754 RADIOLARIA
Rasmussen, B., 2005. Evidence for pervasive petroleum genera-
tion and migration in 3.2 and 2.63 Ga shales. Geology, 33,
497–500.
Rasmussen, B., Glover, J. E., and Foster, C. B., 1993. Polymerisa-
tion of hydrocarbons by radioactive minerals in sedimentary
rocks: diagenetic and economic significance, In Landais, P.
(ed.), Bitumens in Ore Deposits. Berlin: Springer, pp. 490–509.
Savary, V., and Pagel, M., 1997. The effects of water radiolysis on
local redox conditions in the Oklo, Gabon, natural fission
reactors 10 and 16. Geochimica Cosmochimca Acta, 61,
4479–4494.
Cross-references
Biosignatures in Rocks
Carbon (Organic, Degradation)
Extreme Environments
Hydrogen
Ores, Microbial Precipitation and Oxidation
Origin of Life
RADIOLARIA
Volker Thiel
University of Göttingen, Göttingen, Germany
Radiolaria are planktonic marine protozoa showing unicel-
lular organization and heterotrophic mode of nutrition.
They build tests varying in shape from simple scattered
spicules to highly ornated geometric-shaped shells (Adl
et al., 2005). Sizes usually range from hundredths to tenths
of millimeters. The tests are made from opal (hydrated sil-
ica), some from silica and organic material, and some from
strontium sulphate. The name “Radiolaria” derives from the
marked radial skeletal spines that characterize many spe-
cies. Radiolarians are known from the very beginning of
the Paleozoic (early Cambrian of the Yangtze Platform;
Braun et al., 2007). They are important index fossils
and may significantly contribute to marine silica-rich sedi-
ments. Radiolarian cherts (radiolarites), a variety of chert
(see entry Cherts) composed of radiolarian remains, indi-
cate deep water deposition at depths below which siliceous
sediments are stable, but carbonates are dissolved. See entry
“Protozoa (Heterotroph, Eukaryotic)” for further reading.
Bibliography
Adl, S. M., Simpson, A. G. B., Farmer, M. A., Anderson, R. A.,
Anderson, O. R., Barta, J. R., Bowser, S. S., Brugerolle, G.,
Fensome, R. A., Fredericq, S., James, T. Y., Karpov, S., Kugrens,
P., Krug, J., Lane, C. E., Lewis, L. A., Lodge, J., Lynn, D. H.,
Mann, D. G., McCourt, R. M., Mendoza, L., Moestrup, Ø.,
Mozley-Standrisge, S. E., Nerad, T. A., Shearer, C. A., Smirnov,
A. V., Spiegel, F. W., and Taylor, M. F. J. R., 2005. The new
higher level classification of eukaryotes with emphasis on the
taxonomy of protists. Journal of Eukaryotic Microbiology, 52,
399–451.
Braun, A., Chen, J., Waloszek, D., Maas, A., 2007. First Early Cam-
brian Radiolaria. Geological Society, London, Special Publica-
tions, 286, 143–149.
RAMAN MICROSCOPY (CONFOCAL)
Jan Toporski1, Thomas Dieing1, Christine Heim2
1
Wissenschaftliche Instrumente und Technologie GmbH,
Ulm, Germany
2
University of Göttingen, Göttingen, Germany
Synonyms
Confocal Raman imaging (CRI)
Definition
Confocal Raman microscopy (CRM) is a nondestructive
analytical technique that merges Raman spectroscopy
and confocal microscopy for the visualization of molecu-
lar information over a defined sample area.
Introduction
Raman spectroscopy is well suited for studies in mineral-
ogy and petrography, as it provides nondestructive
mineral identification fast and with high specificity. In addi-
tion, Raman spectroscopy allows the characterization of
complex organic materials, which makes it particularly use-
ful in biogeoscience applications (Hild et al., 2008). This
technique has long been applied in geosciences, for exam-
ple, for the identification and characterization of minerals,
or in the observation of mineral phase transitions in high
and ultra-high pressure/temperature experiments. In most
cases, measurements have been carried out in a micro-
Raman set up, i.e., information was obtained from single
or multiple points of interest on a sample. This way, little
detail on the spatial distribution and association of compo-
nents or mineral phases, or chemical variation could be
observed, even though this information may contribute sig-
nificantly to the understanding of a sample’s complexity.
By means of CRM, such sample characteristics can be
evaluated from large scale scans in the centimeter range
to the finest detail with sub-micron resolution. Modern
confocal Raman microscopes allow for such measure-
ments with very high sensitivity and spatial as well as
spectral resolution. CRM is a tool that not only provides
complementary information to data obtained by e.g., elec-
tron microprobe (EMP), energy dispersive x-ray analysis
(EDX), or secondary ion mass spectrometry (SIMS). In
addition to the quantitative and semiquantitative elemental
and/or isotopic data acquired by these techniques, CRM
contributes the visualization of the distribution for molec-
ular information over a defined sample area. Furthermore,
considering that most geomaterials are transparent from
the UV (NUV) to VIS and NIR to some degree, this infor-
mation can be obtained three dimensionally due to the
confocal set-up of the microscopes. The following discus-
sion provides background information and examples that
shall serve to highlight some key analytical features of this
technique for applications in geosciences. A recent and
comprehensive summary on the application of CRM in
Geoscience can be found in Fries and Steele (2010).
 RAMAN MICROSCOPY (CONFOCAL)
Principles of confocal Raman microscopy
CRM essentially merges two techniques into one. First,
Raman spectroscopy, which allows nondestructive chem-
ical analysis; secondly, Confocal microscopy which
allows the user to examine samples with diffraction-
limited resolution as well as to obtain three-dimensional
information from the sample. The theory behind these
two techniques will be explained in the following sections,
followed by an illustration of how images with chemical
sensitivity can be obtained using this combination of
techniques.
Raman spectroscopy
When light of a certain wavelength interacts with
a molecule, most photons are elastically scattered and
therefore have the same energy as the incident photons.
However, a very small fraction (approximately 1 in 106–
107 photons) is in elastically scattered, which means that
the energy of the scattered photon is different than the
energy of the incident photon.
This is called the “Raman effect”, and it was discovered
by Sir Chandrasekhara Raman in 1928 (Raman, 1928;
Raman and Krishnan, 1928). Unlike today, he used
a filtered beam of sunlight as an excitation source and
his eye as a detector for the frequency shifted light. This
was long before the development of the first laser by
Maiman in 1960. Raman was awarded the Nobel Prize
in 1930 for this discovery. The theory behind the Raman
effect was derived five years earlier by Smekal (1923).
The tremendous importance of the Raman effect lies in
the fact that the energy shift between the exciting and
the Raman scattered photon is caused by the excitation
(or annihilation) of a molecular vibration. This energy
shift is thus characteristic and therefore a fingerprint for
the type and coordination of the molecules involved in
the scattering process.
Raman Microscopy (Confocal), Figure 1 Energy level diagram for Raman scattering.
755
Theory
The following section shall provide some basic descrip-
tions and definitions relevant to Raman spectroscopy.
Readers interested in a detailed theoretical background
are referred to Ibach and Lüth (2003).
In quantum mechanics, the scattering process between
a photon and a molecule is described as an excitation of
a molecule to a virtual state lower in energy than a real
electronic state and the (nearly immediate) de-excitation.
The lifetime of the virtual state is extremely short and
can be calculated by the Heisenberg uncertainty relation:
h
Dt  DE  (1)
2
With typical photon energies of 1–2 eV, the lifetime of the
excited state is only about 10–15 s. After this extremely
short time, the molecule falls back either to the vibrational
ground state or to an excited state (Figure 1). When the ini-
tial and final states are identical, the process is called Ray-
leigh scattering.
If the initial state is the ground and the final state
a higher vibrational level, the process is called Stokes scat-
tering, if the initial state is energetically higher than the
final state, this is referred to as Anti-Stokes scattering.
The difference in energy between the incident and the
Raman scattered photon is equal to the energy of
a vibration quantum of the scattering molecule. A plot of
intensity of scattered light versus energy difference is
called a Raman spectrum.
The position of a Raman line is usually given in relative
wavenumbers (1/cm), which is the energy shift relative to
the excitation line:
1 1
n¼  (2)
lincident lscattered
756 RAMAN MICROSCOPY (CONFOCAL)
Raman Microscopy (Confocal), Figure 2 Typical Raman
Spectrum.
lincident and lscattered are the wavelengths of the incident
and Raman scattered photons, respectively.
As can be seen in Figure 2, a typical Raman spectrum is
symmetric to the Rayleigh line and the Anti-Stokes lines
are lower in intensity than the Stokes shifted lines.
From classical scattering theory, one finds that the
intensity I of scattered light is proportional to the 4th power
of the excitation frequency
I / n4 (3)
Exciting a sample with blue light at 400 nm would there-
fore give a 16 times higher Raman signal than using red
light at 800 nm. The problem of using blue (or UV)
excitation light, however, is fluorescence. Many samples
show fluorescence when they are excited with blue light
and Raman emissions are extremely weak compared
to fluorescence. If a sample shows significant fluores-
cence, obtaining a Raman spectrum is usually impossible
because the fluorescence background covers the Raman
signal. In the red (or even IR) region of the spectrum, fluo-
rescence is usually not a problem, but the excitation inten-
sity must be much higher (I / n4). Another problem is that
Silicon detectors cannot be used above 1100 nm (band
gap energy of Si: 1.12 eV). Other IR detectors (such as
InGaAs) show much more thermal and readout noise than
silicon and photon counting detectors with low dark count
rates are not available yet. In real experiments one must
always find a compromise between detection efficiency
and excitation power.
Confocal microscopy
Confocal microscopy allows the user to obtain three-
dimensional information from the sample. It requires
a point source (usually a laser), which is focused onto
the sample. The reflected light (Rayleigh, Raman, fluores-
cence) is collected with the same objective and focused
through a pinhole at the front of the detector (Figure 3).
This ensures that only light from the image focal plane
Raman Microscopy (Confocal), Figure 3 Principal setup of
a confocal microscope.
can reach the detector, which greatly increases image con-
trast and with the proper selection of pinhole size, slightly
pffiffiffi
increases resolution (max. gain in resolution: factor 2).
As can be seen from Figure 3, light originating from
planes other than the focal plane will be out of focus at
the pinhole. Therefore, its contribution to the detected sig-
nal is strongly reduced. Additionally, by changing the dis-
tance between the objective and the sample, the focal
plane is moved within the sample thus allowing depth pro-
filing or even 3D imaging (Wilson, 1990).
Pinhole size
The choice of the pinhole size is important because on one
hand the signal should be as high as possible, while on the
other hand the image should be as confocal as possible
(highest depth resolution). To take full advantage of the
lateral and depth resolution possible with confocal micros-
copy, the size of the pinhole should be adjusted and opti-
mized. To obtain the highest lateral resolution, the pinhole
size should be below vP = 0.5. (The variable n describes
the position in optical
pffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi coordinates and can be derived from
v ¼ 2p
l x2 þ y2 sin a. Here l is the excitation wavelength, x
and y the sample coordinates in the focal plane and a half of
the aperture angle. vP is the radius of the pinhole in optical
coordinates when assuming a magnification of 1.) How-
ever, at this point the transmission through the pinhole is
only 5% of the scattered intensity. In practice, the pinhole
size can be up to vP = 4 without significantly changing depth
resolution and up to vP = 2 without significantly changing
lateral resolution. It can be shown that if vP > 4, the
 RAMAN MICROSCOPY (CONFOCAL)
resolution of at least a conventional microscope remains.
This is due to the fact that for a large detector the resolution
is always determined by the diameter of the excitation
laser spot. Only the depth resolution (and therefore contrast
for a thick sample) is lost in this case. In most cases,
a pinhole size of vP = 2.5 is a good compromise since good
depth resolution is maintained while >75% of the light still
reaches the detector (see Figure 4).
For the experiment, the relation
M pd0
 (4)
NA vP l
should be fulfilled, where M is the magnification, d0 the
diameter of the pinhole, and NA the numerical aperture
of the objective. The left side of this equation is defined
by the objective and the beam path and the right side
by the wavelength, the pinhole size itself and vP. If, for
example, an objective with a magnification of 100 and
a numerical aperture of 0.9 is used at a wavelength of
532 nm the optimum pinhole size would be 50 μm for
maximum depth resolution and 10 μm for maximum lat-
eral resolution.
In actual experiments, one usually has to find a
compromise between the highest resolution and collec-
tion efficiency. This is very important in CRM because
Raman is an extremely weak effect. If a very small pin-
hole is used, the collection efficiency is strongly reduced
(Figure 4).
This graphic shows the intensity on the detector as
a function of pinhole size, normalized to the total intensity
in the image plane. One can see that the collection effi-
ciency is about 75% for maximum depth resolution
(vP = 2.5), but only 6% for maximum lateral resolution
(vP = 0.5).
Using the appropriate pinhole size, it is therefore
always possible to obtain maximum depth resolution.
Raman Microscopy (Confocal), Figure 4 Collection efficiency
as a function of the pinhole size normalized to the total power in
the image plane.
757
Resolution
For sample scanning systems, the magnification printed
on the objective used is of minor importance. The maxi-
mum scan range achievable by the sample scanner deter-
mines the maximum image size, independent of the
magnification of the objective. The more important prop-
erty of the objective is the numerical aperture, which
together with the excitation wavelength determines the lat-
eral resolution of the objective. The magnification is only
important for the choice of the pinhole size.
The maximum resolution of a classical microscope is
given by the Rayleigh criterion
0:61l
Dx ¼ (5)
NA
where Dx is the smallest distance between two point
objects that will appear separated in the image plane, l is
the wavelength of the excitation light, and NA is the
numerical aperture of the microscope objective. In this
case, the image of two point objects will appear just
seperated (Figure 5).
Confocal Raman microscopy
Instrumentation considerations
When combining confocal microscopy and Raman spec-
troscopy the main challenge is the low signal intensity.
As mentioned earlier, only one in about 106 –107 photons
is frequency shifted by the Raman effect. Thus the number
of photons reaching the detector is far less than is the case
for confocal or fluorescence microscopy. The two obvious
Raman Microscopy (Confocal), Figure 5 The intensity
distribution of two point sources which are separated by the
Rayleigh criterion.
758 RAMAN MICROSCOPY (CONFOCAL)
changes would be to increase the laser power and to
increase the integration time. However, there are limita-
tions to these possibilities as shown below:
(a) Laser power: If a power of only 1 mW from a 532 nm
laser is focused diffraction limited using a 100 air
objective with a NA of 0.9, the power density in the
illuminated spot is approximately 106 W/cm². These
levels are only possible because a single point is illu-
minated and the heat effectively dissipates in three
dimensions. Nevertheless, the maximum laser power
on the sample is therefore typically in the range of
1–20 mW.
(b) Integration time: Increasing the integration time will
increase the signal to noise ratio significantly. How-
ever, when CRM or mapping is applied, in which an
image is produced by recording a spectrum at every
image pixel, the integration time per spectrum needs
to be kept to a minimum. An integration time of only
1 s per spectrum will, when recording an image of
128  128 pixels, result in a total acquisition time
of about 4.5 h, which is an inconvenient time-span
for routine application.
Therefore, a system for CRM must be capable of obtaining
the Raman spectra with an acceptable signal-to-noise
ration in less than 50–100 ms. There are several parts of
a confocal Raman microscope which should be optimized
in order to allow such rapid data acquisition. These will be
discussed in the following:
Laser power: As described above, the maximum laser
power is limited and will heavily depend on the destruc-
tion and alteration threshold of the sample used.
Collection efficiency of the objective: Using objectives
with high numerical apertures maximizes the collection
efficiency since light from a larger solid angle is collected.
Throughput of the microscope: In order to enhance the
throughput of the microscope, the components used
within the beam path should be optimized and if possible
minimized since every passive optical element introduces
losses to the signal.
Efficiency of the grating: Highly efficient gratings with
the correct blazing angle for the excitation wavelength
should be used. As an example: a grating blazed at
500 nm will have an absolute efficiency of >60% up to
3000 rel.1/cm when using a 532 nm laser. Using the same
grating with a 785 nm laser will cause the efficiency to
drop to about 30% at 3000 rel.1/cm. The correct grating
blazed at 750 nm, however, shows an efficiency >60%
up to 3000 rel.1/cm when used with the 785 nm laser.
Efficiency of the spectrometer: There are a variety of spec-
trometers available on the market. While mirror-based
spectrometers can generally be used over a wide spectral
range, lens-based spectrometers often show a higher
throughput in the spectral range they are designed for.
Some lens-based spectrometers show a transmission at
532 nm of >60%. Spectrometers using a combination of
lenses and prisms or mirrors generaly have a significantly
lower throughput. Commercially available mirror-based
Czerny-Turner spectrometers only have a transmission
of about 30% at this wavelength.
Efficiency of the detector (CCD): Back-illuminated CCD
cameras show a quantum efficiency (QE) of >90% over
the entire spectral range of interest for 532 nm excitation.
Deep depletion back-illuminated CCD cameras, on the
other hand, show a QE of >90% for 785 nm excitation.
As a comparison, front-illuminated CCD cameras do not
exceed 55% quantum efficiency at any wavelength.
Additionally, the dark current of the cameras needs to
be minimized, which is achieved through efficient Peltier
cooling.
The readout noise is another limiting factor for small
signals. As the analog to digital (A/D) converter of all
cameras will add at least 5–10 electrons read-out noise
to the signal, any signal below approximately 5 electrons
will be lost in the noise. Additionally, the faster the A/D
converter is operating, the higher the read-out noise
will be. Electron-multiplying CCD (EM-CCD) cameras
can be used to overcome this problem. With these
cameras, the signal is amplified before the A/D conver-
sion, allowing the detection of even single photons
and reducing the necessary integration time down to
milliseconds.
Principle of operation
Confocal Raman microscopes generally provide a variety
of modes of operations. The most common are listed
below:
Collection of Raman spectra at selected sample areas
(single spectrum): Single Raman spectra can be collected
at user-selectable sample areas with integration times
ranging from ms to hours. The position of the collected
spectrum can normally be fully controlled in 3D.
A stable and precise positioning system must be included
in the instrument to ensure that the point of interest will
remain fixed under the excitation focus. This is very
important when spectra with longer integration times
for the best quality and signal to noise ratio are to be
obtained from extremely small sample volumes. For
example, using an oil immersion objective (NA 1.4) with
a 532 nm laser and the proper pinhole size allows the sam-
ple volume to be as small as 230  230  550 nm.
Collection of time series of Raman spectra at selected
sample areas (time spectrum): With this mode, time series
of Raman spectra can be obtained to analyze dynamic
sample properties. Thousands of spectra can be obtained
over time and analyzed with integration times ranging
from ms to tens of seconds.
Raman spectral imaging: In the Raman spectral imaging
mode, the sample is moved in X and Y and a full Raman
spectrum is obtained at every pixel measured. From these
data sets images of, e.g., the integrated intensity of various
bands can be generated. This is illustrated in the following
example.
A drill core section from the Äspö Hard Rock Labora-
tory, Sweden, was studied using the large area scan mode
CRM, aiming to characterize secondary fracture fillings in
 RAMAN MICROSCOPY (CONFOCAL) 759

a 1.8–1.4 billion years old diorite. The rock sample was
obtained from 450 m below the surface (kindly provided
by SKB, Swedish nuclear fuel and waste management).
This sample was examined with a 532 nm laser and
a 50 air objective (NA 0.55). The scan range was
8000 μm in X and 2000 μm in Y with 800  200 points
resolution. Each spectrum was integrated for 36 ms.
Figure 6 shows the characteristic spectra of calcite, fluorite
and quartz found in the sample. Integrating over, for
example, the area marked in green in Figure 6d results in
a single value for each of the 160,000 spectra. These spec-
tra can be displayed as a color-coded image as shown in
Figure 6a for quartz. Here, brighter values indicate
a higher integrated intensity of the quartz peak and the dis-
tribution of quartz can thus be obtained from this image.
Other spectra of the same scan show the characteristic fea-
tures of calcite or fluorite (Figure 6d). Using these, the cal-
cite (Figure 6b) and fluorite (Figure 6c) images can be
generated by using additional integral filters for the
marked regions. Other features of the spectra such as the
width of peaks or their position can also be evaluated by
applying the corresponding filters.
Further evaluation of the data allows the averaging of
similar spectra (for which a cluster analysis is often used)
and the subtraction of, for example, pure spectra from
mixed spectra to extract the spectra of the various compo-
nents (spectral de-mixing). These spectra can then be used
with the basis analysis, where each of the spectra recorded
are fitted with a linear combination of the basis spectra.
The result of such an analysis is one image for each basis

Raman Microscopy (Confocal), Figure 6 Spectra (d) and spectral images of quartz (a), calcite (b) and fluorite (c) recorded from the
diorite (a) and the fracture fillings (b and c). The data were recorded with a WITec alpha500R confocal Raman microscope.

Raman Microscopy (Confocal), Figure 7 DE-mixed and averaged spectra of the various components in the diorite and the adjacent
fracture minerals with the combined image on the left.
760 RAMAN MICROSCOPY (CONFOCAL)
Raman Microscopy (Confocal), Figure 8 Variations in the quartz phases due to changes in the crystallographic orientation, the
crystallinity, and the minerals.
spectra which can then be combined to generate a false
color image showing the distribution of all components
(Figure 7).
The color-coded Raman image and corresponding
spectra in Figure 7 allow for the general assignment of
mineral phases and their gross distribution over the
scanned area. In addition to the mineralogical context
information, organic components were identified, spec-
trally characterized and located, trapped between two gen-
erations of fracture fillings (the hydrothermal fluorite and
low temperature calcite, Tullborg et al., 2008; Wallin and
Petermann, 1999). This information allowed to infer at
which point in time a “deep biosphere” (see entry “Terres-
trial Deep Biosphere”) was active within these rocks.
Cluster analysis of the data set revealed discrete areas of
variation in the mineral phases (Figure 8). This is exempli-
fied by the quartz phase where four distinct regions were
identified based on variations in relative peak intensity.
Plotting regions of equal intensities of the quartz line at
ca. 200 cm1 shows discrete regions in the sample
corresponding to each of the identified spectra.
Quartz was selected as an example to highlight the fea-
sibility of color-coded Raman imaging to locate changes
of different mineral phases. These changes can likely be
attributed to different levels of crystallinity and crystal ori-
entation. It is noteworthy that the discrete phase colored
green only occurs at the interface with the plagioclase
minerals, which can be attributed to a secondary phase
due to the alteration and phase changes of the plagioclases.
Since SiO2-phases play an important role in biominer-
aliation, this example highlights the potential benefits con-
focal Raman imaging may provide in understanding the
processes and dynamics involved in these processes.
Summary
CRM is a nondestructive analytical technique that merges
Raman spectroscopy and confocal microscopy for the
visualization of molecular information over a defined
sample area. The technique makes use of the Raman effect
(Raman, 1928), i.e., the energy shift between exciting and
scattered photons which is caused by the excitation (or
annihilation) of a molecular vibration. This energy shift
is characteristic and therefore a fingerprint for the type
and coordination of the molecules involved. By means
of CRM, the spatial distribution and association of compo-
nents in the sample, including organics as well as min-
erals, can be evaluated from large scale scans in the
centimeter range to the finest detail with submicron reso-
lution. This way, CRM may contribute significantly to
the understanding of a sample’s chemical composition,
and complexity, in geological and geobiological studies.
Bibliography
Fries, M., and Steele, A., 2010. Raman spectroscopy and confocal
Raman imaging in mineralogy and petrography. In Dieing, T.,
Hollricher, O., and Toporski, J. (eds.), Confocal Raman Micros-
copy, Heidelberg: Springer.
Hild, S., Marti, O., and Ziegler, A., 2008. Spatial distribution of cal-
cite and amorphous calcium carbonate in the cuticle of the terres-
trial crustaceans Porcellio scaber and Armadillidium vulgare.
Journal of Structural Biology, 142, 100–108.
Ibach, H., and Lüth, H., 2003. Solid State Physics. An Introduction
to Principles of Materials Science, Berlin: Springer.
Raman, C., 1928. A new radiation. Indian Journal of Physics, 2,
387.
Raman, C., and Krishnan, K., 1928. A new type of secondary radi-
ation. Nature, 121, 501.
Smekal, A. G., 1923. Zur Quantentheorie der Dispersion, Naturwis-
senschaften, 11, 873–875.
 REDUCTION SPHEROIDS
Tullborg, E.-L., Drake, H., Sandström, B., 2008. Palaeohy-
drogeology: A method based on fracture mineral studies.
Applied Geochemistry, 23, 1881–1897.
Wallin, B., and Peterman, Z., 1999. Calcite fracture fillings as indi-
cators of palaeohydrology at Laxemar at the Äspö Hard Rock
Laboratory, southern Sweden. Applied Chemistry, 14, 953–962.
Wilson, T., 1990. Confocal Microscopy, London: Academic.
Cross-references
Biosignatures in Rocks
Terrestrial Deep Biosphere
REDUCTION SPHEROIDS
Beda A. Hofmann
Natural History Museum Bern, Bern, Switzerland
Synonyms
Bleaching haloes; Fish eyes; Radioactive concretions;
Radioactive nodules; Reduction mottling; Reduction
spots; Reduktionshöfe
Definition
Reduction spheroids are small-scale (diameter: few milli-
meters to maximum about 20 cm) spheroidal bleached
features in red-bed sediments characterized by the absence
of hematite and often containing a mineralized core
(center, Figure 1). Reduction spheroids result from local
chemical reduction of ferric iron and other elements. Host
rocks are marine and continental red beds and, more
rarely, altered, hematite-stained crystalline rocks.
Reduction spheroids have been described from many
occurrences in red beds of widely variable age worldwide:
Proterozoic of Canada (Tanton, 1948); Cambro-Silurian
marine red beds of the NE USA (Beutner and Charles,
1985); Devonian continental red beds of Scotland
(Parnell, 1985); Carboniferous continental red beds of
New Brunswick and Nova Scotia, Canada (Dyck and
McCorkell, 1983); Permian continental red beds of Ger-
many (Eichhoff and Reineck, 1952; Mempel, 1960;
Schreiter, 1930), Switzerland (Hofmann, 1990, 1991),
Southwest England (Harrison, 1970; Perutz, 1940), and
Cretaceous radiolarian cherts of Oman (Hofmann, 1991).
Reduction spheroids characteristically consist of
a spheroidal volume of rock from which hematite pigment
has been dissolved. Central dark cores often display pro-
nounced concentric zonation. The cores are strongly
enriched in numerous redox-sensitive elements (dominant
V, but also U, Se, As, Ni, Co, Cu, Ag, Au, PGE, and
others). The dominant mineral in reduction spheroid cores
is the vanadium mica roscoelite KV2AlSi3O10(OH)2. Ura-
ninite is another very common mineral, leading to an often
increased radioactivity of reduction spheroids (Figure 2).
Arsenides of Ni, Co, and Cu are also quite com-
mon. Radiometric dating of roscoelite, uraninite, and
761
Reduction Spheroids, Figure 1 Reduction spheroids in Triassic
red bed (marly dolomite), Chinle Formation, Paradox Valley,
Colorado, USA. These reduction spheroids are strongly enriched
in V, Cr, and Au. Diameter of larger reduction spheroid is 8 cm.
Pb-depleted haloes indicates late diagenetic ages
(Hofmann, 1990; Hofmann and Frei, 1996). Reduction
spheroids often occur in large numbers in red beds and
can constitute up to several vol% of the rock. Based on
textural evidence, such as fracture-bound occurrences
and mass-balance calculations (Hofmann, 1991), reduc-
tion spheroids cannot be due to detrital organic-rich parti-
cles. Instead, the formation must be due to locally
catalyzed redox reactions between a mobile reductant
and oxidants. The presence of isotopically light sulfides
in some cores (Hofmann, 1991), indicating diagenetic sul-
fate reduction, as well as the need for a local catalyst,
strongly favors a microbiological origin of reduction
spheroids. Reductants may be mobile hydrocarbons or
molecular hydrogen resulting from the radiolysis of pore
water (Hofmann, 1992). The formation of reduction spots
is most likely due to chemolithotrophic communities.
Kerogen-like organic matter is occasionally present at
some localities (Curiale et al., 1983; Parnell, 1985) but is
lacking at many other occurrences (Hofmann, 1993).
Conclusion
Reduction spheroids are very common in red-bed
sediments, and there are strong indications for an origin
due to redox reactions between a mobile reductant
and oxidized elements locally catalyzed by microbial
activity. Reduction spheroids are thus easily visible
features resulting from redox processes catalyzed by
a deep biosphere of sediments, and represent a type of
biosignature that may also be present in oxidized rocks
on Mars. Reduction spheroids contain small-scale