Showing posts with label Nitrogen. Show all posts
Showing posts with label Nitrogen. Show all posts

Apr 5, 2024

Evolution in action? New study finds possibility of nitrogen-fixing organelles

Nitrogen is a nutrient essential for all life on Earth. Although nitrogen gas (N2) is plentiful, it is largely unavailable to most organisms without a process known as nitrogen fixation, which converts dinitrogen to ammonium -- a major inorganic nitrogen source.

While there are bacteria that are able to reduce dinitrogen to ammonium, researchers at the University of Rhode Island, Institut de Ciències del Mar in Barcelona, University of California at Santa Cruz and the Massachusetts Institute of Technology have discovered nitrogen-fixing symbiotic organisms exhibiting behaviors similar to organelles.

In fact, researchers posit these symbiotic organisms -- UCYN-A, a species of cyanobacteria -- may be evolving organelle-like characteristics.

Their study was recently published in the journal Cell.

UCYN-A live in a symbiotic relationship with a closely related group of marine algae, B. bigelowii, in areas of the open ocean that are often low in nutrients.

Most nitrogen-fixing bacteria have mechanisms to regulate dinitrogen use when fixed sources of nitrogen are available, alleviating the high energetic cost of this process.

However, UCYN-A have lost the genes allowing this and are able to fix nitrogen gas into ammonium even in nutrient-rich environments.

The host, in-turn, provides it with carbon fixed photosynthetically by its chloroplasts.

The study details how researchers found a size relationship between UCYN-A and their symbiotic partner cells -- consistent with the size relationships between other organelles and their hosts.

As organelles get larger, so do their host cells - eventually dividing and replicating.

Mathematical modeling revealed the metabolic trade-offs which regulate the relative cell size through nutrient acquisition and exchange.

"It requires lots of energy as well as electrons to fix nitrogen gas, to make it into something useful," said Keisuke Inomura, assistant professor of oceanography at URI's Graduate School of Oceanography and one of the study's lead authors.

"If UCYN-A are moving along the evolutionary path toward developing into nitrogen-fixing organelles and we find cells aside from B. bigelowii also have such organelles, or are evolving similarly, it could be a game-changer."

While organelles such as mitochondria and chloroplasts are much further along on the evolutionary spectrum, researchers contend that what they are seeing may be a snapshot of the evolutionary process of bacterial-derived organelles that are nitrogen-fixing.

"Our study focuses on a much more recent symbiotic relationship that emerged about 100 million years ago, allowing us to explore the evolution of organelle formation in its early stages," explained Francisco Cornejo, co-lead author and postdoc researcher in the department of marine biology and oceanography at the Institut de Ciències del Mar.

Researchers note, however, that more study is needed to demonstrate whether this is the case.

Read more at Science Daily

Dec 13, 2023

Ultra-hard material to rival diamond discovered

Scientists have solved a decades-long puzzle and unveiled a near unbreakable substance that could rival diamond, as the hardest material on earth, a study says.

Researchers found that when carbon and nitrogen precursors were subjected to extreme heat and pressure, the resulting materials -- known as carbon nitrides -- were tougher than cubic boron nitride, the second hardest material after diamond.

The breakthrough opens doors for multifunctional materials to be used for industrial purposes including protective coatings for cars and spaceships, high-endurance cutting tools, solar panels and photodetectors, experts say.

Materials researchers have attempted to unlock the potential of carbon nitrides since the 1980s, when scientists first noticed their exceptional properties, including high resistance to heat.

Yet after more than three decades of research and multiple attempts to synthesize them, no credible results were reported.

Now, an international team of scientists -- led by researchers from the Centre for Science at Extreme Conditions at the University of Edinburgh and experts from the University of Bayreuth, Germany and the University of Linköping, Sweden -- have finally achieved a breakthrough.

The team subjected various forms of carbon nitrogen precursors to pressures of between 70 and 135 gigapascals -- around one million times our atmospheric pressure -- while heating it to temperatures of more than one and a half thousand degrees celsius.

To identify the atomic arrangement of thecompounds under these conditions, the samples were illuminated by an intense X-ray beam at three particle accelerators -- the European Synchrotron Research Facility in France, the Deutsches Elektronen-Synchrotron in Germany and the Advanced Photon Source based in the United States.

Researchers discovered that three carbon nitride compounds were found to have the necessary building blocks for super-hardness.

Remarkably, all three compounds retained their diamond-like qualities when they returned to ambient pressure and temperature conditions.

Further calculations and experiments suggest the new materials contain additional properties including photoluminescence and high energy density, where a large amount of energy can be stored in a small amount of mass.

Researchers say the potential applications of these ultra-incompressible carbon nitrides is vast, potentially positioning them as ultimate engineering materials to rival diamonds.

The research, published in Advanced Materials, was funded by the UKRI FLF scheme and European research grants.

Dr Dominique Laniel, Future Leaders Fellow, Institute for Condensed Matter Physics and Complex Systems, School of Physics and Astronomy, University of Edinburgh, said: "Upon the discovery of the first of these new carbon nitride materials, we were incredulous to have produced materials researchers have been dreaming of for the last three decades. These materials provide strong incentive to bridge the gap between high pressure materials synthesis and industrial applications."

Read more at Science Daily

Dec 1, 2023

Meteorites likely source of nitrogen for early Earth

Micrometeorites originating from icy celestial bodies in the outer Solar System may be responsible for transporting nitrogen to the near-Earth region in the early days of our solar system. That discovery was published today in Nature Astronomy by an international team of researchers, including University of Hawai'i at Manoa scientists, led by Kyoto University.

Nitrogen compounds, such as ammonium salts, are abundant in material born in regions far from the sun, but evidence of their transport to Earth's orbital region had been poorly understood.

"Our recent findings suggests the possibility that a greater amount of nitrogen compounds than previously recognized was transported near Earth, potentially serving as building blocks for life on our planet," says Hope Ishii, study co-author and affiliate faculty at the Hawai'i Institute of Geophysics and Planetology in the UH Manoa School of Ocean and Earth Science and Technology (SOEST).

Like all asteroids, Ryugu is a small, rocky object that orbits the sun.

The Japan Aerospace Exploration Agency's Hayabusa2 spacecraft explored Ryugu and brought material from its surface back to Earth in 2020.

This intriguing asteroid is rich in carbon and has undergone significant space weathering caused by micrometeorite collisions and exposure to charged ions streaming from the sun.

In this study, the scientists aimed to discover clues about the materials arriving near Earth's orbit, where Ryugu is currently located, by examining the evidence of space weathering in Ryugu samples.

Using an electron microscope, they found that the surface of the Ryugu samples are covered with tiny minerals composed of iron and nitrogen (iron nitride: Fe4N).

"We proposed that tiny meteorites, called micrometeorites, containing ammonia compounds were delivered from icy celestial bodies and collided with Ryugu," said Toru Matsumoto, lead author of the study and assistant professor at Kyoto University.

"The micrometeorite collisions trigger chemical reactions on magnetite and lead to the formation of the iron nitride."

Read more at Science Daily

Nov 29, 2023

Commitments needed to solve aviation's impact on our climate

Concerted efforts and commitments are needed to solve the complex trade-offs involved in reducing the impact of aviation on the climate, according to new research.

Non-CO2 emissions from aircraft -- largely of nitrogen oxides, soot and water vapour -- are known to add to global warming effects alongside the aviation sector's other CO2 emissions.

Soot triggers the formation of contrails and 'contrail cirrus', which are line-shaped clouds produced by aircraft engine exhaust.

This causes an increase in high clouds that can warm the Earth's atmosphere.

In a comprehensive assessment of the potential solutions to limit the non-CO2 emissions produced by aircraft, scientists warn there is 'no silver bullet' and a committed and co-ordinated effort from a range of stakeholders is urgently required.

The research, published today (November 28) in the Royal Society for Chemistry's journal Environmental Science: Atmospheres, outlines aviation's non-CO2 effects on the atmosphere, both in terms of climate and air quality, and how these may change in the future, as well as the effects of future technologies and fuels.

The findings are the result of a two-year study by Manchester Metropolitan University, the University of Oxford, the University of Reading and Imperial College London.

David Lee, Professor in Atmospheric Science at Manchester Metropolitan, said: "What we highlight is the inherent uncertainties that remain in some of these very complex effects on climate from non-CO2 emissions.

"More importantly, reducing the impact of emissions on the climate is not straightforward as practically all routes forward with conventional liquid hydrocarbon fuels involve 'trade-offs', mostly at the expense of emitting more CO2, whether it be technological or operational efforts.

"These trade-offs and uncertainties mean that there are no simple silver bullets or low-hanging fruit to solve the problem. What is often forgotten is, that while the non-CO2 climate impacts of, for example, an individual flight are short lived, a substantial proportion of the emitted CO2 persists for a very long time, literally tens of millennia. This means it is a difficult balancing act if reducing non-CO2 emissions leads to an increase in CO2 emissions."

Professor Keith Shine, Regius Professor of Meteorology and Climate Science at the University of Reading, is an author of the new paper.

He said: "Given the many uncertainties in the size of aviation non-CO2 climate effects, it is premature to adopt any strategy that aims to decrease non-CO2 climate effects but, at the same time, risks increasing CO2 emissions. We must be mindful that aviation affects local air quality as well as climate. Sometimes measures that improve one will be to the detriment of the other."

Aviation is responsible for around 2.5% of the global CO2 emissions caused by human activity.

However, due to the amount non-CO2 emissions it produces, it is responsible for around 3.5% of change in the energy balance of the atmosphere -- known as radiative forcing -- or around 4% of the increase in global mean temperatures.

The sector is difficult to decarbonise because of its strong dependence on fossil kerosene -- jet fuel -- and the long timescales involved in developing new aircraft and replacing older fleets.

Given the aviation sector's strong growth after the COVID-19 pandemic, this contribution to climate change is set to increase, when other sectors are battling to reduce emissions.

In the latest assessment researchers argue for more work to be performed on the complex trade-offs in order to urgently search for solutions.

This difficulty has recently been recognised by the UK government which, through the Natural Environment Research Council (NERC), has announced a £10 million research programme to help inform policy decisions in this area.

Read more at Science Daily

Nov 17, 2023

Plants that survived dinosaur extinction pulled nitrogen from air

Once a favored food of grazing dinosaurs, an ancient lineage of plants called cycads helped sustain these and other prehistoric animals during the Mesozoic Era, starting 252 million years ago, by being plentiful in the forest understory. Today, just a few species of the palm-like plants survive in tropical and subtropical habitats.

Like their lumbering grazers, most cycads have gone extinct. Their disappearance from their prior habitats began during the late Mesozoic and continued into the early Cenozoic Era, punctuated by the cataclysmic asteroid impact and volcanic activity that mark the K-Pg boundary 66 million years ago. However, unlike the dinosaurs, somehow a few groups of cycads survived to the present.

A new study appearing Nov. 16 in the journal Nature Ecology & Evolution has concluded that the cycad species that survived relied on symbiotic bacteria in their roots, which provide them with nitrogen to grow. Just like modern legumes and other plants that use nitrogen fixation, these cycads trade their sugars with bacteria in their roots in exchange for nitrogen plucked from the atmosphere.

What originally interested lead author Michael Kipp is that the tissues of nitrogen-fixing plants can provide a record of the composition of the atmosphere they grew up in. He combines geochemistry with the fossil record to try to understand the Earth's climate history.

Knowing already that modern cycads are nitrogen-fixers, Kipp began analyzing some very old plant fossils during his Ph.D. work at the University of Washington to see if he could get a different look at ancient atmospheres. Most of the old cycads revealed that they weren't nitrogen-fixers, but these also turned out to be the extinct lineages.

"Instead of being a story about the atmosphere, we realized this was a story about the ecology of these plants that changed through time," said Kipp, who spent nearly a decade on this finding, first at UW and then as a postdoctoral researcher at CalTech.

Kipp is joining the Duke faculty this year as an assistant professor of Earth and Climate Sciences in the Nicholas School of the Environment to continue using the fossil record to understand Earth's climate history so that we can understand its possible future.

Much of what we know about ancient atmospheres comes from chemical studies of ancient sea life and sediments, Kipp said. Applying some of those methods to terrestrial plants is a new wrinkle.

"Going into the project, there were no published nitrogen isotope data from fossilized plant foliage," Kipp said. It took a while for him to fine-tune the method and to secure samples of precious plant fossils that museum curators were reluctant to see vaporized to get the data.

"In the few fossil samples that are of surviving (cycad) lineages, and that are not so old -- 20, 30 million years -- we see the same nitrogen signature as we see today," Kipp said. That means their nitrogen came from symbiotic bacteria. But in the older and extinct cycad fossils, that nitrogen signature was absent.

What is less clear is how nitrogen fixation helped the surviving cycads. It may have helped them weather the dramatic shift in climate or it may have allowed them to compete better with the faster-growing angiosperm plants that flourished after the extinction, "or it could be both."

Read more at Science Daily

Sep 13, 2023

Plant-based food alternatives could support a shift to global sustainability

Replacing 50% of meat and milk products with plant-based alternatives by 2050 can reduce agriculture and land use related greenhouse gas (GHG) emissions by 31% and halt the degradation of forest and natural land, according to new research.

According to the study just published in Nature Communications, additional climate and biodiversity benefits could accrue from reforesting land spared from livestock production when meat and milk products are substituted by plant-based alternatives, more than doubling the climate benefits and halving future declines of ecosystem integrity by 2050. The restored area could contribute up to 25% of the estimated global land restoration needs under Target 2 of the Kunming Montreal Global Biodiversity Framework by 2030.

The study is the first to look at the global food security and environmental impacts of plant-based meat and milk consumption at large scales that considers the complexity of food systems. The research was conducted independently by IIASA in partnership with the Alliance of Bioversity and CIAT, as well as USAID, and solicited input from Impossible Foods -- a company that develops plant-based substitutes for meat products -- as a potential user of the data to ensure relevance. The company also provided generic recipes for the plant-based meat substitute products used in the analysis. The data are, however, not specific to Impossible Foods and the science team had complete control over decision making.

"Understanding the impacts of dietary shifts expands our options for reducing GHG emissions. Shifting diets could also yield huge improvements for biodiversity," notes study lead author Marta Kozicka, a researcher in the IIASA Biodiversity and Natural Resources Program.

"Plant-based meats are not just a novel food product, but a critical opportunity for achieving food security and climate goals while also achieving health and biodiversity objectives worldwide. Yet, such transitions are challenging and require a range of technological innovations and policy interventions," adds study coauthor Eva Wollenberg from Alliance of Bioversity International and CIAT and the Gund Institute, University of Vermont.

The authors developed scenarios of dietary changes based on plant-based recipes for beef, pork, chicken, and milk. The recipes were designed to be nutritionally equivalent to the original animal-derived protein products and realistic for the existing food manufacturing capabilities and globally available production ingredients (Fig 1).

The authors found that a 50% substitution scenario would substantially reduce the mounting impacts of food systems on the natural environment by 2050 compared to the reference scenario (Fig 2). The impacts as compared to 2020 include:

  • Global agricultural area declines by 12% instead of expanding.
  • The decline in areas of forest and other natural land is almost completely halted.
  • Nitrogen inputs to cropland are nearly half of the projections.
  • Water use declines by 10% instead of increasing.
  • Without accounting for any carbon sequestration on spared land, GHG emissions could decline by 2.1 Gt CO2eq year-1 (31%) in 2050 (1.6 Gt CO2eq year-1 on average in 2020-2050).
  • Undernourishment globally declines to 3.6%, as compared to 3.8% in the reference scenario (reducing the number of undernourished people by 31 million).


The full environmental benefit of diet shifts can be achieved if the agricultural land spared from livestock and feed production is restored through biodiversity-minded afforestation. In the 50% scenario, the benefits from reduced land-use emissions could double as compared to a scenario without afforestation -- a total reduction of 6.3 Gt CO2eq year-1. At 90% substitution, the reduction of all agriculture and land-use emissions would increase to 11.1 Gt CO2eq year-1 in 2050.

The restoration of forest ecosystems would also improve biodiversity. The 50% scenario would reduce predicted declines in ecosystem integrity by more than half, while the 90% scenario could reverse biodiversity loss between 2030 and 2040.

"While the analyzed dietary shifts serve as a powerful enabler for reaching climate and biodiversity goals, they must be accompanied by targeted production side policies to deliver their full potential. Otherwise, these benefits will be partly lost due to production extensification and resulting GHG and land-use efficiency losses," explains IIASA Biodiversity and Natural Resources Program Director Petr Havlík, who coordinated the study.

The study points out that impacts across regions could differ due to differences in population size and diets, unequal agricultural productivity, and participation in international trade of agricultural commodities. The main impacts on agricultural input use are in China and on environmental outcomes in Sub-Saharan Africa and South America. These regional differences could also be used to design better interventions.

"A global introduction of all novel alternatives has additional benefits compared to the scenarios with limited product or geographical scope, but regional substitution of specific products may be highly effective, especially if combined with regional strategies and purposeful selection of recipes," Kozicka explains.

Read more at Science Daily

Apr 3, 2023

Most of world's salt marshes likely to be underwater by 2100, study concludes

Cape Cod's salt marshes are as iconic as they are important. These beautiful, low-lying wetlands are some of the most biologically productive ecosystems on Earth. They play an outsized role in nitrogen cycling, act as carbon sinks, protect coastal development from storm surge, and provide critical habitats and nurseries for many fish, shellfish, and coastal birds.

And, according to new research from the Marine Biological Laboratory (MBL), more than 90 percent of the world's salt marshes are likely to be underwater by the end of the century.

The findings come from a 50-year study in Great Sippewissett Marsh in Falmouth, Massachusetts. Since 1971, scientists from the MBL Ecosystems Center have mapped vegetative cover in experimental plots in this marsh to examine whether increased nitrogen in the environment would impact species of marsh grass. Due to the study's length, they also were able to detect the effects of climate change on the ecosystem, especially those driven by accelerating sea level rise.

The researchers found that increased nitrogen favored higher levels of vegetation and accretion of the marsh surface, but that no matter what the concentration of nitrogen they applied to the marsh, these ecosystems won't be able to outpace submergence from global sea level rise.

"Places like Great Sippewissett Marsh will likely become shallow inlets by the turn of the century," says MBL Distinguished Scientist Ivan Valiela, lead author of the study. "Even under conservative sea level estimates…more than 90% of the salt marshes of the world will likely be submerged and disappear or be diminished by the end of the century."

"This is not a prediction from isolated scientists worried about little details. Major changes are going to be taking place on the surface of the Earth that will change the nature of coastal environments," says Valiela.

An Ecosystem Engineer

Salt marshes are gently sloping ecosystems and their plants have very narrow preferences for the elevations in which they can grow. Different species grow in the upper elevations (high marsh) versus the low elevation closer to the ocean (low marsh) and have different responses to changes in nitrogen supply. When change happens slowly enough, the grasses can migrate to their preferred elevation.

In the low marsh, cordgrass (Spartina alterniflora) prospered as scientists increased the nitrogen supply. Among high marsh species, the abundance of marsh hay (Spartina patens) in the experimental plots decreased with sea level rise. Saltgrass (Distichlis spicata) increased with nitrogen supply and also acted as what the researchers called an "ecosystem engineer" -- increasing the rate at which marsh elevation rose. Accretion of biomass left behind by the decomposing saltgrass compensated for the increased submergence resulting from rising sea level in these areas.

"Saltgrass disappeared after a few decades, but it left a legacy behind," says MBL Research Scientist Javier Lloret, adding that it was "extremely cool to see that interaction in the dataset."

Regardless of how much nitrogen was added to the environment, the research showed that at the current and future forecasted sea level rise, low marsh species will completely replace high marsh species. As sea levels continue to rise, even these species will be submerged.

"At some point, if sea level continues to increase at the rates that we anticipate, there will even be no more room for the low marsh plants. They're just going to be too submerged to survive." says Valiela.

The only alternative would be for salt marshes to migrate landward.

A Coastal Squeeze

Marshes around the world face what Lloret calls a "coastal squeeze," where sea level rise pushes from one direction and human development pushes from the other. A seawall that may protect a home from flooding will prevent the migration of a marsh naturally moving to higher ground.

"These barriers, whether they be geographic like a hill or a cliff, or people building along the edges of the ecosystem, constrain the potential for landward marsh migration," says MBL Research Assistant Kelsey Chenoweth. "On top of that, sea level rise is accelerating and marshes are having a hard time keeping up."

In a sea level rise scenario like the one we're facing, "the only solution for the plants will be to colonize new areas, to go uphill," says Lloret. "But that migration may just be impossible in some places."

"Sea level rise is the most important threat to salt marshes. We really need to figure out what's going to happen to these ecosystems and learn how to prevent some of the losses from happening or try to adapt to them, so marshes can continue to play these important roles for nature as well as humans," says Lloret.

Half a Century of Science

In 1971, the scientists at the MBL Ecosystems Center had no idea they would be using their data to study global sea level rise.

"This was an experiment that started looking at one ecological control (nitrogen), and then because of the longevity of the project, we were able to add new knowledge about this major accelerating agent of global change -- global sea level rise," says Valiela.

That's the benefit of long-term datasets like the one at Great Sippewissett Marsh.

"You're setting a baseline to the problems that haven't even happened yet," says Chenoweth.

When measuring ecological processes like climate change and eutrophication, the data can ebb and flow over the course of years as the ecosystem responds to external stimuli. The changes operate on a much longer time scale than changes on other biological systems.

"To study a tree, you look at changes through seasons and you should be able to see its whole cycle. For a leaf, you look at patterns between day and night. In single cells, you look at processes that take place at the timescale of minutes or seconds … but for an entire ecosystem, we're talking many years or decades," says Lloret. "You need to be thinking at the scale of decades or even centuries in order to be able to see substantial changes."

Read more at Science Daily

Feb 17, 2023

Does ice in the Universe contain the molecules making up the building blocks of life in planetary systems?

The James Webb Space Telescope -- the most precise telescope ever built -- was decisive in discovering the frozen forms of a long series of molecules, such as carbon dioxide, ammonia, methane, methanol and even more complex molecules, frozen out as ices on the surface of small dust grains.

The dust grains grow in size when being a part of the discs of gas and dust forming around young stars. This means that the researchers could study many of the molecules going into the forming of new exoplanets.

Researchers at the Niels Bohr Institute, University of Copenhagen, combined the discoveries from JWST with data from Atacama Large Millimeter Array (ALMA), making observations in other wavelengths than JWST and researchers from Aarhus University contributed with the necessary investigations in the laboratory.

"With the application of observations, e.g. from ALMA, it is possible for us to directly observe the dust grains themselves, and it is also possible to see the same molecules as in the gas observed in the ice" Lars Kristensen, associate Professor at the Niels Bohr Institute (NBI), explains.

"Using the combined data set gives us a unique insight into the complex interactions between gas, ice and dust in areas where stars and planets form" according to Jes Jørgensen, Professor at NBI.

"This way we can map the location of the molecules in the area both before and after they have been frozen out onto the dust grains and we can follow their path from the cold molecular cloud to the emerging planetary systems around young stars."

The content of ice in the molecular cloud was a decisive discovery

The ices were detected and measured by studying how starlight from beyond the molecular cloud was absorbed by icy molecules at specific infrared wavelengths visible to Webb.

This process leaves behind chemical fingerprints known as absorption spectra which can be compared with laboratory data to identify which ices are present in the molecular cloud.

In this study, the team targeted ices buried in a particularly cold, dense and difficult to investigate region of the Chamaeleon I molecular cloud, a region approximately 600 light-years from Earth which is currently in the process of forming dozens of young stars.

Along with star forming comes planet forming and the perspective for the researchers in the IceAge collaboration is basically to identify the role the ice plays in gathering the molecules necessary to form life.

"This study confirms that interstellar grains of dust are catalysts for the forming of complex molecules in the very diffuse gas in these clouds, something we see in the lab as well," Sergio Ioppolo explains, associate professor at Aarhus University, contributing with some of the experiments in the lab that were compared with the observations.

The sensitivity of JWST was an absolutely necessary precondition for the discovery

"We simply couldn't have observed these ices without Webb," elaborated Klaus Pontoppidan, JWST project scientist at the Space Telescope Science Institute, Baltimore, USA, who was involved in this research.

"The ices show up as dips against a continuum of background starlight. In regions that are this cold and dense, much of the light from the background star is blocked and Webb's exquisite sensitivity was necessary to detect the starlight and therefore identify the ices in the molecular cloud."

The IceAge team has already planned more observations with both Webb and other telescopes.

"These observations together with further laboratory studies will tell us which mixture of ices -- and therefore which elements -- can eventually be delivered to the surfaces of terrestrial exoplanets or incorporated into the atmospheres of giant gas or ice planets.

Read more at Science Daily

Aug 8, 2022

Growing cereal crops with less fertilizer

Researchers at the University of California, Davis, have found a way to reduce the amount of nitrogen fertilizers needed to grow cereal crops. The discovery could save farmers in the United States billions of dollars annually in fertilizer costs while also benefiting the environment.

The research comes out of the lab of Eduardo Blumwald, a distinguished professor of plant sciences, who has found a new pathway for cereals to capture the nitrogen they need to grow.

The discovery could also help the environment by reducing nitrogen pollution, which can lead to contaminated water resources, increased greenhouse gas emissions and human health issues. The study was published in the journal Plant Biotechnology.

Nitrogen is key to plant growth, and agricultural operations depend on chemical fertilizers to increase productivity. But much of what is applied is lost, leaching into soils and groundwater. Blumwald's research could create a sustainable alternative.

"Nitrogen fertilizers are very, very expensive," Blumwald said. "Anything you can do to eliminate that cost is important. The problem is money on one side, but there are also the harmful effects of nitrogen on the environment."

A new pathway to natural fertilizer

Blumwald's research centers on increasing the conversion of nitrogen gas in the air into ammonium by soil bacteria -- a process known as nitrogen fixation.

Legumes such as peanuts and soybeans have root nodules that can use nitrogen-fixing bacteria to provide ammonium to the plants. Cereal plants like rice and wheat don't have that capability and must rely on taking in inorganic nitrogen, such as ammonia and nitrate, from fertilizers in the soil.

"If a plant can produce chemicals that make soil bacteria fix atmospheric nitrogen gas, we could modify the plants to produce more of these chemicals," Blumwald said. "These chemicals will induce soil bacterial nitrogen fixation and the plants will use the ammonium formed, reducing the amount of fertilizer used."

Blumwald's team used chemical screening and genomics to identify compounds in rice plants that enhanced the nitrogen-fixing activity of the bacteria.

Then they identified the pathways generating the chemicals and used gene editing technology to increase the production of compounds that stimulated the formation of biofilms. Those biofilms contain bacteria that enhanced nitrogen conversion. As a result, nitrogen-fixing activity of the bacteria increased, as did the amount of ammonium in the soil for the plants.

"Plants are incredible chemical factories," he said. "What this could do is provide a sustainable alternative agricultural practice that reduces the use of excessive nitrogen fertilizers."

The pathway could also be used by other plants. A patent application on the technique has been filed by the University of California and is pending.

Read more at Science Daily

Jun 23, 2022

What did Megalodon eat? Anything it wanted -- including other predators.

New Princeton research shows that prehistoric megatooth sharks -- the biggest sharks that ever lived -- were apex predators at the highest level ever measured.

Megatooth sharks get their name from their massive teeth, which can each be bigger than a human hand. The group includes Megalodon, the largest shark that ever lived, as well as several related species.

While sharks of one kind or another have existed since long before the dinosaurs -- for more than 400 million years -- these megatooth sharks evolved after the dinosaurs went extinct and ruled the seas until just 3 million years ago.

"We're used to thinking of the largest species -- blue whales, whale sharks, even elephants and diplodocuses -- as filter feeders or herbivores, not predators," said Emma Kast, a 2019 Ph.D. graduate in geosciences who is the first author on a new study in the current issue of Science Advances. "But Megalodon and the other megatooth sharks were genuinely enormous carnivores that ate other predators, and Meg went extinct only a few million years ago."

Her adviser Danny Sigman, Princeton's Dusenbury Professor of Geological and Geophysical Sciences, added, "If Megalodon existed in the modern ocean, it would thoroughly change humans' interaction with the marine environment."

A team of Princeton researchers has now discovered clear evidence that Megalodon and some of its ancestors were at the very highest rung of the prehistoric food chain -- what scientists call the highest "trophic level." Indeed, their trophic signature is so high that they must have eaten other predators and predators-of-predators in a complicated food web, say the researchers.

"Ocean food webs do tend to be longer than the grass-deer-wolf food chain of land animals, because you start with such small organisms," said Kast, now at the University of Cambridge, who wrote the first iteration of this research as a chapter in her dissertation. "To reach the trophic levels we're measuring in these megatooth sharks, we don't just need to add one trophic level -- one apex predator on top of the marine food chain -- we need to add several onto the top the modern marine food web."

Megalodon has been conservatively estimated at 15 meters long -- 50 feet -- while modern great white sharks typically top out around five meters (15 feet).

To reach their conclusions about the prehistoric marine food web, Kast, Sigman and their colleagues used a novel technique to measure the nitrogen isotopes in the sharks' teeth. Ecologists have long known that the more nitrogen-15 an organism has, the higher its trophic level, but scientists have never before been able to measure the tiny amounts of nitrogen preserved in the enamel layer of these extinct predators' teeth.

"We have a series of shark teeth from different time periods, and we were able to trace their trophic level versus their size," said Zixuan (Crystal) Rao, a graduate student in Sigman's research group and a co-author on the current paper.

One way to tuck in an extra trophic level or two is cannibalism, and several lines of evidence point to that in both megatooth sharks and other prehistoric marine predators.

The nitrogen time machine

Without a time machine, there's no easy way to recreate the food webs of extinct creatures; very few bones have survived with teeth marks that say, "I was chewed on by a massive shark."

Fortunately, Sigman and his team have spent decades developing other methods, based on the knowledge that the nitrogen isotope levels in a creature's cells reveal whether it is at the top, middle or bottom of a food chain.

"The whole direction of my research team is to look for chemically fresh, but physically protected, organic matter -- including nitrogen -- in organisms from the distant geologic past," said Sigman.

A few plants, algae and other species at the bottom of the food web have mastered the knack of turning nitrogen from the air or water into nitrogen in their tissues. Organisms that eat them then incorporate that nitrogen into their own bodies, and critically, they preferentially excrete (sometimes via urine) more of nitrogen's lighter isotope, N-14, than its heavier cousin, N-15.

In other words, N-15 builds up, relative to N-14, as you climb up the food chain.

Other researchers have used this approach on creatures from the recent past -- the most recent 10-15 thousand years -- but there hasn't been enough nitrogen left in older animals to measure, until now.

Why? Soft tissue like muscles and skin are hardly ever preserved. To complicate matters, sharks don't have bones -- their skeletons are made of cartilage.

But sharks do have one golden ticket into the fossil record: teeth. Teeth are more easily preserved than bones because they are encased in enamel, a rock-hard material that is virtually immune to most decomposing bacteria.

"Teeth are designed to be chemically and physically resistant so they can survive in the very chemically reactive environment of the mouth and break apart food that can have hard parts," Sigman explained. And in addition, sharks aren't limited to the 30 or so pearly whites that humans have. They are constantly growing and losing teeth -- modern sand sharks lose a tooth every day of their decades-long lives, on average -- which means that every shark produces thousands of teeth over its lifetime.

"When you look in the geologic record, one of the most abundant fossil types are shark teeth," said Sigman. "And within the teeth, there is a tiny amount of organic matter that was used to build the enamel of the teeth -- and is now trapped within that enamel."

Since shark teeth are so abundant and are preserved so well, the nitrogen signatures in enamel provide a way to measure status in the food web, whether the tooth fell from a shark's mouth millions of years ago or yesterday.

Even the largest tooth has only a thin casing of enamel, of which the nitrogen component is only a tiny trace. But Sigman's team has been developing more and more refined techniques for extracting and measuring these nitrogen isotope ratios, and with a little help from dentist drills, cleaning chemicals and microbes that ultimately convert the nitrogen from within the enamel into nitrous oxide, they're now able to precisely measure the N15-N14 ratio in these ancient teeth.

"We're a little bit like a brewery," he said. "We grow microbes and feed our samples to them. They produce nitrous oxide for us, and then we analyze the nitrous oxide they produced."

The analysis requires a custom-built, automated nitrous oxide preparation system that extracts, purifies, concentrates and delivers the gas to a specialized stable isotope ratio mass spectrometer.

"This has been a multiple-decades-long quest that I've been on, to develop a core method to measure these trace amounts of nitrogen," Sigman said. From microfossils in sediments, they moved on to other types of fossils, like corals, fish ear bones and shark teeth. "Next, we and our collaborators are applying this to mammalian teeth and dinosaur teeth."

A deep dive into the literature during lockdown

Early in the pandemic, while her friends were making sourdough starters and bingeing Netflix, Kast pored through the ecologic literature to look for nitrogen isotope measurements of modern marine animals.

"One of the cool things that Emma did was really dig into the literature -- all the data that's been published over decades -- and relate that to the fossil record," said Michael (Mick) Griffiths, a paleoclimatologist and geochemist at William Patterson University and a co-author on the paper.

As Kast quarantined at home, she painstakingly built up a record with more than 20,000 marine mammal individuals and more than 5,000 sharks. She wants to take things much further. "Our tool has the potential to decode ancient food webs; what we need now is samples," said Kast. "I'd love to find a museum or other archive with a snapshot of an ecosystem -- a collection of different kinds of fossils from one time and place, from forams near the very base of the food web, to otoliths -- inner ear bones -- from different kinds of fish, to teeth from marine mammals, plus shark teeth. We could do the same nitrogen isotope analysis and put together the whole story of an ancient ecosystem."

In addition to the literature search, their database includes their own samples of shark teeth. Co-author Kenshu Shimada of DePaul University connected with aquariums and museums, while co-authors Martin Becker of William Patterson University and Harry Maisch of Florida Gulf Coast University gathered megatooth specimens on the sea floor.

Read more at Science Daily

Jun 21, 2022

Agriculture emissions pose risks to health and climate

Agricultural pollution comes from the prairie, but its economic impact on humans is a problem for cities.

A study led by environmental scientists at Rice University's George R. Brown School of Engineering puts numbers to the toll of reactive nitrogen species produced in America's croplands.

The study led by Daniel Cohan, an associate professor of civil and environmental engineering, and graduate student Lina Luo quantifies emissions of nitrogen oxides, ammonia and nitrous oxide from fertilized soils over three years (2011, 2012 and 2017) and compares their impacts by region on air quality, health and climate.

While seasonal and regional impacts differ across types of emission, the study found total annual damages from ammonia were much larger overall -- at $72 billion -- than those from nitrogen oxides ($12 billion) and nitrous oxide ($13 billion).

Air pollution damages are measured by increased mortality and morbidity and the value of statistical life, while monetized damages from climate change include the threats to crops, property, ecosystem services and human health.

On that basis, the researchers found the health impact of air pollution from ammonia and nitrogen oxides, which react to form particulate matter and ozone, substantially outweighed climate impact from nitrous oxide in all regions and years.

The highest social costs arose from agriculture-heavy regions of California, Florida and the Midwest, where ammonia and nitrogen oxides form air pollution upwind of population centers. For both pollutants, emissions peak in the spring after fertilizers are applied.

The study in the American Chemical Society journal Environmental Science & Technology concludes air pollution, health and climate should all be considered in future assessments of how farming practices affect reactive nitrogen emissions.

"We always talk about how carbon dioxide and methane contribute to greenhouse gases, but nitrous oxide is about 300 times more potent than carbon dioxide for its global warming potential," Luo said.

She noted farming strategies that reduce greenhouse gases can increase air pollutants and vice versa. "We need to see if they can reduce all three nitrogen species -- or make some tradeoffs -- and still not decrease crop yield," Luo said.

Nitrogen is essential for crop growth, Cohan added, but the study shows the importance of controlling agricultural emissions has been largely neglected by air quality management and climate policy, even as the Environmental Protection Agency considers tightening air quality standards and the Biden administration seeks to slash greenhouse gas emissions.

He said federal agencies have focused on controlling transportation and industrial emissions, leaving agriculture as the largest source of damaging nitrogen pollutants in the United States, a problem exacerbated by climate change and increased crop production.

"Our group had been studying nitrogen oxide emissions for a number of years and began to realize that we can't just focus on that," Cohan said. "We needed to consider the range of emissions that come from soils, and we became curious about the relative impacts of different air pollutants and greenhouse gases the emanate from agricultural soils.

"A big part of our motivation was realizing that choices in farming practices might cause some emissions to go up and other emissions to go down," he said. For instance, switching from surface broadcast to deep injection of fertilizers would lower ammonia but raise nitrogen oxide emissions. That would benefit nearby cities sensitive to particulate matter levels, but harm regions where ozone is of more concern.

Cohan said when all the emissions are quantified on a monetary basis, ammonia and nitrogen oxides that form air-polluting particulate matter and ozone and contribute to global warming have the greatest impact.

"Those of us who study these pollutants for a living know how potent ammonia is, but the message hasn't gotten through to most regulators and policymakers," Cohan said. "In fact, ammonia is one of the most potent sources of particulate matter because of how it binds with other pollutants to have a multiplying effect.

"That's an important message: We need to take more steps to control ammonia," he said.

If there's a silver lining, Cohan said, it's that pollution from other sources has dropped enough to make agriculture's impact prevalent.

"What's crucial is to take steps that have more of the nitrogen go to the crops, and less of it be released to the air and water," he said. That could involve adding biochar or other amendments to soil, a topic of ongoing study at Rice.

"Before we can do that, we needed to establish a baseline of emissions coming from the soil," Cohan said. "This paper lays that out."

Read more at Science Daily

Jun 16, 2022

Martian meteorite upsets planet formation theory

A new study of an old meteorite contradicts current thinking about how rocky planets like the Earth and Mars acquire volatile elements such as hydrogen, carbon, oxygen, nitrogen and noble gases as they form. The work is published June 16 in Science.

A basic assumption about planet formation is that planets first collect these volatiles from the nebula around a young star, said Sandrine Péron, a postdoctoral scholar working with Professor Sujoy Mukhopadhyay in the Department of Earth and Planetary Sciences, University of California, Davis.

Because the planet is a ball of molten rock at this point, these elements initially dissolve into the magma ocean and then degass back into the atmosphere. Later on, chondritic meteorites crashing into the young planet deliver more volatile materials.

So scientists expect that the volatile elements in the interior of the planet should reflect the composition of the solar nebula, or a mixture of solar and meteoritic volatiles, while the volatiles in the atmosphere would come mostly from meteorites. These two sources -- solar vs. chondritic -- can be distinguished by the ratios of isotopes of noble gases, in particular krypton.

Mars is of special interest because it formed relatively quickly -- solidifying in about 4 million years after the birth of the Solar System, while the Earth took 50 to 100 million years to form.

"We can reconstruct the history of volatile delivery in the first few million years of the Solar System," Péron said.

Meteorite from Mars' interior

Some meteorites that fall to Earth come from Mars. Most come from surface rocks that have been exposed to Mars' atmosphere. The Chassigny meteorite, which fell to Earth in north-eastern France in 1815, is rare and unusual because it is thought to represent the interior of the planet.

By making extremely careful measurements of minute quantities of krypton isotopes in samples of the meteorite using a new method set up at the UC Davis Noble Gas Laboratory, the researchers could deduce the origin of elements in the rock.

"Because of their low abundance, krypton isotopes are challenging to measure," Péron said.

Surprisingly, the krypton isotopes in the meteorite correspond to those from chondritic meteorites, not the solar nebula. That means that meteorites were delivering volatile elements to the forming planet much earlier than previously thought, and in the presence of the nebula, reversing conventional thinking.

"The Martian interior composition for krypton is nearly purely chondritic, but the atmosphere is solar," Péron said. "It's very distinct."

The results show that Mars' atmosphere cannot have formed purely by outgassing from the mantle, as that would have given it a chondritic composition. The planet must have acquired atmosphere from the solar nebula, after the magma ocean cooled, to prevent substantial mixing between interior chondritic gases and atmospheric solar gases.

The new results suggest that Mars' growth was completed before the solar nebula was dissipated by radiation from the Sun. But the irradiation should also have blown off the nebular atmosphere on Mars, suggesting that atmospheric krypton must have somehow been preserved, possibly trapped underground or in polar ice caps.

"However, that would require Mars to have been cold in the immediate aftermath of its accretion," Mukhopadhyay said. "While our study clearly points to the chondritic gases in the Martian interior, it also raises some interesting questions about the origin and composition of Mars' early atmosphere."

Read more at Science Daily

Dec 17, 2021

Deep mantle krypton reveals Earth’s outer solar system ancestry

Krypton from the Earth's mantle, collected from geologic hot spots in Iceland and the Galapagos Islands, reveals a clearer picture of how our planet formed, according to new research from the University of California, Davis.

The different isotopes of krypton are chemical fingerprints for scientists sleuthing out the ingredients that made the Earth, such as solar wind particles and meteorites from the inner and outer solar system. The findings indicate Earth's volatile elements -- essentials such as carbon, water and nitrogen -- arrived as Earth was growing and becoming a planet. This contradicts the popular theory that Earth's volatile elements were mostly delivered near the end of Earth's formation, which is marked by the moon-forming giant impact. Instead, the krypton isotopes suggest planetesimals from the cold outer solar system bombarded the Earth early on, millions of years before the big crunch. The young Earth also hoovered up dust and gas from the solar nebula (the cloud surrounding the sun) and was bombarded by meteorites.

"Our results require concurrent delivery of volatiles from multiple sources very early in Earth's formation," said Sandrine Péron, the lead author of the study. Péron, currently a Marie Sk?odowska-Curie Actions Fellow at ETH Zürich in Switzerland, conducted the research at UC Davis as a postdoctoral fellow working with Professor Sujoy Mukhopadhyay in the Department of Earth and Planetary Sciences.

"This study provides clues for the sources and timing of volatile accretion on Earth, and will help researchers better understand how not only Earth formed, but also other planets in the solar system and around other stars," Péron said. The study is published Dec. 15 in the journal Nature.

Primordial geochemistry

The volcanic hot spots spewing lava in Iceland and the Galapagos are fed by slushy magma plumes rising from the deepest layer of the mantle, near its boundary with the Earth's iron core. The elements and minerals in this deep layer are relatively unchanged since before the moon-forming impact, like a time capsule of the early Earth's chemistry more than 4.4 billion years old.

Mukhopadhyay's lab specializes in making precise measurements of noble gases in rocks from Earth and elsewhere. To sample deep mantle krypton, the researchers collected lava at hot spot plumes. The ancient gases rise to the surface in the erupting lava, getting trapped and entombed as bubbles in a glassy matrix when the lava quenches to a solid, providing some protection from outside contamination. However, even the most abundant krypton isotopes in these bubbles amounts to only a few hundred million atoms, making their detection challenging, Mukhopadhyay said.

Péron designed a new technique for measuring mantle krypton with mass spectrometry, concentrating krypton from rock samples in an environment virtually free of air contamination and neatly separating it from argon and xenon.

"Ours is the first study to precisely measure all krypton isotopes for the mantle, including the rarest krypton isotopes, Kr-78 and Kr-80," she said.

Building a planet

The researchers discovered that the chemical fingerprint of deep mantle krypton closely resembled primitive, carbon-rich meteorites, which may have been delivered from the cold, outer reaches of the solar system. But previous work by Mukhopadhyay and others found that neon, another noble gas in the deep mantle, was derived from the sun. The two different results suggest at least two distinct volatile sources for the Earth's mantle, delivered very early in its history. The researchers also noted less of the rare isotope Kr-86 in the deep mantle compared to known meteorites. The deficit in Kr-86 suggests that known meteorites alone may not account for all the mantle's krypton.

Finally, the new results also have implications for how Earth's atmosphere arose. The ratio of different krypton isotopes in the deep mantle doesn't match the isotope ratio in Earth's atmosphere, the researchers found. This means some gases in the atmosphere, including noble gases like krypton, were delivered to Earth after the moon-forming impact. Otherwise, Earth's mantle and atmosphere would have the same isotopic composition due to isotopic equilibration following the impact, Péron said.

Read more at Science Daily

May 11, 2021

How planets form controls elements essential for life

The prospects for life on a given planet depend not only on where it forms but also how, according to Rice University scientists.

Planets like Earth that orbit within a solar system's Goldilocks zone, with conditions supporting liquid water and a rich atmosphere, are more likely to harbor life. As it turns out, how that planet came together also determines whether it captured and retained certain volatile elements and compounds, including nitrogen, carbon and water, that give rise to life.

In a study published in Nature Geoscience, Rice graduate student and lead author Damanveer Grewal and Professor Rajdeep Dasgupta show the competition between the time it takes for material to accrete into a protoplanet and the time the protoplanet takes to separate into its distinct layers -- a metallic core, a shell of silicate mantle and an atmospheric envelope in a process called planetary differentiation -- is critical in determining what volatile elements the rocky planet retains.

Using nitrogen as proxy for volatiles, the researchers showed most of the nitrogen escapes into the atmosphere of protoplanets during differentiation. This nitrogen is subsequently lost to space as the protoplanet either cools down or collides with other protoplanets or cosmic bodies during the next stage of its growth.

This process depletes nitrogen in the atmosphere and mantle of rocky planets, but if the metallic core retains enough, it could still be a significant source of nitrogen during the formation of Earth-like planets.

Dasgupta's high-pressure lab at Rice captured protoplanetary differentiation in action to show the affinity of nitrogen toward metallic cores.

"We simulated high pressure-temperature conditions by subjecting a mixture of nitrogen-bearing metal and silicate powders to nearly 30,000 times the atmospheric pressure and heating them beyond their melting points," Grewal said. "Small metallic blobs embedded in the silicate glasses of the recovered samples were the respective analogs of protoplanetary cores and mantles."

Using this experimental data, the researchers modeled the thermodynamic relationships to show how nitrogen distributes between the atmosphere, molten silicate and core.

"We realized that fractionation of nitrogen between all these reservoirs is very sensitive to the size of the body," Grewal said. "Using this idea, we could calculate how nitrogen would have separated between different reservoirs of protoplanetary bodies through time to finally build a habitable planet like Earth."

Their theory suggests that feedstock materials for Earth grew quickly to around moon- and Mars-sized planetary embryos before they completed the process of differentiating into the familiar metal-silicate-gas vapor arrangement.

In general, they estimate the embryos formed within 1-2 million years of the beginning of the solar system, far sooner than the time it took for them to completely differentiate. If the rate of differentiation was faster than the rate of accretion for these embryos, the rocky planets forming from them could not have accreted enough nitrogen, and likely other volatiles, critical to developing conditions that support life.

"Our calculations show that forming an Earth-size planet via planetary embryos that grew extremely quickly before undergoing metal-silicate differentiation sets a unique pathway to satisfy Earth's nitrogen budget," said Dasgupta, the principal investigator of CLEVER Planets, a NASA-funded collaborative project exploring how life-essential elements might have come together on rocky planets in our solar system or on distant, rocky exoplanets.

"This work shows there's much greater affinity of nitrogen toward core-forming metallic liquid than previously thought," he said.

The study follows earlier works, one showing how the impact by a moon-forming body could have given Earth much of its volatile content, and another suggesting that the planet gained more of its nitrogen from local sources in the solar system than once believed.

In the latter study, Grewal said, "We showed that protoplanets growing in both inner and outer regions of the solar system accreted nitrogen, and Earth sourced its nitrogen by accreting protoplanets from both of these regions. However, it was unknown as to how the nitrogen budget of Earth was established."

Read more at Science Daily

Jan 24, 2021

Much of Earth's nitrogen was locally sourced

 

Protoplanetary disk illustration
Where did Earth's nitrogen come from? Rice University scientists show one primordial source of the indispensable building block for life was close to home.

The isotopic signatures of nitrogen in iron meteorites reveal that Earth likely gathered its nitrogen not only from the region beyond Jupiter's orbit but also from the dust in the inner protoplanetary disk.

Nitrogen is a volatile element that, like carbon, hydrogen and oxygen, makes life on Earth possible. Knowing its source offers clues to not only how rocky planets formed in the inner part of our solar system but also the dynamics of far-flung protoplanetary disks.

The study by Rice graduate student and lead author Damanveer Grewal, Rice faculty member Rajdeep Dasgupta and geochemist Bernard Marty at the University of Lorraine, France, appears in Nature Astronomy.

Their work helps settle a prolonged debate over the origin of life-essential volatile elements in Earth and other rocky bodies in the solar system.

"Researchers have always thought that the inner part of the solar system, within Jupiter's orbit, was too hot for nitrogen and other volatile elements to condense as solids, meaning that volatile elements in the inner disk were in the gas phase," Grewal said.

Because the seeds of present-day rocky planets, also known as protoplanets, grew in the inner disk by accreting locally sourced dust, he said it appeared they did not contain nitrogen or other volatiles, necessitating their delivery from the outer solar system. An earlier study by the team suggested much of this volatile-rich material came to Earth via the collision that formed the moon.

But new evidence clearly shows only some of the planet's nitrogen came from beyond Jupiter.

In recent years, scientists have analyzed nonvolatile elements in meteorites, including iron meteorites that occasionally fall to Earth, to show dust in the inner and outer solar system had completely different isotopic compositions.

"This idea of separate reservoirs had only been developed for nonvolatile elements," Grewal said. "We wanted to see if this is true for volatile elements as well. If so, it can be used to determine which reservoir the volatiles in present-day rocky planets came from."

Iron meteorites are remnants of the cores of protoplanets that formed at the same time as the seeds of present-day rocky planets, becoming the wild card the authors used to test their hypothesis.

The researchers found a distinct nitrogen isotopic signature in the dust that bathed the inner protoplanets within about 300,000 years of the formation of the solar system. All iron meteorites from the inner disk contained a lower concentration of the nitrogen-15 isotope, while those from the outer disk were rich in nitrogen-15.

This suggests that within the first few million years, the protoplanetary disk divided into two reservoirs, the outer rich in the nitrogen-15 isotope and the inner rich in nitrogen-14.

"Our work completely changes the current narrative," Grewal said. "We show that the volatile elements were present in the inner disk dust, probably in the form of refractory organics, from the very beginning. This means that contrary to current understanding, the seeds of the present-day rocky planets -- including Earth -- were not volatile-free."

Dasgupta said the finding is significant to those who study the potential habitability of exoplanets, a topic of great interest to him as principal investigator of CLEVER Planets, a NASA-funded collaborative project exploring how life-essential elements might come together on distant exoplanets.

"At least for our own planet, we now know the entire nitrogen budget does not come only from outer solar system materials," said Dasgupta, Rice's Maurice Ewing Professor of Earth, Environmental and Planetary Sciences.

"Even if other protoplanetary disks don't have the kind of giant planet migration resulting in the infiltration of volatile-rich materials from the outer zones, their inner rocky planets closer to the star could still acquire volatiles from their neighboring zones," he said.

Read more at Science Daily

Apr 16, 2020

New geochemical tool reveals origin of Earth's nitrogen

Yellowstone National Park
Researchers at Woods Hole Oceanographic Institution (WHOI), the University of California Los Angeles (UCLA) and their colleagues used a new geochemical tool to shed light on the origin of nitrogen and other volatile elements on Earth, which may also prove useful as a way to monitor the activity of volcanoes. Their findings were published April 16, 2020, in the journal Nature.

Nitrogen is the most abundant gas in the atmosphere, and is the primary component of the air we breathe. Nitrogen is also found in rocks, including those tucked deep within the planet's interior. Until now, it was difficult to distinguish between nitrogen sources coming from air and those coming from inside the Earth's mantle when measuring gases from volcanoes.

"We found that air contamination was masking the pristine 'source signature' of many volcanic gas samples," says WHOI geochemist Peter Barry, a coauthor of the study.

Without that distinction, scientists weren't able to answer basic questions like: Is nitrogen left over from Earth's formation or was it delivered to the planet later on? How is nitrogen from the atmosphere related to nitrogen coming out of volcanoes?

Barry and lead author Jabrane Labidi of UCLA, now a researcher at Institut de Physique du Globe de Paris, worked in partnership with international geochemists to analyze volcanic gas samples from around the globe -- including gases from Iceland and Yellowstone National Park -- using a new method of analyzing "clumped" nitrogen isotopes. This method provided a unique way to identify molecules of nitrogen that come from air, which allowed the researchers to see the true gas compositions deep within Earth's mantle. This ultimately revealed evidence that nitrogen in the mantle has most likely been there since our planet initially formed.

"Once air contamination is accounted for, we gained new and valuable insights into the origin of nitrogen and the evolution of our planet," Barry says.

While this new method helps scientists understand the origins of volatile elements on Earth, it may also prove useful as a way of monitoring the activity of volcanoes. This is because the composition of gases bellowing from volcanic centers change prior to eruptions. It could be that the mix of mantle and air nitrogen could one day be used as a signal of eruptions.

This study was supported by the Deep Carbon Observatory and the Alfred P. Sloan Foundation. The research team also included colleagues David Bekaert and Mark Kurz from WHOI, scientists from several other U.S.-based universities, and from France, Canada, Italy, the United Kingdom and Iceland.

From Science Daily

Mar 12, 2020

Water, carbon and nitrogen were not immediately supplied to Earth

Spearheaded by earth scientists of the University of Cologne, an international team of geologists has found evidence that a large proportion of the elements that are important for the formation of oceans and life, such as water, carbon and nitrogen, were delivered to Earth very late in its history. Previously, many scientists believed that these elements were already present when the Earth began to form. However, geological investigations have now shown that most of the water in fact was only delivered to Earth when its formation was almost complete.

The new findings, which are a result of collaboration among scientists from Germany, Denmark, Wales, Australia and Japan, will be published in Nature under the title 'Ruthenium isotope vestige of Earth's pre-late veneer mantle preserved in Archean rocks' on 11 March 2020.

It is a generally accepted fact that volatile elements such as water originate from asteroids, the 'planetary building blocks' that formed in the outer solar system. However, there is ongoing discussion among experts as to when precisely they came to Earth. 'We have now been able to narrow down the timeframe much more precisely', said first author Dr. Mario Fischer-Gödde from the Institute of Geology and Mineralogy at the University of Cologne. 'To do so, we compared the composition of the oldest, approximately 3.8 billion-year-old mantle rocks from the Archean Eon with the composition of the asteroids from which they may have formed, and with the present-day composition of the Earth's mantle.'

To constrain the delivery of the so-called 'volatile' elements to Earth, the researchers measured the isotope abundances of a very rare platinum metal called ruthenium, which was already present in Earth's mantle by Archean time. Like a genetic fingerprint, this rare platinum metal is an indicator for the late growth phase of the Earth. 'Platinum group metals like ruthenium have an extremely high tendency to combine with iron. Therefore, when the Earth formed all ruthenium must have been completely sequestered into the Earth's metallic core', said Fischer-Gödde.

Professor Dr. Carsten Münker added: 'If we still find traces of the rare platinum metals in the Earth's mantle, we can assume that they were only added after the formation of the core was completed. They were certainly added during later collisions of the Earth with asteroids or smaller protoplanets, so called planetesimals.'

Scientists refer to these very late building blocks of the Earth, which were delivered by these collisions, as the 'late veneer'. If ruthenium was added during this stage, it is distributed and well mixed into Earth's mantle by now. The old Archean mantle relics in Greenland, on the other hand, have still preserved Earth's pristine composition.

'The up to 3.8 billion-year-old rocks from Greenland are the oldest preserved mantle rocks. They allow us a glimpse into the early history of the Earth as if through a window', Fischer-Gödde said. Interestingly, Earth's oldest mantle is openly accessible in surface outcrops in southwest Greenland, allowing the geologists to easily collect rock samples.

The pristine ruthenium preserved in the old mantle rocks most likely originates from the inner part of the solar system, the two Cologne-based geologists report. It is presumably the same material that -- for the most part -- also formed Mercury and Venus. The reference values for the asteroidal ruthenium were previously obtained from meteorites found on Earth.

'Our findings suggest that water and other volatile elements such as carbon and nitrogen did indeed arrive on Earth very late, during the "late veneer" phase', Fischer-Gödde concluded. This result is surprising because the scientific community had previously assumed that water-bearing planetary building blocks were already delivered to Earth during the early stages of its formation.

Read more at Science Daily

Apr 26, 2019

New fallout from 'the collision that changed the world'

Neither the continents nor the oceans have always looked the way they do now. These 'paleomaps' show how the continents and oceans appeared before (top) and during (bottom) 'the collision that changed the world,' when the landmass that is now the Indian subcontinent rammed northward into Asia, closing the Tethys Sea and building the Himalayas. Global ocean levels were higher then, creating salty shallow seas (pale blue) that covered much of North Africa and parts of each of the continents. A team of Princeton researchers, using samples gathered at the three starred locations, created an unprecedented record of ocean nitrogen and oxygen levels from 70 million years ago through 30 million years ago that shows a major shift in ocean chemistry after the India-Asia collision. Another shift came 35 million years ago, when Antarctica began accumulating ice and global sea levels fell.
When the landmass that is now the Indian subcontinent slammed into Asia about 50 million years ago, the collision changed the configuration of the continents, the landscape, global climate and more. Now a team of Princeton University scientists has identified one more effect: the oxygen in the world's oceans increased, altering the conditions for life.

"These results are different from anything people have previously seen," said Emma Kast, a graduate student in geosciences and the lead author on a paper coming out in Science on April 26. "The magnitude of the reconstructed change took us by surprise."

Kast used microscopic seashells to create a record of ocean nitrogen over a period from 70 million years ago -- shortly before the extinction of the dinosaurs -- until 30 million years ago. This record is an enormous contribution to the field of global climate studies, said John Higgins, an associate professor of geosciences at Princeton and a co-author on the paper.

"In our field, there are records that you look at as fundamental, that need to be explained by any sort of hypothesis that wants to make biogeochemical connections," Higgins said. "Those are few and far between, in part because it's very hard to create records that go far back in time. Fifty-million-year-old rocks don't willingly give up their secrets. I would certainly consider Emma's record to be one of those fundamental records. From now on, people who want to engage with how the Earth has changed over the last 70 million years will have to engage with Emma's data."

In addition to being the most abundant gas in the atmosphere, nitrogen is key to all life on Earth. "I study nitrogen so that I can study the global environment," said Daniel Sigman, Princeton's Dusenbury Professor of Geological and Geophysical Sciences and the senior author on the paper. Sigman initiated this project with Higgins and then-Princeton postdoctoral researcher Daniel Stolper, who is now an assistant professor of Earth and planetary science at the University of California-Berkeley.

Every organism on Earth requires "fixed" nitrogen -- sometimes called "biologically available nitrogen." Nitrogen makes up 78% of our planet's atmosphere, but few organisms can "fix" it by converting the gas into a biologically useful form. In the oceans, cyanobacteria in surface waters fix nitrogen for all other ocean life. As the cyanobacteria and other creatures die and sink downward, they decompose.

Nitrogen has two stable isotopes, 15N and 14N. In oxygen-poor waters, decomposition uses up "fixed" nitrogen. This occurs with a slight preference for the lighter nitrogen isotope, 14N, so the ocean's 15N-to-14N ratio reflects its oxygen levels.

That ratio is incorporated into tiny sea creatures called foraminifera during their lives, and then preserved in their shells when they die. By analyzing their fossils -- collected by the Ocean Drilling Program from the North Atlantic, North Pacific, and South Atlantic -- Kast and her colleagues were able to reconstruct the 15N-to-14N ratio of the ancient ocean, and therefore identify past changes in oxygen levels.

Oxygen controls the distribution of marine organisms, with oxygen-poor waters being bad for most ocean life. Many past climate warming events caused decreases in ocean oxygen that limited the habitats of sea creatures, from microscopic plankton to the fish and whales that feed on them. Scientists trying to predict the impact of current and future global warming have warned that low levels of ocean oxygen could decimate marine ecosystems, including important fish populations.

When the researchers assembled their unprecedented geologic record of ocean nitrogen, they found that in the 10 million years after dinosaurs went extinct, the 15N-to-14N ratio was high, suggesting that ocean oxygen levels were low. They first thought that the warm climate of the time was responsible, as oxygen is less soluble in warmer water. But the timing told another story: the change to higher ocean oxygen occurred around 55 million years ago, during a time of continuously warm climate.

"Contrary to our first expectations, global climate was not the primary cause of this change in ocean oxygen and nitrogen cycling," Kast said. The more likely culprit? Plate tectonics. The collision of India with Asia -- dubbed "the collision that changed the world" by legendary geoscientist Wally Broecker, a founder of modern climate research -- closed off an ancient sea called the Tethys, disturbing the continental shelves and their connections with the open ocean.

Read more at Science Daily

Apr 12, 2019

Earliest life may have arisen in ponds, not oceans

Did life originate in shallow ponds?
Primitive ponds may have provided a suitable environment for brewing up Earth's first life forms, more so than oceans, a new MIT study finds.

Researchers report that shallow bodies of water, on the order of 10 centimeters deep, could have held high concentrations of what many scientists believe to be a key ingredient for jump-starting life on Earth: nitrogen.

In shallow ponds, nitrogen, in the form of nitrogenous oxides, would have had a good chance of accumulating enough to react with other compounds and give rise to the first living organisms. In much deeper oceans, nitrogen would have had a harder time establishing a significant, life-catalyzing presence, the researchers say.

"Our overall message is, if you think the origin of life required fixed nitrogen, as many people do, then it's tough to have the origin of life happen in the ocean," says lead author Sukrit Ranjan, a postdoc in MIT's Department of Earth, Atmospheric and Planetary Sciences (EAPS). "It's much easier to have that happen in a pond."

Ranjan and his colleagues have published their results today in the journal Geochemistry, Geophysics, Geosystems. The paper's co-authors are Andrew Babbin, the Doherty Assistant Professor in Ocean Utilization in EAPS, along with Zoe Todd and Dimitar Sasselov of Harvard University, and Paul Rimmer at Cambridge University.

Breaking a bond

If primitive life indeed sprang from a key reaction involving nitrogen, there are two ways in which scientists believe this could have happened. The first hypothesis involves the deep ocean, where nitrogen, in the form of nitrogenous oxides, could have reacted with carbon dioxide bubbling forth from hydrothermal vents, to form life's first molecular building blocks.

The second nitrogen-based hypothesis for the origin of life involves RNA -- ribonucleic acid, a molecule that today helps encode our genetic information. In its primitive form, RNA was likely a free-floating molecule. When in contact with nitrogenous oxides, some scientists believe, RNA could have been chemically induced to form the first molecular chains of life. This process of RNA formation could have occurred in either the oceans or in shallow lakes and ponds.

Nitrogenous oxides were likely deposited in bodies of water, including oceans and ponds, as remnants of the breakdown of nitrogen in Earth's atmosphere. Atmospheric nitrogen consists of two nitrogen molecules, linked via a strong triple bond, that can only be broken by an extremely energetic event -- namely, lightning.

"Lightning is like a really intense bomb going off," Ranjan says. "It produces enough energy that it breaks that triple bond in our atmospheric nitrogen gas, to produce nitrogenous oxides that can then rain down into water bodies."

Scientists believe that there could have been enough lightning crackling through the early atmosphere to produce an abundance of nitrogenous oxides to fuel the origin of life in the ocean. Ranjan says scientists have assumed that this supply of lightning-generated nitrogenous oxides was relatively stable once the compounds entered the oceans.

However, in this new study, he identifies two significant "sinks," or effects that could have destroyed a significant portion of nitrogenous oxides, particularly in the oceans. He and his colleagues looked through the scientific literature and found that nitrogenous oxides in water can be broken down via interactions with the sun's ultraviolet light, and also with dissolved iron sloughed off from primitive oceanic rocks.

Ranjan says both ultraviolet light and dissolved iron could have destroyed a significant portion of nitrogenous oxides in the ocean, sending the compounds back into the atmosphere as gaseous nitrogen.

"We showed that if you include these two new sinks that people hadn't thought about before, that suppresses the concentrations of nitrogenous oxides in the ocean by a factor of 1,000, relative to what people calculated before," Ranjan says.

"Building a cathedral"


In the ocean, ultraviolet light and dissolved iron would have made nitrogenous oxides far less available for synthesizing living organisms. In shallow ponds, however, life would have had a better chance to take hold. That's mainly because ponds have much less volume over which compounds can be diluted. As a result, nitrogenous oxides would have built up to much higher concentrations in ponds. Any "sinks," such as UV light and dissolved iron, would have had less of an effect on the compound's overall concentrations.

Ranjan says the more shallow the pond, the greater the chance nitrogenous oxides would have had to interact with other molecules, and particularly RNA, to catalyze the first living organisms.

"These ponds could have been from 10 to 100 centimeters deep, with a surface area of tens of square meters or larger," Ranjan says. "They would have been similar to Don Juan Pond in Antarctica today, which has a summer seasonal depth of about 10 centimeters."

That may not seem like a significant body of water, but he says that's precisely the point: In environments any deeper or larger, nitrogenous oxides would simply have been too diluted, precluding any participation in origin-of-life chemistry. Other groups have estimated that, around 3.9 billion years ago, just before the first signs of life appeared on Earth, there may have been about 500 square kilometers of shallow ponds and lakes worldwide.

"That's utterly tiny, compared to the amount of lake area we have today," Ranjan says. "However, relative to the amount of surface area prebiotic chemists postulate is required to get life started, it's quite adequate."

The debate over whether life originated in ponds versus oceans is not quite resolved, but Ranjan says the new study provides one convincing piece of evidence for the former.

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