Source: PURDUE UNIVERSITY submitted to
FATE AND BIOAVAILABILITY OF EMERGING MICROPOLLUTANTS FROM BIOSOLID-AMENDED AGRICULTURAL SOILS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1002270
Grant No.
2014-67012-21769
Cumulative Award Amt.
$140,365.00
Proposal No.
2013-03218
Multistate No.
(N/A)
Project Start Date
Feb 15, 2014
Project End Date
Feb 14, 2017
Grant Year
2014
Program Code
[A7201]- AFRI Post Doctoral Fellowships
Recipient Organization
PURDUE UNIVERSITY
(N/A)
WEST LAFAYETTE,IN 47907
Performing Department
Agronomy
Non Technical Summary
Polycyclic synthetic musk fragrances (SMF) are used extensively in personal care products, detergents, and industrial applications. Because of their resistance to heat, water, and oil, polyfluoroalkyl substances (PFASs) are used in non-stick cookware, stain-resistant fabric, food packaging, paints, fire-fighting foam, and industrial surfactants and emulsifiers.The recent environmental detection of these micropollutants has raised concern because of evidence of environmental persistence, the risk of bioaccumulation, and the potential for toxicity, carcinogenesis and endocrine disruption. One potential environmental pathway of concern is through the agronomic land application of industrial and municipal biosolids. A recent study found biosolid concentrations of SMFs and PFASs to be in the ppm and ppb concentrations respectively, with both compound classes appearing on multiple high priority watch lists. Little is known, however, about the environmental fate of these compounds within the 4 million dry tons of biosolids that are land-applied for their agronomic benefit each year. This project seeks to address the USDA priority and AFRI challenge area of food safety by filling in scientific gaps and quantifying the fate and bioavailability of two high priority classes of micropollutants - SMFs and PFASs - from biosolid-amended agricultural soils. The information gleaned from the proposed study will help us to better assess the potential risk of the land-application of biosolids to ecological and food safety, aid in the development of best management practices of biosolid waste disposal and associated risk management plans based on trade-offs, and address stakeholders who have expressed concerns about biosolid safety.We hypothesize that biosolids will provide a source of SMFs and PFASs where they will be available for plant uptake from the vadose zone, potentially impacting both human food and feedstock safety. To test this hypothesis, we have 3 primary objectives:Objective 1: To quantify the aerobic degradation kinetics of SMFs and PFASs in biosolids and biosolid-amended soils. A batch aerobic microcosm study will be used to test the hypothesis that SMFs and PFASs will persist in soils and biosolids after land-application.Objective 2: To quantify the bioaccessibility of SMFs and PFASs from biosolids by measuring desorption kinetics. A batch desorption study will be used to test the hypothesis that SMFs and PFASs in biosolids will leach from the biosolid matrix into the vadose zone where they will be available for plant uptake.Objective 3: To quantify the bioavailability and potential bioaccumulation of SMFs and PFASs from biosolid-amended soils. Greenhouse and field sampling studies will be used to test the hypothesis that SMFs and PFASs from biosolid-amended soils are available for bioaccumulation in plant roots and tissues where they may potentially enter the food chain.While primarily focused on research, this project will also include extension and educational outreach including: mentoring K-12 students and undergraduate researchers, developing undergraduate and graduate learning modules, outreach to local stakeholders through the Lafayette Science Café series (which is open and advertised to the public) and to a broader audience through the release of a Purdue Extension Bulletin on our findings.
Animal Health Component
25%
Research Effort Categories
Basic
75%
Applied
25%
Developmental
0%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1020110200010%
1020199200010%
4030110200040%
4030199200010%
4030210200010%
4030110110320%
Knowledge Area
403 - Waste Disposal, Recycling, and Reuse; 102 - Soil, Plant, Water, Nutrient Relationships;

Subject Of Investigation
0110 - Soil; 0210 - Water resources; 0199 - Soil and land, general;

Field Of Science
1103 - Other microbiology; 2000 - Chemistry;
Goals / Objectives
The overall goal of this proposal is address the USDA priority and AFRI challenge area of food safety by filling in the scientific gaps and quantifying the fate and bioavailability of SMFs and PFASs from biosolid-amended agricultural soils. We hypothesize that biosolid will provide a source of these micropollutants where they will be available for environmental transport and plant uptake from the vadose zone, potentially impacting both human food and feedstock safety. To test this hypothesis, we have 3 primary aims specific to SMFs and PFASs:Objective 1: To quantify their aerobic degradation kinetics , thus persistence, in biosolid.Objective 2: To quantify their bioaccessibility of SMFs and PFASs from biosolid by quantifying their desorption kinetics.Objective 3: To quantify their bioavailability and potential bioaccumulation from biosolid-amended soils.
Project Methods
Galaxolide and tonalide will be used as model SMFs. Final selection of the specific model PFASs and precursorswill be based on those detected in the biosolid acquired. If a key model-compound of interest is not present in sufficient concentration, biosolid will be amended with the compound using talc as a carrier.For Objective 1, laboratory batch aerobic degradation microcosm studies will be used to test the hypothesis that SMFs and PFASs will persist after biosolids land-application. Briefly, at least 2 differing agricultural soils will be collected, passed through a 2 mm sieve, characterized, and stored in the dark at 4°C. Prior to biosolid amendment, soil will be added to 125 mL amber glass bottles and preincubated at 75% field capacity for 1 week. Soil microcosms will be amended with biosolid, crimped with airtight rubber septa, gently shaken to mix the soil and biosolid, and stored at room temperature in the dark until time of sacrifice. Soil moisture will be monitored gravimetrically throughout the study. Treatments include: a no biosolid soil blank; 3 biosolid amendment treatments approximating the lower, optimal, and upper bounds of typical field application; and biosolid without soil to quantify the stability of the compounds within the biosolid matrix. The optimal biosolid amendment rate will be determined based on the nutritional needs of a model crop (e.g., corn) taking into account biosolid and soil nutrient analysis, with the lower and upper bound rates equivalent to 0.5 and 4 times the optimal rate, respectively. Sterile (autoclaved) soil controls will be used to discern biotic and abiotic transformations. All treatments and controls will be in triplicate. At time of sacrifice, the headspace will be sampled for volatile parent compounds and metabolites using an airtight syringe fitted with 2 dry solid phase extraction cartridges (SPE) in serial and eluted with solvent. A separate headspace sample will be collected for O2 and CO2 analysis to confirm the microcosms are aerobic and viable. In the event that O2 levels fall below 50% of ambient air, interim headspace measurements of the remaining microcosms will be taken and the headspace purged and re-aerated. The soil microcosms being sacrificed will be extracted using ultrasonic assisted solid-liquid extraction followed by the clean-up of the solvent extracts using SPE to remove co-extracted lipids and matrix constituents.For Objective 2, alaboratory batch desorption study will be used to test the hypothesis that SMFs and PFASs in biosolid will leach from the biosolid matrix into the vadose zone where they will be available for plant uptake. Briefly, desorption reactors will be prepared in 50 mL centrifuge tubes for the following: a no biosolid soil blank; biosolid alone to quantify the desorption kinetics from the biosolid matrix; and 3 biosolid-soil mixtures approximating the lower, optimal, and upper bounds of typical field application to approximate the bioaccessibility in a mixed matrix. Mass to volume (M/V) ratios will be optimized based on soil characterization. A 5 mM CaCl2 solution prepared in sterile ultrapure DI water spiked with 1 g/L sodium azide as a chemical sterilizer will be added to each reactor. All reactors will be prepared in triplicate and rotated in the dark. At each sampling period, the reactors will be centrifuged, a 0.5 mL aliquot of aqueous phase removed from each and replaced with 0.5 mL of CaCl2-azide solution, and returned to the rotator. The SMFs and PFASs will be extracted from the aqueous phase using SPE. At the end of the study, the aqueous phase will be removed and analyzed, the solid phase will be extracted, and a mass balance performed.For Objective 3, greenhouse and field sample validation studies will be used to test the hypothesis that SMFs and PFASs from biosolid-amended soils are available for bioaccumulation in plant roots and tissues where they may potentially enter the food chain.The Greenhouse experiments will utilize in-ground soil beds. Plants will be provided with supplemental lighting supplied by 1000W high pressure sodium light fixtures with a 16 hour photoperiod to mimic the optimal outdoor photoperiod and allow the plants to reach physiological maturity. Irrigation will be used to replace water lost through evapotranspiration and maintain crop-specific optimal soil moisture conditions. The greenhouse soil will be characterized for physiochemical and soil fertility properties prior to use including background SMF and PFAS concentrations and between plantings. Plots will be equipped with leachate collectors to capture excess irrigation water. Leachate will be extracted using SPE and analyzed for SMF and PFAS parent and metabolites to estimate leaching potential. Three crops of agronomic value will be used to assess the potential for plant uptake: red clover (Trifolium pratense) which is used as a forage crop, and corn (Zea mays) and soybean (Glycine max) which are used for livestock feed, human consumption, and industrial uses. These crops will be planted in series to mimic crop rotations over a 16-month period. The rotation will consist of red clover followed by corn, soybean, and red clover. All crops will be planted at the conventional plant densities used in field production. The second planting of red clover will be used to close out the study and allow for the assessment of the differences in uptake between a virgin soil amended with biosolid and a seasoned soil containing both legacy concentrations of SMFs and PFASs and newly amended biosolid. Time to maturation is estimated at 75 d, 140 d (including a 30 d drying period), and 120 d, respectively. Red clover and soybean seed will be inoculated with rhizobia at time of planting. Four treatments will be randomized in each of 3 replicates within each of (at least) 4 trenches (blocks). Treatments will consist of a control with no biosolid amendment and 3 rates of biosolid application representing the lower, optimal, and upper bound rates typical of land application. The optimal rate of biosolid amendment will be determined based on the nutritional needs of each crop taking into account biosolid and soil nutrient analysis, with the lower and upper bound rates equivalent to 0.5 and 4 times the optimal rate, respectively. Biosolid will be mixed into the soil 10 days prior to each planting. After reaching maturity, plant tissue and root samples will be collected as follows:Corn: the grain, stover, and first 20 cm of rootsSoybeans: the pods, stover, first 20 cm of the tap root, and first 20 cm of rootletsRed clover, the above ground biomass and first 20 cm of rootsAll plant samples will be collected, prepared, stored, and analyzed separately. All SMF and PFAS concentrations will be be reported on a dry weight basis.A field sample validation study will be implemented in collaboration with the Metropolitan Water Reclamation District of Greater Chicago's Stickney Water Reclamation Plant (MWRDGC), to assess plant uptake under natural growing conditions. Archived biosolid and plant tissue samples (e.g., sweet corn and high value crops including tomatoes, carrots, etc.) from an ongoing 3 year study on PFAAs will be analyzed for SMFs and PFASs and precursors. Forage and cover crop tissue samples (including our model crops) and corresponding biosolid samples (at time of amendment) will also be collected from MWRDGC partner farms over 2 growing seasons from both fields receiving biosolid-amendment for the first time and fields undergoing long-term application. All plant samples will be collected, prepared, stored, and analyzed. Plant sample processing and analysis of extracts will take place in our laboratory at Purdue University.For all studies, liquid and solid phase extracts will be concentrated in a nitrogen evaporator and reconstituted prior to analysis on the GC-MS or HPLC/MS/MS. Procedural controls will be used to account for any laboratory background contamination.

Progress 02/15/14 to 02/14/16

Outputs
Target Audience:The target audience for the knowledge gained in the final year of this study has included municipalities/utilities, companies, stakeholders, undergraduate and graduate students, the general public, and regulators. These audiences were reached through the dissemination of our findings at national and regional conferences (e.g., Emerging Contaminant Summit,AEESP, ESE, SURF, OIGP),through our HATCH project (W3170),and by incorporating the study findings into undergraduate and graduate courses (i.e.,5 courses across 3 departments and 2 colleges as described in "other products"). In addition to the 2 undergraduate students and 4graduatestudentswho previously worked on this project,3 additional undergraduate students and 1 additional graduate student worked on the research project in the last year. Three of the undergraduate students have continued onto graduate school (University of Michigan, Colorado State University, and Cornell University) in related research. The remaining undergraduate student is continuing on a related follow-up project. Also, of particular note, is that outreach from municipalities, policymakers, and companies has increased in the last year because of the work focused on commercial biosolids as it related to PFASs and ECs. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Since being awarded, this project is responsible for training 1 postdoctoral fellow (the PI, Michael Mashtare, who became a faculty member at Purdue University), 5 undergraduate students (J. Hemmerling, B. McAdams, L. Abu-Ali, T. Banet, and D. Klawitter), and 5 graduate students (C. Dobbs, J. Kim, A. Lacerda, A. Zull, and K. McLaughlin). Four of the undergraduate students continuedonto graduate school in related fields (Univ of Alberta, Colorado State,University of Michigan, and Cornell University). Twoof the graduate students have completed their degrees and are employed in related fields. Two of the graduate students are continuing their research in related areas on non-USDA funding.In addition to research training, approximately 485 students per year are impacted by lecture/material related to (or inspired by) the study outcomes. How have the results been disseminated to communities of interest?As previously described, the results have been disseminated through multiple national, regional, and local conferences, invited talks, symposia, and working groups (HATCH). In addition, this work has been integrated into 7 classes total (5 of which were between 2016-17, 2 of which were in the first and second years) impacting approximately 485 students per year. See products and other products for a complete list. Planned peer reviewed publications (currently in different stages from planning toearly draft)include: Obj 1: Occurrence of emerging contaminants in commercially available biosolids-based fertilizers Obj 1: Persistence of biosolids-borne contaminantsin community garden soils Obj 1 and 2: Comparing per- and polyfluoroalkyl acids (PFAAs) concentrations and leachability between commercial biosolids-based and non-biosolids-based fertilizers Obj 2: Leachability of selected pharmaceutical and personal care products from commercially available biosolids Obj 3: Plant uptake of selected pharmaceutical and personal care products from commercially available biosolids-amended soil What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? In the final year, we focused on the validation and completion of the objectives. For objective 1, final validation of the results were replicated and compared to extractions using EPA-approved methodology and a modified extraction method for the commercial biosolids and related amendments/fertilizers. In addition to the previously described compounds of interest (e.g., azithromycin, carbamazepine, miconazole, triclocarban, and triclosan, synthetic musks), we included 17 PFAAs (with C4-C18 chain lengths) in our final extractions. PFCAs and PSFAs were found in all of the fertilizers. To assess the persistence of ECs in commercial biosolids, long-term (180d) aerobic microcosmstudieswith community garden soils and amended with commercial biosolids (of which, the contaminants were biosolid-borne/native). Results from this study showed measured half-lives for triclosan and triclocarbon to be 80-112 days, depending on the soil, which was within the range of previously reported studies that used solvent spiked amendments. However, estimated half-lives for miconazole and carbamazepine were well beyond 180 days (193-2418 days depending on the compound and soil). For carbamazepine, our study demonstrated longer persistancewhen applied via biosolidsthan previously reported solvent-spiked studies, but were similar toa study which used outdoor mesocosms. A follow-up study that includes solvent spiked amendments and biosolid-amended soils is being conducted using institutional (non-USDA) funds for validation prior to publication. For objective 2, leachability studies were conductedand pore water concentrations were measured with time and compared to Log Kd values in biosolids. A linear relationship between log Kd and log Kow (from the literature) was obtained. For objective 3, a greenhouse study was conducted using basil, kale, green beans, turnips, and swiss chard. Uptake of all five model compounds was detected in the edible parts ofat least 1 of theplant typesat 8X the recommended rate. Detected ranges were ND to 35.7 ug/kg dry plant tissue depending on the plant and contaminant. Carbamazepine showed the highest uptake while triclosan showed the lowest uptake in the study. This study lead to a follow-up hydroponic study using a seed grant (non-USDA) that will continue through 2018.

Publications

  • Type: Conference Papers and Presentations Status: Published Year Published: 2016 Citation: Travis A. Banet, Jihyun R. Kim and Michael L. Mashtare (2016) Persistence of Trace Organic Contaminants from a Commercial Biosolids-Based Fertilizer in Aerobic Soils. SURF Poster Symposium, Purdue University, West Lafayette, IN. August 4.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2017 Citation: Jihyun R. Kim, Lena Abu-Ali, Linda S. Lee and Michael L. Mashtare (2017). Evaluating the Bioavailability of Emerging Contaminants from Commercial Biosolids-Based Fertilizers. Poster Presented at Undergraduate Research and Poster Symposium in Purdue University, West Lafayette IN. April 11.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Rooney Kim Lazcano, Peyman Yosefi, Youn Jeong Choi, Linda S. Lee and Michael L. Mashtare (2018). Per-and Polyfluoroalkyl Acids in Composted Wastes: Commerical Biosolids-based and Nonbiosolids-based Fertilizers. Poster Presented at Emerging Contaminant Summit, Westminster, CO, March 6-7.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2018 Citation: Rooney Kim Lazcano and Michael L. Mashtare (2018). Plant Uptake of Trace Organic Contaminants from Commercially Available Biosolids-based Fertilizer Amended Soil. Poster presentation at the Office of Interdisciplinary Graduate Programs Spring Reception. Purdue University, West Lafayette IN. May 2.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2018 Citation: Kyle McLaughlin and Michael L. Mashtare (2018). Persistance of Biosolids-Borne Contaminants in Urban Garden Soils. Association of Environmental Engineering & Science Professionals (AEESP) Distinguished Lecturer Conference. Purdue University, West Lafayette IN. Feb 2.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2018 Citation: Kyle McLaughlin and Michael L. Mashtare (2018). Aerobic Degradation of Biosolids-Borne Contaminants. Poster presentation at the Office of Interdisciplinary Graduate Programs Spring Reception. Purdue University, West Lafayette IN. May 2.


Progress 02/15/15 to 02/14/16

Outputs
Target Audience:The target audience for the knowledge gained in the second year of this study has included municipalities/utilities, companies, stakeholders, the general public, and regulators. These audiences were reached through the dissemination of our preliminary findings at several working groups/conferences (e.g., WERF, ASA/CSSA/SSSA, etc) and invited talks (e.g., Penn State University). Two undergraduate students and 4 graduate students were part of the research team mentored by the PI in year 2. These research team members included 5 students from Purdue and 1 student from Universidade de Sao Paulo. Four of the 6 students were from underrepresented groups (female and/or racial or ethnic minorities). Four of the students presented their projects ideas and findings at local symposiums with all 4 of the students winning awards for their presentations. Of the 2 undergraduate students, the first followed this experience with an internship, as noted in the year 1 summary, and continued with the research project in the lab in year 2. The second undergraduate student, also as noted in the year 1 summary, is now attending graduate school in a related masters program after completion of her project in May 2015. The PI also incorporated this work into a 1-lecture module on biosolids for an urban agriculture course. The PI also co-organizing a related symposium for the Division of Environmental Chemistry at the 2015 American Chemical Society Conference entitled: Reclamation, Remediation, Restoration: Novel Approaches to Environmental Challenges. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The PI associated with this opportunity transitioned to a faculty position in year 2. In year 2, as a postdoctoral fellow and under the role as a new faculty member, the PI mentored 4 graduate students and 2 undergraduate researchers. The 4 graduate students (C. Dobbs, J. Kim, A. Lacerda, and A. Zull,) and 2 undergraduate students (J. Hemmerling, B. McAdams) presented their work at local conferences (see publications). A. Lacerda was able to incorporate her work into her dissertation. The PI also had the opportunity to incorporate this work into guest lectures, including an invited talk at Penn State, an invited talk to a Purdue student environmental science Club, and as a 1-lecture module in an urban agriculture course. How have the results been disseminated to communities of interest?As previously described, the results have been disseminated through multiple national and local conferences, invited talks, symposia, and working groups. (See products for full list.) What do you plan to do during the next reporting period to accomplish the goals?Under a 1-year no-cost extension, the focus of the next reporting period will be on study completion and validating and publishing the data collected from the first 3 objectives.

Impacts
What was accomplished under these goals? In year 2 we focused on the validation of objective 1, the continuation and validation of objective 2, and initiating objective 3. For objective 1, results from year 1 were replicated and compared to extractions using the EPA-approved methodology as well as a modified extraction method to evaluate reproducibility, extraction efficiency, and matrix effects. These results were presented at local and national conferences. Final validation is almost complete and a publication will be submitted for review by Q3 2016. For objective 2, alternative methods for evaluating the bioaccessibility of the compounds of interest from the biosolids were exercised using Tenax and leach tube studies and validated against year 1 batch studies. The methodologies for objective 2 and preliminary results of the study were presented at a regional symposium and at ASA/CSSA/SSSA. This study is ongoing based on peer feedback and should be completed by Q3 2016. Objective 4 is being initiated with a target completion in Q4 2016. The methodology tied to this objective was presented at a regional conference.

Publications

  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Hemmerling, J. Mashtare, M. L. and Lee, L. S., Identification and Quantitation of Contaminants of Emerging Concern in Commercial Biosolids-Based Fertilizers, Purdue University Undergraduate Research & Poster Symposium, West Lafayette, IN. (Awarded 2nd place in the Engineering Division.)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Hemmerling, J., Mashtare, M. L. and Lee, L. S.. 2015. Identification and Quantitation of Contaminants of Emerging Concern in Commercial Biosolid-based Fertilizers. Purdue AIChE Poster Symposium, West Lafayette, IN.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Lee, L. S., Mashtare, M. L ., Hemmerling, J. and Huertas, A. F. L. 2015 Assessing Organic Contaminants of Emerging Concern in Commercially Available in Biosolid-based Fertilizers. WEF/IWE Residuals and Biosolids Workshop.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Zull, A., Kim, J. R., and Mashtare, M. L. 2015. Desorption Kinetics Determination Using a Tenax Resin. Purdue University Ecological Sciences and Engineering Poster Symposium, West Lafayette, IN. (Award: Peoples Choice Award.)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Dobbs, C. and Mashtare, M. L. 2015. Plant Uptake of Emerging Micropollutants from Commercially-available Biosolids. Purdue University Ecological Sciences and Engineering Poster Symposium, West Lafayette, IN. (Award: 2nd place.)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2015 Citation: Mashtare, M. L. Kim, J. R., Zull, A., and L. S. Lee. Evaluating the Bioavailability of Trace Organic Contaminants from Commercial and Municipal Biosolids-Based Fertilizers. 2015 ASA, CSSA, and SSSA International Annual Meetings, Minneapolis, MN.


Progress 02/15/14 to 02/14/15

Outputs
Target Audience: The target audience for the knowledge gained in the first year of this study included municipalities/utilities, companies, stakeholders, the general public, and regulators. These audiences were reached through the dissemination of our preliminary findings at several conferences (e.g., the Soil in the City Conference, ASA/CSSA/SSSA, SETAC, etc). 4 undergraduate students and 1 graduate student were part of the research team mentored by the PI/Postdoc. These research team members included 2 students from Purdue, and 1 student from each of EARTH University, Universidad Nacional de Columbia,and Universidade de Sao Paulo. 4 of the 5 students were from underrepresented groups (female and/or racial or ethnic minorities). Each of the undergraduate students presented their projects ideas and findings at at least 1 local symposium with 2 of the students winning awards for their presentations. Of the 4 undergraduates students, 1 followed thisexperience with an internship, 1 entered the workforce, 1 returned to complete his undergraduate degree, and 1 continued on in a related masters program. The PI/Postdoc also incorporated this work into guest lectures at the undergraduate and graduate level (soil and environmental chemistry courses) and co-developed a laboratory exercise usingbiosolid extracts for an Aquatic Animal Health course. The PI/Postdoc is also in the process of co-organizing a symposium for the Division of Environmental Chemistry at the 2015 American Chemical Society Conference entitled:Reclamation, Remediation, Restoration: Novel Approaches to Environmental Challenges. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? As noted, the PI/Postdoc mentored 4 undergraduate students and 1 graduate student in the first year of this study. In addition to the objectives previously identified, the students were encouraged to expand on the proposed research (i.e., developing their own small project), where feasible (as noted in the original proposal). Two of the students were interested in extension studies. B. McAdams initiated a study in cooperation with an Indiana farm that had been experiencing significant losses (~1 acre) of their corn crop near railroad tracks. The student was interested in: (1) characterizing the soil to identifywhat contaminants (e.g., pesticides and heavy metals) may be impacting the plant growth; (2) investigating whether the use of amendments (biosolids, biochar, and activated carbon) could increase soil fertility and thus plant health; and (3) evaluating what contaminants (from the soil or biosolid-amended soil) were taken up by the plants. This study is ongoing into year 2.J. Cuvacawas originally interested in trying to remediate soils from a small arms firing range using biosolids and investigating the uptake of native and amended (via biosolids) contaminants into plants. Due to time constraints, this study was limited largely to characterizing soils and biosolids, but a follow-on studywill likely ensue if the student returns to Purdue as a graduate student in 2016, as planned. As mentioned earlier, all 4 undergraduate students presented their work at local or national conferences (see publications). The PI/Postdoc also had the opportunity to incorporate this work into guest lectures and a lab module within the first year. This experience, coupled with the experience of running a small research group has been extremely valuable given his interest in pursuing a career in academia. How have the results been disseminated to communities of interest? As previously described, the results have been disseminated through multiple national and local conferences, symposia, and working groups. What do you plan to do during the next reporting period to accomplish the goals? As noted above, the focus of the next reporting period will be on validating and publishing the data collected from the first 2 objectives, a case study for the extension project by B. Adams in the Purdue undergraduate research journal, and moving forward with Objective 3.

Impacts
What was accomplished under these goals? In year 1 we focused primarily on the first 2 objectives. For Objective 1, 11biosolids-based amendments/fertilizers (including class A cake, heat-dried commercialbiosolids, and composted commercial biosolids) and 9 non-biosolid-based fertilizers (for comparative purposes) were characterized and analyzed for SMFs, PFASs, and a suite of additional emerging contaminants (e.g., target pharmaceuticals, personal care products, etc). The additional suite of emerging contaminants were added in response to feedback from the PI/Postdoc mentoring committee and stakeholders about the need for quantitative data because of safety concerns about biosolids-basedfertilizers. This data, showing persistance of the targeted micropollutants in high ppb to low ppm concentrations has been presented at several conferences and isundergoing further validation in preparation for publication. Aerobic biodegradation studies were initiated as originally proposed and should be completed inthe first half of year 2. For Objective 2, a preliminary study using batch desorption experiments was completed for 3 of thebiosolids and the results presented at ASA/CSSA/SSSA. A follow-up study is planned using a modified method (i.e., Tenax) for validation in year 2 prior to the publication of results. Objective 3, thegreenhouseand field sampling studies are slated for year 2.

Publications

  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Mashtare, M. L., J. Hemmerling, A. Zull, and L. S. Lee. 2014. Evaluating Poly/Perfluoroalkyl Substances in Commercial Biosolids-based Fertilizers. 2014 Society of Environmental Toxicology and Chemistry (SETAC) North America 35th Annual Meeting, Vancouver, BC, Canada.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Mashtare, M. L., J. Hemmerling, F. L. Huertas Ayala, and L. S. Lee. 2014. Evaluating the Concentration and Bioavailabililty of Micropollutants in Commercial Biosolids-based Fertilizers. 2014 ASA, CSSA, and SSSA International Annual Meetings, Long Beach, CA.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: McAdams, B. N., M. L. Mashtare, and L. S. Lee. 2014. Characterization and Reclamation of Railroad-Impacted Soils. Purdue University Ecological Sciences and Engineering Poster Symposium, West Lafayette, IN. (Award: 2nd Place Poster)
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Cuvaca, J., M. L. Mashtare, and L. S. Lee. 2014. Stabilization of Antimony, Lead, and Arsenic in Small Arms Firing Range Soils. Purdue University Ecological Sciences and Engineering Poster Symposium, West Lafayette, IN.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Huertas A., F. L., M. L. Mashtare, and L. S. Lee. 2014. Persistence of Emerging Contaminants from Commercial Biosolids-Based Fertilizers in Aerobic Soils. Purdue University Ecological Sciences and Engineering Poster Symposium, West Lafayette, IN.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Hemmerling, J., M. L. Mashtare, and L. S. Lee. 2014. Evaluating Contaminants of Emerging Concern in Commercial Biosolid-based Fertilizers. SURF Poster Symposium. West Lafayette, IN. (Award: Top Ten Poster).
  • Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Mashtare, M. L., J. Hemmerling, and L. S. Lee. 2014. Evaluating Contaminants of Emerging Concern in Commercial Biosolid-based Fertilizers. Soil in the City Conference, Chicago, IL.