Justin R. Schueller James A. Luoma Nicholas A. Schloesser Todd A. Johnson Courtney A. Kirkeeng 20220114 spreadsheet https://doi.org/10.5066/P910SHBL James Luoma Justin Schueller Nicholas Schloesser Todd Johnson Courtney Kirkeeng 2023 publication Management of Biological Invasions vol. 14, issue 2 n/a Regional Euro-Asian Biological Invasions Centre Oy (REABIC) ppg. 247-362 https://doi.org/10.3391/mbi.2023.14.2.11 The dataset was generated to verify the suitability of the new TFM bar formulation for wide-scale use in the Sea Lamprey Control Program (SLCP). Dataset includes TFM concentrations of three streams (each used twice) where randomized experimental applications of new and old TFM bar formulation dissolution trials were conducted, TFM concentrations of 12 laboratory flume experimental applications of new and old TFM bar formulation dissolution trials, various collected water chemistry parameters, % Active ingredient data from both new and old TFM bar formulation under normal storage and elevated temperature storage conditions, and bar hardness data from both new and old TFM bar formulation under normal storage and elevated temperature storage conditions. Data were collected to verify the suitability of the new 4-Nitro-3-(trifluoromethyl)phenol (TFM) bar formulation for wide-scale use in the SLCP. The following objectives were used to achieve this goal: (1) complete randomized experimental applications of new and old TFM bar formulations in three low-discharge tributaries on consecutive days, (2) experimental applications of new and old TFM bar formulations (including bars previously stored at elevated temperatures) in a laboratory constructed flume, (3) compare and contrast the release profiles of TFM from bars of the new and old formulation as determined from the measured concentrations of TFM in water samples collected every 30 minutes for 24 hours, and (4) evaluate if the duration of TFM release from the new formulation during field applications is sufficiently improved to be acceptable for routine use by the SLCP. Other evaluations included analysis of the % Active ingredient in both the new and old formulations, and hardness determination of the bars at both room and elevated temperatures. 20210603 20210111 ground condition Complete None planned World -92.4609 -76.0693 48.9225 41.4427 ISO 19115 Topic Category biota None lampricide, TFM Bar, Sea Lamprey, Invasive species USGS Metadata Identifier USGS:639115d7d34e0de3a1ef8358 None Great Lakes, Michigan None. Please see 'Distribution Info' for details. None. Users are advised to read the dataset's metadata thoroughly to understand appropriate use and data limitations. Justin Schueller UMESC Chemist mailing and physical

2630 Fanta Reed Road

La Crosse WI 54603 6087816340 jschueller@usgs.gov Funding for the research project provided by the GLFC. Support for the project provided by U.S.-FWS TFM Concentration Data: 1.0 mg/L field spike samples were prepared at the start of each field trial. 1.0 mg/L lab spike samples were prepared at the beginning of each HPLC analysis. 5 standards bracketing the sample concentrations were prepared at the start of each HPLC analysis. Correlation coefficients (r2) exceeded 0.99995 for all standard curves, Spike recoveries ranged from 94.2-104.1%. Field Discharge and Velocity: Discharge and velocity instrumentation had auto QA-QC check and beam check were conducted at the beginning of each day prior to data collection. Temperature: Thermometers are have accuracy verified annually. pH: Meter calibrated daily with pH 7 and 10 standards, and accuracy verified prior to use. Reagents verified for expiration date and correct concentration. Dissolved Oxygen: Meter calibrated daily, and accuracy verified prior to use. Conductivity Meter calibrated daily with 185 and 1000 µS/cm @25˚C standards, and accuracy verified prior to use. Reagents verified for expiration date and correct concentration. Alkalinity: Meter calibrated daily with pH 4 and 7 standards, and accuracy verified prior to use. Hardness, No QA Required, standard titration. Reagents verified for expiration date and correct concentration. Data logically matches with the details we provided. All data falls with expected ranges. Data have been verified for accuracy. Data set is complete. Fixed geographic area as the chemical is only applied in the great lakes basin. NA NA Field Bar Evaluations Applications were completed during an approved time period for a regularly scheduled SLCP stream treatment. Applications were planned in conjunction with the Rifle River (Ogemaw and Arenac County, Michigan) lampricide treatment during August of 2021. Applications were in three low-discharge tributaries of the Rifle River (Peterson, Prather and Dedrich streams, Ogemaw and Arenac County, Michigan). Tributaries were selected by SLCP treatment supervisors who considered study objectives as well as tributary access, hydrology, and sites for applications, discharge measurements and placement of water samplers. To complete study objective one, formulation test order for each tributary were randomly determined and applications were completed on consecutive days. Water velocities and tributary discharge were measured and calculated using methods consistent with the SLCP Technical Operating Procedure 001 (Solomon 2021). A FlowTracker 2 acoustic doppler velocimeter (SonTek – a Xylem brand, San Diego, California) fitted with a top mounting wading rod was used to obtain velocity data and calculate discharge prior to application as well as at 6, 12, and 24 hours after application. The Mean-Section method will be used to calculate discharge. Application procedures followed the SLCP Technical Operating Procedure 015, “Procedures for the Supplemental Application of the TFM Bar Formulation” (Solomon 2021). A target TFM concentration of 2 mg/L (or less) was used for all applications to remove confounding factors for comparison and this concentration is well below historical minimum lethal concentrations in all tributaries. Water samples were collected (in triplicate) every 30 minutes over the 24 hours immediately following the application with an automated water sampler (model #3700, Teledyne-Isco, Inc, Lincoln, Nebraska). Subsamples were stored frozen (-20°C) until analyzed for TFM concentration at UMESC. Sample collection sites were sufficiently downstream of the bar application points to assure uniform mixing of the eluted TFM into the water column. Concentrations of TFM in the samples were determined using established high-performance liquid chromatography (HPLC) methods (USGS 2019). Sample response was compared to a linear regression created with analytical standards and an Agilent model 1260 HPLC (Agilent Technologies Inc., Santa Clara, California) equipped with a diode array detector. 20210813 Lab Bar Evaluations Laboratory Bar trials were conducted with smaller bars prepared in laboratory. Bars were prepared with a hole saw, and then sliced to an appropriate thickness (6.0 cm wide, 0.9 cm deep, 38 grams) Applications were completed during laboratory flume, targeting a temperature of 17 degrees, a discharge of 11 L/min, and a water velocity of 0.04 m/sec. To complete study objective two, formulation test order was fixed, with an old bar formulation, new bar formulation and old and new formulations stored at elevated temps being assayed until triplicate assays were conducted for each bar time (12 individual flume assays). Water velocities and tributary discharge were measured and calculated using a graduate cylinder to measure 5 replicates of water volume leaving the flume in 20 second intervals. The height of the water in the flume (6 inch PVC pipe) was used to calculate average velocity from the discharge measurement. Application procedures followed the SLCP Technical Operating Procedure 015, “Procedures for the Supplemental Application of the TFM Bar Formulation” (Solomon 2021). The same mass of TFM bar (approximately 38 grams) was used for all applications to remove confounding factors for comparison and this concentration is well below historical minimum lethal concentrations in all tributaries. Water samples were collected (in triplicate) every 30 minutes over the 24 hours immediately following the application with an automated water sampler (model #3700, Teledyne-Isco, Inc, Lincoln, Nebraska). Subsamples were stored frozen (-20°C) until analyzed for TFM concentration at UMESC. Sample collection sites were sufficiently downstream of the bar application points to assure uniform mixing of the eluted TFM into the water column. Concentrations of TFM in the samples were determined using established high-performance liquid chromatography (HPLC) methods (USGS 2019). Sample response was compared to a linear regression created with analytical standards and an Agilent model 1260 HPLC (Agilent Technologies Inc., Santa Clara, California) equipped with a diode array detector. 20211215 Data Analysis For objectives 3 and 4 Data were analyzed using R and RStudio software (version 4.1.1, R Core Team 2021 and version 2021.09.0, build 351, RStudio Team 2021, respectively). Simple descriptive statistics were used to summarize water-quality properties, discharge, and water velocity for both the laboratory and field trials. Quantile-quantile plots were used to assess data for homoscedasticity and normality prior to conducting statistical analyses. Differences in field water-quality properties, discharge, and water velocity data were detected using one-way analysis of variance (AOV) tests accounting for stream (Bates et al., 2015) and post-hoc Tukey Honest Significant Difference tests (Montgomery 2017) were used to determine which properties differed. Differences in laboratory flume water-quality properties, discharge, and water velocity data were detected using one-way analysis of variance tests accounting for replicate and post-hoc Tukey Honest Significant Difference tests were used to determine which properties differed. Exponential decay curves were fit to the TFM data for each laboratory and field trial and modeled according to OECD (2014) using the DRC package (Ritz et al. 2015). Model fitness was assessed by calculating the median absolute deviation (MAD) for each application/formulation. The MAD was calculated as the median of the absolute value of the distance between the calculated and the model predicted percentage of TFM remaining in the TFM bars. The predicted times required to release 25, 50, 75 and 90% of the TFM from the bars were determined from each model, with differences between the bar formulations detected using one-way analysis of variance tests (Montgomery 2017) and post-hoc Tukey Honest Significant Difference tests were used to identify specific differences. R Core Team (2021). R: A language and environment for statistical computing. R Foundation for Statistical Computing, Vienna, Austria. URL https://www.R-project.org/ RStudio Team (2021). RStudio: Integrated Development for R. RStudio, PBC, Boston, MA URL http://www.rstudio.com/ Bates, D., Kliegl, R., Vasishth, S., & Baayen, R.H. (2015, arXiv). Parsimonious mixed models Montgomery, D. C. (2017). Design and Analysis of Experiments. John Wiley & Sons, Incorporated. https://books.google.com/books?id=Py7bDgAAQBAJ 20220109 TFM Bar Hardness and % AI Three bars of the new formulation and 3 bars of the old formulation utilized in hardness and % AI determination. From each bar, two subsamples were cut using a 2.5 inch holesaw (6 cm wide 2.0 cm thick, 80-85 grams) Of these two subsamples one was stored at 20˚C, and the other stored at 45˚C for both hardness evaluation and % AI determination. Each had its hardness determined in triplicate (Graigar FHT-1122 Digital Fruit Penetrometer). RT samples were processed for % AI DeterminationAfter allowing the HS samples to acclimate to room temperature, HS samples were processed for % AI Determination. Each subsample was analyzed for % AI in triplicate. 0.500 g of bar was weighed out on a 5-place analytical balance (Sartorius Model MSU225S-100-DI, S/N 29505562), with mass recorded to the fifth decimal place. Material was transferred to a 500 mL volumetric flask, brought to volume with HPLC Grade Methanol (Lot Number: 21060309, VWR) sonicated until all bar material was dissolve, and allowed to cool to room temperature. Flasks were then shock vigorously for 1 minute, and 1.0 mL was transferred to a 100 mL volumetric flask. 0.5 mL of this diluted sample was transferred to an HPLC vial, and analyzed as described previously % TFM in the bar subsamples was calculated as %TFM: Percent TFM = HPLC Concentration (mg/L) x Dilution factor (50) /Sample weight (mg) x 100 (%). 20220111 Field_Decay_Data_1.csv Dataset include Average TFM concentration, and percent of TFM remaining data from objective 1 field TFM bar dissolution trials. Data set used to generate exponential decay data for field trials of TFM bar dissolution and also used in R code to generate Field_Decay_Data_2.csv to be used in other analysis. Producer Defined Stream Numerical Representation of the data for use as factorization in R ("1" = "Peterson New", "2" = "Prather New", "3" = "Dedrich New", "4" = "Peterson Old", "5" = "Prather Old", "6" = "Dedrich Old") Producer Defined 1 Stream = Peterson Bar Formulation = Old Formulation Producer defined 4 Stream = Peterson Bar Formulation = New Formulation Producer defined 2 Stream = Prather Bar Formulation = Old Formulation Producer defined 5 Stream = Prather Bar Formulation = New Formulation Producer defined 3 Stream = Dedrich Bar Formulation = Old Formulation Producer defined 6 Stream = Dedrich Bar Formulation = New Formulation Producer defined StreamA Representation of the data for use as factorization in R ("Stream 1" = "Peterson All Formulations", "Stream 2" = "Prather All Formulations", "Stream 3" = "Dedrich All Formulations") Producer Defined Stream 1 Peterson All Formulations Producer defined Stream 2 Prather All Formulations Producer defined Stream 3 Dedrich All Formulations Producer defined StreamB Stream Name for field data (Stream at which the data was collected). Producer Defined Peterson Peterson Creek data from field portion satisfying objective one. Application point GPS Coordinates: (44.24643°N, 084.06491°W) Producer defined Prather Prather Creek data from field portion satisfying objective one. Application point GPS Coordinates: (44.22499°N, 084.06721°W) Producer defined Dedrich Dedrich Creek data from field portion satisfying objective one. Application point GPS Coordinates: (44.28769°N, 084.07607°W) Producer defined Formulation Which formulation of TFM was used for given TFM Bar dissolution trial Producer Defined New Formulation Lot Number: TFBA210331A Producer defined Old Formulation Lot Number: TFBA210430A Producer defined Time Time post TFM bar application at which the water sample was collected (Hours) 0 = immediately at application. Producer Defined 0.0 24.0 Hours Average TFM concentation data from the triplicate samples collected at sampling time point. Average is the average concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 1.3 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Upper TFM concentation data from the triplicate samples collected at sampling time point. Average is the highest concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 1.321882941 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Lower TFM concentation data from the triplicate samples collected at sampling time point. Average is the Lowest concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 1.273135387 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Std Dev TFM concentation data from the triplicate samples collected at sampling time point. Average is the standard deviation of the concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 0.08 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) TFMReleased Calculated value of the the total mg of TFM released up to the sample collection based on the determined sample 4-Nitro-3-(trifluoromethyl)phenol (TFM) concentration, and discharge measurement from the stream. Producer Defined 0.0 105554.0 milligrams of 4-Nitro-3-(trifluoromethyl)phenol (TFM) TFMUsedM Calculated value of the mg of TFM released in the 30 minutes leading up to the sample collection based on the summation of the previous column up to the given timepoint. Producer Defined 0.0 1489502.0 milligrams of 4-Nitro-3-(trifluoromethyl)phenol (TFM) TFM Used (%) Calculated value of the % of the TFM release based on the summation data in the previous column and the known amount of TFM in the bars based on total bar weight. Producer Defined 0.0 100.0 Percent TFMRemainingP Percent of TFM remaining in the bars placed in the stream based on 100 - TFM Used (%). Column used in R code to model exponential decay of the bars in the field setting. Producer Defined 0.0 100.0 Percent Field_TFM_Conc.csv Dataset include Average TFM concentration. Data set used to generate figures in R to show dissolution of TFM bars in a field setting. Producer Defined Stream Numerical Representation of the data for use as factorization in R ("1" = "Peterson New", "2" = "Prather New", "3" = "Dedrich New", "4" = "Peterson Old", "5" = "Prather Old", "6" = "Dedrich Old") Producer Defined 1 Stream = Peterson Bar Formulation = New Formulation Producer defined 2 Stream = Prather Bar Formulation = New Formulation Producer defined 3 Stream = Dedrich Bar Formulation = New Formulation Producer defined 4 Stream = Peterson Bar Formulation = Old Formulation Producer defined 5 Stream = Prather Bar Formulation = Old Formulation Producer defined 6 Stream = Dedrich Bar Formulation = Old Formulation Producer defined Time Time post TFM bar application at which the water sample was collected (Hours) 0 = immediately at application. Producer Defined 0.0 24.0 Hours Rep TFM concentation data from the triplicate samples collected at sampling time point. Replicate being which of the samples this concentration data is from. Producer Defined 1 First Replicate Producer defined 2 Second Replicate Producer defined 3 Third Replicate Producer defined TFMConc TFM concentration data from the triplicate samples collected at sampling time point. Concentration of the sample as milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 1.321883 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) TFMConcAve Average TFM concentration data from the triplicate samples collected at sampling time point. Concentration of the sample as milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, average data is only available with the first replicate of each triplicate measurement. Producer defined 0 ~ milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Field_Water_Chem_Bar.csv Dataset includes water chem, discharge and velocity data from field bar trials for use in R for simple descriptive statistics and AOVs to compare stream characteristics. Producer Defined Stream Numerical Representation of the data for use as factorization in R ("1" = "Peterson New", "2" = "Prather New", "3" = "Dedrich New", "4" = "Peterson Old", "5" = "Prather Old", "6" = "Dedrich Old") Producer Defined 1 Stream = Peterson Bar Formulation = New Formulation Producer defined 2 Stream = Prather Bar Formulation = New Formulation Producer defined 3 Stream = Dedrich Bar Formulation = New Formulation Producer defined 4 Stream = Peterson Bar Formulation = Old Formulation Producer defined 5 Stream = Prather Bar Formulation = Old Formulation Producer defined 6 Stream = Dedrich Bar Formulation = Old Formulation Producer defined StreamA Numerical Representation of the data for use as factorization in R ("Stream 1" = "Peterson All Formulations", "Stream 2" = "Prather All Formulations", "Stream 3" = "Dedrich All Formulations") Producer Defined 1 Peterson All Formulations Producer defined 2 Prather All Formulations Producer defined 3 Dedrich All Formulations Producer defined Formulation Which formulation of TFM was used for given TFM Bar dissolution trial Producer Defined New Lot Number: TFBA210331A Producer defined Old Lot Number: TFBA210430A Producer defined Time Time post TFM bar application at which the water sample was collected (Hours) 0 = immediately at application. Producer Defined 0 24 Hours Temp Temperature of the stream water at the given timepoint. Temperature given in degrees celcius Producer Defined 13.8 23.1 degrees celcius pH pH of the stream water at the given timepoint. pH given in standard pH units Producer Defined 7.68 8.5 pH pH2 pH of the stream water at the given timepoint. pH given in concentration of hydronium ions molarity units Producer Defined 3.16e-09 2.09e-08 molarity DO Dissolved oxygen of the stream water at the given timepoint. Dissolved oxygen given in milligrams per liter as O2 Producer Defined 7.02 10.53 milligrams per liter as O2 Cond Specific conductance (µS/cm @ 25˚C) of the stream water at the given timepoint. Specific conductance (µS/cm @ 25˚C) given iµS/cm @ 25˚C Producer Defined 336 459 microseimens per centimeter at 25 degrees celcius Alkalinity Alkalinity of the stream water at the given timepoint. Alkalinity given in milligrams per liter as calcium carbonate Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 160 230 milligrams per liter as calcium carbonate Hardness Total Hardness of the stream water at the given timepoint. Total Hardness given in milligrams per liter as calcium carbonate Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 156 236 milligrams per liter as calcium carbonate Discharge Discharge of the stream at the given timepoint. discharge given in cubic meters per second Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 0.008 0.0475 cubic meters per second Velocity Average water velocity of the stream at the given timepoint. Average water velocity given in meters per second Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 0.0352 0.3423 meters per second MaxDepth Max depth of the stream discharge site at the given timepoint. Max depth of the stream discharge site given in meters Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 0.12 0.26 meters Gage Height Staff gage height on the stream at time of water quality collection. Given in meters Producer Defined ~ Sample failed to be recorded Producer defined 0.4 0.5 meters Lab_Decay_Data_1.csv Dataset include Average TFM concentration, and percent of TFM remaining data from objective 1 laboratory TFM bar dissolution trials. Data set used to generate exponential decay data for field trials of TFM bar dissolution and also used in R code to generate Lab_Decay_Data_2.csv to be used in other analysis. Producer Defined BarNumber Numerical Representation of the data for use as factorization in R. ("1" = "Old Form Rep 1", "2" = "New Form Rep 1", "3" = "Old Form-HS Rep 1", "4" = "New Form-HS Rep 1", "5" = "Old Form Rep 2", "6" = "New Form Rep 2", "7" = "Old Form-HS Rep 2", "8" = "New Form-HS Rep 2", "9" = "Old Form Rep 3", "10" = "New Form Rep 3", "11" = "Old Form-HS Rep 3", "12" = "New Form-HS Rep 3") Producer Defined 1 Old Formulation stored at room temperature replicate number 1 Producer defined 2 New Formulation stored at room temperature replicate number 1 Producer defined 3 Old Formulation stored at elevated temperature replicate number 1 Producer defined 4 New Formulation stored at elevated temperature replicate number 1 Producer defined 5 Old Formulation stored at room temperature replicate number 2 Producer defined 6 New Formulation stored at room temperature replicate number 2 Producer defined 7 Old Formulation stored at elevated temperature replicate number 2 Producer defined 8 New Formulation stored at elevated temperature replicate number 2 Producer defined 9 Old Formulation stored at room temperature replicate number 3 Producer defined 10 New Formulation stored at room temperature replicate number 3 Producer defined 11 Old Formulation stored at elevated temperature replicate number 3 Producer defined 12 New Formulation stored at elevated temperature replicate number 3 Producer defined Bar Which formulation of TFM was was used to make the small bar for laboratory flume dissolution Producer Defined Old Formulation Lot Number: TFBA210430A Producer defined New Formulation Lot Number: TFBA210331A Producer defined BarRep Which rep of the given bar formulation and storage condition the given trial is Producer Defined 1 Replicate number 1 Producer defined 2 Replicate number 2 Producer defined 3 Replicate number 3 Producer defined HS Storage conditions of the bar, room temp bars were stored at 20 degrees celcius where as elevated temperature bars were stored at 45 degrees celcius for 24 hours prior to being used in laboratory flume dissolution trials. Producer Defined Room Temperature stored at 20 degrees celcies for 24 hours prior to being used in laboratory flume dissolution trials Producer defined Elevated Temperature stored at 45 degrees celcies for 24 hours prior to being used in laboratory flume dissolution trials Producer defined Time Time post TFM bar application at which the water sample was collected (Hours) 0 = immediately at application. Producer Defined 0.0 24.0 Hours TFMRep TFM concentration data from the triplicate samples collected at sampling time point. Replicate being which of the samples this concentration data is from. Producer Defined 1 First Replicate Producer defined 2 Second Replicate Producer defined 3 Third Replicate Producer defined SampleConc TFM concentration data from the triplicate samples collected at sampling time point. Concentration of the sample as milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 4.22 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Average TFM concentration data from the triplicate samples collected at sampling time point. Average is the average concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, average data is only available with the first replicate of each triplicate measurement. Producer defined 0 4.2 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) StdDev TFM concentration data from the triplicate samples collected at sampling time point. StdDev is the standard deviation of the sample concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, StdDev data is only available with the first replicate of each triplicate measurement. Producer defined 0.0 0.27 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) TFMReleased Calculated value of the the total mg of TFM released up to the sample collection based on the determined sample 4-Nitro-3-(trifluoromethyl)phenol (TFM) concentration, and discharge measurement from the laboratory flume. Producer Defined ~ No data available, TFMReleased data is only available with the first replicate of each triplicate measurement. Producer defined 0 1370 milligrams TFMUsedM Calculated value of the mg of TFM released in the 30 minutes leading up to the sample collection based on the summation of the previous column up to the given timepoint. Producer Defined ~ No data available, Data is only available with the first replicate of each triplicate measurement. Producer defined 0 9618 milligrams TFMUsedP Calculated value of the % of the TFM release based on the summation data in the previous column and the known amount of TFM in the bars based on total bar weight. Producer Defined ~ No data available, Data is only available with the first replicate of each triplicate measurement. Producer defined 0 109 percent CorTFMUsedP Calculated value of the % of the TFM release based on the summation data in the previous column and the known amount of TFM in the bars based on total bar weight. Corrected for end result to be 100% as all bars were completely dissolved by end of the trial Producer Defined ~ No data available, Data is only available with the first replicate of each triplicate measurement. Producer defined 0 100 percent TFMRemainingP Percent of TFM remaining in the bars placed in the stream based on 100 - TFM Used (%). Column used in R code to model exponential decay of the bars in the field setting. Producer Defined ~ No data available, Data is only available with the first replicate of each triplicate measurement. Producer defined 0 100 percent Taverage Total Average TFM concentation data from the triplicate samples of each bar of similar formulation and storage conditions collected at sampling time point. Average is the average concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, Data is only available with the first bar replicate and triplicate replicate measurement. Producer defined 0 3.86 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Tupper Highest TFM concentation data from the triplicate samples of each bar of similar formulation and storage conditions collected at sampling time point. Average is the average concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, Data is only available with the first bar replicate and triplicate replicate measurement. Producer defined 0 4.22 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Tlower Lowest TFM concentation data from the triplicate samples of each bar of similar formulation and storage conditions collected at sampling time point. Average is the average concentration of the triplicate samples in mg/L as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, Data is only available with the first bar replicate and triplicate replicate measurement. Producer defined 0 3.42 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Lab_TFM_Conc.csv Dataset include Average TFM concentration. Data set used to generate figures in R to show dissolution of TFM bars in a lab setting. Producer Defined Stream Numerical Representation of the data for use as factorization in R. ("1" = "Old Form Rep 1", "2" = "New Form Rep 1", "3" = "Old Form-HS Rep 1", "4" = "New Form-HS Rep 1", "5" = "Old Form Rep 2", "6" = "New Form Rep 2", "7" = "Old Form-HS Rep 2", "8" = "New Form-HS Rep 2", "9" = "Old Form Rep 3", "10" = "New Form Rep 3", "11" = "Old Form-HS Rep 3", "12" = "New Form-HS Rep 3") Producer Defined 1 Old Formulation stored at room temperature replicate number 1 Producer defined 2 New Formulation stored at room temperature replicate number 1 Producer defined 3 Old Formulation stored at elevated temperature replicate number 1 Producer defined 4 New Formulation stored at elevated temperature replicate number 1 Producer defined 5 Old Formulation stored at room temperature replicate number 2 Producer defined 6 New Formulation stored at room temperature replicate number 2 Producer defined 7 Old Formulation stored at elevated temperature replicate number 2 Producer defined 8 New Formulation stored at elevated temperature replicate number 2 Producer defined 9 Old Formulation stored at room temperature replicate number 3 Producer defined 10 New Formulation stored at room temperature replicate number 3 Producer defined 11 Old Formulation stored at elevated temperature replicate number 3 Producer defined 12 New Formulation stored at elevated temperature replicate number 3 Producer defined Stream_2 Representation of the data for use as factorization in R ("1" = "Old Form", "2" = "New Form", "3" = "Old Form-HS", "4" = "New Form-HS") Producer Defined 1 Old Form room temp storage Producer defined 2 New Form room temp storage Producer defined 3 Old Form elevated temp storage Producer defined 4 New Form elevated temp storage Producer defined BarRep Which rep of the given bar formulation the given trial is Producer Defined 1 Replicate number 1 Producer defined 2 Replicate number 2 Producer defined 3 Replicate number 3 Producer defined Formulation Which formulation of TFM was was used to make the small bar for laboratory flume dissolution Producer Defined Old Form Lot Number: TFBA210430A Producer defined New Form Lot Number: TFBA210331A Producer defined HeatStress Storage conditions of the bar, room temp bars were stored at 20 degrees Celsius where as elevated temperature bars were stored at 45 degrees celcius for 24 hours prior to being used in laboratory flume Producer Defined N stored at 20 degrees celcies for 24 hours prior to being used in laboratory flume dissolution trials Producer defined Y stored at 45 degrees celcies for 24 hours prior to being used in laboratory flume dissolution trials Producer defined Rep TFM concentation data from the triplicate samples collected at sampling time point. Replicate being which of the samples this concentration data is from. Producer Defined 1 First Replicate Producer defined 2 Second Replicate Producer defined 3 Third Replicate Producer defined Time Time post TFM bar application at which the water sample was collected (Hours) 0 = immediately at application. Producer Defined 0.0 24.0 Hours TFMConc TFM concentration data from the triplicate samples collected at sampling time point. Concentration of the sample as milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined 0.0 4.218999999999999 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) TFMConcAve Average TFM concentration data from the triplicate samples collected at sampling time point. Concentration of the sample as milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Producer Defined ~ No data available, average data is only available with the first replicate of each triplicate measurement. Producer defined 0.000 4.195 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Lab_Water_Chem_Bar.csv Dataset includes water chem, discharge and velocity data from lab flume bar trials for use in R for simple descriptive statistics and AOVs to compare stream characteristics. Producer Defined Stream Numerical Representation of the data for use as factorization in R. ("1" = "Old Form Rep 1", "2" = "New Form Rep 1", "3" = "Old Form-HS Rep 1", "4" = "New Form-HS Rep 1", "5" = "Old Form Rep 2", "6" = "New Form Rep 2", "7" = "Old Form-HS Rep 2", "8" = "New Form-HS Rep 2", "9" = "Old Form Rep 3", "10" = "New Form Rep 3", "11" = "Old Form-HS Rep 3", "12" = "New Form-HS Rep 3") Producer Defined 1 Old Formulation stored at room temperature replicate number 1 Producer defined 2 New Formulation stored at room temperature replicate number 1 Producer defined 3 Old Formulation stored at elevated temperature replicate number 1 Producer defined 4 New Formulation stored at elevated temperature replicate number 1 Producer defined 5 Old Formulation stored at room temperature replicate number 2 Producer defined 6 New Formulation stored at room temperature replicate number 2 Producer defined 7 Old Formulation stored at elevated temperature replicate number 2 Producer defined 8 New Formulation stored at elevated temperature replicate number 2 Producer defined 9 Old Formulation stored at room temperature replicate number 3 Producer defined 10 New Formulation stored at room temperature replicate number 3 Producer defined 11 Old Formulation stored at elevated temperature replicate number 3 Producer defined 12 New Formulation stored at elevated temperature replicate number 3 Producer defined Stream_2 Representation of the data for use as factorization in R ("1" = "Old Form", "2" = "New Form", "3" = "Old Form-HS", "4" = "New Form-HS") Producer Defined 1 Old Form room temp storage Producer defined 2 New Form room temp storage Producer defined 3 Old Form elevated temp storage Producer defined 4 New Form elevated temp storage Producer defined BarRep Which rep of the given bar formulation the given trial is Producer Defined 1 Replicate number 1 Producer defined 2 Replicate number 2 Producer defined 3 Replicate number 3 Producer defined Formulation Which formulation of TFM was was used to make the small bar for laboratory flume dissolution Producer Defined Old Form Lot Number: TFBA210430A Producer defined New Form Lot Number: TFBA210331A Producer defined HeatStress Storage conditions of the bar, room temp bars were stored at 20 degrees Celcius where as elevated temperature bars were stored at 45 degrees Celsius for 24 hours prior to being used in laboratory flume Producer Defined N stored at 20 degrees celcies for 24 hours prior to being used in laboratory flume dissolution trials Producer defined Y stored at 45 degrees celcies for 24 hours prior to being used in laboratory flume dissolution trials Producer defined Time Time post TFM bar application at which the water sample was collected (Hours) 0 = immediately at application. Producer Defined 0 24 Hours Temp Temperature of the stream water at the given timepoint. Temperature given in degrees celcius Producer Defined 16.5 17.4 degrees celcius pH pH of the stream water at the given timepoint. pH given in standard pH units Producer Defined 7.56 8.01 pH DO Dissolved oxygen of the stream water at the given timepoint. Dissolved oxygen given in milligrams per liter as O2 Producer Defined 7.0 9.16 milligrams per liter as O2 Cond Specific conductance (µS/cm @ 25˚C) of the stream water at the given timepoint. Specific conductance (µS/cm @ 25˚C) given iµS/cm @ 25˚C Producer Defined 403 431 microseimens per centimeter at 25 degrees celcius Alkalinity Alkalinity of the stream water at the given timepoint. Alkalinity given in milligrams per liter as calcium carbonate Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 134.4 158.1 milligrams per liter as calcium carbonate Hardness Total Hardness of the stream water at the given timepoint. Total Hardness given in milligrams per liter as calcium carbonate Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 178 195 milligrams per liter as calcium carbonate Discharge Discharge of the stream at the given timepoint. discharge given in liters per minute Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 10.71 11.1 liters per minute Discharge_2 Discharge of the stream at the given timepoint. discharge given in cubic meters per second Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 0.000178504 0.000185004 cubic meters per second Discharge_3 Discharge of the stream at the given timepoint. discharge given in cubic meters per minute Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 0.01071024 0.0111 cubic meters per minute MaxDepth Max depth of the lab flume at application point at the given timepoint. Max depth of the lab flume at application point given in centimeters Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 4.8 4.9 centimeter Velocity Calculated water velocity of the stream at the given timepoint based on depth of the flume and discharge. Average water velocity given in meters per second Producer Defined ~ Data not collected, samples only collected at timepoints 0, 6, 12, and 24 Producer defined 0.0383 0.0405 meters per second SpikeData.csv Comma Separated Value (CSV) file containing data. Producer Defined Sample_Type Type of quality control sample. Field Spike (Field Samples): 1.0 mg/L field spike samples were prepared at the start of each field trial Lab Spike (Lab Samples): 1.0 mg/L lab spike samples were prepared at the beginning of each HPLC analysis for lab generated water samples Lab Spike (Field Samples): 1.0 mg/L lab spike samples were prepared at the beginning of each HPLC analysis for field generated water samples Producer Defined Lab Spike (Lab Samples) 1.0 mg/L lab spike samples were prepared at the beginning of each HPLC analysis for lab generated water samples Producer defined Lab Spike (Field Samples) 1.0 mg/L lab spike samples were prepared at the beginning of each HPLC analysis for field generated water samples Producer defined Field Spike (Field Samples) 1.0 mg/L field spike samples were prepared at the start of each field trial Producer defined Lab Spike (Bar Samples) 3.0 mg/L lab spike samples were prepared at the beginning of each HPLC analysis for bar sample % AI analysis Producer defined Lab_Spike Percent recovery of the 1 mg/L control sample from HPLC analysis Producer Defined 94.19 104.12 percent Hardness_AI.csv Data set for use in R to determine AI% differences in the bar formulations and room temp verses elevated temp storage conditions. Data are also used to determine differences in bar hardness for each respective bar type. Producer Defined Sample Name General Sample name for sample identification, old or new formulation given as old or new. Old Formulation Lot number is TFBA210430A, New Formulation Lot number is TFBA210331A. Next is bar rep number 1-3, indicating which of the three bars from each formulation that the sample comes from. Next is either RT or HS, dictating whether the sample was stored at Room temp or HS indicating that it was stored at elevated temp Storage conditions of the bar, room temp bars were stored at 20 degrees celcius where as elevated temperature bars were stored at 45 degrees celcius for 24 hours prior to being used in laboratory flume. Last is A, B, or C, indicating which triplicate sample is being used in the given respective values. Producer Defined General Sample name for sample identification, old or new formulation given as old or new. Old Formulation Lot number is TFBA210430A, New Formulation Lot number is TFBA210331A. Next is bar rep number 1-3, indicating which of the three bars from each formulation that the sample comes from. Next is either RT or HS, dictating whether the sample was stored at Room temp or HS indicating that it was stored at elevated temp Storage conditions of the bar, room temp bars were stored at 20 degrees celcius where as elevated temperature bars were stored at 45 degrees celcius for 24 hours prior to being used in laboratory flume. Last is A, B, or C, indicating which triplicate sample is being used in the given respective values. HPLC_Conce Concentration in milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) from the HPLC analysis of each respective sample Producer Defined 2.13156 2.41235 milligrams per liter as 4-Nitro-3-(trifluoromethyl)phenol (TFM) Sample_g Mass of Bar weighed out for each respective HPLC in grams Producer Defined 0.49905 0.5048600000000001 grams AI_P Percent active ingredient for each bar sample Producer Defined 21.3 24.08 percent Hardness Hardness of each bar sample as determined with Graigar FHT-1122 Digital Fruit Penetrometer Hardness reported as Kilogram-force per square centimeter Producer Defined 0.5 19.4 Kilogram-force per square centimeter Bar_Number Numerical Representation of the data for use as factorization in R. ("1" = "Old Form Room Temp Rep 1", "2" = "Old Form Room Temp Rep 2", "3" = "Old Form Room Temp Rep 3", "4" = "Old Form Elev Temp Rep 1", "5" = "Old Form Elev Temp Rep 2", "6" = "Old Form Elev Temp Rep 3", "7" = "New Form Room Temp Rep 1", "8" = "New Form Room Temp Rep 2", "9" = "New Form Room Temp Rep 3", "10" = "New Form Elev Temp Rep 1", "11" = "New Form Elev Temp Rep 2", "12" = "New Form Elev Temp Rep 3") Producer Defined 1 Old Formulation, Lot number is TFBA210430A Room temp storage conditions Rep 1 Producer defined 2 Old Formulation, Lot number is TFBA210430A Room temp storage conditions Rep 2 Producer defined 3 Old Formulation, Lot number is TFBA210430A Room temp storage conditions Rep 3 Producer defined 4 Old Formulation, Lot number is TFBA210430A Elevated temp storage conditions Rep 1 Producer defined 5 Old Formulation, Lot number is TFBA210430A Elevated temp storage conditions Rep 2 Producer defined 6 Old Formulation, Lot number is TFBA210430A Elevated temp storage conditions Rep 3 Producer defined 7 New Formulation, Lot number is TFBA210331A Room temp storage conditions Rep 1 Producer defined 8 New Formulation, Lot number is TFBA210331A Room temp storage conditions Rep 2 Producer defined 9 New Formulation, Lot number is TFBA210331A Room temp storage conditions Rep 3 Producer defined 10 New Formulation, Lot number is TFBA210331A Elevated temp storage conditions Rep 1 Producer defined 11 New Formulation, Lot number is TFBA210331A Elevated temp storage conditions Rep 2 Producer defined 12 New Formulation, Lot number is TFBA210331A Elevated temp storage conditions Rep 3 Producer defined Bar_Type Numerical Representation of the data for use as factorization in R. ("1" = "Old Form Room Temp ", "2" = "Old Form Elev Temp",, "3" = "New Form Room Temp", "4" = " New Form Elev Temp") Producer Defined 1 Old Formulation, Lot number is TFBA210430A Room temp storage conditions Producer defined 2 Old Formulation, Lot number is TFBA210430A Elevated temp storage conditions Producer defined 3 New Formulation, Lot number is TFBA210331A Room temp storage conditions Producer defined 4 New Formulation, Lot number is TFBA210331A Elevated temp storage conditions Producer defined U.S. Geological Survey GS ScienceBase mailing address

Denver Federal Center, Building 810, Mail Stop 302

Denver CO 80225 United States 1-888-275-8747 sciencebase@usgs.gov Unless otherwise stated, all data, metadata and related materials are considered to satisfy the quality standards relative to the purpose for which the data were collected. Although these data and associated metadata have been reviewed for accuracy and completeness and approved for release by the U.S. Geological Survey (USGS), no warranty expressed or implied is made regarding the display or utility of the data on any other system or for general or scientific purposes, nor shall the act of distribution constitute any such warranty. Digital Data https://doi.org/10.5066/P910SHBL None 20230807 Justin Schueller UMESC Chemist mailing and physical

2630 Fanta Reed Road

La Crosse WI 54603 USA 608-881-9836 jschueller@usgs.gov FGDC Biological Data Profile of the Content Standard for Digital Geospatial Metadata FGDC-STD-001.1-1999