Thelma S. Berquó

Magnetite in seafloor serpentinite—Some like it hot

Serpentinization of mantle peridotite generates molecular hydrogen that can be exploited by microorganisms to gain metabolic energy; however, the mechanisms that control hydrogen generation and magnetite formation during serpentinization remain poorly understood. We have examined partly to completely serpentinized peridotites recovered during the Ocean Drilling Program and find a remarkable variation in the abundance of magnetite. Some completely serpentinized peridotites have as much as 6.15 wt% magnetite, whereas others are nearly magnetite free (

Surface functionalization of magnetic iron oxide nanoparticles for MRI applications – effect of anchoring group and ligand exchange protocol

Hydrophobic magnetite nanoparticles synthesized from thermal decomposition of iron salts must be rendered hydrophilic for their application as MRI contrast agents. This process requires refunctionalizing the surface of the nanoparticles with a hydrophilic organic coating such as polyethylene glycol. Two parameters were found to influence the magnetic behavior and relaxivity of the resulting hydrophilic iron oxide nanoparticles: the functionality of the anchoring group and the protocol followed for the functionalization. Nanoparticles coated with PEGs via a catecholate-type anchoring moiety maintain the saturation magnetization and relaxivity of the hydrophobic magnetite precursor. Other anchoring functionalities, such as phosphonate, carboxylate and dopamine decrease the magnetization and relaxivity of the contrast agent. The protocol for functionalizing the nanoparticles also influences the magnetic behavior of the material. Nanoparticles refunctionalized according to a direct biphasic protocol exhibit higher relaxivity than those refunctionalized according to a two-step procedure which first involves stripping the nanoparticles. This research presents the first systematic study of both the binding moiety and the functionalization protocol on the relaxivity and magnetization of water-soluble coated iron oxide nanoparticles used as MRI contrast agents.

Mineralogy of Iron Microbial Mats from Loihi Seamount

Extensive mats of Fe oxyhydroxides and associated Fe-oxidizing microbial organisms form in diverse geochemical settings – freshwater seeps to deep-sea vents – where ever opposing Fe(II)-oxygen gradients prevail. The mineralogy, reactivity, and structural transformations of Fe oxyhydroxides precipitated from submarine hydrothermal fluids within microbial mats remains elusive in active and fossil systems. In response, a study of Fe microbial mat formation at the Loihi Seamount was conducted to describe the physical and chemical characteristics of Fe-phases using extended X-ray absorption fine structure spectroscopy, powder X-ray diffraction, synchrotron radiation X-ray total scattering, low-temperature magnetic measurements, and Mössbauer spectroscopy. Particle sizes of 3.5–4.6 nm were estimated from magnetism data, and coherent scattering domain (CSD) sizes as small as 1.6 nm are indicated by pair distribution function (PDF) analysis. Disorder in the nanostructured Fe-bearing phases results in limited intermediate-range structural order: less than that of standard two-line ferrihydrite (Fh), except for the Pohaku site. The short-range ordered natural Fh (FhSRO) phases were stable at 4°C in the presence of oxygen for at least 1 year and during 400°C treatment. The observed stability of the FhSRO is consistent with magnetic observations that point to non-interacting nanoparticles. PDF analyses of total scattering data provide further evidence for FhSRO particles with a poorly ordered silica coating. The presence of coated particles explains the small CSD for the mat minerals, as well as the stability of the minerals over time and against heating. The mineral properties observed here provide a starting point from which progressively older and more extensively altered Fe deposits may be examined, with the ultimate goal of improved interpretation of past biogeochemical conditions and diagenetic processes.

High crystallinity Si‐ferrihydrite: An insight into its Néel temperature and size dependence of magnetic properties

(1) Ferrihydrite, an antiferromagnetic iron oxyhydroxide with resulting magnetization due to uncompensated spins, is of great importance for the cycling of many trace metals in the environment. Four ferrihydrite samples prepared with 1.3 to 3.5 wt% of Si at different synthesis temperatures (7.5C, 22C, 50C, and 75C) were studied by temperature- dependent hysteresis loops, ZFC/FC susceptibility curves, ac susceptibility and Mossbauer spectroscopy. The incorporation of Si into the ferrihydrite during synthesis changed the properties of this mineral. Interestingly, seven sharp lines were observed in the X-ray diffraction pattern of the ferrihydrite samples prepared at 50C and 75C. In general, both XRD and magnetism demonstrate that particle size decreased (from 23 nm to 2 nm) and particle size distribution narrowed as the synthesis temperature was lowered. Those samples prepared between 7.5C and 50C showed the expected superparamagnetic behavior of ferrihydrite below 300 K. The ferrihydrite prepared at 75C was unusually coarse-grained and had a blocking temperature above 300 K. Extrapolation of induced magnetization from the largest particles with the highest crystallinity allowed an estimate of a ferrihydrite Neel temperature of around 422 K. We also present XRD and magnetic data from large natural Si-ferrihydrite collected from a marine shallow-water hydrothermal area that formed at a temperature of approximately 88C.

Inferred time- and temperature-dependent cation ordering in natural titanomagnetites

Despite years of efforts to quantify cation distribution as a function of composition in the magnetite-ulvöspinel solid solution, important uncertainties remain about the dependence of cation ordering on temperature and cooling rate. Here we demonstrate that Curie temperature in a set of natural titanomagnetites (with some Mg and Al substitution) is strongly influenced by prior thermal history at temperatures just above or below Curie temperature. Annealing for 10(-1) to 10(3) h at 350-400 °C produces large and reversible changes in Curie temperature (up to 150 °C). By ruling out oxidation/reduction and compositional unmixing, we infer that the variation in Curie temperature arises from cation reordering, and Mössbauer spectroscopy supports this interpretation. Curie temperature is therefore an inaccurate proxy for composition in many natural titanomagnetites, but the cation reordering process may provide a means of constraining thermal histories of titanomagnetite-bearing rocks. Further, our theoretical understanding of thermoremanence requires fundamental revision when Curie temperature is itself a function of thermal history.

Experimental constraints on fluid-rock reactions during incipient serpentinization of harzburgite

Abstract The exposure of mantle peridotite to water at crustal levels leads to a cascade of interconnected dissolution-precipitation and reduction-oxidation reactions-a process referred to as serpentinization. These reactions have major implications for microbial life through the provision of hydrogen (H2). To simulate incipient serpentinization under well-constrained conditions, we reacted centimeter-sized pieces of uncrushed harzburgite with chemically modified seawater at 300 °C and 35 MPa for ca. 1.5 yr (13 441 h), monitored changes in fluid chemistry over time, and examined the secondary mineralogy at the termination of the experiment. Approximately 4 mol% of the protolith underwent alteration forming serpentine, accessory magnetite, chlorite, and traces of calcite and heazlewoodite. Alteration textures bear remarkable similarities to those found in partially serpentinized abyssal peridotites. Neither brucite nor talc precipitated during the experiment. Given that the starting material contained ~4 times more olivine than orthopyroxene on a molar basis, mass balance requires that dissolution of orthopyroxene was significantly faster than dissolution of olivine. Coupled mass transfer of dissolved Si, Mg, and H+ between olivine and orthopyroxene reaction fronts was driven by steep activity gradients and facilitated the precipitation of serpentine. Hydrogen was released in significant amounts throughout the entire experiment; however, the H2 release rate decreased with time. Serpentinization consumed water but did not release significant amounts of dissolved species (other than H2) suggesting that incipient hydration reactions involved a volume increase of ~40%. The reduced access of water to fresh olivine surfaces due to filling of fractures and coating of primary minerals with alteration products led to decreased rates of serpentinization and H2 release. While this concept might seem at odds with completely serpentinized seafloor peridotites, reaction-driven fracturing offers an intriguing solution to the seemingly self-limiting nature of serpentinization. Indeed, the reacted sample revealed several textural features diagnostic of incipient reaction-driven fracturing. We conclude that fracturing must have far reaching impacts on the rates of serpentinization and H2 release in peridotite-hosted hydrothermal systems.

Detection of iron substitution in natroalunite-natrojarosite solid solutions and potential implications for Mars

Abstract Natroalunite containing substantial amounts of Fe occurs as a prominent secondary phase during acid-sulfate alteration of pyroclastic basalts in volcanic fumaroles in Nicaragua and elsewhere, and has been observed in laboratory simulations of acid-sulfate alteration as well. Reaction path models constrained by field and experimental observations predict that Fe-rich natroalunite should also form as a major secondary phase during alteration of martian basalt under similar circumstances. Here, we evaluate the potential to use spectroscopic methods to identify minerals from the alunite group with chemical compositions intermediate between natroalunite and natrojarosite on the surface of Mars, and to remotely infer their Fe contents. X-ray diffraction and spectroscopic measurements (Raman, visible/ near infrared, mid-infrared, Mössbauer) were obtained for a suite of synthetic solid solutions with a range of Fe contents ranging from natroalunite to natrojarosite. In the visible/near infrared, minerals with intermediate compositions display several spectral features not evident in end-member spectra that could be used to remotely identify these minerals and infer their composition. In addition, Raman spectra, mid-infrared spectra, and X-ray diffraction peaks all show systematic variation with changing Fe content, indicating that these methods could potentially be used to infer mineral compositions as well. The results suggest that alunite group minerals with intermediate Fe compositions may be able to account for some visible/near-infrared and Mössbauer spectral features from Mars that had previously been unidentified or attributed to other phases. Overall, our findings indicate that consideration of solid solutions may lead to new identifications of alunite group minerals on the surface of Mars, and raise the possibility that minerals with compositions intermediate between natroalunite and natrojarosite may be widely distributed on the planet.

Fe 3 O 4 @organic@Au

The synthesis and characterization of core-shell Fe(3)O(4)@organic@Au nanoparticles displaying plasmonic behavior, high magnetism, and high relaxivity is presented. The incorporation of a thin organic layer between the two metals is crucial in maintaining the saturation magnetisation of the superparamagnetic core.