Source: RESEARCH FOUNDATION OF THE CITY UNIVERSITY OF NEW YORK submitted to NRP
FREEZE/THAW PULSING OF NITRIC OXIDE: MECHANISM, MAGNITUDE, AND REGIONAL IMPACTS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1026716
Grant No.
2021-67020-34998
Cumulative Award Amt.
$500,000.00
Proposal No.
2020-04316
Multistate No.
(N/A)
Project Start Date
Sep 1, 2021
Project End Date
Aug 31, 2025
Grant Year
2021
Program Code
[A1401]- Foundational Program: Soil Health
Recipient Organization
RESEARCH FOUNDATION OF THE CITY UNIVERSITY OF NEW YORK
85 ST NICHOLAS TERRACE
NEW YORK,NY 100311246
Performing Department
Environmental Sciences
Non Technical Summary
Nitrogen can be lost from agricultural soils through multiple pathways, including leaching of nitrate in groundwater, and emissions of the greenhouse gas nitrous oxide (N2O). Nitric oxide is a trace gas that is produced by soil microbes and emitted to the atmosphere, where it is is important in the formation of ozone and particulate matter pollution. NO emissions are an important loss pathway for nitrogen from agricultural systems, and these emissions can increase substantially with the addition of fertilizer. Winter NOx (NO + nitrogen dioxide (NO2)) emissions from non-urban sources have been suggested to be an important precursor to particulate matter pollution over the midwestern U.S. Unfortunately, agricultural NOx emissions in the midwestern U.S. are poorly constrained over during winter. In particular, the effects of freeze-thaw events on soil NO emissions are not well understood, even though they are globally important sources of N2O.We will conduct a series of linked activities to improve our understanding of soil NO emissions during winter as well as the rest of the growing season: 1) We will use the eddy covariance technique at the Platte River - High Plains Aquifer Long Term Agricultural Research site (PR-HPA) to conduct continuous, high-frequency measurements NOx fluxes for one year--the first such high frequency observations of NOx from an agricultural system in the United States. 2) We will use high resolution satellite-based observations of NO2 to evaluate the impact of freeze-thaw events on regional atmospheric composition to determine if they are an important source of NOx in the midwestern U.S. 3) We will conduct laboratory incubations of soils from conventional agricultural management and management that incorporates a greater conservation approach at PR-HPA to evaluate biogeochemical and microbial responses to freeze-thaw events, and to identify the physical and biological factors that are responsible for freeze-thaw emissions of NO. The outcomes of this project will address goals a) and b) of the Soil Health Program Area Priority, as well as both suggested topics for FY2020: the effects of management practices on soil microbial community function and the assessment of approaches for enhancing understanding of biogeochemical processes contributing to agricultural sustainability.
Animal Health Component
20%
Research Effort Categories
Basic
80%
Applied
20%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
10201101070100%
Knowledge Area
102 - Soil, Plant, Water, Nutrient Relationships;

Subject Of Investigation
0110 - Soil;

Field Of Science
1070 - Ecology;
Keywords
Goals / Objectives
Nitrogen (N) transformations are a critical component of biogeochemical cycling in agricultural soils. In many ecosystems, state changes in the chemical or physical conditions of soils can trigger short-term pulses of biogeochemical activity that play a large role in annual N budgets. For example, work from our group shows that when substrate such as N fertilizer is added to soils, when dry soils are rewetted, or when soils are frozen and subsequently thaw, microbially-mediated N transformations often proceed at rates higher than at any other time of year, leading to substantial losses of N to the environment. In temperate agricultural ecosystems, freeze-thaw events--and winter emissions more generally--have long been known to be important sources of the greenhouse gas nitrous oxide (N2O; Figure 1). Even though freeze-thaw emissions of N2O were known to be larger in agricultural than natural ecosystems, it is only in the last few years--through the implementation of continuous, high-frequency measurements--that it has become clear just how important these emissions are: Freeze-thaw emissions are estimated to be responsible for roughly half of all N2O emissions from temperate agricultural systems, and one quarter of all agricultural N2O emissions globally.While many studies have investigated the importance of freeze-thaw dynamics on N2O emissions, very few have addressed more reactive N gases such as nitric oxide (NO) even though N2O and NO are produced by the same processes: nitrification and denitrification. In order to constrain N loss pathways from agriculture and to understand agricultural influences on air quality, it is essential to understand winter soil NO emissions, particularly during freeze-thaw events. We will leverage advances in trace gas measurements, detailed molecular analyses, and new, high resolution satellite NO2 observations to quantify the magnitude of winter NOx emissions in the U.S. Corn Belt, to gain insight into approaches for controlling these emissions, and to understand their impacts on regional NO2 concentrations. Specifically, we will 1) conduct in situ observations of NO, NOx, and N2O fluxes using the eddy-covariance technique at the USDA Platte River--High Plains Aquifer (PR-HPA) Long Term Agricultural Research (LTAR) site to quantify freeze-thaw NO pulses and obtain the first well-constrained estimate of NOx losses from agricultural soils in North America, 2) evaluate physical, biogeochemical, and microbial contributions to freeze-thaw NO emissions using laboratory incubations of repacked soil cores, and 3) use satellite observations to detect, explain, and statistically analyze the degree to which freeze-thaw events alter atmospheric NO2 concentrations across the Corn Belt.Novel ideas and contributions: This project incorporates several key novel ideas and contributions. As noted above, freeze-thaw emissions of NO have not been widely investigated and are poorly constrained, particularly in North American agro-ecosystems. Our observations and experiments will evaluate several key questions that have not been explored previously, including:1) providing the first long-term eddy covariance measurements of NOx fluxes from an agricultural system in the United States,2) investigating the impact of freeze-thaw events on atmospheric composition at regional scales,3) evaluating the response of nitrifying bacteria and archaea to freeze-thaw events.
Project Methods
The proposed work consists of field experiments, laboratory incubations, and remote sensing analyses:Field experiments:Site information: The USDA Platte River--High Plains Aquifer (PR-HPA) site includes a cropland business as usual experiment and is implementing an aspirational site starting this year. The cropland business as usual experiment consists of corn-corn and corn-soybean rotations. It has field-scale treatments in place that are instrumented with eddy covariance, meteorological, and pheno-cam instrumentation. These sites are located at the Eastern Nebraska Research and Extension Center (ENREC). The field-scale aspirational irrigated site has been identified at ENREC and will incorporate variable rate irrigation technology and cover crops. Crop yields and livestock performance are measured at appropriate times during the year. Vegetation health and seasonal changes in plant traits are assessed using physiological and optical measurements.Eddy covariance flux measurements: We will outfit the existing flux tower at PR-HPA with a high-frequency high-sensitivity chemiluminescence analyzer to measure NO (CLD 780TR Ecophysics, Switzerland), coupled with a blue light convertor (PLC 762 Photolytic Converter), which photolyzes NO2 into NO, to measure NOx. The CLD 780TR is an in-site system that conducts simultaneous measurements of NO and NOx at 10 Hz with a detection limit of 25 ppt at 3 second averaging. The instrument will be calibrated regularly in the field using a 5 ppm NO gas standard diluted in zero air. To investigate the portion of nitrogen oxide emissions emitted as NO, we will simultaneously measure N2O eddy covariance fluxes by co-deploying a Los Gatos Research Off-Axis Integrated Cavity Output Spectroscopy (ICOS) enhanced performance analyzer (LGR 913-0015). The high-sensitivity LGR instrument also samples at a 10 Hz rate. The LGR system will undergo frequent calibrations in the field and characterization of variations in the cell flush time. To collect these measurements, sample air will be brought into the field lab through Teflon PFA inlet tubing at a fast flow rate controlled by Edwards XDS20i scroll pumps. Eddy-covariance fluxes will be calculated using a set of custom MATLAB scripts.Lab analysesSpecifically, we will evaluate the effects of variation in freezing temperature, freezing degree days (FDDs), and freeze-thaw cycling under conventional and aspirational management approaches:Experiment 1. We will assign replicate cores to different freezing temperatures and FDD treatments. Specifically, replicates will be frozen for 15 days at a) -1°C (15 FDDs) , b) -3°C (45 FDDs), and c) -5°C (75 FDDs), after which the cores will be thawed to 5°C for 14 days. Control cores will be maintained at 5°C, and a second set of replicate cores kept at -3°C will be thawed after 5 days (15 FDDs) to evaluate the ability of FDDs to predict freeze-thaw NO emissions.Experiment 2. After the 14 days at 5°C, replicate cores at the -5°C treatment will undergo two additional freeze-thaw cycles. In each cycle, the cores will be kept for 28 days at -5°C, followed by two weeks at 5°C.Soil cores will be incubated in gas-tight chambers in He-O2 mixtures ranging from 0 to 20% O2 and the fluxes of N2O, N2, and CO2 are directly measured by gas chromatography; NO fluxes are directly measured with a Sievers Nitric Oxide Analyzer with a chemiluminescence detector. A duplicate set of vessels will also be established for partially destructive measurements of gravimetric soil moisture, NO3-, ammonium (NH4+), net N mineralization, net nitrification, microbial biomass, and denitrification enzyme activity. Concentrations of NO2-, NO3-, and NH4+ will be determined colorimetrically on a Lachat QuikChem autoanalyzer (Loveland, CO) following extraction in 2M KCl solution. Net N mineralization and net nitrification will be determined as the difference in starting and ending total inorganic N (mineralization) or NO2- + NO3- (nitrification). Denitrification enzyme activity will be analyzed using the acetylene inhibition method.Soil samples will be taken prior to thaw and daily for the first five days after thaw in experiment 1, and once before and then daily for the first five days after each subsequent thaw in experiment 2. Soils will be collected, placed in whirl-pak bags, and stored at -80 °C. Pre-thaw soils will be considered Tinitial for soil microbial community analysis. We will conduct extraction of nucleic acids from soil samples. Soil microbial DNA and RNA will be co-extracted from triplicate 2 g of soil using the Qiagen RNeasy PowerSoil Total RNA Kit, followed by a RNeasyPowerSoil DNA Elution Kit (Germantown, MD 20874). A combination of existing and novel primers designed using Primer3 software will be synthesized by IntegratedDNATechnologies, Inc. (Coralville, Iowa 52241). Gene targets will be used to evaluate abundance and dynamics of narG, H & I (nitrate reductase), nirS and nirK (nitrite reductase), norB & C (NO reductase), and nosZ I & II (N2O reductase). Quantitative PCR of denitrification genes in environmental samples will be compared to the abundance of 16S rRNA as well as to linear standards of known amounts of template created from plasmid clones. Amplification will be carried out with a Stratagene Mx3000p qPCR System (Agilent Technologies, Santa Clara, CA) using SYBR green detection. We will conduct a repeated measures analysis using the lmer function in the R programming language.Satellite analysisWe will use TROPOMI NO2 tropospheric column data first to evaluate the ground-level observations of NO fluxes over PR-HPA. Comparisons of this time series to the field observations will allow for evaluation of the satellite observations.We will also conduct a regional assessment of the effects of freeze-thaw events on atmospheric NO2 concentrations, focusing on the Corn Belt states of Illinois, Indiana, Iowa, Michigan, Minnesota, Nebraska, and Ohio, and restricting our analysis to pixels with >50% agricultural land cover. We will regrid TROPOMI tropospheric NO2 observations to 0.1° x 0.1° resolution using an area-weighted approach. We will also obtain daily minimum and maximum soil temperature data from the National Centers for Environmental Prediction (NCEP) North American Regional Reanalysis (NARR). We will conduct time series analyses of the NO2 and soil temperature data to determine whether freeze-thaw soil NO emissions can be detected from space, and if so, evaluate their contribution to tropospheric NOx pollution.To observe freeze-thaw emission events, we will evaluate maps of three-day mean tropospheric NO2 VCDs across our study region for periods immediately preceding, during, and following wide-spread soil thaw as indicated by the NARR temperature data. We will also conduct piecewise linear regression analyses of the relationship between the mean soil temperature and mean NO2 VCDs for daily values integrated across the entire study region, focusing on the period before and after spring thaw. We will repeat this analysis but using values for individual pixels as the predictor and response variables.Lastly, we will infer daily surface NOx emissions across the US Corn Belt region using the TROPOMI observations and a simple box model, and will evaluate these modeled fluxes against fluxes calculated from the ground-level measurements.

Progress 09/01/23 to 08/31/24

Outputs
Target Audience:Results from the regional analyses were presented remotely in an oral presentation by Hickman at the American Geophysical Union Fall Meeting in December, 2023. Hickman attended and presented at the USDA/NIFA A1401 (Soil Health) PD meeting in Kansas City, KS in April, 2024. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?NO/NOx flux measurement collection was led by graduate student Madeline Miles at the University of Virginia. This work features as a chapter in her dissertation. Miles has been a part of all team meetings and decision-making. How have the results been disseminated to communities of interest?The regional work and the incubation experiments were presented seperately at the American Geosphysical Union's annual meeting by Hickman and Groffman. What do you plan to do during the next reporting period to accomplish the goals?Manuscripts on the laboratory incubations and satellite analyses will be submitted for publication, with submission expected in 2024. Field results will be published as part of Miles' dissertation. Molecular analyses of the soil cores from the freeze/thaw incubation experiment will be completed at the University of Maryland, with results expected by March, 2025, and a manuscript describing the results of the laboratory experiments will be completed and submitted.

Impacts
What was accomplished under these goals? Note: we had prepared 10 figures for this section of the report, but the reporting portal does not appear to provide a means for uploading them. We would be happy to provide the figures through another avenue if possible. 1) Field component: As noted in the previous report, repeated failure of the CLD instrument requiring multiple repair efforts by the manufacturer, an ineffective pump, and a lightning strike at the field site led to a more limited field campaign than intended. In addition, failure of the N2O analyzer that the PR-HPA LTAR resulted in no measurements of N2O emissions during our experiments. However, measurements of NO fluxes were made between March 2023 and February 2024--to our knowledge the first multi-season high-frequency measurements of NO fluxes in an agricultural system in the U.S. Based on soil temperature measurements, periods of predicted high NOx emissions, and periods of reliable data coverage, we focus on three time windows. The first is May 2023, following the planting of the corn, which is when we would expect the highest fluxes to occur. Second, we focus on two periods with a high likelihood of freeze-thaw pulses: March 2023, when soil temperature measurements indicate rapid periods of freezing and thawing, and January 2024, when soil temperatures thawed after a long freeze. We also report calibrated NO and NOx mixing ratios during these time windows (Figure 1). We observed strong diurnal variations in NO, NO2, and NOx mixing ratios during all three periods (Figure 2). Figure 1. Hourly mean mixing ratios (ppb) of NO (blue) and NOx (red) in March 2023 (a), May 2023 (b) and January 2024 (c). Figure 2. Seasonal diurnal NO (blue) and NO2 (red) mixing ratios for March 2023 (a-b), May 2023 (c-d) and January 2024 (e-f). Shading represents one standard deviation. NO flux () and NO2 flux () measurements FNO and FNO2 during May 2023 are statistically significant and exhibit a clear diurnal pattern (Figure 3,4). In March 2023, fluxes are a smaller than in May but also statistically significant (Figure 5). and exhibit similar diurnal patterns (Figure 6). In January 2024, both FNO and FNOx are below the limit of detection of 0.006 ppb m s-1. Figure 3. FNO (blue) and FNO2 (red) in May 2023. Figure 4. FNO and FNO2 diurnal patterns in May 2023, showing an upward NO flux and downward NO2 flux. Shading represents one standard deviation. Figure 5. FNO (blue) and FNO2 (red) in March 2023 (a) and FNO (blue) and FNOx (purple) in January 2024 (b). Figure 6. FNO and FNO2 diurnal pattern in March 2023, showing an upward NO flux and downward NO2 flux. Shading represents one standard deviation. Figure 7. FNO (a) and NO mixing ratios (b) in March 2023. Shaded areas represent two periods of soils thawing based on soil temperature, March 14-March 17 and March 20-March 22. In March, there were two periods with a particularly high likelihood of soil thawing: March 14-March 17, following which soil temperatures fell again below zero, and March 20-March 22. During both periods, mean FNO were approximately 30% larger than the overall mean (p < 0.010). While this could indicate increased emissions due to the soil thaw, the increase was within associated flux uncertainties and any potential emissions were not as large as others have reported in the literature.38, 39, 41 In January, there was no significant difference in mean NO fluxes during the thaw period compared to the entire period or compared to the period following the thaw (p > 0.050; Figure 8). Figure 8. FNO(a) and NO mixing ratios (b) in January 2024. Shaded area represents a period of soils thawing based on soil temperature measurements over January 26-January 31. The field component has been written as a chapter of Madeline Miles' dissertation. 2) Laboratory component: We conducted two laboratory experiments. For the first experiment, we assigned replicate cores to different freezing temperatures and FDD treatments for 15 days at a) -1 oC (15 FDD) , b) -3 oC (45 FDD), and c) -5 oC (75 FDD), after which the cores were thawed to 5 oC for 14 days. A set of replicate cores was kept at -3 oC and thawed after 5 days (15 FDDfast). Control cores were maintained at 5 oC. For experiment 2, after the 14 days at 5 oC, replicate cores at the -5 oC treatment underwent two additional freeze-thaw cycles. In each cycle, the cores were kept for 28 days at -5 oC, followed by two weeks at 5 oC. Soil freezing treatments produced variable and significant effects on trace gas emissions. Effects were most marked for NO (Figure 9a), with some treatments markedly stimulating emission (75FDD, 15FDD) and one treatment (15FDD Fast) significantly reducing emission compared to the control. Effects on N2O (Figure 9b) and CO2 (Figure 9c) were less marked than effects on NO, but there was significant stimulation of both these fluxes in the most extreme freezing treatment (75FDD) and significant reductions in flux in the 15FDD Fast treatment at several dates. Each of the three freeze events led to a burst of NO emission. In contrast, the second freeze event led to a burst of N2O consumption, and the third event had no effect. For CO2, neither the second or third freeze event had an effect on flux. Figure 9. A. Nitric oxide (NO), B. nitrous oxide (N2O) and C. carbon dioxide (CO2) flux from four single freezing and thawing treatments of different intensity, with a control. Values with different superscripts within a sampling date are significantly different at p < 0.05 in a one-way analysis of variance with a Duncans multiple range test. The more intensive freezing treatment in experiment 2 (225FDD), which included three rounds of freezing for 15 days at -5 oC, produced the most marked increases in all three gases (Figure 10). As in experiment 1, NO was the most responsive gas (Figure 10a), followed by N2O (Figure 10b) and then CO2 (Figure 10c). Figure 10. A. Nitric oxide (NO), B. nitrous oxide (N2O) and C. carbon dioxide (CO2) flux from soils affected by three high intensity freezing and thawing events, with a control. Values are means with standard error. A manuscript reporting this work is nearing completion and will be circulated to co-authors in October or November. The soils used in these incubation experiments were shipped to the Maul lab in Maryland for microbial analysis. DNA extractions have been completed. 3) Regional analyses: As noted in the previous progress report, the regional analyses, encompassing analyses of both satellite and surface station data, have been completed; a draft manuscript has been completed and circulated to some team members and an external reader for specific comments on atmospheric chemistry. After any comments are addressed by co-I Hickman, the draft will be circulated to the entire team for comments, with submission expected in 2024. The draft is available at request. Our analyses hint at the possibility of regional-scale NO emissions related to the freeze/thaw transition, but firm evidence is elusive. Analyses using TROPOMI retrievals suggest that the highest tropospheric NO2 VCDs over agricultural land occur at ERA5 soil temperatures at the freeze/thaw transition (Fig. 11), but the mean temperature response is flat (Fig. 11). The absence of a clear signal in the TROPOMI analyses suggests that freeze/thaw emissions in the Corn Belt may be of a comparatively small magnitude relative to rewetting or fertilizer emissions, which is consistent with most, but not all, previous studies. The analyses using surface station data provide somewhat less equivocal support for increased NO emissions associated with freeze/thaw transitions.

Publications


    Progress 09/01/22 to 08/31/23

    Outputs
    Target Audience:Initial results from the regional analyses were presented remotely in an oral presentation by Hickman at the European Geophysical Union's annual meeting. Changes/Problems:Issues with the CLD analyzer have caused some budget over-runs primarily as a result of costs associated with the additional travel required for Miles to conduct trouble shooting with representatives of Ecophysics as well as for reinstallation of the repaired instrument and loaned instruments. These extra costs have been covered by an internal $5k from the University of Virginia and by co-I Pusede. Because of the delays caused by the instrument issues, additional sources of funding will need to be found to support future travel expenses associated with the field campaign. What opportunities for training and professional development has the project provided?NO/NOx flux measurement collection is being led by graduate student Madeline Miles at the University of Virginia. This work will feature prominently in her dissertation. Miles received in-person training from a representative of Ecophysics, developed the installation and calibration system with her advisor, co-I SallyPusede, and co-developed the instrument software with, while also receiving training from, a professional software engineer. Miles has also been leading troubleshooting of the instrument and engagement with Ecophysics represenatives in resolving numerous issues with the instrument. Miles has been a part of all team meetings and decision-making. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?We will focus on collecting NO/NOx eddy-covariance flux observations over the fall and winter. We will conduct a careful evaluation of the measurements, and we will compute the NO/NOx and N2O fluxes as part of this evaluation. Molecular analyses of the soil cores from the freeze/thaw incubation experiment will be conducted at the University of Maryland, and a manuscript describing the results of the laboratory experiments will be completed and submitted. The draft manuscript describing the regional analyses will be completed and submitted for publication to Atmospheric Chemistry and Physics or to JGR-Atmosphere.

    Impacts
    What was accomplished under these goals? 1) Field component: After lab and field testing and software development, we installed the CLD analyzer and supporting equipment were installed at the PR-HPA site in April 2022.In the fall of 2022, the analyzer was returned to the manufacturer, Ecophysics, for repair of the ozone generators and power board. The analyzer was returned and reinstalled in November 2022. In late November 2022, after issues arose again with the analyzers power supply and ozone generators, an engineer from the manufacturer and as well as a representative from the US office visited the PR-HPA site to replace the ozone generators and troubleshoot additional issues. Shortly after this visit, the ozone generators in the analyzer failed once again, and were replaced in December 2022. In January of 2022, a component of the analyzer failed and was replaced. In February of 2022, the ozone generators failed once more. After this, the manufacturer chose to send a replacement analyzer of a different model (899), while they attempted to diagnose the issue. We returned the original analyzer (780), and the new analyzer was installed in March of 2022. In April of 2022, the PR-HPA site was struck by lightning, which created issues in our equipment and the other equipment at the site. We replaced a power supply/main board component that was damaged by the lightning strike in May of 2022. Since the installation of the new analyzer there have been fewer issues, and we have maintained semi-regular data collection throughout the summer and fall of 2023. We collected and processed flux data from May of 2023. In August of 2023, the manufacturer returned our original analyzer (780), after repairing the malfunctioning components, the original analyzer was reinstalled at the PR-HPA site, and the replacement analyzer (899) was removed. We have tested the performance of the analyzer and should maintain data collection through the winter of 2023. 2) Laboratory component: We conducted laboratory experiments to identify and quantify the influence of physical factors during freeze-thaw periods on the magnitude of NO emissions. Soil cores were collected from the field site and the effects of variation in freezing temperature, freezing degree days (FDDs: the sum of the number of degrees below zero for each respective day below zero--e.g., 12 days at -2°C is equal to 24 FDDs), and freeze-thaw cycling under conventional and aspirational management approaches. In the first experiment, replicate cores were frozen for 15 days at a) -1°C (15 FDDs), b) -3°C (45 FDDs), and c) -5°C (75 FDDs), after which the cores were thawed to 5°C for 14 days. Control cores were maintained at 5°C, and a second set of replicate cores kept at -3°C were thawed after 5 days (15 FDDs-FAST). In a second experiment, after the 14 days at 5°C, replicate cores at the -5°C treatment were subjected to two additional freeze-thaw cycles. In each cycle, the cores were kept for 28 days at -5°C, followed by two weeks at 5°C. We observed marked responses in NO flux in response to our freezing treatments. The most intensive treatment (75 FDDs) produced marked increases in flux relative to the control. This result is consistent with our hypotheses that freezing disrupts soil nitrogen cycle processes in ways that increase NO flux. More surprising was the marked reduction in NO flux with the 15 FDDs-FAST treatment. These results suggest that the nature/speed of freezing has a dramatic effect on N cycling processes and NO flux. The mechanistic underpinnings of all these results will be examined as we analyze data collected on microbial biomass, activity, and community composition during these experiments. DNA primers for target genes responsible for NO/NOx emissions from soils were designed and acquired. Incubation experiment soils from the Cary Institute of Ecosystems studies were shipped to the Maul lab in Maryland and prepped for DNA and RNA extraction, expected to take place in late 2023. 3) Regional analyses: We have processed TROPOMI retrievals and surface observations from the EPA Air Quality System, focusing on the Corn Belt. We have conducted a wide array of analyses of these data, and a draft manuscript is in an advanced stage of preparation. The manuscript is centered on two categories of analyses, using both the satellite retrievals and surface measurements: 1) temperature response analyses and 2) freeze/thaw event analyses. Temperature response analyses: the primary focus on of the temperature response analyses is NOx in agricultural areas, but analyses of multiple related species are included in an effort to interpret the NOx temperature response. All analyses are also conducted for urban areas, which would be expected to be subject to different emissions and chemistry dynamics. The results for winter months are consistent with emissions associated with freeze/thaw events, peaking at temperatures near zero. Summer months show very different temperature response behavior. Statistical analyses suggest variation in photochemistry are unlikely to be an important contribution, and it appears unlikely that changes in NOx lifetime as a result of variation in aerosol formation rates are responsible for the temperature response function. Urban responses are shifted in temperature, suggesting a different underlying set of dynamics, but share some similarities to the agricultural responses. Freeze/thaw event analyses: Time series centered on dates when maximum air temperature shifted from a below-zero period to above zero were analyzed for the EPA-AQS sites. The number of events varied substantially among sites, with varying and inconsistent responses of surface NOx concentrations to thaw events. There was no apparent relationship between FDD at thaw and the NOx reponse to thawing. Results were similar for comparable analyses of TROPOMI data using ERA5 soil temperature data in place of maximum air temperature. Note: we had prepared 4 figures for this section of the report, but the reporting portal does not appear to have the capacity to include images. We would be very happy to provide these figures through alternative means.

    Publications


      Progress 09/01/21 to 08/31/22

      Outputs
      Target Audience: Nothing Reported Changes/Problems:There have been no major changes in the approach, but there have been technical issues with the NO2 analyzer. The manufacturer reported that it has resolved the technical issues and returned the instrument in early November,but after installation at the field site, issues remained. The manufacturer is sending a technician to the site to troubleshoot the last week of November.If we are unable to capture all freeze/thaw events in winter 2022/2023, we will still have an opportunity to do so in winter 2023/2024 during Y3 of funding. We are planning to replace the pump, which malfunctioned under high temperatures, in advance of next summer. There has also been a delay in the analysis of satellite data relative to the original timeline, but this is not expected to result in any obstacles to completion of the project. What opportunities for training and professional development has the project provided?NO/NOx flux measurement collection is being led by graduate student Madeline Miles at the University of Virginia. This work will feature prominently in her dissertation, and she successfully defended her dissertation proposal in August of this year. Madeline received in-person training from a representative of Ecophysics, developed the installation and calibration system with her advisor, co-I SallyPusede, and co-developed the instrument software with, while also receiving training from, a professional software engineer. Miles has been a part of all team meetings and decision-making. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?We will focus on re-installing and collecting NO/NOx eddy-covariance flux observations over the fall and winter. We will conduct a careful evaluation of the measurements, and we will compute the NO/NOx and N2O fluxes as part of this evaluation. Soil cores will be sampled before freeze in 2022 and shipped to the Cary Institute.The freeze/thaw incubation experiments will be conducted, including trace gas, soil biogeochemistry, and molecular analyses, the latter of which will be conducted at the University of Maryland. Freeze/thaw data from SMAP and from the University of Montana will be downloaded. Analysis of freeze/thaw events during the TROPOMI PAL historical record will be analyzed over the Corn Belt and over a 0.1 x 0.1 gridd cell centered on PR-HPA. The analysis will be extended to winter 2022/2023 as data become available.

      Impacts
      What was accomplished under these goals? Toward the goal of collecting NO/NOx eddy covariance measurements, we have accomplished the following: (1) we lab and field tested the CLD analyzer; (2) designed and completed a calibration system; (3) wrote software to access the 10 Hz data; and (4) wrote scripts to process the NO/NOx flux data and compute the eddy covariance fluxes. The CLD analyzer and supporting equipment were installed at the PR-HPA site in April 2022 to test its performance prior to any freeze-thaw episodes. Through this process, we identified several issues that we are working to fix with the manufacturer Ecophysics. First, the instrument had a faulty power supply board that caused the analyzer to reboot frequently. Second, while the instrument was regularly calibrated in the field, it became clear that the sensitivity was unstable. Finally, pre-chamber measurements indicated issues of high interferences and/or an internal leak. We removed the CLD analyzer from the field in July 2022 for repair. The instrument was returned to Ecophysics in Switzerland, where the issues were reported to have been addressed in late October, 2022. Theinstrument was reinstalled atPR-HPA in early November, but issues persisted. The manufacturer is sending a technician for on-site troubleshooting the last week of November, and it is hoped we will have coverage of all thaw events. 45 PVC soil cores were manufactured at the Cary Institute of Ecosystem Studies for shipment to PR-HPA. TROPOMI PAL NO2 data has been downloaded for winters of 2018-2019, 2019-2020, and 2020-2021, the most recent winter data available as of Nov 1, 2022.The data has been regridded to 0.1 x 0.1 resolution.

      Publications