Measuring N and O isotopes in clean green New Zealands water: method - - PowerPoint PPT Presentation

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Measuring N and O isotopes in clean green New Zealands water: method - - PowerPoint PPT Presentation

Nov 21, 2022 29 likes •251 views

Measuring N and O isotopes in clean green New Zealands water: method adaption. National Isotope Centre GNS Science Andy Phillips The Methods available. 1) Ion exchange column collection 2) Microbial bacteria method 3) Enzyme

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SLIDE 1

Measuring N and O isotopes in clean green New Zealand’s water: method adaption.

National Isotope Centre GNS Science

Andy Phillips

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SLIDE 2

GNS Science

GNS Stable Isotope Laboratory

The Methods available.

  • 1) Ion exchange column collection
  • 2) Microbial bacteria method
  • 3) Enzyme method
  • 4) Cadmium reduction
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SLIDE 3

GNS Science

Cadmium Method 1st Step

  • 1ST Attempt
  • Making Spongy Cadmium using Zinc Sticks
  • Sample preseravtion NaOH pellets
  • Imadazole as sample Buffer
  • 2nd Attempt
  • Cadmium powder HCl wash
  • Sample preseravation HCl pH 2-3
  • Addition of Sulfanilic Acid to remove Nitrite

GNS Stable Isotope Laboratory

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SLIDE 4

GNS Science

Nitrate to Nitrite by Cadmium reduction

  • This takes place in 6M NaCl, the excess Cl ions
  • restricts oxygen exchange from the water.
  • NaCl pre-baked at 700C for 2 hrs
  • MgO pre-Baked at 450C for 1 hr
  • Cd powder 0.7g per sample has10% HCl added

to it the clumps that form are chomped up to form a granular consistancy and then rinsed 10 times with DIW and stored under it until ready to use.

GNS Stable Isotope Laboratory

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SLIDE 5

GNS Science

  • Sample was added to 6M sodium chloride

solution,100mg of MgO and 7g of spongy Cadmium in a 50mL centrifuge tube, giving a total volume of 20mL.

  • The bottle was shaken horizontally for 17 hours

for the reduction to take place.

  • Centrifuge to trap all the Cadmium at the base of

the tube.

GNS Stable Isotope Laboratory

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SLIDE 6

GNS Science

Day2 Azide Reaction

  • HNO2 + HN3------N2O + H2O + N2
  • Azide solution was added to Acetic Acid to give

a 1:1 mix and sparged with He for 30mins

  • 450uL Azide mix is injected in sealed 12mL

capped vials containing sample from the Cd step plus 2M NaCl

  • The vials are left for 30mins at room temperature
  • To stop the reaction 450uL of 6M NaOH is

injected into the vial

GNS Stable Isotope Laboratory

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SLIDE 7

GNS Science

GNS Stable Isotope Laboratory

Cd Step ( m L) Azide Step ( µL)

Sample Name Sample Info Nitrate (ppm) mL sample 6M NaCl 100 m g MgO 0.7 g Cd DI w ater Final NO2- Conc Sam ple from Cd A:A 2M NaCl Final ppb N2O nm ol

1 BLANK No Cadmium step 0.012 13.3 6.7 100 0.0 0.01 7500 450 50 7.5 4.3 2 BLANK Cd 0.001 13.3 6.7 100 0.70 0.0 0.00 7500 450 50 0.6 0.4 3 USGS 34 a 1.000 7.0 6.7 100 0.70 6.3 0.35 320 450 7230 14.0 8.0 4 I AEA a 1.000 7.0 6.7 100 0.70 6.3 0.35 320 450 7230 14.0 8.0 5 KNO3 a 1.000 7.0 6.7 100 0.70 6.3 0.35 320 450 7230 14.0 8.0 6 KNO3 c from b Repeat Azide step 1.000 0.35 200 450 7350 8.8 5.0 7 KNO3 d from b Repeat Azide step 1.000 0.35 80 450 7470 3.5 2.0 8 KNO3 e 0.2 ppm 0.200 13.3 6.7 100 0.70 0.0 0.13 840 450 6700 14.0 8.0 9 KNO3 f 0.05 ppm 0.050 13.3 6.7 100 0.70 0.0 0.03 3360 450 4190 14.0 8.0 10 KNO3 g 0.02 ppm 0.020 13.3 6.7 100 0.70 0.0 0.01 7500 450 50 12.5 7.1 11 MAA1 a No Cadmium step 1.000 7.0 6.7 100 6.3 0.35 320 450 7230 14.0 8.0 12 MAA2 a No Cadmium step 1.000 7.0 6.7 100 6.3 0.35 320 450 7230 14.0 8.0 13 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 14 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 15 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 16 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 17 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 18 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 19 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 20 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 21 USGS 34 c from a Repeat Azide step 1.000 0.35 320 450 7230 14.0 8.0 22 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 23 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 24 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 25 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 26 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 27 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 28 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 29 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 30 USGS 34 d from a Repeat Azide step 1.000 0.35 320 450 7230 14.0 8.0 31 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 32 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 33 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 34 0.000 # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 35 0.000 # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 36 0.000 # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 37 Dup (high NO3) # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 38 Dup (low NO3) # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 39 Dup (med NO3) # DI V/ 0! 6.7 100 0.70 # # # # # DI V/ 0! # DI V/ 0! 450 # DI V/ 0! # DI V/ 0! # # # 40 USGS 34 b Dup 1.000 7.0 6.7 100 0.70 6.3 0.35 320 450 7230 14.0 8.0 41 I AEA b Dup 1.000 7.0 6.7 100 0.70 6.3 0.35 320 450 7230 14.0 8.0 42 KNO3 b Dup 1.000 7.0 6.7 100 0.70 6.3 0.35 320 450 7230 14.0 8.0 43 MAA1 b from a Repeat Azide step 1.000 0.35 320 450 7230 14.0 8.0 44 MAA2 b from a Repeat Azide step 1.000 0.35 320 450 7230 14.0 8.0 45 Tester (USGS34 a) Repeat Azide step 1.000 0.35 320 450 7230 14.0 8.0 240.5 23.1 #DIV/0!

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GNS Science

d15N d18O Stdev d15N Stdev d18O USGS 34

  • 5.6
  • 24.9

0.1 0.5 IAEA

  • 1.7

21.6 0.0 0.3 KNO3 0.4 10.1 0.0 0.1 USGS 34 c

  • 5.6
  • 25.1

0.1 0.4 IAEA c

  • 1.7

21.7 0.1 0.2 KNO3 h 0.4 9.9 0.1 0.3 USGS 34 b1-1 h

  • 5.4
  • 24.0

0.3 0.1 USGS 34 b1-1 h

  • 5.6
  • 24.8

0.1 0.1 USGS 34 b1-30 min

  • 5.6
  • 24.8

0.1 0.1 USGS 34 b1-10 min

  • 6.20
  • 22.34

0.4 0.7 Average 0.1 0.2 GNS Stable Isotope Laboratory

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GNS Science

Results

SAMPLES nA d15N d18O

d15N corr for 17O d15N known d18O known d15N line d18O line SLOPE 0.43 0.87 INTERCEPT

  • 4.46
  • 0.44

USGS 34

11.05

  • 5.66
  • 25.2
  • 5.27
  • 1.8
  • 27.9
  • 1.9
  • 28.4

IAEA-NO3

9.64

  • 1.76

21.4

  • 2.42

4.7 25.6 4.7 25.1 KNO3

9.93 0.40

10.1 0.15 10.7 11.73 10.7 12.0 USGS 34

11.08

  • 5.58
  • 24.5
  • 5.21
  • 1.8
  • 27.9
  • 1.7
  • 27.6

IAEA-NO3

10.20

  • 1.72

21.9

  • 2.39

4.7 25.6 4.8 25.6 KNO3

9.07 0.39

10.2 0.14 10.7 11.73 10.7 12.2 MAA1

9.74

  • 29.17
  • 3.1
  • 30.59
  • 60.6
  • 60.7
  • 3.1

MAA2

10.32

  • 5.08
  • 2.6
  • 5.27
  • 3.9
  • 1.9
  • 2.5

Tap Water

9.60

  • 0.90

1.8

  • 0.99

8.0 2.5 Ice Core Water a

4.61

  • 5.60
  • 3.8
  • 5.79
  • 3.1
  • 3.9

Ice Core Water b

4.47

  • 6.24
  • 6.4
  • 6.39
  • 4.5
  • 6.8

USGS 34 c

  • 5.6
  • 25.1
  • 5.24
  • 1.8
  • 28.3

IAEA c

  • 1.7

21.7

  • 2.32

4.9 25.4 KNO3 h 0.4 10.1 0.12 10.6 12.0 USGS 34 b1-10 min

  • 6.20
  • 22.34
  • 5.92
  • 3.4
  • 25.1

USGS 34 b1-1 h

  • 5.4
  • 24.0
  • 5.04
  • 1.4
  • 27.0

USGS 34 b1-1 h

  • 5.6
  • 24.5
  • 5.20
  • 1.7
  • 27.5

USGS 34 b1-30 min

  • 5.6
  • 24.8
  • 5.18
  • 1.7
  • 27.9

GNS Stable Isotope Laboratory

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SLIDE 10

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 11

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GNS Stable Isotope Laboratory

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SLIDE 12

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 13

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 14

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 15

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 16

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 17

GNS Science

GNS Stable Isotope Laboratory

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SLIDE 18

GNS Science

GNS Stable Isotope Laboratory

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GNS Science

Ammonium

  • Using method by Zhang and Altabet
  • Samples need to have had Sulfanilic Acid added
  • 2mL 6M NaCl and 0.8mL Hypobromate + sample
  • 30 mins RT then inject Arsenite to nullify the

Hypobromite.

  • Caps are screwed on and the Azide is added.

GNS Stable Isotope Laboratory

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GNS Science

SAMPLES nA d15N d18O

d15N corr for 17O d15N known d18O known d15N line d18O line SLOPE 0.45 #DIV/0! INTERCEPT

  • 4.66

#DIV/0! N1 8.24

  • 5.10
  • 21.76
  • 4.78

0.4

  • 0.3

#DIV/0! N2 8.93 3.40

  • 21.57

4.15 20.3 19.7 #DIV/0! USGS25 8.38

  • 17.88
  • 21.76
  • 18.22
  • 30.4
  • 30.3

#DIV/0! N1 9.65

  • 4.76
  • 21.61
  • 4.42

0.4 0.5 #DIV/0! N2 10.32 4.02

  • 21.64

4.80 20.3 21.2 #DIV/0! USGS25 10.21

  • 17.83
  • 21.64
  • 18.17
  • 30.4
  • 30.2

#DIV/0! USGS26 8.04 18.30

  • 21.17

19.82 53.6 54.8 #DIV/0! USGS26 10.44 18.73

  • 21.00

20.26 53.6 55.8 #DIV/0! MAA1 4.90

  • 28.49
  • 2.96
  • 29.88
  • 60.6
  • 56.4

#DIV/0! MAA2 5.44

  • 2.79
  • 2.11
  • 2.88
  • 3.9

4.0 #DIV/0! N1400001 2a 20140515 01.raw 8.13

  • 11.92
  • 19.95
  • 12.00
  • 16.4

#DIV/0! N1400003 a 20140515 01.raw 3.92

  • 10.19
  • 17.28
  • 10.26
  • 12.5

#DIV/0! N1400004 6a 20140515 01.raw 9.76

  • 12.78
  • 20.09
  • 12.90
  • 18.4

#DIV/0! N1400007 20140515 01.raw 3.06

  • 8.56
  • 14.50
  • 8.61
  • 8.8

#DIV/0! N1400008 20140515 01.raw 2.82

  • 8.42
  • 17.91
  • 8.38
  • 8.3

#DIV/0! USGS25 20140515 02.raw 8.24

  • 18.15
  • 21.88
  • 18.50
  • 31.0

#DIV/0! N1400009 20140515 01.raw 2.12

  • 7.94
  • 16.88
  • 7.90
  • 7.2

#DIV/0! N1400010 12 20140515 01.raw 2.18

  • 7.67
  • 17.54
  • 7.59
  • 6.6

#DIV/0! N1400013 20140515 01.raw 4.62

  • 2.45
  • 19.72
  • 2.05

5.8 #DIV/0! N1400014 20140515 01.raw 5.35

  • 3.44
  • 20.39
  • 3.06

3.6 #DIV/0! N1400015a 20140515 01.raw 4.24

  • 3.09
  • 19.88
  • 2.71

4.4 #DIV/0! N1400016 20140515 01.raw 0.97

  • 5.51
  • 13.89
  • 5.42
  • 1.7

#DIV/0! USGS25 20140515 03.raw 9.32

  • 18.12
  • 21.77
  • 18.47
  • 30.9

#DIV/0! N1400017 20140515 01.raw 3.99

  • 2.60
  • 20.29
  • 2.19

5.5 #DIV/0! N1400018 20140515 01.raw 1.41

  • 5.51
  • 14.95
  • 5.39
  • 1.6

#DIV/0! N1400001 2b 20140515 01.raw 8.94

  • 10.82
  • 19.60
  • 10.86
  • 13.9

#DIV/0! N1400003 b 20140515 01.raw 4.64

  • 9.84
  • 17.90
  • 9.86
  • 11.6

#DIV/0! N1400004 6b 20140515 01.raw 10.75

  • 12.25
  • 20.07
  • 12.34
  • 17.2

#DIV/0! N1400015b 20140515 01.raw 4.51

  • 2.93
  • 19.57
  • 2.55

4.7 #DIV/0!

GNS Stable Isotope Laboratory

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SLIDE 21

GNS Science

GNS Stable Isotope Laboratory

The People

  • Cedric Douence: Now at IAEA Vienna
  • Simon Stewart: Now at University of Waikato
  • Troy Baisden
  • Jannine Cooper
  • Joan Fitzgerald
  • Ashleigh Immers
  • Melissa Oosterwijk
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SLIDE 22

GNS Science

GNS Stable Isotope Laboratory