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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Opportunities for Utilization of Low-Cost Algae Resources: Techno-Economic Analysis Screening for Near-Term Deployment (Parts 1 and 2)

This report presents a comprehensive techno-economic analysis (TEA) for the production, collection, or procurement of several low-cost algae resources that may otherwise be considered "waste" biomass materials today, as well as the utilization of these materials through exemplary conversion processes to produce renewable fuels and chemicals. In contrast to conventional TEA models attributed to large-scale algae "farming" approaches, which may be able to produce substantially more biomass and thus fuels/products at a national scale in the future, this assessment focuses on understanding opportunities and costs for such "waste" algal biomass resources as may be available at considerably lower cost today. Economics for base case assumptions and a range of sensitivity scenarios are presented, employing conversion technologies that are simple and well understood, and thus may be deployed at smaller community scale in the near term, as a means to support and expand a nascent algae industry on the way to employing a larger commercial algae farm approach for commodity-scale production. Specifically, three algal biomass resources are considered in this assessment, as may be sourced from (1) municipal wastewater treatment (WWT) utilizing algae in place of more conventional technologies for nitrogen/phosphorus removal, (2) collection and removal of harmful algal bloom (HAB) biomass as proliferates in certain inland water bodies, and (3) procurement of residual biomass following commercial lipid extraction (EXT) operations performed at smaller scale by industry today focused on higher-value nutraceutical applications. These three resources are evaluated through two conversion pathways: (1) combined algal biomass processing (CAP) through a simple/low-complexity configuration, and (2) anaerobic digestion (AD). The CAP pathway produces liquid fuels and chemical coproducts (polymer for off-site upgrading to bioplastics), whereas the AD pathway produces biogas (specifically renewable natural gas [RNG]) and crop fertilizer coproducts. To streamline the discussion, this report is broken into two sections: Part 1 focuses on WWT-derived biomass, and Part 2 on HAB and EXT biomass.

09 BIOMASS FUELS↗
NASA NTRS2019

Satellite Ocean Colour: Current Status and Future Perspective

Spectrally resolved water-leaving radiances (ocean colour) and inferred chlorophyll concentration are key to studying phytoplankton dynamics at seasonal and inter-annual scales, for a better understanding of the role of phytoplankton in marine biogeochemistry; the global carbon cycle; and the response of marine ecosystems to climate variability, change and feedback processes. Ocean colour data also have a critical role in operational observation systems monitoring coastal eutrophication, harmful algal blooms, and sediment plumes. The contiguous ocean-colour record reached 21 years in 2018; however, it is comprised of a number of one-off missions such that creating a consistent time-series of ocean-colour data requires merging of the individual sensors (including MERIS, Aqua-MODIS, SeaWiFS, VIIRS, and OLCI) with differing sensor characteristics, without introducing artefacts. By contrast, the next decade will see consistent observations from operational ocean colour series with sensors of similar design and with a replacement strategy. Also, by 2029 the record will start to be of sufficient duration to discriminate climate change impacts from natural variability, at least in some regions. This paper describes the current status and future prospects in the field of ocean colour focusing on large to medium resolution observations of oceans and coastal seas. It reviews the user requirements in terms of products and uncertainty characteristics and then describes features of current and future satellite ocean-colour sensors, both operational and innovative. The key role of in situ validation and calibration is highlighted as are ground segments that process the data received from the ocean-colour sensors and deliver analysis-ready products to end-users. Example applications of the ocean-colour data are presented, focusing on the climate data record and operational applications including water quality and assimilation into numerical models. Current capacity building and training activities pertinent to ocean colour are described and finally a summary of future perspectives is provided.

ocean colour↗
NASA NTRS2007

Great Lakes Hyperspectral Water Quality Instrument Suite for Airborne Monitoring of Algal Blooms

NASA Glenn Research Center and NOAA Great Lakes Environmental Research Lab are collaborating to utilize an airborne hyperspectral imaging sensor suite to monitor Harmful Algal Blooms (HABs) in the western basin of Lake Erie. The HABs are very dynamic events as they form, spread and then disappear within a 4 to 8 week time period in late summer. They are a concern for human health, fish and wildlife because they can contain blue green toxic algae. Because of this toxicity there is a need for the blooms to be continually monitored. This situation is well suited for aircraft based monitoring because the blooms are a very dynamic event and they can spread over a large area. High resolution satellite data is not suitable by itself because it will not give the temporal resolution due to the infrequent overpasses of the quickly changing blooms. A custom designed hyperspectral imager and a point spectrometer mounted on aT 34 aircraft have been used to obtain data on an algal bloom that formed in the western basin of Lake Erie during September 2006. The sensor suite and operations will be described and preliminary hyperspectral data of this event will be presented

Lekki, John↗
NASA NTRS2022

Satellite-derived Cyanobacteria Frequency and Magnitude in Headwaters & Near-dam Reservoir Surface Waters of the Southern U.S.

Reservoirs are dominant features of the modern hydrologic landscape and provide vital services. However, the unique morphology of reservoirs can create suitable conditions for excessive algae growth and associated cyanobacteria blooms in shallow in-flow reservoir locations by providing warm water environments with relatively high nutrient inputs, deposition, and nutrient storage. Cyanobacteria harmful algal blooms (cyanoHAB) are costly water management issues and bloom recurrence is associated with economic costs and negative impacts to human, animal, and environmental health. As cyanoHAB occurrence varies substantially within different regions of a water body, understanding in-lake cyanoHAB spatial dynamics is essential to guide reservoir monitoring and mitigate potential public exposure to cyanotoxins. Cloud-based computational processing power and high temporal frequency of satellites enables advanced pixel-based spatial analysis of cyanoHAB frequency and quantitative assessment of reservoir headwater in-flows compared to near-dam surface waters of individual reservoirs. Additionally, extensive spatial coverage of satellite imagery allows for evaluation of spatial trends across many dozens of reservoir sites. Surface water cyanobacteria concentrations for sixty reservoirs in the southern U.S. were estimated using 300 m resolution European Space Agency (ESA) Ocean and Land Colour Instrument (OLCI) satellite sensor for a five year period (May 2016–April 2021). Of the reservoirs studied, spatial analysis of OLCI data revealed 98% had more frequent cyanoHAB occurrence above the concentration of >100,000 cells/mL in headwaters compared to near-dam surface waters (P < 0.001). Headwaters exhibited greater seasonal variability with more frequent and higher magnitude cyanoHABs occurring mid-summer to fall. Examination of reservoirs identified extremely high concentration cyanobacteria events (>1,000,000 cells/mL) occurring in 70% of headwater locations while only 30% of near-dam locations exceeded this threshold. Wilcoxon signed-rank tests of cyanoHAB magnitudes using paired-observations (dates with observations in both a reservoir's headwater and near-dam locations) confirmed significantly higher concentrations in headwater versus near-dam locations (p < 0.001).

Amber R Ignatius↗
NASA NTRS2012

Applications of MODIS Fluorescent Line Height Measurements to Monitor Water Quality Trends and Algal Bloom Activity

Recent advances in satellite and airborne remote sensing, such as improvements in sensor and algorithm calibrations, processing techniques and atmospheric correction procedures have provided for increased coverage of remote-sensing, ocean-color products for coastal regions. In particular, for the Moderate Resolution Imaging Spectrometer (MODIS) sensor calibration updates, improved aerosol retrievals and new aerosol models has led to improved atmospheric correction algorithms for turbid waters and have improved the retrieval of ocean color in coastal waters. This has opened the way for studying ocean phenomena and processes at finer spatial scales, such as the interactions at the land-sea interface, trends in coastal water quality and algal blooms. Human population growth and changes in coastal management practices have brought about significant changes in the concentrations of organic and inorganic, particulate and dissolved substances entering the coastal ocean. There is increasing concern that these inputs have led to declines in water quality and have increase local concentrations of phytoplankton, which cause harmful algal blooms. In two case studies we present MODIS observations of fluorescence line height (FLH) to 1) assess trends in water quality for Tampa Bay, Florida and 2) illustrate seasonal and annual variability of algal bloom activity in Monterey Bay, California as well as document estuarine/riverine plume induced red tide events. In a comprehensive analysis of long term (2003-2011) in situ monitoring data and satellite imagery from Tampa Bay we assess the validity of the MODIS FLH product against chlorophyll-a and a suite of water quality parameters taken in a variety of conditions throughout a large optically complex estuarine system. A systematic analysis of sampling sites throughout the bay is undertaken to understand how the relationship between FLH and in situ chlorophyll-a responds to varying conditions and to develop a near decadal trend in water quality changes. In situ monitoring locations that correlated well with satellite imagery were in depths greater than seven meters and were located over five kilometers from shore. Water quality parameter of total nitrogen, phosphorous, turbidity and biological oxygen demand had high correlations with these sites, as well. Satellite FLH estimates show improving water quality from 2003-2007 with a slight decline up through 2011. Dinoflagellate blooms in Monterey Bay, California (USA) have recently increased in frequency and intensity. Nine years of MODIS FLH observations are used to describe the annual and seasonal variability of bloom activity within the Bay. Three classes of MODIS algorithms were correlated against in situ chlorophyll measurements. The FLH algorithm provided the most robust estimate of bloom activity. Elevated concentrations of phytoplankton were evident during the months of August-November, a period during which increased occurrences of dinoflagellate blooms have been observed in situ. Seasonal patterns of FLH show the on- and offshore movement of areas of high phytoplankton biomass between oceanographic seasons. Higher concentrations of phytoplankton are also evident in the vicinity of the land-based nutrient sources and outflows, and the cyclonic bay-wide circulation can transport these nutrients to the northern Bay bloom incubation region. Both of these case studies illustrate the utility MODIS FLH observations in supporting management decisions in coastal and estuarine waters.

Fischer, Andrew↗
DOE OSTI2023

Synchrotron-based X-ray fluorescence microscopy mapping the ionome of a toxic freshwater cyanobacterium

Harmful algal blooms (HABs) pose a major environmental concern across the globe. In abundance, cyanobacteria, or so-called green-blue algae can produce extremely dangerous cyanotoxins that harm humans and animals. This study focused on the mapping and distribution of intracellular macro-and micronutrients of the widespread freshwater cyanobacteria Microcystis aeruginosa (M. aeruginosa). Towards a better understanding of trace metal uptake and homeostasis throughout the cell cycle, we quantitatively mapped the spatial distribution of the elements P, K, Fe, Ca, Zn, Mn, and Cu across the ultrastructure of frozen-hydrated single cells using state-of-theart X-ray nanofluorescence imaging at the Advanced Photon Source (APS) at Argonne National Laboratory. Further, bulk cellular nutrient and trace metal content correlated well with the total intracellular elemental content in individual cells obtained by quantitative synchrotron X-ray fluorescence measurements. Multi-dimensional mappings showed P and K atoms colocalized as discrete semicircular hotspots that were analyzed with respect to their stoichiometry. Elevated Cu and Ca concentrations were detected along division plane of cells. P and K were found to have similar spatial elemental distribution with about 65% and 69% of the total cellular P and K, respectively, located at the hotspots. The P and K colocalization were refined further using nanotomography, showing a K envelope surrounding the P core. Inorganic P and organic P compounds were specified using solution-state 31 P nuclear magnetic resonance (NMR) spectroscopy from M. aeruginosa. Of the total extracted P determined by 31 P NMR spectroscopy, 47% were found to be nucleotides while only 11% were polyphosphates. Multimodal X-ray imaging provides a better understanding of intracellular biochemical processes in cyanobacteria, helping us monitor and combat an emerging environmental threat.

31P NMR spectroscopy↗
NASA NTRS2018

Satellite Remote Sensing: Ocean Color

Satellite ocean color instruments routinely provide global, synoptic views of the Earth's marine biosphere. These spaceborne radiometers measure light exiting the top of the atmosphere at discrete wavelengths in the ultraviolet to shortwave infrared region of the spectrum. This includes measurements of the color of the ocean - information used to infer the contents of the sunlit upper ocean, such as concentrations of phytoplankton, suspended sediments, and dissolved organic carbon. Continuous marine biological, ecological, and biogeochemical data records from satellite ocean color instruments now span over twenty years. This time-series not only supports Earth system and climate research, but also ecosystem and watershed management activities, including detection of nuisance and harmful algal blooms.

Biosphere↗
DOE OSTI2024

Detection of Anatoxins in Human Urine by Liquid Chromatography Triple Quadrupole Mass Spectrometry and ELISA

Harmful cyanobacterial blooms are becoming more common and persistent around the world. When in bloom, various cyanobacterial strains can produce anatoxins in high concentrations, which, unlike other cyanobacterial toxins, may be present in clear water. Potential human and animal exposures to anatoxins occur mainly through unintentional ingestion of contaminated algal mats and water. To address this public health threat, we developed and validated an LC-MS/MS method to detect anatoxins in human urine to confirm exposures. Pooled urine was fortified with anatoxin-a and dihydroanatoxin at concentrations from 10.0 to 500 ng/mL to create calibrators and quality control samples. Samples were diluted with isotopically labeled anatoxin and solvent prior to LC-MS/MS analysis. This method can accurately quantitate anatoxin-a with inter- and intraday accuracies ranging from 98.5 to 103% and relative standard deviations < 15%, which is within analytical guidelines for mass spectrometry methods. Additionally, this method qualitatively detects a common degradation product of anatoxin, dihydroanatoxin, above 10 ng/mL. We also evaluated a commercial anatoxin-a ELISA kit for potential diagnostic use; however, numerous false positives were detected from unexposed individual human urine samples. In conclusion, we have developed a method to detect anatoxins precisely and accurately in urine samples, addressing a public health area of concern, which can be applied to future exposure events.

urine↗
DOE OSTI2022

Prescreening-Based Subset Selection for Improving Predictions of Earth System Models With Application to Regional Prediction of Red Tide

We present the ensemble method of prescreening-based subset selection to improve ensemble predictions of Earth system models (ESMs). In the prescreening step, the independent ensemble members are categorized based on their ability to reproduce physically-interpretable features of interest that are regional and problem-specific. The ensemble size is then updated by selecting the subsets that improve the performance of the ensemble prediction using decision relevant metrics. We apply the method to improve the prediction of red tide along the West Florida Shelf in the Gulf of Mexico, which affects coastal water quality and has substantial environmental and socioeconomic impacts on the State of Florida. Red tide is a common name for harmful algal blooms that occur worldwide, which result from large concentrations of aquatic microorganisms, such as dinoflagellate Karenia brevis, a toxic single celled protist. We present ensemble method for improving red tide prediction using the high resolution ESMs of the Coupled Model Intercomparison Project Phase 6 (CMIP6) and reanalysis data. The study results highlight the importance of prescreening-based subset selection with decision relevant metrics in identifying non-representative models, understanding their impact on ensemble prediction, and improving the ensemble prediction. These findings are pertinent to other regional environmental management applications and climate services. Additionally, our analysis follows the FAIR Guiding Principles for scientific data management and stewardship such that data and analysis tools are findable, accessible, interoperable, and reusable. As such, the interactive Colab notebooks developed for data analysis are annotated in the paper. This allows for efficient and transparent testing of the results’ sensitivity to different modeling assumptions. Moreover, this research serves as a starting point to build upon for red tide management, using the publicly available CMIP, Coordinated Regional Downscaling Experiment (CORDEX), and reanalysis data.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Valorizing Hydrothermal liquefaction aqueous phase via nanofiltration: Enhancing biocrude production from algal biomass

The hydrothermal liquefaction aqueous phase (HTL-AP), a nutrient- and carbon-rich waste byproduct of the HTL process, can be recirculated to enhance biocrude production efficiency. To avoid dilution of the HTL feedstock and reduced fuel quality associated with recirculating untreated HTL-AP, this study investigated nanofiltration to concentrate organic compounds and separate nutrients from HTL-AP of three algal biomass sources: an algal wastewater treatment system and two from harmful algal blooms in lakes. Up to 99% of the organics were recovered in the concentrated HTL-AP (retentate), and significant increases in both permeate flux and permeation of nitrogenous compounds were achieved by increasing HTL-AP temperature to 45 °C and pH to 11. Recirculating the concentrated HTL-AP increased biocrude yield by 70%-116% and reduced biocrude nitrogen content by up to 12%. The carbon and energy capture in the biocrude also increased by 66% and 68%, respectively.

09 BIOMASS FUELS↗
DOE OSTI2022

Application-specific optimal model weighting of global climate models: A red tide example

Global climate models (GCMs) and Earth system models (ESMs) provide many climate services with environmental relevance. The High Resolution Model Inter-comparison Project (HighResMIP) of the Coupled Model Intercomparison Project Phase 6 (CMIP6) provides model runs of GCMs and ESMs to address regional phenomena. Developing a parsimonious ensemble of CMIP6 requires multiple ensemble methods such as independent-model subset selection, prescreening-based subset selection, and model weighting. The work presented here focuses on application-specific optimal model weighting, with prescreening-based subset selection. As such, independent ensemble members are categorized, selected, and weighted based on their ability to reproduce physically-interpretable features of interest that are problem-specific. We discuss the strengths and caveats of optimal model weighting using a case study of red tide prediction in the Gulf of Mexico along the West Florida Shelf. Red tide is a common name of specific harmful algal blooms that occur worldwide, causing adverse socioeconomic and environmental impacts. Our results indicate the importance of prescreening-based subset selection as optimal model weighting can underplay robust ensemble members by optimizing error cancellation. Prescreening-based subset selection also provides insights about the validity of the model weights. By illustrating the caveats of using non-representative models when optimal model weighting is used, the findings and discussion of this study are pertinent to many other climate services.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Microcystin-LR aerosol induces inflammatory responses in healthy human primary airway epithelium

Harmful algal blooms plague bodies of freshwater globally. These blooms are often composed of outgrowths of cyanobacteria capable of producing the heptapeptide Microcystin-LR (MC-LR) which is a well-known hepatotoxin. Recently, MC-LR has been detected in aerosols generated from lake water. However, the risk for human health effects due to MC-LR inhalation exposure have not been extensively investigated. In this study, we exposed a fully differentiated 3D human airway epithelium derived from 14 healthy donors to MC-LR-containing aerosol for 3 minutes per day for 3 days. Concentrations of MC-LR ranged from 100 pM to 1 µM. Although there were little to no detrimental alterations in measures of the airway epithelial function (i.e. cell survival, tissue integrity, mucociliary clearance, or cilia beating frequency), a distinct shift in the transcriptional activity was found. Genes related to inflammation were found to be upregulated such as C-C motif chemokine 5 (CCL5; log2FC = 0.56 , p = 0.02) and C-C chemokine receptor type 7 (CCR7; log2FC = 0.83, p = 0.03). Functionally, conditioned media from MC-LR exposed airway epithelium was also found to have significant chemo-attractive properties for primary human neutrophils. Additionally, increases were found in the concentration of secreted chemokine proteins in the conditioned media such as CCL1 (log2FC = 5.07 , p = 0.0001) and CCL5 (log2FC = 1.02, p = 0.046). These results suggest that MC-LR exposure to the human airway epithelium is capable of inducing an inflammatory response that may potentiate acute or chronic disease.

3D human airway epithelium↗
DOE OSTI2023

The Western Lake Erie culture collection: A promising resource for evaluating the physiological and genetic diversity of Microcystis and its associated microbiome

Cyanobacterial harmful algal blooms (cyanoHABs) dominated by Microcystis spp. have significant public health and economic implications in freshwater bodies around the world. These blooms are capable of producing a variety of cyanotoxins, including microcystins, that affect fishing and tourism industries, human and environmental health, and access to drinking water. In this study, we isolated and sequenced the genomes of 21 primarily unialgal Microcystis cultures collected from western Lake Erie between 2017 and 2019. While some cultures isolated in different years have a high degree of genetic similarity (genomic Average Nucleotide Identity >99%), genomic data show that these cultures also represent much of the breadth of known Microcystis diversity in natural populations. Only five isolates contained all the genes required for microcystin biosynthesis while two isolates contained a previously described partial mcy operon. Microcystin production within cultures was also assessed using Enzyme-Linked Immunosorbent Assay (ELISA) and supported genomic results with high concentrations (up to 900 μg L⁻¹) in cultures with complete mcy operons and no or low toxin detected otherwise. These xenic cultures also contained a substantial diversity of bacteria associated with Microcystis, which has become increasingly recognized as an essential component of cyanoHAB community dynamics. These results highlight the genomic diversity among Microcystis strains and associated bacteria in Lake Erie, and their potential impacts on bloom development, toxin production, and toxin degradation. Furthermore, this culture collection significantly increases the availability of environmentally relevant Microcystis strains from temperate North America.

CyanoHABs↗
DOE OSTI2021

SWAT model application for evaluating agricultural conservation practice effectiveness in reducing phosphorous loss from the Western Lake Erie Basin

Lake Erie is threatened by eutrophication and harmful algal blooms due to excess nutrient loading from agricultural sources. Agricultural conservation practices (ACPs) have been developed and implemented to reduce nutrient losses but estimating ACP effectiveness is challenging. The Soil and Water Assessment Tool (SWAT) has been used to investigate ACP effectiveness for water quality improvement. Many SWAT applications have been developed by different investigators to evaluate ACP effectiveness for reducing nutrient, particularly phosphorus (P), loading in the agriculturally-dominated Western Lake Erie Basin (WLEB). Our objective is to establish what has been achieved by past modeling research and make suggestions for future applications and improvements. We synthesized the findings of 28 SWAT modeling studies within the WLEB. Models generally performed satisfactorily against accepted criteria for streamflow and sediment, but performance for P loads, like soluble reactive P, was mostly “unsatisfactory”. The “unsatisfactory” performance maybe due to imperfections and idealizations in model formulations and/or parameterization. Thus, simulations of P transport and transformation processes need improvement. In addition, model parameter selection is the key part of model set-up. Most SWAT modeling studies used default values during initial set-up, then performed calibration and validation. It was found that the calibrated P related parameter values varied widely across different studies, even within the same watershed with some values unrealistic for the study areas. The phenomena of different combinations of model parameters producing similar outputs indicates equifinality. Equifinality in the baseline model may impact results when ACPs are incorporated. Furthermore, the unrealistic values used in ACP assessment undermine the credibility of ACP effectiveness. Future model applications should try to re-examine the calibrated P parameters and make sure they are realistic for the study area as well as reduce equifinality by constraining the model with characterization of watershed conditions, better understanding of hydrologic processes, and parameter values based on real-world observations. As a result, future model applications should focus on improving P transport and transformation processes, using measured watershed characteristics for parameterization, and improving reflections of climate change, which could result in more accurate assessments of ACP effectiveness to meet targeted goals.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Analysis of incentive policies for phosphorus recovery at livestock facilities in the Great Lakes area

Livestock operations have been highly intensified over the last decades, resulting in the advent of large concentrated animal feeding operations (CAFOs). Intensification decreases production costs but also leads to substantial environmental impacts. Specifically, nutrient runoff from livestock waste results in eutrophication, harmful algal blooms, and hypoxia. The implementation of nutrient recovery systems in CAFOs can abate nutrient releases and negative ecosystem responses, although they might negatively affect the economic performance of CAFOs. We design and analyze potential incentive policies for the deployment of phosphorus recovery technologies at CAFOs considering the geospatial vulnerability to nutrient pollution. The case study demonstration consists of 2217 CAFOs in the U.S. Great Lakes area. The results reveal that phosphorus recovery is more economically viable in the largest CAFOs due to economies of scale, although they also represent the largest eutrophication threats. For small and medium-scale CAFOs, phosphorus credits progressively improve the profitability of nutrient management systems. The integration of biogas production does not improve the economic performance of phosphorus recovery systems at most of CAFOs, as they lack enough size to be cost-effective. Furthermore, phosphorus recovery proves to be economically beneficial by comparing the net costs of nutrient management systems with the negative economic impact derived from phosphorus releases. The incentives necessary for avoiding up to 20.7.10 3 ton/year phosphorus releases and achieve economic neutrality in the Great Lakes area are estimated at $223 million/year. Additionally, the fair distribution of limited incentives is studied using a Nash allocation scheme, determining the break-even point for allocating monetary resources.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Nitrate loading projection is sensitive to freeze-thaw cycle representation

Climate change can have substantial impacts on nitrogen runoff, which is a major cause of eutrophication, harmful algal blooms, and hypoxia in freshwaters and coastal regions. We examined responses of nitrate loading to climate change in the Upper Mississippi River Basin (UMRB) with an enhanced Soil and Water Assessment Tool with physically based Freeze-Thaw cycle representation (SWAT-FT), as compared with the original SWAT model that employs an empirical equation. Driven by future climate projections from five General Circulation Models (GCMs) from 1960 to 2099 under the Representative Concentrations Pathways (RCP) 8.5 scenario, we analyzed changes in riverine nitrate loadings, as well as terrestrial surface and subsurface contributions of the UMRB in the 21st century relative to the baseline period of 1960–1999. By the end of the 21st century, the original SWAT model predicted about a 50% increase in riverine nitrate loadings which is nearly twice as much as that estimated by SWAT-FT (ca. 25%). Such a large difference in projected nitrate changes can potentially mislead mitigation strategies that aim to reduce nitrogen runoff from the UMRB. Further analysis shows that the difference between the original SWAT model and SWAT-FT led to substantial discrepancies in the spatial distribution of surface and subsurface nitrate loadings in the UMRB. In general, SWAT-FT predicted more nitrate leaching for northwestern parts of the UMRB which are more sensitive to freeze-thaw cycle, mainly because SWAT-FT simulated less frequent frozen soils. This study highlights the importance of using physically based freeze-thaw cycle representation in water quality modeling. Design of future nitrogen runoff reduction strategies should include careful assessment of effects that land management has on the freeze-thaw cycles to provide reliable projection of water quality under climate change.

Wang, Qianfeng↗
DOE OSTI2024

Identification of Serine-Containing Microcystins by UHPLC-MS/MS Using Thiol and Sulfoxide Derivatizations and Detection of Novel Neutral Losses

Microcystins (MCs) are hepatotoxic cyclic heptapeptides produced by cyanobacteria, and their structural diversity has led to the discovery of more than 300 congeners to date. However, with known amino acid combinations, many more MC congeners are theoretically possible, suggesting many remain unidentified. Herein, two novel serine (Ser)-containing MCs were putatively identified in a Lake Erie cyanobacterial harmful algal bloom (cyanoHAB), using high-resolution UHPLC-MS as well as thiol and sulfoxide derivatization procedures. These MCs contain an α,β-unsaturated carbonyl on methyl dehydroalanine (Mdha) residue that undergoes Michael addition to produce a thiol-derivatized MC. Derivatization reactions using various thiolation reagents were followed by MS/MS, and two Python codes were used for data analysis and structural elucidation of MCs. Two novel MCs containing Ser at position 1 (i.e., next to Mdha) were putatively identified as [Ser 1 ]MC-RR and [Ser 1 ]MC-YR. Using thiol- and sulfoxide-modified [Ser 1 ]MCs, identifications were confirmed by the observation of specific neutral losses of the oxidized thiols or sulfoxides in CID-MS/MS spectra in both positive and negative electrospray ionization (ESI) modes. These novel neutral losses are unique for MCs with Mdha and an adjacent Ser residue. In conclusion, data suggest that a gas-phase reaction occurs between oxygen from adjacent Ser residue and sulfur of the Mdha-bonded thiol or sulfoxide, which leads to the formation and detection of stable cyclic MC ions in MS/MS spectra at m/z values corresponding to the loss of oxidized thiols or oxidized sulfoxides from Ser 1 -containing MCs.

Premathilaka, Sanduni H.↗
DOE OSTI2022

Identification of Novel Microcystins Using High-Resolution MS and MS n with Python Code

Cyanotoxins called microcystins (MCs) are highly toxic and can be present in drinking water sources. Determining the structure of MCs is paramount because of its effect on toxicity. Though over 300 MC congeners have been discovered, many remain unidentified. In this work, a method is described for the putative identification of MCs using liquid chromatography (LC) coupled with high-resolution (HR) Orbitrap mass spectrometry (MS) and a new bottom-up sequencing strategy. Maumee River water samples were collected during a harmful algal bloom and analyzed by LC–MS with simultaneous HRMS and MS/MS. Unidentified ions with characteristic MC fragments (135 and 213 m/z) were recognized as possible novel MC congeners. An innovative workflow was developed for the putative identification of these ions. Python code was written to generate the potential structures of unidentified MCs and to assign ions after the fragmentation for structural confirmation. The workflow enabled the putative identification of eight previously reported MCs for which standards are not available and two newly discovered congeners, MC-HarR and MC-E(OMe)R.

54 ENVIRONMENTAL SCIENCES↗