Isotopic Composition of Organic and Inorganic Carbon from the Mesoproterozoic

Precambrian Research 224 (2013) 169–183

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Precambrian Research

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Isotopic composition of organic and inorganic carbon from the Mesoproterozoic

Jixian Group, North China: Implications for biological and oceanic evolution

a,b a,∗ b a a a a

Hua Guo , Yuansheng Du , Linda C. Kah , Junhua Huang , Chaoyong Hu , Hu Huang , Wenchao Yu

State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences (Wuhan), Wuhan, Hubei 430074, China

Department of Earth & Planetary Sciences, University of Tennessee, Knoxville, TN 37996, United States

a r t i c l e i n f o a b s t r a c t

Article history: Analyses of marine carbon isotope proﬁles have provided much of our current understanding of the

Received 4 July 2012

evolution of Earth surface environments, particularly in the latter portion of the Proterozoic Eon. Earlier

Received in revised form

Mesoproterozoic successions, however, have received comparatively little attention due to the relatively

25 September 2012

subdued nature of carbon isotope variation. In this study, we present high-resolution isotopic proﬁles

Accepted 25 September 2012

from three sections in the Yanshan Basin, North China craton that, combined, comprise the entirety of the

Available online xxx

early Mesoproterozoic (1600–1400 Ma, Calymmian period) Jixian Group. High-resolution proﬁles of both

carbonate and organic carbon provide critical data for global comparison and permit us to better con-

Keywords:

Mesoproterozoic strain both the pattern and origin of isotopic variation in the Mesoproterozoic. Marine carbonate rocks of

the Jixian Group show generally muted isotopic variation with average values near 0‰, consistent with

North China

Carbon isotopes previous observations from the early Mesoproterozoic. Data furthermore record an increase in isotopic

Organic carbon variation through the succession that is interpreted to reﬂect a long-term decrease in pCO2 and, conse-

Ocean oxygenation quently, in the isotopic buffering capacity of marine dissolved inorganic carbon (DIC). By contrast, the

isotopic composition of marine organic matter suggests facies-dependent differences in carbon cycling.

Organic carbon compositions suggest a dominance of autotrophic carbon ﬁxation and aerobic decom-

position in shallow-water environments, and increased remineralization by anaerobic heterotrophs in

deeper-water environments. Correlation between organic carbon composition and depositional environ-

ment are interpreted to reﬂect differences in carbon cycling within benthic microbial mats under low

oxygen conditions and dynamically maintained stratiﬁcation of marine waters.

1. Introduction increased organic carbon burial (Des Marais et al., 1992; Hayes and

Waldbauer, 2006; Holland, 2006) that, in turn, may have resulted in

Combined isotopic records of organic and inorganic carbon global-scale ocean oxygenation. By contrast, the Mesoproterozoic

can provide critical insight into the behavior of the global carbon (1.6–1.0 Ga) has received substantially less attention. Relatively

cycle and have been used extensively to investigate the continu- subdued secular variation recorded in carbon-isotope composition

ally evolving relationship between biology and ocean-atmosphere of marine carbonate (Kah et al., 1999, 2012; Kah and Bartley, 2011)

chemistry (Bartley and Kah, 2004). Paired isotopes of carbon and has been assumed to reﬂect a combination of geologic and ecologic

organic carbon been used, for instance, to infer some of Earth’s ear- stasis (Buick et al., 1995; Brasier and Lindsay, 1998). A growing

liest biological metabolisms (Schidlowski, 2001; Ueno et al., 2001, body of evidence, however, suggests that the Mesoproterozoic Era

2004) and, more recently, to infer the global marine redox state in may represent a critical interval in terms of evolution of the Earth’s

both the Early and Late Proterozoic (Rothman et al., 2003; Kump ocean-atmosphere system (Kah and Bartley, 2011, and references

et al., 2011; Johnston et al., 2012; Och and Shields-Zhou, 2012). therein). For instance, a relatively abrupt increase in both the iso-

Previous efforts to constrain the behavior of the oceanic car- topic composition and isotopic variability of marine carbonate (Kah

bon cycle focused primarily at the two ends of the Proterozoic et al., 1999, 2012; Frank et al., 2003; Bartley et al., 2007), which

Eon. Strongly positive carbon isotope signatures preserved in may reﬂect a global increase in oxygenation, co-occurs with both

marine carbonate rocks (Karhu and Holland, 1996; Halverson et al., increased marine sulfate concentrations and the ﬁrst appearance

2005; Melezhik et al., 2005) are interpreted as resulting from of widespread bedded marine gypsum (Whelan et al., 1990; Kah

et al., 2001), as well as diversiﬁcation within both prokaryotic and

eukaryotic clades (Butterﬁeld, 2000; Johnston et al., 2005; Knoll

∗ et al., 2006). Take together, these observations suggest that the

Corresponding author. Tel.: +86 18986127299.

E-mail addresses: [email protected] (Y. Du), [email protected] (L.C. Kah). availability of oxygen in Earth’s surface environments had, by the

170 H. Guo et al. / Precambrian Research 224 (2013) 169–183

Fig. 1. Simpliﬁed paleogeographic maps during this time period at the North China Platform, which is modiﬁed from Wang et al. (1995) and Chu et al. (2007). The investigated

sections are marked as numbers 1–3.

mid-Mesoproterozoic, reached important geochemical and biologi- 2.2. Sedimentary strata of the Yanshan Basin

cal thresholds. Yet despite evidence for increased oxygenation (Kah

and Bartley, 2011, and references therein), marine environments Sedimentary strata of the Yanshan Basin are represented

appear to have remained relatively oxygen-deﬁcient (Kah et al., by unmetamorphosed and relatively undeformed successions of

2004, 2012), with broad regions of the seaﬂoor overlain by anoxic, the Changcheng (1800–1600 Ma), Jixian (1600–1400 Ma), Xis-

either sulﬁdic or ferruginous, waters (Brocks et al., 2005; Planavsky han (1400–1200 Ma), and Qingbaikou groups (1000–800 Ma)

et al., 2011; Blumenberg et al., 2012). (Qiao et al., 2007; Sun et al., 2012; see Chen et al., 1980 for

In this study, we concentrate on the early Mesoproteorozic antecedent stratigraphic division). The Changcheng system consists

(Calymmian period; 1600–1400 Ma). We present high-resolution of four formations (Changzhougou, Chuanlingguo, Tuanshanzi, and

carbon isotope data for carbonate and organic matter from the Jix- Dahongyu) that unconformably overlie Archean and Paleoprotero-

ian Group, Yanshan Basin, North China. The dataset presented here zoic basement and represent initial deposition with Yanshan rift

currently represents the highest resolution chemostratigraphic basin. Strata consist of >1000 m of alluvial to ﬂuvial conglomerate

dataset from the early Mesoproterozoic and, as such, permits and sandstone that ﬁne and deepen upward into a >2000 m-thick

unprecedented exploration of the isotopic patterns and origin of succession of marine sandstone, silt, shale, and carbonate (Li et al.,

isotopic variation in the early Mesoproteorozic carbon cycle. 2003a,b). Uppermost units of the Changcheng Group notably con-

tain high-potassium volcanic interbeds that are associated with

continued, regional extension (Lu et al., 2002, 2008).

2. Geological setting and age The overlying Jixian Group consists of ﬁve formations

(Gaoyuzhuang, Yangzhuang, Wumishan, Hongshuizhuang, and

2.1. Regional geological setting Tieling), dominated by marine carbonate deposition, that represent

marine transgression and development of a stable cratonic plat-

The North China craton, which refers to the Chinese part of the form across the Yanshan Basin (Ying et al., 2011). Jixian Group strata

Sino-Korea Platform, is a triangular-shaped region with an area of unconformably overlie mixed siliciclastic and carbonate strata of

approximately 1 500 000 km , which covers most of North China the Changcheng Group, although the boundary appears, in places,

(Fig. 1, Zhao et al., 2001). The North China craton consists of variably to be conformable (Chen et al., 1980; Song, 1991; Lu et al., 1996;

exposed gneiss, granite, and amphibolite, as well as shist, marble Zhao, 1997). The majority of Jixian strata consist of ﬁnely lami-

and iron formation (Zhao, 2001; Kusky and Li, 2003; Zhao et al., nated to stromatolitic dolomite, argillaceous dolomite, and chert

2005) that represent a long history of accretion beginning in the deposited under a range of intertidal to supratidal environments.

Archean and ending in the late Paleoproterozoic (Zhao et al., 2005; The Xiamaling Formation, composed mainly of organic-rich

Li et al., 2011a,b, 2012; Nutman et al., 2011; Peng et al., 2011; Wan shale, is the only formation in the newly established Xishan

et al., 2011; Liu et al., 2012a,b; Lü et al., 2012; Peng et al., 2012). Group (Qiao et al., 2007). The Xiamaling Formation unconformably

Proterozoic carbonate strata are well preserved across the North underlies the two formations (Changlongshan and Jingeryu) that

China craton, where they unconformably overlie basement litholo- comprise the Qingbaikou Group and mark the return of domi-

gies. The most extensive accumulations occur within the Yanshan nantly siliciclastic deposition prior to regional uplift of Yanshan

Basin (Xiao et al., 1997; Li et al., 2003a,b) in the northern part of the Basin strata.

craton. The Yanshan Basin represents a continental rift basin that This study focuses on carbonate strata of the Jixian Group, which

developed at the margin of the eastern block of the North China includes, in an ascending order, the Gaoyuzhuang, Yangzhuang,

craton at approximately 1.8 Ga (Lu et al., 2002, 2008; Hou et al., Wumishan, Hongshuizhuang, and Tieling formations (Fig. 2).

2006). Late Paleoproterozoic extension has been recorded across Together, these ﬁve formations represent near continuous marine

the North China craton (Lu et al., 2008, and references therein) and deposition within the Yanshan Basin. All samples were col-

is potentially associated with the breakup of the supercontinent lected near the type Jixian section (Fig. 1), with samples of

Columbia (Rogers and Santosh, 2002; Zhao et al., 2002, 2003, 2004, the Gaoyuzhuang and Yanghzuang formations collected from the

2011). Pingquan section, samples of the Wumishan and Tieling formations

H. Guo et al. / Precambrian Research 224 (2013) 169–183 171

2.2.2. Yangzhuang Formation

At the Pingquan section, the overlying Yangzhuang Formation

is relatively thin (only 16.7 m), and composed predominantly of

alternating red and white sandy to silty dolomicrite. An increase

in more coarsely grained siliciclastic components, as well as the

presence of wave ripples and mud cracks, suggest deposition within

predominantly intertidal to supratidal environments.

2.2.3. Wumishan Formation

The Wumishan Formation, which is nearly 2785 m thick in

the Lingyuan section, is the thickest unit within the Jixian Group.

Four members were subdivided in this formation and the litholo-

gies for each member are brieﬂy described as: (1) argillaceous,

cherty dolomicrite; (2) thick-bedded stromatolitic, and bitumi-

nous dolostones with minor chert; (3) rhythmically layered silt

and dolomicrite, with minor cherty and oolitic layers; (4) cherty

calcitic to dolomitic carbonate intercalated with bituminous and

stromatolitic dolostone. The Wumishan Formation is particularly

notable for its great thickness, abundant stromatolites (including a

wide variety of microdigitate structures with precipitate textures;

cf. Shi et al., 2008; Mei et al., 2010), intraclastic conglomerate, fos-

siliferous chert, and general paucity of terrigenous material, and is

interpreted as representing deposition predominantly in peritidal,

epicontinental environments (Kuang et al., 2012).

2.2.4. Hongshuizhuang and Tieling formation

The Hongshuizhuang and Tieling formation represent the

uppermost carbonate deposition of the Jixian Group. These units

are relatively thin (88 m in the Hualai section and 91 m in

the Lingyuan section, respectively) and conformably overlie the

Wumishan Formation. These units consist of ﬁnely crystalline,

thinly bedded, muddy dolostone interbedded with varicolored,

sometimes pyritic, shale (in the Hongshuizhuang Formation) and

stromatolitic dolostone (in the Tieling Formation). Combined, these

units suggest deposition in predominantly nearshore, peritidal

depositional environments. Mn-bearing SEDEX mineralization in

the lower, shaley member of the Tieling Formation (Lu et al., 1996)

suggests that shaley lithologies at this stratigraphic position may

have acted as a primary conduit for postdepositional, hydrothermal

ﬂuid ﬂow.

2.3. Geochronological age constraints

Fig. 2. Stratigraphic log of the early Mesoproterozoic succession, with geochrono-

The age of Changcheng Group carbonate strata is well con-

logical constraints. Geochronological data are from: Li et al. (2010), Su et al. (2010)

strained within the Yanshan Basin and has been reviewed in detail

and Qiao et al. (2007).

in previous publications (Xiao et al., 1997; Li et al., 2003a,b; Chu

et al., 2007). Deposition of the underlying Changcheng Group,

within the Yanshan Basin, is constrained to have initiated by ca.

collected from the Lingyuan section, and samples of the Hong-

1800 Ma, which is the youngest age of detrital zircons from two

shuizhuang Formation collected from the Huailai section.

sandstone samples in the lowermost Changcheng Group (Wan

et al., 2003). A maximum age of approximately 1800 Ma is also con-

2.2.1. Gaoyuzhuang Formation

sistent with ages of 1769 ± 2.5 Ma for maﬁc intrusions that occur

The Gaoyuzhuang Formation comprises the lower 947 m of the

within basal sedimentary strata of the Changcheng Group (Li et al.,

Jixian Group at the Pingquan section (Fig. 2). From the base, the ±

2000). Additional ages of 1683 67 Ma (U–Pbzircon, Li et al., 1995)

Gaoyuzhuang Formation can be divided into four members, includ-

and 1625 6 Ma (U–Pbzircon, Lu and Li, 1991) obtained from extru-

ing (1) cherty, stromatolitic dolomicrite interbedded with sandy

sive trachytes and trachyandesites of the Tuanshanzi and Dahongyu

to shaley dolomicrite; (2) thinly bedded clayey—and often Mn-

formations, respectively, provide constraint on the upper age of

rich—dolomicrite; (3) organic-rich, clayey dolomicrite with cherty

deposition of the Changcheng Group and, consequently, constraint

concretions; and (4) massive dolomicrite with cherty concretions.

on the lower limit of sedimentation within the Jixian Group.

Generally ﬁnely crystalline, micritic carbonate, planar bedding,

The age of the Jixian Group is less well constrained. Tradi-

and evidence for elevated concentrations of organic matter and

tionally, the Jixian Group has been assumed to be approximately

manganese (Fig. 3) suggest deposition of the Gaoyuzhuang Forma- 40 39

1400–1100 Ma based on Ar/ Ar ages obtained from chert

tion largely within subtidal, oxygen-limited shelf environments;

and glauconite (Zhong, 1977; Li, 1993; Wang et al., 1995), as

although some stromatolitic, cherty intervals, particularly in the

well as a single Pb–Pb model age of 1434 ± 50 for the middle

upper Gaoyuzhuan formation (cf. Seong-Joo and Golubic, 1999)

Gaoyuzhuang Formation (Chung, 1977). Recently, however, Li et al.

may represent periods of shallower-water deposition.

(2010) reported new ages of 1559 ± 12 Ma (U–Pb SHRIMP) and

172 H. Guo et al. / Precambrian Research 224 (2013) 169–183

Fig. 3. Major facies of the Jixian Group. The peritidal facies (supertidal and intertidal) are dominated by a wide variety of shallow water depositional marks, such as

ripples, tabular cross-bedding, wave microbial mats, ministromatolites, intraclastic conglometrate, teepee structures, mud cracks (A–G); The shallow subtidal facies realm

is dominated by column stromatolites, oncolites, cross-bedding structures (H–J). The concretions and muddy dolostones are often present at the deep subtidal facies (K–L);

in this stratigraphic succession, the storm-dominated carbonates are typical depositional facies marks in the shallow shelf (M), and the deep shelf facies realm in the studied

area is dominated by thin and horizontal bedding limestones (N–O).

1560 ± 5 Ma (U–Pb LA-MC-ICPMS) from a single volcanic tuff in SHRIMP) from the upper part of the Tieling Formation in the

the upper Gaoyuzhuang Formation (Yanqing Country, Beijing), sug- Pingquan region. This new date, along with ages of 1368 ± 12 Ma,

± ±

gesting a notably older age for initiation of Jixian Group deposition. 1370 11 Ma, and 1366 9 Ma (U–Pb SHRIMP, Gao et al., 2007,

Similarly, Su et al. (2010) reported an age of 1437 ± 21 Ma (U–Pb 2008a,b, 2009) from a series of closely-spaced tuffs within the

H. Guo et al. / Precambrian Research 224 (2013) 169–183 173

unconformably overlying Xiamaling Formation, constrains the Analytical uncertainty for both major and minor elements averages

deposition of the Jixian Group to between approximately 1600 and 5 wt‰.

1400 Ma, or wholly within the early Mesoproterozic (Calymmian

period) (Qiao et al., 2007).

4. Results and interpretations

3. Materials and analytical methods

4.1. Evaluation of diagenesis

3.1. Sample collection and petrographic analysis

4.1.1. Petrographic preservation of Jixian Group microfacies

Because of the complex post-depositional history of most sed-

A total of 623 carbonate samples were collected from measured

imentary carbonate rocks, post-depositional alteration must be

sections of Jixian Group carbonates. This sample set comprises

considered prior to the interpretation of isotopic compositions. Pet-

259 samples from the Gaoyuzhuang Formation, 13 samples from

rographic analyses provide a ﬁrst-order assessment of depositional

the Yanghzuang Formation, 311 samples from the Wumishan For-

and/or diagenetic heterogeneity that can be used in conjunc-

mation, 4 samples from the Hongshuizhuang Formation, and 36

tion with isotopic and elemental analyses to identify both the

samples from the Tieling Formation. Weathered surfaces and large

most chemically altered samples—i.e., those that are least likely

veins were removed either during ﬁeld collection or secondarily

to preserve meaningful carbon isotopic signatures; and the least

in the laboratory. Thin sections of samples were then evaluated by

chemically altered samples—i.e., those that are most likely to pre-

optical petrography to catalog the range of carbonate fabrics within

serve near-primary isotopic compositions (Kaufman et al., 1991;

each sample. Petrographic analyses provides a ﬁrst-order assess-

Kah et al., 1999; Frank et al., 2003; Bartley et al., 2007).

ment of depositional and/or diagenetic heterogeneity (cf. Kaufman

Within the Jixian Group most samples record little evidence of

et al., 1991; Kah et al., 1999; Frank et al., 2003; Bartley et al., 2007)

extensive post-depositional recrystallization (Fig. 4). The major-

that can be used in conjunction with isotopic and elemental anal-

ity of sampled material—particularly within the Gaoyuzhuang

yses to determine the potential for retaining little altered isotopic

compositions. Formation—consists of calcitic to dolomitic micrite and ﬁne

microspar. The ﬁnely crystalline nature of these components, and

the general absence of more coarsely crystalline phases suggest

3.2. Isotopic analysis of carbonate rocks

that diagenetic stabilization occurred within penecontemporane-

ous marine ﬂuids. Other primary microfacies within these samples

Whole-rock samples were crushed to less than 150 ␮m for

include micrite, coated grains, intraclasts, clotted microbial struc-

geochemical analysis. Samples for carbon and oxygen isotope anal-

tures, and stromatolitic and oncolitic laminae.

ysis were reacted with 100% H3PO4 under vacuum for 24 h at

◦ ◦ Coated grains and ooids of the Jixian Group are typically spher-

25 C for limestone and at 50 C for dolomite. Evolved CO2 was

ical or ellipsoidal in shape, and preserve a radial-concentric cortex

then puriﬁed and its C- and O-isotope composition measured

that surrounds a nucleus composed of micritic intraclasts or sin-

on a Finnigan MAT 251 IRMS (isotope ratio mass spectrometer)

gle quartz grains (Fig. 4A and B). Cortex microfabics commonly

at the State Key Laboratory of Geological Processes and Min-

show clear, well-preserved, acicular crystals arranged radially to

eral Resources, China University of Geosciences (Wuhan). Isotopic

the nucleus and separated by thin, micritic bands. Calcareous

compositions are reported in standard delta notation, where ı

* to dolomitic micritic intraclasts (Fig. 4C and D) are commonly

−

(in ‰) = [(Rsample Rstandard)/Rstandard] 1000, relative to the VPDB

found associated with coated grains in peritidal environments.

(Vienna Pee Dee Belemnite) standard. Precision is better than 0.1‰

13 18 As with the coated grains, intraclasts are typically ﬁnely crys-

for ␦ C and ␦ O, based on multiple analyses of laboratory stan-

talline and show evidence for only minimal post-depositional

dards.

recrystallization. Recrystallization most commonly occurs as par-

tial recrystallization to a slightly more coarsely crystalline phase.

3.3. Isotopic analysis of organic carbon

In these cases, interlocked, anhedral crystal fabrics suggest neo-

morphic recrystallization during early diagenesis. Preservation of

An additional 252 samples were chosen from throughout the

diverse, ﬁne-scale structures in intraclasts and within the cortex

Jixian Group for isotopic analysis of organic carbon. Samples for

of coated grains and ooids suggest preservation of primary deposi-

organic carbon analysis were treated with 10% HCl to remove car-

tional textures (Wright, 1990) and indicate only limited inﬂuence of

◦

bonate, rinsed with distilled water, and freeze-dried at −40 C

post-depositional ﬂuids, even in otherwise coarse-grained, quartz-

overnight. The isotopic composition of organic carbon was then

bearing lithologies.

determined using a Thermo Finnigan MAT 253 IRMS (isotope ratio

Equally diverse microfabrics occur within the microbially lam-

mass spectrometer) at the State Key Laboratory of Geological Pro-

inated facies of the Jixian Group. Finely crystalline clots within

cesses and Mineral Resources, China University of Geosciences

more coarsely crystalline, microsparitic matrix are common within

(Wuhan). Isotopic compositions are reported in standard delta

stromatolitic and oncolitic lithologies (Fig. 4E and F). Such clots

notation relative to the VPDB (Vienna Pee Dee Belemnite) standard.

occur commonly as a result of in situ cyanobacterial calciﬁcation

Precision is better than 0.2‰, based on multiple analyses of labo-

or micrite precipitation during microbial decomposition (Wright,

ratory standards.

1990; Turner et al., 1993; Riding, 2006; Kah and Riding, 2007).

We attribute similar formation mechanisms to small peloids that

3.4. Analysis of major and minor elements occur in association with microbial fabrics. As with intraclastic

and ooilitic fabrics, the diverse and ﬁne-scale fabric preservation

In addition to isotopic analyses, samples from the Gaoyuzhuang observed in microbial fabrics suggests generally restricted inﬂu-

Formation were also analyzed for major (Ca, Mg) and minor (Mn, ence of later diagenetic ﬂuids.

Sr) element concentrations. Samples were dissolved in concen- By contrast to these primary depositional microfabics,

trated hydrochloric acid, and the solutions analyzed on an IRIS some samples within the Jixian Group show clear indication

IntrepidIIXSP ICP-AES (inductively coupled plasma-atomic emis- of recrystallization during post-depositional ﬂuid interactions.

sion spectrometry) at the State Key Laboratory of Biogeology and These samples are typically characterized by coarse, euhe-

Environmental Geology, China University of Geosciences (Wuhan). dral crystalline phases that show little evidence of primary

174 H. Guo et al. / Precambrian Research 224 (2013) 169–183

Fig. 4. Petrographic preservation of the Jixian Group carbonate microfacies. (A) Coated ooids with intraclastic nuclei and well-preserved acicular cortices. Samples from the

Gaoyuzhuang Formation; (B) Aragonite ooid show large radial ‘club’ structures and concentric layers in the outer part of the cortex, Gaoyuzhuang Formation; (C) Intraclasts

mostly contain complex structures, interpreted as representing re-cementation of pre-existing individual intraclast grains, Gaoyuzhuang Formation; (D) Intraclasts with

various sharps and sizes, Gaoyuzhuang Formation; (E) Well-preserved clotted structures, in which sparitic cement contains small peloids with indistinct margins, Wumishan

Formation; (F) Oncoids, spherical or ellipsoidal in shape, with less regular concentric laminations, Wumishan Formation; (G) well preserved ﬁne-grained structures, Wumishan

Formation and (H) coarse-grained structures representing more signiﬁcant degree of diagenesis, Gaoyuzhuang Formation.

depositional textures (Fig. 4H). Dark brown cores to coarsely 4.1.2. Examination of isotopic and elemental trends

crystalline—often dolomitic—phases may represent partial The potential effects of diagenesis on the preservation of marine

retention of primary depositional components, but substan- carbon isotope records can also be evaluated by examination of

tial geochemical remobilization cannot be ruled out. We interpret combined elemental and isotopic trends (Figs. 5 and 6; Table S1).

these phases as having undergone recrystallization in the presence In particular, numerous studies of Paleozoic and Proterozoic carbo-

of post-depositional ﬂuids. nates have shown that carbon isotope composition is less sensitive

H. Guo et al. / Precambrian Research 224 (2013) 169–183 175

2 to diagenetic alteration than either oxygen isotope or trace element

(Mn, Sr) composition, as long as diagenetic ﬂuids are relatively

carbon-poor (Banner and Hanson, 1990; Kaufman et al., 1991;

Banner and Kaufman, 1994).

Carbon and oxygen isotope values of Jixian Group samples show

a range of values between approximately −2‰ and +2‰ for carbon

0 and −4‰ and −11‰ for oxygen. No clear co-variation between

carbon and oxygen isotope composition is observed, suggesting

that post-depositional ﬂuid ﬂow and associated organic diagenesis

-1 likely was not a strong inﬂuence on isotopic compositions (Veizer,

C vs VPDB(‰)

1983; Marshall, 1992). Furthermore, the majority of petrographi- 13

δ Tieling

cally well-preserved samples record oxygen isotope compositions

Hongshuizhuang

-2 between −6 and −9‰. Oxygen isotopes are generally considered

Wumishan

a sensitive indicator of diagenetic processes, even at low degrees

Yangzhuang

Gaoyuzhuang of ﬂuid-rock interaction (Banner and Hanson, 1990). Although the

-3 potential for secular change in the oxygen isotope composition

-20 -18 -16 -14 -12 -10 -8 -6 -4 -2

of past marine systems remains controversial (see Brand, 2004;

δ O vs VPDB(‰) Kasting et al., 2006; Jaffrés et al., 2007, for review), oxygen iso-

tope values recorded here are similar to those recorded by most

Fig. 5. C- and O-isotope compositions of samples from the Jixian Group shown no

petrographically well-preserved, non-evaporitic Proterozoic and

clear covariance except for some samples from the Tieling Formation.

early Paleozoic carbonate rocks (Frank and Lyons, 2000; Kah, 2000;

Bartley et al., 2007; Thompson and Kah, 2012; Kah et al., 2012),

and it has been proposed that such values record early diagenetic

0.5 1000

0.4 800

0.3 600 Sr (ppm) Mg/Ca 0.2 400

0.1 200

0.0 0

-16 -14 -12 -10 -8 -6 -4 -2 -16 -14 -12 -10 -8 -6 -4 -2

δ18 O δ18O

1200 1200

1000 1000

800 800

600 600 Mn (ppm) Mn (ppm) 400 400

200 200

0 0

-16 -14 -12 -10 -8 -6 -4 -2 0 200 400 600 800 1000 δ18 O Sr (ppm)

␦

Fig. 6. Geochemical data from the Gaoyuzhuang Formation. (A) Cross plot of O versus Mg/Ca ratios suggests minor later diagenesis has affected the two end member phases

␦18

(limestone and dolomitic limestone). (B and C) Sr and Mn concentrations of Gaoyuzhuang Formation samples, plotted against O vaules. The elevated Sr concentrations

(>200 ppm) occur predominately in less altered limestones (black squares, B), inferred original mineralogy is aragonite, some well-preserved samples display elevated Mn

concentrations (black squares, C) that suggests carbonate precipitation in the presence of Mn-rich waters. (D) cross-plot of Mn and Sr concentrations of Gaoyuzhuang

Formation samples.

176 H. Guo et al. / Precambrian Research 224 (2013) 169–183

stabilization in isotopically light marine waters (Veizer and Hoefs, propensity to record the effect of reducing ﬂuids during burial

1976; Veizer et al., 1992). diagenesis, Mn concentration (as well as Mn/Sr ratios) have been

If oxygen isotopic compositions between approximately −6 and regarded as sensitive indicators of diagenetic alteration (Veizer,

−9‰ are interpreted to reﬂect little altered marine isotopic compo- 1983; Derry et al., 1992; Lindsay and Brasier, 2000), with a Mn/Sr > 2

sitions, our data indicate that at least a portion of the Gaoyuzhuang regarded as having suffered substantial diagenetic alteration (Derry

and Wumisham formation samples with more positive oxygen iso- et al., 1992, 1994; Kaufman and Knoll, 1995; Montanez˜ et al.,

topic compositions may reﬂect moderately evaporitic depositional 1996). Most Mn/Sr ratios in the Gaoyuzhuang Formation and sev-

conditions, which is consistent with microfabics and microfos- eral other formations within the Jixian Group (Li et al., 1999, 2009;

sil assemblages determined in previous studies (Seong-Joo and Kuang et al., 2009) are typically less than 1, which conforms with

Golubic, 1999). By constrast, nearly all samples from the upper- previous inferences of minimal post-depositional alteration. Sam-

most Tieling Formation preserve oxygen isotope compositions ples with elevated Mn, however, commonly have Mn/Sr between

between −9 and −19‰. Such negative isotopic values, combined 4 and 12. We suggest, however, that these elevated values may

with evidence for SEDEX mineralization within this unit, suggest reﬂect primary compositional differences. A growing number of

the potential for substantial overprinting of primary isotopic values studies suggest that redox-sensitive elements such as Mn (Bartley

during post-depositional, and potentially hydrothermal, ﬂuid-rock et al., 2007; Thompson and Kah, 2012; Kah et al., 2012) and Iron

interaction. (Gilleaudeau and Kah, in press) can also reﬂect low oxygen condi-

Elemental analyses of nearly 200 samples from the tions of ancient seawater and the relative mobility of reduced ions

Gaoyuzhuang Formation permit a more detailed evaluation in microbially dominated environments (cf. Davison, 1982).

of post-depositional diagenesis. We ﬁrst consider effects of

carbonate mineralogy on isotopic and elemental composition. 4.2. Chemostratigraphic results

Gaoyuzhuang Formation carbonates show variation in their degree

of dolomitization, with Mg/Ca ranging from 0.0 to 0.4 (Fig. 6A). As discussed above, petrographic and geochemical data sug-

As with previous studies (Bartley et al., 2007), isotopically light gest that Gaoyuzhuang Formation carbonates are considered to be

␦18

O associated with post-depositional alteration is recorded generally well preserved and likely to retain little-altered carbon

in both calcitic (Mg/Ca < 0.2) and more dolomitic (Mg/Ca > 0.2) isotope compositions. The carbon isotope stratigraphy of both car-

samples, although these samples comprise only 20% of the total bonate (Fig. 7) and organic matter (Fig. 8) in the Yanshan Basin,

sample pool. Among samples inferred to be “less altered” (i.e., North China, are listed in Table S1.

␦18

O > −9‰), those with extensive, fabric-retentive dolomitization The chemostratigraphic patterns derived from marine car-

show slightly more positive oxygen isotope values, suggesting bonates of the Jixian Group are broadly similar to patterns

the potential for either preservation of originally heavier isotopic observed in other Mesoproteorozic carbonate successions older

values, or dolomitization enhanced via evaporative ﬂuid ﬂow (cf. than ∼1300 Ma. Carbon isotope compositions through the Jixian

Kah, 2000; Bartley et al., 2007; Kah et al., 2012). succession range from −2.6‰ to +1.8‰ (with an average value of

−

In addition to Mg/Ca ratios, which are most commonly associ- 0.2‰), and are arranged in a series of alternating positive and neg-

ated with post-depositional dolomitization of primary phases, trace ative excursions. The 946 m thick Gaoyuzhuang Formation records

element content can also be used as a powerful indicator of post- the lowest degree of isotopic variability. With the exception of

depositional recrystallization under a range of ﬂuid compositions an anomalous 50-m thick interval, carbon isotope compositions

(Brand and Veizer, 1980; Banner and Hanson, 1990). Strontium of the Gaoyuzhuang Formation average −0.3‰ (s.d. = 0.6‰) and

concentrations in carbonate rocks of the Gaoyuzhuang Formation range between −1‰ and +1‰. Stability of these isotopic values con-

are typically <200 ppm (Fig. 6B). Strontium is typically elevated in trasts sharply with those preserved within the anomalous interval,

−

marine environments, but is rapidly lost during recrystallization, during which carbon isotope compositions drop to nearly 2.5‰.

even at minimal degrees of water rock interaction. Empirically, A return to more muted isotopic compositions in the 20 m-thick

strontium concentrations near 200 ppm are common for petro- Yangzhuang Formation then give way to increased isotopic vari-

graphically well-preserved Proterozoic limestone (Kaufman and ability in the >2600 m-thick Wumishan Formation, with average

Knoll, 1995). Within the Gaoyuzhuang Formation, the lowest con- values of −0.1‰ (s.d. = 0.8‰), and a total range from −1.8‰ to

centrations (<100 ppm Sr) occur primarily in dolomitized phases, +1.8‰. Basal Wumishan strata record isotopic values near 0‰,

−

which likely reﬂect the preference for Sr to reside in the Ca site which then fall below 1.5‰ before rising rapidly to carbon iso-

of the calcite lattice (Pierson, 1981; Carpenter et al., 1991). Sev- tope values near +2‰, and then falling once again to values below

−

eral samples, however, record strontium concentrations as high as 1.5‰. Above this, a second positive excursion reaches values

1000 ppm (Fig. 6B). These samples may reﬂect (1) minimal non- near +1‰ before falling to values near −1.5‰ and rising a ﬁnal

marine post-depositional diagenesis, (2) elevated concentration of time through the uppermost Wumishan Formation to reach val-

strontium from a primary aragonite depositional phase, or (3) pre- ues near +2.0‰. These moderately positive values are retained

cipitation from evaporative marine ﬂuids with elevated strontium through the 25 m thick Hongshuizhuang Formation, before record-

concentrations (cf. Kah et al., 2012; Gilleaudeau and Kah, in press). ing a precipitous drop to values ≤2.5‰ in the 90 m thick Tieling

Samples with elevated strontium concentrations, however, have Formation.

oxygen isotope compositions within the range of inferred open A chemostratigraphic proﬁle constructed from the carbon iso-

marine samples, suggesting that elevated strontium reﬂects marine tope composition of organic matter, however, shows distinct

stabilization of an originally aragonitic phase, with only a minor differences from that of marine carbonate, particularly between the

degree of post-depositional recrystallization. Gaoyuzhuang and Wumishan formations (Fig. 8). Because marine

Similarly, manganese shows an interesting pattern of enrich- organic carbon is largely derived from the direct autrophic ﬁxation

ment within Gaoyuzhuang Formation carbonates (Fig. 6C and D). of marine DIC (dissolved inorganic carbon), the isotopic compo-

Manganese concentrations are generally <100 ppm, which is inter- sition of marine organic carbon typically co-varies with that of

preted to reﬂect only restricted inﬂuence of post-depositional marine carbonate. Such covariance is observed through the entire

ﬂuid ﬂow. Approximately 25% of samples that are inferred to Wumishan Formation and the upper portion of the Gaoyuzhuang

reﬂect little-altered, open-marine, calcitic deposition (i.e., ␦ O Formation, where the isotopic composition of organic carbon

− −

values between 6 and −9‰ and Mg/Ca < 0.2) also contain man- ranges from 21.6‰ to −30.4‰, with most samples having a

ganese concentrations between 400 and 1200 ppm. Because of its range from −26‰ to −30‰. Such values yield an average isotopic

H. Guo et al. / Precambrian Research 224 (2013) 169–183 177

Fig. 7. C isotope chemostratigraphy correlation of the comprehensive sections in this study with Jixian and Ming Tombs sections in Yanshan Basin. Detailed description of

Jixian and Ming Tombs sections can be found in Chu et al. (2007) and Li et al. (2003a,b), respectively.

13 13 13

␦ − ␦

fractionation ( C = Ccarb Corg) of 28.0‰ (s.d. = 2.0‰), composition of marine carbonate is now well established for much

which is consistent with derivation of organic matter from predom- of the last billion years of Earth history (e.g., Gale et al., 1993; Hill

inantly autotrophic communities. Organic carbon compositions and Walter, 2000; Shen and Schidlowski, 2000; Krull et al., 2004;

of the lower 750 m of the Gaoyuzhuang Formation, however, Halverson et al., 2005, 2010; Bergström et al., 2008; Thompson

range from −26.3‰ to −34.4‰, with values averaging −31.1‰ et al., 2012). Although carbon isotope proﬁles are comparatively

(s.d. = −1.5‰). Such isotopic values, which yield average isotopic rare from Mesoproterozoic and older successions, a growing num-

∼

fractionations of 31.0‰, suggest that the isotopic composition ber of studies suggest a distinctive pattern of isotopic variation

of organic matter in the lower Gaoyuzhuang Formation—in con- through the Mesoproterozoic (cf. Kah et al., 1999, 2001, 2012;

trast to that of the upper Gaoyuzhuang Formation and the entire Bartley et al., 2007). Speciﬁcally, carbon isotope records from the

Wumishan Formation—may reﬂect a degree of decoupling from the early Mesoproterozoic (pre-1300 Ma) show relatively subdued iso-

isotopic composition of marine carbonate. topic signatures that oscillate around an average value near 0‰,

and rarely reach values more negative or positive than approxi-

−

5. Discussion mately 1.5‰ or +1.5‰, respectively (Buick et al., 1995; Knoll et al.,

1995; Frank et al., 1997; Xiao et al., 1997; Lindsay and Brasier, 2000;

5.1. Yanshan Basin as a Mesoproterozoic reference section Lindasy and Brasier, 2004; Bartley et al., 2001; Chu et al., 2007; Kah

et al., 2007). Sparse data sets from rocks deposited between 1300

Carbon isotope stratigraphy has been widely applied to the and 1200 Ma suggest an increase in both the range and variability of

comparison and division of various geological times and bound- carbon isotope data (Frank et al., 2003; Bartley et al., 2007; Chiglino

ary events, and the pattern of secular variation in the isotopic et al., 2010), which leads to distinct isotopic plateaus near +4‰ and

178 H. Guo et al. / Precambrian Research 224 (2013) 169–183

13 13

Fig. 8. The carbon isotopic compositions of organic carbon (␦ Corg), carbonate (␦ Ccarb) in the early Mesoproterozoic Jixian Group, North China.

negative isotopic excursions to ≤2.5‰ that characterize sedimen- which are considered typical for the early Mesoproterozoic. Carbon

tary successions of the later Mesoproterozoic (Whelan et al., 1990; isotope data here oscillate in a repeated succession of positive and

Knoll et al., 1995; Kah et al., 1999, 2001, 2012; Bartley et al., 2001). negative excursions around values near 0‰ (Fig. 7). Data presented

Thick, carbonate-dominated sedimentary successions of the here also highlight the importance of high-resolution sampling.

Yanshan Basin, North China, offer an ideal opportunity to explore Earlier investigations of Jixian Group strata from the Yanshan Basin

secular variation in marine carbon isotopes during the early were constructed from stratigraphic sections measured at Jixian

Mesoproterozoic (from ∼1600 to 1400 Ma). Compared to early (Chu et al., 2007) and near the Ming Tombs (Li et al., 2003a,b).

Mesoproterozoic strata elsewhere, strata within the Yanshan Basin Although each of these successions show strong isotopic similarity

have superb age constraints, including: (1) U–Pbzircon ages of to the data presented here, only the highest resolution sampling

1683 ± 67 Ma and 1625 ± 6 Ma for extrusive volcanics within the reveals, with clarity, the oscillatory nature of marine carbon iso-

underlying Tuanshanzi and Dahongyu formations (Lu and Li, 1991; topes (Fig. 7). We therefore suggest that the carbon isotope values

Li et al., 1995; Lu et al., 2008); (2) U–Pbzircon ages of 1368 12 Ma, presented here have the potential to serve as a reference for the

1370 ± 11 Ma, and 1366 ± 9 Ma for volcanic rocks within the over- entire early Mesoproterozoic.

lying Xiamaling Formation (Gao et al., 2007, 2008a, 2008b, 2009); Interestingly, these data suggest a more complex and protracted

± ±

(3) U–Pbzircon ages of 1559 12 Ma and 1560 5 Ma for several evolution of the Mesoproterozoic carbon isotope record than earlier

volcanic horizons within the upper part of the Gaoyuzhuang For- suggested (see above, Kah et al., 1999, 2012; Kah and Bartley, 2011).

mation (Li et al., 2010) and ages of 1437 Ma from the upper part of Whereas our data support the observation of an increase in both the

the Tieling Formation (Su et al., 2010). average isotopic composition and an increase in the magnitude of

In this study, we present the highest resolution carbon isotope isotopic excursions in the Mesoproterozoic (Bartley and Kah, 2004),

curve, to date, of any Mesoproterozoic succession. More than 623 the data also suggest that these transitions may have occurred

data points reveal values within a narrow range from −2‰ to +2‰, gradually through the Mesoproterozoic. In particular, data from

H. Guo et al. / Precambrian Research 224 (2013) 169–183 179

the Gaoyuzhuang Formation, which record—with the exception Seong-Joo and Golubic, 1999) environments. By constrast, strata

of a single, 50 m-thick interval—only minimal isotopic variation of the upper Jixian Group (here typiﬁed by the Wumishan For-

(from −1‰ to +1‰), are quite similar to the generally isotopically mation) record deposition primarily within peritidal (intertidal to

monotonous signatures from youngest Paleoproterozoic to oldest supratidal) environments. Excursions within the Jixian system iso-

Mesoproterozoic (∼1575 Ma) strata from the McArthur and Mount topic proﬁle (Fig. 7) show no clear relationship to changes in water

Isa basins in Australia (Lindsay and Brasier, 2000). In turn, the dis- depth, and therefore suggest that isotopic variation does not simply

tinct shift to more variable isotopic signatures (from −1.8‰ to reﬂect a marine isotopic gradient.

+1.8‰) typiﬁed by in the Wumishan Formation are strikingly sim-

ilar to isotopic signatures from ∼1400 ma strata from the Helena 5.3. Organic carbon production and remineralization

Formation, Belt Supergroup (Frank et al., 1997), as well as those

recorded in approximately 1500–1400 Ma strata from the Kama- Although isotopic excursions within the Jixian Group do not

Belaya trough, Russia (Kah et al., 2007). This increase in preserved appear to be related directly to water depth and a vertical gra-

isotopic variation appears to continue into Mesoproterozoic strata dient in the isotopic composition of marine carbon that might

deposited between approximately 1300 and 1200 Ma, where suc- be expected under low-oxygen conditions, they may also poten-

cessions preserve isotopic variation that commonly see values that tially reﬂect the in situ remineralization of organic matter, which

range from −2‰ to greater than +2.5‰ (Frank et al., 2003; Bartley will ultimately affect organic carbon burial rates. Using carbon-

et al., 2007). ate and organic carbon samples, we can calculate both the total

fractionation ( C) and the fraction of organic carbon burial

5.2. Origin of carbon isotope variation (forg), at steady state, necessary to produce the observed isotopic

excursions (see Table S1; Kump and Arthur, 1999). In order to

The long-held view of Mesoproterozoic carbon isotope produce observed excursions, organic carbon burial rates would

stability—that the Mesoproterozoic represented a protracted inter- need to ﬂuctuate between approximately 0.15 and 0.25. Such

val of environmental stability (Brasier and Lindsay, 1998)—is not moderate differences in organic carbon burial could easily reﬂect

well supported by the growing body of evidence that suggests that processes either intrinsic to or extrinsic to the Yanshan Basin. If

the Mesoproterozoic may reﬂect a critical time in the evolution intrinsic to the basin, these values would suggest small changes

of Earth surface environments from the standpoint of global tec- in the burial and/or decomposition of organic matter under a

tonic reorganization, changes in both oceanic composition (Kah range of peritidal to subtidal conditions. Such changes could easily

et al., 2001; Bartley and Kah, 2004) and oceanic redox (Shen et al., be achieved under low-oxygen conditions that have been shown

2002; Anbar and Knoll, 2002; Arnold et al., 2004; Scott et al., 2008; to affect both the composition and behavior of benthic micro-

Planavsky et al., 2011), evolution within both prokaryotic (Johnston bial mats (Bartley and Kah, 2004; Brocks et al., 2005; Planavsky

et al., 2005) and eukaryotic clades (Javaux et al., 2004; Knoll et al., et al., 2011; Blumenberg et al., 2012; Gilleaudeau and Kah, in

2006), and the advent of eukarotic multicellularity (Butterﬁeld, press).

2000). Rather, a more plausible explanation of apparent isotopic Low oxygen (and likely stratiﬁed) oceanic conditions can be

stability might lie within the accumulated data for environmental inferred from the differences in isotopic behavior of organic

change (cf. Bartley and Kah, 2004; Kah and Bartley, 2011). In this between the Wumishan and Gaoyuzhuang formations. As dis-

scenario elevated marine carbonate saturation would have resulted cussed in numerous publications (Rothman et al., 2003; Coetzee

in a system wherein marine carbon isotope change was buffered by et al., 2006; Conrad et al., 2007; Baker, 2010; Jiang et al., 2012), the

the composition of marine DIC. Meanwhile, gradual oxygenation carbon isotope composition of bulk organic matter can be inﬂu-

of Mesoproterozoic biosphere would result in both a decreased enced by many factors, including the metabolic behavior of the

buffering capability and an increase in biotic inﬂuence, ultimately standing organic community, potential input from marine versus

resulting in a greater isotopic variability. terrestrial sources of organic matter, degradation of particulate

Under such conditions, short-term isotopic variability preserved organic carbon below the sediment water interface and reminer-

in Mesoproterozoic successions is likely to result from organic car- alization of dissolved organic carbon or other carbon byproducts

bon production and burial, marine stratiﬁcation and overturn, or within the water column. Organic matter that derives predomi-

in situ organic carbon remineralization (Bartley and Kah, 2004). nantly from the autotrophic ﬁxation of marine DIC typically records

In addition, low-oxygen conditions of the Mesoproterozoic would fractionation of 28–30‰ (Hayes et al., 1999; Kump and Arthur,

have promoted geochemical stratiﬁcation of the water column, 1999). By contrast, isotopically lighter values typically reﬂect

with broad regions of even shallow marine seaﬂoor overlain by organic carbon derived from a combination of heterotrophic and

anoxic, sulﬁdic, or possibly ferruginous waters (Brocks et al., 2005; secondary chemoautotrophic activity, along with remineralization

Planavsky et al., 2011; Kah et al., 2009; Kah et al., 2012; Blumenberg of carbon byproducts. Heterotrophic bacteria, for instance, uti-

et al., 2012; Gilleaudeau and Kah, in press). Under such condi- lize C-depleted organic matter as their primary carbon source,

tions, oxidation of organic byproducts (either dissolved organic and express their own kinetic isotopic fractionation, resulting in

carbon, Rothman et al., 2003; or oxidation of microbially produced the formation of organic byproducts (typically CO2) that can be

methane, Conrad et al., 2007) may result in the transient inﬂux depleted by several permil with respect to the original, autotrophic

of isotopically light organic carbon to the marine reservoir. The carbon source (Hollander and Smith, 2001). In another example,

degree of organic mineralization may also be affected by both water under sulfate-depleted conditions undergoing active fermenta-

depth (i.e., a dynamically maintained carbon isotope depth proﬁle; tion, heterotrophic (acetotrophic) methanogenesis has been shown

Kah et al., 2007) or restricted mixing between open marine and to produce biogenic methane with C depletions of up to 10‰

shallow-water epicratonic environments (Gilleaudeau and Kah, in over primary, autotrophic organic carbon (Conrad et al., 2010). If

press). remineralized in situ and added into the overall pool of organic

During the early Mesoproteorozic Era, the Yanshan Basin was matter, this contribution from anaerobic heterotrophs results in

13 13

dominated by stable, epicontinental deposition. Based on ﬁeld and more negative Corg and higher C values (Hollander and

petrographic observation, strata of the lower Jixian Group (here Smith, 2001). Organic matter derived, in part, from the sedi-

typiﬁed by the Gaoyuzhang Formation) record the deepest water mentation of anaerobic microbial biomass, in fact, often records

deposition, with deposition from quiet water, deeper subtidal C values ≥32‰ (Hayes et al., 1999; Teranes and Bernasconi,

environments, to shallow subtidal (and perhaps intertidal; cf. 2005; Li et al., 2011b; Jiang et al., 2012). By contrast, more

180 H. Guo et al. / Precambrian Research 224 (2013) 169–183

extreme C-depletion (15–50‰ depletion over the primary car- 5.4. Implications for ocean-atmosphere evolution

bon source) typically records a pronounced contribution from

secondary chemoautotrophic activity (such as hydrogenitrophic In summary, we suggest that differences in isotopic com-

methanogenesis) and its subsequent remineralization (Conrad position of inorganic and organic carbon samples between the

et al., 2010). Gaoyuzhuang and Wumishan formations most likely reﬂect a

Isotopic depletion of the standing biomass resulting from a combination of buffering of the marine system to DIC and differ-

contribution from heterotrophic and secondary chemoautotrophic ential carbon cycling within benthic microbial mats that reﬂect

bacterial consortia contrasts sharply with the isotopic composition a depth-dependent stratiﬁcation within the overlying water col-

of organic matter derived, in part, from terrigenous components, umn. Despite relatively substantial differences in C, the degree

which often record more positive ␦ Corg and, consequently, lower of organic carbon burial (forg) calculated for these formations

␦ C values. In this latter example, isotopically heavy terrigenous remained within a fairly narrow range, which suggests that the

material most commonly derived from higher plants that have sub- increased isotopic variation observed in marine carbonate between

stantially different mechanisms of carbon cycling. Because such these two successions must have been driven, instead by a differ-

terrigenous materials are believe to have been absent in the early ence in the buffering capacity of the marine DIC system (cf. Bartley

Mesoproterozoic (Kennedy et al., 2006; Battison and Brasier, 2012; and Kah, 2004). We suggest that a decreased buffering capacity

Kenrick et al., 2012), isotopically heavy organic matter is more may have been driven by a long-term decrease in pCO2 through

likely to reﬂect a combination of low organic carbon content and the late Paleoproterozoic, originally suggested by Li et al. (2003a,b),

extensive in situ degradation of primary organic material (cf. Kah and continuing through the Gaoyuzhuang Formation until perhaps

et al., 1999) or, alternatively the post-depositional, thermal decom- 1500 Ma.

position of organic matter (Strauss et al., 1992; Derry, 2010; Tocqué Differences in the isotopic composition of organic carbon, how-

et al., 2005). ever, more likely reﬂect differences in carbon cycling within benthic

As noted above (Section 4.2, Fig. 8), organic carbon signatures microbial mats, wherein well-oxygenated shallow marine water

within the Jixian Group can be divided into three discrete intervals: are characterized by benthic mats dominated by autotrophic car-

isotopically lighter organic carbon in the lower part (lower 750 m) bon ﬁxation and the abiogenic oxidation of this organic matter.

of the Gaoyuzhuang Formation with values averaging −31.1‰ In this case, organic decomposition and remineralization resulted

(with values as low as −34.4‰); Organic carbon values averaging in organic matter with isotopic compositions similar to that of the

−

28.0‰ in the upper 200 m of the Gaoyuzhuang Formation and original autotrophic biomass. By contrast, sub-oxic to anoxic deeper

the entire Wumishan Formation; and highly variable values (from marine waters are characterized by benthic mats that experience a

−22‰ to −34‰) within uppermost Tieling Formation. greater degree of decomposition via anaerobic heterotrophs, which

These data suggest that the majority of the Jixian Group, rep- resulted in isotopic depletion of the carbon byproducts. In situ

resented by extensive, peritidal deposits of the Wumishan and remineralization of isotopically light DOC therefore resulted in

upper Gaoyuzhuang formations, reﬂects a microbial community a greater contribution of isotopically light carbon to the organic

dominated by autotrophic organisms, and an environment which carbon pool. This distribution of chemical characteristics implies

prohibited extensive heterotrophic remineralization of organic unique chemical conditions for the early Mesoproterozoic, in which

matter and, instead, facilitated the oxidative decomposition of ben- anoxic (either sulﬁdic or ferruginous) conditions (Shen et al., 2002;

thic microbial material. Such values are therefore consistent with Brocks et al., 2005; Planavsky et al., 2011; Gilleaudeau and Kah,

peritidal, and presumably well-oxygenated conditions inferred for in press) likely occurred close to oxygenated, well-mixed surface-

the depositional environment, and are consistent with biomarker oceans. These results are consistent with evidence suggesting

data suggesting a high concentration of organic matter from pho- the protracted oxygenation of Proterozoic surface environments

tosynthetic bacteria/algae (Li et al., 2003a,b). By constrast, much and suggest that a dynamic stratiﬁcation of the ocean that was

of the lower Gaoyuzhuang Formation shows substantially lighter maintained primarily by wave-mixing at the ocean-atmosphere

isotopic compositions for organic carbon, which suggests a sub- interface, and in which anoxia would be sustained directly beneath

stantial contribution from a non-photosynthetic origin (Jiang et the zone of active wave mixing.

al., 2012). Such observation is consistent with biomarker data

from the Gaoyuzhuang Formation, which shows a clear bimodal-

ity in n-alkanes that are interpreted to reﬂect a combination 6. Conclusions

of biodegradation and the contribution of non-photosynthetic

bacteria to the biomass (Li et al., 2003a,b), as well as biomarker Here we report high-resolution chemostratigraphic data from

data from similarly-aged strata in the McArthur basin that pre- inorganic and organic carbon samples within the Jixian Group,

serves evidence of anoxic conditions potentially within the photic North China Platform. Strata of the Jixian Group are well

zone (Brocks et al., 2005). Li et al. (2003a,b) also note that a constrained to represent nearly continuous deposition from

very similar distribution of biomarkers occurs in thin, subtidal approximately 1600 to 1400 Ma. Data presented here represent

strata of the Hongshizhuang Formation, which caps the Wumis- the most continuous, high-resolution dataset from the early Meso-

han Formation. Here, we suggest that the combination of isotopic proterozoic, and can be used as a critical reference section for

and biomarker data likely reﬂects the development of anoxic chemostratigraphic comparison.

bottom waters in deeper-water environments represented by Marine carbonate rocks of the Jixian Group show generally

the Gaoyuzhuang and Hongshizhuang formations, which favored muted isotopic compositions with average values near 0‰; isotopic

enhanced heterotrophic remineralization of benthic microbial variation around this average, however, increases from approxi-

mats. mately ±1‰ in the lowermost Gaoyuzhuang Formation to ±1.8‰ in

By contrast, the Tieling Formation records a dramatic and sys- the Wumishan Formation. This increased isotopic variation appears

tematic change in the isotopic composition of both inorganic and to be part of a global trend of increasing isotopic variation that

organic carbon (Fig. 8) that corresponds to strata that also show spans from the Paleoproterozoic through the Neoproterozoic (cf.

substantial ore-grade mineralization. We therefore suggest that Bartley and Kah, 2004) and is consistent with a long-term decrease

isotopic compositions of Tieling strata likely reﬂect the degradation in pCO2 and the decreased buffering capacity of marine DIC. In

of organic carbon during post-depositional, hydrothermal alter- this scenario, variation in marine carbon isotope composition was

ation. likely driven by transient changes in organic matter production and

H. Guo et al. / Precambrian Research 224 (2013) 169–183 181

decomposition. The isotopic composition of marine organic mat- Brocks, J.J., Love, G.D., Summons, R.E., Knoll, A.H., Logan, G.A., Bowden, S.A., 2005.

Biomarker evidence for green and purple sulphur bacteria in a stratiﬁed Palaeo-

ter, however, suggests more dramatic differences in carbon cycling

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between different lithologic units. In particular, the Gaoyuzhuang

Buick, R., Des Marais, D.J., Knoll, A.H., 1995. Stable isotopic compositions of car-

Formation records isotopic compositions of organic matter that bonates from the Mesoproterozoic Bangemall group, northwestern Australia.

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Butterﬁeld, N.J., 2000. Bangiomorpha pubescens n. gen., n. sp.: implications for

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of the manuscript. This research was supported by the National

snowball Earth at 2.3 Ga. Evidence from the Timeball Hill Formation, Transvaal

Basic Research Program of China (Grant no. 2011CB808800), the

Supergroup, South Africa. South African Journal of Geology 109, 109–122.

“111 Project” (Grant no. B08030), and the University of Tennessee Conrad, R., Chan, O.C., Claus, P., Casper, P., 2007. Characterization of methanogenic

Archaea and stable isotope fractionation during methane production in the pro-

Walker Professorship (to LCK).

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