Source: UNIVERSITY OF DELAWARE submitted to NRP
UNDERSTANDING SOURCES, CHEMICAL FORMS, AND STABILITY OF RECALCITRANT AND RESIDUAL PHOSPHORUS POOLS IN AGRICULTURAL SOILS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1012314
Grant No.
2017-67019-26333
Cumulative Award Amt.
$524,600.00
Proposal No.
2016-08499
Multistate No.
(N/A)
Project Start Date
May 15, 2017
Project End Date
May 14, 2022
Grant Year
2019
Program Code
[A1401]- Foundational Program: Soil Health
Recipient Organization
UNIVERSITY OF DELAWARE
(N/A)
NEWARK,DE 19717
Performing Department
(N/A)
Non Technical Summary
Phosphorus (P) is an essential nutrient for all life forms and there is no other substitute for P in sustaining life and food production. Successive and often excessive P inputs (than agronomic output) have resulted in a buildup of P in soil. Various aspects of P cycling in agricultural soils are poorly understood and this has limited our capability to make any predictive assessment on the potential risk of leaching of P from these sources to open waters. The overarching objective of the proposed research is to identify chemical forms of recalcitrant and residual P pools and track their transfer and transformation in soils. This project will apply conventional methods in soil chemistry including elemental and mineralogical, microscopic, and spectroscopicmethods to better resolve soil P processes and integration of multi-scale research results from field-simulated laboratory and field measurements will identify as well as constrain chemical forms of recalcitrant and residual P pools in soils. Results from this research will be transferrable to other comparable soil environments and contribute to the goal of maintaining healthy ecosystems.
Animal Health Component
60%
Research Effort Categories
Basic
25%
Applied
60%
Developmental
15%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
10201102000100%
Knowledge Area
102 - Soil, Plant, Water, Nutrient Relationships;

Subject Of Investigation
0110 - Soil;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The overarching objective of this research is to identify chemical forms of recalcitrant and residual P pools and track their transfer and transformation in soils. The specific objectives include:Objective 1: Identify biogeochemical reactions and pathways that promote formation as well as transformation of recalcitrant and residual P pools in soils. Objective 2: Identify the chemical forms and bonding environments of recalcitrant and residual P pools and assess potential mechanisms that stabilize or mobilize them.Objective 3: Quantify the legacy sources of recalcitrant and residual P pools exported from East Creek, a coastal estuary to the Chesapeake Bay.
Project Methods
It will applymost recent technological developments in a) tender X-ray absorption spectroscopy (TES) (XRF, XANES, and EXAFS) for light elements particularly P, Fe, Ca, and Al to constrain the chemical identity and bonding environment of P in soils and b) phosphate oxygen isotopes (d18OP). It will also apply elemental and mineralogical (ICP-MS and XRD), microscopic (SEM, TEM), spectroscopic [NMR: one-dimensional (1H, 13C, and 31P) and two-dimensional (COSY, HMQC, and HMBC)] methods to better resolve soil P processes andtransformation.

Progress 05/15/17 to 05/14/22

Outputs
Target Audience:Academics; farmer and commodity groups; federal and state government, local government, and stakeholders on the nutrient management Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?All project funded and project related students [Mingjing sun (postdoc),Kathryn Szerlag (Ph.D.), Qiang Li (Ph.D.), Jessica Anton (M.S.), Sarah Tuoni (undergrad), and M. Elavarthi (undergrad)] graduated and landed in their careers. So no significant training was provided this 5th year. However, we continued to train on honing their skills in manuscript writing, highlighting key scientific findings and step by step training on conmpositng research proposals. How have the results been disseminated to communities of interest?Scientific findings are published in peer-reviewed journals, presented at national/international meetings and conferences, and the results are disseminated via publications and presentations. Key interactions f the 5th year of the project include: Four journal peppers and one book chapter were published. Four other manuscripts are under different stages of the review process (see details in the accomplishment section). Two keynotes and seven invited talks delivered. One MS thesis and one Ph.D. dissertation completed. Five volunteered talks by graduate and undergraduate students and collaborators in the project. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Since this is the final report as well, we like to include project accomplishment along with that of 5th year. Published a total of 18 peer-reviewed papers (in high-impact factor journals including ES&T, STOTEN, JGR-B, and Minerals). Five more are still in review process. Edited two special issues in journals and published one book chapter. Delivered threeplenary, two distinguished letctureship, seven keynote talks, 13invited talks, and 28 oral/poster presentations in professional meetings and department seminars in U.S., Europe, and Asia. Among the outcomes listed above, the fifth-year outcomes include one book chapter, eight research papers (published/under review/submitted), two keynote talks, seven invited talks, and four volunteered presentations. One Ph.D. (Kate Szerlag) and one M.S. (Jessica Anton), fully supported by the award, completed their degree and landed their career jobs. Partially funded and trained two undergraduate students and unfunded research collaboration with one Ph.D. student (Qiang Li) and one postdoctoral associate (Mingjing Sun) landed in their professional careers. Preliminary findings from this project yielded one federal grant award: NSF (EPSCoR; Jaisi). Other activities: Two major instrumentation proposals (EGP-USDA) and US DOD were submitted. One was rejected and the other is pending. Collaborations initiated out of this project are continued i) Xu Zhao and Yu Wang (Institute of Soil Sciences Chinese Academy of Sciences, ii) David O'Connell (Trinity College, Ireland), iii) Milko Jorquera (University of La Frontera, Chile), iv) Erich Young (USDA-ARS) and v) Donald Ross (U Vermont). These collaborations are fruitful and have yielded collaborative publications (see publication list of year 4 and 5). Two international grant proposals were submitted, led by Milko Jorquera (University of La Frontera, Chile) with collaborators from U.S., Chile, and Japan and Dr. Jorquera and Jaisi (both funded). Four beamtime proposals to the National Synchrotron Light Source II (NSLS II) and one to the Stanford Synchrotron Radiation Lightsource (SSRL) were awarded. Respectable job placement of the student funded by this project: Kate Szerlag (assistant professor at Westfield State University, MA); Jess Anton (scientist at PFAS Solution, Newark, DE); Mingjing Sun (assistant professor at Emporia University, KS), Qiang Li (postdoc at the University of Wisconsin, WI).

Publications

  • Type: Journal Articles Status: Published Year Published: 2022 Citation: Szerlag, K.D., Elavarthi, M., Siebecker, M.G., Gu, C., McCrone, C., Sparks, D.L. (2022). Systematic study of legacy phosphorus (p) desorption mechanisms in high-p agricultural soils. Minerals 12 (4), 458.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Jing, D., Yan, Y., Ren, T., Lu, X., Wang, X.M., Chen, J., Tan, W., Liu, F., Jaisi, D.P., Feng, X. (2021). Effects of nitrogen application rate on phosphorus transformation in an Alfisol: Results from phosphate-oxygen isotope ratios. Applied Geochemistry, 134(5):105094.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: 3. Li, Q., Yuan, H., Li, H., Main, C., Anton, J., and Jaisi, D.P. (2021). Tracing the sources of phosphorus along the salinity gradient in a coastal estuary using multi-isotopic proxies. Science of the Total Environment, 792, 148353.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: INVITED TALKS: 7. Young, E., Ross, D. and Jaisi, D.P. Phosphorus transport along the agricultural-riparian-stream continuum in cold climates: Managing for improved water quality. ACS Fall Meeting Aug 22-27, 2021, Atlanta GA [Invited Talk]. 8. Kathryn D. Szerlag. Advances in the use of synchrotron-based radiation for spatially-resolved imaging and spectroscopy to speciate phosphorus in soils. SAC review for the Beamline 8-BM (TES), Brookhaven National Lab, Upton, NY, USA, September 15, 2021. (Invited Talk) 9. Gray, K., Jaisi, D.P. Effects of salinity on biogeochemical cycling of phosphorus in coastal soil. 2nd Applied Microbial Ecology Laboratory Webinars: Understanding the role of bacterial communities in anthropogenic-impacted aquatic ecosystems. Sept 20, 2021[Invited]. 10. Campus, B., Jorquera, M., Gray, K., Jaisi, D.P. Jorquera, M.. Spatiotemporal distributions of phosphorus fractions in relation to phosphomonoesterase activity, and bacterial phosphomo-noesterase genes in surface sediments affected by anthropogenic activities. 2nd Applied Microbial Ecology [Invited]. 11. Jaisi, D.P. Holistic view of nutrient cycling in the agroecosystem. Department of Fishery Sciences, Auburn University, Auburn, AL (Jan 28, 2022) (Departmental seminar) [Invited]. 12. Szerlag, K.D. Tackling eutrophication using synchrotron-based radiation to determine phosphorus types in agricultural soils. Biology and Environmental Science Seminar Series. Westfield State University, Westfield, MA (April 22, 2022) (Departmental Seminar). 13. Jaisi, D.P. Tracing the sources of phosphorus in the Love Creek Watershed, Delaware. Center for the Inland Bay (CIB) (Oct 26, 2021) [Invited Talk]. 14. Sparks, D.L. Whither Soil Chemistry: Digging for Gold or Stuck in the Mud. Soil Science Society of America International Soils Meeting (SSSA, 2019). San Diego, CA, USA. Jan 6-9, 2019. (Invited Talk).
  • Type: Theses/Dissertations Status: Published Year Published: 2021 Citation: THESIS AND DISSERTATIONS: 1. Szerlag, K.D. (2021). Advances in the use of synchrotron-based spatially resolved imaging and spectroscopy to speciate phosphorus in soils. Doctoral dissertation, University of Delaware, Newark, DE. 2. Anton, J. M. (2021). Identification of phosphorus sources in the East Creek using isotope signatures of the residual phosphorus pool. Masters degree thesis; University of Delaware, Newark, DE.
  • Type: Book Chapters Status: Published Year Published: 2022 Citation: Jaisi, D.P., Mingus, K.A., Joshi, S.R., Upreti, K., Sun, M., McGrath, J., and Massudieh, A. (2022). Linking sources, transformation, and loss of phosphorus in the soil-water continuum in a coastal environment. In Multi-scale biogeochemical processes in soil ecosystems: Critical reactions and resilience to climate changes (Yu Yang, Marco Keiluweit, Nicola Senesi, and Baoshan Xing, editors).
  • Type: Journal Articles Status: Submitted Year Published: 2022 Citation: Jiang, Z-H. Wan, H.-Y., Yin, X.-J., Lin, J.-X., Wang, J., Lei, X.-T., Li, Q., Huang, S., Kang, K.Q., Jaisi, D.P., Zheng, A.R., Chen, Z.G. Recycling a prominent pathway of phosphorus cycling in Jiulong River Estuary. Water Research
  • Type: Journal Articles Status: Under Review Year Published: 2022 Citation: Li, Q., Gray, K., and Jaisi, D.P. Relative role of sediment transport and localized erosion in phosphorus hydrodynamics of the lower Susquehanna River and northern Chesapeake Bay, USA. JGR-Biogeoscience
  • Type: Journal Articles Status: Submitted Year Published: 2022 Citation: Szerlag, K.D., P. Northrup, R. Tappero, and D.L. Sparks. A multi-modal investigation of mounting techniques for soil P determination via �-XRF and �-XANES. Journal of Synchrotron Radiation
  • Type: Journal Articles Status: Submitted Year Published: 2022 Citation: Szerlag, K.D., P. Northrup, R. Tappero, M.G. Siebecker, D.L. Sparks. A multi-modal, micro-spectroscopic phosphorus speciation tale of two soils. Environmental Science and Technology
  • Type: Journal Articles Status: Submitted Year Published: 2022 Citation: Szerlag, K.D., F. Izaditame, P. Northrup, R. Tappero, M.G. Siebecker, D.L. Sparks. (Phosphorus solid phase speciation and Hedley sequential extraction residues: using �-XRF mapping and �-XANES to speciate P in agricultural soils. The Science of the Total Environment
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: KEYNOTE AND PLENARY TALKS: 1. Sparks, D.L. Shedding Light on Biogeochemical Processes in Earth's Critical Zone. Brazilian Critical Zone Symposium-Integrating Environmental Science. April 15-17, 2019. Piracicaba, Brazil. (Keyntoe Talk). 2. Sparks, D.L. Tracking Kinetic Transformations of Organomineral Associations in a Changing Climate. June 26, 2020, Goldschmidt Meeting, Honolulu, HI (Keynote Talk). 3. Sparks, D.L. Organomineral Association Stability in a Changing Environment. Nov. 11, 2021. Soil Science Society of America Meeting, Phoenix, AZ. (Keynote Talk). 4. Sparks, D.L. Research frontiers in environmental soil geochemistry. In interfacial processes and soil health. Nov. 9, 2020. Huazhong Agricultural University, Wuhan, China. (Plenary Talk). 5. Sparks, D.L. Frontiers in biogeochemical cycling of trace elements in a changing environment. Plenary Presentation. International Conference on the Biogeochemical Cycling of Trace Elements. May 5-8, 2019. Nanjing, China. (Plenary Talk). 6. Sparks, D.L. Impact of a changing environment on soil chemical processes. The Leo M. Walsh Distinguished Lectureship in Soil Science. University of Wisconsin, Madison. April 24, 2019. (Distinguished lecture).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2021 Citation: MEETING PRESENTTIONS: 1. Szerlag, K.D., Northrup, P. Tappero, R. Siebecker, M.G., and Sparks, D.L. (2021). Advances in the use of synchrotron-based spatially resolved imaging and spectroscopy to speciate phosphorus in soils. ASA-CSA-SSSA National Meeting. Salt Lake City, UT. November 7-10, 2021. 2. Jaisi, D.P., Hollenback, A., Stout, L., Massudieh, A., Guan, Y. Advanced analytical methods for linking phosphorus sources and transformation in the soils and waters. 22nd World Congress of Soil Sciences, Jul 31- Aug 5, 2022. Glasgow, UK. 3. Anton, J., Jiang, Z., Jaisi, D.P. Residual and recalcitrant phosphorus pools and isotope signatures to track the legacy sources. 22nd World Congress of Soil Sciences, Jul 31- Aug 5, 2022. Glasgow, UK. 4. Gray, K., Jaisi, D.P., Stout, L., Sparks, D.L. and Jaisi, D.P. Effects of salinity on biogeochemical cycling of phosphorus in coastal soil. Goldschmidt 4-9 July, 2021. 5. Jaisi, D., Li, Q., Anton, J., and Mingus, K. Impact of agricultural runoff of phosphorus in coastal water quality. AGROSYM2021. Jahorina, Bosnia Herzegovina, Oct 6-11, 2021.


Progress 05/15/20 to 05/14/21

Outputs
Target Audience:Academics; farmer and commodity groups; federal, state government including secretary of the state, local government, and stakeholders on the nutrient management Changes/Problems:Pandemic caused delay in research. We applied for 1 yr of NCE, which is approved early in 2021. What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: Kathryn Szerlag (Ph.D. degree completed, 2016-2020) completed both experimental and analytical portion of her research using conventional and advanced soil characterization methods. She used synchrotron method to identify P speciation using the tender energy X-ray absorption spectroscopy (TES) beamline (8-BM) at NSLS II synchrotron light source at Brookhaven National Laboratory (BNL). She graduated and is now a tenure-track assistant professor position at Westfield State University, Massachusetts. Qiang Li (Ph.D. degree completed, 2016-2020)(partially funded only in research) completed dissertation research on sources and cycling of phosphorus in estuaries. He used isotope methods of light elements (C, N, H, O, and PO4) to track sources of nutrient in small and larger watershed. He graduated in 2020 and is a postdoctoral associate in University of Wisconsin, Madison. Jessica Anton (MS degree, defending summer 2021) completed experimental and isotope analyses of residual P pools and complemented with recalcitrant P and now working on the finalizing her thesis. She is scheduled to defend next month but already started career in a military research institute in Aberdeen, MD. Undergraduate student. Two undergraduate student (funded from unversity internships), Sarah Tuoni and M. Elavarthi, are trained in the basics of soil P chemistry in this project. Sarah undertook P pool and processing of nutrient biogeochemistry and Elavarthi worked in the P sorption project. Elavarthi presented in the DENIN Undergraduate Research Symposium in 2020 and was winner among undergraduate presenters. This year, the project has provided the following opportunities to two graduate and one undergraduate student supported by this project: For graduate students: the training was largely on honing skills on data analysis and interpretation. It includes manuscript writing, highlighting key scientific findings, they are trained on reviewing the manuscript and critical thinking skills. Further training included career preparation, interviews, and planning. Jessica Anton landed a job in the military research institute, Qiang Li a postdoc in reported university, and Kathryn Szerlag an assistant professor at Westfield State University. Both PIs are highly committed and have track records of taking additional approaches as needed to achieve stated goals for students. For undergraduate students: i) Training on soil chemistry, including P speciation and method of extraction. Scientific research and research approaches, generating experimental data, quality control, and the interpretation of data. How have the results been disseminated to communities of interest?Scientific findings are published in peer-reviewed journals, presented at the national/international meeting and conferences and the results are disseminated via publications and presentations. Key interactions include: Four publications, two under review (see details in the accomplishment section). One keynote talk and one invited talk One PhD dissertations Four volunteered talks by graduate and undergraduate students and collaborators in the project (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?The scientific achievement of this project exceeded the research objectives listed in the proposal. The project has achieved stated goals and milestones. The NCE applied for and approved will largely be used for wrapping up the outcome of the project into manuscripts. Research findings will be disseminated via publication, presentations at professional society meetings, and to stakeholders at the state and regional levels. Both PIs are dedicated to developing a highly-skilled workforce. More training and activities will be planned in the coming years as the project continues.

Impacts
What was accomplished under these goals? Major activities: Since last year's research progress report, listed below are major activities: Research experimentation and analysis: Series of measurement to characterize the physicochemical properties of high P, Mid-Atlantic agricultural soils and to speciate legacy P using advanced tender energy X-ray absorption spectroscopy (TES) are completed. For the synchrotron work, we used the National Synchrotron Light Source II (NSLS II) beamline 4-BM (XFM) to collect the hard energy (Fe, Ca, Mn, etc.) micro X-ray fluorescence (µ-XRF) maps at the same location as the tender energy (P, Al, S, Si) maps. Further, micro X-ray absorption near edge structure (µ-XANES) spectroscopy were to identify both the speciation and hotspot of P minerals in soil. Completed research on specific isotope signatures of residual and recalcitrant P pools in a watershed. The series of analyses include residual P pool extraction, preprocessing, and processing for isotopes and silver phosphate precipitation and measurement of isotopes. Because this is a new method development on isotope integrity, it took time. We are in safe position to wrap up during the first NCE period of this award. Other activities: A major instrumentation proposal (EGP-USDA) submitted. It included preliminary data generated from this award. Initiated the development of Orbitrap-based method for isotope measurement on organic P molecules in controlled incubation studies and selected field samples. Edited a special issue in Pedosphere journal as the guest editor with Xiaoyuan Yan and Xu Zhao (both from Institute of Soil Sciences Chinese Academy of Sciences, China) on 'Agricultural and environmental challenges in agroecosystems'. Edited a special issue in Soil System Journal on "Challenges and successes in identifying the transfer and transformation of phosphorus from soils to open waters and sediments" with Erich Young (USDA-ARS) and Donald Ross (U Vermont). Collaborations with different researchers initiated/continued i) Xu Zhao and Yu Wang (Institute of Soil Sciences Chinese Academy of Sciences, ii) David O'Connell (Trinity College, Ireland), iv) Milko Jorquera (University of La Frontera, Chile), iv) Erich Young (USDA-ARS). These collaborations started early in the project strengthened during this project year and yielded collaborative publications (see below). An international grant proposal submitted, led by Milko Jorquera (University of La Frontera, Chile) with collaborators from US, Chile and Japan. A collaborative proposal to support a postdoc between Milko Jorquera and Jaisi lab submitted. Qiang Li, partially supported in research, completed his PhD in summer 2020 and started a postdoc position in University of Wisconsin, Madison. Jessica Anton, student funded in this project, is planning to defend her thesis this summer. One undergrad is being trained in the project to wrap up in the NCE period. The major research findings include: Research findings are included below in three most representative abstracts from published book chapter, paper, and meeting presentation: Tracing the sources of phosphorus along the salinity gradient in a coastal estuary using multi-isotopic proxies (STOTEN, under review) Eutrophication in coastal water has compromised ecosystem services such as tourism and fishery production. Identification of phosphorus (P) sources and their load contributions are required for the development of effective nutrient management plans. In this research, multi-isotope proxies were applied to track P sources and evaluate their relative contributions in Love Creek, a coastal estuary in Delaware. The carbon, nitrogen, and phosphate oxygen isotopes of agricultural soils under different agricultural practices are generally similar even though their concentrations are distinctly different from forest soils. Comparison of these parameters among potential land sources (agricultural soils, forest soils, septic wastes, and plant debris) and sink (colloids in water) revealed that the plant debris and soils from forest sources are likely dominant sources of P in freshwater sites. The contribution of terrestrial P sources gradually decreased along the salinity gradient. Agricultural soil sources dominate the saline water portion of the creek. The variation of P loads due to weather-related discharge, changing land use and activities, and seasons were high and reflected the limitation of accurate estimation of sources. Overall, these results provide improved insights into potential sources and biogeochemical processes in the estuary, which are expected to be useful for water quality monitoring programs. Phosphorus Transport along the Cropland-Riparian-Stream Continuum in Cold Climate Agroecosystems: A Review (Soil System, DOI: 10.3390/soilsystems5010015) Phosphorus (P) loss from cropland to ground and surface waters is a global concern. In coldclimates (CCs), freeze-thaw cycles, snowmelt runoff events, and seasonally wet soils increase P loss potential while limiting P removal effectiveness of riparian buffer zones (RBZs) and other practices. While RBZs can help reduce particulate P transfer to streams, attenuation of dissolved P forms is more challenging. Moreover, P transport studies often focus on either cropland or RBZs exclusively rather than spanning the natural cropland-RBZ-stream gradient, defined here as the cropland-RBZ-stream continuum. Watershed P transport models and agronomic P site indices are commonly used to identify critical source areas; however, RBZ effects on P transport are usually not included. In addition, the coarse resolution of watershed P models may not capture finer-scale soil factors affecting P mobilization. It is clear that site microtopography and hydrology are closely linked and important drivers of P release and transport in overland flow. Combining light detection and ranging (LiDAR) based digital elevation models with P site indices and process-based models show promise for mapping and modeling P transport risk in cropland-RBZ areas; however, a better mechanistic understanding of processes controlling mobile P species across regions is needed. Broader predictive approaches integrating soil hydro-biogeochemical processes with real-time hydroclimatic data and risk assessment tools also hold promise for improving P transport risk assessment in CCs. Integration of educational activities to research activities. Two major ways used to integrate educational activities on research done on this project year are: In Fall 2020 class, students were made into groups and worked on a project (25% grade weight). The project was to for identification of sources of P in a mini-watershed. They collection of soil, plant, and water samples preprocessed before sending to analytical lab for elemental analyses. They analyzed nutritional elements (C,N,P, and S). Each group prepared reports on source identification and presented in the class. Research findings from this project (this year and past years) were incorporated into graduate courses of the PIs (PLSC 645: Biogeochemical Cycling of Nutrients and PLSC 608 Environmental Soil Chemistry) in Fall 2020 and Spring 2021 semesters.

Publications

  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Campos, M., Rilling, J.I., Acu�a, J.J., Valenzuela, T., Larama, G., Pe�a-Cort�s, F., Ograme, A., Jaisi, D.P., Jorquera, M.A. (2021). Spatiotemporal variations and relationships of phosphorus, phosphomonoesterases, and bacterial communities in sediments from two Chilean rivers. Science of the Total Environment, 776, 145782.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Wang, Y., Chen, H., Wang, L., Zhu, W.-B., Yuan, J.H., Jaisi, D.P., Zhao, X., Wang, S.-Q. (2021). Using diffusive gradients in thin films technique for in situ measuring labile phosphorus around Oryza sativa L. roots in flooded paddy soils. Pedosphere, 31, 76-82
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Yan, X., Zhao, X., and Jaisi, D. (2021). Agricultural and environmental challenges in agroecosystems. Preface special issue on Pedosphere 31, 1-2
  • Type: Journal Articles Status: Published Year Published: 2020 Citation: OConnell, D.W., Ansems, N., Kukkadapu, Jaisi, D., Cade-Menun, B., Hu, Y., Orihel, D., Wiklund, J., Hall, R., Chessell, H., Behrends, T., and Van Cappellen, P. (2020). Changes in sedimentary phosphorus burial following artificial eutrophication of Lake 227, Experimental Lakes Area, Ontario, Canada. Journal of Geophysical Research- Biogeoscience, 125 (8), e2020JG005713
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Young, E.O., Ross, D. S., Jaisi, D.P., and Vidon, P.G. (2021). Closing phosphorus transport gaps along the croplandriparianstream continuum in cold climate agroecosystems of the USA: a review. Soil System, 2021, 5, 1- 20.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Jiang, Z., Jaisi, D.P. Chen, Z. Biological cycling of phosphorus in river estuary: A case study in Jiulong River Estuary in China Using Phosphorus speciation and stable isotopes. Soil Science Society Soil Science Society of America Annual Meeting, Virtual. Nov 9-13, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Jaisi, D.P., Li, J., Sun, M., Li, Q., and Mingus, K. Impact of agricultural runoff of phosphorus in water quality: Implication of agro-ecosystems management. XI International Scientific Agriculture Symposium "Agrosym 2020. Bosnia and Herzegovina (virtual), 8-9 October 2020
  • Type: Journal Articles Status: Under Review Year Published: 2021 Citation: Jiang, Z.-H., Yin, X.-J., Lin, J.-X., Wang, J., Lei, X.-T., Li, Q., Huang, S., Kang, K.-Q., Zheng, A.-I., Jaisi, D.P., Chen, Z.-G. (2020). Recycling a prominent pathway of phosphorus cycling in River Estuary. Journal of Geophysical Research  Biogeosciences (In review).
  • Type: Journal Articles Status: Under Review Year Published: 2021 Citation: Jing, D., Yan, Y., Ren, T., Lu, J., Wang, X., Chen, J., Tan, W., Liu, F., Jaisi, D.P., Feng, X.-H. Effects of nitrogen application rate on phosphorus transformation in an alfisol: Results from phosphate-oxygen isotope ratios. Geochemical Transection (In review)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Invited talk. Jaisi, D. Phosphorus sources, cycling and impact in coastal water quality. 1st Applied Microbial Ecology Laboratory Webinar: Research network for understanding the role of bacterial communities on organic phosphorus recycling in anthropogenic-impacted aquatic ecosystems (NET-PO), Temuco, Chile (virtual). Sept 17, 2020.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Keynote talk. Jaisi, D. Understanding of sediment provenance and diagenesis using stable isotopes in phosphate. Webinar series on Geo-science for Sustainable Development. Organized by Institute of Himalayan Risk Reduction, Nepal. Sept 06, 2020.
  • Type: Theses/Dissertations Status: Published Year Published: 2020 Citation: Li, Qiang. Characterization of phosphorus sources and bioavailability at different hydrodynamic gradients in coastal environments. PhD Dissertation, University of Delaware, Summer 2020
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Musser, M. and Jaisi, D. (2020). Phosphorus sources, bioavailability, and cycling in the Murderkill River, Delaware. Goldschmidt 2020, Virtual, Jun 21-26, 2020.


Progress 05/15/19 to 05/14/20

Outputs
Target Audience:Academics; farmer and commodity groups; federal, state government including secretary of the state, local government, and stakeholders on the nutrient management Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: Kathryn Szerlag (Ph.D. student, intake Fall 2016) completed a dominant portion of this research using conventional and advanced soil characterization methods. She undertakes research primarily on P speciation using the tender energy X-ray absorption spectroscopy (TES) beamline (8-BM) at NSLS II synchrotron light source at Brookhaven National Laboratory (BNL). She presented her research in various professional societies, including Soil Science Society of America (San Antonio, 2019), ACS meeting (Philadelphia, 2020), Goldschmidt (Barcelona, 2019) and at University of Torino. She accepted the offer of a tenure-track assistant professor position in Massachusetts. Jessica Anton (MS student, intake Fall 2018) is have completed the majority of isotope analyses of three residual P pools and complementing with recalcitrant P. The outcome of her first research was presented at the SSSA meeting in Nov 2019. She expects to complete here degree during this project year. Undergraduate student. An undergraduate student, M. Elavarthi, was trained in the basics of soil P chemistry in this project. She undertook the P sorption project and the outcome of the research was presented and the winner in the DENIN Graduate Student Research Symposium in 2020. This year, the project has provided the following opportunities to two graduate and one undergraduate student supported by this project: For graduate students: i) Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train undergraduate students, to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students on manuscript writing, highlighting key scientific findings; they will be trained on reviewing the manuscript and critical thinking skills; v) both students completed Ph.D. and MS candidacy exam last year and writing thesis/dissertation in the 4th project year in which they were trained to developing research questions and research hypotheses, and vi) improving speaking and poster/presentation skills. While this will evolve over time, both PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals for the students. For undergraduate students: i) Training on soil chemistry, including P speciation and method of extraction. Scientific research and research approaches, generating experimental data, quality control, and the interpretation of data. How have the results been disseminated to communities of interest?Scientific findings are published in peer-reviewed journals, presented at the national/international meeting and conferences and the results are disseminated via publications and presentations. Key interactions include: Three publications: two peer-reviewed publications in JGR- Biogeoscience and a book chapter (see details in the accomplishment section). Four invited talks in ISOTOPES 2019 (Germany), Asian Institute of Technology (Thailand), University of Turino (Italy), and Soil Science Society of America annual meeting (USA). See details in the accomplishment section. Ten volunteered talked by graduate and undergraduate students and collaborators in the project (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?The project in on track with the stated time and milestones in the proposal. Remaining experiments and analyses continue to achieve results to meet or exceed the research objectives listed in the fourth year of the project. Research findings will be disseminated via publication, presentations at professional society meetings, and to stakeholders at the state and regional levels. Both PIs are dedicated to developing a highly-skilled workforce. More training and activities will be planned in the coming years as the project continues.

Impacts
What was accomplished under these goals? Major activities: Since last year's research progress report, listed below are major activities: Completed the data collection for the two specific objectives outlined previously; first to characterize the physicochemical properties of high P, Mid-Atlantic agricultural soils, and second, to speciate legacy P using advanced tender energy X-ray absorption spectroscopy (TES). We completed the desorption experiments using KCl, HNO3, Na2SiO3, and K2SO4. For the synchrotron work, we used the National Synchrotron Light Source II (NSLS II) beamline 4-BM (XFM) to collect the hard energy (Fe, Ca, Mn, etc.) micro X-ray fluorescence (µ-XRF) maps at the same location as the tender energy (P, Al, S, Si) maps collected at NSLS II beamline 8-BM (TES). To better investigate the P chemistry, we also collected micro X-ray absorption near edge structure (µ-XANES) spectroscopy at TES. We were able to successfully overlay the two maps from both beamlines for all samples to determine the P colocation at hotspots with both tender and hard energy elements. This year, we completed the synchrotron data collection for both the soil thin sections and the powder mounted samples. Data analysis will continue in the 4th project year. Completed data collection for our third specific objective on the validation of the Hedley sequential extraction using µ-XRF mapping and µ-XANES analysis. We completed a modified Hedley sequential extraction on ten soils from the East Creek watershed and throughout the Delmarva Peninsula. Solution data analysis is nearly complete. On a select two soils, we harvested the soil residual following each step in the extraction for µ-XRF mapping (TES and XFM) and µ-XANES (TES). We completed the multi-modal µ-XRF and µ-XANES collection on one soil in March 2019, and the second soil was completed in June 2019 and March 2020. Synchrotron data analysis is being done and is nearly complete. Ongoing data generation on specific isotope signatures of residual and recalcitrant P forms. Series of samples from soils and waters (creek) were collected and are being analyzed. Because this is a new method development on isotope integrity, it took time, but the progress is satisfactory and we are moving forward with the newly developed method. The series of analyses include residual P pool extraction, preprocessing, and processing for isotopes and silver phosphate precipitation are undergoing. Once the university opens, isotope data generation and analyses will be done. Ongoing and future works/plans on additional data generation are impacted by Covid-19 closure, but finalizing data analysis and completing manuscripts for the three objectives are undergoing at this time. The major research findings include: Research findings are included below in three most representative abstracts from published book chapter, paper, and meeting presentation: Linking sources, transformation, and loss of phosphorus in the soil-water continuum in a coastal environment. In 'Multi-scale biogeochemical processes in soil ecosystems: Critical reactions and resilience to climate changes' (Yu Yang, Marco Keiluweit, Nicola Senesi, and Baoshan Xing, editors) Understanding of phosphorus (P) cycling in the soil-water continuum requires novel techniques that can connect sources, chemical reactivity, and pathways of transformation. In this chapter, we synthesize recent results on soil chemistry, stable isotopes, and Bayesian-based elemental modeling from agricultural soil and field-ditch-creek transect in a coastal estuary in the Chesapeake Bay watershed. Analysis of 18O labeled P in soil pools confirmed the applicability of the sequential extraction method for soil P study and the combination of these two methods aided on identifying the relative rates of biological cycling of soil P pools. In agricultural soils, where P application usually exceeds the agronomic needs, readily available P pools were found to be transformed into more recalcitrant P pools. Among different P sources in a watershed that can impact downstream water quality, agricultural fields, streambanks, and river bottom sediments were found to be major sources, but their relative roles varied at the upstream and downstream portion of the creek. Tides are found to play two primary functions--forming particulate matter from estuarine sources and importing upstream and diluting the P load from headwater. These findings provide an improved understanding of sources and biogeochemical processes of P in upland soils and loss to open waters and competing needs of resources (e.g., crop and water) that are useful to identify ways to evaluate the trade-off and minimize undesirable consequences. Loading and bioavailability of colloidal phosphorus in the estuarine gradient of the Deer Creek-Susquehanna River transect in the Chesapeake Bay. Journal of Geophysical Research: Biogeosciences, 124, DOI: 10.1029/ 2019JG005135 Phosphorus (P) overloading is a major cause of surface water eutrophication and bottom water hypoxia. The incomplete understanding of different P pools and their corresponding bioavailability in the continuum from sources and sinks has limited the development of appropriate nutrient management strategies. Here we apply multi stable isotope proxies to track colloids and identify whether specific P pools in colloids are biologically cycled at the Deer Creek-Susquehanna River mouth stretch. Results showed that NaOH-Pi is the most dominant P pool in the summer and winter seasons. Oxygen isotope values (d18OP) of NaOH-Pi and HNO3-Pi pools of different size fractions of colloids are much heavier than the ranges of equilibrium values in the ambient water, which suggest that these two pools are recalcitrant against biological uptake. It further means isotopic signatures of these P pools could be used to identify the sources of colloids. Carbon (C) and nitrogen (N) isotope compositions of colloids showed that the contribution of terrestrial sources gradually decreases downstream of the river toward the bay and Deer Creek contributes disproportionately high amounts of colloids to the Susquehanna River. These findings provide valuable information on the loading of colloids and relative bioavailability of colloidal P pools in estuarine ecosystems. Phosphorus solid phase speciation and Hedley sequential extraction residues: using multi-modal μ-XRF mapping and μ-XANES to speciate legacy P in agricultural soils. Soil Science Society of America Annual Meeting, San Antonio. Nov 10-14, 2019. As an essential plant nutrient, phosphorus (P) is often applied to agricultural fields in the form of animal manure or fertilizer. Excess P then becomes detrimental to aquatic ecosystems by causing eutrophication. Extensive research about general P pools in soils using sequential extractions, such as the Hedley extraction, has been done over the years. The Hedley extraction is a critical method used world-wide. However, sequential extractions cannot directly identify the individual solid phase P species within the general P pools and how they may vary. This is information necessary to determine P bioavailability and environmental susceptibility. By utilizing multi-modal µ-XRF mapping followed by µ-XANES spectroscopy in this research, we will present a direct investigation of the P pools in sequential extraction residues from each step of the Hedley method. The spectroscopic data will be compared to wet chemical data to identify what locally causes the differences in bulk solubility of P species.

Publications

  • Type: Book Chapters Status: Accepted Year Published: 2019 Citation: Jaisi, D.P., Mingus, K.A., Joshi, S.R., Upreti, K., Sun, M., McGrath, J., and Massudieh, A. Linking sources, transformation, and loss of phosphorus in the soil-water continuum in a coastal environment. In Multi-scale biogeochemical processes in soil ecosystems: Critical reactions and resilience to climate changes (Yu Yang, Marco Keiluweit, Nicola Senesi, and Baoshan Xing, editors)
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Li, Q., Yuan, H., Li, H., Wang, D., Jin, Y., and Jaisi, D.P. Loading and bioavailability of colloidal phosphorus in the estuarine gradient of the Deer Creek-Susquehanna River transect in the Chesapeake Bay. Journal of Geophysical Research: Biogeosciences, 124, https://doi.org/10.1029/ 2019JG005135
  • Type: Journal Articles Status: Accepted Year Published: 2020 Citation: OConnell, D.W., Ansems, N., Kukkadapu, Jaisi, D., Cade-Menun, B., Hu, Y., Orihel, D., Wiklund, J., Hall, R., Chessell, H., Behrends, T., and Van Cappellen, P. Changes in sedimentary phosphorus burial following artificial eutrophication of Lake 227, Experimental Lakes Area, Ontario, Canada. Journal of Geophysical Research- Biogeoscience (accepted w minor rev).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Invited talk: Jaisi, D.P., Stout, L., Moller, S., Joshi, S.R., Li, J., Chang, S.-J., Li, H., Blake, R.E. Linking phosphate oxygen isotope effects to phosphorus cycling, from molecular to ecosystem scales. Isotopes 2019, Raitenhaslach, Germany, July 7  12, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Invited talk: Shi, W., Min, J., Yan, T., Qiao, Q., Ma, Y., Jaisi, D.P., and Hu, H. Emission flux of fertilizer nitrogen to the environment and its control technology in the lower Yangtze region of China. Soil Science Society of America Annual Meeting, San Antonio. Nov 10-14, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Invited talk: Jaisi D.P. Developing isotope methods for tracing nutrient sources in waters. Asian Institute of Technology, Bangkok, Thailand. Sept 17, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Invited talk: Szerlag, K.D., P. Northrup, R. Tappero, M.G. Siebecker, D.P. Jaisi, D.L. Sparks. The Solid Phase Speciation of Legacy Phosphorus in US Mid-Atlantic Agricultural Soils Using �-XRF Mapping and �-XANES. The University of Torino, Torino, Italy, Aug 27, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Szerlag, K.D., Izaditame, F., Northrup, P., Tappero, R., Jaisi, D.P. and Sparks, D.L. Phosphorus solid phase speciation and hedley sequential extraction residues: using multi-modal ?-XRF mapping and ?-XANES to speciate legacy P in agricultural soils. ASA-CSA-SSSA National Meeting, San Antonio. Nov 10-14, 2019 (Oral).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Anton, J., Mingus, K., Massoudieh, A., and Jaisi, D.P. Determining sources of phosphorus using isotope signatures in residual and recalcitrant phosphorus pools in East Creek, Chesapeake Bay. ASA-CSA-SSSA National Meeting, San Antonio. Nov 10-14, 2019 (Poster).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Li, Q., Yuan, H., Main, C., Li, H. and Jaisi, D.P. Tracing the sources of phosphorus in the Love Creek Watershed, Delaware. ASA-CSA-SSSA National Meeting, San Antonio. Nov 10-14, 2019 (Oral).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Feng, X., Jing, D., Jaisi, D.P., Yan, Y., Ren, T., Lu, J., Wang, X., Tan, W., and Liu, F. Effect of nitrogen application rate on phosphorus transformation in an agricultural soil: a phosphate oxygen isotope study. ASA-CSA-SSSA National Meeting, San Antonio. Nov 10-14, 2019 (Oral).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: OConnell1, D., Ansems, N., Kukkadapu, R. Jaisi,D.P., Cade-Menun, B., Hu, Y., Orihel, D, Wiklund, J., Hall, J., Chessel, H., Behrends, T., Van Cappellen, P. Sedimentary phosphorus speciation dynamics following artificial eutrophication of Lake 227, Experimental Lakes Area, Ontario, Canada by Phosphorus: Environmental fluxes, sustainable use and recovery. EGU 2020, May 4-8, 2020 (Oral).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Szerlag, K.D., Izaditame, F., P. Northrup, R. Tappero, M.G. Siebecker, D.P. Jaisi, D.L. Sparks. 2020. Speciation of legacy P in soils using multi-modal �-XRF mapping and �-XANES. ACS Spring National Meeting, Philadelphia, PA, USA, Mar 22-26 (Oral).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: *Elavarthi, M., K.D. Szerlag, D.L. Sparks. Legacy phosphorus desorption from US Mid-Atlantic agricultural soils. ACS Spring National Meeting, Philadelphia, PA, USA, March 22-26 (Poster).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Elavarthi, M., K.D. Szerlag, D.L. Sparks. Legacy phosphorus desorption from US Mid-Atlantic agricultural soils. DENIN Graduate Student Research Symposium, University of Delaware, Newark, USA, Mar 5, 2020. (Poster, winner)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Szerlag, K.D., P. Northrup, R. Tappero, M.G. Siebecker, D.P. Jaisi, D.L. Sparks. 2019. Direct detection of solid-phase phosphorus speciation in agricultural soils using paired �-XRF mapping and �-XANES. Goldschmidt. Barcelona, Spain, Aug 17-23, 2019. (Oral, flash talk, and poster)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2020 Citation: Elavarthi, M., K.D. Szerlag, D.L. Sparks. 2019. Legacy phosphorus desorption and �XANES speciation from US Mid-Atlantic agricultural soils. DENIN Scholars Summer Undergraduate Research Symposium, Newark, Delaware, USA, Aug 15, 2020 (Poster).


Progress 05/15/18 to 05/14/19

Outputs
Target Audience:Academics; farmer and commodity groups; federal, state government including secretary of the state, local government, and stakeholders on the nutrient management Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: Kathryn Szerlag (Ph.D. student, intake Fall 2016) undertaking major portion of this research using conventional and advanced soil characterization methods. She undertakes research primarily on P speciation using the tender energy X-ray absorption spectroscopy (TES) beamline (8-BM) at NSLS II synchrotron light source at Brookhaven National Laboratory (BNL). She presented her research at the Soil Science Society of America annual meeting in San Diego and another aspect of her research outcomes is going to be presented in the Goldschmidt meeting in Spain. Jessica Anton (MS student, intake Fall 2018) is being trained on isotope methods and forms and fate of residual and recalcitrant P. The outcome of her first research is going to be presented at the SSSA meeting in Nov 2019. She continues to work on this project in next project year. C. McCrone and M. Elavarthi (two undergraduate interns) were trained on the project regarding chemical speciation of phosphorus. Their works on Hedley extraction and P desorption from soil were presented in DENIN Scholars Spring Undergraduate Research Symposium at the University of Delaware in May 2019. Sunendra Joshi and Kristi Mingus completed their MS and PhD degree, but their research outcome of this project just published (Joshi et al. (2018) and Mingus et al. (2019)). This year, the project has provided following opportunities to two graduate and two undergradte students supported by this project: For graduate students: i) Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train undergraduate students, to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students on manuscript writing, highlighting key scientific findings; they will be trained on reviewing manuscript and critical thinking skills; v) both students undergoing Ph.D. and MS candidacy exam and writing research proposal, here they will be trained to developing research questions and research hypotheses, and vi) improving speaking and poster/presentation skills. While this will evolve over time, both PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals for the students. For undergraduate students: i) Training on soil chemistry including P speciation and method of extraction. Scientific research and research approaches, generating scientific data, quality control and quality assurance, interpretation of data. How have the results been disseminated to communities of interest?Scientific findings are published in peer reviewed journals, presented at the national/international meeting and the conferences and the results are disseminated via publications and presentations. Key interactions include: Three peer-reviewed publications in Environmental Science & Technology, Soil Systems and Science of the Total Environment (see details in the accomplishment section). Two invited talks at the University of Delaware, State Key Laboratory of Chinese Academy of Sciences (see details in the accomplishment section). Sevenvolunteered talked by graduate and undergraduate students in the project (see details in the accomplishment section). What do you plan to do during the next reporting period to accomplish the goals?The project has taken momentum and series of experiments and analyses being done and continue to achieve results to meet or exceed the research objectives listed in the third and future years. Research findings will be disseminated via publication, presentations at professional society meetings; stakeholders at state and regional level. Both PIs are dedicated to developing the highly skilled workforce. More training and activities will be planned in coming years as the project continues.

Impacts
What was accomplished under these goals? Major activities include: The main objectives to identify the chemical forms and bonding environments of recalcitrant and residual phosphorus (P) pools and assess potential mechanisms that stabilize or mobilize P pools. Since last year's research progress report, we have nearly completed the two specific objectives outlined previously; first to characterize the physicochemical properties of high P, Mid-Atlantic agricultural soils, and second, to speciate legacy P using advanced tender energy X-ray absorption spectroscopy (TES). We continued the desorption experiments using KCl, HNO3, and Na2SiO3. For the synchrotron work, we used the National Synchrotron Light Source II (NSLS II) beamline 4-BM (XFM) to collect the hard energy (Fe, Ca, Mn) micro X-ray fluorescence (µ-XRF) maps at the same location as the tender energy (P, Al, S, Si) maps previously collected at NSLS II beamline 8-BM (TES). We were able to successfully overlay the two maps to determine the P colocation with both tender and hard energy elements. To better investigate the P chemistry on the surface of the soil particles, we also collected µ-XRF maps (at TES and XFM) and micro X-ray absorption near edge structure (µ-XANES) spectroscopy at TES of the intact particle surface by using powder mounted samples (instead of thin sectioned samples where the particle is sliced apart). Lastly, we collected the bulk P K-edge XANES of the soils at SSRL beamline 14-3 for which we will use our µ-XANES for data analysis. Three publications were made on residual and recalcitrant P in soils (Joshi et al., 2018 SS), particulate matter in the creek water (Mingus et al., 2019, ES&T), and a lake sediment (Yuan et al., 2019). Research on third specific objective is started and working toward the validation of the Hedley sequential extraction using µ-XRF mapping and µ-XANES analysis. We completed a modified Hedley sequential extraction on ten soils from the East Creek watershed and throughout the Delmarva peninsula. On a select two soils, we harvested the soil residual following each step in the extraction for µ-XRF mapping (TES and XFM) and µ-XANES (TES). We completed the µ-XRF and µ-XANES collection on one soil in March 2019 and the second will be analyzed in June 2019. Additionally, we also collected the bulk P K-edge XANES (SSRL 14-3) on the two soils and residuals. Results from specific objectives one through three will be prepared for publication. Future plans for the presentation of this work include the 2019 Goldschmidt conference in Barcelona, Spain (August 18-23). To identify the specific isotope signatures of residual and recalcitrant P forms, series of samples from soils and waters (creek) were collected and are being analyzed. Because this is an untested method, new method development for the isotope integrity is underway. The series of analyses include the Hedley extraction, preprocessing for isotopes and silver phosphate precipitation and isotope measurements are being done. Results from this specific work will be presented in SSSA meeting in San Antonio, TX (November, 10-13, 2019). Continued work on specific objectives one and two include surface area analysis, ZPC, and ammonium oxalate and DCB extractions. Future work for specific objective three include µ-XRF (TES and XFM) and µ-XANES (TES) of the Hedley soil residuals. Solution 31P NMR will be performed for these soils as well. The residual soil isotopes will be further investigated and results from synchrotron and isotope methods will be compared and further discussions will be made. As needed, additional experiments will be planned to make consistent comparison and correlation of methods. The major research findings include: Three most representative abstracts from published papers and meeting presentation are included below: Sources and Pathways of Formation of Recalcitrant and Residual Phosphorus in an Agricultural Soil (Soil Syst. 2018, 2, 45; doi:10.3390/soilsystems2030045): Phosphorus (P) is an essential nutrient for sustaining life and agricultural production. Transformation of readily available P into forms that are unavailable to plants adds costs to P replenishment which eventually translates into lower agronomic benefits and potential loss of soil P into runoff may degrade water quality. Therefore, understanding the sources and pathways of the formation of residual P pools in soils is useful information needed for the development of any technological or management efforts to minimize or inhibit the formation of such P pool and thus maximize availability to plants. In this research, we paired phosphate oxygen isotope ratios (δ18OP) with solid-state 31P NMR and quantitative XRD techniques along with general soil chemistry methods to identify the precipitation pathways of acid-extracted inorganic P (Pi) pools in an agricultural soil. Based on the comparison of isotope values of 0.5 mol L-1 NaOH-Pi, 1 mol L-1 HCl-Pi, and 10 mol L-1 HNO3-Pi pools and correlations of associated elements (Ca, Fe, and Al) in these pools, the HNO3-Pi pool appears most likely to be transformed from the NaOH-Pi pool. The narrow range of isotope values of acid-Pi pools in shallow (tilling depth) and below (where physical mixing is absent) is intriguing but likely suggest leaching of particle-bound P in deeper soils. Overall, these findings provide an improved understanding of the sources, transport, and transformation of acid-Pi pools in agricultural soils and further insights into the buildup of legacy P in soils. Stable isotopes and Bayesian modeling methods of tracking sources and differentiating bioavailable and recalcitrant phosphorus pools in suspended particulate matter (Environ. Sci. Technol. 2019, 53, 69−76; DOI: 10.1021/acs.est.8b05057) Understanding the sources of different phosphorus (P) pools and their bioavailability under imposed biogeochemical environments in a watershed is limited largely due to the lack of appropriate methods. In this research, phosphate oxygen isotope ratios and Bayesian modeling on fingerprinting elements were applied as two novel methods to identify sources and relative recalcitrancy of particulate P pools suspended in water in the continuum of sources from land to the mouth of a coastal estuary to the Chesapeake Bay. Comparative analyses of sizes, relative ratios, and oxygen isotope values of particulate P pools in the creek water suggested that the NaHCO3−P pool was bioavailable, whereas NaOH−P and HCl−P pools were recalcitrant during P transport along the creek. Agricultural field soil, streambank, and river bottom sediments were major sources of particulate P and their contributions varied significantly at the headwater and downstream regions of the creek. Bayesian modeling based on fingerprinting elements suggested that tides played a major role in forming particulate matter from estuarine sources at the creek mouth region and importing it upstream. These findings provide new insights into the origin and fate of particulate P and the fidelity of isotope and fingerprinting methods in source tracking of P in tidally influenced watersheds. ?

Publications

  • Type: Journal Articles Status: Published Year Published: 2018 Citation: Joshi, S.R., Li, W., Bowden, M. and Jaisi, D.P. (2018). Sources and pathways of formation of recalcitrant and residual phosphorus in an agricultural soil. Soil Systems, 2, 45?64.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Mingus, K.A., Liang, X., Massoudieh, A., and Jaisi, D.P. (2019). Stable isotopes and Bayesian modeling methods of tracking sources and differentiating bioavailable and recalcitrant phosphorus pools in suspended particulate matter. Environmental Science & Technology, 53, 69-76.
  • Type: Journal Articles Status: Published Year Published: 2019 Citation: Yuan, H., Li., Q., Kukkadapu, R., Liu, F., Yu, J., Fang, H. Li, H., and Jaisi, D.P. (2019). Identifying sources and cycling of phosphorus in the sediment of a shallow freshwater lake in using phosphate oxygen isotopes. Science of the Total Environment, 676, 823-833.
  • Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: Elavarthi, M., K.D. Szerlag, and D.L. Sparks. Legacy phosphorus desorption from U.S. Mid-Atlantic agricultural soils. DENIN Scholars Summer Undergraduate Research Symposium, Newark, Delaware, USA. Aug 9, 2018
  • Type: Conference Papers and Presentations Status: Other Year Published: 2018 Citation: Northrup P., R. Tappero, G. Flynn, S. Wirick, K.D. Szerlag, D. Sparks, S. and M. Gill Schoonen. Tender energy imaging and spectroscopy at TES (8-BM). The National Synchrotron Light Source II (NSLS-ll) and Center for Functional Nanomaterials (CFN) Users' Meeting, Brookhaven National Laboratory, New York. May 21-23, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Li, Q., Wang, D., Jin, Y., Jaisi, D.P. Loading and bioavailability of particulate phosphorus in the estuarine gradient of the Deer Creek-Susquehanna River transect. 11th International Symposium on Agriculture and Environment. Nanjing China. Oct 14-18, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Jaisi, D.P., Massoudieh, A., and Gan, Y. Linking sources and transformation of phosphorus at the soil-water continuum: Search of advanced analytical methods. The 15th International Conference on the Biogeochemistry of Trace Elements, Nanjing China. May 5-9, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: McCrone, C., K.D. Szerlag, and D.L. Sparks. Investigation of the Hedley sequential extraction in the identification of phosphorus pools and mobility in agricultural soils. DENIN Scholars Spring Undergraduate Research Symposium, Newark, Delaware, USA. May 10, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Joshi, S.R., Li, W., and Jaisi, D.P. Sources and pathways of formation of recalcitrant and residual phosphorus in agricultural soil. Soil Science Society of America, International Soils Meeting. San Diego. Jan 6-9, 2019.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2019 Citation: Szerlag, K.D., P. Northrup, R. Tappero, M.G. Siebecker, D.P. Jaisi, and D.L. Sparks. Solid phase speciation of legacy phosphorus in US Mid-Atlantic Agricultural soils using micro-XRF mapping and micro-XANES. Soil Science Society of America Annual Meeting, San Diego, CA. Jan 6-9, 2019.
  • Type: Other Status: Published Year Published: 2019 Citation: Invited talk: Jaisi. D.P. Linking sources and transformation of phosphorus at the soil-water continuum in a coastal estuarine environment. Stockbridge School of Agriculture at the University of Massachusetts, Amherst, MA. Feb 4, 2019.
  • Type: Other Status: Published Year Published: 2019 Citation: Invited talk: Joshi, S.R., Jaisi, D.P., Li, W., and Kukkadapu, R. Sources and pathways of phosphorus cycling in the Chesapeake Bay: Results from isotopes, EXAFS, NMR, and Mossbauer methods. State Key Lab of Environmental Geochemistry (SKLEG), Guiyang, China. May 9, 2019.


Progress 05/15/17 to 05/14/18

Outputs
Target Audience:Researchers in soil chemistry, Farmer and commodity groups, Federal, state government including secretary of the state, local government, and Stakeholders on the nutrient management Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The major opportunities provided to researchers are as follows: o Kathryn Szerlag (Ph.D. student, intake Fall 2016) continues to hone her skills on conventional and advanced soil characterization. She undertakes research primarily on P speciation primarily using the tender energy X-ray absorption spectroscopy (TES) beamline (8-BM) at NSLS II synchrotron light source at Brookhaven National Laboratory (BNL). She presented her research at the NSL II Annual Users Meeting in May 2018 and another aspect of her research outcomes is going to be presented in the 21st Soil Congress in Rio, Brazil. o Fatemeh Izaditame (Ph.D. student, intake Fall 2016) is being trained on flux and controlled experiments for P mobilization and phase transformation research including stable isotopes. The outcome of her first research is going to be presented at the Goldschmidt conference in August 2018. She continues to work on this project in future project years. This year, the project has provided following opportunities to two graduate students (listed above):i) Training and experience on isotope biogeochemistry; refined processing of samples and isotope measurements; ii) honing skills by work closely and train undergraduate students, to develop their supervisory and interpersonal skills; iii) further develop management skills by working closely on lab/project management; iv) training students on manuscript writing, highlighting key scientific findings; they will be trained on reviewing manuscript and critical thinking skills; v) both students undergoing Ph.D. candidacy exam and writing research proposal, here they will be trained to developing research questions and research hypotheses, and vi) improving speaking and poster/presentation skills. While this will evolve over time, both PIs are highly committed and have track records of taking additional approaches as needed to achieve these goals for the students. How have the results been disseminated to communities of interest?Scientific findings are beginning to be presented at the national meeting and the conferences and the results are disseminated via presentation. Key interactions include: A plenary talk to Brookhaven National Laboratory by Donald Sparks (see detail citation inthe product section) Two invited talks at Brookhaven National Laboratory and American Chemical Society meetings by Deb Jaisi (see detail citation inthe product section) Three volunteered talks by two graduate students in the project (see detail citation inthe product section) What do you plan to do during the next reporting period to accomplish the goals?The project has taken momentum and we expect to do series of experiments and analyses to address questions listed in the second year and future years.Research findings will be disseminated via publication, presentations at professional society meetings; stakeholders at state and regional level. Both PIs are dedicated to developing the highly skilled workforce. More training and activities will be planned in coming years as the project continues. ?

Impacts
What was accomplished under these goals? To achieve the listed research objectives, the following research tasks were executed in the first year: Collection and general characterization of soils. Random raster sampling was adopted to collect soils covering the agricultural fields with particular target for representative locations to identify legacy sources of residual and recalcitrant P pools and to loss pathways. The sampling was done in two seasons in the first year. All collected soils were kept inside the airtight containers and immediately frozen for preservation for biogeochemical studies and kept frozen in the laboratory until analysis.Sediment cores along the creek transect and runoff waters were collected and preserved similarly as that of soils Characterization of soils and particulate matter. Mineralogical and geochemical properties relevant to P cycling included mineralogy, surface area, and particle size distribution using powder X-ray diffraction (XRD), microscopy (SEM and TEM) and BET surface area methods. Elemental concentration and P pools were quantified using ICP and sequential extraction methods. Controlled experiments: Flux experiment on the intact sediment cores collected from the creek bottom are performed to identify selective mobilization and transformation of P pools. Micro-XRF and micro-XANES characterization of soils. In-situ P speciation, local structure, and micron-scale distribution of P in soils were analyzed by using the X-ray microprobe instrument at the Brookhaven National Laboratory (TES 8-BM) to identify the physical association of Ca-P and Fe-P minerals and Al- and Fe-oxide bound P pools. The major research findings include: Two most representative abstracts from meeting presentations are included below Effect of sediment resuspension on nutrient concentrations in coastal waters (Goldschmidt meeting, Aug 2018) Coastal sediments are subject to regular episodes of sediment resuspension due to natural events and anthropogenic activities that can mobilize nutrients into overlying water. However, the mechanisms of mobilization and impacts on water quality are yet to be fully understood. In this study, we aimed to quantify the release of nutrients due to diffusion and sediment resuspension at different shear stress levels at the sediment-water interface in the East Creek, a tidal estuary in the Chesapeake Bay watershed, MD. A laboratory-based erosion chamber was employed to mimic ranges of bottom shear stress in the field (0-0.28 N m2) and concentrations of nutrients in the overlying water and sediment were quantified. Benthic flux measurements showed the fluxes of 4.5, 0.51, and 0.47 mmol m-2 day-1 for ammonium, nitrate, and phosphate, respectively at the room temperature and neutral pH (~7.0). Once the shear stress is applied, the concentration of ammonium increased by 14% but that of nitrate and phosphate decreased by 39% and 45%, respectively in the overlying water at the critical shear stress (0.06 N m-2). These trends continued with increasing bottom shear stress. Variations in the concentrations of nutrients in the overlying water could have caused by the dispersion-induced increase in the reactive surface area of resuspended particles. The decrease in dissolved oxygen during continued experiments probably stimulated reduction of nitrate in the sediment, which leads to a higher ammonium and a lower nitrate flux to the overlying water. Overall, our results demonstrate that sediment resuspension is an important mechanism controlling nutrient concentrations in the water column and provide useful insights into the biogeochemical and physical processes regulating the fate of nutrients in coastal waters. Legacy phosphorus speciation in US Mid-Atlantic agricultural soils using tender energy X-ray absorption spectroscopy (TES): 21st Soil Congress, Rio (Aug 2018) Phosphorus is an essential plant nutrient and is applied to agricultural soils as fertilizer or manure to promote optimal crop yield. Phosphorus loss to water ecosystems can be detrimental to aquatic life and water quality due to eutrophication caused by nutrient enrichment. By determining the phosphorus species present in soils, we are able to better understand phosphorus availability to plants and environmental susceptibility to nutrient enrichment. Little direct evidence exists for the solid phase species of phosphorus in agricultural soils. Direct speciation of phosphorus allows for improvement in fertilizer recommendations, updated best management practices, and informed remediation strategies to prevent phosphorus loss to aquatic environments. Until the recent application of synchrotron radiation to investigate phosphorus in soils, there has not been a direct method to accurately determine phosphorus speciation. This research utilizes multiple tools including phosphorus release kinetics and synchrotron-based techniques to directly investigate the chemical forms and stability of legacy phosphorus from agricultural soils located on the Delmarva Peninsula. We present recent data (March 2018) collected using the tender energy X-ray absorption spectroscopy (TES) beamline (8-BM) at NSLS II. High resolution, micro X?ray fluorescence (µ?XRF) mapping of phosphorus within the soil and its association with silicon, sulfur, and aluminum are presented. Phosphorus K?edge micro X?ray absorption near edge structure (µ?XANES) spectroscopy was used to directly determine phosphorus speciation. A beam size of 4 x 4 µm was used. XANES features in conjunction with aqueous phosphorus release data will help to determine the types of phosphorus (i.e., surface adsorbed or precipitated) occurring within the soils, which have had continual phosphorus application for decades. Ultimately the phosphorus species dictate availability and mobility to both crops and the environment.

Publications

  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Sparks, D.L. The nexus between soils, climate, and water: big challenges and opportunities in the 21st century. Workshop on Soils for a Sustainable Future in National Synchrotron Light Source (NSLS-II)/ Center for Functional Nanomaterials (CFN) annual user meeting at Brookhaven National Laboratory, May 21-23, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Jaisi, D.P. Transfer, and transformation of phosphorus from agricultural wastes to open waters. Workshop on Soils for a Sustainable Future in National Synchrotron Light Source (NSLS-II)/ Center for Functional Nanomaterials (CFN) annual user meeting at Brookhaven National Laboratory, May 21-23, 2018.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Jaisi, D.P. Sun, S.M., Joshi, S., Stout, L., and Bear, K.M. Linking sources and transformation of phosphorus at the soil-water continuum in a coastal estuarine environment. 255th ACS National Meeting and Exposition, New Orleans, Mar 18-22, 2018
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Szerlag, K.D., Northrup, P., Siebecker, M.G., Jaisi, D.P., and Sparks, D.L. Legacy phosphorus speciation in US Mid-Atlantic agricultural soils using tender energy X-ray absorption spectroscopy (TES). Workshop on Soils for a Sustainable Future in National Synchrotron Light Source (NSLS-II)/ Center for Functional Nanomaterials (CFN) annual user meeting at Brookhaven National Laboratory, May 21-23, 2018.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2018 Citation: Ijaditame, F., and Jaisi, D. Effect of sediment resuspension on nutrient concentrations in coastal waters. Goldschmidt, Aug 12-17, 2018.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2018 Citation: Szerlag, K.D., Northrup, P., Siebecker, M.G. Jaisi, D.P., and Sparks, D.L. The chemistry of legacy phosphorus in US Mid-Atlantic agricultural soils. Soil Symposium, Rio 2018: 21st World Congress of Soil Science, Brazil, Aug 12-17, 2018