VOL. 22 NO.

3 (2010)

ARTICLE

Micro-XRF sediment core

scanners: important new tools
for the environmental and
earth sciences
Ian Croudace and Guy Rothwell
National Oceanography Centre, Southampton, S014 3ZH, UK. E-mail: [email protected]

Introduction to extract high-resolution profiles from ised as the Avaatech Core scanner (www.
Non-destructive, high resolution, sedi- sediment cores. Instruments offering avaatech.com).
ment core scanners incorporating X-ray resolutions of 1 cm were available at The SOC concept scanner required a
fluorescence (XRF) spectrometry are that time and researchers could only collaborative venture with a specialist
now widely used by sub-disciplines in realistically decipher cores down to XRF instrument designer and in 2002 an
the earth and environmental sciences centennial and decadal timescales. It arrangement was made with Swedish
and have revolutionised the analysis of became clear that resolutions of at least company Cox Analytical Systems (www.
sediment cores. These powerful instru- 0.1 mm were required to investigate coxsys.se). Cox Analytical Systems based
ments allow the cores to be analysed the variations found in laminated lake in Gothenburg were considered criti-
rapidly with virtually no sample prepa- and marine sediments which would cal partners in the venture as they had
ration. They can record along-core vari- then make it possible to identify events formerly produced a successful XRF
ations for many elements in the Periodic with an annual timescale (for example, microscope, albeit directed mostly at
Table from Al to U and detection limits References 1 and 2). Since they were the forensics market. The SOC–Cox
down to a few ppm can be achieved in developed, these instruments have collaboration proved highly fruitful and
favourable conditions depending on the become invaluable and super-efficient in April 2003 the prototype Itrax instru-
acquisition dwell time. tools for the geoscientist and they allow ment was delivered to the Southampton
Sediment cores from diverse marine non-destructive core investigations to Oceanography Centre. It provided
and lake environments are investigated proceed at unprecedented rates and contactless investigation of cores and
because they often retain excellent resolutions. included innovations such as a high flux
records relating to past processes such The origin of one of the leading core X-ray source, X-ray capillary waveguide, a
as climate change, extreme events (e.g., scanners, the Itrax, began in 2001 when positionable silicon drift detector (SDD),
floods, storms, landslides, earthquakes, the authors of this article, based at the optical and radiographic cameras, and
volcanoes, tsunamis etc.) and pollutant Southampton Oceanography Centre, an ultra-high precision sample drive
inputs. Temporal information can also SOC (now the National Oceanography platform. The instrument was launched
be obtained from elemental profiles in Centre), conceived the need for a new- to the scientific community at a confer-
some cases by identifying high-resolu- style sediment core scanner. 2 They ence held in Southampton in 2003 enti-
tion impulse events of known age (e.g., envisaged an integrated non-destructive tled New Techniques in Sediment Core
volcanic ash layers, storm surges, earth- instrument that would provide high-reso- Analysis that was published as a book in
quakes). Other elemental variations can lution elemental analysis along with opti- 2006.3 The two other key manufacturers
provide insights into climate change cal and X-radiographic imaging. Although also demonstrated their instruments and
oscillations, sediment provenance and two other core scanners existed at the capabilities at the meeting. At the current
marine circulations. time neither system offered such a critical time the Itrax and the Avaatech instru-
In the 1990s, the expanding interest combination. The most notable of these ments are the leading X-ray core scan-
in past climate change and the grow- early core scanners was the CORTEX ners and are installed in approximately
ing collections of scientific cores held developed at the Netherlands Institute equal numbers in leading international
in repositories demanded that fast for Sea Research in the late 1990s,1 scientific institutions throughout the USA,
multi-sensor scanners be developed which evolved and became commercial- Europe and Asia.

6 SPECTROSCOPYEUROPE www.spectroscopyeurope.com
© 2010 Thermo Fisher Scientific Inc. All rights reserved. Copyrights in and to the UV-Vis image are owned by a third party
and licensed for limited use only to Thermo Fisher Scientific by iStockphoto.

Evolutionary technology – revolutionary value.

Generations of researchers have relied on Thermo Scientific

UV-Visible spectrophotometers for their most critical analyses.
Our new family of UV-Vis and fluorescence systems builds on this
tradition, delivering performance and value for life science,
biochemical, pharmaceutical and material science applications.

Evolution Array™ UV-Vis spectrophotometer – fast, full spectrum

data for routine, research and high-throughput applications.

Lumina™ fluorescence spectrometer – delivers high resolution

and exceptional sensitivity for the most accurate measurements.
Complete UV-Vis and Fluorescence Solutions
Evolution™ 300/600 UV-Vis Series – robust optical design, Providing researchers and QC laboratories with
intuitive software, and the highest quality accessories for the reliable, accurate systems, software, and acces-
sories to meet their evolving application needs.
ultimate in analytical performance.

Discover more about the evolution at

www.thermoscientific.com/uv-vis.

FASTLINK / CIRCLE 003 FOR FURTHER INFORMATION

Moving science forward

 VOL. 22 NO. 3 (2010)

ARTICLE
Collection of cores
Sediment cores are collected, often at
considerable cost, from difficult locations
(oceans, enclosed seas, large lakes). A
range of devices are used to extract these
cores such as gravity corers, hydrau-
lic piston corers through to giant piston
corers. Given the cost and logistical diffi-
culty of collecting long cores, international
research groups collaborate to maximise
the scientific value and to ensure the tight Capillary wave-guide
management of the core material. Cores
are often split longitudinally into 1-metre
lengths or sub-sampled into U-channels
before being moisture-sealed and stored
in cold conditions in national core reposi-
tories (e.g., www.boscorf.org). Initial non-
destructive investigation is a crucial stage
before any further destructive sampling
is carried out. Such direct sub-sampling
is essential to obtain accurate data on
a range of crucial parameters such as
palaeotemperature and sediment age.
Palaeolimnologists have collected
many hundreds of metres of lake sedi-
ment cores and have become significant
users of high-resolution XRF core scan-
ners. Lake sediments are often organised
as fine-scale, seasonal layers that contain
valuable proxy records of past climate, see
Table 1. The significant increase in drilling
of large lakes, from the equator to the
poles, with their exceptional long-term Figure 1. Top: schematic of Itrax micro-XRF sediment core scanner showing the main compo-
records (as identified by International nents and the moveable SDD. Bottom: left, The Itrax with sample and measuring turret doors
Continental Scientific Drilling Programme, open; right, core loaded on the Itrax being prepared prior to a run.

Table 1. An illustration of why sediment cores are important. Selection of lakes holding exceptional climate records (XRF core scanners are playing a
crucial role in investigating the core material). Ma: 106 years; ka: 103 years.
Lake Baikal has never been glaciated in its 20–25 million year history and ongoing palaeoclimate research there is important because it offers unparal-
leled opportunities to recover a relatively high latitude record from an intra-continental setting that is isolated from marine influences. The sedimentary
record in Lake Baikal is extremely long and continuous with sedimentation rates varying from 1 cm/ky to 1 m/ky. The Baikal record therefore offers exciting
opportunities to study palaeoclimate change on a variety of temporal scales and resolutions. (Quote from Baikal Drilling Project, www.icdp-online.org.)

Lake Location Sediment thickness Age Origin

(core length recovered)
Lake Malawi Malawi (623 m in seven holes) >7 Ma Tectonic (East African Rift)
Lake Bosumtwi Ghana 1.8 km ~1 Ma Impact crater
5–8 km in some places
Lake Baikal Southern Siberia 20–25 Ma Tectonic (rift-related)
(>100 m)
Lake Suigetsu Japan (73.5 m) ~150 ka
Lake El’gygytgyn Siberian Arctic (>300 m) 3.6 Ma Impact crater from a 1 km asteroid
Lake Ohrid Albania/Macedonia (>700 m) 3–5 Ma Tectonic
Lake Tana Ethiopian highlands (>92 m) >15 ka Tectonic

8 SPECTROSCOPYEUROPE www.spectroscopyeurope.com
 VOL. 22 NO. 3 (2010)

ARTICLE
www.icdp-online.org) means that X-ray analysing sub-samples with wavelength- graphic images that have immense value
core scanners are in big demand. dispersive XRF (WD-XRF) spectroscopy or and provide additional insights that aid
inductively coupled plasma-optical emis- in interpreting the core data. The high-
Practical aspects of sion spectrometry (ICP-OES). Though resolution radiographic image, with a
analysing sediment cores accurate and sensitive, such analytical maximum individual pixel resolution of
In practice, sediment cores, when procedures were slow and could take ~20 μm, can reveal individual sedimen-
collected, can vary up to 12 cm diameter approximately two weeks of laborious tary layers (lamellae), grains, gas bubbles
and from several centimetres to several effort to process and analyse a metre of etc. and assist in the interpretation of
hundred metres in length. Long cores core. the elemental profiles. The radiographs
are normally cut to 1 m or 1.5 m lengths The Itrax (see Figure 1) represents a also allow counting of varves (seasonal
before being stored in cold conditions to highly successful exemplar of a modern couplets) that then allow variations in
prevent drying out until they are investi- XRF core scanner and is able to carry out annual sediment accumulation rate to
gated. Traditionally, in the 1980–1990s a 200 μm resolution scan of a 1 m core be determined.
the analysis of sediment cores was made for major elements in about six hours; Samples are normally measured as
through multiple investigations involving a with 5000 X-ray spectra being collected. longitudinally split cores covered with
combination of medium resolution scan- The analytical dwell-time used is selected 2 μm XRF film to inhibit drying out
ners (multi-sensor core loggers, MSCL) by the operator according to the element during measurement. Cores as long
and destructive sub-sampling at centi- precision required. If trace element data as 1.8 m can be analysed and, if trace
metre scale. The MSCLs do not provide are required then the analysis time would element data are being acquired, the
elemental data and such information, be extended by a factor of three to six. total analysis times may be as long as
when required, was often obtained by The Itrax also acquires optical and radio- 24–48 hours. The beam size of the

Small Spot Micro XRF Spectrometer

for Elemental Analysis
The new SPECTRO MIDEX is a winner for the
rapid and non-destructive analysis of widely
varying samples.
• Precise elemental analysis of a small measuring point

Line Scan •
•
Rapid element mapping of large surfaces
Spacious sample chamber for different sample types
• Large working distance for the analysis of
irregular sample surfaces
• Variable excitation spot size; from 200 μm
to more than 4 mm

Mapping
Discover more exciting details, visit SPECTRO’s
e-Learning center or contact us for additional
information about the new SPECTRO MIDEX at
Tel. +49.2821.892-2102,
[email protected] and
www.spectro.com/midex.

FASTLINK / CIRCLE 004 FOR FURTHER INFORMATION

www.spectroscopyeurope.com SPECTROSCOPYEUROPE 9
 VOL. 22 NO. 3 (2010)

ARTICLE
applications). This rectangular X-ray
beam both excites the sample for XRF
and also passes through the sample
to the radiographic camera. The radi-
ographic “slices” are re-assembled to
generate a 16-bit digital radiographic
image; there is a maximum 20 μm
pixel resolution.

Conventional XRF vs Itrax

Modern X-ray fluorescence analysis
systems [WD-XRF and energy dispersive
XRF (ED-XRF)] are well-established as
Figure 2. Itrax X-radiographic images: A—laminated sediment (200 mm length); B—a 25 mm offering fast, non-destructive and clean
detail (left of centre) from A; C—a Moroccan laminated sediment (3 cm in length) and D—North forms of analysis that can routinely
Sea layered sandstone reservoir rock (5 cm in length). All images are 20 mm wide and scanned deliver elemental concentration data
at a 200 μm step size. Such images are usually co-presented with elemental profiles to extract of high accuracy and reproducibility. In
useful information. conventional XRF systems incorporating
a vacuum, elements from Na to U can
be readily measured in solids and liquids
X-ray capillary waveguides fitted to (ideal for finely laminated lake sedi- with a precision better than ±0.5% in
the Itrax can be either 100 μm × 2 cm ments) or 200 μm × 2 cm (for general many cases. Limits of detection can be

Table 2. Comparison between the Itrax core scanner and a conventional WD-XRF.

Itrax core scanner Conventional WD-XRF

Typical X-ray tube used 3 kW Cr or Mo 4 kW Rh
X-ray detection system Silicon drift detector Gas flow, scintillation, sealed Xe
Practicable XRF scanning resolution ≥100 μm Bulk analysis
X-radiographic spatial resolution (selectable) ≥20 μm
Not possible
Dimension of radiographic slice 100 μm × 2 cm or 200 μm × 2 cm
Analysis area (using a 4 mm diameter entrance 0.004 cm2 (with a 100 μm capillary) ~10 cm2
window for the SDD) 0.008 cm2 (with a 200 μm capillary) (a bulk analysis technique)
High resolution optical image RGB digital camera Not available
Time to obtain a radiographic image for a 1 m core
~0.5 h Not possible
at 200 μm resolution
System software for X-ray spectral and data analysis Available Available
Sample treatment and preparation requirement Non-destructive analysis requiring Requires physical sampling of the core.
a flat exposed surface covered by Sampling is limited to about 5 mm
2 μm polypropylene film to inhibit resolution
drying
Sample analysis medium Air Vacuum or He
Time to acquire data for a 1 m core at 200 μm reso- ~2 h 10 working days in total (includes
lution for selected major and minor elements (K, sample preparation and running 100
Ca, Fe, Sr) samples at 1 cm resolution)
Time to acquire data for a 1 m core at 200 μm reso- ~48 h 10 working days in total (includes
lution (e.g. Al. Si, S, Cl, K, Ca, Fe, As, Pb, Zn, Br, Rb, sample preparation and running 100
Sr, Zr) for selected major and trace elements samples at 1 cm resolution)
Nominal detection limits (100 s); see Table 3 ~100 ppm for Ti 10 ppm for Ti
Dependent on tube anode, excitation condi- ~10 ppm for Sr 0.5 ppm for Sr
tions, count-time, atomic number and sample
composition

10 SPECTROSCOPYEUROPE www.spectroscopyeurope.com
 VOL. 22 NO. 3 (2010)

ARTICLE
Table 3. Examples of some application areas.

Study of cyclic chemical (and mineralogical) changes in marine and lake sediment to infer climate change
Study of laminated lake sediments from arctic and alpine lakes to provide climate variability data over decadal to centennial times-
cales
Counting of varves and chemical cycles in lake sediment to infer variations in sediment accumulation rate and environmental
change
Identification of volcanic ash horizons in lake sediment to date layers (using elemental variations and radiographic images)
Identification of elemental spikes and other compositional changes to indicate abrupt/extreme events such as floods, storms, earth-
quakes, landslides etc.
Studies of redox-driven, elemental redistribution processes
Determination of sedimentary and tectonic processes in marine basins
Identification of records of heavy metal pollution in coastal, estuarine and lake sediment
Environmental forensics

Sapropel
Sapropel –S1: SiSiint. Ba/Ti
Ba/Ti K/Ti
K/Ti Br/Cl
Br/Cl S/Cl
S/Cl As.As Cu/Ti
Cu/Ti Mn/Ti
Mn/Ti Fe/Ti
Fe/Ti Sr/Ca
Sr/Ca
- S1

Figure 3. Itrax optical, radiographic and elemental and element ratio profiles for eastern Mediterranean core section containing a sapropel (shown
highlighted; 800 mm scanned in 20 hours). The upper part of the sapropel (stippled in grey) was oxidised after emplacement and is associated with
element redistributions.

as low as 0.1 ppm for some elements tions. Sediments contained in cores are possible to exploit the rapid analysis
but are more typically in the low ppm certainly not ideal as they are frequently capability of core scanners by “contain-
range for environmental/geological long, wet and commonly organised in erising” them for deployment on sea-
materials. Virtually any sample type layers of varying thickness and grain going vessels.
can be run (pressed powders, glasses, size. Core scanners are specifically The Itrax was designed with several
ceramics, metals, rock, coal, plastic, oil designed to be able to deal with the innovations to efficiently examine sedi-
etc.). Conventional laboratory systems challenges of non-destructively analys- ment cores from all environments (see
are designed for small samples that ing sediments in their relatively unpre- Table 2), including water-cooled 3 kW
can be prepared under ideal condi- pared and almost natural state. It is also X-ray tubes (Mo and Cr anode options)

www.spectroscopyeurope.com SPECTROSCOPYEUROPE 11
 VOL. 22 NO. 3 (2010)

ARTICLE
CaCa Sr
Sr K
K Rb
Rb Fe
Fe Mn
Mn Zn
Zn Pb
Pb Cu
Cu Mo
MoIncoh
incoh.

Figure 4. Itrax optical, radiographic and element profiles for Newport Deep (Severn estuary) core section (500 mm scanned in 15 h). The diagonal
ornament highlights the zone of heavy metal pollution. The Mo incoherent radiation (Compton scatter radiation) is a good indicator of mean atomic
number and is used to assess matrix variations.

Figure 5. An X-radiograph image through “Ice Age” varved lake sediments from Scotland. The yellow line shows the correlation of the Ca variation
with denser sediment layers demonstrating the emerging geochronology role of the Itrax.

coupled to a flat-beam, X-ray capillary Case study I—Mediterranean in Mediterranean sediments and is
wave-guide, SDD detector to ensure sapropelic sediments as known as a result of studying hundreds
good energy resolution at high count- indicators of past climate of metres of cored sediment collected at
rates, 20 μm resolution digital X-ray radi- change different locations by international marine
ographic camera (16-bit range), see, The Mediterranean Sea has been a expeditions. Evidence for these cyclical
for example, Figure 2 and a ultra-high critical study area for oceanographers changes is recorded in the cores visu-
precision motorised sample transport because it holds a sensitive record of ally as dark, organic-rich sediment called
system. past climate. Its small size and partial sapropels that formed during periods
isolation from the global oceans means of wetter climate. The sapropels repre-
that past records of altering climate are sent the deposited remnants of phyto-
Application areas and magnified and can be used to under- plankton blooms that grew in response
case studies stand global changes. to enhanced nutrients supplied by the
Some typical application areas are Changing climate cycles over the last increased run-off from the Nile. Typical
summarised in Table 3 and Figures 3–5. 10,000 years and beyond are recorded deep-sea sediments contain little organic

12 SPECTROSCOPYEUROPE www.spectroscopyeurope.com
 VOL. 22 NO. 3 (2010)

ARTICLE
45
diverse sources such as coal extraction/ growing demand from the lake scientific
40
processing, Pb–Zn smelters, steel plants, community that require many hundreds
incinerators, paper mills, nuclear power of metres of cores to be scanned for
35

stations etc. (see Figure 4). Rapid and radiographic and elemental profiles. With
non-destructive scanning of Newport the need to increase performance and
30

25
Deep submarine sediment cores, along capability it is fortunate that the current
20
with other investigations, allows clear instrument platforms lend themselves to
15 records to be established of changing enhancements through the addition of
10
pollutant inputs such as heavy metals. new sensors, by increasing sensitivity for
5
the low z elements and by offering the
Summary and future potential of accelerating core analysis.
developments
0

1990 1994 1998 2002 2006 2010

For several decades oceanogra- References

Figure 6. A revolution in the analysis of phers investigating marine cores have 1. J.H.F. Jansen, S.J. Van der Gaast, B.
cores as shown by the number of publica-
used a variety of low-medium resolu- Koster and A.J. Vaars, “CORTEX, a
tions citing the use of an X-ray core scanner.
tion (centimetre-scale) scanning tools. shipboard XRF-scanner for element
These devices persist as general scan- analyses in split sediment cores”,
ners for the oceanographic community Marine Geology 151, 143–153
carbon and therefore the sapropel layers, but the “tool box” has been significantly (1998).
containing elevated carbon, stand out augmented by the new generation, 2. I.W. Croudace, A. Rindby and R.G.
clearly from their enclosing creamy high-efficiency, high-resolution X-ray Rothwell, “Itrax: description and eval-
coloured mud. core scanners. Judging from the signifi- uation of a new multi-function X-ray
Sapropels are geochemically distinctive cant increase in publications, from 2003 core scanner”, in New Techniques in
and contain enhanced concentrations of onwards (Figure 6), it is clear that inte- Sediment Core Analysis, Ed by R.G.
carbon and redox-sensitive elements grated, multi-sensor X-ray core scanners Rothwell. Geological Society, London,
such as S, Fe, As, Mo and V, see Figure have revolutionised rapid, non-destruc- Special Publication 267, pp. 51–63
3. Other elements such as Ba, Cu, Ni, Pb tive, high-resolution analysis of sedi- (2006).
and Zn are also enriched and core-scan- ment cores for all user communities. The 3. R.G. Rothwell (Ed.), New Techniques
ner-derived elemental profiles provide rapidly acquired data they generate serve in Sediment Core Analysis. Geological
several important insights into the direc- to guide more specific scientific studies. Society, London, Special Publication
tion of movement of elements during There is also a considerable and ever 267 (2006).
diagenesis, the oxidation of the sapro-
pel and processes that lead to narrow
zones of unusual element enrichments
like Cu. Complete X-Ray Spectrometer
Case study II—coastal
pollution/environmental INCLUDES
forensics 1 X-Ray Detector and Preamplifier
Estuaries and coastal embayments are
2 Digital Pulse Processor and MCA
often sites with long legacies of industri-
alisation (e.g., the rivers Severn, Mersey 3 Power Supply
and Humber in the UK, Bilbao and
Augusta Bay, Sicily). Establishing records
of pollution in such areas is necessary Available with your choice of Si-PIN Detectors or Silicon Drift Detectors
from various legal standpoints (national Si-PIN Spectrum SDD Spectrum
NEW - SUPER SDD
5.9 5.9
and international regulations) and ongo- keV keV
55
Fe 55
Fe
ing work shows it is possible to identify
149 eV FWHM 127 eV FWHM
Counts

Counts

individual polluters through careful multi-

6 mm2 x 500 μm 25 mm2 x 500 μm
faceted investigations that include using 25.6 μs peaking time 6.4 11.2 μs peaking time 6.4
keV keV
core scanners. OEM’s #1 Choice P/B Ratio: 6200/1 P/B Ratio: 8000/1
The Newport Deep (Severn Estuary) for XRF Energy (keV) Energy (keV)

exemplifies an area having a 100+ years

Visit www.amptek.com for complete specifications
industrial history and submarine cores
AMPTEK Inc. [email protected] www.amptek.com
have been found to contain variable
amounts (modest) of pollution from FASTLINK / CIRCLE 005 FOR FURTHER INFORMATION

www.spectroscopyeurope.com SPECTROSCOPYEUROPE 13