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A new, in situ sensing system, Channelized Optical System (CHANOS), was recently developed to make high-resolution, simultaneous measurements of total dissolved inorganic carbon (DIC) and pH in seawater. Measurements made by this single, compact sensor can fully characterize the marine carbonate system. The system has a modular design to accommodate two independent, but similar measurement channels for DIC and pH. Both are based on spectrophotometric detection of hydrogen ion concentrations. The pH channel uses a flow-through, sample-indicator mixing design to achieve near instantaneous measurements. The DIC channel adapts a recently developed spectrophotometric method to achieve flow-through CO2 equilibration between an acidified sample and an indicator solution with a response time of only â¼ 90 s. During laboratory and in situ testing, CHANOS achieved a precision of ±0.0010 and ± 2.5 µmol kg(-1) for pH and DIC, respectively. In situ comparison tests indicated that the accuracies of the pH and DIC channels over a three-week time-series deployment were ± 0.0024 and ± 4.1 µmol kg(-1), respectively. This study demonstrates that CHANOS can make in situ, climatology-quality measurements by measuring two desirable CO2 parameters, and is capable of resolving the CO2 system in dynamic marine environments.
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Carbono/análisis , Agua de Mar/análisis , Espectrofotometría/métodos , Diseño de Equipo , Concentración de Iones de Hidrógeno , Agua de Mar/química , Espectrofotometría/instrumentaciónRESUMEN
Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways (i.e., in deep subsurface plumes, in the initial surface slick, and in the atmosphere) during the Deepwater Horizon oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. Although readily soluble hydrocarbons made up â¼25% of the leaking mixture by mass, subsurface chemical data show these compounds made up â¼69% of the deep plume mass; only â¼31% of the deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to assess release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8 ± 1.9) × 10(6) kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) × 10(6) kg/d derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) × 10(6) kg/d derived using physical and optical methods.
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Quantitative information regarding the endmember composition of the gas and oil that flowed from the Macondo well during the Deepwater Horizon oil spill is essential for determining the oil flow rate, total oil volume released, and trajectories and fates of hydrocarbon components in the marine environment. Using isobaric gas-tight samplers, we collected discrete samples directly above the Macondo well on June 21, 2010, and analyzed the gas and oil. We found that the fluids flowing from the Macondo well had a gas-to-oil ratio of 1,600 standard cubic feet per petroleum barrel. Based on the measured endmember gas-to-oil ratio and the Federally estimated net liquid oil release of 4.1 million barrels, the total amount of C(1)-C(5) hydrocarbons released to the water column was 1.7 10(11) g. The endmember gas and oil compositions then enabled us to study the fractionation of petroleum hydrocarbons in discrete water samples collected in June 2010 within a southwest trending hydrocarbon-enriched plume of neutrally buoyant water at a water depth of 1,100 m. The most abundant petroleum hydrocarbons larger than C(1)-C(5) were benzene, toluene, ethylbenzene, and total xylenes at concentrations up to 78 µg L(-1). Comparison of the endmember gas and oil composition with the composition of water column samples showed that the plume was preferentially enriched with water-soluble components, indicating that aqueous dissolution played a major role in plume formation, whereas the fates of relatively insoluble petroleum components were initially controlled by other processes.
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On May 31, 2010, a direct acoustic measurement method was used to quantify fluid leakage rate from the Deepwater Horizon Macondo well prior to removal of its broken riser. This method utilized an acoustic imaging sonar and acoustic Doppler sonar operating onboard a remotely operated vehicle for noncontact measurement of flow cross-section and velocity from the well's two leak sites. Over 2,500 sonar cross-sections and over 85,000 Doppler velocity measurements were recorded during the acquisition process. These data were then applied to turbulent jet and plume flow models to account for entrained water and calculate a combined hydrocarbon flow rate from the two leak sites at seafloor conditions. Based on the chemical composition of end-member samples collected from within the well, this bulk volumetric rate was then normalized to account for contributions from gases and condensates at initial leak source conditions. Results from this investigation indicate that on May 31, 2010, the well's oil flow rate was approximately 0.10 ± 0.017 m(3) s(-1) at seafloor conditions, or approximately 85 ± 15 kg s(-1) (7.4 ± 1.3 Gg d(-1)), equivalent to approximately 57,000 ± 9,800 barrels of oil per day at surface conditions. End-member chemical composition indicates that this oil release rate was accompanied by approximately an additional 24 ± 4.2 kg s(-1) (2.1 ± 0.37 Gg d(-1)) of natural gas (methane through pentanes), yielding a total hydrocarbon release rate of 110 ± 19 kg s(-1) (9.5 ± 1.6 Gg d(-1)).
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To assess the potential impact of the Deepwater Horizon oil spill on offshore ecosystems, 11 sites hosting deep-water coral communities were examined 3 to 4 mo after the well was capped. Healthy coral communities were observed at all sites >20 km from the Macondo well, including seven sites previously visited in September 2009, where the corals and communities appeared unchanged. However, at one site 11 km southwest of the Macondo well, coral colonies presented widespread signs of stress, including varying degrees of tissue loss, sclerite enlargement, excess mucous production, bleached commensal ophiuroids, and covering by brown flocculent material (floc). On the basis of these criteria the level of impact to individual colonies was ranked from 0 (least impact) to 4 (greatest impact). Of the 43 corals imaged at that site, 46% exhibited evidence of impact on more than half of the colony, whereas nearly a quarter of all of the corals showed impact to >90% of the colony. Additionally, 53% of these corals' ophiuroid associates displayed abnormal color and/or attachment posture. Analysis of hopanoid petroleum biomarkers isolated from the floc provides strong evidence that this material contained oil from the Macondo well. The presence of recently damaged and deceased corals beneath the path of a previously documented plume emanating from the Macondo well provides compelling evidence that the oil impacted deep-water ecosystems. Our findings underscore the unprecedented nature of the spill in terms of its magnitude, release at depth, and impact to deep-water ecosystems.
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Antozoos/efectos de los fármacos , Arrecifes de Coral , Contaminación por Petróleo/efectos adversos , Animales , Antozoos/clasificación , Antozoos/genética , Cromatografía de Gases , Sedimentos Geológicos/análisis , Golfo de México , Datos de Secuencia Molecular , Contaminación por Petróleo/análisis , Filogenia , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/toxicidadRESUMEN
Shared autonomy enables novice remote users to conduct deep-ocean science operations with robotic manipulators.
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We present control policies for use with a modified autonomous underwater glider that are intended to enable remote launch/recovery and long-range unattended survey of the Arctic's marginal ice zone (MIZ). This region of the Arctic is poorly characterized but critical to the dynamics of ice advance and retreat. Due to the high cost of operating support vessels in the Arctic, the proposed glider architecture minimizes external infrastructure requirements for navigation and mission updates to brief and infrequent satellite updates on the order of once per day. This is possible through intelligent power management in combination with hybrid propulsion, adaptive velocity control, and dynamic depth band selection based on real-time environmental state estimation. We examine the energy savings, range improvements, decreased communication requirements, and temporal consistency that can be attained with the proposed glider architecture and control policies based on preliminary field data, and we discuss a future MIZ survey mission concept in the Arctic. Although the sensing and control policies presented here focus on under ice missions with an unattended underwater glider, they are hardware independent and are transferable to other robotic vehicle classes, including in aerial and space domains.
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The release of oil and gas at Mississippi Canyon Block 20 into the Gulf of Mexico has vexed response officials since 2004 when a regional seafloor failure toppled the Taylor Energy Company platform. Despite the completion of nine intervention wells, releases continue from the seafloor, mostly captured by a recently installed containment system. Toward informing resolution, this work applies chemical forensic and statistical analyses to surface sheens, sediments, and reservoir oil samples. Our results indicate sheens are chemically heterogeneous, contain remnant synthetic hydrocarbons likely discharged from well interventions prior to 2012, and require mixing of multiple chemically-distinct oil groups to explain observed variability in diagnostic ratios. Given the respite and opportunity afforded by containment we suggest leveraging ongoing collection activities to assess release dynamics, as well as engaging the National Academies of Science, Engineering, and Medicine, to evaluate potential solutions, associated risks, and to consider policy ramifications.
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Contaminación por Petróleo/análisis , Petróleo/análisis , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente , Sedimentos Geológicos , Golfo de México , Hidrocarburos/análisis , MississippiRESUMEN
Natural CO2 releases from shallow marine hydrothermal vents are assumed to mix into the water column, and not accumulate into stratified seafloor pools. We present newly discovered shallow subsea pools located within the Santorini volcanic caldera of the Southern Aegean Sea, Greece, that accumulate CO2 emissions from geologic reservoirs. This type of hydrothermal seafloor pool, containing highly concentrated CO2, provides direct evidence of shallow benthic CO2 accumulations originating from sub-seafloor releases. Samples taken from within these acidic pools are devoid of calcifying organisms, and channel structures among the pools indicate gravity driven flow, suggesting that seafloor release of CO2 at this site may preferentially impact benthic ecosystems. These naturally occurring seafloor pools may provide a diagnostic indicator of incipient volcanic activity and can serve as an analog for studying CO2 leakage and benthic accumulations from subsea carbon capture and storage sites.
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Dióxido de Carbono/análisis , Agua de Mar , Grecia , Erupciones VolcánicasRESUMEN
Submarine mud volcanoes are important sources of methane to the water column. However, the temporal variability of their mud and methane emissions is unknown. Methane emissions were previously proposed to result from a dynamic equilibrium between upward migration and consumption at the seabed by methane-consuming microbes. Here we show non-steady-state situations of vigorous mud movement that are revealed through variations in fluid flow, seabed temperature and seafloor bathymetry. Time series data for pressure, temperature, pH and seafloor photography were collected over 431 days using a benthic observatory at the active Håkon Mosby Mud Volcano. We documented 25 pulses of hot subsurface fluids, accompanied by eruptions that changed the landscape of the mud volcano. Four major events triggered rapid sediment uplift of more than a metre in height, substantial lateral flow of muds at average velocities of 0.4 m per day, and significant emissions of methane and CO2 from the seafloor.
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We constructed a survey system of radon/methane/nitrate/salinity to find sites of submarine groundwater discharge (SGD) and groundwater nitrate input. We deployed the system in Waquoit Bay and Boston Harbor, MA where we derived SGD rates using a mass balance of radon with methane serving as a fine resolution qualitative indicator of groundwater. In Waquoit Bay we identified several locations of enhanced groundwater discharge, out of which two (Childs and Quashnet Rivers) were studied in more detail. The Childs River was characterized by high nitrate input via groundwater discharge, while the Quashnet River SGD was notable but not a significant source of nitrate. Our radon survey of Boston Harbor revealed several sites with significant SGD, out of these Inner Harbor and parts of Dorchester Bay and Quincy Bay had groundwater fluxes accompanied by significant water column nitrogen concentrations. The survey system has proven effective in revealing areas of SGD and non-point source pollution.
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Contaminación Ambiental/análisis , Metano/análisis , Nitratos/análisis , Radón/análisis , Contaminantes del Agua/análisis , Agua/química , Boston , Contaminación Ambiental/efectos adversos , Geografía , Nitrógeno/análisis , Medición de Riesgo/métodos , Ríos/química , Salinidad , Agua de Mar/química , NavíosRESUMEN
The Deepwater Horizon blowout is the largest offshore oil spill in history. We present results from a subsurface hydrocarbon survey using an autonomous underwater vehicle and a ship-cabled sampler. Our findings indicate the presence of a continuous plume of oil, more than 35 kilometers in length, at approximately 1100 meters depth that persisted for months without substantial biodegradation. Samples collected from within the plume reveal monoaromatic petroleum hydrocarbon concentrations in excess of 50 micrograms per liter. These data indicate that monoaromatic input to this plume was at least 5500 kilograms per day, which is more than double the total source rate of all natural seeps of the monoaromatic petroleum hydrocarbons in the northern Gulf of Mexico. Dissolved oxygen concentrations suggest that microbial respiration rates within the plume were not appreciably more than 1 micromolar oxygen per day.
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Bacterias/metabolismo , Biodegradación Ambiental , Contaminación Ambiental , Hidrocarburos , Petróleo , Agua de Mar , Contaminantes del Agua , Océano Atlántico , Hidrocarburos/metabolismo , Petróleo/metabolismo , Agua de Mar/química , Agua de Mar/microbiología , Contaminantes del Agua/metabolismoRESUMEN
The TETHYS mass spectrometer is intended for long-term in situ observation of dissolved gases and volatile organic compounds in aquatic environments. Its design maintains excellent low mass range sensitivity and stability during long-term operations, enabling characterization of low-frequency variability in many trace dissolved gases. Results are presented from laboratory trials and a 300-h in situ trial in a shallow marine embayment in Massachusetts, U.S.A. This time series consists of over 15000 sample measurements and represents the longest continuous record made by an in situ mass spectrometer in an aquatic environment. These measurements possess sufficient sampling density and duration to apply frequency analysis techniques for study of temporal variability in dissolved gases. Results reveal correlations with specific environmental periodicities. Numerical methods are presented for converting mass spectrometer ion peak ratios to absolute-scale dissolved gas concentrations across wide temperature regimes irrespective of ambient pressure, during vertical water column profiles in a hypoxic deep marine basin off the coast of California, U.S.A. Dissolved oxygen concentration values obtained with the TETHYS instrument indicate close correlation with polarographic oxygen sensor data across the entire depth range. These methods and technology enable observation of aquatic environmental chemical distributions and dynamics at appropriate scales of resolution.