The Stable Carbon and Oxygen Isotopic Composition

of Pedogenic Carbonate and its Relationship to

Climate and Ecology in Southeastern Arizona
By Andrew L. Kowler
December 17, 2007
ABSTRACT
13 18
The stable carbon (δ C) and oxygen (δ O) isotopic composition of terrestrial carbonate has

been used to reconstruct late Quaternary paleoecological and paleoclimatic conditions,

respectively, for many different regions of the world. Quantitative reconstructions of past

variability in climate and the distribution of C3/CAM/C4 vegetation from carbonate in soils and

speleothems depend upon a rigorous examination of the modern soil isotopic system. To
13 18
accomplish this, we examined changes in the δ C and δ O in relation to modern climatic and

ecological conditions along an elevation gradient in southeastern Arizona. Five sites were
18
selected for study, spanning 1,170 m of elevation. Along this gradient, δ13C and δ O values

from ≥50 cm soil depth range from -9.9 to -0.6‰ and from -9.4 to -1.3‰, respectively.

Modeling results suggest that δ13C values were determined by soil respiration rates and the

proportion of C3/CAM/C4 biomass. For sites with low respiration, δ13C values from >50 cm

reflected an atmospheric contribution of up to 55% compared to <20% for sites with much

higher respiration rates. At the lowest respiration sites, maximum observed δ18O values from

>50 cm diverge from minimum (winter) predicted values by +4.3 to +7.1‰, reflecting the

influence of evaporation. In contrast, values for the highest respiration rate site fell entirely

between those predicted from winter and summer rainfall. The latter finding suggests that a

significant proportion of carbonate may form during winter, and that there is a positive

correlation between respiration rate and the ratio of transpiration to evaporation accounting for

soil drying.

Results suggest that the reconstruction of absolute changes in vegetation composition from

carbonate isotopic composition will require quantification of the influence of soil respiration on

δ13C values. In turn, this knowledge can be used to quantify the maximum extent of evaporation

1
on δ18O values, and to reconstruct minimum shifts in the δ18O composition of meteoric water.

Conversely, if the δ18O value of paleo-precipitation is known, carbonate δ18O values might serve

as a proxy for past respiration rates and to infer the magnitude of atmospheric contributions to

δ13C values.

2
INTRODUCTION

Background

13 18
The stable carbon (δ C) and oxygen (δ O) composition of carbonate in soils and in

speleothems has been used to reconstruct late Quaternary paleoecological and paleoclimatic
13 18
conditions for many different regions of the world. The δ C and δ O composition of pedogenic

carbonate has been extensively modeled and analyzed (Cerling, 1984; Quade et al., 1989a;

Cerling and Quade, 1993; Quade et al., 2007) and is reasonably well understood. Carbonate-

containing paleosols suitable for paleoenvironmental reconstruction are widely distributed across

arid and semi-arid regions, with records extending back several million years (e.g. Cerling et al.,

1989; Cerling and Hay, 1986; Quade et al., 1989b; Gabunia et al., 2000; Levin et al., 2004;

Quade et al., 2004). Further, recent advances in uranium-series dating of carbonate rinds

promise to provide key age-control on soil isotopic archives (Ludwig and Paces, 2002; Sharp et

al., 2003).

In contrast to soils, speleothems are attractive targets for paleoclimate reconstructions because

they are datable and may behave as closed systems (Quade, 2004), providing near-continuous records

of climate change with much finer temporal resolution than soils (McDermott, 2004). Because of the

specific geologic setting required for speleothem formation, such records are far less abundant than
18
paleosol records. The δ O composition of carbonate in modern cave speleothems has been carefully

documented (e.g. Ayalon et al., 1998; Bar-Mathews et al., 1995; Schwarcz et al., 1976; Harmon,

1979; Goede et al., 1982), while their δ13C composition is poorly understood. Nonetheless,
13
speleothem δ C values have been widely interpreted under the assumption that carbonate in caves

behaves as it does in soils (e.g. Bar-Mathews et al., 1997, 1999; Baskaran and Krishnamurthy, 1993;

Brook et al., 1990; Denniston et al., 1999, 2000, 2001; Dorale et al., 1992, 1998), although this is not

3
 13
necessarily the case (Quade, 2004). While understanding the soil carbonate δ C system is a primary

condition for understanding that of caves, the scope of our study is limited to treatment of the soil

system.

Previous work on soil carbonate in the southwestern US has produced records of

paleoenvironmental change spanning the late Pleistocene to late Holocene, including a record

from the Ajo Mountains of south-central Arizona (Liu et al., 1996), and others from the Organ

Mountains of southern New Mexico (Buck and Monger, 1999; Cole and Monger, 1994; Monger

et al., 1998). However, soil records cannot be used to quantitatively reconstruct past ecological

conditions until the δ13C composition of pedogenic carbonate is understood in relation to modern

environmental conditions. To this end, our study examines the carbon and oxygen isotopic

system of modern soils with respect to modern ecological and climatic conditions in southeastern

Arizona.

More specifically, we seek to understand the isotopic composition of modern carbonate with

respect to changes in the distribution of C3, C4, and CAM vegetation along an elevation gradient

in southeastern Arizona (Fig. 1). Using this approach, we can quantify for pedogenic carbonate

(1) variation in δ18O composition (δ18Opc) as a function of altitude, because the δ18O value of

meteoric water (δ18Omw) decreases with increase in elevation (Rozanski et al., 1993), and (2)

variation in δ13C composition (δ13Cpc) as a function of vegetation composition and soil

respiration rate. In turn, knowledge of these relationships will enable us to reconstruct past

climate and ecology from paleosol and related records.

4
Study Area

Field studies were conducted in the Basin and Range physiographic province in the

southwestern USA near Tucson, Arizona (Fig. 1). The sites studied range in elevation from 730-

1900 m above mean sea level, and are located across several mountain ranges, including the

Tucson and Catalina Mountains bounding the Tucson Basin, the Santa Rita Mountains to the

southeast, and the Huachuca Mountains further to the south.

Vegetation

The Basin and Range province of southeastern Arizona is complex ecologically as well as

climatically, straddling the boundary between the Sonoran and Chihuahuan Deserts and

containing elements of tropical, temperate, and arctic environments. Tropical grasses (C4) as

well as succulents and cacti (CAM) thrive in this strongly monsoonal environment, where

precipitation is a combination of summer and winter rains (Sheppard et al., 2002). Generally, the

proportion of C4 biomass diminishes as elevation increases, whereas C3 plants (trees, temperate

zone grasses, and most shrubs) are favored by cooler temperatures and greater winter

precipitation.

Ecozones in the Tropical-Subtropical Desert biome of southeastern Arizona include:

Arizona Upland (650-1,100 m), semidesert grassland (1,000-2,000 m), interior chaparral (1,000-

2,000 m), oak (Quercus)–pine (Pinus) woodland (1,600-1,900 m), and Ponderosa pine (P.

ponderosa) forest (>1,900 m) (Brown, 1982). The Arizona Upland subdivision is characterized

by C3 leguminous trees and shrubs, various cacti and succulents (CAM), and C4 grasses.

Dominant genera include the shrubs Larrea and Acacia, succulent Fouquieria splendens, and

grasses Aristida and Trichachne. South of Tucson, the upper limit of the Arizona Upland

5
ecozone merges with semidesert grassland. This ecozone extends from 1,000-2,000 m and can

be characterized as a C4 grassland expanse broken by shrubs, cacti, and succulents. Dominant

genera include the C4 grasses Bouteloua, Aristida, and Trichachne in addition to CAM

succulents Opuntia, Yucca and Agave and the C3 shrub Prosopis. Also within this elevation

range, interior chaparral vegetation is typical of the droughtier soils of the foothills and mountain

slopes where C3 shrub cover can reach 60-70%, typically including Prosopis, Fouquieria

splendens, Quercus, and Arctostaphylos. Thus, C3 plant abundance exceeds that of C4 plants in

chaparral enclaves that occur within extensive tracts of semidesert grassland. From 1,600-

1,900 m, oak-pine-juniper savannas and woodland (Quercus arizonica, Pinus edulis, and

Juniperus deppeana) with well-developed C4 grassland under story occur on coarser soils in the

rugged mountainous terrain. From 1,900-2,000 m, the oak-pine woodland grades into Ponderosa

pine savanna commonly containing Quercus (several species) and an under story of C4 grasses,

including Bouteloua and Schizachyrium. In the transitional zone from 1,600-1,900 m, shrub-

grass associations grade to grassy woodlands. Differences in aspect strongly influence the

dominant plant type. On south-facing slopes, the abundance of CAM and C4 vegetation may

rival that of C3 vegetation, while on north-facing slopes C3 vegetation typically dominates.

Climate

The primary cause of climatic variability in the Southwest is due to shifts in mid-latitude and

subtropical atmospheric circulation regimes as well as proximity to major moisture sources

(Adams and Comrie, 1997). Further, local climate variations occur as a result of the region’s

extreme topography. The most prominent feature of Southwestern climate is the North

American monsoon, which in our study area provides at least 50% of annual precipitation during

6
the summer months. The rest falls mainly from October through March as frontal storms

ushered in by Pacific westerlies, or as dissipating tropical cyclones in September and October

(Sheppard et al., 2002 and references therein). Temperature is also strongly seasonal. Although

these seasonal patterns in precipitation and temperature are independent of elevation, adiabatic

cooling results in reduced temperatures and increased precipitation with elevation increase (Fig.

2).

We calculated temperature dependence on elevation for the Tucson Basin using urban heat

island-adjusted values from the University of Arizona Coop station at 745 m (U.S. HCN, 2007),

and the Palisades Coop station on Mt. Lemmon in the Santa Catalina Mountains at 2422 m

(Desert Research Institute, 2007) for the period from 1965-1981. These stations yield a lapse

rate of 6.6°C/km for winter and 7.3°C/km for summer. Mean annual air temperature (MAAT)

varies from 20.4°C at 745 m, to 9.2°C at 2,422 m, with corresponding mean annual precipitation

(MAP) ranging from 290 mm to 790 mm (Table 1). From this, we calculated MAAT and MAP

lapse rates of 6.6°C/km (R2 = 1, n = 2) and 29.6 cm/km (R2 = 1, n = 2), respectively.

Isotopic Composition of Soil Carbonate

Calcite in soils is either detrital limestone, or calcite formed authigenically. We refer to the

latter as “pedogenic carbonate”, with which we are exclusively concerned in this study.

Pedogenic carbonate (CaCO3) is composed of (1) carbon, originating from both biologically-

derived and atmospheric CO2 in the vadose zone, and (2) oxygen, originating from meteoric

water (Cerling, 1984). Precipitation and dissolution of calcium carbonate in soils can be

summarized as follows:

7
 2+
Ca (aq) + 2HCO3 (aq)
–
CO2 (g) + H2O (aq) + CaCO3 (s) (1)

The precipitation of calcite in soils results from supersaturation of the soil solution with

respect to bicarbonate, associated with the gradual dewatering of soil by transpiration and

evaporation, and offgassing of CO2. Provided that pCO2 remains relatively stable during

carbonate formation, the soil solution will remain in equilibrium with the gas phase, such that the

carbon system can be considered open with respect to the carbon isotopic composition of soil

CO2. In contrast, oxygen isotopes in soil water will evolve during evaporation according to

simple Rayleigh fractionation leading up to calcite precipitation, such that the oxygen system can

be considered closed with respect to the oxygen isotopic composition of meteoric water.

Stable carbon and oxygen composition is reported in the δ (per mil) notation [relative to the
13 18
global Pee Dee Belemnite (PDB) standard] as δ C and δ O, respectively, where:

(
δ (per mil) = Rsample/Rstandard – 1 ) x 1,000 (2)

18 16
and Rsample and Rstandard refer to the 13C/12C (and O/ O) ratios in a sample or standard,

respectively.

Carbon

Cerling (1984), Quade et al. (1989a), and Cerling and Quade (1993) provide evidence that,
-7 -6 2
because the rate of formation of new pedogenic carbonate (~10 - 10 mole/cm /yr) is negligible
-3 -5 2 13
in comparison to the efflux of soil-respired CO2 (~10 - 10 mole/cm /yr), δ Cpc is not inherited
13
from parent material, but is instead controlled by the δ C composition of soil CO2 (δ13Cconc). In
13
turn, δ Cconc is controlled mainly by (1) the proportion of atmospheric contribution to soil CO2

8
as determined by soil respiration rate and resultant soil pCO2 levels, and (2) the proportionate

contributions of C3, C4, and CAM vegetation to soil respiration.

13
Distribution of δ C(CO2) in Soils

Soil CO2 is comprised of soil-respired and atmospheric CO2, the former increasing in

proportion along a down-profile diffusion gradient (Cerling and Quade, 1993; Quade et al.,

1989a). Soil respiration is a combination of root and microbial respiration, the latter resulting

from the microbially-mediated oxidation of organic matter. It has been found that the

proportion of atmospheric to soil-respired CO2 (δ13Cresp) at a given depth is a function of net soil

respiration, where higher respiration rates result in a lower proportion of atmospheric CO2 at

shallower depths (Quade et al., 1989a).

In addition, it is necessary to make a distinction between “soil CO2”, which is the

instantaneous concentration of CO2 at a given depth in a soil quantified in units of ppmV, and

“soil-respired CO2”, which refers to the flux of CO2 passing through a horizontal plane in a soil,
2
quantified in units of mmol/m /hr. In a natural system, the mass transfer of soil gas is
12
controlled by diffusion; owing to the difference between the diffusion coefficients for CO2 and
13 13 13
CO2, δ Cconc should be 4.4‰ enriched relative to δ Cresp (Cerling et al., 1991).

We can illustrate the effects of soil respiration on δ13Cconc at different depths using the

production-diffusion model of Cerling (1984), as revised by Quade et al. (2007). Previous

modeling by Cerling (1984) and Quade et al. (1989a) assumed CO2 production to be uniformly

distributed throughout the upper 1 m of a soil profile, with a characteristic production depth (k)

of 50 cm. Instead, the revised model of Quade et al. (2007) assumes a k of 22.5 cm with an

exponential decrease in production with increasing soil depth.

9
 13
We modeled δ Cconc for a hypothetical soil under a nearly pure stand of C3 vegetation with
13
an abundance-weighted δ C value of -24‰ (Fig. 3). In soils with respiration rates ≤4
2 13
mmol/m /hr, δ Cconc remains relatively constant below about 60 cm, whereas above this rate,

values do not vary much below about 40 cm. At ≥5 mmol/m2/hr, variation in δ13Cconc values at

100 cm soil depth is <1‰. Values are significantly higher at lower rates, reflecting a significant

atmospheric component.

13
Photosynthetic Pathway vs. δ Cresp

It is very difficult to determine the proportionate contribution of root and microbial

respiration to net soil respiration. Cerling (1984) and Quade et al. (1989a) assume that soil-

respired CO2 will bear the isotopic signature of overall root biomass, which is the dominant

source of organic matter fueling microbial activity. Thus, δ13Cresp is determined by the relative

proportion of biomass from vegetation of the three major metabolic pathways. In turn, each of
13
these can be distinguished on the basis of the δ C composition of plant tissue:
13
• C3: trees, most shrubs, and temperate grasses, δ C = -27‰,
13
• C4: tropical grasses and shrubs of the genus Atriplex, δ C = -13‰, and
13
• CAM: succulents of the family Cactaceae and genus Agave, intermediate δ C values.

Temperature vs. δ13Cpc

13
We can predict δ13Cpc for a given temperature (T°C) by using the C isotopic

enrichment factor (ε) between CO2 and calcite from Romanek et al. (1992):

εCaCO3-CO2 = 11.98(±0.13) – 0.12(±0.1)*T(oC) (3)

10
 o o 13
At 0 C, the enrichment factor is ~12‰, and at 25 C, δ Cpc is ~9‰.

Relationship Between δ13Cpc and δ13Cresp

The combined fractionation from diffusion and temperature-dependent fractionation results

13 o
in a net enrichment of δ13Cpc with respect to δ Cresp, between 16.4 and 13.4‰ for 0 and 25 C,

respectively (Quade, 2007). As a result, in soils with high respiration rates with δ13Cresp values
13
of -27 and -12‰, δ Cpc ≈ —12‰ for the pure C3 end member and +2‰ for the pure C4 end

member, respectively.

Oxygen

The oxygen isotopic composition of carbonate in modern soils has received less systematic
18 18
study than carbon isotopes. δ Opc is determined by δ Omw as affected by soil temperature and

the extent of evaporation of soil water prior to carbonate formation.

Controls on δ18Omw

Temperature

Rozanski et al. (1993) report a strong empirical relationship between the annual averages of
18 o
δ Omw and local surface air temperature in the mid-latitudes (+0.7‰/ C). Examination of the

Tucson data set by Wagner (2006) revealed that interannual and intraseasonal temperature for
18
the winter months (October-March) was poorly correlated with δ Omw values. However, the

monthly data exhibit a weak correlation with temperature, with values being higher for the
o 2
summer and lower for the winter (Fig. 4), resulting in a slope of 0.14‰/ C (R = 0.03, p < 0.025).
18 o
In addition, summer monsoon (July-September) δ Omw values do increase 0.41‰/ C (R2 = 0.15,

11
p < 0.1) with increasing temperature, and the monthly values exhibit a similar trend (Fig. 4)

(Wagner, 2006).

Elevation

In any region with topographic relief, orographic precipitation will occur as a vapor mass
18
rises and cools adiabatically, thus driving rainout and O depletion of the resultant precipitation

(Rozanski et al., 1993). For southeastern Arizona, this depletion can be quantified as -1.6‰/km

for both summer (May-September) and winter (October-April) (Wahi, 2005). This estimate,

which was based on stable isotope time-series data in precipitation obtained from several high-

elevation sites in the region, differs significantly from the global average of -2.8‰/km reported

by Rozanski et al. (1993).

Precipitation Amount

Dansgaard (1964) first quantified the strong inverse relationship between mean monthly

δ18Omw and the monthly precipitation amount which became known as the ‘amount effect’. As a

result of rainout, δ18Omw values decrease during months with greater precipitation. In contrast, as

a result of the lower relative humidity below the cloud base and resultant secondary evaporation

of raindrops, δ18Omw values decrease during months with low precipitation.

18
For the Tucson Basin, the anomalously high δ O value for May rainfall reflects the

evaporative enrichment of 18O in light rains occurring in the very dry foresummer. In addition,
18
the average δ Omw value for June is ≥3‰ lower compared to May δ18Omw, even though the

average precipitation is similar for both months. This can also be explained by the amount

effect, as much of the June precipitation occurs during the latter part of the month in years with

12
early monsoonal activity, when increased relative humidity minimizes secondary evaporation.

Statistical analysis of the Tucson precipitation data suggests that the amount effect has a larger

influence than temperature on the inter-annual and inter-seasonal variations (Wagner, 2006).

Further, the trend in the monthly and seasonal data for the summer are -0.2‰/10 mm, while for

the winter the rate of decrease in the monthly data is more than four times greater than that of the
2 2
seasonal averages, -0.35 (R = 0.11, p < 0.01) versus –0.08‰/10 mm (R = 0.27, p < 0.025)

(Wagner, 2006).

18
Controls on δ Opc

Soil Temperature

Pedogenic carbonate forms in equilibrium with soil water, whose oxygen isotopic
18
composition (δ Osw) is related to that of meteoric water (Cerling, 1984; Quade et al., 1989a).

The oxygen isotopic composition of pedogenic carbonate relates that of soil water and its

temperature during carbonate precipitation (Cerling and Quade, 1993 and references therein), as

defined by Kim and O’Neil (1997):

1000lnαCaCO -H O = (18030/T) – 32.42 (4)

3 2

where αCaCO -H O is the equilibrium fractionation factor between pedogenic carbonate and soil
3 2

water for a specified T, which is in K. Large changes in soil temperature correspond to small
18 o o o o
changes in δ Opc as follows: about -0.20‰/ C at 0 C, and -0.24‰/ C at 30 C.

Evaporation

Evaporation and transpiration both serve as dewatering mechanisms following partial or

complete saturation of the soil by meteoric water. While evaporative loss results in kinetic

13
 18
fractionation and enriched δ Osw values, transpiration does not. Thus, the extent of evaporation

depends upon the influence of transpiration on soil drying (Hsieh et al., 1998). The isotopic

evolution of soil water can be modeled as a function of evaporation by applying simple Rayleigh
18
fractionation to soil water with an initial δ O value corresponding to that of meteoric water (e.g.

Quade et al., 2007).

Allison et al. (1984) observed that water in barren desert soils experiences the greatest
18
degree of O enrichment compared to nearby vegetated soils. Other studies (e.g. Hsieh et al.,
18
1998; Liu et al., 1996) have shown that the greatest variability in the δ O value of soil water
18 18
occurs within the upper 40 cm, while δ Osw correlates well with δ Omw at greater soil depths. In

a detailed study of soils along a humid-to-arid climatic gradient in Hawaii, Hsieh et al. (1998)
18
observed for the sites with highest rainfall that δ Osw near the surface was up to 2‰ greater than
18
δ Osw in the deepest part of the profile, while at the driest sites the difference reached +8‰.

Similar to the findings of Allison et al. (1984), in arid soils they found a greater discrepancy
18 18
between δ Osw and δ Omw values below 40 cm compared to humid soils, correlating this to

lower vegetation density and attributing it to (1) a reduced influence of transpiration in soil
18
drying, and (2) low frequency of recharge events, and thus minimal dilution of partially O-
18
enriched antecedent soil water by relatively O-depleted meteoric water.
18
In sum, the potential influence of evaporation on δ Osw is regulated by the relative influence

of transpiration on soil drying, which itself varies as a function of vegetation density as well as

differences in the rate of soil water uptake related to seasonality and depth. Additionally, the

degree of evaporative loss depends upon the rate of evaporation, determined by soil temperature

and humidity, as well as the fraction of initial water remaining at the time of calcite precipitation.

14
Site Descriptions

Setting

A general description of the study sites is given here, and a more detailed summary of site

characteristics can be found in Table 1. Tumamoc is the lowest elevation site, situated on a late

Holocene stream terrace inset into an alluvial fan toeslope at the base of Tumamoc Hill in the

Tucson Mountains. South of Tumamoc, Madera is positioned on a late Holocene stream terrace

inset within the lower section of Madera Canyon, which originates in the Santa Rita Mountains

and is at this location incised into a late Pleistocene alluvial fan surface. Hirabayashi, on an inset

stream terrace of estimated late Holocene age, is the northern most site in our study. Both Cave-

of-the-Bells (COB) sites are in the Santa Rita Mountains; COB West is located on the West side

of a limestone hill mantled with recent colluvial deposits, and COB Terrace is positioned on a

stream terrace of estimated late Holocene age. Finally, two sites are located in Garden Canyon

(GC) of the Huachuca Mountains; the GC Terrace site is on a late Holocene alluvial deposit in

the canyon bottom, and the GC South-facing (GC S-facing) sits on a south-facing middle or late

Holocene debris flow.

Vegetation

Each site was assigned to an appropriate ecozone in Table 1 reflecting the general vegetation

characteristics, while we give a more detailed description of site ecology in this section. We

begin with COB West, the only site with survey data. Vegetation at COB West can be described

as “limestone scrub”, comprised of >15% C4, >25% C3, and >25% CAM plants, while vegetation

at COB Terrace has a less significant CAM component and can be characterized as a C3-

dominated oak-juniper-grassland (Quade, 2007, pers. com.). The average δ13C values measured

15
for C3 and C4 plants at both COB sites are -26.7 and -13.6‰, respectively (Quade, 2007, pers.

com.). These values are consistent with global averages of about -27 and -12‰, respectively

(e.g. Ehleringer, 1988). Although C4 and CAM plants are present at all sites, they are not

dominant.

Because there is no plant survey available for the Tumamoc, Hirabayashi, Madera, and both

GC sites, our estimates of C3/C4 biomass are based on coarse visual estimation, assuming that

percent cover is representative of total plant biomass, and assuming all grasses are C4.

Vegetation at Tumamoc can be best described as creosote bush-grassland with significant

mesquite and CAM components. Cover of trees and shrubs versus grasses, and thus C3/C4

proportions, appear similar among these sites. Vegetation at the Madera locality is mesquite-

grassland with a significant ocotillo component. The Hirabayashi site is open oak-juniper

woodland with significant CAM and C4 grass cover (oak-juniper-grassland). Here, the

distribution, height, and density of grasses, trees, and shrubs closely resemble conditions at COB

West, for which survey data reveals equivalent biomass for C3 and CAM (Quade, 2007, pers.

com.). Vegetation at GC S-facing can also be characterized as oak-juniper-grassland, with the

proportionate cover of trees to shrubs exceeding that at the Madera and Hirabayashi sites.

Vegetation at GC Terrace can be characterized as a closed-canopy Ponderosa-grassland, though

it also contains some oak and juniper influence. Although C3/C4 composition appears similar for

both GC sites, CAM vegetation is much more common on the south-facing slope, where it might

account for as much as 25% of plant cover.

16
METHODS

Site Selection

In order to assure that we sampled carbonate formed in association with modern vegetation

and within the modern climate-meteoric water system, we confined our sampling to stream

terraces adjacent to, and therefore recently abandoned by, active washes. Consistent with

previous studies, we assume that soils which are characterized by incipient carbonate

development, and which have been recognized by Gile et al. (1966) and Machette (1985) as

Stage I, were formed within the last 1-5 ka. Further, by focusing on terrace settings we hoped to

minimize microclimatic and ecological variations associated with differences in aspect and

drainage.

Soil Sampling

We sought to obtain diffusion profiles in order to assess the significance of atmospheric

13
contributions to δ Cpc values, and whether these values are reflective of modern vegetation

composition. To accomplish this, we sampled at approximately 20 cm depth increments to ≥1 m

where possible, obtaining at least one full isotopic profile for each of five elevations along our

gradient. In addition to examining modern carbonate, we examined carbonate from paleosols

formed on basalt flows mantling the north and south slopes of Tumamoc Hill in the Tucson

Mountains, where the Tumamoc site is situated, to assess the long-term effects of aspect on

δ13Cpc values. Lastly, all of the samples used for the elevation transect were collected from ≥50
13
cm to ensure that the signal we obtain from δ Cpc values is dominantly ecological, and not

atmospheric.

17
 In the field, we collected pedogenic nodules and clast coatings from freshly exposed trench

faces and arroyo walls. We encountered two types of Stage I carbonate. In some soils,

carbonate occurs as a soft, powdery coating on the underside of a clast, while in others it occurs

in others as dense cement with a powder-coated exterior. We thoroughly scrubbed coatings prior

to rinsing with deionized water, while abstaining from scrubbing the powdery samples in order

to prevent inadvertent removal of the carbonate. Previous studies indicate that the cement

coatings are more purely pedogenic in composition than the powder coatings, which can contain

considerable amounts of detritus from the surrounding soil matrix (Amundson et al., 1988).

Also at each site, we collected soil organic matter (SOM) in order to measure its carbon
13 13
isotopic composition (δ Csom), from which to calculate a long-term average value for δ Cresp.

However, there are several problems with using δ13Csom to estimate δ13Cresp. For one, SOM may

not be well mixed across the site such that single plants may be overrepresented within a given

sample. To accommodate this, we amalgamated the <2mm fraction of 4-5 samples collected at

each site, then homogenized and ground the remaining fine fraction. Next, because the δ13C

value of organic matter at depth can be altered by microbial activity (Nadelhoffer and Fry, 1988;

Biggs et al., 2002; Beidenbender et al., 2004), we confined our sampling to the uppermost 5 cm

of mineral soil.

Vegetation Survey and Collection

Plant species and density were recorded along a line transect 80 m long at COB West, and

accounted for canopy interception within 5 cm on either side of the measuring tape.

18
Laboratory
o
In the laboratory, carbonate samples were heated at 250 C for 3 hours in vacuuo, then

processed using an automated sample preparation device (Kiel III) fitted to a Finnigan MAT 252
18 13
mass spectrometer at the University of Arizona Stable Isotope Laboratory. δ O and δ C values

were normalized to NBS-19 based on internal lab standards. Precision of repeated standards are
18 13
± 0.11‰ for δ O and ± 0.07‰ for δ C (1σ).

SOM samples were passed through a 250 µm mesh sieve, amalgamated, then pretreated with

2M HCl and repeatedly rinsed with deionized water. CO2 extraction was accomplished by in
o
vacuuo combustion of samples at 900 C for 3 hours in the presence of silver foil and copper

oxide powder; we then determined % organic C manometrically as part of off-line purification.

Internal lab standards are calibrated relative to NBS-22 and USGS-24, and precision of repeated

internal standards was ± 0.09‰ for δ13C (1σ). Next, for measurement of δ13C values of plant

tissue, three individuals from each plant—stem, root, and leaf—were ground, homogenized, and

their δ13C composition measured with a Costech automated CHN analyzer connected to a

Finnigan Delta-plus XL continuous-flow mass spectrometer.

Calculation of Predicted δ18Opc Values

18
We predicted the mean and range of δ Opc values that should result for carbonate formed in

equilibrium with local meteoric water along our elevation gradient by applying αCaCO3-H2O values

(calculated for winter and summer) to corresponding δ18Omw values. For this computation, we

derived equations for mean seasonal temperature (previously shown) and δ18Omw versus

elevation, where winter is defined as October-April and summer as May-September. To

calculate δ18Omw values, we used long-term volume-weighted seasonal means compiled for the

19
Tucson Basin from Eastoe (1998) for the period from 1981-2004/5, in combination with a local

lapse rate of -1.6‰/km for both winter and summer derived by Wahi (2005), using the Tucson

data set in addition to data from higher elevations (Wahi, 2005 and references therein).

RESULTS

Modern Soils

In all, we measured δ18Opc and δ13Cpc of Holocene carbonate from one or more sites at each

of 5 elevation stops, spanning a 1,170 m elevation gradient from 730 to 1900 m (Fig. 1; Table 1).

For the elevation transect, we report ranges of δ18Opc and δ13Cpc values based on samples

obtained from >50 cm depth. Such values are the most likely to reflect δ13C composition of CO2

derived from soil respiration. We have also obtained depth profiles at all localities except at

COB, where we report the results of carbonate sampled from 60 cm soil depth (Quade, 2007,

pers. com.).

Oxygen

Rainfall δ18Omw values (y, in ‰) are related to elevation (x, in meters) by:

y = -10,638x – 103,295 (winter)

y = -12,664x – 104,865 (summer)

From this, we calculated δ18Opc values (y, in ‰) with elevation (x, in meters) by (Fig. 6):

y = -625x – 5068 (winter)

y = -625x - 2568 (summer)

20
Elevation Transect

The δ18Opc composition of Holocene carbonate below 50 cm ranges from -1.3‰ to -9.4‰,

with both maximum and minimum values from 1,900 m, respectively (Fig. 6). At the Tumamoc

locality, values from 4 profiles ranged from -2.7 to -5.8‰; two profiles at Madera ranged from

-6.5 to -8.6‰; 1 profile at Hirabayashi, from -8.7 to -9.3‰; 2 sites at COB with 1 profile each

(Terrace and West), from -5.6 to -6.3‰ and -8.1 to -8.5‰, respectively; finally, at GC one

profile at the Terrace site yielded values from -6.6 to -9.4‰, while 4 profiles from the S-facing

site yielded values from -5.4 to -8.5 ‰, with the exception of the highest value at -1.3‰.

Depth Profiles

At Tumamoc, we sampled carbonate from 10 to 155 cm, and values among 4

stratigraphically similar profiles range from -2.4 to -5.8‰ (Fig. 7). From 45 to 115 cm, the

central section is bounded by abrupt contacts, with moderate B horizon development in the upper

part. This section yielded values between -2.4 and -5.8‰; in the upper section, from -5.2 to

-4.0‰; and in the lower section, from -3.7 to -4.9‰. At Madera, values from 2 profiles range

from -6.5 to -9.8‰ between 60 and 170 cm (Fig. 8). At Hirabayashi, we sampled 1 profile (25

to75 cm) with values between -7.3 and -9.3‰ (Fig. 9). From the GC Terrace site, we obtained

one profile (15 to 95 cm) with values ranging from -6.6 to -9.4‰ (Fig. 10) and at the S-facing

site, 4 profiles collectively yielded values of -5.4 to -9.1‰ from 25-180 cm, with the exception

of the highest value at -1.3‰ (Fig. 11).

21
Carbon

Elevation Transect

δ13Cpc values in Holocene carbonates from ≥50 cm soil depth range from -0.6‰ to -9.9‰

(Fig. 12; Table 1). At Tumamoc, values ranged from -1.2 to -4.5‰; at Madera, from -6.6 to

-9.8‰; at Hirabayashi, from -7.3 to -7.8‰; for the Terrace and West sites at COB, from -0.7 to

-0.8‰ and between -0.6 and -1.2‰, respectively (Fischer et al. in preparation, 2006); and lastly,

at the GC Terrace and S-facing sites, from -4.2 to -9.6‰, and from -0.5 to -6.6‰, respectively.

Depth Profiles

At Tumamoc, values range from -1.2 to -6.3‰ (Fig. 7). Values from the center section

range between -2.0 and -4.1‰; in the upper section, from -1.9 to -6.3‰; and in the lower

section, from -1.6 to -3.5‰. Between the 2 profiles sampled at Madera (Fig. 8), values range

from -6.7 to -9.9‰. At the Hirabayashi site, δ13Cpc values range from -7.3 to -7.9‰ (Fig. 9).

For the GC Terrace site, values range from -5.2 to -9.6‰. Finally, carbonate from the S-facing

site yielded values from -0.6 to -7.1‰ (Fig. 11).

Organic Matter, CO2, and Plant Biomass

The δ13C values for SOM, soil CO2, and plant biomass listed below are unadjusted measured

values, whereas corresponding values reported in Table 1 reflect adjustments which are

explained in the discussion section. δ13Cconc for Tumamoc is -14.8‰; for Hirabayashi, -21.1‰;

for COB West, -17.5‰; and for GC S-facing, -16.6‰. δ13Csom values range from -18.8 to

-22.9‰, and are lowest for the lowest elevation sites at -22.9 and -23.2‰, for Tumamoc and

Hirabayashi, respectively. For the COB Terrace and West sites, δ13Csom values are -18.9 and

22
-19.0‰, respectively, and -18.8‰ for the GC S-facing site. Finally, the abundance-weighted

δ13C value of modern plant biomass (δ13Cbulkplant) was estimated from the measured isotopic

composition of each plant, weighted by the fraction canopy cover for that plant. The δ13Cbulkplant

value for COB West is -23.2‰. δ13Cconc values reported for the COB and Tumamoc localities

are averages, calculated from successive monthly measurements made over the course of a year

(Quade, 2007, pers. com.), whereas values reported for the other sites reflect a single

measurement made in early March of 2007.

DISCUSSION

Carbon

It is our ultimate goal to relate δ13Cpc to C3/CAM/C4 abundance at each site, in effect

establishing a carbon and oxygen isotopic signature for the individual plant associations that

characterize distinct bioclimatic envelopes. As discussed and modeled earlier, the atmospheric

contribution to soil CO2 is significantly diminished below a certain soil depth. For a given soil,

the depth at which this occurs and the significance of atmospheric influence below this depth

both depends largely upon the respiration rate. To quantify the atmospheric component, we must

first determine the respiration rate, for which knowledge of δ13Cresp is necessary. A simple

comparison between δ13Cpc (≥50 cm) and δ13Csom values suggests a significant atmospheric

influence on δ13Cpc values (Fig. 13) for several of our study sites.

For some sites, we have sufficient data to quantitatively assess the relative importance of
13
respiration rate in determining δ Cpc values. We can accomplish this by examining the various

components of the carbon isotope system, including vegetation (δ13Cbulkplant), organic matter
13
(δ Csom), efflux (δ13Cresp), soil gas (δ13Cconc), and carbonate (δ13Cpc). Our current discussion is

23
limited to the set of measured values compiled for each site. Under ideal circumstances, the

δ13Cresp value is best estimated from soil CO2 fluxes collected throughout the year; however, we

do not currently have direct measurements of δ13Cresp. In lieu of this, we follow the suggestion of
13
Cerling et al. (1991) in using δ Csom as a proxy for δ13Cresp. Following the approach of Quade et

al. (2007), our respiration rate estimates assume:

• δ13Cresp = δ13Csom, after applying a +0.36‰ Suess Effect adjustment to δ13Csom

• k = 22.5 cm

• porosity = 0.5

• pressure as calculated from site-specific elevation and MAAT

• specified soil depths

• carbonate formed under similar-to-modern vegetation

To estimate k, Quade et al. (2007) relied on the depth distribution of root biomass, in lieu of

year-round measurements of soil CO2 at different soil depths, assuming that root-respired CO2

and most the dead tissue which fuels microbial respiration are both proportional to overall root

biomass. Further, Richter (1987) provides evidence that CO2 production in soils is exponentially

decreasing with increasing depth. By fitting a simple exponential function to root density in 19

desert soil profiles examined by Schenk and Jackson (2002), Quade et al. (2007) estimated k to

be 22.5 cm. In addition, Quade et al. (2007) calculated that the Suess Effect causes a 1.5 ‰

decrease in the δ13C value of atmospheric CO2 and a corresponding change in plant tissue,

resulting in a ~0.36‰ decrease in δ13Csom in desert soils. Soil respiration rates reported in this

study include this correction.

24
 In Table 1, we report δ13Cresp estimates calculated from δ13Csom and δ13Cbulkplant in the fashion

described above, as well as δ13Cconc and the average of δ13Cpc values from ≥50 cm depth. We

begin with the most complete profile sampled at Tumamoc, where δ13Cpc values decrease with

depth and resemble a CO2 diffusion profile (Fig. 7). An estimated δ13Cresp value of -22.5‰ and a

respiration rate of 0.22 mmol/m2/hr yield a modeled δ13Cpc profile that corresponds to observed

values from this profile. At 0.53 mmol/m2/hr, our modeled values intercept a single point. We

then modeled soil CO2 using a respiration rate of 0.41 mmol/m2/hr to correspond to modern soil

gas (adjusted for the Suess Effect). Measured δ13Cconc falls within the range of values

corresponding to observed δ13Cpc values when we use δ13Csom to estimate δ13Cresp. We conclude

that low soil respiration rates can explain δ13Cpc values at Tumamoc, which initially seemed

higher than what we might have expected (-12 to -9‰) at a C3-dominated site. This conclusion

is consistent with the findings of Quade et al. (1989a), who estimated a respiration rate of 0.18

mmol/m2/hr for a low elevation site in Death Valley (300 m). Further, we found that values from

all Tumamoc sites fit within a range between the two modeled diffusion profiles to which the

estimated respiration rates correspond. Based on the model, observed δ13Cpc values from >60 cm

below the buried surface at Tumamoc reflect a ~30-55% atmospheric component.

At Hirabayashi, we estimate a δ13Cresp value of -22.8‰ and modeled a respiration rate of

2-4 mmol/m2/hr, concordant with observed δ13Cpc values (Fig. 9) and much higher than that

modeled for Tumamoc. A rate of 1.6 mmol/m2/hr results in a theoretical δ13Cpc profile that

intercepts the theoretical value of carbonate formed in equilibrium with modern soil gas, in

agreement with the estimate based on carbonate values. Results of modeling with the δ13Csom

value show that the deepest observed δ13Cpc values reflect a ~0-20% atmospheric component.

25
 For COB West, we compared estimates of δ13Cresp obtained from both δ13Cbulkplant and

δ13Csom values. We did not model diffusion profiles for COB Terrace because δ13Csom and δ13Cpc

values there are similar to COB West, such that resultant respiration rates and % atmospheric

composition will also be similar. Using δ13Cbulkplant, we obtained an estimate of respiration rate

from comparison between δ13Csom and δ13Cpc values (Fig. 14), as well as from a comparison

between δ13Cbulkplant and δ13Cconc values. The mean δ13Cconc value (corrected for the Suess Effect)

is 2.2‰ lower than the mean value of soil CO2 in which carbonate ≥50 cm formed (calculated

from δ13Cpc values), and δ13Cbulkplant is 3.1‰ lower than δ13Csom (both corrected for the Suess

Effect). This finding suggests that either 1) the proportion of C4 and/or CAM biomass has

recently decreased, or 2) δ13Cbulkplant values are biased toward the C3 component with respect to

overall plant biomass.

Alternatively, the observed discrepancy might reflect regular variation in C3/CAM/C4

proportions during the late Holocene, in which case such a deviation from δ13Csom (taken to

represent average late Holocene conditions) is not unique to the modern system. In this case,

δ13Csom, and not δ13Cbulkplant, will yield the most accurate estimate of the long-term δ13Cresp

relating to δ13Cpc values. This holds true if organic matter turnover rates correspond to the length

of time represented by the modern carbonate in our soils, most likely on the order of 102-103

years. In addition, the respiration rates we calculated for the modern and late Holocene

analogues are similar: 0.58 and 0.37 mmol/m2/hr, respectively. We suggest that a low soil

respiration rate is a plausible explanation for the higher-than-expected δ13Cpc values at COB, and

calculated that δ13Cpc values (≥50 cm) are 35-45% atmospheric in composition, similar to

Tumamoc values.

26
 At Madera (Fig. 8), GC S-facing (Fig. 11), and GC Terrace (Fig. 10), we were able to obtain

δ13Cpc diffusion profiles. The profile obtained for one of the Madera profiles has δ13Cpc values

confined to a 0.3‰ range, making it ideal for our modeling exercise. Until we have δ13Csom

measurements for Madera and GC Terrace profiles, however, we cannot estimate respiration

rates for these sites. By comparing δ13Csom with δ13Cpc values corresponding to the most

complete profile obtained at the GC S-facing site (Fig. 11), we estimated a δ13Cresp value of -

18.44‰. With a respiration rate of 8 mmol/m2/hr, we obtained theoretical δ13Cpc values that

correspond to the upper limit of observed values at this profile as well as for most values

observed for the other profiles at this site (Fig. 11). We conclude that the true δ13Cresp is several

‰ more negative than that estimated from δ13Csom, and that the true respiration rate is

significantly lower than 8 mmol/m2/hr. Without a reliable δ13Cresp estimate, however, we cannot

determine the % atmospheric contribution to δ13Cpc values.

Oxygen

At, δ18Opc values at both GC sites, COB Terrace, Hirabayashi, and Tumamoc correlate

poorly with theoretical values predicted for carbonate formed in equilibrium with summer or

winter precipitation (Figs. 6 & 15). We can attribute these differences to (1) a discrepancy

between calculated δ18Omw values and real δ18Omw values due to local amount effects, or (2) 18O-

enrichment of the soil water due to evaporative loss prior to carbonate formation. Because mean

seasonal precipitation δ18Omw values are not dominated by large, low frequency events which

average out over time, pronounced differences in storm frequency or intensity can likely be ruled

out as a source of variability (Wright, 2001). Still, with long-term δ18Omw data from rainfall

available for so few sites, it is not possible to directly examine δ18Omw in relation to elevation

27
and topography at all sites. Instead, δ18O values of surface groundwater—sampled near GC and

along a down slope elevation gradient into the Upper San Pedro Valley—can serve as a proxy for

δ18Omw (Wahi, 2005). Groundwater values fall between predicted values for summer and winter

δ18Omw, suggesting the same for δ18Omw values at corresponding elevations. We conclude that

elevated δ18Opc values, which are observed for most of our sites, can be explained only by

evaporation.

We recall that the degree of influence of evaporation on soil drying is partly a function of

local aridity, in addition to the relative influence of transpiration on soil drying. Further, if the

ratio of transpiration to evaporation is highest in soils with the highest respiration rates, we

would also expect to observe minimal evaporation and enrichment in these soils. If effective

moisture were the main control on evaporation, we would expect δ18Opc values to follow a

negative linear trend with elevation (Fig. 6). At COB Terrace, however, observed δ13Cpc values

diverge from predicted values by a similar amount as Tumamoc (Figs. 6 & 15). While these

sites are climatically dissimilar, they both have similarly low respiration rates, suggesting that

the ratio of transpiration to evaporation, and not precipitation amount, is the dominant control on

evaporation within the elevation range studied. Further evidence for this is provided by the

remarkable concordance between observed and predicted values at Hirabayashi, for which we

estimated high respiration rates.

Aspect

At the COB and GC localities, we sampled soils on hillslopes as well as stream terraces.

Observed δ18Opc values at GC S-facing (Fig. 6) align with our expectation that carbonate formed

in soil on a south-facing slope will be slightly more enriched in 18O due to better drainage, lower

28
relative humidity in the soil, and lower respiration rates. δ13Cpc values at GC S-facing are more

positive than at GC Terrace, reflecting lower respiration rates and/or increased CAM and/or C4

proportions. We suspect that transpiration rates play a significant role in determining δ18Opc

values. However, this cannot be demonstrated conclusively in the absence of reliable respiration

rates, which might be used as a proxy for the ratio of transpiration to evaporation.

At COB West, δ13Cpc and δ13Csom values correspond well with values for COB Terrace,

suggesting that both sites have similar respiration rates. In contrast, δ18Opc values are more

positive at COB Terrace, but the reason for this is not clear. It is also not clear whether this

effect is due to aspect-related differences in vegetation composition, soil respiration rate, or both.

To determine this, we will need to analyze soils from the S-facing slope. In addition, local soil

moisture conditions may differ significantly from aboveground conditions, and could potentially

be of greater importance than transpiration in mediating evaporation.

Finally, we sampled pedogenic carbonate from the north and south slopes of Tumamoc Hill,

where cemented carbonates formed in Quaternary paleosols which developed on basalt. We

observe no significant difference between carbon or oxygen values (Fig. 16). One possible

explanation for this is if carbonate forms dominantly during glacial periods, when C3

proportions, and probably respiration rates, are higher than currently observed. If this is true,

then aspect-related differences in vegetation composition and soil respiration rates would be

minimized during glacial periods, resulting in the observed concordance of δ13Cpc values.

Further, increased root transpiration activity that might result from increased annual precipitation

could moderate aspect-related differences in potential evaporation rates, resulting in δ18Opc

concordance.

29
SUMMARY AND CONCLUSIONS

It is clear from our results that the δ13Cpc values of soil carbonate formed in middle-to-late

Holocene soils reflect the combined influence of vegetation composition and soil respiration, and

that δ18Opc values also reflect changes in the ratio of transpiration to evaporation in addition to

δ18Omw. Although modeled δ13Cpc values remain relatively constant below 50 cm, values might

still reflect a significant atmospheric contribution in soils with low respiration rates, such as

COB and Tumamoc, where respiration rates are estimated to be between 0.2 and 0.6 mmol/m2/hr

and δ13Cpc values reflect a 35-45% and ≤55% atmospheric contribution, respectively.

At the same sites, δ18Opc values are >2‰ more positive than predicted values. We interpret

this deviation as the result of evaporative enrichment of 18O in soil water leading up to carbonate

precipitation, owing to the minimal influence of transpiration on soil dewatering and

corresponding to our interpretation of low respiration rates from lower-than-expected δ13Cpc

values. In contrast, δ18Opc values at the other sites are concordant with, or much closer to

predicted values, likely reflecting the significant influence of transpiration on soil dewatering at

sites with sufficiently high respiration rates; this interpretation is supported by δ13Cpc values from

Hirabayashi, from which we estimated a ≤20% atmospheric contribution.

At COB West, we observed a discrepancy between δ13Cresp values estimated from δ13Csom

versus δ13Cbulkplant, corresponding to observed δ13Cpc and δ13Cconc values, respectively. This

suggests that δ13Csom values reflect a δ13Cresp value consistent with observed δ13Cpc values, likely

reflecting average ecological conditions for the late Holocene. In contrast, plant biomass values,

which are concordant with modern soil gas values, appear to reflect modern δ13Cresp. Finally, we

detect no discernable difference between the δ13Cpc or δ18Opc composition of pedogenic calcretes

from the north and south aspects of Tumamoc Hill. This suggests to us that calcrete formation

30
occurs dominantly during cooler periods when differences in plant composition and soil

respiration rate, and thus the ratio of transpiration to evaporation, are less pronounced than

during arid intervals.

This study leaves many questions unanswered. We did not examine the seasonal

distribution of pedogenic carbonate formation and its influence on δ13Cpc at different depths, or

the influence of the depth distributions of C3 and C4 root systems in determining k. By

quantifying δ13Cconc, soil T, pCO2, δ13Cresp, and flux rate at different depths and times throughout

the year, we will be able to directly determine k. In addition, direct measurement of soil

respiration will enable us to determine the degree of atmospheric contribution to δ13Cpc as well as

to assess the accuracy of using δ13Csom versus δ13Cbulkplant as a proxy for δ13Cresp. Further,

knowledge of seasonal respiration rates will enable us to quantify atmospheric contributions to

δ13Cconc, and seasonal measurement of the δ18O composition of soil CO2 (as a proxy for δ18Osw)

will enable us to quantify the influence of evaporation on soil water, as well as the relationship

between respiration rate and the ratio of transpiration to evaporation.

In conclusion, our continued examination of the carbon and oxygen systems of soils will

enable us to accurately reconstruct proportionate C3/CAM/C4 biomass from pedogenic

carbonate. Our results suggest that, in order to reconstruct absolute changes in vegetation

composition, one must first quantify the influence of soil respiration on δ13Cpc values. In turn,

this knowledge can be use to assess the influence of evaporation on δ8Opc values for

reconstructing relative, and possibly absolute changes in δ18Omw. Conversely, knowledge of the

δ18O composition of paleo-precipitation can enable the use of δ18Opc values to independently

assess the magnitude of atmospheric contributions to δ13Cpc values, especially important in the

absence of information about past soil respiration rates.

31
ACKNOWLEDGMENTS

I would like to thank my committee members for all their advice and assistance. In addition,

I appreciate the extensive assistance I have received from David Dettman, Jeff Pigati, and

Warren Beck while conducting lab work and data analysis.

32
REFERENCES

Adams, D.K. and Comrie, A.C., 1997. The North American Monsoon. Bulletin of the American
Meteorological Society: 2197-2213.

Allison, G.B., Barnes, C.J., Hughes, M.W., and Leany, F.W.J., 1984. The effect of climate and
vegetation on the oxygen-18 and deuterium profiles in soils. In Isotope Hydrology 1983:
International Atomic Energy Agency 1983: 105-123.

Amundson, R.G., Doner, H.E., Sowers, J., and Chadwick, O.A., 1988. The relationship between
modern climate and vegetation and the stable isotope chemistry of Mojave desert soils. Soil
Science Society of America Journal 115: 213-223.

Ayalon, A., Bar Mathews, M., Sass, E., 1998. Rainfall–recharge relationships within a karstic terrain
18
in the eastern Mediterranean semi-arid region, Israel: δ O and δD characteristics. Journal of
Hydrology 207: 18–31.

Bar-Matthews, M., Ayalon, A., Kaufman, A., 1997. Late Quaternary palaeoclimate in the eastern
Mediterranean region from stable isotope analysis of speleothems at Soreq Cave, Israel. Quaternary
Research 47: 155–168.

Bar-Matthews, M., Ayalon, A., Kaufman, A., Wasserburg, G.J., 1999. The eastern Mediterranean
palaeoclimate as a reflection of regional events: Soreq Cave, Israel. Earth and Planetary Science
Letters 166: 85–95.

Bar-Mathews, M., Ayalon, A., Mathews, A., Sass, E., and Halicz, L., 1995. Carbon and oxygen
isotope study of the active water-carbonate system in a karstic Mediterranean cave: implications for
paleoclimate research in semiarid regions. Geochimica et Cosmochimica Acta 60: 337-347.

Baskaran, M. and Krishnamurthy, R.V., 1993. Speleothems as a proxy for the carbon isotope
composition of atmospheric CO2. Geophysical Research Letters 20(7): 603-606.

Biedenbender, S., McClaran, M., Quade, J., and Weltz, M. A., 2004. Landscape patterns of
vegetation change indicated by soil isotope composition. Geoderma 119: 69-83.

Biggs, T., Quade, J., and Webb, R. H., 2002. The δ13C value of soil organic matter in a
semi-arid grassland with mesquite (Prosopis) encroachment in southeast Arizona. Geoderma
110: 109-130.

Brook, G.A., Burney, D.,A., and Cowart, J.B., 1990. Desert palaeoenvironmental data from cave
speleothems with examples from the Chihuahuan, Somali-Chalbi, and Kalahari Deserts.
Palaeogeography, Palaeoclimatology, Palaeoecology 76: 311-329.

Brown, 1982 (ed.). Desert Plants: Biotic Communities of the American Southwest-United States
and Mexico. Boyce Thompson Southwestern Arboretum special issue 4(1-4). Tucson,
University of Arizona Press.

33
Buck, B.J. and Monger, H.C., 1999. Stable isotopes and soil-geomorphology as indicators of
Holocene climate change, northern Chihuahuan Desert. Journal of Arid Environments 43: 357-
373.

Cerling, T. E., 1984. The stable isotopic composition of modern soil carbonate and its relationship to
climate. Earth and Planetary Science Letters 71: 229-240.

Cerling, T. E. and Hay, R.L., 1986. An isotopic study of paleosol carbonates from Olduvai Gorge.
Quaternary Research 25: 63-78.

Cerling, T. E. and Quade, J., 1993. Stable carbon and oxygen isotopes in soil carbonates. In: Swart,
P., McKenzie, J.A., and Lohman, K.C. (eds.): American Geophysical Union Monograph 78: 217-
231.

Cerling, T.E., Quade, J., Wang, Y., Bowman, J.R., 1989. Carbon isotopes in soils and paleosols as
ecology and paleoecology indicators. Nature 341: 138-139.

Cerling, T. E., Solomon, D.K., Quade, J., and Bowman, J.R., 1991. On the isotopic composition of
carbon in soil carbon dioxide. Geochimica et Cosmochimica Acta 55: 3403-3406.

Cole, D.R. and Monger, H.C., 1994. Influence of atmospheric CO2 on the decline of C4 plants
during the last deglaciation. Nature 368: 533-536.

Dansgaard, W., 1964. Stable isotopes in precipitation. Tellus 16(4): 436-468.

Denniston, R.F., Gonzalez, L.A., Asmerom, Y., Baker, R.G., Reagan, M.K., and Bettis, E.A., 1999.
Evidence for increased cool season moisture during the middle Holocene. Geology 27: 815-818.

Denniston, R.F., Gonzalez, L.A., Asmerom, Y., Polyak, V.J., Reagan, M.K., and Saltzman, M.R.,
2001. A high-resolution speleothem record of climatic variability at the Allerod-Younger Dryas
transition in Missouri, central United States. Palaeogeography, Palaeoclimatology, Palaeoecology
176: 147-155.

Denniston, R.F., Gonzalez, L.A., Asmerom, Y., Reagan, M.K., and Recelli-Snyder, H., 2000.
Speleothem carbon isotopic records of Holocene environments in the Ozarks Highlands, USA.
Quaternary International 67: 21-27.

Desert Research Institute, 2007. Western Regional Climate Center Historical Climate
Information. Accessible at http://www.wrcc.dri.edu/CLIMATEDATA.html.

Dorale, J.A., Edwards, R.L., Ito, E., and Gonzalez, L.A., 1998. Climate and vegetation history of the
mid continent from 75 to 25 ka: a speleothem record from Crevice Cave, Missouri, USA. Science
282: 1871-1874.

Dorale, J.A., Gonzalez, L.A., Reagan, M.K., Pickett, D.A., Murrell & Baker, R.G., 1992. A high-
resolution record of Holocene climate change in speleothem calcite from Cold Water Cave, northeast
Iowa. Science 258: 1626-1630.

34
Eastoe, C.J., 1998. Isotopic data for Tucson Basin: summary of work to 1998 (unpublished).

Ehleringer, J.R., 1988. Carbon isotope ratios and physiological processes in aridland plants. In
Rundel, P.W., Ehleringer, J.R., and Nagy, K.A. (eds.): Symposium proceedings: Applications of
stable isotope ratios to ecological research, pp. 41-54 (Springer-Verlag, New York).

Gabunia, L. and thirteen others, 2000. Earliest pleistocene hominid cranial remains from
Dmanisi, Republic of Georgia: taxonomy, geological setting, and age. Science 288: 1019-1025.

Gile, L.H., Peterson, F.F., and Grossman, R.B., 1966. Morphological and genetic
sequences of carbonate accumulation in desert soils. Soil Science 101: 347-360.

Goede, A., Green, D.C., and Harmon, R.S., 1982. Isotopic composition of precipitation, cave drips,
and actively forming speleothems at three Tasmanian cave sites. Halictite 20: 17-27.

Harmon, R.S., 1979. An isotopic study of groundwater seepage in the central Kentucky karst. Water
Resources Research 15(2): 476-480.

Hsieh , J.C., Chadwick, O.A., Kelly, E.F., and Savin, S.M., 1998. Oxygen isotopic composition
of soil water: Quantifying evaporation and transpiration. Geoderma 82: 269-293.

Kim, S.T. and O’Neil, J. R., 1997. Equilibrium and non-equilibrium oxygen isotope effects in
synthetic carbonates. Geochimica et Cosmochimica Acta 61: 3461-3475.

Levin, N., Quade, J., Simpson, S., Semaw, S., and Rogers, M., 2004. Isotopic evidence for Plio-
Pleistocene environmental change at Gona, Ethiopia. Earth and Planetary Science Letters 219:
93-100.

Liu, B., Phillips, F. M., and Campbell, A. R., 1996. Stable carbon and oxygen isotopes of
pedogenic carbonates, Ajo Mountains, southern Arizona: implications for paleoenvironmental
change. Palaeogeography, Palaeoclimatology, Palaeoecology 124: 233-246.

Ludwig, K.R. and Paces, J.B., 2002. Uranium-series dating of pedogenic silica and carbonate,
Crater Flat, Nevada: Geochimica et Cosmochimica Acta 66(3), 487-506.

Machette, M. A.,1985. Calcic soils of the southwestern United States. In Weide, D.L. and
Faber, M.L. (eds.):.Soils and Quaternary geology of the southwestern United States. Geological
Society of America Special Paper 203: 1-21.

McDermott, F., 2004. Palaeo-climate reconstruction from stable isotope variations in

speleothems: a review. Quaternary Science Reviews 23: 901–918.

Monger, H.C., Cole, D.R., Gish, J.W., and Giordano, T.H., 1998. Stable carbon and oxygen
isotopes in Quaternary pedogenic carbonates as indicators of ecogeomorphic changes in the
northern Chihuahuan Desert, USA. Geoderma 82: 137-172.

35
Nadelhoffer, K. J., and Fry, B., 1988. Controls on natural nitrogen-15 and carbon-13
abundances in forest soil organic matter. Soil Science Society of America Jounal 52: 1633-1640.

Quade, J., 2004. Isotopic records from ground-water and cave speleothem calcite in North
America. In Gillespie, A., Porter, S.C., and Atwater, B.F. (eds.): The Quaternary period in the
United States, pp. 205-220 (Elsevier, New York).

Quade, J., Cerling, T.E., and Bowman, J.R., 1989a. Systematic variations in the carbon and
oxygen isotopic composition of pedogenic carbonate along elevation transects in the southern
Great Basin, USA. Geological Society of America Bulletin 101: 464-475.

Quade, J., Cerling, T.E., and Bowman, J.R., 1989b. Development of Asian monsoon revealed by
marked ecological shift during the latest Miocene in northern Pakistan. Nature 342: 163-166.

Quade, J., Levin, N., Semaw, S., Simpson, S., Rogers, M., Stout, D., 2004. Paleoenvironments
of the earliest toolmakers. Geological Society of America Bulletin 116: 1529-1544.

Quade, J., Rech, J.A., Latorre, C., Betancourt, J.L., Gleeson, E., and Kalin, M.T.K., 2007. Soils
at the hyperarid margin: the isotopic composition of pedogenic carbonate from the Atacama
desert, northern Chile. Geochimica et Cosmichimica Acta 71: 3772-3795.

Richter, J., 1987. The Soil as a Reactor (Catena Verlag, Cremlingen).

Romanek, C. S., Grossman, E. T., and Morse, J. W., 1992. Carbon isotopic fractionation in
synthetic aragonite and calcite: effects of temperature and precipitation rate. Geochimica et
Cosmochimica Acta 56: 419-430.

Rozanski, K., Aruguas-Araguas, L., and Gonfiantini, R., 1993. Isotopic patterns in modern
global precipiation. In Swart, P., McKenzie, J.A., and Lohman, K.C. (eds.): Continental
Indicators of Climate. American Geophysical Union Monograph 78, pp. 1-36.

Schenk, H. J. and Jackson, R. B., 2002. The global biogeography of roots. Ecological
Monographs 72(3): 311–328.

Schwarcz, H.P., Harmon, R.S., Thompson, P., and Ford, D.C., 1976. Stable isotope studies of fluid
inclusions in speleothems and their paleoclimatic significance. Geochimica et Cosmochimica Acta
40: 657-665.

Sharp, W.D., Ludwig, K.R., Chadwick, O.A., Amundson, R., Glaser, L., 2003. Dating fluvial
terraces by 230Th/U on pedogenic carbonate, Wind River Basin, Wyoming: Quaternary Research
59: 139-150.

Sheppard, P. R., Comrie, A. C., Packin, G. D., Angersbach, K., and Hughes, M. K., 2002. The
climate of the US Southwest. Climate Research 21: 219-238.

U.S. Historical Climatology Network (HCN), 2007. Monthly temperature and precipitation data.
Available at http://cdiac.ornl.gov/epubs/ndp019/ndp019.html.
36
Wagner, J.D.M., 2006. Speleothem record of southern Arizona paleoclimate, 54 to 2.5 ka.
Unpublished Ph.D. thesis, University of Arizona.

Wahi, A. K., 2005. Quantifying mountain system recharge in the Upper San Pedro Basin,
Arizona. Unpublished M.S. thesis, University of Arizona.

Wright, W.E., 2001. δD and δ18O in mixed conifer systems in the U.S. Southwest: the potential
of δ18O in Pinus ponderosa Tree Rings as a Natural Environmental Recorder. Unpublished M.S.
thesis, University of Arizona.

37
TABLE AND FIGURE CAPTIONS

Table 1. Elevation, location, MAAT, MAP, vegetation, and δ13C (VPDB) values for
transect sites. δ13C values are measured for pedogenic carbonate, abundance-weighted
vegetation, and soil gas, and estimated for δ13Cresp. δ13Cpc values are the average of
values from ≥50 cm soil depth; δ13Cconc values are corrected for the Suess Effect; and
δ13Cresp values are calculated from δ13Csom and δ13Cbulkplant values (both Suess-corrected).

Figure 1. Location of soil study sites in and around the Tucson Basin, in southeastern
Arizona.

Figure 2. MAAT and MAP for 3 stations in southeastern Arizona: (1) Tucson (740 m),
(2) Santa Rita Experimental Range (1310 m), and (3) Mt. Lemmon in the Santa Catalina
Mountains (2425 m).

Figure 3. δ13Cconc (VPDB) as a function of soil depth (cm) for soil respiration rates ranging
from 0.1 to 9.0 mmol/m2/hr, using the diffusion model for soil CO2 (Cerling, 1984, 1991;
Quade, et al., 1989a; Quade et al., 2007). Boundary conditions include 0.9 atm total
pressure, δ13Catmosphere = -6.5‰ with pCO2 = 270 ppmV for the pre-industrial atmosphere,
o
free air porosity of 0.5, a tortuosity of 0.6, temperature = 21.7 C, δ13Cresp = -24‰, and
exponential production, where k = 22.5 cm.

Figure 4. Monthly weighted averages of δ18Omw values (red circles, error bars are one
standard deviation), average temperature (green squares), and average precipitation
amount (blue triangles) for Tucson from 1981-2005, adapted from Wagner (2005).

Figure 5. δ13Cpc (VPDB) versus δ18Opc (VPDB) values from ≥50 cm in late Holocene soils
in southeastern Arizona.

Figure 6. δ18Opc (VPDB) from ≥50 cm versus site elevation, showing values of carbonate
predicted to form in equilibrium with summer and winter precipitation (solid lines), for
sites studied in southeastern Arizona.

Figure 7. δ18Opc (VPDB) and δ13Cpc (VPDB) versus depth for a late Holocene soil profile at
Tumamoc, for which δ13Cpc is modeled (solid lines) for the respiration rates shown
(mmol/m2/hr) using the model described in Quade et al. (2007) where elevation is 730 m,
o
T = 22.1 C, δ = 0.5, and δ13Cresp = -22.5‰. Open symbols represent values from other
profiles at Tumamoc, for which respiration rate was not modeled.

Figure 8. δ18Opc (VPDB) and δ13Cpc (VPDB) versus depth for 2 late Holocene soil profiles
at Madera, for which values are distinguished as solid versus open symbols.

Figure 9. δ18Opc (VPDB) and δ13Cpc (VPDB) versus depth for a late Holocene soil at
Hirabayashi. δ13Cpc is modeled (solid lines) for the respiration rates shown (mmol/m2/hr)
o
using the model described in Quade et al. (2007), where elevation is 1460 m, T = 17.0 C,

38
 δ = 0.5, and δ13Cresp = -22.8‰..

Figure 10. δ18Opc (VPDB) and δ13Cpc (VPDB) versus depth for a late Holocene soil profile
at GC Terrace.

Figure 11. δ18Opc (VPDB) and δ13Cpc (VPDB) versus depth for a late Holocene
soil profile at GC S-facing, for which δ13Cpc is modeled (solid lines) for the respiration
rates shown (mmol/m2/hr) using the model described in Quade et al. (2007), where
o
elevation is 1900 m, T = 13.9 C, δ = 0.5, and δ13Cresp = -18.4‰. Open symbols represent
values from other profiles at this site for which respiration rate was not modeled.

Figure 12. δ13Cpc (VPDB) values from ≥50cm soil depth versus site elevation for late
Holocene soils in southeastern Arizona.

Figure 13. δ13Cpc (VPDB) versus δ13Csom (VPDB) for soils studied in southeastern Arizona.
The lower two solid lines represent modeled isotopic values defining high respiration-rate
soils (10 mmoles/m2/hr) between 0 and 25°C. The dashed lines represent a range of soil
respiration rates (labeled) calculated for 25°C. Solid circles represent observed δ13Cpc
values. In general, these values plot above the field defined for high respiration-rate
soils, suggesting a significant atmospheric component.

Figure 14. δ13Cpc (VPDB) from 60 cm depth in a late Holocene soil at COB West, for which
δ13Cpc is modeled (solid lines) for the respiration rates shown (mmol/m2/hr) using the
o
model described in Quade et al. (2007) where elevation is 1650 m, T = 15.6 C, δ = 0.5,
and δ13Cresp = -18.6‰.

Figure 15. Predicted versus observed δ18Opc (VPDB) values, where predicted values are
calculated to form in equilibrium with mean annual δ18Omw.

Figure 16. δ18O (VPDB) and δ13C (VPDB) values of pedogenic calcrete sampled from the
north and south aspects of Tumamoc Hill.

39
Table 1. Summary of Sites
EL

δ
13

13
EV

δ
13
C con

C res
MA
MA
LO

EC
AT

LO

C pc
SE
C

P
AT
IO

LA

OZ
N

TT
AL

p
c
G
N

(m

(‰
(‰

(‰
T

ON
IN
(°C
(W
IT

(m

(N

G
Y

)
E

)
)

)
)

SOM PLANT
o o
Tumamoc 730 31 43.423’ 110 46.041’ 22.1 280 Terrace creosote-grassland -13.3 -22.5 x -2.1

Madera 1105 32o 20.406’ 110o 43.044’ 19.4 358 Terrace mesquite-grassland x x x -8.7

Hirabayashi 1450 31o 27.411’ 110o 22.324’ 17.0 480 Terrace oak-juniper-grassland -16.7 -22.8 x -7.7

West Hillslope limestone scrub -13.1 -18.6 -21.8 -0.9

COB 1660 32o 13.298’ 111o 0.634’ 15.6 539
Terrace Terrace oak-juniper-grassland x -18.5 x -0.7

S-facing Hillslope oak-juiper-grassland -15.1 -18.4 x -5.0

GC 1900 31o 46.881’ 110o 53.176’ 13.9 605
Terrace Terrace Ponderosa-grassland x x x -7.4
 Santa Catalina Mountains

Hirabayashi
1450 m

Tumamoc
730 m

Tucson Mountains

Tucson
Basin

Madera
1105 m
Cave-of-the-Bells
1660 m

Santa Rita Mountains

Garden Canyon
1900 m

Huachuca Mountains

Figure 1
 35.0
35 Precipitation
35 Temperature
30.0
30
Mt. Lemmon
30
25.0
(2425 m)
25
25
20.0
20
20
15.0
15
15
10.0
10
10
55.0
5
00.0
0

35.0
35 Precipitation
Temperature
30.0
30 Santa Ritas
25.0
(1310 m)
25
20.0
20
15.0
15
10.0
10
5.0
5
Temperature (oC) 0.0
0
Precipitation (cm/month)

35.0
35 Precipitation
Temperature
30.0
30 Tucson
(740 m)
25.0
25
20.0
20
15.0
15
10.0
10
5.0
5
0.0
0 y r y ril ly st r er r r
ar ch ay ne be be be
nu ua ar Ap M Ju Ju gu ob
br M Au em ct em em
Ja Fe pt O ov ec
J F M A M J J A S O N D Se N D

Figure 2
 0

10
5.0
5.0

4.0
4.0
20 6.0
6.0
7.0
7.0
30 8.0
8.0
e p t h (c(cm)
(cm
m)

40
DDepth

50

60

70

80

0.1
0.5
3.0

2.0

1.0
2.0 1.0 0.5 0.1 0.05 0.01

0.01
3.0

0.05
90

100
-25 -20 -15 -10 -5 0

δ CCO2 (VPDB)
13

Figure 3
 Tucson Precipitation wt. δ18Omw (VSMOW)

-10
5

-5
0

Figure 4
0
2
4
6

Month
8
10
12
0
20
30

10

Temperature (C)
0
80

40

Amount (mm)
 δ18Opc (VPDB)
-12 -10 -8 -6 -4 -2 0
0

-2

-4

δ13Cpc (VPDB)
-6

-8
GC Terrace
GC S-facing
COB Terrace
COB West
Hirabayashi -10
Madera
Tumamoc

-12

Figure 5
 2000

1800

1600
GC Terrace
GC S-facing
Elevation (m)

1400
winter
COB Terrace
COB West
1200 Hirabayashi
Madera
Tumamoc
1000
summer

800

600
-12 -10 -8 -6 -4 -2 0

δ 18Opc (VPDB)

Figure 6
 0-
pedogenic A
structure
20-
stratified carbon
gravels oxygen
40-
stratified
alluvium
60- 2Bw
disconformity 2Bw
80-

100- 2C
Depth (cm)

120- 3C1

140-
3C2
160-

0.22
0.53
8.0
180-

200-
-1 2
-1 0
-8
-6
-4
-2

0
2
4
δ ‰ (VPDB)
Figure 7
 0-
unbedded
gravels A carbon
20- oxygen
stratified
alluvium
40-

60-
C
80-
Depth (cm)

100-

120-

140-

160-

180-

200-
-12

-10

-8

-6

-4

-2

4
δ ‰ (VPDB)

Figure 8