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  <front>
    <journal-meta>
<journal-id journal-id-type="publisher">BG</journal-id>
<journal-title-group>
<journal-title>Biogeosciences</journal-title>
<abbrev-journal-title abbrev-type="publisher">BG</abbrev-journal-title>
<abbrev-journal-title abbrev-type="nlm-ta">Biogeosciences</abbrev-journal-title>
</journal-title-group>
<issn pub-type="epub">1726-4189</issn>
<publisher><publisher-name>Copernicus GmbH</publisher-name>
<publisher-loc>Göttingen, Germany</publisher-loc>
</publisher>
</journal-meta>

    <article-meta>
      <article-id pub-id-type="doi">10.5194/bg-11-6755-2014</article-id><title-group><article-title>Dependence of the cyclization of branched tetraethers on soil moisture
in alkaline soils from arid–subhumid China: implications for palaeorainfall
reconstructions on the Chinese Loess Plateau</article-title>
      </title-group><?xmltex \runningtitle{CBT as a palaeorainfall proxy on the CLP}?><?xmltex \runningauthor{H.~Wang et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="no" rid="aff1 aff2">
          <name><surname>Wang</surname><given-names>H.</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff1 aff3">
          <name><surname>Liu</surname><given-names>W.</given-names></name>
          <email>liuwg@loess.llqg.ac.cn</email>
        </contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff4">
          <name><surname>Zhang</surname><given-names>C. L.</given-names></name>
          <email>archaeazhang_1@tongji.edu.cn</email>
        </contrib>
        <aff id="aff1"><label>1</label><institution>State Key Laboratory of Loess and Quaternary Geology, IEE, CAS,
Xi'an, 710075, China</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>University of Chinese Academy of Sciences, Beijing 100049, China</institution>
        </aff>
        <aff id="aff3"><label>3</label><institution>School of Human Settlement and Civil Engineering, Xi'an Jiaotong
University, Xi'an 710049, China</institution>
        </aff>
        <aff id="aff4"><label>4</label><institution>State Key Laboratory of Marine Geology, Tongji University, Shanghai
200092, China</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">W. Liu (liuwg@loess.llqg.ac.cn) and C. L. Zhang (archaeazhang_1@tongji.edu.cn)</corresp></author-notes><pub-date><day>8</day><month>December</month><year>2014</year></pub-date>
      
      <volume>11</volume>
      <issue>23</issue>
      <fpage>6755</fpage><lpage>6768</lpage>
      <history>
        <date date-type="received"><day>11</day><month>January</month><year>2014</year></date>
           <date date-type="rev-request"><day>27</day><month>June</month><year>2014</year></date>
           <date date-type="rev-recd"><day>25</day><month>October</month><year>2014</year></date>
           <date date-type="accepted"><day>27</day><month>October</month><year>2014</year></date>
           
      </history>
      <permissions>
<license license-type="open-access">
<license-p>This work is licensed under a Creative Commons Attribution 3.0 Unported License. To view a copy of this license, visit <ext-link ext-link-type="uri" xlink:href="http://creativecommons.org/licenses/by/3.0/">http://creativecommons.org/licenses/by/3.0/</ext-link></license-p>
</license>
</permissions>

      <self-uri xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014.html">This article is available from https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014.html</self-uri>
<self-uri xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014.pdf">The full text article is available as a PDF file from https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014.pdf</self-uri>
<abstract>
    <p>The use of branched glycerol dialkyl glycerol tetraethers (bGDGTs) in
loess–palaeosol sequences (LPSs) has shown promises in continental
palaeotemperature reconstructions. Thus far, however, little is known about
the effect of soil moisture on their distributions in the water-limited
Chinese Loess Plateau (CLP). In this study, the relationships between
environmental variables and the cyclization of branched tetraethers (CBT)
were investigated in arid–subhumid China using 97 surface soils in the CLP
and its vicinity, as well as 78 soils with pH &gt; 7 which have been
previously published. We find that CBT correlates best with soil water
content (SWC) or mean annual precipitation (MAP) for the overall data set.
This indicates that CBT is mainly controlled by soil moisture instead of
soil pH in alkaline soils from arid–subhumid regions, where water
availability is a limiting factor for the producers of bGDGTs. Therefore, we
suggest that CBT can potentially be used as a palaeorainfall proxy on the
alkaline CLP. According to the preliminary CBT–MAP relationship for modern
CLP soils (CBT <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.0021 <inline-formula><mml:math display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> MAP <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 1.7, <inline-formula><mml:math display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn>37</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow><mml:mi>r</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>0.93</mml:mn></mml:mrow></mml:math></inline-formula>),
palaeorainfall history was reconstructed from three LPSs (Yuanbao, Lantian,
and Mangshan) with published bGDGT data spanning the past 70 ka. The
CBT-derived MAP records of the three sites consistently show
precession-driven variation resembling the monsoon record based on
speleothem <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O, supporting CBT as a reasonable proxy for
palaeorainfall reconstruction in LPS. The direct application of CBT as a
palaeorainfall proxy in corroboration with the bGDGT-based temperature proxy
may enable us to further assess the temperature/hydrological association for
palaeoclimate studies on the CLP.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p>The deposits of wind-blown dust (i.e. loess) on the Chinese Loess Plateau
(CLP; Fig. 1) are natural archives of past climate change.
Characteristically, the plateau consists of a sequence of alternating loess
and palaeosol layers, which have accumulated at least since 2.6 Ma BP (before present; Liu,
1985; Liu and Ding, 1998), with the records extending back to late Oligocene
(Heller and Liu, 1982; Guo et al., 2002; Qiang et al., 2011). The cyclic
alternation of loess and palaeosol provides highly visible records of
regional climate history resulting from changing monsoon intensity on
glacial–interglacial timescales (An, 2000, and references therein; Porter,
2001). For the past 3 decades, numerous proxies have been shown to be
indicative of monsoon intensity in loess–palaeosol sequences (LPSs), including
the traditional pedogenic magnetic susceptibility (e.g. Liu, 1985; Zhou et al.,
1990; Maher et al., 1994) and grain size distributions (e.g. Ding, 1994;
Sun et al., 2006), the geochemistry of iron oxides (e.g. Ding et al., 2001), the
<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O of rhizoconcretions and land snail shells (Li et al.,
2007), the <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C of total organic matter (An et al., 2005; Liu
et al., 2005a, b; Ning et al., 2008; Rao et al., 2013) or carbonate (Liu et
al., 2011), the <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>13</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>C and <inline-formula><mml:math display="inline"><mml:mi mathvariant="italic">δ</mml:mi></mml:math></inline-formula>D of leaf wax <inline-formula><mml:math display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula>-alkanes (Zhang
et al., 2003, 2006; Liu and Huang, 2005; Liu et al., 2005b), phytolith (Lu
et al., 2006, 2007), and trace metal ratios (Li and Li, 2014). However,
since many proxies suffer from inherent weaknesses such as uncertainties of
interpretation (e.g. controversy of precipitation-controlled vs.
temperature-controlled) or sample unavailability (Yang et al., 2014a), the
development of new palaeoclimatic proxies specific for temperature or
precipitation is still necessary for this climatologically important region.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1"><caption><p>Sketch map of the CLP and its surroundings showing the location  of
sampling sites for surface soils collected in this study (modified from Xia
et al., 2012). The sites of three LPS sections with published bGDGT data
(Yuanbao, Lantian and Mangshan) are also shown. The relative position of the
study region in China is indicated in the upper left.</p></caption>
        <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f01.png"/>

      </fig>

      <p>Recent advances in analytical methods using high-performance liquid
chromatography (HPLC)–mass spectrometry (MS) techniques enabled the
identification of a range of new lipid biomarkers – glycerol dialkyl
glycerol tetraethers – GDGTs (Hopmans et al., 2000; Sinninghe Damsté et
al., 2000), as well as the subsequent understanding of their environmental
occurrence and geochemical importance (reviewed in Schouten et al., 2013a).
Particularly, the branched GDGTs (bGDGTs; Fig. 2) are ubiquitous in soils
(Hopmans et al., 2004; Weijers et al., 2006a, 2007a; Sinninghe Damsté et
al., 2008; Tierney and Russell, 2009; Peterse et al.,
2009a, b, 2012;  Huguet et al., 2010;  Loomis et al., 2011; Tierney et al., 2012; Yang et al.,
2012, 2014a; Wang et al., 2013; Liu et al., 2013). They are presumed to
originate from the cell membranes of unknown bacterial species (Weijers et
al., 2006b; Sinninghe Damsté et al., 2011) with a heterotrophic
lifestyle (Pancost and Sinninghe Damsté, 2003; Oppermann et al., 2010;
Weijers et al., 2010). By the study of bGDGT distributions in &gt; 130 globally distributed soils, Weijers et al. (2007a) found that the
relative extent of cyclopentane moieties, expressed as the cyclization ratio
of branched tetraethers (CBT), is negatively correlated to soil pH, whereas
the degree of methylation for the nine bGDGTs, expressed as the methylation
index of branched tetraethers (MBT), is positively correlated with the mean
annual air temperature (MAAT) and to some extent to soil pH. Therefore,
palaeosoil pH and MAAT can be quantified using CBT and the combination of MBT
and CBT (MBT/CBT), respectively (Weijers et al., 2007a).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p>Molecular structures of bGDGTs and the mass to charge ratios of
protonated molecular ions (after Weijers et al., 2007a).</p></caption>
        <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f02.pdf"/>

      </fig>

      <p>An extended survey of 278 globally distributed surface soils further
confirmed that CBT relates best to soil pH, while the simplified form of MBT
(i.e. MBT' based on the seven most common bGDGTs) and CBT were shown to
correlate with MAAT (<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn>0.59</mml:mn></mml:mrow></mml:math></inline-formula>, RMSE <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 5.0 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C; Peterse et
al., 2012). Yang et al. (2014a) further investigated the distribution of
GDGTs in &gt; 100 surface soils across a large climatic gradient of
China, and proposed an alternative transfer function for MAAT reconstruction
based on the fractional abundances of bGDGTs for use in arid/semiarid
regions. This calibration applies a stepwise selection method (SSM) and has
a higher determination factor (<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn>0.87</mml:mn></mml:mrow></mml:math></inline-formula>) and lower root mean
square error (RMSE <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 1.7 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C) in Chinese soils than the local MBT/CBT
proxy calibration (<inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi>R</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msup><mml:mo>=</mml:mo><mml:mn>0.86</mml:mn></mml:mrow></mml:math></inline-formula>, RMSE <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 1.8 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C; Yang et al.,
2014a). Recently, however, De Jonge et al. (2013) identified a new set of
bGDGT isomers for hexamethylated bGDGTs and pentamethylated bGDGTs, the
so-called 6-methyl bGDGTs, which co-elute with 5-methyl bGDGTs that are used
to calculate the CBT and MBT' indices commonly used so far. Further
separation of bGDGTs using an improved chromatographic method showed that
the presence of 6-methyl bGDGTs may introduce scatter in the relationships
between previous bGDGT indices and MAAT and pH. Hence, new indices with
improved soil pH and MAAT estimates, i.e. the CBT' comprising the 6-methyl
bGDGTs and the MAT<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">mr</mml:mi></mml:msub></mml:math></inline-formula> – a multiple linear regression, might be more
promising for accurate palaeoclimate reconstructions (De Jonge et al., 2014).</p>
      <p>The sensitivity of soil bGDGT distribution to environmental variation offers
new tools to quantitatively infer past continental climate change in LPS.
Initial application of the bGDGT palaeothermometer to LPSs from the Mangshan
(Peterse et al., 2011, 2014), Lantian (Gao et al., 2012), Yuanbao (Jia et
al., 2013), and Weinan (Yang et al., 2014a, b) sections on the CLP indicates
that bGDGTs might have recorded past changes in air temperature driven by
local solar insolation. Unexpectedly, however, the CBT-reconstructed pH is
lower for loess than for palaeosols (Jia et al., 2013; Peterse et al., 2014),
in contradiction with the well-accepted view that loess formed under drier
climate conditions and should be more alkaline. In fact, Xie et al. (2012)
and Yang et al. (2014a) have recently observed a negative correlation
between CBT and soil pH when pH is &lt; 7, but a slightly positive
correlation between CBT and soil pH or flattening off of CBT with increasing
pH when pH is &gt; 7, implying that some other factor(s) may play a
role in the cyclization of bGDGTs in alkaline soils. Based on the negative
CBT–MAAT correlation in their studied alkaline soils, Yang et al. (2014a)
proposed that temperature is possibly the dominant factor controlling the
cyclization of bGDGTs in these environments; but this remains to be tested
due to the covariation between MAP and MAAT in their data set.</p>
      <p>Water availability is important in affecting the distribution of bGDGTs in
modern soils (Loomis et al., 2011; Peterse et al., 2012; Dirghangi et al.,
2013; Menges et al., 2014). This might be particularly true for soils in
water-limited environments (arid, semiarid, and subhumid regions) where soil
moisture or mean annual precipitation (MAP) has been found to influence MBT'
and may lead to a “cold bias” of reconstructed MAAT based on the MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT
index (Peterse et al., 2012; Dirghangi et al., 2013; Menges et al., 2014).
Until now, however, the effect of soil moisture on the CBT index has rarely
been explored in alkaline soils from water-limited regions. In the present
study, therefore, we analysed the distribution of bGDGTs in the CLP and the
adjacent arid/semiarid areas using 97 surface soils. Combining them with
recently reported bGDGT data in 78 other Chinese soils with pH values
&gt; 7 (Xie et al., 2012; Yang et al., 2012, 2014a), we aimed to
understand the environmental controls on the CBT index in alkaline soils in
arid–subhumid China  and ultimately  to evaluate if CBT can be used as a
direct proxy for palaeorainfall reconstruction in LPS.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p>Correlations between the distribution of bGDGTs (fractional
abundances, CBT and MBT') and environmental variables (MAAT, MAP and soil
pH) for the Chinese alkaline soils (<inline-formula><mml:math display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 165) compiled in Yang et al. (2014a) and this study,
with significant correlations (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.05)
indicated in bold.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="13">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:colspec colnum="12" colname="col12" align="right"/>
     <oasis:colspec colnum="13" colname="col13" align="right"/>
     <oasis:thead>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">IIIa</oasis:entry>  
         <oasis:entry colname="col4">IIIb</oasis:entry>  
         <oasis:entry colname="col5">IIIc</oasis:entry>  
         <oasis:entry colname="col6">IIa</oasis:entry>  
         <oasis:entry colname="col7">IIb</oasis:entry>  
         <oasis:entry colname="col8">IIc</oasis:entry>  
         <oasis:entry colname="col9">Ia</oasis:entry>  
         <oasis:entry colname="col10">Ib</oasis:entry>  
         <oasis:entry colname="col11">Ic</oasis:entry>  
         <oasis:entry colname="col12">CBT</oasis:entry>  
         <oasis:entry colname="col13">MBT'</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Soil pH</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.12</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.29</bold></oasis:entry>  
         <oasis:entry colname="col5"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.19</bold></oasis:entry>  
         <oasis:entry colname="col6"><bold>0.26</bold></oasis:entry>  
         <oasis:entry colname="col7"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.19</bold></oasis:entry>  
         <oasis:entry colname="col8"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.08</oasis:entry>  
         <oasis:entry colname="col9"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.13</oasis:entry>  
         <oasis:entry colname="col10"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.24</bold></oasis:entry>  
         <oasis:entry colname="col11"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.23</bold></oasis:entry>  
         <oasis:entry colname="col12"><bold>0.22</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.22</bold></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.13</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.01</oasis:entry>  
         <oasis:entry colname="col6">0.00</oasis:entry>  
         <oasis:entry colname="col7">0.02</oasis:entry>  
         <oasis:entry colname="col8">0.32</oasis:entry>  
         <oasis:entry colname="col9">0.10</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.00</oasis:entry>  
         <oasis:entry colname="col12">0.01</oasis:entry>  
         <oasis:entry colname="col13">0.01</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">MAP</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.56</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.50</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.48</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.78</bold></oasis:entry>  
         <oasis:entry colname="col7"><bold>0.69</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.56</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.51</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.81</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.70</bold></oasis:entry>  
         <oasis:entry colname="col12"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.74</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.76</bold></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.00</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.00</oasis:entry>  
         <oasis:entry colname="col6">0.00</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.00</oasis:entry>  
         <oasis:entry colname="col9">0.00</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.00</oasis:entry>  
         <oasis:entry colname="col12">0.00</oasis:entry>  
         <oasis:entry colname="col13">0.00</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">MAAT</oasis:entry>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.61</bold></oasis:entry>  
         <oasis:entry colname="col4"><bold>0.28</bold></oasis:entry>  
         <oasis:entry colname="col5"><bold>0.42</bold></oasis:entry>  
         <oasis:entry colname="col6"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.63</bold></oasis:entry>  
         <oasis:entry colname="col7"><bold>0.53</bold></oasis:entry>  
         <oasis:entry colname="col8"><bold>0.48</bold></oasis:entry>  
         <oasis:entry colname="col9"><bold>0.60</bold></oasis:entry>  
         <oasis:entry colname="col10"><bold>0.74</bold></oasis:entry>  
         <oasis:entry colname="col11"><bold>0.63</bold></oasis:entry>  
         <oasis:entry colname="col12"><inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula><bold>0.59</bold></oasis:entry>  
         <oasis:entry colname="col13"><bold>0.76</bold></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"><inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.00</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.00</oasis:entry>  
         <oasis:entry colname="col6">0.00</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.00</oasis:entry>  
         <oasis:entry colname="col9">0.00</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.00</oasis:entry>  
         <oasis:entry colname="col12">0.00</oasis:entry>  
         <oasis:entry colname="col13">0.00</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

</sec>
<sec id="Ch1.S2">
  <title>Material and methods</title>
<sec id="Ch1.S2.SS1">
  <title>Regional setting and sample collection</title>
      <p>The CLP is the largest region of loess deposits in the world. It is
characterized by temperate semiarid and subhumid climate, modified by
latitude, longitude, and terrain. Both the MAAT and the MAP show a clear
decrease northwestward (Fig. 1). Dominated by the strength of the East Asian
summer monsoon (EASM) system, the precipitation occurs mostly in the summer
months (from May to September), which accounts for approximately 68–87 %
of the total annual precipitation (Ding, 1994; Liu et al., 2005a). The
present-day CLP is mainly covered by shrub (e.g. <italic>Sophora viciifolia and Vitex chinensis</italic>) and grasses (e.g.
<italic>Artemisia</italic> and  Gramineae) (Liu, 1985). In general, the vegetation progressively becomes sparser and
less dense from southeast to northwest, resulting from increasing dryness
(Liu et al., 2005c).</p>
      <p>A total of 97 samples were collected in late September, 2012, from 33 sites
in the CLP and the surrounding areas (Fig. 1, Supplement Table 1). For
each site, 2–5 samples were collected at locations tens to hundreds of
metres apart, except for site DengkouB with only one sample being collected.
Samples from the CLP (WLPS-1–WLPS-18 and WLPS-79–WLPS-97, totaling 37
samples) were collected from natural grassland or grassland that has been in
restoration for &gt; 10 a. At each sampling location, three
randomly collected samples were pooled and mixed to make one composite
sample representing that location. Most samples were collected from the
uppermost layer of soil with a depth of less than 5 cm and they were
transported to the laboratory immediately after collection and stored at <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>20 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. The details of the samples are provided in the Supplement
Table 1.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Environmental parameters </title>
      <p>The SWC (soil water
content) of the soils was obtained by weighting the sample before and after
freeze-drying it.</p>
      <p>Soil pH was measured following Wang et al. (2012): ca. 4 g of freeze-dried
sample was added in 10 mL of distilled water; the mixture was stirred for 1 min, left to stand for 30 min, and pH of the supernatant was measured with a
Sartorius PB-10 pH meter. The standard deviation for triplicate measurements
was <inline-formula><mml:math display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula>0.03.</p>
      <p>The meteorological data for our sampling sites were obtained from the China
Meteorological Data Sharing Service System (<uri>http://cdc.cma.gov.cn/</uri>). For
each sampling site, MAP, MAAT, mean annual ground surface temperature
(MAGST), mean annual relative humidity (MARH) and mean annual evaporation
(MAE) were generally estimated from the nearest weather station. However, if
there were 2–3 stations nearby, the meteorological data from all of them
were averaged for the sampling site. A further correction to the
meteorological MAGST and MAAT values for each sample was made according to a
lapse rate of <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.6 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C/100 m.</p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>Analysis of bGDGTs</title>
      <p>The freeze-dried and homogenized samples (30–50 g) were extracted (4 <inline-formula><mml:math display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10 min) with dichloromethane (DCM) : methanol (<inline-formula><mml:math display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) using an
accelerated solvent extractor (ASE 350, Dionex) at 100 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and
1500 psi. The total extract was dried under N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula> in a water bath. A known
amount of C<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn>46</mml:mn></mml:msub></mml:math></inline-formula> GDGT internal standard (IS; Huguet et al., 2006) was then
added to the extract, which was redissolved in DCM : methanol (<inline-formula><mml:math display="inline"><mml:mrow><mml:mn mathvariant="normal">9</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) and
divided into two halves. One half was dried under N<inline-formula><mml:math display="inline"><mml:msub><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:math></inline-formula>, redissolved in
hexane/isopropanol (<inline-formula><mml:math display="inline"><mml:mrow><mml:mn>99</mml:mn><mml:mo>:</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>,  <inline-formula><mml:math display="inline"><mml:mrow><mml:mi>v</mml:mi><mml:mo>/</mml:mo><mml:mi>v</mml:mi></mml:mrow></mml:math></inline-formula>) and filtered over a 0.45 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m PTFE (polytetrafluoroethylene) filter.</p>
      <p>An aliquot (10 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>L) of sample was injected for HPLC-atmospheric pressure
chemical ionization (APCI)-MS analysis according to a procedure slightly
modified from Schouten et al. (2007) and Zhang et al. (2012). Separation of
bGDGTs was achieved on an Alltech Prevail Cyano column (150 mm <inline-formula><mml:math display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 2.1 mm,
3 <inline-formula><mml:math display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>m). The elution gradient was isocratic (5 min) at 99 %
hexane <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> 1 % isopropanol followed by a linear gradient to 1.8 % propanol
in 45 min. After each analysis, the column was cleaned by back-flushing
using 90 % hexane <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> 10 % propanol. The flow rate was set at 0.2 mL min<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. In
order to increase sensitivity and reproducibility, selective ion monitoring
(SIM) mode of the [M<inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>H]<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> (protonated molecular ion) of the different
bGDGTs (Fig. 2) was used to detect and quantify them. Quantification of each
bGDGT was achieved by calculating the peak area in the chromatogram and
comparing it with that of the IS. Ionization efficiency for bGDGTs and the
IS was assumed identical.</p>
      <p>The CBT index was calculated following Weijers et al. (2007a):
            <disp-formula content-type="numbered" id="Ch1.E1"><mml:math display="block"><mml:mrow><mml:mi mathvariant="normal">CBT</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mi mathvariant="normal">log</mml:mi><mml:mo>(</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Ib</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">IIb</mml:mi><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Ia</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">IIa</mml:mi><mml:mo>)</mml:mo><mml:mo>)</mml:mo><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula></p>
      <p>The MBT' index was calculated according to the following equation (Peterse
et al., 2012):
<?xmltex \hack{\bgroup\fontsize{9.5}{9.5}\selectfont}?>
            <disp-formula content-type="numbered" id="Ch1.E2"><mml:math display="block"><mml:mrow><mml:msup><mml:mi mathvariant="normal">MBT</mml:mi><mml:mo>′</mml:mo></mml:msup><mml:mo>=</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Ia</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Ib</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Ic</mml:mi><mml:mo>)</mml:mo><mml:mo>/</mml:mo><mml:mo>(</mml:mo><mml:mi mathvariant="normal">Ia</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Ib</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">Ic</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">IIa</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">IIb</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">IIc</mml:mi><mml:mo>+</mml:mo><mml:mi mathvariant="normal">IIIa</mml:mi><mml:mo>)</mml:mo><mml:mo>.</mml:mo></mml:mrow></mml:math></disp-formula>
          <?xmltex \hack{\egroup}?></p>
      <p>The MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT-derived MAAT and MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> pH-derived MAAT was calculated as
follows (Peterse et al., 2012):

                <disp-formula content-type="numbered" specific-use="align"><mml:math display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E3"><mml:mtd/><mml:mtd/><mml:mtd><mml:mrow><mml:mi mathvariant="normal">MAAT</mml:mi><mml:mo>=</mml:mo><mml:mn>0.81</mml:mn><mml:mo>-</mml:mo><mml:mn>5.67</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">CBT</mml:mi><mml:mo>+</mml:mo><mml:mn>31.0</mml:mn><mml:mo>×</mml:mo><mml:mtext>MBT'</mml:mtext><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mlabeledtr id="Ch1.E4"><mml:mtd/><mml:mtd/><mml:mtd><mml:mrow><mml:mi mathvariant="normal">MAAT</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>23.20</mml:mn><mml:mo>+</mml:mo><mml:mn>2.86</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">pH</mml:mi><mml:mo>+</mml:mo><mml:mn>33.71</mml:mn><mml:mo>×</mml:mo><mml:mtext>MBT'</mml:mtext><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula></p>
      <p>MAAT was also estimated using the Chinese SSM calibration model based on the
fractional abundance of bGDGTs (Yang et al., 2014a):

                <disp-formula content-type="numbered" specific-use="align"><mml:math display="block"><mml:mtable displaystyle="true"><mml:mlabeledtr id="Ch1.E5"><mml:mtd/><mml:mtd/><mml:mtd><mml:mrow><mml:mi mathvariant="normal">MAAT</mml:mi><mml:mo>=</mml:mo><mml:mn>20.9</mml:mn><mml:mo>-</mml:mo><mml:mn>13.4</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">IIa</mml:mi><mml:mo>-</mml:mo><mml:mn>17.2</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">IIIa</mml:mi><mml:mo>-</mml:mo><mml:mn>17.5</mml:mn></mml:mrow></mml:mtd></mml:mlabeledtr><mml:mtr><mml:mtd/><mml:mtd><mml:mrow><?xmltex \hack{\hspace*{5mm}}?><mml:mo>×</mml:mo><mml:mi mathvariant="normal">IIb</mml:mi><mml:mo>+</mml:mo><mml:mn>11.2</mml:mn><mml:mo>×</mml:mo><mml:mi mathvariant="normal">Ib</mml:mi><mml:mo>.</mml:mo></mml:mrow></mml:mtd></mml:mtr></mml:mtable></mml:math></disp-formula></p>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Soil data set compilation </title>
      <p>In addition to the soils newly collected in the CLP and the surrounding
areas in this study, we included other alkaline (pH &gt; 7) soil
samples in China with published bGDGT data available to generate the largest
possible data set for determining the environmental controls on the
distribution of bGDGTs in Chinese alkaline soils (Supplement Table 1).
This combined data set consisted of 97 soils analysed in this study, 37 soils
in Xie et al. (2012) and Yang et al. (2012), and 41 soils in Yang et al. (2014a). The MAP, pH and MAAT ranges for this data set are 7.2–9.2,
140–1138 mm, and 3.8–16.8 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, respectively. Two soils (XJBC-3 and
XJBC-5) of Yang et al. (2014a) collected at the northwestern margin of the
Taklimakan Desert were not included in the data set because they were likely
from the wet sites with surface/groundwater supply, and may not represent
typical soils with a MAP of ca. 60 mm.</p>
</sec>
<sec id="Ch1.S2.SS5">
  <title>Statistical analyses</title>
      <p>We performed a redundancy analysis (RDA) on the combined data set to visualize
the environmental controls on the variation in fractional abundances of
bGDGTs in Chinese alkaline soils employing the software Canoco for Windows
4.5 (ter Braak and Smilauer, 2002). According to previous studies (Peterse
et al., 2012; Yang et al., 2014a), MAP, soil pH and MAAT are set as
environment data while species data are the fractional abundances of
individual bGDGTs. Detrended correspondence analysis (DCA) on the fractional
abundances of bGDGTs showed that the gradient length was 1.4, much lower
than 3 (ter Braak, 1988; ter Braak and Prentice, 1988; Yang et al., 2014a).
Therefore, variability in the bGDGTs was linear and RDA was appropriate in
this case.</p>
      <p>The Pearson correlation coefficients between environmental variables and
bGDGT distributions were determined with the Windows SPSS 16.0 software program.
We accepted a <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> value of &lt; 0.05 as being significant.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results and discussion</title>
<sec id="Ch1.S3.SS1">
  <title>Statistical results </title>
      <p>The results of the RDA show that the first two RDA axes cumulatively explained
51.9 % of the bGDGT distribution data and 99.9 % of the relationships
between bGDGTs and environmental factors. The first axis (axis 1) alone
explains 50.3 % of the variance of bGDGT distribution and captures the
gradients in MAP and MAAT. However, the correlation coefficient of axis 1
and MAP is 0.81, higher than that for axis 1 and MAAT (0.74). Soil pH
correlates more weakly (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.24) with axis 1. In addition, based on the
angles between the fractional abundances of bGDGTs and environmental
factors, the relative abundances of bGDGTs with a high degree of cyclization
(Ib, Ic, IIb, IIc, IIIb and IIIc) correlate positively with MAP (Fig. 3).
For acyclic bGDGTs, Ia varied positively with MAAT and MAP, whereas IIa and
IIIa varied negatively with MAAT and MAP.</p>
      <p>The relationships between bGDGT distributions and environmental variables
(i.e. pH, MAP and MAAT) can be further demonstrated by the correlation
coefficients calculated by SPSS (Table 1). As expected, each individual
bGDGT correlates significantly (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01) with MAP and MAAT, with the
correlation coefficients much higher than those with soil pH (except for
IIIb exhibiting the weakest correlation with MAAT). For the proportions of
cyclic bGDGTs and acyclic bGDGT IIa, they are most closely related to MAP
(<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.81, 0.70, 0.69, 0.56, 0.50, 0.48 and <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.78 for Ib, Ic, IIb, IIc, IIIb,
IIIc and IIa, respectively). For the proportions of acyclic Ia and IIIa,
they are most closely related to MAAT (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.60 for Ia and <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.61 for
IIIa). These are in agreement with the visualized RDA results (Fig. 3).
Moreover, the MBT index representing the degree of methylation for bGDGTs
correlates significantly (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01) with both MAAT (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.76) and
MAP (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.76), while the CBT index expressing the relative extent of
cyclopentane moieties in bGDGTs is most related to MAP (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.74,
<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01) and to a lesser extent to MAAT (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.59, <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01).</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p>RDA triplot showing the relationships between
environmental variables (red arrows) and fractional abundances of the nine
bGDGTs (blue arrows) for the 165 Chinese alkaline soil samples compiled in
Yang et al. (2014a) and in this study. Numbers refer to samples listed in
Supplementary Table 1.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f03.png"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS2">
  <title>Insensitivity of CBT to soil pH variation in alkaline soils </title>
      <p>For the Chinese alkaline soil data set, pH seems unaccountable for the
variance in the distribution of bGDGTs (Fig. 3) and there is only a slightly
positive relationship between CBT and pH (Table 1 and Fig. 4; <inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.22,
<inline-formula><mml:math display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mn>0.01</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 165). This seems different from previous regional or global
soil investigations at a large pH range, which have showed a strong positive
control of pH on the relative abundance of bGDGTs containing cyclopentyl
rings and thus CBT correlated negatively with pH (Weijers et al., 2007a;
Peterse et al., 2009b, 2012; Menges et al., 2014). However,
we note that the proportion of alkaline soils is relatively small in each
soil sample set of the aforementioned studies. In fact, by extending the pH
to &gt; 9, Xie et al. (2012) and Yang et al. (2014a) have pointed
out that the CBT index appears to be unable to distinguish pH variation, due
to the weak positive CBT–pH relationship or a flattening off of CBT when the
pH is &gt; 7, despite that the CBT values still exhibit a
significant (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01) negative correlation with soil pH when pH is
&lt; 7 (Fig. 4). The flattening off of CBT at higher soil pH values is
also observed by Peterse et al. (2010), who analysed bGDGTs in long-term
soil pH manipulation plots in Scotland. Moreover, in lacustrine systems, a
seemingly similar pattern also exists in the surface sediments of 23 lakes
in China and Nepal (Sun et al., 2011), as well as in suspended particulate
matter (SPM) from 23 lakes in the USA (Schoon et al., 2013). The weak
correlation between CBT and pH under alkaline conditions suggests that
variation in CBT might be problematic for tracing pH variation in alkaline
soils.</p>
      <p>The insensitivity of CBT to soil pH variation in alkaline soils might be
caused by the inaccurate identification and subsequent quantification of
5-methyl bGDGTs. It has been observed that higher pH may decrease the
fractional abundances of 5-methyl IIa but increase the fractional abundances
of 6-methyl IIa in globally distributed soils (De Jonge et al., 2014). Since
the two isomers are regarded as “normal” IIa (which is positively
correlated with pH) in the calculation of CBT (which is negatively
correlated with pH) using the traditional HPLC method (Weijers et al.,
2007a), the CBT values would be overestimated if 6-methyl IIa exists. The
exclusion of 6-methyl bGDGTs in the CBT index (defined as CBT<inline-formula><mml:math display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mrow><mml:mn mathvariant="normal">5</mml:mn><mml:mi mathvariant="normal">ME</mml:mi></mml:mrow></mml:msub><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>,
however, exhibits only slight improvement in relation to soil pH when pH is
&gt; 7 for the global soil data set (De Jonge et al., 2014).
Therefore, De Jonge et al. (2014) further defined a new proxy for soil pH
reconstruction, the so-called CBT' index, which comprises the pH-dependent
6-methyl bGDGTs and separates the opposite relations of 6-methyl IIa and
5-methyl IIa with pH. It correlates strongly with pH in globally distributed
soils, with the RMSE (root mean square error) of the subset of arid soils decreasing
from 2.9 to 0.3 pH units (De Jonge et al., 2014). The newly proposed CBT' index seems more
promising for pH reconstruction in palaeoclimate studies, particularly in
arid and alkaline soils.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p>Plot of soil pH vs. CBT for the Chinese alkaline soils used in this
study (indicated by blue solid circles), with previously published data from
Yang et al. (2012), Xie et al. (2012), and Yang et al. (2014a). Also shown
is the correlation between pH and CBT in other Chinese soils with pH &lt; 7 (Weijers et al., 2007; Xie et al., 2012; Yang et al., 2012,
2014a).</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f04.pdf"/>

        </fig>

      <p>Alternatively, the absence of a clear CBT–pH relationship under alkaline
conditions possibly reflects that a certain threshold is reached for
bGDGT producers in adapting their membrane lipids to pH. For the global soil
data set, the correlations between the relative abundance of cyclic 5-methyl
bGDGTs (e.g. Ib and IIb) and pH are indeed very weak under alkaline
conditions (De Jonge et al., 2014). Previously, Weijers et al. (2007a)
proposed two likely mechanisms for the negative CBT–pH relationship when pH
is &lt; 7. Firstly, it is important for the microbes to keep the
internal pH constant within the cell, and therefore the bGDGT-producing
bacteria tend to reduce the production of cyclopentyl moieties (causing
higher CBT) at lower pH for better membrane packing and lower membrane
permeability, which helps to protect cells against low pH (Weijers et al.,
2007a). When pH is &gt; 7, however, there seems to be no need for
soil bacteria to overcome the inhibition of acidity. Secondly, the proton
permeability (i.e. the pH gradient) of the cell membrane plays a crucial
role in driving energy reactions over the cell membrane (e.g. Booth, 1985).
Introduction of cyclopentyl moieties would allow more water molecules to get
trapped in the membrane and consequently increase the membrane proton
permeability, whereas a steeper proton gradient (thus lower ambient pH) is
counteracted by a more impermeable membrane resulting from fewer cyclopentyl
moieties and thus higher CBT (Weijers et al., 2007a). Under alkaline
conditions, however, further adaptation of the cell membrane would not be
needed to overcome H<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> leakage (Schoon et al., 2013)  if the
bGDGT producers turn to use Na<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> for energy transduction as neutrophiles
and alkaliphiles, which are able to perform energy transduction by
establishing a Na<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> gradient in combination with an H<inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>+</mml:mo></mml:msup></mml:math></inline-formula> gradient
(Speelmans et al., 1995; Schoon et al., 2013). These mechanisms could
possibly explain the apparent insensitivity of CBT to pH in alkaline
conditions theoretically. Hence, variation in CBT values should be
attributed as a response to other factor(s) for the alkaline soils.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F5"><caption><p>Linear regression plots of <bold>(a)</bold> CBT vs. SWC and <bold>(b)</bold> CBT vs. pH for 97
surface soils in this study. The light green shade in <bold>(a)</bold> indicates
three Yongdeng soil samples collected immediately after a rainfall.</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f05.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6" specific-use="star"><caption><p>Plots showing the correlations of CBT with environmental variables
and the relationships between MAP and MAAT for various alkaline soil
data sets (<bold>a–c</bold>: integrated Chinese alkaline soils; <bold>d–f</bold>: alkaline soils in the
USA (De Jonge et al., 2014); <bold>g–i</bold>: alkaline soils in the Iberian
Peninsula; Menges et al., 2014). Solid circles in <bold>(a–c)</bold> represent soils newly collected
in this study, while circles are published data from Yang et al. (2012, 2014a) and Xie
et al. (2012).</p></caption>
          <?xmltex \igopts{width=398.338583pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f06.pdf"/>

        </fig>

</sec>
<sec id="Ch1.S3.SS3">
  <title>Sensitivity of CBT to soil moisture in alkaline soils</title>
      <p>Soil moisture can potentially affect the distribution of bGDGTs in modern
soils (Loomis et al., 2011; Peterse et al., 2012; Dirghangi et al., 2013;
Menges et al., 2014). SWC is a direct measurement of soil moisture. Notably
for our soils collected in the CLP and its adjacent arid/semiarid areas, the
CBT index correlates more strongly with SWC (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.67, <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01,
<inline-formula><mml:math display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 97; Fig. 5a) than with soil pH (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.50, <inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01, <inline-formula><mml:math display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 97;
Fig. 5b), pointing to a likely negative control of soil moisture on the CBT
index in alkaline soils in the water-limited regions. Some of the scatters
in the SWC–CBT relationship might be due to that our measured SWC is an
instantaneous value that is liable to differences in local rainfall for
different sites and may not accurately represent the average soil moisture
condition during the growth of bGDGT producers. For instance, soils at site
Yongdeng (MAP: 284 mm) should be drier than those at the adjacent site
Gulang (MAP: 352 mm). However, the measured SWC values for soils in Yongdeng
(13, 13, and 12 %) collected immediately after a rainfall
(according to our field note) were much higher than those for Gulang (3,
6, and 3 %). In such a case, the use of SWC at this sampling time
could lead to an overestimation of the effect of soil moisture availability
on bGDGT producers in Yongdeng (Fig. 5a). Omitting the Yongdeng samples, the
CBT–MAP relationship was improved (<inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.75). For extensive surface soil
investigations, therefore, variation in SWC at the time of sampling can only
roughly reflect differences in mean soil moisture conditions.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7"><caption><p><bold>(a)</bold> Calibration plot of CBT vs. local MAP of surface CLP soils
collected in this study. <bold>(b)</bold> MAP vs. residual MAP (meteorological MAP –
estimated MAP using the surface soil calibration in the CLP). Grey shade
marks the data within the RMSE (50 mm).</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f07.pdf"/>

        </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8"><caption><p>Comparison of variations in CBT-inferred MAP, bGDGT-derived
temperature and magnetic susceptibility (MS) records of three LPS sections
<bold>(a, b, c)</bold> with speleothem-based EASM record (Wang et al., 2001, 2008) and
local insolation (Huybers, 2006) <bold>(d)</bold>. The three LPS sections are from
Yuanbao (<bold>a</bold>, Jia et al., 2013), Lantian (<bold>b</bold>, Gao et al., 2012) and Mangshan
(<bold>c</bold>, Peterse et al., 2014), respectively. The grey shade, light grey shade,
blue dashed line, and orange dashed line indicate MIS 1, MIS 3, onset of
precipitation enhancement (OP), and onset of deglacial warming (OM),
respectively.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f08.png"/>

        </fig>

      <p>In contrast, MAP data would be more representative of the mean soil
moisture than the instantaneous SWC value when continuous local soil
moisture observation data were not available. Therefore, the MAP that is
generally available in the data sets of previous studies is used to represent
soil moisture in further discussions. As is expected, amongst the three
environmental variables (MAAT, MAP, and soil pH) MAP is the dominant one
that affects the relative abundance of cyclic bGDGTs with cyclopentyl
moieties and thus the CBT index for the Chinese alkaline soils (Fig. 3,
Table 1), further supporting soil moisture as the dominant environmental
control on the CBT index in alkaline soils.</p>
      <p>It might be argued that the negative MAP–CBT relationship (Fig. 6a) is
possibly an artifact of CBT and MAAT being negatively correlated (Fig. 6b)
and MAP and MAAT being intercorrelated (Fig. 6c). However, the correlation
of MAP–CBT is stronger than that of MAAT–CBT (<inline-formula><mml:math display="inline"><mml:mrow><mml:mi>r</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>0.74</mml:mn></mml:mrow></mml:math></inline-formula> for MAP–CBT and
<inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.59 for MAAT–CBT; Table 1), particularly when only considering the soils
newly collected in this study (<inline-formula><mml:math display="inline"><mml:mrow><mml:mi>r</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>0.72</mml:mn></mml:mrow></mml:math></inline-formula> for MAP–CBT and <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.28 for
MAAT–CBT, <inline-formula><mml:math display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 97; Fig. 6a, b). Moreover, we observed that the negative
relationship between MAP and CBT is also significant (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01) in
alkaline soils of two other regional data sets that show no MAAT–CBT
correlation (in the USA: <inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.80 for MAP–CBT and 0.26 for MAAT–CBT; Fig. 6d, e;
De Jonge et al., 2014) or inverse MAAT–CBT correlation (across the
Iberian Peninsula: <inline-formula><mml:math display="inline"><mml:mi>r</mml:mi></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.65 for MAP–CBT and 0.59 for MAAT–CBT; Fig. 6g, h; Menges et al., 2014). The results of these studies in different
regions collectively suggest that the negative correlation between CBT and
MAP might be valid for alkaline soils in water-limited regions, despite that
the influence of temperature on CBT cannot be excluded at present.</p>
      <p>The reason why CBT correlates with soil moisture in alkaline soils in
arid–subhumid regions remains speculative as the exact biological source of
bGDGTs is unknown. A likely explanation for the positive correlation between
MAP and the relative abundance of cyclic bGDGTs (and thus the negative
MAP–CBT relationship) might be that, under drier conditions, a more dense
packing of membrane lipids is needed for bGDGT-producing organism(s) to
avoid overevaporation of intracellular water. As a result, the formation of
cyclopentyl moieties, which could result in loosening of the packing of the
membrane lipids (Weijers et al., 2007a), is inhibited in soils at lower MAP
values. Another possible reason for the MAP–CBT relationship in alkaline
soils in water-limited regions might be a response of the community change
of bGDGT producers with different soil moisture conditions; however, we
currently know nothing about what organism(s) would produce more acyclic
bGDGTs in drier soils under alkaline conditions. Further studies are needed
to explore the exact  underlying mechanism responsible for the observed
moisture dependence of the CBT index in alkaline soils from arid–subhumid
regions.</p>
      <p>It should be noted that we only suggest the relation between CBT and soil
moisture valid in alkaline soils from arid–subhumid regions. There is no
evidence for a strong relation between soil moisture and CBT over the whole
pH range of the global calibration set (De Jonge et al., 2014) or other
regional data sets (e.g. Menges et al., 2014; Yang et al., 2014a). In fact,
both pH (Weijers et al., 2007) and soil moisture (as discussed previously)
might be important in controlling the membrane lipid composition of soil
bGDGT producers. In humid regions where water availability is not a limiting
factor, changes in soil pH might dominate the variations in CBT values
(Weijers et al., 2007; Peterse et al., 2012). In contrast, water
availability is generally a limiting factor for the growth of microorganisms
in soils from arid–subhumid regions (e.g. Wang et al., 2013; Menges et al.,
2014). Since it seems that CBT is insensitive to soil pH in alkaline soils
(Xie et al., 2012; Yang et al., 2014a and Sect. 3.2), variations in CBT
might be predominantly controlled by changes in soil moisture. In acid soils
in arid–subhumid regions, however, both pH and soil moisture can influence
the CBT values. Therefore, we tentatively restrict the CBT–soil moisture
relationship to alkaline soils from arid–subhumid regions.</p>
</sec>
<sec id="Ch1.S3.SS4">
  <?xmltex \opttitle{Implications for palaeorainfall reconstruction on \hack{\\} the CLP }?><title>Implications for palaeorainfall reconstruction on <?xmltex \hack{\\}?> the CLP </title>
      <p>The significant (<inline-formula><mml:math display="inline"><mml:mi>p</mml:mi></mml:math></inline-formula> &lt; 0.01) correlation between CBT and MAP in Chinese
alkaline soils implies that the CBT index may be a useful tool for
palaeorainfall reconstruction in LPS. When only CLP soils collected in this
study were considered, the positive CBT–MAP correlation exhibits an obvious
improvement (Fig. 7a):
            <disp-formula content-type="numbered" id="Ch1.E6"><mml:math display="block"><mml:mrow><?xmltex \hack{\hbox\bgroup\fontsize{9}{9}\selectfont$\displaystyle}?><mml:mtext mathvariant="normal">CBT</mml:mtext><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>0.0021</mml:mn><mml:mo>×</mml:mo><mml:mtext>MAP</mml:mtext><mml:mo>+</mml:mo><mml:mn>1.7</mml:mn><mml:mo>(</mml:mo><mml:mi>r</mml:mi><mml:mo>=</mml:mo><mml:mo>-</mml:mo><mml:mn>0.93</mml:mn><mml:mo>,</mml:mo><mml:mi>p</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn>0.01</mml:mn><mml:mo>,</mml:mo><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn>37</mml:mn><mml:mo>)</mml:mo><mml:mo>.</mml:mo><?xmltex \hack{$\egroup}?></mml:mrow></mml:math></disp-formula></p>
      <p>We apply this initial calibration on three LPSs with published bGDGT data
covering the past 70 ka, in order to validate the CBT index as a
palaeorainfall proxy on the CLP. The residual errors of the estimated MAP
are &lt; 127 mm, with a RMSE of 50 mm and without following a clear
trend with MAP (Fig. 7b). Analytically, the standard deviation for CBT is
0.01, equivalent to 6 mm of MAP, indicating that palaeorainfall estimates
can be obtained with high analytical reproducibility. Located from west to
east on the southern CLP, the three LPSs are the Yuanbao (Fig. 8a; Jia et
al., 2013), Lantian (Fig. 8b; Gao et al., 2012), and Mangshan (Fig. 8c;
Peterse et al., 2014) sections, respectively. The CBT-derived MAP records
exhibit pronounced precession-driven variation in rainfall amount at the
three sites. Within dating uncertainties, the fluctuations of each record
resemble the speleothem <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O record from the Hulu (Wang et
al., 2001) and Sanbao (Wang et al., 2008) caves in southeastern China (Fig. 8d),
which are widely regarded as a robust record for the EASM intensity,
predominantly for monsoon precipitation (Peterse et al., 2014). All these
records indicate that rainfall amount was highest during marine isotope
stage (MIS) 1, relatively higher during MIS 3, and lowest during MIS 2 and
probably MIS 4. Overall, the consistency of the CBT-inferred MAP records
with the independent speleothem <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O monsoon rainfall record
(Wang et al., 2001, 2008) strongly supports the CBT index as a
palaeorainfall proxy on the CLP.</p>
      <p>According to the preliminary modern CBT–MAP calibration, the minimum MAP
values for the three sites (559 mm, 726 mm, and 616 mm for Yuanbao, Lantian,
and Mangshan, respectively) since the last glacial occurred at the Last
Glacial Maximum (LGM), while the maximum values (780 mm, 834 mm, and 858 mm
for Yuanbao, Lantian, and Mangshan, respectively) were reached during the
Holocene, showing an overall ca. 200 mm enhancement in MAP on average during
the transitional deglacial period in the southern CLP. Moreover, the maximum
and minimum values of reconstructed MAP for the Yuanbao LPS are much lower
than those of Lantian and Mangshan LPSs. This is in agreement with the modern
isohyet's pattern showing a decreasing MAP from east to west CLP (Fig. 1).
However, these quantitative results based on CBT data measured by different
laboratories should be interpreted with caution, since recent round-robin
studies with dozens of laboratories have shown that GDGT indices may vary
due to differences in interlaboratory instrumental characteristics
(Schouten et al., 2013b).</p>
      <p>The CBT–MAP relationship in alkaline soils provides an empirical basis for
the direct reconstruction of palaeorainfall based on the CBT index on the
CLP instead of linking them via pH. Previously, the CBT index has been used
successfully as a qualitative indicator of past precipitation in tropical
Africa, given that large-scale changes in soil pH reflect changes in
regional precipitation (Weijers et al., 2007b, and references therein).
Recently, Peterse et al. (2014) proposed that the comparison of CBT-derived
pH (likely precipitation-induced) and bGDGT-derived temperature in the LPS
might enable us to further assess the relative timing and magnitude of
hydrological and thermal changes in continental East Asia, independently of
potential biases associated with age model uncertainties. However, the
reconstructed pH is unexpectedly higher in palaeosols than in loess (Jia et
al., 2013; Peterse et al., 2014), resulting in an inference of lower
precipitation when palaeosols formed according to the assumption of Weijers
et al. (2007b) that higher palaeosoil pH is related to drier conditions. In
this study, we show that the CBT index possibly correlates directly with
precipitation intensity, providing an explanation for the perplexing results
of previous studies (Jia et al., 2013; Peterse et al., 2014). In view of the
great potential of bGDGTs in reconstructing continental air temperature
(Weijers et al., 2007a; Peterse et al., 2012; De Jonge et al., 2014; Yang et
al., 2014a), the application of the CBT index derived from the same suite of
lipids as a palaeorainfall proxy might be particularly promising on the CLP.</p>
</sec>
<sec id="Ch1.S3.SS5">
  <title>Temperature proxies based on bGDGTs</title>
      <p>The MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT-derived MAATs are consistently lower than the meteorological
MAAT for the Chinese alkaline soils (Fig. 9a). This is in agreement with a
number of recent investigations which observed that the  MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT proxy
underestimates MAAT in arid and alkaline conditions (Peterse et al., 2012;
Dirghangi et al., 2013; Menges et al., 2014; Yang et al., 2014a). Such a
“cold bias” of MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT-derived MAAT in arid soils can be attributed in part
to an enhanced hydrological (MAP) influence on MBT' (Peterse et al., 2012;
Dirghangi et al., 2013; Menges et al., 2014). For this data set, the MBT'
values are indeed generally lower than those for the globally distributed
soils (Peterse et al., 2012) with the same MAAT (Fig. 9b). Recently, De
Jonge et al. (2014) further suggest  the underestimation of MAAT for arid
soils may be forthcoming from the fact that higher pH (induced by more
aridity; Xie et al., 2012) could increase the production of 6-methyl bGDGTs.
When using the traditional cyano HPLC column, the co-eluting 6-methyl bGDGTs
increase  the peak areas of the “normal” 5-methyl bGDGTs for IIa, IIb, IIc
and IIIa. This would decrease the calculated MBT' and reconstructed
temperature, whereas it is actually caused by a higher pH rather than lower
temperature. Moreover, the insensitivity of CBT to soil pH variation in
alkaline soils might also be responsible for the “cold bias” of
MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT-derived MAAT. Actually, when applying the global MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> pH MAAT
calibration (Peterse et al., 2012), in which CBT is replaced by measured soil
pH, we observed that the reconstructed temperature for the Chinese alkaline
soil data set is improved (Fig. 9a). Overall, therefore, due to the problem
in both MBT' and CBT indices, the MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT temperature proxy should be
applied with caution for quantitative palaeotemperature reconstructions in
soils from arid–subhumid regions.</p>
      <p>Given the uncertainty in the MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT proxy in arid/semiarid regions, Yang
et al. (2014a) proposed an alternative transfer function (i.e. the Chinese
SSM calibration) for temperature reconstruction based on the fractional
abundances of bGDGTs. According to this calibration, the reconstructed MAAT
compares favourably to meteorological MAAT for the Chinese alkaline soil
data set (Fig. 9a), with a mean difference of 1.8 <inline-formula><mml:math display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C and no
obvious bias. Therefore, the Chinese SSM calibration might be generally more
applicable for quantitative palaeotemperature reconstructions in alkaline soils
from arid–subhumid China, in particular on the CLP.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9"><caption><p>Linear regression plots of <bold>(a)</bold> reconstructed MAAT vs. meteorological
MAAT and <bold>(b)</bold> MBT' vs. meteorological MAAT. In <bold>(a)</bold>, calculated MAAT based on
the global MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> CBT calibration and MBT' <inline-formula><mml:math display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> pH calibration (Peterse et al.,
2012) is indicated in grey triangles and dark solid circles, respectively,
while calculated MAAT based on the Chinese SSM calibration (Yang et al.,
2014a) is indicated in blue solid circles. In <bold>(b)</bold>, grey triangles indicate
data compiled by Peterse et al. (2012) while solid circles represent Chinese
alkaline soil samples (97 from this study and 78 from Yang et al., 2012;
Xie et al., 2012; and Yang et al., 2014a).</p></caption>
          <?xmltex \igopts{width=199.169291pt}?><graphic xlink:href="https://www.biogeosciences.net/11/6755/2014/bg-11-6755-2014-f09.pdf"/>

        </fig>

<?xmltex \hack{\newpage}?>
</sec>
</sec>
<sec id="Ch1.S4" sec-type="conclusions">
  <title>Summary</title>
      <p>In this study, we have investigated the environmental controls on the
distribution of bGDGTs for surface soils on the CLP and in other alkaline
soils from arid–subhumid China. In contrast to most previous studies
covering a large range of soil pH values, no obvious relationship was
observed between soil pH and CBT for our alkaline soil data set. Further
examination of other environmental factors showed that CBT is best
correlated with SWC and MAP, indicating that soil moisture might have played
an important role on the cyclization ratio of bGDGTs in alkaline soils in
the water-limited environment.</p>
      <p>A preliminary regional calibration of MAP and CBT was established by using
37 well-drained natural soils on the CLP
(CBT <inline-formula><mml:math display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> <inline-formula><mml:math display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.0021 <inline-formula><mml:math display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> MAP <inline-formula><mml:math display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 1.7). With a RMSE of 50 mm for the estimated MAP, this correlation might be
useful for inferring past rainfall variation in this climatologically
important region. According to this calibration, variation in reconstructed
MAP for the past 70 ka based on three sets of published bGDGT data on the
CLP (Yuanbao: Jia et al., 2013; Lantian: Gao et al., 2012; Mangshan: Peterse
et al., 2014) is in agreement with the speleothem <inline-formula><mml:math display="inline"><mml:mrow><mml:msup><mml:mi mathvariant="italic">δ</mml:mi><mml:mn>18</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>O record,
within age model uncertainties. The combination of the CBT rainfall
indicator with the bGDGT temperature proxy derived from the same suite of
lipids tells a similar story of the lag of monsoon precipitation relative to
continental temperature at the three sites, independent of chronology.
Moreover, the maximum and minimum values of reconstructed MAP for the drier
Yuanbao section on the eastern CLP are systematically lower than those of
the more humid Lantian and Mangshan sections on the western CLP. This
evidence  collectively support the CBT index as a promising new
palaeorainfall proxy on the CLP, although further research is needed to
explore the detailed mechanisms for the negative CBT–MAP relationship in
alkaline soils from arid–subhumid regions.</p>
</sec>

      
      </body>
    <back><app-group>
        <supplementary-material position="anchor"><p><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="http://dx.doi.org/10.5194/bg-11-6755-2014-supplement" xlink:title="zip">doi:10.5194/bg-11-6755-2014-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><ack><title>Acknowledgements</title><p>We would like to thank Hui Zhao for help in the  preparation of figures. The China
Meteorological Data Sharing Service System is thanked for providing free
climatic data. We also thank the anonymous reviewers for their constructive comments. This research was financially supported by the key deployment
project from the Chinese Academy of Sciences (no. KZZD-EW-04-06), the
national key funds of China (no. 2013CB955901), the Chinese Academy of
Sciences (no. XDA05120402), National Natural Science Foundation of China
grants no. 41030211 (WL) and 41373072 (CLZ), and the open fund of SKLLQG CAS
(no. Y352000317). LC-MS analysis was performed in the State Key Laboratory
of Marine Geology through the  National Thousand Talents Program  at
Tongji University (CLZ).<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?>
Edited by: A. Neftel</p></ack><ref-list>
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