Determination of photochemically available iron in ambient aerosols

Experiments to determine the concentration of photochemically available Fe in ambient aerosol samples were carried out using a novel photochemical extraction procedure. Ambient aerosol samples, which were collected on Teflon filters, were suspended in an aqueous solution within a photochemical reactor and irradiated. Under these conditions, which were favorable to the photochemical weathering of aerosol particles, the relative amount of Fe(II)_(aq) to Fe_(total) was shown to increase. The extent and rate of Fe(II)_(aq) photoproduction was used to characterize the Fe in aerosol samples collected from Whiteface Mountain, New York, Pasadena, California, San Nicholas Island, California, and Yosemite National Park, California. Photochemically available Fe concentrations found ranged from <4 ng m^(−3) (0.07 nmole m^(−3)) to 308 ng m^(−3) (5.52 nmole m^(−3)), Fe_(total) concentrations ranged from 10 ng m^(−3) (0.18 nmole m^(−3)) to 3400 ng m^(−3) (61 nmole m^(−3)), and the percentage of photochemically available Fe to Fe_(total) ranged from 2.8% to 100%. Aerosol samples were also collected during biomass burning events in southern California; these samples showed insignificant changes in the photochemically available Fe (compared to nonbiomass burning samples) in conjunction with large increases of Fe_(total). Calculations based on these experiments also provide further evidence that redox reactions of Fe in cloudwater could be an important in situ source of oxidants (OH, HO_2/O_2^−). The estimated oxidant production rate in cloudwater based on these experiments is between 0 and 60 nM s^(−1), with an average value of 16 nM s^(−1). This estimated in situ oxidant production rate due to Fe chemistry is approximately equal to previous estimates of the oxidant flux to cloudwater from the gas phase

Coupled x-ray fluorescence and x-ray absorption spectroscopy for microscale imaging and identification of sulfur species within tissues and skeletons of scleractinian corals

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Analytical Chemistry 90 (2018): 12559–12566, doi:10.1021/acs.analchem.8b02638.Identifying and mapping the wide range of sulfur species within complex matrices presents a challenge for under-standing the distribution of these important biomolecules within environmental and biological systems. Here, we present a coupled micro X-ray fluorescence (μXRF) and X-ray absorption near edge structure (XANES) spectroscopy method for determining the presence of specific sulfur species in coral tissues and skeletons at high spatial resolution. By using multiple energy stacks and principal component analysis of a large spectral database, we were able to more accurately identify sulfur species components and distinguish different species and distributions of sulfur formerly unresolved by previous studies. Specifically, coral tissues were domi-nated by more reduced sulfur species, such as glutathione disulfide, cysteine and sulfoxide, as well as organic sulfate as represented by chondroitin sulfate. Sulfoxide distributions were visually correlated with the presence of zooxanthellae endosymbionts. Coral skeletons were composed primarily of carbonate-associated sulfate (CAS), along with minor contributions from organic sulfate and a separate inorganic sulfate likely in the form of adsorbed sulfate. This coupled XRF-XANES approach allows for a more accurate and informative view of sulfur within biological systems in situ, and holds great promise for pairing with other techniques to allow for a more encompassing understanding of elemental distributions within the environment.We thank Ray Dalio for funding the Micronesian expedition and K. Hughen,This material is based upon work supported by the Na-tional Science Foundation Graduate Research Fellowship under Grant No. 1122374 and a Ford Foundation Dissertation Fellowship for Gabriela Farfan

Manganese mineralogy and diagenesis in the sedimentary rock record

Oxidation of manganese(II) to manganese(III,IV) demands oxidants with very high redox potentials; consequently, manganese oxides are both excellent proxies for molecular oxygen and highly favorable electron acceptors when oxygen is absent. The first of these features results in manganese-enriched sedimentary rocks (manganese deposits, commonly Mn ore deposits), which generally correspond to the availability of molecular oxygen in Earth surface environments. And yet because manganese reduction is promoted by a variety of chemical species, these ancient manganese deposits are often significantly more reduced than modern environmental manganese-rich sediments. We document the impacts of manganese reduction and the mineral phases that form stable manganese deposits from seven sedimentary examples spanning from modern surface environments to rocks over 2 billion years old. Integrating redox and coordination information from synchrotron X-ray absorption spectroscopy and X-ray microprobe imaging with scanning electron microscopy and energy and wavelength-dispersive spectroscopy, we find that unlike the Mn(IV)-dominated modern manganese deposits, three manganese minerals dominate these representative ancient deposits: kutnohorite (CaMn(CO_3)_2), rhodochrosite (MnCO_3), and braunite (Mn(III)_6Mn(II)O_8SiO_4). Pairing these mineral and textural observations with previous studies of manganese geochemistry, we develop a paragenetic model of post-depositional manganese mineralization with kutnohorite and calcian rhodochrosite as the earliest diagenetic mineral phases, rhodochrosite and braunite forming secondarily, and later alteration forming Mn-silicates

Mid-Proterozoic Ferruginous Conditions Reflect Postdepositional Processes

To evaluate the mechanics of mid‐Proterozoic environmental iron transport and deposition, we coupled microscale textural and bulk rock magnetic techniques to study the ~1.4‐Ga lower Belt group, Belt Supergroup, Montana and Idaho. We identified a pyrrhotite‐siderite isograd that marks metamorphic iron‐bearing mineral reactions beginning in subgreenschist facies samples. Even in the best‐preserved parts of the basin, secondary overprints were common including recrystallization of iron‐bearing sulfides, base metal sulfides, and nanophase pyrrhotite. Despite these overprints, a record of redox chemistry was preserved in the early diagenetic framboidal pyrite and detrital iron oxides including trace nanoscale magnetite that remained after sulfidization in anoxic and sulfidic sedimentary pore fluids. Based on these results, we interpret the Belt Basin as having oxic waters, at least in shallow‐water environments, with no indication of abundant ferrous iron in the water column; this is consistent with the cooccurrence of early eukaryotic fossils within the same strata

Iron mineralogy and redox conditions during deposition of the mid-Proterozoic Appekunny Formation, Belt Supergroup, Glacier National Park

The redox state of the mid-Proterozoic oceans, lakes, and atmospheres is still debated, but it is vital for understanding the emergence and rise of macroscopic organisms and eukaryotes. The Appekunny Formation, Belt Supergroup, Montana, contains some of these early macrofossils dated between 1.47 Ga and 1.40 Ga and provides a well-preserved record of paleoenvironmental conditions. We analyzed the iron chemistry and mineralogy in samples from Glacier National Park, Montana, by pairing bulk rock magnetic techniques with textural techniques, including light microscopy, scanning electron microscopy, and synchrotron-based X-ray absorption spectroscopy. Field observations of the Appekunny Formation combined with mineralogical information allowed revised correlations of stratigraphic members across the park. However, late diagenetic and/or metasomatic fluids affected primary iron phases, as evidenced by prevalent postdepositional phases including base-metal sulfides. On the west side of the park, pyrrhotite and chlorite rims formed during burial metamorphism in at least two recrystallization events. These complex postdepositional transformations could affect bulk proxies for paleoredox. By pairing bulk and textural techniques, we show primary records of redox chemistry were preserved in early diagenetic and often recrystallized framboidal pyrite, submicron magnetite grains interpreted to be detrital in origin, and red-bed laminae interpreted to record primary detrital oxides. Based on these observations, we hypothesize that the shallow waters of the mid-Proterozoic Belt Basin were similar to those in modern marine and lacustrine waters: fully oxygenated, with detrital reactive iron fluxes that mineralized pyrite during organic diagenesis in suboxic, anoxic, and sulfidic conditions in sedimentary pore waters

Hierarchical biota-level and taxonomic controls on the chemistry of fossil melanosomes revealed using synchrotron X-ray fluorescence

Fossil melanosomes, micron-sized granules rich in melanin in vivo, provide key information for investigations of the original coloration, taxonomy and internal anatomy of fossil vertebrates. Such studies rely, in part, on analysis of the inorganic chemistry of preserved melanosomes and an understanding of melanosome chemical taphonomy. The extent to which the preserved chemistry of fossil melanosomes is biased by biotic and abiotic factors is, however, unknown. Here we report the discovery of hierarchical controls on the inorganic chemistry of melanosomes from fossil vertebrates from nine biotas. The chemical data are dominated by a strong biota-level signal, indicating that the primary taphonomic control is the diagenetic history of the host sediment. This extrinsic control is superimposed by a biological, tissue-level control; tissue-specific chemical variation is most likely to survive in fossils where the inorganic chemistry of preserved melanosomes is distinct from that of the host sediment. Comparative analysis of our data for fossil and modern amphibians reveals that most fossil specimens show tissue-specific melanosome chemistries that differ from those of extant analogues, strongly suggesting alteration of original melanosome chemistry. Collectively, these findings form a predictive tool for the identification of fossil deposits with well-preserved melanosomes amenable to studies of fossil colour and anatomy

Maturation experiments reveal bias in the chemistry of fossil melanosomes

Fossil melanosomes are a major focus of paleobiological research because they can inform on the original coloration, phylogenetic affinities, and internal anatomy of ancient animals. Recent studies of vertebrate melanosomes revealed tissue-specific trends in melanosome-metal associations that can persist in fossils. In some fossil vertebrates, however, melanosomes from all body regions are enriched only in Cu, suggesting diagenetic overprinting of original chemistry. We tested this hypothesis using laboratory experiments on melanosomes from skin and liver of the African clawed frog Xenopus laevis. After maturation in Cu-rich media, the metal chemistry of melanosomes from these tissues converged toward a common composition, and original differences in Cu oxidation state were lost. Elevated Cu concentrations and a pervasive Cu(II) signal are likely indicators of diagenetically altered melanosomes. These results provide a robust experimental basis for interpretating the chemistry of fossil melanosomes

Synchrotron x-ray fluorescence analysis reveals diagenetic alteration of fossil melanosome trace metal chemistry

A key feature of the pigment melanin is its high binding affinity for trace metal ions. In modern vertebrates trace metals associated with melanosomes, melanin-rich organelles, can show tissue-specific and taxon-specific distribution patterns. Such signals preserve in fossil melanosomes, informing on the anatomy and phylogenetic affinities of fossil vertebrates. Fossil and modern melanosomes, however, often differ in trace metal chemistry; in particular, melanosomes from fossil vertebrate eyes are depleted in Zn and enriched in Cu relative to their extant counterparts. Whether these chemical differences are biological or taphonomic in origin is unknown, limiting our ability to use melanosome trace metal chemistry to test palaeobiological hypotheses. Here, we use maturation experiments on eye melanosomes from extant vertebrates and synchrotron rapid scan-x-ray fluorescence analysis to show that thermal maturation can dramatically alter melanosome trace element chemistry. In particular, maturation of melanosomes in Cu-rich solutions results in significant depletion of Zn, probably due to low pH and competition effects with Cu. These results confirm fossil melanosome chemistry is susceptible to alteration due to variations in local chemical conditions during diagenesis. Maturation experiments can provide essential data on melanosome chemical taphonomy required for accurate interpretations of preserved chemical signatures in fossils