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.”

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.

A new look at what’s in ‘fracking’ fluids raises red flags

Scientists are getting to the bottom of what's in fracking fluids — with some troubling results. -  Doug Duncan/U.S. Geological Survey
Scientists are getting to the bottom of what’s in fracking fluids — with some troubling results. – Doug Duncan/U.S. Geological Survey

As the oil and gas drilling technique called hydraulic fracturing (or “fracking”) proliferates, a new study on the contents of the fluids involved in the process raises concerns about several ingredients. The scientists presenting the work today at the 248th National Meeting & Exposition of the American Chemical Society (ACS) say that out of nearly 200 commonly used compounds, there’s very little known about the potential health risks of about one-third, and eight are toxic to mammals.

The meeting features nearly 12,000 presentations on a wide range of science topics and is being held here through Thursday by ACS, the world’s largest scientific society.

William Stringfellow, Ph.D., says he conducted the review of fracking contents to help resolve the public debate over the controversial drilling practice. Fracking involves injecting water with a mix of chemical additives into rock formations deep underground to promote the release of oil and gas. It has led to a natural gas boom in the U.S., but it has also stimulated major opposition and troubling reports of contaminated well water, as well as increased air pollution near drill sites.

“The industrial side was saying, ‘We’re just using food additives, basically making ice cream here,'” Stringfellow says. “On the other side, there’s talk about the injection of thousands of toxic chemicals. As scientists, we looked at the debate and asked, ‘What’s the real story?'”

To find out, Stringfellow’s team at Lawrence Berkeley National Laboratory and University of the Pacific scoured databases and reports to compile a list of substances commonly used in fracking. They include gelling agents to thicken the fluids, biocides to keep microbes from growing, sand to prop open tiny cracks in the rocks and compounds to prevent pipe corrosion.

What their analysis revealed was a little truth to both sides’ stories – with big caveats. Fracking fluids do contain many nontoxic and food-grade materials, as the industry asserts. But if something is edible or biodegradable, it doesn’t automatically mean it can be easily disposed of, Stringfellow notes.

“You can’t take a truckload of ice cream and dump it down the storm drain,” he says, building on the industry’s analogy. “Even ice cream manufacturers have to treat dairy wastes, which are natural and biodegradable. They must break them down rather than releasing them directly into the environment.”

His team found that most fracking compounds will require treatment before being released. And, although not in the thousands as some critics suggest, the scientists identified eight substances, including biocides, that raised red flags. These eight compounds were identified as being particularly toxic to mammals.

“There are a number of chemicals, like corrosion inhibitors and biocides in particular, that are being used in reasonably high concentrations that potentially could have adverse effects,” Stringfellow says. “Biocides, for example, are designed to kill bacteria – it’s not a benign material.”

They’re also looking at the environmental impact of the fracking fluids, and they are finding that some have toxic effects on aquatic life.

In addition, for about one-third of the approximately 190 compounds the scientists identified as ingredients in various fracking formulas, the scientists found very little information about toxicity and physical and chemical properties.

“It should be a priority to try to close that data gap,” Stringfellow says.

A new look at what’s in ‘fracking’ fluids raises red flags

Scientists are getting to the bottom of what's in fracking fluids — with some troubling results. -  Doug Duncan/U.S. Geological Survey
Scientists are getting to the bottom of what’s in fracking fluids — with some troubling results. – Doug Duncan/U.S. Geological Survey

As the oil and gas drilling technique called hydraulic fracturing (or “fracking”) proliferates, a new study on the contents of the fluids involved in the process raises concerns about several ingredients. The scientists presenting the work today at the 248th National Meeting & Exposition of the American Chemical Society (ACS) say that out of nearly 200 commonly used compounds, there’s very little known about the potential health risks of about one-third, and eight are toxic to mammals.

The meeting features nearly 12,000 presentations on a wide range of science topics and is being held here through Thursday by ACS, the world’s largest scientific society.

William Stringfellow, Ph.D., says he conducted the review of fracking contents to help resolve the public debate over the controversial drilling practice. Fracking involves injecting water with a mix of chemical additives into rock formations deep underground to promote the release of oil and gas. It has led to a natural gas boom in the U.S., but it has also stimulated major opposition and troubling reports of contaminated well water, as well as increased air pollution near drill sites.

“The industrial side was saying, ‘We’re just using food additives, basically making ice cream here,'” Stringfellow says. “On the other side, there’s talk about the injection of thousands of toxic chemicals. As scientists, we looked at the debate and asked, ‘What’s the real story?'”

To find out, Stringfellow’s team at Lawrence Berkeley National Laboratory and University of the Pacific scoured databases and reports to compile a list of substances commonly used in fracking. They include gelling agents to thicken the fluids, biocides to keep microbes from growing, sand to prop open tiny cracks in the rocks and compounds to prevent pipe corrosion.

What their analysis revealed was a little truth to both sides’ stories – with big caveats. Fracking fluids do contain many nontoxic and food-grade materials, as the industry asserts. But if something is edible or biodegradable, it doesn’t automatically mean it can be easily disposed of, Stringfellow notes.

“You can’t take a truckload of ice cream and dump it down the storm drain,” he says, building on the industry’s analogy. “Even ice cream manufacturers have to treat dairy wastes, which are natural and biodegradable. They must break them down rather than releasing them directly into the environment.”

His team found that most fracking compounds will require treatment before being released. And, although not in the thousands as some critics suggest, the scientists identified eight substances, including biocides, that raised red flags. These eight compounds were identified as being particularly toxic to mammals.

“There are a number of chemicals, like corrosion inhibitors and biocides in particular, that are being used in reasonably high concentrations that potentially could have adverse effects,” Stringfellow says. “Biocides, for example, are designed to kill bacteria – it’s not a benign material.”

They’re also looking at the environmental impact of the fracking fluids, and they are finding that some have toxic effects on aquatic life.

In addition, for about one-third of the approximately 190 compounds the scientists identified as ingredients in various fracking formulas, the scientists found very little information about toxicity and physical and chemical properties.

“It should be a priority to try to close that data gap,” Stringfellow says.

‘Fracking’ in the dark: Biological fallout of shale-gas production still largely unknown

Eight conservation biologists from various organizations and institutions, including Princeton University, found that shale-gas extraction in the United States has vastly outpaced scientists' understanding of the industry's environmental impact. With shale-gas production projected to surge during the next 30 years, determining and minimizing the industry's effects on nature and wildlife must become a top priority for scientists, industry and policymakers, the researchers said. The photo above shows extensive natural-gas operations at Jonah Field in Wyoming. -  Photo courtesy of EcoFlight.
Eight conservation biologists from various organizations and institutions, including Princeton University, found that shale-gas extraction in the United States has vastly outpaced scientists’ understanding of the industry’s environmental impact. With shale-gas production projected to surge during the next 30 years, determining and minimizing the industry’s effects on nature and wildlife must become a top priority for scientists, industry and policymakers, the researchers said. The photo above shows extensive natural-gas operations at Jonah Field in Wyoming. – Photo courtesy of EcoFlight.

In the United States, natural-gas production from shale rock has increased by more than 700 percent since 2007. Yet scientists still do not fully understand the industry’s effects on nature and wildlife, according to a report in the journal Frontiers in Ecology and the Environment.

As gas extraction continues to vastly outpace scientific examination, a team of eight conservation biologists from various organizations and institutions, including Princeton University, concluded that determining the environmental impact of gas-drilling sites – such as chemical contamination from spills, well-casing failures and other accidents – must be a top research priority.

With shale-gas production projected to surge during the next 30 years, the authors call on scientists, industry representatives and policymakers to cooperate on determining – and minimizing – the damage inflicted on the natural world by gas operations such as hydraulic fracturing, or “fracking.” A major environmental concern, hydraulic fracturing releases natural gas from shale by breaking the rock up with a high-pressure blend of water, sand and other chemicals, which can include carcinogens and radioactive substances.

“We can’t let shale development outpace our understanding of its environmental impacts,” said co-author Morgan Tingley, a postdoctoral research associate in the Program in Science, Technology and Environmental Policy in Princeton’s Woodrow Wilson School of Public and International Affairs.

“The past has taught us that environmental impacts of large-scale development and resource extraction, whether coal plants, large dams or biofuel monocultures, are more than the sum of their parts,” Tingley said.

The researchers found that there are significant “knowledge gaps” when it comes to direct and quantifiable evidence of how the natural world responds to shale-gas operations. A major impediment to research has been the lack of accessible and reliable information on spills, wastewater disposal and the composition of fracturing fluids. Of the 24 American states with active shale-gas reservoirs, only five – Pennsylvania, Colorado, New Mexico, Wyoming and Texas – maintain public records of spills and accidents, the researchers report.

“The Pennsylvania Department of Environmental Protection’s website is one of the best sources of publicly available information on shale-gas spills and accidents in the nation. Even so, gas companies failed to report more than one-third of spills in the last year,” said first author Sara Souther, a postdoctoral research associate at the University of Wisconsin-Madison.

“How many more unreported spills occurred, but were not detected during well inspections?” Souther asked. “We need accurate data on the release of fracturing chemicals into the environment before we can understand impacts to plants and animals.”

One of the greatest threats to animal and plant life identified in the study is the impact of rapid and widespread shale development, which has disproportionately affected rural and natural areas. A single gas well results in the clearance of 3.7 to 7.6 acres (1.5 to 3.1 hectares) of vegetation, and each well contributes to a collective mass of air, water, noise and light pollution that has or can interfere with wild animal health, habitats and reproduction, the researchers report.

“If you look down on a heavily ‘fracked’ landscape, you see a web of well pads, access roads and pipelines that create islands out of what was, in some cases, contiguous habitat,” Souther said. “What are the combined effects of numerous wells and their supporting infrastructure on wide-ranging or sensitive species, like the pronghorn antelope or the hellbender salamander?”

The chemical makeup of fracturing fluid and wastewater is often unknown. The authors reviewed chemical-disclosure statements for 150 wells in three of the top gas-producing states and found that an average of two out of every three wells were fractured with at least one undisclosed chemical. The exact effect of fracturing fluid on natural water systems as well as drinking water supplies remains unclear even though improper wastewater disposal and pollution-prevention measures are among the top state-recorded violations at drilling sites, the researchers found.

“Some of the wells in the chemical disclosure registry were fractured with fluid containing 20 or more undisclosed chemicals,” said senior author Kimberly Terrell, a researcher at the Smithsonian Conservation Biology Institute. “This is an arbitrary and inconsistent standard of chemical disclosure.”

‘Fracking’ in the dark: Biological fallout of shale-gas production still largely unknown

Eight conservation biologists from various organizations and institutions, including Princeton University, found that shale-gas extraction in the United States has vastly outpaced scientists' understanding of the industry's environmental impact. With shale-gas production projected to surge during the next 30 years, determining and minimizing the industry's effects on nature and wildlife must become a top priority for scientists, industry and policymakers, the researchers said. The photo above shows extensive natural-gas operations at Jonah Field in Wyoming. -  Photo courtesy of EcoFlight.
Eight conservation biologists from various organizations and institutions, including Princeton University, found that shale-gas extraction in the United States has vastly outpaced scientists’ understanding of the industry’s environmental impact. With shale-gas production projected to surge during the next 30 years, determining and minimizing the industry’s effects on nature and wildlife must become a top priority for scientists, industry and policymakers, the researchers said. The photo above shows extensive natural-gas operations at Jonah Field in Wyoming. – Photo courtesy of EcoFlight.

In the United States, natural-gas production from shale rock has increased by more than 700 percent since 2007. Yet scientists still do not fully understand the industry’s effects on nature and wildlife, according to a report in the journal Frontiers in Ecology and the Environment.

As gas extraction continues to vastly outpace scientific examination, a team of eight conservation biologists from various organizations and institutions, including Princeton University, concluded that determining the environmental impact of gas-drilling sites – such as chemical contamination from spills, well-casing failures and other accidents – must be a top research priority.

With shale-gas production projected to surge during the next 30 years, the authors call on scientists, industry representatives and policymakers to cooperate on determining – and minimizing – the damage inflicted on the natural world by gas operations such as hydraulic fracturing, or “fracking.” A major environmental concern, hydraulic fracturing releases natural gas from shale by breaking the rock up with a high-pressure blend of water, sand and other chemicals, which can include carcinogens and radioactive substances.

“We can’t let shale development outpace our understanding of its environmental impacts,” said co-author Morgan Tingley, a postdoctoral research associate in the Program in Science, Technology and Environmental Policy in Princeton’s Woodrow Wilson School of Public and International Affairs.

“The past has taught us that environmental impacts of large-scale development and resource extraction, whether coal plants, large dams or biofuel monocultures, are more than the sum of their parts,” Tingley said.

The researchers found that there are significant “knowledge gaps” when it comes to direct and quantifiable evidence of how the natural world responds to shale-gas operations. A major impediment to research has been the lack of accessible and reliable information on spills, wastewater disposal and the composition of fracturing fluids. Of the 24 American states with active shale-gas reservoirs, only five – Pennsylvania, Colorado, New Mexico, Wyoming and Texas – maintain public records of spills and accidents, the researchers report.

“The Pennsylvania Department of Environmental Protection’s website is one of the best sources of publicly available information on shale-gas spills and accidents in the nation. Even so, gas companies failed to report more than one-third of spills in the last year,” said first author Sara Souther, a postdoctoral research associate at the University of Wisconsin-Madison.

“How many more unreported spills occurred, but were not detected during well inspections?” Souther asked. “We need accurate data on the release of fracturing chemicals into the environment before we can understand impacts to plants and animals.”

One of the greatest threats to animal and plant life identified in the study is the impact of rapid and widespread shale development, which has disproportionately affected rural and natural areas. A single gas well results in the clearance of 3.7 to 7.6 acres (1.5 to 3.1 hectares) of vegetation, and each well contributes to a collective mass of air, water, noise and light pollution that has or can interfere with wild animal health, habitats and reproduction, the researchers report.

“If you look down on a heavily ‘fracked’ landscape, you see a web of well pads, access roads and pipelines that create islands out of what was, in some cases, contiguous habitat,” Souther said. “What are the combined effects of numerous wells and their supporting infrastructure on wide-ranging or sensitive species, like the pronghorn antelope or the hellbender salamander?”

The chemical makeup of fracturing fluid and wastewater is often unknown. The authors reviewed chemical-disclosure statements for 150 wells in three of the top gas-producing states and found that an average of two out of every three wells were fractured with at least one undisclosed chemical. The exact effect of fracturing fluid on natural water systems as well as drinking water supplies remains unclear even though improper wastewater disposal and pollution-prevention measures are among the top state-recorded violations at drilling sites, the researchers found.

“Some of the wells in the chemical disclosure registry were fractured with fluid containing 20 or more undisclosed chemicals,” said senior author Kimberly Terrell, a researcher at the Smithsonian Conservation Biology Institute. “This is an arbitrary and inconsistent standard of chemical disclosure.”

Modern ocean acidification is outpacing ancient upheaval, study suggests

<IMG SRC="/Images/964394569.jpg" WIDTH="350" HEIGHT="237" BORDER="0" ALT="The deep-sea benthic foram Aragonia velascoensis went extinct about 56 million years ago as the oceans rapidly acidified. – Ellen Thomas/Yale University”>
The deep-sea benthic foram Aragonia velascoensis went extinct about 56 million years ago as the oceans rapidly acidified. – Ellen Thomas/Yale University

Some 56 million years ago, a massive pulse of carbon dioxide into the atmosphere sent global temperatures soaring. In the oceans, carbonate sediments dissolved, some organisms went extinct and others evolved.

Scientists have long suspected that ocean acidification played a part in the crisis-similar to today, as manmade CO2 combines with seawater to change its chemistry. Now, for the first time, scientists have quantified the extent of surface acidification from those ancient days, and the news is not good: the oceans are on track to acidify at least as much as they did then, only at a much faster rate.

In a study published in the latest issue of Paleoceanography, the scientists estimate that surface ocean acidity increased by about 100 percent in a few thousand years or more, and stayed that way for the next 70,000 years. In this radically changed environment, some creatures died out while others adapted and evolved. The study is the first to use the chemical composition of fossils to reconstruct surface ocean acidity at the Paleocene-Eocene Thermal Maximum (PETM), a period of intense warming on land and throughout the oceans due to high CO2.

“This could be the closest geological analog to modern ocean acidification,” said study coauthor Bärbel Hönisch, a paleoceanographer at Columbia University’s Lamont-Doherty Earth Observatory. “As massive as it was, it still happened about 10 times more slowly than what we are doing today.”

The oceans have absorbed about a third of the carbon humans have pumped into the air since industrialization, helping to keep temperatures lower than they would be otherwise. But that uptake of carbon has come at a price. Chemical reactions caused by that excess CO2 have made seawater grow more acidic, depleting it of the carbonate ions that corals, mollusks and calcifying plankton need to build their shells and skeletons.

In the last 150 years or so, the pH of the oceans has dropped substantially, from 8.2 to 8.1–equivalent to a 25 percent increase in acidity. By the end of the century, ocean pH is projected to fall another 0.3 pH units, to 7.8. While the researchers found a comparable pH drop during the PETM–0.3 units–the shift happened over a few thousand years.

“We are dumping carbon in the atmosphere and ocean at a much higher rate today-within centuries,” said study coauthor Richard Zeebe, a paleoceanographer at the University of Hawaii. “If we continue on the emissions path we are on right now, acidification of the surface ocean will be way more dramatic than during the PETM.”

Ocean acidification in the modern ocean may already be affecting some marine life, as shown by the partly dissolved shell of this planktic snail, or pteropod, caught off the Pacific Northwest.


The study confirms that the acidified conditions lasted for 70,000 years or more, consistent with previous model-based estimates.

“It didn’t bounce back right away,” said Timothy Bralower, a researcher at Penn State who was not involved in the study. “It took tens of thousands of years to recover.”

From seafloor sediments drilled off Japan, the researchers analyzed the shells of plankton that lived at the surface of the ocean during the PETM. Two different methods for measuring ocean chemistry at the time-the ratio of boron isotopes in their shells, and the amount of boron –arrived at similar estimates of acidification. “It’s really showing us clear evidence of a change in pH for the first time,” said Bralower.

What caused the burst of carbon at the PETM is still unclear. One popular explanation is that an overall warming trend may have sent a pulse of methane from the seafloor into the air, setting off events that released more earth-warming gases into the air and oceans. Up to half of the tiny animals that live in mud on the seafloor-benthic foraminifera-died out during the PETM, possibly along with life further up the food chain.

Other species thrived in this changed environment and new ones evolved. In the oceans, dinoflagellates extended their range from the tropics to the Arctic, while on land, hoofed animals and primates appeared for the first time. Eventually, the oceans and atmosphere recovered as elements from eroded rocks washed into the sea and neutralized the acid.

Today, signs are already emerging that some marine life may be in trouble. In a recent study led by Nina Bednarsek at the U.S. National Oceanic and Atmospheric Administration, more than half of the tiny planktic snails, or pteropods, that she and her team studied off the coast of Washington, Oregon and California showed badly dissolved shells. Ocean acidification has been linked to the widespread death of baby oysters off Washington and Oregon since 2005, and may also pose a threat to coral reefs, which are under additional pressure from pollution and warming ocean temperatures.

“Seawater carbonate chemistry is complex but the mechanism underlying ocean acidification is very simple,” said study lead author Donald Penman, a graduate student at University of California at Santa Cruz. “We can make accurate predictions about how carbonate chemistry will respond to increasing carbon dioxide levels. The real unknown is how individual organisms will respond and how that cascades through ecosystems.”

Modern ocean acidification is outpacing ancient upheaval, study suggests

<IMG SRC="/Images/964394569.jpg" WIDTH="350" HEIGHT="237" BORDER="0" ALT="The deep-sea benthic foram Aragonia velascoensis went extinct about 56 million years ago as the oceans rapidly acidified. – Ellen Thomas/Yale University”>
The deep-sea benthic foram Aragonia velascoensis went extinct about 56 million years ago as the oceans rapidly acidified. – Ellen Thomas/Yale University

Some 56 million years ago, a massive pulse of carbon dioxide into the atmosphere sent global temperatures soaring. In the oceans, carbonate sediments dissolved, some organisms went extinct and others evolved.

Scientists have long suspected that ocean acidification played a part in the crisis-similar to today, as manmade CO2 combines with seawater to change its chemistry. Now, for the first time, scientists have quantified the extent of surface acidification from those ancient days, and the news is not good: the oceans are on track to acidify at least as much as they did then, only at a much faster rate.

In a study published in the latest issue of Paleoceanography, the scientists estimate that surface ocean acidity increased by about 100 percent in a few thousand years or more, and stayed that way for the next 70,000 years. In this radically changed environment, some creatures died out while others adapted and evolved. The study is the first to use the chemical composition of fossils to reconstruct surface ocean acidity at the Paleocene-Eocene Thermal Maximum (PETM), a period of intense warming on land and throughout the oceans due to high CO2.

“This could be the closest geological analog to modern ocean acidification,” said study coauthor Bärbel Hönisch, a paleoceanographer at Columbia University’s Lamont-Doherty Earth Observatory. “As massive as it was, it still happened about 10 times more slowly than what we are doing today.”

The oceans have absorbed about a third of the carbon humans have pumped into the air since industrialization, helping to keep temperatures lower than they would be otherwise. But that uptake of carbon has come at a price. Chemical reactions caused by that excess CO2 have made seawater grow more acidic, depleting it of the carbonate ions that corals, mollusks and calcifying plankton need to build their shells and skeletons.

In the last 150 years or so, the pH of the oceans has dropped substantially, from 8.2 to 8.1–equivalent to a 25 percent increase in acidity. By the end of the century, ocean pH is projected to fall another 0.3 pH units, to 7.8. While the researchers found a comparable pH drop during the PETM–0.3 units–the shift happened over a few thousand years.

“We are dumping carbon in the atmosphere and ocean at a much higher rate today-within centuries,” said study coauthor Richard Zeebe, a paleoceanographer at the University of Hawaii. “If we continue on the emissions path we are on right now, acidification of the surface ocean will be way more dramatic than during the PETM.”

Ocean acidification in the modern ocean may already be affecting some marine life, as shown by the partly dissolved shell of this planktic snail, or pteropod, caught off the Pacific Northwest.


The study confirms that the acidified conditions lasted for 70,000 years or more, consistent with previous model-based estimates.

“It didn’t bounce back right away,” said Timothy Bralower, a researcher at Penn State who was not involved in the study. “It took tens of thousands of years to recover.”

From seafloor sediments drilled off Japan, the researchers analyzed the shells of plankton that lived at the surface of the ocean during the PETM. Two different methods for measuring ocean chemistry at the time-the ratio of boron isotopes in their shells, and the amount of boron –arrived at similar estimates of acidification. “It’s really showing us clear evidence of a change in pH for the first time,” said Bralower.

What caused the burst of carbon at the PETM is still unclear. One popular explanation is that an overall warming trend may have sent a pulse of methane from the seafloor into the air, setting off events that released more earth-warming gases into the air and oceans. Up to half of the tiny animals that live in mud on the seafloor-benthic foraminifera-died out during the PETM, possibly along with life further up the food chain.

Other species thrived in this changed environment and new ones evolved. In the oceans, dinoflagellates extended their range from the tropics to the Arctic, while on land, hoofed animals and primates appeared for the first time. Eventually, the oceans and atmosphere recovered as elements from eroded rocks washed into the sea and neutralized the acid.

Today, signs are already emerging that some marine life may be in trouble. In a recent study led by Nina Bednarsek at the U.S. National Oceanic and Atmospheric Administration, more than half of the tiny planktic snails, or pteropods, that she and her team studied off the coast of Washington, Oregon and California showed badly dissolved shells. Ocean acidification has been linked to the widespread death of baby oysters off Washington and Oregon since 2005, and may also pose a threat to coral reefs, which are under additional pressure from pollution and warming ocean temperatures.

“Seawater carbonate chemistry is complex but the mechanism underlying ocean acidification is very simple,” said study lead author Donald Penman, a graduate student at University of California at Santa Cruz. “We can make accurate predictions about how carbonate chemistry will respond to increasing carbon dioxide levels. The real unknown is how individual organisms will respond and how that cascades through ecosystems.”