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Using stable isotopes of water to characterize the hydrological cycle in a northern Minnesota black spruce-sphagnum bog forest Kaycee Reynolds Environmental Sciences Division, Oak Ridge National Laboratory Introduction Site Description Methods Results Conclusions Acknowledgements Spatial and temporal variation in isotopic ratios of hydrogen ( 2 H/ 1 H or D/H) and oxygen ( 18 O/ 16 O) in surface water allows characterization of the hydrological cycle in terrestrial ecosystems. Processes such as evaporation, precipitation, uptake of water by roots and vertical or lateral mixing of source water all affect hydrogen (δD) and oxygen (δ 18 O) isotopic ratios. Climate change will increase temperature and CO 2 levels affecting evaporation and plant water use. We can track the effects of changes in temperature and CO 2 on the hydrological cycle by monitoring δD and δ 18 O in source water. The objectives of this study included: calibrating the Picarro L1102-i Isotopic Liquid Water Analyzer, developing and verifying a working procedure for this instrument, and analyzing baseline water samples from a field site that will be subjected to climate change treatments. Spruce and Peatland Responses Under Climatic and Environmental Change (SPRUCE) project: Exploration of the ecological response to various temperature increases and elevated concentrations of atmospheric carbon dioxide Experimental work conducted on the southern margin of the boreal peatland forest, which is considered especially at risk due to impending climate change The 8.1 h ombrotrophic Picea mariana-Sphagnum bog forest is located in the USDA Forest Service Marcell Experimental Forest in northern Minnesota Climate change manipulations will take place in open-top enclosures subjecting the environment to various levels of warming and CO 2 exposure Calibration of Instrument The Picarro L1102-i simultaneously measures the isotopic ratios of hydrogen (D/H) and oxygen ( 18 O/ 16 O) using Wavelength-Scanned Cavity Ring-down Spectroscopy. Calibration is done by comparing the reference values to measured values of three International Atomic Energy Agency (IAEA) standards: Picarro Method Settings Method Picarro Needle Penetration Stable Isotopic Analysis Test samplers nested at 0.0, 0.25, 0.5, 1.0, 2.0 and 3.0 m from the surface of the hollow were used to collect water samples from the bog Each sample run on the instrument was compared to internal standards and expressed as negative δ values (δD and δ 18 O): Temporal Variation in Isotopic Ratios Conclusions Following calibration, the instrument yielded isotopic ratio results with: An average standard error of <0.05 ‰ for δ 18 O and <0.15 ‰ for δD An average standard deviation of <0.06 ‰ for δ 18 O and <0.3 ‰ for δD Temporal Variation: Shallow surface waters (<0.25 m) have become enriched over the three month period from July to October Deeper water (>2 m) isotopic ratios have remained relatively stable Spatial Variation: In terms of depth below the bog, the deeper the surface water, the more depleted the isotopic ratios of oxygen and hydrogen Aerial photograph of the landscape around the S-1 bog Primary Standard δ 18 O Reference Value δD Reference Value VSMOW2 0 0 GISP -24.78 -189.5 SLAP2 -55.5 -427.5 Site Depth (mm) Evaporator 44.5 Waste 1 10.0 Waste 2 40.0 Wash 1 44.3 Wash 2 40.0 Internal Standard Average Normalized δ 18 O Average Normalized δD Deep Blue -0.14 -0.16 DI -8.42 -47.67 Mountain (MTN) -21.37 -159.57 Hollow -13.38 --94.94 Spatial Variation in Isotopic Ratios This research was made possible by the U.S. Department of Energy, the Office of Science at Oak Ridge National Laboratory managed by UT-Battelle, ORISE, Steve Sebestyen and the USDA Forest Service for providing samples, the Environmental Sciences Division and the continued support of my mentor Jeffrey M. Warren. δ 18 O and δD values for more than 40 bog samples taken from July to October. Over time, waters near the surface of the bog (<0.25 m) have become increasingly enriched, while deeper water (>2 m) displayed no such pattern. δ 18 O and δD values for samples taken on September 2, 2011 from 0, 0.25, 1, 2 and 3 meters below the surface of the hollow. Deeper water was more depleted in both δ 18 O and δD than the surface water. This pattern was maintained for depth analysis on all sampling days. Relevant References Name Setting Cycle LC-Inj Syringe 5 μL Samp Vol 4.5 μL Air Vol 0 nL Pre Cln Slv1 0 Pre Cln Slv2 0 Pre Cln Sp1 2 Fill Speed 500 nL/s Fill Strokes 1 Pullup Del 5.0 s Inject to Vaporizer Inject Sp 1.0 μL/s Pre Inj Del 2.0 s Pst Inj Del 2.0 s Pst Cln Slv1 0 Pst Cln Slv2 2 Vlv Cln Slv1 0 Vlv Cln Slv2 0 Visit: http://mnspruce.ornl.gov/ for more information -13.00 -12.00 -11.00 -10.00 -9.00 -8.00 -7.00 -6.00 7/18 7/25 8/1 8/8 8/15 8/22 8/29 9/5 9/12 9/19 9/26 10/3 10/10 δ 18 O (deviation from VSMOW2) δ 18 O Values from July to October 2011 Test 6 (0 m) Test 5 (0.25 m) Test 2 (2 m) Test 1 (3 m) -90.00 -85.00 -80.00 -75.00 -70.00 -65.00 -60.00 -55.00 -50.00 -45.00 -40.00 7/18 7/25 8/1 8/8 8/15 8/22 8/29 9/5 9/12 9/19 9/26 10/3 10/10 δD (‰ deviation from VSMOW2) δD Values from July to October 2011 Test 6 (0 m) Test 5 (0.25 m) Test 2 (2 m) Test 1 (3 m) -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0 -14.00 -12.00 -10.00 -8.00 -6.00 -4.00 -2.00 0.00 Depth of samples from surface of Hollow (m) δ 18 O Values (‰) Sample Depth vs. δ 18 O Value -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0 -100.00 -80.00 -60.00 -40.00 -20.00 0.00 Depth of sample from surface of Hollow (m) δD Values () Sample Depth vs. δD Value -450.00 -400.00 -350.00 -300.00 -250.00 -200.00 -150.00 -100.00 -50.00 0.00 50.00 -60.00 -50.00 -40.00 -30.00 -20.00 -10.00 0.00 δD Values (‰) δ 18 O Values (‰) Calibrating Picarro Standards Primary (IAEA) Standards Internal (Secondary) Standards Bog Water (September 2, 2011) Standards and Calibration Primary standards were used to calibrate internal standards, which are run daily. The Picarro is extremely precise. For each secondary standard shown above, there are actually 9 separate points on the graph, nearly impossible to distinguish from one another due to instrumental precision. Water Content on Graphical User Interface Raw Output File from Coordinator 1. Picarro L1102-i Analyzer User’s Guide, Picarro Inc., Sunnyvale, CA, 2009. 2. Picarro Community [Online]. Available: http://www.picarro.com/community/picarro_community/ 3. P. Gupta. (2009, April). Demonstration of high-precision continuous measurements of water vapor isotopologues in laboratory and remote field deployments using wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) technology. Rapid Commun. Mass Spectrom. [Online]. 23, 2534-2542. Available: http://onlinelibrary.wiley.com/doi/10.1002/rcm.4100/full

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  • Using stable isotopes of water to characterize the hydrological cycle in a

    northern Minnesota black spruce-sphagnum bog forest Kaycee Reynolds

    Environmental Sciences Division, Oak Ridge National Laboratory

    Introduction

    Site Description

    Methods Results

    Conclusions

    Acknowledgements

    Spatial and temporal variation in isotopic ratios of

    hydrogen (2H/1H or D/H) and oxygen (18O/16O) in

    surface water allows characterization of the

    hydrological cycle in terrestrial ecosystems.

    Processes such as evaporation, precipitation,

    uptake of water by roots and vertical or lateral

    mixing of source water all affect hydrogen (δD)

    and oxygen (δ18O) isotopic ratios.

    Climate change will increase temperature and CO2

    levels affecting evaporation and plant water use.

    We can track the effects of changes in temperature

    and CO2 on the hydrological cycle by monitoring

    δD and δ18O in source water.

    The objectives of this study included: calibrating

    the Picarro L1102-i Isotopic Liquid Water

    Analyzer, developing and verifying a working

    procedure for this instrument, and analyzing

    baseline water samples from a field site that will

    be subjected to climate change treatments.

    Spruce and Peatland Responses Under Climatic and

    Environmental Change (SPRUCE) project:

    • Exploration of the ecological response to various temperature

    increases and elevated concentrations of atmospheric carbon

    dioxide

    • Experimental work conducted on the southern margin of the

    boreal peatland forest, which is considered especially at risk due

    to impending climate change

    • The 8.1 h ombrotrophic Picea mariana-Sphagnum bog forest is

    located in the USDA Forest Service Marcell Experimental Forest

    in northern Minnesota

    • Climate change manipulations will take place in open-top

    enclosures subjecting the environment to various levels of

    warming and CO2 exposure

    Calibration of Instrument

    •The Picarro L1102-i simultaneously measures the isotopic ratios of

    hydrogen (D/H) and oxygen (18O/16O) using Wavelength-Scanned

    Cavity Ring-down Spectroscopy.

    •Calibration is done by comparing the reference values to measured

    values of three International Atomic Energy Agency (IAEA)

    standards:

    Picarro Method Settings

    Method Picarro

    Needle Penetration

    Stable Isotopic Analysis

    • Test samplers nested at 0.0, 0.25, 0.5, 1.0, 2.0 and 3.0 m from the

    surface of the hollow were used to collect water samples from the

    bog

    • Each sample run on the instrument was compared to internal

    standards and expressed as negative δ values (δD and δ18O):

    Temporal Variation in Isotopic Ratios Conclusions

    Following calibration, the instrument yielded isotopic ratio results

    with:

    •An average standard error of