chondrites and reasoned that if they could compare that to an object that was known to crystallize while Earth was actively accreting then they could gauge when water appeared on Earth.

To test this hypothesis, the research team, which also includes Francis McCubbin from the Institute of Meteoritics at the University of New Mexico and Brian Monteleone of WHOI, utilized meteorite samples provided by NASA from the asteroid 4-Vesta. The asteroid 4-Vesta, which formed in the same region of the solar system as Earth, has a surface of basaltic rock—frozen lava. These basaltic meteorites from 4-Vesta are known as eucrites and carry a unique signature of one of the oldest hydrogen reservoirs in the solar system. Their age—approximately 14 million years after the solar system formed—makes them ideal for determining the source of water in the inner solar system at a time when Earth was in its main building phase. The researchers analyzed five different samples at the Northeast National Ion Microprobe Facility—a state-of-the-art national facility housed at WHOI that utilizes secondary ion mass spectrometers. This is the first time hydrogen isotopes have been measured in eucrite meteorites.

The measurements show that 4-Vesta contains the same hydrogen isotopic composition as carbonaceous chondrites, which is also that of Earth. That, combined with nitrogen isotope data, points to carbonaceous chondrites as the most likely common source of water.

“The study shows that Earth’s water most likely accreted at the same time as the rock. The planet formed as a wet planet with water on the surface,” Marschall said.

While the findings don’t preclude a late addition of water on Earth, it shows that it wasn’t necessary since the right amount and composition of water was present at a very early stage.

“An implication of that is that life on our planet could have started to begin very early,” added Nielsen. “Knowing that water came early to the inner solar system also means that the other inner planets could have been wet early and evolved life before they became the harsh environments they are today.

Scientists successfully use krypton to accurately date ancient Antarctic ice

This is the sampling trench for dust studies on Taylor Glacier. Windblown dust from local sources contaminates the upper ice layers and uncontaminated samples are obtained from a meter below the glacier's surface. -  (Photo courtesy of Hinrich Schaefer)
This is the sampling trench for dust studies on Taylor Glacier. Windblown dust from local sources contaminates the upper ice layers and uncontaminated samples are obtained from a meter below the glacier’s surface. – (Photo courtesy of Hinrich Schaefer)

A team of scientists has successfully identified the age of 120,000-year-old Antarctic ice using radiometric krypton dating – a new technique that may allow them to locate and date ice that is more than a million years old.

The ability to discover ancient ice is critical, the researchers say, because it will allow them to reconstruct the climate much farther back into Earth’s history and potentially understand the mechanisms that have triggered the planet to shift into and out of ice ages.

Results of the discovery are being published this week in the Proceedings of the National Academy of Sciences. The work was funded by the National Science Foundation and the U.S. Department of Energy.

“The oldest ice found in drilled cores is around 800,000 years old and with this new technique we think we can look in other regions and successfully date polar ice back as far as 1.5 million years,” said Christo Buizert, a postdoctoral researcher at Oregon State University and lead author on the PNAS article. “That is very exciting because a lot of interesting things happened with the Earth’s climate prior to 800,000 years ago that we currently cannot study in the ice core record.”

Krypton dating is much like the more-heralded carbon-14 dating technique that measures the decay of a radioactive isotope – which has constant and well-known decay rates – and compares it to a stable isotope. Unlike carbon-14, however, krypton is a noble gas that does not interact chemically and is much more stable with a half-life of around 230,000 years. Carbon dating doesn’t work well on ice because carbon-14 is produced in the ice itself by cosmic rays and only goes back some 50,000 years.

Krypton is produced by cosmic rays bombarding the Earth and then stored in air bubbles trapped within Antarctic ice. It has a radioactive isotope (krypton-81) that decays very slowly, and a stable isotope (krypton-83) that does not decay. Comparing the proportion of stable-to-radioactive isotopes provides the age of the ice.

Though scientists have been interested in radiokrypton dating for more than four decades, krypton-81 atoms are so limited and difficult to count that it wasn’t until a 2011 breakthrough in detector technology that krypton-81 dating became feasible for this kind of research. The new atom counter, named Atom Trap Trace Analysis, or ATTA, was developed by a team of nuclear physicists led by Zheng-Tian Lu at Argonne National Laboratory near Chicago.

In their experiment at Taylor Glacier in Antarctica, the researchers put several 300-kilogram (about 660 pounds) chunks of ice into a container and melted it to release the air from the bubbles, which was then stored in flasks. The krypton was isolated from the air at the University of Bern, Switzerland, and sent to Argonne for krypton-81 counting.

“The atom trap is so sensitive that it can capture and count individual atoms,” said Buizert, who is in OSU’s College of Earth, Ocean, and Atmospheric Sciences. “The only problem is that there isn’t a lot of krypton in the air, and thus there isn’t much in the ice, either. That’s why we need such large samples to melt down.”

The group at Argonne is continually improving the ATTA detector, researchers there say, and they aim to perform analysis on an ice sample as small as 20 kilograms in the near future.

The researchers determined from the isotope ratio that the Taylor Glacier samples were 120,000 years old, and validated the estimate by comparing the results to well-dated ice core measurements of atmospheric methane and oxygen from that same period.

Now the challenge is to locate some of the oldest ice in Antarctica, which may not be as easy as it sounds.

“Most people assume that it’s a question of just drilling deeper for ice cores, but it’s not that simple,” said Edward Brook, an Oregon State University geologist and co-author on the study. “Very old ice probably exists in small isolated patches at the base of the ice sheet that have not yet been identified, but in many places it has probably melted and flowed out into the ocean.”

There also are special regions where old ice is exposed at the edges of an ice field, Brook pointed out.

“The international scientific community is really interested in exploring for old ice in both types of places and this new dating will really help,” Brook said. “There are places where meteorites originating from Mars have been pushed out by glaciers and collect at the margins. Some have been on Earth for a million years or more, so the ice in these spots may be that old as well.”

Buizert said reconstructing the Earth’s climate back to 1.5 million years is important because a shift in the frequency of ice ages took place in what is known as the Middle Pleistocene transition. The Earth is thought to have shifted in and out of ice ages every 100,000 years or so during the past 800,000 years, but there is evidence that such a shift took place every 40,000 years prior to that time.

“Why was there a transition from a 40,000-year cycle to a 100,000-year cycle?” Buizert said. “Some people believe a change in the level of atmospheric carbon dioxide may have played a role. That is one reason we are so anxious to find ice that will take us back further in time so we can further extend data on past carbon dioxide levels and test this hypothesis.”

Scientists successfully use krypton to accurately date ancient Antarctic ice

This is the sampling trench for dust studies on Taylor Glacier. Windblown dust from local sources contaminates the upper ice layers and uncontaminated samples are obtained from a meter below the glacier's surface. -  (Photo courtesy of Hinrich Schaefer)
This is the sampling trench for dust studies on Taylor Glacier. Windblown dust from local sources contaminates the upper ice layers and uncontaminated samples are obtained from a meter below the glacier’s surface. – (Photo courtesy of Hinrich Schaefer)

A team of scientists has successfully identified the age of 120,000-year-old Antarctic ice using radiometric krypton dating – a new technique that may allow them to locate and date ice that is more than a million years old.

The ability to discover ancient ice is critical, the researchers say, because it will allow them to reconstruct the climate much farther back into Earth’s history and potentially understand the mechanisms that have triggered the planet to shift into and out of ice ages.

Results of the discovery are being published this week in the Proceedings of the National Academy of Sciences. The work was funded by the National Science Foundation and the U.S. Department of Energy.

“The oldest ice found in drilled cores is around 800,000 years old and with this new technique we think we can look in other regions and successfully date polar ice back as far as 1.5 million years,” said Christo Buizert, a postdoctoral researcher at Oregon State University and lead author on the PNAS article. “That is very exciting because a lot of interesting things happened with the Earth’s climate prior to 800,000 years ago that we currently cannot study in the ice core record.”

Krypton dating is much like the more-heralded carbon-14 dating technique that measures the decay of a radioactive isotope – which has constant and well-known decay rates – and compares it to a stable isotope. Unlike carbon-14, however, krypton is a noble gas that does not interact chemically and is much more stable with a half-life of around 230,000 years. Carbon dating doesn’t work well on ice because carbon-14 is produced in the ice itself by cosmic rays and only goes back some 50,000 years.

Krypton is produced by cosmic rays bombarding the Earth and then stored in air bubbles trapped within Antarctic ice. It has a radioactive isotope (krypton-81) that decays very slowly, and a stable isotope (krypton-83) that does not decay. Comparing the proportion of stable-to-radioactive isotopes provides the age of the ice.

Though scientists have been interested in radiokrypton dating for more than four decades, krypton-81 atoms are so limited and difficult to count that it wasn’t until a 2011 breakthrough in detector technology that krypton-81 dating became feasible for this kind of research. The new atom counter, named Atom Trap Trace Analysis, or ATTA, was developed by a team of nuclear physicists led by Zheng-Tian Lu at Argonne National Laboratory near Chicago.

In their experiment at Taylor Glacier in Antarctica, the researchers put several 300-kilogram (about 660 pounds) chunks of ice into a container and melted it to release the air from the bubbles, which was then stored in flasks. The krypton was isolated from the air at the University of Bern, Switzerland, and sent to Argonne for krypton-81 counting.

“The atom trap is so sensitive that it can capture and count individual atoms,” said Buizert, who is in OSU’s College of Earth, Ocean, and Atmospheric Sciences. “The only problem is that there isn’t a lot of krypton in the air, and thus there isn’t much in the ice, either. That’s why we need such large samples to melt down.”

The group at Argonne is continually improving the ATTA detector, researchers there say, and they aim to perform analysis on an ice sample as small as 20 kilograms in the near future.

The researchers determined from the isotope ratio that the Taylor Glacier samples were 120,000 years old, and validated the estimate by comparing the results to well-dated ice core measurements of atmospheric methane and oxygen from that same period.

Now the challenge is to locate some of the oldest ice in Antarctica, which may not be as easy as it sounds.

“Most people assume that it’s a question of just drilling deeper for ice cores, but it’s not that simple,” said Edward Brook, an Oregon State University geologist and co-author on the study. “Very old ice probably exists in small isolated patches at the base of the ice sheet that have not yet been identified, but in many places it has probably melted and flowed out into the ocean.”

There also are special regions where old ice is exposed at the edges of an ice field, Brook pointed out.

“The international scientific community is really interested in exploring for old ice in both types of places and this new dating will really help,” Brook said. “There are places where meteorites originating from Mars have been pushed out by glaciers and collect at the margins. Some have been on Earth for a million years or more, so the ice in these spots may be that old as well.”

Buizert said reconstructing the Earth’s climate back to 1.5 million years is important because a shift in the frequency of ice ages took place in what is known as the Middle Pleistocene transition. The Earth is thought to have shifted in and out of ice ages every 100,000 years or so during the past 800,000 years, but there is evidence that such a shift took place every 40,000 years prior to that time.

“Why was there a transition from a 40,000-year cycle to a 100,000-year cycle?” Buizert said. “Some people believe a change in the level of atmospheric carbon dioxide may have played a role. That is one reason we are so anxious to find ice that will take us back further in time so we can further extend data on past carbon dioxide levels and test this hypothesis.”

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.”

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.”