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.”

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.

No laughing matter: Nitrous oxide rose at end of last ice age

Researchers measured increases in atmospheric nitrous oxide concentrations about 16,000 to 10,000 years ago using ice from Taylor Glacier in Antarctica. -  Adrian Schilt
Researchers measured increases in atmospheric nitrous oxide concentrations about 16,000 to 10,000 years ago using ice from Taylor Glacier in Antarctica. – Adrian Schilt

Nitrous oxide (N2O) is an important greenhouse gas that doesn’t receive as much notoriety as carbon dioxide or methane, but a new study confirms that atmospheric levels of N2O rose significantly as the Earth came out of the last ice age and addresses the cause.

An international team of scientists analyzed air extracted from bubbles enclosed in ancient polar ice from Taylor Glacier in Antarctica, allowing for the reconstruction of the past atmospheric composition. The analysis documented a 30 percent increase in atmospheric nitrous oxide concentrations from 16,000 years ago to 10,000 years ago. This rise in N2O was caused by changes in environmental conditions in the ocean and on land, scientists say, and contributed to the warming at the end of the ice age and the melting of large ice sheets that then existed.

The findings add an important new element to studies of how Earth may respond to a warming climate in the future. Results of the study, which was funded by the U.S. National Science Foundation and the Swiss National Science Foundation, are being published this week in the journal Nature.

“We found that marine and terrestrial sources contributed about equally to the overall increase of nitrous oxide concentrations and generally evolved in parallel at the end of the last ice age,” said lead author Adrian Schilt, who did much of the work as a post-doctoral researcher at Oregon State University. Schilt then continued to work on the study at the Oeschger Centre for Climate Change Research at the University of Bern in Switzerland.

“The end of the last ice age represents a partial analog to modern warming and allows us to study the response of natural nitrous oxide emissions to changing environmental conditions,” Schilt added. “This will allow us to better understand what might happen in the future.”

Nitrous oxide is perhaps best known as laughing gas, but it is also produced by microbes on land and in the ocean in processes that occur naturally, but can be enhanced by human activity. Marine nitrous oxide production is linked closely to low oxygen conditions in the upper ocean and global warming is predicted to intensify the low-oxygen zones in many of the world’s ocean basins. N2O also destroys ozone in the stratosphere.

“Warming makes terrestrial microbes produce more nitrous oxide,” noted co-author Edward Brook, an Oregon State paleoclimatologist whose research team included Schilt. “Greenhouse gases go up and down over time, and we’d like to know more about why that happens and how it affects climate.”

Nitrous oxide is among the most difficult greenhouse gases to study in attempting to reconstruct the Earth’s climate history through ice core analysis. The specific technique that the Oregon State research team used requires large samples of pristine ice that date back to the desired time of study – in this case, between about 16,000 and 10,000 years ago.

The unusual way in which Taylor Glacier is configured allowed the scientists to extract ice samples from the surface of the glacier instead of drilling deep in the polar ice cap because older ice is transported upward near the glacier margins, said Brook, a professor in Oregon State’s College of Earth, Ocean, and Atmospheric Sciences.

The scientists were able to discern the contributions of marine and terrestrial nitrous oxide through analysis of isotopic ratios, which fingerprint the different sources of N2O in the atmosphere.

“The scientific community knew roughly what the N2O concentration trends were prior to this study,” Brook said, “but these findings confirm that and provide more exact details about changes in sources. As nitrous oxide in the atmosphere continues to increase – along with carbon dioxide and methane – we now will be able to more accurately assess where those contributions are coming from and the rate of the increase.”

Atmospheric N2O was roughly 200 parts per billion at the peak of the ice age about 20,000 years ago then rose to 260 ppb by 10,000 years ago. As of 2014, atmospheric N2Owas measured at about 327 ppb, an increase attributed primarily to agricultural influences.

Although the N2O increase at the end of the last ice age was almost equally attributable to marine and terrestrial sources, the scientists say, there were some differences.

“Our data showed that terrestrial emissions changed faster than marine emissions, which was highlighted by a fast increase of emissions on land that preceded the increase in marine emissions,” Schilt pointed out. “It appears to be a direct response to a rapid temperature change between 15,000 and 14,000 years ago.”

That finding underscores the complexity of analyzing how Earth responds to changing conditions that have to account for marine and terrestrial influences; natural variability; the influence of different greenhouse gases; and a host of other factors, Brook said.

“Natural sources of N2O are predicted to increase in the future and this study will help up test predictions on how the Earth will respond,” Brook said.

Abandoned wells can be ‘super-emitters’ of greenhouse gas

One of the wells the researchers tested; this one in the Allegheny National Forest. -  Princeton University
One of the wells the researchers tested; this one in the Allegheny National Forest. – Princeton University

Princeton University researchers have uncovered a previously unknown, and possibly substantial, source of the greenhouse gas methane to the Earth’s atmosphere.

After testing a sample of abandoned oil and natural gas wells in northwestern Pennsylvania, the researchers found that many of the old wells leaked substantial quantities of methane. Because there are so many abandoned wells nationwide (a recent study from Stanford University concluded there were roughly 3 million abandoned wells in the United States) the researchers believe the overall contribution of leaking wells could be significant.

The researchers said their findings identify a need to make measurements across a wide variety of regions in Pennsylvania but also in other states with a long history of oil and gas development such as California and Texas.

“The research indicates that this is a source of methane that should not be ignored,” said Michael Celia, the Theodore Shelton Pitney Professor of Environmental Studies and professor of civil and environmental engineering at Princeton. “We need to determine how significant it is on a wider basis.”

Methane is the unprocessed form of natural gas. Scientists say that after carbon dioxide, methane is the most important contributor to the greenhouse effect, in which gases in the atmosphere trap heat that would otherwise radiate from the Earth. Pound for pound, methane has about 20 times the heat-trapping effect as carbon dioxide. Methane is produced naturally, by processes including decomposition, and by human activity such as landfills and oil and gas production.

While oil and gas companies work to minimize the amount of methane emitted by their operations, almost no attention has been paid to wells that were drilled decades ago. These wells, some of which date back to the 19th century, are typically abandoned and not recorded on official records.

Mary Kang, then a doctoral candidate at Princeton, originally began looking into methane emissions from old wells after researching techniques to store carbon dioxide by injecting it deep underground. While examining ways that carbon dioxide could escape underground storage, Kang wondered about the effect of old wells on methane emissions.

“I was looking for data, but it didn’t exist,” said Kang, now a postdoctoral researcher at Stanford.

In a paper published Dec. 8 in the Proceedings of the National Academy of Sciences, the researchers describe how they chose 19 wells in the adjacent McKean and Potter counties in northwestern Pennsylvania. The wells chosen were all abandoned, and records about the origin of the wells and their conditions did not exist. Only one of the wells was on the state’s list of abandoned wells. Some of the wells, which can look like a pipe emerging from the ground, are located in forests and others in people’s yards. Kang said the lack of documentation made it hard to tell when the wells were originally drilled or whether any attempt had been made to plug them.

“What surprised me was that every well we measured had some methane coming out,” said Celia.

To conduct the research, the team placed enclosures called flux chambers over the tops of the wells. They also placed flux chambers nearby to measure the background emissions from the terrain and make sure the methane was emitted from the wells and not the surrounding area.

Although all the wells registered some level of methane, about 15 percent emitted the gas at a markedly higher level — thousands of times greater than the lower-level wells. Denise Mauzerall, a Princeton professor and a member of the research team, said a critical task is to discover the characteristics of these super-emitting wells.

Mauzerall said the relatively low number of high-emitting wells could offer a workable solution: while trying to plug every abandoned well in the country might be too costly to be realistic, dealing with the smaller number of high emitters could be possible.

“The fact that most of the methane is coming out of a small number of wells should make it easier to address if we can identify the high-emitting wells,” said Mauzerall, who has a joint appointment as a professor of civil and environmental engineering and as a professor of public and international affairs at the Woodrow Wilson School.

The researchers have used their results to extrapolate total methane emissions from abandoned wells in Pennsylvania, although they stress that the results are preliminary because of the relatively small sample. But based on that data, they estimate that emissions from abandoned wells represents as much as 10 percent of methane from human activities in Pennsylvania — about the same amount as caused by current oil and gas production. Also, unlike working wells, which have productive lifetimes of 10 to 15 years, abandoned wells can continue to leak methane for decades.

“This may be a significant source,” Mauzerall said. “There is no single silver bullet but if it turns out that we can cap or capture the methane coming off these really big emitters, that would make a substantial difference.”


Besides Kang, who is the paper’s lead author, Celia and Mauzerall, the paper’s co-authors include: Tullis Onstott, a professor of geosciences at Princeton; Cynthia Kanno, who was a Princeton undergraduate and who is a graduate student at the Colorado School of Mines; Matthew Reid, who was a graduate student at Princeton and is a postdoctoral researcher at EPFL in Luzerne, Switzerland; Xin Zhang, a postdoctoral researcher in the Woodrow Wilson School at Princeton; and Yuheng Chen, an associate research scholar in geosciences at Princeton.

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.

The breathing sand

An Eddy Correlation Lander analyzes the strength of the oxygen fluxes at the bottom of the North Sea. -  Photo: ROV-Team, GEOMAR
An Eddy Correlation Lander analyzes the strength of the oxygen fluxes at the bottom of the North Sea. – Photo: ROV-Team, GEOMAR

A desert at the bottom of the sea? Although the waters of the North Sea exchange about every two to three years, there is evidence of decreasing oxygen content. If lower amounts of this gas are dissolved in seawater, organisms on and in the seabed produce less energy – with implications for larger creatures and the biogeochemical cycling in the marine ecosystem. Since nutrients, carbon and oxygen circulate very well and are processed quickly in the permeable, sandy sediments that make up two-thirds of the North Sea, measurements of metabolic rates are especially difficult here. Using the new Aquatic Eddy Correlation technique, scientists from GEOMAR Helmholtz Centre for Ocean Research Kiel, Leibniz Institute of Freshwater Ecology and Inland Fisheries, the University of Southern Denmark, the University of Koblenz-Landau, the Scottish Marine Institute and Aarhus University were able to demonstrate how oxygen flows at the ground of the North Sea. Their methods and results are presented in the Journal of Geophysical Research: Oceans.

“The so-called ‘Eddy Correlation’ technique detects the flow of oxygen through these small turbulences over an area of several square meters. It considers both the mixing of sediments by organisms living in it and the hydrodynamics of the water above the rough sea floor”, Dr. Peter Linke, a marine biologist at GEOMAR, explains. “Previous methods overlooked only short periods or disregarded important parameters. Now we can create a more realistic picture.” The new method also takes into account the fact that even small objects such as shells or ripples shaped by wave action or currents are able to impact the oxygen exchange in permeable sediments.

On the expedition CE0913 with the Irish research vessel CELTIC EXPLORER, scientists used the underwater robot ROV KIEL 6000 to place three different instruments within the “Tommeliten” area belonging to Norway: Two “Eddy Correlation Landers” recorded the strength of oxygen fluxes over three tidal cycles. Information about the distribution of oxygen in the sediment was collected with a “Profiler Lander”, a seafloor observatory with oxygen sensors and flow meters. A “Benthic chamber” isolated 314 square centimetres of sediment and took samples from the overlying water over a period of 24 hours to determine the oxygen consumption of the sediment.

“The combination of traditional tools with the ‘Eddy Correlation’ technique has given us new insights into the dynamics of the exchange of substances between the sea water and the underlying sediment. A variety of factors determine the timing and amount of oxygen available. Currents that provide the sandy sediment with oxygen, but also the small-scale morphology of the seafloor, ensure that small benthic organisms are able to process carbon or other nutrients. The dependencies are so complex that they can be decrypted only by using special methods”, Dr. Linke summarizes. Therefore, detailed measurements in the water column and at the boundary to the seafloor as well as model calculations are absolutely necessary to understand basic functions and better estimate future changes in the cycle of materials. “With conventional methods, for example, we would never have been able to find that the loose sandy sediment stores oxygen brought in by the currents for periods of less water movement and less oxygen introduction.”

Original publication:
McGinnis, D. F., S. Sommer, A. Lorke, R. N. Glud, P. Linke (2014): Quantifying tidally driven benthic oxygen exchange across permeable sediments: An aquatic eddy correlation study. Journal of Geophysical Research: Oceans, doi:10.1002/2014JC010303.

Links:

GEOMAR Helmholtz Centre for Ocean Research Kiel

Eddy correlation information page

Leibniz Institute of Freshwater Ecology and Inland Fisheries, IGB

University of Southern Denmark

University of Koblenz-Landau

Scottish Marine Institute

Aarhus University

Images:
High resolution images can be downloaded at http://www.geomar.de/n2110-e.

Video footage is available on request.

Contact:
Dr. Peter Linke (GEOMAR FB2-MG), Tel. 0431 600-2115, plinke@geomar.de

Maike Nicolai (GEOMAR, Kommunikation & Medien), Tel. 0431 600-2807, mnicolai@geomar.de

New tracers can identify frack fluids in the environment

Scientists have developed new geochemical tracers that can identify hydraulic fracturing flowback fluids that have been spilled or released into the environment.

The tracers, which were created by a team of U.S. and French researchers, have been field-tested at a spill site in West Virginia and downstream from an oil and gas brine wastewater treatment plant in Pennsylvania.

“This gives us new forensic tools to detect if ‘frac fluids’ are escaping into our water supply and what risks, if any, they might pose,” said Duke University geochemist Avner Vengosh, who co-led the research.

“By characterizing the isotopic and geochemical fingerprints of enriched boron and lithium in flowback water from hydraulic fracturing, we can now track the presence of frac fluids in the environment and distinguish them from wastewater coming from other sources, including conventional oil and gas wells,” Vengosh said.

Using the tracers, scientists can determine where fracturing fluids have or haven’t been released to the environment and, ultimately, help identify ways to improve how shale gas wastewater is treated and disposed of.

Vengosh and his colleagues published their peer-reviewed findings October 20 in the journal Environmental Science & Technology. Their study, which was funded in part by the National Science Foundation, is the first to report on the development of the boron and lithium tracers.

Nathaniel R. Warner, Obering Postdoctoral Fellow at Dartmouth College, was lead author of the study. “This new technology can be combined with other methods to identify specific instances of accidental releases to surface waters in areas of unconventional drilling,” he said. “It could benefit industry as well as federal and state agencies charged with monitoring water quality and protecting the environment.”

Hydraulic fracturing fluids, or frac fluids, typically contain mixes of water, proprietary chemicals and sand. Mixtures can vary from site to site. Drillers inject large volumes of the fluids down gas wells at high pressure to crack open shale formations deep underground and allow natural gas trapped within the shale to flow out and be extracted. After the shale has been fractured, the frac fluids flow back up the well to the surface along with the gas and highly saline brines from the shale formation.

Some people fear that toxic frac fluid chemicals in this flowback could contaminate nearby water supplies if flowback were accidentally spilled or insufficiently treated before being disposed of.

“The flowback fluid that returns to the surface becomes a waste that needs to be managed,” Vengosh explained. “Deep-well injection is the preferable disposal method, but injecting large volumes of wastewater into deep wells can cause earthquakes in sensitive areas and is not geologically available in some states. In Pennsylvania, much of the flowback is now recycled and reused, but a significant amount of it is still discharged into local streams or rivers.”

Vengosh said it’s possible to identify the presence of frac fluid in spilled or discharged flowback by tracing synthetic organic compounds that are added to the fluid before it’s injected down a well. But the proprietary nature of these chemicals, combined with their instability in the environment, limits the usefulness of such tracers.

By contrast, the new boron and lithium tracers remain stable in the environment. “The difference is that we are using tracers based on elements that occur naturally in shale formations,” Vengosh said.

When drillers inject frac fluids into a shale formation, they not only release hydrocarbon but also boron and lithium that are attached to clay minerals within the formation, he explained. As the fluids react and mix at depth, they become enriched in boron and lithium. As they are brought back to the surface, they have distinctive isotopic fingerprints that are different from other types of wastewater, including wastewater from a conventional gas or oil well, as well as from naturally occurring background water.

“This type of forensic research allows us to clearly delineate between the possible sources of wastewater contamination,” Vengosh said.

Scientists discover carbonate rocks are unrecognized methane sink

Since the first undersea methane seep was discovered 30 years ago, scientists have meticulously analyzed and measured how microbes in the seafloor sediments consume the greenhouse gas methane as part of understanding how the Earth works.

The sediment-based microbes form an important methane “sink,” preventing much of the chemical from reaching the atmosphere and contributing to greenhouse gas accumulation. As a byproduct of this process, the microbes create a type of rock known as authigenic carbonate, which while interesting to scientists was not thought to be involved in the processing of methane.

That is no longer the case. A team of scientists has discovered that these authigenic carbonate rocks also contain vast amounts of active microbes that take up methane. The results of their study, which was funded by the National Science Foundation, were reported today in the journal Nature Communications.

“No one had really examined these rocks as living habitats before,” noted Andrew Thurber, an Oregon State University marine ecologist and co-author on the paper. “It was just assumed that they were inactive. In previous studies, we had seen remnants of microbes in the rocks – DNA and lipids – but we thought they were relics of past activity. We didn’t know they were active.

“This goes to show how the global methane process is still rather poorly understood,” Thurber added.

Lead author Jeffrey Marlow of the California Institute of Technology and his colleagues studied samples from authigenic compounds off the coasts of the Pacific Northwest (Hydrate Ridge), northern California (Eel River Basin) and central America (the Costa Rica margin). The rocks range in size and distribution from small pebbles to carbonate “pavement” stretching dozens of square miles.

“Methane-derived carbonates represent a large volume within many seep systems and finding active methane-consuming archaea and bacteria in the interior of these carbonate rocks extends the known habitat for methane-consuming microorganisms beyond the relatively thin layer of sediment that may overlay a carbonate mound,” said Marlow, a geobiology graduate student in the lab of Victoria Orphan of Caltech.

These assemblages are also found in the Gulf of Mexico as well as off Chile, New Zealand, Africa, Europe – “and pretty much every ocean basin in the world,” noted Thurber, an assistant professor (senior research) in Oregon State’s College of Earth, Ocean, and Atmospheric Sciences.

The study is important, scientists say, because the rock-based microbes potentially may consume a huge amount of methane. The microbes were less active than those found in the sediment, but were more abundant – and the areas they inhabit are extensive, making their importance potential enormous. Studies have found that approximately 3-6 percent of the methane in the atmosphere is from marine sources – and this number is so low due to microbes in the ocean sediments consuming some 60-90 percent of the methane that would otherwise escape.

Now those ratios will have to be re-examined to determine how much of the methane sink can be attributed to microbes in rocks versus those in sediments. The distinction is important, the researchers say, because it is an unrecognized sink for a potentially very important greenhouse gas.

“We found that these carbonate rocks located in areas of active methane seeps are themselves more active,” Thurber said. “Rocks located in comparatively inactive regions had little microbial activity. However, they can quickly activate when methane becomes available.

“In some ways, these rocks are like armies waiting in the wings to be called upon when needed to absorb methane.”

The ocean contains vast amounts of methane, which has long been a concern to scientists. Marine reservoirs of methane are estimated to total more than 455 gigatons and may be as much as 10,000 gigatons carbon in methane. A gigaton is approximate 1.1 billion tons.

By contrast, all of the planet’s gas and oil deposits are thought to total about 200-300 gigatons of carbon.

A unique approach to monitoring groundwater supplies near Ohio fracking sites

This image shows a drilling rig in Carroll County, Ohio. -  Amy Townsend-Small
This image shows a drilling rig in Carroll County, Ohio. – Amy Townsend-Small

A University of Cincinnati research project is taking a groundbreaking approach to monitoring groundwater resources near fracking sites in Ohio. Claire Botner, a UC graduate student in geology, will outline the project at The Geological Society of America’s Annual Meeting & Exposition. The meeting takes place Oct. 19-22, in Vancouver.

Botner’s research is part of UC Groundwater Research of Ohio (GRO), a collaborative research project out of UC to examine the effects of fracking (hydraulic fracturing) on groundwater in the Utica Shale region of eastern Ohio. First launched in Carroll County in 2012, the GRO team of researchers is examining methane levels and origins of methane in private wells and springs before, during and after the onset of fracking. The team travels to the region to take water samples four times a year.

Amy Townsend-Small, the lead researcher for GRO and a UC assistant professor of geology, says the UC study is unique in comparison with studies on water wells in other shale-rich areas of the U.S. where fracking is taking place – such as the Marcellus Shale region of Pennsylvania.

Townsend-Small says water samples finding natural gas-derived methane in wells near Pennsylvania fracking sites were taken only after fracking had occurred, so methane levels in those wells were not documented prior to or during fracking in Pennsylvania.

Hydraulic fracturing, or fracking, involves using millions of gallons of water mixed with sand and chemicals to break up organic-rich shale to release natural gas resources.

Proponents say the practice promises a future in lower energy prices, an increase in domestic jobs and less dependence on foreign oil from unstable overseas governments.

Opponents raise concerns about increasing methane gas levels (a powerful greenhouse gas) and other contamination involving the spillover of fracking wastewater in the groundwater of shale-rich regions.

“The only way people with private groundwater will know whether or not their water is affected by fracking is through regular monitoring,” says Townsend-Small.

The Ohio samples are being analyzed by UC researchers for concentrations of methane as well as other hydrocarbons and salt, which is pulled up in the fracking water mixture from the shales. The shales are ancient ocean sediments.

Botner’s study involves testing on 22 private wells in Carroll County between November 2012 and last May. The first fracking permits were issued in the region in 2011. So far, results indicate that any methane readings in groundwater wells came from organic matter. In less than a handful of cases, the natural methane levels were relatively high, above 10 milligrams per liter. However, most of the wells carried low levels of methane.

The UC sampling has now been expanded into Columbiana, Harrison, Stark and Belmont counties in Ohio. Researchers then review data on private drinking water wells with the homeowners. “We’re working on interacting with these communities and educating them about fracking as well as gathering scientific data, which is lacking on a very sensitive issue,” says Botner. “It can also be reassuring to receive data on their water supplies from an objective, university resource.”

The team also is seeking additional funding to begin monitoring groundwater wells near wastewater injection wells, where fracking brine is deposited after the wells are drilled.

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Funding for Botner’s research to be presented at the GSA meeting is supported by a grant from the Missouri-based Deer Creek Foundation.

Botner is among UC graduate students and faculty who are presenting more than two dozen research papers, PowerPoint presentations or poster exhibitions at the GSA meeting. The meeting draws geoscientists from around the world representing more than 40 different disciplines.

UC’s nationally ranked Department of Geology conducts field research around the world in areas spanning paleontology, Quaternary geology, geomorphology, sedimentology, stratigraphy, tectonics, environmental geology and biogeochemistry.

The Geological Society of America, founded in 1888, is a scientific society with more than 26,500 members from academia, government and industry in more than 100 countries. Through its meetings, publications and programs, GSA enhances the professional growth of its members and promotes the geosciences in the service of humankind.

Geologists dig into science around the globe, on land and at sea

University of Cincinnati geologists will be well represented among geoscientists from around the world at The Geological Society of America’s Annual Meeting and Exposition. The meeting takes place Oct. 19-22, in Vancouver, Canada, and will feature geoscientists representing more than 40 different disciplines. The meeting will feature highlights of UC’s geological research that is taking place globally, from Chile to Costa Rica, Belize, Bulgaria, Scotland, Trinidad and a new project under development in the Canary Islands.

UC faculty and graduate students are lead or supporting authors on more than two dozen Earth Sciences-related research papers and/or PowerPoint and poster exhibitions at the GSA meeting.

The presentations also cover UC’s longtime and extensive exploration and findings in the Cincinnati Arch of the Ohio Valley, world-renowned for its treasure trove of paleontology – plant and animal fossils that were preserved when a shallow sea covered the region 450 million years ago during the Paleozoic Era.

Furthermore, in an effort to diversify the field of researchers in the Earth Sciences, a UC assistant professor of science education and geology, Christopher Atchison, was awarded funding from the National Science Foundation and the Society of Exploration Geophysics to lead a research field trip in Vancouver for students with disabilities. Graduate and undergraduate student participants will conduct the research on Oct. 18 and then join events at the GSA meeting. They’ll be guided by geoscience researchers representing the United Kingdom, New Zealand, Canada and the U.S. Those guides include Atchison and Julie Hendricks, a UC special education major from Batavia, Ohio, who will be using her expertise in American Sign Language (ASL) to assist student researchers representing Deaf and Hard of Hearing communities.

The meeting will also formally introduce Arnold Miller, UC professor of geology, as the new president-elect of the national Paleontological Society Thomas Lowell, professor of geology, is a recently elected Fellow of the Geological Society of America – a recognition for producing a substantial body of research. Lowell joins colleagues Warren Huff, professor of geology, and Lewis Owen, professor and head of the Department of Geology, as GSA Fellows.

Here are highlights of the UC research to be presented at the GSA meeting Oct. 19-22:

Staying Put or Moving On? Researchers Develop Model to Identify Migrating Patterns of Different Species

Are plant and animal species what you might call lifelong residents – they never budge from the same place? That’s a relatively common belief in ecology and paleoecology – that classes of organisms tend to stay put over millions of years and either evolve or go extinct as the environment changes. UC researchers developed a series of numerical models simulating shifting habitats in fossil regions to compare whether species changed environments when factoring geological and other changes in the fossil record. They found that geologically driven changes in the quality of the fossil record did not distort the real ecological signal, and that most species maintained their particular habitat preferences through time. They did not evolve to adapt to changing environments, but rather, they migrated, following their preferred environments. That is to say, they did not stay in place geographically but by moving, they were able to track their favored habitats. Field research for the project was conducted in New York state as well as the paleontological-rich region of Cincinnati; Dayton, Ohio, Lexington, Ky.; and Indiana. Funding for the project was supported by The Paleontological Society; The Geological Society of America; The American Museum of Natural History and the UC Geology Department’s Kenneth E. Caster Memorial Fund.

Presenter: Andrew Zaffos, UC geology doctoral student

Co-authors: Arnold Miller, Carlton Brett

Pioneering Study Provides a Better Understanding of What Southern Ohio and Central Kentucky Looked Like Hundreds of Millions of Years Ago

The end of the Ordovician period resulted in one of the largest mass extinction events in the Earth’s history. T.J. Malgieri, a UC master’s student in geology, led this study examining the limestone and shales of the Upper Ordovician Period – the geologic Grant Lake Formation covering southern Ohio and central Kentucky – to recreate how the shoreline looked some 445 million years ago. In this pioneering study of mud cracks and deposits in the rocks, the researchers discovered that the shoreline existed to the south and that the water became deeper toward the north. By determining these ecological parameters, the ramp study provides a better understanding of environments during a time of significant ecological change. Malgieri says the approach can be applied to other basins throughout the world to create depth indicators in paeloenvironments.

Presenter: T.J. Malgieri, UC geology master’s student

Co-authors: Carlton Brett, Cameron Schalbach, Christopher Aucoin, UC; James Thomka (UC, University of Akron); Benjamin Dattilo, Indiana University Purdue University Ft. Wayne

UC Researchers Take a Unique Approach to Monitoring Groundwater Supplies Near Ohio Fracking Sites

A collaborative research project out of UC is examining effects of fracking on groundwater in the Utica Shale region of eastern Ohio. First launched in Carroll County in 2012, the team of researchers is examining methane levels and origins of methane in private wells and springs before, during and after the onset of fracking. The team travels to the region to take water samples four times a year.

Presenter: Claire Botner, a UC geology master’s student

Co-author: Amy Townsend-Small, UC assistant professor of geology

Sawing Through Seagrass to Reveal Clues to the Past

Kelsy Feser, a UC doctoral student in geology, is working at several sites around St. Croix in the Virgin Islands to see if human developments impact marine life. The research focuses on shells of snails and clams that have piled up on the sea floor for thousands of years. Digging through layers of thick seagrass beds on the ocean floor, Feser can examine deeper shells that were abundant thousands of years ago and compare them to shallower layers that include living clams and snails. Early analysis indicates a greater population of potentially pollution-tolerant mussels in an area near a landfill on the island, compared with shells from much earlier time periods. Feser is doing this sea grass analysis around additional sites including tourist resorts, an oil refinery, a power plant and a marina. Funding for the research is provided by the Paleontological Society, the GSA, the American Museum of Natural History and the UC Geology Department.

Presenter: Kelsy Feser, UC geology doctoral student

Co-authors: Arnold Miller

Turning to the Present to Understand the Past

In order to properly interpret changes in climate, vegetation, or animal populations over time, it is necessary to establish a comparative baseline. Stella Mosher, a UC geology master’s student, is studying stable carbon, nitrogen, sulfur and strontium isotopes in modern vegetation from the Canary Islands in order to quantify modern climatic and environmental patterns. Her findings will provide a crucial foundation for future UC research on regional paleoclimatic and paleoenvironmental shifts.

Presenter: Stella Mosher, graduate student in geology

Co-authors: Brooke Crowley, assistant professor of geology; Yurena Yanes, research assistant professor of geology

A Study on the Impact of Sea Spray

Sulfur is an element of interest in both geology and archaeology, because it can reveal information about the diets of ancient cultures. This study takes a novel approach to studying how sea spray can affect the sulfur isotope values in plants on a small island, focusing on the island of Trinidad. Researchers collected leaves from different plant species to get their sulfur isotope value, exploring whether wind direction played a role in how plants were influenced by the marine water from sea spray. Vegetation was collected from the edges of the island to the deeply forested areas. The study found that sulfur isotope values deeper inland and on the calmer west coast were dramatically lower in indicating marine water than vegetation along the edges and the east coast. The findings can help indicate the foraging activities of humans and animals. Funding for the study was supported by the Geological Society of America, the UC Graduate Student Association and the UC Department of Geology.

Presenter: Janine Sparks, UC geology doctoral student

Co-authors: Brooke Crowley, UC assistant professor, geology/anthropology; William Gilhooly III, assistant professor, Earth Sciences, Indiana University-Purdue University Indianapolis

Proxy Wars – The Paleobiology Data Debate

For the past several decades, paleobiologists have built large databases containing information on fossil plants and animals of all geological ages to investigate the timing and extent of major changes in biodiversity – changes such as mass extinctions that have taken place throughout the history of life. Biodiversity researcher Arnold Miller says that in building these databases, it can be a challenge to accurately identify species in the geological record, so it has been common for researchers to instead study biodiversity trends using data compiled at broader levels of biological classification, including the genus level, under the assumption that these patterns are effective proxies for what would be observed among species if the data were available. Miller has been involved in construction of The Paleobiology Database, an extensive public online resource that contains global genus- and species-level data, now permitting a direct, novel look at the similarities and differences between patterns at these two levels. Miller’s discussion aims to set the record straight as to when researchers can effectively use a genus as a proxy for a species and also when it’s inappropriate. This research is funded by the NASA Astrobiology Program.

Presenter: Arnold Miller, UC professor of geology

A Novel New Method for Examining the Distribution of Pores in Rocks

Oil and gas companies take an interest in the porosity of sedimentary rocks because those open spaces can be filled with fuel resources. Companies involved with hydraulic fracturing (“fracking”) are also interested in porosity because it could be a source for storing wastewater as a result of fracking. In this unique study, UC researchers made pore-size measurements similar to those used in crystal size distribution (CSD) theory to determine distribution of pores as a function of their sizes, using thin sections of rock. In addition to providing accurate porosity distribution at a given depth, their approach can be extended to evaluate variation of pore spaces as a function of depth in a drill core, percent of pores in each size range, and pore types and pore geometry. The Texas Bureau of Economic Geology provided the rock samples used in the study. Funding for the study was supported by the Turkish Petroleum Corporation.

Presenter: Ugurlu Ibrahim, master’s student in geology

Co-author: Attila Kilinc, professor of geology

Researchers Turn to 3-D Technology to Examine the Formation of Cliffband Landscapes

A blend of photos and technology takes a new twist on studying cliff landscapes and how they were formed. The method called Structure-From-Motion Photogrammetry – computational photo image processing techniques – is used to study the formation of cliff landscapes in Colorado and Utah and to understand how the layered rock formations in the cliffs are affected by erosion.

Presenter: Dylan Ward, UC assistant professor of geology

Testing the Links Between Climate and Sedimentation in the Atacama Desert, Northern Chile

The Atacama Desert is used as an analog for understanding the surface of Mars. In some localities, there has been no activity for millions of years. UC researchers have been working along the flank of the Andes Mountains in northern Chile, and this particular examination focuses on the large deposits of sediment that are transported down the plateau and gather at the base. The researchers are finding that their samples are not reflecting the million-year-old relics previously found on such expeditions, but may indicate more youthful activity possibly resulting from climatic events. The research is supported by a $273,634 grant from the National Science Foundation to explore glacio-geomorphic constraints on the climate history of subtropical northern Chile.

Presenter: Jason Cesta, UC geology master’s student

Co-author: Dylan Ward, UC assistant professor of geology

Uncovering the Explosive Mysteries Surrounding the Manganese of Northeast Bulgaria

UC’s geology collections hold minerals from field expeditions around the world, including manganese from the Obrochishte mines of northeastern Bulgaria. Found in the region’s sedimentary rock, manganese can be added to metals such as steel to improve strength. It’s widely believed that these manganese formations were the result of ocean water composition at the time the sediments were deposited in the ocean. In this presentation, UC researchers present new information on why they believe the manganese formations resulted from volcanic eruptions, perhaps during the Rupelian stage of the geologic time scale, when bentonite clay minerals were formed. The presentation evolved from an advance class project last spring under the direction of Warren Huff, a UC professor of geology.

Presenter: Jason Cesta, UC geology master’s student

Co-authors: Warren Huff, UC professor of geology; Christopher Aucoin; Michael Harrell; Thomas Malgieri; Barry Maynard; Cameron Schwalbach; Ibrahim Ugurlu; Antony Winrod

Two UC researchers will chair sessions at the GSA meeting: Doctoral student Gary Motz will chair the session, “Topics in Paleoecology: Modern Analogues and Ancient Systems,” on Oct. 19. Matt Vrazo, also a doctoral student in geology, is chairing “Paleontology: Trace Fossils, Taphonomy and Exceptional Preservation” on Oct. 21, and will present, “Taphonomic and Ecological Controls on Eurypterid Lagerstäten: A Model for Preservation in the Mid-Paleozoic.”

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UC’s nationally ranked Department of Geology conducts field research around the world in areas spanning paleontology, quaternary geology, geomorphology, sedimentology, stratigraphy, tectonics, environmental geology and biogeochemistry.

The Geological Society of America, founded in 1888, is a scientific society with more than 26,500 members from academia, government, and industry in more than 100 countries. Through its meetings, publications, and programs, GSA enhances the professional growth of its members and promotes the geosciences in the service of humankind.