Organic matter (OM) sulfurization can enhance the preservation and sequestration of carbon in anoxic sediments, and it has been observed in sinking marine particles from marine O2‐deficient zones. The magnitude of this effect on carbon burial remains unclear, however, because the transformations that occur when sinking particles encounter sulfidic conditions remain undescribed. Here, we briefly expose sinking marine particles from the eastern tropical North Pacific O2‐deficient zone to environmentally relevant sulfidic conditions (20°C, 0.5 mM [poly]sulfide, 2 days) and then characterize the resulting solid‐phase organic and inorganic products in detail. During these experiments, the abundance of organic sulfur in both hydrolyzable and hydrolysis‐resistant solids roughly triples, indicating extensive OM sulfurization. Lipids also sulfurize on this time scale, albeit less extensively. In all three pools, OM sulfurization produces organic monosulfides, thiols, and disulfides. Hydrolyzable sulfurization products appear within ≤200‐μm regions of relatively homogeneous composition that are suggestive of sulfurized extracellular polymeric substances (EPS). Concurrently, reactions with particulate iron oxyhydroxides generate low and fairly uniform concentrations of iron sulfide (FeS) within these same EPS‐like materials. Iron oxyhydroxides were not fully consumed during the experiment, which demonstrates that organic materials can be competitive with reactive iron for sulfide. These experiments support the hypothesis that sinking, OM‐rich and EPS‐rich particles in a sulfidic water mass can sulfurize within days, potentially contributing to enhanced sedimentary carbon sequestration. Additionally, sulfur‐isotope and chemical records of organic S and iron sulfides in sediments have the potential to incorporate signals from water column processes.

Climate change is driving an expansion of marine oxygen-deficient zones, which may alter the global cycles of carbon, sulfur, nitrogen, and trace metals. Currently, however, we lack a full mechanistic understanding of how oxygen deficiency affects organic carbon cycling and burial. Here, we show that cryptic microbial sulfate reduction occurs in sinking particles from the eastern tropical North Pacific oxygen-deficient zone and that some microbially produced sulfide reacts rapidly to form organic sulfur that is resistant to acid hydrolysis. Particle-hosted sulfurization could enhance carbon preservation in sediments underlying oxygen-deficient water columns and serve as a stabilizing feedback between expanding anoxic zones and atmospheric carbon dioxide. A similar mechanism may help explain more-extreme instances of organic carbon preservation associated with marine anoxia in Earth history.

Manganese-bearing minerals in ancient strata provide a particularly informative record of the redox potentials of ancient Earth surface environments due to the high specificity of species that can oxidize Mn(II). However, little is known about how this sedimentary archive might have been altered by processes occurring long after lithification, including the effects of metamorphism, fluid mobilization, and metasomatisrn. We investigated Mn mineralization across known metamorphic gradients in the Kaapvaal craton, South Africa, in Archean and early Paleoproterozoic age carbonate-, shale-, and iron formation-bearing marine strata. We sampled contemporaneous strata that record the drowning of the Campbellrand-Malmani carbonate platform and a transition to iron formation deposition in a range of localities, from two metamorphosed (greenschist and above, affected by the intrusion of the Bushveld igneous complex) and four better-preserved (sub-greenschist) deep subsurface drill cores. To evaluate the geochemistry and mineralization tied directly to petrographic textures and cross-cutting relationships, we combined bulk geochemistry with light and electron microscopy and synchrotron microprobe X-ray absorption spectroscopy and imaging to produce Mn speciation maps at the requisite micrometer length scales for these textures. Samples with lesser degrees of post-depositional transformation contained minor amounts of Mn(II) in early diagenetic marine carbonate cements and detrital carbonate grains, while metamorphosed samples typically contained Mn concentrated into a combination of coarse-grained and vein-filling carbonate phases (ankerite, siderite, and rhodochrosite), garnet and amphibole. Chemical imaging analyses of these more metamorphosed samples show that Mn is held by phases and textures that mineralized post-deposition and lithification, demonstrating that Mn was mobilized - at least locally - by metasomatic fluids, although it is difficult to distinguish whether this Mn was original to these strata or was introduced secondarily. Our results confirm that Mn can be mobilized and therefore caution should be applied when interpreting Mn enrichments in sedimentary rocks, especially when Mn enrichment is not geographically extensive and coincides with metamorphic processes.

Coastal environments like mangrove forests are increasingly recognized as potential hotspots for organic carbon burial, giving them a crucial and yet poorly constrained role in the global carbon cycle. Mangrove sediments are frequently anoxic, which facilitates elevated organic matter (OM) burial via several mechanisms, including sulfurization - abiotic reactions between dissolved (poly) sulfide and OM that decrease its lability. Although sulfurization was estimated to account for roughly half of OM preservation in a Bermuda mangrove forest, both its mechanisms and its global significance remain poorly understood. In this study, we investigate S cycling in mangrove forest sediments from Little Ambergris Cay, Turks and Caicos Islands, an environment with predominantly microbial OM inputs and no major source of terrestrial iron. We characterize the Sand C-isotope composition and organic S speciation of sedimentary OM fractions with varying degrees of resistance to acid hydrolysis, along with other inorganic S phases. Near the surface of a 3-mm-diameter, O-2-releasing root, abundant organic and elemental S with a S-34-depleted composition indicates microbial sulfur cycling and OM sulfurization. A mixture of pyrite, elemental S, and organic S form a plaque within the outer 50 mu m m of the root, which also contains strongly S-34-depleted sulfate in its xylem. OM sulfurization products in the sediments include both the alkyl sulfides and disulfides associated with the root plaque and more oxidized forms, especially sulfonates. Hydrolysis-resistant organic S in the sediments is consistently 3-5 h more S-34-enriched than coexisting elemental S, matching the reported kinetic isotope fractionation factor for OM sulfurization via reaction with polysulfides. These sediments also contain a substantial pool of solid-phase, hydrolyzable organic S with a seawater sulfate-like isotope composition, largely in the form of sulfate esters, which may represent excretions from abundant gastropods. The coexistance of sulfurized OM and aerobic macrofauna highlights how understanding spatial scales and/or temporal cycles in local redox state is critical for predicting net OM preservation, especially in dynamic, coastal environments. Future attempts to mechanistically predict changes in carbon storage in coastal systems will benefit from incorporating OM sulfurization as both a sink for microbially produced sulfide and a mechanism for enhanced carbon sequestration.

Map-X is a planetary instrument concept for 2D X-Ray Fluorescence (XRF) spectroscopy. The instrument is placed directly on the surface of an object and held in a fixed position during the measurement. The formation of XRF images on the CCD detector relies on a multichannel optic configured for 1:1 imaging and can be analyzed through the point spread function (PSF) of the optic. The PSF can be directly measured using a micron-sized monochromatic X-ray source in place of the sample. Such PSF measurements were carried out at the Stanford Synchrotron and are compared with ray tracing simulations. It is shown that artifacts are introduced by the periodicity of the PSF at the channel scale and the proximity of the CCD pixel size and the optic channel size. A strategy of sub-channel random moves was used to cancel out these artifacts and provide a clean experimental PSF directly usable for XRF image deconvolution.

1Division of Geological and Planetary Sciences, California Institute of Technology, 1200 East California Boulevard, Pasadena, CA 91125, USA; 2Tintina Resources Inc., 17 E. Main Street, P.O. Box 431, White Sulphur Springs, MT, 59645, USA;3Stanford Synchrotron Radiation Lightsource, Menlo Park, CA 94025, USA;4EarthLife Science Institute, Tokyo Institute of Technology, Meguro-ku, Toyko 152-8550, Japan;*sslotz@caltech.edu

Large-scale Synchrotron Rapid Scanning X-ray Fluorescence (SRS-XRF) elemental mapping and X-ray absorption spectroscopy are applied here to fossil leaf material from the 50 Mya Green River Formation (USA) in order to improve our understanding of the chemistry of fossilized plant remains. SRS-XRF of fossilized animals has previously shown that bioaccumulated trace metals and sulfur compounds may be preserved in their original distributions and these elements can also act as biomarkers for specific biosynthetic pathways. Similar spatially resolved chemical data for fossilized plants is sparsely represented in the literature despite the multitude of other chemical studies performed. Here, synchrotron data from multiple specimens consistently show that fossil leaves possess chemical inventories consisting of organometallic and organosulfur compounds that: (1) map discretely within the fossils, (2) resolve fine scale biological structures, and (3) are distinct from embedding sedimentary matrices. Additionally, the chemical distributions in fossil leaves are directly comparable to those of extant leaves. This evidence strongly suggests that a significant fraction of the chemical inventory of the examined fossil leaf material is derived from the living organisms and that original bioaccumulated elements have been preserved in situ for 50 million years. Chemical information of this kind has so far been unknown for fossilized plants and could for the first time allow the metallome of extinct flora to be studied.

The chemical speciation and distribution of potentially toxic metal(loid)s in mine wastes is critical to assessing the risks posed by these wastes and predicting the potential bioavailability of the metal(loid)s present. Of additional potential importance is the role of particle size in the fate, transport, and toxicity of contaminated mining materials. Spectroscopic analyses of size-separated mine tailings and adjacent background samples from the Randsburg Historic Mining District, California were conducted to quantify the speciation and distribution of arsenic (As) as a function of particle size. Micro-X-ray fluorescence (μXRF) mapping of separate size fractions was used to identify multiple populations of particles with different As:Fe ratios, indicating a variety of distinct arsenic-bearing species. Bulk extended X-ray absorption fine structure (EXAFS) spectroscopy identified phases including arseniosiderite, Ca2Fe33+(AsO4)3O3·3H2O, and As(V) sorbed to iron hydroxides (ferrihydrite, goethite), confirming a strong statistical correlation between arsenic and iron observed in both μXRF studies and bulk chemical analyses. Differences in As speciation between the mine tailings and background samples also suggest that weathering of crystalline As-bearing phases in tailings leads to sorption of dissolved arsenic to iron hydroxides in nontailings background material.

Well-preserved fossils of pivotal early bird and nonavian theropod species have provided unequivocal evidence for feathers and/or downlike integuments. Recent studies have reconstructed color on the basis of melanosome structure; however, the chemistry of these proposed melanosomes has remained unknown. We applied synchrotron x-ray techniques to several fossil and extant organisms, including Confuciusornis sanctus, in order to map and characterize possible chemical residues of melanin pigments. Results show that trace metals, such as copper, are present in fossils as organometallic compounds most likely derived from original eumelanin. The distribution of these compounds provides a long-lived biomarker of melanin presence and density within a range of fossilized organisms. Metal zoning patterns may be preserved long after melanosome structures have been destroyed.