PICARRO G5101- i d 15 N 2 O Site Specific Isotope and Concentration - PowerPoint PPT Presentation

PICARRO G5101- i d 15 N 2 O Site Specific Isotope and Concentration Analyzer

Designed for Nitrogen Pathway Research • Nitrification and denitrification occurs through many pathways • Compound specific isotopic signatures plus site-specific isotopic information, are crucial to tracing these pathways

Picarro CRDS in the Mid-Infrared 990 ppb N 2 O Isotopic N 2 O 9 14 N 2 16 O 14 N 2 16 O 14 N 2 16 O • Measurement of 8 both isotopomers is possible without Loss [ppm/cm] painful sample prep 7 6 Alpha Beta 14 N 2 16 O 5 15 N 14 N 16 O 14 N 15 N 16 O 15 N 14 N 16 O 14 N 15 N 16 O 14 N 2 16 O H 2 O 4 2187.0 2187.1 2187.2 2187.3 2187.4 2187.5 2187.6 2187.7 0 0 .1 0 .2 0.3 0.4 0.5 0.6 0.7 -1 ] Wavenumber [cm

G5101- i Instrument Specifications High precision at ambient concentrations 3

Picarro G5101- i Can Interface with Key Peripherals Small Sample Isotope Module (SSIM) 16- Port Valve Manifold

Features and Benefits of the G5101- i for Soil Feature Benefit Best precision at ambient No special sample prep or gas separation is concentrations needed to get great data Lowest instrument drift Highest accuracy with fewest calibrations No liquid nitrogen cooling Easier to use, more field ready Minimal drift over ambient More accurate data in real world conditions temperature Rugged Design Able to travel to and from field sites Continuous measurement Continuous Data User-friendly software and Easy to use with minimal human intervention automatable functions 5

PERFORMANCE RESULTS Data taken from recently shipped Picarro Model G5101-i

Performance Data Contents 1. Picarro Laboratory: Instrument Performance Testing – Linearity – Precision – Drift – Small (discrete) sample repeatability 2. University of Saskatchewan: Instrument Performance – Drift – Linearity – Isotope Concentration dependence – enriched soil samples

Allan Deviation for N 2 O Concentration Analyzer 2 Analyzer 1 Deviation 1 hr Both analyzers perform better than the Picarro specifications and the GAW inter-laboratory uncertainty recommendations Picarro Guaranteed Specification GAW Specification

Allan Deviation for Alpha Transition 14 N 15 N 16 O 14 N 15 N 16 O Deviation Time (seconds) Analyzer 1 Analyzer 2 Both analyzers perform better than the Picarro guaranteed specifications Picarro Guaranteed Specification

Allan Deviation for Beta Transition 15 N 14 N 16 O 15 N 14 N 16 O Deviation Analyzer 1 Analyzer 2 Both analyzers perform better than the Picarro guaranteed specifications Picarro Guaranteed Specification

Measurements of Three N 2 O Gas Standards 11

[N 2 O] Peak to Peak Drift over 50 Hours 1 Hour Averages 3600 sec Average Results 327.10 Drift = 0.044ppb / 53 hrs 327.09 327.09 327.08 N2O (ppb) 327.08 1 Hour Averages 327.07 327.07 327.06 327.06 327.05 327.05 0 5 10 15 20 25 30 35 40 45 50 55 Elapsed time (hr) Analyzer #1 Max (peak to peak) Drift = 0.044 ppb over 53 hours Analyzer #2 Max (peak to peak) Drift = 0.03 ppb over 53 hours

Alpha δ 15 N Peak to Peak Drift over 50 hours 1 Hour Averages 3600 sec Average Results 41.40 Drift = 1.15 permil / 53 hrs 41.20 d15N Alpha (permil) 41.00 40.80 1 Hour Averages 40.60 40.40 40.20 1 Hour Averages 40.00 0 5 10 15 20 25 30 35 40 45 50 55 Elapsed Time (hr) Analyzer #1 Max (peak to peak) Drift = 1.15 ‰ over 53 hours Analyzer #2 Max (peak to peak) Drift = 0.69 ‰ over 53 hours

Beta δ 15 N Peak to Peak Drift over 50 hours 1 Hour Averages 3600 sec Average Results 141.60 Drift = 0.95permil / 53 hrs 141.50 141.40 d15N beta (permil) 141.30 141.20 141.10 1 Hour Averages 141.00 140.90 140.80 140.70 140.60 0 5 10 15 20 25 30 35 40 45 50 55 Elapsed Time (hr) Analyzer #1 Max (peak to peak) Drift = 0.95 ‰ over 53 hours Analyzer #2 Max (peak to peak) Drift = 0.5 ‰ over 53 hours

G5101- i + SSIM

Summary of SSIM2 with G5101- i Testing • Three Samples Tested – Sample zero: 329-ppb N 2 O gas cylinder as reference gas. – Sample one: 1000 ppb N 2 O sample bag (1 liter) connected to port 1. – Sample two: 332 ppb N 2 O sample bag (1 liter) connected to port 2. • Each sample measured 5 times then reference sample measured two times, repeat. • Each measurement takes 3-minute. Both sample bags lasted 30 measurements. • When reference gas cylinder directly connected to G5101- i , alpha was measured as 1.28 ‰ and beta as 0.0 ‰. 16

Sample zero: 329-ppb N 2 O gas cylinder as reference gas 17

Sample one: 1000 ppb N 2 O sample bag (1 liter) 18

Sample two: 332 ppb N 2 O sample bag (1 liter) 19

Testing performed by Picarro and Rich Farrell’s team at the University of Saskatchewan October 2012 SOIL SAMPLE TESTING RESULTS

Picarro Collaborator: Rich Farrell, Associate Professor, College of Agriculture and Bioresources Saskatoon, Saskatchewan, Canada

N 2 O Concentration Drift over Time

N 2 O Isotopomer Drift over Time

Allan Deviation for Alpha Isotopomer 10 0 15 N 2 O a (‰) 0.5 permil in 100 sec 10 0 10 1 10 2 10 3 10 4 Time (seconds)

Allan Deviation for Beta Isotopomer 10 0 15 N 2 O b (‰) 0.5 permil in 100 sec 10 0 10 1 10 2 10 3 10 4 Time (seconds)

Isotopic Linearity with N 2 O Concentrations

Picarro iN 2 O Set Up for Soil Samples Soil Samples Picarro G5101- i Gas Sampling

Rise and Fall Time with 5000‰ Sample

Rise and Fall Time with 5000‰ Sample

Example 15 N Enriched Measurements N 2 O Concentration (ppb) 1400 1240 1200 1000 800 599 600 527 475 N2O Concentration (ppb) 413.6 397.4 400 278.5 200 0 Sample #8, Sample #7, Sample #6, Sample #5, Sample #4, Sample #3, Sample #2, Enriched Enriched Enriched Enriched Purenet Residue, Purenet Residue, Purenet Wheat Residue, Canola Residue, Canola Residue, Pea Residue, Pea Pea Straw plot Pea Straw plot plot 122A, Plant, 0.886 ppm Plant, 0.808 ppm Plant, 0.984 ppm Plant, 0.674 ppm 107, 0.03486% 5A, 0.08254% 0.19108% excess, excess, 0.5ppm excess, 0.7ppm 1.95ppm

Example 15 N Enriched Measurements 12000 10320 10300 10100 10120 9994 9786 9688 10000 9497 8000 6000 Alpha (per mil) Beta (per mil) 4000 2000 120 125 98.7 96.1 92.85 87.87 0 Sample #8, Sample #7, Sample #6, Sample #5, Sample #4, Sample #3, Sample #2, Enriched Residue, Enriched Residue, Enriched Residue, Enriched Residue, Purenet Residue, Purenet Residue, Purenet Wheat Canola Plant, 0.886 Canola Plant, 0.808 Pea Plant, 0.984 Pea Plant, 0.674 Pea Straw plot 107, Pea Straw plot 5A, plot 122A, ppm ppm ppm ppm 0.03486% excess, 0.08254% excess, 0.19108% excess, 0.5ppm 0.7ppm 1.95ppm This range of measurement could not be done on IRMS.

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