A cool time in the Early Jurassic: First continental palaeoclimate estimates from oxygen and...

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Carbonates and Evaporites ISSN 0891-2556 Carbonates EvaporitesDOI 10.1007/s13146-015-0276-z

A cool time in the Early Jurassic: firstcontinental palaeoclimate estimates fromoxygen and hydrogen isotope ratios in chertfrom Navajo Sandstone carbonate lenses,Utah (USA)Ray Kenny

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ORIGINAL ARTICLE

A cool time in the Early Jurassic: first continental palaeoclimateestimates from oxygen and hydrogen isotope ratios in chertfrom Navajo Sandstone carbonate lenses, Utah (USA)

Ray Kenny1

Accepted: 6 September 2015

� Springer-Verlag Berlin Heidelberg 2015

Abstract Cool continental palaeoclimate estimates

ranging from *9 to 18 �C were inferred from oxygen and

hydrogen isotope composition of chert precipitated con-

temporaneously with algal carbonate in interdune, fresh-

water lakes of the Early Jurassic Navajo Sandstone (USA).

The oxygen and hydrogen isotope composition also indi-

cate that meteoric waters were involved in the crystal-

lization history of the chert. These results are consistent

with previous studies that suggest that the interdune car-

bonate lenses in the Navajo Sandstone are freshwater car-

bonates precipitated in a wet-climate, pluvial episode.

Approximate palaeotemperature estimates from oxygen

and hydrogen isotope composition of silicified wood

samples adjacent to a carbonate lens yield palaeotemper-

ature estimates of *33 to 43 �C. These data are consistentwith burial diagenetic temperatures and support the inter-

pretation that the algal chert precipitated contemporane-

ously with the algal carbonate. The results of this study

demonstrate that the potential for obtaining quantitative,

continental palaeoclimate estimates from freshwater chert

found throughout the geologic record.

Keywords Late Pliensbachian � Stable isotope

geochemistry � Interdune carbonate � Palaeotemperatures �Chert

Introduction

The Early Jurassic Navajo Sandstone (Pliensbachian–

Toarcian age) of the western USA is a thick (up to 600 m),

cross-bedded sandstone deposited near the western margins

of the Pangaean Supercontinent. The depositional envi-

ronment and predominantly arid climatic conditions are

internationally recognized and have been described by

numerous researchers (e.g. Peterson and Pipiringos 1979;

McKee 1979). The Navajo Sandstone represents one of the

largest, most widespread ([365,000 km2), and well-ex-

posed arid-climate, aeolian deposits preserved in the rock

record (Blakey et al. 1988; Kocurek 2003). Although the

Navajo Sandstone is predominantly characterized by large-

scale aeolian cross-sets, interdune, freshwater carbonate

lenses (Fig. 1), petrified coniferous trees, and three-metre

high stromatolites locally occur in the lower part of the

formation along the southern margins in Utah (Gilland

1979; Winkler et al. 1991; Loope et al. 2004; Hencmann

and Kenny 2008; Wilkens et al. 2008; Stokes 1991; Parrish

and Falcon-Lang 2007; Eisenberg 2003). Loope and Rowe

(2003) described bioturbated sedimentary structures asso-

ciated with wet interdune areas and argued that the

observed structures record a long-lived, monsoon-domi-

nated, pluvial episode (Loope et al. 2001, 2004). Henc-

mann and Kenny (2008) provided chemical analyses and

oxygen and carbon isotope data from one interdune car-

bonate lens, which is consistent with carbonate precipita-

tion in a freshwater lake. Hencmann and Kenny (2008)

suggested that the observed 13C-poor algal carbonate

adjacent to chert nodules were likely derived from (1) a

terrestrial biogenic source; or, (2) relatively high, in situ

biological productivity; or, (3) the decay of organic,

microbial material in the sediment (e.g. Pentecost and

Spiro 1990). 18O-poor algal carbonate adjacent to chert

& Ray Kenny

Kenny_r@fortlewis.edu

1 Geosciences Department, Fort Lewis College, Durango,

CO 81301, USA

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DOI 10.1007/s13146-015-0276-z

Author's personal copy

nodules, likely resulted from the low 18O values in mete-

oric waters, a process well documented by previous studies

(Gross 1964; Allen and Mathews 1982; Kenny 1992).

Wilkens et al. (2008) and Wilkens (unpub. Ph.D. thesis,

Arizona State University, Tempe, Arizona 2008) concluded

that the palaeontology and palaeoecology of numerous,

southern margin carbonate lenses were consistent with a

long-term and widespread pluvial episode. Collectively,

these previous studies unequivocally indicate that the

interdune algal carbonates are freshwater precipitates. In

this study, chert was sampled from interdune carbonate

precipitated along algal laminae (Fig. 2) exposed at several

localities in southeastern Utah (Fig. 3); silicified wood

adjacent to one carbonate lens was also sampled. The chert

samples were analysed for oxygen and hydrogen isotope

ratios to determine whether continental palaeoclimate

estimates could be obtained; the silicified wood was anal-

ysed for oxygen and hydrogen isotope ratios to determine

whether palaeotemperature estimates would cluster in dis-

crete or similar palaeotemperature envelopes on a dD–d18Odiagram.

Isotope analysis

Oxygen and hydrogen isotope ratio data for nineteen,

white, algal chert from four interdune carbonate outcrops,

and three silicified wood samples from one location are

shown in Fig. 4; the data are given in Table 1. Five mil-

limetre size or smaller interior chert chips were quarried

Fig. 1 Early Jurassic interdune carbonate lens (b) crops out betweenthe arid-climate, aeolian, and cross-bedded Navajo Sandstone (a),overlying the Late Triassic/Early Jurassic Kayenta Formation (c).Shay Mountain Quadrangle, Utah, USA (view is toward the southwest

across Indian Creek, southeastern Utah). Cliff height (X) is approx-

imately 30 m. The interdune carbonate lenses in the study area obtain

a maximum thickness of *5 metres and are laterally exposed

for *1.5 km

Fig. 2 Dark surface patina (desert varnish) on chert nodules precip-

itated and oriented along algal crenulations in the Navajo Sandstone

interdune carbonate (pen length *13 cm). In the lab, chert samples

used for isotopic analyses were quarried to obtain fresh, unweathered

interior (\5 mm) chips; the chips which were visually inspected

under a binocular microscope to ensure purity and exclude any

inclusions and surface contaminants

Fig. 3 Regional geography and approximate chert sample locations;

black dots indicate location of field sites. UTM coordinates for the

sample locations are provided in Table 1

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from field samples collected in contact with algal laminae;

light-coloured (iron oxide poor) and white silica separates

were selected from the silicified wood samples. The mil-

limeter-size sample chips were visually inspected and

analysed under a binocular microscope for the presence of

iron oxides or other impurities. A hand-held magnet was

passed over the samples to detect and remove any (mag-

netic) iron oxide. Oxygen and hydrogen isotope analyses

were conducted following the well-established, in situ laser

extraction method of Sharp (1990) and Sharp et al. (2001);

isotope data were obtained from four separate stable iso-

tope labs which yielded repeatable data. All data are

reported relative to V-SMOW in standard d-notation. d18Orepresents total (structural) oxygen in chert and silica; dDis derived from non-surface hydroxyl groups extracted

from within the chert. All analyses have a precision

of ±0.2 and ±2 % for d18O and dD, respectively.

Results

The oxygen and hydrogen isotope ratio data derived from the

algal chert and silicified wood form domains elongated away

from Line A on a dD–d18O diagram (Fig. 4). Line A is the

inferred locus of isotopic compositions of cherts in

equilibrium with modern sea water at various temperatures

(Knauth and Epstein 1976). Chert data are interpreted in

terms of palaeotemperatures by comparing them with tem-

perature lines drawn parallel to the meteoric water line

(Fig. 4) as established by Knauth and Epstein (1976). Chert

and silica data elongated away from Line A, as is the case in

this study, indicate that meteoric (fresh) waters were

involved in the crystallization history of the chert. These data

are in agreement with previous studies that suggest that the

interdune carbonate lenses of the Navajo Sandstone precip-

itated under freshwater conditions (Stokes 1991; Hencmann

and Kenny 2008; Wilkens et al. 2008). Palaeotemperature

estimates for the chert range from *9 to 18 �C and *33 to

43 �C for the silicifiedwood (Fig. 4). The shift in oxygen and

hydrogen isotope composition between the silicified wood

and algal chert data indicates that meaningful oxygen and

hydrogen isotope differences exist between (1) the elevated

burial temperatures and (2) the cooler temperatures derived

from the algal-mound chert. These data show that meteoric

waters were involved in the crystallization history of both the

silicified wood and algal chert but under demonstrably dif-

ferent temperature regimes. The algal chert data indicate that

the palaeoclimate during freshwater carbonate and chert

precipitation was considerably cooler than the arid-climate

indicators for most of the Navajo Sandstone.

Fig. 4 Oxygen and hydrogen isotopic values for (1) the Early

Jurassic, interdune algal cherts of the Navajo Sandstone (solid

circles), and (2) silicified wood (crosses). The isotopic data are

interpreted in terms of palaeotemperatures by comparing them with

temperature lines drawn parallel to the meteoric water line (Knauth

and Epstein (1976). Line A is the inferred locus of isotopic

compositions of cherts in equilibrium with modern sea water at

various temperatures. Isotopic values for Early Jurassic cherts

indicate precipitation in the presence of meteoric water at temper-

atures ranging from *9 to 18 �C; silicified wood samples plot in a

separate temperature envelope (*33 to 43 �C) and likely formed

under burial conditions

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Discussion

Analyses of oxygen and hydrogen isotope ratios in chert

have yielded reasonable and reproducible palaeoclimate

estimates which have been verified by independent proxy

data which are highly resistant to alteration and isotopic

exchange, including clay minerals and iron-oxyhydroxide

material (Abruzzese et al. 2005). Oxygen and hydrogen

isotopes in chert record the isotopic composition of total

oxygen and trace hydroxyl groups preserved in silica and

chert at the time of precipitation and crystallization

(Knauth and Epstein 1976). Approximate palaeoclimate

estimates based on analyses of the oxygen and hydrogen

isotope ratios in marine silica and chert are well established

(Knauth and Epstein 1976; Knauth and Lowe 2003; Hren

et al. 2009). Kenny and Knauth (1992) demonstrated that

oxygen and hydrogen isotopic composition of secondary

(authigenic) silica precipitated in palaeokarst chert lags

could be used to estimate near-surface continental weath-

ering temperatures. Kenny (2010) reported continental

weathering temperatures from secondary silica precipitated

during a tropical karst event that developed on the Mis-

sissippian Redwall Limestone of northern Arizona (USA).

Abruzzese et al. (2005) suggested that oxygen and hydro-

gen isotope ratios in freshwater chert could be used as an

indicator of regional climatic variation in the Cenozoic.

Despite the fact that silica and chert have been successfully

used to estimate palaeoclimatic conditions, the temperature

assignments made with the method of Knauth and Epstein

(1976) are subject to several uncertainties. (1) The curve

for quartz-water isotope fractionation with temperature is

not known well for low temperatures. The temperature

lines, used in this method (Fig. 4), are extrapolated from

better understood, high-temperature, quartz-water curves.

(2) Isotopic values in early chert must be preserved through

time. Microorganisms embedded in Precambrian chert

attest to the chemical integrity and physical stability of

silica (Schopf et al. 2007; Knauth and Lowe 2003).

Remarkable preservation of microorganisms (e.g. Knoll

1992; Schopf 1993; Horodyski and Knauth 1994; Sugitania

Table 1 Algal-mound and algal-crenulation chert data

d18O SMOW

(%)adD SMOW

(%)aDescription and Location (All Quadrangle maps are in Utah, USA; all UTM coordinates are Z12)

30.35 -90.98 White algal-mound chert (\1 cm diameter). Shay Mountain Quadrangle (*631097 mE; 4199722 mN)

33.22 -88.89 White chert, algal stromatolite flank breccia. Shay Mountain Quadrangle (*631097 mE; 4199722 mN)

32.41 -88.14 White algal-mound chert (*1 cm diameter). Shay Mountain Quadrangle (*630760 mE; 4198830 mN)

32.2 -109.0 White algal crenulation chert (\1 cm diameter). Monticello Lake Quadrangle (*632240 mE; 4205900 mN)

30.0 -127.1 White algal crenulation chert (\1 cm diameter). Photograph Gap Quadrangle (*633120 mE; 4209900 mN)

29.6 -122.2 White algal crenulation chert (\1 cm diameter). Photograph Gap Quadrangle (*633700 mE; 4209700 mN)

27.74 -110.4 White algal-mound chert (\1 cm diameter). Shay Mountain Quadrangle (*631097 mE; 4199722 mN)

27.86 -116.1 Thin-bedded, stringer chert, granular microcrystalline quartz (\1 cm diameter). Shay Mountain Quadrangle

(*630760 mE; 4198830 mN)

29.28 -88.0 White algal-mound chert (\1 cm diameter). Shay Mountain Quadrangle (*630760 mE; 4198830 mN)

32.78 -89.6 White chert, algal stromatolite flank. Shay Mountain Quadrangle (*630760 mE; 4198830 mN)

32.8 -89.8 White algal chert (\1 cm diameter). Photograph Gap Quadrangle (*633700 mE; 4209700 mN)

29.78 -109.3 White algal-mound chert (\1 cm diameter). Shay Mountain Quadrangle (*633097 mE; 4209900 mN)

32.47 -84.6 Crenulated white chert. Shay Mountain Quadrangle (*631097 mE; 4199722 mN)

29.59 -106.0 White algal crenulation chert (\1 cm diameter). Monticello Lake Quadrangle (*632250 mE; 4205910 mN)

30.69 -100.4 White granular microcrystalline quartz. Shay Mountain Quadrangle (*630760 mE; 4198830 mN)

29.51 -99.87 White algal chert (\1 cm diameter). Davis Gulch Quadrangle (*500750 mE; 4131700 mN)

30.81 -91.5 White algal chert (\1 cm diameter). Davis Gulch Quadrangle (*500700 mE; 4131690 mN)

29.16 -89.2 White algal crenulation chert (\1 cm diameter). Tenmile Point Quadrangle (*585973 mE; 4285262 mN)

29.46 -109.1 White algal crenulation chert (\1 cm diameter). Tenmile Point Quadrangle (*585989 mE; 4285243 mN)

25.76 -38.1 Silicified wood. Tenmile Point Quadrangle (*585989 mE; 4285243 mN)

26.04 -38.2 Silicified wood. Tenmile Point Quadrangle (*585989 mE; 4285243 mN)

25.04 -73.8 Silicified wood. Tenmile Point Quadrangle (*585989 mE; 4285243 mN)

a Reproducibility of d18O is ±0.2 %; reproducibility of dD is ±2 %. Reproducibility is based on duplicate runs and standards. Samples were

analysed at silicate isotope facilities at University of New Mexico, Stanford University, Southern Methodist University, and the University of

Texas—Austin

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et al. 2007) and previous oxygen and hydrogen isotope

ratio studies on chert by Kenny and Knauth (1992) suggest

excellent preservation of original isotopic values in chert

dating from the Late Proterozoic. Brassier et al. (2002)

argued that some of the oldest, previously reported bacte-

rial microfossils from the *3.5 Ga Apex Group chert may

be geochemical artefacts; other Late Proterozoic micro-

fossils preserved in chert have not been disputed. (3) The

temperature estimates in Fig. 4 also depend on the

assumption that d18O values of sea water have not changed

significantly throughout geologic time. The generally lower

d18O values of ancient carbonates (e.g. from the Silurian

Period) has been used as an argument that d18O values of

the past oceans was lower than modern values (Veizer et al.

1986; Veizer and Prokoph 2015). However, Knauth and

Roberts (1991) provide arguments that they consider fatal

to using carbonates to monitor the oxygen isotope com-

position of past seawater. Specifically, Knauth and Roberts

(1991) presented data, including direct analysis of unal-

tered ocean water preserved in halite, which precludes the

proposed *5 to 6 % oxygen isotope ratio changes in

seawater as far back as the Silurian Period. In order to

adequately determine the diagenetic history of carbonate

samples used to monitor the oxygen isotopic composition

of past seawater, both 13C and 18O co-variant values are

needed. Veizer and Prokoph (2015) analysed oxygen iso-

tope ratios in carbonates to propose secular oxygen isotope

ratio changes in ocean water during the Phanerozoic, but

co-variant 13C values for the 18O analyses have not been

included in their published dataset. Both 13C and 18O co-

variant values are needed to determine if the platform

carbonates are original precipitates, have been diageneti-

cally altered at the molecular level, or have been partially

altered by meteoric waters during the transformation of the

host sediment into limestone (e.g. Knauth and Kennedy

2009). Zempolich et al. (1988) analysed co-variant carbon

and oxygen isotope ratios in Proterozoic Beck Spring

carbonates to argue that the Beck Spring ocean was not

significantly different from modern sea water. Clumped

isotope thermometry is a new approach that uses isotopo-

logues (which are independent of the bulk isotopic com-

position) to examine the temperature dependence of bond

formation between two rare, heavy isotopes within a single

molecule to independently determine the d18O composition

of the fluid in a carbonate sample (Eiler 2007, 2011;

Henkes et al. 2013). Cummins et al. (2014) used clumped

isotope analysis to address the complicated uncertainties

related to diagenetic alteration of d18O in carbonates used

to estimate the oxygen isotopic composition of past sea-

water. Cummins et al. (2014) measured a large suite of

well-preserved Silurian (ca. 433 Ma) carbonate fossils and

determined that the Silurian oceans had oxygen isotopic

composition similar to the modern ocean. Clumped isotope

research on carbonates from other geologic time periods

has also been reported yielding similar results (Henkes

et al. 2014). Collectively, the clumped isotope research

largely supports previous studies by Knauth and Epstein

(1976) and Knauth and Roberts (1991) which suggest that

the d18O of Earth’s ocean waters have remained broadly

consistent through time.

Enrichment of 18O in chert may result if silica precipi-

tation occurred under evaporative conditions. Abruzzese

et al. (2005) documented a large range of oxygen isotope

values (*20 %) in Eocene andMiocene Epoch chert which

they attributed to large-scale changes in the isotopic com-

position of lake water due to evaporation. The relatively

narrow range of oxygen values in the interdune chert of this

study (*5.5 %) suggests that evaporative processes were

likely insignificant and evaporative enrichment was likely

minimal during the crystallization history of the chert.

O’Neil and Hay (1973) reported elevated oxygen isotope

values from Magadiite cherts that formed in strong saline

lake deposits of East Africa. Oxygen isotope values in

Magadiite cherts ranged from 33.8 to 38.3 % and were

determined to be compatible with precipitation from a brine

and meteoric water mix (O’Neil and Hay 1973). No oxygen

isotope values in the 33.8 to 38.3 % range were obtained

from this study suggesting that the cherts likely did not form

in a saline-rich lake. Palaeontological and palaeoecological

works by Wilkens et al. (2008) and Winkler et al. (1991)

demonstrate that the species preserved in the carbonate

would not have thrived under strong saline conditions.

Further, at one locality, silicified wood occurs in situ adja-

cent to the interdune carbonate lenses that contain algal

chert; the presence of long-lived coniferous trees does not

imply saline nor elevated alkaline conditions (Parrish and

Falcon-Lang 2007). Nevertheless, the presence of these

fossils does not preclude the possibility of a geochemical

shift from a meteoric water-dominated palaeoenvironment

to a saline-dominated palaeoenvironment, and the geo-

chemical environment of the ancient freshwater lakes of the

Navajo Sandstone is not precisely known.

Elevated temperatures from post-precipitation meta-

morphic processes could produce low oxygen and hydro-

gen isotope values in chert and silica. However, none of the

field sites in this study have been affected by igneous or

high-grade metamorphic processes. As such, oxygen and

hydrogen isotopic analyses from this study should yield

meaningful palaeoclimatic information for the Early

Jurassic Period.

Chert nodules in this study (in size up to a few cm in

diameter) were oriented along algal crenulations and

stratigraphically bound by algal laminae, suggesting that

silica precipitated contemporaneously with algal carbonate

(Fig. 2). If this interpretation is correct, then the

palaeotemperature estimates from the oxygen and

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hydrogen isotope ratios in chert principally reflect long-

term, near-surface temperature estimates of the freshwater

lake in which the chert precipitated. McCombie (1959) first

showed that long-term temperature of a freshwater lake is

broadly similar to local continental temperature estimates.

More recent studies have also shown that air- and water-

surface temperatures are often highly correlated on both

short- and long-term timescales (Shuter et al. 1983; Liv-

ingstone and Lotter 1998). As such, the quantitative

palaeotemperature estimates from chert co-precipitated

with freshwater carbonate should broadly reflect long-term

palaeoclimate conditions at the time of precipitation.

Studies on the origin of algal silica and algal chert

suggest that diurnal modulation of pH due to the activity of

algal symbionts and/or the presence of degraded cells

promote direct precipitation of silica (Ferris et al. 1988;

Eggins et al. 2004; Souza-Egipsy et al. 2005). Accordingly,

locally elevated pH is probably the critical factor enabling

the precipitation of silica at low temperatures; pH fluctu-

ations would not produce isotopic fractionation of oxygen

or hydrogen isotopes in the silica precipitate. If these

conditions are satisfied, then the oxygen and hydrogen

isotopic compositions in freshwater chert should depend-

ably reflect the near-surface environment and be a valuable

tool for estimating long-term continental palaeoclimate

conditions.

Three silicified wood samples, which almost assuredly

precipitated under burial conditions, were analysed for

oxygen and hydrogen isotope composition to determine if

notable isotopic distinctions exist between the algal chert

and the silicified wood (Fig. 4). Non-volcanoclastic silici-

fication of wood occurs slowly under burial conditions and

at elevated temperatures (Sigleo 1979; Hesse 1989). The

non-volcanoclastic silicified wood sampled adjacent to one

interdune carbonate lens plots in a separate and notably

warmer temperature envelope relative to the algal chert

when plotted on a dD–d18O diagram (Fig. 4). This suggests

that the oxygen and hydrogen isotope values preserved in

the algal chert and the silicified wood represent different

environmental conditions likely derived from two different

temporal events: (1) an early event plausibly related to

contemporaneous precipitation of silica and algal carbonate

and (2) a later, post-depositional event, related to silica

precipitation under burial conditions. The disparate oxygen

and hydrogen isotope compositions lend further support to

the suggestion that chert nodules extracted from the algal

mounds did not form under burial conditions and likely

formed contemporaneously with the algal carbonate as

indicated by the field relationships. The palaeotemperature

estimates on algal chert from this study broadly agree with

field evidence that indicate the freshwater carbonate lenses

formed under cooler, wet climate conditions (Loope and

Rowe 2003).

Research into the Early Jurassic climate indicates that an

extended period of global cooling likely occurred during

the Late Pliensbachian. Tanner et al. (2001) used carbon

isotope compositions of pedogenic calcite to infer that the

pedogenic carbonate formed under a cool palaeoclimate.

Caruthers et al. (2013) compared marine organism

extinction data from western North America with European

data and determined that marine extinctions were multi-

phased, likely triggered by volcanic activity, and resulted

from a widespread, global cooling event. However, Tanner

et al. (2001) suggested that widespread extinctions of both

continental and marine biota likely did not result from

volcanic outgassing. Both researchers suggest that a global

cooling event likely occurred during the Late Pliens-

bachian, but disagree on the causal mechanism. The iso-

topic results from this study provide quantitative evidence

of a cool, continental palaeoclimate during the Early

Jurassic in southern Utah. These data broadly support the

inferred global climate shift detailed by Tanner et al.

(2001) and Caruthers et al. (2013). It is tempting to spec-

ulate that the interdune freshwater lakes of the Navajo

Sandstone are correlative with the Late Pliensbachian,

global climate episode. However, a lack of index fossils in

the Navajo Sandstone precludes any direct correlation with

the proposed Late Pliensbachian global cooling event.

Conclusions

The Early Jurassic Navajo Sandstone contains unaltered

chert co-precipitated with freshwater, interdune, algal

carbonate. Analysis of oxygen and hydrogen isotope ratios

in chert yield continental palaeoclimate estimates ranging

from *9 to 18 �C (obtained using the palaeotemperature

method developed by Knauth and Epstein 1976). The

quantitative palaeoclimate estimates support previous

geochemical and field studies that suggest that the fresh-

water, interdune lake carbonate likely precipitated under

cool and wet climate conditions. This study demonstrates

that quantitative palaeoclimate estimates can be obtained

from chert nodules co-precipitated with freshwater, algal

carbonate and that this approach should provide analogous

results for similar outcrops found throughout the geologic

record.

Acknowledgments Comments from two anonymous reviewers

helped improve the manuscript. A part of this study was supported by

a Fort Lewis College Traditional Scholarship and Research Grant.

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