Record of environmental change by α-cellulose δ 13C of sphagnum ...

Chinese Science Bulletin 

© 2009 SCIENCE IN CHINA PRESS 

Springer 

Record of environmental change by α-cellulose 13 C of 

sphagnum peat at Shennongjia, 4000―1000 aBP 

ZHU Yun 1,2 , CHEN Ye 1,2† , ZHAO ZhiJun 1,2 , XIAO JiaYi 1,2 , ZHANG MaoHeng 1,2 , SHU Qiang 1,2 

& ZHAO HongYan 1,2 

1 College of Geography Science, Nanjing Normal University, Nanjing 210046, China; 

2 Jiangsu Key Laboratory of Environmental Change and Ecological Construction, Nanjing 210046, China 

The Dajiuhu Basin at Shennongjia, located within typical East Asian Monsoon region, preserves a 

sub-alpine sphagnum peat deposition in its central area. The topmost 120 cm of the peat covers the last 

4000 years according to AMS 14 C dating of pollen concentration. Carbon isotope of α-cellulose, extracted 

from sphagnum peat, provides a quantitative reconstruction of atmospheric relative humidity, 

based on transfer functions of C3 plants carbon isotopic fractionation equation and the bryophyte 

photosynthesis CO2 absorption rate equation. 13 C, TOC and C/N variations reveal that the Dajiuhu area 

has experienced a long-term tendency to dry during 4000―1000 aBP, with a major transition happening 

around 3000 aBP. Four relative dry events are identified at 3400―3200, 3000―2600, 2200―2000 and 

1600―1400 aBP, respectively, corresponding to those climate events documented in many global 

records. Three periodicities, 664 a, 302 a and 277 a enclosed in the atmospheric humidity of Dajiuhu are 

correlated to the cycles of solar activities. The weakening of East Asia summer monsoon during this 

period registered in the Dajiuhu peat is consistent with the synchronous weakening of Indian Monsoon. 

This trend may be attributed to gradual decrease of Northern Hemispheric summer solar insolation and 

the consequently southward migration of Intertropical Convergent Zone (ITCZ). 

Shennongjia, sphagnum peat, late Holocene, α-cellulose δ 13 C, atmospheric relative humidity 

Peat sediment is an important archive for reconstructing 

past global change because it is easy to be precisely 

dated, sensitive to climate change and of high resolution 

[1,2] . Since the pilot work of Blytt [3] in the1950s, who 

used peat to reconstruct climate change in the Scandinavian 

Peninsula, much progress has been made in methodology. 

Pollen analysis, organic macromolecules fossils 

and geochemical analysis are extensively applied [4–6] . 

Carbon, hydrogen and oxygen isotopes of cellulose of 

plant residue in peat have been proved to be reliable paleoclimatic 

proxy. The peat deposition in China has also 

been studied for paleoenvironmental purpose, such as 

works in the Zoige Basin, east margin of the Tibetan 

Plateau [7] , Jinchuan, northeast China [8] and Leizhou Penisula, 

south China [9] . Among these investigations, Hong 

et al. [10] have proposed that 13 C of C3 plant cellulose is 

an sensitive indicator for quantitative reconstruction of 

atmospheric humidity, as testified at Hongyuan and Jinchuan. 

At these locations, the deposition is primarily 

herbal peat, and the 13 C of cellulose in herbs is dominantly 

controlled by the relative opening status of leaf 

stoma [11] . While for non-stomatal, non-vascular plants 

(such as mosses), the significance of cellulose 13 C of 

their residues in peat has not been reported in China. 

The Dajiuhu Basin at Shennongjia is located within 

the typical East Asian Monsoon region. Abundant pre- 

Received January 19, 2009; accepted April 22, 2009; published online May 25, 2009 

doi: 10.1007/s11434-009-0383-0 

† Corresponding author (email: chenye@njnu.edu.cn) 

Supported by Program for Changjiang Scholars and Innovative Research Team in 

University (Grant No. IRT0533) and National Natural Science Foundation of China 

(Grant Nos. 40671193 and 40631003) 

Citation: Zhu Y, Chen Y, Zhao Z J, et al. Record of environmental change by -cellulose 13 C of sphagnum peat at Shennongjia, 4000―1000 aBP. Chinese Sci Bull, 

2009, 54: 3731―3738, doi: 10.1007/s11434-009-0383-0 

SPECIAL TOPIC 

ARTICLES 

GEOLOGY

cipitation, low temperature during growing season due 

to relatively high elevation, permit the swamp development 

and sphagnum peat formation in its central segment 

[12,13] . Because of its unique geographic situation, a 

lot of researches have been conducted in the Dajiuhu 

Basin. For example, Li and Liu et al. [14,15] carried out 

pollen analysis for paleo-vegetation reconstruction, He 

et al. [16] used magnetic parameters as climatic proxy; 

Zhao et al. [17] suggested geochemical elements variation 

could be the indicators of human disturbance of the basin; 

Ma et al. [18] reconstructed the history of monsoon 

variation since Late Glacial. Here we attempt to delineate 

the paleoclimatic significance of -cellulose 13 C 

in sphagnum peat, and then discuss the environmental 

change and monsoon variation of Shengnongjia during 

Late Holocene. 

1 Overview and material 

The Dajiuhu Basin (31°24′―31°33′N, 109°56′―110°11′E) 

is an intermountain basin at southwest Shennongjia. It 

has a flat bottom with an average elevation around 1730 

m and is surrounded by carbonate mountains more than 

2200 m high. Precipitation gather into the basin through 

creaks sourced the adjacent mountains, and water outlets 

are several sinkholes at its north corner. Ground water 

table is generally high and sometimes shallow lakes may 

form. Mean annual temperature at the Dajiuhu Basin is 

7.4℃, highest monthly average occurs in July (18.8℃) 

and the lowest in January (4.9℃). Annual precipitation 

here reaches 1528.4 mm, mostly occur from April to 

October, when atmospheric relative humidity can be 

80% or higher. 

A core (45 m), named DJH-2, was recovered in the 

center of the basin in 2006 (Figure 1), where human 

disturbance can be ignored. Here we report the result of 

study on its uppermost 120 cm of the core. Brown-yellow 

to grey-yellow clay occurs at intervals of 73―80 

cm and 110―120 cm in depth, the rest sedimentation is 

dark brown peat (Figure 2). The core was sampled at 1 

cm intervals for TOC, TN and -cellulose 13 C measurement. 

The uppermost 30 cm was not sampled due to 

the contamination of modern roots. Ten samples collected 

at ~10 cm intervals within the peat deposition 

were selected to identify the composition of plant residue. 

Figure 1 Location of the Dajiuhu Basin. 

Figure 2 The depth-age model of DJH-2 core section (uppermost 

120 cm). 

2 Methods and measurements 

Large discrepancy frequently occurs in 14 C dates when 

different materials in sediments are used for dating. Previous 

works of Zhou et al. [19] verified that among various 

target materials, pollen extraction might be the best 

to represent the time of the identical stratum in which 

they were preserved. Pollen extraction was carried out at 

the Jiangsu Key Lab of Environmental Change and 

Ecological Construction, Nanjing Normal University. 

Then they were submitted to Keck AMS Radiocarbon 

Laboratory, University of California, Irvine, US for 

AMS measurement. The dating results were calibrated 

by Calib 4.3 program [20] . Five samples at depths of 33, 

51, 83, 99 and 117 cm correspond to 1115 ± 37, 1635 ± 9, 

3732 www.scichina.com | csb.scichina.com | www.springer.com/scp | www.springerlink.com

2600 ± 20, 3300 ± 38 and 3865 ± 53 cal. aBP, respectively. 

The depth-age correlation indicates a nearly stable sedimentary 

rate (Figure 2). The time scale of the core is 

established by linear interpolation and extrapolation according 

to sedimentary rate. Each sample (1 cm intervals) 

represents about 47 years. 

TOC and TN were determined with Vario MAX CNS 

Macro Elemental Analyzer at the Jiangsu Key Laboratory 

of Environmental Change and Ecological Construction, 

Nanjing Normal University. Samples were dried, 

ground, and then treated with hydrochloric acid to remove 

carbonate before measurement. The temperature 

of combustion tube and reduction tube of Vario MAX 

was 900℃ and 830℃ respectively, and the inaccuracy 

of measurement was within 0.05%. 

Ten samples were analyzed at Research Institute for 

Peat and Mire Science, Northeast Normal University, in 

order to identify the composition of plant debris. The 

plant debris within the clay intervals (120―110 cm and 

80―73 cm) consists of herbaceous plants (Carex mainly), 

and that of peat is dominantly composed by mosses 

(~80%, mainly sphagnum), indicating that the peat sedimentation 

here belongs to typical sphaqnum peat. 

Plant residue in peat, generally a complex, consists of 

cellulose, humic acid, lignin and so on. These components 

bear different 13 C values with variation between 

0.3‰―4‰ [21] . The 13 C value of bulk organic residues 

represents the comprehensive contribution of all components. 

However, composition of the residue tends to 

alternate because of differential conservation, the 13 C 

value will change. Among these components, cellulose 

is stable and resistant to the chemical and physical environment 

during burial, thus it can preserve original information 

when cellulose synthesis is conducted [22] . 

Therefore, it necessitates the extraction of cellulose from 

plant residue for isotope analysis. Cellulose can be divided 

into three types, i.e. , , . Among them, 

-cellulose is predominate and has been regularly employed 

in paleoclimate researches. 

In this study, -cellulose was extracted following the 

procedures described by Deniro [23] , and subjected to 

infrared spectroscopy examination for purity test. Then 

they were combusted in glass tube and the obtained CO2 

gas was purified and introduced into MAT-252 for isotope 

measurement. Standard and parallel samples were 

inserted during measurement for inspection; the measurement 

error was within 0.2‰. Infrared spectroscopy 

analysis and carbon isotopes analysis measurement were 

completed at the State Key Laboratory of Gas Geochemistry, 

Lanzhou Institute of Geology, Chinese 

Academy of Sciences. 

3 Results 

3.1 The significance of sphagnum -cellulose 13 C 

According to various pathways of photosynthesis, plants 

can be divided into three types: C3, C4 and CAM. Here 

at the Dajiuhu Basin, the organic debris in the peat we 

analyzed are predominately composed of C3 species, the 

differences of carbon isotope arisen from photosynthesis 

pathway can be neglected. 

Carbon in plants is drawn from atmosphere CO2. 

Carbon isotope fractionation of C3 plant is described by 

the following equation [24] : 

13 Cp = 13 Ca a(ba) ([CO2]i/[CO2]a) 

+ (fT* + eRd/k)/[CO2]a, (1) 

A = ([CO2]a [CO2]i)/r. (2) 

At the right part of eq. (1), the last fraction is related 

to photorespiration and dark respiration, which usually 

produce tiny fractionation and can be neglected. 13 Cp 

and 13 Ca are the carbon isotopic composition of plant 

tissues cellulose and atmosphere CO2, respectively, 

which can be obtained from C4 plant fossil or ice core 

record. a is a constant around 4.4‰, denotes to the enrichment 

factor associated with different diffusivities of 

13 CO2 and 12 CO2. b is a constant around 27‰, it represents 

isotope fractionation generated by selective fixation 

of 12 CO2 in Rubisco reaction in C3 plant photosynthesis. 

[CO2]i and [CO2]a is CO2 concentration in cell 

gap and atmosphere of plant growth respectively. Because 

the change of [CO2]i/[CO2]a is significantly larger 

than that of 13 Ca in eq. (1), 13 Cp change is mainly 

dependent on change in [CO2]i/[CO2]a ratio. A is CO2 

absorption speed of plant lamina, and r is diffusion resistance 

of CO2. 

Unlike vascular plants that regulate carbon and water 

exchange by controlling stomatal apertures on leaf surfaces, 

mosses (such as sphaqnum), non-vascular bundle 

plant, lack stomata or an epidermis with an impermeable 

cuticle. Consequently, mosses are unable to regulate the 

uptake of atmospheric CO2. How efficiently it makes 

use of CO2 in the process of photosynthesis is dominated 

by water film thickness on its leaf surface [25] . White et 

al. [26] , Rice and Giles [27] , Murray et al. [28] , Williams and 

Zhu Y et al. Chinese Science Bulletin | October 2009 | vol. 54 | no. 20 3733 

GEOLOGY ARTICLES SPECIAL TOPIC

Flanaga [29] have studied the environmental significance 

of mosses cellulose 13 C value. Their works reveal that, 

when the precipitation is relatively light, leaves surface 

has no or very thin water film, transparent water cells 

are small with large gaps in between cells, as a result 

CO2 can enter diachyma through atmosphere easily, the 

difference between diachyma and atmosphere CO2 

chroma decreases, and the ratio of [CO2]i/[CO2]a in- 

creases. Under this circumstance, because of sufficient 

CO2 in the process of photosynthesis, carbon isotope 

fractionation is mainly controlled by photosynthesis en- 

zyme leading to fractionation effect, resulting in partial 

negative carbon isotope values. With more precipitation, 

water film wrapping mosses obstructs the direct entry of 

CO2 into the channel of chloroplast, so that CO2 has to 

enter diachyma through the water medium. As the CO2 

diffusion in the water is four orders of magnitude slower 

than in the air, the concentration of CO2 is reduced, the 

difference between diachyma and atmosphere CO2 is 

increased and the value of [CO2]i/[CO2]a decreases. 

Even though the diffusion of 12 CO2 is faster than 13 CO2, 

due to limitation of the total amount of CO2 getting to 

chloroplast, the effect of carbon isotope fractionation for 

carboxylic enzyme of Rubisco reaction weakens, and 

carbon isotope values are more affected by the diffusion 

of CO2 leading to fractionation effects, resulting in 

phiancia carbon isotope values. The comparison experiment 

of the relationship between the effect of water 

film and bryophyte carbon isotope values has also 

pointed out that 12 C would be prior to be combined and 

utilized in case of a relatively smaller precipitation than 

a lot of it. Therefore, increased precipitation resulted in 

the increased δ 13 C in sphagnum and vice versa. 

As mentioned above, two intervals of herbaceous 

dominated deposit (80―73 cm and 110―120 cm) occur 

in the core. Since 13 C of identical specie is more reli- 

able to reflect environmental condition, we only use the 

data from the sphagnum peat for discussion. In order to 

examine the reproducibility of the data from core DJH-2, 

samples taken in larger intervals from another core 

named DJH-C close by were measured for comparison. 

The parallel variation of data from the two cores con- 

firms that 13 C (Figure 3(a), (c)) record is reliable. 

From a view of longer period, the CO2 absorption rate 

A of plant leaves is also affected by a number of other 

environmental factors (such as temperature and CO2 

Figure 3 Contrast of -cellulose 13 C value ((a) solid square block) 

and atmospheric relative humidity ((b) hollow square block) of 

DJH-2 core, -cellulose 13 C (c) value of DJH-C core. 

concentration in atmosphere, etc.). Combining these 

factors, White et al. [26] proposed the following equation 

of CO2 absorption rate of plant leaves in the process of 

bryophyte photosynthesis: 

Amoss = Pmaxv(T)f(I)i(W)j([CO2]a)k(O), r is constant, (3) 

Pmax = P ○ max (1+T), (4) 

j([CO2]a) = + [CO2]a, (5) 

i(W) = (WWdry)/(WoptWdry), (6) 

where k(O) denotes CO2 uptake rate affected by other 

factors (such as soil fertility, etc.), which can be overlooked; 

f (I) is the function of illumination intensity, and 

how much illumination intensity affects plant carbon 

isotope changes so far can not be accurately determined, 

so here we do not consider the effects of illumination 

intensity, f (I) is around 1; Pmaxv(T) indicates the function 

of temperature changes, in which v(T) is related to 

short-term (a few days or weeks) temperature changes, 

and can be set to 1 in the period this study concerned; 

P ○ max is the maximum CO2 uptake rate at the current 

average temperature in the study region; is a constant, 

and T represents temperature change. Schleser et al. [30] 

have shown that temperature change has little effect on 

plant carbon isotope change, and 1℃ up or down leads 

to less than only 0.3‰ of the plant 13 C change. With 

an ignore on the temperature change effect, White et 

al. [26] reconstructed the evolution process of atmosphere 

CO2 concentration since Holocene by eq. (3); j([CO2]a) 

is the function of atmosphere CO2 change, = 280 ppm, 

=3.7×10 3 ppm, and [CO2]a stands for atmosphere 

CO2 concentration, which can be obtained from ice core 


or C4 plant data; i(W) is the function of atmosphric relative 

humidity change, Wdry and Wopt is 0% and 80% respectively. 

Based on these equations, the atmospheric relative 

humidity record of Dajiuhu area was figured out using 

-cellulose 13 C data (Figure 3(b)). It is clear that the 

humidity is co-varying with -cellulose 13 C data, indicating 

that the humidity may be a reliable proxy for 

precipitation. The slight difference between the two 

curves during 1000―2000 aBP may be attributed to 

stronger carbon fixation of sphaqnum photosynthesis 

due to increasing CO2 concentration at this interval [31] . 

During 4000―1000 aBP, the atmospheric relative 

humidity at the Dajiuhua Basin was varying between 

52% and 80%, with a mean value around 64%. This 

value is lower than the present one (80%), indicating a 

relatively drier condition comparing with the modern 

circumstance. There was a prominent humidity changeover 

around 3000 aBP, the average atmospheric relative 

humidity was 73% before 3000 aBP, and it decreased 

to 61% thereafter. Besides this long-term transformation, 

four short drier events were observed at 

3400―3200, 3000―2600, 2200―2000 and 1600― 

1400 aBP, during which the humidity was 71%, 60%, 

54% and 59% respectively. 

3.2 TOC and C/N 

TOC content of an unique layer in the stratum is affected 

by organic accumulation rate when it was laid down, and 

organic decomposition rate during burial [32] . The organic 

accumulation in swamp is generally high, cool and wet 

climate favors the preservation of organic matter. C/N 

ratio is an indicator to determine the relative controbution 

to TOC of aquatic and terrestrial plants [33] : when the 

major component of organic matter is endogenous, C/N 

ratio is generally less than 10, and otherwise C/N ratio 

will be larger. 

TOC content of the core is varying from 1.5% to 

45.7%, and that C/N is between 4.2 and 19.3 (Figure 

4(a), (b)). Before 3600 aBP, C/N was low with an average 

of 9.6, TOC content was 4.8% in average, indicating 

that TOC was mainly contributed by hydrophyte in a 

shallow lake. Meanwhile, the gradual upwards increase 

of C/N and TOC have seen a circumstance of water 

body shrinkage and swamp expansion. After 3600 aBP, 

C/N rose to above 16, TOC increased greatly to 40%, 

indicating steady swamp deposition, terrestrial plants 

became dominated. An exception is the interval of 

Figure 4 Comparison of TOC content (a), C/N (b), and atmospheric 

relative humidity (c) records of Dajiuhu peat, 18 O value (d) 

of Sanbao cave stalagmite, and 13 C value of Hongyuan peat (e) 

during 1000―4000 aBP. 

2500―2300 aBP, when TOC dropped abruptly, a yellow 

silty clay layer was intercalated, while C/N did not show 

any alternation. This might be interpreted by a small 

pond at the drilling site due to local relief in the swamp. 

4 Discussions 

During the period of 4000―1000 aBP, the central part 

of the Dajiuhu Basin has been dominated by lake and 

swamp deposition, while the long term tendency was to 

be cooler and drier. This trend is also observed in large 

fossil plants and pollen records [17] . Stalagmite oxygen 

isotope at Sanbao cave in Shennongjia reveals a similar 

history [34] . 

The changeover of climate characteristics around 

3000 aBP has been widely documented in China. The 

Dunde Ice Core records revealed that 3000 aBP is a 

boundary from warm to cold over the last 5000 aBP [35] , 

consisting with the simultaneous lake records on the 

Tibetan Plateau [36,37] . Ecosystem deterioration dropped 

down around 3100 aBP on the Loess Plateau [38] . Even at 



Hainan Island, south China, climate began to be more 

unstable, pointing to a major transition of climate in the 

tropical region [39] . 

The century-scale climatic events, which happened at 

3400―3200, 3000―2600, 2200―2000 and 1600― 

1400 aBP may be worldwide synchronous. The 3400― 

3200 aBP event has been reported from the Greenland 

Ice Core [40] and Dunde ice core [41] . The 2200―2000 aBP 

event has been reported in the record from the Qinghai 

Lake.This event is temporally corresponding to the Cold 

and Dry Dark Ages (150 BC―150 AD) [42] . The event at 

1600―1400 aBP is correlated to the late phase of New 

Ice Age. It has seen the expansion of desert in north 

China [43] and can be corresponding to the Era of Disunity 

in China [44] . 

The event at 3000 ― 2600 aBP was recorded in 

Zoige [19] , Jinchuan [45] and Hongyuan [46] . Meanwhile, 

notable ice advancement took place in the western China 

[47] , and desert expansion occurred across northern 

China [43] . Even in south China, sudden and large magnitude 

climate fluctuations began at 3000 aBP [48] , as recorded 

in the Longgan Lake [49] . Historical literature documented 

a cooling event around 2700 aBP [44] . This 

event may have forced the ancestors of earlier Zhou 

Dynasty to migrate eastward in 1150 BC [50] and resulted 

in a recession or interruption of Neolithic culture succession 

as well [51] . A recent synthesis by Mayewski et 

al. [52] on global paleoclimatic records verified the rapid 

global climate changing during 3500―2500 aBP, and 

this early phase of New Ice Age [53] may have great impact 

on global civilization history [54] . 

Summer precipitation at Dajiuhu accounts for more 

than 86% of its annual amount [55] . Hence, the atmospheric 

humidity revealed by carbon isotope of sphagnum 

α-cellulose in 1000―4000 aBP reflects the variation of 

East Asian Summer Monsoon [34] . General consistency is 

shown when we compare the 13 C of sphagnum 

-cellulose from Dajiuhu with stalagmite 18 O in Sanbao 

cave [34] and Carex cellulose 13 C from Hongyuan [56] 

(Figure 4). This indicates that evolution of the East 

Asian Monsoon and Indian Monsoon during late Holocene 

was under the controll of an identical mechanism 

[57] . Power spectral analysis [58] on the atmosphric 

relative humidity records of Dajiuhu reveals three periodicities, 

i.e., 664 a, 302 a and 277 a passed the red 

noise testing (90% confidence) (Figure 5). 664 a is con- 

Figure 5 The power spectrum analyse of atmosphric relative 

humidity record in the Dajiuhu Basin. 

sistent with the prominent 649 a cycle discovered by 

Damon et al. [59] and the solar activity function at the 

sixth (704 a) level. The 302 a cycle is close to the solar 

activity function at the fifth (352 a) level. The 277 a 

cycle is related to solar modulation and Gleissberg 

cycle [60,61] . This indicates that the Asian monsoon precipitation 

is modulated by the solar output variation. 

However, some minor discrepancy presents between the 

Dajiuhu record and Hongyuan record. For example, the 

1500 aBP event is more prominent in Hongyuan peat, 

but 2000―2200 aBP event is more obvious in Dajiuhu 

and Sanbao caves. This might suggest that although the 

East Asian Monsoon and Indian Monsoon are controlled 

by the same mechanism, differential response may exist 

on century scale. 

5 Conclusions 

(1) 13 C of non-vascular plants responses to climate 

change in a different way from vascular plants. For 

non-vascular plants, photosynthesis efficiency of using 

CO2 is controlled by the water film thickness at leaf 

surface, increased water film thickness will cause the 

rise of 13 C. There is a positive correlation between the 

water film thickness and precipitation, and, therefore, 

the value of 13 C of non-vascular plant -cellulose can 

reflect the changes of precipitation. 

(2) The atmospheric relative humidity of Dajiuhu 

changes during 1000―4000 aBP were quantitatively 

reconstructed using sphagnum peat -cellulose 13 C 


data. A major climate change took place around 3000 

aBP. Four notable dry events which happened at 3400― 

3200, 3000―2600, 2200―2000 and 1600―1400 aBP 

have global consistency. 

(3) The co-variation of East Asian summer monsoon 

revealed in Dajiuhu peat, Sanbao cave stalagmite and 

the Indian Monsoon recorded in Hongyuan peat points 

to identical forcing mechanism of the two sub-systems. 

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