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Constraints on the sedimentation history of San Francisco Bay from 14C and 10Be

Industrialization and urbanization around San Francisco Bay as well as mining and agriculture in the watersheds of the Sacramento and San Joaquin rivers have profoundly modified sedimentation patterns throughout the estuary. We provide some constraints on the onset of these erosional disturbances with 10Be data for three sediment cores: two from Richardson Bay, a small embayment near the mouth of San Francisco Bay, and one from San Pablo Bay, mid-way between the river delta and the mouth. Comparison of pre-disturbance sediment accumulation determined from three 14C-dated mollusk shells in one Richardson Bay core with more recent conditions determined from the distribution of 210Pb and 234Th [Fuller, C.C., van Geen, A., Baskaran, M, Anima, R.J., 1999. Sediment chronology in San Francisco Bay, California, defined by 210Pb, 234Th, 239,240Pu.] shows that the accumulation rate increased by an order of magnitude at this particular site. All three cores from San Francisco Bay show subsurface maxima in 10Be concentrations ranging in magnitude from 170 to 520 x 106 atoms/g. The transient nature of the increased 10Be input suggests that deforestation and agricultural develop- ment caused basin-wide erosion of surface soils enriched in 10Be. probably before the turn of the century.

California

A record of hydrocarbon input to San Francisco Bay as traced by biomarker profiles in surface sediment and sediment cores

San Francisco Bay is one of the world's largest urbanized estuarine systems. Its water and sediment receive organic input from a wide variety of sources; much of this organic material is anthropogenically derived. To document the spatial and historical record of the organic contaminant input, surficial sediment from 17 sites throughout San Francisco Bay and sediment cores from two locations Richardson Bay and San Pablo Bay were analyzed for biomarker constituents. Biomarkers, that is, 'molecular fossils', primarily hopanes, steranes, and n-alkanes, provide information on anthropogenic contamination, especially that related to petrogenic sources, as well as on recent input of biogenic material. The biomarker parameters from the surficial sediment and the upper horizons of the cores show a dominance of anthropogenic input, whereas the biomarker profiles at the lower horizons of the cores indicate primarily biogenic input. In the Richardson Bay core the gradual upcore transition from lower maturity background organics to a dominance of anthropogenic contamination occurred about 70-100 years ago and corresponds to the industrial development of the San Francisco Bay area. In San Pablo Bay, the transition was very abrupt, reflecting the complex depositional history of the area. This sharp transition, perhaps indicating a depositional hiatus or erosional period, dated at pre-1952, is clearly visible. Below, the hiatus the biomarker parameters are immature; above, they are mature and show an anthropogenic overlay. Higher concentrations of terrigenous n-alkanes in the upper horizons in this core are indicative of an increase in terrigenous organic matter input in San Pablo Bay, possibly a result of water diversion projects and changes in the fresh water flow into the Bay from the Delta. Alternatively, it could reflect a dilution of organic material in the lower core sections with hydraulic mining debris.

California

Chlorinated hydrocarbon pesticides and polychlorinated biphenyls in sediment cores from San Francisco Bay

Sediment cores of known chronology from Richardson and San Pablo Bays in San Francisco Bay, CA, were analyzed for a suite of chlorinated hydrocarbon pesticides and polychlorinated biphenyls to reconstruct a historic record of inputs. Total DDTs (DDT = 2,4'- and 4,4'-dichlorodiphenyltrichloroethane and the metabolites, 2,4'- and 4,4'-DDE, -DDD) range in concentration from 4-21 ng/g and constitute a major fraction (> 84%) of the total pesticides in the top 70 cm of Richardson Bay sediment. A subsurface maximum corresponds to a peak deposition date of 1969-1974. The first measurable DDT levels are found in sediment deposited in the late 1930's. The higher DDT inventory in the San Pablo relative to the Richardson Bay core probably reflects the greater proximity of San Pablo Bay to agricultural activities in the watershed of the Sacramento and San Joaquin rivers. Total polychlorinated biphenyls (PCBs) occur at comparable levels in the two Bays (< 1-34 ng/g). PCBs are first detected in sediment deposited during the 1930's in Richardson Bay, about a decade earlier than the onset of detectable levels of DDTs. PCB inventories in San Pablo Bay are about a factor of four higher in the last four decades than in Richardson Bay, suggesting a distribution of inputs not as strongly weighed towards the upper reaches of the estuary as DDTs. The shallower subsurface maximum in PCBs compared to DDT in the San Pablo Bay core is consistent with the imposition of drastic source control measures four these constituents in 1970 and 1977 respectively. The observed decline in DDT and PCB levels towards the surface of both cores is consistent with a dramatic drop in the input of these pollutants once the effect of sediment resuspension and mixing is taken into account.

California

Uranium biogeochemistry across the redox transition zone of a permanently stratified fjord: Framvaren, Norway

During August 1995, the vertical concentration profile of dissolved and particulate uranium exhibited strong non-conservative characteristics in the upper 30 m of Framvaren Fjord. There was a pronounced peak in both particulate (> 0.2 ??m; 1.09 nM) and dissolved (< 0.2 ??m; 17.06 nM) uranium in the finely stratified waters at the O2/H2S interface which is positioned well within the euphotic zone at about 20-21 m. Such concentration maxima at the redox boundary are also observed for dissolved organic carbon (DEC), Sr and Ba. Dissolved U levels seen in the water column from 18 m down to 30 m exceeded the high salinity (salinity = 35) U concentrations (13.63 ?? 0.84 nM; Chen, J.H., Edwards, R.L., Wasserburg, G.L., 1986. 238U, 234U and 232Th in seawater. Earth Planet Sci. Lett. 80, 241-251.) observed uniformly in the open ocean. A prolific population of S microbes (e.g., Chromatium, Chlorobium sp.) flourishes at the O2/H2S interface. The source of elevated U at the redox boundary must be due to microbial uptake and subsequent release processes rather than dilution from oceanic uranium. Uranium oxidation state determinations in waters from 1, 22 and 30 m depth reveal that reduced U(IV) is not present in significant abundance, and that the chemical and/or biological reduction of hexavalent uranium is largely inhibited. Our results suggest that U and other trace constituents such as DOC, Sr, Ba, Fe(II), Mn(II) are greatly modified by direct and indirect microbial transformation reactions which are most concentrated across the redox transition zone in Framvaren Fjord.

Marine Chemistry

210Pb and 210Po, manganese and iron cycling across the O2/H2S interface of a permanently anoxic fjord: Framvaren, Norway

Vertical profiles of dissolved and particulate 201 Po and 210 Pb were measured across the redox transition zone at Station F1 in Framvaren Fjord, Norway. In this fjord, a sharp decrease in pH above the O 2 /H 2 S interface facilitates the aerobic dissolution of MnO 2 . In contrast, Fe(II) concentrations begin to increase only at the O 2 /H 2 S interface depth. Activity profiles reveal that dissolved 210 Po and 210 Pb are sequestered efficiently by particulates in surface waters. As polonium-210 and lead-210 activities descend down into the aerobic manganese reduction (AMR) zone, they are remobilized during the reductive dissolution of the carrier phase oxyhydroxides. Both 210 Po and 210 Pb are highly enriched at the O 2 /H 2 S interface where an active community of microbes, such as anoxygenic phototrophs (e.g., Chromatium, Chlorobium sp.), thrives. The coincident peaks in 210 Po and 210 Pb and microbial biomass suggest a strong biological influence on the behavior of these radionuclides. There is a strong covariance between the vertical distribution of Mn and Pb, indicating that their redox cycling is closely coupled and is likely microbially mediated.

Framveran Fjord

Formation of natural gas hydrates in marine sediments 1. Conceptual model of gas hydrate growth conditioned by host sediment properties

The stability of submarine gas hydrates is largely dictated by pressure and temperature, gas composition, and pore water salinity. However, the physical properties and surface chemistry of deep marine sediments may also affect the thermodynamic state, growth kinetics, spatial distributions, and growth forms of clathrates. Our conceptual model presumes that gas hydrate behaves in a way analogous to ice in a freezing soil. Hydrate growth is inhibited within fine-grained sediments by a combination of reduced pore water activity in the vicinity of hydrophilic mineral surfaces, and the excess internal energy of small crystals confined in pores. The excess energy can be thought of as a "capillary pressure" in the hydrate crystal, related to the pore size distribution and the state of stress in the sediment framework. The base of gas hydrate stability in a sequence of fine sediments is predicted by our model to occur at a lower temperature (nearer to the seabed) than would be calculated from bulk thermodynamic equilibrium. Capillary effects or a build up of salt in the system can expand the phase boundary between hydrate and free gas into a divariant field extending over a finite depth range dictated by total methane content and pore-size distribution. Hysteresis between the temperatures of crystallization and dissociation of the clathrate is also predicted. Growth forms commonly observed in hydrate samples recovered from marine sediments (nodules, and lenses in muds; cements in sands) can largely be explained by capillary effects, but kinetics of nucleation and growth are also important. The formation of concentrated gas hydrates in a partially closed system with respect to material transport, or where gas can flush through the system, may lead to water depletion in the host sediment. This "freeze-drying" may be detectable through physical changes to the sediment (low water content and overconsolidation) and/or chemical anomalies in the pore waters and metastable presence of free gas within the normal zone of hydrate stability.

Journal of Geophysical Research B: Solid Earth

The global variation in the iron isotope composition of marine hydrogenetic ferromanganese deposits: Implications for seawater chemistry?

The iron (Fe) isotope compositions of 37 hydrogenetic ferromanganese deposits from various oceans have been analysed by MC-ICPMS; they permit the construction of a global map of Fe isotopic values. The isotopic compositions range between -1.2 and -0.1??? in ??57FeIRMM14. Averages for the Atlantic and the Pacific are -0.41 and -0.88???, but their standard deviations are identical (0.27, 1 ??) and the data very largely overlap. No correlation is found with Pb or Nd isotope compositions and there is no evidence that the observed oceanic Fe isotopic heterogeneity is directly controlled by variations in continental sources. The small quantities of Fe that can be introduced from hydrothermal sources render as unlikely the possibility that the isotopic variations reflect variable proportions of continental and hydrothermal Fe, as recently proposed. The more likely explanation is that the variations are induced locally within the ocean. The exact sources of fractionation remain unclear. Likely possibilities are the dissolution and reprecipitation processes that liberate Fe from sediments during anoxic events, dissolution in surface waters or processes occurring during growth of the crusts. ?? 2004 Elsevier B.V. All rights reserved.

Earth and Planetary Science Letters

Biologic origin of iron nodules in a marine terrace chronosequence, Santa Cruz, California

The distribution, chemistry, and morphology of Fe nodules were studied in a marine terrace soil chronosequence northwest of Santa Cruz, California. The Fe nodules are found at depths <1 m on all terraces. The nodules consisted of soil mineral grains cemented by Fe oxides. The nodules varied in size from 0.5 to 25 mm in diameter. Nodules did not occur in the underlying regolith. The Fe-oxide mineralogy of the nodules was typically goethite; however, a subset of nodules consisted of maghemite. There was a slight transformation to hematite with time. The abundance of soil Fe nodules increased with terrace age on the five terraces studied (aged 65,000-226,000 yr). Scanning electron microscopy (SEM) revealed Fe-oxide-containing fungal hyphae throughout the nodules, including organic structures incorporating fine-grained Fe oxides. The fine-grained nature of the Fe oxides was substantiated by M??ssbauer spectroscopy. Our microscopic observations led to the hypothesis that the nodules in the Santa Cruz terrace soils are precipitated by fungi, perhaps as a strategy to sequester primary mineral grains for nutrient extraction. The fungal structures are fixed by the seasonal wetting and dry cycles and rounded through bioturbation. The organic structures are compacted by the degradation of fungal C with time. ?? Soil Science Society of America. All rights reserved.

Soil Science Society of America Journal

Ocean acidification in the Gulf of Mexico: Drivers, impacts, and unknowns

Ocean acidification (OA) has resulted in global-scale changes in ocean chemistry, which can disturb marine organisms and ecosystems. Despite its extensively populated coastline, many marine-dependent communities, and valuable economies, the Gulf of Mexico (GOM) remains a relatively understudied region with respect to acidification. In general, the warm waters of the GOM are better buffered from acidification compared to higher latitude seas, yet long-term acidification has been documented in several GOM regions. OA within the GOM is recognized as spatially variable, particularly within the coastal zone where numerous physical and biogeochemical processes contribute to carbonate chemistry dynamics. The historical progression of OA within the entire GOM is difficult to assess because only a few dedicated long-term monitoring sites have recently been established, and full-water column observations are limited. However, environmental drivers on smaller scales that affect GOM acidification were found to include freshwater, nutrient, and carbonate discharge from large rivers; ocean warming, circulation and residence times; and episodic extreme weather events. GOM marine ecosystems provide essential services, including coastline protection and carbon dioxide removal, and habitats for many marine species that are economically and ecologically important. However, organismal and ecosystem responses to OA are not well constrained for the GOM due to a lack of studies examining the specific effects of OA on regionally relevant species under contemporary and projected conditions. Tackling the vast number of remaining scientific unknowns in this region can be best coordinated through regional capacity networks, such as the Gulf of Mexico Coastal Acidification Network (GCAN), working to achieve a system-wide understanding of Gulf OA and its impacts. Here we synthesize the current peer-reviewed literature on GOM acidification across the ocean-estuarine continuum and identify critical knowledge, research, and monitoring gaps that require future attention.

Progress in Oceanography

Monitoring marine eruptions

Introduction Submarine volcanoes produce much of the same seismicity and eruptive activity as subaerial volcanoes and can pose hazards to society. Although they can be monitored with similar techniques and methods as described in other chapters of this volume, their submerged location brings unique challenges. This chapter addresses these challenges and provides recommendations for monitoring volcanoes fully or partly in marine environments to meet the capabilities described in other chapters of this volume. The United States and its territories host dozens of submarine volcanoes with most (around 60) in the Commonwealth of the Northern Mariana Islands. Approximately 20 of the Northern Mariana Islands submarine volcanoes are known to be hydrothermally active, and 10 have confirmed eruptions since the 1950s (for example, Baker and others, 2008; Tepp and others, 2019a). Nine of those volcanoes were considered by the National Volcanic Threat Assessment (Ewert and others, 2018) to have a combination of eruptive type and summit depth that poses a higher risk of hazardous eruptions, although only one was listed as a moderate (level 3) threat. Other notable submarine volcanoes of interest to the United States that have historically erupted are Axial Seamount off the Washington State coast, Kamaʻehuakanaloa in Hawaiʻi, and Vailuluʻu seamount in American Samoa. All of these, however, have a low risk of hazards because of their depth (greater than 600 meters below sea level) and eruptive type and so are not included in the National Volcanic Threat Assessment. In addition to submarine volcanoes, the submerged flanks of island volcanoes can also be a source of hazardous submarine eruptions—for example, the 1877 eruption of Mauna Loa, Hawai‘i, in Kealakekua Bay (Wanless and others, 2006). The most notable submarine eruption in recent times was the 2022 eruption of Hunga Tonga–Hunga Haʻapai in Tonga, which was one of the largest eruptions on Earth in the past 100 years. It created a massive volcanic plume, unprecedented shock waves, and far-reaching tsunami (Lynett and others, 2022). Other recent submarine eruptions in the Pacific Ocean Basin have produced subaerial plumes that reached aircraft heights (Carey and others, 2014) and large pumice rafts that can affect marine traffic and harbors (for example, Jutzeler and others, 2014; Kornei, 2019). These examples illustrate the potential hazards of major submarine eruptions. Yet, submarine volcanoes are largely unmonitored, and many eruptions occur that are unnoticed or only identified hours or days afterward. Within U.S. territory, submarine volcanoes in the Northern Mariana Islands have been known to produce eruptive activity that can affect society. Reports from fishermen and other marine vessels in the Northern Mariana Islands have noted underwater explosions, sea-surface discoloration, and bubbling water, all of which are known to be signs of submarine volcanic activity. South Sarigan seamount, located about 160 kilometers (km) north of Saipan, erupted in 2010 from greater than 150 meters below the sea surface, resulting in a gas and ash plume that reached more than 11.9 km into the atmosphere (for example, Searcy, 2013; Embley and others, 2014), high enough to affect international air traffic. Precursory and co-eruptive seismicity was detected on the regional Northern Mariana Islands seismic network (Searcy, 2013) and on global monitoring instruments (Green and others, 2013). Monitoring of submarine volcanoes is best accomplished with marine-based instrumentation, which is also useful for monitoring small island volcanoes that may not have the land area necessary for comprehensive subaerial monitoring. The primary marine-based instrumentation used for submarine volcanoes includes ocean-bottom pressure sensors to assess sea-floor deformation, ocean-bottom seismometers (OBSs) to detect seismicity, and both moored and ocean-bottom hydrophones to detect submarine explosions. Other sensors offer important monitoring data, such as turbidity, temperature, and chemistry of hydrothermal emissions. Marine-based instruments are typically deployed in campaign-style networks with no real-time telemetry owing to cost considerations and technical limitations. However, when necessary, marine instruments can be operated in real time using cables to transmit data to land-based facilities; other technologies for this purpose are in use or in development, such as acoustic transmission from the instrument to a moored buoy (Matsumoto and others, 2016) and a winch-based system with a satellite antenna that is part of the instrument mooring (Matsumoto and others, 2019). Emerging technologies for marine-based monitoring may be considered as part of a future monitoring plan. These technologies include ocean gliders and floats with on-board hydrophones that have been used to record earthquakes and submarine eruptions (for example, Matsumoto and others, 2013; Sukhovich and others, 2015) and fiber-optic cables that have been used as strainmeters to detect earthquakes (for example, Marra and others, 2018; Lindsey and others, 2019). Land-based instruments and satellites can also provide some capability for monitoring submarine volcanoes, but they provide more limited observations than marine-based instrumentation.

Scientific Investigations Report

Geochemical variations in a core of hydrogeologic units near Freehold, New Jersey

Solutes were determined for 26 pore-water samples extracted from Tertiary and Cretaceous core material from a 1,320-foot-deep test borehole at Freehold, New Jersey. The cored materials are sediments that form a multilayered aquifer system of seven aquifers and eight confining units in the New Jersey Coastal Plain. The sediments are of marine origin in the upper 650 feet of the core and primarily nonmarine below 650 feet. Total concentrations of silica and major anions (SO 4 -2 and Cl - ) and cations (Ca +2 , Mg +2 , total Fe, Mn +2 , Na + , and K + ) in the pore-water samples varied with depth. Three core intervals are defined by water- chemistry variations, the environment of deposition (marine or nonmarine), and the degree of alteration (weathered or unweathered) of the units. Calcium, magnesium, sulfate, and total-ion concentrations were greater in the midcore (unweathered marine) interval than in the upper (weathered marine) and lower (fluviodeltaicsilicate) intervals of the core. Generally, pore-water chemical types in confining units were distinct from those found in aquifers–particularly in the midcore interval. In this interval, observed variations in pore-water chemistry in part reflect carbonate dissolution and cation exchange reactions common in Coastal Plain sediments. However, high concentrations of sulfate in unweathered marine sediments indicate novel processes may be important factors influencing pore-water chemistry in confining units.

Groundwater

A preliminary survey of marine contamination from mining-related activities on Marinduque Island, Philippines: porewater toxicity and chemistry results from a field trip, October 14-19, 2000

As a follow-up of an initial overview of environmental problems caused by mining activities on Marinduque Island, Philippines, USGS and TAMU-CC scientists went to Marinduque in October 2000 to do a preliminary assessment of potential impacts of mining-related activities on the marine environment. Like the previous visit in May 2000, the marine assessment was conducted at the invitation of Philippine Congressman Edmund O. Reyes. In this report we present the results of sediment porewater toxicity tests and chemical analyses. Toxicity tests consist of laboratory analyses for the assessment of adverse effects caused by environmental contaminants to animals or plants. Sediments (sand or mud) are known to accumulate contaminants (e.g., copper and other heavy metals). Therefore, it is common to perform toxicity tests using different phases of the sedimentary environment in order to analyze adverse effects of contaminants accumulated in the sediment. Sediment pore water (or interstitial water, i.e., the water distributed among the sediment grains) is a sedimentary phase which controls the bioavailability of contaminants to bottom dwelling aquatic organisms (both plants and animals). There are several different kinds of organisms with which toxicity tests can be performed. Among those, tests with sea urchin early life stages (gametes and embryos) are very common due to their high sensitivity to contaminants, ease of maintenance under laboratory conditions, and ecological importance, particularly in coral reefs. The basis of these tests is the exposure of gametes or embryos to the pore water to be analyzed for toxicity. If the pore water contains contaminants in levels that can adversely affect a number of marine species, fertilization and/or embryological development of sea urchins is inhibited. Chemical analyses provide additional information and aid in the interpretation of the toxicity test results. For the current study, chemical analyses were performed for the measurement of porewater concentrations of several heavy metals associated with copper mining activities. Pore waters for toxicological and chemical analyses were collected at several stations on the coast of Marinduque, near the mouths of the Boac and Mogpog rivers, and near the causeways formed by mine tailings disposal. Porewater samples were also collected at the Tres Reyes Marine Reserve, so that these non-contaminated samples could serve as a reference for test performance. Sea urchin embryological development and fertilization were only significantly impaired by two porewater samples, suggesting the presence of contaminants in toxic amounts at those stations. The toxic samples were collected near the up current side of the Calancan (Marcopper) mine tailings causeway (stations 2 and 3 – see figure 10). The pore water from station 2 also had the highest levels of heavy metals, particularly cadmium, cobalt, copper, nickel, lead and zinc (Table 5). The concentrations of cobalt, nickel and zinc were also elevated 2 at station 3. Copper concentrations were also elevated at the two river mouth stations (8 and 9) and near the CMI tailings causeway (station 7). Visual observations also indicated biological degradation due to heavy siltation and smothered coral at a gradient off the Calancan causeway, suggesting that siltation might also be causing a physical impact. This preliminary survey suggests that effects related to past mining activities are still evident and warrant a more comprehensive study to assess their severity and areal extent.

Open-File Report

Chemistry, isotopic composition, and origin of a methane-hydrogen sulfide hydrate at the Cascadia subduction zone

Although the presence of extensive gas hydrate on the Cascadia margin, offshore from the western U.S. and Canada, has been inferred from marine seismic records and pore water chemistry, solid gas hydrate has only been found at one location. At Ocean Drilling Program (ODP) Site 892, offshore from central Oregon, gas hydrate was recovered close to the sediment-water interface at 2–19 m below the seafloor (mbsf) at 670 m water depth. The gas hydrate occurs as elongated platy crystals or crystal aggregates, mostly disseminated irregularly, with higher concentrations occurring in discrete zones, thin layers, and/or veinlets parallel or oblique to the bedding. A 2- to 3-cm thick massive gas hydrate layer, parallel to bedding, was recovered at ∼ 17 mbsf. Gas from a sample of this layer was composed of both CH 4 and H 2 S. This sample is the first mixed-gas hydrate of CH 4 H 2 S documented in ODP; it also contains ethane and minor amounts of CO 2 . Measured temperatures of the recovered core ranged from 2 to −1.8°C and are 6 to 8 degrees lower than in-situ temperatures. These temperature anomalies were caused by the partial dissociation of the CH 4 H 2 S hydrate during recovery without a pressure core sampler.During this dissociation, toxic levels of H 2 S (δ 34 S, +27.4‰) were released. The δ 13 C values of the CH 4 in the gas hydrate, −64.5 to −67.5‰ (PDB) , together with δD values of −197 to −199‰ (SMOW) indicate a primarily microbial source for the CH 4 . The δ 18 O value of the hydrate H 2 O is +2.9‰ (SMOW) , comparable with the experimental fractionation factor for sea-ice. The unusual composition (CH 4 H 2 S) and depth distribution (2–19 mbsf) of this gas hydrate indicate mixing between a methane-rich fluid with a pore fluid enriched in sulfide; at this site the former is advecting along an inclined fault into the active sulfate reduction zone. The facts that the CH 4 H 2 S hydrate is primarily confined to the present day active sulfate reduction zone (2–19 mbsf), and that from here down to the BSR depth (19–68 mbsf) the gas hydrate inferred to exist is a ≥99% CH 4 hydrate, suggest that the mixing of CH 4 and H 2 S is a geologically young process. Because the existence of a mixed CH 4 H 2 S hydrate is indicative of moderate to intense advection of a methane-rich fluid into a near surface active sulfate reduction zone, tectonically active (faulted) margins with organic-rich sediments and moderate to high sedimentation rates are the most likely regions of occurrence. The extension of such a mixed hydrate below the sulfate reduction zone should reflect the time-span of methane advection into the sulfate reduction zone.

Earth and Planetary Science Letters

Otolith microchemistry of tropical diadromous fishes: spatial and migratory dynamics

Otolith microchemistry was applied to quantify migratory variation and the proportion of native Caribbean stream fishes that undergo full or partial marine migration. Strontium and barium water chemistry in four Puerto Rico, U.S.A., rivers was clearly related to a salinity gradient; however, variation in water barium, and thus fish otoliths, was also dependent on river basin. Strontium was the most accurate index of longitudinal migration in tropical diadromous fish otoliths. Among the four species examined, bigmouth sleeper Gobiomorus dormitor , mountain mullet Agonostomus monticola , sirajo goby Sicydium spp. and river goby Awaous banana , most individuals were fully amphidromous, but 9-12% were semi-amphidromous as recruits, having never experienced marine or estuarine conditions in early life stages and showing no evidence of marine elemental signatures in their otolith core. Populations of one species, G. dormitor , may have contained a small contingent of semi-amphidromous adults, migratory individuals that periodically occupied marine or estuarine habitats (4%); however, adult migratory elemental signatures may have been confounded with those related to diet and physiology. These findings indicate the plasticity of migratory strategies of tropical diadromous fishes, which may be more variable than simple categorization might suggest.

Journal of Fish Biology

Baseline monitoring of the western Arctic Ocean estimates 20% of the Canadian Basin surface waters are undersaturated with respect to aragonite

Marine surface waters are being acidified due to uptake of anthropogenic carbon dioxide, resulting in surface ocean areas of undersaturation with respect to carbonate minerals, including aragonite. In the Arctic Ocean, acidification is expected to occur at an accelerated rate with respect to the global oceans, but a paucity of baseline data has limited our understanding of the extent of Arctic undersaturation and of regional variations in rates and causes. The lack of data has also hindered refinement of models aimed at projecting future trends of ocean acidification. Here, based on more than 34,000 data records collected in 2010 and 2011, we establish a baseline of inorganic carbon data (pH, total alkalinity, dissolved inorganic carbon, partial pressure of carbon dioxide, and aragonite saturation index) for the western Arctic Ocean. This data set documents aragonite undersaturation in ~20% of the surface waters of the combined Canada and Makarov basins, an area characterized by recent acceleration of sea ice loss. Conservative tracer studies using stable oxygen isotopic data from 307 sites show that while the entire surface of this area receives abundant freshwater from meteoric sources, freshwater from sea ice melt is most closely linked to the areas of carbonate mineral undersaturation. These data link the Arctic Ocean’s largest area of aragonite undersaturation to sea ice melt and atmospheric CO 2 absorption in areas of low buffering capacity. Some relatively supersaturated areas can be linked to localized biological activity. Collectively, these observations can be used to project trends of ocean acidification in higher latitude marine surface waters where inorganic carbon chemistry is largely influenced by sea ice meltwater.

PLoS ONE

Planktic foraminiferal test size and weight response to the late Pliocene environment

Atmospheric carbon dioxide ( p CO 2 atm ) is impacting the ocean and marine organisms directly via changes in carbonate chemistry and indirectly via a range of changes in physical parameters most dominantly temperature. To assess potential impacts of climate change on carbonate production in the open ocean, we measured size and weight of planktic foraminifers during the late Pliocene at p CO 2 atm concentrations comparable to today and global temperatures 2 to 3 °C warmer. Size of all foraminifers was measured at Atlantic Ocean Deep Sea Drilling Project (DSDP) Site 610, Ocean Drilling Program (ODP) Site 999, and Integrated Ocean Drilling Program (IODP) Site U1313. Test size was smaller during the Pliocene than in modern assemblages under the same environmental conditions. During the cold marine isotope stage (MIS) M2, size increased at Site 999, potentially linked to intensified stratification of the surface ocean in response to the closure of the Central American Seaway. At Site U1313, test size tracks the warming throughout the late Pliocene. Size-normalized weight (SNW) of Globigerina bulloides at Site U1313 decreased during warmer temperature intervals. SNW of Globigerinoides ruber (white) at Site 999 displays high-frequency variability not correlated to temperature. Yet during the glacial period within MIS M2, test weight was higher during higher temperatures. Our results support studies in the modern ocean, which challenge the view that carbonate chemistry is the primary driver for calcification. To better understand processes driving changes in SNW, computer tomography was used to quantify calcite to volume ratios. During interglacial periods, lower calcite volume but higher test volume suggests less suitable conditions for calcification. As this signal is not evident in SNW, subtle changes in calcification might not be observed by the weight-based method.

Paleoceanography and Paleoclimatology

West Florida Shelf: A natural laboratory for the study of ocean acidificiation

Declining oceanic pH and carbonate-ion concentrations are well-known consequences of increased atmospheric and surface-ocean partial pressure of carbon dioxide (pCO2). The possible subject of shifts in seawater carbonate chemistry on biocalcification and survival rates of marine organisms provides questions amenable to both experimental and field study (Kleypas and Langdon, 2006). To date, limited quantitative data exist with which to formalize and test hypotheses regarding such impacts, particularly in continental-shelf settings. The continental shelves of Florida provide an ideal natural laboratory in which to test latitudinal (and temperature and depth) shifts in habitat ranges of calcifying organisms. Both the east and west Florida shelves extend from warm temperate to subtropical latitudes; additionally, the west Florida shelf has very little siliciclastic influx to mask the carbonate production. This study utilizes the natural laboratory of the west and southwest Florida shelf (fig 1.1) to examine the transition from foramol (predominately foraminifera and molluscan) carbonate sediments, characteristic of the west-central Florida shelf, to chlorozoan (algal and coral) sediments characteristic of the southwest Florida shelf. The west Florida shelf is a mixed siliciclastic carbonate ramp that to the south transitions to the carbonate-dominated southwest Florida shelf (Enos, 1977; Brooks and others, 2003). The west Florida shelf is a distally steepened carbonate ramp that is ~250 kilometers (km) wide (Read, 1985). It is covered by a veneer of unconsolidated sediment consisting of mainly biogenic carbonate and quartz in the near shore, with subordinate amounts of phosphate. The sediment-distribution pattern is largely a function of proximity to source, with physical processes playing a minor role in distribution. The carbonate sand-and-gravel fraction is produced by organisms within the depositional basin of the west Florida shelf (Brooks and others, 2003). The southwest Florida shelf is a rimmed carbonate margin where organisms produce virtually all of the substrate; it also exhibits a greater sediment thickness as compared to the west Florida shelf (Enos, 1977). Temperature, which is usually associated with latitude, plays a major role in locations of foramol versus chlorozoan assemblages, but other factors beyond latitude influence temperature on the west and southwest Florida shelves. The potential of cooler, deep-water upwelling and transport over the bottom waters of the shelf may have a significant role in the species assemblage at the sediment/water interface and ultimately on location of foramol versus chlorozoan production. Deep water transported onto and over the shelf may also have environmental ramifications beyond temperature by bringing in water of different chemistry.

Open-File Report

Geochemistry of a marine phosphate deposit: A signpost to phosphogenesis

The Permian age Phosphoria Formation in southeastern Idaho and adjoining states represents possibly the largest marine phosphate deposit in the world. The Meade Peak Member, which contains the highest concentrations and amount of carbonate fluorapatite in the formation, was not significantly altered by mechanical reworking during deposition or subsequently by chemical weathering. Thus, its present composition reflects properties of the Phosphoria Sea that were critical to its accumulation and possibly to the accumulation of most major marine phosphate deposits. These properties included the chemistry of the water column, the hydrography, and the level of primary productivity. Calculated accumulation rates of the PO 4 3− and trace nutrients – Cd, Cu, Ni, and Zn – recorded a dynamic upwelling rate of c. 30 m year −1 that supported primary productivity of 2g C m −2 day −1 . High accumulation rates of the hydrogenous redox-sensitive trace metals – Cr, Mo, U, and V – reflect bottom-water redox conditions that were dominantly suboxic, maintained by a balance between the oxidation of ~ 8% of the organic detritus that settled out of the photic zone and advection of bottom water with a residence time of c .10 years. A limited flux into the basin of siliciclastic lithogenous debris contributed further to elevated concentrations of the seawater-derived sediment fractions.

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