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Journal of Asian Earth Sciences 40 (2011) 1250–1256

Contents lists available at ScienceDirect

Journal of Asian Earth Sciences


journal homepage: www.elsevier.com/locate/jseaes

Normalizing XRF-scanner data: A cautionary note on the interpretation


of high-resolution records from organic-rich lakes
L. Löwemark a,*, H.-F. Chen b, T.-N. Yang c, M. Kylander a, E.-F. Yu d, Y.-W. Hsu d, T.-Q. Lee c, S.-R. Song e,
S. Jarvis f
a
Department of Geological Sciences, Stockholm University, 10691 Stockholm, Sweden
b
Institute of Applied Geosciences, National Taiwan Ocean University, Keelung 20224, Taiwan
c
Institute of Earth Sciences, Academia Sinica, Taipei 11529, Taiwan
d
Department of Earth Sciences, National Taiwan Normal University, Taiwan
e
Institute of Geosciences, National Taiwan University, Taipei 10617, Taiwan
f
National Oceanography Centre, Southampton, United Kingdom

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

Article history: X-ray fluorescence (XRF) scanning of unlithified, untreated sediment cores is becoming an increasingly
Available online 16 June 2010 common method used to obtain paleoproxy data from lake records. XRF-scanning is fast and delivers
high-resolution records of relative variations in the elemental composition of the sediment. However,
Keywords: lake sediments display extreme variations in their organic matter content, which can vary from just a
XRF-scanning few percent to well over 50%. As XRF scanners are largely insensitive to organic material in the sediment,
Normalization increasing levels of organic material effectively dilute those components that can be measured, such as
Lake sediment
the lithogenic material (the closed-sum effect). Consequently, in sediments with large variations in
organic material, the measured variations in an element will to a large extent mirror the changes in
organic material. It is therefore necessary to normalize the elements in the lithogenic component of
the sediment against a conservative element to allow changes in the input of the elements to be
addressed. In this study we show that Al, which is the lightest element that can be measured using
the Itrax XRF-scanner, can be used to effectively normalize the elements of the lithogenic fraction of
the sediment against variations in organic content. We also show that care must be taken when choosing
resolution and exposure time to ensure optimal output from the measurements.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction treated sediment at sub-millimeter resolution (e.g., Croudace


et al., 2006; Haschke, 2006; Richter et al., 2006; Sakamoto et al.,
The recognition that the anthropogenic emission of CO2 is likely 2006). Depending on the X-ray tube used, elements from Al to U
to cause a significant warming of the global climate (IPCC, 2007) can be detected with detection limits in the ppm range for many
has fueled an intense search for records of past climate variability elements. The elemental variations in the sediment contain clues
to constrain model simulations of how the climate reacts to about environmental shifts and climatic changes as well as of pos-
changes in different forcings. A relatively new technique that is sible anthropogenic influence on the sedimentary system.
gaining importance is the micro X-ray fluorescence (XRF) scanning The usefulness of the XRF-scanning technique is, however, lim-
of sedimentary records (Rothwell and Rack, 2006). This technique ited by a few factors. The most obvious is that elemental variations
provides high-resolution relative variations of most elements and are measured as counts rather than concentrations, and that cali-
has been applied to sediments from a large range of settings, both bration to actual concentrations requires quantitative analysis of
lacustrine and marine sediments spanning from subtropical (Diek- the bulk sediment chemistry. Other sedimentary factors influenc-
mann et al., 2008; Haug et al., 2003; Yancheva et al., 2007) to Arctic ing XRF measurements are water content, surface roughness, and
(Löwemark et al., 2008) environments. grain size variations (Böning et al., 2007; Tjallingii et al., 2007;
XRF-core scanning is a fast, non-destructive technique that Weltje and Tjallingii, 2008). Furthermore, the aging of the X-ray
delivers information about elemental variations directly from un- tube also influences the counts measured, making it difficult to
compare different sections of the same core unless they were mea-
sured with the same X-ray tube relatively closely in time. These
* Corresponding author. Tel.: +46 8 164749. limitations are of technical nature and can be easily overcome by
E-mail address: loewemark@gmail.com (L. Löwemark). a stringent sampling and measurement protocol.

1367-9120/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jseaes.2010.06.002
L. Löwemark et al. / Journal of Asian Earth Sciences 40 (2011) 1250–1256 1251

An additional problem, related to the composition of the mea- The aim of this study is to investigate to what extent Al mea-
sured sediment, has the potential to cause much more severe mis- sured by the XRF-scanner can be used to normalize the other ele-
interpretations. As the X-ray fluorescence signal emitted from the ments to allow a better assessment of their relative changes.
sample surface is a function of the composition of the sediment, Normalizing elemental data against a conservative element is com-
large variations in light elements, outside the measuring range of mon practice in settings where biological or diagenetic processes
the XRF-detector such as carbon, oxygen, and nitrogen, can cause might influence some of the major elements. In the case of lacus-
a dilution effect resulting in lower counts for heavier elements. trine sediments, Al likely is a suitable candidate as it forms a major
In other words, an increase in the organic matter content will re- part of most minerals but is little affected by diagenetic and biolog-
sult in a decrease in the absolute counts detected for all measured ical processes.
elements, and vice versa, the well-known closed-sum effect (Cal-
vert, 1983; Rollinson, 1993). Conventional XRF is often performed 2. Materials and methods
after loss on ignition, therefore already only reflecting the litho-
genic component of the sediment. As the strength of the XRF-scan- This study is based on a sediment core from the subtropical Li–
ning method lies in the relative variations in the elements Yu Pond in central western Taiwan (Fig. 1). Li–Yu Pond was cored
(Croudace et al., 2006), it becomes important to normalize the to a depth of 20 m, but only the uppermost 8 m, roughly equivalent
measured counts in order to obtain an environmentally relevant to the last 4 ky, were used in this study. The core was drilled in
signal. Otherwise, all interpretations run the risk of becoming a approximately 1 m sections by first pushing a steel tube into the
mirror of organic matter (or carbonate) variations. sediment, after which an inner tube was lowered inside the first

Fig. 1. Map showing the locations of Li–Yu Pond (Li-Yu Tan) in Taiwan. Inset map shows location of Taiwan in SE Asia.
1252 L. Löwemark et al. / Journal of Asian Earth Sciences 40 (2011) 1250–1256

Table 1
Radiocarbon ages used for age control of the uppermost 8 m of the Li–Yu Pond record (Hsu, 2007).
14
Depth (cm) Sample ID/lab code Material C age (BP) Age range (Cal. y BP) Cal. age error (Cal. y BP)
47 R28804-1/NZA 21661 Plant fragment 117 ± 30 8–278 143 ± 135
132 R28804-2/NZA 21662 Plant fragment 1297 ± 35 1170–1290 1230 ± 60
210 R28804-3/NZA 21663 Plant fragment 1423 ± 30 1284–1360 1322 ± 38
290 R28804-4/NZA 21664 Plant fragment 1629 ± 35 1415–1607 1511 ± 96
414 R28804-5/NZA 21665 Plant fragment 1713 ± 30 1535–1705 1620 ± 85
638 R28804-6/NZA 21666 Plant fragment 2511 ± 30 2468–2740 2604 ± 136
656.5 R28804-7/NZA 21667 Plant fragment 2523 ± 30 2482–2744 2613 ± 131

to collect the sediment. This process was then repeated until the tube. Nevertheless, the general trend is in good agreement with the
basement in the basin was reached. The XRF-scans were performed data obtained from the Cr-tube. Aluminium-values in the lower
on U-channels originally subsampled at Academia Sinica for min- part of the core are relatively stable, but with a few rapid shifts.
eral–magnetic studies. The U-channels were transported to Stock- In contrast, the upper part shows a number of rapid oscillations
holm University and scanned on the Itrax XRF-core scanner at the that roughly mirror variations in TOC; peaks in TOC correspond
Department of Geological Sciences and Geochemistry. For details to minima in Al.
on the Itrax XRF-scanner please refer to Croudace et al. (2006). Titanium, also determined with both X-ray tubes, shows a sim-
The core was measured with 2 mm resolution and an exposure ilar pattern as Al. In the lower part of the core the Ti-levels are
time of 8 s with the Mo-tube, and with a resolution of 5 mm and rather stable, while they are considerably more variable in the
30 s exposure time with the Cr-tube. The energy spectrum emitted upper part. As with Al, dips in Ti tend to correspond to maxima
by the Cr-tube primarily excites electrons in lighter elements, mak- in TOC (Fig. 2). However, in comparison to Al, there are only small
ing it more suitable for measurements of elements lighter than Cr, differences in the shape of the profiles obtained from the two X-ray
while the energy spectrum emitted by the Mo-tube primarily ex- tubes, although the actual number of counts differ by more than
cites electrons in the shells of heavier elements, making it less suit- one order of magnitude. The Fe record shows a somewhat similar,
able for measurements of elements lighter than K, but suitable for although spikier, pattern to Ti having a correlation coefficient of
measurement on heavier elements. Here we present Fe and Ti- 0.45 (both elements obtained with the Mo-tube). Lows in Fe gener-
data, two elements often used in paleoenvironmental studies, to- ally tend to occur in intervals with high TOC. When Ti and Fe are
gether with Al-data, which is used to normalize the Fe and Ti mea- normalized against Al, the Ti/Al and the Fe/Al curves still show a
surements to allow an assessment of relative variations in the strong resemblance to each other (r = 0.95), but a slightly new pat-
lithological component of the sediment. For the calculation of ele- tern appears. The lower part is still fairly stable with minor varia-
ment/Al-ratios the Li–Yu Pond data were resampled with 5 mm tions, but in the upper part, the element-to-Al ratios display a
resolution. The calculated ratios then were plotted both raw and distinctly different pattern from the elemental counts. In particu-
smoothed with a 5-point moving average. Analyses of TOC and lar, several intervals characterized by increased Ti and Fe levels,
TN of organic-containing samples followed standard procedures display low element-to-Al ratios, and vice versa. It is especially
(Chen et al., 2009; Ku et al., 2005). In brief, an aliquot of decalcified interesting to notice that the upper intervals characterized by high
sample was wrapped in a tin capsule and then combusted using a TOC levels (over 10%) and low element counts show increased ele-
ThermoQuest EA1110 elemental analyzer at the Department of ment-to-Al ratios. This suggests a change in the composition of the
Geosciences, National Taiwan University (NTU) to measure the lithogenic component. The calculated element-to-Al ratios display
TOC and TN contents, and thus the atom/atom TOC/TN ratio. The a number of extreme peaks caused by very low, or zero, Al counts.
precision of measurement was 0.2 wt.% and 0.3 wt.% for TOC and In the plots this problem is in part overcome by the removal of ex-
TN, respectively. TOC of the core was measured every 20 cm for treme outliers and by presenting a 5-point running average.
the whole core with additional analyses (45 data in total) wher-
ever significant changes in layers and many biogeochemical prop-
4. Discussion
erties were observed. These additional analyses were done to
increase resolution, and then to better understand changes in bio-
The most striking feature of the XRF records is probably the
geochemical properties of the core. Age control on the upper 8 m
high-frequency variability (Fig. 2). In part this is noise, but it also re-
from Li–Yu Pond was obtained from seven radiocarbon dates mea-
flects the way that the XRF-scanner measurements are performed.
sured at the Rafter Radiocarbon Laboratory, Institute of Geological
The obtained XRF-scanner measurements reflect the composition
and Nuclear Sciences, New Zealand (Hsu, 2007) (Table 1).
of a thin (sub-mm) layer on top of the sediment surface and can
therefore display considerable high-amplitude variability caused
3. Results by variations in the sediment composition over small distances.
These small scale variations tend to become averaged out by con-
The uppermost 8 m of Li–Yu Pond consist of an alternating se- ventional measurements which represent an average of the bulk
quence of greenish, grayish, brownish layers of mud with interca- composition over a cm or more. It is therefore not surprising that
lated siltier or sandier layers (Hsu, 2007). TOC values show XRF-scanner data display considerably more high-frequency,
relatively little variability in the lower 6 m with values typically high-amplitude variability than conventional measurements. The
between 1% and 4%, while the uppermost 2 m display rapid swings data quality is also affected by cracks or gaps in the sample surface.
from below 1% to well above 10% (Fig. 2). Aluminium was mea- These can be caused by the coring or sampling process, or due to
sured with both the Cr- and the Mo-tube. As anticipated, the Mo- desiccation of the sediment during storage or measurement. While
data show considerably lower counts and a much lower signal- gaps are fairly easy to detect as indicated by sharp drops in all ele-
to-noise ratio than the Cr-data (Fig. 2). This is only partly due to ments over the interval, cracks tend to result in extreme spikes fol-
the shorter exposure time used with the Mo-tube, as mentioned lowed by dips. Gaps and cracks can usually be easily identified in
previously; the emitted energy spectrum from the Cr-tube is better the line scan photograph and X-ray radiographs produced during
suited to excite electrons in lighter elements compared to the Mo- scanning (Fig. 3). Surface roughness and variations in water content
L. Löwemark et al. / Journal of Asian Earth Sciences 40 (2011) 1250–1256 1253

Fig. 2. Total organic carbon and XRF-counts measured in the Li–Yu Tan. Al measured with the Cr-tube (black) shows considerably higher counts and less variability compared
to the data obtained with the Mo-tube (gray). The Ti-records measured with Cr (black) and Mo-tubes (gray) display similar record although with different absolute counts.
When normalized against Al, the variations in Ti and Fe display a similar pattern (gray lines are raw data, black line show 5-point moving average with outliers removed from
the data set). Gray bars indicate the position of major cracks and gaps in the sedimentary record.

(Tjallingii et al., 2007) also influence the data quality to some de- through the sediment parts of the fluorescence might get absorbed
gree, but these factors are much more difficult to identify compared by overlying atoms. However, the fluorescence from one element
to gaps and cracks. might become enhanced because its atoms interact with and are
Titanium and Fe values display a number of sharp peaks and excited by fluorescent photons from a second element. This results
dips concomitant with similar features in the Al-record, which in a corresponding decrease in detected fluorescence of the second
therefore are attributable to gaps and cracks in the sediment. This element as a portion of its fluorescent photons are attenuated by
is confirmed by the inspection of instrument parameters such as the first element and fail to reach the detector. The secondary fluo-
the mean standard error (MSE, an expression of the fit between rescence therefore enhances the counts of certain elements while
theoretical to measured XRF spectra) and total counts per second decreasing the counts of others (Berth, 1969). This matrix effect
and from studies of X-ray radiographs of the sediment (Fig. 3). can be corrected for if the approximate concentrations of the dif-
When ignoring the artifacts caused by cracks in the sediment, ferent elements in the sample are known. In the case of unlithified
the elemental records still indicate a number of abrupt changes sediment cores where both water content and organic carbon con-
in the depositional system. In a similar setting in southeastern Chi- tent vary it is usually not in practice possible to correct for the ma-
na, the Huguang Maar, variations in the Ti content in the sediment trix effect.
were interpreted as variations in aeolian dust controlled by varia- The matrix effect is somewhat related to the dilution effect
tions in the strength of the East Asian winter monsoon (Yancheva being caused by variations in biogenic material. An increase in or-
et al., 2007). It is tempting to interpret the observed variations in ganic material, consisting primarily of C, H, N, will inevitably lead
elements in a similar manner, directly reflecting a climatic signal. to a decrease in the concentration of all other elements, and
However, although these changes certainly do reflect changes in accordingly, to a decrease in the measured counts of these other
the depositional system, the environmental interpretation is com- individual elements (closed-sum effect). Consequently, an ob-
plicated by two important factors, the matrix effect and the dilu- served increase or decrease in an element does not by necessity
tion effect. mean that there has been an increase or decrease in the flux of that
In the ideal case, the counts measured should be directly pro- element, rather this may have been caused by a change in the
portional to the concentration of the element in the sediment. In deposition rate of the diluting agent, which in lakes usually is or-
reality, however, the signal depends on the presence and concen- ganic matter. In the marine realm, this effect is well-known and
trations of other elements that might attenuate or enhance the handled through flux calculations, comparison with a standard,
XRF-signal (Beckhoff et al., 2006). For example, X-ray fluorescence or normalization against a conservative element (Brumsack,
from atoms deeper in the sample must first pass through the upper 2006). Normalization to Al allows the relative variations in the lith-
sediment layers on their way to the detector. During this transfer ogenic component of the sediment to be addressed. This informa-
1254 L. Löwemark et al. / Journal of Asian Earth Sciences 40 (2011) 1250–1256

Fig. 3. Detail of Section 4 in Li–Yu Pond from measurement with the Mo-tube. X-ray radiograph showing variations in sediment density and two cracks (light bands). Total
counts (1000 counts s 1), mean square error between measured data and fit (MSE), Ti- and Fe-counts all display distinct dips in relation to the cracks. The Al-data here was
measured with the Mo-tube and contain too much noise to allow a comparison with the X-ray radiograph.

tion can be used to separate the aeolian, terrestrial, and biogenic biological or redox processes. Elements such as Fe or Mn are
input into the system. unsuitable because of their redox sensitive nature while elements
To illustrate the effect of dilution by TOC on the measured like Ca or Si are strongly affected by biological processes. Other
intensity of an element in the lithogenic component, a typical major elements such as Na, K, Sr, or Mg are easily dissolved and
example is calculated. The TOC content of subtropical lake sedi- weathered, also making them unsuitable for normalization. Tita-
ment typically varies between a few percent to over 50% (Maxwell, nium is an important component in many minerals, is abundant,
2001; Selvaraj et al., 2007). However, as organic matter also con- and biologically not very active. However, Ti is enriched in heavy
sists of a large portion of other light elements such as H, O, N, minerals and in aeolian dust and is therefore used as a proxy for
and S, the organic component of the sediment can be considerably high-current regimes (Schnetger et al., 2000) or enhanced wind
higher than indicated by TOC alone. The carbon component of the activity (Wehausen and Brumsack, 1999; Yancheva et al., 2007).
organic matter increases with the maturity of the organic matter, Furthermore, Ti content is also highly influenced by the composi-
but in unlithified sediment, the percentage of C in organic matter tion of the original protolith (Rundnick and Fountain, 1995; Rund-
often is lower than 50% (Cambardella et al., 2000; Tyson, 1995). nick and Gao, 2003). The most suitable element therefore is likely
As a result, sediment with a TOC content around 25% (organ- Al. It is abundant, little active biologically, and is not particularly
ic = 50%) might only contain 50% lithogenic material. Assuming affected by redox variations (Brumsack, 2006). As Al is a major
for simplicity’s sake, that the organic matter in the lake sediment structural component in the sand, silt and clay that enters the
consists to 50% of carbon, and to 50% of H, N, O, and S, then the lith- basin, a normalization of the other elements against Al allows us
ogenic component would make up about 100% (2  TOC). Conse- to see how the proportion of the individual elements in the litho-
quently, if the TOC level rises from for example 1% to 25%, the genic part of the sediment have changed relative to each other over
elements in the lithogenic component would decrease by about time.
50%. This effect of dilution by organic material is well know (the After normalization, the pattern displayed by Ti/Al and Fe/Al
closed-sum effect) (Calvert, 1983; Rollinson, 1993), but there is differ markedly from the Ti- and Fe-records in the studied core.
no straight forward method to deal with it since XRF-scanners It now becomes apparent that the three intervals characterized
deliver counts rather than concentrations. In marine settings, the by enhanced TOC levels, 480–440 cm, 170–120 cm, and 80–
sedimentary composition is often compared to the average compo- 50 cm, are also distinguished by strong increases in Ti- and Fe-
sition of a typical sediment, such as black shales (cf. Tribovillard to-Al ratios. It is tempting to interpret these concomitant changes
et al., 2006). In more variable settings, as in lakes for instance, it in TOC levels and in element-to-Al ratios as a climatic signal likely
is often more useful to look at the relative variations of the differ- caused by a change in weathering conditions. That the enhanced
ent elements compared to a major, conservative element. Prefera- Ti/Al levels should be caused by an increase in aeolian dust input
bly, the element should not itself be a proxy nor affected by seems unlikely. Although element-to-Al ratios are high in TOC-rich
L. Löwemark et al. / Journal of Asian Earth Sciences 40 (2011) 1250–1256 1255

intervals, the absolute counts in Ti and Fe actually decrease, indi- malized or standardized against a standard or a conservative
cating a drop in the input of these elements. Weathering is primar- element.
ily influenced by precipitation and temperature, and the rate of s The most suitable element to be used for normalization will in
weathering for various minerals is generally the reverse of Bowen’s most settings be Al since it is abundant, among the last to be
reaction series, meaning that minerals rich in quartz and Al remain affected by weathering, and is also little affected by biological
in the soil while more easily dissolved elements would be weath- and redox processes.
ered from the soil and transported to the depositional basin (Brady, s However, Al-measurements are hampered by the poor detec-
1990; Fang et al., 2003; Selly, 1994). Consequently, the simulta- tion limits for Al, requiring the sediments to be measured with
neous increase of TOC and Ti- and Fe-to-Al ratios observed in Li– different X-ray tubes to obtain the full spectrum of elements,
Yu Pond could be interpreted to be the result of periods of in- and the use of long exposure times to ensure reliable Al-data.
creased precipitation leading to increased chemical weathering in
the catchment, enhanced flushing of soil organic matter into the We therefore strongly recommend that a normalization or stan-
lake, and possibly also to higher lake levels causing dysoxic condi- dardization of XRF-scanner data is performed before any paleoen-
tions on the lake floor enhancing preservation of organic material vironmental interpretation is attempted. This is particularly
(cf. Yancheva et al., 2007). However, increased TOC could also be important in settings where large fluctuations in the organic frac-
due to peat formation during lake level low-stands, a thorough tion of the sediment can be anticipated.
paleoenvironmental interpretation of the Li–Yu Pond record is be-
yond the scope of this study. Acknowledgments
From the above discussion it should be clear that elemental
variations obtained by XRF-scanning, although a very powerful This study was supported by the National Science Council of the
tool, cannot be taken at face value, at least not in settings that ROC under Grant NSC NSC 97-2116-M-019-004 to CHF. YEF
show large variations in the non-lithogenic component of the sed- acknowledges grants from NSC, Academia Sinica, and from Na-
iment. Aluminium-normalization as outlined above is a powerful tional Taiwan Normal University. LL and YTN also acknowledges
way to standardize the obtained XRF-scanner data to make com- financial support from Swedish Research Council. Nathalie Ljung-
parisons between different intervals and sites possible. However, gren is thanked for assistance with the Itrax measurements. Anders
Al-normalization of XRF-scanner data is also marked by a number Rindby is thanked for help with the discussion on XRF-scanner
of limitations. The most severe being the poor detection of Al. methodology. We gratefully acknowledge the constructive reviews
While data obtained using the Cr-tube give reasonable Al-data, by Nicolaj K. Larsen and one anonymous reviewer who helped im-
the detection of heavier elements is not optimal, thus requiring a prove this study.
second run with the Mo-tube for each core and a switch of tubes.
This procedure effectively doubles the machine time, increases
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