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• 101. [Article] Utilizing Humidity and Temperature Data to Advance Monitoring and Prediction of Meteorological Drought

  The fraction of land area over the Continental United States experiencing extreme hot and dry conditions has been increasing over the past several decades, consistent with expectation from anthropogenic ...

  Citation × Citation Citation Abstract Copy Title: Utilizing Humidity and Temperature Data to Advance Monitoring and Prediction of Meteorological Drought Author: Behrangi, Ali, Loikith, Paul C., Fetzer, Eric J., Nguyen, Hai M., Granger, Stephanie L. Year: 2015 The fraction of land area over the Continental United States experiencing extreme hot and dry conditions has been increasing over the past several decades, consistent with expectation from anthropogenic climate change. A clear concurrent change in precipitation, however, has not been confirmed. Vapor pressure deficit (VPD), combining temperature and humidity, is utilized here as an indicator of the background atmospheric conditions associated with meteorological drought. Furthermore, atmospheric conditions associated with warm season drought events are assessed by partitioning associated VPD anomalies into the temperature and humidity components. This approach suggests that the concurrence of anomalously high temperature and low humidity was an important driver of the rapid development and evolution of the exceptionally severe 2011 Texas and the 2012 Great Plains droughts. By classification of a decade of extreme drought events and tracking them back in time, it was found that near surface atmospheric temperature and humidity add essential information to the commonly used precipitation-based drought indicators and can advance efforts to determine the timing of drought onset and its severity. Title: Utilizing Humidity and Temperature Data to Advance Monitoring and Prediction of Meteorological Drought Author: Behrangi, Ali, Loikith, Paul C., Fetzer, Eric J., Nguyen, Hai M., Granger, Stephanie L. Year: 2015 The fraction of land area over the Continental United States experiencing extreme hot and dry conditions has been increasing over the past several decades, consistent with expectation from anthropogenic climate change. A clear concurrent change in precipitation, however, has not been confirmed. Vapor pressure deficit (VPD), combining temperature and humidity, is utilized here as an indicator of the background atmospheric conditions associated with meteorological drought. Furthermore, atmospheric conditions associated with warm season drought events are assessed by partitioning associated VPD anomalies into the temperature and humidity components. This approach suggests that the concurrence of anomalously high temperature and low humidity was an important driver of the rapid development and evolution of the exceptionally severe 2011 Texas and the 2012 Great Plains droughts. By classification of a decade of extreme drought events and tracking them back in time, it was found that near surface atmospheric temperature and humidity add essential information to the commonly used precipitation-based drought indicators and can advance efforts to determine the timing of drought onset and its severity. Close

• 102. [Article] Thermal Decomposition of Electronic Cigarette Liquids

  Electronic cigarette liquid (e-liquid) is a solution of propylene glycol and/or glycerol with varying concentrations of nicotine and flavorants. Inhalation of vaporized e-liquid is a method of nicotine ...

  Citation × Citation Citation Abstract Copy Title: Thermal Decomposition of Electronic Cigarette Liquids Author: Jensen, Robert Paul Year: 2016 Electronic cigarette liquid (e-liquid) is a solution of propylene glycol and/or glycerol with varying concentrations of nicotine and flavorants. Inhalation of vaporized e-liquid is a method of nicotine delivery that is growing in popularity and is commonly regarded as safe relative to smoking traditional tobacco products. The thermal decomposition of glycerol and propylene glycol is typical of alcohols and has been investigated, although not exhaustively. In this work, samples of propylene glycol and glycerol were vaporized using an electronic cigarette (e-cigarette) and were analyzed for evidence of decomposition using nuclear magnetic resonance (NMR) spectroscopy. E-cigarettes are shown to degrade glycerol and propylene glycol into a diverse array of oxidation and dehydration products including glyceraldehyde, lactaldehyde, dihydroxyacetone, hydroxyacetone, glycidol, acrolein, propanal, acetone, allyl alcohol, acetic acid, acetaldehyde, formic acid, and formaldehyde. Evidence is presented that the abundance of these decomposition products may depend upon the temperature of the metal heating element but could also depend upon some catalytic aspect of the metal surface. The combination of formaldehyde with alcohols such as glycerol and propylene glycol was explored; hemiformals are stable hemiacetals that can be detected by NMR spectroscopy and are shown to be subject to hydrolysis when diluted in water. Investigations into smoking a glycerol-based tobacco mixture known as shisha using charcoals instead of metal heating elements also resulted in the dehydration of glycerol and sugars. Title: Thermal Decomposition of Electronic Cigarette Liquids Author: Jensen, Robert Paul Year: 2016 Electronic cigarette liquid (e-liquid) is a solution of propylene glycol and/or glycerol with varying concentrations of nicotine and flavorants. Inhalation of vaporized e-liquid is a method of nicotine delivery that is growing in popularity and is commonly regarded as safe relative to smoking traditional tobacco products. The thermal decomposition of glycerol and propylene glycol is typical of alcohols and has been investigated, although not exhaustively. In this work, samples of propylene glycol and glycerol were vaporized using an electronic cigarette (e-cigarette) and were analyzed for evidence of decomposition using nuclear magnetic resonance (NMR) spectroscopy. E-cigarettes are shown to degrade glycerol and propylene glycol into a diverse array of oxidation and dehydration products including glyceraldehyde, lactaldehyde, dihydroxyacetone, hydroxyacetone, glycidol, acrolein, propanal, acetone, allyl alcohol, acetic acid, acetaldehyde, formic acid, and formaldehyde. Evidence is presented that the abundance of these decomposition products may depend upon the temperature of the metal heating element but could also depend upon some catalytic aspect of the metal surface. The combination of formaldehyde with alcohols such as glycerol and propylene glycol was explored; hemiformals are stable hemiacetals that can be detected by NMR spectroscopy and are shown to be subject to hydrolysis when diluted in water. Investigations into smoking a glycerol-based tobacco mixture known as shisha using charcoals instead of metal heating elements also resulted in the dehydration of glycerol and sugars. Close

• 103. [Article] Impacts of Permafrost Degradation on a Stream in Taylor Valley, Antarctica

  The McMurdo Dry Valleys (MDV) of Antarctica are an ice-free landscape that supports a complex, microbially dominated ecosystem despite a severely arid, cold environment (< 5 cm water equivalent/y, − 18 ...

  Citation × Citation Citation Abstract Copy Title: Impacts of Permafrost Degradation on a Stream in Taylor Valley, Antarctica Author: Sudman, Zachary, Gooseff, Michael N., Fountain, Andrew G., Levy, Joseph S. Year: 2017 The McMurdo Dry Valleys (MDV) of Antarctica are an ice-free landscape that supports a complex, microbially dominated ecosystem despite a severely arid, cold environment (< 5 cm water equivalent/y, − 18 °C mean annual air temperature). Recent observations of permafrost degradation in the coastal zones of the MDV suggest that this region is nearing a threshold of rapid landscape change. In 2012, substantial thermokarst development was observed along several kilometers of the west branch of Crescent Stream in Taylor Valley mostly in the form of bank failures, whereas the adjacent east branch was unaffected. The objective of this study was to quantify the changes to the stream banks of the west branch of Crescent Stream and to determine the impacts on the composition of the stream bed material. Three annually repeated terrestrial LiDAR scans were compared to determine the rates of ground surface change caused by thermokarst formation on the stream bank. The areal extent of the thermokarst was shown to be decreasing; however, the average vertical rate of retreat remained constant. Field measurements of bed materials indicated that the west branch and the reach downstream of the confluence (of east and west branches) consistently contained more fines than the unaffected east branch. This suggests that the finer bed material is a result of the thermokarst development on the west branch. These finer bed material compositions are likely to increase the mobility of the bed material, which will have implications for stream morphology, stream algal mat communities, and downstream aquatic ecosystems. Title: Impacts of Permafrost Degradation on a Stream in Taylor Valley, Antarctica Author: Sudman, Zachary, Gooseff, Michael N., Fountain, Andrew G., Levy, Joseph S. Year: 2017 The McMurdo Dry Valleys (MDV) of Antarctica are an ice-free landscape that supports a complex, microbially dominated ecosystem despite a severely arid, cold environment (< 5 cm water equivalent/y, − 18 °C mean annual air temperature). Recent observations of permafrost degradation in the coastal zones of the MDV suggest that this region is nearing a threshold of rapid landscape change. In 2012, substantial thermokarst development was observed along several kilometers of the west branch of Crescent Stream in Taylor Valley mostly in the form of bank failures, whereas the adjacent east branch was unaffected. The objective of this study was to quantify the changes to the stream banks of the west branch of Crescent Stream and to determine the impacts on the composition of the stream bed material. Three annually repeated terrestrial LiDAR scans were compared to determine the rates of ground surface change caused by thermokarst formation on the stream bank. The areal extent of the thermokarst was shown to be decreasing; however, the average vertical rate of retreat remained constant. Field measurements of bed materials indicated that the west branch and the reach downstream of the confluence (of east and west branches) consistently contained more fines than the unaffected east branch. This suggests that the finer bed material is a result of the thermokarst development on the west branch. These finer bed material compositions are likely to increase the mobility of the bed material, which will have implications for stream morphology, stream algal mat communities, and downstream aquatic ecosystems. Close

• 104. [Article] “Reference QuenchProbe”—An Alternative Probe Design for In-Situ Estimation of Cooling Rates, Heat Flux, and Hardenability During Immersion Quenching of Hardenable Steels

  This article reviews some of the limitations of the standard cooling curve analysis and the Jominy hardenability test in extending the results to actual quenching in industrial setups and reports the development ...

  Citation × Citation Citation Abstract Copy Title: “Reference QuenchProbe”—An Alternative Probe Design for In-Situ Estimation of Cooling Rates, Heat Flux, and Hardenability During Immersion Quenching of Hardenable Steels Author: Prasanna Kumar, T. S., Hernández-Morales, B., Totten, George E. Year: 2014 This article reviews some of the limitations of the standard cooling curve analysis and the Jominy hardenability test in extending the results to actual quenching in industrial setups and reports the development of a new portable tool—Reference QuenchProbe—for estimating cooling rates, hardness, and microstructure distributions in hardenable steel grades during immersion quenching, which can be used by the heat treater in the plant. The specimen is made of the same grade of steel as the quenched component with section thickness matching that of the component, which is a departure from standard laboratory tests. The test is carried out in the plant under actual conditions dispensing the need to correlate the standard cooling curve data and end quench hardenability tests done in the laboratory to industrial practice. To test the suite of mathematical models associated with the Reference QuenchProbe hardware and software, specimens of different grades of steels were instrumented with a single thermocouple near the surface of the specimen. Using the cooling data at the point of measurement, the cooling rates, microstructure, and hardness at other critical locations were computed. An enthalpy-based non-linear inverse heat conduction model was coupled with austenite decomposition models for handling the latent heat liberated during quenching. Several steels ranging from low carbon to medium alloy steels were both end-quenched by water and immersion quenched in several industrial quenchants. The computed hardness of end quenched and immersion quenched specimens were shown to be in good agreement with the measured values. The Reference QuenchProbe is thus shown to generate data needed for heat treatment process design including quenchant selection, which can be directly used in practice. Title: “Reference QuenchProbe”—An Alternative Probe Design for In-Situ Estimation of Cooling Rates, Heat Flux, and Hardenability During Immersion Quenching of Hardenable Steels Author: Prasanna Kumar, T. S., Hernández-Morales, B., Totten, George E. Year: 2014 This article reviews some of the limitations of the standard cooling curve analysis and the Jominy hardenability test in extending the results to actual quenching in industrial setups and reports the development of a new portable tool—Reference QuenchProbe—for estimating cooling rates, hardness, and microstructure distributions in hardenable steel grades during immersion quenching, which can be used by the heat treater in the plant. The specimen is made of the same grade of steel as the quenched component with section thickness matching that of the component, which is a departure from standard laboratory tests. The test is carried out in the plant under actual conditions dispensing the need to correlate the standard cooling curve data and end quench hardenability tests done in the laboratory to industrial practice. To test the suite of mathematical models associated with the Reference QuenchProbe hardware and software, specimens of different grades of steels were instrumented with a single thermocouple near the surface of the specimen. Using the cooling data at the point of measurement, the cooling rates, microstructure, and hardness at other critical locations were computed. An enthalpy-based non-linear inverse heat conduction model was coupled with austenite decomposition models for handling the latent heat liberated during quenching. Several steels ranging from low carbon to medium alloy steels were both end-quenched by water and immersion quenched in several industrial quenchants. The computed hardness of end quenched and immersion quenched specimens were shown to be in good agreement with the measured values. The Reference QuenchProbe is thus shown to generate data needed for heat treatment process design including quenchant selection, which can be directly used in practice. Close

• 105. [Article] STRUCTURE-ACTIVITY RELATIONSHIPS IN NI-FE (OXY)HYDROXIDE OXYGEN EVOLUTION ELECTROCATALYSTS

  The oxygen evolution reaction (OER) is kinetically slow and hence a significant efficiency loss in electricity-driven water electrolysis. Understanding the relationships between architecture, composition, ...

  Citation × Citation Citation Abstract Copy Title: STRUCTURE-ACTIVITY RELATIONSHIPS IN NI-FE (OXY)HYDROXIDE OXYGEN EVOLUTION ELECTROCATALYSTS Author: Batchellor, Adam Year: 2017 The oxygen evolution reaction (OER) is kinetically slow and hence a significant efficiency loss in electricity-driven water electrolysis. Understanding the relationships between architecture, composition, and activity in high-performing catalyst systems are critical for the development of better catalysts. This dissertation discusses areas both fundamental and applied that seek to better understand how to accurately measure catalyst activity as well as ways to design higher performing catalysts. Chapter I introduces the work that has been done in the field to date. Chapter II compares various methods of determining the electrochemically active surface area of a film. It further discusses how pulsed and continuous electrodepostition techniques effect film morphology and behavior, and shows that using a simple electrodeposition can create high loading films with architectures that outperform those deposited onto inert substrates. The reversibility of the films, a measure of the films transport efficiency, is introduced and shown to correlate strongly with performance. Chapter III uses high energy x-ray scattering to probe the nanocrystalline domains of the largely amorphous NiFe oxyhydroxide catalysts, and shows that significant similarities in the local structure are not responsible for the change in performance for the films synthesized under different conditions. Bond lengths for oxidized and reduced catalysts are determined, and show no significant phase segregation occurs. Chapter IV seeks to optimize the deposition conditions introduced in Chapter II and to provide a physical representation of how tuning each of the parameters affects film morphology. The deposition current density is shown to be the most important factor affecting film performance at a given loading. Chapter V highlights the different design considerations for films being used in a photoelectrochemical cell, and how in situ techniques can provide information that may otherwise be unobtainable. Chapter VI serves as a summary and provides future directions. This dissertation contains previously published coauthored material. Title: STRUCTURE-ACTIVITY RELATIONSHIPS IN NI-FE (OXY)HYDROXIDE OXYGEN EVOLUTION ELECTROCATALYSTS Author: Batchellor, Adam Year: 2017 The oxygen evolution reaction (OER) is kinetically slow and hence a significant efficiency loss in electricity-driven water electrolysis. Understanding the relationships between architecture, composition, and activity in high-performing catalyst systems are critical for the development of better catalysts. This dissertation discusses areas both fundamental and applied that seek to better understand how to accurately measure catalyst activity as well as ways to design higher performing catalysts. Chapter I introduces the work that has been done in the field to date. Chapter II compares various methods of determining the electrochemically active surface area of a film. It further discusses how pulsed and continuous electrodepostition techniques effect film morphology and behavior, and shows that using a simple electrodeposition can create high loading films with architectures that outperform those deposited onto inert substrates. The reversibility of the films, a measure of the films transport efficiency, is introduced and shown to correlate strongly with performance. Chapter III uses high energy x-ray scattering to probe the nanocrystalline domains of the largely amorphous NiFe oxyhydroxide catalysts, and shows that significant similarities in the local structure are not responsible for the change in performance for the films synthesized under different conditions. Bond lengths for oxidized and reduced catalysts are determined, and show no significant phase segregation occurs. Chapter IV seeks to optimize the deposition conditions introduced in Chapter II and to provide a physical representation of how tuning each of the parameters affects film morphology. The deposition current density is shown to be the most important factor affecting film performance at a given loading. Chapter V highlights the different design considerations for films being used in a photoelectrochemical cell, and how in situ techniques can provide information that may otherwise be unobtainable. Chapter VI serves as a summary and provides future directions. This dissertation contains previously published coauthored material. Close

• 106. [Article] A Study on the Current State of Contaminants of Concern Research, With a Focus on Biosolids and Regulations

  Wastewater treatment plants are a major source of contaminants of emerging concern, as these facilities are the main receptors of these products via household, commercial, and industrial drains, and transport ...

  Citation × Citation Citation Abstract Copy Title: A Study on the Current State of Contaminants of Concern Research, With a Focus on Biosolids and Regulations Author: Fulton, Maren Year: 2016 Wastewater treatment plants are a major source of contaminants of emerging concern, as these facilities are the main receptors of these products via household, commercial, and industrial drains, and transport via stormwater runoff. Biosolids are composed of numerous constituents, with a number of environmentally persistent and potentially toxic contaminants of emerging concern identified as present in large concentrations. Research is needed to understand the transport and fate mechanisms of these compounds in biosolids. Additionally, this research is needed to determine a new priority framework to regulate CECs, both on the national level and regional levels. Wastewater treatment plant influent and effluent treatment regulations and practices may be improved upon as more knowledge accrues regarding contaminants of emerging concern behavior in the environment. The United States environmental regulatory process is a constant work in progress. Inherited from decades-old public health traditions, environmental regulatory programs arose to address the issues of public health as water and air quality issues surfaced. The Toxic Substances Control Act (TSCA) (15 U.S.C. 2601), enacted in 1976, provided the EPA regulatory authority to protect the environment and consumers’ health against risks posed by chemicals in commerce. TSCA only retroactively addressed chemical hazards, after they had been deemed unsafe and previously unrestricted in the public. A bill to overhaul TSCA, the Frank R. Lautenberg Chemical Safety for the 21st Century Act (House Amendment to the Senate Amendment to H.R. 2576, TSCA Modernization Act of 2015), was passed by the Senate on June 7, 2016 and sent on for President Obama’s signature. The amended law will give the EPA new authority to evaluate the safety of a new chemical before it enters the marketplace. It will also allow EPA to evaluate the safety of chemicals already known to be risks, including chemicals found to persist in the human body and in the environment. The Columbia River is presented as a case study as an example of a significant waterbody with research and regulatory gaps concerning CECs. The Columbia River waterbody was chosen as it represents an important natural resource for which data gaps exist on CEC sources and pathways into the waterbody, and which also does not receive adequate protective regulations under the national regulatory framework. Title: A Study on the Current State of Contaminants of Concern Research, With a Focus on Biosolids and Regulations Author: Fulton, Maren Year: 2016 Wastewater treatment plants are a major source of contaminants of emerging concern, as these facilities are the main receptors of these products via household, commercial, and industrial drains, and transport via stormwater runoff. Biosolids are composed of numerous constituents, with a number of environmentally persistent and potentially toxic contaminants of emerging concern identified as present in large concentrations. Research is needed to understand the transport and fate mechanisms of these compounds in biosolids. Additionally, this research is needed to determine a new priority framework to regulate CECs, both on the national level and regional levels. Wastewater treatment plant influent and effluent treatment regulations and practices may be improved upon as more knowledge accrues regarding contaminants of emerging concern behavior in the environment. The United States environmental regulatory process is a constant work in progress. Inherited from decades-old public health traditions, environmental regulatory programs arose to address the issues of public health as water and air quality issues surfaced. The Toxic Substances Control Act (TSCA) (15 U.S.C. 2601), enacted in 1976, provided the EPA regulatory authority to protect the environment and consumers’ health against risks posed by chemicals in commerce. TSCA only retroactively addressed chemical hazards, after they had been deemed unsafe and previously unrestricted in the public. A bill to overhaul TSCA, the Frank R. Lautenberg Chemical Safety for the 21st Century Act (House Amendment to the Senate Amendment to H.R. 2576, TSCA Modernization Act of 2015), was passed by the Senate on June 7, 2016 and sent on for President Obama’s signature. The amended law will give the EPA new authority to evaluate the safety of a new chemical before it enters the marketplace. It will also allow EPA to evaluate the safety of chemicals already known to be risks, including chemicals found to persist in the human body and in the environment. The Columbia River is presented as a case study as an example of a significant waterbody with research and regulatory gaps concerning CECs. The Columbia River waterbody was chosen as it represents an important natural resource for which data gaps exist on CEC sources and pathways into the waterbody, and which also does not receive adequate protective regulations under the national regulatory framework. Close

• 107. [Article] Modeling Regional Secondary Organic Aerosol Using the Master Chemical Mechanism

  A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model ...

  Citation × Citation Citation Abstract Copy Title: Modeling Regional Secondary Organic Aerosol Using the Master Chemical Mechanism Author: Li, Jingyi, Cleveland, Meredith, Ziemba, Luke D., Griffin, Robert J., Barsanti, Kelley, Pankow, James F., Ying, Qi Year: 2015 A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model (CMAQ) to predict the regional concentrations of secondary organic aerosol (SOA) from volatile organic compounds (VOCs) in the eastern United States (US). In addition to the semi-volatile SOA from equilibrium partitioning, reactive surface uptake processes were used to simulate SOA formation due to isoprene epoxydiol, glyoxal and methylglyoxal. The CMAQ-MCM-SOA model was applied to simulate SOA formation during a two-week episode from August 28 to September 7, 2006. The southeastern US has the highest SOA, with a maximum episode-averaged concentration of ∼12 μg m−3. Primary organic aerosol (POA) and SOA concentrations predicted by CMAQ-MCM-SOA agree well with AMS-derived hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA) urban concentrations at the Moody Tower at the University of Houston. Predicted molecular properties of SOA (O/C, H/C, N/C and OM/OC ratios) at the site are similar to those reported in other urban areas, and O/C values agree with measured O/C at the same site. Isoprene epoxydiol is predicted to be the largest contributor to total SOA concentration in the southeast US, followed by methylglyoxal and glyoxal. The semi-volatile SOA components are dominated by products from β-caryophyllene oxidation, but the major species and their concentrations are sensitive to errors in saturation vapor pressure estimation. A uniform decrease of saturation vapor pressure by a factor of 100 for all condensable compounds can lead to a 150% increase in total SOA. A sensitivity simulation with UNIFAC-calculated activity coefficients (ignoring phase separation and water molecule partitioning into the organic phase) led to a 10% change in the predicted semi-volatile SOA concentrations. Title: Modeling Regional Secondary Organic Aerosol Using the Master Chemical Mechanism Author: Li, Jingyi, Cleveland, Meredith, Ziemba, Luke D., Griffin, Robert J., Barsanti, Kelley, Pankow, James F., Ying, Qi Year: 2015 A modified near-explicit Master Chemical Mechanism (MCM, version 3.2) with 5727 species and 16,930 reactions and an equilibrium partitioning module was incorporated into the Community Air Quality Model (CMAQ) to predict the regional concentrations of secondary organic aerosol (SOA) from volatile organic compounds (VOCs) in the eastern United States (US). In addition to the semi-volatile SOA from equilibrium partitioning, reactive surface uptake processes were used to simulate SOA formation due to isoprene epoxydiol, glyoxal and methylglyoxal. The CMAQ-MCM-SOA model was applied to simulate SOA formation during a two-week episode from August 28 to September 7, 2006. The southeastern US has the highest SOA, with a maximum episode-averaged concentration of ∼12 μg m−3. Primary organic aerosol (POA) and SOA concentrations predicted by CMAQ-MCM-SOA agree well with AMS-derived hydrocarbon-like organic aerosol (HOA) and oxygenated organic aerosol (OOA) urban concentrations at the Moody Tower at the University of Houston. Predicted molecular properties of SOA (O/C, H/C, N/C and OM/OC ratios) at the site are similar to those reported in other urban areas, and O/C values agree with measured O/C at the same site. Isoprene epoxydiol is predicted to be the largest contributor to total SOA concentration in the southeast US, followed by methylglyoxal and glyoxal. The semi-volatile SOA components are dominated by products from β-caryophyllene oxidation, but the major species and their concentrations are sensitive to errors in saturation vapor pressure estimation. A uniform decrease of saturation vapor pressure by a factor of 100 for all condensable compounds can lead to a 150% increase in total SOA. A sensitivity simulation with UNIFAC-calculated activity coefficients (ignoring phase separation and water molecule partitioning into the organic phase) led to a 10% change in the predicted semi-volatile SOA concentrations. Close

• 108. [Article] Mixing Times of Organic Molecules Within Secondary Organic Aerosol Particles: A Global Planetary Boundary Layer Perspective

  When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale ...

  Citation × Citation Citation Abstract Copy Title: Mixing Times of Organic Molecules Within Secondary Organic Aerosol Particles: A Global Planetary Boundary Layer Perspective Author: Maclean, Adrian M., Butenhoff, Christopher L., Grayson, James W., Barsanti, Kelley, Jimenez, Jose L., Bertram, Allan K. Year: 2017 When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1 h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are < 1 h within SOA in the planetary boundary layer (PBL), the region of the atmosphere where SOA concentrations are on average the highest. First, a parameterization for viscosity as a function of temperature and RH was developed for α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of ∼ 1000 µg m−3. Based on this parameterization, the mixing times within α-pinene SOA are < 1 h for 98.5 % and 99.9 % of the occurrences in the PBL during January and July, respectively, when concentrations are significant (total organic aerosol concentrations are > 0.5 µg m−3 at the surface). Next, as a starting point to quantify how often mixing times of organic molecules are < 1 h within α-pinene SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature independent parameterization for viscosity using the room temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of ~70 μg m-3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are < 1 h for 27 and 19.5% of the occurrences in the PBL during January and July, respectively, when concentrations are significant. However, associated with these conclusions are several caveats, and due to these caveats we are unable to make strong conclusions about how often mixing times of organic molecules are < 1 h within pinene SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose–water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83% of the mixing times within anthropogenic SOA in the PBL are < 1 h for January and July, respectively, when concentrations are significant. These percentages are likely lower limits due to the assumptions used to calculate mixing times. Title: Mixing Times of Organic Molecules Within Secondary Organic Aerosol Particles: A Global Planetary Boundary Layer Perspective Author: Maclean, Adrian M., Butenhoff, Christopher L., Grayson, James W., Barsanti, Kelley, Jimenez, Jose L., Bertram, Allan K. Year: 2017 When simulating the formation and life cycle of secondary organic aerosol (SOA) with chemical transport models, it is often assumed that organic molecules are well mixed within SOA particles on the timescale of 1 h. While this assumption has been debated vigorously in the literature, the issue remains unresolved in part due to a lack of information on the mixing times within SOA particles as a function of both temperature and relative humidity. Using laboratory data, meteorological fields, and a chemical transport model, we estimated how often mixing times are < 1 h within SOA in the planetary boundary layer (PBL), the region of the atmosphere where SOA concentrations are on average the highest. First, a parameterization for viscosity as a function of temperature and RH was developed for α-pinene SOA using room-temperature and low-temperature viscosity data for α-pinene SOA generated in the laboratory using mass concentrations of ∼ 1000 µg m−3. Based on this parameterization, the mixing times within α-pinene SOA are < 1 h for 98.5 % and 99.9 % of the occurrences in the PBL during January and July, respectively, when concentrations are significant (total organic aerosol concentrations are > 0.5 µg m−3 at the surface). Next, as a starting point to quantify how often mixing times of organic molecules are < 1 h within α-pinene SOA generated using low, atmospherically relevant mass concentrations, we developed a temperature independent parameterization for viscosity using the room temperature viscosity data for α-pinene SOA generated in the laboratory using a mass concentration of ~70 μg m-3. Based on this temperature-independent parameterization, mixing times within α-pinene SOA are < 1 h for 27 and 19.5% of the occurrences in the PBL during January and July, respectively, when concentrations are significant. However, associated with these conclusions are several caveats, and due to these caveats we are unable to make strong conclusions about how often mixing times of organic molecules are < 1 h within pinene SOA generated using low, atmospherically relevant mass concentrations. Finally, a parameterization for viscosity of anthropogenic SOA as a function of temperature and RH was developed using sucrose–water data. Based on this parameterization, and assuming sucrose is a good proxy for anthropogenic SOA, 70 and 83% of the mixing times within anthropogenic SOA in the PBL are < 1 h for January and July, respectively, when concentrations are significant. These percentages are likely lower limits due to the assumptions used to calculate mixing times. Close

• 109. [Article] Understanding the Importance of Intermittently Fragmented Stream Habitat for Isolated Westslope Cutthroat Trout (<i>Oncorhynchus clarki lewisi</i>) in the Colville National Forest, Washington

  Climate change and anthropogenic effects have vastly reduced Westslope Cutthroat Trout (Oncorhynchus clarki lewisi, WCT) habitat throughout their range, including the Colville National Forest in northeastern ...

  Citation × Citation Citation Abstract Copy Title: Understanding the Importance of Intermittently Fragmented Stream Habitat for Isolated Westslope Cutthroat Trout (<i>Oncorhynchus clarki lewisi</i>) in the Colville National Forest, Washington Author: Carpenter, Forrest Michael Year: 2016 Climate change and anthropogenic effects have vastly reduced Westslope Cutthroat Trout (Oncorhynchus clarki lewisi, WCT) habitat throughout their range, including the Colville National Forest in northeastern Washington where this study was conducted. Many native salmonid populations have declined in abundance since the early 1900s due to a variety of climate- and human-driven forces. Westslope Cutthroat Trout are especially sensitive to habitat loss or degradation and to climate change. Together, climate change, habitat degradation, and non-native salmonid invasions are contributing to increasingly fragmented WCT populations. Ongoing and predicted future warming trends are expected to further fragment these populations and isolate them in headwater stream reaches, with populations in the spatial margins of their distributions facing greater risk. Native salmonid populations are often separated or isolated by natural or artificial upstream migration barriers (i.e., waterfalls, culverts, etc.). Prior to continuing conservation and management actions targeting WCT, it is imperative to understand habitat requirements of this keystone species in fragmented areas. Field survey data were collected in the summer of 2015 on channel geomorphic characteristics and WCT presence/absence in 26 streams located in the Colville National Forest. A clear spatial separation was observed between Eastern Brook Trout (Salvenius fontinalis, EBT) and WCT above four culvert road crossings and the habitat in both of these areas was compared statistically to identify explicit differences. This dataset was also analyzed using logistic regression modeling to determine the best habitat predictors of the presence of isolated WCT populations existing upstream of these crossing. In general, stream habitat in the Middle and South Forks of Mill Creek had low large substrate, high fine sediments, and exhibited pool-riffle channel morphology. Pool habitat supporting isolated WCT was significantly smaller, in terms of volume and surface area, than pool habitat supporting sympatric populations of WCT and EBT, largely due to the headwater nature of channel units supporting isolated WCT populations. Additionally, due to the extreme drought conditions during 2015, stream flow was substantially diminished in the study area causing these reaches to be highly fragmented and largely disconnected from the rest of the stream channel. Fine sediments were generally higher in headwater reaches supporting isolated WCT, including in pools and riffles, which was unexpected, mainly because they exist above sediment delivery points in the longitudinal extent of the system. Logistic regression analysis indicated that the presence of isolated WCT populations was primarily positively associated with an increase in large wood and boulders, and negatively associated with increasing gravel, bedrock, habitat unit length, depth, and width (Significant x2, R2=0.174, misclassification rate = 14.9%, α=0.05). The final model correctly predicted 37.5% of isolated WCT presence observations and 96.5% of the WCT/EBT presence observations significantly better than by chance alone (k=0.81). This model, in fact, may be useful in identifying limited habitat due to the fragmented nature of the channel units supporting IWCT. Large wood and boulders were positively correlated to WCT presence, likely because both are important in the formation of pools and cascades. Channel unit length, width, depth, active channel width as well as gravel and bedrock substrates, were all negatively associated with WCT presence. This suggests that isolated WCT are primarily associated with small headwater cascades with complex shelter, which may provide greater thermal and predation refuge compared to shallow glide or large pool habitats. Future model analysis should include additional habitat variables such as water temperature, stream gradient, and species interactions to strengthen the prediction of Westslope Cutthroat Trout presence. Overall, I concluded that differences in stream habitat above and below blocking culverts are not driving Westslope Cutthroat Trout distributions in the study area due to confounding factors such as the presence of problematic barriers and small sample size. I also conclude that future conservation and management decisions specific to WCT should prioritize complex cascade habitat in headwater stream reaches because of the type and quantity of habitat they may provide, especially during severe drought or low flow conditions. Title: Understanding the Importance of Intermittently Fragmented Stream Habitat for Isolated Westslope Cutthroat Trout (<i>Oncorhynchus clarki lewisi</i>) in the Colville National Forest, Washington Author: Carpenter, Forrest Michael Year: 2016 Climate change and anthropogenic effects have vastly reduced Westslope Cutthroat Trout (Oncorhynchus clarki lewisi, WCT) habitat throughout their range, including the Colville National Forest in northeastern Washington where this study was conducted. Many native salmonid populations have declined in abundance since the early 1900s due to a variety of climate- and human-driven forces. Westslope Cutthroat Trout are especially sensitive to habitat loss or degradation and to climate change. Together, climate change, habitat degradation, and non-native salmonid invasions are contributing to increasingly fragmented WCT populations. Ongoing and predicted future warming trends are expected to further fragment these populations and isolate them in headwater stream reaches, with populations in the spatial margins of their distributions facing greater risk. Native salmonid populations are often separated or isolated by natural or artificial upstream migration barriers (i.e., waterfalls, culverts, etc.). Prior to continuing conservation and management actions targeting WCT, it is imperative to understand habitat requirements of this keystone species in fragmented areas. Field survey data were collected in the summer of 2015 on channel geomorphic characteristics and WCT presence/absence in 26 streams located in the Colville National Forest. A clear spatial separation was observed between Eastern Brook Trout (Salvenius fontinalis, EBT) and WCT above four culvert road crossings and the habitat in both of these areas was compared statistically to identify explicit differences. This dataset was also analyzed using logistic regression modeling to determine the best habitat predictors of the presence of isolated WCT populations existing upstream of these crossing. In general, stream habitat in the Middle and South Forks of Mill Creek had low large substrate, high fine sediments, and exhibited pool-riffle channel morphology. Pool habitat supporting isolated WCT was significantly smaller, in terms of volume and surface area, than pool habitat supporting sympatric populations of WCT and EBT, largely due to the headwater nature of channel units supporting isolated WCT populations. Additionally, due to the extreme drought conditions during 2015, stream flow was substantially diminished in the study area causing these reaches to be highly fragmented and largely disconnected from the rest of the stream channel. Fine sediments were generally higher in headwater reaches supporting isolated WCT, including in pools and riffles, which was unexpected, mainly because they exist above sediment delivery points in the longitudinal extent of the system. Logistic regression analysis indicated that the presence of isolated WCT populations was primarily positively associated with an increase in large wood and boulders, and negatively associated with increasing gravel, bedrock, habitat unit length, depth, and width (Significant x2, R2=0.174, misclassification rate = 14.9%, α=0.05). The final model correctly predicted 37.5% of isolated WCT presence observations and 96.5% of the WCT/EBT presence observations significantly better than by chance alone (k=0.81). This model, in fact, may be useful in identifying limited habitat due to the fragmented nature of the channel units supporting IWCT. Large wood and boulders were positively correlated to WCT presence, likely because both are important in the formation of pools and cascades. Channel unit length, width, depth, active channel width as well as gravel and bedrock substrates, were all negatively associated with WCT presence. This suggests that isolated WCT are primarily associated with small headwater cascades with complex shelter, which may provide greater thermal and predation refuge compared to shallow glide or large pool habitats. Future model analysis should include additional habitat variables such as water temperature, stream gradient, and species interactions to strengthen the prediction of Westslope Cutthroat Trout presence. Overall, I concluded that differences in stream habitat above and below blocking culverts are not driving Westslope Cutthroat Trout distributions in the study area due to confounding factors such as the presence of problematic barriers and small sample size. I also conclude that future conservation and management decisions specific to WCT should prioritize complex cascade habitat in headwater stream reaches because of the type and quantity of habitat they may provide, especially during severe drought or low flow conditions. Close