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Ferrihydrite (Fh) is a major Fe(III)-(oxyhydr)oxide nanomineral distinguished by its poor crystallinity and thermodynamic metastability. While it is well known that in suboxic conditions aqueous Fe(II) rapidly catalyzes Fh transformation to more stable crystalline Fe(III) phases such as lepidocrocite (Lp) and goethite (Gt), because of the low solubility of Fe(III) the mass transfer pathways enabling these rapid transformations have remained unclear for decades. Here, using a selective extractant, we isolated and quantified a critical labile Fe(III) species, one that is more reactive than Fe(III) in Fh, formed by the oxidation of aqueous Fe(II) on the Fh surface. Experiments that compared time-dependent concentrations of solid-associated Fe(II) and this labile Fe(III) against the kinetics of phase transformation showed that its accumulation is directly related to Lp/Gt formation in a manner consistent with the classical nucleation theory. 57Fe isotope tracer experiments confirm the oxidized Fe(II) origin of labile Fe(III). The transformation pathway as well as the accelerating effect of Fe(II) can now all be explained on a unified basis of the kinetics of Fe(III) olation and oxolation reactions necessary to nucleate and sustain growth of Lp/Gt products, rates of which are greatly accelerated by labile Fe(III).

The reduction potential of Fe(II)-Fe(III) (oxyhydr)oxide systems provides an important control on the biogeochemical cycling of redox-sensitive elements such as carbon and nitrogen as well as trace metals and organic contaminants in natural systems. As such, an in-depth understanding of the factors controlling the reduction potential of such systems is critical to predicting the likely transformation, transport and fate of these species in natural and perturbed environments. In this study the mineralogy and reduction potential of ferrihydrite suspensions at pH 6.50 and pH 7.00 were determined over the course of their Fe(II)-catalyzed transformation to lepidocrocite and goethite using X-ray absorption spectroscopy and mediated electrochemical approaches. The measured reduction potentials were compared to those of analogous Fe(II)-Fe(III) (oxyhydr)oxide suspensions reacted for 5 min containing pure ferrihydrite (Fh), lepidocrocite (L) and goethite (Gt). The reduction potentials of the pure Fe(II)-Fe(III) (oxyhydr)oxide suspensions were, respectively, +47.5, −13.5 and −122.3 mV vs. SHE at pH 6.5, and −22.9, −84.1 and −189.7 mV vs. SHE at pH 7. These values are in good agreement with reduction potentials calculated using the Nernst equation and reported thermodynamic solubility products indicating that these suspensions had reached equilibrium within 5 min. The reduction potential of the pH 6.50 Fe(II)-ferrihydrite suspension decreased from +47.4 mV to –126.4 mV over a week, and from −20.1 mV to −188.4 mV (all vs. SHE) after 24 h at pH 7. The changes in reduction potential over time matched well to those calculated from the relative proportion of each pure Fe(III) (oxyhydr)oxide present suggesting that Fe3+ activity was influenced by the mix of iron oxides present rather than the most insoluble solid species. Finally, evidence is provided that adsorbed Fe(II) has the capacity to reduce a significantly larger fraction of a reducible species than the aqueous Fe(II) species with which it is in equilibrium. As an Fe(III) (oxyhydr)oxide suspension in equilibrium with aqueous and adsorbed Fe(II) species possesses a single, unique reduction potential, this suggests that adsorbed Fe(II) is a more facile reductant than aqueous Fe(II).

Using a novel combination of in situ potentiometric experiments and quick-scanning XAS we present Fe K-edge XAS spectra (to k = 12 A −1 ) during Fe III hydrolysis and precipitation in 0.33 M Fe(ClO 4 ) 3 , Fe(NO 3 ) 3 , FeCl 3 and Fe 2 (SO 4 ) 3 solutions up to pH 4.8. Edge-sharing Fe III polymers appeared almost immediately upon hydrolysis with strong evidence for a μ-oxo dimer species forming in the Fe(ClO 4 ) 3 , Fe(NO 3 ) 3 and FeCl 3 solutions. The effects of SO 4 on hydrolysis and polymerization pathways included inhibition of both the formation of the μ-oxo dimer and double corner Fe III bonding, ultimately resulting in the precipitation of schwertmannite. As such, under these experimental conditions, double corner Fe III bonding appears to be critical to the formation of ferrihydrite. The spectral trends indicated that the decomposition/transformation of the dimer was sudden and broadly coincident with shortening average Fe–O bond distances, increased Fe neighbors at ∼3.43 A and a pre-edge energy transformation suggestive of decreased ligand field strength as well as increasing proportions of tetrahedral Fe III . This result suggests that the incorporation of tetrahedral Fe III into ferrihydrite occurs only at the latter stages of extended polymerization.

In this study, the kinetics of Fe(II) oxidation in the presence of the iron oxyhydroxides ferrihydrite, Si-ferrihydrite, schwertmannite, lepidocrocite and goethite are investigated over the pH range 4–5.5. Despite limited sorption of Fe(II), the rate of Fe(II) oxidation is up to 70-fold faster than in the absence of any Fe oxyhydroxide phase over pH 4.5–5.5. Enhanced Fe(II) oxidation was minor or negligible at pH 4 with undetectable amounts of Fe(II) adsorbed to the iron oxyhydroxides at this pH. Heterogeneous rate constants derived from kinetic modeling were normalized to the concentration of adsorbed Fe(II) and deviated by no more than 13.8% at pH 4.5, 5 and 5.5, indicating that oxidation is proportional to the concentration of adsorbed Fe(II). Average rate constants were found to be: 2.12 ± 0.20, 1.30 ± 0.09, 1.69 ± 0.22, 1.20 ± 0.08 and 0.68 ± 0.09 M−1 s−1 for ferrihydrite, goethite, lepidocrocite, schwertmannite and Si-ferrihydrite, respectively. The role of reactive oxygen species, such as hydrogen peroxide, the hydroxyl radical and superoxide, towards the overall oxidation of Fe(II) was examined but found to have only a minor impact on Fe(II) oxidation when compared to the effect of heterogeneous oxidation.

The identification of the mineral species controlling the solubility of Al in acidic waters rich in sulfate has presented researchers with several challenges. One of the particular challenges is that the mineral species may be amorphous by X-ray diffraction. The difficulty in discerning between adsorbed or structural sulfate is a further complication. Numerous studies have employed theoretical calculations to determine the Al mineral species forming in acid sulfate soil environments. The vast majority of these studies indicate the formation of a mineral species matching the stoichiometry of jurbanite, Al(OH)SO 4 ·5H 2 O. Much debate, however, exists as to the reality of jurbanite forming in natural environments, particularly in view of its apparent rare occurrence. In this work the use of Al, S and O K-edge XANES spectroscopy, in combination with elemental composition analyses of groundwater precipitates and a theoretical analysis of soluble Al concentrations ranging from pH 3.5 to 7, were employed to determine the mineral species controlling the solubility of Al draining from acid sulfate soils into Blacks Drain in north-eastern New South Wales, Australia. The results indicate that a mixture of amorphous Al hydroxide (Al(OH) 3 ) and basaluminite (Al 4 (SO 4 )(OH) 10 ·5H 2 O) was forming. The use of XANES spectroscopy is particularly useful as it provides insight into the nature of the bond between sulfate and Al, and confirms the presence of basaluminite. This counters the possibility that an Al hydroxide species, with appreciable amounts of adsorbed sulfate, is forming within these groundwaters. Below approximately pH 4.5, prior to precipitation of this amorphous Al(OH) 3 /basaluminite mixture, our studies indicate that the Al 3+ activity of these acidic sulfate-rich waters is limited by the availability of dissolved Al from exchangeable and amorphous/poorly crystalline mineral species within adjacent soils. Further evidence suggests the Al 3+ activity below pH 4.5 is then further controlled by dilution with either rainwater or pH 6–8 buffered estuarine water, and not a notional Al(OH)SO 4 mineral species.

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43–77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)–Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.

The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid 55Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.

The rate at which iron– and aluminium–natural organic matter (NOM) complexes dissociate plays a critical role in the transport of these elements given the readiness with which they hydrolyse and precipitate. Despite this, there have only been a few reliable studies on the dissociation kinetics of these complexes suggesting half-times of some hours for the dissociation of Fe(III) and Al(III) from a strongly binding component of NOM. First-order dissociation rate constants are re-evaluated here at pH 6.0 and 8.0 and 25 °C using both cation exchange resin and competing ligand methods for Fe(III) and a cation exchange resin method only for Al(III) complexes. Both methods provide similar results at a particular pH with a two-ligand model accounting satisfactorily for the dissociation kinetics results obtained. For Fe(III), half-times on the order of 6–7 h were obtained for dissociation of the strong component and 4-5 min for dissociation of the weak component. For aluminium, the half-times were on the order of 1.5 h and 1-2 min for the strong and weak components, respectively. Overall, Fe(III) complexes with NOM are more stable than analogous complexes with Al(III), implying Fe(III) may be transported further from its source upon dilution and dispersion.

Insoluble organic matter (IOM) has been obtained from two carbonaceous chondrite meteorites and subjected to analysis by laser desorption mass spectrometry (LDMS) using standard operating conditions that were optimized for fullerene detection (3–6 μJ pulses at 337 nm focused to a spot size of approximately 100 μm in diameter). The preparation process yields no free C60 in the IOM, and other experiments suggest that this material does not contain appreciable amounts of fullerenes. Nevertheless, a pronounced high-mass envelope is observed in LDMS, extending from 720 amu to about 4000 amu, with peaks spaced apart every 24 amu (corresponding to the gain or loss of C2 units). We attribute this high-mass envelope to the existence of various fullerene molecules. The present work demonstrates that these fullerene molecules are created by the laser desorption laser ionization process under typical laser conditions used for studying free fullerenes in organic solvent extracts of natural samples (toluene and 1,2,4-trichlorobenzene). The implications of this false positive detection of fullerene molecules on the reports of fullerenes in other meteoritic samples have been investigated by introducing IOM into typical fullerene extraction procedures and examining the LDMS results. We found that IOM is capable of producing false positive signals in these experiments. The effect of ambient laboratory contamination producing fullerene signals is also described. It is found that extensive centrifugation of the meteoritic extracts is able to reduce the observed fullerene envelope, which points to an association of this envelope with IOM particulates that have passed through the filtering steps. We suggest the exercise of extreme caution in interpreting fullerene data from LDMS experiments.

Fullerenes have been detected in carbonaceous chondrite meteorites and in breccia samples from meteorite impact craters, but questions have been raised about contradictory results from similar samples and the sensitivities and accuracies of different analytical methods. We analyzed samples from three impact craters and detected C60 in samples from several locations; we also observed differences in the detection capabilities of various analytical techniques used in the search for fullerenes. The presence of C60 in rocks from the Onaping Formation of the Sudbury impact crater was confirmed. Low levels of C60 were also detected for the first time in samples from the Gardnos (Norway) and Ries (Germany) impact structures. We detected C60 in these samples using surface-enhanced laser desorption/ ionization (SELDI), but the related technique of microprobe laser-desorption, laser-ionization mass spectrometry (μL2MS) did not observe C60 above detection limits. We attribute the absence of μL2MS signal to aggregate formation caused by phthalic acid esters, which appear to easily contaminate samples either during storage or demineralization in plastic containers. The μL2MS technique is incapable of detecting aggregated C60, but aggregation does not suppress detection in SELDI. Phthalate-induced aggregation did, however, enhance SELDI detection of C60 in some cases, and we suggest that this enhancement may help explain previously reported differences in C60 detection from natural samples between laser desorption mass spectrometry (LDMS, a technique analogous to SELDI that has detected fullerenes in meteorite and impact breccia samples) and high-pressure liquid chromatography (HPLC). This work highlights the effects of phthalates and other indigenous compounds or contaminants on certain mass spectrometric techniques and lends support to the idea that several complementary analytical methods should be employed to investigate complex natural samples.

Using microprobe laser-desorption, laser-ionization mass spectrometry (L 2 MS), we measured the distributions of alkylated and unalkylated polycyclic aromatic hydrocarbons (PAHs) in the free organic material of 20 carbonaceous chondrites. These meteorites represent a variety of meteorite classes and alteration histories, including CI, CK, CM, CO, CR, CV, and Tagish Lake. This work provides information on free organic compounds that is complementary to studies of the structure and composition of meteoritic macromolecular content. For the nine CM2 meteorites analyzed, we observe that higher relative abundances of alkylated PAHs correlate with more intense aqueous activity. We attribute this correlation to the differences in solubility and volatility between unalkylated and alkylated PAHs. Naphthalene and its alkylation series are more susceptible to the effects of aqueous exposure than the less-soluble PAH phenanthrene and its alkylated derivatives. These observations are consistent with the possibility of chromatographic separations on the meteorite parent bodies. We identify six CM2 meteorites with similar PAH distributions that may represent the original, unaltered organic composition of the parent body. Increased metamorphic intensity reduces the abundance of all PAHs. The thermally metamorphosed CK chondrites had no detectable levels of typical meteoritic PAHs. This observation might be explained either by a loss of PAHs caused by volatilization or by a significantly different organic content of the CK parent body. Copyright © 2005 Elsevier Ltd

Organic material in meteorites provides insight into the cosmochemistry of the early solar system. The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende and Murchison carbonaceous chondrites was investigated by use of a technique called microprobe laser-desorption laser-ionization mass spectrometry, which permits spatial resolution with approximately a 40-μm spot size. Sharp chemical gradients of PAHs are associated with specific meteorite features. The ratios of various PAH intensities relative to the smallest PAH, naphthalene, are nearly constant across the sample. These findings suggest a common origin for PAHs dating before or during the formation of the parent body, consistent with proposed interstellar formation mechanisms.

Controversy surrounds the interpretation of various nano-phenomena as being living organisms. Incubation of fetal bovine serum under standard cell culture conditions results in the formation of free entities in solution, here referred to as nanoforms. These nanoforms, when examined by transmission electron microscopy, have a distinct ovoid morphology ranging in size from tens to hundreds of nanometers. They are composed of hydroxyapatite and proteins and constitute a novel form of protein-associated mineralization. No detectable cell structure resembling bacteria is apparent. However, immunodetection of the proteins associated with the nanoforms, by two specific monoclonal antibodies, suggests a possible biogenic origin. The significance of nanoforms for the recognition of biological activity in ancient geological systems is discussed. The mode of mineralization in nanoforms is also compared to matrix-mediated calcification in vertebrates.

We report results of a consortium study of a large interplanetary dust particle known as cluster L2008#5. This cluster is composed of fifty-three fragments (>5 pm in diameter) and several hundred fines ( Several methods were used to estimate the degree of heating that this cluster experienced. Variations in the inferred peak temperatures experienced by different fragments suggest that a thermal gradient was maintained. The cluster as a whole was not strongly heated; it is estimated to have a low earth-encounter velocity which is consistent with origin from an object in an asteroidal orbit rather than from a comet, which would most likely have a high entry velocity. Our conclusions show that cluster L2008#5 consists of a chemically and mineralogically diverse mixture of fragments. We believe that cluster L2008#5 represents a heterogeneous breccia and that it was most likely derived from an object in an asteroidal orbit. We also present an important cautionary note for attempts to interpret individual, small-sized 10–15 μm IDPs as representative of parent bodies. It is not unique that individual building blocks of IDPs, such as discrete olivine, pyroxene, sulfide grains, regions of carbonaceous material, and other noncrystalline material, are found in several fragments; however, it is unique that these building blocks are combined in various proportions in related IDPs from one large cluster particle.

We have analyzed the H4 ordinary chondrite Forest Vale for polycyclic aromatic hydrocarbons (PAHs) using two-step laser mass spectrometry (L 2 MS) and for amino acids using a standard Chromatographic method. Indigenous PAHs were identified in the matrices of freshly cleaved interior faces but could not be detected in pulverized silicates and chondrules. No depth dependence of the PAHs was found in a chipped interior piece. Amino acids, taken from the entire sample, consisted of protein amino acids that were nonracemic, indicating that they are terrestrial contaminants. The presence of indigenous PAHs and absence of indigenous amino acids provides support for the contention that different processes and environments contributed to the synthesis of the organic matter in the solar system.