The volatile contents of the Apollo 15 lunar volcanic glasses

163 Pages·2009·2.65 MB·English

Goldschmidt Conference Abstracts 2009 A1139
The volatile contents of the Apollo 15 Experimental study of the system
lunar volcanic glasses U(VI) (cid:150) organic compounds (cid:150) H O as
2
a function of pH at 25(cid:176)C, 0.1 MPa
A.E. SAAL1, E.H. HAURI2, J.A. VAN ORMAN3
AND M.J. RUTHERFORD1 C. SABATER1, C. NGUYEN-TRUNG2, M. GRIV(cid:201)1,
1Brown University, Providence, RI 02192 E. POURTIER2, A. KIPROP2, L. RICHARD2 AND L. DURO1
(*correspondence: [email protected])
1Amphos21, Valldoreix, Spain
([email protected])
([email protected])
2DTM, Carnegie Institution of Washington, DC 20015
2Nancy-UniversitØ, G2R, 54506 Vandoeuvre-lŁs-Nancy cedex,
([email protected])
France
3Case Western Reserve University, Cleveland, OH 44106

([email protected])
There is an increasing interest in evaluating the influence

of the hydrophilic fraction of sedimentary organic matter on
The general consensus is that the Moon formed and
the migration of radionuclides around nuclear waste
evolved through a single or series of catastrophic heating
geological storage sites. In that respect, phenol, benzoic acid,
events in which most of the highly volatile elements,
and salicylic acid may be considered as reference compounds
especially hydrogen, were evaporated away. That notion has
for type-III, higher-plant-derived organic matter. Their
changed with the new report showing evidences of indigenous
interactions with U(VI) and Th(IV) ions have been the subject
water in lunar volcanic glasses1. Because these glasses are the
of several experimental studies. However, reliable data for
most primitive melts erupted on the surface of the satellite,
U(VI) and Th(IV) complexes with phenol, benzoic acid and
this result represents the best evidence for the presence of a
salicylic acid remain scarce.
deep source within the Moon relatively rich in volatile. Here
The present work is a systematic experimental study of
we report new volatile data (C, HO, F, S, Cl) for over 200
2 U(VI) (cid:150) Organic compounds (cid:150) HO ternary systems as a
individual Apollo 15 lunar glasses with composition ranging 2
function of pH and the concentrations of uranyl (VI) and
from very-low to high Ti contents (sample 15427,41;
organic ligand at 25(cid:176)C and 0.1 MPa using a combination of
15426,138; 15426,32). Our new SIMS detection limits
three techniques: UV-visible spectroscopy, ATR-FTIR, and
(~0.15 ppm C; ~0.4 ppm HO, ~0.05 ppm F, ~0.21 ppm
2 ESI-MS. The present study was undertaken (1) to detect the
S, ~ 0.04 ppm Cl by weight determined by the repeated
presence of possible uranyl(VI)-organic complexes, and (2) to
analysis of synthetic forsterite located on each sample mount),
determine their number and their stability domain.
represent at least 2 orders of magnitude improvement over
A uranyl (VI) nitrate stock solution was prepared from
previous analytical techniques. After background correction
recrystallized schoepite by dissolution in HNO solution. The
the volatile contents have the following ranges: C 3
resulting concentration was 0.506 M uranyl(VI). A phenol
0-0.14– 0.13 ppm is within background; 0-70 – 0.4 ppm for
solution was prepared by dissolution of a determined amount
HO; 1.6-60 – 0.1 ppm for F; 58-885 – 1.3 ppm for S; and
2 of phenol in HO. All solutions were prepared and handled in
0-3 – 0.02 ppm for Cl. Our new values represent an increase 2
closed containers to prevent the dissolution of CO. The pH of
in the volatile concentrations by a factor of 2 from previously 2
each sample was adjusted using either HNO or NaOH
reported data1. Two outstanding features of the data are the 3
solution. The pH was measured using a Ross combination
significant correlation among HO, Cl, F and S contents, and
2 glass/reference elecrode standardized against buffer pH 4, 7,
the clear relationship between the volatile and the major
and 10. UV-visible and ATR-FTIR spectroscopic
element contents of the glasses. The data support the
measurements were made at various uranium (10-4 (cid:150) 10-1 m)
hypothesis that there were significant differences in the initial
and phenol (10-4 (cid:150) 10-1 m) concentrations to form various
volatile content, and/or the mechanism of degassing and
phenol/uranyl(VI) molal ratios in the range 0 (cid:150) 103 over a pH
eruption among these glasses was different. Most importantly,
range of 2 (cid:150) 12.
the data suggest that the measured HO is indigenous to the
2 UV-visible absorption measurements of 10-3 M U(VI)
Moon. Our results suggest that, contrary to the prevailing
solutions with phenol/uranyl(VI) molal ratio ranging from 0 to
ideas, the bulk Moon is not uniformly depleted in highly
102 at pH = 4 have revealed the presence of a uranyl(VI)-
volatile elements, and the presence of water, in particular,
phenolate aqueous complex. Its individual UV-visible
must be included to constrain models for the thermal and
spectrum shows an absorption maximum around 417 nm.
chemical evolution of the Moon(cid:146)s interior.

[1] Saal et al. (2008) Nature 454, 192-195.
A1140 Goldschmidt Conference Abstracts 2009
Paxillus involutus hyphae: Imaging Thermodynamic and structural
their structure and interaction with stability of (CO ) n=2-4: An ab initio
2 n
mineral surfaces using AFM and QTAIM Study
L. SACCONE1, S.A. GAZZE1, K.V. RAGNARSDOTTIR2, SEYED A. SADJADI, S.K. BUTT AND KONO H. LEMKE
J.R. LEAKE3, A.L. DURAN3, K.R. HALLAM4
Department of Earth Sciences, University of Hong Kong,
AND T.J. MCMASTER1
Pokfulam Road, Hong Kong, SAR
1H.H. Wills Physics Laboratory, University of Bristol, Tyndall
Avenue, Bristol BS8 1TL, U.K Quantum chemical and experimental studies of weakly
2School of Engineering and Natural Sciences, University of bound molecular complexes are of fundamental importance in
Iceland, Hjardarhagi 6, 107 Reykjavik, Iceland shaping our understanding of molecular interactions in the
3Animal & Plant Sciences, University of Sheffield, S10 2TN, condensed phase. The gas phase carbon dioxide clustering
U.K reaction according to n(CO) = (CO ) provides a suitable
2 2 n
4Interface Analysis Centre, University of Bristol, Bristol, model for such studies and, can as such provide valuabe
BS2 8BS, U.K insight into the stability of carbon dioxide clusters in the
Earth(cid:146)s atmosphere, the occurrence of carbon dioxide clouds
Experiment on Mars as well supercritical phenomena in the lower
Plant and ectomycorrhizal interactions with minerals were Venusian atmosphere [1]. The first experimental data on the
investigated under axenic culture conditions. Chlorite and CO multimer series stems from microwave spectroscopic
2
biotite flakes were inserted in an axenic microcosm depleted work at 1.6K, that revealed the existence of a slipped parallel
in Fe with Pinus sylvestris (Scots pine) colonised with the C symmetry for the carbon dioxide dimer [2]. Only one
2h
ectomycorrhizal fungus Paxillus involutus. Fungal hyphae study exists where (CO) bonding patterns, structures and
2 2
structures on the mineral were imaged at the nanoscale. their relationship to the theoretical binding energy have been
Atomic Force Microscopy (AFM), operating in contact discussed in detail [3]. Unfortunately, there are no reliable
and tapping modes was used for topographic imaging, and experimental thermodynamic data (Gibbs energy, enthalpy
pixel-by-pixel force spectroscopy, or force volume mapping, and entropy) for either the dimerization reaction or formation
was used to build up adhesion and elastic moduli maps of the of higher clusters from starting CO.
2
hyphae and surrounding mineral surface, to determine the Here we report new CO cluster structure parameters as
2
physical properties of the fungal mineral surface interactions. well as new values for ∆G, ∆H and ∆S for (CO ) clustering
2 n
Fungal hyphae and the mineral surface were imaged after reactions up n=4 building on both QTAIM and ab initio
several months of fungal colonisation. Images were also taken approaches at MP2/cc-pVTZ level of theory and atmospheric
after partial cleaning of the fungi from the mineral surface T. For instance, MP2 level (CO) geometric parameters from
2 2
with gentle wiping, and after their complete removal, to record this study are in excellent with microwave data (Figure below)
any fungal-induced changes on the mineral surface. The [2]. The corresponding CO dimerization enthalpy and entropy
2
images have been correlated with Scanning Electron are -1.5 kJ•mol-1 and -70.7 J•K-1•mol-1, respectively, indicating
Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) that the dimer and higher clusters may be present in
and other surface-sensitive techniques. appreciable levels in the 60-80km altitude range of the
AFM images of fungal hyphae and a layer covering the Martian atmosphere and thus an important requirement for
surface are shown in Figure 1. Globular features covering the CO cloud nucleation.
2
mineral surface were visible at the nanoscale on both chorite
and biotite, whereas geometrical patterns of approximately 4
nm in height and between 0.5 (cid:181)m and 1 (cid:181)m in width were
only observed on the biotite. These were more pronounced
after partial removal of the hyphae and the layer covering the
surface.

[1] Montmessin et al, 2006, Icarus, 183, 403; [2] Jucks et al,
1988, JCP, 88, 2185; [3] Bone et al, 1996, JPC, 100, 10892.

Figure 1: AFM images of a branching hypha (left) and layer
on chlorite (Images field of view ranges from 40 (cid:181)m to 4.21
(cid:181)m, left to right)
Goldschmidt Conference Abstracts 2009 A1141
OAE(cid:146)s and the interdependence of P, Mineralogy, chemistry and
N and trace metals distribution of mine tailings from the
Murgul (Artvin) Cu deposit and their
B. SAGEMAN, M. HURTGEN, D. ADAMS,
R. BARCLAY AND Y.J. JOO environmental impacts, NE Turkey
Department of Earth and Planetary Science, Northwestern
E.S. SAĞLAM*AND M. AK˙AY
University, Evanston IL
(*correspondence: [email protected]) Karadeniz Technical University, Department of Geological
Engineering, 61080, Trabzon Turkey
Cretaceous ocean anoxic events, especially the early (*correspondence: [email protected])
Aptian and Cenomanian-Turonian (C-T) events, are believed ([email protected])
to reflect episodes of increased primary production leading to
a global-scale enhancement of organic matter preservation; Murgul Cu deposit is the largest copper mine of Turkey
preservation is mainly attributed to intense oxygen depletion and is in production since pre-Republican era. Based on water
resulting from exceptional fluxes of organic matter. Three and stream sediment sampling in 2005 (dry season) when the
fundamental questions pervade the study of these events: 1) deposit was in regular operation and in 2006 when it was
What initiated the heightened production? Did it include inactive or irregular in operation, this study aims at
increase in average rates of production, a significant change in determining the impact of mine tailings disposed of into the
the total area of productive surface waters, or some streams draining the deposit.
combination of both? 2) What maintained elevated production Due to disposal of mine waste and tailings into the
levels for some 500 to 600 kyrs? and 3) What change in the streams, particles originating from the Murgul mine are highly
biogeochemical system terminated these events? Given that enriched in the alluvium. Stream sediment samples of 2005
productivity is thought to play the key role, our attention period contain 4.33 - 50.87% Fe, 0.2 - 38.49% S, 9.2- 1926.6
naturally turns to the biolimiting nutrients known to control ppm As, 210.4- 27439.6 ppm Ba, 0.8 - 23.2 ppm Cd, 272.1-
primary production in modern oceans. These include reactive 9332.5 ppm Cu, 0.03 - 0.92 ppm Hg, 28.2- 682 ppm Pb, 2.4-
phosphorous, ultimately sourced by weathering of uplifted 2800 ppb Au and 196 - 3697 ppm Zn. In 2006 samples,
land masses or by recycling from anoxic sediments, reactive however, the concentration of these elements show about 50%
nitrogen, mainly sourced by bacterial transformations of N decrease.
2
and NH , and trace metals such as Fe, Mo, and Zn, which play The samples are divided into two groups based on the
3
critical enzymatic roles in the bacterial and algal communities XRD analyses: Those collected from the areas of streams
that perform primary production and decomposition processes. affected and unaffected by the waste and tailings disposal
Since the redox state of the marine realm exerts a strong contain mainly quartz and pyrite, and quartz, illite, albite,
influence on each of these systems, it stands to reason that chlorite and kaolinite, respectively. Quantitative analyses of
they might be interdependent through the course of an ocean the first group of samples indicate about 90% quartz and
anoxic event. In this talk we collate observations drawn from a pyrite. Average pyrite contents of 2005 samples are much
series of studies of the C-T OAE2 in order to develop an higher than 2006 samples in contrast to quartz content due to
hypothesis about the linkage between P, N, and trace metals dilution at times of no-mine production. However, the second
during OAE(cid:146)s. These studies include a stomatal index-based group of samples shows no mineralogical and compositional
reconstruction of pCO across the event, as well as a record of change with respect to the sampling period.
2
changes in reactive Fe and S isotopes from epieric and oceanic Tailings from the floatation discharge in 2005 period
sites. The hypothesis states that OAE(cid:146)s are self-limiting extend to large distances from the mine site, and
because exceptional events of primary production lead to concentrations of Fe, S, As, Ba, Cd, Cu, Hg, Pb and Zn
pervasive oxygen deficiency, which results in the eventual increase with distance. This is in accord with the distribution
drawdown of redox-sensitive trace metals. Even if P of heavy metals in water samples. The concentrations of the
regenerated from anoxic sediments finds a way to surface same elements in 2006 samples, however, show a gradual
waters, N-limitation ultimately controls OAE duration when decrease downstream from the discharge site.
metal inventories reach some lower threshold. Local colloidal ferrihydrite occurrences were observed
about 8 km downsteam from the mine site due to heavy of
suspended particles containing sulphides. They are in the form
<2 cm thick shells covering the pebbles in the alluvium, and
show that pyrite was oxidised resulting in acid mine drainage.
However, pH values along the Murgul stream are neutral
(pH= 7-8) which prevent the production of acid mine drainage
despite the abundance of sulphides in the alluvium. The
presence of ferrihydrite, on the other hand, is evidence to
show that production of acidic pH in stream water, similar to
those in the pits, is inevitable after the mine closure, unless
measures are taken to prevent this.
A1142 Goldschmidt Conference Abstracts 2009
Spectral dependence of aerosol Environmental impact of mining
absorption over an urban coastal industry
zone
L.V. SAHAKYAN1 AND A.K. SAGHATELYAN2
AUROMEET SAHA1*, MARC MALLET2, Center for Ecological-Noosphere Studies of NAS of RA,
JACQUES PIAZZOLA3 AND SERGE DESPIAU3 Abovyan 68 str, 0025, Yerevan, Armenia
([email protected], [email protected])
1CARTEL, UniversitØ de Sherbrooke, Sherbrooke, Canada

(*correspondence: [email protected])
The results of the monitoring of heavy metal (HM)
2Laboratoire d(cid:146)Aerologie, UniversitØ Paul Sabatier, Toulouse,
pollution of the soils of Armenia(cid:146)s industrial regions have
France ([email protected])
indicated that the specificity of Armenia(cid:146)s territory is its
3LSEET-LEPI, UniversitØ du Sud Toulon-Var, La Garde,
metallogenic specialization for Mo, Cu, Pb and a number of
France ([email protected], [email protected])
other metals, that predetermines their high natural background

often overstepping the established maximum acceptable
Spectral dependence of aerosol light absorption and Black
concentration (MAC) for separate elements.
Carbon (BC) concentrations were measured over Toulon, an
While assessing man-made pollution, such a fact supports
urban coastal region in South France during 2005-2006.
a necessity to consider the level of chemical element
Average monthly BC concentrations varied between 0.3 and
concentrations in natural geochemical anomalies, typical of
1.0 microgram/m3 which was ~2-5% of the aerosol mass
which are high values of element contents.
(PM10). Angstroms absorption coefficient estimated from the
Thus, one actually assesses summary concentration of
spectral dependence of absorption coefficients varied between
chemical elements in the environment formed as a result of the
0.95 and 1.6. Our results show excess absorption as high as
overlay of 2 constituents: primary elevated natural (geogenic)
~33% at shorter wavelengths during winter season and
and technogenic. A typical result of such an inclination is
negligible absorption during summer months. The
ecological situation around the Kajaran deposit.
implications of the results would be discussed.
This research covers the areas of Kajaran c. and 3 tailing

repositories. The mining and dressing plant is a city-forming
enterprise: it directly borders upon the city with a population
of some 9 thousand people.The city lies in the area of sulfide
copper-molybdenum deposit and is a natural biogeochemical
province enriched by Mo and Cu.
The complex investigations were carried out to reveal
envionmental impact of mining industry. The research
indicated that the contents of HM for study soils, crops, fodder
grasses, air, are excessive vs. MAC, including high toxic
elements. The assessment of risk factors indicates that the
citizens are exposed to a heavy load of environmental
pollution with HM that can enter the organism through
respiratory ways and food chains.
To assess the level of the impact of pollution upon the
organism, as indicators children were selected as the most
sensitive risk group in the populace. From 12 children of
preschool age hair samples were collected. In most cases,
concentrations of toxic elements are excessive vs. the lowest
and sometimes peak accepted levels.
The obtained research outcomes evidence the presence of
significant risk factors to the public health as a result of
operation of the Kajaran mining and dressing plant. The
research was performed in period 2005 to 2007 by the order of
the municipality of Kajaran under support of the OSCE Office
in Yerevan.
Goldschmidt Conference Abstracts 2009 A1143
Mineralogical and geochemical The fluid-absent melting of phase E
characteristics of the borate bearing in the MgO-SiO -H O system
2 2
Kirka volcanosedimentary lacustrine
A. SAIKIA* AND M.W. SCHMIDT
basin, Gocenoluk Area, Eskisehir,
Institute for Mineralogy and Petrology, ETH Zurich
Western Anatolia, Turkey: (*correspondence: [email protected])

Preliminary results
Significant amounts of water are recycled into the Earth(cid:146)s
T. SAHIN1*, A. TEMEL1 AND P. SYLVESTER2 interior via hydrous phases in a subducting slab. High pressure
experimental investigations have established that several
1Hacettepe University, Department of Geological Engineering, dense hydrous magnesium silicates (DHMS) are stable at
06800, Beytepe-Ankara, Turkey mantle conditions in model mantle compositions. These
(*correspondence: [email protected]) phases act as water carriers in the subducting slab and water so
([email protected]) carried may initiate mantle melting, most likely when a
2Memorial University of Newfoundland, Department of Earth subducted slab begins to thermally relax. In the absence of a
Sciences, St John(cid:146)s, NL A1B 3X5, Canada free fluid at or near transition zone pressures, melting will
([email protected]) depend on these hydrated phases. These will break down
through fluid-absent melting in perfect analogy to the well
In the Gocenoluk (Kirka) area, volcanosedimentary rocks known granulite facies fluid-absent melting in crustal rocks. In
are composed of clays, carbonates, tuffs and borates. XRD particular, such fluid-absent melting (of the DHMS or any
(whole rock and clay fractions) and ICP-MS analysis were other hydrous phase) is independent of the termination of the
carried out on samples taken from four different drillholes. In fluid-saturated solidus through a second endpoint.
2008 drilling into the Miocene Gocenoluk (Kirka) borate For the DHMS, nothing is known about the proportions of
deposit encountered between 421 and 1204m of drillcore. This melt formed through fluid-absent melting, the composition of
project aims to determine the genesis of this mineralization such melts and the variation in the melt composition at
using solution and laser ablation-ICP-MS analyses of ore and different pressure temperature regimes, which has siginifcant
gangue minerals. XRD-whole rock analysis show that there implications for partial melting models of the mantle.
are calcite, dolomite, quartz, feldspar, mica, clays and borate In this study we have experimentally investigated the
minerals (borax, colemanite ulexite minerals, with minor fluid-absent melting phase relations of the dense hydrous
probertite, inyoite, nobleite and kernite), whereas XRD-clay magnesium silicate Phase E, a DHMS phase stable at
fraction analysis indicate that major clay mineral is smectite, transition zone conditions of the earth(cid:146)s mantle in a model
and minor clay minerals are illite, kaolinite and chlorite. In MgO-SiO-H O system. A stochiometric oxide mix of Phase E
2 2
Gocenoluk basin, Ca-borate reacts to form Na-Ca borate and composition was used as the starting material. Rocking
finally Na-borate minerals. The twenty one samples of borate, multianvil experiments were carried out between 13.5-16 GPa
calcite, dolomite and clay minerals were selected and analyzed at temperatures ranging from 1000-1600(cid:176)C using 14/8 and
by ICP-MS for trace element concentrations. In carbonates the 10/3.5 pressure assemblies. The compositions of the
concentrations of Sr and Li increase from 189 to 765ppm and coexisting phases in the quenched run products were analysed
from 27 to 59ppm respectively in direct proportion to vertical using electron microprobe and secondary electron microscopy.
with stratigraphic position (from 197 to 738m from top to The following reactions were found to account for the
bottom). Lithium is enriched in borate and clay minerals with mineralogical changes observed at the investigated P-T
concentrations of 61 and 1045ppm, respectively. conditions E = Fo+ En + Melt, Hy-wad = E+ Fo+ En , E+ En
= Hy-wad+ Melt , E = Fo + Hy-wad + Melt, Hy-wad = Fo +
En + Melt ( E: Phase E, Hy-wad: Hydrous wadsleyite, En:
Enstatite, Fo: Forsterite). Preliminary data show complete
decomposition of Phase E by 1200(cid:176)C at 13.5 GPa and by
1100(cid:176)C at 14.5 GPa producing significant proportions of melt.
Further experiments are presently carried out to determine the
melt compositions by diamond trap technique in the MSH
system and in a model peridotite system.
A1144 Goldschmidt Conference Abstracts 2009
Spectroscopic investigation of Study of micro-crystallinity of SiO in
2
Mahadevpur H4/5 ordinary two Indian Fulgurites
chondrite
BHASKAR J. SAIKIA1,2 AND N.C.SARMAH1
BHASKAR J. SAIKIA1,2 AND G. PARTHASARATHY3 1Department of Physics, Dibrugarh University, Dibrugarh,
Assam- 786 004, India([email protected])
1Department of Physics, Dibrugarh University, Dibrugarh,
2G. B. Pant Institute of Himalayan Environment and
Assam-786004, India
Development, Kosi-Katarmal, Almora, Uttarakhand-
2G. B. Pant Institute of Himalayan Environment and
263643, India ([email protected])
Development, Kosi-Kartarmal, Almora, Uttarakhand-

263643, India ([email protected])
At this high temperature silica of soil or rocks melts and
3National Geophysical Research Institute, Hyderabad-500 007,
passes through a relatively rapid cooling which causes the
India ([email protected] )
glass to solidify. Fulgurites are appreciated as having value in

the interpretation of melts formed during meteorite evolution,
We report here for the first time the Fourier-transform
re-entry, and meteorite impact [1-3]. The core of the fulgurite
infrared (FTIR), Laser-Raman, X-ray fluorescence (XRF)
is more silica-rich with comparison to its branches. This
spectroscopic investigations of the Mahadevpur H4/5 ordinary
variation could be due to the melt processes, vaporization and
chondrite that fell at Mahadevpur, India, on 21 February 2007,
condensation of silicates in the core, quenching processes, and
9:10hr.(IST)[1]. Particular interest is given on the 10(cid:181)m
devolatilization processes. The unmelted gains of the host
(1000cm-1), 20(cid:181)m (500cm-1) and 3.4(cid:181)m (2800(cid:150) 3000cm-1)
soil/rocks embedded into the outside of the fulgurite.
region of IR spectra. The major IR and Raman bands observed
Unmelted and partially melted quartz gains can be observed
in 500-1000cm-1 region is due to olivine group. In olivine
within the fulgurites. The appearance of residual micro-
group [(Mg,Fe) SiO4], the SiO4− tetrahedra are isolated in the
4 crystalline quartz in the sample throws light on the
structure and linked by cations Fe2+or Mg2+ in octahedral
temperature of fusion of the formation. At high
positions. The effect of by cations Fe2+(r = 0.74¯) or Mg2+ (r
temperature and pressure, silica polymorphs pass through a
= 0.66¯) in octahedral positions of olivine group in the
slow reconstructive recrystallization, during which existing
meteorite sample has been investigated. The special interest is
Si(cid:150)O bonds are broken and new bonds are made to allow
given in systematic band shifts in forsterite- fayalite series.
atoms to move to appropriate positions in the more stable
The optical density and extinction coefficient of the meteorite
polymorph. The structure of most SiO polymorphous, both
sample has been calculated using standard relation. The trace 2
crystalline and amorphous, is based on SiO tetrahedra.
of aliphatic functional groups (CH and CH ) is found in the 4
2 3 Amorphous silica is one of the polymorphous of silica and at
spectral region around 2800-3000cm-1, which is important to
high temperature it can easily transform from quartz. The
Astrobiology. The XRF and EPMA data were collected as
present investigation we report the optical properties and
described by Bhandari et al. [2], Dhingra et al. [3]. Raman
micro-crystallinity of micro particle of SiO in two Indian
spectrum is recorded using a Perkin-Elmer System 2000 2
glassy fulgurites samples by comparing the ratio of intensity
FTRaman spectrometer. The mineralogical composition of this
of the characteristic IR peaks at 10(cid:181)m (1000cm-1) and 20(cid:181)m
meteorite is: olivine (Fo80.8 Fa19.3), orthopyroxene (En81
(500cm-1) region. The investigation is based on powder X-ray
Fs17 Wo1) and clinopyroxene (En58 Fs8 Wo35).
diffraction (XRD), X-ray fluorescence (XRF) and Fourier-

transform infrared (FT-IR) spectroscopic methods. The
[1] Weisberg et al. (2008) Meteoritics & Planetary Science
crystallinity parameter is calculated by using a standard
43, 1551(cid:150)1588, [2] Bhandari et al. (2005) Meteoritics &
procedure which can be used to estimate the distribution of
Planetary Sciences 40, 1015-1021. [3] Dhingra et al. (2004)
micro crystalline SiO in fulgurites.
Meteoritics & Planetary Sciences 39, A121-132. 2

[1] Weeks et al. (1980) J. Non-Cryst. Solids, 38, 129-134. [2]

Essene & Fisher (1986) Science, 234, 189-193. [3] Wasserman
et al. (2002) LPSC XXXIII, abs. 1308.
Goldschmidt Conference Abstracts 2009 A1145
Adsorption of pollutants on silicate Strategies for economization of iron
surfaces from aerosols by in Crocosphaera watsonii as revealed
computational geochemistry by global proteomic analyses
C.I. SAINZ-DIAZ1*, C. IUGA2, M. FRANCISCO-MARQUEZ3 MAK A. SAITO1, VLADIMIR BULYGIN2, DAWN MORAN3,
AND A. VIVIER-BUNGE2 ERIN BERTRAND4 AND JOHN WATERBURY5
1Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad 1([email protected])
de Granada, Av. Fuentenueva s/n,18002-Granada, Spain 2([email protected])
(*correspondence: [email protected]) 3([email protected])
2Departamento de Qu(cid:237)mica, Universidad Aut(cid:243)noma 4([email protected])
Metropolitana, Iztapalapa, Mexico 5([email protected])
([email protected], [email protected])
3Fac. Estudios Superiores Zaragoza, Universidad Aut(cid:243)noma Crocosphaera watsonii is a diazotrophic cyanobacterium
Nacional de MØxico, MØxico ([email protected]) found in tropical ocean environments and is considered one of
the major contributors to marine nitrogen fixation. These
Carbonyl and heterocyclic compounds are directly emitted oligotrophic marine environments are often extremely
into the troposphere from biogenic and anthropogenic sources. depleted in nutritive trace elements such as iron and cobalt.
The reactions of hydroxy free radicals with volatile organic The high requirement of iron in the nitrogenase complex poses
pollutants are common in the troposphere [1]. Silicates and questions about how this organism can sustain its required
clay particles are present as components of atmospheric cellular iron quota. The iron and molybdenum cellular quotas
aerosols. Heterogeneous reactions of atmospheric gases on have previously been observed to double at night when
aerosol particles play an important role in atmospheric nitrogen fixation is known to occur in this microbe (Tuit et al.,
chemistry. Although dust particles are abundant in the Earth(cid:146)s 2003). Using mass spectrometry based global quantitative
atmosphere, however the kinetics and adsorption mechanisms proteomic analysis we clearly demonstrate the synthesis of the
for these reactions are not well understood. three iron containing proteins from the nitrogenase complex
Quantum mechanics methods based on Density Functional during the dark period followed by their complete degradation
Theory are used to study the adsorption of thiophene on a during the photoperiod. Similarly flavodoxin is also
crystal surface of pyrophyllite and the hydrogen abstraction synthesized only during the dark period, suggesting it is the
reaction of OH free radicals with linear-chain aldehydes enzyme responsible for electron transfer to nitrogenase in
adsorbed on models of silicate surfaces by using (SiO) Crocosphaera. These results point to a portion of the iron
4 n
cluster models [2] and a crystal structure of pyrophyllite [3]. cellular quota that is dynamic, being used for both
We find that the silicate surface is a good quencher of free photosynthesis and nitrogen fixation during different times of
radicals and aldehydes, adsorbed on the silicate surface, can the day in order to optimize iron use efficiency. The
react with OH free radicals to yield surface-bound formyl implications for the development of proteomic geochemical
radicals and water. The presence of silicate surface does not biomarkers will also be discussed.
change significantly the activation energy and theoretical
kinetic studies show that this reaction is less favored on the
silicate surfaces than in gas phase.

Figure 1: Formaldehyde adsorbed on silicate surface model.

[1] Alvarez-Idavoy et al. (2001) J. Am. Chem. Soc. 123, 2018.
[2] Iuga et al. (2008) J. Phys. Chem. C 112, 4590-4600. [3]
Sainz-D(cid:237)az et al. (2002) Am. Mineral. 87, 958-965.
A1146 Goldschmidt Conference Abstracts 2009
Trace element distributions and Formation conditions and stability of
phytoplankton colimitations on a full a toxic tridecameric Al polymer
depth ocean section in the South under a soil environment
Atlantic Ocean
T. SAITO*, A. ETOU, SHUQIN BAI, Y. OKAUE,
MAK A. SAITO1, ABIGAIL E. NOBLE2, ALYSIA COX3 AND AND T. YOKOYAMA
TYLER J. GOEPFERT4 Department of chemistry, Faculty of Sciences, Kyushu
University, 4-2-1, Ropponmatsu, Chuo-ku, Fukuoka-shi,
1([email protected])
Fukuoka 810-8560, Japan
2([email protected])

3([email protected])
Aluminum ion and its hydrolytic species show
4([email protected])
phytotoxicity, especially the tridecameric Al polymer (Keggin

type Al polycation, [AlOAl (OH) (HO) ]7+) has the
The distributions of trace elements (Co, Fe, and Mn) and 13 4 12 24 2 12
strongest toxicity among them. Hunter and Ross[1] reported
macronutrients on a zonal section in the South Atlantic from
the evidence that the Al is present in the organic soil
the subtropical gyre to the Benguela Upwelling system were 13
horizons in Forest. Therefore, it is important to study the
examined in November-December of 2007. Surface depletion
formation conditions and the stability of the Al . The Al
of cobalt was observed across much of the section, 13 13
consists of twelve 6-coodinated Al that can not be detected
demonstrating the importance of micronutrient processes on
and one 4-coordinated Al that gives a sharp peak around 60
cobalt geochemistry in this region. In addition a large plume
ppm in the 27Al NMR spectra. First the pH region where the
of cobalt was observed emanting from the Benguela
peak around 60 ppm can be detected by 27Al NMR
Upwelling and spreading well into the South Atlantic basin,
spectroscopy was examined, corresponding to the pH region
concurrent with a low oxygen tongue. Analyses of iron and
where the Al can be formed. The result suggests that Al
manganese suggest that the source components and 13 13
can be formed at pH 3.6 (cid:150) 5.7 in aqueous solution. Because of
scavenging parameters are unique across these hybrid-type
the seven positive charges on Al , it can be reasonably
elements. Incubation experiments on this section found 13
deduced that Al has high adsorption and coordination
evidence for nitrogen-iron, nitrogen-cobalt, and iron-light 13
properties on the surface of soil and microbe covered with
colimitation in the South Atlantic, in a region generally
carboxylic groups. The adsorption behavior of Al on Chelex
considered to be nitrogen limited. Together these results 13
100 with iminodiacetate groups, as a model compound of their
demonstrate the value of high-resolution sectional analysis of
surface, was examined. It was found that Al can be stably
trace metals, as well as pointing to the need for efficient 13
adsorbed onto the Chelex 100 by weak electrostatic
biochemical assays for nutrient colimitation.
interaction. Additionally, decomposition of the Al did not
13
occur even after adsorption, and its pH stability region was
wide compared to that in aqueous solution. The effects of
silicic acid on the formation and stability of Al was also
13
examined. When silicic acid coexsisted, the formation of Al
13
was inhibited, on the other hand the reaction between the Al
13
and silicic acid was extremely slow.

[1] Hunter D. and Ross D. (1991) Science, 251, 1056-1058.
Goldschmidt Conference Abstracts 2009 A1147
Highly saline Palaeoproterozoic Distribution of trace metals in
seawater inferred from fluid petroleums of different maturity
inclusions in 2.4 Ga Ongeluk levels
Formation
CS. SAJGO1*, S.D. OLSEN2 AND J. FEKETE1
TAKUYA SAITOU1*,TAKAZO SHIBUYA2, 1Institute for Geochemical Res., Hung. Acad. Sci., Buda(cid:246)rsi œt
TSUYOSHI KOMIYA1, KOUKI KITAJIMA3, 45, Budapest, H-1112, Hungary
SHINJI YAMAMOTO1, MANABU NISHIZAWA1, (*correspondence: [email protected],
YUICHIRO UENO1 AND SHIGENORI MARUYAMA1 [email protected])
2Rogaland Research, Post Box 8046 4068 Stavanger, Norway
1Tokyo Institute of Technology, Tokyo 152-8551, Japan
([email protected])
(*[email protected])
2Japan Agency for Marine-Earth Science and Technology,
A set of trace metals (V, Ni, Co, Fe, Zn, and Mo, As, Hg)
Yokosuka 237-0061, Japan
in a suite of oil samples (studied and classified on the basis of
3The University of Tokyo, Tokyo 164-8639, Japan
biomarker data) from Hungary [1] was analysed by ICP-MS

[2]. The carbon isotopic composition of the C saturate and
15+
We present microthermometry of fluid inclusions in
aromatic hydrocarbon fractions were also measured.
hydrothermally precipitated quartz in 2.4 Ga Ongeluk
Formation, Kaapvaal Craton, South Africa. The studied lavas Discussion of Results
probably erupted during Palaeoproterozoic Snowball Earth
The stability of biomarkers and some metal complexes
event [1, 2], thus is prime target to obtain the information of
have shown similar thermal dependence. The median values of
seawater composition during the snowball period. The quartz
determined trace elements are displayed in Table Ia and Ib
crystals fill drainage cavities of pillowed basaltic lava and
groupped in maturity ranked oils [1].
were probably precipitated soon after eruption under seawater

[3]. The primary fluid inclusions show final melting Table Ia: Maturity sensitive trace metals in maturity groups
temperatures from -31.4(cid:176)C to -3.6(cid:176)C for ice and from -48.3(cid:176)C (ppb)
to -22.0(cid:176)C for hydrohalite. Their homogenization temperatures ranking of oils Co V Ni Mo
range from 74.9(cid:176)C to 160(cid:176)C. These results indicate that the
LtM least-mature 111 425 11140 32,0
fluid composition can be assumed as a NaCl-CaCl -HO
2 2
LM low-mature 62 431 3229 13,0
system. Thus, the salinity of fluid inclusion can be calculated
from its melting point. We found that the fluids show various MM moderate mature 15 111 1236 1,6
NaCl/CaCl2 ratio (0.1 (cid:150) 16.8 molar ratio). This variation is M mature 7 32 581 3,0
consistent with albitization of igneous plagioclase (Ca/Na
VM very-mature 2 4 13 0,4
exchange reaction), which commonly occur in seafloor
Table Ib.Trace meteals in maturity groups (ppb)
alteration processes. Hence, the fluid may record altered 2.4
Fe Zn As Hg ∑ of Ia+Ib
Ga seawater. Based on the extrapolation of this albitization
trend, we conclude that the salinity of the 2.4 Ga seawater LtM 7145 116 222 845 27395
would have been at least two times higher than that of modern LM 6605 213 134 1150 15385
seawater. The estimated salinity is higher than previous
MM 13430 687 230 626 16833
estimate of the early seawater based on total amount of
M 2783 482 56 545 4548
continental salt deposits [4], thus requires some sort of
concentration process. The high salinity could be expected, if VM 64 6 47 70 977
the Ongeluk ocean was quantitatively frozen. Thus our result
is consistent with the (cid:147)hard(cid:148) snowball scenario. The metals (associated with the polar components and
asphaltenes) in Table IA demonstrate direct maturity
[1] Evans et al. (1997) Nature 386 262-266. [2] Kopp et al. dependence [3]. The maturity dependence of metals in Table
(2005) PNAS 102 11131-11136. [3] Gutzmer et al. (2003) Ib are more complicated, partly governed by source facies and
Chem. Geol. 201 37-53. [4] Knauth (1998) Nature 395 554- migration effects (picked up during migration) [4]. The
555. evaluation of carbon isotopic data is also difficult because of
the overlapping maturation and organic facies effects.

[1] Sajgo (2000) Org. Geochem 31, 1301-1323. [2] Olsen et
al. (1995) Analyst 120, 1379-1390. [3] Lewan and Maynard
(1982) GCA 46, 2547-2560. [4] Punanova et al. (1988)
Geokhimiya No. 9, 1360-1366.
A1148 Goldschmidt Conference Abstracts 2009
Contribution of sclerotia of Effects of pH and silica on the
Cenococcum species to soil organic polymerisation rate of an amino acid
carbon in low pH forest soils.
K. SAKATA1, N. KITADAI1 AND S. NAKASHIMA1
N. SAKAGAMI1* AND M. WATANABE2 1Department of Earth and Space Science, Osaka University,
Machikaneyama-cho, Toyonaka, Osaka 560-0043 Japan
1Tokyo Institute of Technology, Kanagawa 226-8502, Japan
([email protected])
(*correspondence: [email protected])

2Tokyo Metropolitan University, Tokyo 192-0397, Japan
In the chemical evolution of life, amino acids should be

polymerised into peptides. Although it is known that solution
Recognition of sclerotia as soil organic component
pH and presence of minerals significantly influence
Cenococcum geophilum is known to be one of the most
polymerisation rates, quantitative effects of pH and minerals
frequently encountered ectomycorrhizal fungi in temperate
have not yet been investigated. In this study, the effects of pH
and arctic-alpine climatic zone, and their sclerotia (figure 1)
and silica on the polymerisation rates of an amino acid
are preserved in soils with Cenococcum mycorrhizae [1]. Such
(glycine: Gly) were quantitatively evaluated.
sclerotia contain carbon (C) approximately 50% by mass and
8.0ml of 100mM Gly or 50 mM GlyGly solutions, having
their persistence for a long term as a structural organic
pH from 6 to 9, were put into Teflon bottles and heated at 140
component in soil is known by isotopic studies, although their
degree C from 1 to 14 days. After heating, concentrations of
chemical properties are fairly different from soil humic
glycine (Gly), glycylglycine (GlyGly) and diketopiperazine
substances [2,3]. Implication of sclerotial C was discussed
(DKP) were measured by liquid chromatography (LC).
from sclerotial biomass and environmental conditions in cool-
In this study, the following reaction pathways are
alpine forest soils in central and northern Japan, and Harz
assumed: Gly to GlyGly (the second order reaction), GlyGly
Mts., Germany.
to DKP (the first order reaction), DKP to GlyGly (the first
order reaction), GlyGly to Gly (the first order reaction).
Results of heating experiments on Gly and GlyGly solutions
were fitted by the above four reactions to obtain corresponding
rate constants.
GlyGly formation rate constants increased for increasing
pH. Dissociated species of amino acids are known to change
from zweitterion to anion with increasing pH. The
deprotonated anionic amino group is considered to have
Figure 1: a) Spherical sclerotia of Cenococcum species in
higher reactivity and so is favourable for peptide formation.
Abies veitchii forest (1740m a.s.l.) and b) non-spherical
Amorphous silica was then added to the above
sclerotia in Pinus pumila forest (2740m a.s.l.) at Mt. Ontake,
experimental systems. The GlyGly formation rates with and
central Japan.
without silica will be compared and roles of mineral surfaces

will be discussed.
Results and discussions

Formation of sclerotia could be considered as a primitive
phenomenon in humification process under low pH condition.
Sclerotial C was equivalent to microbial C comparing to [4]. C
reserved as sclerotia may contribute to enlarge mean residence
time of C in subalpine forest soil. Sclerotia formed in high
altitude were likely to be an important source of assimilated C
from host species, for micro-organisms in soils. A
complementary role as C pool was suggested for sclerotia in
symbiosis of plant and micro-organism .

[1] Trappe (1964) Lloydia 27, 100-106. [2] Watanabe et al.
(2007) Eur. J. Soil Sci. 58, 786-793. [3] Watanabe et al.
(2007) Soil Sci. Plant Nutr. 53, 125-131. [4] Uchida et al.
(1998) Ecological Res. 13, 17−26