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Chapter 5: Impact of sedimentary-exhalative hydrothermal systems on marine chemistry and mass extinctions: Applications for ore genesis research and mineral exploration

Times of metal-rich brine discharge into ancient ocean basins, associated with the formation of sedimentary-exhalative (sedex) Zn-Pb-Ba ore deposits, coincided with short-duration positive excursions (“spikes”) in the global marine Sr isotope record. While these spikes are unexplained by conventional oceanic models, chronostratigraphic correlations, combined with mass balance evidence and oceanographic modeling, suggest that the flux of radiogenic Sr from sedex brines during ore formation is sufficient to explain these previously enigmatic 87 Sr/ 86 Sr spikes. We review existing 87 Sr/ 86 Sr data and present new data as verification of these global 87 Sr/ 86 Sr spikes and their correlations with the formation of giant sedex ore deposits. Major events include an 1 ×10 −4 (~0.7078–~0.7079) excursion contemporaneous with formation of the Rammelsberg deposit at ~389 Ma; spikes on the order of 1 to 3 × 10 −4 , coeval with formation of the Meggen deposit at ~381 Ma, several ore deposits in the Macmillan Pass district at ~379 to 375 Ma, and the Silvermines deposits at ~352 Ma; and two >6 × 10 −4 spikes coincident with formation of the giant Navan deposit at ~346 Ma and Red Dog deposits at ~337 Ma. Moreover, the timing of peak 87 Sr/ 86 Sr spikes correlates with global δ 13 C and δ 18 O spikes, deposition of metal-rich black shales and ironstones, metal-induced malformation (teratology) of marine organisms, and mass extinctions. The relationships among these features were poorly understood, but our new model explains how the flux of key biolimiting nutrients and metals contained in sedex brines, demonstrably equivalent to or exceeding that of the total modern riverine flux to the ocean, spurred ocean eutrophication, which, ultimately, through a series of positive feedback mechanisms, may have triggered global chemical and biological events. If, as we hypothesize, sedex hydrothermal systems are recorded in the global marine isotopic, geologic, and biological records, our findings define a new approach to the study of and exploration for sedex deposits. We demonstrate that fluid inclusion solute chemistry and isotopic and stratigraphic studies of sedex deposits, coupled with chronostratigraphic correlation and high-resolution 87 Sr/ 86 Sr isotope chemostratigraphy, can be used to answer long-standing questions about geologic processes responsible for formation of these extraordinary deposits. This approach provides evidence for the age, duration, and fluxes of fluids and metals vented into the ocean by these giant hydrothermal systems. Accordingly, the marine 87 Sr/ 86 Sr curve constitutes a global exploration tool that could be applied to assess the mineral potential of sedimentary basins. To illustrate the potential of this tool to identify favorable stratigraphic ages and basins with potential for undiscovered giant sedex deposits, we highlight several spikes, on par with those characteristic of the Red Dog and Navan deposits, which have not been correlated with known metal deposits. Given these strong temporal correlations, mass balance estimates, and results of ocean chemistry modeling, our study suggests that further work is warranted to determine the extent to which periodic venting of hydrothermal basinal brines into the ocean has influenced the evolution of marine chemistry. Ultimately, these global signatures can be applied to the study of and exploration for sedex deposits.

Book chapter↗

Sedex hydrothermal systems triggered upheavals to marine chemistry and mass extinctions: Applications for ore genesis research and mineral exploration

New USGS research reveals that the discharge of metal-rich brine that formed sedex deposits on ancient seafloors had profound effects on global ocean chemistry and biologic evolution. For example, brine expulsion caused short-duration positive excursions (“spikes”) in the global marine Sr isotope record. While these spikes are unexplained by conventional oceanic models, our chronostratigraphic correlations of major sedex events, combined with mass balance evidence and oceanographic modeling, confirm that the flux of radiogenic Sr from sedex brines during ore formation was sufficient to cause these once enigmatic 87Sr/86Sr spikes. Recognition that the timing of peak 87 Sr/ 86 Sr spikes correlates exactly with global δ 13 C (and δ 18 O) spikes, climate change, deposition of metal-rich black shales and ironstones, metal-induced malformation (teratology) of marine organisms, and mass extinctions, establishes a causal relationship between sedex deposits and these dramatic events in earth history. The relationships among these features are not fully understood. However, our new model demonstrates that the flux of key biolimiting nutrients and metals contained in sedex brines exceeds that of the total modern riverine flux to the ocean. Undoubtably, these immense nutrient fluxes spurred ocean eutrophication, which, ultimately, through a series of positive feedback mechanisms, may be a previously unrecognized trigger of global ocean anoxic events (OAEs) that produced these chemical and biological perturbations. A derivative result from this integrative research is the recognition that OAEs resulted in the formation of “bathtub rim” deposits at redox boundaries along continental margins that concentrated various redox sensitive critical minerals. For example, we have identified midcontinent phosphorite deposits that contains heavy REE grades and tonnages that rival any REE deposit in the world. The recognition that sedex-forming fluid expulsion events are recorded in the global marine isotopic, geologic, and biological records, defines a new approach to the study of and exploration for sedex deposits. Traditional ore genesis research, coupled with chronostratigraphic correlation and high-resolution 87 Sr/ 86 Sr isotope chemostratigraphy can be used to answer long-standing questions about geologic processes responsible for formation of these extraordinary deposits. This approach allows us to constrain, for the first time, the age, duration, and fluxes of fluids and metals vented into the ocean by these giant hydrothermal systems. Accordingly, the fact that large mineralizing events are recorded in the marine sedimentary record opens the tantalizing prospect that we have the ability to conduct effective resource assessments and define prospective basins anywhere in the world. This innovative approach allows for identification of favorable stratigraphic ages and basins and remote evaluation of the size (and, thus, the mineral potential) of undiscovered mineral deposits. This methodology could be applied on regional basin-wide assessments, to evaluate sedimentary basin prospectivity, resource favorability of specific horizons therein, and to the evaluation of the potential of early-stage prospects.

Geological Society of Nevada Newsletter↗

Marine chemistry of the permian phosphoria formation and basin, Southeast Idaho

Major components in the Meade Peak Member of the Phosphoria Formation are apatite, dolomite, calcite, organic matter, and biogenic silica-a marine fraction; and aluminosilicate quartz debris-a terrigenous fraction. Samples from Enoch Valley, in southeast Idaho, have major element oxide abundances of Al2O3, Fe2O3, K2O, and TiO2 that closely approach the composition of the world shale average. Factor analysis further identifies the partitioning of several trace elements-Ba, Ga, Li, Sc, and Th and, at other sites in southeast Idaho and western Wyoming, B, Co, Cs, Hf, Rb, and Ta-totally into this fraction. Trace elements that fail to show such correlations or factor loadings include Ag, As, Cd, Cr, Cu, Mo, Ni, Se, the rare earth elements (REE), U, V, and Zn. Their terrigenous contribution is determined from minimum values of trace elements versus the terrigenous fraction. These minima too define trace element concentrations in the terrigenous fraction that approximately equal their concentrations in the world shale average. The marine fraction of trace elements represents the difference between the bulk trace element content of a sample and the terrigenous contribution. Of the trace elements enriched above a terrigenous contribution, Ag, Cr, Cu, Mo, and Se show strong loadings on the factor with an organic matter loading and U and the REE on the factor with a strong apatite loading. Cd, Ni, V, and Zn do not show a strong correlation with any of the marine components but are, nonetheless, strongly enriched above a terrigenous contribution. Interelement relationships between the trace elements identify two seawater sources-planktonic debris and basinal bottom water. Relationships between Cd, Cu, Mo, Zn, and possibly Ni and Se suggest a solely biogenic source. Their accumulation rates, and that of PO3-4, further identify the level of primary productivity as having been moderate and the residence time of water in the basin at 4.5 yr. Enrichments of Cr, U, V, and the REE, above both terrigenous and biogenic contributions, define bottom-water redox conditions as having been oxygen depleted, that is, denitrifying but not sulfate reducing.

Economic Geology↗

The release of dissolved actinium to the ocean: A global comparison of different end-members

The measurement of short-lived 223Ra often involves a second measurement for supported activities, which represents 227Ac in the sample. Here we exploit this fact, presenting a set of 284 values on the oceanic distribution of 227Ac, which was collected when analyzing water samples for short-lived radium isotopes by the radium delayed coincidence counting system. The present work compiles 227Ac data from coastal regions all over the northern hemisphere, including values from ground water, from estuaries and lagoons, and from marine end-members. Deep-sea samples from a continental slope off Puerto Rico and from an active vent site near Hawaii complete the overview of 227Ac near its potential sources. The average 227Ac activities of nearshore marine end-members range from 0.4??dpm m- 3 at the Gulf of Mexico to 3.0??dpm m- 3 in the coastal waters of the Korean Strait. In analogy to 228Ra, we find the extension of adjacent shelf regions to play a substantial role for 227Ac activities, although less pronounced than for radium, due to its weaker shelf source. Based on previously published values, we calculate an open ocean 227Ac inventory of 1.35 * 1018??dpm 227Acex in the ocean, which corresponds to 37??moles, or 8.4??kg. This implies a flux of 127??dpm m-2 y- 1 from the deep-sea floor. For the shelf regions, we obtain a global inventory of 227Ac of 4.5 * 1015??dpm, which cannot be converted directly into a flux value, as the regional loss term of 227Ac to the open ocean would have to be included. Ac has so far been considered to behave similarly to Ra in the marine environment, with the exception of a strong Ac source in the deep-sea due to 231Paex. Here, we present evidence of geochemical differences between Ac, which is retained in a warm vent system, and Ra, which is readily released [Moore, W.S., Ussler, W. and Paull, C.K., 2008-this issue. Short-lived radium isotopes in the Hawaiian margin: Evidence for large fluid fluxes through the Puna Ridge. Marine Chemistry]. Another potential mechanism of producing deviations in 227Ac/228Ra and daughter isotope ratios from the expected production value of lithogenic material is observed at reducing environments, where enrichment in uranium may occur. The presented data here may serve as a reference for including 227Ac in circulation models, and the overview provides values for some end-members that contribute to the global Ac distribution. ?? 2007 Elsevier B.V. All rights reserved.

Marine Chemistry↗

Seawater as the source of minor elements in black shales, phosphorites and other sedimentary rocks

Many of the minor elements in seawater today have a concentration-depth profile similar to that of the biologically essential nutrients, NO-3 and PO3-4. They show a relative depletion in the photic zone and enrichment in the deep ocean. The difference between their surface- and deep-ocean values, normalized to the change in PO3-4, approaches the average of measured minor-element: P ratios in marine plankton, although individual analyses of the latter show extreme scatter for a variety of reasons. Despite this scatter in the minor-element analyses of plankton, agreement between the two sets of data shows unequivocally that an important marine flux of many minor elements through the ocean is in the form of biogenic matter, with a composition approaching that of plankton. This interpretation is further supported by sediment studies, particularly of sediments which accumulate in shelf-slope environments where biological productivity in the photic zone is exceptionally high and organic carbon contents of the underlying sediment elevated. The interelement relations observed for some of these sediments approach the average values of plankton. These same interelement relations are observed in many marine sedimentary rocks such as metalliferous black shales and phosphorites, rocks which have a high content of marine fractions (e.g., organic matter, apatite, biogenic silica and carbonates). Many previous studies of the geochemistry of these rocks have concluded that local hydrothermal activity, and/or seawater with an elemental content different from that of the modern ocean, was required to account for their minor-element contents. However, the similarity in several of the minor-element ratios in many of these formations to minor-element ratios in modern plankton demonstrates that these sedimentary rocks accumulated in environments whose marine chemistry was virtually identical to that seen on continental shelf-slopes, or in marginal seas, of the ocean today. The accumulation of the marine fraction of minor elements on these ancient sea floors was determined largely by the accumulation of organic matter, settling from the photic zone and with a composition of average plankton. A second marine fraction of minor elements in these rocks accumulated through precipitation and adsorption from seawater. The suite of elements in this fraction reflects redox conditions in the bottom water, as determined by bacterial respiration. For example, high Mn, high Cr+V and high Mo concentrations, above those which can be attributed to the accumulation of planktonic matter, characterize accumulation under bottom-water oxidizing, denitrifying and sulfate-reducing conditions, respectively. ?? 1994.

Chemical Geology↗

Timescales and processes of methane hydrate formation and breakdown, with application to geologic systems

Gas hydrate is an ice-like form of water and low molecular weight gas stable at temperatures of roughly -10ºC to 25ºC and pressures of ~3 to 30 MPa in geologic systems. Natural gas hydrates sequester an estimated one-sixth of Earth’s methane and are found primarily in deepwater marine sediments on continental margins, but also in permafrost areas and under continental ice sheets. When gas hydrate is removed from its stability field, its breakdown has implications for the global carbon cycle, ocean chemistry, marine geohazards, and interactions between the geosphere and the ocean-atmosphere system. Gas hydrate breakdown can also be artificially driven as a component of studies assessing the resource potential of these deposits. Furthermore, geologic processes and perturbations to the ocean-atmosphere system (e.g., warming temperatures) can cause not only dissociation, but also more widespread dissolution of hydrate or even formation of new hydrate in reservoirs. Linkages between gas hydrate and disparate aspects of Earth’s near-surface physical, chemical, and biological systems render an assessment of the rates and processes affecting the persistence of gas hydrate an appropriate Centennial Grand Challenge. This paper reviews the thermodynamic controls on methane hydrate stability and then describes the relative importance of kinetic, mass transfer, and heat transfer processes in the formation and breakdown (dissociation and dissolution) of gas hydrate. Results from numerical modeling, laboratory, and some fields studies are used to summarize the rates of hydrate formation and breakdown, followed by an extensive treatment of hydrate dynamics in marine and cryospheric gas hydrate systems.

Journal of Geophysical Research-Solid Earth↗

The solusphere - its inferences and study

Water is a fundamental geologic agent active in rock decomposition, erosion, and synthesis. Solutes in water are of particular interest to geochemists as sources of raw material for synthesis or as products of decomposition. When geochemical studies move from the laboratory into natural environment many variables relating to solute hydrology must be considered. As a focal point there has been designed a graphical representation of solute hydrology, the solusphere, which embodies the concepts of land-water occurrence and movement on which are superimposed geologic, biologic, physical, chemical, and cultural processes affecting solutes. The solusphere is demonstrated by passing an imaginary plane through the centre of the earth. This plane intercepts concentric zones designated as rock flowage, saturation, aeration, surface activity, and atmosphere. Transport processes carry solutes within and between zones without alteration or conversion. However, whether stationary or in motion, the water's solute character is constantly subject to (1) alteration processes that change concentration by addition or subtraction of solutes or solvent without loss of solute identities, and (2) conversion processes that change the chemical state and form of solutes. The geochemist is concerned with specific conversion processes, but he also must consider transport, alteration, and other conversion processes that are continually modifying the materials with which he is dealing in nature. The solusphere is an attempt to organize processes affecting the chemical quality of land waters into a unified field of science much like the field of marine chemistry.

Geochimica et Cosmochimica Acta↗

Cascadia Margin cold seeps: Subduction zone fluids, gas hydrates, and chemosynthetic habitats

Priority Geographic Area: The outer continental shelf and upper continental slope from Canada/U.S. border offshore Washington State to the Mendocino Fracture Zone (Northern California), entirely within the U.S. Exclusive Economic Zone (EEZ), from the outermost shelf to at least 2000 m water depth (Figure 1). Description of Priority Area: Since 2015, over a thousand water column gas plumes originating at seafloor gas seeps have been discovered landward of the Cascadia deformation front (e.g., Embley et al., 2016; Johnson et al., 2015, 2019; Merle and Embley, 2016; NA-95 Cruise Report, 2018; Riedel et al., 2018), adding to those that had long been known on Hydrate Ridge (e.g., Heeschen et al., 2003; Tréhu et al., 2004). The recently-discovered seeps stretch from offshore Vancouver Island to the Mendocino Fracture Zone and from the outer shelf to ~2000 m water depth, occurring both landward and seaward of the nominal limit for gas hydrate stability zone on the upper continental slope (Figure 1). Hundreds of seeps likely remain undiscovered. Water column imaging is incomplete both within the target geographic area and farther seaward, between the 2000 m isobath and the deformation front, which is the subject of an imaging study described in a white paper by Watt et al. The recently-discovered Cascadia Margin cold seeps partially overlap an important active margin gas hydrate province (Spence et al., 2001; Tréhu et al., 2003, 2004), as well as an area where sediments on the North American plate are folded and faulted and affected by fluids generated in the subduction complex beneath the Cascadia forearc (e.g., Saffer and Tobin, 2011). Several Ocean Drilling Program expeditions have focused on hydrate systems offshore Vancouver and Oregon (e.g., Riedel et al., 2009; Tréhu et al., 2004) and on the connection between the shallow and deep hydrogeologic systems. Cabled observatories now continuously monitor physical, chemical, and venting processes on south Hydrate Ridge (OOI; e.g., Philip et al., 2016a) and offshore Vancouver Island (NEPTUNE; e.g. Römer et al., 2016). Outside of these well-studied gas hydrate areas, a subset of the recently-discovered Cascadia seeps, including some that we visited with R/V Falkor in 2019 (e.g., https://schmidtocean.org/cruise/methane-seeps-at-edge-of-hydrate-stability/), also likely emit methane associated with shallow subseafloor gas hydrate systems. Other seeps are delivering not only methane, but also deep-derived gases (Baumberger et al., 2018, 2020) to the seafloor. Many Cascadia Margin seeps have also been recognized at water depths too shallow (e.g., 175 m) to be connected to gas hydrate dynamics. These seeps are postulated to be emitting gas and fluids that originated deep in accretionary wedge before migrating up normal faults generated during forearc extension associated with large earthquakes (Johnson et al., 2019). Only a small fraction of the recently discovered U.S. Cascadia Margin water column gas plumes has so far been verified by ROVs (Hercules from E/V Nautilus in 2016 and 2018; SuBastian from R/V Falkor in 2018 and 2019) to correspond to seafloor seeps. Careful scientific mapping, investigation, and sampling at the seeps have also been limited (e.g., Baumberger et al., 2018, 2020; Merle and Embley, 2016; Seabrook et al., 2018; Greinert et al. 2019). This white paper focuses on expanding exploration of already-identified U.S. Cascadia Margin cold seeps through a multipronged and multidisciplinary discovery program that could be accomplished with a variety of NOAA assets. The goals of the proposed exploration activities are to develop high-resolution maps of seep fields from deep ocean vehicles; to verify (and sample) seafloor gas emissions at the locations of water column plumes for compositional and isotopic studies; to map, sample, and conduct analyses on chemosynthetic communities and deep-sea coral habitats near seep sites to document species distributions and habitats as a function of depth and latitude along the margin; to collect seep geologic samples that can constrain the timing of methane emissions through geochronology; and to record environmental data (e.g., CTD) near the seafloor and in the water column above the seeps. Seafloor mapping using shipboard systems (multibeam/backscatter) would be needed to characterize seafloor features near seep sites. Water column imaging (EK60/80 and/or multibeam WCD data) conducted before and after seafloor explorations would capture active methane plumes and constrain temporal variations in seep emissions (e.g., Kannberg et al., 2013; Philip et al., 2016a, 2016b), which are known to vary on time scales as rapid as tidal cycles on this margin (e.g., Römer et al., 2016). What are the characterization and data needs in this area? Check all that apply: __x_ Biology, Geology, Physical Oceanography, Chemistry ___ Marine Archaeology ___ Other Provide a list or brief description of the data needed within this area, from your perspective: 1. Water column backscatter to image active gas plumes 2. High-resolution multibeam bathymetry, seafloor backscatter, and shallow sub-bottom imaging 3. Visual characterization and ground truthing of potential seeps, including high-resolution mapping and photography from near-seafloor vehicles; collection of seep-associated species, corals, sediments, authigenic carbonates, gases, and seawater Describe relevance to national security, conservation, and/or the economy: The Cascadia margin seeps provide significant ecosystem services, including habitat for commercially important fishes and support for diversity along the continental margin. Methane seeps are also biological hotspots for krill, plankton, and crustaceans, which in turn sustain higher trophic levels (e.g., whales). Methane-derived authigenic carbonates serve as a hard substrate for deep-sea corals and sponges on millennial time scales. The studies proposed here will elucidate the relationship among seep environments, deep-sea corals, sponges, fisheries, and other organisms and provide new insight into subduction zone and hydrate-associated fluids in this important seismogenic zone. The studies address fishery management concerns and inform future conservation of sensitive species (e.g., deep-sea corals) and benthic habitats. From your perspective, what makes this area unique? The Cascadia Margin seeps are a critical component of the leaky margin that stretches from Baja California to the Aleutian Arc along the Pacific coastline of North America. Cold seeps have been intensely studied on the Gulf of Mexico and U.S. Atlantic passive margins with a focus on chemosynthetic communities, deep-sea corals, and leakage of microbially-generated and/or thermogenic hydrocarbons; however, the recently-discovered Cascadia Margin seeps, as well as active margin seep systems in general, remain more poorly characterized. Such seeps not only contribute to the ocean carbon cycle (e.g., Pohlman et al., 2011), thereby fueling the base of the food chain in these settings, but also emit subduction zone fluids that provide clues about processes within the seismogenic zone and the accretionary complex. The Cascadia seeps area allows both biological (e.g., benthic habitats, coral distributions) and physical processes (e.g., generation of subduction zone fluids) to be studied along both depth (perpendicular to the deformation front) and latitudinal gradients.

California, Oregon, Washington↗

Exxon Valdez Oil Spill Restoration Project final report: Monitoring for evaluation of recovery and restoration of injured nearshore resources

In 2012, we completed three consecutive years of full field sampling in WPWS for EVOS Restoration Project 10100750. Nearshore monitoring was conducted in collaboration with the NPS SWAN I&M program and, beginning in 2012, as part of the EVOSTC GWA program. Data collection was done in accordance with standard operating procedures set forth to monitor marine water chemistry and quality, marine intertidal invertebrates, kelps and seagrasses, marine birds, black oystercatchers, and sea otters. Summer sampling in 2012 represented the fourth year of sampling in WPWS (an initial year of sampling was done in WPWS in 2007; EVOS Restoration Project 070750). Based on our monitoring of nearshore species in WPWS, and comparisons of data from WPWS and other areas within the Gulf of Alaska, we have no evidence of continued injury to biological resources at the spatial scales we are monitoring. A key finding is that recovery of the sea otter population is no longer constrained by exposure to lingering oil; this is consistent with related EVOSTC studies on harlequin ducks (Restoration Project 12120114-Q). We anticipate continued annual nearshore monitoring in WPWS and at KATM and KEFJ under GWA, with data summaries and analyses including all three areas to provide a larger spatial and temporal context to the understanding of processes and patterns in nearshore ecosystems of the GOA which were impacted by the EVOS of 1989.

Alaska↗

Crystal chemistry of thallium in marine ferromanganese deposits

Our understanding of the up to 7 orders of magnitude partitioning of thallium (Tl) between seawater and ferromanganese (FeMn) deposits rests upon two foundations: (1) being able to quantify the Tl(I)/Tl(III) ratio that reflects the extent of the oxidative scavenging of Tl by vernadite (δ-MnO 2 ), the principle manganate mineral in oxic and suboxic environments, and (2) being able to determine the sorption sites and bonding environments of the Tl(I) and Tl(III) complexes on vernadite. We investigated these foundations by determining the oxidation state and chemical form of Tl in FeMn crusts and nodules from the global oceans at a Tl concentration ranging from several hundred ppm (mg/kg) down to the low ppm level. Seventeen hydrogenetic crusts and eleven nodules from the Pacific, Atlantic, Arctic, and Indian Oceans and Baltic Sea were characterized by chemical analysis, X-ray diffraction, Raman spectroscopy, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, Tl L 3 -edge high energy-resolution XANES (HR-XANES) spectroscopy, and extended X-ray absorption fine structure (EXAFS) spectroscopy. The Tl concentration increases linearly from 1.5 to 319 ppm with the Mn/Fe ratio in Fe-vernadite from hydrogenetic crusts, whereas the percentage of Tl(III) to total Tl varies between 62 and 100% independent of both the Mn/Fe and Mn(III)/Mn(IV) ratios. The data, complemented by molecular modeling of the Tl(III) coordination and by XANES calculations, suggest that the enrichment of Tl in Fe-vernadite is driven by (1) the oxidative uptake of octahedrally coordinated Tl(III) above the vacant Mn(IV) sites and on the layer edges of the vernadite layers, and (2) the sorption of Tl(I) on the crystallographic site of Ba at the surface of the vernadite layers, which is an analogue to the surface site of K. Thus, Tl has a high affinity for vernadite regardless of its oxidation state, and the lack of correlation between Tl(III) and the Mn/Fe ratio in FeMn crusts is explained by the affinity of Tl(I) for the Ba site. The Tl concentration varies between 2 and 112 ppm in surface and buried nodules independent of the Mn/Fe ratio, and the percentage of Tl(III) varies between 0 and 100%. Nodules subjected to sediment diagenesis with replacement of layered vernadite by tunneled todorokite are depleted in Tl and have more reduced thallium. Knowledge of the complex interplay of mineralogy, surface chemical processes, and crystallographic siting is required to understand the variability of Tl concentrations, redox state, and acquisition processes by marine FeMn deposits.

ACS Earth and Space Chemistry↗

Editorial: From cold seeps to hydrothermal vents: Geology, chemistry, microbiology, and ecology in marine and coastal environments

This Research Topic compiles contemporary studies on cold seeps, hydrothermal vents, mud volcanoes, and related seafloor features that are associated with focused fluid emissions and the transfer of carbon, other chemical species, and sometimes heat from the geosphere to the ocean. Because these features sometimes tap fluids and gas originating kilometers below the seafloor, they provide an important window into deep processes that are otherwise inaccessible to scientists. At the shallow portion of their journey, migrating fluids nearing the seafloor contribute to a range of unique biological, physical, and chemical processes within the sediments themselves and at the sediment-water interface. Seafloor fluid emissions play a critical role in global biogeochemical cycles, ocean chemistry, and possibly even climate change. Seafloor leakage points often emit hydrocarbon gases (especially methane and CO 2 ) and are sometimes the loci for deposition of seafloor minerals that have economic value. A burgeoning area of research focuses on natural products generated at these features, seeking compounds with potential pharmaceutical or other applications. Multidisciplinary studies have become routine for characterization of seafloor fluid emission sites, attesting to the inseparability of geologic, physical, chemical, and biological processes in these settings. It is increasingly common for researchers to combine in a single research cruise: subbottom imaging and seafloor mapping; porewater and water column geochemistry and gas sampling; sediment retrieval for lithologic, biostratigraphic, and solid phase analyses; and studies of benthic and subseafloor communities at the microbial to macrofaunal scales. This multidisciplinary approach has the advantage of ensuring the spatial and temporal coincidence of surveys and samples, an important factor at highly dynamic seafloor fluid emission sites. In addition, researchers often use remotely operated vehicles (ROVs), autonomous underwater vehicles (AUVs), or human-occupied vehicles (HOVs) to record video of the seafloor, compile photomosaics, collect targeted samples, and survey with high-resolution geophysical near-seafloor systems, providing a degree of detail about seafloor fluid emission sites that is unprecedented compared to most areas of the deep ocean. While rarer, long-term cabled observatories or shorter-term deployments of portable observatories are also used at some loci for seafloor fluid flux and are particularly helpful for capturing temporal variations at these dynamic features. Here we summarize the Research Topic’s contribution to multidisciplinary seafloor emission studies in the categories of cold seeps, mud volcanoes, and hydrothermal vents. Figure 1 shows the geographic distribution of the studies in this Research Topic and key features referred to in this Introduction.

Frontiers in Earth Science↗

Flow and geochemistry of groundwater beneath a back-barrier lagoon: The subterranean estuary at Chincoteague Bay, Maryland, USA

To better understand large-scale interactions between fresh and saline groundwater beneath an Atlantic coastal estuary, an offshore drilling and sampling study was performed in a large barrier-bounded lagoon, Chincoteague Bay, Maryland, USA. Groundwater that was significantly fresher than overlying bay water was found in shallow plumes up to 8 m thick extending more than 1700 m offshore. Groundwater saltier than bay surface water was found locally beneath the lagoon and the barrier island, indicating recharge by saline water concentrated by evaporation prior to infiltration. Steep salinity and nutrient gradients occur within a few meters of the sediment surface in most locations studied, with buried peats and estuarine muds acting as confining units. Groundwater ages were generally more than 50 years in both fresh and brackish waters as deep as 23 m below the bay bottom. Water chemistry and isotopic data indicate that freshened plumes beneath the estuary are mixtures of water originally recharged on land and varying amounts of estuarine surface water that circulated through the bay floor, possibly at some distance from the sampling location. Ammonium is the dominant fixed nitrogen species in saline groundwater beneath the estuary at the locations sampled. Isotopic and dissolved-gas data from one location indicate that denitrification within the subsurface flow system removed terrestrial nitrate from fresh groundwater prior to discharge along the western side of the estuary. Similar situations, with one or more shallow semi-confined flow systems where groundwater geochemistry is strongly influenced by circulation of surface estuary water through organic-rich sediments, may be common on the Atlantic margin and elsewhere.

Marine Chemistry↗

The role of pH up-regulation in response to nutrient-enriched, low-pH groundwater discharge

Coral reefs and their ecosystems are threatened by both global stressors, including increasing sea-surface temperatures and ocean acidification (OA), and local stressors such as land-based sources of pollution that can magnify the effects of OA. Corals can physiologically control the chemistry of their internal calcifying fluids (CF) and can thereby regulate their calcification process. Specifically, increasing aragonite saturation state in the CF (Ω CF ) may allow corals to calcify even under external low saturation conditions. Questions remain regarding the physiological processes that govern the CF chemistry and how they change in response to multiple stressors. To address this knowledge gap, the boron δ 11 B and B/Ca were analyzed in tropical corals, Porites lobata, collected at submarine groundwater seeps impacted by the release of treated wastewater in west Maui, Hawai'i, to document the interactions between high nutrient / low pH seep water on CF carbonate chemistry. Results show substantial up-regulation of pH and dissolved inorganic carbon (DIC) with respect to seawater in P. lobata corals collected from within the wastewater impacted area at Kahekili Beach Park compared to the control site at Olowalu Beach. The Ω CF was 9 to 10 times higher than ambient seawater Ω, and 13 to 26% higher than in corals from the control site and from values previously observed in tropical Porites spp. corals. Such elevated up-regulation suggests that corals exposed to nutrient-enriched, low pH effluent sustain CF supersaturated with respect to aragonite, possibly as an internal coping mechanism to combat multiple stressors from land-based sources of pollution. This elevated up-regulation has implications to coral vulnerability to future climate- and ocean-change.

Hawaii↗

A comparison of two methods for determining copper partitioning in oxidized sediments

Model estimations of the proportion of Cu in oxidized sediments associated with extractable organic materials show some agreement with the proportion of Cu extracted from those sediments with ammonium hydroxide. Data were from 17 estuaries of widely differing sediment chemistry. The modelling and extraction methods agreed best where concentrations of organic materials were either in very high concentrations, relative to other sediment components, or in very low concentrations. In the range of component concentrations where the model predicted Cu should be distributed among a variety of components, agreement between the methods was poor. Both approaches indicated that Cu was predominantly partitioned to organic materials in some sediments, and predominantly partitioned to other components (most probably iron oxides and manganese oxides) in other sediments, and that these differences were related to the relative abundances of the specific components in the sediment. Although the results of the two methods of estimating Cu partitioning to organics correlated significantly among 24 stations from the 17 estuaries, the variability in the relationship suggested refinement of parameter values and verification of some important assumptions were essential to the further development of a reasonable model.

Marine Chemistry↗

Sources of aerosol nitrate to the Gulf of Aqaba: Evidence from δ15N and δ18O of nitrate and trace metal chemistry

The nitrogen (N) and oxygen (O) isotopic composition (δ 15 N and δ 18 O) of water soluble aerosol nitrate was measured in aerosol samples collected in Eilat, Israel, from August 2003 to November 2004. During this period δ 15 N values ranged from − 6.9‰ to + 1.9‰ and δ 18 O from + 65.1‰ to + 84.9‰ and exhibited strong seasonal variability with higher average δ 15 N values observed in the summer and higher δ 18 O values in the winter. Nitrate isotopic composition was compared with bulk chemical composition and extractable ion and trace metals on co-collected samples linking nitrate isotopic composition to various sources of aerosols to this region. Atmospheric processes impacting the isotopic signatures of nitrate were also considered. Based on back trajectory analyses, the majority of NO 3 − came from air masses originating over the Mediterranean Sea (34%), Western Europe (20%) and the local Negev desert (19%), which contain a larger anthropogenic imprint compared to southern and eastern air masses which are dominated by mineral dust. The potential role of reactive mineral dust aerosols as a regulator of NO 3 − isotopic composition is considered; however, based on factor analysis, neither δ 15 N nor δ 18 O were associated with mineral dust components (such as Fe or Al), but rather with anthropogenic indicators such as Cu, Cd, P and Pb. Seasonality in primary NO x cycling reactions driven by seasonal changes in solar radiation, relative humidity and temperature also influence the observed isotopic signatures. The isotope data, together with trace element analysis, suggests that seasonal variations in both δ 15 N NO3 and δ 18 O NO3 are related to both NO x source and transport processes as well as NO x chemical reactions in the atmosphere. The flux-weighted δ 15 N of aerosol NO 3 − in this area averaged − 2.6‰ making aerosol deposition a substantial contributor of low δ 15 N nitrogen to the oligotrophic waters of the Gulf of Aqaba. Thus, while the flux of atmospheric N to oligotrophic marine systems is smaller than the upward flux of NO 3 − from deep water, it nonetheless represents an important source of new N having a low δ 15 N. Further, if this low δ 15 N signature is not considered, it could interfere with N-fixation estimates based on isotopic composition of dissolved nitrate or particulate organic nitrogen. Thus, atmospheric deposition should be constrained for accurate estimates of marine N-fixation when based on δ 15 N in the ocean. Indeed, in the Gulf of Aqaba, low upper water δ 15 N NO3 values could be related to inputs of atmospheric NO 3 − as well as N-fixation.

Gulf of Aqaba, Eliat↗

The release of dissolved nutrients and metals from coastal sediments due to resuspension

Coastal sediments in many regions are impacted by high levels of contaminants. Due to a combination of shallow water depths, waves, and currents, these sediments are subject to regular episodes of sediment resuspension. However, the influence of such disturbances on sediment chemistry and the release of solutes is poorly understood. The aim of this study is to quantify the release of dissolved metals (iron, manganese, silver, copper, and lead) and nutrients due to resuspension in Boston Harbor, Massachusetts, USA. Using a laboratory-based erosion chamber, a range of typical shear stresses was applied to fine-grained Harbor sediments and the solute concentration at each shear stress was measured. At low shear stress, below the erosion threshold, limited solutes were released. Beyond the erosion threshold, a release of all solutes, except lead, was observed and the concentrations increased with shear stress. The release was greater than could be accounted for by conservative mixing of porewaters into the overlying water, suggesting that sediment resuspension enhances the release of nutrients and metals to the dissolved phase. To address the long-term fate of resuspended particles, samples from the erosion chamber were maintained in suspension for 90. h. Over this time, 5-7% of the particulate copper and silver was released to the dissolved phase, while manganese was removed from solution. Thus resuspension releases solutes both during erosion events and over a longer timescale due to reactions of suspended particles in the water column. The magnitude of the annual solute release during erosion events was estimated by coupling the erosion chamber results with a record of bottom shear stresses simulated by a hydrodynamic model. The release of dissolved copper, lead, and phosphate due to resuspension is between 2% and 10% of the total (dissolved plus particulate phase) known inputs to Boston Harbor. Sediment resuspension is responsible for transferring a significant quantity of solid phase metals to the more bioavailable and mobile dissolved phase. The relative importance of sediment resuspension as a source of dissolved metals to Boston Harbor is expected to increase as continuing pollutant control decreases the inputs from other sources. ?? 2010 Elsevier B.V.

Marine Chemistry↗

Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.

Marine Chemistry↗

Requirements for modeling trace metal partitioning in oxidized estuarine sediments

The fate of particulate-bound metals is of particular importance in estuaries because major biological energy flows involve consumption of detrital particles. The biological impact of particulate-bound metals is strongly influenced by the partitioning of metals among sediment components at the oxidized sediment-water interface. Adequate methods for directly measuring this partitioning are not available, thus a modeling approach may be most useful. Important requirements for such a model include: (1) determinations of metal binding intensities which are comparable among sediment components important in oxidized sediments; (2) comparable determinations of the binding capacities of the several forms of each component; (3) operational determinations of the abundance in natural sediments of components of defined binding capacity; (4) assessments of the influence of particle coatings and multicomponent aggregation on the available binding capacity of each substrate; (5) consideration of the effect of Ca and Mg competition on binding to different components; and (6) determinations of the kinetics of metal redistribution among components in oxidized sediments.

Marine Chemistry↗