Azu Etd 13772 Sip1 M

The Influence of Climate and Landscape on Hydrological
Processes, Vegetation Dynamics, Biogeochemistry and the

Transfer of Effective Energy and Mass to the Critical Zone
Item Type text; Electronic Dissertation
Authors Zapata-Rios, Xavier
Publisher The University of Arizona.
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is made possible by the University Libraries, University of Arizona.
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except with permission of the author.
Download date 26/02/2021 05:21:03
Link to Item http://hdl.handle.net/10150/555944

1
THE INFLUENCE OF CLIMATE AND LANDSCAPE ON HYDROLOGICAL PROCESSES,

VEGETATION DYNAMICS, BIOGEOCHEMISTRY AND THE TRANSFER OF
EFFECTIVE ENERGY AND MASS TO THE CRITICAL ZONE
by
Xavier Zapata-Ríos
__________________________
A Dissertation Submitted to the Faculty of the
DEPARTMENT OF HYDROLOGY AND WATER RESOURCES
In Partial Fulfillment of the Requirements
For the Degree of
DOCTOR OF PHILOSOPHY
WITH A MAJOR IN HYDROLOGY
In the Graduate College
THE UNIVERSITY OF ARIZONA
2015
2
THE UNIVERSITY OF ARIZONA

GRADUATE COLLEGE
As members of the Dissertation Committee, we certify that we have read the dissertation
prepared by Xavier Zapata-Rios, titled the Influence of Climate and Landscape on Hydrological
Processes, Vegetation Dynamics, Biogeochemistry and the Transfer of Effective Energy and
Mass to the Critical Zone and recommend that it be accepted as fulfilling the dissertation
requirement for the Degree of Doctor of Philosophy.
_____________________________________________________________ Date: 03/13/15
Jennifer McIntosh
_______________________________________________________________ Date: 03/13/15
Peter A. Troch
________________________________________________________________ Date: 03/13/15
Jon Chorover
________________________________________________________________ Date: 03/13/15
Paul D. Brooks
Final approval and acceptance of this dissertation is contingent upon the candidate’s submission
of the final copies of the dissertation to the Graduate College.
I hereby certify that I have read this dissertation prepared under my direction and recommend
that it be accepted as fulfilling the dissertation requirement.
________________________________________________________________ Date: 03/13/15
Dissertation Director: Jennifer McIntosh
________________________________________________________________Date: 03/13/15
Dissertation Director: Peter A. Troch

3
STATEMENT BY AUTHOR
This dissertation has been submitted in partial fulfillment of the requirements for an
advanced degree at the University of Arizona and is deposited in the University Library to be
made available to borrowers under rules of the Library.
Brief quotations from this dissertation are allowable without special permission, provided
that an accurate acknowledgement of the source is made. Requests for permission for extended
quotation from or reproduction of this manuscript in whole or in part may be granted by the head
of the major department or the Dean of the Graduate College when in his or her judgment the
proposed use of the material is in the interest of scholarship. In all other instances, however
permission must be obtained from the author.
SIGNED: Xavier Zapata-Ríos

4
DEDICATION
I want to dedicate this work to people who have provided me with great learning opportunities at
some point in my educational path. This work is dedicated to great mentors and friends including
Crnl. Jorge Salvador y Chiriboga, Dr. Robert E. Rhoades, Dr. Rolf Ermshaus, and Dr. René M.
Price.
5
TABLE OF CONTENTS
ABSTRACT.................................................................................................................................................. 9
CHAPTER 1: INTRODUCTION ............................................................................................................... 11
1.1. The Critical Zone ........................................................................................................................ 11
1.2 Climate and landscape controls on hydrology and vegetation .......................................................... 12
1.3 Research Objectives .................................................................................................................... 14
1.4 Dissertation format...................................................................................................................... 17
1.5 References ......................................................................................................................................... 19
CHAPTER 2: PRESENT STUDY.............................................................................................................. 23
2.1 Summary of Paper 1: Climatic and landscape controls on water transit times and silicate mineral
weathering in the critical zone. ............................................................................................................... 23
2.1.1 Study objectives ......................................................................................................................... 23
2.1.2 Major findings ............................................................................................................................ 24
2.2 Summary of Paper 2: Influence of terrain aspect on water partitioning, vegetation structure, and
vegetation greening in high elevation catchments in northern New Mexico .......................................... 27
2.2.2 Major findings ............................................................................................................................ 28
2.3 Summary of Paper 3: Influence of climate variability on water partitioning and effective energy and
mass transfer (EEMT) in the critical zone .............................................................................................. 30
2.3.2 Major findings ............................................................................................................................ 30
2.4 References ......................................................................................................................................... 32
APPENDIX A: ............................................................................................................................................ 34
CLIMATIC AND LANDSCAPE CONTROLS ON WATER TRANSIT TIMES AND SILICATE
MINERAL WEATHERING IN THE CRITICAL ZONE .......................................................................... 34
ABSTRACT............................................................................................................................................ 35
1.0 INTRODUCTION ...................................................................................................................... 37
2.0 METHODS ....................................................................................................................................... 39
2.1 STUDY AREA ............................................................................................................................. 39
2.2 FIELD INVESTIGATIONS ......................................................................................................... 41
6
3.0 RESULTS ......................................................................................................................................... 46

3.1 Landscape characteristics .............................................................................................................. 46
3.2 EEMT ............................................................................................................................................ 46
3.3 Water stable isotopes .................................................................................................................... 47
3.4 Water Chemistry ........................................................................................................................... 48
3.5 Water transit times (WTT) ............................................................................................................ 48
3.6 Bedrock composition and mass balance analysis.......................................................................... 49
4.0 DISCUSSION ................................................................................................................................... 50
5.0 SUMMARY ...................................................................................................................................... 54
6.0 ACKNOWLEDGEMENTS .............................................................................................................. 55
7.0 REFERENCES ................................................................................................................................ 56
8.0 FIGURES .......................................................................................................................................... 66
9.0 TABLES ........................................................................................................................................... 75
APPENDIX B: ............................................................................................................................................ 80
INFLUENCE OF TERRAIN ASPECT ON WATER PARTITIONING, VEGETATION STRUCTURE,
AND VEGETATION GREENING IN HIGH ELEVATION CATCHMENTS IN NORTHERN NEW
MEXICO ..................................................................................................................................................... 80
ABSTRACT............................................................................................................................................ 81
1.0 INTRODUCTION ...................................................................................................................... 83
2.0 METHODOLOGY ........................................................................................................................... 85
2.1 Study area...................................................................................................................................... 85
2.2 Catchment characteristics ............................................................................................................. 87
2.3 Vegetation characteristics ............................................................................................................. 87
2.4 Water partitioning and vegetation greening .................................................................................. 89
3.0 RESULTS ......................................................................................................................................... 94
3.1 Catchment characteristics ............................................................................................................. 94
3.2 Vegetation classification and structure ......................................................................................... 95
3.3 Water partitioning ......................................................................................................................... 95
3.4 Vegetation greening ...................................................................................................................... 98
3.5 Horton index ................................................................................................................................. 98
4.0 DISCUSSION ................................................................................................................................... 99
4.1 Hydrological partitioning ............................................................................................................ 100
4.2 Vegetation water use ................................................................................................................... 102
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4.3 Vegetation structure and NDVI response ................................................................................... 103

4.4 Water partitioning and vegetation interactions ........................................................................... 105
4.5 Implications for the critical zone ................................................................................................ 106
4.6 Future studies .............................................................................................................................. 107
5.0 SUMMARY .................................................................................................................................... 107
6.0 ACKNOWLEDGEMENTS ............................................................................................................ 108
7.0 REFERENCES ............................................................................................................................... 109
8.0 FIGURES ........................................................................................................................................ 120
9.0 TABLES ......................................................................................................................................... 127
10.0 SUPLEMENTAL MATERIAL .................................................................................................... 132
APPENDIX C: .......................................................................................................................................... 138
INFLUENCE OF CLIMATE VARIABILITY ON WATER PARTITIONING AND EFFECTIVE
ENERGY AND MASS TRANSFER (EEMT) IN A SEMI-ARID CRITICAL ZONE ........................... 138
ABSTRACT.......................................................................................................................................... 139
1.0 INTRODUCTION .......................................................................................................................... 141
2.0 METHODS ..................................................................................................................................... 144
2.1 Study site..................................................................................................................................... 144
2.2 Climatological stations ................................................................................................................ 145
2.3 Climate variability................................................................................................................. 145
2.4 EEMT estimation .................................................................................................................. 146
2.5 Water availability, water partitioning and climate controls on water availability ...................... 150
3.0 RESULTS ....................................................................................................................................... 150
3.1 Changes in climate ...................................................................................................................... 150
3.2 Water availability ........................................................................................................................ 152
3.3 EEMT .......................................................................................................................................... 153
EEMTemp ........................................................................................................................................... 153
3.4 Climate controls on discharge ..................................................................................................... 155
4.0 DISCUSSION ................................................................................................................................. 156
4.1 Climate variability....................................................................................................................... 156
4.2 Changes in discharge and evapotranspiration ............................................................................. 157
4.3 EEMT components ..................................................................................................................... 158
5.0 SUMMARY .................................................................................................................................... 162
8
6.0 ACKNOWLEDGEMENTS ............................................................................................................ 163

7.0 REFERENCES ............................................................................................................................... 164
8.0 FIGURES ........................................................................................................................................ 172
9.0 TABLES ......................................................................................................................................... 178
10.0 SUPPLEMENTARY INFORMATION ....................................................................................... 182
APPENDIX D: .......................................................................................................................................... 186
NOBLE GASES AND SF6 CONCENTRATIONS FROM SPRINGS AROUND REDONDO PEAK,
NEW MEXICO ......................................................................................................................................... 186
1.0 NOBLE GASES.............................................................................................................................. 186
2.0 SF6 ................................................................................................................................................... 188
3.0 REFERENCES ............................................................................................................................... 192
9
ABSTRACT
The Critical Zone (CZ) is the surficial layer of the planet that sustains life on Earth and extends
from the base of the weathered bedrock to the top of the vegetation canopy. Its structure
influences water fluxes, biogeochemistry and vegetation. In this dissertation, I explore the
relationships between climate, water fluxes, vegetation dynamics, biogeochemistry, and effective
energy and mass transfer fluxes (EEMT) in a semi-arid critical zone. This research was carried
out in the upper Jemez River Basin in northern New Mexico across gradients of climate and
elevation. The main research objectives were to (i) quantify relations among inputs of mass and
energy (EEMT), hydrological and biogeochemical processes within the CZ, (ii) determine water
fluxes and vegetation dynamics in high elevation mountain catchments with different terrain
aspect and solar radiation, and (iii) study temporal variability of climate and its influence on the
CZ water availability, forest productivity and energy and mass fluxes. The key findings of this
study include (i) significant correlations between EEMT, water transit times (WTT) and mineral
weathering products around Redondo Peak. Significant correlations were observed between
dissolved weathering products (Na+ and DIC) and maximum EEMT. Similarly, 3H
concentrations measured at the springs were significantly correlated with maximum EEMT; (ii)
terrain aspect strongly controls energy, water distribution, and vegetation productivity in high
elevation ecosystems in catchments draining different aspects of Redondo Peak. The
predominantly north facing catchment, when compared to the other two eastern catchments,
receives less solar radiation, exhibits less forest cover and smaller biomass, has more surface
runoff and smaller vegetation water consumption. Furthermore, the north facing catchment
showed smaller NDVI values and shorter growing season length as a consequence of energy
limitation, and (iii) from 1984 to 2012 a decreasing trend in water availability, increased
10
vegetation water use, a reduction in both forest productivity and EEMT was observed at the
upper Jemez River Basin. These changes point towards a hotter, drier and less productive
ecosystem which may alter critical zone processes in high elevation semi-arid systems.
11
CHAPTER 1: INTRODUCTION
1.1. The Critical Zone
The Critical Zone (CZ) is the uppermost layer of the planet that supports life on earth and
extends from the base of the weathered bedrock to the top of the vegetation canopy. Within the
CZ, energy and water fluxes are essential elements that trigger coupled chemical, physical,
biological and geological processes [Brantley et al., 2007]. The CZ can be conceptualized as an
open system non-linear reactor that is constantly evolving with respect to energy and water
fluxes [Figure 1; Chorover et al., 2011; Rasmussen et al., 2011]. Energy and water create an
internal structure organization within this reactor, driving processes such as soil organic
stabilization, pedon horizonation, flow path formation, and mineral weathering among others.
Dissipative products are generated as a result of these internal processes and leave the reactor as
physical and chemical denudation, sediments, water fluxes, solutes, gases and latent heat, etc.
[Chorover, et al., 2011].
Understanding the formation, evolution and functioning of the CZ has been identified as
a research priority for the earth science community in order to predict the CZ response to
ongoing changes in climate and land cover [National Research Council, 2001]. Gradients of
climate and energy have been considered ideal places to study the variability of water and carbon
fluxes and their influence in CZ development e.g. soil formation, biogeochemistry, and
ecohydrology [Chorover et al., 2011]. Moreover, observations of processes along spatial
gradients can provide useful information and can be used as proxies for variability on time
[Troch et al., 2008]. This space for time approach can provide estimations of landscape behavior
under future climate regimes [Wagener et al., 2010; Singh et al., 2011].
12
1.2 Climate and landscape controls on hydrology and vegetation
The long-term coevolution between climate, topography, soils and vegetation has been
shown to leave a detectable organization in biophysical properties within the landscape that in turn
influences the structure and function of hydrological systems [Sivapalan, 2005; Troch et al., 2008;
Hopp et al., 2009; Ehret et al., 2014; Eagleson, 1986]. Despite the significant progress that has
been made in the last few decades to understand hydrological processes at small spatial and short
temporal scales, this knowledge has been very difficult to upscale to larger spatial and longer
temporal scales due to spatial heterogeneities of the landscape and complex hydrologic,
biogeochemical, and ecological feedbacks [Sivapalan, 2005; McDonnell et al., 2007; Troch et al.,
2008; Wagener et al., 2010]. In addition, natural and human forces are altering the hydrological
cycle in unprecedented ways adding complexity for hydrologist to understand and predict these
changes [Eagleson, 1986; Troch et al., 2008; Wagener et al., 2010; Ehret et al., 2014]. The ability
to provide solutions for future water management and decision making across wide range of space
and time scales depends on reliable estimations of water distribution, fluxes, water storage and
quality [Sivapalan, 2005]. Understanding how climate, topography, soils and vegetation interact
and have coevolved might provide key information on how they will interact in the future and may
result in a new hydrological theory that allows for better hydrological predictions under climate
and land cover changes [Hopp et al., 2009; Sivapalan, 2005; McDonnell et al., 2007; Troch et al.,
2008]. All the drivers of landscape evolution take place at the surface of our planet within the
critical zone (CZ).
The National Science Foundation (NSF) has funded 13 Critical Zone Observatories
(CZO) across the continental United States along different gradients in climate and energy. One
13
of these observatories, the Santa Catalina Mountains and Jemez River Basin (JRB-CZO), has
been established within the Valles Caldera National Preserve (VCNP) in the upper Jemez River
Basin in northern New Mexico. One of the JRB-CZO sites is a volcanic resurgent dome known
as Redondo Peak (3430 m) which is located at the center of the VCNP and it is the second
highest elevation peak in the Jemez Mountains. Relief and parent material are similar at this site,
however differences in terrain aspect control wind exposure, radiation, micro-climate, vegetation
[Lyon et al., 2008] and the mass and energy transferred to the CZ [Chorover et al, 2011]. The
JRB-CZO sites provide unique research conditions to study microclimate, water partitioning,
vegetation water use, water storage, streamflow response and water residence time along an
energy gradient during a period characterized by years with extremes in precipitation.
High elevation semi-arid regions are water limited environments where the timing and
amount of water availability is a fundamental factor that controls processes such as weathering,
organic matter decomposition, soil respiration, nutrient uptake, and biomass production among
others [Bales et al., 2006]. Understanding the hydrological processes in high elevation semi-arid
regions has been limited by a lack of integrated measurements of governing fluxes and states,
variability of landscape properties such as soil and vegetation, and small-scale hydroclimatic
variability related to elevation, aspect, and vegetation structure that affect the magnitude and
partitioning of water and energy fluxes [Musselman et al., 2008; Veatch et al., 2009; Rinehart et
al., 2008; Molotch et al., 2009; Bales et al., 2006; Gustafson et al., 2010]. This research is
particularly pertinent to the southwestern US because the Jemez River Basin in northern New
Mexico is part of the head waters that feed the Rio Grande, the third largest river in the country,
which sustains regional water supplies for millions of people [Bales et al., 2006]. The hydrology
in this semi-arid mountainous region is snow dominated and spring snowmelt provides
14
ecosystems with most of their annual influx of water [ Bales et al., 2006]. Recent research has
shown a climate-driven trend toward earlier snowmelts and reduced snowpacks in this region
[Stewart et al., 2005; Mote et al., 2005]. There are high confidence predictions that snowpacks
will continue to decline in northern New Mexico through the year 2100 and projections of
snowpack accumulation for mid-century (2041-2070) show a marked reduction for snow water
equivalent (SWE) of about 40% [Cayan et al., 2013]. The possible alterations in hydrologic
pathways such as evaporation, runoff, infiltration, storage, water residence time, vegetation
response due to these reductions remain poorly understood [Bales et al., 2006].
1.3 Research Objectives
The dissertation examines empirical observations in the critical zone across different spatial and
time scales to find fundamental relationships between climate, water fluxes, vegetation
dynamics, biogeochemistry, and mass and energy fluxes. Figure 1 illustrates a conceptual model
of the CZ, highlighting input/output fluxes and processes that store and create an internal
structural organization. In this dissertation, variables were selected as indicators to study these
input/output fluxes and processes. The indicator variables selected include water residence time,
Horton index, base cations and Na+ concentrations, mass of mineral dissolution, NDVI, net
primary productivity and dissolved inorganic carbon.

15
Figure 1. Conceptual model of the critical zone (CZ). The CZ extends from the base of the
bedrock to the top of the canopy. It receives fluxes of radiation, carbon and water that drive
internal processes that creates an internal structural organization. Dissipative products leave the
CZ as physical, chemical denudation, baseflow, solutes, DIC/DOC fluxes. Indicators are
variables that were selected specifically in this dissertation to understand input and output fluxes
and energy storage.
Water, energy, carbon mass balance equations and mineral weathering reactions illustrated in
figure 1 are the following:
1. Water mass balance

𝜕𝜃
𝐿 =𝑃−𝐸−𝑆−𝑈 [L]
𝜕𝑡
16
𝑊 =𝐸+𝑈 [L]
P= precipitation, E= evapotranspiration, S= surface run-off, U=baseflow, W=wetting
2. Energy balance
𝜕𝑇
𝐶𝑝 𝑚 = 𝑅𝑛 − 𝜆𝐸 − 𝐻 − 𝐺 − 𝐵𝑖𝑜 [ML2T-2]
𝜕𝑡
T= temperature, cp = heat capacity, m =mass, Rn= net radiation, λE= latent heat, H= sensible
heat, G=subsurface heat flux, Bio= energy uptake by vegetation during photosynthesis.
3. Carbon mass balance

𝜕𝐶
= 𝐶𝑂2 − 𝑅𝑒𝑠𝑝 − 𝐷𝐼𝐶 − 𝐷𝑂𝐶 − 𝑃𝑂𝐶 [ML-2T-1]
𝜕𝑡
Resp=respitation, DIC= dissolved inorganic carbon, DOC= dissolved organic carbon, POC=
particulate organic carbon.
4. Mineral weathering
+
𝑃𝑟𝑖𝑚𝑎𝑟𝑦 𝑀𝑖𝑛𝑒𝑟𝑎𝑙𝑠(𝑠) + 𝐻2 𝑂(𝑙) + 𝐻(𝑎𝑞) ⇔𝑆𝑒𝑐𝑜𝑛𝑑𝑎𝑟𝑦 𝑀𝑖𝑛𝑒𝑟𝑎𝑙𝑠(𝑠) + 𝑐𝑎𝑡𝑖𝑜𝑛𝑠(𝑎𝑞)
+ 𝑆𝑖𝑙𝑖𝑐𝑖𝑐 𝐴𝑐𝑖𝑑(𝑎𝑞)
The main research questions tackled during this dissertation are:
(1) What are the relations between inputs of mass and energy, hydrological and
biogeochemical processes within the CZ? I hypothesized that energy and mass flowing
into the CZ control its structure thereby influencing hydrologic and biogeochemical
processes. In the first paper of this dissertation, I investigated whether the quantification
of energy and mass entering the CZ can predict CZ processes, specifically water
residence times and mineral weathering. I posited that around Redondo Peak longer
residence times and larger mineral weathering fluxes would be observed in waters
17
draining its north facing slopes where higher inputs of mass and energy entering the CZ
have been quantified.
(2) What are the water fluxes and vegetation dynamics in high elevation mountain
catchments with different terrain aspect and solar radiation? The second paper in this
dissertation analyzes the interactions and feedbacks between water availability and
vegetation at the catchment scale. Three high elevation streams with different terrain
aspects draining Redondo Peak were studied in this paper. I hypothesized that the
differences in aspect and solar radiation among catchments would influence the short
term partitioning of water and vegetation dynamics around Redondo Peak.
(3) What are the impacts of climate temporal variability on the CZ water availability, forest
productivity and energy and mass fluxes? The study presented in the third paper took
place in the upper Jemez River Basin with an area of 1200 km2. I hypothesized that
changes in climate are affecting the CZ by decreasing water availability, altering forest
productivity, and decreasing influxes of mass and energy.
1.4 Dissertation format
The dissertation has been organized in three studies focusing on the influence of climate and
landscape position on the CZ water fluxes, vegetation dynamics, water transit times, mineral
weathering and mass and energy transfer at different spatial scales. Following this first
introductory chapter, chapter 2 presents a summary of three papers prepared to be submitted for
peer-review publication. These papers are included individually in the appendices.
APPENDIX A. Climatic and landscape controls on water transit times and silicate mineral
weathering in the critical zone.

18
APPENDIX B. Influence of terrain aspect on water partitioning, vegetation structure, and
vegetation greening in high elevation catchments in northern New Mexico.
APPENDIX C. Influence of climate variability water partitioning and effective energy and mass
transfer (EEMT) in a semi-arid critical zone.

19
1.5 References
Bales, R. C., N. P. Molotch, T. H. Painter, M. D. Dettinger, R. Rice, and J. Dozier (2006),
Mountain hydrology of the western United States, Water Resour. Res., 42, W08432.
Brantley, S. L., M. B. Goldhaber, and K. V. Ragnarsdottir (2007), Crossing disciplines and
scales to understand the Critical Zone, Elements, 3, 307-314.
Cayan, D., M. Tyree, K. E. Kunkel, C. Castro, A. Gershunov, J. Barsugli, A. J. Ray, J. Overpeck,
M. Anderson, J. Russell, B. Rajagopalan, I. Rangwala, and P. Duffy. 2013. “Future Climate:
Projected Average.” In Assessment of Climate Change in the Southwest United States: A Report
Prepared for the National Climate Assessment, edited by G. Garfin, A. Jardine, R. Merideth, M.
Black, and S. LeRoy, 101–125. Washington, DC: Island Press.
Chorover, J. et al. (2011), How Water, Carbon, and Energy Drive Critical Zone Evolution: The
Jemez-Santa Catalina Critical Zone Observatory, Vadose Zone Journal, 10, 884-899.
Eagleson, P. (1986), The Emergence of Global-Scale Hydrology, Water Resour. Res., 22, S6-
S14.
Ehret, U. et al. (2014), Advancing catchment hydrology to deal with predictions under change,
Hydrology and Earth System Sciences, 18, 649-671.
Gustafson, J. R., P. D. Brooks, N. P. Molotch, and W. C. Veatch (2010), Estimating snow
sublimation using natural chemical and isotopic tracers across a gradient of solar radiation,
Water Resour. Res., 46, W12511.

20
Hopp, L., C. Harman, S. L. E. Desilets, C. B. Graham, J. J. McDonnell, and P. A. Troch (2009),
Hillslope hydrology under glass: confronting fundamental questions of soil-water-biota co-
evolution at Biosphere 2, Hydrology and Earth System Sciences, 13, 2105-2118.
Lyon, S. W., P. A. Troch, P. D. Broxton, N. P. Molotch, and P. D. Brooks (2008), Monitoring
the timing of snowmelt and the initiation of streamflow using a distributed network of
temperature/light sensors, Ecohydrology, 1, 215-224.
McDonnell, J. J. et al. (2007), Moving beyond heterogeneity and process complexity: A new
vision for watershed hydrology, Water Resour. Res., 43, W07301.
Molotch, N. P., P. D. Brooks, S. P. Burns, M. Litvak, R. K. Monson, J. R. McConnell, and K.
Musselman (2009), Ecohydrological controls on snowmelt partitioning in mixed-conifer sub-
alpine forests, Ecohydrology, 2, 129-142.
Mote, P., A. Hamlet, M. Clark, and D. Lettenmaier (2005), Declining mountain snowpack in
western north America, Bull. Am. Meteorol. Soc., 86, 39-+.
Musselman, K. N., N. P. Molotch, and P. D. Brooks (2008), Effects of vegetation on snow
accumulation and ablation in a mid-latitude sub-alpine forest, Hydrol. Process., 22, 2767-2776.
National Research Council (2001). Basic research opportunities in earth science. National
Academy Press. Washington, D.C.

21
Rasmussen, C., P. A. Troch, J. Chorover, P. Brooks, J. Pelletier, and T. E. Huxman (2011), An
open system framework for integrating critical zone structure and function, Biogeochemistry,
102, 15-29.
Rinehart, A. J., E. R. Vivoni, and P. D. Brooks (2008), Effects of vegetation, albedo, and solar
radiation sheltering on the distribution of snow in the Valles Caldera, New Mexico,
Ecohydrology, 1, 253-270.
Singh, R., T. Wagener, K. van Werkhoven, M. E. Mann, and R. Crane (2011), A trading-space-
for-time approach to probabilistic continuous streamflow predictions in a changing climate -
accounting for changing watershed behavior, Hydrology and Earth System Sciences, 15, 3591-
3603.
Sivapalan, M (2005), Pattern, process and function: elements of a new unified hydrologic theory
at the catchment scale, in Encyclopedia of Hydrologic Sciences, vol. 1, part 1, edited by M.G.
Anderson, chap.13, pp.193-219, John Wiley, Hoboken, N.J.
Stewart, I., D. Cayan, and M. Dettinger (2005), Changes toward earlier streamflow timing across
western North America, J. Clim., 18, 1136-1155.
Troch P.A., G.A. Carrillo, I. Heidbuechel, D. Rajagopal, M. Seitanek, T.H.M. Volkmann, M.
Yaeger (2008) Dealing with landscape heterogeneity in watershed hydrology: a review of recent
progress toward new hydrological theory. Geography Compass 2: 10.1111/j.1749-
8198.2008.0086.x
22
Veatch, W., P. D. Brooks, J. R. Gustafson, and N. P. Molotch (2009), 'Quantifying the effects of
forest canopy cover on net snow accumulation at a continental, mid-latitude site', Ecohydrology,
2, 115-128.
Wagener, T., M. Sivapalan, P. A. Troch, B. L. McGlynn, C. J. Harman, H. V. Gupta, P. Kumar,
P. S. C. Rao, N. B. Basu, and J. S. Wilson (2010), The future of hydrology: An evolving science
for a changing world, Water Resour. Res., 46, W05301.

23
CHAPTER 2: PRESENT STUDY
The interactions between climate and topography and their influence on hydrologic processes,
vegetation dynamics, biogeochemistry and the effective mass and energy to the CZ are explored
in three studies appended to this dissertation. The following pages summarize the major findings
and implications of these studies.
2.1 Summary of Paper 1: Climatic and landscape controls on water transit times and silicate
mineral weathering in the critical zone.
2.1.1 Study objectives
The CZ can be conceptualized as an open system reactor that is continually transforming
energy and water fluxes [Chorover et al., 2011]. In the present study, we test the predictive
power of a postulated controlling factor on Water Transit Times (WTT) and mineral weathering
derived from climatic data termed effective energy and mass transfer (EEMT) to the CZ
[Rasmussen et al., 2011]. The objective of the present study is to test whether EEMT and/or
landscape characteristics are dominant controlling variables on WTT times and the main silicate
weathering mass balance reactions in a terrain characterized by a relatively uniform bedrock
geology.
Our study site is located around Redondo Peak, a rhyolitic volcanic resurgent dome, in
northern New Mexico. At Redondo Peak springs drain slopes along an energy gradient created
by differences in terrain aspect. This investigation uses major solute concentrations, mass
24
balance weathering reactions, and the age tracer tritium and compares them to EEMT and
landscape characteristics.
The selected springs drain different aspects of Redondo Peak at elevations between 2816
and 3170 m. Contributing areas of springs vary in size from 56 to 1038 (x103 m2) and their mean
cosine angle covers a wide range of aspects from -0.5 south to 0.96 north. The mean slope of
contributing areas range between 10 to 20 degrees, and the median water flow path length ranges
from 360 to 600 meters with a median gradient between 0.12 and 0.32.
2.1.2 Major findings
The major findings of this study include:
(1) EEMT values for the Redondo Peak region vary between 22 and 59 MJ m-2 year-1.
Large EEMT values above 30 MJ.m-2.year-1 were found on Redondo Peak and low
EEMT values below 30 MJ m-2 year-1 were found along shaded areas by topography
such as Redondo Creek in the southwestern part of Redondo.
(2) The mean aspect of a spring contributing area positively correlates with mean EEMT
(R2=0.31; p>0.1), maximum EEMT (R2=0.90; p<0.0001), and the range of EEMT
(R2=0.82; p=0.0007).
(3) Based on the maximum EEMT versus aspect relationship, north facing slopes receive up
to 25% more EEMT than south facing slopes.
(4) Spring waters around Redondo Peak are dominated by Ca+, Na+, Si and HCO3- and have
an isotopic signature that indicates they are predominantly derived from infiltration of
snowmelt.
25
(5) Dissolved inorganic carbon (DIC) concentrations strongly correlate with the products of
silicate weathering, including the sum of all base cations (R2=0.92; p<0.0001) and Na+
concentrations (R2=0.86; p=0.001).
(6) Significant correlations were found between all base cations and Na+ concentrations
versus aspect, maximum and range of EEMT. Na+ is a cation that is not generally cycle
to a great degree biologically and it shows the strongest correlations with aspect and
EEMT.
(7) Water with higher concentrations of solutes is found along north facing slopes (R2=0.56;
p<0.05), which are characterized in this study by higher EEMT values (R2=0.51;
p<0.05).
(8) Maximum flow path length and contributing area are the only two landscape
characteristics that show statistically significant correlations with both base cations and
Na+ concentrations. Larger concentrations of base cations are observed in springs with
longer flow paths (R2=0.54; p<0.05) and larger contributing areas (R2=0.54; p<0.05)
(9) Mean EEMT and other landscape variables, such as mean elevation, mean slope, median
flow path length (L), median flow path slope (G), and L/G are poor predictors of both
base cations and Na+ concentrations.
(10) Tritium concentrations measured at the springs ranged from 5.1 to 7.9 TU and
water apparent age in the springs ranged from 0.2 to 8.1 years.
(11) Mineralogical analyses of Redondo Peak bedrock samples indicate predominance
of primary phases sanidine, oligoclase, anorthoclase, and quartz, accompanied by minor
minerals, including apatite, hematite, zircon, titanite, ilmenite, faujasite.

26
(12) Spring waters are undersaturated with respect to silica, halite, calcite, gypsum,
sanidine and albite, but saturated to supersaturated with respect to secondary minerals
gibbsite, goethite, hematite and kaolinite
(13) Longer WTT based on tritium analysis of springs draining north-facing terrains.
Mineral dissolution fluxes increase with WTT, likely due to enhanced water-rock
reaction, and chemical weathering consumes more atmospheric CO2 along north facing
slopes.
Results from this study demonstrate the close interrelationship between landscape,
hydrological and biogeochemical processes. This study provides evidence that fluxes of energy
and mass, quantified as EEMT, at the catchment scale can effectively predict short time-scale
(months to years) processes within the CZ structure like WTT and silicate mineral weathering.
These results also suggest that basic climatic data embodied in the EEMT term can be used to
scale hydrological and hydrochemical responses in other sites.

27
2.2 Summary of Paper 2: Influence of terrain aspect on water partitioning, vegetation structure,
and vegetation greening in high elevation catchments in northern New Mexico
Vegetation and water availability are primary controls on ecosystems structure (Brooks &
Vivoni, 2008), therefore, it is important to study and understand their role within the critical
zone. Understanding the feedbacks between water and vegetation in mountainous semiarid
catchments can help improve climate change predictions and associated hydrologic and ecologic
shifts (Newman et al., 2006; Molotch et al., 2009; Vivoni et al., 2012). Furthermore, field
studies along landscape gradients may provide insight on the relationship among topography,
vegetation, and water (Kelly and Goulden, 2008; Newman et al., 2006; Chorover et al., 2011).
The objective of this study is to investigate from 2000 to 2012 how terrain aspect
influences vegetation structure, the dynamics of hydrological partitioning, and vegetation
greening in three high elevation semi-arid catchments using direct and remote sensing
observations. A uniform geology and relief around Redondo Peak, located in the center of the
VCNP, make this site an ideal location to empirically study how topographically controlled
microclimate (Lyon et al., 2008; Chorover et al., 2011) influences the integrated vegetation and
hydrological response. This investigation focuses on three catchments with perennial streams: La
Jara (LJ), History Grove (HG) and Upper Jaramillo (UJ) (Figure 1c). The three catchments
together cover approximately an area of 10 km2.

28
Vegetation structure was quantified from 1 m LiDAR data while vegetation greening was
quantified using remotely sensed NDVI. Hydrological partitioning at the catchment scale was
estimated with a metric of catchment-scale water fluxes and vegetation water use (Horton index;
HI).
The major findings of this study are:
(1) The predominantly north facing catchment (UJ), when compared to the other two eastern
catchments (LJ and HG), receives less solar radiation, and exhibits less forest cover and
smaller biomass, has more surface runoff (~15% of P) as a consequence of a smaller
vaporization (85% of P) and smaller vegetation water consumption (HI=0.85).
(2) The north facing catchment (UJ) showed smaller peak NDVI values (5.98) and shorter
growing season length (76.3 days) as a consequence of energy limitation.
(3) In contrast, the two eastern catchments (LJ and HG) receive larger solar radiation, have
more biomass and forest cover (>76%), and smaller surface runoff (<10% P), higher
vaporization (>90%P) and vegetation water consumption (HI=0.95).
(4) The eastern catchments (Lj and HG) had larger vegetation greening (6.28-6.58) and a
longer growing season (113-156 days).
(5) Snowpack conditions, such as maximum SWE and duration of the snow on the ground,
explain over 95% of water partitioning (HI) that in turn influenced annual vegetation
greening (R2=0.48 - 0.67; p<0.05).

29
This catchment scale study in perennial streams indicates that terrain aspect at a similar
altitude (2700 – 3435m) strongly controls energy, water distribution, and vegetation productivity
in high elevation ecosystems. Terrain aspect differences in water partitioning fluxes among
catchments during wet years can be larger than the water partitioning fluxes variability induced
only by climate variability in a single catchment. This study demonstrates that water and energy
limits forest productivity and terrain aspect is a landscape characteristic that can further
exacerbate the availability of these resources. Aspect controls on water availability and reduced
carbon compounds resulting from primary production influences the inputs of EEMT and
processes occurring within the CZ.

30
2.3 Summary of Paper 3: Influence of climate variability on water partitioning and effective
energy and mass transfer (EEMT) in the critical zone
The objective of this study was to evaluate climate variability and its influence on the
temporal changes of water partitioning and EEMT at the catchment scale in a semi–arid CZ over
the last few decades. This investigation took place in the upper part of the Jemez River Basin in
northern New Mexico, a basin dominated by a wide forest cover and limited human
infrastructure, where the Santa Catalina-Jemez River Critical Zone Observatory has established
a research site to study CZ processes [Chorover et al., 2011]. Micro-climate variability was
studied based on daily records from two SNOTEL stations using records from 1984 through
2012. Water availability and EEMT were estimated during the same time period based on
precipitation and temperature from the precipitation-elevation regressions on independent slopes
model (PRISM), empirical daily observations of catchment scale discharge, and satellite derived
net primary productivity (MODIS).
The major findings of this study include:
(1) Clear increasing trends in temperature and decreasing trends in precipitation and
maximum SWE at the two SNOTEL stations indicated. Temperature changes include
warmer winters (+1.0-1.3 °C/decade), and generally warmer year round temperatures
(+1.2-1.4 °C/decade). Precipitation changes include, a decreasing trend in

31
precipitation during the winter (-41.6-51.4 mm/decade), during the year (-69.8-73.2
mm/decade) and max SWE (-33.1-34.7 mm/decade).
(2) At the upper Jemez River Basin ,all the water partitioning components showed
statistical significant decreasing trends including precipitation (-61.7mm/decade),
discharge (-17.6 mm/decade) and vaporization (-45.7 mm/decade). Similarly, Q50 an
indicator of snowmelt timing is occurring -4.3 days/decade earlier.
(3) Basin scale precipitation (R2=0.56; p=0.003) and baseflow (R2=0.41; p=0.02) were
the strongest controls on NPP variability indicating that forest productivity in the
upper Jemez River Basin is water limited. An increasing trend in Horton index
suggests that water limitation and vegetation water use are increasing in the basin.
(4) This study showed a positive correlation between water availability and EEMT. For
every 10 mm of change in baseflow, EEMT varies proportionally in 0.6-0.7 MJ m-

2
year-1.
(5) From 1984-2012 changes in climate, water availability, and NPP have influenced
EEMT in the upper Jemez River Basin. A decreasing trend in EEMT of 1.2 to 1.3 MJ
m-2 decade-1was calculated in this same time frame.
As the landscape moves towards a drier and hotter climate, changes in EEMT of this magnitude
are likely to influence critical zone processes.

32
2.4 References
Brooks, P. D. and E. R. Vivoni (2008), Mountain ecohydrology: quantifying the role of
vegetation in the water balance of montane catchments, Ecohydrology, 1, 187-192.
Kelly, A. E. and M. L. Goulden (2008), Rapid shifts in plant distribution with recent climate
change, Proc. Natl. Acad. Sci. U. S. A., 105, 11823-11826.
Newman, B. D., B. P. Wilcox, S. R. Archer, D. D. Breshears, C. N. Dahm, C. J. Duffy, N. G.
McDowell, F. M. Phillips, B. R. Scanlon, and E. R. Vivoni (2006), Ecohydrology of water-
limited environments: A scientific vision, Water Resour. Res., 42, W06302.
102, 15-29.
33
Vivoni, E. R. (2012), Spatial patterns, processes and predictions in ecohydrology: integrating
technologies to meet the challenge, Ecohydrology, 5, 235-241.

34
APPENDIX A:
CLIMATIC AND LANDSCAPE CONTROLS ON WATER TRANSIT TIMES AND
SILICATE MINERAL WEATHERING IN THE CRITICAL ZONE
Manuscript in review by the journal Water Resources Research
Authors:
Xavier Zapata-Rios1*, Jennifer McIntosh1, Laura Rademacher2, Peter A. Troch1, Paul D.
Brooks3,1, Craig Rasmussen4, Jon Chorover4
1. Department of Hydrology and Water Resources, The University of Arizona, Tucson, Arizona,
USA
2. Earth and Environmental Sciences, University of the Pacific, Stockton, California, USA
3. Department of Geology and Geophysics, University of Utah, Salt Lake City, Utah, USA
4. Soil, Water and Environmental Science, The University of Arizona, Tucson, Arizona, USA
* Corresponding author:
1133 E James E Rogers Way
J W Harshbarger Bldg Rm 122, PO Box 210011
The University of Arizona
Tucson AZ 85721-0011
Email: xavierzapata@email.arizona.edu
35
ABSTRACT
The critical zone (CZ) can be conceptualized as an open system reactor that is continually
transforming energy and water fluxes into an internal structural organization and dissipative
products. In this study, we test a controlling factor on water transit times (WTT) and mineral
weathering called Effective Energy and Mass Transfer (EEMT). We hypothesize that EEMT,
quantified based on local climatic variables, can effectively predict WTT within – and mineral
weathering products from – the CZ. This study compares the ability EEMT versus static landscape
characteristics in predicting WTT, aqueous phase solutes, and silicate weathering products. Our
study site is located around Redondo Peak, a rhyolitic volcanic resurgent dome, in northern New
Mexico. At Redondo Peak springs drain slopes along an energy gradient created by differences in
terrain aspect. This investigation uses major solute concentrations, mass balance weathering
reactions, and the age tracer tritium and compares them to EEMT and landscape characteristics.
Results indicate significant correlations between EEMT, WTT and mineral weathering products.
Significant correlations were observed between dissolved weathering products (Na+ and DIC) and
maximum EEMT. Similarly, 3H concentrations measured at the springs were significantly
correlated with maximum EEMT. In contrast, landscape characteristics such as contributing area
of spring, slope gradient, elevation, and flow path length were not as effective predictive variables
of WTT, solute concentrations, and mineral weathering products. These results highlight the
interrelationship between landscape, hydrological, and biogeochemical processes and suggest that
basic climatic data embodied in EEMT can be used to scale hydrological and hydrochemical
responses in other sites.

36
KEYWORDS
Critical Zone, Effective Energy and Mass Transfer (EEMT), terrain aspect, water transit times,
weathering of silicates.
37
1.0 INTRODUCTION
The Critical Zone (CZ) is the uppermost land surface layer of the planet that extends
from the base of the weathered bedrock to the top of the vegetation canopy. Within the CZ,
energy and water fluxes drive coupled chemical, physical, biological and geological processes
that support life [Brantley et al., 2007]. Understanding the formation, evolution and functioning
of the CZ is fundamental for predicting its response to ongoing changes in climate and land
cover [National Research Council, 2001].
Mineral weathering is a fundamental process occurring within the CZ that influences soil
development and nutrient release [White and Brandley, 1995], as well as the buffering of acids
derived from the atmosphere and biosphere [Velbel and Price, 2007]. Furthermore, weathering of
silicate minerals impacts the global carbon cycle through the consumption of atmospheric CO2
[Berner et al., 1983; Berner, 1995; Maher and Chamberlain, 2014], and the aqueous phase
products of chemical weathering are determinants of the chemical composition of natural waters
[Bricker et al., 1986; Drever, 1988]. During weathering, atmospheric CO2 and silicate minerals
are converted to alkalinity and dissolved cations [Maher and Chamberlain, 2014]. Many silicate
weathering studies demonstrate that hydrologic factors, and particularly water transit time
(WTT), play an important regulatory role on weathering of silicates [Velbel, 1993; White et al.,
2001; Gabet et al., 2006; Maher 2010, 2011].
Water transit time (WTT) refers to the elapsed time between when water enters and exits
the hydrologic system [McGuire and McDonnell, 2006]. WTT is a good indicator of the
hydrologic response of a system over a period of time and provides information about flow path
heterogeneity, subsurface storage capacity, water input-output fluxes, mineral weathering, and
38
solute transport [McGuire and McDonnell, 2006]. Over the last decade, research efforts have
focused on understanding the factors that control WTT at diverse spatial scales and in different
geographic regions [McGlynn et al., 2003; McGuire et al., 2005; Rodgers et al., 2005; Soulsby
et al., 2006; Stewart et al., 2010; Mueller et al., 2012; many others]. In these investigations, the
role of landscape structure, topography, soils, geology and climate on WTT have been tested at
different sites with results that have been difficult to transfer from one specific research site to
others [Vitvar et al., 2005; Tetzlaff et al.,2009]
In the present study, we test the predictive power of a postulated controlling factor on
WTT and mineral weathering derived from climatic data termed effective energy and mass
transfer (EEMT) to the CZ [Rasmussen et al., 2011]. The CZ can be conceptualized as an open
system reactor that is continually transforming energy and water fluxes [Figure 1; Chorover et
al., 2011]. Energy and water fluxes generate internal structural organization within this reactor,
driving processes such as soil organic carbon stabilization, pedon horizonation, flow path
formation, and mineral weathering, among others. Dissipative products resulting from CZ
internal processes leave the reactor via physical and chemical denudation, sediments transport,
water solutes, gas fluxes, and latent heat [Chorover et al., 2011; Rasmussen et al., 2011].
Energy based pedogenic models attempt to quantify energy fluxes to the soil system that
drive mineral weathering and CZ development. Some initial work and semi-quantitative
approaches describing soil formation factors (climate, biota, relief, parent material, and time)
were developed by Dokuchaev [1967], Jenny [1941], Runge [1973], and Smeck et al. [1983].
Later, these soil forming factors were quantified in terms of energy [Volobuev, 1964; Phillips,
2009; Rasmussen et al., 2005; Rasmussen and Tabor, 2007]. The EEMT term in particular is
39
focused on the energy and mass transfer to the subsurface in the form of heat energy associated
with effective precipitation (water in excess from evapotranspiration) and chemical energy
associated with reduced carbon compounds produced through primary production. Recent
research along elevation gradients in the western US documented a significant correlation
between EEMT and regolith depth, chemical depletion, and denudation rates and demonstrated
weak and no correlations considering climatic variables alone such mean annual air temperature
and mean annual precipitation [Rasmussen et al., 2005, 2011; Rasmussen and Tabor 2007]. The
relationship between inputs of energy into the CZ at a mountain scale (~40 km2) and the
influence on WTT and mineral weathering has not been explored previously.
Redondo Peak within the Jemez Mountains in northern New Mexico is a research site
within the larger Catalina-Jemez Critical Zone Observatory (CZO) that was established to
understand CZ processes [Chorover et al., 2011]. Around Redondo Peak, a volcanic rhyolitic
resurgent dome, head water springs and streams discharge along different sides of the mountain.
The differences in terrain aspect around Redondo Peak create a natural gradient of energy inputs
to the CZ. Previous research at this site has observed differences in solar radiation, water
availability, dissolved organic carbon fluxes, and WTT across different terrain aspects of
Redondo Peak [Lyon et al., 2008; Broxton et al., 2009; Perdrial et al., 2014]. The objective of
the present study is to test whether EEMT and/or landscape characteristics are dominant
controlling variables on WTT times and the main silicate weathering mass balance reactions in a
terrain characterized by a relatively uniform bedrock geology.
2.0 METHODS
2.1 STUDY AREA

40
Redondo Peak lies within the Valles Caldera National Preserve (VCNP) in the Jemez
Mountains of northern New Mexico (35˚50’-36˚00’ N; 106˚24’-106˚37’ W). The VCNP is a 21
km wide caldera formed by the collapse of a magma chamber approximately 1.25 Ma before
present [Wolff et al., 2011]. The rim of the caldera extends to elevations above 2800 masl and
encloses a basin floor that ranges in elevation between 2500 and 2750 masl. Redondo Peak, with
maximum elevation of 3435 masl, is a resurgent dome formed by magma flow through ring
fracture faults and is located in the center of the caldera [Lyon et al., 2008]. Redondo Peak is
characterized by a gradient in terrain aspect that influences wind exposure, radiation, snowmelt,
sublimation, evapotranspiration and groundwater recharge [Lyon et al., 2008].
Several springs and first-order streams drain all sides of Redondo Peak feeding the Jemez
River basin, which is a tributary of the Rio Grande River [Ellis et al., 1993] (Figure 2). The
geology of Redondo Peak is dominated by Pleistocene aged, densely to partially welded
Bandelier Tuff and older rhyolitic and andesitic rocks associated with older volcanic events
[Goff et al., 2006; Wolff et al., 2011]. Soils across the dome are generally characterized by well-
drained Mollisols, Inceptisols and Alfisols that span coarse sandy loam to clay loam textures and
contain an abundance of partially to highly decomposed organic matter in surface soil horizons
[http://websoilsurvey.nrcs.usda.gov/app/HomePage.htm]. Vegetation at higher elevations is
dominated by Spruce-fir (Picea pungens), ponderosa pine (Pinus ponderosa), aspen (Populas
tremuloides), and gambel oak (Quercus gambelii); lower elevations and valley bottoms are
dominated by forest meadows and grasslands [Muldavin et al., 2006; Coop and Givnish, 2007].
The semi-arid climate in this region is continental in nature and highly variable. The climate is
characterized by a bimodal precipitation pattern, with ca. 50% of the total annual precipitation
falling as snow and rain during the winter months and ca. 50% falling as rainfall during the
41
summer monsoon season [Sheppard et al., 2002]. According to 31 years of records (1981-2012)
at the Quemazon SNOwpack TELemetry (SNOTEL) station (35°55’ N; 106°24’ W; 2896 masl),
located 5 km east from Redondo Peak, the average annual precipitation is 711 mm, and the
average summer and winter temperatures are 10.7˚C and -1.1 ˚C, respectively.
2.2 FIELD INVESTIGATIONS
2.2.1 Landscape analysis
The springs around Redondo Peak selected for this study are characterized by perennial
discharge. The springs drain slopes with different aspects (orientations) at elevations above 2800
masl (Table 1). Springs with low discharge, draining the foothills or other domes in the VCNP
were not considered in this analysis. Landscape characteristics of springs investigated in this study
include aspect, contributing area, water flow length, and slope gradients. Landscape
characteristics were defined using a 722 km2 airborne LiDAR flight coverage acquired July 2010
and processed by the National Center for Airborne Laser Mapping (NCALM). The LiDAR
coverage has an average point density of 9.68 points per m2 and vertical and horizontal RMSE
resolutions of 0.1 m and 1.0 m, respectively. For this study, a spring’s contributing area is an
idealized region where energy and matter are transferred to the CZ. Within these boundaries it is
assumed that water flow is routed and discharged into the springs and mineral weathering
transformations occur. Contributing areas from springs and topographic analysis within each basin
were defined using the catchment delineation procedures from TauDEM version 5.0
(http://hydrology.usu.edu/taudem/taudem5.0/index.html. Accessed May, 2014) and following
procedures similar to those of McGuire et al. [2005]. An accumulated area grid was obtained
applying a multidirectional flow algorithm to define a flow network. Then, flow path length and
42
gradients were computed along each flow line within a spring’s contributing area [McGuire et al.,
2005]. The mean aspect of contributing areas was calculated following the methodology indicated
in Broxton et al. [2009], as an average of the x and y composite vectors for each aspect cell. The
average aspect calculated in radians was expressed as the cosine of the angle such that north facing
terrains have a value of 1 and south facing terrains have a value of -1.
2.2.2 Effective Energy and Mass Transfer (EEMT)
The EEMT model is based on the hypothesis that soil and the larger CZ tend to self-organize
to optimize the transmission of energy flowing through the system [Rasmussen et al., 2005;
Rasmussen and Tabor, 2007]. This self-organization, entropy maximization, and use of energy
of natural systems is described by principles of open system thermodynamics and traditional
quantitative models of soil development [Rasmussen et al., 2005; Kleidon et al., 2012]. The
EEMT model quantifies external energy inputs to the CZ by integrating into one single variable
the climatic and biotic forcings [Rasmussen et al., 2005; Rasmussen and Tabor, 2007]. For a
more detailed description and derivation of EEMT see Rasmussen et al. [2005, 2011],
Rasmussen and Tabor [2007], and Chorover et al. [2011]. In the present work, we quantified
EEMT following the algorithm described in Chorover et al. [2011] based on a multiple linear
regression model between EEMT and variables that exert first-order controls on photosynthesis
and effective precipitation including topographically modified temperature, precipitation, and
vapor pressure deficit:
EEMTm=-3.13+0.00879 (T+273.15) + 0.562PPT + 0.03256 (T-17.65)(PPT-9.0)-
0.00235VPD + 0.00062(PPT-9.0)(VPD-662) (1)

43
where,
EEMTm = EEMT (MJ.m-2) on a monthly basis, T= air temperature (˚C), PPT = precipitation (cm)
and VPD = vapor pressure deficit (Pa)
EEMT quantification may be applied across multiple spatial (e.g., pedon, catchment, biome) and
temporal (e.g., days, months, years) scales. The energy input to the CZ provided by effective
precipitation and net ecosystem production was estimated from climatic data during 10 years
from 2000 to 2009 [Chorover et al., 2011].
2.2.3 Mineral weathering
Mineral weathering processes were investigated using spring water aqueous phase chemistry.
This methodology examines major solute concentrations in water as products of mineral
weathering reactions [Rademacher et al., 2001; Anderson and Dietrich, 2001; Biron et al., 1999;
Campbell et al., 1995; Goddéris et al., 2006; Godsey et al., 2009, Hooper et al., 1990]. Nine
perennial springs were sampled monthly from 2011 to 2013 except during those winter months
when sites were inaccessible. All spring samples were analyzed for pH, electrical conductivity,
dissolved oxygen and temperature in the field. Water samples for cation analysis were collected
in acid-washed 250 ml high density polyethylene (HDPE) bottles and acidified with concentrated
optima grade nitric-acid. Water samples for dissolved inorganic carbon (DIC) and anions were
collected in 500 ml DI-washed and combusted (475ºC, 4h) amber glass bottles. Before water
collection, all the bottles were rinsed three times with sample water, then filled completely to
eliminate headspace and stored cool (4°C) until laboratory analysis. Water samples from springs
were collected for tritium (3H) analysis in duplicate 500 mL HDPE bottles during low flow
conditions in the fall 2013.

44
Precipitation samples (snow and rainfall) were collected from 2011 to 2013 during the period of
maximum snow accumulation and the monsoon season from July to September. Snow samples
were collected during the winters in 2011 and 2013 from snow pits following the methodology
described in Gustafson et al. [2010], stored in one gallon Ziploc bags, and maintained frozen
until they were allowed to melt overnight at room temperature. Bulk rain water samples were
collected weekly in two DI-washed 500 ml HDPE bottles at multiple elevations around Redondo
Peak (See Figure 2 for locations of precipitation sampling). One 500 ml bottle for stable isotope
analysis contained a thin layer of mineral oil to prevent water loss by evaporation. All the water
samples were filtered promptly with a 0.45 μm nylon filter in the laboratory and splits were sent
to the corresponding laboratories for further analysis. In addition, this study incorporates
precipitation data collected during previous studies around Redondo Peak [Gustafson et al.,
2010; Broxton et al., 2009]
Major cations were measured by inductively coupled plasma mass spectrometry (ICP-
MS) (ELAN DRC-II, Perkin Elmer, Shelton CT) at the University of Arizona Laboratory for
Emerging Contaminants (ALEC). DIC samples were analyzed with a Shimadzu TOC-VCSH
Carbon analyzer (Shimadzu Scientific Instruments, Columbia) in ALEC. All the water samples
were analyzed for δ18O with a DLT-100 Laser Spectrometer for liquid water stable isotopes with
a reported instrument precision of ±0.12 ‰ VSMOW at the University of Arizona. Tritium
samples were analyzed by liquid scintillation counting in a Quantulus 1220 liquid scintillation
counter with a 0.7 TU detection limit following an eightfold electrolytic enrichment at the
University of Arizona Environmental Isotope Laboratory. Water ages were calculated using the
standard tritium decay equation assuming a constant tritium concentration from precipitation
[Stewart et al., 2010]. Eastoe et al. [2012] observed that tritium concentrations in precipitation
45
at Albuquerque station (70 km from field area) have remained stable, around 9.0 TU, since the
early 1990s. A concentration of 8.0 TU was used for age calculations based on a weighted
average of tritium concentrations considering only winter precipitation in the Albuquerque
station since 1990. Tritium concentrations in precipitation at Albuquerque have been measured
since 1962, and the data are available as part of the Global Network of Isotopes in Precipitation
(GNIP) (http://www-naweb.iaea.org/napc/ih/IHS_resources_gnip.html, Accessed January, 2014).
In addition, a quantitative mineralogical analysis was carried out on unweathered
bandelier tuff and rhyolite rock samples. Mineral composition was determined by quantitative x-
ray diffraction on random powder mounts using a PANanalytical X’Pert PRO-MPD x-ray
diffraction system at the Center for Environmental Physics and Mineralogy (CEPM) at the
University of Arizona [Vazquez-Ortega et al., 2015].
The chemical data were used in geochemical models MINTEQA2 and NETPATH to
investigate saturation indices, chemical reactions during mineral weathering, and the mass of
minerals dissolving and precipitating along flow paths. MINTEQA2 is an equilibrium speciation
model that calculates the equilibrium mass distribution among dissolved and adsorbed species
and multiple solid phases [Allison et al., 1991]. NETPATH is a model for simulating net
geochemical reactions and calculating the mass-balance reactions between an initial and final
water along a hydrologic flow path [Plummer et al., 1994]. Precipitation chemistry was
corrected for evaporative concentration of solutes based on the assumption that increases in Cl-
were entirely a result of evapotranspiration [Rademacher et al., 2001; Burns et al., 2003].
Precipitation chemistry, corrected for evapotranspiration, was assumed as the initial pre-
weathering composition and the chemistry from spring discharge was used as the final post-
46
weathering composition. Information on mineral phases and their stoichiometry was based on
rock mineralogical analysis. NETPATH calculates the mass of minerals per kilogram of water
that dissolve or precipitate along the flow path in every possible combination of the selected
phases that accounts for the observed changes in water chemistry [Plummer et al., 1994]. The
chemical evolution and mass balance calculated by NETPATH between an initial and final water
composition is assumed to only occur along flow paths [Plummer et al., 1994; Rademacher et
al., 2001].
Finally, the estimations of EEMT and the aspect and landscape characteristic in each
contributing area of the springs were compared to base cations concentrations and dissolved
inorganic carbon concentrations, WTT, and mineral weathering dissolution measured at the
springs.
3.0 RESULTS
3.1 Landscape characteristics
The selected springs drain different aspects of Redondo Peak at elevations between 2816
and 3170 m. Contributing areas of springs vary in size from 56 to 1038 (x103 m2) and their mean
cosine angle covers a wide range of aspects from -0.5 south to 0.96 north. The mean slope of
contributing areas range between 10 to 20 degrees, and the median water flow path length ranges
from 360 to 600 meters with a median gradient between 0.12 and 0.32 (Table 1).
3.2 EEMT
An annual EEMT map (MJ m-2 year-1) for the entire VCNP is presented in Chorover et
al. [2011; figure 2E]. EEMT values for the Redondo Peak region vary between 22 and 59 MJ m-
47
2
year-1. A visual inspection of the map shows large EEMT values above 30 MJ.m-2.year-1on
Redondo Peak and low EEMT values below 30 MJ m-2 year-1 along shaded areas by topography
such as Redondo Creek in the southwestern part of Redondo. Mean, maximum, and the range of
EEMT (maximum – minimum EEMT) within contributing areas of springs vary from 39 to
43MJ m-2 year-1 , 40 to 50 MJ m-2 year-1 , and 1.8 to 11.4 MJ m-2 year-1 , respectively (Table 1).
The mean aspect of a spring contributing area positively correlates with mean EEMT (R2=0.31;
p>0.1), maximum EEMT (R2=0.90; p<0.0001), and the range of EEMT (R2=0.82; p=0.0007)
(Figure 3). Based on the maximum EEMT versus aspect relationship, north facing slopes receive
up to 25% more EEMT than south facing slopes (Figure 3).
3.3 Water stable isotopes
The stable isotope composition of precipitation exhibits a seasonal pattern with higher
δ18O values during the monsoon season and lower values during the winter. There is an
altitudinal isotopic effect observed in winter precipitation (1‰ decrease/increase in δ18O per
1000 m elevation change), but no corresponding effect observed for summer precipitation
[Broxton et al., 2009; Adams et al., 1995]. The weighted mean and standard deviation of the
δ18O values of the snow and rainfall samples are -15.0±2.5 ‰ and -6.2±2.9 ‰, respectively.
Isotopic variability of the spring waters is considerably more dampened and lies between values
from snow and monsoon rainfall (Table 2). δ18O values from snow, rainfall and springs indicate
that the springs are predominantly recharged by spring snowmelt (Figure 5), which is consistent
with findings from previous research demonstrating that the source of subsurface hydrologic
recharge in the VCNP is snowmelt dominated [Broxton et al., 2009].

48
3.4 Water Chemistry
Spring waters are dominated by Ca2+, Na+, Si and HCO3- ions (Table 2). Dissolved
inorganic carbon (DIC) concentrations strongly correlate with the products of silicate
weathering, including the sum of all base cations (R2=0.92; p<0.0001) and Na+ concentrations
(R2=0.86; p=0.001) (Figure 4a). Figures 4b-d indicate significant correlations between all base
cations and Na+ concentrations versus aspect, maximum and range of EEMT. Na+ is a cation
that is not generally cycle to a great degree biologically and it shows the strongest correlations
with aspect and EEMT. Water with higher concentrations of solutes is found along north facing
slopes (R2=0.56; p<0.05), which are characterized in this study by higher EEMT values
(R2=0.51; p<0.05). Maximum flow path length and contributing area are the only two landscape
characteristics that show statistically significant correlations with both base cations and Na+
concentrations (Figure 4e-f). Larger concentrations of base cations are observed in springs with
longer flow paths (R2=0.54; p<0.05) and larger contributing areas (R2=0.54; p<0.05). As
indicated in Table 3, mean EEMT and other landscape variables, such as mean elevation, mean
slope, median flow path length (L), median flow path slope (G), and L/G are poor predictors of
both base cations and Na+ concentrations.
3.5 Water transit times (WTT)
Tritium concentrations measured at the springs ranged from 5.1 to 7.9 TU (Table 2).
Water apparent age in the springs ranged from 0.2 to 8.1 years (Table 2). Table 3 shows a
significant relation between terrain aspect versus apparent water age (R2=0.74; p<0.01) and
maximum EEMT versus apparent water age (R2=0.61; p<0.01). Water samples in springs with
49
longer WTT based on tritium apparent ages had correspondingly higher Na+ concentrations (p <
0.05, Figure 6).
3.6 Bedrock composition and mass balance analysis
Mineralogical analyses of Redondo Peak bedrock samples indicate predominance of
primary phases sanidine, oligoclase, anorthoclase, and quartz, accompanied by minor minerals,
including apatite, hematite, zircon, titanite, ilmenite, faujasite [Table 4; for detailed mineralogy
see Vazquez-Ortega et al., 2015]. Spring waters are undersaturated with respect to silica, halite,
calcite, gypsum, sanidine and albite, but saturated to supersaturated with respect to secondary
minerals gibbsite, goethite, hematite and kaolinite (Table 5). Saturation index results from
MINTEQA2 were used to select mineral phases for inclusion in NETPATH (sanidine,
oligoclase, anorthoclase, quartz, calcite, kaolinite, gypsum, gibbsite, goethite, albite, biotite,
albite, hornblende, halite and CO2 gas). NETPATH then generated 64 models that produced a
mass balance between the input waters (evaporated snow chemistry) and spring discharge using
the selected phases. Figure 7 shows the mean and standard deviation of the mineral mass balance
from the 64 possible combinations of mineral phases that explain the chemistry observed for two
springs with contrasting aspect. The results from NETPATH are consistent with the results from
MINTEQA2 and indicate for all the springs the same minerals dissolving and precipitating. The
model predicts that gibbsite, goethite, hematite and kaolinite precipitate and all the remaining
minerals dissolve along the hydrologic flow paths. Mineral dissolution calculated using
NETPATH is strongly correlated with aspect and EEMT; the highest mineral weathering
dissolution amounts were observed in springs discharging north-facing aspects (Table 3; Figure
8).
50
4.0 DISCUSSION
This study provides evidence that energy and mass fluxes quantified using EEMT
modeling can predict, at a large scale (~40 km2), measured components of CZ hydrologic and
aqueous geochemical function, such as WTT and incongruent weathering of silicates. The
predictive power of EEMT observed in this study is consistent with previous work that
demonstrated in the western US strong relations between EEMT and Si fluxes from granitoid
watersheds and soil carbon content [Rasmussen et al., 2005]. Around Redondo Peak, Perdrial et
al. [2014] measured higher soluble organic carbon effluxes from catchments draining north-
facing aspects characterized in this study by higher EEMT values. Moreover, along elevation
gradients on different parent materials in the western US, strong correlations were observed
between EEMT and pedogenic indices (pedon depth, total pedon clay content, free Fe oxide to
tal Fe oxide ratio, chemical index of alteration minus potassium of the first subsurface genetic
horizon) [Rasmussen et al., 2011]. In the study by Rasmussen et al., [2011] poor and no
correlations were observed between mean annual temperature and precipitation alone versus
pedogenic indices proving that EEMT is a better predictor than only climatic variables. The
methodology to estimate EEMT based on average climate data as presented in this study and
initially described in Rasmussen et al., [2005] and Rasmussen and Tabor, [2007], was validated
with empirical estimations of EEMT at the catchments scale in 86 catchments in the US,
showing a significant linear correlation between modeled and empirical EEMT values
[Rasmussen and Gallo, 2013].
The results from the current study demonstrate that in a terrain underlain by rhyolite
rocks, higher EEMT is associated with longer WTT and enhanced weathering. Similarly,
51
Broxton et al. [2009] observed longer WTT of surface water along north facing aspects of
Redondo Peak that have been characterized in this study by larger EEMT. Based on water stable
isotopes, the mean and standard deviation of WTT was 123±29 days for streams draining all
aspects of Redondo Peak, with a maximum difference between south and north facing slopes of
50 days [Broxton et al., 2009]. However, stable isotope tracers can only be used to understand
young water systems not older than 5 years [Stewart et al., 2010], therefore this study
complemented previous age dating analysis with tritium. The results of this investigation are
also consistent with laboratory and field studies that have demonstrated that weathering of
silicates increase with WTT [Velbel, 1993; Gabet et al., 2006; Maher, 2010; Maher, 2011; White
et al., 2001; Burns et al., 2003; Rademacher et al., 2001; Rademacher et al., 2005].
This study indicates metrics of mineral weathering are correlated with the range and
maximum values of EEMT distributed over the catchment contributing to spring discharge. The
observation that mean EEMT showed less predictive power is consistent with the concept of sub-
catchment “hot spots” contributing disproportionately to a given catchment discharge. The fact
that EEMT is not uniformly distributed across a catchment, and that it exhibits strong
topographic variation from effects of aspect and topographic convergence of hydrologic flow,
particularly in water limited systems, has led to inclusion of such landscape structural parameters
into more recent versions of the EEMT calculation than the one employed in the current study
[Rasmussen et al., 2015]. Such an approach could be employed in future analyses of comparable
data sets to better resolve why the range and maximum EEMT values are better predictors that
mean values.
52
Base cations and especially Na+ concentrations, around Redondo Peak show strong
correlations with dissolved inorganic carbon and WTT, suggesting they may be used as indirect
tracers of water WTT with significant improvements in spatial and temporal resolutions of WTT.
Saturation indices (SI) prove that Na+ is behaving quite conservatively in this system, therefore
the increase in concentrations with increase in WTT can be attributed to primary mineral
weathering reactions. Chemical formulae of supersaturated secondary phases also indicate that
secondary mineral formation do not provide a sink for Na+, which is also supported by a
previous geochemical study around Redondo, where Na+ was identified as a conservative tracer
and used in an end-member mixing analysis [Liu et al., 2008b]. Liu et al. [2008a; 2008b],
observed that groundwater contributions dominate runoff generation throughout the year around
Redondo Peak, with limited contributions from overland flow and shallow subsurface flow. In
addition, base cations concentrations in surface water draining Redondo Peak exhibit
chemostatic behavior, which suggests a constant source of water supply to surface water, likely
from a well-mixed reservoir [Porter, 2012; Perdrial et al., 2014]. Moreover, dissolved organic
carbon (DOC) concentrations measured in the springs and first order springs are significantly
lower than DOC concentrations from soil waters during baseflow conditions [Porter, 2012;
Perdrial et al., 2014], which supports the hypothesis that groundwater is the dominant source of
water in the Redondo system and base cations in the springs are products of primary mineral
weathering reactions.
The correlations among energy and mass inputs to the CZ (EEMT), WTT, and mineral
weathering products can provide a methodology for indirect estimations of WTT and mineral
weathering products. EEMT estimations based on climatic variables, can be used to scale
hydrological and hydrochemical responses in other sites. Base cations concentrations combined
53
with EEMT maps can provide estimations of WTT at large spatial scales, thus enabling
parameter estimations in hydrological models.
CZ structure influences water movement and solute transport, and an understanding of
CZ heterogeneous structure and organization can contribute to the predictability of hydrological
response, especially in regions with scarce hydrological information [Troch et al., 2008].
Concentrations of solutes in water increase with apparent water age as a result of chemical
weathering [Drever, 1988; Herczeg and Edmunds, 2000]. Major solutes in water are derived
predominantly from water-rock interactions in the unsaturated and saturated zones. In most
hydrological systems solutes concentrations increase as water moves down gradient, therefore
higher concentrations of ions are associated with older waters and hence major ions may be used
as indirect water dating tools [Herczeg and Edmunds, 2000; Rademacher et al., 2001].
Significant work on reactive tracers as indicators of water WTT times has been primarily
conducted in aquifers [Hendry and Schwarts, 1990; Edmunds and Smedley, 2000; Burton et al.,
2002], however, a few studies have successfully demonstrated the evolution of water chemistry
in shallow groundwater and surface water by taking advantage of piezometers and springs for the
application of age tracers: for example in the riparian groundwater in the Panola Mountain
Research Watershed dominated by granitic rocks strong correlations were found between SiO2,
Na+ and Ca2+ and water age [Burns et al., 2003]. In the Sagehen basin in California, which is
dominated by andesite and granodiorite rocks, studies suggest that water ages can be predicted
based on major cation concentrations measured at springs [Rademacher et al., 2001; Rademacher
et al., 2005]. Similarly, in New Zealand in a region comprised of andesitic volcanic ash, good
correlations were observed between mean transit time and silica concentrations in surface water
at the catchment scale [Morgestern et al., 2010].

54
5.0 SUMMARY
Results from this study demonstrate the close interrelationship between landscape,
hydrological and biogeochemical processes. Our study highlights statistically significant
relations between effective energy and mass transfer (EEMT) to the subsurface critical zone,
WTT, and mineral weathering in springs draining catchments along a gradient of energy
controlled by differences in terrain aspect around Redondo Peak, in northern New Mexico.
Spring waters around Redondo Peak are dominated by Ca+, Na+, Si and HCO3- and have an
isotopic signature that indicates they are predominantly derived from infiltration of snowmelt.
Terrain aspect controls EEMT where north facing slopes receive 25% more EEMT than south
facing slopes. Larger concentrations of total base cations and Na+ were observed in springs with
longer flow paths, larger contributing areas, and north facing slopes. This result is consistent
with longer WTT based on tritium analysis of springs draining north-facing terrains. Mineral
dissolution fluxes increase with WTT, likely due to enhanced water-rock reaction, and chemical
weathering consumes more atmospheric CO2 along north facing slopes. This study provides
evidence that fluxes of energy and mass, quantified as EEMT, at the catchment scale can
effectively predict short time-scale (months to years) processes within the CZ structure like WTT
and silicate mineral weathering. These results also suggest that basic climatic data embodied in
the EEMT term can be used to scale hydrological and hydrochemical responses in other sites.
55
6.0 ACKNOWLEDGEMENTS
We are grateful to collaborators Chief Scientist Bob Parmenter and Research Hydrologist Scott
Compton, at the Valles Caldera National Preserve. LiDAR data acquisition and processing were
completed by the National Center for Airborne Laser Mapping (NCALM), funded by the
National Science Foundation Award EAR-0922307, and coordinated by Qinghua Guo for the
Jemez River Basin and Santa Catalina Mountains Critical Zone Observatory funded by the
National Science Foundation Award EAR-0724958. Logistical support and/or data were
provided by the NSF-supported Jemez River Basin and Santa Catalina Mountains Critical Zone
Observatory EAR-0724958 and EAR-1331408). Data access and data sharing policy are
available at the Catalina – Jemez River basin Critical Zone Observatory
http://criticalzone.org/catalina-jemez/data
56
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66
8.0 FIGURES
Figure 1. Conceptualization of dominant critical zone (CZ) processes (after Chorover et al.,
2011 and Rasmussen et al., 2011).
67
Figure 2. a) Location of the research site in northern New Mexico, b) Location of the Valles
Caldera National Preserve within the upper Jemez River Basin, c) Redondo peak and springs
draining different terrain aspects
68
50 12
Range of EEMT (MJ/m year)

Max EEMT (MJ/m year) R2=0.90****
10
48
2
2
8
46
6
44
4
42 2
R2=0.82***
40 0
-1.0 -0.5 0.0 0.5 1.0
cos (aspect)
Max EEMT
Range EEMT
Figure 3. Maximum and range (maximum – minimum) of EETM values versus mean aspect
within springs’ contributing areas. (*** p ≤ 0.001; **** p≤0.0001). There is not a statistically
significant relationship between mean aspect and mean EEMT (R2=0.31; p>0.1)
69
a) b)
600 600
concentration (umol/L)
2 2
R =0.92*** R =0.56*
500 500
400 400
300 300
200
200
100
100
2
R =0.86***
0 2
R =0.71**
0
2 4 6 8 10 12 -1.0 -0.5 0.0 0.5 1.0
DIC (mg/L) cos (aspect)
c) d)
600 600
2 2
R =0.51* R =0.71**
500 500
400 400
300 300
200 200
100 100
2 2
R =0.67** R =0.73**
0 0
40 42 44 46 48 50 0 2 4 6 8 10 12
2 2
Max EEMT (MJ/m year) Range EEMT (MJ/m year)
e) f)
600 600
2 2
R =0.54* R =0.54*
500 500
400 400
300 300
200 200
100 100 2
2
R =0.51* R =0.61**
0 0
500 1000 1500 2000 2500 0 500 1000
2
Max flow length (m) Contributing Area (x 1000 m )
Na
Base cations
70
Figure 4. Concentrations of base cations, Na+ and DIC in spring water versus EEMT and
landscape characteristics. Statistical significance (*p≤0.05; **p≤0.01; *** p ≤ 0.001)
71
3300
3200
Elevation (m)
3100
3000 Mean snow

Mean rainfall
2900 Springs
1St dev snow
2800 1St dev rain
2700
-18 -16 -14 -12 -10 -8 -6 -4
δ18O (‰)
Figure 5. δ18O values of precipitation and springs relative to elevation.

72
10 30 250
2
R =0.56* R2=0.43*
8 25 200
Na (umol/L)
Tritium (TU)
Age (years)
20 150
6
15 100
4
R2=0.61** 10 50
2 5 0
0 0 -50
40 42 44 46 48 50 0 2 4 6 8 10
Max EEMT (MJ/m2 year) Age (years)
Figure 6. Max EEMT versus tritium concentration and apparent age (left). Apparent age versus
Na+ concentrations (right). Statistical significance (*p≤0.05; **p≤0.01)
73
Mineral dissolution / precipitation (millimoles/Kg)

1.0
0.8 UJ2s
Es
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6 +
+
+
+
+
-
+
-
-
+
+
-
+
Hematite
Goethite
Kaolinite
Gibbsite
Hornblende
Anorthoclase
Sanidine
Calcite
Oligocla
Biotite
CO2 gas
Gypsum
Albite
SiO2
NaCl
Figure 7. Mineral dissolution (+) and precipitation (-) for a north aspect draining (UJ2s) and
south aspect draining (Es) spring. Symbols represent mean mineral dissolution and precipitation
and error bars represent 1 standard deviation from 64 mass balance models checked with
NETPATH. The mass balance models determined by NETPATH represent every possible
geochemical mass balance reaction between the initial and final water given a set of chemical
constrains and phases.
74
Anorthoclase (millimoles/kg)
Anorthoclase (millimoles/kg)
0.4 0.4
0.3 R2=0.71** 0.3 2

R =0.76**
0.2 0.2
0.1 0.1
0.0 0.0
-0.1 -0.1
-1.0 -0.5 0.0 0.5 1.0 40 42 44 46 48 50
cosine aspect Max EEMT (MJ/m2 year)
Figure 8. Dissolution of Anothoclase estimated using NETPATH (Plummer et al., 1994) versus
aspect and max EEMT. Statistical significance (**p≤0.01)
75
9.0 TABLES
Table 1. List of springs draining Redondo Peak arranged from low to high elevation. Climate
and landscape characteristics defined in a spring’s contributing area.
Climate controls Landscape controls

Median
flow
Maximum path
cos Mean Max Range contributing Mean flow Median flow gradient
Springs Latitude Longitude aspect EEMT EEMT EEMTǂ Elevation area slope Length length (L)§ (G)§ L/G§
MJ/m2 MJ/m2 MJ/m2

Code degrees degrees (-) year year year (m) (x 103 m2) (degrees) (m) (m) (-) (m)
LJ3s 35.872 -106.529 -0.12 39.72 41.09 2.01 2816 63 16.08 896 462 0.32 1460.6
UR1s 35.882 -106.573 0.72 42.18 46.46 9.65 2842 287 19.94 1862 602 0.17 3489.3
UJ2s 35.896 -106.538 0.96 41.45 48.19 9.43 2848 1038 17.53 1482 474 0.26 1809.9
Es 35.892 -106.511 -0.51 38.89 40.63 2.63 2860 97 13.95 610 361 0.14 2514.6
UJ1s 35.896 -106.546 0.81 41.42 47.64 8.82 2876 69 15.90 851 450 0.28 1595.6
UR2s 35.89 -106.567 0.87 41.43 49.53 11.43 2877 404 17.23 2140 509 0.24 2111.4
HGs 35.889 -106.552 -0.47 40.18 41.19 1.77 2908 232 10.82 992 399 0.13 3056.9
LJ2s 35.877 -106.543 0.27 42.99 45.37 4.53 3070 541 12.78 1922 549 0.12 4498.0
LJ1s 35.881 -106.549 0.06 43.08 44.27 1.93 3170 56 13.66 766 510 0.18 2822.3
Note:
ǂRange EEMT: Max-Min EEMT
§According to McGuire et al., 2005
Table 2. Chemical composition of precipitation and springs . Weighted mean; standard deviation in parenthesis
Water number Temp. EC pH DIC Ca2+ Na+ Mg2+ K+ Si Cl- NO3- SO4- δ18O Tritium Age
samples
code samples (˚C) (μS/cm) ------------------------------(umol/L)--------------------------------- ‰ TU Years
snow 40 - - 5.69 0.09 <5.0 2.43 1.54 <5.0 2.8 18.8 16.5 8.7 -15.0
(0.1) (3.4) (1.1) (5.4) (16.2) (31.9) (13.8) (2.50)*
rainfall 60 - - 6.32 0.19 10.0 4.99 3.0 < 5.0 2.3 14.6 12.4 8.2 -6.2
(0.2) (13.5) (4.5) (3.4) (3.4) (15.8) (9.78) (8.0) (2.90)*
Es 5 13.1 47.6 6.5 0.3 155.2 89.6 23.0 30.3 449.8 37.2 51.9 50.9 -12.7 7.9 0.2
(3.9) (1.6) (0.03) (23.5) (3.2) (2.0) (23.0) (172.2) (12.1) (23.8) (7.5) (0.03) ±0.39 ±0.9
HGs 9 10.6 37.7 6.2 0.33 139.2 109.6 32.5 17.4 447.6 34.1 38.6 50.4 -12.8 6.0 5.1
(3.9) (16.6) (0.03) (50.6) (13.9) (5.4) (14.1) (229.8) (10.6) (17.7) (16.8) (0.21) ±0.43 ±1.3
LJ1s 7 9.6 52.3 6.9 0.3 111.7 85.4 22.0 43.7 431.9 33.2 5.8 41.4 -13.1 5.6 6.4
(3.1) (9.6) (0.13) (27.1) (10.8) ( 7.1) (20.7) (73.7) (20.2) (0.8) (30.4) (0.51) ±0.39 ±1.3
LJ2s 14 7.7 60.9 7.4 0.36 139.4 139.3 19.9 23.8 276.4 20.0 14.8 25.0 -13.2 5.7 6.1
(0.9) (11.7) (0.07) (32.0) (13.9) (4.9) (24.2) (145.3) (18.5) (5.3) (3.0) (0.10) ±0.42 ±1.4
LJ3s 13 5.6 38.1 6.6 0.38 144.9 122.4 24.6 21.8 371.3 17.6 20.4 36.4 -12.8 6.2 4.6
(0.6) (9.0) (0.1) (46.6) (7.1) (7.9) (10.4) (186.4) (6.8) (10.9) (19.6) (0.16) ±0.37 ±1.1
UJ1s 5 9.8 56.2 6.5 0.41 135.7 143.8 20.2 9.7 237.8 19.8 42.3 33.0 -12.5 5.6 6.4
(3.0) (9.8) (0.11) (21.1) (12.4) (2.1) (4.8) (95.1) (4.9) (15.9) (13.4) (0.06) ±0.43 ±1.4
UJ2s 8 7.1 78.8 7.1 0.59 226.9 212.1 45.9 16.3 473.2 19.6 20.0 57.7 -12.9 5.4 7.0
(0.4) (5.5) (0.05) (71.3) (21.4) (4.9) (11.4) (140.2) (3.4) (6.3) (28.0) (0.03) ±0.38 ±1.3
UR1s 6 11.5 62.6 6.4 0.55 232.3 148.1 28.4 13.0 232.1 22.7 12.0 30.9 -12.4 5.9 5.5
(7.4) (6.2) (0.12) (35.5) (15.0) (6.7) (9.3) (164.4) (21.6) (4.7) (7.1) (0.07) ±0.41 ±1.7
UR2s 7 12.4 60.6 6.6 0.65 193.9 197.6 18.6 13.7 296.4 12.8 35.2 29.0 -12.1 5.1 8.1
(2.3) (7.3) (0.26) (35.1) (38.9) (6.9) (14.3) (170.3) (4.2) (17.7) (13.0) (0.16) ±0.40 ±1.5
* Including data from Broxton et al., 2009 and Gustafson et al., 2010
76
77
Table 3. Linear regression between climate / landscape variables and solutes, mineral dissolution
and water age
Base Water
HCO3 Na+ Cations Anorthoclaseǂ age
(umol/L) (umol/L) (umol/L) (mmol/L) (years)
--------------------R2----------------------
Cosine aspect (-) 0.71** 0.71** 0.56* 0.71** 0.74**

CLIMATE
Max EEMT (MJ/m2) 0.67** 0.67** 0.51* 0.76*** 0.78***
Range EEMT (MJ/m2) 0.82*** 0.73** 0.71** 0.85*** 0.45*
Mean EEMT (MJ/m2) 0.04 0.04 0.03 0.10 0.49*

Mean Elevation (m) 0.18 0.16 0.22 0.10 0.06
Contributing Area (m2) 0.38 0.61* 0.54* 0.27 0.19
LANDSCAPE
Mean slope (degrees) 0.59* 0.37 0.56* 0.42 0.21

Max flow path length (m) 0.57* 0.51* 0.54* 0.69** 0.38
Median flow path length (L) (m) 0.24 0.13 0.18 0.25 0.47*
Median flow path slope (G) (-) 0.17 0.19 0.08 0.11 0.15
L/G (m) 0.05 0.06 0.02 0.02 0.00
Notes
ǂ Same R2 and p values were found for sanidine and oligoclase
§According to McGuire et al., 2005
Statistical significance
‘* P ≤ 0.05
** P ≤ 0.01
*** P ≤ 0.001
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Table 4. Chemical composition of the most abundant minerals in the Valles

Caldera rhyolite (see Vazquez-Ortega et al., 2015, for details).
Rhyolite Chemical formula
Sanidine K0.36 Na0.54 Al1.02 Si2.99O8
Anorthoclase Na0.70 K0.23 Al1.05 Si2.94 O8
Oligoclase Na0.69 Ca0.24 Al1.23 Si2.76 O8
Quartz SiO2
Minor minerals Apatite, Hematite, Zircon, Titanite, Ilmenite, Faujasite

79
Table 5. Mineral saturation index log [IAP/Kso] estimated with MINTEQA2
Spring code UR1s UR2s UJ1 UJ2s Es LJ1s LJ2s LJ4s HGs
Sample ID Log Kǂ NMS1234 NMS1235 NMS1237 NMS1236 NMS1240 NMS1230 NMS1229 NMS1238 NMS1241
SiO2 -2.71 -0.55 -0.61 -0.64 -0.52 -0.65 -0.43 -0.62 -0.66 -0.39
GIBBSITE 8.77 1.98 0.44 1.79 0.35 0.71 1.33 0.27 0.66 0.35
GOETHITE 0.50 4.94 4.75 4.19 5.21 4.40 5.15 4.65 3.74 4.02
HEMATITE -4.00 12.19 11.82 10.69 12.73 11.11 12.61 11.61 9.78 10.36
NaCl 1.58 -10.29 -10.34 -10.17 -9.98 -9.89 -10.24 -10.23 -9.97 -10.08
CALCITE -8.48 -1.89 -2.11 -2.85 -1.56 -2.50 -1.70 -2.12 -2.08 -2.49
GYPSUM -4.85 -3.70 -3.89 -3.92 -3.06 -3.48 -3.07 -3.86 -3.24 -3.35
KAOLINITE 5.73 6.66 3.53 6.11 3.54 4.62 5.69 3.18 3.91 3.82
SANIDINE 1.06 -128.24 -117.43 -128.38 -131.30 -128.80 -129.65 -133.14 -140.43 -130.94
ALBITE 2.59 -85.35 -79.77 -84.70 -87.60 -85.64 -86.57 -89.02 -92.52 -86.92
ǂ MINTEQ database
Note: Mineral reactions

SiO2SiO2 + 2H2O = H4SiO4
Gibbsite
Al(OH)3 + 3H+ = Al+3 + 3H2O
Goethite
FeOOH + 3H+ = Fe+3 + 2H2O
Hematite
Fe2O3 + 6H+ = 2Fe+3 + 3H2O
NaCl
NaCl = Na+ + Cl-
Calcite
CaCO3 = Ca+2 + CO3-2
Gypsum
CaSO4:2H2O = Ca+2 + SO4-2 + 2H2O
Kaolinite
Al2Si2O5(OH)4 + 6H+ = 2Al+3 + 2H4SiO4 + H2O
Sanidine
KAlSi3O8 + 4H2O + H+ = Al3+ K+ + 3H4SiO4
Albite
NaAlSi3O8 + 4H+ + 4H2O = Na+ + Al+3 + 3H4SiO4
80
APPENDIX B:
INFLUENCE OF TERRAIN ASPECT ON WATER PARTITIONING, VEGETATION

STRUCTURE, AND VEGETATION GREENING IN HIGH ELEVATION CATCHMENTS IN
NORTHERN NEW MEXICO
Manuscript to be submitted to the journal of ecohydrology
Authors:
Xavier Zapata-Rios1*, Peter A. Troch1, Paul D. Brooks2, 1, Jennifer McIntosh1, Qinghua Guo3
1. Department of Hydrology and Water Resources, University of Arizona, Tucson, Arizona,
USA
3. Sierra Nevada Research Institute, University of California Merced, Merced, California,
USA
81
ABSTRACT
We investigated vegetation structure, water partitioning dynamics and vegetation greening from
2000 through 2012 in three catchments draining north and east aspects of Redondo Peak in
northern New Mexico. Vegetation structure was quantified from 1 m LiDAR data while
vegetation greening was quantified using remotely sensed NDVI. Hydrological partitioning at
the catchment scale was estimated with a metric of catchment-scale water fluxes and vegetation
water use (Horton index; HI). The predominantly north facing catchment, when compared to the
other two eastern catchments, receives less solar radiation, and exhibits less forest cover and
smaller biomass, has more surface runoff (~15% of P) as a consequence of a smaller
vaporization (85% of P) and smaller vegetation water consumption (HI=0.85). Moreover, the
north facing catchment showed smaller peak NDVI values (5.98) and shorter growing season
length (76.3 days) as a consequence of energy limitation. In contrast, the two eastern catchments
receive larger solar radiation, have more biomass and forest cover (>76%), and smaller surface
runoff (<10% P), higher vaporization (>90%P) and vegetation water consumption (HI=0.95).
The eastern catchments had larger vegetation greening (6.28-6.58) and a longer growing season
(113-156 days). Snowpack conditions, such as maximum SWE and duration of the snow on the
ground, explain over 95% of water partitioning (HI) that in turn influenced annual vegetation
greening (R2=0.48 - 0.67; p<0.05). This catchment scale study in perennial streams indicates that
terrain aspect at a similar altitude (2700 – 3435m) strongly controls energy, water distribution,
and vegetation productivity in high elevation ecosystems.

82
KEY WORDS:
Aspect, vegetation structure, hydrological partitioning, Horton index, NDVI, mountain
catchments, critical zone, New Mexico

83
1.0 INTRODUCTION
In mid and high latitude regions, the orientation of the land surface, referred to as terrain aspect,
controls the partitioning of energy and precipitation, influencing microclimate, vegetation
characteristics and water flow paths [Broxton et al., 2009; Gutierrez-Jurado et al., 2013; Desta et
al., 2004; Newman et al., 2006]. Energy and water availability controlled by aspect differences
has been proposed as an important regulator of plant microhabitats that in turn influence growth
and production of plants in terrestrial ecosystems, particularly in semi-arid regions [Lieth, 1975;
Webb et al., 1986; Noy-Meir, 1973; Wilkinson and Humphreys, 2006; Hinckley et al., 2012].
Aspect influences hydrologic processes occurring above the land surface, such as snow
accumulation, snowmelt, sublimation, soil moisture and evapotranspiration [Musselman et al.,
2008; Veatch et al., 2009; Gustaffson et al., 2010; Molotch et al., 2009; McDowell et al., 2007;
Small and McConnell, 2008; Vivoni et al., 2008; Rinehart et al. 2008; Harpold et al. 2014]. Past
research on the role of aspect on subsurface hydrologic processes showed that terrain orientation
influences soil moisture content, soil water retention capacity [Geroy, 2011], hydraulic
conductivity [Casanova et al., 2000] and water movement in hillslopes [Hinckley et al., 2012].
Similarly, in our study site, at Redondo Peak located in northern New Mexico, aspect
influences energy, water availability, biogeochemistry and soil development [Lyon et al., 2008;
Broxton et al., 2009; Perdrial et al., 2014; Zapata-Rios et al., in review]. North facing slopes at
this site have delayed snowmelt, more water availability in streams [Lyon et al., 2008], longer
water residence times and larger mineral weathering dissolution rates [Broxton et al., 2009;
Zapata-Rios et al., in review], larger dissolved inorganic and dissolved organic carbon
concentrations [Perdrial et al., 2014].

84
The investigations relating aspect, vegetation, and hydrological feedbacks have primarily
concentrated on plots, slope transects and small scale drainages [Gutierrez-Jurado et al., 2006;
Gutierrez-Jurado et al., 2013; Hinckley et al., 2012; Desta et al., 2004], while the effects of aspect
on vegetation and hydrological partitioning in perennial streams at the catchment scale remains
less understood [Newman et al., 2006]. Understanding the feedbacks between water and vegetation
in mountainous semiarid catchments can help improve climate change predictions and associated
hydrologic and ecologic shifts [Newman et al., 2006; Molotch et al., 2009; Vivoni et al., 2012].
Furthermore, field studies along landscape gradients may provide insight on the relationship
among topography, vegetation, and water [Kelly and Goulden, 2008; Newman et al., 2006;
Chorover et al., 2011]. This comparison of ecosystems across environmental gradients can inform
us how climate shapes ecosystems over long time scales, which in turn may help in predicting
future changes in climate and land cover [Anderson-Teixeira et al., 2011; Chorover et al., 2011].
The Santa Catalina Mountains-Jemez River Basin (SCM-JRB) critical zone observatory
(CZO) has established a research site in northern New Mexico within the Valles Caldera National
Preserve (VCNP) to study critical zone development and processes along an energy gradient
created by differences in terrain aspect [Chorover et al., 2011] (http://criticalzone.org/catalina-
jemez/). It has been posited by researchers of this observatory that water availability and reduced
carbon compounds resulting from primary production are the dominant energy fluxes that drive
critical zone development and function [Chorover et al., 2011; Rasmussen et al., 2011].
Vegetation and water availability are primary controls on ecosystems structure [Brooks and
Vivoni, 2008], therefore, it is important to study and understand their role within the critical zone.
The objective of this study is to investigate how terrain aspect influences vegetation structure, the
dynamics of hydrological partitioning, and vegetation greening in three high elevation semi-arid
85
catchments using direct and remote sensing observations. A uniform geology and relief around
Redondo Peak, located in the center of the VCNP, make this site an ideal location to empirically
study how topographically controlled microclimate [Lyon et al., 2008; Chorover et al., 2011]
influences the integrated vegetation and hydrological response.
2.0 METHODOLOGY
2.1 Study area
The Valles Caldera National Preserve (VCNP) (35°50’-36°00’ N; 106°24’-106°37’W)
encompasses 359 km2 and is located within the upper part of the Jemez River Basin, a tributary of
the Rio Grande (Figure 1a; 1b). The VCNP encloses a nearly circular caldera that is approximately
21 km in diameter and was formed by the collapse of a magma chamber, around 1.25 Ma. After
the caldera’s formation, there were subsequent episodes of volcanism, resulting in the creation of
a number of internal domes, including Redondo Peak (3435 m.a.sl) [Wolff et al., 2011]. The
geology of Redondo Peak is dominated by densely welded Bandelier Tuff (Tshrige Member) and
associate rhyolite/rhyodacite rocks [Goff et al., 2006; Wolff et al., 2011]. Redondo Peak is located
approximately in the center of the caldera and headwater streams flow along the different sides of
the mountain (Figure 1c). This natural drainage configuration has created catchments with a
similar geology [Goff et al., 2006] and relief, but with different terrain aspect affecting wind
exposure, radiation, and snow cover duration [Lyon et al., 2008].
The climate is semi-arid, continental and highly variable [Sheppard et al., 2002]. The area
is characterized by warm summers and cold winters. The long-term monitoring SNOwpack
TELemetry (SNOTEL) station Quemazon (35°55’ N; 106°24’ W; 2896 m.a.s.l), which is located
5 km to the northeast from Redondo Peak, has been recording climatic variables since 1989. The
86
mean temperature from 1989 through 2012 was -0.87 °C during winter (October – April) and 11.2
°C during summer months (May-September). The minimum temperature occurs between
December-January and the maximum temperature between June-July, with recorded extreme
values of -20°C and 25°C, respectively. The study area has a bimodal precipitation pattern; it
accumulates an annual winter snowpack between December and April, while the North American
monsoon brings high intensity, short duration rainfall between July and September. The annual
precipitation at the Quemazon station from 1989 through 2012 ranged from 322 and 1021 mm,
with a mean value of 708 mm. Fifty percent of the total annual precipitation occurs during winter
(October-April) and 80% of the winter annual precipitation falls as snow. Most winter precipitation
is caused by frontal activity from the west due to Pacific Ocean storms. The summer monsoon
originates by weak southeasterly flow from the Gulf of Mexico and short high intensity surges
from the Gulf of California and the eastern Pacific Ocean [Sheppard et al., 2002].
Based on information available at the USDA National Cooperative Soil Survey
(http://websoilsurvey.nrcs.usda.gov/app/HomePage.htm), the soil around Redondo Peak is mostly
derived from tuff as colluvium material. The upper elevations have soils with a coarse sandy loam
and cobbly loam texture. In the eastern and lower part of Redondo, loamy soils and cobbly coarse
sandy loam textures predominate. The northern lower part of Redondo is characterized by fine
textures and slightly decomposed plant material.
The prevalent vegetation types around Redondo Peak are spruce-fir forest, mixed conifer
forest, woodland, and forest meadow. Spruce-fir forest extends in elevation typically between 2900
and 3430 m. Engelmann spruce (Picea engelmannii) and corkbark fir (A. lasiocarpa var. arizonica
) occupy the highest elevations and north-facing slopes above 2700m. Mixed conifer forest occurs
87
in elevation between 2540 to 3050 m. Forest meadow land cover elevation ranges from 2560 to
3175 m and it is composed by grasslands. The primary grasslands components are Thurber fescue-
Kentucky bluegrass and Arizona fescue-Kentucky bluegrass [Muldavin and Tonne, 2003]. No
forest disturbances by logging and fire took place around Redondo Peak in the last four decades
preceding and including this study [Anderson-Teixeira et al., 2011; Balmat, 2004].
2.2 Catchment characteristics
This investigation focuses on three catchments with perennial streams: La Jara (LJ),
History Grove (HG) and Upper Jaramillo (UJ) (Figure 1c). The three catchments together cover
approximately an area of 10 km2. Topographic characteristics of the catchments were defined
using a 722 km2 airborne LiDAR flight coverage (Figure 1c). LiDAR data acquisition (July
2010) and processing were completed by the National Center for Airborne Laser Mapping
(NCALM). The LiDAR coverage has on average a 9.68 point density per m2 and 30 cm vertical
and 20 cm horizontal RMSE resolution. Catchment and stream network delineation and terrain
attributes such as area, slope and predominant aspect were defined using the catchment
delineation procedures from the spatial analysis tools in ArcGIS 10.1. The amount of annual
solar radiation in the catchments was quantified using the solar radiation analysis tools in
ArcGIS 10.1.
2.3 Vegetation characteristics

Land cover classes within the three catchments were estimated using a vegetation map of
the VCNP developed by Muldavin et al. [2006], which is based on an analysis of aerial
photography from the year 2000, Landsat satellite images from 1999 and 2001, and ground control
points. Indicators of vegetation structure were defined using the LiDAR data with 1.0 m
88
resolution. Mean tree height, diameter at breast height (DBH), fractional canopy cover, and leaf
area index (LAI) products were created using a regression analysis [Andersen et al., 2005]. This
methodology extracts a subset of LiDAR points that were normalized by subtracting the ground
points from a digital elevation model (DEM). A height profile was calculated on the normalized
points according to the following groups: minimum, maximum, mean, standard deviations,
coefficient of variation and the percentiles (1st, 5th, 10th, 25th, 50th, 75th, 90th, 95th, 99th). The LiDAR
derived height predictors were compared against field measurements by stepwise regression
[Andersen et al., 2005]. The best models were selected and applied to the entire Redondo Peak
area. This process was accomplished by iterating through each pixel of the product grid, extracting
LiDAR points that fall within that pixel and calculating the pixel value using the relation found in
the previously mentioned analysis.
Fractional canopy cover (CC) was determined by analyzing the canopy height model
(CHM) at 1 m spatial resolution. The value of the canopy cover pixel was calculated as the ratio
of CHM pixels that have a value above a threshold to the total number of extracted pixels from the
CHM [Lucas et al., 2006]. The difference between trees and shrubs was defined by a height
threshold of 1.5 m. Each pixel in the canopy cover grid was iterated and CHM pixel values were
extracted when they fall within the canopy cover pixel. Leaf area index (LAI) was determined
using the LiDAR vegetation points after being normalized by the DEM. Each pixel in the LAI grid
was iterated and LiDAR points that fell within the pixel were extracted. An average scan angle
was calculated using the extracted LiDAR points as indicated in the following equation:

n
anglei
ang  i 1
n (1)
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where ang is the average scan angle, n is the number of extracted points and 𝑎𝑛𝑔𝑙𝑒(𝑖) is the scan
angle for a single extracted point i. The gap fraction (GF) was calculated using the following
equation:
n ground
GF 
n (2)
Where nground is the number of extracted points for z values smaller than 1.5 m (equivalent to the
height of a hemispherical camera) and n is the total number of extracted points. Finally, the LAI
was calculated using the following equation:
cos(ang)  ln(GF )
LAI  
k (3)
where 𝑘 is the extinction coefficient and assumed equal to 0.5 [Morsdorf et al. 2006; Richardson
et al., 2009]. The vegetation products were extracted at the catchment scale and mean and
standard deviation values were computed. Differences in vegetation structure in the catchments
were tested with both a Mann-Whitney U test and pair t test.
2.4 Water partitioning and vegetation greening
The water partitioning and vegetation greening analysis for the three catchments around
Redondo Peak was developed using a three step process. First, the Horton index as a metric of
catchment scale water fluxes and vegetation water use was calculated for the water years 2008 to
2012 as discharge data was available for this period only. Second, vegetation greening was
analyzed using the available MODIS NDVI data from 2000 to 2012. As water partitioning
information was available for the years 2008 onwards only, single and multivariate linear
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regression analysis were estimated with the objective of finding a statistical model to extend
Horton index records back to 2000. Finally, once the best statistical model was selected, Horton
index was extrapolated back to 2000 resulting in a dataset that matches the 13 year records of
NDVI.
2.4.1 Water partitioning
2.4. 1.1 Precipitation

Five automatic weather stations have been in operation since 2004 as part of the VCNP
monitoring network (http://www.wrcc.dri.edu/vallescaldera/). The five stations are spread out
within the VCNP and are located at elevations between 2598m and 3232m (Table S1). The
stations record weather conditions, including atmospheric pressure, temperature, wind speed,
relative humidity, precipitation and solar radiation. Each station is controlled by a Campbell
Scientific CR1000 data logger and information from the sensors are summarized in 10 minutes
intervals. In addition, an eddy covariance flux tower has been operating within the study area
since 2005 and is part of New Mexico Upland Flux Network
(http://biology.unm.edu/Litvak/Upland.html). The tower was set up by the NSF Science and
Technology Center for the Sustainability of Semi-arid Hydrology (SAHRA). The tower site
(VCM; 35° 53.3’ N;106° 31.9’W; 3003 m.a.s.l) is located in the upper part of Redondo Peak
surrounded by Douglas and white fir, blue spruce and southwestern white pine (Figure 1c). The
eddy covariance derived surface fluxes of water and energy were measured at 10 Hz using a 3-
axis sonic anemometer (CSAT-3, Campbell Scientific, Logan, UT, USA) and an open path
infrared gas analyzer (Li-7500, LiCor Biosciences; Lincoln, NE, USA). 1998). At this site,
precipitation is measured by way of a TE525 Texas electronics 6” tipping bucket rain gauge.
Precipitation was distributed at the catchment scale using an elevation lapse rate during the
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winter months [Gustafson et al. 2010] and an average precipitation from all the stations during
the summer. The lapse rate was evaluated with the observed annual precipitation at the eddy
covariance VCM flux tower with an error not larger than 6% on an annual time scale.
2.4.1.2 Streamflow
From 2008 to 2012, streamflow was monitored at the outlets of each catchment (LJ -
2702 m; HG - 2681 m; and UJ - 2723 m) using pressure measurements recorded every 15
minutes with Onset HOBO U20 and In Situ Level TROLL 500 15 psig pressure transducers in
45° trapezoidal flumes. Since the HOBO U20 instruments are non-vented to the atmosphere, the
pressure from these sensors was corrected with atmospheric pressure recorded at the flume sites.
The corrected pressures were then transformed into water heights and streamflow by way of
standard equations for 45° trapezoidal flumes. The automatic readings by the pressure
transducers were validated by manual measurements taken at the flumes. Daily discharge was
then calculated and normalized by basin area.
2.4.1.3 Hydrological partitioning and Horton index
Catchment scale hydrological partitioning was calculated following the Horton index
methodology from 2008-2012 [Troch et al., 2009; Brooks et al., 2011]. The Horton index is a
dimensionless metric of water partitioning at the catchment scale that reflects the influences of
both topography and vegetation and ranges from 0 to 1 [Voepel et al., 2011]. The Horton index
is defined as the ratio between V and W, and it represents a measure of catchment-scale
vegetation water use [Horton, 1933; Troch et al., 2009] (equation 4).
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𝑉 𝑃−𝑄
𝐻𝐼 = = (4)
𝑊 𝑃−𝑆
Water partitioning at the catchment scale was based on the analysis of precipitation (P)
and discharge (Q). Precipitation was partitioned between storm runoff (S) and catchment wetting
(W). W represents the fraction of precipitation potentially available for vegetation and was
calculated as precipitation minus storm runoff (P-S). S was computed by way of a baseflow
separation method. Daily stream flow records were partitioned into base flow (U) and storm flow
(S) using a one-parameter recursive filter [Lyne and Hollick, 1979; Arnold and Allen, 1999;
Eckhardt, 2005]:
1−𝑎
𝑈𝑘 = 𝑎𝑈𝑘−1 + (𝑄𝑘 − 𝑄𝑘−1 ) (5)
2
𝑈𝑘 ≤ 𝑄𝑘
Where a is a filter parameter set to 0.925. This filter was passed twice, backward and forward in
time, to improve the partitioning of base flow and storm runoff at the beginning of the time
series. Then, daily values of streamflow, baseflow and storm runoff were integrated to an annual
time scales. Catchment wetting was further partitioned between vaporization and a base flow
component. Vaporization (V) at the catchment scale was calculated as precipitation minus
discharge (P-Q). The hydrological partitioning analysis was quantified on an annual scale to
minimize changes in catchment water storage. Troch et al. [2009] showed that the methodology
to separate baseflow from storm runoff plays little influence in the computation of the Horton
index. For further details about the Horton index development see Troch et al. [2009].
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2.4.2 Vegetation greening
The normalized difference vegetation index (NDVI), a remote sensing measurement of
vegetation greenness [Reed et al., 1994], was used as an indicator of vegetation productivity and
for the quantification of the interannual and inter-catchment vegetation response. NDVI is a
vegetation index independent of any hydrological partitioning variable considered in this study
and is widely used for monitoring vegetation conditions, global and regional climate, and
modeling global biogeochemical and hydrological processes [Reed et al., 1994; Van Leeuwen et
al., 2006; Hashimoto et al., 2012]. NDVI was extracted from NASA’s Moderate Resolution
Imaging Spectroradiometer (MODIS) Land Products MOD13Q1 and available through the Land
Processes Distributed Active Archive Center (LP DAAC) (https://lpdaac.usgs.gov/products/).
The global MOD13Q1 NDVI data is provided every 16 days at a 250-meter spatial resolution.
An average NDVI value was calculated for each catchment based on each individual NDVI
image. In the NDVI images, pixels with clouds and snow were not considered for the analysis
and only pixels cataloged in the quality layer with good reliability were included.
A multi-temporal NDVI profile (catchment scale NDVI versus time) was created for each
catchment from 2000 to 2012 [Reed et al., 1994]. Two metrics were selected for the
quantification of the vegetation response and length of the growing season [Reed et al., 1994]. A
time integrated NDVI response per catchment was selected as an indicator of vegetation
productivity [Reed et al., 1994]. The time integrated NDVI response was defined as the area
under the NDVI curve between the end of the snowmelt season and end of the growing season,
between April and September each year (Figure S1). The mean annual NDVI of the three
catchments was close to 0.6 and NDVI values above the mean were observed every year during
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the growing season between April and September. Therefore 0.6 was selected as a signal of the
onset of an increase in photosynthetic activity [Reed et al., 1994]. The number of days when the
catchment scale NDVI value exceeds 0.6 was used as indicator of growing season length.
Statistically significant differences between the NDVI time series from the three catchments
were examined with the Mann-Whitney U test.
2.4.3 Climate controls on Horton index
Single and multivariate regression were used to investigate the climate controls on
Horton index using data from 2008 to 2012. The climate variables from the Quemazon SNOTEL
considered in the regression analyses were total annual precipitation, summer and winter
precipitation, maximum SWE, timing of initial snow cover, timing of snow melt, duration of
snow accumulation and snow cover, total annual, winter and summer temperatures. Previous
research has demonstrated that Horton index values vary predictably in a catchment due to
climate and landscape and therefore can be predicted based on these variables [Troch et al.,
2009; Voepel et al., 2011).Therefore using the best fitted regression model with climate
variables, Horton index values were extrapolated back to the year 2000. Climate controls using
the above mentioned variables were also tested against NDVI data.
3.0 RESULTS
3.1 Catchment characteristics
The three catchments are located above 2680 m in elevation. LJ is the highest elevation
catchment with the largest area and steepest slope (Table 1). HG and UJ share similar
elevations, catchment size, and slope. The catchments are characterized by differences in terrain
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aspect, and 58% of UJ area has a predominant northern aspect. In contrast, in HG and LJ 59%
and 70 % of their surface area drain to the east (Figure 1c). Aspect differences are reflected in
the total annual incoming solar radiation, where the east facing catchments (LJ and HG) received
approximately 30% more solar energy than the north facing catchment (UJ) (Table 1).
3.2 Vegetation classification and structure
According to land use classification by Muldavin et al. [2006] the catchments are
predominantly covered by evergreen forest, with an extension of 81% in LJ, 76% in HG and
74% in UJ (Table 2). Mean tree height (m) is larger in LJ (15.0 m), followed by HG (14.7 m)
and UJ (12.2 m). Similarly, DBH (cm) is larger in trees located in the eastern catchments (LJ
and HG) with a mean value of 31.3 cm versus 27.4 cm for UJ. In the same way, fractional
canopy cover is larger in the eastern catchments with values of 0.71 and 0.66 (LJ and HG) and
0.57 in the northern catchment (UJ). Mean LAI is 1.41, 1.26 and 1.03 for LJ, HG and UJ,
respectively (Figure 2). The land cover classification and the vegetation structure indicators
derived from LiDAR indicate that the north facing catchment (UJ) has less above ground
biomass than the southeastern catchments (LJ and HG) (Figure 2).
3.3 Water partitioning
3.3.1 Precipitation
During the study period (2008-2012), the three catchments received varying amounts of
annual precipitation. The years 2008, 2009, and 2012 registered catchment scale precipitation
values above the 31-years mean annual precipitation at the Quemazon SNOTEL station (708
mm). In contrast, precipitation during 2009 and 2010 was below the mean annual precipitation
96
recorded at the Quemazon SNOTEL station. Precipitation in LJ was the largest, followed by HG
and UJ with nearly similar annual precipitation values (Figure 3a). LJ is characterized by a
highest terrain elevation and received approximately 50 mm more precipitation than the other
catchments during the winter season (Figure 3b). During the summer monsoon season, the three
catchments received similar precipitation (Figure 3c).
3.3.2 Streamflow response
The study catchments are snowmelt dominated with hydrographs characterized by a
significant increase in runoff during spring, reaching a peak at the end of March and beginning
of April, and followed by a steady discharge recession that continues until the following spring
snowmelt onset. Sporadic increases in discharge occur between July and September as a result
of heavy rainfall events during the monsoon season. For the rest of the year, daily runoff for the
three catchments is characterized by low flow conditions, the 75th percentile do not exceed a
discharge of 0.23 mm/day in the three catchments (Figure S2). During the study period, total
annual discharge was strongly correlated to max SWE and the duration of snow on the ground
measured at the Quemazon SNOTEL station (R2>0.95; p<0.05) (Table S2). Other snow
parameters such as timing of initial snow cover, peak of SWE, timing of melt, average air winter
temperature [Harpold et al., 2012] were also tested as controls on discharge, however they did
not show strong relationships with catchment scale discharge in the multivariate regression
analysis. Indicators of magnitude (peak flow and mean discharge) and timing of discharge (day
of the water year = DOWY peak flow occurs) show that discharge measured in the north facing
catchment (UJ) was the largest and least variable relative to the discharge in the other sites (LJ
and HG) (Table 3). In average mean total annual discharge in UJ is 63% and 39% higher than LJ
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and HG, respectively (Figure 3d). During the five years, discharge on average in UJ represented
15%, in HG 11% and LJ 8% of total annual precipitation. With the exception of the wettest year
(2010), peak flow in the northern catchment (UJ) occurred later than in the eastern catchments
(LJ and HG) (Table 3). Runoff ratio, computed annually as the ratio between discharge to
precipitation, was consistently larger in UJ during the five years of analysis. Runoff ratios ranged
between 0.08 for the eastern catchments and 0.14 for the northern catchment and they were
strongly related to maximum SWE (Figure 3e).
3.3.3 Base flow and storm runoff
Base flow was the largest and dominant component of discharge representing over 90%
of the total discharge in the three catchments. However, the north facing catchment (UJ) showed
consistently the largest and least variable base flow during the study period. Storm runoff
represented less than 10% of annual discharge in all the catchments and once again the north
facing catchment (UJ) consistently had larger and less variable storm runoff compared to the
other two catchments. The ratio between storm runoff to base flow for all the catchments was
more similar during wet years, while the largest differences in this ratio were observed during the
relatively dry years of 2011 and 2012 (Figure 3f). Base flow, storm runoff, and discharge were
the water partitioning components with the largest variability in all of the three sites.
3.3.4 Vaporization and wetting
The fraction of precipitation (P) that infiltrates and it is potentially availably for
vegetation (W) was very high and above 98% of P in all the catchments. A large portion of W
was lost by vaporization (Figure 3g). On average vaporization represented 92% from the total
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annual precipitation in LJ, 91% in HG and 85% in UJ. Water loss by vaporization was smaller in
the north facing catchment (UJ) than in the eastern catchments (LJ and HG). A summary of all
the water partitioning components during the study period for the three catchments can be found
in table S3.
3.4 Vegetation greening
The catchment’s NDVI time series from 2000 to 2012 were statistically different with p
values < 0.02. Mean NDVI at the catchment scale for the 12 years was 0.59, 0.58 and 0.56 for LJ,
HG and UJ, respectively and the standard deviation was similar for the three catchments and equal
to 0.1. The time integrated NDVI times series and length of the growing season were statistically
significantly different between the catchments with p values <0.02. The north facing catchment
(UJ) had the smallest vegetation response indicated by the time integrated NDVI metric (ū=5.98,
σ=0.32, C.V.=0.05) followed by HG (ū=6.28, σ=0.35, C.V.=0.06) and LJ (ū=6.58, σ=0.35,
C.V.=0.34) (Figure 4). In addition, the indicator of growing season length was statistically
significantly different among the three catchments (p < 0.05) (Figure 4). Upper Jaramillo had the
shortest and more variable growing season (ū=76.3, σ=40.9, C.V.=0.54), while LJ had the longest
growing season (ū=156.4, σ=30.7, C.V.=0.2). The indicator of growing season length in HG had
values in between the other two catchments (ū=113.2, σ=36.6, C.V.=0.3)
3.5 Horton index
Climatic variables such as maximum SWE and duration of snow accumulation and snow
cover were the strongest predictors of Horton index around Redondo Peak (Table 5). Based on
these strong multiple regression models (Table 5), Horton index records were back calculated in
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time to the year 2000 with a resulting mean value of 0.86 for the north catchment (UJ) and 0.92
for the eastern catchments (LJ and HG). The Horton index was larger in the east facing
catchments (LJ and HG), suggesting that vegetation uses more of the available water in these two
catchments than in the northern site (UJ). LJ had the largest and less variable Horton index (𝑥̅ =
0.92; 𝜎 = 0.03; 𝐶. 𝑉. =0.03) whereas UJ had the lowest and more variable Horton index (𝑥̅ =
0.86; 𝜎 = 0.05; 𝐶. 𝑉. =0.06). The inter-catchment variability of the Horton index due to aspect
differences can be larger than the interannual Horton index variability by climate in the
individual catchments (e.g WY2005; Table 5). During extreme wet years e.g. 2001 and 2005 the
variability in Horton index among the catchments increased indicating larger differences in water
partitioning among catchments because of aspect differences. In wet years, aspect drive
differences among catchments in water partitioning than are more important to the effects of
climate in the individual catchments. In contrast, during dry years e.g. 2002 and 2006 the
difference in Horton index among the catchments decreases (Table 5).
Climatic variables recorded at the Quemazon SNOTEL station and Horton index were
tested as controls of vegetation greening between 2000 and 2012. Horton index was the strongest
predictor of vegetation greening for the three study catchments (R2>0.48; p<0.05). Annual P and
maximum SWE did also show a statistical linear correlation with vegetation greening. Variables
such as air winter and summer temperatures did not show statistical significant linear correlation
with NDVI (Figure 5).
4.0 DISCUSSION
A conceptual model and summary of vegetation structure, water partitioning and NDVI
response in contrasting aspects around Redondo Peak are presented in Figure 6. The results of
100
this investigation indicate that the catchment with a predominant north facing aspect (UJ)
received less solar radiation and contains less biomass than the two eastern catchments (LJ and
HG). Furthermore, UJ had more surface water available as indicated by a larger base flow and
discharge due to smaller vaporization fluxes and a smaller Horton index. Vegetation greening
and length of growing season were consequently smaller in the northern catchment. In contrast,
the eastern catchments had smaller surface water availability indicated by annual base flow and
discharge fluxes as they received more solar radiation, have larger vaporization and vegetation
water consumption. Similarly NDVI response and length of growing season was longer in the
two eastern catchments.
4.1 Hydrological partitioning
During the study period, snowmelt was the dominant process controlling runoff
generation around Redondo Peak (Figure S2; table S2). The peak stream discharge recorded at
the catchments flumes during the five years is related to the winter snowpack conditions, similar
to findings by Gottfried et al. [2002] and DaqingYang et al. [2009]. When compared to the years
2008 through 2010, the drier 2011 winter resulted in a reduced snowmelt discharge (Table 3)
similar to findings between wet and dry years at other high elevation regions [Williams et al.,
2002]. An analysis of water stable isotopes also indicated that snowmelt is the major contributor
of water to the landscape around Redondo Peak [Broxton et al., 2009; Zapata-Rios et al., in
review]. The estimated runoff ratios in this study were similar to runoff ratios of 0.03 and 0.11 in
an 870m2 runoff experiment in a ponderosa pine forest on the Pajarito plateau located in close
proximity to the study area [Wilcox et al., 1997]. Base flow was the largest and predominant
component of discharge in all the catchments, similar to findings by Liu et al. [2008], who found
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that overland flow was not significant in streamflow generation in two streams around Redondo
Peak based on a geochemical analysis. Moreover, base cations concentration of first order
streams draining Redondo show a chemostatic behavior, suggesting a fairly constant source of
water supply from a well-mixed reservoir [Porter, 2012; Perdrial et al., 2014].
Annual vaporization (V) represented over 85% of annual precipitation and the largest
water loss in the catchments. Similar estimations of annual V have been published for other
semi-arid sites. For instance, Baker [1982] estimated in a ponderosa pine forest in north central
Arizona an annual average ET of 506 mm representing 78% of total annual precipitation. In a
nearby ponderosa pine forest close to Redondo Peak, Brandes and Wilcox [2000] estimated an
average ET during the growing season of 476 mm during the years 1993 through 1995,
representing 95% of annual precipitation. Water loss by vaporization was smaller in the north
facing catchment (UJ) than in the eastern catchments (LJ and HG). This lower rate of
vaporization in UJ is consistent with what would be expected for an area that receives less solar
radiation and has smaller biomass than the other (eastern) catchments included in this study
(Table 1; figure 3f). Data from the VCM flux tower provide further evidence of precipitation
partitioning into vaporization and the contribution of winter precipitation to water availability.
Precipitation (P), potential evapotranspiration (PET) and vaporization (V) recorded at this station
(Figure S3) showed significantly higher water availability during the winter due to more
precipitation than vaporization demand, whereas during the summer season, the difference
between precipitation and vaporization decreased. Summer precipitation did not cover
vaporization water demand in 2008, 2009 and 2010. In 2007 and 2011, the contribution of
summer precipitation was slightly higher than vaporization.

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In contrast to the east-facing catchments, the north-facing catchment was characterized
by larger surface water availability as a consequence of smaller vaporization and water use by
vegetation. More water availability at this site is consistent with observations of large mineral
weathering rates and longer water residence times along north facing slopes [Zapata-Rios et al.,
in review; Broxton et al., 2009]. Likewise, Hinckley et al.[2012] found different hydrologic
responses in hillslopes with contrasting aspect, where their results indicate that north facing
slopes store water more effectively in the near surface and have longer residence times in
contrast to south facing slopes, and more water infiltrates into the ground which may pass
quickly to deeper weathered bedrock.
4.2 Vegetation water use
Vegetation in the east-facing catchment uses more of the available water than the north-
facing catchments, as indicated by a higher and less variable Horton index. This finding is
consistent with Troch et al.[2009] who found that semi-arid catchments have a higher and less
variable Horton index than more humid catchments. The Horton index increases as a catchment
becomes drier and get closer to 1 in drier regions and during dry years [Troch et al., 2009].
Huxman et al. [2004] found that the average rain-use efficiency (RUE), estimated as the ratio of
aboveground net primary production to annual precipitation, decreases as precipitation increases.
In contrast, during dry years REU converges to a common maximum RUE similar to the drier
regions, regardless of biome type. It has been demonstrated that vegetation of a region uses the
largest proportion of the water available (W) and therefore the Horton index presents little
variability from year to year despite substantial variability in precipitation [Horton, 1933; Troch
et al., 2009]. Southern aspects are associated with greater insolation, increased potential
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evapotranspiration and in general drier conditions [Wilkinson and Humphreys, 2006]. A higher
Horton index along eastern catchments is consistent with the large water availability of plants
(W) and drier landscape conditions in areas with greater insolation. More water stressed trees are
more likely found on south facing slopes [Safranyik and Carroll, 2006] and plants are using more
of its available water on dry landscape positions according to our study.
4.3 Vegetation structure and NDVI response
Frequently larger biomass has been found in all forest types of the northern hemisphere
along north facing slopes [Sharma et al., 2011]. For instance, at lower elevations in northern
New Mexico, vegetation in north-facing slopes consists of more mesic plant species in contrast
to more xeric species in the south-facing slopes [Gutierrez-Jurado et al., 2006]. In this study we
found smaller biomass and smaller NDVI values along the north facing catchment at high
elevations (Table 2, Figure 2). A carbon balance study around Redondo Peak has also quantified
smaller above ground biomass in the north facing catchment [Perdrial et al., 2013; Perdrial et al.,
in prep]. The catchment scale biomass observations in this study are in agreement with results
from modeling and empirical studies that have indicated that mountain forest productivity are
sensitive to energy limitations [Christensen et al., 2008; Tague et al., 2009; Trujillo et al., 2012;
Anderson-Texeira et al., 2011]. Energy limitations in forest productivity have been observed at
colder sites along high elevations in northern New Mexico and Redondo Peak [Anderson-
Texeira et al., 2011]. The north facing catchment where a smaller biomass was quantified
receives a reduced solar loading compared to the eastern sites (Table 1). Similarly, sap flux
sensors installed in dominant spruce and fir trees species located in slopes with contrasting
aspect in Redondo Peak at 3000 m of elevation showed radiation as a main control of sap flux
104
rate during the summer, whereas air and soil temperatures were the dominant controls throughout
the rest of the year [Mitra and Papuga, 2012]. Additionally, the eastern catchments showed a
longer growing season that increases the opportunity of carbon uptake by trees and accumulation
of biomass as indicated in past research [Groffman et al., 2012; Rochefort et al., 1994; White et
al., 1999). Analogous biomass observations were reported in a study across an oak dominated
temperate watershed in Pennsylvania, where trees on the south aspect stored more carbon per
year than trees on the northern aspect [Smith, 2013]. The observations on vegetation biomass in
different slopes around Redondo Peak are in line with previous research and indicate that energy
and a short growing season length can limit forest productivity at the local scale in high elevation
ecosystems [Rochefort et al., 1994].
In high elevation regions snowmelt controls the timing and magnitude of both runoff and
soil moisture, recharging subsurface water pools and providing water for plants during the
growing season [Molotch et al., 2009; Vivoni et al., 2008]. Molotch et al. [2009] found in a field
plot investigation that the beginning of the growing season and the initiation of snowmelt
infiltration lag behind each other by a few days. These processes occur in Redondo every year
between the middle of March until the middle of April and their timing depends on the amount
of snowpack and air temperature during the winter season [Molotch et al., 2009]. Peak soil
moisture occurs within few days of snow disappearance and vegetation responds rapidly to water
availability [Molotch et al., 2009]. The NDVI time series at the catchment scale in this study
indicate similar response of vegetation with increasing NDVI values between the middle of
March and middle of April, where the timing of peak NDVI occurs before the monsoon season
begins (Figure S1).

105
According to our flux tower data (Figure S3) and the observations by Vivoni et al.
[2008], soil moisture in the upper layers of the soil disappears around June at the beginning of
the summer and get replenished weeks later with the onset of the monsoon rains, when
vegetation again absorbs a large fraction of rainfall and soil moisture derived from the North
American monsoon season. The NDVI profiles showed the same dynamics at the catchment
scale where NDVI increases at the end of the snowmelt period followed by a short drop in NDVI
during the summer at beginning of June. NDVI increases again during the North American
monsoon season, a pattern also observed by Molotch et al. [2009] and Vivoni et al. [2008] at
small plot scales. In addition, NDVI time series indicated a longer growing season along the
eastern catchments, consistent with findings by Lyon et al. [2008], who found that snowmelt
occurred early and more readily along terrains with larger solar radiation. Furthermore, Lyon et
al. [2008] found that aspect exerts a strong control on the timing of snowmelt and water
availability. For instance, their observations indicated that snowmelt occurs later and first-order
streams get dry slower along north facing slopes.
4.4 Water partitioning and vegetation interactions
Snowpack conditions strongly control Horton index that in turn influences vegetation
greening. This study indicates that the partitioning of water in the landscape is critical for the
annual vegetation productivity. Similarly, Trujillo et al. [2012] found that snowpack thickness
and snow duration can lead to changes in annual productivity and ultimately changes in forest
stand structure and long term water use. Vegetation water use and productivity are influenced by
snow accumulation and melt, particularly in water limited environments [Tague and Dugger,
2010; Molotch et al., 2009]. Therefore, future ecohydrological responses in high elevation
106
ecosystems may depend on snowpack processes and changes in snow distribution, snowmelt, soil
moisture, soil temperature [Molotch et al., 2009]. As previous studies have suggested, this study
corroborates that a decrease in snow accumulation and melt water might reduce water
availability and forest productivity [Molotch et al., 2009; Trujillo et al., 2012].
4.5 Implications for the critical zone
The critical zone is the heterogeneous surficial layer of the planet that extends from the
canopy to the base of the groundwater, and where complex interactions between rocks, soil,
water, atmosphere, and biota take place [National Research Council, 2001]. It remains highly
uncertain how landscape position and climate variability shape the critical zone structure and
function [Chorover et al., 2011]. Both water availability (Eppt) and carbon compounds derived
from net primary productivity (Ebio) have been recognized as fundamental sources of effective
energy and mass transfer (EEMT) to the critical zone [Rasmussen and Tabor, 2007; Rasmussen
et al., 2011; Chorover et al., 2011]. Previous research quantified higher EEMT along north
facing slopes around Redondo Peak [Chorover et al., 2011; Zapata-Rios et al., in review]. More
water availability at the north facing catchment found in this study is consistent with previous
studies that found higher EEMT along the north facing slopes in Redondo Peak. A higher EEMT
in the north facing slope of Redondo Peak is consistent with previously reported higher carbon
storage in soil at cooler and wetter sites [Perdrial et al., in prep]. At these sites, trees have lower
respiration rates relative to their carbon uptake. In addition higher dissolved organic carbon
concentrations has been measured in stream waters and springs in north facing slopes [Perdrial et
al., 2014] indicating that carbon compounds as an a energy source to the CZ are also larger in
north facing catchment in agreement with the larger EEMT estimations.

107
4.6 Future studies
Additional factors beyond water and energy can affect the productivity of high elevation
ecosystems such as soil, nutrients, light, and roots distribution that need further ecological
investigation. For example, details about roots depth and their distribution in the subsurface are
unknown around Redondo Peak and can provide an important source of information about plant
water use and water pools that provide moisture during the growing season.
On May 31, 2013, the Thompson ridge fire affected the southwestern part of Valles Caldera
and a large area of Redondo Peak. The fire consumed a total of 97 km 2 of forest. The three
catchments included in this study (LJ, HG and UJ) had a fire severity ranging from moderate to
high covering 65%, 81% and 34% of the total catchment area, respectively. The results from this
study documents pre-fire water partitioning - vegetation interactions in high elevation forest in
northern New Mexico. Having the baseline data presented in this study, presents a unique
opportunity for futures studies to further understand vegetation water use and their influence on
water partitioning in high elevation semi-arid areas in a post-fire scenario.
5.0 SUMMARY
In Redondo Peak in northern New Mexico we studied three adjacent first order catchments
that share similar physical characteristics, but drain different aspects, allowing for an empirical
study of how topographically controlled microclimate influences hydrological and vegetation
response. Results from this investigation provide evidence that aspect influences the magnitude of
water partitioning fluxes and vegetation response at the catchment scale. For instance, differences
in water partitioning fluxes during wet years among catchments can be larger than the water
108
partitioning fluxes variability induced by climate variability only at the individual catchment scale.
In contrast, we found that during dry years the catchments behave more similar with one another.
Moreover, this study suggests that terrain aspect is a landscape characteristic that can exacerbate
the availability of plant limiting resources such as water and energy. The main findings of this
study include a significant difference in forest cover and biomass between the northern and eastern
catchment with the northern catchment showcasing a smaller forest cover and biomass. In the
northern catchment, smaller vaporization, wetting and plant water consumption was observed and
consequently there was more water available as surface runoff and baseflow. In contrast,
aboveground biomass was more abundant in the eastern catchments which received a larger solar
loading than the northern catchment. In the eastern site of Redondo, vaporization and vegetation
water consumption was larger and there was less water available as surface runoff and baseflow.
Vegetation greening indicates larger and longer growing season along the eastern catchments.
Water partitioning around Redondo Peak is highly related to snowpack conditions such as max
SWE and duration of snow on the ground that in turn determines annual vegetation greening.
This research was supported by the national Critical Zone Observatory program via NSF EAR-
0724958, NSF EAR-0632516 and NSF EAR-0922307. Robert Parmenter from the VCNP
provided access to the meteorological data from the VCNP network. We appreciate the field
assistance of Scott Compton and Mark Losleben.

109
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8.0 FIGURES
Figure 1. The Jemez River basin is located in (a) northern New Mexico with (b) headwaters in
the Valles Caldera National Preserve (VCNP). Our first order study catchments: (c) La Jara,
History Grove, and Upper Jaramillo originate on different aspects of the highest peak (Redondo
Peak).
121
25 40
Tree height (m)

20 35
DBH (cm)
15 30
10 25
5 20
LJ HG UJ LJ HG UJ
2.5
1.00
Canopy cover
2.0
0.75
1.5
LAI
0.50 1.0
0.25 0.5
0.0
LJ HG UJ LJ HG UJ
Figure 2. Lidar derived indicators of vegetation structure in the three study catchments. Whiskers
represent one standard deviation. Mean tree height, mean diameter at the breast height (DBH),
fractional canopy cover and leaf area index (LAI) are larger in the LJ and HG, the eastern
catchments. UJ, the northern catchment, has smaller biomass than the two eastern catchments.
Statistical differences between the northern and eastern catchments were tested with the Mann-
Whitney U test p values <0.05.
122
Annual Precipitation (mm)

850 500 500
Summer Precip (mm)

Winter Precip. (mm)
a) b) c)
800 450 450
750 400 400
700 350 350
650 300 300
600 250 250

2008 2009 2010 2011 2012 2008 2009 2010 2011 2012 2008 2009 2010 2011 2012
200 0.3 0.15
Quick flow-baseflow
Discharge (mm)
d) e) f)
Runoff ratio (-)
150
0.2 0.10
ratio (-)
100
0.1 0.05
50
0.0 0.00
0
2008 2009 2010 2011 2012 2008 2009 2010 2011 2012 2008 2009 2010 2011 2012
800 850 1.00

750 g) h) i)
800 0.95
V (mm)
HI (V / W)
700
W (mm)
650 750 0.90

600 0.85
700
550
650 0.80
500
450 600 0.75
2008 2009 2010 2011 2012 2008 2009 2010 2011 2012 2008 2009 2010 2011 2012
La Jara
History Grove
Upper Jaramillo
Figure 3. Water partitioning in the study’s three experimental catchments. The three study
catchments showcase similar variability in (a) annual, (b) winter and (c) summer precipitation.
However, LJ the highest elevation catchment receives the largest amount of precipitation,
approximately 50 mm more than HG and UJ. Mean discharge (d), runoff ratio (e) and quick to
baseflow ratio (f) are consistently large and less variable in UJ, the north facing catchment.
Vaporization (V), wetting (W) and Horton index (HI), shown in plots (g) through (h), are smaller
in UJ. HI is an indicator of climate and landscape controls of available water to vegetation. HI is
smaller in UJ and larger in LJ and HG, the east facing catchments. A higher HI in the eastern
catchments indicates vegetation uses more of its available water than in UJ. These plots indicate
the catchments process precipitation differently. Both, W and V variability are controlled
principally by climate but W is further influenced by landscape characteristics while V is
secondarily controlled by vegetation. A lower V is expected in a catchment that receives a
smaller solar loading and in contrast higher V values are expected in the two catchments facing
123
east. W depends on catchment landscape characteristics and indicates water availability to

vegetation. W is consistently smaller in the north facing catchment.
124
7.5 250
Integrated NDVI
Days NDVI >0.6

7.0 200
(Apr - Sep)
6.5 150
6.0 100
5.5 50
5.0 0
LJ HG UJ LJ HG UJ
Figure 4. NDVI response metrics between the three study catchments from 2000 through 2012.
The north facing catchment (UJ) has the smallest vegetation greening indicated by the integrated
NDVI response and the shortest growing season length. Statistical differences in NDVI response
between eastern and northern catchments was tested with both the Mann-Whitney U test and pair
t test p values <0.05.
125
2
R Integrated NDVI (Apr-Sep)
1.0 1.0
LJ
0.8 HG 0.8
Annual P
Winter P
0.6 UJ 0.6
* *
0.4 * m=0.002 0.4
0.2 0.2
0.0 0.0
LJ HG UJ LJ HG UJ
1.0 LJ 1.0
0.8 0.8
Summer P
m=0.003
* *
0.6 * HG 0.6
SWE
0.4 m=0.002 0.4

UJ
0.2 0.2
m=0.002
0.0 0.0
LJ HG UJ LJ HG UJ
1.0
LJ
0.8
* m=-10.1
0.6 *
* HG
HI
0.4 m=-5.5
UJ
0.2
m=-4.7
0.0
LJ HG UJ
Figure 5. Precipitation at the long-term Quemazon SNOTEL monitoring station versus integrated
vegetation response from 2000 through 2012 in the three study catchments. Annual
precipitation, SWE, and Horton index (HI) indicate strong relations with vegetation response.
However Horton index is the strongest predictor of vegetation greening. NDVI decreases as a
catchment becomes drier as indicated by an increase in HI. Winter P and Summer P are not
good predictors of vegetation greening (m represent the slope of the best linear regression, *
statistical significant p<0.05).
126
Figure 6. Conceptual model of vegetation structure, water partitioning and vegetation greening
between contrasting slopes (northern and eastern) around Redondo Peak. The eastern slopes
receive more solar loading and have larger biomass. Snow represents 40% of annual
precipitation and controls water partitioning around Redondo Peak. Eastern slopes have larger
vaporization, and vegetation takes advantages of a larger portion of its water availability. Also
they have larger NDVI response and longer growing season. In contrast, in the northern slopes
there is more water availability as baseflow and discharge, and the annual rates of vaporization
and Horton index are smaller.
127
9.0 TABLES
Table 1. Physical characteristics of the three study catchments draining Redondo Peak: La Jara
(LJ), History Grove (HG), and Upper Jaramillo (UJ) presented in decreasing elevation order.
The three study catchments are characterized by differences in terrain aspect which affect inputs
of solar radiation, mass, and energy into the critical zone.
Catchment LJ HG UJ
Mean elevation (m) 3,100.0 2,948.0 2,925.0
Elevation range (m) 2,702-3,429 2,681-3,308 2,723-3,324
Area (m2) 3,671,870.0 2,421,410.0 3,055,060.0
Catchment slope
Mean (SD†) 0.29 (0.17) 0.24 (0.13) 0.27 (0.19)
Predominant terrain aspect East East North
Total Annual incoming solar radiation
(KWh.m-2)
Mean (SD†) 73.98(14.46) 74.90 (10.04) 57.21(12.49)
†SD= standard deviation

128
Table 2. Main vegetation land cover classes in the three study catchments according to Muldavin
et al. (2006). The eastern catchments of LJ and HG have the largest forested areas within the
study site. Forest cover represents the largest land cover in the eastern catchments of LJ and HG.
LJ HG Upper Jaramillo UJ
Land cover
classes Area (m2) % Area (m2) % Area (m2) %
Coniferous forest 2,912,352.0 79.3 1,761,676.0 71.6 2,088,532.0 67.0
Aspen Forest 71,340.0 1.9 80,144.0 3.3 168,272.0 5.4
Shrubland 14,468.0 0.4 14,848.0 0.6 8,472.0 0.3
Meadow 391,056.0 10.7 487,188.0 19.8 423,152.0 13.6
Grassland 53,992.0 1.5 37,888.0 1.5 55,232.0 1.8
Wetland 2,316.0 0.1 2,132.0 0.1 4,636.0 0.1
Others† 226,328.0 6.2 77,700.0 3.2 366,740.0 11.8
TOTAL 3,671,852.0 2,461,576.0 3,115,036.0

†Sparsely vegetated rock outcrop, Felsenmeer rock field, roads-disturbed ground and open water.
129
Table 3. Magnitude and timing of discharge indicators in the three study catchments from water
years 2008 through 2012. During the five years of analysis, UJ was characterized by the largest
and less variable discharge, and the timing of the maximum peak discharge occurred later than in
LJ and HG, the eastern catchments. The differences between the three study catchments
indicated by the discharge indices decreased in 2010, the wettest year within the analysis period.
Water Year
Discharge indices Catch. 2008 2009 2010 2011 2012 Mean STDEV C.V.
LJ 0.50 0.86 1.80 0.23 0.74 0.83 0.60 0.72
Peak flow HG 0.59 1.89 3.02 0.27 1.06 1.37 1.11 0.81
mm/day UJ 1.21 1.68 3.22 0.86 1.38 1.67 0.92 0.55
Magnitude
Mean discharge LJ 0.15 0.15 0.33 0.13 0.22 0.19 0.09 0.49
mm/day HG 0.18 0.24 0.31 0.08 0.17 0.20 0.09 0.46
UJ 0.28 0.28 0.41 0.15 0.28 0.28 0.11 0.39
LJ 208 211 200 216 184 208.8 6.70 0.03

Timing DOWY Peak flow HG 186 208 203 307 178 226.0 54.81 0.24
DOWY ǂ UJ 214 217 199 326 187 239.0 58.53 0.24
ǂ DOWY= day of the water year
130
Table 4. Climatic controls on Horton index. Multiple linear regression parameters showing
influence of maximum SWE, snow cover duration, and snow accumulation on HI using data
from the long-term Quemazon SNOTEL station (2008 - 2012). HI during the 5 years study
period is highly correlated with snow variables. Other snow parameters like timing to initial
snow cover, peak of SWE, timing of melt, average air winter temperature were not strong
predictors of HI.
Catchment LJ p HG p UJ p
Intercept 1.07 0.001 1.12 0.0001 1.08 0.004
Max SWE (mm) -0.0001 0.023 -0.0002 0.004 -0.001 0.07
snow accumulation 0.001

(days) -0.001
snow cover (days) -0.001 0.01 -0.0004 0.04
R2 0.99 0.98 0.95
p 0.001 0.002 0.05

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Table 5. Interannual and intercatchment variability of the Horton index (HI). The Horton index
variability among the three study catchments within a single year can be as large as the Horton
index variability due to climate change during the study period e.g. WY 2010. This suggests
strong aspect differences in microclimate around Redondo and in the way the catchments filter
precipitation. The intercatchment differences can be larger than the hydrological response due to
the natural precipitation variability in a single catchment.
Horton Index (HI) Intercatchment comparison
Water
Years LJ HG UJ Mean Stdev C.V.†
2000 0.92 0.95 0.89 0.92 0.03 0.03
2001 0.88 0.88 0.78 0.85 0.06 0.07
2002 0.97 0.99 0.93 0.96 0.03 0.03
2003 0.89 0.92 0.84 0.88 0.04 0.04
2004 0.93 0.93 0.86 0.91 0.04 0.05
2005 0.90 0.89 0.79 0.86 0.06 0.07
2006 0.93 0.97 0.92 0.94 0.03 0.03
2007 0.90 0.90 0.82 0.87 0.05 0.06
2008 0.93 0.91 0.87 0.90 0.03 0.03
2009 0.95 0.89 0.87 0.90 0.04 0.04
2010 0.87 0.84 0.78 0.83 0.04 0.05
2011 0.94 0.95 0.92 0.94 0.02 0.02
2012 0.92 0.92 0.86 0.90 0.03 0.04
Mean 0.92 0.92 0.86
Stdev 0.03 0.04 0.05

interannual
comparison C.V. 0.03 0.04 0.06
†C.V. coefficient of variation

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10.0 SUPLEMENTAL MATERIAL
Table S1. Valles Caldera National Preserve meteorological stations listed according to elevation.
Mean annual precipitation and temperature for water years 2008 through 2012. A water year (WY)
is considered from October 1st to Sept 30th.
Latitude Longitude Elevation Average WY 2008-2012

Station Name Air
(˚) (˚) (m)
Precipitation Temperature
(mm) (˚C)
San Antonio 35.98 -106.57 2598 514 4.8
Headquarters
35.86 -106.52 2644
(HQ) 680 4.7
Los Posos 35.92 -106.42 2738 601 4.7
Valle Toledo 35.97 -106.46 2750 585 6.1
Redondo 35.88 -106.55 3232 789 3.6

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1.0
0.8
Mean NDVI
0.6
Area (April-Sep)
0.4
LJ
HG
0.2 UJ
0.0
10/07 4/08 10/08 4/09 10/09 4/10 10/10 4/11 10/11 4/12 10/12
Time (months)
Figure S1. Vegetation response for the three study catchments from 2008 through 2012 base on
a time series of mean catchment scale NDVI derived from the NASA’s Moderate Resolution
Imaging Spectroradiometer (MODIS). NDVI is not presented for the month of October through
the end of March due to slow vegetation activity from winter season. Vegetation response was
quantified with the integrated NDVI response estimated as the area under the NDVI curve
between April and September. The length of the growing season was estimated as the number of
days when NDVI values are above 0.6. NDVI values above 0.6 are generally observed between
May and September each year.
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3 Winter (Oct-Apr)
La Jara
History Grove
Discharge (mm/day)
Upper Jaramillo
0
7/07 11/07 3/08 7/08 11/08 3/09 7/09 11/09 3/10 7/10 11/10 3/11 7/11 11/11 3/12 7/12 11/12
Date (month/year)
Figure S2. Stream hydrographs for water years 2008 through 2012 recorded at the flumes in
LJ,HG and UJ. Discharge shows large interannual variability driven largely by winter
precipitation in all years. However, the relative yield is highest in UJ, intermediate in LJ and
lowest in HG. The hydrograph of UJ (north facing catchment) indicates that this catchment
responds more readily to rainfall events than LJ and HG (both facing east) suggesting differences
in the partitioning of precipitation between the catchments. Grey bars represent winter season
between October and April.
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Table S2. Climatic controls on discharge. Multiple linear regression parameters showing
influence of maximum SWE, snow cover duration, and snow accumulation on discharge using
the data from the long-term Quemazon SNOTEL station (2008 - 2012). Other snow parameters
like timing to initial snow cover, peak of SWE, timing of melt, average air winter temperature
were not strong predictors of discharge.
Catchment LJ p HG p UJ p
Intercept -49.53 0.07 -92.47 0.09 -65.35 0.08
Max SWE (mm) 0.1 0.07 0.13 0.07 0.21 0.04
snow accumulation 0.01

0.73
(days)
snow cover (days) 0.91 0.02 0.8 0.04
R2 0.98 0.95 0.94
P 0.02 0.05 0.06

136
P, PET, V (mm/season)
1000
800
600
400
P
200 PET
V
0
S07 W08 S08 W09 S09 W10 S10 W11 S11 W12 S12
Time (seasons)
Figure S3. Records of precipitation (P), potential evapotranspiration (PET) and vaporization (V)
from the VCM eddy covariance flux tower. The winter season shows a marked surplus of water
availability due to higher P than V during this period, whereas during the summer season, the
difference between P and V decreases. Summer P does not cover water demand by V in 2008,
2009 and 2010. In the 2007 and 2011, the contribution of summer P is slightly higher than V. The
high PET during winter and summer indicates that this system is water and not energy limited.
Precipitation (P) Discharge (Q) Baseflow (U) Storm runoff (S) Vaporization (V) Wetting (W)
Year LJ HG UJ LJ HG UJ LJ HG UJ LJ HG UJ LJ HG UJ LJ HG UJ
2008 737 702 697 56 67 93 53 64 89 3 3 4 681 635 604 734 699 693
2009 789 736 728 46 88 101 42 80 91 3 8 10 743 648 627 786 728 718
2010 698 653 647 101 111 151 91 102 137 10 10 14 597 542 496 688 644 633
2011 681 629 621 40 31 55 38 29 49 2 1 5 642 598 566 680 627 615
2012 792 716 705 67 64 103 64 58 96 4 6 7 724 652 602 788 710 698
Mean 739 687 680 62 72 101 58 67 93 4 6 8 678 615 579 735 682 671
Stdev 50.68 44.81 44.30 24.04 30.05 34.28 21.05 26.91 31.25 3.20 3.47 3.88 59.65 46.01 51.30 51.65 43.65 44.46
C.V†. 0.07 0.07 0.07 0.39 0.42 0.34 0.37 0.40 0.34 0.74 0.61 0.48 0.09 0.07 0.09 0.07 0.06 0.07
†C.V. coefficient of variation

Table S3. Water partitioning at the catchment scale in LJ, HG and UJ from 2008 through 2012.
Mean, standard deviation and coefficient of variation (CV) are indicated at the bottom of the table
137
138
APPENDIX C:
INFLUENCE OF CLIMATE VARIABILITY ON WATER PARTITIONING AND

EFFECTIVE ENERGY AND MASS TRANSFER (EEMT) IN A SEMI-ARID CRITICAL
ZONE
Authors:
Xavier Zapata-Rios1*, , Paul D. Brooks2, 1, Peter A. Troch1, Jennifer McIntosh1
1. Department of Hydrology and Water Resources, University of Arizona, Tucson, Arizona,
USA
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ABSTRACT
The Critical Zone (CZ) is the heterogeneous, near-surface layer of the planet that regulates life-
sustaining resources. Previous research has demonstrated that a quantification of the influxes of
effective energy and mass (EEMT) to the CZ can predict its structure and function. In this study,
we quantify how climate variability in the last three decades (1984-2012) has affected water
availability and the temporal trends in EEMT. This study takes place in the 1200 km2 upper
Jemez River Basin in northern New Mexico. The analysis of climate, water availability, and
EEMT was based on records from two high elevation SNOTEL stations, PRISM data, catchment
scale discharge, and satellite derived net primary productivity (MODIS). Records from the two
SNOTEL stations showed clear increasing trends in winter and annual temperatures (+1.0-1.3
°C/decade; +1.2-1.4 °C/decade, respectively), decreasing trends in winter and annual
precipitation (-41.6-51.4 mm/decade; -69.8-73.2 mm/decade, respectively) and maximum Snow
Water Equivalent (SWE;-33.1-34.7 mm/decade). The water partitioning fluxes at the basin scale
showed statistically significant decreasing trends in precipitation (-61.7mm/decade), discharge (-
17.6 mm/decade) and vaporization (-45.7 mm/decade). Similarly Q50, an indicator of snowmelt
timing, is occurring 4.3 days/decade earlier. Results from this study indicated a decreasing trend
in water availability, a reduction in forest productivity (4 g_C.m-2 per 10 mm of reduction in
Precipitation) and EEMT (1.2 – 1.3 MJ.m2.decade-1), and increased vegetation water use
efficiency. During the study period, a decreasing trend in EEMT was observed of 1.2 and 1.3
MJ/ m2 decade. These changes in EEMT point towards a hotter, drier and less productive
ecosystem which may alter critical zone processes in high elevation semi-arid systems.
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KEY WORDS
EEMT, Jemez River Basin, climate variability, critical zone, Northern New Mexico.
141
1.0 INTRODUCTION
The critical zone (CZ) is the surficial layer of the planet that extends from the top of the
vegetation canopy to the base of aquifers [Chorover et al., 2011; Brandley et al., 2007]. Within
its boundaries complex interactions between air, water, biota, organic matter, soils and rocks take
place that are critical for sustaining live on Earth [Brandley et al., 2007]. The CZ has been
conceptualized and studied as a weathering engine or reactor where interacting chemical,
physical and biological processes drive weathering reactions [Anderson et al., 2007; Chorover et
al., 2011]. Over long time scales, the CZ has evolved in response to climatic and tectonic forces
and has been recently influenced by human activities [Steffen et al., 2007]. Understanding how
climate and land use changes affect CZ structure and related processes has become a priority for
the science community due to the implications it may have on the functioning of life supporting
resources. It has been hypothesized by the researchers from the Jemez River Basin (JRB) –
Santa Catalina Mountains (SCM) Critical Zone Observatory (CZO)
[http://criticalzone.org/catalina-jemez/] that a quantification of the inputs of the effective energy
and mass transfer (EEMT) to the CZ can provide insight about its structure and function
[Chorover et al., 2011]. CZ areas that receive greater EEMT influxes have been shown to have
greater structural organization as well as more dissipative products leaving it [Rasmussen et al.,
2011; Zapata-Rios et al., submitted]. The opposite has been observed in regions with less
EEMT.
EEMT is a variable that quantifies energy and mass transfer to the critical zone
[Rasmussen et al., 2011; Chorover et al., 2011]. EEMT integrates within a single variable the
energy and mass associated with water in excess from evapotranspiration, quantified as effective
precipitation (Eppt), and reduced carbon compounds resulting from primary production (Ebio)
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[Rasmussen et al., 2011]. It has been demonstrated that other possible energy fluxes to the CZ
such as potential energy from transport of sediments, geochemical potential of chemical
weathering, external inputs of dust, heat exchange between soil and atmosphere, and other
sources of energy coming from anthropogenic sources are orders of magnitude smaller [Phillips,
2009; Rasmussen et al., 2011; Rasmussen, 2012]. Therefore the two dominant terms embodied
in EEMT are Eppt and Ebio.
Previous research has shown that EEMT can become a tool to predict regolith depth, rate
of soil production and soil properties [Rasmussen et al., 2005; Rasmussen et al, 2011; Pelletier
and Rasmussen, 2009a,b; Rasmussen and Tabor, 2007]. For instance, strong correlations were
found between EEMT, soil carbon, and clay content in soils on igneous parent materials from
California and Oregon [Rasmussen et al., 2005]. Furthermore, transfer functions were
successfully determined between EEMT and pedogenic indices, including pedon depth, clay
content, and chemical indices of soil alteration along an environmental gradient on residual
igneous parent material [Rasmussen and Tabor, 2007]. EEMT has also been incorporated in
geomorphic and pedogenic models on granitic rocks to describe landscape attributes and regolith
thickness [Pelletier and Rasmussen, 2009 a,b]. Rasmussen and Tabor [2007] demonstrated that
regolith depth on stable low gradient slopes increased exponentially with increasing EEMT.
Similarly, Pelletier et al. [2013] found that high EEMT values are associated with large above
ground biomass, deeper soils, and longer distance to the valley bottoms across hillslopes in the
Santa Catalina Mountains in southern Arizona. More recently, EEMT estimations haven been
strongly correlated with water transit times, water solutes concentrations and dissolution of
silicates on a rhyolitic terrain in northern New Mexico [Zapata et al., in review]. In these
studies, the main constituents of EEMT (Eppt and Ebio) were quantified as an average value based
143
on climate records from long-term regional databases as these variables exert first-order controls
on photosynthesis and effective precipitation [Rasmussen et al., 2011; Chorover et al., 2011].
It is still uncertain how climate variability influences CZ structure and function
[Chorover et al., 2011]. Climate variability might directly influence changes in the transfer of
mass and energy to the CZ as climate has a direct control on both Eppt and Ebio. In the mountains
of the southwestern United States, a large percentage of annual precipitation falls as snow, which
is stored during the winter and released as snowmelt during the spring [Clow, 2010]. The water
from the winter snowpack constitutes the main source of regional water supplies and the largest
component of runoff [Bales et al., 2006; Nayak et al., 2010]. The regional snowpack has been
documented to be declining in the southwestern US [Mote et al., 2005; Clow, 2010] and
alterations to the snowpack are likely to produce changes in vegetation, impact water availability
[Bales et al., 2006; Harpold et al., 2012; Trujillo et al., 2012] and influence inputs of EEMT.
For instance, significant increasing trends in air temperature and decreasing trends in winter
precipitation in the last decades have been documented in the Upper Rio Grande region in
northern New Mexico [Harpold et al., 2012].
The objective of this study was to evaluate climate variability and its influence on the
temporal changes of water partitioning and EEMT at the catchment scale in a semi–arid CZ over
the last few decades. This investigation took place in the upper part of the Jemez River Basin in
northern New Mexico, a basin dominated by a wide forest cover and limited human
infrastructure, where the Santa Catalina-Jemez River Critical Zone Observatory has established
a research site to study CZ processes [Chorover et al., 2011]. Micro-climate variability was
studied based on daily records from two SNOTEL stations using records from 1984 through
144
2012. Water availability and EEMT were estimated during the same time period based on
precipitation and temperature from the precipitation-elevation regressions on independent slopes
model (PRISM), empirical daily observations of catchment scale discharge, and satellite derived
net primary productivity (MODIS).
2.0 METHODS
2.1 Study site
The Jemez River is a tributary of the upper reach of the Rio Grande and is located
between Jemez and Sierra Nacimiento Mountains in northern New Mexico (Figure 1a). Its
headwaters originate within the 360 Km2 Valles Caldera National Preserve which contains 30%
of the total basin surface (Figure 1b). The upper Jemez River Basin is located at the southern
margin of the Rocky Mountains ecoregion between latitudes 35.6˚ and 36.1˚ north and
longitudes -106.3˚and -106.9˚west. The basin is characterized by a mean elevation of 2591 m
and a gradient in elevation ranging from 1712 to 3435 m. Based on a 10 m digital elevation
model, the catchment drains 1218 km2 above the US Geological Survey (USGS) gauge “Jemez
River near Jemez” (35.66˚ N and 106.74˚ W; USGS 08324000) located at an elevation of 1712m.
The basin has a predominant south aspect and a mean catchment slope of 13.7˚. The geology
consists of rocks of volcanic origin with predominant basaltic and rhyolitic compositions that
overlie tertiary to Paleozoic sediments along the western margin of the Rio Grande rift
[Shevenell et al., 1987]. Common soil types in the basin are aridisols, alfisols, mollisols and
inceptisols [Allen et al., 1991, 2002]. Precipitation has a bimodal pattern with 50% of annual
precipitation occurring during the winter months (primarily as snow) from October to April and
originates from westerly frontal systems. The remaining 50% of precipitation falls as
145
convectional rainfall during the monsoon season between July and September [Sheppard, 2002].
According to the National Land Cover Database (NLCD), the basin is a forested catchment with
79% under evergreen, deciduous and mixed forest cover and only 0.5% of area covered by
development and agriculture [http://www.mrlc.gov/nlcd06_leg.php] (Table 1).
2.2 Climatological stations
There are two Natural Resources Conservation Service snowpack telemetry (SNOTEL)
stations within the study area with long-term records since 1980
(http://www.wcc.nrcs.usda.gov/snow/; Figure 1b). The Quemazon station is located at an
elevation of 2896 m (35.92 ̊ N and 106.39 ̊ W) and the Señorita Divide#2 station is located at an
elevation of 2622 m (36.00 ̊ N and 106.83 ̊ W). The stations collect real-time precipitation, snow
water equivalent (SWE), air temperature, soil moisture and temperature, and wind speed and
direction. Air temperature records began at the Señorita Divide#2 in 1988 and at the Quemazon
station in 1989. There are no stations with long-term records at the lower part of the basin.
2.3 Climate variability
Climate variability was studied based on 13 variables from the two SNOTEL stations,
derived from daily air temperature, precipitation, and maximum SWE, following a similar
methodology and data processing procedure as in Harpold et al. [2012]. The variables analyzed
were winter, summer and annual air temperature ( ̊C), annual and winter precipitation (mm),
maximum SWE (mm), maximum SWE to winter precipitation ratio (-), 1st of April SWE (mm),
first day snow cover (water year day), last day snow cover (water year day), length of snow on
the ground (number of days) and SM50, which is the day of the year in which half of the
146
snowpack melts (number of days). Climate records for data analysis were aggregated by water
year (from October 1st to September 30th). Winter season was considered to be between October
and April and summer season between May and September. The analysis of climate was
conducted from 1984 as a starting year to avoid the anomalous wet years recorded at the
beginning of 1980s that were caused by the Pacific Decadal Oscillation (PDO) and El Niño-
Southern Oscillation (ENSO) [Harpold et al., 2012; and references therein]. The presence of a
monotonic increasing or decreasing trend in the 13 climate variables recorded at the two
individual stations was evaluated from 1984 through 2012 by applying the nonparametric Mann-
Kendall test with a α=0.10 level of significance and the nonparametric Sen’s slope estimator of a
linear trend [Yue et al., 2012; Sen, 1968].
2.4 EEMT estimation
In this investigation EEMT was calculated as the sum of Eppt and Ebio (equation 1). We
applied two different methods to estimate Eppt and Ebio. Following a similar methodology
described in Rasmussen and Gallo [2013], EEMTemp was empirically estimated at the catchment
scale based on baseflow estimations and average basin scale net primary productivity (NPP)
derived from MODIS satellite data. On the other hand, EEMTmodel was estimated at the
catchment scale based on long term climate records from Precipitation elevation Regressions on
Independent Slopes Model (PRISM) developed by the climate group at Oregon State University
(http://www.wcc.nrcs.usda.gov/ftpref/support/climate/prism/) and described in Rasmussen et al.
[2005; 2011].
𝐸𝐸𝑀𝑇 = 𝐸𝑝𝑝𝑡 + 𝐸𝑏𝑖𝑜 (𝐽 𝑚−2 𝑠 −1 ) (1)

147
EEMTemp
Upper Jemez River Basin precipitation and air temperature from 1984 through 2012 was
obtained using PRISM data at an 800 meters spatial resolution [Daly et al., 2002]. Daily
discharge data was available from 1984 through 2012 from the USGS Jemez River near Jemez
gauge station (http://waterdata.usgs.gov/nwis). The upper Jemez River has not been subjected to
flow regulation and almost 60% of the annual discharge occurs during the snowmelt period
between March and May. Daily discharge records were normalized by catchment area and mean
daily discharge was aggregated into water years.
Catchment scale water partitioning fluxes (1984-2012) were calculated following the
Horton index approach of Troch et al. [2009] and Brooks et al. [2011]. The Horton index is an
indicator of water partitioning at the catchment scale and integrates both effects of landscape and
vegetation in water partitioning [Voepel et al., 2011]. The Horton index represents a metric of
catchment scale vegetation water use and was calculated as follows:
𝑉 𝑃−𝑄
𝐻𝐼 = = (2)
𝑊 𝑃−𝑆
where, V represents vaporization, W catchment wetting, P catchment scale precipitation, Q
discharge and S quickflow.
Precipitation (P) on the land surface was partitioned between quickflow (S) and
catchment wetting (W). S represents water that directly contributes to streamflow discharge as a
response to precipitation events, thus this amount of water is not transferred to the critical zone.
W is the total amount of water that infiltrates the soil, of which a portion is available for
vaporization (V) including vegetation uptake. The remaining portion of W flows though the
148
critical zone and contributes to baseflow (U). V was estimated at the annual scale as the
difference between P and discharge (Q). Q was separated between S and U using a one-
parameter low-pass filter [Lyne and Hollick, 1979; Arnold and Allen, 1999; Eckhardt, 2005;
Troch et al., 2009] (equation 3).
1−𝑎
𝑈𝑘 = 𝑎𝑈𝑘−1 + (𝑄𝑘 − 𝑄𝑘−1 ) (3)
2
𝑈𝑘 ≤ 𝑄𝑘
where a is a filter parameter set to 0.925. This filter was passed twice, backward and forward in
time to improve the partitioning of U and S at the beginning of the time series. After this, daily
values of Q, U, and S were integrated to annual time scales. Alterations in snowmelt timing were
evaluated with Q50, which indicates the day of the water year when 50% of the total annual
discharge is recorded at the catchment outlet [Clow, 2010; Stewart et al., 2005].
The term Epptemp was calculated as stated in equation (4) based on estimations of U and
mean PRISM derived air temperature at the catchment scale [Rasmussen et al., 2011; Rasmussen
and Gallo, 2013].
𝐸𝑝𝑝𝑡 = 𝑈 ∗ 𝐶𝑤 ∗ 𝛥𝑇 (𝐽 𝑚−2 𝑠 −1 ) (4)
In equation 4, Cw is the specific heat of water (4187 J kg-1 K-1) and ΔT is the difference in
temperature between ambient temperature and 0 °C calculated as Tambient minus Tref (273.15 °K).
Net primary productivity
Mean annual NPP at the catchment scale was estimated at a 1 km spatial resolution for
the years 2000 through 2012 using data MOD17A3 from MODIS [Zhao and Running, 2010]
149
(http://modis-land.gsfc.nasa.gov/npp.html). Ebio was calculated as indicated in equation (5) and
presented in Rasmussen et al. [2011] and Rasmussen and Gallo [2013].
𝐸𝑏𝑖𝑜 = 𝑁𝑃𝑃 ∗ ℎ𝑏𝑖𝑜 (𝐽 𝑚−2 𝑠 −1 ) (5)
where, hbio is the specific biomass enthalpy and equivalent to 22 kJ m-2 s-1 [Lieth, 1975; Phillips,
2009]. As MODIS data was only available from the year 2000 onwards, single and multivariate
linear regression analysis were estimated with the objective of finding a statistical model to
extend Ebioemp records back to 1984. Using a similar approach as Rasmussen and Tabor [2007],
linear regressions were explored between Ebioemp and climate variables from the SNOTEL
stations and the entire basin.
EEMTmodel
Epptmodel was calculated based on estimations of effective precipitation (Peff) which is
defined as the amount of water that enters the CZ in excess of evapotranspiration and is available
to flow through the CZ [Rasmussen et al., 2005; equation 6]
𝐸𝑝𝑝𝑡𝑖 𝑚𝑜𝑑𝑒𝑙 = 𝑃𝑒𝑓𝑓𝑖 ∗ 𝐶𝑤 ∗ ∆𝑇 (6)
where Peffi is monthly effective precipitation calculated as the difference between monthly PRISM
precipitation and monthly potential evapotranspiration calculated using the Thornthwaite equation
[Rasmussen et al., 2005; Thornthwaite, 1948]. Cw and ∆T are the same parameters described in
equation (4). Eppti model was calculated on a monthly basis only for the months when precipitation
is larger than evapotranspiration (Peffi > 0) and these values were integrated in water years.
Ebiomodel was estimated as indicated in equation 5 and NPP was calculated following an empirical
relationship based on air temperature [equation 7; Lieth, 1975].

150
3000 𝑑𝑎𝑦𝑠 𝑖
𝑁𝑃𝑃𝑖 = ∗ (7)
1+ 𝑒 1.315−0.119 𝑇𝑎 365 𝑑𝑎𝑦𝑠/𝑦𝑒𝑎𝑟
NPPi is monthly NPP in g.m-2.year-1 and Ta is monthly air temperature. Daysi over the number
of days in a year is an NPP time correction. Similar to equation 5, Ebiomodel was calculated for
the months where Peffi >0 only. For a detailed description of EEMT see Rasmussen et al. [2005;
2011; 2015], Rasmussen and Tabor [2007] and Rasmussen and Gallo [2013].
2.5 Water availability, water partitioning and climate controls on water availability
A trend analysis was conducted using data from 1984 through 2012 on each component
of the water partitioning analysis (P, Q, U, S, V, W, Q50), Horton index and EEMT using the
nonparametric Mann-Kendall test and the Sen’s slope estimator of a linear trend with a α=0.10
level of significance [Yue et al., 2012; Sen, 1968]. Relationships between climate, hydrological
variables and EEMT were examined by simple and multiple linear regression analysis with
parameters fit through a least square iterative process [Haan, 1997].
3.0 RESULTS
3.1 Changes in climate
Records from the Quemazon SNOTEL station from 1984 to 2012 indicated a mean
annual precipitation of 701 mm, of which 50% fell during the winter months with a mean
maximum SWE of 242.5 mm. The mean annual and winter temperatures at this site were 3.98 ̊
C and -0.87 ̊ C, respectively. During the same time period, Señorita Divide#2 station had a mean
annual precipitation of 686 mm, of which 61% fell during the winter with a mean maximum
SWE recorded of 239.2 mm. The mean annual and winter temperatures at the Señorita Divide#2
site were 4.23 and -0.90 ̊ C, respectively (Table 2).

151
During the three decades of analysis, seven out of the 13 climate variables in both
stations showed a statistically significant trend (Table 3). Mean winter, summer and annual air
temperatures at the Quemazon station increased significantly by 1.3°C, 1.0 °C and 1.4 °C per
decade, respectively. Similarly, the same variables at the Señorita Divide#2 station increased 1.0
°C, 1.0 °C and 1.2 °C per decade, respectively. The rates of increase in winter and annual air
temperature were larger in Quemazon, the higher elevation station. Annual precipitation
decreased in both stations at similar rates per decade. Quemazon station decreased
69.8mm/decade (p≤0.01) and Señorita Divide#2 decreased 73.2 mm/ decade (p≤0.05). Winter
precipitation decreased faster at the Señorita Divide #2, the lower elevation station (59.4
mm/decade; p≤0.05) than at the Quemazon station (41.6 mm/decade; p≤0.1). Maximum SWE
decreased in both stations at similar rates, -34.7 mm/decade at Señorita Divide #2 and -33.1
mm/decade at the Quemazon station (p≤0.1). There was no significant trend in the ratio between
SWE to winter precipitation at either station. Observed April 1st SWE also decreased -60.5
mm/decade (p≤0.05) and -54.4 mm/decade (p≤0.1) at the Quemazon and Señorita Divide#2
stations, respectively. The day of occurrence of maximum SWE recorded at the Quemazon
station showed a significant trend indicating that maximum SWE is occurring 5.7 days earlier
every decade (p≤0.05). However, this same trend was not observed at the Señorita Divide#2
station. Variables such as SM50, initiation of snow cover, and snow cover duration did not
indicate any trend of change in either station at the 90% confidence level. In contrast, there is a
decreasing trend in the last day of snow cover, which is happening about 6 days sooner per
decade in the Quemazon station (p<0.05). Last day of snow cover at the Señorita Divide #2
station did not show a significant trend (Table 3).

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3.2 Water availability
Mean precipitation in the Jemez River Basin from 1984 to 2012 was 617 mm with
observed extreme values of 845 mm in 1985 and 336 mm in 2002. During the analysis period,
winter precipitation represented 54% of total annual precipitation. Mean annual precipitation at
the catchment scale correlated significantly with the mean annual precipitation recorded at the
Quemazon (R2=0.45; p<0.0001) and Señorita Divide#2 stations (R2=0.73; p<0.0001). In this
same timeframe average, minimum and maximum basin scale temperatures were 6.1, -1.5 and
13.6 ̊ C, respectively. In general, January was the coldest and July the warmest month. Basin
scale mean annual and winter temperature indicated a statistically significant increasing trend of
0.5° C and 0.4 ° C per decade (not shown). Mean annual temperature in the Jemez River Basin
significantly correlated with the mean annual temperature recorded at the Quemazon (R2=0.29;
p<0.006) and Señorita Divide#2 stations (R2=0.67; p<0.0001) (not shown).
Mean river basin discharge during the study period was 0.15 mm/day and the maximum
and minimum historical streamflow discharges were 2.97 and 0.008 mm/day, respectively. In the
29 years of daily discharge records, 90% of the time discharge surpassed 0.03 mm/day and 10%
of the time exceeded 0.38 mm/day. Peak discharge occurred between March and May and 58%
of the annual discharge flowed between these months.
From 1984 to 2012, three percent of annual precipitation became quickflow and
contributed directly to the streamflow discharge (3% P; standard deviation STDEV=1.2% P). As
a result, 97% of the annual precipitation (STDEV=1.2% P) infiltrated and was available for
vegetation uptake. This 97% of annual precipitation is further partitioned between vaporization
and baseflow. The amount of water vaporized into the atmosphere represented 91% of the annual
153
precipitation (STDEV=3.4% P). Baseflow corresponded to 6.1% of the annual precipitation
(STDEV=2.2% P) and represented the largest component of discharge (73.2% Q; STDEV =
5.4% Q). Quickflow represented the remaining 26.8% of annual discharge (STDEV=5.4%Q).
During the study period, the mean Horton index was 0.94 (STDEV=0.02).
There was a significant decreasing trend in precipitation and all the water partitioning
components in the upper Jemez River Basin as quantified by the Mann-Kendall test (MKT)
(Figure 2). Precipitation in the basin decreased at a rate of -61.7 mm per decade (p=0.02) (Figure
2a) while discharge decreased at a rate of -17.6 mm per decade (p=0.001) (Figure 2b). The two
components of discharge, baseflow and quickflow decreased at a rate of -12.4 mm (p<0.001) and
-5.1 mm (p=0.005) per decade, respectively (Figure 2c, 2d). Water loss by vaporization
decreased -45.7 mm per decade (p=0.04; Figure 2e) and wetting decreased -56.7 mm per decade
(p<0.02; Figure 2f). As a result, an increasing water limitation trend was observed in the upper
Jemez River Basin as indicated by the decrease in all the water partitioning variables and
increase of 0.014 per decade in the Horton index (p=0.002) (Figure2g). In addition to the
decreasing trend in the amount of basin scale discharge, Q50 showed that 50% of annual
discharge is occurring 4.3 days earlier per decade (p=0.03).
3.3 EEMT
EEMTemp
Using the available 2000 through 2012 remote sensing data, mean MODIS NPP was
found to be 450 g_C/m2 (STDEV=57.1 g_C/m2). Using these 13 years of data, no trend in the
mean annual NPP for the upper Jemez River Basin was found. However, mean annual NPP was
positively correlated with basin scale precipitation (R2=0.56; p=0.003) and baseflow (R2=0.41;
p=0.02) (Figure 3). These results indicated that forest productivity in the upper Jemez River
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Basin is primarily limited by water availability since other climate variables recorded at the two
SNOTEL stations were not good predictors of NPP. From 1984 through 2012 mean Epptemp was
1.03 MJ m2 year-1 (STDEV=0.49 MJ m2 year-1) and mean Ebioemp was 9.89 MJ m2 year-1
(STDEV=1.26 MJ m2 year-1). Multivariate regression analysis indicated that precipitation at the
Quemazon station and the upper Jemez River Basin were the best predictors of Ebioemp
(R2=0.66; p=0.06). Using this multivariate linear regression model, Ebioemp data was
extrapolated for the years 1984 through 1999. Using the combined dataset from extrapolated and
measured Ebioemp the mean annual Ebioemp was 10.8 MJ m2 year-1 (STDEV=1.37 MJ m2 year-1)
for the period from 1984 to 2012. Mean EEMTemp was 11.83 MJ m2 year-1 (STDEV=1.74 MJ m2
year-1) and Ebioemp represented 92% (STDEV=0.03%) of the total EEMTemp during the study
period.
EEMTmodel
From 1984 through 2012 mean Epptmodel was 0.1 MJ m2 year-1 (STDEV=0.07 MJ m2
year-1) and mean Ebiomodel was 6.72 MJ m2 year-1 (STDEV=2.33 MJ m2 year-1). During this same
period, mean EEMTmodel was 6.82 MJ m2 year-1 (STDEV=2.38 MJ m2 year-1) and Ebiomodel
represented 99% (STDEV=1.2%) of the total EEMTmodel.
EEMTemp was on average 1.7 times larger than EEMTmodel. Both EEMTemp and
EEMTmodel showed a significant linear correlation (R2=0.42; p=0.0002) and a similar decreasing
trend of 1.2 MJ.m2.decade-1 (p≤0.01) and 1.3 MJ.m2.decade-1 (p≤0.05), respectively (Figure 4).
Detailed estimations of EEMTemp and EEMTmodel and its components can be found in table S1
(supplementary material). Figure 5 highlights changes of EEMT in the upper Jemez River Basin
155
in relation to water availability from 1984 to 2012. EEMT was positively correlated to annual
baseflow, increasing during wet years and decreasing during dry years.
3.4 Climate controls on discharge
When compared to the climate variables from the Quemazon station, data from the
Señorita Divide#2 showed the strongest linear correlations with discharge (Table S2). The five
variables with the strongest linear correlations to discharge were winter precipitation (R2=0.72;
p=0.00001), maximum SWE (R2=0.55; p=0.00001), last day of snow cover (R2=0.54;
p=0.00001), annual precipitation (R2=0.50; p=0.00001), and annual temperature (R2=0.49;
p=0.00010). Variables such as first day of snow cover, SWE to winter P ratio and SM50 did not
shown any relation.
Similarly, climate variables from Señorita Divide#2 showed the strongest linear
correlations with Horton index (Table S3). The five variables with the strongest linear
correlations to Horton index were winter precipitation (R2=0.59; p=0.00001), maximum SWE
(R2=0.59; p=0.00001), last day of snow cover (R2=0.55; p=0.00001), occurrence of 50% max
SWE (R2=0.41; p=0.00010), and annual temperature (R2=0.40; p=0.00070). SM50 was the only
variable that did not show a strong linear correlation with Horton index at the Señorita Divide#2
station.
Based on a multivariate regression analysis, annual temperature, max SWE and the length
of snow on the ground were the best predictors of discharge and explain above 80% of discharge
variability in the basin (R2>0.80; p<0.0001) (Table 3). The predictive power of this model was
similar regardless of whether data from the Quemazon or Señorita Divide#2 stations was used.
156
From these three predicting variables, annual temperature and max SWE showed decreasing
trends that influence the observed decrease in water availability in the basin. Analysis of
residuals of the linear model between climate variables and Jemez River discharge indicated that
maximum SWE and the duration of the snow cover are the better predictors of discharge
residuals variability. As it is shown in figure S1, Q residuals increased during extreme dry and
wet years.
4.0 DISCUSSION
4.1 Climate variability
Global climate is changing and the instrumental records in the southwestern US for the
last three decades indicate a decline in precipitation and increasing air temperatures in the region
[Hughes and Diaz, 2008; Folland et al., 2001]. Global climate models further predict drier
conditions and a more arid climate for the 21st century in this region [Seager et al., 2007]. For
instance, global climate models indicate, for the future in the southwestern US according to a
low and high emissions scenarios, a substantial increase in air temperature between 0.6 to 2.2 °C
and 1.3 to 5.0 °C for the period 2021-2050 and by end of the 21st century, respectively [Barnett
et al., 2004; Cayan et al., 2013]. An increase in winter temperature of about 0.6 °C per decade
was reported from 1984-2012 at a regional level in the upper Rio Grande Basin [Harpold et al.,
2012]. In line with these other studies, we found that mean annual and winter air temperature in
the upper Jemez River Basin have increased 0.5 °C and 0.4 °C per decade, respectively.
Changes in climate have been found to be a predominant influence in snowpack decline
as oppose to changes in land use, forest canopy or other factors [Hamlet et al., 2005; Boisvenue
and Running, 2006]. There are high confidence predictions that snowpacks will continue to
157
decline in northern New Mexico through the year 2100 and projections of snowpack
accumulation for mid-century (2041-2070) show a marked reduction for SWE of about 40%
[Cayan et al., 2013]. Harpold et al., [2012] found a decrease in annual precipitation and
maximum SWE for the Upper Rio Grande Basin of -33 and -40 mm per decade, respectively. In
this study, a clear decreasing trend in annual, winter precipitation and max SWE was observed in
records from 1984-2012 in the two high elevation SNOTEL stations. Records in this study
showed approximately twice the rate of decrease in annual precipitation and a smaller decrease
in max SWE of about 7 mm per decade compared to the regional results from Harpold et al.
[2012]. Harpold et al. [2012] report that SM50 (-2 days per decade), snow cover length (-4.2
days per decade), day of maximum SWE (-3.31 days per decade), and last day of snow cover (-
3.45 days per decade) for the Rio Grande Basin showed statistically significant trends. However,
based on our analysis from the individual SNOTEL stations, these variables did not show any
statistically significant trends.
4.2 Changes in discharge and evapotranspiration
Decreasing trends in discharge ranging from 10 to 30% are expected during the 21st
century for the western US [Milly et al., 2005] and maximum peak streamflow is expected to
happen one month earlier by 2050 [Barnett et al., 2005]. Furthermore, it has been reported that
streamflow in snowmelt dominated river basins are more sensitive to wintertime increases in
temperature [Barnett et al., 2005]. In this study, we have found that 50.5 % of annual streamflow
occurred between (April) and beginning of the summer (June). This result is congruent with
other studies in snowmelt dominated systems in the region (Clow, 2010). Previous research in
the southwest has found that the timing of snowmelt is shifting to early times ranging from a few
158
days to weeks [Stewart et al., 2005; Mote et al., 2005; McCabe and Clark, 2005]. For instance,
Clow [2010] reports that in southern Colorado rivers, there is a trend toward earlier snowmelt
that varied from 4.0 to 5.9 days per decade and April 1st SWE decreased between 51 and 95 mm
per decade. In this study, it was found that snowmelt timing in the upper Jemez River Basin
occurred 4.3 days earlier per decade and April 1st SWE decreased between 54 – 60 mm/decade.
Changes in evapotranspiration are related to changes in precipitation, humidity, air
temperature, irradiance and wind speed [Barnet et al., 2005]. However, the magnitude and
direction of changes in evapotranspiration are still a source of debate and investigation [Ohmura
and Wild, 2002]. Pan evaporation in various countries in the northern Hemisphere show that
evaporation has been progressively decreasing over the past 50 years [Barnett et al., 2005]. A
reduction in evapotranspiration is expected in snowmelt dominated systems, as early snowmelt
provides water to the landscape when potential evapotranspiration is low and reducing soil
moisture during months with high evapotranspiration demand [Barnett et al., 2005]. In addition,
rising CO2 concentrations will likely increase plant water use efficiency, enhance stomatal
closure and reduce transpiration [Betts et al., 2005]. In this study, we found evidence of a
decrease in vaporization of 45.7 mm/decade in the upper Jemez River basin.
4.3 EEMT components
Water partitioning
Troch et al. [2009] demonstrated that the Horton index gets closer to 1 in drier regions
and during dry years. Similarly, in a study based on 86 catchments in different biomes and
ecosystems across the US, Horton index values increased as catchments became more water
159
limited [Brooks et al., 2011]. Huxman et al. [2004] showed that the average rain-use efficiency
(RUE), estimated as the ratio of aboveground net primary production to annual precipitation,
decreases as precipitation increases. In contrast, during dry years RUE converges to common
maximum RUE similar to the drier regions, regardless of biome type. The increase in water use
efficiency by vegetation as the upper Jemez River basin becomes drier indicated by the Horton
index variability (0.94; STDEV=0.02) is consistent with the above mentioned studies.
Forest productivity
Reduced carbon compounds resulting from primary production are a fundamental energy
component of EEMT [Rasmussen et al., 2011]. Modeling and empirical studies indicate that
mountain forest productivity in the southwest is sensitive to water and energy limitations
[Christensen et al., 2008; Tague et al., 2009; Anderson-Teixeira et al., 2011; Zapata-Rios et al.,
in prep]. Trujillo et al. [2012] found that NDVI greening increased and decreased proportionally
to the changes in snowpack accumulation along a gradient in elevation in the Sierra Nevada,
while Zapata et al., [in prep] found similar results across a gradient of energy created by aspect
differences at higher elevations in the Jemez Mountains. Furthermore, energy limitations to
productivity have been observed in colder sites at high elevations [Trujillo et al., 2012;
Anderson-Teixeira et al., 2011; Zapata et al. in prep]. Since the mid-1980 increases in wildfires
and tree mortality rates have been documented in high elevation forests due to an increase in
spring and summer temperatures and decrease in water availability [Westerling et al., 2006; Van
Mantgem, P.J et al., 2009]. Results from this study indicated that in the upper Jemez River
Basin, forest productivity was primarily responding to water availability (Figure 3).
EEMT variability
160
All of the above results indicate that the Jemez River Basin is highly susceptible to
changes in climate that can affect water availability and ecosystem productivity which impacts
EEMT. Rasmussen et al. [2005] estimated low rates of EEMTmodel < 15 MJ.m-2.year-1 for the
majority of the continental US and proved that Ebio was the dominant component of EEMT with
contributions above 50% of total EEMT in different soil orders. Regions dominated by Ebio
corresponded to regions facing water limitation and where Ebio accounted for up to 93% of the
total energy and carbon flux to the CZ [Rasmussen et al., 2011; Rasmussen and Gallo, 2013]. In
semi-arid regions vaporization represents over 90% loss of annual precipitation [Newman et al.,
2006] while groundwater recharge accounts for less than 10% of annual precipitation [Scanlon et
al., 2006]. Under these conditions, little water remains for critical zone processes in semi-arid
regions. Other studies have found that the contributions of Ebio can be three to seven orders of
magnitude larger than other sources of energy influxes to the CZ [Phillips, 2009; Amundson et
al., 2007]. In this study, we confirmed that for the upper Jemez River Basin, Ebio was the
dominant term from the total EEMT and Eppt contributions were small.
A comparison of EEMTmodel and EEMTemp in 86 catchments across the US characterized
by having minimum snow influence indicated that model and empirical values were strongly
linearly correlated (R2=0.75; p<0.0001) and EEMTmodel values were larger than EEMTemp
[Rasmussen and Gallo, 2013]. One limitation of the EEMTmodel method is that it calculates
energy during the months when air temperature is above zero only and assumes no energy
associated with precipitation falling as snow. In a snowmelt dominated systems as the upper
Jemez River Basin where snowmelt is the main source of water availability to ecosystems [Bales
et al., 2006], EEMT estimations based only on climate data will likely underestimate the energy
transfer to the CZ. Therefore, using EEMTemp methodology may be more suitable for snowmelt
161
dominated systems. In this study we found the expected linear correlation between EEMTmodel
and EEMTemp (R2=0.42; p<0.001) however, EEMTmodel values were smaller than EEMTemp
values. Although the two methods used in this study to calculate EEMT indicated different
absolute values of EEMT, the rates of decrease of EEMT per decade are congruent with each
other (EEMTemp=1.2 MJ.m2.decade-1 ; EEMTmodel = 1.3 MJ.m2.decade-1) (Figure 5).
The rates of EEMT change between 1.2 to 1.3 MJ.m2. per decade found in this study in
the upper Jemez River Basin can be significant for critical zone processes. In a study conducted
in a similar semi-arid region in the Santa Catalina Mountains located in southern Arizona,
Rasmussen et al. [2015] estimated differences in EEMT of about 25 MJ m2 year-1 between the
upper elevation (2800 m) covered by mixed conifer forest and low elevation (800 m) covered by
a dry semi-arid desert scrub ecosystem. These changes in EEMT along the 2000 m elevation
gradient in the Catalina Mountains are equivalent to a difference of 1.25 MJ m2 year-1 per 100
meters in elevation change. Furthermore, Rasmussen et al. [2015] determined differences of 3.9
MJ m2 year-1 between contrasting north and south facing slopes, and of 0.9 MJ.m2.year-1
according to topographic wetness between water gaining and water losing portions of the
landscape.
Although the quantification of EEMT using the methodologies applied in this study are
suitable for large spatial scales, it is limited in that it is not taking into account small scale
variabilities induced by topography in solar energy, effective precipitation, NPP and
redistribution of water by differences in micro-topography. Therefore, EEMT estimations at
small scales (pedon to hillslopes) need to follow a different approach as indicated in Rasmussen
et al. [2015].
162
5.0 SUMMARY
We investigated how changes in climate in the southwest affect the trends in water
availability, vegetation productivity and the annual influxes of EEMT to the CZ. This
investigation took place in the 1200 km2 upper Jemez River basin a semi-arid basin in northern
New Mexico using records from 1984-2012. Results at the two SNOTEL stations indicated clear
increasing trends in temperature and decreasing trends in precipitation and maximum SWE.
Temperature changes include warmer winters (+1.0-1.3 °C/decade), and generally warmer year
round temperatures (+1.2-1.4 °C/decade). Precipitation changes include, a decreasing trend in
precipitation during the winter (-41.6-51.4 mm/decade), during the year (-69.8-73.2 mm/decade)
and max SWE (-33.1-34.7 mm/decade). At the upper Jemez River Basin ,all the water
partitioning components showed statistical significant decreasing trends including precipitation
(-61.7mm/decade), discharge (-17.6 mm/decade) and vaporization (-45.7 mm/decade). Similarly,
Q50 an indicator of snowmelt timing is occurring -4.3 days/decade earlier. Basin scale
precipitation (R2=0.56; p=0.003) and baseflow (R2=0.41; p=0.02) were the strongest controls on
NPP variability indicating that forest productivity in the upper Jemez River Basin is water
limited. An increasing trend in Horton index suggests that water limitation and vegetation water
use are increasing in the basin. This study showed a positive correlation between water
availability and EEMT. For every 10 mm of change in baseflow, EEMT varies proportionally in
0.6-0.7 MJ m-2year-1. From 1984-2012 changes in climate, water availability, and NPP have
influenced EEMT in the upper Jemez River Basin. A decreasing trend in EEMT of 1.2 to 1.3 MJ
m-2 decade-1was calculated in this same time frame. As the landscape moves towards a drier and
hotter climate, changes in EEMT of this magnitude are likely to influence critical zone processes.
163
We thank the funding provided by the NSF-supported Jemez River Basin and Santa Catalina
Mountains Critical Zone Observatory EAR-0724958 and EAR-1331408).

164
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172
8.0 FIGURES
Figure 1. a) Relative location of study area within the northwestern state of New Mexico, b)
upper Jemez River Basin, ~1200 km2, delimited above the USGS gauge station “Jemez River
near Jemez” (USGS 08324000) based on a 10 m digital elevation model (DEM).
173
a) b)
900 140
Precipitation (mm)
120 Precipitation
Discharge (mm)
800 m = -6.17
100 p=0.02 (MKT)
700
80
600
60
500
40
400 20 Discharge
m = -1.76
300 0 p=0.001 (MKT)
1980 1985 1990 1995 2000 2005 2010 1980 1985 1990 1995 2000 2005 2010
90 50
c) d)
Quickflow (mm)
80
Base flow (mm)
Base flow
70 40 m = -1.24
p<0.001 (MKT)
60 30
50
20
40
30 10
Quickflow
20 m = -0.51
0
10 p=0.005 (MKT)
1980 1985 1990 1995 2000 2005 2010 1980 1985 1990 1995 2000 2005 2010
800 900
e) f) Vaporization (V)
700 800 m = -4.57
p=0.04 (MKT)
600 700
W (mm)
V (mm)
500 600
400 500
300 400 Wetting (W)
m = -5.67
200 300 p=0.02 (MKT)
1980 1985 1990 1995 2000 2005 2010 1980 1985 1990 1995 2000 2005 2010
0.98 220
g) h) HI
0.96 210 m = 0.0014
p=0.002 (MKT)
Q50 (DOWY)
0.94 200
HI
0.92 190
0.90 180
Q50
0.88 170 m = -0.43
p=0.03 (MKT)
0.86 160
1980 1985 1990 1995 2000 2005 2010 1980 1985 1990 1995 2000 2005 2010
Time (years)
174
Figure 2. Precipitation and water partitioning at the upper Jemez River catchment scale. There
was a significant decreasing trend quantified by the Mann-Kendall test (MKT) in the Jemez
River Basin precipitation and all the components of the water partitioning. For instance,
precipitation at the catchment scale decreased during the last three decades at a rate of 6.17 mm
per year and discharge at 1.76 mm per year. From 1984-2012, Horton index (HI) increased as
the basin dried up, indicating that vegetation used more of its available water with increasing
water limitation in the basin. Q50 indicated that discharge is occurring 4.3 days earlier per
decade.
175
0.60 0.60
NPP (g_C m-2 year-1)

NPP (g_C m-2 year-1)
0.55 0.55
0.50
0.50
0.45
0.45
0.40
0.40
0.35 2 2
R =0.56 R =0.41
0.30 0.35
p=0.003 p=0.02
0.25 0.30
300 400 500 600 700 800 10 20 30 40 50
P Jemez River (mm/year) Baseflow (mm/year)
Figure 3. a) Positive linear correlation between precipitation in the upper Jemez River Basin and
annual NPP in the upper Jemez River Basin derived from MODIS; b) Linear correlation between
baseflow and annual NPP in the upper Jemez River Basin. Forest productivity is water limited in
the upper Jemez River Basin. Other variables such as annual, winter and summer air temperature
did not correlate with NPP.
176
a) b)
18 18
m= -0.124 R2=0.42
16 16
EEMTmodel (MJ.m-2.year-1)
p<0.01 (MKT) p=0.0002
EEMT (MJ.m-2.year-1)
14
14
12
12
10
8 10
6 8
4 6 1
m= -0.129 1:
2
p<0.05 (MKT) 4
0
1980 1985 1990 1995 2000 2005 2010 4 6 8 10 12 14 16 18
Water years EEMTemp (MJ.m-2.year-1)
EEMTemp
EEMTmodel
Figure 4. a) EEMTemp and EEMTmodel showed similar significant decreasing trends from 1984-
2012 of 1.2 and 1.3 MJ m-2 year-1 b) EEMTemp and EEMTmodel showed a significant linear
correlation.
177
16
R2=0.61
14 p<0.0001
EEMT (MJ.m-2.year-1)
m=0.07
12
10
8
R2=0.21
6
p<0.01
4 m=0.06
2
20 40 60 80
Baseflow (mm)
EEMTemp
EEMTmodel
Figure 5. Relationship between water availability and EEMT. Baseflow and EEMT showed a
positive linear correlation. As water availability in the Jemez River basin decreases indicated by
baseflow, EEMT also decreases.
178
9.0 TABLES
Table 1. Land use classification of the Jemez River Basin area. 79.7% of the total basin is
covered by forest according to the National Land Cover Database (NLCD)
[http://www.mrlc.gov/nlcd06_leg.php]
Area
Land use class (Km2) %
Evergreen forest 847.7 69.60
Deciduous forest 92.6 7.61
Mixed forest 29.8 2.44
Grassland/herbaceous 128.0 10.51
Shrub/scrub 85.0 6.98
Pasture/Hay 1.8 0.14
Barren land (rock, sand, clay) 1.3 0.10
Developed 6.1 0.50
Cultivated crops 0.1 0.01
Wetlands 25.2 2.07
Open water 0.4 0.03
Total 1218.0 100.00
179
Table 2. Site and meteorological information for the SNOTEL Quemazon and Señorita Divide
#2 stations located at high elevations in the upper part of the Jemez River Basin.
Mean Air Mean

Temperature Precipitation
(˚C) (mm)
Max
Station Station Elevation Latitude Longitude Active SWE
Id Name (m) (N) (W) since Yearǂ Winter† Yearǂ Winter† (mm)
708 Quemazon 2896 35.92° -106.39° 1980 3.98 -0.87 700.78 347.45 242.53
Senorita
744 Divide #2 2622 36.00° -106.83° 1980 4.23 -0.90 685.98 422.87 239.20
Note:
The analysis of precipitation since WY 1984
ǂWater Year: Oct 1st to Sep 30th
†Winter: Oct 1st to March 31st
Temperature data availability since 1989 for the Quemazon and 1988 for the Senorita Divide #2 station
180
Table 3. Climatic time series trends for the Quemazon and Señorita Divide #2 SNOTEL stations
from 1984-2012. A trend in the precipitation time series was evaluated with the Mann-Kendall
test (MKT) and Sen’s slope estimator. Trends were considered statistically significant at p≤0.1.
The results showed an increasing trend in winter, summer and annual temperature in the two
stations. Annual and winter precipitation, maximum SWE and 1st of April SWE decreased in
both stations during the 29 years analyzed. The last day of snow cover decreases significantly
only at the Quemazon station. No significant trend was observed for the SWE: winter P ratio,
duration of snowmelt SM50 and length of snow on the ground.
Quemazon Señorita Divide #2

Q Sen's slope Sig Q Sen's slope Sig
Variable estimator † estimator †
Winter Temp 0.13 *** 0.10 *
Summer Temp 0.10 ** 0.10 **
Annual temp 0.14 *** 0.12 ***
Annual Precip(mm) -6.98 ** -7.32 *
Winter Precip (mm) -4.16 + -5.94 *
Max SWE (mm) -3.31 + -3.47 +
SWE:winter P ratio -0.005 -0.002
1 April SWE -6.05 * -5.44 +
Max SWE day -0.57 * -0.33
SM50 (days) -0.02 0.12
1st day snow cover
(day) -0.50 0.17
last day snow cover
(day) -0.65 * -0.31
snow on ground (days) -0.12 -0.60
†Statistical
significance
+ P<0.1
* P < 0.05
** P < 0.01
*** P < 0.001
181
Table 4. Discharge predictors for the Jemez River basin based on climate variables recorded at
Quemazon and Señorita Divide#2 SNOTEL stations. Annual temperature, max SWE and the
length of snow on the ground were the best predictors of discharge in the basin. The
predictability power of discharge was similar from climatic variables recorded at the Quemazon
and Señorita Divide#2 stations. Annual temperature and max SWE climatic variables had a
decreasing trend that influenced the decrease in water availability in the basin.
Quemazon Señorita Divide#2

p values p values
Intercept -7.57 0..071 37.75 0.0128
Annual Temp (˚ C) -7.23 0.0035 -3.5 0.07
Max SWE (mm) 0.14 0.0003 0.21 0.0001
Snow on the ground (days) 0.32 0.03 -0.18 0.05
R2 0.81 0.80
p <0.0001 <0.0001
182
10.0 SUPPLEMENTARY INFORMATION
60 60
40 R2=0.35 40 R2=0.38
Q residuals (mm)
Q residuals (mm)
p=0.0004 p=0.0002
20 20
0 0
-20 -20
-40 R2=0.61 -40 R2=0.63

p<0.0001 p<0.0001
-60 -60
0 100 200 300 400 500 600 0 50 100 150 200 250
Max SWE (mm) Snow on ground (days)

Quemazon
Señorita
Figure S1. Plot of residuals between max SWE and snow on the ground from the linear model
presented in Figure 2b. Maximum SWE and duration of the snow cover are the better predictors
of discharge residuals variability. Q residuals increase during extreme dry and wet years.
183
Table S1. Empirical and modelled EEMT values estimated for the upper Jemez River basin.
Ebioemp was estimated by multivariable linear regression from annual Precipitation at the
Quemazon station and Jemez River basin between 1984-1999 (R2=0.75; p=0.0009)
EEMTemp EEMTmodel
Water
year Epptemp Ebioemp EEMTemp Epptmodel Ebiomodel EEMTmodel
1984 1.28 11.27 12.55 0.05 5.09 5.14
1985 2.37 12.43 14.80 0.20 5.47 5.67
1986 1.42 12.48 13.90 0.19 9.34 9.53
1987 1.60 11.15 12.75 0.09 8.71 8.80
1988 1.16 11.21 12.37 0.14 8.52 8.66
1989 0.87 9.28 10.15 0.05 4.18 4.24
1990 0.80 11.77 12.56 0.14 5.45 5.58
1991 1.35 13.61 14.96 0.27 14.22 14.49
1992 1.77 11.47 13.24 0.14 9.11 9.26
1993 1.49 11.43 12.93 0.07 8.51 8.58
1994 0.75 11.96 12.71 0.15 8.79 8.94
1995 1.74 11.93 13.67 0.19 8.72 8.91
1996 0.33 10.13 10.46 0.02 4.94 4.96
1997 1.37 12.12 13.48 0.11 7.83 7.94
1998 1.04 10.94 11.98 0.04 4.98 5.02
1999 1.04 11.47 12.51 0.21 10.90 11.11
2000 0.60 8.42 9.02 0.06 5.35 5.42
2001 1.09 10.20 11.30 0.08 5.73 5.81
2002 0.35 8.36 8.71 0.05 5.78 5.83
2003 0.62 9.67 10.28 0.04 5.95 5.99
2004 0.77 10.03 10.81 0.18 5.89 6.07
2005 1.30 10.98 12.28 0.08 5.66 5.74
2006 0.48 11.08 11.56 0.03 5.23 5.26
2007 1.00 12.56 13.57 0.06 5.74 5.80
2008 0.88 10.45 11.33 0.01 5.24 5.24
2009 0.65 9.39 10.03 0.09 6.03 6.12
2010 0.73 10.39 11.13 0.08 5.20 5.29
2011 0.39 8.43 8.82 0.03 4.29 4.31
2012 0.50 8.65 9.15 0.03 4.12 4.16
184
Table S2. Relationship between climatic variables and discharge in the Jemez River Basin (1984-
2012) based on records from the Quemazon and Señorita Divide#2 SNOTEL stations. The
variables are listed in decreasing order according to the linear R2 value from the Señorita
Divide#2 station.
Discharge
Señorita Divide#2
Quemazon station station
2
Variable slope R p slope R2 p
Winter P (mm) 0.18 0.24 0.00550 0.19 0.72 0.00001
1 April SWE 0.18 0.64 0.00010 0.16 0.56 0.00001
Max SWE (mm) 0.23 0.71 0.00010 0.19 0.55 0.00001
last day snow cover
(day) 2.01 0.66 0.00001 1.83 0.54 0.00001
Annual P (mm) 0.10 0.19 0.01480 0.13 0.50 0.00001
- -
Annual temp 11.03 0.27 0.00850 10.90 0.49 0.00010
50% max SWE day 1.92 0.48 0.00010 1.71 0.41 0.00010
Summer Temp -2.04 0.01 0.58740 -4.94 0.32 0.00320
Winter Temp -8.57 0.17 0.04400 -9.58 0.29 0.00530
snow in ground (days) 0.88 0.44 0.00001 0.37 0.25 0.00390
Max SWE day 1.15 0.31 0.00120 0.65 0.13 0.04800
1st day snow cover
(day) -0.51 0.09 0.10290 -0.30 0.12 0.05570
SWE:winter P ratio 69.29 0.40 0.00020 52.28 0.09 0.09240
SM50 (days) -0.22 0.00 0.73350 0.24 0.01 0.58760
185
Table S3. Relationship between climatic variables and Horton index from the Jemez River basin
(1984-2012) based on records from the Quemazon and Señorita Divide#2 SNOTEL stations.
The variables are listed in decreasing order according to the linear R2 value from the Señorita
Divide#2 station.
Horton index
Señorita Divide#2
Quemazon station station
Variable slope R2 p slope R2 p
- -
Winter P (mm) 0.0001 0.22 0.00850 0.0001 0.59 0.00001
- -
1 April SWE 0.0001 0.60 0.00001 0.0001 0.55 0.00001
- -
Max SWE (mm) 0.0002 0.67 0.00001 0.0002 0.59 0.00001
last day snow cover - -
(day) 0.0017 0.62 0.00001 0.0016 0.52 0.00001
- -
Annual P (mm) 0.0001 0.09 0.09940 0.0001 0.29 0.00160
Annual temp 0.0103 0.32 0.00430 0.0086 0.40 0.00070
- -
50% max SWE day 0.0017 0.50 0.00001 0.0015 0.41 0.00010
Summer Temp 0.0019 0.01 0.57230 0.0038 0.25 0.01160
Winter Temp 0.0079 0.19 0.03300 0.0079 0.26 0.00910
- -
snow in ground (days) 0.0007 0.34 0.00060 0.0004 0.31 0.00100
- -
Max SWE day 0.0010 0.33 0.00070 0.0006 0.15 0.03140
1st day snow cover
(day) 0.0003 0.04 0.26470 0.0003 0.18 0.01890
- -
SWE:winter P ratio 0.0588 0.39 0.00020 0.0620 0.18 0.01700
-
SM50 (days) 0.0002 0.01 0.64710 0.0001 0.00 0.74040
186
APPENDIX D:
NOBLE GASES AND SF6 CONCENTRATIONS FROM SPRINGS AROUND
REDONDO PEAK, NEW MEXICO
Figure 1. Springs draining Redondo Peak
1.0 NOBLE GASES

Recharge elevation, recharge temperature and excess air was calculated based on noble gases
concentrations from springs (table 1). These variables were inferred applying inverse modeling
and the known concentrations of Ne, Ar, Kr and Xe according to the methodology described in
Aeschbach-Hertig et al. (1999) (Table 2). Water recharge around Redondo Peak (3435 m) occurs
in all the springs at high elevations above 2970 meters and above 3200 m in 7 springs. The annual
air temperature recorded in Redondo station at 3200 m in elevation was 3.8˚C, and water recharge
temperatures were estimated between 4.5 and 9.7˚C. There were three springs including Redondo
Meadow, East spring and Redondo spring 3 with temperatures above 7˚C (Figure 2).
187
Table 1. Noble gases concentrations from the springs

Sample Spring Name Spring Ar total Ne total Kr total Xe total He4
I.D. ID (ccSTP/g) (ccSTP/g) (ccSTP/g) (ccSTP/g) (ccSTP/g)
NMS1129 South spring LJ2 2.91E-04 1.56E-07 6.92E-08 1.03E-08 3.70E-08
NMS1130 Top of la Jara LJ1 2.90E-04 1.55E-07 6.99E-08 1.00E-08 3.62E-08

NMS1134 Upper Redondo pond UR1 2.92E-04 1.55E-07 6.97E-08 9.95E-09 3.67E-08
NMS1135 Upper Redondo spring 3 UR3 2.74E-04 1.49E-07 6.49E-08 9.40E-09 3.80E-08
NMS1136 Upper Jaramillo wall UJ1 2.84E-04 1.53E-07 7.09E-08 1.03E-08 3.62E-08
NMS1137 Upper Jaramillo spring 3 UJ2 2.82E-04 1.59E-07 7.04E-08 1.01E-08 3.73E-08
NMS1138 La Jara seep LJ4 2.97E-04 1.58E-07 7.39E-08 1.10E-08 3.67E-08
NMS1140 East spring Es 2.77E-04 1.52E-07 6.76E-08 9.77E-09 3.59E-08

NMS1141 Top of History Grove HGs 2.80E-04 1.52E-07 7.03E-08 1.02E-08 3.59E-08
Table 2. Recharge elevation, temperature and excess air based on an analysis of Ne, Ar, Kr and
Xe
Spring Spring Spring Recharge Temp Excess Air

discharge ID elevation (˚C) A cc/kg = ml
elevation (m)
(m)
South spring 3069 LJ2 3200 5.93 0.84
Top of la Jara 3195 LJ1 3336 5.71 0.91
Upper Redondo pond 2839 UR1 3433 5.43 1.03
Upper Redondo spring 3 2917 UR3 3252 7.92 0.70
Upper Jaramillo wall 2848 UJ1 3323 4.90 0.77
Upper Jaramillo spring 3 2876 UJ2 3222 6.32 1.03
La Jara seep 2817 LJ4 3043 4.53 0.70
East spring 2860 Es 2979 7.77 0.58
Top of History Grove 2908 HGs 2978 6.61 0.43
188
10.00
9.00
8.00
Temperature (C)
7.00
6.00
5.00
4.00
3.00
2.00
2700 2900 3100 3300 3500
Recharge elevations (m)
Recharge Temp. Ave. Annual Air Temp
Figure 2. Recharge elevation and recharge temperature in springs inferred with noble gases
concentrations
2.0 SF6
SF6 concentrations from springs can be grouped in two classes (Figure 4). There is a first group
with SF6 concentrations above 200 fg/kg and a second group with concentrations below 150 fg/kg.
These differences in SF6 concentrations between the two groups define differences in water ages
(Table 3). SF6 water ages derived from the group 1 were very similar to the water ages estimated
with tritium (reported in Appendix A). Understanding the differences in SF6 concentrations from
the two groups needs further research and spring’s resampling. Moreover, there was an inverse
relationship between SF6 concentrations and excess air (Figure 4). Figure 5 and Figure 6 shows
tritium ages versus SF6 group 1 and group 2. Although these plots show large difference in ages,
SF6 ages were strongly correlated with cations e.g. Na+ similar to the results based on tritium ages
(Figure 7).
189
Table 3. SF6 concentrations and Age
Utah Lab
SF6 values
SF6 Age excess air (cm3

Group Springs fg/kg (years) STP/Kg)
1 Top of History Grove 313.37 5.2 0.83
1 Upper Redondo Pond 283.51 8.7 0.88
1 East Spring 370.63 0.7 0.91
1 Upper Jaramillo Wall (UJ2) 303.38 7.2 0.79
2 Upper Redondo Spring 3 231.76 11.2 0.78
2 La Jara Seep 211.20 15.2 0.99
3 South spring 141.67 21.2 1.30
3 Top of La Jara 111.00 24.2 1.34
3 Upper Jaramillo Spring 3 (UJ1) 100.77 25.7 1.54
400
350
y = -270.69x + 514.91
300 R² = 0.7369
SF6 (fg/kg)
250
200
150
100
50
0
0.00 0.50 1.00 1.50 2.00
Excess air (cm3 STP/kg)
Figure 4. SF6 concentrations versus excess air in the springs. Springs can be grouped into two
groups.
190
25
20 y = 1.6519x - 1.3767
R² = 0.8696
SF6 group 1 and 2
15
10
-5
0.00 2.00 4.00 6.00 8.00 10.00 12.00
Tritium Age (Arizona)
Figure 5. SF6 ages from springs with SF6 concentrations above 200 fg/kg versus Tritium ages
from Arizona
45.00 y = 3.8317x - 0.3425

40.00 R² = 0.9081
35.00
SF6 group 1 and 2
30.00
25.00
20.00
15.00
10.00
5.00
0.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00
Tritium Age (Arizona)
Figure 6. SF6 ages from the second group (<150 fg/kg).

191
250
200
Na (umol/L)
150
100
y = 7.269x + 81.847
R² = 0.7189
50
0
0 5 10 15 20 25
SF6 (age)
Figure 7. Na vs SF6 age based on the samples from the group (SF6>200 fg/kg)
192
3.0 REFERENCES
Aeschbach-Hertig, W., F. Peeters, U. Beyerle, and R. Kipfer, 1999. Interpretation of dissolved
atmospheric noble gases in natural waters. Water Resour. Res. 35:2779-2792

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The Influence of Climate and Landscape on Hydrological

Processes, Vegetation Dynamics, Biogeochemistry and the

Item Type text; Electronic Dissertation

Authors Zapata-Rios, Xavier

Publisher The University of Arizona.

Rights Copyright © is held by the author. Digital access to this material

Download date 26/02/2021 05:21:03

Link to Item http://hdl.handle.net/10150/555944

THE INFLUENCE OF CLIMATE AND LANDSCAPE ON HYDROLOGICAL PROCESSES,

A Dissertation Submitted to the Faculty of the

DEPARTMENT OF HYDROLOGY AND WATER RESOURCES

In Partial Fulfillment of the Requirements

For the Degree of

WITH A MAJOR IN HYDROLOGY

In the Graduate College

THE UNIVERSITY OF ARIZONA

THE UNIVERSITY OF ARIZONA

_____________________________________________________________ Date: 03/13/15

_______________________________________________________________ Date: 03/13/15

________________________________________________________________ Date: 03/13/15

________________________________________________________________ Date: 03/13/15

________________________________________________________________ Date: 03/13/15

Dissertation Director: Jennifer McIntosh

Dissertation Director: Peter A. Troch

SIGNED: Xavier Zapata-Ríos

3.0 RESULTS ......................................................................................................................................... 46

4.3 Vegetation structure and NDVI response ................................................................................... 103

6.0 ACKNOWLEDGEMENTS ............................................................................................................ 163

elevation ecosystems in catchments draining different aspects of Redondo Peak. The

1.1. The Critical Zone

[Chorover, et al., 2011].

ecohydrology [Chorover et al., 2011]. Moreover, observations of processes along spatial

1.2 Climate and landscape controls on hydrology and vegetation

critical zone (CZ).

energy gradient during a period characterized by years with extremes in precipitation.

1.3 Research Objectives

primary productivity and dissolved inorganic carbon.

CZ as physical, chemical denudation, baseflow, solutes, DIC/DOC fluxes. Indicators are

and energy storage.

figure 1 are the following:

1. Water mass balance

P= precipitation, E= evapotranspiration, S= surface run-off, U=baseflow, W=wetting

3. Carbon mass balance

The main research questions tackled during this dissertation are:

have been quantified.

term partitioning of water and vegetation dynamics around Redondo Peak.

productivity, and decreasing influxes of mass and energy.

1.4 Dissertation format

peer-review publication. These papers are included individually in the appendices.

weathering in the critical zone.

APPENDIX B. Influence of terrain aspect on water partitioning, vegetation structure, and

vegetation greening in high elevation catchments in northern New Mexico.

transfer (EEMT) in a semi-arid critical zone.

Bales, R. C., N. P. Molotch, T. H. Painter, M. D. Dettinger, R. Rice, and J. Dozier (2006),

Brantley, S. L., M. B. Goldhaber, and K. V. Ragnarsdottir (2007), Crossing disciplines and

scales to understand the Critical Zone, Elements, 3, 307-314.

Cayan, D., M. Tyree, K. E. Kunkel, C. Castro, A. Gershunov, J. Barsugli, A. J. Ray, J. Overpeck,

M. Anderson, J. Russell, B. Rajagopalan, I. Rangwala, and P. Duffy. 2013. “Future Climate:

Black, and S. LeRoy, 101–125. Washington, DC: Island Press.

Hydrology and Earth System Sciences, 18, 649-671.

Gustafson, J. R., P. D. Brooks, N. P. Molotch, and W. C. Veatch (2010), Estimating snow

Water Resour. Res., 46, W12511.

Hopp, L., C. Harman, S. L. E. Desilets, C. B. Graham, J. J. McDonnell, and P. A. Troch (2009),