ALBERT

Description: Felsic volcanic rocks are abundant in ancient greenstone belts and important host rocks for volcanogenic massive sulfide (VMS) deposits. About half of all VMS deposits are hosted by dacite or rhyolite, an association that reflects anomalous heat flow during rifting, partial melting of basaltic crust, and fractional crystallization in high-level magma chambers. For over 30 years, geochemical signatures of these rocks (e.g., F classification of Archean rhyolites) have been widely used to identify possible hosts for VMS deposits in ancient greenstone belts. However, comparisons with modern oceanic settings have been limited, owing to a lack of samples of felsic volcanic rocks from the sea floor. This is changing with increasing exploration of the oceans. In this study, we have compiled high-quality geochemical analyses of more than 2,200 unique samples of submarine felsic volcanic rocks (>60 wt % SiO2) from a wide range of settings, including mid-ocean ridges, ridge-hot-spot intersections, intraoceanic arc and back-arc spreading centers, and ocean islands. The compiled data show significant geochemical diversity spanning the full range of compositions of rhyolites found in ancient greenstone belts. This diversity is interpreted to reflect variations in crustal thickness, the presence or absence of slab-derived fluids (dry melting versus wet melting), and mantle anomalies. Highly variable melting conditions are thought to be related to short-lived microplate domains, such as those caused by diffuse spreading and multiple overlapping spreading centers. Systematic differences in the compositions of felsic volcanic rocks in the modern oceanic settings are revealed by a combination of principal components analysis, unsupervised hierarchical clustering, and supervised random forest classification of the compiled data. Dacites and rhyolites from midocean ridge settings have moderately depleted mantle signatures, whereas rocks from ridge-hot-spot intersections and ocean islands reflect enriched mantle sources. Felsic volcanic rocks from arc-back-arc systems have strongly depleted mantle signatures and well-known subduction-related chemistry (strong large ion lithophile element enrichment in combination with strong negative Nb-Ta anomalies and low heavy rare earth elements [HREEs]). This contrasts with felsic volcanic rocks in Archean greenstone belts, which show high field strength element and HREE enrichment (so-called FIIIb-type) due to a less depleted mantle, a lack of wet melting, and variable crustal contamination. The differences between modern and ancient volcanic rocks are interpreted to reflect the lower mantle temperatures, thinner crust, and subduction-related processes in present-day settings. We suggest that the abundance of FIIIb-type felsic volcanic rocks in Archean greenstone belts is related to buoyant microplate domains with thickened oceanic crust that were better preserved on emerging Archean cratons, whereas in post-Archean tectonic settings most of these rocks are subducted.

Description: The 3-D subseafloor architecture of submarine hydrothermal systems is largely unknown, particularly at arc volcanoes. The alteration of volcanic rocks in these systems produces dramatic changes in their magnetic prop- erties. Here, we present the first comprehensive study of paleomagnetic measurements from oriented samples of hydrothermally altered dacites from Brothers volcano (Kermadec arc), drilled during International Ocean Discovery Program (IODP) Expedition 376. These data have enabled insight into the progressive evolution of magnetic minerals in subseafloor volcanic rocks affected by variable types and degrees of hydrothermal alteration in response to varying fluid temperatures, chemistry, and associated mineralization; from initial chlo- ritization typical of relatively low-temperature interaction with seawater to extremely altered rocks affected by higher-temperature, very acidic magmatic fluids. Hydrothermally altered samples show a significant reduction in natural remanent magnetization intensity (10–4 to 10–2 A/m) compared with unaltered samples (1–10 A/m), suggesting that primary titanomagnetite grains are destroyed during the hydrothermal alteration process. Except for a small region in proximity to the mineral- ized stockwork zone, no chemical remanent magnetization is observed in association with hydrothermal altera- tion, consistent with the widespread formation of diamagnetic and/or paramagnetic minerals such as pyrite, rutile, and leucoxene, which do not carry any natural remanent magnetization. Demagnetization experiments show that most of the oriented samples possess a stable characteristic rema- nent magnetization induced by the residual primary magnetic minerals formed at the time the rocks cooled on the sea floor. Partially chloritized dacites, however, are characterized by large magnetic susceptibilities, low Koenigsberger ratios, and very low magnetic coercivities, consistent with initial dissolution of smaller, single- domain magnetic grains, indicating that intensely hydrothermally altered rocks are better paleomagnetic indica- tors than initially chloritized samples at the periphery of the hydrothermal systems. The significant magnetic contrast between fresh and hydrothermally altered rocks, in addition to a thick layer (〉300 m) of demagnetized rocks observed at Brothers volcano, confirms the empirical results that magnetic anomalies are important geophysical tools to determine the geometry of hydrothermal systems at submarine arc volcanoes.

Description: Published

Description: 1605–1627

Description: OSA1: Variazioni del campo magnetico terrestre, imaging crostale e sicurezza del territorio

Description: JCR Journal

Description: Goniodomin A (GDA, 1) is a phycotoxin produced by at least four species of Alexandrium dinoflagellates that are found globally in brackish estuaries and lagoons. It is a linear polyketide with six oxygen heterocyclic rings that is cyclized into a macrocyclic structure via lactone formation. Two of the oxygen heterocycles in 1 comprise a spiro-bis-pyran, whereas goniodomin B (GDB) contains a 2,7-dioxabicyclo[3.3.1]nonane ring system fused to a pyran. When H2O is present, 1 undergoes facile conversion to isomer GDB and to an α,β-unsaturated ketone, goniodomin C (GDC, 7). GDB and GDC can be formed from GDA by cleavage of the spiro-bis-pyran ring system. GDA, but not GDB or GDC, forms a crown ether-type complex with K+. Equilibration of GDA with GDB and GDC is observed in the presence of H+ and of Na+, but the equilibrated mixtures revert to GDA upon addition of K+. Structural differences have been found between the K+ and Na+ complexes. The association of GDA with K+ is strong, while that with Na+ is weak. The K+ complex has a compact, well-defined structure, whereas Na+ complexes are an ill-defined mixture of species. Analyses of in vitro A. monilatum and A. hiranoi cultures indicate that only GDA is present in the cells; GDB and GDC appear to be postharvest transformation products.

Description: The uptake ability toward arsenic(V), chromium(VI), and boron(III) ions of ad hoc functionalized magnetic nanostructured devices has been investigated. To this purpose, ligands based on meglumine have been synthesized and used to coat magnetite nanoparticles (Fe3O4) obtained by the co-precipitation methodology. The as-prepared hybrid material was characterized by infrared spectroscopy (IR), X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy combined with energy-dispersive X-ray analysis. Moreover, its magnetic hysteresis properties were measured to evaluate its magnetic properties, and the adsorption kinetics and isothermal models were applied to discern between the different adsorption phenomena. Specifically, the better fitting was observed by the Langmuir isotherm model for all metal ions tested, highlighting a higher uptake in arsenic (28.2 mg/g), chromium (12.3 mg/g), and boron (23.7 mg/g) sorption values if compared with other magnetic nanostructured materials. After adsorption, an external magnetic stimulus can be used to efficiently remove nanomaterials from the water. Finally the nanomaterial can be reused up to five cycles and regenerated for another three cycles.

Description: Published

Description: 10775–10788

Description: 1A. Geomagnetismo e Paleomagnetismo

Description: JCR Journal

Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in James, B., de Vos, A., Aluwihare, L., Youngs, S., Ward, C., Nelson, R., Michel, A., Hahn, M., & Reddy, C. Divergent forms of pyroplastic: lessons learned from the M/V X-Press Pearl ship fire. ACS Environmental Au, 2(5), (2022): 467–479, https://doi.org/10.1021/acsenvironau.2c00020.

Description: In late May 2021, the M/V X-Press Pearl container ship caught fire while anchored 18 km off the coast of Colombo, Sri Lanka and spilled upward of 70 billion pieces of plastic or “nurdles” (∼1680 tons), littering the country’s coastline. Exposure to combustion, heat, chemicals, and petroleum products led to an apparent continuum of changes from no obvious effects to pieces consistent with previous reports of melted and burned plastic (pyroplastic) found on beaches. At the middle of this continuum, nurdles were discolored but appeared to retain their prefire morphology, resembling nurdles that had been weathered in the environment. We performed a detailed investigation of the physical and surface properties of discolored nurdles collected on a beach 5 days after the ship caught fire and within 24 h of their arrival onshore. The color was the most striking trait of the plastic: white for nurdles with minimal alteration from the accident, orange for nurdles containing antioxidant degradation products formed by exposure to heat, and gray for partially combusted nurdles. Our color analyses indicate that this fraction of the plastic released from the ship was not a continuum but instead diverged into distinct groups. Fire left the gray nurdles scorched, with entrained particles and pools of melted plastic, and covered in soot, representing partial pyroplastics, a new subtype of pyroplastic. Cross sections showed that the heat- and fire-induced changes were superficial, leaving the surfaces more hydrophilic but the interior relatively untouched. These results provide timely and actionable information to responders to reevaluate cleanup end points, monitor the recurrence of these spilled nurdles, gauge short- and long-term effects of the spilled nurdles to the local ecosystem, and manage the recovery of the spill. These findings underscore partially combusted plastic (pyroplastic) as a type of plastic pollution that has yet to be fully explored despite the frequency at which plastic is burned globally.

Description: This work was supported by the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution (WHOI), with funding provided by the Weston Howland Jr. Postdoctoral Scholarship. Additional support was provided by the WHOI Marine Microplastics Catalyst Program, the WHOI Marine Microplastics Innovation Accelerator Program, the WHOI Investment in Science Fund, the March Marine Initiative (a program of March Limited, Bermuda), The Seaver Institute, Gerstner Philanthropies, the Wallace Research Foundation, the Richard Saltonstall Charitable Foundation, the Harrison Foundation, Hollis and Ermine Lovell Charitable Foundation, and the Richard Grand Foundation. AdV was supported by funding from the Schmidt Foundation.

Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Walsh, A. N., Reddy, C. M., Niles, S. F., McKenna, A. M., Hansel, C. M., & Ward, C. P. Plastic formulation is an emerging control of its photochemical fate in the ocean. Environmental Science & Technology, 55(18), (2021): 12383–12392, https://doi.org/10.1021/acs.est.1c02272.

Description: Sunlight exposure is a control of long-term plastic fate in the environment that converts plastic into oxygenated products spanning the polymer, dissolved, and gas phases. However, our understanding of how plastic formulation influences the amount and composition of these photoproducts remains incomplete. Here, we characterized the initial formulations and resulting dissolved photoproducts of four single-use consumer polyethylene (PE) bags from major retailers and one pure PE film. Consumer PE bags contained 15–36% inorganic additives, primarily calcium carbonate (13–34%) and titanium dioxide (TiO2; 1–2%). Sunlight exposure consistently increased production of dissolved organic carbon (DOC) relative to leaching in the dark (3- to 80-fold). All consumer PE bags produced more DOC during sunlight exposure than the pure PE (1.2- to 2.0-fold). The DOC leached after sunlight exposure increasingly reflected the 13C and 14C isotopic composition of the plastic. Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry revealed that sunlight exposure substantially increased the number of DOC formulas detected (1.1- to 50-fold). TiO2-containing bags photochemically degraded into the most compositionally similar DOC, with 68–94% of photoproduced formulas in common with at least one other TiO2-containing bag. Conversely, only 28% of photoproduced formulas from the pure PE were detected in photoproduced DOC from the consumer PE. Overall, these findings suggest that plastic formulation, especially TiO2, plays a determining role in the amount and composition of DOC generated by sunlight. Consequently, studies on pure, unweathered polymers may not accurately represent the fates and impacts of the plastics entering the ocean.

Description: Funding was provided by the Seaver Institute, the Gerstner Family Foundation, Woods Hole Oceanographic Institution, and the National Science Foundation Graduate Research Fellowship Program (A.N.W.). The Ion Cyclotron Resonance user facility at the National High Magnetic Field Laboratory is supported by the National Science Foundation Division of Chemistry and Division of Materials Research through DMR-1644779 and the State of Florida.

Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Colson, B. C., & Michel, A. P. M. Flow-through quantification of microplastics using impedance spectroscopy. ACS Sensors, 6(1), (2021): 238–244, doi:10.1021/acssensors.0c02223.

Description: Understanding the sources, impacts, and fate of microplastics in the environment is critical for assessing the potential risks of these anthropogenic particles. However, our ability to quantify and identify microplastics in aquatic ecosystems is limited by the lack of rapid techniques that do not require visual sorting or preprocessing. Here, we demonstrate the use of impedance spectroscopy for high-throughput flow-through microplastic quantification, with the goal of rapid measurement of microplastic concentration and size. Impedance spectroscopy characterizes the electrical properties of individual particles directly in the flow of water, allowing for simultaneous sizing and material identification. To demonstrate the technique, spike and recovery experiments were conducted in tap water with 212–1000 μm polyethylene beads in six size ranges and a variety of similarly sized biological materials. Microplastics were reliably detected, sized, and differentiated from biological materials via their electrical properties at an average flow rate of 103 ± 8 mL/min. The recovery rate was ≥90% for microplastics in the 300–1000 μm size range, and the false positive rate for the misidentification of the biological material as plastic was 1%. Impedance spectroscopy allowed for the identification of microplastics directly in water without visual sorting or filtration, demonstrating its use for flow-through sensing.

Description: The authors thank the Richard Saltonstall Charitable Foundation and the National Academies Keck Futures Initiative (NAKFI DBS13) for their funding support.

Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Gosselin, K. M., Nelson, R. K., Spivak, A. C., Sylva, S. P., Van Mooy, B. A. S., Aeppli, C., Sharpless, C. M., O’Neil, G. W., Arrington, E. C., Reddy, C. M., & Valentine, D. L. Production of two highly abundant 2-methyl-branched fatty acids by blooms of the globally significant marine cyanobacteria Trichodesmium erythraeum. ACS Omega, 6(35), (2021): 22803–22810, https://doi.org/10.1021/acsomega.1c03196.

Description: The bloom-forming cyanobacteria Trichodesmium contribute up to 30% to the total fixed nitrogen in the global oceans and thereby drive substantial productivity. On an expedition in the Gulf of Mexico, we observed and sampled surface slicks, some of which included dense blooms of Trichodesmium erythraeum. These bloom samples contained abundant and atypical free fatty acids, identified here as 2-methyldecanoic acid and 2-methyldodecanoic acid. The high abundance and unusual branching pattern of these compounds suggest that they may play a specific role in this globally important organism.

Description: This work was funded with grants from the National Science Foundation grants OCE-1333148, OCE-1333162, and OCE-1756254 and the Woods Hole Oceanographic Institution (IR&D). GCxGC analysis made possible by WHOI’s Investment in Science Fund.

Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Mazzotta, M. G., Reddy, C. M., & Ward, C. P. Rapid degradation of cellulose diacetate by marine microbes. Environmental Science & Technology Letters, 9(1), (2022): 37-41. https://doi.org/10.1021/acs.estlett.1c00843.

Description: The persistence of cellulose diacetate (CDA), a biobased plastic used in textiles and single-use consumer products, in the ocean is currently unknown. Here, we probe the disintegration and degradation of CDA-based materials (25 μm films, 510 μm foam, and 97 g/m2 fabric) by marine microbes in a continuous flow seawater mesocosm. Photographic evidence and mass loss measurements demonstrate that CDA-based materials disintegrate in months. Disintegration is marked by the increasing esterase and cellulase activity of the biofilm community, suggesting that marine microbes degrade CDA. The natural abundance stable (13C) and radiocarbon (14C) isotopic signature of carbon dioxide respired during short-term bottle incubations confirms the rapid degradation of both acetyl and cellulosic components of CDA by seawater microbial communities. These findings challenge the paradigm set by governmental agencies and advocacy groups that CDA-based materials persist in the ocean for decades, and represent a positive step toward identifying high-utility, biobased plastics with low environmental persistence.

Description: M.G.M., C.M.R., and C.P.W. thank Eastman Chemical Co. and Woods Hole Oceanographic Institution (WHOI) for scientific and financial support.

Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Xie, L., Liu, X., Caratenuto, A., Tian, Y., Chen, F., DeGiorgis, J. A., Wan, Y., & Zheng, Y. Environmentally friendly and efficient hornet nest envelope-based photothermal absorbers. Acs Omega, 6(50), (2021): 34555–34562, https://doi.org/10.1021/acsomega.1c04851.

Description: Water shortage is a critical global issue that threatens human health, environmental sustainability, and the preservation of Earth’s climate. Desalination from seawater and sewage is a promising avenue for alleviating this stress. In this work, we use the hornet nest envelope material to fabricate a biomass-based photothermal absorber as part of a desalination isolation system. This system realizes an evaporation rate of 3.98 kg m–2 h–1 under one-sun illumination, with prolonged evaporation rates all above 4 kg m–2 h–1. This system demonstrates a strong performance of 3.86 kg m–2 h–1 in 3.5 wt % saltwater, illustrating its effectiveness in evaporation seawater. Thus, with its excellent evaporation rate, great salt rejection ability, and easy fabrication approach, the hornet nest envelope constitutes a promising natural material for solar water treatment applications.

Description: The authors acknowledge the support from the National Science Foundation, USA, through grant number CBET-1941743 and the National Science Foundation under EPSCoR Cooperation Agreement OIA-1655221.

Description: Author Posting. © American Chemical Society, 2014. This article is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Environmental Science and Technology 38 (2014): 4732–4738, doi:10.1021/es4053076.

Description: We present an extensive survey of floating plastic debris in the eastern North and South Pacific Oceans from more than 2500 plankton net tows conducted between 2001 and 2012. From these data we defined an accumulation zone (25 to 41°N, 130 to 180°W) in the North Pacific subtropical gyre that closely corresponds to centers of accumulation resulting from the convergence of ocean surface currents predicted by several oceanographic numerical models. Maximum plastic concentrations from individual surface net tows exceeded 106 pieces km–2, with concentrations decreasing with increasing distance from the predicted center of accumulation. Outside the North Pacific subtropical gyre the median plastic concentration was 0 pieces km–2. We were unable to detect a robust temporal trend in the data set, perhaps because of confounded spatial and temporal variability. Large spatiotemporal variability in plastic concentration causes order of magnitude differences in summary statistics calculated over short time periods or in limited geographic areas. Utilizing all available plankton net data collected in the eastern Pacific Ocean (17.4°S to 61.0°N; 85.0 to 180.0°W) since 1999, we estimated a minimum of 21 290 t of floating microplastic.

Description: This work was supported by Sea Education Association, NFWF-NOAA Marine Debris Program (Nos. 2009-0062-002, NA10OAR4320148, Amend. 71), and NSF (Nos. OCE-0087528, OCE-1155379, OCE-1260403, OCE-1352422).

Description: © The American Chemical Society, 2016. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Analytical Chemistry 88 (2016): 7154–7162, doi:10.1021/acs.analchem.6b01260.

Description: Discovery and identification of molecular biomarkers in large LC/MS data sets requires significant automation without loss of accuracy in the compound screening and annotation process. Here, we describe a lipidomics workflow and open-source software package for high-throughput annotation and putative identification of lipid, oxidized lipid, and oxylipin biomarkers in high-mass-accuracy HPLC-MS data. Lipid and oxylipin biomarker screening through adduct hierarchy sequences, or LOBSTAHS, uses orthogonal screening criteria based on adduct ion formation patterns and other properties to identify thousands of compounds while providing the user with a confidence score for each assignment. Assignments are made from one of two customizable databases; the default databases contain 14 068 unique entries. To demonstrate the software’s functionality, we screened more than 340 000 mass spectral features from an experiment in which hydrogen peroxide was used to induce oxidative stress in the marine diatom Phaeodactylum tricornutum. LOBSTAHS putatively identified 1969 unique parent compounds in 21 869 features that survived the multistage screening process. While P. tricornutum maintained more than 92% of its core lipidome under oxidative stress, patterns in biomarker distribution and abundance indicated remodeling was both subtle and pervasive. Treatment with 150 μM H2O2 promoted statistically significant carbon-chain elongation across lipid classes, with the strongest elongation accompanying oxidation in moieties of monogalactosyldiacylglycerol, a lipid typically localized to the chloroplast. Oxidative stress also induced a pronounced reallocation of lipidome peak area to triacylglycerols. LOBSTAHS can be used with environmental or experimental data from a variety of systems and is freely available at https://github.com/vanmooylipidomics/LOBSTAHS.

Description: This research was supported by the Gordon and Betty Moore Foundation through Grant GBMF3301 to B.A.S.V.M. This research was also funded in part by a grant to B.A.S.V.M. from the Simons Foundation and is a contribution of the Simons Collaboration on Ocean Processes and Ecology (SCOPE). J.R.C. acknowledges support from a U.S. Environmental Protection Agency (EPA) STAR Graduate Fellowship (Fellowship Assistance Agreement No. FP-91744301-0).

Description: Author Posting. © American Chemical Society, 2019. This article is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Kivenson, V., Lemkau, K. L., Pizarro, O., Yoerger, D. R., Kaiser, C., Nelson, R. K., Carmichael, C., Paul, B. G., Reddy, C. M., & Valentine, D. L. (2019). Ocean Dumping of Containerized DDT Waste Was a Sloppy Process. Environmental Science and Technology (2019), doi:10.1021/acs.est.8b05859.

Description: Industrial-scale dumping of organic waste to the deep ocean was once common practice, leaving a legacy of chemical pollution for which a paucity of information exists. Using a nested approach with autonomous and remotely operated underwater vehicles, a dumpsite offshore California was surveyed and sampled. Discarded waste containers littered the site and structured the suboxic benthic environment. Dichlorodiphenyltrichloroethane (DDT) was reportedly dumped in the area, and sediment analysis revealed substantial variability in concentrations of p,p-DDT and its analogs, with a peak concentration of 257 μg g–1, ∼40 times greater than the highest level of surface sediment contamination at the nearby DDT Superfund site. The occurrence of a conspicuous hydrocarbon mixture suggests that multiple petroleum distillates, potentially used in DDT manufacture, contributed to the waste stream. Application of a two end-member mixing model with DDTs and polychlorinated biphenyls enabled source differentiation between shelf discharge versus containerized waste. Ocean dumping was found to be the major source of DDT to more than 3000 km2 of the region’s deep seafloor. These results reveal that ocean dumping of containerized DDT waste was inherently sloppy, with the contents readily breaching containment and leading to regional scale contamination of the deep benthos.

Description: This material is based upon work supported by the National Science Foundation Graduate Research Fellowship for V.K. under Grant No. 1650114. Expeditions AT-18-11 and AT-26-06 were funded by the NSF (OCE-0961725 and OCE-1046144). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. We thank the captain and crew of the RV Atlantis, the pilots and crew of the ROV Jason, the crew of the AUV Sentry, the scientific party of the AT-18-11 and AT-26-06 expeditions, Justin Tran for assistance with the preparation of multibeam data, M. Indira Venkatesan for a helpful discussion of the NOAA datasets, and Nathan Dodder for advice on the procedure for compound identification.

Description: Author Posting. © American Chemical Society, 2011. This article is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Environmental Science and Technology 45 (2011): 9931–9935, doi:10.1021/es202816c.

Description: The impacts on the ocean of releases of radionuclides from the Fukushima Dai-ichi nuclear power plants remain unclear. However, information has been made public regarding the concentrations of radioactive isotopes of iodine and cesium in ocean water near the discharge point. These data allow us to draw some basic conclusions about the relative levels of radionuclides released which can be compared to prior ocean studies and be used to address dose consequences as discussed by Garnier-Laplace et al. in this journal.(1) The data show peak ocean discharges in early April, one month after the earthquake and a factor of 1000 decrease in the month following. Interestingly, the concentrations through the end of July remain higher than expected implying continued releases from the reactors or other contaminated sources, such as groundwater or coastal sediments. By July, levels of 137Cs are still more than 10 000 times higher than levels measured in 2010 in the coastal waters off Japan. Although some radionuclides are significantly elevated, dose calculations suggest minimal impact on marine biota or humans due to direct exposure in surrounding ocean waters, though considerations for biological uptake and consumption of seafood are discussed and further study is warranted.

Description: Funding for this work to KOB is from the Gordon and Betty Moore Foundation as well as the Chemical Oceanography Program of the US National Science Foundation.

Description: Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(16), (2019): 9398-9406, doi:10.1021/acs.est.9b02395.

Description: Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010–0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p 〈 0.001, ρ = 0.90, range = 145–15,900 mg/L), Mn + Fe concentrations (p 〈 0.001, ρ = 0.82, range = 〈0.005–18.5 mg/L), and pH (p 〈 0.001, ρ = −0.67, range = 6.2–9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn–Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

Description: This article was improved by the reviews of John Izbicki and anonymous reviewers for the journal. This work was funded by the California State Water Resources Control Board’s Regional Groundwater Monitoring in Areas of Oil and Gas Production Program and the USGS Cooperative Water Program. A.V., A.J.K., and Z.W were supported by USDA-NIFA grant (#2017-68007-26308). Any use of trade, firm, or product names is for description purposes only and does not imply endorsement by the U.S. Government.

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in McLean, C., & Kujawinski, E. B. AutoTuner: high fidelity and robust parameter selection for metabolomics data processing. Analytical Chemistry, 92(8), (2020): 5724-5732, doi:10.1021/acs.analchem.9b04804.

Description: Untargeted metabolomics experiments provide a snapshot of cellular metabolism but remain challenging to interpret due to the computational complexity involved in data processing and analysis. Prior to any interpretation, raw data must be processed to remove noise and to align mass-spectral peaks across samples. This step requires selection of dataset-specific parameters, as erroneous parameters can result in noise inflation. While several algorithms exist to automate parameter selection, each depends on gradient descent optimization functions. In contrast, our new parameter optimization algorithm, AutoTuner, obtains parameter estimates from raw data in a single step as opposed to many iterations. Here, we tested the accuracy and the run-time of AutoTuner in comparison to isotopologue parameter optimization (IPO), the most commonly used parameter selection tool, and compared the resulting parameters’ influence on the properties of feature tables after processing. We performed a Monte Carlo experiment to test the robustness of AutoTuner parameter selection and found that AutoTuner generated similar parameter estimates from random subsets of samples. We conclude that AutoTuner is a desirable alternative to existing tools, because it is scalable, highly robust, and very fast (∼100–1000× speed improvement from other algorithms going from days to minutes). AutoTuner is freely available as an R package through BioConductor.

Description: We thank Titus Brown and Ben Temperton for advice on the algorithm validation, Arthur Eschenlauer for constructive feedback on the software design, Krista Longnecker for continuous support and discussions, Gabriel Leventhal for mathematics advice, the users of AutoTuner for debugging help through Github, and David Angeles-Albores and two anonymous reviewers for critical feedback on the manuscript. Funding support included the National GEM Consortium and NSF graduate research program fellowships (C.M.) and grants from the MIT Microbiome Center (Award 6936800, E.B.K.) and the Simons Foundation (Award ID #509034, E.B.K.).

Description: Author Posting. © American Chemical Society, 2020. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Chemical Research in Toxicology, 33(4), (2020): 860-879, doi:10.1021/acs.chemrestox.9b00476.

Description: The Ah receptor (AHR) has been studied for almost five decades. Yet, we still have many important questions about its role in normal physiology and development. Moreover, we still do not fully understand how this protein mediates the adverse effects of a variety of environmental pollutants, such as the polycyclic aromatic hydrocarbons (PAHs), the chlorinated dibenzo-p-dioxins (“dioxins”), and many polyhalogenated biphenyls. To provide a platform for future research, we provide the historical underpinnings of our current state of knowledge about AHR signal transduction, identify a few areas of needed research, and then develop concepts such as adaptive metabolism, ligand structural diversity, and the importance of proligands in receptor activation. We finish with a discussion of the cognate physiological role of the AHR, our perspective on why this receptor is so highly conserved, and how we might think about its cognate ligands in the future.

Description: This review is dedicated in memory of the career of Alan Poland, one of the truly great minds in pharmacology and toxicology. This work was supported by the National Institutes of Health Grants R35-ES028377, T32-ES007015, P30-CA014520, P42-ES007381, and U01-ES1026127, The UW SciMed GRS Program, and The Morgridge Foundation. The authors would like to thank Catherine Stanley of UW Media Solutions for her artwork.

Description: Author Posting. © American Institute of Physics, 2017. This article is posted here by permission of American Institute of Physics for personal use, not for redistribution. The definitive version was published in Physics Today 70, no. 11 (2017): 78, doi:10.1063/PT.3.3773.

Description: With only a minimal flapping, the wandering albatross can circumnavigate the globe. During its peregrinations over the Southern Ocean, the seabird exploits wind shear—the gradient of wind speed—to extract energy for its sustained flight. That same maneuver, called dynamic soaring, is used by pilots of radio-controlled gliders. In flights that take advantage of the shear associated with wind blowing over mountain ridges, the gliders reach air speeds of an astonishing 500 mph. Engineers are currently developing autonomous unmanned vehicles that can use the technique to supplement different sources of energy for sustained flight over the oceans. Possible applications include environmental monitoring, surveillance, and search and rescue.

Description: 2018-11-01

Description: Author Posting. © American Chemical Society, 2019. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology 53(14), (2019):8244-8251, doi:10.1021/acs.est.9b02344.

Description: Perylene is a frequently abundant, and sometimes the only polycyclic aromatic hydrocarbon (PAH) in aquatic sediments, but its origin has been subject of a longstanding debate in geochemical research and pollutant forensics because its historical record differs markedly from typical anthropogenic PAHs. Here we investigate whether perylene serves as a source-specific molecular marker of fungal activity in forest soils. We use a well-characterized sedimentary record (1735 to 1999) from the anoxic-bottom waters of the Pettaquamscutt River basin, RI, USA to examine mass accumulation rates and isotope records of perylene, and compare them with total organic carbon and the anthropogenic PAH fluoranthene. We support our arguments with radiocarbon (14C) data of higher plant leaf-wax n-alkanoic acids. Isotope-mass balance calculations of perylene and n-alkanoic acids indicate that ~40 % of sedimentary organic matter is of terrestrial origin. Further, both terrestrial markers are pre-aged on millennial time-scales prior to burial in sediments and insensitive to elevated 14C concentrations following nuclear weapons testing in the mid-20th Century. Instead, changes coincide with enhanced erosional flux during urban sprawl. These findings suggest that perylene is definitely a product of soil derived fungi, and a powerful chemical tracer to study spatial and temporal connectivity between terrestrial and aquatic environments.

Description: We thank John King, Sean Sylva, Brad Hubeny, Peter Sauer, and Jim Broda for their help in sampling; Carl Johnson and Daniel Montluçon for their incessant help with analyses; as well as Mark Yunker for critical discussion on the perils of perylene. Professor Phil Meyers and two anonymous reviewers provided comments that improved the quality of the manuscript. U.M.H. acknowledges the Swiss National Science Foundation for his postdoctoral fellowship and T.I.E. and K.A.H. acknowledges the NSF for research grants CHE-0089172 and OCE-9708478.

Description: 2020-06-19

Description: Author Posting. © American Institute of Physics, 2009. This article is posted here by permission of American Institute of Physics for personal use, not for redistribution. The definitive version was published in Physics Today 62 n.11 (2009): 39-44.

Description: Most species of large whales are endangered because for centuries whaling fleets have decimated their populations. In the late 1960s, marine-mammal biologists discovered that fishermen setting nets for tuna in the Pacific Ocean were killing more than 100,000 dolphins a year. The cause of marine-mammal conservation became so popular at the dawn of the environmental movement that one of the first environmental accomplishments of the US Congress was to enact the Marine Mammal Protection Act of 1972, which prohibits the killing or injuring of marine mammals. Today, small remnant populations of whales, such as the North Atlantic right whale, are threatened by entanglement in fishing gear and collisions by ships. Indeed, marine biologists have estimated that hundreds of thousands of marine mammals are killed each year in fishing gear. Inadvertent effects of human activities can pose a serious risk to coastal populations, as evidenced by the recent extinction of the Chinese river dolphin due to fishing, pollution, and overdevelopment of the Yangtze River. A few decades ago, conservation efforts focused on reducing the intentional hunting of marine mammals. Nowadays, when hunts for marine mammals are better controlled, the slow degradation of habitat from a combination of sources may have a bigger impact. For example, biologists have documented cases in which the effects of coastal development—including noise, pollution, and dredging—have caused marine mammals to abandon critical breeding habitat. Noise in particular is at issue in legal actions that have been brought against the US Navy for sonar exercises that may have caused whales to strand and die.

Description: © American Chemical Society, 2016. This article is distributed under the terms of the AuthorsChoice License. The definitive version was published in Environmental Science & Technology 50 (2016): 7397–7408, doi:10.1021/acs.est.5b04617.

Description: With the expansion of offshore petroleum extraction, validated models are needed to simulate the behaviors of petroleum compounds released in deep (〉100 m) waters. We present a thermodynamic model of the densities, viscosities, and gas–liquid−water partitioning of petroleum mixtures with varying pressure, temperature, and composition based on the Peng–Robinson equation-of-state and the modified Henry’s law (Krychevsky−Kasarnovsky equation). The model is applied to Macondo reservoir fluid released during the Deepwater Horizon disaster, represented with 279–280 pseudocomponents, including 131–132 individual compounds. We define 〉n-C8 pseudocomponents based on comprehensive two-dimensional gas chromatography (GC × GC) measurements, which enable the modeling of aqueous partitioning for n-C8 to n-C26 fractions not quantified individually. Thermodynamic model predictions are tested against available laboratory data on petroleum liquid densities, gas/liquid volume fractions, and liquid viscosities. We find that the emitted petroleum mixture was ∼29–44% gas and ∼56–71% liquid, after cooling to local conditions near the broken Macondo riser stub (∼153 atm and 4.3 °C). High pressure conditions dramatically favor the aqueous dissolution of C1−C4 hydrocarbons and also influence the buoyancies of bubbles and droplets. Additionally, the simulated densities of emitted petroleum fluids affect previous estimates of the volumetric flow rate of dead oil from the emission source.

Description: This research was made possible by grants from the NSF (OCE- 0960841, OCE-1043976, and EAR-0950600) and the Gulf of Mexico Research Initiative (GoMRI) to the C-IMAGE and DEEP-C consortia.

Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Widner, B., Kido Soule, M. C., Ferrer-González, F. X., Moran, M. A., & Kujawinski, E. B. Quantification of amine- and alcohol-containing metabolites in saline samples using pre-extraction benzoyl chloride derivatization and ultrahigh performance liquid chromatography tandem mass spectrometry (UHPLC MS/MS). Analytical Chemistry, 93(11), (2021): 4809-4817, https://doi.org/10.1021/acs.analchem.0c03769.

Description: Dissolved metabolites serve as nutrition, energy, and chemical signals for microbial systems. However, the full scope and magnitude of these processes in marine systems are unknown, largely due to insufficient methods, including poor extraction of small, polar compounds using common solid-phase extraction resins. Here, we utilized pre-extraction derivatization and ultrahigh performance liquid chromatography electrospray ionization tandem mass spectrometry (UHPLC-ESI-MS/MS) to detect and quantify targeted dissolved metabolites in seawater and saline culture media. Metabolites were derivatized with benzoyl chloride by their primary and secondary amine and alcohol functionalities and quantified using stable isotope-labeled internal standards (SIL-ISs) produced from 13C6-labeled benzoyl chloride. We optimized derivatization, extraction, and sample preparation for field and culture samples and evaluated matrix-derived biases. We have optimized this quantitative method for 73 common metabolites, of which 50 cannot be quantified without derivatization due to low extraction efficiencies. Of the 73 metabolites, 66 were identified in either culture media or seawater and 45 of those were quantified. This derivatization method is sensitive (detection limits = pM to nM), rapid (∼5 min per sample), and high throughput.

Description: Funding included the Gordon and Betty Moore Foundation (Award GBMF5503 to M.A.M. and E.B.K.), Simons Foundation International (Award 409923 to E.B.K.), and the National Science Foundation (Award 1656311 to M.A.M.).

Description: © 2009 The Authors. This article is distributed under the terms of the Creative Commons Attribution (3.0) License. The definitive version was published in Sensors 9 (2009): 404-429, doi:10.3390/s90100404.

Description: An instrument has been built to carry out continuous in-situ measurement of small differences in water pressure, conductivity and temperature, in natural surface water and groundwater systems. A low-cost data telemetry system provides data on shore in real time if desired. The immediate purpose of measurements by this device is to continuously infer fluxes of water across the sediment-water interface in a complex estuarine system; however, direct application to assessment of sediment-water fluxes in rivers, lakes, and other systems is also possible. Key objectives of the design include both low cost, and accuracy of the order of ±0.5 mm H2O in measured head difference between the instrument’s two pressure ports. These objectives have been met, although a revision to the design of one component was found to be necessary. Deployments of up to nine months, and wireless range in excess of 300 m have been demonstrated.

Description: © American Chemical Society, 2015. This article is posted here by permission of American Chemical Society; copying and redistribution for non-commercial research and education purposes only. The definitive version was published in ACS Nano 10 (2016): 6-37, doi:10.1021/acsnano.5b07826.

Description: The microbiome presents great opportunities for understanding and improving the world around us and elucidating the interactions that compose it. The microbiome also poses tremendous challenges for mapping and manipulating the entangled networks of interactions among myriad diverse organisms. Here, we describe the opportunities, technical needs, and potential approaches to address these challenges, based on recent and upcoming advances in measurement and control at the nanoscale and beyond. These technical needs will provide the basis for advancing the largely descriptive studies of the microbiome to the theoretical and mechanistic understandings that will underpin the discipline of microbiome engineering. We anticipate that the new tools and methods developed will also be more broadly useful in environmental monitoring, medicine, forensics, and other areas.

Description: This research was supported by the Office of Naval Research Grant #N000141410051 (P.S.W., G.C.L.W., and T.Y.), the Genomic Science Program of the U.S. DOE-OBER,

Description: Author Posting. © American Chemical Society, 2018. This is an open access article published under an ACS AuthorChoice License. The definitive version was published in Environmental Science and Technology Letters 5 (2018): 226–231, doi:10.1021/acs.estlett.8b00084.

Description: Chemical dispersants are one of many tools used to mitigate the overall environmental impact of oil spills. In principle, dispersants break up floating oil into small droplets that disperse into the water column where they are subject to multiple fate and transport processes. The effectiveness of dispersants typically decreases as oil weathers in the environment. This decrease in effectiveness is often attributed to evaporation and emulsification, with the contribution of photochemical weathering assumed to be negligible. Here, we aim to test this assumption using Macondo well oil released during the Deepwater Horizon spill as a case study. Our results indicate that the effects of photochemical weathering on Deepwater Horizon oil properties and dispersant effectiveness can greatly outweigh the effects of evaporative weathering. The decrease in dispersant effectiveness after light exposure was principally driven by the decreased solubility of photo-oxidized crude oil residues in the solvent system that comprises COREXIT EC9500A. Kinetic modeling combined with geospatial analysis demonstrated that a considerable fraction of aerial applications targeting Deepwater Horizon surface oil had low dispersant effectiveness. Collectively, the results of this study challenge the paradigm that photochemical weathering has a negligible impact on the effectiveness of oil spill response and provide critical insights into the “window of opportunity” to apply chemical dispersants in response to oil spills in sunlit waters.

Description: This work was supported, in part, by National Science Foundation Grant OCE-1333148, Gulf of Mexico Research Initiative Grants 015, SA 16-30, the DEEP-C consortium, and the Clark Family Foundation, Inc. EPA funding was provided to R.N.C. from the Oil Spill Liability Trust Fund.

Description: The transport and deposition of gold from colloidal suspensions in hydrothermal fluids has been a persistent theme in ore deposits research. Studies of active geothermal systems show that a complete model of gold transport must include both dissolved and particulate forms. However, samples of the hydrothermal fluids are commonly spiked with aqua regia after collection in order to put any solids back into solution, thus preventing a quantitative assessment of the particle load. Although attempts have been made to filter the solids, gold nanoparticles (Au NPs) will mostly pass the 0.2-µm filters that are in common use, and a simple technique for analyzing suspended particles in the liquids has been lacking. In this study, we demonstrate how time-resolved acquisition of mass 197 in a conventional inductively coupled plasma-mass spectrometer (ICP-MS) can be used to detect and measure Au NPs in the filtered liquids, with an example of well-characterized fluids from the Reykjanes geothermal field on Iceland. The technique allows for precise monitoring of the solution as it is introduced into the plasma with the capability of identifying individual particles carried in suspension. Results show that Au particles passing the 0.2-µm filters are abundant in the studied samples, and measurements of the individual particles can be used to determine their size. The experiment highlights the potential of emerging ICP-MS techniques, including very fast data acquisition and multielement analysis of single particles in timeof-flight mode, for characterization of NPs in hydrothermal fluids.

Description: Microplastics (MPs) in aquatic organisms are raising increasing concerns regarding their potential damage to ecosystems. To date, Raman and Fourier transform infrared spectroscopy techniques have been widely used for detection of MPs in aquatic organisms, which requires complex protocols of tissue digestion and MP separation and are time- and reagentconsuming. This novel approach directly separates, identifies, and characterizes MPs from the hyperspectral image (HSI) of the intestinal tract content in combination with a support vector machine classification model, instead of using the real digestion/separation protocols. The procedures of HSI acquisition ( 1 min) and data analysis (5 min) can be completed within 6 min plus the sample preparation and drying time (30 min) where necessary. This method achieved a promising efficiency (recall 〉98.80%, precision 〉96.22%) for identifying five types of MPs (particles 〉0.2 mm). Moreover, the method was also demonstrated to be effective on field fish from three marine fish species, revealing satisfying detection accuracy (particles 〉0.2 mm) comparable to Raman analysis. The present technique omits the digestion protocol (reagent free), thereby significantly reducing reagent consumption, saving time, and providing a rapid and efficient method for MP analysis.

Description: Tinakula is the first seafloor massive sulfide deposit described in the Jean Charcot troughs and is the first such deposit described in the Solomon Islands—on land or the seabed. The deposit is hosted by mafic (basaltic-andesitic) volcaniclastic rocks within a series of cinder cones along a single eruptive fissure. Extensive mapping and sampling by remotely operated vehicle, together with shallow drilling, provide insights into deposit geology and especially hydrothermal processes operating in the shallow subsurface. On the seafloor, mostly inactive chimneys and mounds cover an area of ~77,000 m2 and are partially buried by volcaniclastic sand. Mineralization is characterized by abundant barite- and sulfide-rich chimneys that formed by low-temperature (〈250°C) venting over ~5,600 years. Barite-rich samples have high SiO2, Pb, and Hg contents; the sulfide chimneys are dominated by low-Fe sphalerite and are high in Cd, Ge, Sb, and Ag. Few high-temperature chimneys, including zoned chalcopyrite-sphalerite samples and rare massive chalcopyrite, are rich in As, Mo, In, and Au (up to 9.26 ppm), locally as visible gold. Below the seafloor, the mineralization includes buried intervals of sulfide-rich talus with disseminated sulfides in volcaniclastic rocks consisting mainly of lapillistone with minor tuffaceous beds and autobreccias. The volcaniclastic rocks are intensely altered and variably cemented by anhydrite with crosscutting sulfate (± minor sulfide) veins. Fluid inclusions in anhydrite and sphalerite from the footwall (to 19.3 m below seafloor; m b.s.f.) have trapping temperatures of up to 298°C with salinities close to, but slightly higher than, that of seawater (2.8–4.5 wt % NaCl equiv). These temperatures are 10° to 20°C lower than the minimum temperature of boiling at this depth (1,070–1,204 m below sea level; m b.s.l.), suggesting that the highest-temperature fluids boiled below the seafloor. The alteration is distributed in broadly conformable zones, expressed in order of increasing depth and temperature as (1) montmorillonite/nontronite, (2) nontronite + corrensite, (3) illite/smectite + pyrite, (4) illite/smectite + chamosite, and (5) chamosite + corrensite. Zones of argillic alteration are distinguished from chloritic alteration by large positive mass changes in K2O (enriched in illite/smectite), MgO (enriched in chamosite and corrensite), and Fe2O3 (enriched in pyrite associated with illite/smectite alteration). The δ18O and δD values of clay minerals confirm increasing temperature with depth, from 124° to 256°C, and interaction with seawater-dominated hydrothermal fluids at high water/rock ratios. Leaching of the volcanic host rocks and thermochemical reduction of seawater sulfate are the primary sources of sulfur, with δ34S values of sulfides, from –0.8 to 3.4‰, and those of sulfate minerals close to seawater sulfate, from 19.3 to 22.5‰.

Description: Microplastics are ubiquitous across ecosystems, yet the exposure risk to humans is unresolved. Focusing on the American diet, we evaluated the number of microplastic particles in commonly consumed foods in relation to their recommended daily intake. The potential for microplastic inhalation and how the source of drinking water may affect microplastic consumption were also explored. Our analysis used 402 data points from 26 studies, which represents over 3600 processed samples. Evaluating approximately 15% of Americans’ caloric intake, we estimate that annual microplastics consumption ranges from 39000 to 52000 particles depending on age and sex. These estimates increase to 74000 and 121000 when inhalation is considered. Additionally, individuals who meet their recommended water intake through only bottled sources may be ingesting an additional 90000 microplastics annually, compared to 4000 microplastics for those who consume only tap water. These estimates are subject to large amounts of variation; however, given methodological and data limitations, these values are likely underestimates.

Description: Latest knowledge on the reactivity of charged nanoparticulate complexants toward aqueous metal ions is discussed in mechanistic detail. We present a rigorous generic description of electrostatic and chemical contributions to metal ion binding by nanoparticulate complexants, and their dependence on particle size, particle type (i.e., reactive sites distributed within the particle body or confined to the surface), ionic strength of the aqueous medium, and the nature of the metal ion. For the example case of soft environmental particles such as fulvic and humic acids, practical strategies are delineated for determining intraparticulate metal ion speciation, and for evaluating intrinsic chemical binding affinities and heterogeneity. The results are compared with those obtained by popular codes for equilibrium speciation modeling (namely NICA-Donnan and WHAM). Physicochemical analysis of the discrepancies generated by these codes reveals the a priori hypotheses adopted therein and the inappropriateness of some of their key parameters. The significance of the characteristic time scales governing the formation and dissociation rates of metal−nanoparticle complexes in defining the relaxation properties and the complete equilibration of the metal− nanoparticulate complex dispersion is described. The dynamic features of nanoparticulate complexes are also discussed in the context of predictions of the labilities and bioavailabilities of the metal species.

Description: The female flowers (“cones”) of the hop plant (Humulus L.) produce compounds that contribute to the flavor and other properties of beer. Hop leaves and cones produce many of the same compounds, which also confer agronomic traits such as insect and disease resistance. Targeted and untargeted ultraperformance liquid chromatography-quadrupole time-of-flight–mass spectrometry with Waters MSE technology (UPLC-QTof-MSE) metabolomics were used to compare leaf phytochemical compositions of greenhouse-grown southwestern American wild Humulus neomexicanus (A. Nelson and Cockerell) Rydb. against a group of commercial hop cultivars consisting of both pure European Humulus lupulus L. and European–North American hybrids. Principal component analysis showed a clear distinction in chemical profiles between the two groups. H. neomexicanus leaves had a significantly higher content of total α acids (p = 4.4 × 10–9), total bitter acids (p = 2.6 × 10–6), cohumulone (p = 1.0 × 10–13), humulone + adhumulone (p = 9.1 × 10–4), and the prenylflavonoids xanthohumol (p = 0.013) and desmethylxanthohumol (p = 0.029) as well as significantly higher densities of glandular trichomes (p = 1.3 × 10–6), the biosynthetic site of those compounds. Most flavonol glycosides measured were also significantly more abundant in H. neomexicanus (p = 1.5 × 10–22 to 0.0027), whereas phenolic acids were consistently, but generally nonsignificantly (p 〉 0.05), more abundant in the cultivars. The higher bitter acid, prenylflavonoid, and flavonol glycoside content of H. neomexicanus leaves may help to confer more favorable insect and disease-resistance properties.

Description: Marine macroalgae, seaweeds, are exceptionally prolific producers of halogenated natural products. Biosynthesis of halogenated molecules in seaweeds is inextricably linked to reactive oxygen species (ROS) signaling as hydrogen peroxide serves as a substrate for haloperoxidase enzymes that participate in the construction these halogenated molecules. Here, using red macroalga Asparagopsis taxiformis, a prolific producer of the ozone depleting molecule bromoform, we provide the discovery and biochemical characterization of a ROS-producing NAD(P)H oxidase from seaweeds. This discovery was enabled by our sequencing of Asparagopsis genomes, in which we find the gene encoding the ROS-producing enzyme to be clustered with genes encoding bromoform-producing haloperoxidases. Biochemical reconstitution of haloperoxidase activities establishes that fatty acid biosynthesis can provide viable hydrocarbon substrates for bromoform production. The ROS production haloperoxidase enzymology that we describe here advances seaweed biology and biochemistry by providing the molecular basis for decades worth of physiological observations in ROS and halogenated natural product biosyntheses.

Description: Iron is an indispensable metabolic cofactor in both pro- and eukaryotes, which engenders a natural competition for the metal between bacterial pathogens and their human or animal hosts. Bacteria secrete siderophores that extract Fe3+ from tissues, fluids, cells, and proteins; the ligand gated porins of the Gram-negative bacterial outer membrane actively acquire the resulting ferric siderophores, as well as other iron-containing molecules like heme. Conversely, eukaryotic hosts combat bacterial iron scavenging by sequestering Fe3+ in binding proteins and ferritin. The variety of iron uptake systems in Gram-negative bacterial pathogens illustrates a range of chemical and biochemical mechanisms that facilitate microbial pathogenesis. This document attempts to summarize and understand these processes, to guide discovery of immunological or chemical interventions that may thwart infectious disease.

Description: Fusarium oxysporum is a destructive root-infecting plant pathogen that causes significant yield losses in many economically important crop species. Hence, a deeper understanding of pathogen infection strategies is needed. With liquid chromatography-tandem mass spectrometry and gas chromatography-time of flight mass spectrometry platforms, we analyzed the metabolic changes in a time-course experiment with Arabidopsis accessions either resistant (Col-0) or susceptible (Ler-0) to isolates of Fusarium oxysporum forma specialis matthioli infection. We showed a concurrent effect of Fusarium-derived polyols and the mycotoxin beauvericin in the suppression of the immune response of susceptible hosts. A significant increase in oxidized glutathione in the resistant host was probably associated with effective reactive oxygen species-mediated resistance responses. Through a combination of targeted and untargeted metabolomics, we demonstrated the concurrent action of several Arabidopsis defense systems as well as the concurrent action of several virulence systems in the fungal attack of susceptible Arabidopsis.

Description: While thousands of environmental metagenomes have been mined for the presence of novel biosynthetic gene clusters, such computational predictions do not provide evidence of their in vivo biosynthetic functionality. Using fluorescent in situ enzyme assay targeting carrier proteins common to polyketide (PKS) and nonribosomal peptide synthetases (NRPS), we applied fluorescence-activated cell sorting to tunicate microbiome to enrich for microbes with active secondary metabolic capabilities. Single-cell genomics uncovered the genetic basis for a wide biosynthetic diversity in the enzyme-active cells and revealed a member of marine Oceanospirillales harboring a novel NRPS gene cluster with high similarity to phylogenetically distant marine and terrestrial bacteria. Interestingly, this synthase belongs to a larger class of siderophore biosynthetic gene clusters commonly associated with pestilence and disease. This demonstrates activity-guided single-cell genomics as a tool to guide novel biosynthetic discovery.

Description: Microplastic (MP) pollution has been found in the Southern Ocean surrounding Antarctica, but many local regions within this vast area remain uninvestigated. The remote Weddell Sea contributes to the global thermohaline circulation, and one of the two Antarctic gyres is located in that region. In the present study, we evaluate MP (〉300 μm) concentration and composition in surface (n = 34) and subsurface water samples (n = 79, ∼11.2 m depth) of the Weddell Sea. All putative MP were analyzed by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. MP was found in 65% of surface and 11.4% of subsurface samples, with mean (±standard deviation (SD)) concentrations of 0.01 (±0.01 SD) MP m–3 and 0.04 (±0.1 SD) MP m–3, respectively, being within the range of previously reported values for regions south of the Polar Front. Additionally, we aimed to determine whether identified paint fragments (n = 394) derive from the research vessel. Environmentally sampled fragments (n = 101) with similar ATR-FTIR spectra to reference paints from the research vessel and fresh paint references generated in the laboratory were further subjected to micro-X-ray fluorescence spectroscopy (μXRF) to compare their elemental composition. This revealed that 45.5% of all recovered MP derived from vessel-induced contamination. However, 11% of the measured fragments could be distinguished from the reference paints via their elemental composition. This study demonstrates that differentiation based purely on visual characteristics and FTIR spectroscopy might not be sufficient for accurately determining sample contamination sources.

Description: Magnetite-bearing granophyre and quartz dolerite are the evolved fractions of differentiated dolerite (diabase) sills and are an important host to Archean gold deposits because they are chemical traps for orogenic fluids. Despite their economic importance, there is a poor understanding of how melt composition, crystal fractionation, sill geometry, and depth of emplacement increase the volume of host rock that is most favorable for gold precipitation during orogenesis. We use drill core logging, whole-rock geochemistry, magnetic susceptibility, gold assay, and thermodynamic modeling data from 11 mineralized and unmineralized ca. 2.7 Ga differentiated dolerites in the Eastern Goldfields superterrane (Yilgarn craton, Western Australia) to better understand the influence of igneous and emplacement processes on gold prospectivity. Orogenic gold favors differentiated dolerites, derived from iron-rich parental magmas, that crystallize large volumes of magnetite-bearing quartz dolerite (〉25% total thickness). Mineralized sills are commonly 〉150 m thick and hosted by thick and broadly coeval sedimentary sequences. Sill thickness is an important predictor for gold prospectivity, as it largely controls cooling rate and hence fractionation. The parental melts of gold-mineralized sills fractionated large amounts of clinopyroxene and plagioclase (possibly up to 50%) at depth before emplacement in the shallow crust. A second fractionation event at shallow levels (

Description: The Annaberg-Buchholz district is a classic occurrence of hydrothermal five-element (U-Ag-Bi-Co-Ni-As) veins in the Erzgebirge (Germany) with an historic production of ~8,700 metric tons (t) Co ore, 496 t U ore, and 26.9 t Ag. Multiple mineralization stages are recognized in polyphase veins hosted by Proterozoic paragneiss. Fluorite-barite-Pb-Zn mineralization occurs across the entire vertical profile of the district, whereas U and five-element stages are restricted to the upper 400 m below surface, coinciding with a graphite-rich gneiss lithology. Here, we present field and petrographic observations, electron probe microanalysis and fluid inclusion data, as well as thermodynamic calculations to characterize five-element and fluorite-barite-Pb-Zn associations, and to constrain the origin of the vertical zoning in the Annaberg-Buchholz district. Microthermometric analyses of fluid inclusions related to the fluorite-barite-Pb-Zn stage yield homogenization temperatures between 78° and 140°C and salinities between 21.9 and 27.7 equiv wt % (NaCl-CaCl2). A correlation of fluid inclusion Na/ (Na + Ca) ratios with salinity suggests fluid mixing as a likely precipitation mechanism and relates ore formation tentatively to regional tectonics of the Mesozoic opening of the Atlantic. Thermodynamic calculations indicate that U is more sensitive to reduction than As, predicting that arsenide minerals are precipitated more distally relative to uraninite upon reduction along the fluid-flow path. This implies that the observed vertical zoning is not a primary feature but is the result of hydrothermal remobilization. The observations made in the Annaberg-Buchholz district have general importance to the understanding of U-rich five-element mineralization and may be relevant for exploration targeting in unconformity-related U deposits.

Description: The Anarraaq clastic-dominated (CD) Zn-Pb-Ag deposit (Red Dog district, Alaska, USA) has an inferred mineral resource of 19.4 Mt at 14.4% Zn, 4.2% Pb, and 73 g/t Ag and is spatially associated with a separate ~1 Gt barite body. This study presents new cross sections and petrographic evidence from the Anarraaq area. The barite body, previously shown to have formed in a shallow subsurface environment akin to a methane cold seep, contains multiple generations of barite with locally abundant calcite masses, which are discordant to sedimentary laminae, and is underlain by an interval of massive pyrite containing abundant framboids and radiolarians. Calcite and pyrite are interpreted to have formed by methane-driven diagenetic alteration of host sediment at the sulfate-methane transition (SMT). The sulfide deposit contains two zones of Zn-Pb mineralization bounded by faults of unknown displacement. The dominant hydrothermal minerals are marcasite, pyrite, sphalerite, quartz, and galena. The presence of hydrothermal pseudomorphs after barite, early pyrite resembling diagenetic pyrite associated with the barite body, and hydrothermal quartz and sphalerite filling voids formed by dissolution of carbonate all suggest that host sediment composition and origin was similar to that of the barite body prior to hydrothermal mineralization. Rhenium-osmium isochron ages of Ikalukrok mudstone (339.1 ± 8.3 Ma), diagenetic pyrite (333.0 ± 7.4 Ma), and hydrothermal pyrite (334.4 ± 5.3 Ma) at Anarraaq are all within uncertainty of one another and of an existing isochron age (~338 Ma) for the Main deposit in the Red Dog district. This indicates that the Anarraaq deposit formed soon after sedimentation and that hydrothermal activity was approximately synchronous in the district. The initial Os composition of the Anarraaq isochrons (0.375 ± 0.019–0.432 ± 0.025) is consistent with contemporaneous seawater, indicating that a mantle source was not involved in the hydrothermal system. This study highlights the underappreciated but important role of early, methane-driven diagenetic processes in the paragenesis of some CD deposits and has important implications for mineral exploration.

Description: To guide future exploration, this predominantly field based study has investigated the structural evolution of the central Kiruna area, the type locality for iron oxide-apatite deposits that stands for a significant amount of the European iron ore production. Using a combination of geologic mapping focusing on structures and stratigraphy, petrography with focus on microstructures, X-ray computed tomography imaging of sulfide-structure relationships, and structural 2D-forward modeling, a structural framework is provided including spatial-temporal relationships between iron oxide-apatite emplacement, subeconomic Fe and Cu sulfide mineralization, and deformation. These relationships are important to constrain as a guidance for exploration in iron oxide-apatite and iron oxide copper-gold prospective terrains and may help to understand the genesis of these deposit types. Results suggest that the iron oxide-apatite deposits were emplaced in an intracontinental back-arc basin, and they formed precrustal shortening under shallow crustal conditions. Subsequent east-west crustal shortening under greenschist facies metamorphism inverted the basin along steep to moderately steep E-dipping structures, often subparallel with bedding and lithological contacts, with reverse, oblique to dip-slip, east-block-up sense of shears. Fe and Cu sulfides associated with Fe oxides are hosted by structures formed during the basin inversion and are spatially related to the iron oxide-apatite deposits but formed in fundamentally different structural settings and are separated in time. The inverted basin was gently refolded and later affected by hydraulic fracturing, which represent the last recorded deformation-hydrothermal events affecting the crustal architecture of central Kiruna.

Description: Divergent genetic models have been proposed for clastic dominant (CD-type) massive sulfide Zn-Pb mineralization in the Proterozoic Carpentaria Zn Province. Due to varying degrees of tectonic overprint, it has been difficult to accurately constrain structural and paragenetic timing aspects of the CD-type genetic model, and the most basic timing constraints (syngenetic vs. epigenetic, synextension vs. syninversion) remain debated. The recently discovered Teena Zn-Pb deposit is hosted by an exceptionally well preserved subbasin that permits relative timing relationships to be well defined. Using a combination of geophysical, structural, sedimentological, and petrographic datasets, a new model for subbasin development and syndiagenetic hydrothermal replacement mineralization is developed for the Teena mineral system. At Teena, sulfide mineralization was deposited from lateral fluid flow beneath an impermeable seal several hundred meters below the paleosurface and maximum flood surface, after formation of fine-grained diagenetic pyrite (py1) and dolomite nodules. Sulfide mineralization resulted from syndiagenetic carbonate replacement and pore space cementation where thermochemical sulfate reduction took place. The sulfide mineralization is therefore partly cospatial but not cogenetic with its thick pyritic hanging wall, and its lateral alteration footprint is much smaller than predicted by sedimentary exhalative (SEDEX) models. An additional zone of low-grade Zn-Pb mineralization in the footwall W-Fold Shale Member represents a different style of mineralization not previously reported for Carpentaria CD-type Zn deposits: it is associated with strata-bound lenses of hydrothermal dolomite (HTD) that formed by both replacement and carbonate dissolution and infill, which yielded diverse cavity-infill textures that include coarse-bladed dolomite fans cemented by interstitial sphalerite, dolomite, and quartz. Volumetrically minor Zn mineralization is also present in a fault conduit hydrothermal breccia and in hanging-wall synorogenic vein sets derived by hydrothermal leaching and remobilization of Zn from the underlying mineralized zones. Whereas both the Teena and nearby McArthur River Zn-Pb deposits are located along the northern margin of the 3rd-order Hot Spring-Emu subbasin, they formed in separate 4th-order subbasins in association with local extensional growth faults. Growth fault movement in the Teena subbasin was initiated during deposition of the W-Fold Shale Member and persisted episodically until a weak structural disconformity associated with sedimentary facies regression developed in the Upper HYC unit. Shifting patterns in depocenter location, sedimentary facies development, mineralization, and alteration zonation are attributed to progressive growth and linkage of segments of a regionally anomalous ENE-trending, synsedimentary fault zone. Similar patterns of extensional subbasin development were repeated in other Zn-mineralized subbasins throughout the River supersequence across the northern Carpentaria Zn Province, and formed in response to a short-lived episode of north-northwest–south-southeast regional extension around ca 1640 ± 5 Ma, triggered by far-field subduction events.

Description: In many orogenic gold deposits, gold is located in quartz veins. Understanding vein development at the microstructural scale may therefore provide insights into processes influencing the distribution of gold, its morphology, and its relationship to faulting. We present evidence that deformation processes during aseismic periods produce characteristic quartz microstructures and crystallographic preferred orientations, which are observed across multiple deposits and orogenic events. Quartz veins comprise a matrix of coarse, subidiomorphic, and columnar grains overprinted by finer-grained quartz seams subparallel to the fault trace, which suggests an initial stage of cataclastic deformation. The fine-grained quartz domains are characterized by well-oriented quartz c-axis clusters and girdles oriented parallel to the maximum extension direction, which reveals that fluid-enhanced pressure solution occurred subsequent to grain refinement. Coarser anhedral gold is associated with primary quartz, whereas fine-grained, “dusty” gold trails are found within the fine-grained quartz seams, revealing a link between aseismic deformation and gold morphology. These distinct quartz and gold morphologies, observed at both micro- and macroscale, suggest that both seismic fault-valving and aseismic deformation processes are both important controls on gold distribution.

Description: Rutile from a wide range of orogenic gold deposits and districts, including representative world-class deposits, was investigated for its texture and trace element composition using scanning electron microscopy, electron probe microanalysis, and laser ablation-inductively coupled plasma-mass spectrometry. Deposits are hosted in various country rocks including felsic to ultramafic igneous rocks and sedimentary rocks, which were metamorphosed from lower greenschist to middle amphibolite facies and with ages of mineralization that range from Archean to Phanerozoic. Rutile presents a wide range of size, texture, and chemical zoning. Rutile is the dominant TiO2 polymorph in orogenic gold mineralization. Elemental plots and partial least square-discriminant analysis suggest that the composition of the country rocks exerts a strong control on concentrations of V, Nb, Ta, and Cr in rutile, whereas the metamorphic facies of the country rocks controls concentrations of V, Zr, Sc, U, rare earth elements, Y, Ca, Th, and Ba in rutile. The trace element composition of rutile in orogenic gold deposits can be distinguished from rutile in other deposit types and geologic settings. Elemental ratios Nb/V, Nb/Sb, and Sn/V differentiate the rutile trace element composition of orogenic gold deposits compared with those from other geologic settings and environments. A binary plot of Nb/V vs. W enables distinction of rutile in metamorphic-hydrothermal and hydrothermal deposits from rutile in magmatic-hydrothermal deposits and magmatic environments. The binary plot Nb/Sb vs. Sn/V distinguishes rutile in orogenic gold deposits from other geologic settings and environments. Results are used to establish geochemical criteria to constrain the source of rutile for indicator mineral surveys and potentially guide mineral exploration.

Description: Yuhengtang is a representative slate-hosted Au deposit in the Jiangnan orogenic belt, South China, with a reserve of ~55 t Au and an average grade of ~3.9 g/t. Gold mineralization is characterized by veinlet and disseminated ores comprising native gold, auriferous pyrite, and arsenopyrite. Paragenesis of the Yuhengtang deposit can be divided into three stages. Pre-ore stage 1 is composed of bedding-parallel layers of pyrite in slate of the Neoproterozoic Banxi Group. Main ore stage 2 represents the Au mineralization stage, and two distinct types of mineralization can be distinguished: visible Au-arsenopyrite-pyrite in quartz veinlets and auriferous arsenopyrite-pyrite disseminated within altered slate. Post-ore stage 3 consists of quartz-pyrite-calcite-ankerite veins. In this study, we integrate electron microprobe, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and high-resolution ion microprobe (SHRIMP) analyses to document textural, isotopic, and compositional variation among texturally complex pyrite and arsenopyrite assemblages in veinlet and disseminated ores. Additionally, LA-ICP-MS sulfur isotope mapping of pyrite highlights the covariation behavior between trace elements and sulfur isotopes at the grain scale, thus allowing the factors controlling sulfur isotope fractionation in hydrothermal Au deposits to be constrained. Pyrite, of sedimentary origin (stage 1), hosts negligible Au (

Description: Tasmania is the most important tin province in Australia, having been endowed with 〉0.65 Mt Sn. Some granitic intrusions in western Tasmania have distinctive tourmaline- and quartz-rich magmatic-hydrothermal features, whether they are mineralized (e.g., Heemskirk Granite) or barren (Pieman Heads Granite). The Devonian Heemskirk and Pieman Heads plutons crop out on the western coast of Tasmania and are characterized by similar mineralogical and geochemical compositions and ages. The magmatic-hydrothermal textural features include tourmaline patches, tourmaline orbicules, and tourmaline-muscovite veins, as well as miarolitic cavities and quartz-fluorite-sulfide veins in the Heemskirk Granite. Cathodoluminescence (CL) imaging, laser ablation-inductively coupled plasma-mass spectrometry, and microthermometric analyses of quartz have revealed the physicochemical evolution of the magmatic-hydrothermal fluids from which these tourmaline- and quartz-bearing assemblages precipitated. High Ti quartz (20–28 ppm) in tourmaline patches, orbicules, and cavities typically have homogeneous CL-bright intensity, whereas CL-dark fractures have cut and/or offset the CL-bright and -gray domains that characterize low Ti quartz (3.4–8.5 ppm) from the tourmaline veins. The earliest fluid inclusion assemblages in the quartz-tourmaline orbicules and cavities have a salinity range from 3 to 14 wt % NaCl equiv with intermediate density and were probably trapped at lithostatic pressures of 1.57 ± 0.2 kbar and temperatures of 550° to 570°C, suggesting a depth of 5.9 ± 0.8 km. Prolonged depressurization and cooling may have led to the evolution of a brine (~39 wt % NaCl equiv salinity) from the primary magmatic liquid, which formed halite-bearing hypersaline inclusions in the tourmaline orbicules. Continuous pressure decrease explains the intense brittle failure and fluid migration outward from the apical portions of the pluton, where magmatic fluids partially mixed with and were cooled by external meteoric water. These mechanisms triggered the formation of tourmaline-muscovite-quartz veins and local cassiterite-bearing greisens from a moderate-salinity fluid (~12 wt % NaCl equiv) at temperatures of ~300°C and hydrostatic pressures of 120 bars. Retrograde dissolution textures evident from CL-bright quartz cores surrounded by oscillatory growth zones with gray CL response characterize the low Ti (

Description: The Teena Zn-Pb deposit is located in the Carpentaria Zn Province (Australia), which contains some of the largest clastic dominant (CD-type) massive sulfide Zn-Pb deposits in the world. The timing of the main stage of hydrothermal sulfide mineralization in the Teena subbasin is constrained to the midstage of burial diagenesis, during a period of short-lived regional extension. To distinguish hydrothermal alteration from spatially and temporally overlapping burial diagenetic alteration, and to establish the primary controls on hydrothermal mass transfer, it is necessary to evaluate the various foot- and hanging-wall alteration assemblages that formed between early- (eogenesis) and late- (mesogenesis) stage diagenesis. To achieve this, we have statistically evaluated a large lithogeochemistry dataset (n 〉2,500) and selected a subset (n = 65) of representative samples for detailed mineralogical (X-ray diffraction, illite crystallinity) and petrographic (scanning electron microscopy) analyses; hyperspectral core imaging data were then used to upscale key paragenetic observations. We show that sulfide mineralization was predated by multiple diagenetic alteration assemblages, including stratiform pyrite, dolomite nodules and cement, disseminated hematite and authigenic K-feldspar. These assemblages formed during eogenesis in multiple subbasins across the broader McArthur Basin and are not part of the synmineralization alteration footprint. Whereas pyrite and dolomite formed primarily from the in situ degradation of organic matter, feldspar authigenesis was the product of K metasomatism that was focused along permeable coarse-grained volcaniclastic sandstone beds within the host-rock sequence. The immature volcaniclastic input is broadly representative of the siliciclastic compositional end member in the subbasin, which formed the protolith for phyllosilicate (illite, phengite, chlorite) formation during burial diagenesis. There is no evidence of extensive phyllosilicate alteration in any of the geochemical, mineralogical (illite crystallinity), or petrographic datasets, despite some evidence of K-feldspar replacement by sphalerite in the Lower and Main mineralized lenses. Rather, the high Zn grades formed via dolomite replacement, which is resolvable from a chemical mass balance analysis and consistent with petrographic observations. There are significant exploration implications associated with carbonate-replacement sulfide mineralization during mesogenesis: (1) the capacity for secondary porosity generation in the host rock is as important as its sulfate-reducing capacity; (2) hydrothermal mineralization has a short-range cryptic lateral and vertical synmineralization alteration footprint due to acid neutralization by a carbonate-rich protolith; and (3) the distribution and chemistry of premineralization phases (e.g., pyrite, dolomite nodules) cannot be directly related to the mineralization footprint, which is localized to the 4th-order subbasin scale. Future exploration for this deposit style should therefore be focused on identifying units that contain a mixture of organic carbon and carbonate in the protolith, at favorable stratigraphic redox boundaries, and proximal to feeder growth faults.

Description: Carlin-type gold deposits in northern Nevada are inferred to overlie concealed late Eocene plutons, which are increasingly thought to have provided magmatic input to the meteoric water-dominated fluids from which the gold was precipitated. The Larderello, Monte Amiata, and Latera geothermal systems in the Northern Apennines of southern Tuscany and northern Latium, central Italy, may represent Pliocene to present-day analogues because of their demonstrated association with subsurface plutons and jasperoid-hosted antimony-gold mineralization. The plutons, which at depths of 〉5–7 km remain at least partially molten, continue to supply heat and magmatic fluids to the meteoric water-dominated geothermal systems. Formerly mined antimony deposits of Pliocene or younger age are exposed on the peripheries of the CO2 ± H2S-emitting geothermal systems, and antimony sulfides are still actively precipitating. Stibnite and submicroscopic gold in disseminated pyrite, along with Au/Ag of

Description: Precambrian iron oxide copper-gold (IOCG) deposits are generally encountered with multistage hydrothermal overprints and hence have complex isotopic records. Precise dating of ore-forming and overprinting events and assessment of time-resolved metal sources are fundamental for understanding ore genesis. Here, we quantify the evolution history by integrating in situ U-Pb dating of texturally constrained allanite and Sm-Nd isotope data of ores and major rare earth element (REE) minerals in the breccia-hosted Lanniping Fe-Cu deposit in Kangdian region, southwestern China. The economically mineralized breccia in Lanniping Fe-Cu deposit is characterized by pervasive and texturally destructive replacement of polymictic clasts, including host metasedimentary packages, the intruded dolerite, and pre-ore halokinetic breccia. Ore minerals in cements are mainly composed of magnetite, chalcopyrite, bornite, and variable amounts of REE-rich minerals (e.g., apatite and allanite/epidote). Two types of allanite were identified in ores. Type I prismatic allanite texturally intergrown with magnetite has a SHRIMP U-Pb age of 1728 ± 20 Ma (1σ), which matches a zircon U-Pb age of 1713 ± 14 Ma (2σ) for the dolerite clasts and provides the direct age constraint on the Fe-Cu mineralization event. Type II anhedral allanite shows complex zoning and is spatially associated with, but texturally later than, magnetite, apatite, and chalcopyrite. This type of allanite yields significantly younger SHRIMP dates of 1015 ± 33 (1σ) and 800 ± 16 Ma (1σ) for cores and rims, respectively, which correspond to discrete regional magmatic events and hence record hydrothermal overprint/remobilization events of ore minerals in the deposit. Integrated Sm-Nd isotope compositions of type I allanite, apatite, and whole ores generally align along the reference Sm-Nd isochron of 1728 Ma, further confirming the primary ore formation at ~1.7 Ga. Corresponding εNd(1728 Ma) values ranging from –2.8 to 0.3 are significantly higher than those of the host metasedimentary rocks (–9.5 to –6.2) but comparable to those of contemporaneous igneous intrusions (–0.3 to 5.3) in the region, demonstrating that REE components of the primary ores were dominantly sourced from rocks of mantle-derived affinity. Both cores and rims of the younger type II allanite grains have Nd isotope compositions consistent with the unique time-evolved line of the ~1.7 Ga ores, implying that REEs incorporated into type II allanite were ultimately sourced from the primary ores in this deposit. The combined texture, chemical, U-Pb, and Sm-Nd isotope data thus demonstrate that REE remobilization was localized during post-ore hydrothermal overprint with negligible external inputs of REEs to the primary ores in the Lanniping deposit. In this contribution, we not only date primary ore formation but also recognize several younger allanite generations that record internal metal redistributions in response to post-ore tectonothermal events. Our study highlights the potential of ore-associated REE minerals such as allanite for resolving the age of multiple stages of hydrothermal events in complex ore deposits by ion probe, provided that careful examination of textural and paragenetic relationship of ores is conducted. Our finding of these younger allanite generations also exemplifies the significance of evaluation on time-resolved metal input for better characterizing the evolution history of the IOCG deposits.

Description: Ore formation in porphyry Cu-Au-(Mo) systems involves the exsolution of metal-bearing fluids from magmas and the transport of the metals in magmatic-hydrothermal plumes that are subject to pressure fluctuations. Deposition of ore minerals occurs as a result of cooling and decompression of the hydrothermal fluids in partly overlapping ore shells. In this study, we address the role of vapor-like fluids in porphyry ore formation through numerical simulations of metal transport using the Gibbs energy minimization software, GEM-Selektor. The thermodynamic properties of the hydrated gaseous metallic species necessary for modeling metal solubility in fluids of moderate density (100–300 kg/m3) were derived from the results of experiments that investigated the solubility of metals in aqueous HCl- and H2S-bearing vapors. Metal transport and precipitation were simulated numerically as a function of temperature, pressure, and fluid composition (S, Cl, and redox). The simulated metal concentrations and ratios are compared to those observed in vapor-like and intermediate-density fluid inclusions from porphyry ore deposits, as well as gas condensates from active volcanoes. The thermodynamically predicted solubility of Cu, Au, Ag, and Mo decreases during isothermal decompression. At elevated pressure, the simulated metal solubility is similar to the metal content measured in vapor-like and intermediate-density fluid inclusions from porphyry deposits (at ~200–1,800 bar). At ambient pressure, the metal solubility approaches the metal content measured in gas condensates from active volcanoes (at ~1 bar), which is several orders of magnitude lower than that in the high-pressure environment. During isochoric cooling, the simulated solubility of Cu, Ag, and Mo decreases, whereas that of Au reaches a maximum between 35 ppb and 2.6 ppm depending on fluid density and composition. Similar observations are made from a compilation of vapor-like and intermediate-density fluid inclusion data showing that Cu, Ag, and Mo contents decrease with decreasing pressure and temperature. Increasing the Cl concentration of the simulated fluid promotes the solubility of Cu, Ag, and Au chloride species. Molybdenum solubility is highest under oxidizing conditions and low S content, and gold solubility is elevated at intermediate redox conditions and elevated S content. The S content of the vapor-like fluid strongly affects metal ratios. Thus, there is a decrease in the Cu/Au ratio as the S content increases from 0.1 to 1 wt %, whereas the opposite is the case for the Mo/Ag ratio; at S contents of 〉1 wt %, the Mo/Ag ratio also decreases. In summary, thermodynamic calculations based on experiments involving gaseous metallic species predict that vapor-like fluids may transport and efficiently precipitate metals in concentrations sufficient to form porphyry ore deposits. Finally, the fluid composition and pressure-temperature evolution paths of vapor-like and intermediate-density fluids have a strong effect on metal solubility in porphyry systems and potentially exert an important control on their metal ratios and zoning.

Description: Owing to the superimposition of water-rock interaction and external fluids, magmatic source signatures of ore-forming fluids for vein-type tin deposits are commonly overprinted. Hence, there is uncertainty regarding the involvement of magmatic fluids in mineralization processes within these deposits. Tourmaline is a common gangue mineral in Sn deposits and can crystallize from both the magmas and the hydrothermal fluids. We have therefore undertaken an in situ major, trace element, and B isotope study of tourmaline from the Yidong Sn deposit in South China to study the transition from late magmatic to hydrothermal mineralization. Six tourmaline types were identified: (1) early tourmaline (Tur-OE) and (2) late tourmaline (Tur-OL) in tourmaline-quartz orbicules from the Pingying granite, (3) early tourmaline (Tur-DE) and (4) late tourmaline (Tur-DL) in tourmaline-quartz dikelets in the granite, and (5 and 6) core (Tur-OC) and rim (Tur-OR), respectively of hydrothermal tourmaline from the Sn ores. Most of the tourmaline types belong to the alkali group and the schorl-dravite solid-solution series, but the different generations of magmatic and hydrothermal tourmaline are geochemically distinct. Key differences include the hundredfold enrichment of Sn in hydrothermal tourmaline compared to magmatic tourmaline, which indicates that hydrothermal fluids exsolving from the magma were highly enriched in Sn. Tourmaline from the Sn ores is enriched in Fe3+ compared to the hydrothermal tourmaline from the granite and displays trends of decreasing Al and increasing Fe content from core to rim, relating to the exchange vector Fe3+Al–1. This reflects oxidation of fluids during the interaction between hydrothermal fluids and the mafic-ultramafic wall rocks, which led to precipitation of cassiterite. The hydrothermal tourmaline has slightly higher δ11B values than the magmatic tourmaline (which reflects the metasedimentary source for the granite), but overall, the tourmaline from the ores has δ11B values similar to those from the granite, implying a magmatic origin for the ore-forming fluids. We identify five stages in the magmatic-hydrothermal evolution of the system that led to formation of the Sn ores in the Yidong deposit based on chemical and boron isotope changes of tourmaline: (1) emplacement of a B-rich, S-type granitic magma, (2) separation of an immiscible B-rich melt, (3) exsolution of an Sn-rich, reduced hydrothermal fluid, (4) migration of fluid into the country rocks, and (5) acid-consuming reactions with the surrounding mafic-ultramafic rocks and oxidation of the fluid, leading to cassiterite precipitation.

Description: The Freiberg district hosts one of the largest series of epithermal polymetallic vein deposits in Europe. The availability of a systematic collection of historical samples provides an excellent opportunity to study the anatomy of these epithermal systems. Detailed petrographic investigations, geochemical analyses, and fluid inclusion studies were conducted on several vertical profiles within the Freiberg district to decipher mineralogical and geochemical zoning patterns. Six distinctive mineral associations have been recognized within the Freiberg epithermal veins; sphalerite-pyrite-quartz and galena-quartz±carbonate associations are most abundant in the central sector, as well as in the deepest sections of veins on the periphery of the district. A high-grade sphalerite-Ag-sulfides-carbonate association occurs laterally between the central and peripheral sectors and at intermediate depth in veins on the periphery. Shallow and peripheral zones are dominated by an exceptionally Ag-rich Ag-sulfides-quartz association, whereas the shallowest veins locally comprise Ag-poor stibnite-quartz and quartz-carbonate associations. Fluid inclusion assemblages returned low salinities (

Description: The late Neoarchean, ~2.53 to 2.51 Ga Dagushan banded iron formation (BIF), is a typical Algoma-type BIF located in the northeast part of the North China craton. Despite having undergone upper greenschist to lower amphibolite facies metamorphism, the Dagushan BIF retains evidence of varied depositional facies, making it an ideal archive to evaluate the paleomarine environment and the paragenesis of the ore minerals. A transition from oxide to silicate to carbonate facies BIF is evident in a northward direction. The mineralogical composition shifts from magnetite and quartz in the south through a magnetite-quartz-cummingtonite/stilpnomelane assemblage in the transition zone to magnetite-siderite in the north. Such a distinct distribution of mineralogical facies correlates well with the depositional environment of the BIF. The carbonate facies BIFs formed in a near-shore, proximal environment, whereas the oxide and silicate facies BIF assemblages formed in deeper waters, distal to the paleoshoreline. The BIF samples display characteristic seawater-like rare earth element + yttrium (REE + Y) profiles with positive La and Y anomalies and heavy REE enrichment relative to the light REEs when normalized to post-Archean Australian shale. Positive Eu anomalies suggest a high-temperature hydrothermal contribution to the BIF. The absence of a negative Ce anomaly in nearly all samples, coupled with positive δ56Fe in magnetite in all mineralogical facies, indicates a dominantly anoxic water column contemporaneous with deposition of the BIF. At ~2.53 Ga in the Anshan area, seawater was mostly anoxic and rich in ferrous iron. Dissolved ferrous iron in upwelling hydrothermal fluids was oxidized and precipitated as Fe(III) oxyhydroxides in the photic zone leading to BIF formation. Proximal to hydrothermal vents, magnetite formed via the reaction of Fe(III) oxyhydroxides and aqueous Fe(II) supplied from the hydrothermal fluids and microbial dissimilatory iron reduction (DIR) coupled to organic carbon oxidation. Proximal to a paleoshoreline, siderite formed through DIR, as evidenced by the depleted δ13C values and the presence of graphite. Silicates, such as stilpnomelane and cummingtonite, are considered to be the metamorphic products of early diagenetic silicates (e.g., nontronite) that formed in the water column from admixtures of Fe(III) oxyhydroxides and amorphous silica.

Description: Processes controlling the metal endowment of arc-related porphyry Mo deposits are not well understood. Located in northeastern China, the arc-related Luming porphyry Mo deposit has a proven reserve of 0.75 Mt Mo at an average grade of 0.092 wt % and is characterized by multiple pulses of alteration and mineralization. These features make this deposit an ideal location to investigate the role of multiple pulses of magmatism and fluid release in the evolution and formation of an arc-related porphyry Mo deposit. Molybdenum mineralization at Luming is typically observed as a series of molybdenite-bearing veins hosted within a composite intrusive complex, referred to as the Luming Intrusive Suite. Crosscutting relationships between intrusive units and offset veins indicate that the Luming Intrusive Suite is composed of five major, successive granitic intrusions: the premineralization plutonic biotite monzogranite and monzogranite units, and the synmineralization stock- and dike-like porphyritic monzogranite, granite porphyry, and syenogranite units. Each synmineralization unit is associated with similar vein sequences that comply with the general form of early EB-type biotite veins, through A-type quartz ± biotite and B-type quartz-molybdenite veins, to late D-type quartz-molybdenite ± pyrite ± chalcopyrite, molybdenite, quartz-pyrite ± calcite, and calcite ± clays veins. The intensity and volume of alteration and mineralization within a given synmineralization unit decrease from early- through inter- to late-mineralization units. Although minor Mo mineralization is associated with potassic alteration along B-type veins, the majority of the ore is associated with D-type quartz-molybdenite-pyrite and molybdenite veins rimmed by sericite-chlorite-pyrite alteration, which are primarily hosted in the two premineralization units. A combination of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon U-Pb and hydrothermal biotite 40Ar/39Ar studies, together with available isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS) molybdenite Re-Os data, has resulted in a substantial reappraisal of the timing of magmatism and its association with molybdenite mineralization at Luming. The volumetrically dominant premineralization intrusive units have indistinguishable zircon U-Pb weighted mean 206Pb/238U ages ranging from 187.5 ± 2.8 to 186.5 ± 3.6 Ma (2σ), whereas the synmineralization units yield weighted mean 206Pb/238U ages from 178.6 ± 2.2 to 175.6 ± 3.0 Ma (2σ). The zircon U-Pb weighted mean 206Pb/238U ages of the synmineralization units are indistinguishable from the mean molybdenite Re-Os model (178.1 ± 2.7; 2σ) and hydrothermal biotite 40Ar/39Ar plateau (174.7 ± 1.1 Ma; 2σ) ages within uncertainty, confirming a genetic link with mineralization. Melt inclusion data show that the synmineralization intrusions were Mo poor, with Mo concentrations

Description: New regional- to vein-scale geologic mapping and structural analysis of the Carboniferous Pataz gold vein system (~10 Moz Au) reveal critical insights into the structural control on gold mineralization along the Eastern Andean Cordillera of northern Peru. The Pataz basement comprises continental volcanic arc and marginal to marine sedimentary rocks, which experienced intensive D2 deformation associated with Late Famatinian northeast to southwest compressive fold-and-thrust belt development. The D2 event produced an E-NE–dipping structural grain, including (1) tilted and F2 folded S1 foliations, (2) local F2 axial planar S2 foliations, and (3) subparallel D2 thrust faults. Intrusions, constituting the ca. 342 to 332 Ma (Mississippian) Pataz batholith, were emplaced along strike of the prominent Río Marañón fault and inherited the D2 basement structures, as evident in the orientation of suprasolidus magmatic flow zones and intrusive contacts within the batholith. Progressive horst-and-graben development affecting the volcanic carapace of the Pataz batholith records late syn- to postmagmatic uplift and transition into a NW-SE–extensional regime. We show that the E-NE–dipping, batholith-hosted gold vein system formed through synchronous activation of two geometric fault-fill vein types, following (1) the moderately E-NE–dipping D2 basement-inherited competency contrasts within the batholith and (2) shallow NE-dipping Andersonian footwall thrusts, during NE-directed shortening (D3a). Both geometric vein types display an early paragenetic stage (I) of quartz-pyrite, progressing texturally from hydraulic breccia into crack-seal laminated shear veins. A second (II), undeformed quartz-pyrite-sphalerite-galena paragenetic stage is observed to fill previously established dilational sites adjacent to newly formed D3b normal faults, which likely formed during regional NW-SE–extensional horst-graben development. Kinematics and relative timing indicate that, upon batholith solidification, D3a transpressional dextral strike-slip ruptures along the Río Marañón fault superimposed a lower-order Riedel-type fault system. Fluid-assisted fault activation preferentially impinged on the D2 basement-inherited competency contrasts within the batholith. Subsequent transition into a transtensional regime led to the D3b normal faulting, providing a feeder system for stage II fluid influx. The tectonic switch may be explained either by increasing tensile strain accommodation upon progressive strike-slip movement within a regional dilational jog or by larger-scale crustal relaxation of the late Gondwana margin upon final Pangea assembly. Our new structural model for the Pataz vein system evolution highlights the importance of basement structural inheritance in controlling the localization of gold mineralization along polycyclic supercontinent margins. We provide valuable insights for exploration targeting of complex vein arrays within rheologically heterogeneous host rocks.

Description: Globally, significant examples of hydrothermal Cu-Co mineralization are rare within Archean greenstone belts, especially relative to the endowment of these terranes with other world-class hydrothermal ore deposits, particularly Au deposits. Using U-Pb geochronology of hydrothermal apatite, this study provides the first absolute age constraints on the timing of mineralization for the Carlow Castle Cu-Co-Au deposit. Carlow Castle is a complex, shear zone-hosted, veined Cu-Co-Au mineral system situated within the Paleo-Mesoarchean Roebourne greenstone belt of the Pilbara craton of northwestern Western Australia. Although U-Pb geochronology of this deposit is challenging due to low levels of radiogenic Pb in synmineralization apatite, mineralization is best estimated at 2957 ± 67 Ma (n = 61). Additionally, analysis of alteration phases associated with Carlow Castle mineralization suggests that it is dominated by a propylitic assemblage that is characteristic of alkaline fluid chemistry and peak temperatures 〉300°C. Within proximal portions of the northwest Pilbara craton, the period of Carlow Castle’s formation constrained here is associated with significant base-metal volcanogenic massive sulfide mineralization and magmatic activity related to back-arc rifting. This rifting and associated magmatic activity are the most likely source of Carlow Castle’s unique Cu-Co-Au mineralization. Carlow Castle’s Mesoarchean mineralization age makes it among the oldest discovered Cu-Co-Au deposits globally, and unique in the broader context of hydrothermal Cu-Co-Au deposits. Globally, hydrothermal Cu-Co mineralization occurs almost exclusively as Proterozoic and Phanerozoic stratiform sediment-hosted Cu-Co deposits due to the necessity of meteorically derived oxidized ore fluids in their formation. This research therefore has implications for exploration for atypical Cu-Co deposits and Cu-Co metallogenesis through recognition of comparably uncommon magmatic-hydrothermal Cu-Co-Au ore-forming processes and, consequently, the potential for analogous Cu-Co-Au mineralization in other Archean greenstone belts.

Description: The interaction between mafic-ultramafic magma and crustal sulfide is considered a key process in the formation of magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Integrated S/Se and multiple sulfur isotope studies are the most robust in constraining the role of crustal sulfur during ore genesis. In the present study, we report the first integrated S/Se and multiple sulfur isotope study of magmatic sulfide occurrences in the Labrador Trough, namely, on the recently discovered Idefix PGE-Cu and Huckleberry Cu-Ni-(PGE) prospects. Whole-rock and in situ S/Se values (~810–3115) of magmatic sulfides and their host rocks are consistent with S loss during postmagmatic hydrothermal alteration, negating their use in interpreting the origin of S. Values of ∆33S ~0 indicate no record of the assimilation of Archaean sulfur. Disseminated (–0.5 to +2.5‰) and globular (3.0–4.5‰) sulfides at Idefix as well as globular sulfides (2.1–9.6‰) at Huckleberry have δ34S values greater than the accepted mantle range, suggesting that crustal S played a role in the formation of these sulfides. In contrast, disseminated and net-textured sulfides at Huckleberry have variable δ34S values (–4.6 to +3.2‰) that are mostly within the accepted mantle range, excluding one anomalous sample that records relatively higher δ34S values (11.9–15.0‰). It is proposed that sulfide melt segregated in response to the addition of small proportions of crustal S prior to the final emplacement of the host intrusions, i.e., in a feeder conduit or staging chamber. Isotopic exchange between the sulfide melt and silicate magma has diluted and, in places, eradicated a crustal δ34S signature.

Description: The Jinding deposit, located in the northern part of Lanping basin in southwest China, is the second largest Zn-Pb deposit in China and the third largest Mississippi Valley-type deposit identified globally. The deposit consists of several large tabular orebodies within the Jinding dome. Two stages of sulfide mineralization (sphalerite, galena, and pyrite) are identified, which are mainly hosted in the siliciclastic strata of Early Cretaceous and Paleocene age. The early sulfide minerals are mostly fine grained (