Research links soil mineral surfaces to key atmospheric processes

Pictured are, from left, are David Bish, Melissa Donaldson and Jonathan Raff. -  Indiana University
Pictured are, from left, are David Bish, Melissa Donaldson and Jonathan Raff. – Indiana University

Research by Indiana University scientists finds that soil may be a significant and underappreciated source of nitrous acid, a chemical that plays a pivotal role in atmospheric processes such as the formation of smog and determining the lifetime of greenhouse gases.

The study shows for the first time that the surface acidity of common minerals found in soil determines whether the gas nitrous acid will be released into the atmosphere. The finding could contribute to improved models for understanding and controlling air pollution, a significant public health concern.

“We find that the surfaces of minerals in the soil can be much more acidic than the overall pH of the soil would suggest,” said Jonathan Raff, assistant professor in the School of Public and Environmental Affairs and Department of Chemistry. “It’s the acidity of the soil minerals that acts as a knob or a control lever, and that determines whether nitrous acid outgasses from soil or remains as nitrite.”

The article, “Soil surface acidity plays a determining role in the atmospheric-terrestrial exchange of nitrous acid,” will be published this week in the journal Proceedings of the National Academy of Sciences. Melissa A. Donaldson, a Ph.D. student in the School of Public and Environmental Affairs, is the lead author. Co-authors are Raff and David L. Bish, the Haydn Murray Chair of Applied Clay Mineralogy in the Department of Geological Sciences.

Nitrous acid, or HONO, plays a key role in regulating atmospheric processes. Sunlight causes it to break down into nitric oxide and the hydroxyl radical, OH. The latter controls the atmospheric lifetime of gases important to air quality and climate change and initiates the chemistry leading to the formation of ground-level ozone, a primary component of smog.

Scientists have known about the nitrous acid’s role in air pollution for 40 years, but they haven’t fully understood how it is produced and destroyed or how it interacts with other substances, because HONO is unstable and difficult to measure.

“Only in the last 10 years have we had the technology to study nitrous acid under environmentally relevant conditions,” Raff said.

Recent studies have shown nitrous acid to be emitted from soil in many locations. But this was unexpected because, according to basic chemistry, the reactions that release nitrous acid should take place only in extremely acidic soils, typically found in rain forests or the taiga of North America and Eurasia.

The standard method to determine the acidity of soil is to mix bulk soil with water and measure the overall pH. But the IU researchers show that the crucial factor is not overall pH but the acidity at the surface of soil minerals, especially iron oxides and aluminum oxides. At the molecular level, the water adsorbed directly to these minerals is unusually acidic and facilitates the conversion of nitrite in the soil to nitrous acid, which then volatilizes.

“With the traditional approach of calculating soil pH, we were severely underestimating nitrous acid emissions from soil,” Raff said. “I think the source is going to turn out to be more important than was previously imagined.”

The research was carried out using soil from a farm field near Columbus, Ind. But aluminum and iron oxides are ubiquitous in soil, and the researchers say the results suggest that about 70 percent of Earth’s soils could be sources of nitrous acid.

Ultimately, the research will contribute to a better understanding of how nitrous acid is produced and how it affects atmospheric processes. That in turn will improve the computer models used by the U.S. Environmental Protection Agency and other regulatory agencies to control air pollution, which the World Health Organization estimates contributes to 7 million premature deaths annually.

“With improved models, policymakers can make better judgments about the costs and benefits of regulations,” Raff said. “If we don’t get the chemistry right, we’re not going to get the right answers to our policy questions regarding air pollution.”

Research links soil mineral surfaces to key atmospheric processes

Pictured are, from left, are David Bish, Melissa Donaldson and Jonathan Raff. -  Indiana University
Pictured are, from left, are David Bish, Melissa Donaldson and Jonathan Raff. – Indiana University

Research by Indiana University scientists finds that soil may be a significant and underappreciated source of nitrous acid, a chemical that plays a pivotal role in atmospheric processes such as the formation of smog and determining the lifetime of greenhouse gases.

The study shows for the first time that the surface acidity of common minerals found in soil determines whether the gas nitrous acid will be released into the atmosphere. The finding could contribute to improved models for understanding and controlling air pollution, a significant public health concern.

“We find that the surfaces of minerals in the soil can be much more acidic than the overall pH of the soil would suggest,” said Jonathan Raff, assistant professor in the School of Public and Environmental Affairs and Department of Chemistry. “It’s the acidity of the soil minerals that acts as a knob or a control lever, and that determines whether nitrous acid outgasses from soil or remains as nitrite.”

The article, “Soil surface acidity plays a determining role in the atmospheric-terrestrial exchange of nitrous acid,” will be published this week in the journal Proceedings of the National Academy of Sciences. Melissa A. Donaldson, a Ph.D. student in the School of Public and Environmental Affairs, is the lead author. Co-authors are Raff and David L. Bish, the Haydn Murray Chair of Applied Clay Mineralogy in the Department of Geological Sciences.

Nitrous acid, or HONO, plays a key role in regulating atmospheric processes. Sunlight causes it to break down into nitric oxide and the hydroxyl radical, OH. The latter controls the atmospheric lifetime of gases important to air quality and climate change and initiates the chemistry leading to the formation of ground-level ozone, a primary component of smog.

Scientists have known about the nitrous acid’s role in air pollution for 40 years, but they haven’t fully understood how it is produced and destroyed or how it interacts with other substances, because HONO is unstable and difficult to measure.

“Only in the last 10 years have we had the technology to study nitrous acid under environmentally relevant conditions,” Raff said.

Recent studies have shown nitrous acid to be emitted from soil in many locations. But this was unexpected because, according to basic chemistry, the reactions that release nitrous acid should take place only in extremely acidic soils, typically found in rain forests or the taiga of North America and Eurasia.

The standard method to determine the acidity of soil is to mix bulk soil with water and measure the overall pH. But the IU researchers show that the crucial factor is not overall pH but the acidity at the surface of soil minerals, especially iron oxides and aluminum oxides. At the molecular level, the water adsorbed directly to these minerals is unusually acidic and facilitates the conversion of nitrite in the soil to nitrous acid, which then volatilizes.

“With the traditional approach of calculating soil pH, we were severely underestimating nitrous acid emissions from soil,” Raff said. “I think the source is going to turn out to be more important than was previously imagined.”

The research was carried out using soil from a farm field near Columbus, Ind. But aluminum and iron oxides are ubiquitous in soil, and the researchers say the results suggest that about 70 percent of Earth’s soils could be sources of nitrous acid.

Ultimately, the research will contribute to a better understanding of how nitrous acid is produced and how it affects atmospheric processes. That in turn will improve the computer models used by the U.S. Environmental Protection Agency and other regulatory agencies to control air pollution, which the World Health Organization estimates contributes to 7 million premature deaths annually.

“With improved models, policymakers can make better judgments about the costs and benefits of regulations,” Raff said. “If we don’t get the chemistry right, we’re not going to get the right answers to our policy questions regarding air pollution.”

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.

New study measures methane emissions from natural gas production and offers insights into 2 large sources

A team of researchers from the Cockrell School of Engineering at The University of Texas at Austin and environmental testing firm URS reports that a small subset of natural gas wells are responsible for the majority of methane emissions from two major sources — liquid unloadings and pneumatic controller equipment — at natural gas production sites.

With natural gas production in the United States expected to continue to increase during the next few decades, there is a need for a better understanding of methane emissions during natural gas production. The study team believes this research, published Dec. 9 in Environmental Science & Technology, will help to provide a clearer picture of methane emissions from natural gas production sites.

The UT Austin-led field study closely examined two major sources of methane emissions — liquid unloadings and pneumatic controller equipment — at well pad sites across the United States. Researchers found that 19 percent of the pneumatic devices accounted for 95 percent of the emissions from pneumatic devices, and 20 percent of the wells with unloading emissions that vent to the atmosphere accounted for 65 percent to 83 percent of those emissions.

“To put this in perspective, over the past several decades, 10 percent of the cars on the road have been responsible for the majority of automotive exhaust pollution,” said David Allen, chemical engineering professor at the Cockrell School and principal investigator for the study. “Similarly, a small group of sources within these two categories are responsible for the vast majority of pneumatic and unloading emissions at natural gas production sites.”

Additionally, for pneumatic devices, the study confirmed regional differences in methane emissions first reported by the study team in 2013. The researchers found that methane emissions from pneumatic devices were highest in the Gulf Coast and lowest in the Rocky Mountains.

The study is the second phase of the team’s 2013 study, which included some of the first measurements for methane emissions taken directly at hydraulically fractured well sites. Both phases of the study involved a partnership between the Environmental Defense Fund, participating energy companies, an independent Scientific Advisory Panel and the UT Austin study team.

The unprecedented access to natural gas production facilities and equipment allowed researchers to acquire direct measurements of methane emissions.

Study and Findings on Pneumatic Devices

Pneumatic devices, which use gas pressure to control the opening and closing of valves, emit gas as they operate. These emissions are estimated to be among the larger sources of methane emissions from the natural gas supply chain. The Environmental Protection Agency reports that 477,606 pneumatic (gas actuated) devices are in use at natural gas production sites throughout the U.S.

“Our team’s previous work established that pneumatics are a major contributor to emissions,” Allen said. “Our goal here was to measure a more diverse population of wells to characterize the features of high-emitting pneumatic controllers.”

The research team measured emissions from 377 gas actuated (pneumatic) controllers at natural gas production sites and a small number of oil production sites throughout the U.S.

The researchers sampled all identifiable pneumatic controller devices at each well site, a more comprehensive approach than the random sampling previously conducted. The average methane emissions per pneumatic controller reported in this study are 17 percent higher than the average emissions per pneumatic controller in the 2012 EPA greenhouse gas national emission inventory (released in 2014), but the average from the study is dominated by a small subpopulation of the controllers. Specifically, 19 percent of controllers, with measured emission rates in excess of 6 standard cubic feet per hour (scf/h), accounted for 95 percent of emissions.

The high-emitting pneumatic devices are a combination of devices that are not operating as designed, are used in applications that cause them to release gas frequently or are designed to emit continuously at a high rate.

The researchers also observed regional differences in methane emission levels, with the lowest emissions per device measured in the Rocky Mountains and the highest emissions in the Gulf Coast, similar to the earlier 2013 study. At least some of the regional differences in emission rates can be attributed to the difference in controller type (continuous vent vs. intermittent vent) among regions.

Study and Findings on Liquid Unloadings

After observing variable emissions for liquid unloadings for a limited group of well types in the 2013 study, the research team made more extensive measurements and confirmed that a majority of emissions come from a small fraction of wells that vent frequently. Although it is not surprising to see some correlation between frequency of unloadings and higher annual emissions, the study’s findings indicate that wells with a high frequency of unloadings have annual emissions that are 10 or more times as great as wells that unload less frequently.

The team’s field study, which measured emissions from unloadings from wells at 107 natural gas production wells throughout the U.S., represents the most extensive measurement of emissions associated with liquid unloadings in scientific literature thus far.

A liquid unloading is one method used to clear wells of accumulated liquids to increase production. Because older wells typically produce less gas as they near the end of their life cycle, liquid unloadings happen more often in those wells than in newer wells. The team found a statistical correlation between the age of wells and the frequency of liquid unloadings. The researchers found that the key identifier for high-emitting wells is how many times the well unloads in a given year.

Because liquid unloadings can employ a variety of liquid lifting mechanisms, the study results also reflect differences in liquid unloadings emissions between wells that use two different mechanisms (wells with plunger lifts and wells without plunger lifts). Emissions for unloading events for wells without plunger lifts averaged 21,000 scf (standard cubic feet) to 35,000 scf. For wells with plunger lifts that vent to the atmosphere, emissions averaged 1,000 scf to 10,000 scf of methane per event. Although the emissions per event were higher for wells without plunger lifts, these wells had, on average, fewer events than wells with plunger lifts. Wells without plunger lifts averaged fewer than 10 unloading events per year, and wells with plunger lifts averaged more than 200 events per year.Overall, wells with plunger lifts were estimated to account for 70 percent of emissions from unloadings nationally.

Additionally, researchers found that the Rocky Mountain region, with its large number of wells with a high frequency of unloadings that vent to the atmosphere, accounts for about half of overall emissions from liquid unloadings.

The study team hopes its measurements of liquid unloadings and pneumatic devices will provide a clearer picture of methane emissions from natural gas well sites and about the relationship between well characteristics and emissions.

The study was a cooperative effort involving experts from the Environmental Defense Fund, Anadarko Petroleum Corporation, BG Group PLC, Chevron, ConocoPhillips, Encana Oil & Gas (USA) Inc., Pioneer Natural Resources Company, SWEPI LP (Shell), Statoil, Southwestern Energy and XTO Energy, a subsidiary of ExxonMobil.

The University of Texas at Austin is committed to transparency and disclosure of all potential conflicts of interest of its researchers. Lead researcher David Allen serves as chair of the Environmental Protection Agency’s Science Advisory Board and in this role is a paid Special Governmental Employee. He is also a journal editor for the American Chemical Society and has served as a consultant for multiple companies, including Eastern Research Group, ExxonMobil and the Research Triangle Institute. He has worked on other research projects funded by a variety of governmental, nonprofit and private sector sources including the National Science Foundation, the Environmental Protection Agency, the Texas Commission on Environmental Quality, the American Petroleum Institute and an air monitoring and surveillance project that was ordered by the U.S. District Court for the Southern District of Texas. Adam Pacsi and Daniel Zavala-Araiza, who were graduate students at The University of Texas at the time this work was done, have accepted positions at Chevron Energy Technology Company and the Environmental Defense Fund, respectively.

Financial support for this work was provided by the Environmental Defense Fund (EDF), Anadarko Petroleum Corporation, BG Group PLC, Chevron, ConocoPhillips, Encana Oil & Gas (USA) Inc., Pioneer Natural Resources Company, SWEPI LP (Shell), Statoil, Southwestern Energy and XTO Energy, a subsidiary of ExxonMobil.

Major funding for the EDF’s 30-month methane research series, including their portion of the University of Texas study, is provided for by the following individuals and foundations: Fiona and Stan Druckenmiller, the Heising-Simons Foundation, Bill and Susan Oberndorf, Betsy and Sam Reeves, the Robertson Foundation, TomKat Charitable Trust and the Walton Family Foundation.

New study measures methane emissions from natural gas production and offers insights into 2 large sources

A team of researchers from the Cockrell School of Engineering at The University of Texas at Austin and environmental testing firm URS reports that a small subset of natural gas wells are responsible for the majority of methane emissions from two major sources — liquid unloadings and pneumatic controller equipment — at natural gas production sites.

With natural gas production in the United States expected to continue to increase during the next few decades, there is a need for a better understanding of methane emissions during natural gas production. The study team believes this research, published Dec. 9 in Environmental Science & Technology, will help to provide a clearer picture of methane emissions from natural gas production sites.

The UT Austin-led field study closely examined two major sources of methane emissions — liquid unloadings and pneumatic controller equipment — at well pad sites across the United States. Researchers found that 19 percent of the pneumatic devices accounted for 95 percent of the emissions from pneumatic devices, and 20 percent of the wells with unloading emissions that vent to the atmosphere accounted for 65 percent to 83 percent of those emissions.

“To put this in perspective, over the past several decades, 10 percent of the cars on the road have been responsible for the majority of automotive exhaust pollution,” said David Allen, chemical engineering professor at the Cockrell School and principal investigator for the study. “Similarly, a small group of sources within these two categories are responsible for the vast majority of pneumatic and unloading emissions at natural gas production sites.”

Additionally, for pneumatic devices, the study confirmed regional differences in methane emissions first reported by the study team in 2013. The researchers found that methane emissions from pneumatic devices were highest in the Gulf Coast and lowest in the Rocky Mountains.

The study is the second phase of the team’s 2013 study, which included some of the first measurements for methane emissions taken directly at hydraulically fractured well sites. Both phases of the study involved a partnership between the Environmental Defense Fund, participating energy companies, an independent Scientific Advisory Panel and the UT Austin study team.

The unprecedented access to natural gas production facilities and equipment allowed researchers to acquire direct measurements of methane emissions.

Study and Findings on Pneumatic Devices

Pneumatic devices, which use gas pressure to control the opening and closing of valves, emit gas as they operate. These emissions are estimated to be among the larger sources of methane emissions from the natural gas supply chain. The Environmental Protection Agency reports that 477,606 pneumatic (gas actuated) devices are in use at natural gas production sites throughout the U.S.

“Our team’s previous work established that pneumatics are a major contributor to emissions,” Allen said. “Our goal here was to measure a more diverse population of wells to characterize the features of high-emitting pneumatic controllers.”

The research team measured emissions from 377 gas actuated (pneumatic) controllers at natural gas production sites and a small number of oil production sites throughout the U.S.

The researchers sampled all identifiable pneumatic controller devices at each well site, a more comprehensive approach than the random sampling previously conducted. The average methane emissions per pneumatic controller reported in this study are 17 percent higher than the average emissions per pneumatic controller in the 2012 EPA greenhouse gas national emission inventory (released in 2014), but the average from the study is dominated by a small subpopulation of the controllers. Specifically, 19 percent of controllers, with measured emission rates in excess of 6 standard cubic feet per hour (scf/h), accounted for 95 percent of emissions.

The high-emitting pneumatic devices are a combination of devices that are not operating as designed, are used in applications that cause them to release gas frequently or are designed to emit continuously at a high rate.

The researchers also observed regional differences in methane emission levels, with the lowest emissions per device measured in the Rocky Mountains and the highest emissions in the Gulf Coast, similar to the earlier 2013 study. At least some of the regional differences in emission rates can be attributed to the difference in controller type (continuous vent vs. intermittent vent) among regions.

Study and Findings on Liquid Unloadings

After observing variable emissions for liquid unloadings for a limited group of well types in the 2013 study, the research team made more extensive measurements and confirmed that a majority of emissions come from a small fraction of wells that vent frequently. Although it is not surprising to see some correlation between frequency of unloadings and higher annual emissions, the study’s findings indicate that wells with a high frequency of unloadings have annual emissions that are 10 or more times as great as wells that unload less frequently.

The team’s field study, which measured emissions from unloadings from wells at 107 natural gas production wells throughout the U.S., represents the most extensive measurement of emissions associated with liquid unloadings in scientific literature thus far.

A liquid unloading is one method used to clear wells of accumulated liquids to increase production. Because older wells typically produce less gas as they near the end of their life cycle, liquid unloadings happen more often in those wells than in newer wells. The team found a statistical correlation between the age of wells and the frequency of liquid unloadings. The researchers found that the key identifier for high-emitting wells is how many times the well unloads in a given year.

Because liquid unloadings can employ a variety of liquid lifting mechanisms, the study results also reflect differences in liquid unloadings emissions between wells that use two different mechanisms (wells with plunger lifts and wells without plunger lifts). Emissions for unloading events for wells without plunger lifts averaged 21,000 scf (standard cubic feet) to 35,000 scf. For wells with plunger lifts that vent to the atmosphere, emissions averaged 1,000 scf to 10,000 scf of methane per event. Although the emissions per event were higher for wells without plunger lifts, these wells had, on average, fewer events than wells with plunger lifts. Wells without plunger lifts averaged fewer than 10 unloading events per year, and wells with plunger lifts averaged more than 200 events per year.Overall, wells with plunger lifts were estimated to account for 70 percent of emissions from unloadings nationally.

Additionally, researchers found that the Rocky Mountain region, with its large number of wells with a high frequency of unloadings that vent to the atmosphere, accounts for about half of overall emissions from liquid unloadings.

The study team hopes its measurements of liquid unloadings and pneumatic devices will provide a clearer picture of methane emissions from natural gas well sites and about the relationship between well characteristics and emissions.

The study was a cooperative effort involving experts from the Environmental Defense Fund, Anadarko Petroleum Corporation, BG Group PLC, Chevron, ConocoPhillips, Encana Oil & Gas (USA) Inc., Pioneer Natural Resources Company, SWEPI LP (Shell), Statoil, Southwestern Energy and XTO Energy, a subsidiary of ExxonMobil.

The University of Texas at Austin is committed to transparency and disclosure of all potential conflicts of interest of its researchers. Lead researcher David Allen serves as chair of the Environmental Protection Agency’s Science Advisory Board and in this role is a paid Special Governmental Employee. He is also a journal editor for the American Chemical Society and has served as a consultant for multiple companies, including Eastern Research Group, ExxonMobil and the Research Triangle Institute. He has worked on other research projects funded by a variety of governmental, nonprofit and private sector sources including the National Science Foundation, the Environmental Protection Agency, the Texas Commission on Environmental Quality, the American Petroleum Institute and an air monitoring and surveillance project that was ordered by the U.S. District Court for the Southern District of Texas. Adam Pacsi and Daniel Zavala-Araiza, who were graduate students at The University of Texas at the time this work was done, have accepted positions at Chevron Energy Technology Company and the Environmental Defense Fund, respectively.

Financial support for this work was provided by the Environmental Defense Fund (EDF), Anadarko Petroleum Corporation, BG Group PLC, Chevron, ConocoPhillips, Encana Oil & Gas (USA) Inc., Pioneer Natural Resources Company, SWEPI LP (Shell), Statoil, Southwestern Energy and XTO Energy, a subsidiary of ExxonMobil.

Major funding for the EDF’s 30-month methane research series, including their portion of the University of Texas study, is provided for by the following individuals and foundations: Fiona and Stan Druckenmiller, the Heising-Simons Foundation, Bill and Susan Oberndorf, Betsy and Sam Reeves, the Robertson Foundation, TomKat Charitable Trust and the Walton Family Foundation.

Technology-dependent emissions of gas extraction in the US

The KIT measurement instrument on board of a minivan directly measures atmospheric emissions on site with a high temporal resolution. -  Photo: F. Geiger/KIT
The KIT measurement instrument on board of a minivan directly measures atmospheric emissions on site with a high temporal resolution. – Photo: F. Geiger/KIT

Not all boreholes are the same. Scientists of the Karlsruhe Institute of Technology (KIT) used mobile measurement equipment to analyze gaseous compounds emitted by the extraction of oil and natural gas in the USA. For the first time, organic pollutants emitted during a fracking process were measured at a high temporal resolution. The highest values measured exceeded typical mean values in urban air by a factor of one thousand, as was reported in ACP journal. (DOI 10.5194/acp-14-10977-2014)

Emission of trace gases by oil and gas fields was studied by the KIT researchers in the USA (Utah and Colorado) together with US institutes. Background concentrations and the waste gas plumes of single extraction plants and fracking facilities were analyzed. The air quality measurements of several weeks duration took place under the “Uintah Basin Winter Ozone Study” coordinated by the National Oceanic and Atmospheric Administration (NOAA).

The KIT measurements focused on health-damaging aromatic hydrocarbons in air, such as carcinogenic benzene. Maximum concentrations were determined in the waste gas plumes of boreholes. Some extraction plants emitted up to about a hundred times more benzene than others. The highest values of some milligrams of benzene per cubic meter air were measured downstream of an open fracking facility, where returning drilling fluid is stored in open tanks and basins. Much better results were reached by oil and gas extraction plants and plants with closed production processes. In Germany, benzene concentration at the workplace is subject to strict limits: The Federal Emission Control Ordinance gives an annual benzene limit of five micrograms per cubic meter for the protection of human health, which is smaller than the values now measured at the open fracking facility in the US by a factor of about one thousand. The researchers published the results measured in the journal Atmospheric Chemistry and Physics ACP.

“Characteristic emissions of trace gases are encountered everywhere. These are symptomatic of gas and gas extraction. But the values measured for different technologies differ considerably,” Felix Geiger of the Institute of Meteorology and Climate Research (IMK) of KIT explains. He is one of the first authors of the study. By means of closed collection tanks and so-called vapor capture systems, for instance, the gases released during operation can be collected and reduced significantly.

“The gas fields in the sparsely populated areas of North America are a good showcase for estimating the range of impacts of different extraction and fracking technologies,” explains Professor Johannes Orphal, Head of IMK. “In the densely populated Germany, framework conditions are much stricter and much more attention is paid to reducing and monitoring emissions.”

Fracking is increasingly discussed as a technology to extract fossil resources from unconventional deposits. Hydraulic breaking of suitable shale stone layers opens up the fossil fuels stored there and makes them accessible for economically efficient use. For this purpose, boreholes are drilled into these rock formations. Then, they are subjected to high pressure using large amounts of water and auxiliary materials, such as sand, cement, and chemicals. The oil or gas can flow to the surface through the opened microstructures in the rock. Typically, the return flow of the aqueous fracking liquid with the dissolved oil and gas constituents to the surface lasts several days until the production phase proper of purer oil or natural gas. This return flow is collected and then reused until it finally has to be disposed of. Air pollution mainly depends on the treatment of this return flow at the extraction plant. In this respect, currently practiced fracking technologies differ considerably. For the first time now, the resulting local atmospheric emissions were studied at a high temporary resolution. Based on the results, emissions can be assigned directly to the different plant sections of an extraction plant. For measurement, the newly developed, compact, and highly sensitive instrument, a so-called proton transfer reaction mass spectrometer (PTR-MS), of KIT was installed on board of a minivan and driven closer to the different extraction points, the distances being a few tens of meters. In this way, the waste gas plumes of individual extraction sources and fracking processes were studied in detail.

Warneke, C., Geiger, F., Edwards, P. M., Dube, W., Pétron, G., Kofler, J., Zahn, A., Brown, S. S., Graus, M., Gilman, J. B., Lerner, B. M., Peischl, J., Ryerson, T. B., de Gouw, J. A., and Roberts, J. M.: Volatile organic compound emissions from the oil and natural gas industry in the Uintah Basin, Utah: oil and gas well pad emissions compared to ambient air composition, Atmos. Chem. Phys., 14, 10977-10988, doi:10.5194/acp-14-10977-2014, 2014.

Technology-dependent emissions of gas extraction in the US

The KIT measurement instrument on board of a minivan directly measures atmospheric emissions on site with a high temporal resolution. -  Photo: F. Geiger/KIT
The KIT measurement instrument on board of a minivan directly measures atmospheric emissions on site with a high temporal resolution. – Photo: F. Geiger/KIT

Not all boreholes are the same. Scientists of the Karlsruhe Institute of Technology (KIT) used mobile measurement equipment to analyze gaseous compounds emitted by the extraction of oil and natural gas in the USA. For the first time, organic pollutants emitted during a fracking process were measured at a high temporal resolution. The highest values measured exceeded typical mean values in urban air by a factor of one thousand, as was reported in ACP journal. (DOI 10.5194/acp-14-10977-2014)

Emission of trace gases by oil and gas fields was studied by the KIT researchers in the USA (Utah and Colorado) together with US institutes. Background concentrations and the waste gas plumes of single extraction plants and fracking facilities were analyzed. The air quality measurements of several weeks duration took place under the “Uintah Basin Winter Ozone Study” coordinated by the National Oceanic and Atmospheric Administration (NOAA).

The KIT measurements focused on health-damaging aromatic hydrocarbons in air, such as carcinogenic benzene. Maximum concentrations were determined in the waste gas plumes of boreholes. Some extraction plants emitted up to about a hundred times more benzene than others. The highest values of some milligrams of benzene per cubic meter air were measured downstream of an open fracking facility, where returning drilling fluid is stored in open tanks and basins. Much better results were reached by oil and gas extraction plants and plants with closed production processes. In Germany, benzene concentration at the workplace is subject to strict limits: The Federal Emission Control Ordinance gives an annual benzene limit of five micrograms per cubic meter for the protection of human health, which is smaller than the values now measured at the open fracking facility in the US by a factor of about one thousand. The researchers published the results measured in the journal Atmospheric Chemistry and Physics ACP.

“Characteristic emissions of trace gases are encountered everywhere. These are symptomatic of gas and gas extraction. But the values measured for different technologies differ considerably,” Felix Geiger of the Institute of Meteorology and Climate Research (IMK) of KIT explains. He is one of the first authors of the study. By means of closed collection tanks and so-called vapor capture systems, for instance, the gases released during operation can be collected and reduced significantly.

“The gas fields in the sparsely populated areas of North America are a good showcase for estimating the range of impacts of different extraction and fracking technologies,” explains Professor Johannes Orphal, Head of IMK. “In the densely populated Germany, framework conditions are much stricter and much more attention is paid to reducing and monitoring emissions.”

Fracking is increasingly discussed as a technology to extract fossil resources from unconventional deposits. Hydraulic breaking of suitable shale stone layers opens up the fossil fuels stored there and makes them accessible for economically efficient use. For this purpose, boreholes are drilled into these rock formations. Then, they are subjected to high pressure using large amounts of water and auxiliary materials, such as sand, cement, and chemicals. The oil or gas can flow to the surface through the opened microstructures in the rock. Typically, the return flow of the aqueous fracking liquid with the dissolved oil and gas constituents to the surface lasts several days until the production phase proper of purer oil or natural gas. This return flow is collected and then reused until it finally has to be disposed of. Air pollution mainly depends on the treatment of this return flow at the extraction plant. In this respect, currently practiced fracking technologies differ considerably. For the first time now, the resulting local atmospheric emissions were studied at a high temporary resolution. Based on the results, emissions can be assigned directly to the different plant sections of an extraction plant. For measurement, the newly developed, compact, and highly sensitive instrument, a so-called proton transfer reaction mass spectrometer (PTR-MS), of KIT was installed on board of a minivan and driven closer to the different extraction points, the distances being a few tens of meters. In this way, the waste gas plumes of individual extraction sources and fracking processes were studied in detail.

Warneke, C., Geiger, F., Edwards, P. M., Dube, W., Pétron, G., Kofler, J., Zahn, A., Brown, S. S., Graus, M., Gilman, J. B., Lerner, B. M., Peischl, J., Ryerson, T. B., de Gouw, J. A., and Roberts, J. M.: Volatile organic compound emissions from the oil and natural gas industry in the Uintah Basin, Utah: oil and gas well pad emissions compared to ambient air composition, Atmos. Chem. Phys., 14, 10977-10988, doi:10.5194/acp-14-10977-2014, 2014.

Antarctica: Heat comes from the deep

The Antarctic ice sheet is a giant water reservoir. The ice cap on the southern continent is on average 2,100 meters thick and contains about 70 percent of the world’s fresh water. If this ice mass were to melt completely, it could raise the global sea level by 60 meters. Therefore scientists carefully observe changes in the Antarctic. In the renowned international journal Science, researchers from Germany, the UK, the US and Japan are now publishing data according to which water temperatures, in particular on the shallow shelf seas of West Antarctica, are rising. “There are many large glaciers in the area. The elevated temperatures have accelerated the melting and sliding of these glaciers in recent decades and there are no indications that this trend is changing,” says the lead author of the study, Dr. Sunke Schmidtko from GEOMAR Helmholtz Centre for Ocean Research Kiel.

For their study, he and his colleagues of the University of East Anglia, the California Institute of Technology and the University of Hokkaido (Japan) evaluated all oceanographic data from the waters around Antarctica from 1960 to 2014 that were available in public databases. These data show that five decades ago, the water masses in the West Antarctic shelf seas were already warmer than in other parts of Antarctica, for example, in the Weddell Sea. However, the temperature difference is not constant. Since 1960, the temperatures in the West Antarctic Amundsen Sea and the Bellingshausen Sea have been rising. “Based on the data we were able to see that this shelf process is induced from the open ocean,” says Dr. Schmidtko.

Around Antarctica in greater depth along the continental slope water masses with temperatures from 0.5 to 1.5°C (33-35°F) are predominant. These temperatures are very warm for Antarctic conditions. “These waters have warmed in West Antarctica over the past 50 years. And they are significant shallower than 50 years ago,” says Schmidtko. Especially in the Amundsen Sea and Bellingshausen Sea they now increasingly spill onto the shelf and warm the shelf.

“These are the regions in which accelerated glacial melting has been observed for some time. We show that oceanographic changes over the past 50 years have probably caused this melting. If the water continues to warm, the increased penetration of warmer water masses onto the shelf will likely further accelerate this process, with an impact on the rate of global sea level rise ” explains Professor Karen Heywood from the University of East Anglia.

The scientists also draw attention to the rising up of warm water masses in the southwestern Weddell Sea. Here very cold temperatures (less than minus 1.5°C or 29°F) prevail on the shelf and a large-scale melting of shelf ice has not been observed yet. If the shoaling of warm water masses continues, it is expected that there will be major environmental changes with dramatic consequences for the Filchner or Ronne Ice Shelf, too. For the first time glaciers outside the West Antarctic could experience enhanced melting from below.

To what extent the diverse biology of the Southern Ocean is influenced by the observed changes is not fully understood. The shelf areas include spawning areas for the Antarctic krill, a shrimp species widespread in the Southern Ocean, which plays a key role in the Antarctic food chain. Research results have shown that spawning cycles could change in warmer conditions. A final assessment of the impact has not yet been made.

The exact reasons for the increase of the heating and the rising of warm water masses has not yet been completely resolved. “We suspect that they are related to large-scale variations in wind systems over the southern hemisphere. But which processes specifically play a role must be evaluated in more detail.” says Dr. Schmidtko.

Antarctica: Heat comes from the deep

The Antarctic ice sheet is a giant water reservoir. The ice cap on the southern continent is on average 2,100 meters thick and contains about 70 percent of the world’s fresh water. If this ice mass were to melt completely, it could raise the global sea level by 60 meters. Therefore scientists carefully observe changes in the Antarctic. In the renowned international journal Science, researchers from Germany, the UK, the US and Japan are now publishing data according to which water temperatures, in particular on the shallow shelf seas of West Antarctica, are rising. “There are many large glaciers in the area. The elevated temperatures have accelerated the melting and sliding of these glaciers in recent decades and there are no indications that this trend is changing,” says the lead author of the study, Dr. Sunke Schmidtko from GEOMAR Helmholtz Centre for Ocean Research Kiel.

For their study, he and his colleagues of the University of East Anglia, the California Institute of Technology and the University of Hokkaido (Japan) evaluated all oceanographic data from the waters around Antarctica from 1960 to 2014 that were available in public databases. These data show that five decades ago, the water masses in the West Antarctic shelf seas were already warmer than in other parts of Antarctica, for example, in the Weddell Sea. However, the temperature difference is not constant. Since 1960, the temperatures in the West Antarctic Amundsen Sea and the Bellingshausen Sea have been rising. “Based on the data we were able to see that this shelf process is induced from the open ocean,” says Dr. Schmidtko.

Around Antarctica in greater depth along the continental slope water masses with temperatures from 0.5 to 1.5°C (33-35°F) are predominant. These temperatures are very warm for Antarctic conditions. “These waters have warmed in West Antarctica over the past 50 years. And they are significant shallower than 50 years ago,” says Schmidtko. Especially in the Amundsen Sea and Bellingshausen Sea they now increasingly spill onto the shelf and warm the shelf.

“These are the regions in which accelerated glacial melting has been observed for some time. We show that oceanographic changes over the past 50 years have probably caused this melting. If the water continues to warm, the increased penetration of warmer water masses onto the shelf will likely further accelerate this process, with an impact on the rate of global sea level rise ” explains Professor Karen Heywood from the University of East Anglia.

The scientists also draw attention to the rising up of warm water masses in the southwestern Weddell Sea. Here very cold temperatures (less than minus 1.5°C or 29°F) prevail on the shelf and a large-scale melting of shelf ice has not been observed yet. If the shoaling of warm water masses continues, it is expected that there will be major environmental changes with dramatic consequences for the Filchner or Ronne Ice Shelf, too. For the first time glaciers outside the West Antarctic could experience enhanced melting from below.

To what extent the diverse biology of the Southern Ocean is influenced by the observed changes is not fully understood. The shelf areas include spawning areas for the Antarctic krill, a shrimp species widespread in the Southern Ocean, which plays a key role in the Antarctic food chain. Research results have shown that spawning cycles could change in warmer conditions. A final assessment of the impact has not yet been made.

The exact reasons for the increase of the heating and the rising of warm water masses has not yet been completely resolved. “We suspect that they are related to large-scale variations in wind systems over the southern hemisphere. But which processes specifically play a role must be evaluated in more detail.” says Dr. Schmidtko.