Evapotranspiration Partitioning Using: A Thesis

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Evapotranspiration Partitioning using

Stable Isotope Fractionation

A Thesis

Submitted in Partial Fulfilment

Of

the Requirements For the Degree of

Master of Technology

by

PRAVESH SINGH

16103055

To

DEPARTMENT OF CIVIL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY KANPUR

January, 2019

i
Dedicated to my Baba

ii
iii
iv
Abstract

A major challenge in ecohydrological studies is evapotranspiration (ET) partitioning,

which limits our understanding of soil-plant-atmospheric continuum. In this study, ET

partitioning was performed for rice and wheat crops in an experimental plot located at IIT

Kanpur using stable isotope fractionation method. The isotope method works because the

isotopic signatures of evaporation (E) and transpiration (T) are known to differ significantly.

First, experimental setups are designed to sample atmospheric water, soil water and

plant water. The setup consisted of an air intake structure for collecting water vapour at multiple

heights using liquid nitrogen (LN2) trap, cryogenic distillation for extracting water from soil

and plant, and a high-speed centrifuge for extracting soil water using Tetrachloroethylene (TCE)

as a displacement liquid. A cold trap using Peltier element was also designed to sample

atmospheric water.

Next, isotopic compositions of ET, E and T were determined using Keeling plot,

Craig- Gordon model and steady-state assumptions, respectively. Sensitivity analysis was

performed to identify variables that significantly affect ET partitioning, and emphasis was laid

to measure those variables accurately. For the rice season, the ET partitioning was performed

only for one day, i.e. 26 October 2017. The results suggested that on that day, the transpiration

fraction in evapotranspiration was 85.6%. For the wheat season, multiple samples during

different stages of crop growth were collected. The results showed that the transpiration fraction

in ET varies between 38% and 96% depending upon the crop growth stage and availability of

water. A comparison of transpiration fraction obtained from the isotope fractionation and

hydrometric methods suggested that the results from the two methods are similar for most of the

days. However, there were differences on some days which were attributed to uncertainties in

the estimation of temperature and relative humidity.

v
Acknowledgement

Foremost, I would like to express my profound gratitude to my thesis supervisor Dr Shivam

Tripathi for his motivation, encouragement, enthusiasm, constant support and exemplary

guidance.His guidance helped me in all the time during my entire journey at IIT Kanpur. It was

a memorable experience to work under his supervision.

I want to thank Dr Rajesh Srivastava, Dr Ashu Jain, Dr Saumyen Guha, Dr Richa Ojha and

other faculty members for their invaluable lectures which helped me to develop skills needed

for this work. I want to thank Hydraulics Lab staff, my batchmates Aditya, Anshul, Ephrem,

Priyanka, Saurabh, Seeta Ram for their support and constructive suggestions.

Last but not the least; I would like to thank my grandfather Shri Jhinku Singh and the rest of my

family for standing with me every time.

Thank you IIT Kanpur…

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Table of Contents

Abstract ......................................................................................................................................... v
Acknowledgement ........................................................................................................................ v
List of Tables ............................................................................................................................. xvi
LIST OF ABBREVIATIONS .................................................................................................. xviii
1 INTRODUCTION ................................................................................................................ 1
1.1 Rice and Wheat ............................................................................................................. 1
1.1.1 Rice (Oryza Sativa) ............................................................................................... 1
1.1.2 Wheat (Triticum Aestivum) .................................................................................. 2
1.2 Future challenge in crop production ............................................................................. 2
1.3 Need for the ecohydrological approach ........................................................................ 3
1.4 Methods to partition ET ................................................................................................ 4
1.4.1 Stable Isotope Fractionation Method .................................................................... 5
1.5 Motivation and objectives of the thesis ......................................................................... 9
2 LITERATURE REVIEW.................................................................................................... 11
2.1 Craig-Gordon (CG) Model .......................................................................................... 13
2.1.1 Kinetic fractionation factor (𝛆𝐤) ......................................................................... 14
2.1.2 Equilibrium fractionation factor (𝛂𝐞𝐪)............................................................... 16
2.2 Keeling Plot................................................................................................................. 17
2.3 Review of Sample Collection Techniques .................................................................. 18
2.3.1 Atmospheric water vapour .................................................................................. 18
2.3.2 Soil Water ........................................................................................................... 20
2.3.3 Plant Water .......................................................................................................... 25
3 STUDY AREA AND MATERIALS .................................................................................. 29
3.1 Study Area................................................................................................................... 29
3.2 Weather Condition ...................................................................................................... 29
3.3 Soil properties ............................................................................................................. 32
3.4 Crop Details ................................................................................................................ 33
3.4.1 Rice ..................................................................................................................... 33
3.4.2 Wheat .................................................................................................................. 35
3.5 Data collection ............................................................................................................ 37
3.5.1 Automatic Weather Station (AWS)..................................................................... 37
3.5.2 Air Intake structure (AIS) ................................................................................... 38
4 METHODOLOGY.............................................................................................................. 40

vii
4.1 Atmospheric Water Vapour Sample collection ........................................................... 40
4.1.1 Peltier element trap ............................................................................................. 40
4.1.2 Air Intake Structure (AIS) using LN2 trap .......................................................... 42
4.2 Soil and Plant water .................................................................................................... 44
4.2.1 Cryogenic Vacuum distillation (CVD) apparatus ............................................... 44
4.2.2 Displacement liquid centrifugation ..................................................................... 45
4.3 Sampling Protocol ....................................................................................................... 49
4.4 Analysis of water samples for Isotope analysis .......................................................... 50
4.4.1 Sample loading .................................................................................................... 50
4.4.2 Working Principle of LWIA ............................................................................... 52
4.5 Senstivity analysis ....................................................................................................... 53
4.5.1 Transpiration Factor ............................................................................................ 53
4.5.2 Variation of uncertainty in absolute water content ............................................. 56
4.5.3 Craig Gordon (CG) Model .................................................................................. 58
5 RESULTS AND DISCUSSION ......................................................................................... 62
5.1 Results for Rice season ............................................................................................... 62
5.2 Results for Wheat Season............................................................................................ 66
5.2.1 Comparison of isotope and hydrometric methods............................................... 91
5.2.2 Background noise in Isotopic Composition of ET .............................................. 92
5.2.3 Average Isotopic Composition of Hydrological Fluxes ...................................... 98
6 SUMMARY AND CONCLUSION REMARKS ............................................................. 101
7 LIMITATION AND FUTURE SCOPE ............................................................................ 104
A) APPENDIX ....................................................................................................................... 105
A.1 Time of Extraction ......................................................................................................... 105
A.2 Comparison of performance of DFC and CVD.............................................................. 105
A.3 Model for Data Imputation............................................................................................. 106
A.3.1 Model Development ................................................................................................ 106
A.3.2 Testing of models for T and RH.............................................................................. 115
REFERENCES.......................................................................................................................... 136
BIBLIOGRAPHY OR GENERAL REFERENCES ................................................................. 142

viii
List of Figures

Figure 1.1 Paddy yield in major Asian countries with their percentage contribution to world's

productivity ................................................................................................................................... 1

Figure 1.2 Wheat yield in major Asian countries with their percentage contribution to world's

productivity ................................................................................................................................... 2

Figure 1.3 Isotopes of hydrogen.................................................................................................... 6

Figure 1.4 For isotopes bond dissociation energies are different for different molecules ............ 8

Figure 1.5 Variation of Rice and Wheat Yield in India ................................................................ 9

Figure 1.6 Future projection of percentage wise contribution of different sectors (Data were

taken from standing sub-committee report of MoWR) ............................................................... 10

Figure 2.1 Craig- Gordon model ................................................................................................. 13

Figure 2.2 Experimental set up to collect atmospheric water vapour using liquid nitrogen cold

trap (Peters and Yakir, 2009) ...................................................................................................... 19

Figure 2.3 Experimental set up for azeotropic distillation (Recesz and Woods, 1990) .............. 21

Figure 2.4 Squeezer machine (Banito et al., 2005) ..................................................................... 22

Figure 2.5 Centrifuge tube with inbuilt water collection set up (Reynolds (1984)).................... 23

Figure 2.6 Soil water extraction setup (Dalton, 1989) ................................................................ 26

Figure 2.7 Cryogenic vacuum distillation (West et al., 2006) .................................................... 26

Figure 2.8 Cryogenic vacuum distillation (Orlowski et al., 2013) .............................................. 27

Figure 3.1 Study area .................................................................................................................. 29

Figure 3.2 Variation of average monthly temperature at study site ............................................ 30

Figure 3.3 Variation of average monthly relative humidity at study site .................................... 30

Figure 3.4 Variation of average monthly wind speed at study site ............................................. 31

Figure 3.5 Variation of average net solar radiation and pressure at study site ........................... 31

Figure 3.6 Windrose diagram with average wind speed ............................................................. 32

Figure 3.7 Windrose diagram with maximum wind speed ......................................................... 32

Figure 3.8 Average dry density at the study site ......................................................................... 32

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Figure 3.9 Soil water retention curve of soil at the study site (Brooks-Corey (BC) Model) ...... 33

Figure 3.10 Particle size distribution curve for the soil at the study site .................................... 33

Figure 3.11 Rice cultivation procedure ....................................................................................... 34

Figure 3.12 Wheat cultivation procedure .................................................................................... 36

Figure 3.13 Variation of plant height and leaf area index of wheat plant ................................... 36

Figure 3.14 Actual figure showing different components of automatic weather station at study

site ............................................................................................................................................... 38

Figure 3.15 Actual figure showing air intake structure at study site ........................................... 39

Figure 4.1 Working principle of Peltier element......................................................................... 40

Figure 4.2 Things needed to design and construct Peltier element based cold trap .................... 41

Figure 4.3 Variation of temperature of cold and hot side of Peltier element cold trap setup when

there was no air circulated........................................................................................................... 42

Figure 4.4 Temperature variation of cold side of Peltier element cold trap with and without air

flow ............................................................................................................................................. 42

Figure 4.5 On field picture of air intake structure ....................................................................... 43

Figure 4.6 Atmospheric water vapour sample collection ............................................................ 44

Figure 4.7 Cryogenic vacuum distillation for soil and plant water extraction ............................ 45

Figure 4.8 Working principle of displacement liquid centrifugation method ............................. 46

Figure 4.9 Soil water extraction using displacement liquid centrifugation using

tetrachloroethylene ...................................................................................................................... 48

Figure 4.10 LGR's Liquid water isotope analyser at our institute ............................................... 50

Figure 4.11 Loading of standard and actual samples of the tray for isotopic analysis................ 51

Figure 4.12 Process of automatic injection of samples in the optical cavity .............................. 52

Figure 4.13 Variation of uncertainty in transpiration fraction with the difference in source

isotopic composition at different values of uncertainty .............................................................. 54

Figure 4.14 Variation of uncertainty in transpiration fraction with transpiration fraction at

different values of uncertainty .................................................................................................... 55

x
Figure 4.15 Variation of uncertainty in transpiration fraction with uncertainty in ET, T and E at

different values of uncertainty .................................................................................................... 56

Figure 4.16 Variation of uncertainty in absolute water vapour concentration with the

temperature at different values of uncertainty............................................................................. 58

Figure 4.17 Variation of uncertainty in absolute water vapours concentration with the

temperature at different values of uncertainty............................................................................. 58

Figure 4.18 Variation of uncertainty in the isotopic composition of evaporation with the change

in temperature at different values of relative humidity ............................................................... 60

Figure 4.19 Variation of uncertainty in the isotopic composition of evaporation with the change

in relative humidity with different values of n ............................................................................ 61

Figure 5.1 AWS data on 26 October, 2017 ................................................................................. 62

Figure 5.2 Wind rose for 26 October, 2017 ................................................................................ 63

Figure 5.3 Isotopic composition of different water sources collected on 26-10-2017 ................ 64

Figure 5.4 Variation in the isotopic composition of rice leaf water during the experiment

duration ....................................................................................................................................... 64

Figure 5.5 Keeling Plot for 26 October, 2017 ............................................................................. 65

Figure 5.6 Isotopic composition of different water sources collected during wheat cultivation 66

Figure 5.7 Isotopic composition of different water sources collected during entire study (both

rice and wheat season) ................................................................................................................ 67

Figure 5.8 Variation of the average isotopic composition of water vapour during the entire study

with the standard deviation ......................................................................................................... 68

Figure 5.9 Comparison of the isotopic composition of water vapour at the bottommost and the

topmost level at 11 am ................................................................................................................ 69

Figure 5.10 Comparison of the isotopic composition of water vapour at the bottommost and the

topmost at 1 pm ........................................................................................................................... 70

Figure 5.11 Variation of the average isotopic composition of soil water during the entire study

with a standard deviation ............................................................................................................ 71

Figure 5.12 Comparison of the isotopic composition of soil water at 0- 10 cm and 10 - 20 cm 72

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Figure 5.13 Comparison of the isotopic composition of plant water and leaf water .................. 73

Figure 5.14 AWS data on 17 February, 2018 ............................................................................. 74

Figure 5.15 Windrose on 17 February ........................................................................................ 75

Figure 5.16 Soil water isotopic composition of Deuterium on 17 February ............................... 75

Figure 5.17 Soil water isotopic composition on 𝑂18 on 17 February ....................................... 75

Figure 5.18 Variation of air temperature with height.................................................................. 76

Figure 5.19 Variation of relative humidity with height .............................................................. 76

Figure 5.20 Variation of the isotopic composition of water vapour with height ........................ 76

Figure 5.21 Variation of the isotopic composition of water vapour with height ........................ 76

Figure 5.22 Keeling plot on 17 February, 2018 ......................................................................... 77

Figure 5.23 Keeling plot based on oxygen 17 February, 2018 between 13:00- 14:00 ............... 78

Figure 5.24 Variation of stem water on 28 February, 2018 ........................................................ 79

Figure 5.25 Keeling plot for 28 February, 2018 for 11:00-12:00 & 13:00- 14:00 ...................... 80

Figure 5.26 Keeling plot for 13 March, 2018 ............................................................................. 81

Figure 5.27 Keeling plot for 13 March, 2018 11:00-12:00 & 13:00- 14:00 ............................... 82

Figure 5.28 Keeling plot for 27 March, 11:00-12:00 & 13:00- 14:00 ........................................ 83

Figure 5.29 Keeling plot for 31 March, 2018 ............................................................................. 84

Figure 5.30 Keeling plot for 31 March, 2018 11:00-12:00 & 13:00- 14:00 ............................... 85

Figure 5.31 Keeling plot for 8 April, 2018 ................................................................................. 85

Figure 5.32 Variation on the isotopic composition of water vapour on 11 April, 2018 ............. 86

Figure 5.33 Keeling plot for 13 April, 2018 ............................................................................... 87

Figure 5.34 Comparison of transpiration factor obtained by the hydrometric method and stable

isotope fractionation method for wheat....................................................................................... 92

Figure 5.35 Experimental plot on May 2, 2018 ( AIS represents air intake structure) ............... 92

Figure 5.36 AWS data on 2 May, 2018 ...................................................................................... 93

Figure 5.37 Windrose on 2 May ................................................................................................. 94

Figure 5.38 Soil moisture, electrical conductivity and temperature variation with depth .......... 95

Figure 5.39 Soil isotopic composition variation with depth (Hydrogen) .................................... 95

xii
Figure 5.40 Soil isotopic composition variation with depth (Oxygen) ....................................... 95

Figure 5.41 Variation of air temperature with height.................................................................. 96

Figure 5.42 Variation of relative humidity with height .............................................................. 96

Figure 5.43 Variation of the isotopic composition of water vapour with height ........................ 96

Figure 5.44 Variation of the isotopic composition of water vapour with height ........................ 96

Figure 5.45 Keeling plot for 2 May, 2018 .................................................................................. 97

Figure 5.46 Keeling plot for 2 May, 2018 .................................................................................. 98

Figure 5.47 Isotopic composition of oxygen isotope different fluxes and samples measured (or

calculated) during the wheat season ............................................................................................ 99

Figure 5.48 Isotopic composition of hydrogen isotope different fluxes and samples measured (or

calculated) during the wheat season .......................................................................................... 100

Figure A.1 Performance of cryogenic vacuum distillation apparatus ....................................... 105

Figure A.2 Comparison of performance of displacement fluid centrifugation and cryogenic

vacuum distillation .................................................................................................................... 106

Figure A.3 Graph showing relationship correlation of T1aws with all the temperature ........... 108

Figure A.4 Scatter plot between T1aws and T1ais.................................................................... 109

Figure A.5 Scatter plot between T1aws and T2ais.................................................................... 110

Figure A.6 Scatter plot between T1aws and T3ais.................................................................... 110

Figure A.7 Scatter plot between T1aws and T4ais.................................................................... 111

Figure A.8 Scatter plot between T1aws, T1ais and SHF .......................................................... 111

Figure A.9 Graph showing relationship correlations of RH1aws with all the RH .................... 113

Figure A.10 Scatter plot between RH1aws and RH1 ................................................................ 114

Figure A.11 Scatter plot between RH1aws and RH2ais ........................................................... 114

Figure A.12 Scatter plot between RH1aws and RH3ais ........................................................... 115

Figure A.13 Scatter plot between RH1aws and RH4ais ........................................................... 115

Figure A.14 Testing of different models for predicting temperature ........................................ 116

Figure A.15 Testing of different models for predicting relative humidity ................................ 116

Figure A.16 AWS data on 28 February .................................................................................... 117

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Figure A.17 Windrose on 28 February ..................................................................................... 117

Figure A.18 Soil isotopic composition on 28 February ............................................................ 118

Figure A.19 Soil isotopic composition on 28 February ............................................................ 118

Figure A.20 Variation of air temperature with height............................................................... 119

Figure A.21 Variation of air relative humidity with height ...................................................... 119

Figure A.22 Variation of the isotopic composition of water vapour with height ..................... 119

Figure A.23 Variation of the isotopic composition of water vapour with height ..................... 119

Figure A.24 AWS data on 13 March ........................................................................................ 120

Figure A.25 Windrose on 13 March ......................................................................................... 120

Figure A.26 Soil isotopic composition on 13 March ................................................................ 121

Figure A.27 Soil isotopic composition on 28 February ............................................................ 121

Figure A.28 Variation of air temperature with height ............................................................... 122

Figure A.29 Variation of air relative humidity with height ...................................................... 122

Figure A.30 Variation of the isotopic composition of water vapour with height ..................... 122

Figure A.31 Variation of the isotopic composition of water vapour with height ..................... 122

Figure A.32 AWS data on 27 March ........................................................................................ 123

Figure A.33 Windrose on 27 March ......................................................................................... 123

Figure A.34 Soil isotopic composition on 27 March ................................................................ 124

Figure A.35 Soil isotopic composition on 27 March ................................................................ 124

Figure A.36 Variation of air temperature with height ............................................................... 124

Figure A.37 Variation of air relative humidity with height ...................................................... 124

Figure A.38 Variation of the isotopic composition of water vapour with height ..................... 125

Figure A.39 Variation of the isotopic composition of water vapour with height ..................... 125

Figure A.40 AWS data on 31 March ........................................................................................ 125

Figure A.41 Windrose on 31 March ......................................................................................... 126

Figure A.42 Soil isotopic composition on 31 March ................................................................ 126

Figure A.43 Soil isotopic composition on 31 March ................................................................ 126

Figure A.44 Variation of air temperature with height ............................................................... 127

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Figure A.45 Variation of air relative humidity with height ...................................................... 127

Figure A.46 Variation of the isotopic composition of water vapour with height ..................... 127

Figure A.47 Variation of the isotopic composition of water vapour with height ..................... 127

Figure A.48 AWS data on 8 April ............................................................................................ 128

Figure A.49 Windrose on 8 April ............................................................................................. 128

Figure A.50 Soil isotopic composition on 8 April .................................................................... 129

Figure A.51 Soil isotopic composition on 8 April .................................................................... 129

Figure A.52 Variation of air temperature with height ............................................................... 130

Figure A.53 Variation of air relative humidity with height ...................................................... 130

Figure A.54 Variation of the isotopic composition of water vapour with height ..................... 130

Figure A.55 Variation of the isotopic composition of water vapour with height ..................... 130

Figure A.56 AWS data on 11 April .......................................................................................... 131

Figure A.57 Windrose on 11 April ........................................................................................... 131

Figure A.58 AWS data on 13 April .......................................................................................... 132

Figure A.59 Windrose on 13 April ........................................................................................... 132

Figure A.60 Soil isotopic composition on 13 April .................................................................. 133

Figure A.61 Soil isotopic composition on 13 April .................................................................. 133

Figure A.62 Variation of air temperature with height ............................................................... 134

Figure A.63 Variation of air relative humidity with height ...................................................... 134

Figure A.64 Variation of the isotopic composition of water vapour with height ..................... 134

Figure A.65 Variation of the isotopic composition of water vapour with height ..................... 134

Figure A.66 Processed vs true isotopic composition of standard samples for oxygen isotope . 135

Figure A.67 Processed vs true isotopic composition of standard samples for hydrogen isotope

................................................................................................................................................... 135

xv
List of Tables

Table 1.1 Difference between hydrometric and SIF based methods of ET partitioning. .............. 5

Table 1.2 Abundance of different stable isotopes of oxygen and hydrogen ................................. 6

Table 1.3 Properties of Different Isotopologues of Water ............................................................ 7

Table 1.4 Difference between equilibrium fractionation and kinetic fractionation factor ............ 8

Table 2.1 Comparison of different ET partitioning studies done using stable isotope

fractionation method. .................................................................................................................. 12

Table 2.2 Molecular diffusivity ratio as reported by different studies ........................................ 15

Table 2.3 Comparison of different displacement liquid .............................................................. 24

Table 2.4 Comparisons of different methods of soil water extraction ........................................ 28

Table 3.1 Properties of rice variety used in the study ................................................................. 34

Table 3.2 Properties of wheat variety used in the study.............................................................. 35

Table 3.3 Variation of plant height and leaf area index of wheat plant ...................................... 37

Table 3.4 Different components of automatic weather station and their accuracy ..................... 38

Table 3.5 Different components of air intake structure and their accuracy ................................ 38

Table 4.1 Materials and their specifications used in construction of Peltier element cold trap .. 41

Table 4.2 Property of tetrachloroethylene ................................................................................... 47

Table 4.3 Experimental procedure days and schedules for different activities ........................... 49

Table 4.4 Isotopic composition of standard samples used in LGR's LWIA ............................... 51

Table 5.1 Parameters of the CG model applied to estimate 𝜕𝐸 for 26th October, 2017............ 65

Table 5.2 Transpiration fractions on 26 October ........................................................................ 66

Table 5.3 Parameters of CG model applied to estimate ∂E during wheat season ........................ 88

Table 5.4 Transpiration fraction during wheat season (average) ................................................ 90

Table 5.5 Transpiration fraction during wheat season ................................................................ 90

Table 5.6 Parameters of CG model applied to estimate 𝜕𝐸 for 2 May, 2018 ............................ 97

Table A.1 Correlation of different automatic weather station variables with temperature ....... 107

Table A.2 Different models for predicting T1ais ...................................................................... 108

xvi
Table A.3 Models predicting T2ais, T3ais, and T4ais .............................................................. 109

Table A.4 Correlations of different automatic weather station variables with relative humidity

................................................................................................................................................... 112

Table A.5 Different models for predicting RH1ais ................................................................... 113

Table A.6 Models predicting RH2ais, RH3ais, and RH4ais ..................................................... 114

xvii
LIST OF ABBREVIATIONS

AIS: Air intake structure

AWS: Automatic Weather Station

BP: Barometric Pressure (mbar)

CG: Craig Gordon

CVD: Cryogenic vacuum distillation

DOY: Day of year

EC: Electrical Conductivity (mS\m)

E: Evaporation (mm\day)

ET: Evapotranspiration (mm\day)

GSR: Global Solar Radiation (watt\m2)

GISP: Greenland Ice Sheet Precipitation

HFE: Hydrofluroether

LN2: Liquid nitrogen

I: Infiltration (mm\day)

In: Interception (mm\day)

IC: Isotopic composition(‰)

LAI: Leaf area index (m2\m2)

LWIA: Liquid water isotope analyser

LGR: Los Gatos research

L: Lysimetric

MSL: Means sea level

ML: Microlysimeter

OA- ICOS: Off-axis integrated cavity output spectroscopy

xviii
Pr: Percolation (mm\day)

PHB: Pioneer hybrid rice

PH: Plant height (cm)

PP: Polypropylene

P: Precipitation (mm)

RCF: Relative centrifugal force (g)

RH: Relative humidity (%)

RPM: Rotation per minute (min-1)

R: Runoff (m3/s)

SIF: Stable isotope fractionation

SLAP: Standard Light Antarctic Precipitation

S: Storage

T: Temperature (°C)

T: Transpiration (mm/day)

TCE: Tetrachloroethylene

VSMOW: Vienna Standard Mean Oceanic Water

WD: Wind Direction (°)

WS: Wind Speed (m/sec)

xix
1 INTRODUCTION

1.1 Rice and Wheat

1.1.1 Rice (Oryza Sativa)

Rice (Oryza Sativa) is one of the oldest crops (8,500-11,500 BC) which are cultivated by

humans, has now become the life and livelihood of more than 50% of the world’s population.

Rice is the third most cultivated crop in the world after maize and wheat.Rice provides 20% of

the world’s dietary energy supply(Sivanagaraju, 2006).Asiaalone produces about 90% of the

world’s rice production. In Asia, India has the largest area under rice (41.66 million ha)

accounting for 29.4 per cent of the global rice area (Sivanagaraju, 2006). FromFigure 1.1, it is

clear that China and India together contribute about 50 percent of the world’s rice production.

An average yield of rice in the world is about 4,328.7 Kg/ Hect. Most of the Asian countries

including India have yield below the world average.

Figure 1.1 Paddy yield in major Asian countries with their percentage contribution to world's productivity

Rice production in Asia and Africa are small-scale (average plot size in these areas are very

less) as compared to Latin American countries which is one of the limiting force for reduced

yield in these areas. In different regions depending on climate, water availability and

1
topography rice cultivation strategiesare different. In areas near to low lying river basins, flat

areas or near deltas flooded condition for rice cultivation is used.

1.1.2 Wheat (Triticum Aestivum)

Wheat (Triticum Aestivum) is also one of the oldest (5,000 BC) cereal crop cultivated by

humans. It is used as food for more than two billion people. Worldwide, wheat provides nearly

55% of the carbohydrates and 20% of the food calories consumed globally (Breiman and Graur,

1995).India is the fourth largest producer of wheat in the world after Russia, the USA and

China, and accounts forroughly 10% of the world’s total production of wheat.FromFigure 1.2, it

is clear that the average yield of wheat in the world is about 3,038.7 Kg/ Hect, and India is

below the world’s average world average. But for wheat,the gap is less as compared to gap in

Rice.

Figure 1.2 Wheat yield in major Asian countries with their percentage contribution to world's productivity

1.2 Future challenge in crop production

The rapid increase in population, climate change and depletion in natural resources will severely

affect the food security of the world population (Yadav et al., 2010). No doubt there is

remarkable growth in food production in the lastthree decades but still, to overcome the above-

mentionedproblems, this increase is not sufficient. Despite impressive growth in food

2
production, the risks were exposed by the food crisis in recent years. In recent times, many

researchers have found that there has been a change in precipitation patterns (intensity has been

increased and heavier episodic rainfall with longer dry periods (Meehl et al, 2007))

Intergovernmental Panel on Climate Change [IPCC] projected that the atmospheric CO2

concentration might increase up to 730 – 1020 ppm by 2100 and the global average temperature

may rise roughly up to 0.2 C per decade (Meehl et al, 2007). These predicted climatic changes

will have severe impacts on crop yield as these changes affect crop evapotranspiration, crop

growth and development (Lobell et al., 2011; Long et al., 2006; Ray et al., 2015).

1.3 Need for the ecohydrological approach

One of the major ecohydrological challenges is evapotranspiration partitioning, which limits our

understanding for soil-plant- atmospheric continuum as well as feedback between vegetation

and available water (Newman et al., 2006; Wu et al., 2007).Available water is mostly affected

by the spatial and temporal distribution of precipitation and how different components of the

water cycle redistribute this precipitated water (Newman et al., 2006). Differentcomponent of

water cycle includes runoff (R), infiltration (I), evapotranspiration (ET), precipitation (P),

interception (In), storage (S) and percolation (Pr). Depending on location and time,contribution

of these components varies for region to region and time to time. In most of the cases, ET

contributes maximum,and it may reach up to 95 percent in water limited areas (Sutanto et al.,

2014).

Water-limited areas are those areas in which the ratio of annual precipitation and annual

potential evapotranspiration varies from 0.03 to 0.75 (Newman et al., 2006). These areas

include arid, semiarid, and sub-humid regions which account more than 50 percent of world

land area. Due to recent changes in climatewater-limited areas are increasing at avery rapid

rate(Newman et al., 2006). The rapid growth of population has put excessive stress on nature

and natural ecosystems. To meet over going demands, there is a needforproper understanding of

different components of the water cycle.

3
Due to difficulty in measuring canopy evaporation (Interception), evaporation and transpiration

separately, generally these terms are lumped togetherin most of the models. These components

when lumped together may induce errors in simulations as these have different physical

characteristics and timescale. For example, evaporation is the fast process as (it is related to the

surface or shallow subsurface) compared to transpiration (deeper depth of soil).

1.4 Methods to partition ET

Traditionally the number of methods is used to partition evapotranspiration which may be

grouped mainly in two parts.

1) Hydrometric methods: In this method, different components of the water cycle are

measured directly in the field. The criticalcomponents that are typically measured in this

method include – precipitation, irrigation, evaporation, transpiration, interception, soil

moisture and percolation.

2) Stable isotope fractionation (SIF) method: Use of naturally occurring stable isotope of

water has given a new and very powerful tool to hydrologist to understand soil- plant-

atmospheric continuum(Sutanto et al., 2014). In this method, generally H2 O18 and

HDO16 isotopologuesare used as tracers.The difference in mass, bond dissociation energy

and vapour pressure results in the fractionation of isotopologues. When evaporation starts

lighter isotopologues requirea lesser amount of energy due to which residual water contains

a higher fraction of heavier isotopes. During transpiration,no fractionation occurs from

source water to stem water which results in a significant difference in isotopic signatures of

evaporation and transpiration water. This distinct difference in isotopic signature makes

stable isotope fractionation method an interesting method to partition ET (Sutanto et

al.,2014, Zhang et al., 2011).Table 1.1compares the hydrometric methods and SIF method

of ET partitioning.

4
Table 1.1 Difference between hydrometric and SIF based methods of ET partitioning.
Properties Hydrometric methods SIF method

Techniques Direct measurement Measurement using the isotopic signature of

different processes

Scale Point scale Plot-scale

Advantage More reliable Partitioning at watershed level can be done.

Less cost

Relatively easier

Disadvantage Spatial density is limited Accuracy is highly sensitive to specific quantities

by measuring device which may result in higher uncertainty if not

correctly measured.

Some assumptions may be hard to be met.

1.4.1 Stable Isotope Fractionation Method


1.4.1.1 The stable isotope of water

Isotopes are the elements having the same number of the proton but the different number of the

neutron. Isotopes are generally of two types.

a) Stable Isotopes: These are isotopes in which combination of neutron and proton is such

that their nuclei do not undergo any decay e.g. H, D, T, O16 and O18 etc.

b) Radioactive Isotopes:These are isotopes in which combination of neutron and proton is

such that their nuclei are not stable. They continuously emit alpha, beta and gamma rays

to become stable. C14, U238, O19 to O26 etc.

5
Figure 1.3 Isotopes of hydrogen

Hydrogen has 7 (H, D, T, H4, H5, H6 and H7)and oxygen has15 (O12 to O26) possible

isotopes.Out of these isotopes,hydrogen has two stable isotopes (H and D),and oxygen has only

three stables Isotopes (O16, O17 and O18).

Most commonly available isotopes of hydrogen and oxygen are following-

Table 1.2 Abundance of different stable isotopes of oxygen and hydrogen


Element Isotope Abundance Ratio Nature

Hydrogen D 0.02 Stable


𝑫
𝑯
= 0.0002
H 99.98 Stable

T very less Radioactive

Oxygen 𝑂18 0.2 Stable


𝑶𝟏𝟖
𝑶𝟏𝟔
= 0.002
𝑂16 99.76 Stable

𝑂17 0.04 Stable

Isotopologues are molecules which differ in their isotopic composition. Above isotopes when

combined can make six isotopologues of water as H2 O16,H2 O17, H2 O18, HDO16 , D2 O16and

T2 O16.Table 1.3contains the most commonly available isotopologues of water.

6
Table 1.3 Properties of Different Isotopologues of Water
Properties 𝐇𝟐 𝐎𝟏𝟔 𝐇𝟐 𝐎𝟏𝟖 𝐇𝐃𝐎𝟏𝟔

Natural Abundance 99730 1.999 × 10−3 3.106 × 10−4

Molecular weight (g/mole) 18.011 20.015 19.017

Density (g/cc) (20 °C, 1 atm) 0.99821 1.11064

Max Density at (°C) 3.98 4.3

Triple point (°C) 0.01 0.38 ± 0.05 2.04 ± 0.05

Critical T (°C) 373.946

Critical P (°C) 22.064

Viscosity at 20 °C 1.0016 1.0564 1.1248

(𝐏𝐚. 𝐬 × 𝟏𝟎−𝟑 )

Diffusion coefficient at 25°C 2.30 2.66 2.34

(𝐜𝐦𝟐 /𝐬 × 𝟏𝟎𝟓 )

Measuring absolute ratio requires sophisticated instrumentsthat are very. Therefore,instead of

absolute, relative change in ratio is generally measured. In order to minimise instrumental error

or to avoid inter laboratory variations values are measure with respect to the known reference.

Thisreference is Vienna Standard Mean Oceanic Water (VSMOW). Therefore isotopic

concentration is expressed as

𝑂 18 𝑂 18
(𝑂16 ) − (𝑂16 )
𝑠𝑎𝑚𝑝𝑙𝑒 𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒
𝜕18 𝑂𝑠𝑎𝑚𝑝𝑙𝑒 =( 𝑂 18
) × 1000 ‰
( 16 ) Eq. (1.1)
𝑂 𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒

The value of the isotopic composition is reported in delta (𝜕) of VSMOW.

7
1.4.1.2 Fractionation of water molecule

Changes in the isotopic ratio of heavy to lighter isotopes are known as fractionation (Clark and

Fritz, 1997). Fractionation occurs when changes in phase occurs due to bond breaking,and bond

formation. From the Figure 1.4it is clear that bond dissociation energy of different

isotopologues are different due to which for a particular temperature lighter isotope will

dissociate first leading to a higher concentration in a loosely held phase (water vapour) and

depletion in residual phase (residual water).

Figure 1.4 For isotopes bond dissociation energies are different for different molecules
(Clark and Fritz, 1997)

Two primary types of fractionation considered in our study are compared inTable 1.4.

Table 1.4 Difference between equilibrium fractionation and kinetic fractionation factor
S.N. Equilibrium fractionation Kinetic fractionation

Nature Occurs when chemical equilibrium Unidirectional

Effect of T Highest at low temperature

Governing factor Related to bond stability Related to the speed of

isotope

Example H216O(l) + H218O(g) ↔ H218O(l) + H216O(l) -> H216O(g)faster

H216O(g) H218O(l) -> H218O(g)slower

8
1.5 Motivation and objectives of the thesis

The euphoria generated by the first green revolution in India is very quickly subsiding as

problems like overpopulation,and climate change are becoming more intense with each passing

year. Undoubtedly, green revolution has saved millions of lives by making nation self-sufficient

in wheat and rice crops but due to improper management of irrigation water has also created

significant problems like waterlogging and increases in soil salinity. Before the green revolution

in India riceyield was more as compared to wheat yield, but after 1967 increase in wheat

production has been very rapid.In India,the rise in food productivity is about 500% in the last 40

years has taken in the cost of depletion of 172%, 133% and 74% reduction of groundwater in

Punjab, Haryana and Uttar Pradesh respectively (Sivanagaraju (2006), Yadav et al.(2010)).

These problems have threatened the future food security of India as well as the world as India’s

contribution to the world food industry is significant.

Figure 1.5 Variation of Rice and Wheat Yield in India

Figure 1.6shows that the percentage of water used by different sectors in India for the years

2025 and 2025.As anticipated by standing sub-committee report of MoWR that consumption of

water by the energysector will increase rapidly in upcoming years and there will be a reduction

in water consumption by agriculture sector from 85% to 81%. Agriculture sector will continue

to the primary user of water in upcoming years. By mid of this century, India will share more

9
than 17 % of the world’s population and only 4 % of water resources due to which areas under

water stress will increase significantly. To meet upcoming demand, there is a need for some

basic infrastructural changes which includes increasing irrigation efficiency and efficient

farming.

Figure 1.6 Future projection of percentage wise contribution of different sectors (Data were taken from standing sub-
committee report of MoWR)

Irrigation efficiency can be increased in multiple ways that includesaving water loss due to soil

evaporation. Quantification of soil evaporation and useful water for the plant (also known as

transpiration) is difficult as generally these terms are lumped insingle term evapotranspiration.

Globally numbers of studies have been done using multiple methods to partition ET at plot level

to watershed level,but we were unable to find any study from India. Some authors have tried to

partition ET using the hydrometric method,but there was not any study using SIF

method.Therefore our objectives of this thesis work are-

1. To design an experimental set-up for applying stable isotope method for partitioning ET

in a rice-wheat field in the Ganga basin.

2. Partition ET using stable isotope fractionation method and compare the results with the

hydrometric method.

10
2 LITERATURE REVIEW

Evapotranspiration is a hydrological term which is made by combining evaporation and

transpiration. Generally, for agriculture, transpiration is a desired component of ET and

evaporationis considered as a loss. To meet future water demand and to overcome increasing

water scarcity, it is necessary to find the individual contributions of T and E in ET.Earliest

partitioning was done by Harrold et al., (1959) who tried to stop evaporation by just covering

the soil. The invention of methods such as micro-lysimeters to measure under-canopy E (Boast

and Robertson, 1982; Walker, 1984), Sap flow measurements based partitioning (Sakuratani,

1981) and the stable water isotope based partitioning method (Wang and Yakir, 2000; Yakir and

Sternberg, 2000; Williams et al., 2004; Zhang et al., 2011) are popular and advanced

partitioning approaches.A significant limitation of studies is that point based partitioning was

done. Inthe beginning of 21stcentury, a new approach to partition evapotranspiration was

proposed by Wang and Yakir (2000) that usesthe isotope method to partition evapotranspiration.

They used the Keeling plot to find the isotopic composition of ET and Craig Gordon (1965)

model to find the isotopic composition of E and T. At that time there were two main limitations

of isotope method to partition ET (i) cost of analysis of isotope sample (ii) sample collection

itself was very tedious and challenging. With the development of field-basedinstruments

problems have been addressed to some extent. Some of the studies that have used isotope

method of ET partitioning and their main findings are listed inTable 2.1.

Zhang et al. (2011) performed these experiments in China to partition ET for winter wheat and

to find out the depth which contributesthe maximum to root water uptake. They found that

effective depth of root water uptake was 40 cm even when irrigation was applied to 100 cm

depth. Studies done by Wu et al. (2011) and Wei etal. (2015) found that the ratio of

transpiration and evapotranspiration are 0.78 and 0.8 for rice and maize, respectively. Aouade

etal. (2016) studied winter wheat and found that keeling plot method worked well for oxygen

but not for hydrogen isotopes.

11
Table 2.1 Comparison of different ET partitioning studies done using stable isotope fractionation method.
Research Crop Site Method Major Finding

group

Wang and Wheat Israel SIF Combined concentration and


Yakir, (2000) isotopic gradient analysis
Zhang et al., Wheat China SIF Root water uptake occurs mainly
(2011) ML between 0 - 40 cm depth. Depth of
water supplied is 100 cm
Maximum evaporative losses
reachesup-to 30 %
Wu et al. Maize China EC
(2013) SIF 𝐹𝑇 = 0.71𝐿𝐴𝐼 0.14 , 𝑅 2 = 0.87
L 𝑇
= 0.78
𝐸𝑇
They showed that CG method and
chamber based methods are robust.

Wei et al Rice Tsukuba(Japan) SIF 𝐹𝑇 = 0.67𝐿𝐴𝐼 0.25 𝑅2 = 0.80


(2015) with Uncertainty of FT estimation was
flooded 𝑇
14.6 ±10, 𝐸𝑇
= 0.80
irrigation
Bhone Rain S. Korea PM 56 Rain fed rice had higher agronomic
Nay-Htoon fed& SIF and ecosystem water use efficiency
(2016) flooded Transpiration fraction was found
rice 0.65 and 0.4 for rain fed and flooded
Aouade et Winter Morocco EC after and before irrigation
al.(2016) wheat SIF respectively using SIF
ML E = 1.76 and 1.34 mm/day & T =
3.85 and 5.45 mm/day in 2011-12
& 2012-13 respectively
Keeling plot method worked well
for D but not for 𝑂18
(SIF- Stable isotope fractionation, ML- Microlysimeter, L- Lysimeter, EC- Eddy covariance, PM- Penman-Monteith)

12
2.1 Craig-Gordon (CG) Model

CG model is based on Langmuir linear resistance model for evaporation. Assumptions involved

in the CG model are-

1. At Interface of liquid and water relative humidity is equal to 1.

2. There is no divergence or convergence of air in the vertical air column.

3. Fractionation does not occur during turbulent transport.

Figure 2.1 Craig- Gordon model

According to the CG model isotopic composition of soil evaporation is given by


1
δ s (α ) − hδ v − εeq − (1 − h)εk
eq
δE =
(1 − h) + 10−3 (1 − h)εk Eq. (2.1)

where δ E = Isotopic composition of soil evaporation

δ s = Isotopic composition of soil water at water evaporation front

13
δ v = Isotopic composition of near groundwater vapour

h = Relative humidity of air normalised by saturation vapour pressure at the soil surface

2.1.1 Kinetic fractionation factor (𝛆𝐤 )

Kinetic fractionation factor is given by

𝐷 𝑛
(1 − ℎ)θ (( ) − 1)
𝐷𝑖

𝜌𝑚
θ = 𝜌𝑚 +𝜌𝑇
can be assumed to be 1 for a small water body whose evaporation flux does not

perturb the ambient moisture significantly and 𝜌𝑚 &𝜌𝑇 are molecular and turbulent resistances

n = 0.5 for highly turbulent condition, n = 2/3 for a laminar flow, n = 1 for static condition

(only diffusion)

𝐷𝑖
= Ratio of molecular diffusion coefficients of heavier to lighter isotopologues
𝐷

𝐷𝑖 𝑚 𝑚𝑖 +𝑚𝑔
𝐷
= (
𝑚𝑖 𝑚+ 𝑚𝑔
) where 𝑚 &𝑚𝑖 are molecular masses of heavier to lighter isotopologues and 𝑚𝑔

is molecular mass of gas in which water diffuses.

𝐷 𝐷 16 𝐷𝐻 𝑂18
Craig et al. (1965) calculated 𝐷𝑖to be 𝐷𝐻𝐷𝑂 = 0.983 and𝐷2
= 0.969 using kinetic theory of
𝐻2 𝑂16 𝐻2 𝑂16

𝐷𝑖
gases. VonEhhalt and Knott (1965) using experiments found 𝐷
to be 0.985± 0.003 and 0.971 ±

0.001 for hydrogen and oxygen isotopologues. Merlivat (1977) showed by performing different

types of experiments (controlled laminar flow experiment and transporting vapours of water
𝐷𝐻𝐷𝑂16
through diffusion tube) that coefficients of diffusion of the isotopic molecules in the air =
𝐷𝐻 𝑂16
2

𝐷𝐻 𝑂18
2
0.9755 ± 0.0009 and 𝐷 = 0.9723±0.0007.Cappa et al. (2003) did diffusion-controlled
𝐻2 𝑂16

fractionation during evaporation under non equilibrium conditions. They did their experiments

considering the surface cooling of liquid as a crucial factor while considering the fractionation.

14
𝐷𝐻 𝑂18 𝐷𝐻𝐷𝑂16
2
They reported values of isotopic molecular diffusivity ratios are, = 0.9691 and =
𝐷𝐻 𝑂16 𝐷𝐻 𝑂16
2 2

𝐷𝑖
0.9839.Table 2.2summarises the values of reported in different literatures. In this study we
𝐷

have used values reported by Cappa et al. (2003).

Mathieu and Baric (1996), Soderberg et al. (2012)in the new formulation that requires relatively

less observation,modified exponent(n)for condition having negligibleturbulence

𝐷 𝑛′
εk = Kinetic fractionation factor = ((𝐷 ) − 1)
𝑖

1 𝜃 − 𝜃𝑟𝑒𝑠
𝑛′ = 1 − ( )
2 𝜃𝑠𝑎𝑡 − 𝜃𝑟𝑒𝑠

Table 2.2 Molecular diffusivity ratio as reported by different studies


Literature 𝑫𝑯𝑫𝑶𝟏𝟔 𝑫𝑯𝟐𝑶𝟏𝟖 Method of finding
𝑫𝑯𝟐𝑶𝟏𝟔 𝑫𝑯𝟐𝑶𝟏𝟔

Craig et al. (1965) 0.983 0.969 Kinetic theory of gases

(theoretical)

Ehhalt and Knott 0.985± 0.003 0.971 ± 0.001 Experimental

(1965)

Merlivat (1977) 0.9755 ± 0.0009 0.9723±0.0007 Controlled laminar flow

experiments

Cappa et al. 0.9839 0.9691 Diffusion-controlled

(2003) fractionation during

evaporation under non

equilibrium conditions

experiments

αeq = Equilibrium fractionation factor = F (T)

1
εeq= (1 − α ) × 100
eq

15
2.1.2 Equilibrium fractionation factor (𝛂𝐞𝐪 )

Majoube (1971) did a number of extensive experiments for low temperatures (0°C –100°C).The

αeq derived from those experiments is given by

𝐷 103 106
103 lnαeq ( ) = 52.612 − 76.248 ( ) + 24.844 ( 2 ) Eq. (2.2)
𝐻 𝑇 𝑇

3
𝑂18 103 106
10 lnαeq ( 16 ) = −2.0667 − 0.4156 ( ) + 1.137 ( 2 ) Eq. (2.3)
𝑂 𝑇 𝑇

Horita and Wesolowski (1995) did experiments for 0°C -340°C and reported following Eq.

𝐷 𝑂 18
(2.4)&Eq. (2.5) for and , respectively.
𝐻 𝑂 16

3
𝐷 𝑇 𝑇 2
10 lnαeq ( ) = −161.04 + 794.84 ( 3 ) − 1620.1 ( 6 )
𝐻 10 10
Eq. (2.4)
𝑇3 109
+ 1158.8 ( 9 ) + 2.9992 ( 3 )
10 𝑇

𝑂18 103 106


103 lnαeq ( ) = −7.685 + 6.7123 ( ) − 1.6664 ( )
𝑂16 𝑇 𝑇2

109 Eq. (2.5)


+0.35041 ( 3 )
𝑇

16
2.2 Keeling Plot

Keeling plots are plots on which x-axis contains inverse of absolute water concentration and y-

axis contains the isotopic composition of water vapour. The intercept of best fitted line

represents isotopic composition of ET. This was first used by Keeling during 1958 to find and

interpret fluctuations in 𝜕13 C values of ambient CO2 and to identify the contributing sources

(Pataki et al. 2001).

Assumptions involved Keeling plots are

1) The Keeling plot approach is based on mass conservation considerations during the

exchange of gases (Kohler et al. 2006).

2) The concentration of flux in canopy reflects the background atmospheric concentration

and the concentration of other gases added by the ecosystem.

The concentration of evapotranspiration can be represented as

𝐶𝐸𝑇 = 𝐶𝑎 + 𝐶𝑣 Eq. (2.6)

where,𝐶𝑎 and𝐶𝑣 are the concentrations of ambient air and water vapour in air, respectively.

𝜕𝐸𝑇 𝐶𝐸𝑇 = 𝜕𝐴 𝐶𝐴 + 𝜕𝑣 𝐶𝑣 Eq. (2.7)

where 𝜕𝐸𝑇 , 𝜕𝑎 and 𝜕𝑣 are isotopic composition of ET, ambient air and water vapour,

respectively.

Using aboveEq. (2.6)&Eq. (2.7) we can get

𝐶𝐴 (𝜕𝐴 − 𝜕𝑣 )
𝜕𝐸𝑇 = + 𝜕𝑣 Eq. (2.8)
𝐶𝑣

Eq. (2.8)can be arranged as

1
𝜕𝑣 = 𝜕𝐸𝑇 + (𝐶𝐴 (𝜕𝑣 − 𝜕𝐴 )) Eq. (2.9)
𝐶𝑣

17
By comparing Eq. (2.9)with standard form of equation of line (y = c + mx) we can get y = 𝜕𝑣 ,

1
intercept on y-axis = 𝜕𝐸𝑇 and m = (𝐶𝐴 (𝜕𝑣 − 𝜕𝐴 )) and x = 𝐶
𝑣

2.3 Review of Sample Collection Techniques

To use stable isotope fractionation method for evapotranspiration partition the most crucial part

is sample collection. Basically three types of samples are required.

1. Atmospheric water vapour at multiple heights

2. Soil water at different depths

3. Plant water

2.3.1 Atmospheric water vapour

Most commonly used method for water vapour collection is by using cryogenic traps which

uses air condensing mechanism to collect atmospheric water vapour. These vapour traps

generally use either Liquid Nitrogen (LN2),or dry ice (Helliker et al. (2002), Peters and Yakir,

2009) since both the liquids are at extremely low temperature. The temperature of LN2 and dry

ice are -191°C and -80 °C. Helliker et al. (2002) developed a rapid and precise method for

sampling and finding the isotopic composition of water vapour in the atmosphere. They used

dry air ethanol slush as coolant liquid for their setup. They concluded that their method of

sampling water vapour reduces the sampling period drastically. Peters and Yakir (2009 have

developed a rapid, reliable and portable system for water vapour collection using dry ice as

coolant liquid. They showed the ability of their system to have similar isotopic composition

when used with conventional traps. The flow rate used in their study was 450ml/min to ensure

that sufficient time is given to condense all vapour present in the air.

18
Figure 2.2 Experimental set up to collect atmospheric water vapour using liquid nitrogen cold trap (Peters and Yakir,
2009)

19
2.3.2 Soil Water

For extracting soil water, we first need to understand how water is stored in soil and its types.

Numbers of methods have been developed for extracting soil water butthe selection of a suitable

method is very important as not all methods are suitable for all application.

There are two types of methods to extract soil water for isotopic analysis

1. Field-based method

1.1 Soil suction lysimeter

2. Laboratory-based methods

2.1 Azeotropic distillation

2.2 Squeezing

2.3 Drainage centrifuge and centrifuge with displacement liquid

2.4 Cryogenic distillation

2.3.2.1 Soil suction lysimeter

Soil suction lysimeters are used for in-situ soil water extraction. It contains one pours ceramic

cup through which soil water enters in it. This method works only if capillary pressure inside

the cup is higher than the soil, therefore, extraction volume reduces drastically if capillary

pressure is below -70 kPa (Bonito et al., 2008)

2.3.2.2 Azeotropic Distillation

Azeotropes are the mixtures which havea boiling point different from these constituents.

Toluene and water form an azeotropic mixture which has a boiling point of 84.1°C which is

significantly different from the boiling point of water (100°C) and toluene (110°C) (Recesz and

Woods, 1990). At room temperature, toluene floats on water which is easily separable.

Kerosene also serves as azeotrope for water.To use this method, first,toluene and soil are mixed

such that water present in the soil makes azeotrope mixture with water. After that the mixture is

heated at 84.1°C.At this temperature,mixture evaporates which is then condensed in a

20
condensing setup. After condensation, toluene floats on top of water and water is taken for its

isotopic analysis.

Figure 2.3 Experimental set up for azeotropic distillation (Recesz and Woods, 1990)

Recesz and Woods (1990) observed that the method serves as a simple, inexpensive and fast

method for soil water extraction (20 min). The safety issue is the major concern in this method.

They reported the accuracy of 2‰and 0.2‰for oxygen and hydrogen isotopes, respectively.

Ingraham and Shadel (1992) compared this method with cryogenic vacuum distillation method

and found both the methods give fractionated sample,however, azeotropic method served well

as it has better temperature control. Leaney et al. (1993) found that fractionation can occur in

this method which may be up to 3‰for hydrogen isotope in case of clay soil.

2.3.2.3 Squeezing

This method works on the principle that soil and water are impressible therefore when very high

pressure is applied on them air present in soil is expelled,and escape of water from pores of soil

takes place (Bonito et al., 2005 ). Most of the water extraction using this method is during

primary consolidation only. Bonito et al. (2005) found that in the case of sandy loam soil,

extraction efficiency (percentage of soil water extracted to the amount of water present in the

21
soil sample) 27.4%. Entwisele and Reeder(1993) found that for moisture content less than 7 %

no water can be extracted.

Figure 2.4 Squeezer machine (Banito et al., 2005)

The soil sample from which water is to extract is placed inside a squeezing cell in which

pressure is applied by using ahydraulic pump. TheHydraulic pump is capable of increasing

pressure from 70 MPa to 160 MPa. There is a temperature controller which controls the

temperature of squeezing sample. Once pressure is applied due to primary consolidation, pore

water is squeezed out which is collected in syringe placed near the squeezing cell. Orlowaski et

al. (2016) used different methods for soil water extraction and they found that the squeezing

method performed well as compared to cryogenic vacuum distillation method.

2.3.2.4 Centrifuge

The Centrifugal method of soil water extraction works on the principle of drainage by

centrifugal force. This method can be classifiedinto two parts

a) Drainage Centrifuge

Reynolds (1984) used centrifuge tube (shown in Figure 2.5) at a speed of 10000 rpm for a

variable time. He found that certain weight of soil and rotational speed make optimum

combination otherwise centrifuge tube may get damaged. He reported that centrifuge time less

than one hour give low yield of soil water. He also warned that complete removal of water is not

22
possible in this method so care should be taken for representative sample collection. At

highestspeed, pressure applied can reach up to 1500 kPa (Bonito etal. 2005)

Figure 2.5 Centrifuge tube with inbuilt water collection set up (Reynolds (1984))

Bonito etal.(2005)reported that complete removal of pore water is not possible using this

method. Theyreported that even at 14,500 rpm 5-15% pore water might remain in the soil. They

concluded that if appropriately done the extraction efficiency can be upto 90%.

Fraters et al. (2017) tried to find out the effect of centrifuge time and rotational speed on water

extraction. They used centrifugation at two relative centrifugal forces (RCF) (733 and 6597g)

and five centrifuge times (20, 35, 60, 120 and 240 min). They found that RCF is a more

important factor than centrifuge time.

Orlowski et al. (2016) tried five different methods to extract soil water for isotope analysis.

They reported centrifugation method performed relatively well as compared to other techniques

like cryogenic distillation and microwave. They reported that since there is no phase change of

water in this method, therefore, it performs well. They also reported that soil type hasa major

effect on the efficiency of the soil water extraction method used.

23
b) Centrifuge with a displacement liquid

To overcome the capillary potential of water in the soil, if a displacement liquid is used, it can

drastically increase the yield. In this process, a displacement liquid is selected whose density is

higher than water which forces water to come out of pores.

Kinniburgh and Miles (1983) said that mechanics involved in displacement method of soil water

extraction is quite tedious and not clearly understood, particularly with regards to trapped air.

They formulated a simple model which assumes that at equilibrium driving pressure is in

equilibrium with capillary pressure.Many researchers have tried different types of displacement

liquid to extract soil water some of them are listed in Table 2.3.

Table 2.3 Comparison of different displacement liquid


S.N. Literature Displacement Density Limitation

Liquid (g/cc)

1. Mubarak and Olsen (1976) Carbon Tetrachloride 1.59 Highly toxic, special

centrifuge bottles are

needed.

2. Batley and Gills(1979) Fluorocarbon Ozone layer

(FC78: 3M) depleting substance.

Banned in Montreal

protocol (1987)

3. Whealen and Carbon Tetrachloride 1.59

Barrow(1980) 1.1.1-trichloroethane 1.32 Carcinogen

Tetrachloroethylene 1.62

4. Kinniburgh and Trifluoroethane (F113) 1.57 Low boiling point

Miles(1983)

5. Jin and Edmunds(2010) HFE 7100 1.5 Expensive

24
In isotope hydrology, following are the main considerations in the selection of a displacement

liquid

1. Effect on isotopic composition: Displacement liquid used as soil water extraction

should not change the isotopic composition of water present in the soil. Thisis generally

tested is displacement liquids containing hydrogen or oxygen atom.

2. Availability: Montreal protocol (1987) was the first worldwide agreement to protect the

environment by regulating the production, distribution and transportation of ozone-

depleting substances. Most of the displacement liquids used earlier in use are banned by

this protocol. Example includes Carbon tetrachloride and 1,1,1- trichloroethane.

Therefore the selection of displacement liquid requires a lot of research.

3. Cost: Cost is also a very important factor as these liquids are very costly.

2.3.3 Plant Water

Cryogenic vacuum distillation (CVD) is a simple, user-friendly and efficient method to extract

both soil and plant water (Dalton, 1988, Orlowaski et al., 2013). During waterextraction sample

is heated under a defined vacuum and when vapour evaporates it is condensed in a liquid

nitrogen trap. Various variations of CVD have been reported in the literature. Some important

variations of CVD are described below.

Dalton(1989): To study plant water uptake Dalton(1989) designed an experimental setup which

used water isotopes to verify physical processes related to plant water uptake directly. He

planted six tomato plants in a very fine sandy soil,andthe nutrient solution was applied. The

entire setup was covered to minimise soil evaporation. Each pot was weighted to find the weight

of transpired water. Soil samples were taken for extraction using vacuum distillation. Extraction

unit consisted of a safety trap, cold finger, ethanol (-64 °C) and a vacuum pump. Entire setup

runs for 12 hours for complete soil water extraction.

25
Figure 2.6 Soil water extraction setup (Dalton, 1989)

1) West et al. (2006): Objective of their study was to find out the minimum time required

to extract unfractionated soil, stem and leaf water. They did their analysis of different

types of soils (2), different types of the stems (3) and different kinds of the leaves (3).

Their experimental setup had a vacuum of 8 Pa.

Figure 2.7 Cryogenic vacuum distillation (West et al., 2006)

They concluded in the study that after a certain extraction time there is no change in the

value of isotopic composition obtained. They reported that extraction time required for

soil may range from 20 min to 40 min (20 min for sandy soil, 40 min for clay), for stem

it may range from 60 min to 75 min, and for leaf it may range from 20 min to 30 min.

26
2) Orlowski et al. (2013 and 2016): They designed a multi-port vacuum distillation

apparatus capable of extracting 18 samples at a time. They performed different

functionality test on their equipment and found itperformed well. They questioned the

applicability of the CVD method under fixed extraction time. They found that there is

the larger error in this method as compared to other methods like squeezing or

centrifugation.

Figure 2.8 Cryogenic vacuum distillation (Orlowski et al., 2013)

They reported that if the effect of time of extraction and the applied pressure is

excluded, then the temperature is the most important factor which affectsthe isotopic

composition.

27
Table 2.4 Comparisons of different methods of soil water extraction
Method Advantage Limitation

Soil suction lysimeter No phase change of water occurs The range of suction
Bonito et al.(2008) Portable pressure is limited Yield
Complete Recovery is not essential Low sampling rates at
capillary pressures below
– 70 kPa
sorption of solutes from
the pore water (Bonito et
al.,)
Centrifuge No phase change of water occurs Low yield for fine grade
Reynolds (1984) Quick and easy soils
Edmunds and Bath (1976) Centrifugation covers a wider range Low moisture content
Fraters et al. (2017) of pore sizes causes no/negligible yield
Orlowski et al. (2016) Complete Recovery is not essential

Centrifuge with No phase change of water occurs Most of the displacement


displacement liquid Higher yield liquids are ozone
Mubarak and Olsen (1976) Quick and easy degrading
Batley and Gills(1979) Centrifugation covers a wider range Toxic
Kinniburgh and Miles(1983) of pore sizes
Jin and Edmunds(2010) Complete Recovery is not essential
Cryogenic distillation Frequently used Complete Recovery is
Dalton (1988) Complete sample can be obtained essential
West et al.(2006) No toxic solvents are used
Orlowski et al.(2013)
Azeotropic distillation Well-developed method Toxic solvents are used
Recesz and Woods (1990) like (Phenol and
Ingraham and Shadel (1992) Kerosene ) for water
Leaney et al. (1993) Risk involved is high
Complete Recovery is
essential
Squeezing Very less contact with atmosphere Extraction time can be
Entwisele and Reeder (1993) Complete Recovery is not essential very high
Bonito et al.(2005) Low extraction efficiency
Orlowski et al. (2016)

28
3 STUDY AREA AND MATERIALS

3.1 Study Area

Experiments were conducted in an experimental rice-wheat field (Figure 3.1 ) located at Indian

Institute of Technology Kanpur (26.5168N, 80.2314E; altitude 135.94 m from MSL) in Middle

Gangetic plains of Uttar Pradesh, India. Kanpur is a semi-arid region with average rainfall

between 820-940 mm and anaverage annual temperature of 25.83°C. The experimental plot was

divided into 21 subplots of size 4 m × 4 m (Figure 3.1).

Figure 3.1 Study area


3.2 Weather Condition

Monthly average metrological data collected at the site are plotted (Figure 3.2 to Figure 3.7)

below. From the graphs following conclusion can be drawn. It is seen that maximumand

minimum temperature at the study site occurs during May and January, respectively. The

reverse is with the case of relative humidity, which is maximum in January and minimum in

July.

29
Figure 3.2 Variation of average monthly temperature at study site

Figure 3.3 Variation of average monthly relative humidity at study site

It was noted that the maximum and minimum average wind speed (monthly average) occurs

during June and October, respectively. It was found that maximum and minimum Barometric

pressure was found during October and July, respectively. Maximum solar radiation was found

during June.

30
Figure 3.4 Variation of average monthly wind speed at study site

Figure 3.5 Variation of average net solar radiation and pressure at study site

S September O October N November D December

J January F February M March A April

M May J June J July

Windrose diagrams were drawn,and it was observed that most prevailing wind direction is SW

wind. It was observed that when the windrose (Figure 3.7) is drawn using maximum wind speed

then wind direction was more scattered between SW ascompared to wind rose (Figure 3.6)

drawn using average wind speed.

31
Figure 3.6 Windrose diagram with average wind speed Figure 3.7 Windrose diagram with maximum wind speed

3.3 Soil properties

Soil properties were found using different tests. Specific gravity was measured using

Pycnometer method(IS 2720-3-1). Dry density was measured using the core cutter method (IS

2720-29). For finding the soil texture sieve analysis was done. Soil water retention curve was

drawn using the filter paper method. The results obtained are shown in Figure 3.8 to Figure

3.10.

Figure 3.8 Average dry density at the study site

32
Figure 3.9 Soil water retention curve of soil at the study site (Brooks-Corey (BC) Model)

Figure 3.10 Particle size distribution curve for the soil at the study site

3.4 Crop Details

The rice and wheat crops used in the study are described below.

3.4.1 Rice

In India, wet cultivation of rice is more popular. Generally, paddy seeds are shown in a small

farm area then transplantation of rice plant is done in the flooded field. Continuous availability

of water during rice growth is required for optimum productivity. Depending on the suitability,

it was decided to use Pioneer Rice Hybrid 71 (PHB 71) rice variety which has the following

qualities.

33
Table 3.1 Properties of rice variety used in the study
S.N. Features Property

1 Name PHB 71

2 Owner Pioneer Hybrid India Seeds

3 Feature Drought/ Stress Tolerant/ Salinity Tolerant

4 Growth duration 130- 135 days

5 Plant height 110-130 cm

6 Yield potential 6500-7000 kg/hectare

7 Area Haryana, Tamil Nadu, Uttar Pradesh

The various steps required in rice cultivation are shown using picture in Figure 3.11

Figure 3.11 Rice cultivation procedure


a) Paddy plants, b) Transplanting rice plant, c) Pesticide control, d) Measuring LAI, e) Removing dried seeds,
and f) Rice seeds

34
3.4.2 Wheat

In India, mostly winter wheat is cultivated.The locallypopular variety of wheatK 7903

(HALNA) was used for our research purpose. The seed is developed by Chandrashekhar Azad

University of Agriculture and Technology (CSUAT), Kanpur.

Table 3.2 Properties of wheat variety used in the study


S.N. Features Property

1 Developed by Chandrashekhar Azad University of Agriculture

and Technology (CSUAT), Kanpur

2 Name K 7903 (HALNA)

3 Feature Irrigated

4 Duration 126-134 days

5 Plant Height 70-80 cm

6 Yield Potential 4000-4500 kg/hectare

7 Area Uttar Pradesh

8 Plantation date 5 January

Figure 3.12 shows various steps involved in wheat cultivation procedure. Figure 3.13 shows

plant height and leaf area index (LAI) measured for the wheat crop. The corresponding values

are produced in Table 3.3.

35
Figure 3.12 Wheat cultivation procedure
a) Manual application of wheat seeds, b) Emergence of wheat plants, c) Tillering,d) Stem extension stage, e)
Headling stage started, f) Headling stage finished, g) Ripening stage began, and h) Harvesting of wheat

Figure 3.13 Variation of plant height and leaf area index of wheat plant

36
Table 3.3Variation of plant height and leaf area index of wheat plant
S.N. DOY Plant Height (mm) 𝒎𝟐
LAI (𝒎𝟐)

1 40 11.5±0.48 0.42 ±0.05

2 48 15.11 ±0.37 1.28 ±0.18

3 59 30.73 ±0.66 3.22 ±0.20

4 63 36.35 ±0.95 4.41 ±0.27

5 72 58.85 ±0.71 4.78 ±0.31

6 87 67.16 ±0.57 3.51 ±0.17

7 98 66.08 ±0.74 3.24 ±0.62

8 103 64.69 ±0.93 1.98 ±0.09

3.5 Data collection

3.5.1 Automatic Weather Station (AWS)

AnAWS at study site was installed before the actual start of experiments. Figure 3.14 shows

AWS installed at study site. Specifications of various components of AWS are listed in theTable

3.4.

37
Figure 3.14 Actual figure showing different components of automatic weather station at study site

Table 3.4 Different components of automatic weather station and their accuracy
S.N. Features Accuracy

1 Temperature (T) ± 0.2°C

2 Relative Humidity (RH) ± 3%

3 Precipitation (P) ±5%

4 Global Solar Radiation (GSR) ±5%

5 Wind Speed (WS) ± 0.5 m/s

6 Wind Direction (WD) ± 5°

7 Barometric Pressure (BP) ±0.2 hPa

8 Evaporation (E) ±1%

3.5.2 Air Intake structure (AIS)

In this study a structure was made which contains sensors listed inTable 3.5. AIS was

constructed in such a manner that its heights can be adjusted depending on plant height. It has

structure has four T & RH sensors were installed. Air was sucked from all the four heights using

pipes simultaneously. Figure 3.15 shows AIS installed at the study site.

Table 3.5 Different components of air intake structure and their accuracy
S.N. Features Property

1 Temperature (T) ± 0.2° C

2 Relative Humidity (RH) ± 0.8 %

3 Soil Moisture (w) ±3%

4 Soil Temperature (ST) ± 0.8° C

5 Soil Electrical Conductivity (EC) ±2%

38
Figure 3.15 Actual figure showing air intake structure at study site

39
4 METHODOLOGY

This chapter describes the methodology used for

I. Collection of atmospheric, soil and plant water sample for isotopic analysis

II. Isotopic analysis of collected samples

III. Sensitivity analysis of partitioning methods

IV. Filling gaps in metrological observations

4.1 Atmospheric Water Vapour Sample collection

4.1.1 Peltier element trap

This trap works on the principle of thermoelectric cooling (based on the Peltier effect). When

two dissimilar materials are joined together at on junction and setup is attached to a DC

current then it brings heat from one side to the other. Therefore one side becomes cooler,and

one side becomes heated. The heated side is attached to a heat sink which brings the

temperature of the hotter junction to ambient and cooler side becomes more and cooler.Figure

4.1shows the working principle of Peltier module.

Figure 4.1 Working principle of Peltier element

Figure 4.2 shows different components of Peltier element trap developed in the studyand Table

4.1presents the specifications of the components used in Peltier trap. We tried to make a setup

using Peltier modules through which atmospheric water vapour can be collected. Things needed

for Peltier trap

40
Figure 4.2 Things needed to design and construct Peltier element based cold trap
a) Design of copper tube, b) On field application of Peltier element based cold trap, c) Nitrile insulator, d)
Peltier element, and e) fan with a heat sink

Table 4.1 Materials and their specifications used in construction of Peltier element cold trap
S.N. Material Property Values

1 Copper Thermal conductivity 385

(W/mK)

2 Nitrile Insulator Thermal conductivity 0.24

(W/mK)

3 Peltier Element Name TEC1-12715

Size (mm) 50 x 50 x 3.9

Imax (A) 15.6

∆Tmax (C) 68

4 Heatsink Fan Speed (RPM) 900-1500

Dimension (cm) 11.9 x 10.9 x 16.3

41
Figure 4.3 Variation of temperature of cold and hot side of Peltier element cold trap setup when there was no air
circulated

Figure 4.4 Temperature variation of cold side of Peltier element cold trap with and without air flow

However, the Peltier element trap designed in this study could achieve temperature up to -20 °C

when there was no air circulation (Figure 4.3). When air was flowing, it can achieve up to -5 °C

(Figure 4.4) which is sufficient to trap all the water present in the air. This trap required very

high power input and electrical efficiency was found to be very low. Therefore we continued

with LN2 trap for rest of study.

4.1.2 Air Intake Structure (AIS)using LN2 trap

42
One of the most critical steps involved in this thesis was to design a robust setup by which

atmospheric water vapour can be collected at four different heights simultaneously. For this

purpose, we designed LN2 trap described below.

The designed AIS consisted of 4 temperature

and 4 relative humidity sensors whose heights

were adjusted depending on the height of

plants. The bottommost sensor was fixed at

0.15 m above the ground. Teflon tubes were

used as pipes in the AIS. All the tubeswere

connected to a manifold which had flow

regulators. The manifold was then connected

to an oil-free vacuum pump. Other ends of

tubes were connected with acold trap which

was placed in a Dewar flask consisting on

LN2.All dewar flasks were of size 1 l which


Figure 4.5 On field picture of air intake structure
was coated with silver nitrate coated.

The Dewar flasks were made from glass blowing laboratory at IIT Kanpur. We made wooden

stands in which Dewar flasks can be placed so that operation with the cold trap with liquid

nitrogen is easy. Bottom of these stands was filled with cotton.

43
Figure 4.6 Atmospheric water vapour sample collection
a) T and RH sensor, b) Installation of Teflon tubes through which air will be sucked by vacuum pump, c)
Dewar flask with all connections done, d) Pouring LN2 into Dewar flasks,and e) Finally collected
atmospheric water vapour samples

4.2 Soil and Plant water

4.2.1 Cryogenic Vacuum distillation (CVD) apparatus

Cryogenic vacuum distillation apparatus consists of a heating plate on which a stainless steel

beaker is placedwith water. Plant samples are placed in a flask which is connected with

distillation apparatus. Other end of the distillation setup is immersed in liquid nitrogen Dewar

flask.The entiresetup of distillation is maintained at a very high low vacuum of about 20.265 Pa

(~0.0002 atm.). Low vacuum is necessary as it reduces the boiling point drastically due to which

time required to complete distillation reduces significantly. In case of soil, it was observed that

some of the soil particles were getting mixed with evaporated water. In order to prevent, cotton

was placed on top of glass flask in which sample was placed.Figure 4.7 shows CVD apparatus

used in this study.

44
Figure 4.7 Cryogenic vacuum distillation for soil and plant water extraction

4.2.2 Displacement liquid centrifugation

One of the greatest challenges in this method was to select the most suitable displacement

liquid. The density of displacement liquid should be greater than that of water but less than the

density of soil. Tetrachloroethylenewas selected as displacement liquid whose properties are

listed below (Table 4.2)

45
Figure 4.8 Working principle of displacement liquid centrifugation method

𝒓𝟐

𝒑𝒄 = ∫ ∆𝝆 𝒘𝟐 𝒓 𝒅𝒓 Eq. (4.1)
𝒓𝟏

ρ = 𝜌𝑑 - 𝜌𝑤

𝜌𝑑 = density of displacement liquid

𝜌𝑤 = density of water

46
Table 4.2 Property of tetrachloroethylene
S.N. Material Property

1. Chemical structure

2. Chemical Formula C2 Cl4

3. Molecular mass 165.82 g.

4. Appearance Colourless

5. Density 1.62g/cc

6. Boiling Point 121.1°C

7. Main Hazard Dangerous for the environment

8. Toxicity Moderate to low (Carcinogen)

After displacement liquid was selected as tetrachloroethylene,the next main challenge was to

decide asuitable speed of the rotor. Selection of rotor speed depends onnumber of factors like

type of soil, water content of the soil, minimum solution volume requirement and the material of

the centrifuge bottle. Inthis study we used polypropylene (PP) bottles were used for

centrifugation as we were not able to get any other superior bottles. The PP bottles can have

maximum relative centrifugation force (RCF) about 9,400 g.Using this data, we calculated the

maximum possible speed of rotor using the Eq. (4.2)

𝑅𝐶𝐹
ω= √ × 1000
𝑟 × 1.118 Eq. (4.2)

RCF = relative centrifugal force

Ω = rotational speed (revolution per minute)

r = centrifugal radius in mm (= 115 mm for setup used in the study)

47
9,400
=√ × 1000 = 8,550.55 rpm
115 × 1.118

The rotor speed was fixed to 8,000 rpm.

Figure 4.9Soil water extraction using displacement liquid centrifugation using tetrachloroethylene

48
Table 4.3 Experimental procedure days and schedules for different activities
DOY LAI and PH Irrigation Sample collection

29 ##

40 ##

48 ## ##

49 ##

59 ## ##

63 ##

64 ##

72 ## ##

78 ##

86 ##

87 ##

90 ##

97

98 ##

103 ##

111 ##

4.3 Sampling Protocol

Water vapour and soil samples were collectedtwo times on a sampling day once between 11am-

12 pm and next between 1pm-2pm.Stem samples were taken at 12:00 noon.Once samples were

collected, they were immediately stored in bottles which were then tightly wrapped with Para

filmto prevent any loss of moisture. After that the bottles were placed in a refrigerator untill

they were analysed in LGR’s Liquid water isotope analyser.

49
4.4 Analysis of water samples for Isotope analysis

The water isotope analyses of collected samples were conducted using Los Gatos Research’s

Liquid Water Isotope Analyser (LGR’s LWIA). Figure 4.10 shows LWIA at our institute.

Figure 4.10 LGR's Liquid water isotope analyser at our institute

Instrument operates on principle of off-axis integrated cavity output spectroscopy (OA- ICOS)

to quantify deuterium and oxygen isotope simultaneously. This laser-based water isotope

analyser has following advantages-

1) Very high speed of sample analysis (up to 800 injections per day)

2) Low power requirement (average 70W)

3) Lower average cost per sample

4.4.1 Sample loading

For isotope analysis, the extracted samples were placed in 2 ml glass vials in the tray which

includes five standard samples and two dummy water sample as shown in Figure 4.11. It is

necessary to use calibrated stable water isotope standards within each measuring campaign after

every 5th sample the internal standards are measured.

50
Figure 4.11 Loading of standard and actual samples of the tray for isotopic analysis

For the instrument used in the study the following 5 standard samples are provided by LGR

which are listed inTable 4.4.

Table 4.4 Isotopic composition of standard samples used in LGR's LWIA


S.N. Sample δ2H (‰) δ18O (‰)

1. VSMOW (Vienna Standard Mean Ocean Water) 0.00 0.00

2. SLAP (Standard Light Antarctic Precipitation) -427.50 -55.5

3. GISP (Greenland Ice Sheet Precipitation) -189.50 -24.76

4. LGR-3C -97.30 -13.39

5. LGR-5C -9.20 -2.69

51
For every sample,auto sampler takes six sequential 1.2

µL aliquot of a water sample using a Hamilton syringe

(Figure 4.12). Samples are then injected to the optical

cell of the instrument. To avoid the memory effect of

the previoussamplefirst, three samples are

discarded,and last three samples are averaged and

reported asthe final result.

Figure 4.12 Process of automatic injection of


samples in the optical cavity

4.4.2 Working Principle of LWIA

Very high vacuum is created before the samples enter the optical cell,in which the samples

vaporised. The tuneable diode laser of the LWIA produces near infrared radiation passing the

vaporised water sample in the optical cell. The optical cellhas two highreflecting mirrors which

are designed in such a manner that there is thousands ofthe collisions of photons with the

vaporised sample produced. As a result, when laser photons leave the optical cell are focused by

a lens on a photo-detector, which then detects the optical absorption. Measured absorptions are

compared with the absorption of the internal standard of known isotopic signature. Once the

process is completed, water vapour in the optical cell is evacuated. The accuracy of this method

is about 0.2 ‰ for 𝑂18 /𝑂16and 0.6 ‰ for D/H isotopes.

52
4.5 Senstivity analysis

Sensitivity analysis is performed to find the contribution of different factors in the estimates of

transpiration factor FT.

4.5.1 Transpiration Factor

In ET partitioning transpiration fraction

𝜕𝐸𝑇 − 𝜕𝐸
𝐹𝑇 = Eq. (4.3)
𝜕𝑇 − 𝜕𝐸
2 2 2
2
𝜕𝐹𝑇 𝜕𝐹𝑇 𝜕𝐹𝑇
(𝜕𝐹𝑇 ) = ( 𝜕𝜕 ) + ( 𝜕𝜕 ) + ( 𝜕𝜕 ) Eq. (4.4)
𝜕𝜕𝐸𝑇 𝐸𝑇 𝜕𝜕𝑇 𝑇 𝜕𝜕𝐸 𝐸

where 𝜕𝐸𝑇 , 𝜕𝑇 and 𝜕𝐸 are isotopic composition of ET, T and E, respectively.

Differentiating and squaring both side of Eq. (4.3)

To estimae terms in RHS, Eq. (4.3)is differentiated w.r.t. 𝜕𝐸𝑇 , 𝜕𝑇 and 𝜕𝐸 . The obtained

expressions are as follows.

𝜕𝐹𝑇 1
=( ) Eq. (4.5)
𝜕𝜕𝐸𝑇 𝜕𝑇 − 𝜕𝐸

𝜕𝐹𝑇 𝜕𝐸𝑇 − 𝜕𝐸
= − Eq. (4.6)
𝜕𝜕𝑇 (𝜕𝑇 − 𝜕𝐸 )2

𝜕𝐹𝑇 (𝜕𝑇 − 𝜕𝐸𝑇 )


=− Eq. (4.7)
𝜕𝜕𝐸 (𝜕𝑇 − 𝜕𝐸 )2

Using Eq. (4.5), Eq. (4.6)and Eq. (4.7)

2 2 2
2
1 (𝜕𝐸𝑇 − 𝜕𝐸 ) (𝜕𝑇 − 𝜕𝐸𝑇 )
(𝜕𝐹𝑇 ) = (( ) 𝜕𝜕𝐸𝑇 ) + (− 𝜕𝜕𝑇 ) + (− 𝜕𝜕 ) Eq. (4.8)
𝜕𝑇 − 𝜕𝐸 (𝜕𝑇 − 𝜕𝐸 )2 (𝜕𝑇 − 𝜕𝐸 )2 𝐸

1
= [(𝜕𝜕𝐸𝑇 )2 + 𝐹𝑇 2 (𝜕𝜕𝑇 )2 + (1 − 𝐹𝑇 )2 (𝜕𝜕𝐸 )2 ] Eq. (4.9)
(𝜕𝑇 − 𝜕𝐸 )2

From Eq. (4.9)it is clear that uncertainty in the transpiration fraction is dependent on the

following

53
1) Inversly proporsional to square of difference in the isotopic composition of sources

from which the mixture is made

2) Transpiration fraction value itself

3) Uncertainty in isotopic compositions of ET, T and E

In the following sub-sections the contribution of different sources of uncertainity is investigated

using synthetic data.

4.5.1.1 Difference in isotopic composition of sources

AssumingFT = 0.5, uncertainities in isotopic signature ot ET, T and E are same 𝜕𝜕𝐸𝑇 = 𝜕𝜕𝑇 =

𝜕𝜕𝐸 = σ2

Figure 4.13 Variation of uncertainty in transpiration fraction with the difference in source isotopic composition at
different values of uncertainty
From Figure 4.13 it is clear that asthe difference between the isotopic compositions of sources

increases, the uncertainty in transpiration factor reduces. On theother hand, if the difference

between the isotopic compositions of sources is less than the uncertainty in transpiration factor

is observed to high. The uncertainty curve shifts upwards (uncertainty increases) with the

increase inuncertainty of isotopic composition of ET, T and E (all assumed to be same).

54
4.5.1.2 FT fraction

Assuming difference in isotopic composition of T and E 𝜕𝑇 − 𝜕𝐸 = 30, uncertainities in

isotopic signature ot ET, T and E are same 𝜕𝜕𝐸𝑇 = 𝜕𝜕𝑇 = 𝜕𝜕𝐸 = σ2

Figure 4.14 Variation of uncertainty in transpiration fraction with transpiration fraction at different values of
uncertainty

From Figure 4.14 it can be seen thatthe transpiration factor (FT) approaches to 0.5, uncertainties

were minimum. Uncertainties increases symmetrically around FT = 0.5.

4.5.1.3 Due to uncertainty in the measurement of the isotopic composition of T, E, and

ET

Assuming 𝜕𝑇 − 𝜕𝐸 = 30 and uncertainities in isotopic signature ot ET, T and E are same

𝜕𝜕𝐸𝑇 = 𝜕𝜕𝑇 = 𝜕𝜕𝐸 = σ2

55
Figure 4.15 Variation of uncertainty in transpiration fraction with uncertainty in ET, T and E at different values of
uncertainty

From Figure 4.15it is found that uncertainty in transpiration fraction increases parabolically

with uncertainty in ET, T and E.

The sensitivity analysis suggest that the uncertainty in FT is high when

I. The difference in isotopic composition of E and T is less

II. When the transpiration factor is very high or very low

4.5.2 Variation of uncertainty in absolute water content

Application of SIF partitioning requires absolute water content [𝐻2 𝑂] at different heights.

Given the measurements of temperature (T) and relative humidity (RH) the absolute water

content can be estimated by using the following formula given by McRae (1980).

𝑃𝑠
[𝐻2 𝑂] = 10 𝑅𝐻 Eq. (4.10)
𝑃𝑎

𝑃𝑠 = 𝑃𝐴 exp(13.3185𝑡 − 1.9760𝑡 2 − 0.6445𝑡 3 − 0.1299𝑡 4 ) Eq. (4.11)

373.15 Eq. (4.12)


𝑡 =1−
𝑇

56
where 𝑃𝑠 is saturation vapour pressure and 𝑃𝑎 is atmospheric pressure. 𝑃𝐴 is standard

atmospheric pressure (1013.25 mbar).

Differentiating and squaring both side of Eq. (4.10)

2 2 2
2
𝜕[𝐻2 𝑂] 𝜕[𝐻2 𝑂] 𝜕[𝐻2 𝑂]
(𝜕[𝐻2 𝑂]) = ( 𝜕(𝑅𝐻)) + ( (𝜕𝑇)) + ( (𝜕𝑃𝑎 )) Eq. (4.13)
𝜕(𝑅𝐻) 𝜕𝑇 𝜕𝑃𝑎

To estimae terms in RHS, Eq. (4.10)is differentiated w.r.t. RH, T and 𝑃𝑎 . The obtained

expressions are as follows.

𝜕[𝐻2 𝑂] 𝑃𝑠 [𝐻2 𝑂]
= 10 == Eq. (4.14)
𝜕(𝑅𝐻) 𝑃𝑎 𝑅𝐻

𝜕[𝐻2 𝑂] 𝑃𝑠 −[𝐻2 𝑂]
= −10 𝑅𝐻 2 = Eq. (4.15)
𝜕𝑃𝑎 𝑃𝑎 𝑃𝑎 2

𝜕[𝐻2 𝑂] 𝜕[𝐻2 𝑂] 𝜕𝑃𝑠 𝜕𝑡


=( )( )( ) Eq. (4.16)
𝜕𝑇 𝜕𝑃𝑠 𝜕𝑡 𝜕𝑇

Synthetic data are used to study the uncertainity in estimate of [𝐻2 𝑂] for different values of T

and RH for different assumed uncertainity of T and RH.

4.5.2.1 Temperature

For following assumed values, the effect of T in range of 0°C to 40°C was investigated

AssumingPa = 1000.3 mbar, PA= 1013.25 mbar and RH = 0.5;

57
Figure 4.16 Variation of uncertainty in absolute water vapour concentration with the temperature at different values
of uncertainty
From Figure 4.16 it can be observed that for low-temperature values uncertainty in absolute

water content is low but as the value of temperature increases uncertainty increases.

4.5.2.2 Humidity

For following assumed values, the effect of RH in range of 0 to 1 was investigated

AssumingPa = 1000.3 mbar, PA= 1013.25 mbar and T = 20°C.

Figure 4.17 Variation of uncertainty in absolute water vapours concentration with the temperature at different values
of uncertainty

From Figure 4.17 it can be seen that for the lowvalue of relative humidity, uncertainty in

absolute water content is high but as relative humidity approaches to 1 value of uncertainty in

absolute water content reduces rapidly and finally approaches zero.

4.5.3 Craig Gordon (CG) Model

The CG model estimates the isotopic composition of evaporated water given air temperature

(T), soil temperature (Ts), relative humidity (RH), isotopic composition of soil water (𝜕𝑠 ),

isotopic composition of water vapour (𝜕𝑣 ).

1
𝜕𝑠 (α ) − ℎ𝜕𝑣 −∈𝑒𝑞 − (1 − ℎ) ∈𝑘
eq Eq. (4.17)
𝜕𝐸 =
(1 − ℎ) + 10−3 (1 − ℎ) ∈𝑘

58
𝜕𝑠 , 𝜕𝑣 = Isotopic composition of soil evaporation front and water vapour respectively

ℎ = Normalised RH w.r.t. soil & air temperature

1
∈𝑒𝑞 = (1 − ) × 1000
αeq

1.137×106 0.4516×103
𝑇2
− 𝑇
− 2.0667
αeq = +1
1000

𝐷𝑖
∈𝑘 = 𝑛 (1 − ) × 1000
𝐷

1 𝜃 − 𝜃𝑟𝑒𝑠
𝑛 = 1− ( )
2 𝜃𝑠𝑎𝑡 − 𝜃𝑟𝑒𝑠

The measured quantities in the CG model are𝜕𝑣 , 𝜕𝑠 , αeq & ℎ. To study the senstivity of CG

model Eq. (4.17)is differentiated w.r.t. 𝜕𝑣 , 𝜕𝑠 , αeq & ℎ

2 2 2
2
𝜕𝜕𝐸 𝜕𝜕𝐸 𝜕𝜕𝐸
(𝜕𝜕𝐸 ) = ( (𝜕𝜕𝑠 )) + ( (𝜕𝜕𝑣 )) + ( (𝜕ℎ))
𝜕𝜕𝑠 𝜕𝜕𝑣 𝜕ℎ

2 Eq. (4.18)
𝜕𝜕𝐸
+ ( (𝜕αeq ))
𝜕 ∝+

1
𝜕𝜕𝐸 αeq Eq. (4.19)
=
𝜕𝜕𝑠 (1 − ℎ)(1 + 10−3 ∈𝑘 )

𝜕𝜕𝐸 −ℎ
= Eq. (4.20)
𝜕𝜕𝑣 (1 − ℎ)(1 + 10−3 ∈𝑘 )

𝜕𝜕𝐸 ∈𝑘 𝜕𝑠 +∝+ (−∈𝑘 𝜕𝑣 −∈𝑒𝑞 ∈𝑘 ) + 𝜕𝑠 −∝+ 𝜕𝑣 −∝𝑒𝑞 ∝+ )


= Eq. (4.21)
𝜕ℎ 1000(αeq (1 − ℎ + 10−3 ∈𝑘 (1 − ℎ))2

𝑠 −𝜕 1000
𝜕𝜕𝐸 (αeq )2
− (α )2 −1000 − 𝜕𝑠 Eq. (4.22)
eq
= −3
=
𝜕αeq (1 − ℎ)(1 + 10 ∈𝑘 ) (∝ ) (1 − ℎ)(1 + 10−3 ∈𝑘 )
+ 2

59
𝜕αeq 451.6 2274000
= 0.001 ( 2 − ) Eq. (4.23)
𝜕𝑇 𝑇 𝑇3

Synthetic data are used to study the uncertainity in estimate of𝜕𝐸 .

4.5.3.1 Variation in isotopic composition of evaporation for different T and RH

Assuming 𝜕𝑠 = -8‰, 𝜕𝑣 = -21‰, ∈𝑘 = 16.4, 𝜎𝜕𝑠 = 𝜎𝜕𝑣 = 0.1 , and 𝜎ℎ = 𝜎𝑇 = 0.01

Figure 4.18 Variation of uncertainty in the isotopic composition of evaporation with the change in temperature at
different values of relative humidity

FromFigure 4.18it can be seen that as the value of relative humidity is increasing uncertainty in

the isotopic composition of evaporation is increasing. It is also observed that as the value of

temperature is increasing,uncertainty in the isotopic composition of evaporation is reducing.

4.5.3.2 Variation in isotopic composition of evaporation for different RH and n

Assuming 𝜕𝑠 = -8‰, 𝜕𝑣 = -21‰, ∈𝑘 = 16.4, 𝜎𝜕𝑠 = 𝜎𝜕𝑣 = 0.1 , T = 20°c and 𝜎ℎ = 𝜎𝑇 = 0.01

60
Figure 4.19 Variation of uncertainty in the isotopic composition of evaporation with the change in relative humidity
with different values of n

From Figure 4.19it can be seen that as the value of relative humidity is increasing, uncertainty

in the isotopic composition of evaporation is increasing,andthe rate of increase is very rapid as

value is approaches1. It can be seen that the effect of n of the isotopic composition of

evaporation is negligible. For the higher value of n, curve shifts downwards.

Overall, the results suggest that the estimate of 𝜕𝐸 is sensitive to variation of RH and

irrespective of n.

61
5 RESULTS AND DISCUSSION

In this study, the ET partitioning was performed for both rice and wheat crops. The results for

rice are first shown followed by the results for wheat.

5.1 Results for Rice season

During the rice season, we were able to collect samples of isotopic water vapour composition

for only one day, 26 October, 2017.The AWS data for sampling day are shown inFigure 5.1.

Figure 5.1 AWS data on 26 October, 2017


(BP- Barometric pressure (mbar), SHF- Soil Heat flux (watt/m2), GSR- Global solar radiation (watt/m2), Max WS-
Maximum wind speed (m/s). WS- Wind speed (m/s), Temperature (°C), RH- relative humidity (%), VPD- Vapour
pressure deficit (kPa))

On 26 October the temperature increased from 32.16°C to 34.86°C during 10:00 to 15:00 and

then reduced to 34°C by 16:30.The relative humidity value also reduced during this period. The

wind speed fluctuated between 1 m/s to 2 m/s during this period. The GSR reached a maximum

62
value of 990 Watt/m2 during noon. The barometric pressure was found to be continuously

reducing. The windrose diagram for the sampling day is also plotted inFigure 5.2. It can be seen

that the prevailing wind direction on that day was NE.

Figure 5.2 Wind rose for 26 October, 2017

Global Meteoric Water Line is a line which gives the relationship

between hydrogen and oxygen isotope ratios in natural terrestrial waters, expressed as a

worldwide average. Harmon Craig (Craig ,1961) first developed this line. The equation of this

line is 𝜕𝐷 = 8.0. 𝜕𝑂18 + 10 ‰

A plot showingthe isotopic composition of different samples collected on October 26, 2017 is

presented in Figure 5.3where clusters of collected data can be seen. The clusters for ponded

water and atmospheric water vapour (WV) are conspicuous. As expected ponded water is more

enriched and water vapour is more depleted in heavier isotopes. This is obvious because when

evaporation takes place, the residual water is more enriched in heavier isotope and the water

vapours get depleted in isotopic composition. It is also seen that leaf water is very much

enrichedwith respect to stem water. This can be attributed to evaporation taking place from the

leaf surface.

63
Figure 5.3 Isotopic composition of different water sources collected on 26-10-2017

Temporal variation of the isotopic composition of leaf water is plotted inFigure 5.4. It can be

seen that as transpiration rate increases after sunshine,leaf water becomes more and more

enriched. The maximum enrichment is found at 12:00 noon.

Figure 5.4 Variation in the isotopic composition of rice leaf water during the experiment duration

The isotopic composition of evaporation was calculated using Craig Gordon model.

Theimportant parameters, used in the model are listed inTable 5.1.

64
Table 5.1Parameters of the CG model applied to estimate𝜕𝐸 for 26th October, 2017
𝑻𝒂𝒊𝒓 (K) 𝑻𝑺 (K) h’ 𝛆𝒌 𝛆𝒆𝒒 𝛂𝐞𝐪 𝛅𝒔 (‰) 𝛅𝒗 (‰) 𝛅𝑬 (‰)

299.35 298.05 0.344 31.88 77.31 1.08378 -31.05 -61.58 -156.149

The Keeling plot (Figure 5.5)was drawn with absolute water concentration on the x axis and

isotopic composition of water vapour on the y-axis. The intercept of the best-fitted line on that

data represents the isotopic composition of ET.The isotopic composition of ET was estimated to

be -63.7‰.The isotopic composition of T was calculated using steady-state assumption which

says that, the isotopic composition of T is same as theisotopic composition of the stem water.

This steady-state assumption is applicable during 11 am to 1 pm when the transpiration rate is

maximum and nearly constant.

Figure 5.5 Keeling Plot for 26 October, 2017

Once the isotopic composition of E, T and ET are known,a two source mixing model

transpiration fraction is used to calculate. For October 26, 2017 the FT between 11:00 to 12:00

noon is estimated to be 0.856.

65
Table 5.2 Transpiration fractions on 26 October
S.N. 𝛅𝑬 (‰) 𝛅𝑻 (‰) 𝛅𝑬𝑻 (‰) 𝑭𝑻 (‰)

1. -156.15 -48.15 -63.7 0.856

5.2 Results for Wheat Season

The isotopic compositions of all the water samples collected during the wheat season are shown

inFigure 5.6. Distinct clusters of data can be clearly seen.Water vapours isotopic composition

cluster is at the leftmost corner as those contain lighter isotope as compared to other sources of

water. Leaf water is seenatthe rightmost corner of the graph which shows the most enriched

water. There is an overlap in soil and stem water isotopic composition, however the soil water

samples are slightly enriched compared to stem water. Both stem and soil water are enriched in

comparison to water vapour and depleted in comparision to leaf water.

Figure 5.6 Isotopic composition of different water sources collected during wheat cultivation

Figure 5.7compares isotopic composition of water samples during rice and wheat seasons.It is

observed that during summer time (wheat), isotopic composition of water vapour is more

depleted compared to winter time (rice). Ponded water on the rice fields is found to be more

66
enriched in heavier isotopes as compared to irrigation water during wheat season. Ponded water

on the rice fields is also found to be depleted as compared to soil water in wheat fields. We do

not have sufficient rainfall samples,so we were not able to draw local meteoric water line

(LMWL).

Figure 5.7 Isotopic composition of different water sources collected during entire study (both rice and wheat season)

67
Figure 5.8 Variation of the average isotopic composition of water vapour during the entire study with the standard
deviation

Figure 5.9shows isotopic composition of water vapour for the topmost (PH+2) and the

bottommost height (0.15 m) collected at 11:00 am during the wheat season. It is observed

thatfor deuterium the water vapour at PH+2 was more depleted in heavier isotope as compared

to water vapour sample at 0.15 m above ground. The pattern was same for the oxygen isotope,

except for DOY 90 & 108 when the isotopic composition at the two levels were very close to

each other.

68
Figure 5.9 Comparison of the isotopic composition of water vapour at the bottommost and the topmost level at 11 am

Compared to 11:00 am, the isotopic composition of WV at PH+2 and 0.15 m are much close to

each other at 13:00 (Figure 5.10). This could be because of increased transpiration rate at 13:00.

The sample collected on DOY 86 behaved differently from other samples. This difference could

be attributed to a flooding event that happened in the experimental field between DOY 78 to

DOY 80.

69
Figure 5.10 Comparison of the isotopic composition of water vapour at the bottommost and the topmost at 1 pm

Soil evaporation front is an area through which maximum evaporation takes place. In our study

duration, this evaporation front never went below15 cm. We found that most of the time soil

evaporation front was located between 0cm to 10 cm. From theFigure 5.11,it can be easily seen

that soil between 5-10 cm was on an average more enriched as compared to 0-5 cm soil. The

standard deviation was found to be loweratthe topmost level and the bottommost soil level

70
Figure 5.11 Variation of the average isotopic composition of soil water during the entire study with a standard
deviation

Figure 5.11showed that the evaporation occurs mostly from top 10 cm of soil. Figure 5.12shows

the comparison of isotopic composition of soil samples collected at 0- 10 cm and 10- 20 cm.

The Figure 5.11 suggests that 0- 10 cm layer is enriched during most of the wheat season. On

DOY 103 some irregularity is observed as the bottom layer is more enriched as compared to the

top layer. This may be because evaporation front has reached below 10 cm.

71
Figure 5.12 Comparison of the isotopic composition of soil water at 0- 10 cm and 10 - 20 cm

Figure 5.13 compares the isotopic composition of stem and leaf water during the wheat season.

As expected, the leaf water is more enriched as compared to stem water because of evaporation

happening from the leaf surface. Further, no significant changes in isotopic composition of stem

and leaf water is observed during the wheat season.

72
Figure 5.13 Comparison of the isotopic composition of plant water and leaf water

73
AWS data for 17 February, 2018 are shown in Figure 5.14.The temperature increased from

21.68°C to 27.39°C during 10:00 to 15:00 and then reduced to 26.68°C. The relative humidity

value during this period changed from 63.26% to 43.93%.The wind speed fluctuated between 1

m/s to 4 m/s during this period. The GSR reached a maximum value of 990 watt/m2 during

noon. The barometric pressure was found to be continuously reducing. The windrose diagram

for the sampling day is also plotted inFigure 5.15, which shows that prevailing wind direction

on that day was SW.

Figure 5.14 AWS data on 17 February, 2018


(BP- Barometric pressure (mbar), SHF- Soil Heat flux (watt/m2), GSR- Global solar radiation (watt/m2), Max WS-
Maximum wind speed (m/s). WS- Wind speed (m/s), Temperature (°C), RH- relative humidity (%), VPD- Vapour
pressure deficit (kPa))

74
Figure 5.15 Windrose on 17 February

From Figure 5.16and Figure 5.17 it is clear that the location of soil evaporation front is located

between 0-5 cm depths of soil as soil water at this depth is more enriched as compared to other

depths.

Figure 5.16 Soil water isotopic composition of Figure 5.17 Soil water isotopic composition on𝑂18 on 17
Deuterium on 17 February February

Figure 5.18 to Figure 5.21 show the air temperature, relative humidity and isotopic composition

of water vapours at different heights, respectively.

75
Figure 5.18 Variation of air temperature with height Figure 5.19 Variation of relative humidity with height

Figure 5.20 Variation of the isotopic composition of Figure 5.21 Variation of the isotopic composition of
water vapour with height water vapour with height

The Keeling plots for Feb 17, 2018 are shown in Figure 5.22&Figure 5.23. Figure 5.22is drawn

using data from entire day (11:00-12:00 and 13:00- 14:00) while Figure 5.23is drawn during

13:00-14:00. None of the keeling plots for 11:00- 12:00 performed well, therefore are not

shown here. From Figure 5.22&Figure 5.23isotopic composition of ET can be found by looking

at the intercept of best fitted line on the y-axis.

76
Figure 5.22 Keeling plot on 17 February, 2018

77
Figure 5.23 Keeling plot based on oxygen 17 February, 2018 between 13:00- 14:00

Variations inthe isotopic composition of the stem water are plotted inFigure 5.24. It can be seen

that in the noon, isotopic composition of stem water is not changing very much. During this

time, steady state assumptions are valid which states that the isotopic composition of the stem

water is equal to the isotopic composition of the transpiration water which is equal to the

isotopic composition of the source water. During that time,the leaf water is highly enriched.

78
Figure 5.24Variation of stem water on 28 February, 2018

Figure 5.25to Figure 5.31 are the Keeling plots drawn for the days Feb 28, March 13, 27&31

and 8 April and different days. The intercept of best fitted lines provides an estimate of ∂ET. The

isotopic composition of evaporation water (∂E) and the isotopic composition of transpiration

water (∂T) are listed in Table 5.4&Table 5.5.

79
Figure 5.25 Keeling plot for 28 February, 2018 for 11:00-12:00 & 13:00- 14:00

80
Figure 5.26 Keeling plot for 13 March, 2018

81
Figure 5.27 Keeling plot for 13 March, 2018 11:00-12:00 & 13:00- 14:00

82
Figure 5.28 Keeling plot for 27 March, 11:00-12:00 & 13:00- 14:00

83
Figure 5.29 Keeling plot for 31 March, 2018

84
Figure 5.30 Keeling plot for 31 March, 2018 11:00-12:00 & 13:00- 14:00

Figure 5.31 Keeling plot for 8 April, 2018

85
On 11 April, 2018 there was rainfallevent; therefore, isotope method for ET partitioning cannot

be applied. The temperature had reduced rapidly on that day once the rain had started (Figure

A.56in appendix) while the relative humidity increased. Generally, it is observed that as one

moves from bottom to top, the isotopic composition of water vapour gets depleted in heavier

isotopes. However, a reverse trend observed after the precipitation event. We found that the

isotopic composition of water vapour near the ground was more depleted than PH+2 (Figure

5.32). The trend isclear for hydrogen isotope but in case of oxygen isotope, there is an

anomalyat 12:00 noon .

Figure 5.32 Variation on the isotopic composition of water vapour on 11 April, 2018

86
Figure 5.33 Keeling plot for 13 April, 2018

87
Table 5.3 Parameters of CG model applied to estimate ∂Eduring wheat season
symbols used in table are described in section 2.1

Isotope Time DOY 𝑻𝒂𝒊𝒓 (K) 𝑻𝑺 (K) h’ 𝛆𝒌 𝛆𝒆𝒒 𝛂𝐞𝐪 𝛅𝒔 (‰) 𝛅𝒗 (‰) 𝛅𝑬 (‰)

1. D 11:00- 12:00 48 301.70 296.54 0.55 31.89 78.73 1.0854 -20.87 -80.55 -146.33

O 13:00- 14:00 48 301.70 296.54 0.55 16.40 9.42 1.0095 -3.10 -16.13 -24.07

D 11:00- 12:00 48 303.144 298.825 0.47 31.89 76.58 1.0829 -20.87 -78.84 -138.41

O 13:00- 14:00 48 303.144 298.825 0.47 16.4 9.23 1.0093 -20.87 -16.76 -24.35

2. D 11:00- 12:00 59 305.96 298.33 0.74 31.89 77.0432 1.083474 -16.85 -70.51 -180.408

O 13:00- 14:00 59 305.96 298.33 0.74 16.40 9.27 1.009359 -1.13 -11.97 -22.0224

D 11:00- 12:00 59 308.19 298.33 0.73 31.89 78.88 1.085633 -16.85 -69.93 -188.709

O 13:00-14:00 59 308.19 298.33 0.73 16.4 9.43 1.009519 -1.13 -14.70 -15.0859

3. D 11:00-12:00 72 308.76 299.50 0.54 31.89 75.96 1.0822 -1.66 -60.18 -125.78

O 13:00- 14:00 72 308.76 299.50 0.54 16.4 9.18 1.0093 -0.05 -12.13 -21.85

D 11:00- 12:00 72 311.22 297.57 0.52 31.89 77.75 1.0843 -1.66 -62.85 -125.49

O 13:00- 14:00 72 311.22 297.57 0.52 16.4 9.33 1.0094 -0.05 -13.39 -20.97

4. D 11:00-12:00 86 304.94 295.97 0.79 31.89 79.28 1.0861 -11.73 -60.96 -224.38

O 13:00- 14:00 86 304.94 295.97 0.79 16.4 9.46 1.0096 -1.20 -13.77 -15.11

88
D 11:00- 12:00 86 307.12 298.64 0.69 31.89 79.28 1.0831 -11.73 -56.68 -182.86

O 13:00- 14:00 86 307.12 298.64 0.69 16.4 9.46 1.0093 -1.20 -14.55 -17.37

5. D 11:00- 12:00 90 306.31 298.98 0.59 31.89 76.44 1.0827 -22.71 -60.96 -177.04

O 13:00- 14:00 90 306.31 298.98 0.59 16.4 9.22 1.0093 -1.69 -13.77 -22.70

D 11:00- 12:00 90 309.51 300.92 0.54 31.89 74.66 1.0806 -22.71 -56.68 -168.07

O 13:00- 14:00 90 309.51 300.92 0.54 16.4 9.07 1.0091 -1.69 -14.55 -22.29

6. D 11:00- 12:00 98 307.66 298.27 0.69 31.89 77.1 1.0835 -14.80 -62.76 -181.09

O 13:00- 14:00 98 307.66 298.27 0.69 16.4 9.28 1.0094 1.63 -14.39 -8.48

7. D 11:00- 12:00 108 308.95 298.48 0.68 31.89 76.91 1.0833 11.95 -53.80 -119.55

O 13:00- 14:00 108 308.95 298.48 0.68 16.4 9.26 1.0093 0.35 -12.27 -17.90

89
Once ∂ET(Keeling plot), ∂E(CG model) and ∂T(stem water)are obtained the transpiration fraction

FT was estimated using two source model (section4.5.1). The results so obtained are

summarised inTable 5.4&Table 5.5.

Table 5.4 Transpiration fraction during wheat season (average)


S.N Date Time 𝛅𝑬 𝛅𝑻 𝛅𝑬𝑻 𝑭𝑻

(DOY) (‰) (‰) (‰)

1. 17 Feb (48) Avg. -142.37 -35.98 -47.15 0.895

17 Feb (48) Avg. -24.21 -4.69 -5.46 0.960

2. 28 Feb (59) Avg. -184.56 -37.58 -96.04 0.602

28 Feb (59) Avg. -18.55 -5.50 -9.29 0.709

3. 13 March (72) Avg. -21.41 -7.28 -9.82 0.820

13 March (72) Avg. -125.33 -49.06 -53.35 0.944

4. 27 March* (86) Data didn’t performed well

5. 31 March (90) Avg. -22.50 -4.41 -14.92 0.419

Table 5.5 Transpiration fraction during wheat season


S.N Date Time 𝛅𝑬 𝛅𝑻 𝛅𝑬𝑻 𝑭𝑻

(DOY) (‰) (‰) (‰)

1. 17 Feb (48) 13:00-14:00 -24.35 -4.69 -6.35 0.915

2. 13 March (72) 13:00-14:00 -21.85 -7.28 -11.78 0.691

3. 27 March* (86) Data didn’t performed well

4. 31 March (90) 11:00-12:00 -22.70 -4.41 -15.73 0.381

31 March (90) 13:00-14:00 -22.29 -4.41 -13.98 0.464

5. 8 April (98) 11:00-12:0 -181.09 -24.52 -33.97 0.939

6. 11 April (103)** 11:00-12:00 Rainy Day

7. 13 April (108) 11:00-12:00 -17.90 -1.06 -8.57 0.55

* Keeling plots didn’t performed well

90
** Rainy day

The results suggest that the transpiration fraction varied during wheat season. After irrigation

and rainfall event transpiration fraction was high as 95 %. During the late season FT dropped to

around 30%

5.2.1 Comparison of isotope and hydrometric methods

As we know that

𝜕𝐸𝑇 −𝜕𝐸
𝐹𝑇 = 𝜕𝑇 −𝜕𝐸
and

0 < 𝐹𝑇 < 1 therefore to satisfy the following condition

𝜕𝐸𝑇 > 𝜕𝐸 &𝜕𝐸𝑇 < 𝜕𝑇 , Unfortuanately for some of the times this conditions was not satisfied and

those data and keeling plots are discared.

Finally, transpiration fraction using stable isotope fractionation method was compared with

transpiration fraction obtained using the hydrometric method (Figure 5.34).These plotted values

are average values of transpiration fraction obtained for 11:00-12:00 and 13:00- 14:00. From

Figure 5.34it is evident that SIF and hydrometric methods matched for DOY 48, 59, 72, 90. For

DOY 86, the transpiration fraction was not available using SIF as (the Keeling plots performed

poorly). For DOY 98 and 108, differencesare higher and may be attributed to the limitation of

model to predict T and RH accurately. DOY 103 was rainy day, therefore SIF method could not

be used.

91
Figure 5.34 Comparison of transpiration factor obtained by the hydrometric method and stable isotope fractionation
method for wheat

5.2.2 Background noise in Isotopic Composition of ET

To check the contribution of background noise in the estimation of 𝜕𝐸𝑇 due to nearby plants, we

performed an experiment (after the wheat crop was harvested 2 May, 2018) and the

experimental field was barren. The experiment was performed in same study plot. Plot was

surrounded by other vegetation including a big Limonia acidissima (Kaitha) tree.

Figure 5.35 Experimental plot on May 2, 2018 ( AIS represents air intake structure)

92
If the experimental field has no crop 𝐹𝑇 = 0, Then 𝜕𝐸𝑇 should be fully contributed by 𝜕𝐸 and

𝐹𝐸 should be equal to 1. The difference between 𝜕𝐸𝑇 and 𝜕𝐸 can provide a measure for the

magnitude of background noise.

Figure 5.36 AWS data on 2 May, 2018

Figure 5.36 shows AWS data for May 02, 2018.Global solar radiation was found to be

irregular. It increased before noon and then reduced about 12 then again increased on that

day becomes cloudy day. The wind velocity was seen to be very high during that day as

compared to other sampling day. The atmospheric pressure sensor behaved abnormally

during that day.From Figure 5.37 it can be infered that themost prevailing direction of the

wind was NE.

93
Figure 5.37 Windrose on 2 May

Figure 5.38 to Figure 5.40 represent soil moisture, electrical conductivity, soil temperature, and

soil isotopic composition,. Measure on May 2, 2018. Figure 5.41 to Figure 5.44show air

temperature, relative humidity and isotopic composition of water vapour at all the four heights.

94
Figure 5.38 Soil moisture, electrical conductivity and temperature variation with depth

Figure 5.39 Soil isotopic composition variation with


Figure 5.40 Soil isotopic composition variation with depth
depth (Hydrogen) (Oxygen)

95
Figure 5.41 Variation of air temperature with height Figure 5.42 Variation of relative humidity with height

Figure 5.43 Variation of the isotopic composition of Figure 5.44 Variation of the isotopic composition of
water vapour with height water vapour with height

96
Table 5.6 Parameters of CG model applied to estimate 𝜕𝐸 for 2 May, 2018

𝑻𝒂𝒊𝒓 𝑻𝑺 (K) h’ 𝛆𝒌 𝛆𝒆𝒒 𝛂𝐞𝐪 𝛅𝒔 (‰) 𝛅𝒗 (‰) 𝛅𝑬 (‰)

(K)

309.44 312.38 0.36 31.88 64.92 1.0694 -8.18 -62.53 -106.65

312.20 315.90 0.28 31.89 62.11 1.0662 -8.18 -59.16 -102.54

The isotopic composition of evaporation water on May 2, 2018 at two times 11 am-12:00 pm

and 1:00 pm -2 pm were -106.65‰ and -102.54‰. Keeling plots were drawn for deuterium

(Figure 5.45) as well as oxygen isotope (Figure 5.46). However, the Keeling plots for oxygen

did not perform well therefore were not considered in analysis.

Figure 5.45 Keeling plot for 2 May, 2018

97
Figure 5.46 Keeling plot for 2 May, 2018

If the experimental plot has no crop, the isotopic composition of the evapotranspired water

should be nearly equal to the isotopic composition of the evaporated water. From the Figure

5.45andFigure 5.46, we can see that there is some differences in the isotopic composition of ET

and E. We found that contribution E on ET was 82.06 % and 86.88 % between 11:00 – 12:00

noon and 13:00- 14:00, respectively.Thus from this experiment it can be concluded that

vegetation present outside the experimental plot modified the isotopic composition of ET.

5.2.3 Average Isotopic Composition of Hydrological Fluxes

Figure 5.47 and Figure 5.48 show the isotopic composition of different hydrological fluxes

measured (or calculated) during the wheat season. Precipitation water was found to be highly

enriched. There is significant difference in the isotopic composition of evaporation water and

transpiration water. Soil water between 5 -10 cm was found to be more enriched as compared to

other depth. Leaf water is highly enriched as compared to stem water because of evaporation

from the leaf surface.

98
Figure 5.47 Isotopic composition of oxygen isotope different fluxes and samples measured (or calculated) during the
wheat season

99
Figure 5.48Isotopic composition of hydrogen isotope different fluxes and samples measured (or calculated) during
the wheat season

100
6 SUMMARY AND CONCLUSION REMARKS

This was the first ever study done in India for evapotranspiration partitioning using stable

isotope fractionation method. The main challenge in this study was the construction of an

experimental setup to partition ET during rice and wheat seasons. Most of our efforts

werefocussed on arranging raw materials and equipment for constructing the setup. The

summary and the main conclusions drawn from the study are listed below.

1. Experimental setups designed to sample atmospheric water, soil water and plant water are

briefly summarized below:

a. Atmospheric water: Atmospheric water vapour collection was done using an air intake

structure which was capable of collecting water vapours at four heights simultaneously.

Air was forced to pass through cold trap which was immersed in liquid nitrogen so that

the entire water vapour can be trapped.

Apart from a liquid nitrogen cold trap, we also checked the feasibility of a Peltier

element based cold trap, which consisted of a copper set-up insulated using a nitrile

insulator. This trap performed well, and we could achieve temperature up to -20°C.

However, because of the large DC power requirement, it was not feasible to collect

atmospheric water samples at multiple heights using the Peltier element based cold trap.

b. Soil and plant water: For extraction of soil and plant water, cryogenic vacuum

distillation (CVD) apparatus was used. The time required for removal of soil water for

our soil sampled was found to be 80 minutes. To find extraction efficiency of the

developed CVD apparatus, a completely dried soil was mixed with tap water of known

isotopic composition water and after running it for 80 minutes, the isotopic composition

of the extracted water was compared with the tap water. We found the extraction

efficiency was quite good and that the set-up could be used to reliably estimate isotopic

composition of the soil and plant water.

101
Soil water extraction was also done using the displacement liquid centrifugation technique.

In this method, we used tetrachloroethylene as a displacement liquid. This method

performed better than the cryogenic vacuum distillation method. However, we felt the need

for more systematic investigation to draw final conclusions.

2. The ET partitioning was performed using a simple two-source mixing model, which required

estimation of isotopic composition of evapotranspiration (𝜕𝐸𝑇 ), evaporation (𝜕𝐸 ) and

transpiration (𝜕𝑇 ).

3. The Keeling plots were used to estimate isotopic composition of evapotranspiration. We had

collected water vapour samples in two sets between 11:00-12:00 and 13:00-14:00. Due to

functional limitation and cost-constraints,thewater vapour samples could be collected at only

four heights simultaneously, which caused uncertainty in the estimation𝜕𝐸𝑇 .

4. The Craig-Gordon (CG) model was used to calculate the isotopic composition of Evaporation.

During the rice season, the experimental plot was flooded and hence the condition was similar

to lake evaporation. In case of wheat, finding the location of soil evaporation front was a

challenging task. We took soil samples at four different depths 0-5 cm, 5-10 cm, 10-15 cm and

15- 20 cm and found that soil evaporation front fluctuates mostly between 0- 10 cm because the

soil water samples were more enriched at that depth.

The sensitivity analysis of the CG model suggested that its results are very much sensitive to

relative humidity especially when relative humidity is high. Therefore we used the best

available temperature and relative humidity sensorsavailable in the market at a reasonable cost.

5. The isotopic composition of transpiration was estimated using the stem water under the stead-

state assumption. To check the applicability of steady-state assumption, we collected plant stem

water samples at different times and found that the isotopic composition of stem water is almost

constant between 11:00 to 13:00. Hence for ET partitioning, all the stem samples were collected

during this time interval.

6. For the rice season, we could collect samples only for one day, i.e. 26 October 2017. The

results suggested that on that day, the transpiration fraction in evapotranspiration was 85.6%.

102
7. For the wheat season, we collected multiple samples during different stages of crop growth.

The transpiration fraction in ET varied between 38% and 96% depending upon the crop growth

stage and availability of water. The water available for crop varied because of rainfall and

irrigation.

8. The comparison of transpiration fraction obtained from isotope fractionation and hydrometric

methods suggested that the results from the two methods are similar for most of the days.

However, there were differences on some days which were attributed touncertainties in the

estimation of temperature and relative humidity (as these variables could not be observed on

those days).

9. To find the contribution of nearby trees on ET partitioning, an experimentwas done on May 2,

2018 when the experimental field had no crop. Since there was no crop, we expected only soil

evaporation will contribute to ET. However, we found that transpiration fraction was around

15%, which was the contribution of nearby trees and vegetation.

103
7 LIMITATION AND FUTURE SCOPE

The study presented in this thesis has many limitations arising due to constraints in money,

time, technology and our understanding of the physical processes. Some of them are listed

below-

1) We were not able to collect sufficient number samples during the rice season.

2) A number of data points for the Keeling plots were less due to the functional limitation

of the experimental set-up. This can be improved if a field deployable Water Vapour

Isotope Analyser is used in future.

3) We have done our study assuming steady-state assumption but in actual case this

assumption may not always betrue. So non steady-state transpiration fraction can be

investigated in futurestudies.

4) We used tetrachloroethylene as displacement liquid in centrifugation. However,

systematic studies are needed to evaluate its performance. Future studies can also be

performed to find the effect of soil grain size, soil type, water content and speed of rotor

on extraction efficiency of this method.

If in future efficient Peltier element cold traps are available which can run on solar power, then

the sampling of atmospheric water can be automated.

104
A) APPENDIX

A.1 Time of Extraction

To find time required for complete removal of water from soil sample experiments were done.

50g oven dried soil sample was mixed with water (10%) of known isotopic composition. Water

samples were collected for different time durations and isotopic composition was found. From

Figure A.1it can be seen that after 60 minutes yield of obtained water is almost constant.

Difference of isotopic composition is also reducing. Therefore extraction time was selected as

80 minutes for experimental plot soil.

Figure A.1 Performance of cryogenic vacuum distillation apparatus

A.2 Comparison of performance of DFC and CVD

To compare DFC and CVD oven dried soil sample was mixed with lab water of known isotopic

composition. Once properly mixed water was extracted using both methods and isotopic

composition was compared. Figure A.2compares methods to extract soil water extraction using

displacement fluid centrifugation and cryogenic vacuum distillation. It has been observed that

DFC works well as compared to CVD. It has been observed that both methods resulted

fractionated sample.

105
Figure A.2 Comparison of performance of displacement fluid centrifugation and cryogenic vacuum distillation

A.3 Model for Data Imputation

Due to some unfortunate events temperature and relative humidity data for a few days were not

recorded. To fill missing values simple linear regression equation is used. .The model develops

a linear relationship between observed variables at AWS and AIS at different heights.

A.3.1 Model Development

A.3.1.1 Temperature

Table A.1contains the correlation of different AWS variables with temperature of AIS at all four

depths.

106
Table A.1 Correlation of different automatic weather station variables with temperature
S.N. Variables T1ais T2ais T3ais T4ais

1 T1aws 0.9803 0.9795 0.9754 0.9577

2 RH1aws -0.5947 -0.5941 -0.5944 -0.5589

3 T2aws 0.9799 0.9794 0.9758 0.9581

4 RH2aws -0.5981 -0.5975 -0.5981 -0.5625

5 Wind Speed -0.0149 -0.0079 0.0045 -0.0007

6 Avg. Wind Speed -0.0346 -0.0259 -0.0113 -0.0149

7 Max. Wind Speed -0.0567 -0.0439 -0.0364 -0.0450

8 Wind Direction -0.2701 -0.2674 -0.2535 -0.2328

9 Solar Global -0.0501 -0.0406 -0.0251 0.0073

10 Barometric Pressure -0.6214 -0.6152 -0.6235 -0.6009

11 SHF 1 0.6142 0.6095 0.6226 0.6347

107
Figure A.3 Graph showing relationship correlation of T1aws with all the temperature

From the aboveTable A.1and Figure A.3, it is clear that T1aws is best correlated with T1 of

AIS.

Table A.2 Different models for predicting T1ais


Variable Model Variables Equation 𝑹𝟐

M1 T T1ais = 0.955T1aws+1.629 0.9610


Temperature

M2 T and SHF T1ais = 0.9384T1aws+0.0089SHF+2.0163 0.9615

108
Table A.3 Models predicting T2ais, T3ais, and T4ais
S.N. Equation 𝑹𝟐

1 T1ais = (0.955±0.0.032)T1aws+(1.629±0.8844) 0.9610

2 T1ais = (0.9384±0.0403)T1aws+(0.0089±0.0132)SHF+2.0163±(1.1288) 0.9615

3 T2ais = (1.019±0.00685)T1ais-(0.4223±0.1924) 0.9984

4 T3ais = (1.002±0.01)T1ais+(0.4727±0.2875) 0.9962

5 T4ais = (1.008±0.0307)T1ais+(1.551±0.8587) 0.9677

Figure A.4to Figure A.7shows correlation between different variables predicted.

Figure A.4 Scatter plot between T1aws and T1ais

Value of R2 for M 1 was found to be 0.9610 if only temperature data of AWS was used as

input parameter.

109
Figure A.5 Scatter plot between T1aws and T2ais

Figure A.6 Scatter plot between T1aws and T3ais

110
Figure A.7 Scatter plot between T1aws and T4ais

Once the value of T1ais was calculated,then T2ais, T3ais and T4aisis calculated using equations

listed inTable A.4. From Figure A.4to Figure A.7it can be seen that the values of temperatures

are more scattered for T4ais.

M 2 is created using two input parameters (Tais and SHF). Figure A.8shows data used in M 2. It

was observed that there is a slight increase in the value of R2 was observed.

Figure A.8 Scatter plot between T1aws, T1ais and SHF

111
A.3.1.2Relative Humidity

Table A.4 contains the correlation of different AWS variables with relative humidity of AIS at

all four depths.

Table A.4 Correlations of different automatic weather station variables with relative humidity
S.N. Variables RH1ais RH2ais RH3ais RH4ais

1 T1aws -0.4791 -0.4577 -0.4427 -0.3792

2 RH1aws 0.9511 0.9466 0.9423 0.8691

3 T2aws -0.4773 -0.4566 -0.4424 -0.3815

4 RH2aws 0.9489 0.9450 0.9414 0.8720

5 Wind Speed 0.0339 0.0285 0.0125 -0.0276

6 Avg. Wind Speed 0.1478 0.1408 0.1168 0.0387

7 Max. Wind Speed 0.0771 0.0744 0.0571 0.0032

8 Wind Direction 0.0870 0.0794 0.0596 0.0187

9 Solar Global -0.2872 -0.2939 -0.3154 -0.3471

10 Barometric Pressure 0.3845 0.3723 0.3798 0.4186

11 SHF 1 -0.4657 -0.4676 -0.4745 -0.5390

112
Figure A.9 Graph showing relationship correlations of RH1aws with all the RH

FromTable A.4, T1aws and SHF have the + correlation with T1ais. While creating models, first

T1ais is predicted, and then different temperatures like T2ais, T3ais and T4ais are calculated

using different equation listed inTable A.6.

Two models M 1 and M 2 are developed using T, T& SHF data, respectively (Table A.5).

Table A.6contains the correlation of different AWS variables with temperature of AIS at all four

depths.Figure A.10toFigure A.13showcorrelation between different variables predicted.

Table A.5 Different models for predicting RH1ais


Variabl Mode Variables Equation 𝑹𝟐

e l

M1 RH RH1ais = 0.9592RH1aws+0.2806 0.9006

M2 RH, WS and P RH1ais = 0.9674RH1aws+0.21WS- 0.9615


RH

0.0783P+77.9975

Table A.6lists the different equations developed to predict RH.

113
Table A.6 Models predicting RH2ais, RH3ais, and RH4ais
S.N. Equation 𝑹𝟐

1 RH1ais = (0.9592±0.05185)RH1aws+(0.2806±0.28) 0.9006

2 RH1ais = 0.9674RH1aws+0.21WS-0.0783P+77.9975

3 RH2ais = (0.984±0.008)RH1ais+(0.4535±0.3605) 0.9976

4 RH3ais = (0.9464±0.015)RH1ais+(1.7±0.6712) 0.9912

5 RH4ais = (0.7603±0.0475)RH1ais+(11.23±2.1469) 0.8763

Figure A.10 Scatter plot between RH1aws and RH1

Figure A.11 Scatter plot between RH1aws and RH2ais

114
Figure A.12 Scatter plot between RH1aws and RH3ais

Figure A.13 Scatter plot between RH1aws and RH4ais

A.3.2 Testing of models for T and RH

Once we have different models to find the values of temperature and relative humidity, testing

of theperformance of models for unused data.

115
Figure A.14 Testing of different models for predicting temperature

When testing of both the models wasdone, it was observed that extra term did not significantly

change % error instead in some of the points error got increased as compared to model 1 (Figure

A.14). Therefore, further in our study, we will use model 1 for predicting temperature.

When testing of both the models wasdone, it was observed that extra term did not significantly

change % error instead in some of the cases error got increased as compared to model 1 (Figure

A.15). Therefore, further in our study, we will use model 1 for predicting relative humidity. In

most of the cases, model 2 has performed poorly with respect to model 1.

Figure A.15 Testing of different models for predicting relative humidity

116
Figure A.16 AWS data on 28 February

Figure A.17Windrose on 28 February

117
Figure A.18 Soil isotopic composition on 28 February
Figure A.19 Soil isotopic composition on 28 February

118
Figure A.20 Variation of air temperature with height Figure A.21 Variation of air relative humidity with
height

Figure A.22 Variation of the isotopic composition of Figure A.23 Variation of the isotopic composition of
water vapour with height water vapour with height

119
Figure A.24 AWS data on 13 March

Figure A.25Windrose on 13 March

120
Figure A.26 Soil isotopic composition on 13 March
Figure A.27 Soil isotopic composition on 28 February

121
Figure A.28 Variation of air temperature with height Figure A.29 Variation of air relative humidity with
height

Figure A.30 Variation of the isotopic composition of Figure A.31 Variation of the isotopic composition of
water vapour with height water vapour with height

122
Figure A.32 AWS data on 27 March

Figure A.33Windrose on 27 March

123
Figure A.34 Soil isotopic composition on 27 March Figure A.35 Soil isotopic composition on 27 March

Figure A.36 Variation of air temperature with height Figure A.37 Variation of air relative humidity with
height

124
Figure A.38 Variation of the isotopic composition of Figure A.39 Variation of the isotopic composition of
water vapour with height water vapour with height

Figure A.40 AWS data on 31 March

125
Figure A.41Windrose on 31 March

Figure A.42 Soil isotopic composition on 31 March Figure A.43 Soil isotopic composition on 31 March

126
Figure A.44 Variation of air temperature with height Figure A.45 Variation of air relative humidity with
height

Figure A.46 Variation of the isotopic composition of Figure A.47 Variation of the isotopic composition of
water vapour with height water vapour with height

127
Figure A.48 AWS data on 8 April

Figure A.49Windrose on 8 April

128
Figure A.50Soil isotopic composition on 8 April Figure A.51 Soil isotopic composition on 8 April

129
Figure A.52 Variation of air temperature with height Figure A.53 Variation of air relative humidity with
height

Figure A.54 Variation of the isotopic composition of Figure A.55 Variation of the isotopic composition of
water vapour with height water vapour with height

130
Figure A.56 AWS data on 11 April

Figure A.57Windrose on 11 April

131
Figure A.58 AWS data on 13 April

Figure A.59Windrose on 13 April

132
Figure A.60 Soil isotopic composition on 13 April Figure A.61 Soil isotopic composition on 13 April

133
Figure A.62 Variation of air temperature with height Figure A.63 Variation of air relative humidity with
height

Figure A.64 Variation of the isotopic composition of Figure A.65 Variation of the isotopic composition of
water vapour with height water vapour with height

134
Processed vs True Isotopic Composition of Standard Samples

Figure A.66Processed vs true isotopic composition of standard samples for oxygen isotope

Figure A.67Processed vs true isotopic composition of standard samples for hydrogen isotope

135
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