Quaternary International 514 (2019) 5–15

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Quaternary International
journal homepage: www.elsevier.com/locate/quaint

Current perspectives on the capabilities of high resolution XRF core scanners T

a,∗ b c d
Ian W. Croudace , Ludvig Löwemark , Rik Tjallingii , Bernd Zolitschka
a
GAU-Radioanalytical, University of Southampton, National Oceanography Centre, Southampton, SO14 3ZH, United Kingdom
b
Department of Geosciences, National Taiwan University, P.O. Box 13-318, 106, Taipei, Taiwan
c
GFZ German Research Centre for Geosciences, Telegrafenberg, 14473, Potsdam, Germany
d
University of Bremen, Institute of Geography, Celsiusstr. 2, D-28359, Bremen, Germany

ARTICLE INFO ABSTRACT

Keywords: The introduction and application of high resolution XRF core scanners has made an enormous contribution to
XRF core scanner palaeoclimate science over the last two decades. These core scanners have become essential analytical tools for
High resolution analysis the investigation of sedimentary and other natural cumulative records of environmental change. Their wide-
Non-destructive analysis spread adoption by the environmental and geoscience communities has had a significant impact on the ability to
μXRF analysis
systematically record high resolution chemical profiles in marine and lake sediments and soils. The range of
Palaeoclimate
applications has broadened beyond sedimentology and palaeoclimatology and now extends into scanning
samples of speleothems, corals, mumiyo mounds, rocks, sedimentary nodules, archaeological artefacts, tree
sections and melt segregations. Other areas exploiting the capability of XRF core scanners are mineral ex-
ploration, geotechnical characterisation, soil remediation studies and carbon capture and storage research. As a
consequence of their ability to efficiently determine detailed, non-destructive elemental records in sediments
and soils, scientific papers published since the year 2000 now number more than 1000.

1. Introduction 1000 papers in the scientific literature as well as two specialist books
(Rothwell et al., 2006 and Croudace and Rothwell, 2015) and now a
International scientific interest in XRF core scanners was triggered Quaternary International Special Issue.
by the rapid expansion of palaeoclimate research from 2000 onward Non-destructive, high resolution XRF core scanners undoubtedly led
and the arrival of two commercial high resolution core scanner (CS) to an advance in the acquisition of detailed down-core elemental pro-
systems based on prototypes that originated in European marine re- files of sediments (Jansen et al., 1998; Croudace et al., 2006; Richter
search institutions. These instruments, the Avaatech-CS (The et al., 2006; Rothwell and Croudace, 2015). Most established instru-
Netherlands) and the Itrax-CS (Southampton and Sweden) received a ments were designed to scan in a down-core linear mode (1D) but
significant international launch at the ‘New Techniques in Sediment smaller, efficient, highly capable XRF XeY mapping systems (2D) are
Core Analysis’ Conference held in Southampton in September 2003. now available (e.g. Bruker M4 Tornado). The XRF core scanners in-
Proceedings of the Conference, including four papers on the capabilities itially developed were optimised for studying layered sediment but they
of the two core scanners, were later published in a Geological Society of can be used to study elemental variations in almost any natural or
London Special Publication (Croudace et al., 2006; Rothwell et al., synthetic solid system. The success of the technology is exemplified by
2006; Thomson et al., 2006; Richter et al., 2006). After a decade, other the fact that there are now well over one hundred XRF core scanners
manufacturers also contributed to the range of capable XRF core globally distributed among many leading international research in-
scanner systems (Geotek in 2009; Bruker in 2012; Minalyze in 2014). stitutions. These powerful instruments enable automated analyses to be
The impacts of these instruments have been presented in a series of made efficiently and rapidly on virtually any solid with little sample
international workshops that were largely instrument specific. By 2017, preparation and at sediment layer resolutions down to sub-annual in-
there was broad interest in drawing all the different core scanner tervals. The key requirement for an effective investigation is scanning
communities together for the ‘XRF Core Scanning 2017’ Conference of a flat analytical surface to enable determination of elements from Mg
(Taipei, 2017) that led to a Journal Special Issue (Table 1). Since their through U. The highest sensitivity for the lowest Z element (Na, Mg and
first commercial appearance in 2003, the investigation of sediment Al) depends significantly on the X-ray tube used for excitation and
cores and other records by XRF core scanners have led to more than whether a helium path (for wet sediment) or a vacuum (for

∗
Corresponding author.
E-mail address: [email protected] (I.W. Croudace).

https://doi.org/10.1016/j.quaint.2019.04.002
Received 12 March 2019; Received in revised form 1 April 2019; Accepted 1 April 2019
Available online 05 April 2019
1040-6182/ © 2019 Elsevier Ltd and INQUA. All rights reserved.
I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

Table 1
Topics included in the QI:XRF Core scanner Special Issue.
Overview Current perspectives on the capabilities of high resolution XRF core scanners. Croudace et al. (2019b)
Methodology Practical guidelines and recent advances in the Itrax XRF core-scanning procedure Itrax specialists, 2019
Methodology The potential power and pitfalls of using the X-ray fluorescence molybdenum incoherent: coherent scattering ratio as a proxy Woodward and Gadd (2019)
for sediment organic content
Methodology Signal-to-noise ratios, instrument parameters and repeatability of Itrax XRF core scan measurements of floodplain sediments Jones et al. (2019)
Methodology Trace metal analysis of sediment cores using a novel X-ray fluorescence core scanning method Hennekam et al. (2019)
Methodology X-ray fluorescence scanning of discrete samples: an economical perspective Profe and Ohlendorf (2019)
Methodology The iBox-FC: A new containment vessel for Itrax X-ray fluorescence core-scanning of freeze cores Gregory et al. (2019)
Methodology Utilisation of XRF core scanning on peat and other highly organic sediments Longman et al. (2019)

Palaeoclimate Is XRF core scanning a viable method for coral palaeoclimate temperature reconstructions? Ellis et al. (2019)
Palaeoclimate Aridification of the Egyptian Sahara 5000–4000 cal BP revealed from X-ray fluorescence analysis of Nile Delta sediments at Pennington et al. (2019)
Kom al-Ahmer/Kom Wasit
Palaeoclimate Temperature and precipitation variability in eastern Anatolia: results from independent component analysis of Lake Van Ön and Özeren, 2019
sediment data spanning the last 250 kyr
Palaeoclimate Testing annual tree-ring chemistry by X-ray fluorescence for dendroclimatic studies in high elevation forests from the Spanish Sánchez-Salguero et al.,
Pyrenees 2019

Sedimentology Deciphering ∼45,000 years of Arctic Ocean lithostratigraphic variability through multivariate statistical analysis Kaboth-Bahr et al. (2019)
Sedimentology Application of multivariate statistical analyses to Itrax core scanner data for the identification of deep-marine sedimentary López-érez et al., 2019
facies: A case study in the Galician Continental Margin

Volcanology Towards characterising rhyolitic tephra layers from New Zealand with rapid, non-destructive micro-XRF core scanning Peti et al. (2019)

Seismic Processes Geochemical features of the pseudotachylytes in the Longmen Shan thrust belt, eastern Tibet Wang et al. (2019)

Geoarchaeology 200-year industrial archaeological record preserved in an Isle of Man saltmarsh sediment sequence: Geochemical and Croudace et al. (2019a)
radiochronological evidence
Geoarchaeology What caused the cultural hiatus in the Iron-Age Kiwulan Site, northeastern Taiwan? Huang et al. (2019a)

impregnated sediment) are used. Continued important technological 1.1. Historical evolution of high resolution XRF scanners
improvements to detection systems now allow a high resolution ele-
mental record to be acquired for a 1 m-long core in a few hours com- Avaatech: The CORTEX (Corescanner Texel) developed at the
pared with the situation a decade ago where 24–48 h was typical for a Royal Netherlands Institute of Sea Research (NIOZ) in the late 1990s
full trace and major element scan. (Jansen et al., 1998) and was the first X-ray core scanning system. The
The arrival of non-destructive, high resolution, automatic XRF core instrument continues to evolve and current instruments still uses a low
scanning technology in the early 2000s introduced a crucial new tool power X-ray tube and a slit collimation system. Initially built to support
for palaeoclimate researchers. Most early work was carried out in shipboard measurements, the instrument was used for a broad range of
oceanographic laboratories studying marine sediments but interest high resolution palaeoceanographic and sedimentological research, e.g.
quickly transitioned to include research institutions studying lake se- small-scale orbital and sub-orbital features preserved in sediment se-
diment. The early iconic research on finely laminated marine sediments quences. There are currently over thirty Avaatech-CS systems world-
from the anoxic Cariaco Basin demonstrated the huge capability of XRF wide.
core-scanners. These studies showed the ability of core scanners to Itrax: The second XRF core scanner was the prototype Itrax-CS. This
identify the impact of hydrological cycles during the last glacial period was originally conceived in the year 2000 by Ian Croudace in
(Peterson et al., 2000). The developments were initially stimulated by Southampton who recognised the scientific potential for a single in-
the increasing interest in studying high resolution elemental records as strument that integrated a high-power X-ray tube (up to 3 kW) with a
proxies for Holocene variability of the ITCZ (Haug et al., 2001) and 200 μm X-ray capillary wave guide, an X-radiography system and an
relating the collapse of the Mayan civilization to climatic impact (Haug optical camera to enable co-registration of high resolution elemental,
et al., 2003). Even at this early stage, the capability of the non-de- visual and density/textural data. With colleagues G. Rothwell and J.
structive X-ray technique, in combination with additional scanning Thomson (Croudace et al., 2006; Rothwell et al., 2006; Thomson et al.,
methods, such as digital imagery, gamma-ray density, P-wave velocity 2006) and research funding from the UK Office of Science and Tech-
and magnetic susceptibility, was clear (Röhl and Abrams, 2000). It was nology, a project was initiated that led to Cox Analytical Systems
also noted by Zolitschka et al. (2001) that when applied to lake sedi- (Gothenburg, Sweden) being invited as technical partners. In early
ment cores, these techniques supported a new field that required rapid 2003, following a 15-month collaborative development, the prototype
acquisition of analytical data to provide the time resolution necessary Itrax-CS was delivered to Southampton and was showcased at the New
for new insights into palaeoeclimatic variability and their forcing fac- Techniques in Sediment Core Analysis Conference later in the same
tors. year. There are currently over fifty Itrax-CS systems worldwide and new
The growing acquisition of high resolution XRF core scanner tech- models are now being added to the range.
nology by the geoscience community has led to an almost exponential Tatscan: Two XRF core scanners were developed in Japan by
growth in publications and there are currently around 1000 scientific Sakamoto and co-workers but their use was largely confined to Japan. A
papers published in high impact journals. This paper, the Special Issue significant number of research publications (e.g. Sakamoto et al., 2006)
on High Resolution XRF Core Scanners (Table 1) presents insights arose from their use and one instrument was originally installed on the
into the historical development of XRF core scanning systems, as well as Research Vessel Chikyu.
examples of recent environmental applications (Fig. 1; Fig. 2) and ca- Geotek: In 1990 Geotek launched the Multi-Sensor Core Logger
libration approaches. It also presents an overview of the study of finely (MSCL) an automated and non-destructive core scanning system by
laminated lacustrine sediments (seasonal couplets) that currently re- installing an instrument at the United States Geological Survey (USGS).
present one of the most active areas of application of XRF core scanner The MSCL was developed to measure both physical and some geo-
technologies. chemical parameters. In 2009, the small integrated InnovX XRF

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

Fig. 1. Study areas benefiting from XRF core scanners and referred to in this Special Issue (Images from Croudace collection).

instrument was added as an option onto the MSCL platform with later elemental mapping of impregnated sediment blocks taken from cores.
enhanced XRF variants being made available (Olympus Delta, Olympus These systems are equipped with capillary X-Ray waveguides to facil-
Vanta). The system is argued to be a cost-effective entry level into XRF itate efficient excitation and high resolution spectral acquisition.
core scanning (Schillereff et al., 2015; Boyle et al., 2015). There are However, with acquisition times of > 5 h/mm2, mapping of sediment
now over 250 MSCL installations worldwide. In 2013 Geotek launched surfaces was initially limited to the mapping of small sediment areas
a compact, helium-flushed XRF sensor with claimed downcore resolu- (Dulski et al., 2015). Progressive improvements in both X-ray source
tions of 0.1 mm coupled and good sensitivity for the light energy ele- excitation and silicon-drift X-ray detectors (SDD devices) have reduced
ments (Na, Mg, Al, and Si). measurement times to ∼1 min/mm2 (e.g. Bruker M4-Tornado), which
Bruker M4 Tornado: Small bench-top micro-XRF systems designed allows elemental mapping of entire impregnated sediment blocks (ca.
for sample sizes of 10–20 cm have existed for ca. 20 years and were 100 × 20 mm) in only a few hours. These high resolution 3-D / x-y-z
developed as a microanalytical tool for use in many sectors (geoscience, systems are ideally suited to the examination of small samples of im-
biomedical, materials, forensics, electronic etc). One of the most re- pregnated, finely-laminated sediments and compete with modern SEM
cently developed systems, that evolved from the EDAX Eagle III micro- systems in terms of elemental mapping.
XRF instrument (e.g. Haschke, 2006; Dulski et al., 2015). The M4 Minalyzer CS: This is a mobile, self-contained instrument designed
Tornado can investigate samples up to 19 × 19 cm and has been ap- mostly for non-destructive analysis of rock drill cores directly in core
plied to many sample types including detailed high resolution trays and was particularly directed at the metalliferous mining sector.

Fig. 2. Images from a radioactive sedimentary

reduction nodule (Permian, Littleham Cove,
UK). The hand specimen is approximately 15 cm
across. The images (clockwise from top left)
show a photograph of a cut specimen, a vana-
dium (V) X-ray map (Bruker M4 Tornado μXRF
system), V and Fe line scans along the equatorial
axis (Itrax) and an autoradiograph (acquired
over 2 days using a phosphor plate) revealing
the uranium distribution. All images are from
the Croudace collection.

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

Fig. 3. Interpretation and validation of Early-Holocene varved lake sediment from the record of Meerfelder Maar XRF record (Martin-Puertas et al., 2017). a) Bi-plot
of log-ratio transformed XRF data showing the distribution of the data and the correlation of the elements. The bi-plot of principal components 1 and 2 explains about
83% of the total variance in the data. The element correlations show positive correlations for element associated with detrital siliciclastics (from K, Ti), redox-
sensitive elements (from Mn, Fe) and carbonates (from Ca, Sr). The total data set was divided in 6 hierarchical clusters that represent groups of similar compositions.
b) Clusters 3 and 4 describe the main compositional variation of the organic varve component that deposited in Meerfelder Maar during the Early-Holocene. The bi-
plots of clusters 3 shows a negative correlation for Si and Ti (opposite direction) and a more positive correlation for Si and Ti in cluster 4 (similar direction). c) XRF
element mapping of the impregnated sediment block MFM-A4 40–50 (Cluster 3) shows Si of diatom layers (green) and mixed Si-Ti detrital layers (orange), whereas
MFM-D4 41–51 (Cluster 4) shows a stronger separation between diatoms layers (Si) and detrital layers (Ti, red). The XRF mapping results perfectly link XRF data and
thin section microscopic observations. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

Developed by Minalyze AB (Gothenburg, Sweden), the instrument was Tjallingii, 2008; Weltje et al., 2015). Therefore, log-ratios of element
launched in 2015. Drill cores are optically documented by a high re- intensities provide a linear solution for the interpretation of element
solution colour camera and 3-D laser and scanned using a collimated intensity records in terms of chemical compositions by a simple trans-
beam from an X-ray tube operating up to 50 kV and 24 mA to provide formation.
elemental data and sample density. Scanning paths are automatically The development of the log-ratio calibration model provided a ro-
defined from the 3-D laser topography and a robotic system executes bust solution for quantification of XRF core scanning records and it is
the XRF analysis. Low-energy X-ray detection is facilitated by the use of also consistent with the statistical theory of compositional data analyses
a confined vacuum or helium atmosphere in front of the detector, (Aitchison, 1982; Weltje et al., 2015). Consequently, log-ratios of ele-
thereby allowing analysis of elements as light as Mg. The 3-D data are ment intensities provide a reliable basis for statistical analysis of XRF
also used to measure structural features such as cracks and joints with core scanning data, unlike element count intensities or element ratios
results being displayed in a cloud-based viewer (Sjöqvist et al., 2015). (Bloemsma, 2015; Weltje et al., 2015). Statistically robust uncertainty
estimations need to be calculated using replicate measurements (three
times or more) to indicate confidence limits of the measured element
1.2. Calibration and validation of XRF core scanner data intensities (Weltje and Tjallingii, 2008). Statistical analysis based on
log-ratios of XRF element intensity records offer a powerful tool to
The outstanding benefits of XRF core scanners are their ability to explore element correlations. Unlike data expressed as relative abun-
provide automatic, non-destructive, rapid and high resolution along dances (e.g. ppm, g/kg, wt%), log-ratios do not suffer from the effects of
core elemental analysis. The most common XRF scanner output applied constant-sum constraints (Aitchison, 1982). Therefore, log-ratio trans-
by users are element intensity records (in counts or cps) produced by formation of core data is free of intrinsic correlations and provides
XRF scanning that are representative of variations in material chemical statistically reliable results (Weltje et al., 2015).
composition. The elemental output can, however, be adversely affected Visualization of statistically-robust core data provides a profound
by physical effects such as non-flat, irregular, or cracked surfaces as approach for the interpretation of element records acquired by XRF
well as by variations of the sample/sediment matrix (e.g. Jansen et al., core scanning and validates these records in terms of environmental
1998; Croudace et al., 2006; Tjallingii et al., 2007; Weltje et al., 2015). processes (e.g. inferring depositional environments). A bi-plot provides
Apart from matrix effects, these variations are effectively eliminated by a graphical display of principal component analyses (PCA) that project
normalizing element intensities by calculating element ratios or pro- both data distributions and element correlations (Aitchison and
portions of a constant number of elements (e.g. Jansen et al., 1998; Greenacre, 2002). In the case of XRF data, the direction and length of
Croudace et al., 2006; Weltje and Tjallingii, 2008; Löwemark et al., the elements displayed in a bi-plot reveal the correlation and strength of
2011; Weltje et al., 2015). Matrix effects cause nonlinear absorption the correlations, which helps to link the elements measured with the
and enhancement of element intensities and are not effectively com- observed sediment fractions (e.g. Bloemsma, 2015; Martin-Puertas
pensated by normalization (Weltje and Tjallingii, 2008). Unlike XRF et al., 2017; Ramisch et al., 2018). For instance, the bi-plot visualization
analyses of discrete powder or glass bead samples, matrix effects cannot of the Early-Holocene varved sediments from Meerfelder Maar (Fig. 3a)
be quantified for XRF core scanning records due to highly variable reveal that these sediments mainly consist of detrital siliciclastics (in-
nature of sediment properties down core. However, the log-ratio cali- ferred from K, Ti), redox-sensitive components (inferred from Mn, Fe)
bration model provides a solution via estimation of relative matrix ef- and carbonates (inferred from Ca, Sr).
fects. It has been demonstrated that log-ratios of XRF intensities are Another statistical application for visualization of similarities and
linearly related to log-ratios of geochemical concentrations (Weltje and

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

differences of variables is provided by hierarchical clustering which mostly from 1982 to 2010. The investigation acquired radionuclide and
divides the total data set into groups of similar compositions thereby geochemical data from sediment cores to understand the fate of the
helping establish geochemical boundaries for the sediment succession discharged radioactive compounds in the estuary. By combining geo-
(Lengger et al., 2013; Bloemsma, 2015; Martin-Puertas et al., 2017). chemical (heavy metal pollution signals) and textural evidence (litho-
Although the number of clusters is not objectively selected, grouping of logical and erosion features) with radiochronological indicators of se-
the data into individual clusters is entirely based on statistical analyses diment accumulation it was concluded that the complete OBT discharge
and therefore free of subjectivity. Moreover, hierarchical clustering record was preserved in the sediment cores. By contrast, however, in-
allows visualization of compositional differences and similarities in a dustrial records of heavy metals (Cu, Zn and Pb) and atmospheric in-
stratigraphically unconstrained way and objective determination of li- puts of 137Cs and 210Pb were significantly disrupted. Explaining the
thological boundaries. Bi-plots of the individual clusters help to visua- disrupted record required a major estuarine event. The Severn Estuary
lize compositional differences of these individual clusters for detailed and Bristol Channel often receive the impact of strong westerlies and on
information on the changes of the sediment compositions and of de- December 13th, 1981 an unusually fierce winter storm, coinciding with
positional environments. For example, the bi-plots of multivariate sta- high tides, produced a 2 m storm surge (near Newport) that led to
tistical clusters of the Early-Holocene varved sediments from Meer- significant erosion of intertidal areas. The first evidence that the storm
felder Maar distinguish periods when Si is mainly bound to minerogenic surge had also caused significant sub-tidal erosion of sediment was
matter from those where Si is driven by diatom concentrations found in a core that showed a storm pebble layer (Croudace et al.,
(Fig. 3b). 2012). This layer occurred at the same position in the sediment core as
Further validation of XRF records and statistical analyses of core major inflections in radiochronological and heavy metal data and
scanner data can be obtained by comparison with detailed observations showed that part of the sedimentary record must have been lost through
and other proxy records. However, most destructive proxy records have erosion. This event occurred only months before the radio-
sampling resolutions of typically 1–10 mm at best and make detailed pharmaceutical site had begun its operations and discharges in early
comparison of XRF core scanning records with sampling resolutions 1982.
of < 1 mm (finely laminated sediments) problematic. Such finely la- Another major storm surge led to significant coastal damage in low
minated sediments are typically studied using micro-XRF mapping of lying areas of countries bordering the southern North Sea in 1953. The
impregnated sediment blocks using scanning electron microscopic Netherlands, Belgium and the UK were particularly badly impacted by
(SEM) methods or more recently the Bruker M4-Tornado micro-XRF. the surge and more than 2000 people lost their lives. Studies of salt-
The potential of XRF mapping is demonstrated by the results of two marsh sediments at Wrangle and Holkham on the east coast of England
impregnated sediment blocks of the Early-Holocene varved sediments aimed to determine if records of the storm surge were preserved in the
from Meerfelder Maar (Fig. 3c). The XRF maps revealed a strict se- stratigraphic record (Tsobanoglou et al., 2010; Swindles et al., 2018).
paration of diatom layers (inferred from Si) and siliciclastic detrital Detailed sedimentological characterisation accompanied by Itrax core
layers (inferred from Ti) during periods when Si is mainly bound to scanning and radiometric dating, were used to identify past storm surge
minerogenic matter (cluster 4), confirming the interpretation made by deposits and the timing of past surge events. Such studies are important
multivariate statistical analysis (Martin-Puertas et al., 2017). in determining the frequency and magnitude of storm surges which in
The development of the log ratio-calibration model (Weltje and turn inform coastal zone risk management.
Tjallingii, 2008; Weltje et al., 2015) has provided a reliable and sta-
tistically robust way to use and interpret XRF element intensities. 2.2. XRF core scanning and lake sedimentary records
Combining the processing of XRF scanning records using log-ratios of
element intensities, robust statistical analysis, detailed elemental In the absence of long instrumental records of climatic and en-
mapping and microscopic observations of sediment textures and mi- vironmental variabilities, XRF core scanner data can provide potentially
neralogy all lead to improvement in the reconstruction of depositional powerful proxy records of environmental change (Davies et al., 2015;
environments and climatic reconstructions. Another promising devel- Zolitschka et al., 2001, 2015). Their high resolution makes them ideally
opment involves the reliable prediction of grain-size distributions from suited to detect climatic change such as hydroclimatic and erosional
XRF core scanning data (Bloemsma et al., 2012). Overall, the applica- variability from millennial to sub-decadal time scales. In some cases,
tion of multivariate statistical methods provides a potential for ex- they are also excellent at detecting events via identification of products
tracting quantitatively reliable records from XRF core scanning data. of storms, storm surges, volcanic eruptions, earthquakes and polar ice
cover reflected through changes in mineralogy, elemental composition
2. Application areas and texture.
Cultural eutrophication studies: Anthropogenically-induced eu-
2.1. XRF core scanning and storm records in coastal marine sediments trophication and pollution in lake sediments is widespread and can be
magnified where the impacts of population, tourism and farming
The identification of storm records in coastal sediment sequences is combine to promote algal production (e.g. Jenny et al., 2016). A gra-
important forunderstanding pollution histories for regulatory agencies phic example (Fig. 5) is reported for sediment cores collected from
and in coastal zone risk management. XRF core scanners represent a Windermere (a seasonally stratified lake in the English Lake District
practical and efficient tool for non-destructively acquiring elemental National Park). The progressive rise in pastoral farming, agricultural
profiles and radiographic information to support such investigations. runoff and human sewage inputs, along with early wastewater treat-
One example where the determination of long-term storm records in ment, provided nutrients for the seasonal growth of algae leading to
sediments is important is in assessing risks for major engineering pro- deposition of diatomaceous laminae. The uppermost sedimentary re-
jects (e.g. the new Hinkley Point PWR reactor site in the Bristol cord is lithologically distinctive, being organic-rich (gyttja) with dis-
Channel). tinct heavy metal enrichments in the top 25 cm (representing a period
XRF core scanning made a major contribution to an investigation of from ca. 1850 to the present). Geochemical profiles of the sediment
sub-tidal sediments from the Severn Estuary. The Estuary, well-known cores (measured by Itrax and WDXRF) show a record of heavy metal
for its 15 m tidal range, is a component part of the large funnel-shaped enrichment (e.g. Zn, As, Cu, Pb). Microfabric and geochemical analyses
Bristol Channel. The study was undertaken on behalf of the UK (Fig. 5) also demonstrate that diffusion of reduced mobile Mn and Fe
Environment Agency that was concerned about the impact of estuarine occurred from the anoxic sediment and was precipitated at the redox
discharges of organically-bound tritium from a radiopharmaceutical boundary near the sediment-water interface (Fielding et al., 2019).
site near Cardiff, UK (Fig. 4Croudace et al., 2012). The site operated Other geochemical data show enrichment of Hg and document that the

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

Fig. 4. Itrax scan of a sub-tidal sediment core from the Newport Deep (Severn Estuary, UK) with selected elemental profiles (depth scale is in mm). The sharp rise in
Zn, Zn/Ca (and Pb and Pb/Ca) between 350 and 300 mm depth (stippled) represents the transition from pre-industrial background concentrations to historical
industrial inputs. The increase coincides with a distinct pebble layer at 300 mm depth (visible as the dark zone in the radiograph). The layer is identified as marking a
sedimentary hiatus caused by erosive loss generated by a storm surge, supported by geochemical and radionuclide evidence. This storm layer was the first regional
evidence for significant sub-tidal erosion caused by the powerful December 13th, 1981 storm (Croudace et al., 2012).

Fig. 5. Effects of cultural eutrophication as revealed from elemental distributions in lake core SC57 from the south basin of Windermere (Cumbria, UK). The onset of
the organic rich sediment at ∼25 cm depth is equivalent to 1850 and reflects the initial impact of cultural eutrophication in the lake caused by significant increases in
population, tourism, pastoral farming and sewage inputs. The red continuous lines represent Itrax data and are compared with quantitative WDXRF data (green
continuous line with red filled circles; adapted from Fielding et al., 2019). The WDXRF concentration maxima are Mn 9.6 wt%, Fe 9.03 wt%, Ti 0.47 wt%, P 0.80 wt
%, Ba 2000 ppm, Cu 109 ppm, Zn 1680 ppm, As 81 ppm and Pb 590 ppm. (For interpretation of the references to colour in this figure legend, the reader is referred to
the Web version of this article.)

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

Pb component (from 1930 to 1990) has a stable isotope composition from the catchment area into the lake. This erosional signal is linked to
dominated by leaded petrol (Miller et al., 2014). hydroclimatic fluctuations (i.e. an Atlantic precipitation signal) as
Palaeoseismic studies: The sedimentary records in lakes and human impact on this lacustrine system was insignificant until the
marine margins can incorporate mass transport deposits (MTDs) caused Middle Ages (Chassiot et al., 2018). Rainfall variability seems to be
by slope-failures triggered by seismic activity (Gracia et al., 2013; controlled by negative phases of the NAO in concert with low total solar
Strasser et al., 2013). Lake sediments are established recorders of pa- irradiance jointly triggering catchment soil erosion and mass-move-
laeoseismicity in seismically active regions but less tectonically-active ments (Chassiot et al., 2018). Furthermore, Fe and Mn distinguish
areas may also host mass transport deposits (MTDs). One example re- oxygenated Middle-to Late-Holocene bottom waters from anoxic con-
ported by Fielding et al. (2018) describes an Itrax-studied lacustrine ditions over the last ca 700 years. In the latter case, both elements co-
sediment core from Windermere (the largest lake in England) that vary with organically bound Br, while Fe and Mn are distinctly linked to
contains a visually and chemically distinct, 2 cm thick MTD. Evidence is terrigenous detrital elements (Ti, K, Zr, Rb, Sr, Ca) for the earlier sec-
provided that the MTD was triggered by an earthquake with a local tion of the record (Chassiot et al., 2018). This trend from an oligo-
magnitude of 4.7 ML occurring on 26th of December 1979 with an trophic lacustrine system with clastic sediment influx to a higher
epicentre 70 km north of the lake. The earthquake was one of the lar- trophic level with organic sediments reflects the lake's ontogeny, a
gest in the UK during the last 100 years. process promoted by cultural eutrophication during the last millen-
The role of earthquakes and climate in the formation of diamictic nium.
sediments was examined by Woodward et al. (2018) in a New Zealand The last 4500 year palaeolimnology of Lake Butrint, a coastal la-
alpine lake. Different events with environmental significance are dia- goon in southwestern Albania has been studied with a multiproxy ap-
mictic layers determined by facies classification based on XRF core- proach that included XRF core-scanning (Morellón et al., 2016). Ti/Ca
scanning in combination with magnetic susceptibility, grain size ana- was interpreted to characterise minerogenic sediment influx from the
lysis and μCT-scanning on a last 2000 years of a sediment record from catchment area with Increasing Ti/Ca supported by lower lake-water
Lake Chappa'ai in the Southern Alps of New Zealand. Although it was salinity (decrease in Sr) due to more humid conditions with higher
possible to distinguish diamictic sediment layers from increased iron runoff during the LIA. However, if Ti/Ca and Sr rise con-
(Fe) and decreased organic matter (inc/coh), their depositional pro- temporaneously, this points to cultural soil erosion without climatic
cesses were inferred to be linked to strong earthquakes. However, ice- forcing. Additionally, more saline, dry and warm periods with limited
rafted debris, rockfalls as well as snowmelt or other runoff events were clastic input relate to Roman and Medieval Warm Periods. All changes
also considered as possible causes of the diamict layers. are accompanied by variations of redox conditions as indicated by Fe/
Storm records: Frequency and intensity of storms was re- Mn (Morellón et al., 2016).
constructed for wind-exposed Loch Hosta, a lake located at the western Information about the strength and position of Southern
shore of one of the Outer Hebridean Islands, U.K. (Orme et al., 2016). Hemispheric Westerlies has been obtained from the sediment record of
This study is based on Ca/K as an indicator of calcium-rich marine Laguna Azul in southern Patagonia, Argentina (Zolitschka et al., 2019).
beach sand being blown into the coastal lake. In combination with in- An Early-Holocene rise of Fe/Mn indicates strong meromixis with dis-
strumental calibration, high resolution XRF data allow reconstruction tinct anoxia at the lake bottom interpreted as the result of intensified
of enhanced storminess during the climatic deterioration of the Little westerly winds causing a drastic lake-level drop with salinization of the
Ice Age (LIA). Additionally, the ca. 60-year cyclicity relates this pa- lake water. During the Late-Holocene, Ca/Ti corresponds to minor lake-
laeostorm record to the North Atlantic Oscillation (NAO) and North level fluctuations with addition of Ca to the sediment (calcite pre-
Atlantic sea-surface temperatures (Orme et al., 2016). cipitation) during lower lake levels caused by windier, warmer and
Another wind-related study tested long-term changes of tropical drier hydroclimatic conditions. In the absence of tributaries, Ti was
cyclone activity in the western North Atlantic region. At Robinson Lake, linked at Laguna Azul to detrital minerogenic matter reflecting lake-
a lagoon at the Atlantic coast of Nova Scotia (Canada) and close to the shore erosion caused by fluctuating lake levels (Zolitschka et al., 2019).
north-western limit of tropical cyclone pathways, Br/Ti indicates past XRF core-scanning also complements grain-size analysis but with
cyclone activity (Oliva et al., 2018). As Br is a proxy for marine organic much higher resolution. This approach was applied to a sediment re-
matter (Ziegler et al., 2008) and Ti is depleted in coarse-grained sedi- cord from the flooded sinkhole of Cenote Jennifer in northern Cuba
ment fractions, Br/Ti relates to high magnitude storms that transport (Peros et al., 2017). Higher concentrations of Cl and Br were used to
coarse sediment rich in marine organic matter into Lake Robinson detect increases in salinity caused by regional drying. Palaeoclimate
(Oliva et al., 2018). In this way, increased magnitude and frequency of reconstructions from Cenote Jennifer document a multistage 8.2 ka
tropical cyclones was detected for CE 1475–1670, i.e. for the early LIA. event (Peros et al., 2017) in agreement with greyscale data obtained
Hydroclimatic studies: There are many hydroclimatic research from Cariaco Basin (Hughen et al., 1996).
studies across all climatic zones where elemental variability (e.g. Ti, Ti/ Another Holocene sediment record with high resolution XRF core-
Ca, Zr/Ti determined using XRF-CS) have been used as proxies for scanning data comes from thermokarst Lake Herschel (Herschel Island,
precipitation-driven sediment erosion (Hassall, 2017; Schillereff et al., northern Yukon, Canada) that documented the life cycle of an Arctic
2019; Chiverrell et al., 2019; Zolitschka et al., 2019). high resolution freshwater ecosystem (Fritz et al., 2018). Variability of Mn/Fe was re-
hydroclimatic records from tropical, continental Asia are relatively lated to changing redox conditions with consequences to the pre-
scarce and XRF core-scanning of the sediment record from Shuangchi servation of organic matter as indicated by inc/coh supported by dis-
Lake (Hainan Island, southern China) filled a gap in climate re- crete analyses of sediment total organic carbon. Additionally, Rb/Sr as
constructions (Zhang et al., 2018). Supported by grain size analyses, Zr/ a grain-size proxy is interpreted as a signal of reduced precipitation and
Rb and Si/Ti were interpreted as representing a higher median grain runoff from the catchment area and/or response to reduced weathering,
size, while Rb/Sr and Rb/K are related to finer grain sizes. Grain-size a process sensitive to temperature variations. Finally, Sr/Ca was used as
variability was in turn interpreted as a precipitation signal that docu- a salinity proxy that documented the development from a shallow
mented higher rainfall during the LIA consistent with other East Asian saline to a deeper freshwater lake over the course of the Holocene (Fritz
palaeorecords. This evidence suggested a contraction of the Inter- et al., 2018).
tropical Convergence Zone and a strengthening of the Pacific Walker Holocene hydroclimatic variability was reconstructed using Ca/Fe
Circulation as the underlying climatic driver (Zhang et al., 2018). for Lake Strzeszyńskie in western Poland (Pleskot et al., 2018). Ca is
Clastic events identified in the 7000 year-long lacustrine sediment diluted in the sediments during wetter and colder periods due to the
record from Lac Pavin (Massif Central, France) indicated that increases formation of a deeper lake, while Fe increases, at the same time, are
in Ti were a reliable indicator of detrital minerogenic matter transferred caused by redox processes induced by the development of more anoxic

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

bottom water conditions. Accordingly, under drier and warmer climatic terrigenous source indicator. Statistical links between detrital layer
conditions the lake level drops. This causes higher concentrations of Ca thickness and Ti to winter precipitation were established by calibration
and also of nutrients resulting in eutrophication with intensified calcite studies to produce a 2700 year-long annual scale reconstruction of
precipitation from the water column, while a shallower lake has oxy- snowfall (Czymzik et al., 2018).
genated bottom waters and thus lower levels of Fe (Pleskot et al., 2018). The varved sediment record extracted from Etoliko Lagoon, on the
These reconstructions correspond to other palaeorecords from Poland Ionian coast of Western Greece, spans the last 500 years (Koutsodendris
and to the lake-level reconstruction for Central Europe (Magny, 2004). et al., 2017). During the final stages of the LIA (since CE 1740), the
As such, Ca/Fe is a proxy for supraregional hydroclimatic variability for sensitivity of sediments to record climatic changes was enhanced and is
the site of Lake Strzeszyńskie (Pleskot et al., 2018). best documented by a three-fold increase in varve thickness, which goes
The extraction of hydroclimatological records from lake sediments along with environmental variability documented by μXRF data. Ti/Ca
from the South Pacific Convergence Zone (SPCZ) is currently underway was driven by influx of minerogenic matter (Ti) versus autochthonous
with a focus on reconstructing the movement of the SPCZ over mil- sediment by calcite precipitation (Ca). Increased Ti/Ca reflected in-
lennial timescales (Hassall, 2017; Maloney et al., 2019). In tropical lake creased catchment runoff and a resulting deeper lake, which was also
systems where soil in-wash is mainly determined by rainfall amount, reflected by stronger anoxia that drove higher Fe/Mn. At the same time,
high resolution micro-XRF variability of insoluble soil-derived elements Si/Ti, a proxy for lacustrine (diatom) productivity, increased due to
(Ti in particular) present in the catchment soils are a proxy for changes nutrient influx via catchment runoff. During a cold phase of the LIA
in precipitation. This approach will ultimately allow reconstructions of from CE 1790–1830, Ti/Ca decreased indicating reduced runoff and
precipitation records that will augment the existing short instrumental enhanced calcite precipitation – with both linked to drier conditions
datasets. (Koutsodendris et al., 2017). This in turn causes the lake level to drop
with reduced anoxia (decreasing Fe/Mn) as well as higher salinity
2.3. XRF core-scanning and varves (increasing Sr/Ca) and higher concentration of nutrients (increasing Si/
Ti). Consequently, the well dated high resolution μXRF data set in
In general, high resolution XRF core-scanning provides powerful combination with precise dating from Etoliko Lagoon enabled
proxy datasets with which to interpret processes affecting lake sedi- Koutsodendris et al. (2017) to conclude that large-scale NAO shifts
ments. However, achievement of the full potential of this method is caused the observed climate variability during the LIA.
mostly hampered by age/depth models that rely on limited age control. While the interpretation of XRF data for Etoliko Lagoon is de-
Therefore, allying XRF core-scanning with annually laminated (varved) scriptive, a multivariate statistical approach is applied to evaluate the
sediment records provides an ideally matched combination. While entire XRF core-scanning data-set for the Early-Holocene varved sedi-
micro-XRF core scanning typically provides a spatial resolution of ments from Meerfelder Maar, a crater lake in the West Eifel Volcanic
0.2 mm, the varves comes with a global mean annual resolution of Field in Germany (Martin-Puertas et al., 2017). This showed that
1.84 mm yr−1 (Ojala et al., 2012). This allows XRF core-scanning to multivariate statistics, applied to high resolution XRF core-scanning
theoretically provide a mean resolution of nine data points per year, data in combination with microfacies analyses (Fig. 5) and the multi-
thereby opening a gateway to a new dimension of environmental re- proxy approach allow an objective determination of depositional en-
construction that will feed the growing demands of high resolution vironments in terms of sediment sources and formation (Martin-Puertas
ecosystem and climate modelling. et al., 2017).
A gravity core with very finely laminated sediments was recovered A multivariate statistical procedure was applied to the varved se-
from proglacial Lake Donguz-Orun (Central Caucasus, Russia) and was diment record from Lake Montcortés (Central Pyrenees, Northern
assumed to be varved (Alexandrin et al., 2018). As a typical proglacial Spain) to determine shifts in oxic/anoxic conditions with the aim to
varve consists of a coarse-grained summer and a fine-grained winter distinguish climatic from human influences on the palaeolimnology
couplet, this distinct textural variation was checked by micro-XRF core- since CE 1500 (Vegas-Vilarrubia et al., 2018). Principal component and
scanning data. Here Zr/Rb was interpreted to record coarse-grained numerical clustering analyses allowed establishment of the evolution of
sediments, while Rb/Sr corresponds to fine-grained sediments. Both oxic/anoxic conditions for the sediment record that resulted from
alternate consistently in the record from Lake Donguz-Orun. The manifold climatic and anthropogenic influences on the lacustrine eco-
counting of Rb/Sr and Zr/Rb maxima produced, within the respective system and catchment. Forty-five percent of the sediment record in-
error margins, the same number of couplets as years determined by dicated years with mixing conditions confirming the meromictic con-
radiometric dating (137Cs, 210Pb) (Alexandrin et al., 2018). The terri- ditions are not required to preserve a continuously varved sediment
genous elements Fe and Ti were used for generation of a climate change record (cf., Zolitschka et al., 2015). The majority of varved sediment
signal with both elements correlating positively with instrumental re- records the intensity of anoxia increased during the 20th century due to
cords of annual precipitation (causing runoff) and summer temperature the effects of cultural eutrophication (Jenny et al., 2016). However,
(causing glacier melt) from a nearby weather station (Alexandrin et al., Lake Montcortés is different as it documents intensified anoxia in the
2018). second half of the 20th century despite ongoing and economically en-
Another clastic depositional system is Chevalier Bay, a coastal em- forced regional depopulation since CE 1900, which caused oxygenation
bayment on Melville Island (Northwest Territories, High Arctic of the lake bottom only at the beginning of the 20th century. This points
Canada). Its varved sediment record provides a well-constrained to global warming as the critical factor driving anoxia at Lake Mon-
chronology back to CE 1670 (Amann et al., 2017). After carrying out a tcortés (Vegas-Vilarrubia et al., 2018).
calibration study, the coarse-grained nival spring sub-laminae, best
characterised by Zr/K, were regarded as a proxy for snowmelt-related 2.4. XRF core scanners and other palaeoenvironmental records
sediment transfer into Chevalier Bay. This calibration documents con-
finement of the signal to an extended winter season (November through Dendrochemical studies: The application of XRF core scanners for
March) and thus provides one of the few well-calibrated records of high spatial resolution elemental analysis of annually-resolved tree-
winter temperature and snowfall conditions for the High Arctic (Amann rings in wood sections is well established (e.g., Smith et al., 2014).
et al., 2017). Micro-XRF instruments provide a non-destructive tool for this emerging
Springtime snowmelt floods have also been archived in the varved field and potentially allow tree responses to environmental conditions
sediment of Lake Kortejärvi (Eastern Finland). The 2700-year record to be critically tested. Hevia et al. (2018) note from their research that
studied using microfacies analysis and μXRF scanning documents a high resolution records from old trees growing in remote, high eleva-
significant correlation between detrital layer thickness and Ti as a tion areas allow reconstruction of environmental changes. Century-

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

scale chronologies of chemical variation at inter- and intra-annual re- cells to be assessed.
solution are few and a μXRF study of elemental profiles in wood from Environmental protection: The rapid and non-destructive cap-
Pyrenean high altitude pine forests growing on acidic and basic soils abilities of XRF core scanners allows the efficient monitoring of reactor
was evaluated. By studying changes in tree age and diameter relative to vessels holding contaminated soil. During experimental runs, designed
environmental influences (e.g., climate warming), elemental variations to simulate natural and anthropogenic conditions, leaching using var-
in sapwood (SW) and heartwood (HW) during the pre-industrial ious agents was applied. The purpose was to infer how key pollutant
(1700–1849) and industrial (1850–2008) periods were investigated. elements (Ni, Cd, Pb) might behave in nature as a response to acidic
Tree-ring growth, wood density and relative element concentrations on precipitation or the release of acidic waste waters. The transport and
annual and seasonal scales (early-wood, EW; late-wood, LW) were subsequent re-deposition of pollutant elements were studied over time.
compared with climate variables (temperature and precipitation) and The study was performed by the Department of Bioenvironmental
volcanic eruptions in the 18th and 19th centuries. Differences were Systems Engineering at the National Taiwan University.
identified for many elements between SW and HW along the stem and Another recently developed method (Huang et al., 2019b) uses the
also between EW and LW within rings. Long-term positive and negative efficiency of XRF core scanners to measure multiple, sequentially de-
trends were observed for Ca and K, respectively, while Cl, P and S ployed sachets of ion exchange resins to assess environmental pollution
showed increasing trends over the industrial period. of natural waters. The procedure has the potential to become a standard
Mumiyo mounds: Hard waxy, laminated structures that form near method for large scale monitoring and detection of heavy metal pol-
the nests on ice-free rocky slopes of some sea birds are termed mumiyo lution in non-marine aqueous systems. The ion exchange resin sachets
mounds (Ainley et al., 2006). These represent long-standing accumu- are placed in the waters for a certain period of time, then retrieved and
lations of ejected stomach oil (a fishy, oily mixture used to feed young placed in sample holders, and then run through an XRF core scanner.
and regurgitated by some sea birds to defend their nests from other The amount of heavy metals taken up by the resin is directly propor-
marauding sea birds). In some cases, evidence is found that these ejecta tional to the concentration in the water. The XRF core-scanner results
form laminated accumulations that span millennia. A common pro- can be used to identify and quantify sources and distribution of heavy
ducer of mumiyo mounds is the Snow Petrel (Pagodroma nivea), a metal pollution in, for example, river networks and irrigation channel
common Southern Ocean sea bird, that feeds over pack-ice covered seas systems. Other potential applications include long term monitoring of
and nests on ice-free rocky slope on the Antarctic margin. The food water quality of aquacultures, industrial waste water drainage systems,
available to these birds generally needs to be found within a day's flying as well as natural river catchments. The low cost and easy handling of
and is dominated by either krill or fish which in turn depend on sea ice the resin samples makes them suitable for large-scale citizen science
cover. The relative bias in diet impacts on the elemental chemistry of projects such as engaging local schools to participate in the monitoring
the mumiyo. Geochemical and 14C dating studies of some deposits show of local surface water quality.
that many generations of P. nivea must have re-occupied the same ice- Mineral exploration: XRF core scanning is now established as an
free nesting sites for as long as 35,000 years (Thor and Low, 2011; Berg efficient non-destructive tool in the international mining industry to
et al., 2019). Combining Itrax elemental studies with stable isotope and rapidly extract elemental information from rock core sections and to
biomarker analyses of profiles through mumiyo mounds indicate food inform metalliferous exploration strategies (Sjöqvist et al., 2015). The
web and Antarctic climate fluctuations over the time-scale of their ac- recently developed Minalyze Core Scanner combines rapid XRF core
cumulation (Berg et al., 2019). scanning with advanced topographic mapping and high resolution
imagery to enable three-dimensional visualization of core features such
3. Other applications as faults, veins, and geological structures superimposed on geochemical
data obtained from XRF scanning. As matrix effects in lithified core
Aside from sedimentological studies and related applications material typically are smaller than for unlithified, wet marine and la-
(Figs. 1–5, Table 1), high resolution XRF scanning technology has been custrine sediments, it is sufficient for a small number of reference ma-
applied in other fields such as forensic geochemistry, environmental terials to be employed to convert data from semi-quantitative to
remediation and protection as well as mineral exploration. quantitative.
Forensic geochemistry: Geochemical data used to support legal
investigations of illegal environmental pollution fall into the realm of 4. Conclusions
environmental or geochemical forensics. An example of such an in-
vestigation involving sediment core scanning is the Augusta Harbour XRF sediment core scanners have become crucial analytical tools in
(Sicily) study. This highly polluted harbour was the subject of a legal the environmental geosciences providing proxy indicators of past en-
investigation to establish whether companies responsible for causing vironmental change. Increasingly these scanners are now being applied
significant heavy metal pollution (particularly Hg, Cu, Ba etc) could be in other scientific areas. Their key attributes are the ability to auto-
identified and made accountable for the cost of environmental re- matically acquire high resolution elemental profiles rapidly and non-
mediation. High resolution XRF core scanning data and radionuclide destructively. Most high resolution XRF core scanners have been de-
dating contributed key scientific evidence to assist in the legal process signed to scan along the length of metre long cores (1D) but smaller x-y-
(Croudace et al., 2015). z (2D) systems that allow elemental mapping at high spatial resolution
Environmental remediation: Remediation of contaminated soil have become important complementary systems.
(e.g. radionuclides, heavy metals) either in-situ or in engineered tanks is High resolution XRF core scanners offer many opportunities for
an important practice. One method investigated used a low voltage generating large amounts of data and users need to beware the temp-
electrokinetic process to drive electrolytic reactions in soil con- tation of over-interpreting their data. A proper appreciation of the
taminated by U and Pu from a nuclear weapons site in the southern UK variabilities and controls on elemental excitation efficiencies by X-rays,
(Agnew et al., 2011). Pilot-scale experimental tanks filled with the the impact of tube ageing, sample matrix, grain size and low Z elements
contaminated soil were subjected to the electrokinetic process for two on sensitivity as well as an understanding of the typical geochemical
weeks. The tanks were then scanned using an XRF core scanner to abundances of elements in the system studied are essential pre-re-
evaluate the extent of migration and distribution of elements through quisites for instrument users. In most cases, users should aim to use
the treated soil. The experiment allowed a mechanistic understanding calibrated instrumental data to validate elemental profiles or ratios
of element mobility and rates of migration to be developed. The based on initial count-rate data. Applying such calibrations should be
leaching and accumulation processes of heavy metals in soils require seen as crucial to provide robust sediment records. The importance of
both temporal and spatial variations in metal concentrations in the test visualising closed-sum data using ratios and log ratios should also be

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I.W. Croudace, et al. Quaternary International 514 (2019) 5–15

understood by users. Well established elemental indicators are widely Croudace, I.W., Romano, E., Rothwell, R.G., Bergamin, L., 2015. Application of micro-
used by the community (e.g. Ti variations as a proxy for terrigenous XRF core scanners to environmental forensic investigations: a case study of polluted
harbour sediment from Augusta Bay, Sicily. In: In: Croudace, I.W., Rothwell, R.G.
minerogenic matter) and a few XRF-derived ratios (inc/coh as a proxy (Eds.), Micro-XRF Studies of Sediment Cores (Springer Series-Developments in
for organic matter; Fe/Mn as a proxy for redox conditions; Rb/Sr as a Palaeoenvironmental Research, vol. 17.
grain-size proxy) but a critical appraisal and justification on a case by Croudace, I.W., Rothwell, R.G. (Eds.), 2015. XRF Studies of Sediment Cores. Springer,
DPER Series 17, Dordrecht.
case basis is always necessary. Croudace, I.W., Teasdale, P.A., Cundy, A.B., 2019a. 200-year industrial archaeological
Investigators using μ-XRF core scanners require an in-depth record preserved in an Isle of Man saltmarsh sediment sequence: Itrax and radio-
knowledge of the systems under evaluation. For example, in a lacustrine chronological evidence. Quat. Int. http://dx.doi.org/10.1016/j.quaint.2018.09.045.
Croudace, I.W., Löwemark, L., Tjallingii, R., Zolitschka, B., 2019b. Current perspectives
system knowledge of the catchments geology, hydrological conditions, on the capabilities of high resolution XRF core scanners. Quat. Int. https://doi.org/
land use patterns and the overall climatic realities are required to 10.1016/j.quaint.2019.04.002.
properly interpret elemental profile data. Good time control is in- Czymzik, M., Haltia, E., Saarni, S., Saarinen, T., Brauer, A., 2018. Differential North
Atlantic control of winter hydroclimate in late Holocene varved sediments of Lake
variably required in many studies and can be inferred from micro-
Kortejärvi, eastern Finland. Boreas 47, 926–937.
textural and geochemical properties in some cases or from radiometric Davies, S.J., Lamb, H.F., Roberts, S.J., 2015. In: Croudace, I.W., Rothwell, R.G. (Eds.),
and other means. Long environmental reconstructions with annual re- Micro-XRF Core Scanning in Palaeolimnology: Recent Developments. Springer Series
solution also make proper use of the technical capabilities of XRF core- DPER 17; Springer, Dordrecht.
Dulski, P., Brauer, A., Mangili, C., 2015. Combined μ-XRF and microfacies techniques for
scanning. lake sediment analyses. In: Croudace, I.W., Rothwell, R.G. (Eds.), Micro-XRF Studies
of Sediment Cores. Springer Science and Business Media, Dordrecht, pp. 325–349.
Acknowledgements Ellis, B., Grant, K., Mallela, J., Abram, N., 2019. Is XRF core scanning a viable method for
coral palaeoclimate temperature reconstructions? Quat. Int. https://doi.org/10.
1016/j.quaint.2018.11.044.
As Guest Editors for the Special Issue on XRF Core Scanners we are Fielding, J.J., Kemp, A.E.S., Bull, J.M., Cotterill, C.J., Pearce, R.B., Avery, R.S., Langdon,
grateful to the National Taiwan University and its academic staff who P.G., Croudace, I.W., 2018. Palaeoseismology from microfabric and geochemical
analysis of lacustrine sediments, Windermere, UK. J. Geol. Soc. 175, 903–914.
generously and enthusiastically hosted and organised the International Fielding, J.J., Croudace, I.W., Kemp, A.E.S., Pearce, R.B., Bull, J.M., Cotterill, C.J.,
XRF Core Scanning 2017 Conference and Field Excursion held in Langdon, P.G., Avery, R., 2019. A 200 year history of lake pollution, eutrophication
Taipei (March 2017). Particular thanks go to Jyh-Jaan Steven Huang and partial recovery from Windermere, UK, reconstructed from geochemistry and
sediment fabric analysis (in preparation).
for his role in the organisation. The meeting stimulated many of the Fritz, M., Unkel, I., Lenz, J., Gajewski, K., Frenzel, P., Paquette, N., Lantuit, H., Körte, L.,
contributions found in the QI Special Issue. We also appreciate the Wetterich, S., 2018. Regional environmental change versus local signal preservation
support and/or technical data supplied by the instrument manu- in Holocene thermokarst lake sediments: a case study from Herschel Island, Yukon
(Canada). J. Paleolimnol. 60, 77–96.
facturers. Finally, we thank the two anonymous reviewers who helped
Gracia, E., Lamarche, G., Nelson, H., Pantosti, D., 2013. Preface: marine and lake pa-
improve the manuscript. leoseismology. Nat. Hazard Earth Sys. 13, 3469–3478.
Gregory, B.R.B., Patterson, R.T., Reinhardt, E.G., Galloway, J.M., 2019. The iBox-FC: a
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