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

PICARRO G5101-i

d15N2O 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

Wavenumber [cm

• 1]

2187.0 2187.1 2187.2 2187.3 2187.4 2187.5 2187.6 2187.7

Loss [ppm/cm]

4 5 6 7 8 9 990 ppb N

2O

14N2 16O 14N2 16O 14N2 16O

14N2 16O

15N14N16O 14N15N16O

H2O

15N14N16O 14N15N16O

0 0 .1 0 .2 0.3 0.4 0.5 0.6 0.7

14N2 16O

• Measurement of

both isotopomers is possible without painful sample prep

Isotopic N2O

Alpha Beta

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G5101-i Instrument Specifications

High precision at ambient concentrations

Picarro G5101-i Can Interface with Key Peripherals

Small Sample Isotope Module (SSIM) 16- Port Valve Manifold

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Features and Benefits of the G5101-i for Soil

Feature Benefit Best precision at ambient concentrations No special sample prep or gas separation is 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 temperature More accurate data in real world conditions Rugged Design Able to travel to and from field sites Continuous measurement Continuous Data User-friendly software and automatable functions Easy to use with minimal human intervention

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 N2O Concentration

Picarro Guaranteed Specification

Deviation

1 hr GAW Specification Both analyzers perform better than the Picarro specifications and the GAW inter-laboratory uncertainty recommendations Analyzer 1 Analyzer 2

Allan Deviation for Alpha Transition

Picarro Guaranteed Specification

14N15N16O

Both analyzers perform better than the Picarro guaranteed specifications

14N15N16O

Deviation

Analyzer 1 Analyzer 2

Time (seconds)

Allan Deviation for Beta Transition

Picarro Guaranteed Specification

15N14N16O 15N14N16O

Both analyzers perform better than the Picarro guaranteed specifications

Deviation

Analyzer 1 Analyzer 2

Measurements of Three N2O Gas Standards

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[N2O] Peak to Peak Drift over 50 Hours

3600 sec Average Results

327.05 327.05 327.06 327.06 327.07 327.07 327.08 327.08 327.09 327.09 327.10 5 10 15 20 25 30 35 40 45 50 55 Elapsed time (hr) N2O (ppb)

Drift = 0.044ppb / 53 hrs

1 Hour Averages Analyzer #2 Max (peak to peak) Drift = 0.03 ppb over 53 hours Analyzer #1 Max (peak to peak) Drift = 0.044 ppb over 53 hours 1 Hour Averages

3600 sec Average Results

40.00 40.20 40.40 40.60 40.80 41.00 41.20 41.40 5 10 15 20 25 30 35 40 45 50 55 Elapsed Time (hr) d15N Alpha (permil) Drift = 1.15 permil / 53 hrs

Alpha δ15N Peak to Peak Drift over 50 hours

1 Hour Averages 1 Hour Averages Analyzer #2 Max (peak to peak) Drift = 0.69 ‰ over 53 hours Analyzer #1 Max (peak to peak) Drift = 1.15 ‰ over 53 hours 1 Hour Averages

3600 sec Average Results

140.60 140.70 140.80 140.90 141.00 141.10 141.20 141.30 141.40 141.50 141.60 5 10 15 20 25 30 35 40 45 50 55 Elapsed Time (hr) d15N beta (permil)

Drift = 0.95permil / 53 hrs

Beta δ15N Peak to Peak Drift over 50 hours

1 Hour Averages 1 Hour Averages Analyzer #2 Max (peak to peak) Drift = 0.5 ‰ over 53 hours Analyzer #1 Max (peak to peak) Drift = 0.95 ‰ over 53 hours

G5101-i + SSIM

Summary of SSIM2 with G5101-i Testing

• Three Samples Tested

– Sample zero: 329-ppb N2O gas cylinder as reference gas. – Sample one: 1000 ppb N2O sample bag (1 liter) connected to port 1. – Sample two: 332 ppb N2O 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 ‰.

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Sample zero: 329-ppb N2O gas cylinder as reference gas

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Sample one: 1000 ppb N2O sample bag (1 liter)

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Sample two: 332 ppb N2O sample bag (1 liter)

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SOIL SAMPLE TESTING RESULTS

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

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

Picarro Collaborator:

N2O Concentration Drift over Time

N2O Isotopomer Drift over Time

Allan Deviation for Alpha Isotopomer

100 100 101 102 103 104

15N2Oa (‰)

Time (seconds) 0.5 permil in 100 sec

Allan Deviation for Beta Isotopomer

100 100 101 102 103 104

15N2Ob (‰)

Time (seconds) 0.5 permil in 100 sec

Isotopic Linearity with N2O Concentrations

Picarro iN2O 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 15N Enriched Measurements

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

N2O Concentration (ppb)

N2O Concentration (ppb)

Example 15N Enriched Measurements

9786 10100 9497 10120 98.7 92.85 120 9994 10320 9688 10300 96.1 87.87 125 2000 4000 6000 8000 10000 12000 Sample #8, Enriched Residue, Canola Plant, 0.886 ppm Sample #7, Enriched Residue, Canola Plant, 0.808 ppm Sample #6, Enriched Residue, Pea Plant, 0.984 ppm Sample #5, Enriched Residue, Pea Plant, 0.674 ppm Sample #4, Purenet Residue, Pea Straw plot 107, 0.03486% excess, 0.5ppm Sample #3, Purenet Residue, Pea Straw plot 5A, 0.08254% excess, 0.7ppm Sample #2, Purenet Wheat plot 122A, 0.19108% excess, 1.95ppm Alpha (per mil) Beta (per mil)

This range of measurement could not be done on IRMS.

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