Source: UNIVERSITY OF COLORADO submitted to NRP
TOWARD SUSTAINABLE CROP SULFUR USE: PROBING THE LINK BETWEEN HIGH SULFUR APPLICATIONS AND METHYLMERCURY PRODUCTION
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
ACTIVE
Funding Source
Reporting Frequency
Annual
Accession No.
1027665
Grant No.
2022-67019-36103
Cumulative Award Amt.
$655,176.00
Proposal No.
2021-09322
Multistate No.
(N/A)
Project Start Date
Jan 1, 2022
Project End Date
Dec 31, 2025
Grant Year
2022
Program Code
[A1401]- Foundational Program: Soil Health
Recipient Organization
UNIVERSITY OF COLORADO
(N/A)
BOULDER,CO 80309
Performing Department
INSTAAR
Non Technical Summary
The ways that people are altering the sulfur (S) cycle are changing--from mining and fossil fuel combustion to agricultural S additions. Past research in the Florida Everglades linked high crop S applications to methylmercury production, a neurotoxin that bioaccumulates in the food chain, putting wildlife and people at risk. The link between high S applications to crops and methylmercury has not been studied in upland (non-wetland) agricultural systems where many crops are grown. This research explores the connection between agricultural S applications and methylmercury productionin the Napa River Watershed (California, US) -- a perfect regional crop system where wine grapes are grown exclusively and high S applications are used by most grape growers. The investigators will develop approaches using stable isotope biogeochemistry to measure rates of methylmercury productionand determine whether agricultural S runoff causes methylmercury contamination of wetlands downstream from vineyard agriculture. The research includes strong collaborations with grape growers, University of California Cooperative Extension, Napa County Open Space, California Department of Pesticide Regulation, and the State Water Boards to conduct the project and use its findings to inform S management. Itdirectly addresses USDA/NIFA research priorities in the Bioenergy, Natural Resources, and Environment Program related to understanding and improving soil health (A1401), increasing water quantity and quality (A1411), and reducing nutrient loading to surface and groundwater. Ultimately, the project will yield new insights and analysis approaches that are broadly applicable to agriculture in the US and internationally.
Animal Health Component
30%
Research Effort Categories
Basic
40%
Applied
30%
Developmental
30%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1020110200080%
9031131310020%
Goals / Objectives
The overarching goal of the research project is to address the outstanding question: Do high agricultural sulfur (S) inputs stimulate methylmercury (MeHg) production in upland watersheds? In addressing this question, the research team will tackle the following four research objectives:Quantify potential net Hg methylation rates in vineyard (high S) and non-agricultural (low S) soils;Determine the effects of substrate additions on potential net Hg methylation rates in vineyard (high S) and non-agricultural (low S) soils;Investigate whether agricultural S runoff causes MeHg contamination of wetlands.Importantly, they will couple these research objectives to complete two major extension objectives:Share research progress and results with the local agricultural industry and discuss potential pathways to optimize agricultural S use;Inform S monitoring and regulation conducted by California State officials.Together, these efforts will yield greater understanding of the consequences of high S applications to croplands. Importantly, the project will engage stakeholders in all stages of the research to ensure that findings are usable and meaningfully inform S management in the future.
Project Methods
The methods for the project include a combination of in-field and laboratory techniques. Specifically, soils and sediments from four vineyardand four non-vineyard (i.e., forest and grassland areas) locations will be collected for incubation with addition of the stable isotopes of mercury (Hg) to determine potential rates of methylation and demethylation in the laboratory. Methylation and demethylation rates will be measured under ambient (i.e., field) and spiked (with sulfur and carbon sources) conditions to determine substrate limitations to MeHg production. In addition, a field study at the terminus of the Napa River Watershed -- where vineyards meetfreshwater wetlands -- will be instrumented with three transects of pore water samplers and plots for soil and sediment collection (n = 6 locations per transect). Concentrations of S species, Hg, dissolved organic C, and the stable isotopes of S will be measured along the transects in pore waters and surface water to determine the chemical evolution and S stable isotope signature of agricultural runoff into the wetlands. Within the wetlands, sediment will be collected along the transects to measure potential rates of Hg methylation and demethylation in the laboratory, using the same approaches developed in the incubation study. The combination of these two major efforts will grant insight into both the potential rates of MeHg production within the upper watershed, as well as whether agricultural S runoff stimulates MeHg production within adjacent freshwater wetlands.

Progress 01/01/24 to 12/31/24

Outputs
Target Audience:The past year of our project was dominated by lab protocol development and analyses. Thus, we were in the mode of generating results. However, like in our first year, we did discuss the project with participating farmers and open space managers. In addition, PI Hinckley and Co-PI Jacqueline Gerson gave presentations on the research to national and international scientific audiences, including The International Mercury Meeting (Capetown, South Africa), the American Geophysical Union Meetings in Washington DC, Harvard University, and the BIOGEOMON meeting in Puerto Rico. Changes/Problems:We had multiple changes during the last project period -- moving some of our mercury analyses from University of California, Santa Cruz to Michigan State University. However, all went smoothly during this project period, and we have all results completed. Now, we are focused on wrapping up the written and oral communication aspects of the project; I do not anticipate any further issues. What opportunities for training and professional development has the project provided?The project has provided multiple opportunities for student and postdoctoral training and professional development, including: Ph.D. student J. "Nettie" Calvin is getting trained on all aspects of the project from the analytical chemistry lab work, to fieldwork, to project planning and reporting. Most of Nettie's training is in the analytical chemistry lab where she is using advanced techniques in isotope analysis using mass spectroscopy. Co-PI Peter Weiss-Penzias and collaborator Professor Carl Lamborg and the staff in the Marine Analytical Laboratory at University of California, Santa Cruz Postdoctoral Scholar, Dr. Jacqueline Gerson not only worked as a central member of the project team, but went from an Assistant Professor position at Michigan State University to Cornell University. Dr. Gerson has received several invitations to speak about her research and this project. These invitations included: the International Mercury Meetings in Capetown South Africa, Cornell University, and the American Geophysical Union Meetings in Washington DC. In addition, Co-PI Gerson trained a Postdoctoral Scholar, a graduate student, and a technician on this project. PI Hinckley received invitations to speak about the project at Harvard University and the BIOGEOMON Conference in Puerto Rico. How have the results been disseminated to communities of interest?Our communications have largely been informal, to involved farmers and open space managers, as well as to the scientific community (e.g., agriculture, biogeochemistry, Earth sciences). Now that we have all samples analyzed and are interpreting the results of the project, we will be poised to discuss with more farmers in California, as well as with the CalEPA and California Department of Pesticide Regulation. What do you plan to do during the next reporting period to accomplish the goals?During the next reporting period, we are focused on data analysis and writing peer-reviewed publications for all three sub-studies. PI Hinckley will also arrange an event with Dr. Monica Cooper (University of California Cooperative Extension) for vineyard and open space managers in Winter 2025 (Napa, CA), and a meeting with CalEPA and California Department of Pesticide Regulation in Sacramento, CA. In addition, PI Hinckley has been invited to speak about the project to agricultural audiences on the podcast DIRT.

Impacts
What was accomplished under these goals? During the past project year, we were completely focused on finishing all laboratory analyses at the University of Colorado, Boulder, Michigan State University, and University of California, Santa Cruz. We have successfully quantified net mercury methylation rates, sulfate reduction rates, pools of sulfur, carbon, and mercury species across all three research objectives. This was an extraordinary number of samples/analyses across the research objectives that In addition, we have honed our protocols for future use by our research groups and others studying mercury methylation in upland soil ecosystems. Finally, we drafted papers for Research Objective 1 (based on the dissertation chapter by J.C. Calvin) and Research Objective 3 (led by Co-PI Gerson).

Publications

  • Type: Peer Reviewed Journal Articles Status: Published Year Published: 2023 Citation: Gerson, J.R. and Hinckley, E.L.S., 2023. It is time to develop sustainable management of agricultural sulfur. Earth's Future, 11(11), p.e2023EF003723.
  • Type: Theses/Dissertations Status: Published Year Published: 2024 Citation: Calvin, JC. 2024. The Influence of Anthropogenic Nitrogen and Sulfur on Mercury Methylation: from Wetland Sediment to Upland Soil. Ph.D. Dissertation. University of California, Santa Cruz.


Progress 01/01/23 to 12/31/23

Outputs
Target Audience:The second year of this project was dominated by (1) conducting field sampling and laboratory processing for research objectives 1 (net mercury methylation rates in soils), 2 (substrate addition experiments to test net mercury methylation response), and 3 (sampling water, sediment, and soil along transects from vineyard to wetlands); and (2) conducting laboratory analyses of all samples, including net mercury methylation rates in soils, as well as biogeochemical variables in soils, sediments, and waters. Our audiences for this project were primarily scientific professionals. Members of our project team presented project results at the Mercury In the Atmosphere and Ecosystems Workshop, University of Colorado, Boulder (May 2023),Goldschmidt Conference in Lyon, France (July 2023), American Geophysical Union Meetings, San Francisco, CA (December 2023), and at multiple universities (Cornell University, The Pennsylvania State University, and Harvard University). In addition, the project team shared results informally with cooperating farmers in Napa Valley, CA, as well as secondary school educators at a workshop in Lake County, CA (December 2023). Changes/Problems:During the short timeframe of our project, we have developed and conducted methods for analysis of net mercury methylation rates in soils. To date, such analyses have primarily been done in marine and estuarine sediments. Not only the development of the techniques, but also the methods themselves, have been extremely laborious and time-intensive; currently, we must coordinate time on the analytical instrumentation at the University of California, Santa Cruz, with Dr. Carl Lamborg's group (collaborator), as well as others. As such, in order to complete all of our analyses within the project timeframe, we need to move the samples associated with Research Objectives 2 and 3 to Dr. Jacqueline Gerson's Mercury Laboratory. Because Dr. Gerson was a postdoc on this project and helped to develop the methods, she is able to replicate the set-up and ensure quality control across the two laboratories. While we have a solution to getting this work done, our request for a budget change is still pending with USDA. We look forward to finalizing the approval so that we can continue with the analyses in parallel at the two laboratories. What opportunities for training and professional development has the project provided?Our project has provided multiple opportunities for training and professional development. Specifically: Ph.D. student Nettie Calvin has worked on developing and masteringall aspects of the analytical chemistry lab work associated with the net mercury methylation rates, including advanced techniques in isotope analysis using mass spectroscopy. Co-PI Peter Weiss-Penzias and collaborator Professor Carl Lamborg and the staff in the Marine Analytical Laboratory at University of California, Santa Cruz, as well as Postdoctoral Scholar Dr. Jacqueline Gerson, are responsible for providing Nettie the training. MS student Travis Esquivel is getting trained in the analytical chemistry lab work, focusing most of his time with sample preparation and data processing. Co-PI Weiss-Penzias and Nettie Calvin have been responsible for training Travis. PhD student Douglas Castro has analyzed soil, sediment, and water samples for sulfate and dissolved organic carbon concentrations. This effort has required that he learn the Metrohm Ion Chromatograph and Shimadzu TOC Analyzer at the University of Colorado, Boulder. PI Hinckley and Postdoctoral Scholar JacquelineGerson have been responsible for training Douglas. Postdoctoral Scholar Dr. Jacqueline Gerson continued developing her leadership efforts associated with field campaigns, designing the laboratory experiments (RO2), and developing the analytical chemistry techniques. In addition, she started as an Assistant Professor at Michigan State University in August 2023 and has transitioned to being a Collaborator on the project. Dr. Gerson gave talks on the project at the 2023 Goldschmidt Conference in Lyon France, the American Geophysical Union Meetings in San Francisco. PI Hinckley and Dr. Gerson are co-convening a session at the 2023 Goldschmidt Conference in Lyon, France, focused on coupled biogeochemical cycles. PI Hinckley was invited to give talks that included preliminary results from the project at the Mercury in the Atmosphere and Ecosystems Workshop at the University of Colorado, Boulder; as well as seminars at Cornell University, The Pennsylvania State University, and Harvard University. How have the results been disseminated to communities of interest?As we are deep in conducting our laboratory analyses of samples generated in the field and laboratory experiments, we have remained cautious about sharing our study to communities of interest until we have our finalized values and project completed. Agricultural sulfur and its potential link to methylmercury production (a neurotoxin) is a sensitive topic. However, we have shared our project initial results at scientific meetings and at university seminars (see reporting above), have completed a review paper (published in 2023 in Earth's Future), and shared initial results with cooperating farmers in Napa Valley, as well as area secondary teachers who participated in a curriulum workshop organized by PI Hinckley in December 2023. What do you plan to do during the next reporting period to accomplish the goals?During the next reporting period, we have some large goals to complete: 1) Finish field work associated with RO3 (Winter 2024). At thattime, all project field work will be complete. 2) Finish all laboratory analyses for RO1, RO2, and RO3. Due to the laborious and time-consuming nature of the net methylation rate incubations, we have requested a budget revision that includes a subcontract to Dr. Jacqueline Gerson (former postdoc on the project) to analyze samples from RO2 and RO3 in her laboratory at Michigan State University. This request is currently pending with USDA, and we eagerly await approval so that we can continue this work. 3) Continue to present results at scientific meetings (Dr. Gerson will present at the International Mercury Meeting in Capetown, S. Africa, July 2024), and team members will continue to present at national conferences, workshops, and university seminars. 4) Hold meetings with California winegrowers and State officials to communicate results. 5) Draft and submit peer-reviewed manuscripts.

Impacts
What was accomplished under these goals? Our project team had a very productive second year. Our primary activities included: (1) completing all field sampling associated with research objectives 1 and 2 (measuring rates of net mercury methylation and associated biogeochemical variables across different land use types in Napa Valley, and conducting substrate addition experiments to test potential net mercury methylation rates); and completing the majority of field sampling associated with research objective 3 (measuring rates of net mercury methylation and associated biogeochemical variables across a vineyard-to-wetland interface). These massive field campaigns have yielded hundreds of samples to analyze. Our University of California, Santa Cruz (UCSC) team has been working on analyzing methylmercury and total mercury concentrations in sediments (RO1), as well as the net methylation rates during the dry and wet seasons (RO1). Our University of Colorado, Boulder (CU) team has been analyzing all of the soil, sediment, and water samples for sulfate, dissolved organic carbon, and total carbon (RO3). Due to the laborious and time-consuming nature of the net mercury methylation analyses, we also developed a plan for former postdoc on the project, Dr. Jacqueline Gerson, to analyze samples from RO2 and RO3 for net mercury methylation rates at her new mercury biogeochemistry laboratory at Michigan State University, where she is an Assistant Professor. This request for a new subcontract award is pending with USDA now. In summary, this year has been focused on field and laboratory activities, with communication of our first results at national and international scientific conferences, as well as in university seminars. We look forward to sharing more results -- and sharing them more widely -- after our next project year when we anticipate that our field and laboratory work will be complete.

Publications

  • Type: Journal Articles Status: Published Year Published: 2023 Citation: Gerson JR and Hinckley ES. 2023. Managing sulfur use in agricultural systems to meet crop needs and reduce environmental consequences. Earths Future 11. DOI: 10.1029/2023EF003723 Received the EOS Editors Highlight


Progress 01/01/22 to 12/31/22

Outputs
Target Audience:The first year of this project was dominated by (1) developing and testing analytical methods for measurement of net mercury methylation rates; (2) developing and testing field methods for extraction of soil and sediment cores under anoxic conditions; (3) establishing site permissions and choosing sample site locations; and (4) conducting field sampling and laboratory processing for research objectives 1 (net mercury methylation rates in soils) and 3 (sampling water, sediment, and soil along transects from vineyard to wetlands). While in our preliminary phase, we did discuss the project with participating farmers and open space managers. In addition, PI Hinckley and Postdoctoral Researcher Dr. Jacqueline Gerson gave a presentation to the California Department of Fish and Wildlife's annual Napa-Sonoma Marshes Restoration Group Meeting. This is a diverse group of researchers and managers who are investigating target species populations in the marshes, as well as management strategies to maintain water quality and biodiversity. Our point of contact with CA Department of Fish and Wildlife, Karen Taylor, has welcomed us into this community (she also helped us to get permitting to conduct sampling on CDFW marsh and baylands for research objective 3). There is a lot of interest in our project, and recognition that the pressures of the nearby agricultural industry, as well as the chemistry of runoff to to the baylands, are an important consideration for wildlife health. The title of our presentation was, "What are the consequences of sulfur applications to Napa Valley vineyards for wetlands of the San Pablo Bay?" There were approximately 40 attendees at the meeting. Changes/Problems:The most significant issue that we have had with this project is that the Inductively-Coupled Plasma Mass Spectrometer (ICP-MS) in collaborator Dr. Carl Lamborg's laboratory at University of California, Santa Cruz, has been down this fall. We must couple the Tekran (for mercury analysis) to the ICP-MS for analysis of the mercury isotope incubations, which are used to calculate rates of net mercury methylation. This fall, we became aware that theinstrument had a part that needed to be replaced before we could run our first set of incubation samples from research objective 1,but then University of California workers went on strike, so the laboratory manager was out for several weeks and the lab with the ICP-MS was temporarily shut down. As of early December 2022, the part is ordered and the laboratory manager anticipates helping Ph.D. student Nettie Calvin and Co-PI Weiss-Penziasto conduct test runs of the Tekran and ICP-MS system in January 2023. We aim to have the results we need to inform our second experiment in research objective 1 and first experiment in research objective 2 prior tothe target field sampling dates for these experiments (late February and mid-March 2023). Co-PI Peter Weiss-Penzias and Nettie Calvin are working with Dr. Carl Lamborg to address this situation swiftly so that we can continue moving forward. What opportunities for training and professional development has the project provided?The project is providing several opportunities for student and postdoctoral training and professional development. Specifically: Ph.D. student Nettie Calvin is getting trained on all aspects of the project from the analytical chemistry lab work, to field work, to project planning and reporting. Most of Nettie's training is in the analytical chemistry lab where she is using advanced techniques in isotope analysis using mass spectroscopy. Co-PI Peter Weiss-Penzias and collaborator Professor Carl Lamborg and the staff in the Marine Analytical Laboratory at University of California, Santa Cruz, as well as Postdoctoral Scholar Dr. Jacqueline Gerson, are responsible for providing Nettie the training. MS student Travis Esquivel is getting trained in the analytical chemistry lab work, focusing most of his time with sample preparation and data processing. Co-PI Weiss-Penzias and Nettie Calvin have been responsible for training Travis. Undergraduate student McKenna Smith is getting trained primarily on field work (sample collection, labeling), and lab work (cleaning glassware to trace metal clean standards). Co-PI Weiss-Penzias and Nettie Calvin have been responsible for training McKenna. Undergraduate student Michelle Rothman is getting trained primarily on field work (sample collection, labeling), and lab work (cleaning glassware to trace metal clean standards). Co-PI Weiss-Penzias and Nettie Calvin have been responsible for training Michelle. Postdoctoral Scholar Dr. Jacqueline Gerson joined the project in August 2022 and has brought her expertise in large-scale field projects, as well as rigorous mercury biogeochemistry to the project. Dr. Gerson has been critical to site establishment and field sampling, as well as establishing our QA/QC protocols for the mercury analyses. PI Hinckley hired, supervises, and trains Dr. Gerson. Dr. Gerson has received several invitations to speak about her research and this project. These invitations include: the American Geophysical Union Meetings (declined, due to time-sensitive field work on this project), the Napa-Sonoma Marsh Restoration Group Meeting, the Department of Civil and Environmental Engineering and the Department of Geological Sciences at University of Colorado, Boulder. PI Hinckley and Dr. Gerson are co-convening a session at the 2023 Goldschmidt Conference in Lyon, France, focused on coupled biogeochemical cycles. How have the results been disseminated to communities of interest?Thus far, in the initial stages of our project, we have been cautious about sharing our study to communities of interest. Agricultural sulfur and its potential link to methylmercury production (a neurotoxin) is a sensitive topic. However, we have shared our project plans and preliminary results with (1) cooperating vineyard managers and open space managers, and (2) the Napa-Sonoma Marsh Restoration Group. We expect to share forthcoming results more broadly in 2023. What do you plan to do during the next reporting period to accomplish the goals?During the second project year, we have multiple activities planned to forward the research and communicate the results. These activities include: Conducting the second rounds of sampling for research objectives 1 and 3. Conducting research objective 2: the substrate (sulfate and organic carbon) addition experiment to determine if methylmercury production is substrate-limited in soils and sediments. Performing all analytical work (measurement of mercury species, quantification of net mercury methylation rates, and other related variables) associated with research objectives 1-3. Optimizing the analytical method that involves the ICP-MS at University of California, Santa Cruz. This instrument, housed in Dr. Carl Lamborg's laboratory, has been down so we have not yet been able to use it. In addition, the lengthy University of California strike this fall slowed our progress with gaining access (the laboratory manager was on strike). We look forward to getting this instrument ready for our sample analyses and to generate data by late January 2023. We will arrange a briefing with the California Department of Pesticide Regulation and California Environmental Protection Agency to talk about this project and our initial findings on agricultural sulfur transport and mercury methylation rates.

Impacts
What was accomplished under these goals? Our project team had a very productive first year. Our primary activities included:assembling/hiring our group members, developing the field and lab methods, establishing our primary field sites, and conducting our first sampling efforts. We hired two undergraduate students who are getting trained in conducting team-based research on this project; a master's student who is designing a companion study to this one in which he will measure mobilization of methylmercury into surface waters within the Napa River Watershed; a Ph.D. student who is developing the methodologies for sampling net mercury methylation rates and including this project in her dissertation research; and a Postdoctoral Scholar who is an expert in mercury biogeochemistry and keen to learn more about the interaction of metals and sulfur cycling in agricultural systems. One of the undergraduate students was able to leverage this project to obtain funds from the University of California, Santa Cruz, to conduct sediment sampling in the Napa-Sonoma marshes. From these samples, she worked with the Ph.D. student to quantify concentrations of total mercury, methylmercury, and net mercury methylation rates -- dialing in the methods for this project and generating preliminary data. PI Hinckley, Co-PI Weiss-Penzias, the Postdoctoral Scholar (Dr. Gerson), and the Ph.D. student (Nettie Calvin) worked together to develop the protocols for field sampling -- different strategies were necessary to obtain upland soils versus lowland sediments for the methylation incubations and to preserve the samples until anoxic conditions. In addition, Nettie Calvin worked to optimize measurements of mercury species in the laboratory at the University of California, Santa Cruz, with her co-advisor, Dr. Carl Lamborg, who serves as an advisor on the analytical methods for this project. In addition, PI Hinckley worked with existing and new collaborators (both vineyard managers and open space managers) across the Napa River Watershed to secure sites for this three-year project. In addition, she worked with Dr. Gerson to secure a site at the vineyard-to-baylands interface for research objective 3. Importantly, this site connects 400 continuous vineyard acres to the downstream marshes, which will allow the project team to determine whether agricultural sulfur runoff stimulates mercury methylation in the marsh and bay sediments at the terminus of the Napa River Watershed. Acquisition of this site required permissions from a private vineyard owner and the California Department of Fish and Wildlife. The entire project team conducted the first experiment in research objective 1: collecting soils and sediments from vineyards and open space areas to determine whether agricultural sulfur stimulates mercury methylation in upland soils. Samples were incubated with mercury isotopes to measure methylation and demethylation, as planned. In addition, companion cores were collected to quantify mercury species and other related variables (organic carbon, pH, sulfate, and reduced sulfur species) at the University of California, Santa Cruz, and the University of Colorado, Boulder laboratories. These analyses are currently underway by project team members in the respective laboratories. Most recently, Dr. Gerson conducted the first round of sampling for research objective 3: investigating whether agricultural sulfur runoff causes methylmercury contamination of wetlands. She processed the sediment samples for mercury isotope incubations and has begunelemental analyses on the soils, sediments, and waters measured at the University of Colorado, Boulder. Finally, we gave our first presentation to the Napa-Sonoma Marsh Restoration Group (overseen by California Department of Fish and Wildlife) to discuss the study underway and share our preliminary results.

Publications

  • Type: Journal Articles Status: Under Review Year Published: 2022 Citation: Gerson, J.R. and E.S. Hinckley. It Is Time to Develop Sustainable Management of Agricultural Sulfur. Journal of Experimental Botany. (Invited; in review)