Annual Report for the MicroAnalytical Facility (MAF)

01 July 2017 – 30 June 2018

MicroAnalytical Facility (MAF)

Director: Paul V. Doskey

Chemical Advanced Resolutions Methods (ChARM) Laboratory

Co-Director: Lynn R. Mazzoleni Co-Director: Michael R. Gretz

Laboratory for Environmental Analysis of Forests (LEAF)

Director: Andrew J. Burton

Molecular Biogeochemistry Laboratory (MBL)

Director: Paul V. Doskey

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Abstract The principal goal of the MicroAnalytical Facility (MAF) and associated Laboratories (i.e., ChARM, LEAF, and MBL) is to provide analyses and user access to equipment and instrumentation for elemental, ionic, molecular, and isotopic analysis for environmental, biomedical, health, and materials research. A wide variety of instrumentation is available including gas and liquid chromatographs with various detection systems and spectrometers. The volume of activity for much of the equipment and instrumentation in ChARM, LEAF, and MBL is high; however, usage varies from year to year. The LEAF and ChARM laboratories support research technical staff to assist users.

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Volume I

FY 2018 Annual Report for the MAF Purpose and Mission Statement The MicroAnalytical Facility (MAF) is composed of the Chemical Advanced Resolutions Methods (ChARM) Laboratory, the Laboratory for Environmental Analysis of Forests (LEAF), and the Molecular Biogeochemistry Laboratory (MBL). The mission of the MAF is to provide and assist users with elemental, molecular, ionic, and isotopic analyses for environmental, biomedical, health, and materials research. The MAF supports the Michigan Tech educational mission by providing students with hands-on training in cutting-edge, trace analytical chemistry. The ChARM Laboratory is dedicated to providing advanced research instrumentation for chromatographic separation and mass spectrometric and spectroscopic analysis of molecular and elemental species important in both basic and applied research applications. A central mission of ChARM is to provide advanced resolution measurements for environmental and biological complex mixtures, which enable research and development. The LEAF provides Michigan Tech investigators (1) expert advice on sampling and analytic techniques for chemical species in water, soil, and plant tissues, (2) supervision of students preparing samples for analysis, (3) space and equipment to perform sample grinding, extractions, filtering, and microwave digestion, and (4) analytic instrumentation for quantitative analysis of molecular and elemental composition of liquids and solids and isotopes of C and N in liquids, solids, and gases. The MBL offers Michigan Tech investigators (1) expert advice on research and development of sampling and analytic techniques for organic species in air, water, soil, and sediment matrices, (2) supervision of students for sampling, isolation, and analysis, (3) space and equipment to perform isolations from environmental matrices, and (4) analytic instrumentation for quantitative organic molecular characterization. Core Facility Equipment and Instrumentation ChARM - The ChARM Laboratory has a combined 3200 square feet of laboratory space in GLRC 233 of the Great Lakes Research Center and laboratories 616-618 of the Chemical Sciences Building, which were formerly designated as the Molecular Atmospheric Chemistry Laboratory (MACL). The Laboratory provides advanced research instrumentation for chromatographic separation and mass spectrometric and spectroscopic analysis of molecular, ionic, and elemental species important in both basic and applied research applications. Sample preparation and analysis by gas/liquid chromatography, mass spectrometry, ultraviolet-visible spectroscopy, and analytical microscopy is

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supported. Key instrumentation and equipment available in the ChARM Laboratory includes the following, some of which are pictured below: Mass Spectrometry Instrumentation

• Ultrahigh Resolution Hybrid Ion Trap Orbitrap Mass Spectrometer (Orbitrap Elite)

• Ambient Pressure Ionization Ion Trap Mass Spectrometer (LCQ Fleet)

• Gas Chromatograph/Ion Trap Mass Spectrometer

• Inductively Coupled Plasma-Mass Spectrometer

Liquid Chromatography Instrumentation

• Two-Dimensional, Ultra-High-Pressure Liquid Chromatograph (UltiMate 3000)

• Ultra High-Pressure Liquid Chromatograph (Accela)

• Ion Chromatograph/Dual Analysis/Cations, Anions (Dionex 2100 and 1100)

• Capillary Electrophoresis System (Beckman)

Other Supporting Instrumentation

• OC/EC analyzer (Sunset ECOC Analyzer)

• HD Video Microscope

• Microbalance Thermo Scientific Two Dimensional Liquid Chromatograph/Ultra High Resolution-

Orbitrap Elite Mass Spectrometer (Orbitrap Elite MS)

The Orbitrap Elite is a Hybrid Linear Ion Trap/Orbitrap mass spectrometer, which includes a dual pressure linear ion trap MS and a compact high-field Orbitrap MS with electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization sources. The instrument design enables high-quality, fast MSn characterization with ultrahigh resolution measurements (R = 240,000 at m/z 400). The 2-D UltiMate3000 UHPLC consists of dual gradient

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and high pressure gradient pumps (i.e., DPG-3000 and HPG-3000, respectively). The 2-D UHPLC supports pressures up to 620 bar at flow rates up to 10 mL min-1.

Thermo Scientific High Pressure Liquid Chromatograph-LCQ Fleet Mass Spectrometer

The LCQ Fleet Ion Trap Mass Spectrometer includes a 3-D quadrupole ion trap MS with electrospray ionization and atmospheric pressure chemical ionization sources. The instrument enables excellent full-scan sensitivity and fast MSn characterization. The Accela LC offers flow rates up to 5 mL min-1 and a maximum operating pressure of 600 bar.

Thermo Scientific Ion Chromatography System

The ICS-2100 is a reagent-free ion chromatography system for anion analysis with conductivity detection and electrolytic eluent generation for gradient separations. The ICS-1100 system is a traditional isocratic ion chromatography system for cation analysis. The systems are run in parallel for simultaneous analyses of anions and cations. LEAF - The LEAF consists of the Forest Ecology Laboratory (Horner 163), the Plant/Soil Analytical Laboratory (Horner 161), a sample preparation room (Horner

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191), and a mass spectrometer room (Horner 163A) in Horner Hall of the U.J. Noblet Forestry Building. Together these rooms comprise a 2,200 square foot, fully functional, plant, soil, gas, and water analytical facility. In addition to analytical instruments, equipment for processing and storing samples is also available (microwave digestion, SPEX mill for grinding, walk-in cold room, and freezer). The LEAF provides analytical capabilities (1) for elemental (C, N, S, O) analysis of solids, (2) for stable isotopes of C and N in solid, liquid, and gas samples, (3) for gas chromatographic analysis of CO2, CH4, and phospholipid fatty acids (PLFAs), (4) for rapid flow analysis of NO3

-, NH4+, and PO4

3- in liquids, and (5) for analysis of multiple elements (trace metals, cations) in solids and liquids. Key instrumentation and equipment available in LEAF includes the following:

Thermo-Finnigan DeltaPlus Isotope Ratio Mass Spectrometer

The Thermo-Finnigan Delta plus IRMS was purchased in 2001. The instrument has C, N, and O collectors and operates in continuous-flow mode. The peripherals are a Costech 4010 EAS with a Conflo III interface and a Thermo-Finnigan Gas Bench II. Analyses include 13C, 15N, %C, and %N of solids, 13C in atmospheric CO2, and 18O in water.

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Costech 4010 Elemental Combustion System

The Costech 4010 ECS system was purchased in 2014 to replace an older system. The elemental analyzer is used to determine the total carbon, nitrogen, hydrogen, oxygen, and sulfur content of a sample.

PerkinElmer Optima 7000DV ICP-OES

The inductively coupled plasma optical emission spectrometer (ICP-OES) was purchased in 2011. The ICP-OES can be used to determine 70 different elements at concentrations below 1 mg/L, many in the mg/L range.

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Shimadzu Total Organic Carbon Analyzer with Total Nitrogen Detector

The Shimadzu Total Organic Carbon (TOC) Analyzer was purchased in 2008 to replace two older instruments. The TOC analyzer is used to measure the total, organic and inorganic carbon and total nitrogen content of water samples.

Perstorp Analytical Autoanalzyer

The system was purchased in 1995. The autoanalzyer is configured to measure ammonia and nitrate/nitrite nitrogen and orthophosphate.

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Agilent 6850 Gas Chromatographs

The gas chromatographs (GCs) were purchased in 2007 and are used to separate and quantitatively analyze compounds in gas or liquid samples. One GC has a manual injector and integrator and is currently configured for CO2 analyses. The GC has a HP-Plot-U capillary column and a thermal conductivity detector. The other GC has an autosampler and ChemStation for data analysis and is currently configured for PLFA analysis. The GC is equipped with a flame ionization detector and a HP-Ultra2 capillary column. The instrument has MIDI software installed for microbial identification. MBL – The MBL is located in G012 in Horner Hall of the U.J. Noblet Forestry Building. Sampling equipment is available to collect gas-, vapor-, and aerosol-phase chemical species in air. Gas-sampling valves and cryogenic preconcentration units are used to directly inject whole samples collected in glass vials, canisters, or solid sorbents to gas chromatographs for analysis of trace gases and gas-phase organic matter (OM), respectively. Vapor-phase OM collected on solid sorbents and OM in aerosol, soil, and sediment are isolated from matrices by accelerated solvent extraction. Liquid-liquid extraction is used to isolate OM from water. Solvents are reduced by accelerated solvent evaporation and nitrogen blowdown to prepare samples for analysis. A wide array of high-resolution and multidimensional gas chromatographs with a variety of detectors and an ultra high-pressure liquid chromatograph with spectrofluorometric and ultraviolet/visible detectors are available for quantitative organic molecular characterization. Key instrumentation and equipment available in the MBL includes the following:

Sampling Equipment

• Automated multiport sampler for volatile organic compounds (2; custom made)

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• Summa® passivated stainless steel canisters (70, 1.8 L; 50, 6 L; Scientific Instrumentation Specialists, Moscow, ID)

• Automated High-Volume Air Sampler for vapor- and aerosol-phase OM (DIGITEL DHA-80; Hegnau, Switzerland)

Isolation Equipment

• 2-Channel Supercritical Fluid Extractor (1, Spe-ed SFE-2, Applied Separations, Allentown, PA)

• Accelerated Solvent Extractor (1, Dionex ASE 350, Thermo Scientific, West Palm Beach, FL)

• Accelerated Solvent Evaporator System (Rocket™ Evaporator, Thermo Scientific, West Palm Beach, FL)

Analytic Instrumentation

• Cryogenic preconcentration, high-resolution gas chromatograph with dual flame ionization detectors for volatile organic compounds (2, custom made with HP5890s; Agilent Technologies, Wilmington, DE)

• High-resolution gas chromatograph with flame ionization and electron capture detectors (2; HP5890; Agilent Technologies, Wilmington, DE)

• High-resolution gas chromatograph with electron capture detector (1; HP5890; Agilent Technologies, Wilmington, DE)

• High-resolution gas chromatograph with thermal conductivity detector (1; HP5890; Agilent Technologies, Wilmington, DE)

• Multidimensional gas chromatograph with dual flame ionization detectors for semivolatile organic compounds (1; 6890; Agilent Technologies, Wilmington, DE)

• Multidimensional gas chromatograph with dual electron capture detectors for semivolatile organic compounds (1; 6890; Agilent Technologies, Wilmington, DE)

• Multidimensional gas chromatograph with time-of-flight mass spectrometric detector (1; Pegasus 4D; LECO Corporation, St. Joseph, MI)

• Ultra high-pressure liquid chromatograph with spectrofluorometric and ultraviolet/visible detectors (1; Dionex Ultimate 3000; Dionex, Thermo Scientific, West Palm Beach, FL)

Operational Summary ChARM – Dr. Maryam Khaksari, the ChARM laboratory research specialist, is responsible for managing and operating the 2D-LC and high resolution Orbitrap Elite MS and associated equipment in the laboratory. The instrumentation and equipment benefit users from multiple disciplines across campus and also users

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external to campus. In addition to managing the laboratory, Dr. Khaksari assists in the design and testing of analytical strategies, training users, conducting data analysis, and generating reports. The safety inspection report for FY 2018 is attached. The Obitrap Elite MS has been used by 15 investigators in units across campus and in one graduate level course for a total of 1264 hours following installation in November 2016. A total of 28 students have used the Orbitrap Elite for their research. Detailed information on the Orbitrap Elite use patterns by investigator and affiliated unit are summarized in Table 1. The use patterns include all Table 1. Instrument use pattern by investigator and department for the Orbitrap

Elite MS in ChARM for FY 2018.

Investigator Department Activity User Time (h)

Lynn Mazzoleni Chemistry MRI method development, peat fire

277.33

Lynn Mazzoleni (CH5241; Advanced Mass Spectrometry Laboratory)

Chemistry Analysis of dissolved organic phosphorus

63.5

Paul Doskey School of Forest Resources and Environmental Science

Analysis of dissolved organic matter in peat porewater

124.66

XinFeng Xie School of Forest Resources and Environmental Science

Liquid Wood Analysis

25.04

Daisuke Minakata Civil and Environmental Engineering

MRI method development 37.77

Martin Auer Civil and Environmental Engineering

Analysis of personal care and pharmaceutical compounds

11.5

Caryn Heldt Chemical Engineering

Osmolyte Analysis

105.05

Adrienne Minerick / Maryam Khaksari

Chemical Engineering

MRI method development 26.55

Tarun Dam

Chemistry Unknown ID 1

Marina Tanasova Chemistry Accurate mass measurement

12.61

Martin Thompson Chemistry Peptide Analysis 8.5 Shiyue Fang Chemical

Engineering Accurate mass measurement

20.96

Michael Mullins Chemical Engineering

Analysis of oleic acid 0.5

Enterprise Chemical Engineering

Whiskey Analysis 41.36

Total 758.83

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charged and uncharged user times. During the first year (November 2016-June 2017), some reduced and free instrument time was offered (~20% of the time was charged) to research groups to develop a user base. In year two (July 2017-June 2017), more user time was paid by grants (~50%); however, free instrument time was provided for method development for grant proposal writing and/or exploring instrument capabilities.

The Orbitrap Elite MS use pattern including all user times (charged and uncharged) are summarized in Fig. 1. Instrument calibration and maintenance time is not charged to the users; however, on average 1.5 hours of time is required for each user appointment. The total instrument user time with respect to our capacity is plotted in Fig. 2. The use pattern for the IC system is summarized in Fig. 3. Figure 1. Instrument use patterns for the Orbitrap Elite MS for November 2016 - June 2018.

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Figure 2. Instrument use patterns for the Orbitrap Elite MS for July 2017 - June 2018.

Figure 3. Instrument use patterns for the IC System for July 2017 - June 2018.

The ICP-MS instrument in the ChARM Laboratory is currently being used for the project entitled “High Temperature Plasticity of Microalloyed Aluminum: Influence of Rapid Solidification and Wrought Processing on Precipitation Strengthening and Deformation Mechanisms” granted by Office of Naval Research (ONR). The primary investigator of the project is Dr. Paul Sanders of the Materials Science and Engineering Department. Dr. Bowen Li, Research Professor in Materials

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Science and Engineering, and his PhD student, Huaguang Wang, will also be using the ICP-MS in FY 2019. Researchers from the two research groups and Dr. Khaksari worked together in FY 2018 to bring the instrument into working condition. The GC-MS will be used for 30 hours in FY 2019 for analysis of PCBs. The project is funded through the Portage Health Foundation. The principal investigator of the study is Dr. Judith Perlinger of the Civil and Environmental Engineering Department. The Confocal Microscope was installed in FY 2018 and a training session will be held in early FY 2019. Dr. Sangyoon Han of the Department of Biomedical Engineering is composing grant proposals for projects that will use the Confocal Microscope. The proposals, which will be submitted to NIH NIGMS, include the following:

• Nascent adhesion mechano-sensing: The study will investigate differential adhesion molecular recruitment and traction force development in cells on substrates with a wide range of stiffness.

• Shear flow mechano-transduction: The study will investigate how a monolayer of endothelial cells will respond to the laminar vs. turbulent flow in terms of traction force and cell-extracellular matrix adhesions.

The following is a list of manuscripts and conference presentations developed from the use of instrumentation and equipment in the ChARM Laboratory. The list includes 12 published, 5 submitted, and 4 in-preparation manuscripts and 18 conference presentations. Principal investigators are underlined. 2018 Published Manuscripts

Khaksari M, Mazzoleni LR, Ruan C, Song P, Hershey ND, Kennedy RT, Burns MA, Minerick AR, "Detection and Quantification of Vitamins in Microliter Volumes of Biological Samples by LC-MS for Clinical Screening”. AIChE J. Accepted Author Manuscript. DOI:10.1002/aic.16345

Varanasi L, Coscarelli E, Khaksari M, Mazzoleni LR, Minakata D, “Transformations of Dissolved Organic Matter Induced by UV Photolysis, Hydroxyl Radicals, Chlorine Radicals, and Sulfate Radicals in Aqueous-Phase UV-Based Advanced Oxidation Processes”. Journal of Water Research, 135 (2018) 22-30. DOI:org/10.1016/j.watres.2018.02.015

Shahsavari S, Gooding J, Wigstrom T, Fang S, “dM-Dim for Carboxylic Acid Protection”. Tetrahedron Letters, 59 (2018) 1763-1766. DOI:org/10.1016/j.tetlet.2018.03.076

Begoyan V, Xia S, Khanan, S, Ferrier A, Rao S, Tanasova M, “Multicolor GLUT5-Permeable Fluorescent Probes for Fructose Transport Analysis”. Chem. Commun., 2018, 54, 3855-3858. DOI:10.1039/C7CC09809J

Kannan S, Begoyan V, Fedie J, Xia S, Weseliński L, Tanasova M, Rao S, “Metabolism-driven High Throughput Cancer Identification with GLUT5-specific Molecular Probes”. Biosensors, 2018, e39. DOI:10.3390/bios8020039

Singh S, Begoyan V, Tanasova M, Waters K, Seel M, Pandey R, “Coumarins: Spectroscopic measurements and first principles calculations of C4-substituted 7-aminocoumarins”. J. Phys. Org. Chem. 2018, e3852. DOI:org/10.1002/poc.3852

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2017 Published Manuscripts

Fang M, Adhikari R, Bi J, Mazi W, Dorh N, Wang J, Conner N, Ainsley J, Karabencheva-Christova TG, Luo FT, Tiwari A, Liu H, “Fluorescent Probes for Sensitive and Selective Detection of pH Changes in Live Cells in Visible and Near-infrared Channels”. Journal of Materials Chemistry B, 5 (2017) 9579-9590. DOI:10.1039/c7tb02583a

Khaksari M, Mazzoleni LR, Ruan C, Kennedy RT, Minerick AR, "Determination of Water-Soluble

and Fat Soluble Vitamins in Tears and Blood Serum of Infants and Parents by Liquid Chromatography/Mass Spectrometry". Experimental Eye Research, 155 (2017) 54-63. DOI:10.1016/j.exer.2016.12.007

Khaksari M, Mazzoleni LR, Ruan C, Kennedy RT, Minerick AR, "Data representing two separate

LC-MS methods for detection and quantification of water-soluble and fat-soluble vitamins in tears and blood serum". Data in Brief, 11 (2017) 316-330. DOI:10.1016/j.dib.2017.02.033

Shahsavari S, Gooding J, Wigstrom T, Fang S, “Formation of Hindered Arylcarbamates using

Alkyl Aryl Carbonates under Highly Reactive Conditions”. Journal of ChemistrySelect, 2 (2017) 3959-3963. DOI:10.1002/slct.201700364

Khanal A, Fang S, “Solid Phase Stepwise Synthesis of Polyethylene Glycol”, Chemistry - A

European Journal. 23 (2017) 1533-1542. DOI:10.1002/chem.201703004 Weseliński ŁJ, Begoyan V, Xia S, Ferrier A, Tanasova M, “Tuning Cross-Coupling Approaches for

Modification of Highly-functionalized Heterocycles”. Journal of ACS Omega, 2 (2017) 7002-7015. DOI:10.1021/acsomega.7b01159

Submitted Manuscripts

Xia S, Fedie JR, Kannan S, Begoyan V, Ferrier A, Rao S, Tanasova M, “Cancer Toolbox: GLUT5-Specific Fluorescent Probes as Reporters of Malignancy”. Submitted to the ASC Chemical Biology Journal, under revision, 2017.

Fang M, Xia S, Bi J, Wigstrom TP, Johnston T, Pap A, Valenzano L, Wang J, Tanasova M, Luo F-T, Liu H, “A Near-infrared Fluorescent Probe for Highly Selective and Sensitive Imaging of Biological Zn(II) Ions in Live Cells”. Submitted to Sensors & Actuators: B. Chemical Journal, under review, 2018.

Shahsavari S, McNamara C, Sylvester M, Bromley E, Joslin S, Lu B-Y and Fang S, “Amine protecting groups deprotectable under nearly neutral oxidative conditions”. Beilstein Journal of organic chemistry, revision under review.

Eriyagama D, Shahsavari S, Halami B, Lu B-Y, Wei F and Fang S, “High Throughput, Large Scale and Long Synthetic Oligodeoxynucleotide Purification Using the Catching Full-Length Sequence by Polymerization Technology”. Organic Process Research and Development, Submitted.

Halami B, Shahsavari S, Nelson Z, Prehoda L, Eriyagama D, and Fang S, “Incorporation of Sensitive Ester and Chloropurine Groups into Oligodeoxynucleotides Through Solid Phase Synthesis”. ChemistrySelect, Submitted.

Manuscripts in Preparation

Kirillova EN, Samburova V, Bhattarai C, Sengupta D, Moosmüller H, Khlystov A, Mazzoleni LR, “Molecular Characterization of Water-Soluble Organic Carbon (WSOC) from Biomass Burning Aerosol using Ultrahigh Resolution Orbitrap Elite Mass Spectrometry”. in preparation to be submitted to the Journal of Environmental Science and Technology, 2018.

Song Z, Khaksari M, Lilleskov EA, Kane ES, and Doskey PV, “Molecular biogeochemistry of a poor fen. I. Dissolved organic matter in porewater”. Biogeochemistry, in preparation, 2018.

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Song Z, Khaksari M, Lilleskov EA, Kane ES, and Doskey PV, “Molecular biogeochemistry of a poor fen. II. Dissolved nitrogen species in porewater”. Biogeochemistry, in preparation, 2018.

Song Z, Khaksari M, Lilleskov EA, Kane ES, and Doskey PV, “Molecular biogeochemistry of a poor fen. III. Water-extractable organic matter in peat”. Biogeochemistry, in preparation, 2018.

Conference Presentations

Joshi PU, Kriz S, Schroeder M, Heldt CL, "Determination of Binodal Curves and Tie Lines for Aqueous Two-Phase Systems with Osmolytes for Bioseparations". American Institute of Chemical Engineers Annual Meeting, Pittsburg, PA, October, 2018. (Poster)

Begoyan VV, Weselinski LJ; Tanasova M, “Unveiling the conformational preferences of fructose transporters”. 255-th ACS Meeting, New Orleans, LA, USA, March 18-22, 2018.

Ferrier A, Begoyan VV, Tanasova M, “Development of Fluorogenic Probes for Sugar Transport Analysis”. 255-th ACS Meeting (Sci-Mix), New Orleans, LA, USA, March 18-22, 2018.

Varanasi L, Coscarelli E, Khaksari M, Mazzoleni L, Minakata D, “Transformation of dissolved organic matter in UV-based advanced oxidation processes”. ACS National Meeting, New Orleans, LA, March 18-22, 2018.

Schum S, Rose E, Khaksari M, Kirillova E, Samburova E, Mazzoleni LR, “More Comprehensive Molecular Characterization of Organic Aerosol using Ultrahigh Resolution Orbitrap Elite Mass Spectrometry with ESI, APCI, and APPI”. Upper Peninsula American Chemical Society Regional Poster Session, Marquette, MI, April 14, 2018. (Poster)

Rose E, Khaksari M, Leverton T, Schum S, Brege M, and Mazzoleni LR, "Evaluation of Negative Ion Electrospray Ionization Aggregation Artifacts using Ultrahigh Resolution Mass Spectrometry". Upper Peninsula ACS Student Research Symposium, Marquette, MI, April 2018 (Poster)

Brege M, Khaksari M, Leverton T, and Mazzoleni LR, "Detection of 20,000 molecular formulas in Suwanee River fulvic acid coupling liquid chromatography to Orbitrap Elite mass spectrometry with electrospray ionization". Upper Peninsula ACS Student Research Symposium, Marquette, MI, April 2018 (Poster)

Kirillova EN, Samburova V, Bhattarai C, Sengupta D, Moosmüller H, Khlystov A, and Mazzoleni LR, “Molecular Characterization of Water-Soluble Organic Carbon (WSOC) from Biomass Burning of Wildland Fuels Using Ultrahigh Resolution Orbitrap Elite Mass Spectrometry”, American Association of Aerosol Research Annual Conference, Raleigh NC, October 2017.

Varanasi L, Coscarelli E, Perram D, Khaksari M, Mazzoleni LR, Minakata D, “Transformation of dissolved organic matter in engineered ultraviolet (UV) photolysis and UV-based advanced oxidation processes”. Association of Environmental Engineering and Science Professors (AEESP), University of Michigan, Ann Arbor, MI, June 2017.

Kirillova EN, Samburova V, Bhattarai C, Sengupta D, Moosmüller H, Khlystov A, Mazzoleni LR, “Molecular Characterization of Water-Soluble Organic Carbon (WSOC) from Biomass Burning Aerosol using Ultrahigh Resolution Orbitrap Elite Mass Spectrometry”. American Society for Mass Spectrometry (ASMS) Annual Conference, Indianapolis, IN, June 2017. (Poster)

Khaksari M, Auer M, Kuczynski A, Mazzoleni LR, “Non-Targeted Screening of More than 600 Ethoxylated Homologs and Their Transformation Products in Water Samples Using High Resolution-Mass Spectrometry”. ASMS Annual Conference, Indianapolis, IN, June 2017. (Poster)

Xia S, Begoyan V, Tanasova M, “Multicolor Probes for Analysis of Carbohydrate Transport Activity”. 253-rd ACS Meeting, San Francisco, CA, April 2017.

Fedie JR, Xia S, Tanasova M, “Fluorescent Probes for Targeting Fructose Transport”. 253-rd ACS Meeting, San Francisco, CA, April 2017.

Varanasi L, Coscarelli E, Perram D, Khaksari M, Mazzoleni LR, Minakata D, “Transformation of Dissolved Organic Matter in Engineered Ultraviolet (UV) Photolysis and UV-based Advanced

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Oxidation Processes”. World Water Day, Michigan Technological University, Houghton, MI, March 2017.

Varanasi L, Coscarelli E, Khaksari M, Mazzoleni LR, Minakata D, “Transformation of Dissolved Organic Matter in Engineered Ultraviolet (UV) Photolysis and UV-based Advanced Oxidation Processes”. ACS Upper Peninsula Student Research Symposium, Marquette, MI, March 2017.

Coscarelli E, Varanasi L, Khaksari M, Mazzoleni LR, Minakata D, “Impact of Dissolved Organic Matter and its Transformation to Ultraviolet Photolysis Process in Engineered Water and Wastewater Treatment Systems”. Undergraduate Research Symposium, Michigan Technological University, Houghton, MI, March 2017. (Poster)

Ferrier A, Weselinski LJ, Tanasova M, “Synthesis of a Fructopyranose Mimic as a Carbohydrate Probe for Fructose Transporters”. ACS Upper Peninsula Student Research Symposium, Marquette, March 2017.

Xia S, Begoyan V, Tanasova M, “Multicolor Probes for Analysis of Carbohydrate Transport Activity”. ACS Upper Peninsula Student Research Symposium, Marquette, March 2017.

LEAF – Ms. Jennifer Eikenberry is the technical staff for LEAF. Her responsibilities include (1) controlling laboratory use and activities, (2) safety training, (3) cleaning and organizing the laboratory, (4) communicating progress of sample analyses to researchers, (5) tracking samples, (6) analyzing samples and reporting results, (7) maintaining and repairing the instruments, (8) ordering supplies, (9) billing for services, and (10) laboratory safety and chemical disposal. The safety inspection report for FY 2018 is attached. Instrument use varies greatly by year and depends on the types of research projects and the funding available to researchers for sample processing and analysis. Usage for each instrument since user fees were established or the instrument was installed and ready for use are shown in Table 2. Details for the volume of usage over the last 6 years show the annual variation (Fig. 4). Investigators from across campus and their students have used the instrumentation over the past 6 years (Fig. 5). Table 2. Total number of samples or elements that have been analyzed on LEAF

instrumentation.

Instrument Number Calendar Dates GCs 21,603a May 2003 – 20 June 2018 EA 31,553a July 2003 - 20 June 2018 DOC/TN 25,823a May 2003 – 20 June 2018 IRMS 49,040a August 2001 – 20 June 2018 Autoanalyzer 7,875a January 2010 – 20 June 2018 ICP 44,546b May 2011 – 20 June 2018 Total: 180,440

aNumber of samples analyzed. bNumber of elements analyzed.

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Figure 4. Total number of samples or elements analyzed on LEAF instrumentation by fiscal year.

Figure 5. Estimated number of investigators from FY 2012 to FY 2017 by department or school who are users of LEAF instrumentation.

FY12 FY13 FY14 FY15 FY16 FY17 FY18

GC 523 150 196 0 0 1924 0EA 1497 2873 1705 3374 2767 1297 1408DOC/TN 2188 2756 3279 2176 1334 1257 1355IRMS 2742 2116 1598 1393 2528 1333 1341Autoanalyzer 838 1076 1540 548 355 604 334ICP 6913 5520 8399 6608 4371 7884 4221

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The provided analyses have contributed to numerous publications. We recently asked past users of the instruments to provide a list of publications resulting from the analyses provided by LEAF. The results of the voluntary survey indicated that the data produced contributed to at least 106 peer-reviewed journal publications and 54 theses/dissertations. In just the last 5 years (2014-2018), there were 63 peer-reviewed journal publications and 31 theses/ dissertations. Journal Articles 2014-2018

Baker, A. H., et al. (2016). "Solute-Derived Thermal Stabilization of Nano-sized Grains in Melt-Spun Aluminum." Metallurgical and Materials Transactions A 47(8): 4287-4300.

Ballantyne, D. M., et al. (2014). "Long-Term Water Table Manipulations on Great Lakes Peatland Carbon Fluxes." Wetland Ecology and Management 22: 35-47.

Bess, J. A. and R. A. Chimner (2014). "Ditch Restoration in a Large Northern Michigan Fen." Ecological Restoration 32: 260-274.

Bhosle, S. M., et al. (2016). "Dependence of nanotextured titanium orthopedic surfaces on electrolyte condition." Journal of Surface Engineered Materials and Advanced Technology 6: 164-175.

Bowen, P., et al. (2017). "Evaluation of Wrought Zn-Al alloys (1, 3, and 5 wt% Al) Through Mechanical and In Vivo Corrosion Testing for Stent Applications." Journal of Biomedical Materials Research: Part B.

Chimner, R. A., et al. (2014). "Developing and Evaluating Rapid Field Methods to Estimate Peat Carbon." Wetlands 34: 1241-1246.

Chimner, R. A., et al. (2017). "Multi-decadal changes in water table levels alter peatland carbon cycling." Ecosystems 20: 1042-1057.

Chimner, R. A. and S. C. Resh (2014). "Water Sources of Riparian Bur Oak Using Stable Water Isotopes in Homestead National Monument, Nebraska." Natural Areas Journal 34: 56-64.

Coble, A. A., et al. (2016). "Uptake of ammonium and soluble reactive phosphorus in forested streams: influence of dissolved organic matter composition." Biogeochemistry 131: 355-372.

Coble, A. A., et al. (2016). "Temporal patterns of dissolved organic matter biodegradability are similar across three rivers of varying size." Journal of Geophysical Research - Biogeosciences 121: 1617-1631.

Coble, A. P. and M. A. Cavaleri (2015). "Light acclimation optimizes leaf functional traits despite height-related constraints in a canopy shading experiment." Oecologia 177: 1131-1143.

Coble, A. P., et al. (2016). "How vertical patterns in leaf traits shift seasonally and the implications for modeling canopy photosynthesis in a temperate deciduous forest." Tree Physiology 36: 1077-1091.

Comas, X., et al. (2017). "Estimating belowground carbon stocks in peatlands of the Ecuadorian páramo using ground penetrating radar (GPR)." Journal of Geophysical Research – Biogeosciences.

Crowther, T. W., et al. (2016). "Quantifying global soil C losses in response to warming." Nature 540: 104-108.

Deane, K., et al. (2017). "Precipitate Evolution and Strengthening in Supersaturated Rapidly Solidified Al-Sc-Zr Alloys." Metallurgical and Materials Transactions A 48: 2030-2039.

Drelich, A., et al. (2017). "Novel durable antimicrobial ceramic with embedded copper sub-microparticles for a steady-state release of copper ions." Materials 10(7): 775.

Gahagan, A., et al. (2015). "Carbon fluxes, storage and harvest removals through 60 years of stand development in red pine plantations and mixed hardwood stands in Northern Michigan, USA." Forest Ecology and Management 337: 88-97.

Gao, Z., et al. (2017). "Facile colorimetric detection of silver ions with picomolar sensitivity." Analytical Chemistry 89: 3622-3629.

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Gao, Z., et al. (2017). "Platinum decororated gold nanoparticles with dual functionalities for ultrasensitive colorimetric in vitro diagnostics." Nano Letters 17: 5572-5579.

Haselhuhn, A. S., et al. (2016). "Structure-property relationships of common aluminum weld alloys utilized as feedstock for GMAW-based 3-D metal printing." Materials Science and Engineering: A 673: 511-523.

Haselhuhn, A. S., et al. (2017). "Hypoeutectic Aluminum–Silicon Alloy Development for GMAW-Based 3-D Printing Using Wedge Castings." International Journal of Metalcasting 11(4): 843–856.

Haselhuhn, A. S., et al. (2015). "In situ formation of substrate release mechanisms for gas metal arc weld metal 3-D printing." Journal of Materials Processing Technology 226: 50-59.

Hribljan, J. A., et al. (2015). "Carbon storage and long-term rate of accumulation in high-altitude Andean peatlands of Bolivia." Mires and Peat 15: 1-14.

Hribljan, J. A., et al. (2017). "Implications of altered hydrology for substrate quality and trace gas production in a poor fen peatland." Soil Science Society of America Journal.

Hribljan, J. A., et al. (2014). "The effect of long-term water table manipulations on dissolved organic carbon dynamics in a poor fen peatland." Journal of Geophysical Research - Biogeosciences 119(4): 577-595.

Hribljan, J. A., et al. (2017). "Multi-date, multi-sensor remote sensing reveals high density of carbon-rich mountain peatlands in the páramo of Ecuador." Global Change Biology 23: 5412-5425.

Hribljan, J. A., et al. (2016). "Peatland Carbon Stocks and Accumulation Rates in the Ecuadorian Páramo." Wetland Ecology and Management 24: 113-127.

Jin, H., et al. (2018). "Novel high-strength, low-alloys Zn-Mg (<0.1 wt% Mg) and their arterial biodegradation." Materials Science and Engineering C 84: 67-79.

Kane, E. S., et al. (2014). "Peat porewater dissolved organic carbon concentration and lability increase with warming: a field temperature manipulation experiment in a poor-fen." Biogeochemistry 119: 161-178.

Kangas, L. C., et al. (2016). "Artificial microtopography and herbivory protection facilitates wetland tree (Thuja occidentalis L.) survival and growth in created wetlands." New Forests 47: 73-86.

Kerkove, M. A., et al. (2014). "The Diffusion Coefficient of Scandium in Dilute Aluminum-Scandium Alloys." Metallurgical and Materials Transactions A 45A: 3800-3805.

Kerkove, M. A., et al. (2014). "The diffusion coefficient of scandium in dilute aluminum-scandium alloys." Metallurgical and Materials Transactions A 45(9): 3800-3805.

Klemetsrud, B., et al. (2016). "Characterization of products from fast micro-pyrolysis of municipal solid waste (MSW) biomass." ACS Sustainable Chemistry and Engineering 4(10): 5415-5423.

Klinger, J., et al. (2015). "Predicting Properties of Torrefied Biomass by Intrinsic Kinetics." Energy & Fuels 29: 171-176.

Klinger, J., et al. (2015). "Predicting Properties of Gas and Solid Streams by Intrinsic Kinetics of Fast Pyrolysis of Wood." Energy & Fuels 30(1): 318-325.

Lee, B. P. and S. Konst (2014). "Novel hydrogel actuator inspired by reversible mussel adhesive protein chemistry." Advanced Materials 26: 3415-3419.

Lee, B. P., et al. (2015). "Modulating the movement of hydrogel actuator based on catechol-iron ion coordination chemistry." Sensors and Actuators B: Chemical 206: 456-462.

Lee, B. P., et al. (2014). "Novel hydrogel actuator based on biomimetic chemistry." Materials Research Society Proceedings 1710: mrss14-1710-XX1708-1701.

Lee, B. P., et al. (2016). "Effect of metal ion type on the movement of hydrogen actuator based on catechol-metal ion coordination chemistry." Sensors and Actuators B: Chemical 227: 248-354.

Li, J., et al. (2017). "An enzyme-free signal amplification technique for ultrasensitive colorimetric assay of disease biomarkers." ACS Nano 11: 2052-2059.

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Liu, H., et al. (2017). "Fluorescent probes for sensitive and selective detection of pH changes in live cells in visible and near-infrared channels." Journal of Materials Chemistry B.

Marcarelli, A. M., et al. (2015). "Sand aggradation alters biofilm standing crop and metabolism in a low-gradient Lake Superior tributary." Journal of Great Lakes Research 41: 801-807.

Marlor, K. M., et al. (2014). "Disturbance and Wetland Type Alter Reed Canary Grass Cover in Northern Michigan." Invasive Plant Science and Management 7: 121-131.

Murray, B. D., et al. (2014). "A migratory ungulate facilitates cross-boundary nitrogen transport in forested landscapes." Ecosystems 17: 1002-1013.

Ott, C. A. and R. A. Chimner (2016). "Long Term Peat Accumulation in Temperate Forested Peatlands (Thuja occidentalis Swamps) in the Great Lakes Region." Mires and Peat 18: 1-9.

Potvin, L., et al. (2014). "Effects of water table position and plant functional group on plant community, aboveground production, and peat properties in a peatland mesocosm experiment (PEATcosm)." Plant and Soil 387: 277-294.

Poznak, A. and P. Sanders (2016). "The Influence of Low Temperature Clustering on Strengthening Precipitation in Al-Mg-Si Alloys." Light Metals: 237-243.

Poznanovic, S. K., et al. (2015). "Sharing rotting wood in the shade: ectomycorrhizal communities of co-occurring birch and hemlock seedling." Mycorrhiza 25: 153-164.

Premer, M. I., et al. (2016). "Vegetation response to logging residue removals in Great Lakes aspen forests: Long-term trends under operational management." Forest Ecology and Management 382: 257-268.

Sánchez, M. E., et al. (2017). "Carbon dioxide and methane fluxes in grazed and ungrazed mountain peatlands in the Ecuadorian Andes." Mires and Peat 19(20): 1-18.

Schrank, A. J., et al. (2015). "Characterization and Classification of Vernal Pool Vegetation, Soil, and Amphibians of Pictured Rocks National Lakeshore." The American Midland Naturalist 174: 161-179.

Shearier, E. R., et al. (2016). "In vitro cytotoxicity, adhesion, and proliferation of human vascular cells exposed to zinc." ACS Biomaterials Science & Engineering 2(4): 634-342.

Tahtinen, B., et al. (2014). "Does ungulate foraging in forest canopy gaps produce a spatial subsidy with cascading effects on vegetation?" Forest Science 60: 819-829.

Ukaew, S., et al. (2017). "Effects of torrefaction temperature and acid pretreatment on the yield and quality of fast pyrolysis bio-oil from rice straw." Journal of Applied and Analytical Pyrolysis.

Veverica, T. J., et al. (2016). "Ionic liquid extraction unveils previously occluded humic-bound iron in peat pore water." Soil Science Society of America Journal 80: 771-782.

Xia, X., et al. (2015). "Pd-Ir core-shell nanocubes: A type of highly efficient and versatile peroxidase mimic." ACS Nano 9: 9994-10004.

Ye, H., et al. (2017). "Polyvinylpyrrolidone (PVP)-capped Pt nanocubes with superior peroxidase-like activity." ChemNanoMat, 3: 33-38.

Ye, H., et al. (2016). "Peroxidase-like properties of ruthenium nanoframes." Science Bulletin 61: 1739-1745.

Ye, H., et al. (2016). "Ru nanoframes with an fcc structure and enhanced catalytic properties." Nano Letters 16: 2812-2817.

Yeboah, D., et al. (2014). "Variation in wood density and carbon content of tropical plantation tree species from Ghana." New Forests 45: 35-52.

Zhao, S., et al. (2017). "Structural characteristics and in vitro biodegradation of a novel Zn-Li alloy prepared by induction melting and hot rolling." Metallurgical and Materials Transactions A 48A(3): 1204-2015.

Zhao, S., et al. (2017). "Zn-Li alloy after extrusion and drawing: structural, mechanical characterization, and biodegradation in abdominal aorta of rat." Materials Science and Engineering C – Materials for Biological Applications 76: 301-312.

Zheng, J. and P. V. Doskey (2015). "Modeling Nitrous Oxide Production and Reduction in Soil through Explicit Representation of Denitrification Enzyme Kinetics." Environmental Science and Technology 49(4): 2132-2139.

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Theses and Dissertations 2014-2018

Bess, J. A. (2015). Restoration of Headwater and Coastal Fens in the Lake Superior Basin of Upper Michigan. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

Bowen, P. K. (2015). Biocorrosion Rate and Mechanism of Metallic Magnesium in Model Arterial Environments. Materials Science and Engineering, Michigan Technological University. PhD.

Carter, K. (2017). Effects of In-Situ Leaf-Level Canopy Warming in A Northern Hardwood Forest. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

Coble, A. A. (2015). Biogeochemical Cycling in Lake Superior Tributaries: Seasonality, Quantity and Quality of Export. Biological Sciences, Michigan Technological University. PhD.

Coble, A. P. (2015). Investigating within-canopy variation of functional traits and cellular structure of sugar maple (Acer saccharum) leaves. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

Davis, J. (2016). Vegetation Dynamics and Nitrogen Cycling Responses to Simulated Emerald Ash Borer Infestation in Fraxinus nigra-Dominated Wetlands of Upper Michigan, USA. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

del Aguilla-Pasquel, J. (2017). Methane Fluxes and Porewater Dissolved Organic Carbon Dynamics from Different Peatlands Types in the Pastaza-Marañon Basin of the Peruvian Amazon. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

Deneau, K. (2016). The Effects of Black Locust (Robinia pseudoacacia L.) on Understory Vegetation and Soils in a Northern Hardwood Forest. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

Dijkstra, M. (2015). Climate Anomalies and Primary Production in Lake Superior. Environmental Engineering, Michigan Technological University. PhD.

Donepudi, Y. (2017). Impact of pretreatment methods on fast pyrolysis of biomass. Mechanical Engineering-Engineering Mechanics, Michigan Technological University. PhD.

Eberhard, E. K. (2017). Co-Occurrence of Nitrogen Fixation and Denitrification Across a Stream Nitrogen Gradient in a Western Watershed. Biological Sciences, Michigan Technological University. MS.

Hatfield, L. (2018). Waste Not, Want Not: Using Source-Separated Urine to Cultivate Maize in the Southern Highlands, Tanzania. Biological Sciences, Michigan Technological University. MS.

Jacobson, G. (2017). The Influence of Native Woody Species, Combretum glutinosum and Piliostigma reticulatum, on Soil Fertility in Dialacoto, Senegal. Biological Sciences, Michigan Technological University. MS.

Jarvi, M. (2015). Ecophysiological Responses of Sugar Maple Roots to Climatic Conditions. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

Klemetsrud, B. (2016). Experimental and Theoretical Investigation of Sustainable Fast Pyrolysis Biofuels from Woody Biomass. Chemical Engineering, Michigan Technological University. PhD.

Klinger, J. L. (2015). Thermochemical Degradation Mechanisms and Kinetics of Fast Pyrolysis and Torrefaction Processing of Woody Feedstocks. Mechanical Engineering-Engineering Mechanics, Michigan Technological University. PhD.

Kratz, C. (2014). Impacts of Climate Change on Soil Microorganisms in Northern Hardwood Forests. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

Mau, A. C. (2015). Instantaneous photosynthetic response to temperature of mature forest canopies and experimentally warmed seedlings. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

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McNamara, C. (2016). Thermomechanical Processing of Aluminum Micro-alloyed with Sc, Zr, Ti, B, and C. Materials Sciences and Engineering, Michigan Technological University. PhD.

Mosier, S. (2015). Interactive Effects of Climate Change and Fungal Communities on the Decomposition of Wood-Derived Carbon in Forest Soils. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

Olson, J. C. (2014). Investigating the Impacts of Streambed Habitat Heterogeneity on Ecosystem Structure and Processes Using Basic and Applied Perspectives. Biological Sciences, Michigan Technological University. MS.

Premer, M. (2015). Evaluating the Long-Term Effects of Logging Residue Removals in Great Lakes Aspen Forests. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

Schwartz, R. (2016). Carbon Cycling and Restoration in Temperate Forested Peatlands. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

Shearier, E. (2015). Three-dimensional Mesenchymal Stem Cell Spheroids and Zn-based Biomaterials as Potential Cardiovascular Treatments. Biomedical Engineering, Michigan Technological University. PhD.

Shomali, A. A. (2017). Formulation and Testing of Biodegradable Polymeric Coating on Zinc Wires in Cardiovascular Stent Application. Materials Science and Engineering, Michigan Technological University. MS.

Ukaew, S. (2016). Life Cycle Assessments of Hydrocarbon Jet Fuels Produced from Rapeseed Grown in Rotation with Winter Wheat and Fast Pyrolysis of Torrefied Rice Straw. Chemical Engineering, Michigan Technological University. PhD.

Van Grinsven, M. (2015). Implications of Emerald Ash Borer Disturbance on Black Ash Wetland Watershed Hydrology, Soil Carbon Efflux, and Dissolved Organic Matter Composition. School of Forest Resources and Environmental Science, Michigan Technological University. PhD.

Veverica, T. J. (2014). Ionic Liquid Extraction Unveils Previously Occluded Humicbound Iron in Peat Porewater. School of Forest Resources and Environmental Science, Michigan Technological University. MS.

Walczyk, A. (2018). Evaluating the Interactive Role of Soil Nutrients and Ploidy Level on Competitive Outcomes of Chamerion angustifolium. Biological Sciences, Michigan Technological University. MS.

Yin, Z. (2017). Microstructural Evaluation and Mechanical Properties of Zn-Ti Alloys for Biodegradable Stent Applications. Materials Science and Engineering, Michigan Technological University. MS.

Zhao, S. (2017). Structural Characteristics and Corrosion Behavior of Bio-degradable Zn-Li Alloys in Stent Application. Materials Science and Engineering, Michigan Technological University. PhD.

Zheng, J. (2014). Denitrification in soils: From genes to environmental outcomes. Atmospheric Sciences, Michigan Technological University. PhD.

MBL – Use of the UHPLC was steady in FY 2018 and supported by Drs. Doskey’s (SFRES), Minakata’s (CEE), and Datta’s (BL) projects. User fees have not been established for MBL instrumentation and equipment and instead users provide consumables for the analyses. Use of the instrumentation has been critical to the thesis projects of students in BL, CEE, and SFRES. There is no staff support for the MBL, and thus, Dr. Doskey works directly with students. The MBL is being moved, and thus, a safety inspection was not performed.

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Financial Summary The MBL has not established user fees. The ChARM Laboratory set user fees for the Orbitrap Elite MS, LCQ Fleet MS, and IC systems in FY 2016. Income and expenses for the ChARM Laboratory are summarized in Table 3. The most detailed financial information exists for LEAF, which has been in operation for several years. The income and expenses of operating LEAF are variable from year to year and based on (1) the number of samples submitted, (2) the use charge rate set by the use charge committee for a given year, (3) changes in the costs of consumables and parts, (4) large purchases and labor for major instrument repairs, and (5) increases in labor costs. A summary of the income and expenses for the last five years is presented in Table 5. There is no use charge associated with the GCs or the autoanalyzer. Users pay for consumables and labor costs. Table 3. Income and expenses for ChARM instrumentation.

Fiscal Year Orbitrap Elite MSa

LCQ Fleet MSa

IC Systema OCECa

FY 2018 $11,812 / $23,914 $0 / $122 $2,834 / $5,054 $0/$0

FY 2017 $4,550 / $6,773 $1,560 / $6,212 $4,380 / $4,256 $0 / $617

FY 2016 - $5,548 / $750 $1,850 / $0 $0 / $400

Total Income / Expenses $16,362 / $30,687 $7,108 / $7,084 $9,064 / $9,310 $0 / $1,017 aData entries listed as Income / Expenses. Table 4. Income and expenses for LEAF instrumentation.

Fiscal Year IRMSa EA and DOCa

ICP-OESa

FY 2017 $12,586 / $12,755 $15,324 / $15,879 $23,824 / $25,919 FY 2016 $23,786 / $18,628 $15,924 / $19,211 $18,085 / $16,209 FY 2015 $12,602 / $12,250 $25,408 / $21,272 $13,687 / $14,496 FY 2014 $9,748 / $14,711 $23,674 / $27,792 $14855 / $16,354 FY 2013 $9,683 / $21,808 $28,881 / $29,563 $5,095 / $9,947 FY 2012 $19,845 / $17,937 $23,355 / $22,777 $8,861 / $13,047 Total Income / Expenses $75,664 / $85,334 $132,566 / $136.494 $84,407 / $95,972

aData entries listed as Income / Expenses. Facility Development The MAF website (maf.mtu.edu) includes information for each of the associated laboratories. A list of available instruments and equipment for each associated laboratory and contact information for directors and staff members is posted. A detailed list of the laboratory management practices is provided for the ChARM Laboratory, which includes guidance on how to reserve instrument time, training

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requirements, use rates, laboratory best practices, safety and cleanliness rules, and citation recommendations. The website was last updated in December 2017 with new hire contact information and new use charge rates. Plans are underway to further develop the website by adding a library of publications that acknowledge use of ChARM Laboratory equipment, instrumentation, and staff support. ChARM – The intent was to charge user fees for most of the instrument time in FY 2018; however, some research groups continued to collect preliminary data for planned proposal submissions. The strategy helped grow the user base and provided data for publications. We will focus our efforts in FY 2019 on assisting PIs with proposal development. Goals for the ChARM Laboratory for FY 2018: • Continue to present and advertise ChARM capabilities to relevant departmental

and interdisciplinary groups on campus.

• Provide expertise in advanced mass spectrometry methods and operation of an Orbitrap Elite, UltiMate 3000 LC System, LC/MS, GC/MS, and ICP/MS. Collaborate with university researchers and guide users in preparing and analyzing samples.

• Educate and supervise users in instrument use and data interpretation. Establish user policies, documentation, trouble-shooting protocols, and instructions on instrument operation. Help supervise and teach graduate students to use Laboratory instrumentation and equipment.

LEAF – A principal goal for LEAF in FY 2019 is to replace a deionized (DI) water system and for maintenance and updating of the IRMS. Funds were obtained in the FY 2019 to accomplish these goals. The DI water system, which is critical to preparing standards to calibrate the heavily used ICP-OES, is 15 years old and replacement parts are no longer available. The IRMS has experienced steady use over a period of 15 years and is central to current projects with the US Forest Service and NSF. Summary and Conclusions – The MAF associated Laboratories (i.e., ChARM, LEAF, and MBL) provide and assist users with capabilities for preparation of environmental, biological, and engineered matrices for molecular, elemental, ionic, and isotopic analysis. The Facility supports Michigan Tech’s educational mission by providing users with hands-on training in cutting-edge trace chemical analyses. A wide variety of instrumentation is available including chromatographic instrumentation with various detection systems and spectrometers. There was a steady volume of activity in the MAF associated Laboratories in FY 2018; however, some instruments were utilized to a much

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greater extent than others. The most heavily used instruments in ChARM, LEAF, and MBL were (1) the Orbitrap Elite MS, IC System, GC-MS, and the video microscope, (2) the IRMS, EA, ICP, and DOC, and (3) the UHPLC, respectively. The LEAF is an established Laboratory with user fees and has found success in developing a user base that is sufficient to support the operation and a research technical staff. The ChARM Laboratory and MBL were established as part of the MAF in FY 2015 and have been operating primarily by providing access to instrumentation and having users provide consumables. A research technical staff for ChARM was hired in September 2016 and user fees were established for instrumentation. A user base for the Orbitrap Elite MS was identified in FY 2018 and proposals are planned for submission in FY 2019 to support the research technical staff. Facility development in FY 2019 will include increased efforts to identify a stable user base across the MAF associated Laboratories.

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Volume II

Detailed Analysis of Finance, Operation, and Development of the MAF

The LEAF was in operation long before the MAF was established in FY 2015, and thus, the focus of Volume II is on LEAF. Facility Staff – Technical staff supporting the MAF include Dr. Maryam Khaksari (ChARM) and Ms. Jennifer Eikenberry (LEAF). Technical staff perform analyses for investigators, train students to operate equipment and instrumentation, and maintain the equipment and instrumentation in operating condition. Support for their positions is derived from user fees for LEAF and ChARM equipment and instrumentation. Detailed Operational Analysis – Usage of the major instruments in LEAF varies from year to year (Fig. 4). Projects for which the GCs were purchased have concluded, and thus, usage is low. However, there is a project that plans to use a GC for PLFA analysis in FY 2019. The autoanalyzer is used every year; however, the frequency of use is low due to the large amount of time and labor that is required to prepare the instrument and reagents for analysis. The total number of samples analyzed on the ICP-OES was lower in FY 2018 than FY 2017; however, daily usage of the instrument was not lower. The number of sample submissions for the ICP-OES in FY 2018 was about the same. In FY 2018, there were 113 requests for analyses and an average of 37 samples per request. In FY 2017, there were 93 requests for analyses and an average of 85 samples per request, which resulted in a higher overall number of samples analyzed in FY 2017. The difference in number of samples analyzed is due to more use of the ICP-OES for chemistry and engineering research and less use for biology and ecology research, which typically requires more analyses per request.

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Safety Analysis and Corrective Action – ChARM – The inspection for FY 2018 was conducted by Environmental Health and Safety on February 12, 2018. A summary of items to be corrected and the actions taken are presented in Table 1. Table 1. Items to be corrected and actions taken in GLRC 223.

Items to be corrected Actions taken Minimum of 36” clearance for electrical panels.

Electrical panel controlled through panel on UPS system. There is now appropriate clearance for electrical panels. Completed 02/12/2018.

Fume hood in Rm 219 not balanced with room air.

Hood sash needs to be opened more slowly to prevent momentary unbalancing. Inspection completed by Facilities Management (03/02/2018).

LEAF – The inspection for FY 2018 was conducted by Environmental Health and Safety on February 2, 2018. A summary of items to be corrected in Laboratories 161,163, and 191 and the actions taken are presented in Table 2. Table 2. Items to be corrected and actions taken in the LEAF Laboratories.

Items to be corrected Actions taken Low molecular weight polyethylene glycol (PEG 300 or PEG 400) should be available for first aid.

PEG is available for phenol exposure. Completed 04/10/2018.

Need to check hood operation in relation to make up air going into room. Room 163 should be negative in relation to the adjacent lab.

Facilities made adjustments to the make-up air. Work Order 99010 completed 03/08/2018.

Make sign “official” so that everyone knows electrical panel cannot blocked.

A sign was re-printed. Completed 02/13/2018.

Replace the guard on the grinder mill. Guard replaced. Completed 02/13/2018. Fix the back of the lab chairs. The backs of chairs were repaired or

removed. Completed 02/07/2018. Make the label clearer on the aqueous stable isotope reference materials for water.

Re-labeled to make it clear that the reference materials are water and non-hazardous. Completed 02/07/2018.

MBL – The MBL is being moved from the Dow building, and thus, the Laboratory was not inspected. Detailed Income and Expense Analysis – Income for the LEAF facility comes solely from user fees (Tables 3-5). Contracts from government researchers and

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other university investigators are charged the standard user rate for sample analysis plus the required overhead. Table 3. Combined expenses and income for the isotope ratio mass

spectrometer (IRMS) for FY 2012 – FY 2018.

FY 2012 FY 2013 FY 2014 FY 2015 FY 2016 FY 2017 FY 2018 Income $19,845 $9,683 $9,748 $12,602 $23,786 $12,586 $14,906 Clerical/ Technical

$9,385 $10,081 $6,436 $4,585 $8,565 $4,729 $7,847

Fringe Benefits

$3,402 $3,831 $2,510 $1,674 $3,212 $1,773 $3,061

Services $518 $679 $570 $258 $0.10 $0 $0 Supplies-gases

$4,475 $2,509 $2,856 $3,272 $3,437 $2,338

Supplies-parts, chemicals, consumables

$1,529 $1,855 $1,529 $2,572 $1,776 $1,961

Gas cylinder rental

$1,212 $832 $1,349 $1,005 $1,040 $1,013

Table 4. Combined expenses and income for the inductively coupled plasma

optical emission spectrometer (ICP-OES) for FY 2012 – FY 2018.

FY 2012 FY 2013 FY 2014 FY 2015 FY 2016 FY 2017 FY 2018 Income $8,861 $5,095 $14,855 $13,688 $10,685 $23,824 $20,311 Clerical/ Technical

$6,320 $3,571 $6,335 $6,084 $7,576 $11,854 $13,185

Fringe Benefits

$2,291 $1,357 $2,471 $2,221 $2,841 $4,445 $5,142

Supplies-gases

$2,120 $2,873 $4,515 $3,213 $3,439 $5,844 $3,810

Supplies-parts, chemicals, consumables

$1,483 $1,131 $2,048 $1,431 $1,271 $2,025 $2,287

Gas cylinder rental

$834 $875 $986 $1,548 $1,079 $1,750 $1,132

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Table 5. Combined expenses for the total organic carbon analyzer (DOC) and elemental analyzer (EA) for FY 2012 – FY 2017.

FY 2012 FY 2013 FY 2014 FY 2015 FY 2016 FY 2017 FY 2018 Income $23,355 $28,881 $25,408 $25,408 $15,924 $15,324 $16,464 Clerical/ Technical

$11,800 $17,063 $15,809 $10,824 $9,817 $7,172 $9,679

Fringe Benefits

$3,947 $5,320 $6,122 $3,951 $3,682 $2,690 $3,775

Supplies-gases

$2,533 $3,925 $3,400 $3,586 $3,923 $2,439

Supplies-parts, chemicals, consumables

$3,644 $1,507 $2,275 $1,414 $1,410 $1,718

Gas cylinder rental

$870 $429 $822 $712 $682 $552

Internal funding for MAF for FY 2019 included an award of $87,806. The funding will be distributed as follows: $10,200 for repair of the LC/MS in the ChARM Laboratory, $49,892 for ChARM Laboratory user fees, $16,671, for maintenance required on the IRMS in LEAF, $5,935 for replacement of the DI water system in LEAF, and $5,108 to erase the FY 2018 deficit. Developmental Plans –Developing a stable user base that is sufficient for full funding of technical staff for the MAF associated laboratories is the principal goal for future development of the shared facility. A fully developed MAF will require technical staff to manage activities of LEAF and ChARM. The LEAF has been successful at operating via user fees and partially offsetting the salary of a technical staff. The technical staff for the ChARM Laboratory will be partially supported in FY 2019 via the FY 2019 core facility award. Sufficient user fees will have to be charged to fund the balance of the technical staff’s salary. A principal goal for LEAF in FY 2019 is to have a pool of funds immediately available when needed for non-routine repair of instruments. The funds would be used for manufacturer’s service technicians, repair parts, and tools for major problems that are not a part of routine maintenance or considered consumable parts replacements. Examples may be replacements of electrical circuit boards, computers, or a failed vacuum pump. Instruments can be out of service for months while trying to obtain funding for troubleshooting and repairs, which results in a delay in getting data to researchers, or the researchers sending their samples to another institution. Also, if repairs are not made when they are needed, it could result in more costly repairs in the future. Instrument use charges can be used for this purpose; however it is not permitted to generate a surplus of funds from instrument use charges, so if repairs and service are

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performed, it creates a large deficit in the use accounts. Increasing use fees, using departmental funds, or the overhead return on the use charge index must be used to erase the deficit. Changing the use fees from year to year to make up for these occasional large expenditures is difficult for researchers who have budgeted a specific amount of funds for sample analyses. Departmental funds are not appropriate to use to support shared facilities that are used by the entire university community. Overhead return accounts generated from use charges typically do not contain sufficient funds for major repairs. Risks and Challenges – The greatest challenge for the MAF is creating a sufficient cash flow to keep instruments and equipment running and to cover the salary of technical staff. Including maintenance and instrument replacement in user fees drives up the per sample costs to users making it difficult to remain competitive. Meeting the challenge with the only source of support being soft money is particularly difficult in the early stages of the Facility development. Offsetting some of the salary of technical staff through unit funds would help in this regard. An additional challenge, which was realized in FY 2017, was the loss of space for the MBL due to University policy that allows units to buy and sell space. Space is designated as “University space”, and thus, the ability of a unit to buy and sell space, and in particular shared facility space, runs counter to the designation of space as “University space”. Unlike laboratory space occupied by Tech faculty, shared facilities are a resource, which are available to investigators and students across campus, including those of the unit in which the shared facilities are located. Thus, allowing a unit to sell space occupied by a shared facility runs counter to the mission of the shared facilities. In addition, moving a shared facility from a laboratory with infrastructure uniquely developed for its purpose to another laboratory where the infrastructure must be duplicated is a waste of Tech resources and the time of the director of the associated laboratory of the shared facility. Summary Comments – The LEAF was in operation long before the MAF was established in FY 2015, and thus, the focus of Volume II is on LEAF. The MAF currently has two research technical staff responsible for activities in LEAF and ChARM. Use of instrumentation in LEAF varies from year to year with no overall trends in use. All items identified in the annual safety analyses of the MAF associated Laboratories that required attention were corrected. User fees support operation of LEAF. An FY 2019 internal award ($$87,806) for MAF will be used to support a research technical staff for ChARM and maintenance and replacement of equipment in LEAF. The principal development plan for MAF continues to be identifying a stable user base to support technical staff to handle the volume of activity in the MAF associated Laboratories.