Comparison of solid-phase and pore-water approaches for assessing the quality of marine and estuarine sediments

USGS Publications Warehouse

Carr, Robert Scott; Chapman, Duane C.

1992-01-01

As part of our continuing evaluation of the pore-water approach for assessing sediment quality, we made a series of side-by-side comparisons between the standard 10-day amphipod whole sediment test with the corophiid Grandidierella japonica and a suite of tests using pore water extracted from the same sediments. the pore-water tests evaluated were the sea urchin (Arbacia punctulata) sperm cell test and morphological development assay, the life-cycle test with the polychaete Dinophilus gyrociliatus, and acute exposures of red drum (Sciaenops ocellatus) embryo-larval stages. Sediment and surface microlayer samples were collected from contaminated sites. Whole-sediment, pore-water, and surface microlayer toxicity tests were performed. Pore-water toxicity tests were considerably more sensitive than the whole-sediment amphipod test, which is currently the most sensitive toxicity test now recommended for determining the acceptability of dredged material for open ocean disposal.

Modeling of Vapor Bubble Growth Under Nucleate Boiling Conditions in Reduced Gravity

NASA Technical Reports Server (NTRS)

Buyevich, Yu A.; Webbon, Bruce W.

1995-01-01

A dynamic model is developed to describe the evolution of a vapor bubble growing at a nucleation site on a superheated surface under arbitrary gravity. The bubble is separated from the surface by a thin microlayer and grows due to the evaporation from the microlayer interface. The average thickness of the microlayer increases as the bubble expands along the surface if the evaporation rate is lower than some critical value. The corresponding threshold value of the surface temperature has to be associated with the burn-out crisis. Two main reasons make for bubble separation, which are the buoyancy force and a force caused by the vapor momentum that comes to the bubble with vapor molecules. The latter force is somewhat diminished if condensation takes place at the upper bubble surface in subcooled liquids. The action of the said forces is opposed by inertia of the additional mass of liquid as the bubble center rises above the surface and by inertia of liquid being expelled by the growing bubble in radial directions. An extra pressure force arises due to the liquid inflow into the microlayer with a finite velocity. The last force helps in holding the bubble close to the surface during an initial stage of bubble evolution. Two limiting regimes with distinctly different properties can be singled out, depending on which of the forces that favor bubble detachment dominates. Under conditions of moderately reduced gravity, the situation is much the same as in normal gravity, although the bubble detachment volume increases as gravity diminishes. In microgravity, the buoyancy force is negligible. Then the bubble is capable of staying near the surface for a long time, with intensive evaporation from the microlayer. It suggests a drastic change in the physical mechanism of heat removal as gravity falls below a certain sufficiently low level. Inferences of the model and conclusions pertaining to effects caused on heat transfer processes by changes in bubble hydrodynamics induced by gravity are discussed in connection with experimental evidence, both available in current and in as yet unpublished literature.

Surface microlayer enrichment of volatile organic compounds and semi-volatile organic compounds in drinking water source.

PubMed

Huang, Zhi; Zhou, Wen; Yu, Ya-juan; Zhang, Ai-qian; Han, Shuo-kui; Wang, Lian-sheng

2004-01-01

Enrichment of volatile organic compounds(VOC) and semi-volatility organic compounds(SVOC) in surface microlayer(SM) of three drinking water sources were studied. The enrichment factor(EFs) were 0.67 to 13.37 and 0.16 to 136, respectively. The results showed some VOC and most SVOC could enrich in SM. Some EFs of SVOC was quite high. Suspension and temperature could affect EFs of SVOC, slim wind and water movement do not destroy enrichment of organic in SM.

Sterols as biomarkers in the surface microlayer of the estuarine areas.

PubMed

Alsalahi, Murad Ali; Latif, Mohd Talib; Ali, Masni Mohd; Dominick, Doreena; Khan, Md Firoz; Mustaffa, Nur Ili Hamizah; Nadzir, Mohd Shahrul Mohd; Nasher, Essam; Zakaria, Mohamad Pauzi

2015-04-15

This study aims to determine the concentration of sterols used as biomarkers in the surface microlayer (SML) in estuarine areas of the Selangor River, Malaysia. Samples were collected during different seasons through the use of a rotation drum. The analysis of sterols was performed using gas chromatography equipped with a flame ionisation detector (GC-FID). The results showed that the concentrations of total sterols in the SML ranged from 107.06 to 505.55 ng L(-1). The total sterol concentration was found to be higher in the wet season. Cholesterol was found to be the most abundant sterols component in the SML. The diagnostic ratios of sterols show the influence of natural sources and waste on the contribution of sterols in the SML. Further analysis, using principal component analysis (PCA), showed distinct inputs of sterols derived from human activity (40.58%), terrigenous and plant inputs (22.59%) as well as phytoplankton and marine inputs (17.35%). Copyright © 2015 Elsevier Ltd. All rights reserved.

Occurrence and Distribution of Microplastics in the Sea Surface Microlayer in Jinhae Bay, South Korea.

PubMed

Song, Young Kyoung; Hong, Sang Hee; Jang, Mi; Han, Gi Myung; Shim, Won Joon

2015-10-01

Microplastic contamination of the marine environment is a worldwide concern. The abundance of microplastics was evaluated in the sea surface microlayer in Jinhae Bay, on the southern coast of Korea. The microplastics in this study are divided into paint resin particles and plastics by polymer type. The mean abundance of paint resin particles (94 ± 68 particles/L) was comparable to that of plastics (88 ± 68 particles/L). Fragmented microplastics, including paint resin particles, accounted for 75 % of total particles, followed by spherules (14 %), fibers (5.8 %), expanded polystyrene (4.6 %), and sheets (1.6 %). Alkyd (35 %) and poly(acrylate/styrene) (16 %) derived from ship paint resin were dominant, and the other microplastic samples consisted of polypropylene, polyethylene, phenoxy resin, polystyrene, polyester, synthetic rubber, and other polymers. The abundance of plastics was significantly (p < 0.05) higher in Jinhae Bay, which is surrounded by a coastal city, than along the east coast of Geoje, which is relatively open sea. The floating microplastic abundance in surface water was the highest reported worldwide.

Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea.

PubMed

Guigue, Catherine; Tedetti, Marc; Giorgi, Sébastien; Goutx, Madeleine

2011-12-01

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05-0.41 and 0.04-4.3 μg l(-1) in the SSW, peaking up to 38 and 1366 μg l(-1) in the SML, respectively. Dissolved and particulate PAHs ranged 1.9-98 and 1.9-21 ng l(-1) in the SSW, amounting up 217 and 1597 ng l(-1) in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9-11.5 in the dissolved phase. Copyright © 2011 Elsevier Ltd. All rights reserved.

Evolution of Vapor Bubbles Nucleation Sites in Low Gravity

NASA Technical Reports Server (NTRS)

Buyevich, Yu A.; Webbon, Bruce W.

1995-01-01

When liquid is expelled by a vapor bubble growing at a nucleation site on a superheated surface, a thin microlayer underneath the bubble is left behind. It is evaporated from the free microlayer surface that provides for bubble growth. The average thickness of the microlayer determining the evaporation rate increases with time if the latter does not exceed a threshold value associated with the burn-out crisis. The bubble is described as a spherical segment with its flattened part adjoining the microlayer. This introduces two independent variables - the radius of the spherical part of the bubble surface and the polar angle that defines the relative area of the flattened part. They are to be found out from a set of two strongly nonlinear equations resulting from mass and momentum conservation laws. The first one depends on both microlayer thickness and nonmonotonously changing bubble base area. The second involves two major factors favoring bubble detachment - the buoyancy and a force due to the initial momentum of vapor input into the bubble. The former force depends on gravity whereas the latter one does not. It is why the limiting regimes of bubble evolution that correspond to normal or moderately reduced gravity and to microgravity feature drastically different properties. In the first case, the buoyancy dominates and the bubble evolves in such a manner as to become a full sphere at a moment that can be viewed as that of detachment. The detachment volume grows as gravity decreases. In the second case, the buoyancy is negligible and the bubble stays near the surface, while its volume continues to increase for a sufficiently long time. The findings are discussed in connection with experimental data obtained under different gravity conditions, some unpublished experiments being included. They help to understand why the pool boiling heat transfer coefficient frequently increases as gravity falls down and eventually vanishes.

Diversity of yeasts associated with the sea surface microlayer and underlying water along the northern coast of Taiwan.

PubMed

Chang, Chin-Feng; Lee, Ching-Fu; Lin, Kao-Yung; Liu, Shiu-Mei

2016-01-01

Yeast communities inhabiting the sea surface microlayer (SSML) on the northern coast of Taiwan were examined using a cultivation method and compared with those inhabiting the underlying water (UW) at a 50-cm depth. Culturable yeasts were recovered from the SSML and UW samples collected in the morning during 4 field campaigns, and 420 strains were isolated. The 420 isolates were grouped into 43 species using a polyphasic molecular approach, including sequence analysis of the 26S rDNA D1/D2 domain and 5.8S-ITS region. From the SSML samples, 12 genera and 39 species, including 7 new species of Cryptococcus sp. (1), Candida spp. (4), and Rhodotorula spp. (2), were isolated. From the UW samples, 10 genera and 21 species, including one new species of Rhodotorula sp. (1), were isolated. Rhodotorula mucilaginosa was the most abundant species present in the yeast community in SSML (37.6%) and UW (21.6%) samples. Basidiomycetous yeasts (63.6%) and pigmented yeasts (64.5%) comprised the major yeast population. The yeast community in the SSML had a higher species number and abundance than the UW. Moreover, although the majority of yeast community species were from the SSML, individual species distribution in the SSML was unequal. Copyright © 2015 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

Distribution and Identification of Luminous Bacteria from the Sargasso Sea

PubMed Central

Orndorff, S. A.; Colwell, R. R.

1980-01-01

Vibrio fischeri and Lucibacterium harveyi constituted 75 of the 83 luminous bacteria isolated from Sargasso Sea surface waters. Photobacterium leiognathi and Photobacterium phosphoreum constituted the remainder of the isolates. Luminescent bacteria were recovered at concentrations of 1 to 63 cells per 100 ml from water samples collected at depths of 160 to 320 m. Two water samples collected at the thermocline yielded larger numbers of viable, aerobic heterotrophic and luminous bacteria. Luminescent bacteria were not recovered from surface microlayer samples. The species distribution of the luminous bacteria reflected previously recognized growth patterns; i.e., L. harveyi and V. fischeri were predominant in the upper, warm waters (only one isolate of P. phosphoreum was obtained from surface tropical waters). PMID:16345575

Ocean haline skin layer and turbulent surface convections

NASA Astrophysics Data System (ADS)

Zhang, Y.; Zhang, X.

2012-04-01

The ocean haline skin layer is of great interest to oceanographic applications, while its attribute is still subject to considerable uncertainty due to observational difficulties. By introducing Batchelor micro-scale, a turbulent surface convection model is developed to determine the depths of various ocean skin layers with same model parameters. These parameters are derived from matching cool skin layer observations. Global distributions of salinity difference across ocean haline layers are then simulated, using surface forcing data mainly from OAFlux project and ISCCP. It is found that, even though both thickness of the haline layer and salinity increment across are greater than the early global simulations, the microwave remote sensing error caused by the haline microlayer effect is still smaller than that from other geophysical error sources. It is shown that forced convections due to sea surface wind stress are dominant over free convections driven by surface cooling in most regions of oceans. The free convection instability is largely controlled by cool skin effect for the thermal microlayer is much thicker and becomes unstable much earlier than the haline microlayer. The similarity of the global distributions of temperature difference and salinity difference across cool and haline skin layers is investigated by comparing their forcing fields of heat fluxes. The turbulent convection model is also found applicable to formulating gas transfer velocity at low wind.

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

USGS Publications Warehouse

Lion, Leonard W.

1982-01-01

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.

Visualization of soil structure and pore structure modifications by pioneering ground beetles (Cicindelidae) in surface sediments of an artificial catchment

NASA Astrophysics Data System (ADS)

Badorreck, Annika; Gerke, Horst H.; Weller, Ulrich; Vontobel, Peter

2010-05-01

An artificial catchment was constructed to study initial soil and ecosystem development. As a key process, the pore structure dynamics in the soil at the surface strongly influences erosion, infiltration, matter dynamics, and vegetation establishment. Little is known, however, about the first macropore formation in the very early stage. This presentation focuses on observations of soil pore geometry and its effect on water flow at the surface comparing samples from three sites in the catchment and in an adjacent "younger" site composed of comparable sediments. The surface soil was sampled in cylindrical plastic rings (10 cm³) down to 2 cm depth in three replicates each site and six where caves from pioneering ground-dwelling beetles Cicindelidae were found. The samples were scanned with micro-X-ray computed tomography (at UFZ-Halle, Germany) with a resolution of 0.084 mm. The infiltration dynamics were visualized with neutronradiography (at Paul-Scherer-Institute, Switzerland) on slab-type soil samples in 2D. The micro-tomographies exhibit formation of surface sealing whose thickness and intensity vary with silt and clay content. The CT images show several coarser- and finer-textured micro-layers at the sample surfaces that were formed as a consequence of repeated washing in of finer particles in underlying coarser sediment. In micro-depressions, the uppermost layers consist of sorted fine sand and silt due to wind erosion. Similar as for desert pavements, a vesicular pore structure developed in these sediments on top, but also scattered in fine sand- and silt-enriched micro-layers. The ground-dwelling activity of Cicindelidae beetles greatly modifies the soil structure through forming caves in the first centimetres of the soil. Older collapsed caves, which form isolated pores within mixed zones, were also found. The infiltration rates were severely affected both, by surface crusts and activity of ground-dwelling beetles. The observations demonstrate relatively high abiotic and biotic dynamics of soil pore structure in the soil surface even during the very early development stages. The structure formation has potentially great effects on changing runoff and infiltration by forming sealing layers or preferential flow paths.

A marine biogenic source of atmospheric ice-nucleating particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, T. W.; Ladino, L. A.; Alpert, Peter A.

2015-09-09

The formation of ice in clouds is facilitated by the presence of airborne ice nucleating particles1,2. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice3–11. Here we show that material in the sea surface microlayer, which is enriched in surface active organic material representative of that found in sub-micron sea- spray aerosol12–21, nucleates ice under conditions that occur in mixed-phase clouds and high-altitude ice clouds. The ice active material is likely biogenic and is less than ~0.2 ?m in size. We also showmore » that organic material (exudate) released by a common marine diatom nucleates ice when separated from cells and propose that organic material associated with phytoplankton cell exudates are a candidate for the observed ice nucleating ability of the microlayer samples. By combining our measurements with global model simulations of marine organic aerosol, we show that ice nucleating particles of marine origin are dominant in remote marine environments, such as the Southern Ocean, the North Pacific and the North Atlantic.« less

Soil sealing and vesicular layer formation as initial structure development and its effect on infiltration

NASA Astrophysics Data System (ADS)

Badorreck, A.; Gerke, H. H.; Weller, U.; Vontobel, P.

2009-04-01

In the Lusatia mining district (NE-Germany) an artificial catchment was constructed to study initial ecosystem development and runoff generation. As a key process in this early stage, we investigate the surface structure dynamics as it strongly influences erosion, infiltration, matter dynamics, and vegetation establishment. The presented work focuses on observations of soil pore structure formation at the surface at five sites in the catchment and in an adjacent "younger" area composed of comparable sediments. Moreover we've conducted infiltration experiments in the lab and field to relate the soil pore structure to the hydraulic properties. The surface soil was sampled in cylindrical rings (10 cm³) down to 2 cm depth from which bulk density profiles were obtained using X-ray computed tomography (CT) (at UFZ- Halle, Germany) with a resolution of 0.084 mm. The influence of structure on infiltration was investigated using neutron radiography (at the NEUTRA facility of the Paul-Scherrer-Institut, Villigen, Switzerland) to visualise two-dimensional (2D) infiltration patterns. The slab-type samples were equilibrated to different initial water contents and then exposed to drip irrigation (to simulate rainfall) while a series of neutron radiographs were taken. In addition, field measurements with a miniature tension infiltrometer were conduced. The micro-tomographies exhibit formation of surface sealing whose thickness and intensity vary with silt and clay content. The CT images show several coarser- and finer-textured micro-layers at the sample surfaces that were formed as a consequence of repeated washing in of finer particles in underlying coarser sediment. In micro-depressions, the uppermost layers consist of sorted fine sand and silt due to wind erosion. Similar as for desert pavements, a vesicular pore structure developed in these sediments on top, but also scattered in fine sand- and silt-enriched micro-layers. The infiltration rates were severely affected by the surface crusts; however, the rates were independent of the vesicular pore layer.

Steady State Vapor Bubble in Pool Boiling

PubMed Central

Zou, An; Chanana, Ashish; Agrawal, Amit; Wayner, Peter C.; Maroo, Shalabh C.

2016-01-01

Boiling, a dynamic and multiscale process, has been studied for several decades; however, a comprehensive understanding of the process is still lacking. The bubble ebullition cycle, which occurs over millisecond time-span, makes it extremely challenging to study near-surface interfacial characteristics of a single bubble. Here, we create a steady-state vapor bubble that can remain stable for hours in a pool of sub-cooled water using a femtosecond laser source. The stability of the bubble allows us to measure the contact-angle and perform in-situ imaging of the contact-line region and the microlayer, on hydrophilic and hydrophobic surfaces and in both degassed and regular (with dissolved air) water. The early growth stage of vapor bubble in degassed water shows a completely wetted bubble base with the microlayer, and the bubble does not depart from the surface due to reduced liquid pressure in the microlayer. Using experimental data and numerical simulations, we obtain permissible range of maximum heat transfer coefficient possible in nucleate boiling and the width of the evaporating layer in the contact-line region. This technique of creating and measuring fundamental characteristics of a stable vapor bubble will facilitate rational design of nanostructures for boiling enhancement and advance thermal management in electronics. PMID:26837464

Study on detection of terrestrial and marine fractions in marine organic molecules by spectrophoto- and spectrofluorometric methods

NASA Astrophysics Data System (ADS)

Drozdowska, Violetta; Wróbel, Iwona; Piskozub, Jacek

2017-04-01

The sea surface is a highly productive and active interface between the sea and the atmosphere. Sea surface films are created by organic matter from sea and land sources and they dissipate due to loss of material at the sea surface, including microbial degradation, chemical and photo chemical processes, and loss due to absorption and adsorption onto particulates. However the surface microlayer is almost ubiquitous and cover most of the surface of the ocean, even under conditions of high turbulence. Surface active molecules (surfactants) present in the surface microlayer (SML) may modify the number of physical processes taking place there: among others they affect the depth of penetration of solar radiation and gas exchange. Therefore, research on the influence of surfactants on the sea surface properties become an important task, especially in coastal waters and in vicinity of the river mouths. Surfactants comprises a mixture of organic molecules rich in lipids, polymeric and humus whose proportions determine the various properties of the SML. A unique structure of the energy levels of the organic molecules results in a unique spectral distribution of the light intensity absorbed and emitted by the molecules. Hence, the absorption and fluorescence spectra of organic compounds may allow the identification of the sources of organic matter. Additionally, several absorption (E2:E3, S, SR) and fluorescence (fluorescence intensities at peaks: A, C, M, T, the ratio (M+T)/(A+C), HIX) indices help in describing the changes in molecular size and weight as well as composition of organic matter during the humification processes and caused by photobleaching and biodegradation. Investigations included the region of Gulf of Gdańsk, along a transect from the Vistula River outlet to open sea. The fluorescence and absorption measurements of the samples collected from a surface films and a subsurface layer (SS, a depth of 1 m) during three research cruises in Gulf of Gdańsk, the Baltic Sea, as well as hydrophysical studies and meteorological observations allowed to assess (i) the contribution of two terrestrial components (A and C) decreased with increasing salinity ( 1.64% and 1.89 % in SML and 0.78 and 0.71 % in SS, respectively), while the contribution of, in-situ, in the sea produced components (M and T) increased with salinity ( 0.52% and 2.83% in SML and 0.98% and 1.87 % in SS, respectively), (ii) the biggest relative changes of the FDOM component composition, along the transect from the Vistula River outlet to Gdańsk Deep, were recorded for component T, both in SML and SS (about 18.5 % and 12.3 %, respectively), (iii) the ratio E2:E3 points to discrete changes in molecular weight/size, effected by photobleaching, while (iv) HIX index reflects the humification/condensation processes more sensitively and effectively in SS. The organic molecules included in the SML can specifically modify the physical processes associated with the sea surface microlayers. It should be necessary to continue a study on the physical properties of surface microlayer in the future, especially in less urbanized and more natural and pristine region, like Arctic.

Exopolymer Particles in the Sea Surface Microlayer (SML) of the Coastal Pacific Ocean

NASA Astrophysics Data System (ADS)

Thornton, D. C.; Brooks, S. D.; Chen, J.

2015-12-01

Exchanges of matter and energy between the ocean and atmosphere occur through the sea surface microlayer (SML). The SML is biogeochemically distinct from the underlying water and overlying atmosphere in terms of physical environment, chemical composition, and biological community. We sampled the Pacific Ocean in coastal waters off the state of Oregon (United States) along a seaward transect out from the mouth of the Columbia River (3 stations) and in deeper waters beyond the shelf break (2 stations) in July 2011. SML samples were collected using the glass plate method and the underlying water was sampled using a peristaltic pump from 1, 5 and 10 m depth. The samples were analyzed for carbohydrates and exopolymer particles. Carbohydrates were significantly enriched in the SML compared with the underlying water. The concentration of polysaccharides was higher than monosaccharides at all depths. We enumerated two classes of exopolymer particles: transparent exopolymer particles (TEP) and Coomassie staining particles (CSP). TEP are composed of acid polysaccharides and CSP are formed from proteins. While TEP have been widely studied, CSP are generally overlooked, despite the biogeochemical significance of proteins. Our data showed that TEP and CSP concentrations were enriched in the SML compared with the underlying waters in most cases. The ubiquitous presence of empty diatom frustules in the samples indicates that the collapse of a diatom bloom was the source of the exopolymers. Further, we conducted image analysis of particle size and abundance, which indicated that TEP and CSP are not the same particles and form distinct populations in the ocean. Our data confirm recent observations indicating that TEP are an important component of the SML. In addition, these data show that CSP are also important components of the SML.

Fundamental investigations of clay/polymer nanocomposites and applications in co-extruded microlayered systems

NASA Astrophysics Data System (ADS)

Decker, Jeremy John

The second and fourth generations of hydroxylated dendritic polyesters (HBP2, HBP4) were combined with unmodified sodium montmorillonite clay (Na +MMT) in water to generate a broad range of polymer clay nanocomposites from 0 to 100% wt/wt Na+MMT. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to investigate intercalation states of the clay galleries. It was shown that interlayer spacings were independent of generation number and changed over the composition range from 0.5 nm to 3.5 nm in 0.5 nm increments that corresponded to a flattened HBP conformation within the clay tactoids. The HBP4/Na+MMT systems were investigated to study the vitrified Rigid Amorphous Fraction (RAF) induced by the clay surfaces. Differential Scanning Calorimetry (DSC) showed changes in heat capacity, Delta Cp, at Tg, that decreased with clay content, until completely suppressed at 80 wt% Na+MMT due to confinement. RAF was quantified from these changes in heat capacity and verified by the analysis of orthopositronium lifetime temperature scans utilizing positron annihilation lifetime spectroscopy (PALS): verifying the glassy nature of the RAF at elevated temperatures. Mathematical relationships allowed for correlation of the interlayer spacings with DeltaC p. RAF formation correlated to intercalated HBP4, and external surfaces of the clay tactoids. The interdiffusion of a polymer pair in microlayers was exploited to increase the concentration of nanoclay particles. When microlayers of a nanocomposite composed of organically modified montmorillonite (M2(HT)2 ) inside maleic anhydride grafted linear low-density polyethylene (LLDPE-g-MA) and low-density polyethylene (LDPE) were taken into the melt, the greater mobility of the linear LLDPE-g-MA chains compared to the branched LDPE chains caused shrinkage of the nanocomposite microlayers, concentrating the M 2(HT)2 contained within. Analysis of the clay morphology within these layers demonstrated an increase in clay particle lengths and aspect ratios, which was attributed to the growth of skewed aggregates during concentration. The melt induced clay concentration and increased clay particle dimensions caused significant decreases in the permeability of the nanocomposite microlayers and reduced the overall permeability of the multilayered films. Morphology and transport behavior of these microlayered films were compared to a series of bulk nanocomposites using a second LLDPE-g-MA containing M 2(HT)2 with varying clay content.

Dynamic Bubble Surface Tension Measurements in Northwest Atlantic Seawater

NASA Astrophysics Data System (ADS)

Kieber, D. J.; Long, M. S.; Keene, W. C.; Kinsey, J. D.; Frossard, A. A.; Beaupre, S. R.; Duplessis, P.; Maben, J. R.; Lu, X.; Chang, R.; Zhu, Y.; Bisgrove, J.

2017-12-01

Numerous reports suggest that most organic matter (OM) associated with newly formed primary marine aerosol (PMA) originates from the sea-surface microlayer. However, surface-active OM rapidly adsorbs onto bubble surfaces in the water column and is ejected into the atmosphere when bubbles burst at the air-water interface. Here we present dynamic surface tension measurements of bubbles produced in near surface seawater from biologically productive and oligotrophic sites and in deep seawater collected from 2500 m in the northwest Atlantic. In all cases, the surface tension of bubble surfaces decreased within seconds after the bubbles were exposed to seawater. These observations demonstrate that bubble surfaces are rapidly saturated by surfactant material scavenged from seawater. Spatial and diel variability in bubble surface evolution indicate corresponding variability in surfactant concentrations and/or composition. Our results reveal that surface-active OM is found throughout the water column, and that at least some surfactants are not of recent biological origin. Our results also support the hypothesis that the surface microlayer is a minor to negligible source of OM associated with freshly produced PMA.

Physicochemical signatures of natural surfactant sea films from coastal Middle Adriatic stations

NASA Astrophysics Data System (ADS)

Frka, Sanja; Pogorzelski, Stanislaw; Kozarac, Zlatica; Ćosović, Božena

2013-04-01

Boundary layers between different environmental compartments represent critical interfaces for biological, chemical and physical processes. The sea surface microlayer (SSM) as a top layer of the sea surface represents natural interface between the atmosphere and ocean. Although < 1 mm in thickness the SML plays a key role in the global biogeochemical cycling because all gaseous, liquid and particulate materials must pass through this interface when exchanging between the ocean and the atmosphere. The SSM thus represents a very important driver enhancing air-water exchange processes. A variety of natural and anthropogenic organic compounds, particularly those which are surface active (SA) are generally enriched in the SML. It is widely acknowledged that the SSM is complex matrix of SA organics as carbohydrates, proteins, lipids and humic substances. Although lipid material is much less abundant than carbohydrates and proteins in the SML, their contribution to surface activity may be disproportionately large. The surfactant films at the air-sea interface change its physicochemical properties reducing air-sea exchange possesses by impeding molecular diffusion across the interface and influencing the hydrodynamic characteristics of water motion at the interface. Various biological, chemical and physical processes lead to the alteration of the film chemical composition, surface physical properties, surface concentration and spatial distribution of film-forming components. Instead of analyzing its chemical composition, it should be possible to scale the SML surface pressure-area (π-A) isotherms in terms of structural parameters which appear to be a sensitive and quantitative measure of the film physicochemical composition, surface concentration and miscibility of its film-forming components. We will present a large data set obtained by electrochemical and monolayer techniques, accompanied with the novel scaling approach for physicochemical characterization of SA substances of the natural microlayers from coastal Middle Adriatic stations including saline Rogoznica Lake and Krka river estuarine station. Higher primary production during late spring-early autumn is reflected in the presence of microlayers of higher surfactant activity containing on average molecules of lower molecular masses (Mw=0.65±0.27 kDa) and higher miscibility (y=6.46±1.33) and elasticity (E=18.33±2.02 mN/m) modulus in comparison to structural parameters (average Mw=2.15±1.58 kDa; y=3.51±1.46; E=6.41±1.97 mN/m) obtained for microlayers from period of lower organic matter production. Higher inhibition effect on the reduction process of cadmium ions is observed for natural microlayers abundant with SA material from more productive period. This kind of distribution is explained as the consequence of competitive adsorption of hydrophobic lipid-like substances of lower Mw which highly influence the surface structural properties of natural air-water interface forming there segregated surface films during more productive period. This study will offer different perspective on contemporary SML concept taking into account the lipids that act as end-members highly influencing seasonal change of SA concentration and surface structural properties of natural films at the air-water interface.

Sum-Frequency Generation Spectroscopy for Studying Organic Layers at Water-Air Interfaces: Microlayer Monitoring and Surface Reactivity

NASA Astrophysics Data System (ADS)

Laß, Kristian; Kleber, Joscha; Bange, Hermann; Friedrichs, Gernot

2015-04-01

The sea surface microlayer, according to commonly accepted terminology, comprises the topmost millimetre of the oceanic water column. It is often enriched with organic matter and is directly influenced by sunlight exposure and gas exchange with the atmosphere, hence making it a place for active biochemistry and photochemistry as well as for heterogeneous reactions. In addition, surface active material either is formed or accumulates directly at the air-water interface and gives rise to very thin layers, sometimes down to monomolecular thickness. This "sea surface nanolayer" determines the viscoelastic properties of the seawater surface and thus may impact the turbulent air-sea gas exchange rates. To this effect, this small scale layer presumably plays an important role for large scale changes of atmospheric trace gas concentrations (e.g., by modulating the ocean carbon sink characteristics) with possible implications for coupled climate models. To date, detailed knowledge about the composition, structure, and reactivity of the sea surface nanolayer is still scarce. Due to its small vertical dimension and the small amount of material, this surfactant layer is very difficult to separate and analyse. A way out is the application of second-order nonlinear optical methods, which make a direct surface-specific and background-free detection of this interfacial layer possible. In recent years, we have introduced the use of vibrational sum frequency generation (VSFG) spectroscopy to gain insight into natural and artificial organic monolayers at the air-water interface. In this contribution, the application of VSFG spectroscopy for the analysis of the sea surface nanolayer will be illustrated. Resulting spectra are interpreted in terms of layer composition and surfactant classes, in particular with respect to carbohydrate-containing molecules such as glycolipids. The partitioning of the detected surfactants into soluble and non-soluble ("wet" and "dry") surfactants will be discussed. Furthermore, the application of a combined VSFG/Langmuir trough experiment to investigate the reaction kinetics of heterogeneous oxidation processes will be highlighted. The ozonolysis of monolayers of unsaturated fatty acids serves as model system for natural aging processes of surfactant layers at the sea surface. Finally, a VSFG time series study of the sea surface nanolayer at a western Baltic Sea near-shore sampling station will be presented. The observed seasonality reveals a significant temporal shift with respect to the spring algal bloom showing that high organic material content in the microlayer does not necessarily correlate with high nanolayer abundance. This interesting finding and implications for the formation of surfactant material by degradation of biological material will be discussed briefly.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

NASA Astrophysics Data System (ADS)

Mungall, Emma L.; Abbatt, Jonathan P. D.; Wentzell, Jeremy J. B.; Lee, Alex K. Y.; Thomas, Jennie L.; Blais, Marjolaine; Gosselin, Michel; Miller, Lisa A.; Papakyriakou, Tim; Willis, Megan D.; Liggio, John

2017-06-01

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Biodegradation of artificial monolayers applied to water storages to reduce evaporative loss.

PubMed

Pittaway, P; Herzig, M; Stuckey, N; Larsen, K

2015-01-01

Repeat applications of an artificial monolayer to the interfacial boundary layer of large agricultural water storages during periods of high evaporative demand remains the most commercially feasible water conservation strategy. However, the interfacial boundary layer (or microlayer) is ecologically distinct from subsurface water, and repeat monolayer applications may adversely affect microlayer processes. In this study, the natural cleansing mechanisms operating within the microlayer were investigated to compare the biodegradability of two fatty alcohol (C16OH and C18OH) and one glycol ether (C18E1) monolayer compound. The C16OH and C18OH compounds were more susceptible to microbial degradation, but the C18E1 compound was most susceptible to indirect photodegradation. On clean water the surface pressure and evaporation reduction achieved with a compressed C18E1 monolayer was superior to the C18OH monolayer, but on brown water the surface pressure dropped rapidly. These results suggest artificial monolayers are readily degraded by the synergy between photo and microbial degradation. The residence time of C18OH and C18E1 monolayers on clear water is sufficient for cost-effective water conservation. However, the susceptibility of C18E1 to photodegradation indicates the application of this monolayer to brown water may not be cost-effective.

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer.

PubMed

Mungall, Emma L; Abbatt, Jonathan P D; Wentzell, Jeremy J B; Lee, Alex K Y; Thomas, Jennie L; Blais, Marjolaine; Gosselin, Michel; Miller, Lisa A; Papakyriakou, Tim; Willis, Megan D; Liggio, John

2017-06-13

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate.

Investigation of pollution characteristics of polychlorinated biphenyls in the typical drinking water sources in Jiangsu Province, China.

PubMed

Hong, Ye; Chunhong, Zhou; Xiaoxiong, Zeng

2009-11-01

Concentration and composition of polychlorinated biphenyls (PCBs) in the typical drinking water sources in Jiangsu Province were studied by scene investigation and physical and chemical analyses as well. Total amount of PCBs in some surface water and surface microlayers exceeded the standard (20 ng/l) in the "Environmental Quality Standard of Surface Water". There were less PCBs in suspended substances and bottom mud. It reflected that there was less PCB pollution in drinking water sources in Jiangsu Province for quite a long period. The main kind of PCBs in the typical drinking water sources was dichlorobiphenyl. Monochlorobiphenyl and trichlorobiphenyl ranked next to dichlorobiphenyl. In the study of PCB distribution in drinking water sources, it was found that the concentration of PCBs in surface microlayer was higher than that in deep water. The concentration of PCBs along the Yangtze River bank was more than that in the middle of Yangtze River. PCBs in the typical drinking water sources mostly came from by-products in industrial production.

Violacein-producing Collimonas sp. from the sea surface microlayer of costal waters in Trøndelag, Norway.

PubMed

Hakvåg, Sigrid; Fjaervik, Espen; Klinkenberg, Geir; Borgos, Sven Even F; Josefsen, Kjell D; Ellingsen, Trond E; Zotchev, Sergey B

2009-11-12

A new strain belonging to the genus Collimonas was isolated from the sea surface microlayer off the coast of Trøndelag, Norway. The bacterium, designated Collimonas CT, produced an antibacterial compound active against Micrococcus luteus. Subsequent studies using LC-MS identified this antibacterial compound as violacein, known to be produced by several marine-derived bacteria. Fragments of the violacein biosynthesis genes vioA and vioB were amplified by PCR from the Collimonas CT genome and sequenced. Phylogenetic analysis of these sequences demonstrated close relatedness of the Collimonas CT violacein biosynthetic gene cluster to those in Janthinobacterium lividum and Duganella sp., suggesting relatively recent horizontal gene transfer. Considering diverse biological activities of violacein, Collimonas CT shall be further studied as a potential producer of this compound.

Violacein-Producing Collimonas sp. from the Sea Surface Microlayer of Costal Waters in Trøndelag, Norway

PubMed Central

Hakvåg, Sigrid; Fjærvik, Espen; Klinkenberg, Geir; Borgos, Sven Even F.; Josefsen, Kjell D.; Ellingsen, Trond E.; Zotchev, Sergey B.

2009-01-01

A new strain belonging to the genus Collimonas was isolated from the sea surface microlayer off the coast of Trøndelag, Norway. The bacterium, designated Collimonas CT, produced an antibacterial compound active against Micrococcus luteus. Subsequent studies using LC-MS identified this antibacterial compound as violacein, known to be produced by several marine-derived bacteria. Fragments of the violacein biosynthesis genes vioA and vioB were amplified by PCR from the Collimonas CT genome and sequenced. Phylogenetic analysis of these sequences demonstrated close relatedness of the Collimonas CT violacein biosynthetic gene cluster to those in Janthinobacterium lividum and Duganella sp., suggesting relatively recent horizontal gene transfer. Considering diverse biological activities of violacein, Collimonas CT shall be further studied as a potential producer of this compound. PMID:20098599

Air--sea gaseous exchange of PCB at the Venice lagoon (Italy).

PubMed

Manodori, L; Gambaro, A; Moret, I; Capodaglio, G; Cescon, P

2007-10-01

Water bodies are important storage media for persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) and this function is increased in coastal regions because their inputs are higher than those to the open sea. The air-water interface is extensively involved with the global cycling of PCBs because it is the place where they accumulate due to depositional processes and where they may be emitted by gaseous exchange. In this work the parallel collection of air, microlayer and sub-superficial water samples was performed in July 2005 at a site in the Venice lagoon to evaluate the summer gaseous flux of PCBs. The total concentration of PCBs (sum of 118 congeners) in air varies from 87 to 273 pg m(-3), whereas in the operationally defined dissolved phase of microlayer and sub-superficial water samples it varies from 159 to 391 pg L(-1). No significant enrichment of dissolved PCB into the microlayer has been observed, although a preferential accumulation of most hydrophobic congeners occurs. Due to this behaviour, we believe that the modified two-layer model was the most suitable approach for the evaluation of the flux at the air-sea interface, because it takes into account the influence of the microlayer. From its application it appears that PCB volatilize from the lagoon waters with a net flux varying from 58 to 195 ng m(-2)d(-1) (uncertainty: +/-50-64%) due to the strong influence of wind speed. This flux is greater than those reported in the literature for the atmospheric deposition and rivers input and reveals that PCB are actively emitted from the Venice lagoon in summer months.

Photodegradation of selected polycyclic aromatic hydrocarbons in surface microlayer under direct solar irradiance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, K.; Dickhut, R.M.

1995-12-31

Photodegradation kinetics of selected polycyclic aromatic hydrocarbons (PAHs) in the presence of various particle and dissolved phases were examined in surface microlayer (SM) and surface water under direct solar irradiance during different seasons. Halflives of PAHs during different seasons in the various media were determined. The results showed shorter halflives measured at the surface for PAHs in the SM media than in surface water. Submergence depth also significantly affected rate constants, and halflives for PAH compounds were 1.4 to 5 times shorter at the surface than at 14cm depth below the surface. In bulk SM media, the annual average halflivesmore » varied from 1.3 to 43 hours (midday) with different PAH compounds, and in filtered SM from 1.8 to 56.9 hours (midday). The effects of particles and DOC on the photodegradation of PAHs were also inspected. The results showed particulates and DOC both enhanced or decreased the photodegradation rate constants for selected PAHs. Overall, PAH photoreactivity is related to the compound`s maximum net atomic charge (MNAC) on the most reactive carbon center of a specific PAH molecule.« less

Microlayer source of oxygenated volatile organic compounds in the summertime marine Arctic boundary layer

PubMed Central

Abbatt, Jonathan P. D.; Wentzell, Jeremy J. B.; Lee, Alex K. Y.; Thomas, Jennie L.; Blais, Marjolaine; Miller, Lisa A.; Papakyriakou, Tim; Liggio, John

2017-01-01

Summertime Arctic shipboard observations of oxygenated volatile organic compounds (OVOCs) such as organic acids, key precursors of climatically active secondary organic aerosol (SOA), are consistent with a novel source of OVOCs to the marine boundary layer via chemistry at the sea surface microlayer. Although this source has been studied in a laboratory setting, organic acid emissions from the sea surface microlayer have not previously been observed in ambient marine environments. Correlations between measurements of OVOCs, including high levels of formic acid, in the atmosphere (measured by an online high-resolution time-of-flight mass spectrometer) and dissolved organic matter in the ocean point to a marine source for the measured OVOCs. That this source is photomediated is indicated by correlations between the diurnal cycles of the OVOC measurements and solar radiation. In contrast, the OVOCs do not correlate with levels of isoprene, monoterpenes, or dimethyl sulfide. Results from box model calculations are consistent with heterogeneous chemistry as the source of the measured OVOCs. As sea ice retreats and dissolved organic carbon inputs to the Arctic increase, the impact of this source on the summer Arctic atmosphere is likely to increase. Globally, this source should be assessed in other marine environments to quantify its impact on OVOC and SOA burdens in the atmosphere, and ultimately on climate. PMID:28559340

Enrichment of Extracellular Carbonic Anhydrase in the Sea Surface Microlayer and Its Effect on Air-Sea CO2 Exchange

NASA Astrophysics Data System (ADS)

Mustaffa, N. I. H.; Striebel, M.; Wurl, O.

2017-12-01

This paper describes the quantification of extracellular carbonic anhydrase (eCA) concentrations in the sea surface microlayer (SML), the boundary layer between the ocean and the atmosphere of the Indo-West Pacific. We demonstrated that the SML is enriched with eCA by 1.5 ± 0.7 compared to the mixed underlying water. Enrichment remains up to a wind speed of 7 m s-1 (i.e., under typical oceanic conditions). As eCA catalyzes the interconversion of HCO3- and CO2, it has been hypothesized that its enrichment in the SML enhances the air-sea CO2 exchange. We detected concentrations in the range of 0.12 to 0.76 nM, which can enhance the exchange by up to 15% based on the model approach described in the literature.

Changes in optical characteristics of surface microlayers in the Peruvian upwelling region hint to photochemically and microbially-mediated DOM turnover

NASA Astrophysics Data System (ADS)

Engel, A.; Galgani, L.

2016-02-01

The coastal upwelling system off Peru is characterized by high biological activity and associated subsurface oxygen minimum zone, leading to an enhanced emission of atmospheric trace gases. High biological productivity in the water column may promote the establishment of enriched organic surface films, key environments for processes regulating gas fluxes across the water-air interface. During M91 cruise to the Peruvian upwelling, we focused our attention on the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples in 38 stations determining DOC concentrations, amino acids composition, marine gels, CDOM and bacterial abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slopes (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources. Profound changes in spectral slope properties were observed suggesting smaller MW CDOM in the SML compared to underlying water. Microbial and photochemical degradation are likely the main drivers for organic matter cycling in the top layer of the ocean. Consequences on the formation of inorganic and organic species highly relevant for air-sea gas exchange and for climate dynamics will be discussed.

A comparison of microscopic and spectroscopic identification methods for analysis of microplastics in environmental samples.

PubMed

Song, Young Kyoung; Hong, Sang Hee; Jang, Mi; Han, Gi Myung; Rani, Manviri; Lee, Jongmyoung; Shim, Won Joon

2015-04-15

The analysis of microplastics in various environmental samples requires the identification of microplastics from natural materials. The identification technique lacks a standardized protocol. Herein, stereomicroscope and Fourier transform infrared spectroscope (FT-IR) identification methods for microplastics (<1mm) were compared using the same samples from the sea surface microlayer (SML) and beach sand. Fragmented microplastics were significantly (p<0.05) underestimated and fiber was significantly overestimated using the stereomicroscope both in the SML and beach samples. The total abundance by FT-IR was higher than by microscope both in the SML and beach samples, but they were not significantly (p>0.05) different. Depending on the number of samples and the microplastic size range of interest, the appropriate identification method should be determined; selecting a suitable identification method for microplastics is crucial for evaluating microplastic pollution. Copyright © 2015 Elsevier Ltd. All rights reserved.

New Photosensitized Processes at Aerosol and Ocean Surfaces

NASA Astrophysics Data System (ADS)

Rossignol, S.; Aregahegn, K. Z.; Ciuraru, R.; Bernard, F.; Tinel, L.; Fine, L.; George, C.

2014-12-01

From a few years now, there is a growing body of evidence that photoinduced processes could be of great importance for the tropospheric chemistry. Here, we would like to present two additional outcomes of this new area of research, firstly the photosensitized direct VOC uptake by aerosols and, secondly, the photoinduced chemical formation of unsaturated VOC from marine microlayer proxy. It was recently shown that the chemistry of glyoxal toward ammonium ions into droplets and wet aerosols leads to the formation of light-absorbing compounds. Among them, we found that imidazole-2-carboxaldehyde (IC) acts as a photosensitizer and is able to initiate the growth of organic aerosols via the uptake of VOC, such as limonene. Given its potential importance, the mechanism of this photoinduced uptake was investigated thanks to aerosol flow tube experiments and UPLC-ESI-HRMS analysis. Results reveal hydrogen abstraction on the VOC molecule by the triplet state of IC leading to the VOC oxidation without any traditional oxidant. As well as aerosol, the sea-surface microlayer, known to be enriched in light-absorbing organics, is largely impacted by photochemical processes. Recent studies have pointed out for example the role of photosentitized processes in the loss of NO2 and ozone at water surfaces containing photoactive compounds such as chlorophyll. In order to go further, we worked from sea-surface microlayer proxy containing humic acids as photoactive material and organic acids as surfactants. Beside oxidation processes, we monitored by high resolution PTR-MS the release in the gas phase of unsaturated compounds, including C5 dienes (isoprene ?). A strong correlation between the measured surface tension and the C5 diene concentration in the gas phase was evidenced, clearly pointing toward an interfacial process. This contribution will highlight the similarities between both systems and will attempt to present a general chemical scheme for photosensitized chemistry at interfaces.

Changes in optical characteristics of surface microlayers hint to photochemically and microbially-mediated DOM turnover in the upwelling region off Peru

NASA Astrophysics Data System (ADS)

Galgani, L.; Engel, A.

2015-12-01

The coastal upwelling system off Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. During the Meteor (M91) cruise to the Peruvian upwelling system in 2012, we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like Chromophoric Dissolved Organic Matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. In order to understand organic matter cycling in surface films, we analyzed SML and underlying water samples at 38 stations determining DOC concentration, amino acid composition, marine gels, CDOM and bacterial and phytoplankton abundance as indicators of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and Excitation-Emission Matrix fluorescence (EEMs), which allow to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. We identified five fluorescent components of the CDOM pool, of which two had excitation/emission characteristics of protein-like fluorophores and were highly enriched in the SML. CDOM composition and changes in spectral slope properties suggested a local microbial release of HMW DOM directly in the SML as a response to light exposure in this extreme environment. Our results suggest that microbial and photochemical processes play an important role for the production, alteration and loss of optically active substances in the SML.

Atmospheric deposition flux estimates for chlorpyrifos and trifluralin in the chukchi sea

USDA-ARS?s Scientific Manuscript database

During the 1993 U.S.-Russian BERPAC expedition, residues of agricultural pesticides were detected in seawater, ice, surface microlayer, fog, and air of the Bering and Chukchi Seas. Gas exchange, wet deposition, and dry particle deposition fluxes of trifluralin and chlorpyrifos were estimated using m...

Seasonal signatures in SFG vibrational spectra of the sea surface nanolayer at Boknis Eck Time Series Station (SW Baltic Sea)

NASA Astrophysics Data System (ADS)

Laß, K.; Bange, H. W.; Friedrichs, G.

2013-02-01

The very thin sea surface nanolayer on top of the sea surface microlayer, sometimes just one monomolecular layer thick, forms the interface between ocean and atmosphere. Due to the small dimension and tiny amount of substance, knowledge about the development of the layer in the course of the year is scarce. In this work, the sea surface nanolayer at Boknis Eck Time Series Station (BE), southwestern Baltic Sea, has been investigated over a period of three and a half years. Surface water samples were taken monthly by screen sampling and were analyzed in terms of organic content and composition by sum frequency generation spectroscopy, which is specifically sensitive to interfacial layers. A yearly periodicity has been observed with a pronounced abundance of sea surface nanolayer material (such as carbohydrate-rich material) during the summer months. On the basis of our results we conclude that the abundance of organic material in the nanolayer at Boknis Eck is not directly related to phytoplankton abundance. We suggest that indeed sloppy feeding of zooplankton together with photochemical and/or microbial processing of organic precursor compounds are responsible for the pronounced seasonality.

Seasonal signatures in SFG vibrational spectra of the sea surface nanolayer at Boknis Eck Time Series Station (SW Baltic Sea)

NASA Astrophysics Data System (ADS)

Laß, K.; Bange, H. W.; Friedrichs, G.

2013-08-01

The very thin sea surface nanolayer on top of the sea surface microlayer, sometimes just one monomolecular layer thick, forms the interface between ocean and atmosphere. Due to the small dimension and tiny amount of substance, knowledge about the development of the layer in the course of the year is scarce. In this work, the sea surface nanolayer at Boknis Eck Time Series Station (BE), southwestern Baltic Sea, has been investigated over a period of three and a half years. Surface water samples were taken monthly by screen sampling and were analyzed in terms of organic content and composition by sum frequency generation spectroscopy, which is specifically sensitive to interfacial layers. A yearly periodicity has been observed with a pronounced abundance of sea surface nanolayer material (such as carbohydrate-rich material) during the summer months. On the basis of our results we conclude that the abundance of organic material in the nanolayer at Boknis Eck is not directly related to phytoplankton abundance alone. We speculate that indeed sloppy feeding of zooplankton together with photochemical and/or microbial processing of organic precursor compounds is responsible for the pronounced seasonality.

Chemical Controls of Ozone Dry Deposition to the Sea Surface Microlayer

NASA Astrophysics Data System (ADS)

Carpenter, L.; Chance, R.; Tinel, L.; Saint, A.; Sherwen, T.; Loades, D.; Evans, M. J.; Boxhall, P.; Hamilton, J.; Stolle, C.; Wurl, O.; Ribas-Ribas, M.; Pereira, R.

2017-12-01

Oceanic dry deposition of atmospheric ozone (O3) is both the largest and most uncertain O3 depositional sink, and is widely acknowledged to be controlled largely by chemical reactions in the sea surface microlayer (SML) involving iodide (I-) and dissolved organic material (DOM). These reactions not only determine how quickly O3 can be removed from the atmosphere, but also result in emissions of trace gases including volatile organic compounds and may constitute a source of secondary organic aerosols to the marine atmosphere. Iodide concentrations at the sea surface vary by approximately an order of magnitude spatially, leading to more than fivefold variation in ozone deposition velocities (and volatile iodine fluxes). Sea-surface temperature is a reasonable predictor of [I-], however two recent parameterisations for surface I- differ by a factor of two at low latitudes. The nature and reactivity of marine DOM to O3 is almost completely unknown, although studies have suggested approximately equivalent chemical control of I- and DOM on ozone deposition. Here we present substantial new measurements of oceanic I- in both bulk seawater and the overlying SML, and show improved estimates of the global sea surface iodide distribution. We also present analyses of water-soluble DOM isolated from the SML and bulk seawater, and corresponding laboratory studies of ozone uptake to bulk and SML seawater, with the aim of characterizing the reactivity of O3 towards marine DOM.

The Ocean's Vital Skin: Toward an Integrated Understanding of the Sea Surface Microlayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engel, Anja; Bange, Hermann W.; Cunliffe, Michael

Despite the huge extent of the ocean’s surface, until now relatively little attention has been paid to the sea surface microlayer (SML) as the ultimate interface where heat, momentum and mass exchange between the ocean and the atmosphere takes place. Via the SML, large-scale environmental changes in the ocean such as warming, acidification, deoxygenation, and eutrophication potentially influence cloud formation, precipitation, and the global radiation balance. Due to the deep connectivity between biological, chemical, and physical processes, studies of the SML may reveal multiple sensitivities to global and regional changes. Understanding the processes at the ocean’s surface, in particular involvingmore » the SML as an important and determinant interface, could therefore provide an essential contribution to the reduction of uncertainties regarding ocean-climate feedbacks. This review identifies gaps in our current knowledge of the SML and highlights a need to develop a holistic and mechanistic understanding of the diverse biological, chemical, and physical processes occurring at the ocean-atmosphere interface. We advocate the development of strong interdisciplinary expertise and collaboration in order to bridge between ocean and atmospheric sciences. Although this will pose significant methodological challenges, such an initiative would represent a new role model for interdisciplinary research in Earth System sciences.« less

The Ocean's Vital Skin: Toward an Integrated Understanding of the Sea Surface Microlayer

DOE PAGES

Engel, Anja; Bange, Hermann W.; Cunliffe, Michael; ...

2017-05-30

Despite the huge extent of the ocean’s surface, until now relatively little attention has been paid to the sea surface microlayer (SML) as the ultimate interface where heat, momentum and mass exchange between the ocean and the atmosphere takes place. Via the SML, large-scale environmental changes in the ocean such as warming, acidification, deoxygenation, and eutrophication potentially influence cloud formation, precipitation, and the global radiation balance. Due to the deep connectivity between biological, chemical, and physical processes, studies of the SML may reveal multiple sensitivities to global and regional changes. Understanding the processes at the ocean’s surface, in particular involvingmore » the SML as an important and determinant interface, could therefore provide an essential contribution to the reduction of uncertainties regarding ocean-climate feedbacks. This review identifies gaps in our current knowledge of the SML and highlights a need to develop a holistic and mechanistic understanding of the diverse biological, chemical, and physical processes occurring at the ocean-atmosphere interface. We advocate the development of strong interdisciplinary expertise and collaboration in order to bridge between ocean and atmospheric sciences. Although this will pose significant methodological challenges, such an initiative would represent a new role model for interdisciplinary research in Earth System sciences.« less

Candida neustonensis sp. nov., a novel ascomycetous yeast isolated from the sea surface microlayer in Taiwan.

PubMed

Chang, Chin-Feng; Lee, Ching-Fu; Liu, Shiu-Mei

2010-01-01

A new ascomycetous yeast species, Candida neustonensis is proposed in this study based on four strains (SN92(T), SN47, SJ22, SJ25) isolated from sea surface microlayer in Taiwan. These four yeast strains were morphologically, physiologically and phylogenetically identical to each other. No sexual reproduction was observed on 5% malt extract agar, corn meal agar, V8 agar, McClary's acetate agar and potato-dextrose agar. Phylogenetic analysis of the sequences of the D1/D2 domain of the large subunit (LSU) rRNA gene places C. neustonensis as a member of the Pichia guilliermondii clade, it also reveals that the phylogenetically closest relatives of C. neustonensis are C. fukuyamaensis (4.4% divergence), C. xestobii (4.4% divergence) and P. guilliermondii (4.5% divergence). C. neustonensis also is clearly distinguished from other known species in the P. guilliermondii clade based on the results of physiology tests. From these comparison analyses, the following novel yeast species is proposed: Candida neustonensis sp. nov., with strain SN92(T) (= BCRC 23108(T) = JCM 14892(T) = CBS 11061(T)) as the type strain.

Model and Assessment of the Contribution of Dredged Material Disposal to Sea-Surface Contamination in Puget Sound

DTIC Science & Technology

1986-02-01

DISPOSAL TO SEA-SURFACE CONTAMINATION IN PUGET SOUND J. T., Hardy Marine Research Laboratory Sequim , Washington C. E. Cowan Pacific Northwest Laboratory...spawning season. ( 1 I -"I CONCLUSIONS AND RECOMMENDATIONS Significant SSM contamination and toxicity already exists in Elliott Bay . Dredge dieposal could...disposal area of 900 ft. Typical contaminant concentrations on dredged material and baseline concentrations in the microlayer of Elliott Bay (Hardy et

On the chemical dynamics of extracellular polysaccharides in the high Arctic surface microlayer

NASA Astrophysics Data System (ADS)

Gao, Q.; Leck, C.; Rauschenberg, C.; Matrai, P. A.

2012-07-01

The surface microlayer (SML) represents a unique system of which the physicochemical characteristics may differ from those of the underlying subsurface seawater (SSW). Within the Arctic pack ice area, the SML has been characterized as enriched in small colloids of biological origin, resulting from extracellular polymeric secretions (EPS). During the Arctic Summer Cloud Ocean Study (ASCOS) in August 2008, particulate organic matter (POM, with size range > 0.22 μm) and dissolved organic matter (DOM, < 0.22 μm, obtained after filtration) samples were collected and chemically characterized from the SML and the corresponding SSW at an open lead centered at 87.5° N and 5° E. Total organic carbon was persistently enriched in the SML with a mean enrichment factor (EF) of 1.45 ± 0.41, whereas sporadic depletions of dissolved carbohydrates and amino acids were observed. Monosaccharide compositional analysis reveals that EPS in the Arctic lead was formed mainly of distinctive heteropolysaccharides, enriched in xylose, fucose and glucose. The mean concentrations of total hydrolysable neutral sugars in SSW were 94.9 ± 37.5 nM in high molecular weight (HMW) DOM (> 5 kDa) and 64.4 ± 14.5 nM in POM. The enrichment of polysaccharides in the SML appeared to be a common feature, with EFs ranging from 1.7 to 7.0 for particulate polysaccharides and 3.5 to 12.1 for polysaccharides in the HMW DOM fraction. A calculated monosaccharide yield suggests that polymers in the HMW DOM fraction were scavenged, without substantial degradation, into the SML. Bubble scavenging experiments showed that newly aggregated particles could be formed abiotically by coagulation of low molecular weight nanometer-sized gels. Aerosol particles, artificially generated by bubbling experiments, were enriched in polysaccharides by factors of 22-70, relative to the source seawater. We propose that bubble scavenging of surface-active polysaccharides could be one of the possible mechanisms for the enrichment of polysaccharides in the high Arctic open lead SML.

On the chemical dynamics of extracellular polysaccharides in the high Arctic surface microlayer

NASA Astrophysics Data System (ADS)

Gao, Q.; Leck, C.; Rauschenberg, C.; Matrai, P. A.

2012-01-01

The surface microlayer (SML) represents a unique system of which the physicochemical characteristics may differ from those of the underlying subsurface seawater (SSW). Within the Arctic pack ice area, the SML has been characterized as enriched in small colloids of biological origin, resulting from extracellular polymeric secretions (EPS). During the Arctic Summer Cloud-Ocean Study (ASCOS) in August 2008, particulate and dissolved organic matter (POM, DOM) samples were collected and chemically characterized from the SML and the corresponding SSW at an open lead centered at 87.5° N and 5° E. Total organic carbon was persistently enriched in the SML with a mean enrichment factor (EF) of 1.45 ± 0.41, whereas sporadic depletions of dissolved carbohydrates and amino acids were observed. Monosaccharide compositional analysis reveals that EPS in the Arctic lead was formed mainly of distinctive heteropolysaccharides, enriched in xylose, fucose and glucose. The mean concentrations of total hydrolysable neutral sugars in SSW were 94.9 ± 37.5 nM in high molecular weight (HMW) DOM and 64.4 ± 14.5 nM in POM. The enrichment of polysaccharides in the SML appeared to be a common feature, with EFs ranging from 1.7 to 7.0 for particulate polysaccharides and 3.5 to 12.1 for polysaccharides in the HMW DOM fraction. A calculated monosaccharide yield suggests that polymers in the HMW DOM fraction were scavenged, without substantial degradation, into the SML. Bubble scavenging experiments showed that newly aggregated particles could be formed abiotically by coagulation of low molecular weight nanometer-sized gels. Experimentally-generated aerosol particles were enriched in polysaccharides by factors of 22-70, relative to the source seawater. We propose that bubble scavenging of surface-active polysaccharides was one of the possible mechanisms for the enrichment of polysaccharides in the SML.

Microplastic in two South Carolina Estuaries: Occurrence, distribution, and composition.

PubMed

Gray, Austin D; Wertz, Hope; Leads, Rachel R; Weinstein, John E

2018-03-01

Here we report on the distribution of microplastic contamination in two developed estuaries in the Southeastern United States. Average concentration in intertidal sediments of Charleston Harbor and Winyah Bay, both located in South Carolina, U.S.A., was 413.8 ± 76.7 and 221.0 ± 25.6 particles/m 2 , respectively. Average concentration in the sea surface microlayer of Charleston Harbor and Winyah Bay was 6.6 ± 1.3 and 30.8 ± 12.1 particles/L, respectively. Concentration in intertidal sediments of the two estuaries was not significantly different (p = 0.58), however, Winyah Bay contained significantly more microplastics in the sea surface microlayer (p = 0.02). While microplastic concentration in these estuaries was comparable to that reported for other estuaries worldwide, Charleston Harbor contained a high abundance of black microplastic fragments believed to be tire wear particles. Our research is the first to survey microplastic contamination in Southeastern U.S. estuaries and to provide insight on the nature and extent of contamination in these habitats. Copyright © 2018 Elsevier Ltd. All rights reserved.

Abundance and Distribution Characteristics of Microplastics in Surface Seawaters of the Incheon/Kyeonggi Coastal Region.

PubMed

Chae, Doo-Hyeon; Kim, In-Sung; Kim, Seung-Kyu; Song, Young Kyoung; Shim, Won Joon

2015-10-01

Microplastics in marine environments are of emerging concern due to their widespread distribution, their ingestion by various marine organisms, and their roles as a source and transfer vector of toxic chemicals. However, our understanding of their abundance and distribution characteristics in surface seawater (SSW) remains limited. We investigated microplastics in the surface microlayer (SML) and the SSW at 12 stations near-shore and offshore of the Korean west coast, Incheon/Kyeonggi region. Variation between stations, sampling media, and sampling methods were compared based on abundances, size distribution, and composition profiles of microsized synthetic polymer particles. The abundance of microplastics was greater in the SML (152,688 ± 92,384 particles/m(3)) than in SSW and showed a significant difference based on the sampling method for SSWs collected using a hand net (1602 ± 1274 particles/m(3)) and a zooplankton trawl net (0.19 ± 0.14 particles/m(3)). Ship paint particles (mostly alkyd resin polymer) accounted for the majority of microplastics detected in both SML and SSWs, and increased levels were observed around the voyage routes of large vessels. This indicates that polymers with marine-based origins become an important contributor to microplastics in coastal SSWs of this coastal region.

Study on organic matter fractions in the surface microlayer in the Baltic Sea by spectrophotometric and spectrofluorometric methods

NASA Astrophysics Data System (ADS)

Drozdowska, Violetta; Wrobel, Iwona; Markuszewski, Piotr; Makuch, Przemysław; Raczkowska, Anna; Kowalczuk, Piotr

2017-08-01

The fluorescence and absorption measurements of the samples collected from a surface microlayer (SML) and a subsurface layer (SS), at a depth of 1 m, were studied during three research cruises in the Baltic Sea along with hydrophysical studies and meteorological observations. Several absorption (E2 : E3, S, SR) and fluorescence (fluorescence intensities at Coble classified peaks: A, C, M, T the ratio M + T/A + C, HIX (humification index)) indices of colored and fluorescent dissolved organic matter (CDOM and FDOM) helped to describe the changes in molecular size and weight as well as in composition of organic matter. The investigation allowed the assessment of a decrease in the contribution of two terrestrial components (A and C) with increasing salinity ( ˜ 1.64 and ˜ 1.89 % in the SML and ˜ 0.78 and ˜ 0.71 % in the SS, respectively) and an increase in components produced in situ (M and T) with salinity ( ˜ 0.52 and ˜ 2.83 % in the SML and ˜ 0.98 and ˜ 1.87 % in the SS, respectively). Hence, a component T reveals the biggest relative changes along the transect from the Vistula River outlet to Gdansk Deep, in both the SML and SS, although an increase was higher in the SML than in the SS ( ˜ 18.5 and ˜ 12.3 %, respectively). The ratio E2 : E3 points to greater changes in the molecular weight of CDOM affected by a higher rate of photobleaching in the SML. The HIX index reflects a more advanced stage of humification and condensation processes in the SS. Finally, the results reveal a higher rate of degradation processes occurring in the SML than in the SS. Thus, the specific physical properties of surface active organic molecules (surfactants) may modify, in a specific way, the solar light spectrum entering the sea and a penetration depth of the solar radiation. Research on the influence of surfactants on the physical processes linked to the sea surface becomes an important task, especially in coastal waters and in the vicinity of the river mouths.

Microhydrodynamics of flotation processes in the sea surface layer

NASA Astrophysics Data System (ADS)

Grammatika, Marianne; Zimmerman, William B.

2001-10-01

The uppermost surface of the ocean forms a peculiarly important ecosystem, the sea surface microlayer (SML). Comprising the top 1-1000 μm of the ocean surface, the SML concentrates many chemical substances, particularly those that are surface active. Important economically as a nursery for fish eggs and larvae, the SML unfortunately is also especially vulnerable to pollution. Contaminants that settle out from the air, have low solubility, or attach to floatable matter tend to accumulate in the SML. Bubbles contribute prominently to the dynamics of air-sea exchanges, playing an important role in geochemical cycling of material in the upper ocean and SML. In addition to the movement of bubbles, the development of a bubble cloud interrelates with the single particle dynamics of all other bubbles and particles. In the early sixties, several in situ oceanographic techniques revealed an "unbelievably immense" number of coastal bubbles of radius 15-300 μm. The spatial and temporal variation of bubble numbers were studied; acoustical oceanographers now use bubbles as tracers to determine ocean processes near the ocean surface. Sea state and rain noises have both been definitively ascribed to the radiation from huge numbers of infant micro bubbles [The Acoustic Bubble. Academic Press, San Diego]. Our research programme aims at constructing a hydrodynamic model for particle transport processes occurring at the microscale, in multi-phase flotation suspensions. Current research addresses bubble and floc microhydrodynamics as building blocks for a microscale transport model. This paper reviews sea surface transport processes in the microlayer and the lower atmosphere, and identifies those amenable to microhydrodynamic modelling and simulation. It presents preliminary simulation results including the multi-body hydrodynamic mobility functions for the modelling of "dynamic bubble filters" and floc suspensions. Hydrodynamic interactions versus spatial anisotropy and size of particle clouds are investigated.

A high-fidelity approach towards simulation of pool boiling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yazdani, Miad; Radcliff, Thomas; Soteriou, Marios

2016-01-15

A novel numerical approach is developed to simulate the multiscale problem of pool-boiling phase change. The particular focus is to develop a simulation technique that is capable of predicting the heat transfer and hydrodynamic characteristics of nucleate boiling and the transition to critical heat flux on surfaces of arbitrary shape and roughness distribution addressing a critical need to design enhanced boiling heat transfer surfaces. The macro-scale of the phase change and bubble dynamics is addressed through employing off-the-shelf Computational Fluid Dynamics (CFD) methods for interface tracking and interphase mass and energy transfer. The micro-scale of the microlayer, which forms atmore » early stage of bubble nucleation near the wall, is resolved through asymptotic approximation of the thin-film theory which provides a closed-form solution for the distribution of the micro-layer and its influence on the evaporation process. In addition, the sub-grid surface roughness is represented stochastically through probabilistic density functions and its role in bubble nucleation and growth is then represented based on the thermodynamics of nucleation process. This combination of deterministic CFD, local approximation, and stochastic representation allows the simulation of pool boiling on any surface with known roughness and enhancement characteristics. The numerical model is validated for dynamics and hydrothermal characteristics of a single nucleated bubble on a flat surface against available literature data. In addition, the prediction of pool-boiling heat transfer coefficient is verified against experimental measurements as well as reputable correlations for various roughness distributions and different surface orientations. Finally, the model is employed to demonstrate pool-boiling phenomenon on enhanced structures with reentrance cavities and to explore the effect of enhancement feature design on thermal and hydrodynamic characteristics of these surfaces.« less

The bacterial community composition of the surface microlayer in a high mountain lake.

PubMed

Hörtnagl, Paul; Pérez, Maria Teresa; Zeder, Michael; Sommaruga, Ruben

2010-09-01

The existence of bacterioneuston in aquatic ecosystems is well established, but little is known about its composition and dynamics, particularly in lakes. The bacterioneuston underlies extreme conditions at the air-water boundary, which may influence its dynamics in a different way compared with the bacterioplankton. In this study, we assessed quantitative changes in major bacterial groups of the surface microlayer (SML) (upper 900 microm) and the underlying water (ULW) (0.2-0.5 m depth) of an alpine lake during two consecutive ice-free seasons. Analysis of the bacterial community composition was done using catalyzed reporter deposition FISH with oligonucleotide probes. In addition, several physicochemical parameters were measured to characterize these two water layers. Dissolved organic carbon was consistently enriched in the SML and the dissolved organic matter pool presented clear signals of photodegradation and photobleaching. The water temperature was generally colder in the SML than in the subsurface. The bacterial community of the SML and the ULW was dominated by Betaproteobacteria and Actinobacteria. The bacterial community composition was associated with different combinations of physicochemical factors in these two layers, but temporal changes showed similar trends in both layers over the two seasons. Our results identify the SML of alpine lakes as a microhabitat where specific bacterial members such as of Betaproteobacteria seem to be efficient colonizers.

The Surface Microlayer: Review of Literature and Evaluation of Potential Effects of Dredge Activities in Puget Sound.

DTIC Science & Technology

1987-01-01

Heyrand. 1975. Polonium - 210 - Its vertical oceanic transport by zoo- plankton metabolic activity. Marine Chemistry 3:105-110. Collins, J. 1974. Oil and...Toxicology Environ. Health 7:991-1000. Hose, J.E., J.B. Hannah, D. Dijulio, M.L. Landolt, B.S. Miller, W.T. Iwaoka, and S.P. Felton. 1982. Effects of benzo(a...A184 885 THE SURFACE MICROLAVER, REVIEWJ OF LITERATURE AND 1/2 EVALUATION OF POTENTIAL EFFECTS OF DREDGE ACTIVITIES IN PUGET SOUND(U) EVANS-HAMILTON

Synthetic ultraviolet light filtering chemical contamination of coastal waters of Virgin Islands National Park, St. John, U.S. Virgin Islands

USGS Publications Warehouse

Bargar, Timothy A.; Alvarez, David; Garrison, Virginia H.

2015-01-01

Contamination of surface waters by synthetic ultraviolet light (UV) filtering chemicals is a concern for the Virgin Islands National Park (VINP). Discrete water samples were collected from VINP bays to determine UV filter chemical presence in the coastal waters. Spatial distribution and the potential for partitioning between subsurface waters and the sea surface microlayer (SML) were also examined. The UV filter chemicals 4-methylbenzylidene camphor, benzophenone-3, octinoxate, homosalate, and octocrylene were detected at concentrations up to 6073 ng/L (benzophenone-3). Concentrations for benzophenone-3 and homosalate declined exponentially (r2 = 0.86 to 0.98) with distance from the beach. Limited data indicate that some UV filter chemicals may partition to the SML relative to the subsurface waters. Contamination of VINP coastal waters by UV filter chemicals may be a significant issue, but an improved understanding of the temporal and spatial variability of their concentrations would be necessary to better understand the risk they present.

Graphene-copper composite with micro-layered grains and ultrahigh strength

PubMed Central

Wang, Lidong; Yang, Ziyue; Cui, Ye; Wei, Bing; Xu, Shichong; Sheng, Jie; Wang, Miao; Zhu, Yunpeng; Fei, Weidong

2017-01-01

Graphene with ultrahigh intrinsic strength and excellent thermal physical properties has the potential to be used as the reinforcement of many kinds of composites. Here, we show that very high tensile strength can be obtained in the copper matrix composite reinforced by reduced graphene oxide (RGO) when micro-layered structure is achieved. RGO-Cu powder with micro-layered structure is fabricated from the reduction of the micro-layered graphene oxide (GO) and Cu(OH)2 composite sheets, and RGO-Cu composites are sintered by spark plasma sintering process. The tensile strength of the 5 vol.% RGO-Cu composite is as high as 608 MPa, which is more than three times higher than that of the Cu matrix. The apparent strengthening efficiency of RGO in the 2.5 vol.% RGO-Cu composite is as high as 110, even higher than that of carbon nanotube, multilayer graphene, carbon nano fiber and RGO in the copper matrix composites produced by conventional MLM method. The excellent tensile and compressive strengths, high hardness and good electrical conductivity are obtained simultaneously in the RGO-Cu composites. The results shown in the present study provide an effective method to design graphene based composites with layered structure and high performance. PMID:28169306

Sea surface microlayers: A unified physicochemical and biological perspective of the air-ocean interface

NASA Astrophysics Data System (ADS)

Cunliffe, Michael; Engel, Anja; Frka, Sanja; Gašparović, Blaženka; Guitart, Carlos; Murrell, J. Colin; Salter, Matthew; Stolle, Christian; Upstill-Goddard, Robert; Wurl, Oliver

2013-02-01

The sea surface microlayer (SML) covers more than 70% of the Earth's surface and is the boundary layer interface between the ocean and the atmosphere. This important biogeochemical and ecological system is critical to a diverse range of Earth system processes, including the synthesis, transformation and cycling of organic material, and the air-sea exchange of gases, particles and aerosols. In this review we discuss the SML paradigm, taking into account physicochemical and biological characteristics that define SML structure and function. These include enrichments in biogenic molecules such as carbohydrates, lipids and proteinaceous material that contribute to organic carbon cycling, distinct microbial assemblages that participate in air-sea gas exchange, the generation of climate-active aerosols and the accumulation of anthropogenic pollutants with potentially serious implications for the health of the ocean. Characteristically large physical, chemical and biological gradients thus separate the SML from the underlying water and the available evidence implies that the SML retains its integrity over wide ranging environmental conditions. In support of this we present previously unpublished time series data on bacterioneuston composition and SML surfactant activity immediately following physical SML disruption; these imply timescales of the order of minutes for the reestablishment of the SML following disruption. A progressive approach to understanding the SML and hence its role in global biogeochemistry can only be achieved by considering as an integrated whole, all the key components of this complex environment.

Radon daughter disequilibria and lead systematics in the western North Atlantic

NASA Astrophysics Data System (ADS)

Hussain, N.; Church, T. M.; VéRon, Alain J.; Larson, R. E.

1998-01-01

Concentrations of 222Rn and 210Pb were measured in the North Atlantic troposphere in 1989 between April 12 and 28, during the Sulfide Experiment (SEX) Cruise I, and those of 222Rn, 210Pb and 210Po, between October 24 and November 9, during the SEX Cruise II. Concentrations of 210Pb and 210Po were also measured in the rain water, surface seawater, and marine microlayer collected during the SEX Cruise II Other data used and published previously include stable lead and its isotopes [Vèron et al., 1992, 1993] on parallel samples. Low 222Rn contents, of the order of 0.1 and 0.3 Bq m-3, were found in the marine air, while continental air showed nearly 10 times higher concentrations of 222Rn. These results corroborate with the air mass trajectory analyses and continental signatures of stable lead isotopes. Significant correlation is found between 222Rn and 210Pb on the aerosol, indicative of excess continental 222Rn supporting the ingrowth of 210Pb from the atmosphere, in spite of its first-order removal by precipitation. Correlation between 210Pb and stable Pb on the aerosol and in the precipitation document the source of pollutant lead from the continental surface. Mean residence times of marine aerosol based on 210Pb is estimated to be 5.4±1.8 days during the April cruise and 19.7±1.9 days during the October cause. Corresponding deposition velocity for 210Pb is estimated to be 1.9±1.9 cm s-1, a value that suggests the dominant role of precipitation scavenging, or aerosol scavenging by larger host phases such as dust or sea salt. Excess 210Po activities are found on the aerosol relative to what would be expected based on 210Pb and the aerosol residence times. In surface seawaters, deficiencies of 210Po are observed. Mechanisms of 210Po enrichment in atmospheric aerosol may include enrichments from the organic components of marine microlayer, sea-salt aerosol, dust, or air-sea exchange of volatile organo-polonium species.

Origins and fates of PAHs in the coastal marine environment off San Diego (California)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, E.Y.; Yu, C.C.; Vista, C.L.

1995-12-31

The main inputs of anthropogenic hydrocarbons to the coastal marine environment off San Diego include the Point Lama wastewater outfall (City of San Diego), Tijuana River (crossing the boarder between the US and Mexico) and several storm drains along the coastline and in San Diego Bay, inadvertent spills, and aerial deposition. Samples collected (in January and June 1994) from the Point Loma wastewater effluent, Tijuana River runoff, and microlayer, sediment trap, and surface sediment at several locations adjacent to the Point Loma outfall, entrance of Tijuana River into the ocean, and San Diego Bay (near the San Diego International Airport)more » were analyzed to determine the origins and fates of PAHs in the coastal marine environment. Alkyl homologue distributions (AHDS) for naphthalene indicated a mainly petrogenic origin for low molecular-weight PAHs in the effluent, water column particle, and sediment near the outfall. Parent compound distributions (PCDS) for PAHs with molecular weights 178, 202, 228, 252, 276, and 278 showed combustion-related inputs in the water column particle and sediment, especially for mid to high molecular-weight PAHs. PAHs with molecular weight equal to or higher than 252 were not detected in the effluent. The compositions of PAHs were substantially different in the effluent particulates and filtrates, implying a great deal about the fates of PAHs from the outfall and their bioaccumulation by organisms. PAHs detected in Tijuana River runoff had similar AHDs and PCDs to those of the Point Loma outfall effluent. AHDs in the San Diego Bay sediment exhibited marked seasonal variation; low molecular-weight PAHs were significantly combustion-related in January and more petrogenic in June. Microlayer samples generally contained dominant combustion-generated PAHs. The impact of the wastewater outfall discharge on the nearby water column and sediment appeared compromised by other non-point source inputs.« less

Research and Logistical Support for the Office of Naval Research Accelerated Research Initiative on Marine Microlayer Processes

DTIC Science & Technology

1991-12-13

1962)] Broekmann et al. 11980111 Petermann [ 197/61, Oleophilic pollutant accumula- Hartung and Klinger 11970]" .. 7 tion Seba and Corcoran 11969...wave tanks by using different organic Petermann , and G. Hent schel, Artificial surface films in the sea chemical films, wave-wave interactions must be...Phys. Oceanogr., 8, 142-150, Petermann , I.. Der Einfluss der 6brflichenspannung wssnger Sys-!l1977. teme auf die Kinetik der Gasabsorption

High wind speeds prevent formation of a distinct bacterioneuston community in the sea-surface microlayer

PubMed Central

Stolle, Christian; Giebel, Helge-Ansgar; Brinkhoff, Thorsten; Ribas-Ribas, Mariana; Hodapp, Dorothee; Wurl, Oliver

2017-01-01

Abstract The sea-surface microlayer (SML) at the boundary between atmosphere and hydrosphere represents a demanding habitat for bacteria. Wind speed is a crucial but poorly studied factor for its physical integrity. Increasing atmospheric burden of CO2, as suggested for future climate scenarios, may particularly act on this habitat at the air–sea interface. We investigated the effect of increasing wind speeds and different pCO2 levels on SML microbial communities in a wind-wave tunnel, which offered the advantage of low spatial and temporal variability. We found that enrichment of bacteria in the SML occurred solely at a U10 wind speed of ≤5.6 m s−1 in the tunnel and ≤4.1 m s−1 in the Baltic Sea. High pCO2 levels further intensified the bacterial enrichment in the SML during low wind speed. In addition, low wind speed and pCO2 induced the formation of a distinctive bacterial community as revealed by 16S rRNA gene fingerprints and influenced the presence or absence of individual taxonomic units within the SML. We conclude that physical stability of the SML below a system-specific wind speed threshold induces specific bacterial communities in the SML entailing strong implications for ecosystem functioning by wind-driven impacts on habitat properties, gas exchange and matter cycling processes. PMID:28369320

High wind speeds prevent formation of a distinct bacterioneuston community in the sea-surface microlayer.

PubMed

Rahlff, Janina; Stolle, Christian; Giebel, Helge-Ansgar; Brinkhoff, Thorsten; Ribas-Ribas, Mariana; Hodapp, Dorothee; Wurl, Oliver

2017-05-01

The sea-surface microlayer (SML) at the boundary between atmosphere and hydrosphere represents a demanding habitat for bacteria. Wind speed is a crucial but poorly studied factor for its physical integrity. Increasing atmospheric burden of CO2, as suggested for future climate scenarios, may particularly act on this habitat at the air-sea interface. We investigated the effect of increasing wind speeds and different pCO2 levels on SML microbial communities in a wind-wave tunnel, which offered the advantage of low spatial and temporal variability. We found that enrichment of bacteria in the SML occurred solely at a U10 wind speed of ≤5.6 m s-1 in the tunnel and ≤4.1 m s-1 in the Baltic Sea. High pCO2 levels further intensified the bacterial enrichment in the SML during low wind speed. In addition, low wind speed and pCO2 induced the formation of a distinctive bacterial community as revealed by 16S rRNA gene fingerprints and influenced the presence or absence of individual taxonomic units within the SML. We conclude that physical stability of the SML below a system-specific wind speed threshold induces specific bacterial communities in the SML entailing strong implications for ecosystem functioning by wind-driven impacts on habitat properties, gas exchange and matter cycling processes. © FEMS 2017.

Microlayered flow structure around an acoustically levitated droplet under a phase-change process.

PubMed

Hasegawa, Koji; Abe, Yutaka; Goda, Atsushi

2016-01-01

The acoustic levitation method (ALM) has found extensive applications in the fields of materials science, analytical chemistry, and biomedicine. This paper describes an experimental investigation of a levitated droplet in a 19.4-kHz single-axis acoustic levitator. We used water, ethanol, water/ethanol mixture, and hexane as test samples to investigate the effect of saturated vapor pressure on the flow field and evaporation process using a high-speed camera. In the case of ethanol, water/ethanol mixtures with initial ethanol fractions of 50 and 70 wt%, and hexane droplets, microlayered toroidal vortexes are generated in the vicinity of the droplet interface. Experimental results indicate the presence of two stages in the evaporation process of ethanol and binary mixture droplets for ethanol content >10%. The internal and external flow fields of the acoustically levitated droplet of pure and binary mixtures are clearly observed. The binary mixture of the levitated droplet shows the interaction between the configurations of the internal and external flow fields of the droplet and the concentration of the volatile fluid. Our findings can contribute to the further development of existing theoretical prediction.

A genetic algorithm-based optimization model for pool boiling heat transfer on horizontal rod heaters at isolated bubble regime

NASA Astrophysics Data System (ADS)

Alavi Fazel, S. Ali

2017-09-01

A new optimized model which can predict the heat transfer in the nucleate boiling at isolated bubble regime is proposed for pool boiling on a horizontal rod heater. This model is developed based on the results of direct observations of the physical boiling phenomena. Boiling heat flux, wall temperature, bubble departing diameter, bubble generation frequency and bubble nucleation site density have been experimentally measured. Water and ethanol have been used as two different boiling fluids. Heating surface was made by several metals and various degrees of roughness. The mentioned model considers various mechanisms such as latent heat transfer due to micro-layer evaporation, transient conduction due to thermal boundary layer reformation, natural convection, heat transfer due to the sliding bubbles and bubble super-heating. The fractional contributions of individual mentioned heat transfer mechanisms have been calculated by genetic algorithm. The results show that at wall temperature difference more that about 3 K, bubble sliding transient conduction, non-sliding transient conduction, micro-layer evaporation, natural convection, radial forced convection and bubble super-heating have higher to lower fractional contributions respectively. The performance of the new optimized model has been verified by comparison of the existing experimental data.

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

NASA Astrophysics Data System (ADS)

Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

2015-04-01

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and unsaturated aldehydes were detected and a reaction pathway, initiated by a H-abstraction of the surfactant by the excited HA*, has been proposed. This mechanism infers that the presence of the surface microlayer will enhance protonation and self-reactions, leading to the formation of dimers as suggested in [6]. These products could explain the formation of the unsaturated products observed. To confirm the hypothesis of an initiative step of H-abstraction, the system was simplified using OH radicals, generated by the photolysis of H2O2, in presence of an artificial organic layer of nonanoic acid. The VOCs produced, monitored by PTR/SRI-TOF-MS in NO+ and H3O+ ionization mode, were less abundant compared to the system with HA, but the same classes of products could be observed, including oxidation products such as aldehydes but also unsatured products like dienes. The underlying water was sampled before and after the experiment and analysed by HR-ESI-MS, showing mostly enrichment of oxidative products, such as hydroxy- and keto-acids immediately derived from the photochemical oxidation of the nonanoic acid layer. These products, showing lower volatility and higher polarity, partition preferentially to the bulk water. The results of this simplified system confirm the reaction mechanism proposed and the role an organic layer can play in the photochemical formation of VOCs, which could influence the marine boundary layer chemistry. 1. Peter S. Liss, R.A.D., ed. Sea Surface and Global Change. 1997, Cambridge University Press: Cambridge. 509. 2. Griffith, E.C. and V. Vaida, In situ observation of peptide bond formation at the water-air interface. Proceedings of the National Academy of Sciences, 2012. 109(39): p. 15697-15701. 3. Sinreich, R., et al., Ship-based detection of glyoxal over the remote tropical Pacific Ocean. Atmospheric Chemistry and Physics, 2010. 10(23): p. 11359-11371. 4. Kieber, R.J., X.L. Zhou, and K. Mopper, Formation of carbonyl-compounds from uv-induced photodegradation of humic substances in natural-waters - fate of riverine carbon in the sea. Limnology and Oceanography, 1990. 35(7): p. 1503-1515. 5. R. Ciuraru, L. Fine, M. van Pinxteren, B. D'Anna, H. Herrmann, C. George, Unravelling new processes at interfaces: chemical isoprene production at the sea surface. submitted. 6. Griffith, E.C., et al., Photoinitiated Synthesis of Self-Assembled Vesicles. Journal of the American Chemical Society, 2014. 136(10): p. 3784-3787.

The Hygroscopicity Parameter of Marine Organics in Sea Spray Aerosols

NASA Astrophysics Data System (ADS)

Boyer, M.; Chang, R. Y. W.

2015-12-01

The effects of aerosols on climate are poorly understood, specifically with respect to their influence on cloud properties. Since oceans cover >70% of Earth's surface, sea spray aerosols (SSA), which act efficiently as cloud condensation nuclei (CCN), may have important implications on Earth's radiation budget. Surface active organic species readily accumulate in the sea surface microlayer (SML), located at the ocean-atmosphere interface, and transfer onto nascent SSA. While it is understood that SSA are commonly enriched with organics, the resulting effect of the organic content on CCN activation remains unresolved. The hygroscopicity parameter, kappa (k), allows for the cloud nucleating properties of individual components to be predicted in particles of mixed composition; however, most studies typically infer k from ambient measurements without assessing the contribution of the individual components to the overall k. In this study, a method for quantifying the cloud nucleating properties of the organic species in surface seawater using k-Kohler theory is proposed. Ambient SML and bulk water samples will be collected and atomized to generate particles such that the overall k can be inferred from CCN measurements. The inorganic and organic components will be quantified, and the organic component will be separated so that the hygroscopicity of only the organic constituents can be determined. By comparing the inferred k values for the samples before and after removal of the inorganic component, the hygroscopicity of the organic constituents alone can be calculated, providing insight on the effect of organic species on CCN activation in SSA.

The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles

NASA Astrophysics Data System (ADS)

Wang, Xiaofei; Deane, Grant B.; Moore, Kathryn A.; Ryder, Olivia S.; Stokes, M. Dale; Beall, Charlotte M.; Collins, Douglas B.; Santander, Mitchell V.; Burrows, Susannah M.; Sultana, Camille M.; Prather, Kimberly A.

2017-07-01

The oceans represent a significant global source of atmospheric aerosols. Sea spray aerosol (SSA) particles comprise sea salts and organic species in varying proportions. In addition to size, the overall composition of SSA particles determines how effectively they can form cloud droplets and ice crystals. Thus, understanding the factors controlling SSA composition is critical to predicting aerosol impacts on clouds and climate. It is often assumed that submicrometer SSAs are mainly formed by film drops produced from bursting bubble-cap films, which become enriched with hydrophobic organic species contained within the sea surface microlayer. In contrast, jet drops formed from the base of bursting bubbles are postulated to mainly produce larger supermicrometer particles from bulk seawater, which comprises largely salts and water-soluble organic species. However, here we demonstrate that jet drops produce up to 43% of total submicrometer SSA number concentrations, and that the fraction of SSA produced by jet drops can be modulated by marine biological activity. We show that the chemical composition, organic volume fraction, and ice nucleating ability of submicrometer particles from jet drops differ from those formed from film drops. Thus, the chemical composition of a substantial fraction of submicrometer particles will not be controlled by the composition of the sea surface microlayer, a major assumption in previous studies. This finding has significant ramifications for understanding the factors controlling the mixing state of submicrometer SSA particles and must be taken into consideration when predicting SSA impacts on clouds and climate.

Fundamental study of FC-72 pool boiling surface temperature fluctuations and bubble behavior

NASA Astrophysics Data System (ADS)

Griffin, Alison R.

A heater designed to monitor surface temperature fluctuations during pool boiling experiments while the bubbles were simultaneously being observed has been fabricated and tested. The heat source was a transparent indium tin oxide (ITO) layer commercially deposited on a fused quartz substrate. Four copper-nickel thin film thermocouples (TFTCs) on the heater surface measured the surface temperature, while a thin layer of sapphire or fused silica provided electrical insulation between the TFTCs and the ITO. The TFTCs were micro-fabricated using the liftoff process to deposit the nickel and copper metal films. The TFTC elements were 50 mum wide and overlapped to form a 25 mum by 25 mum junction. TFTC voltages were recorded by a DAQ at a sampling rate of 50 kHz. A high-speed CCD camera recorded bubble images from below the heater at 2000 frames/second. A trigger sent to the camera by the DAQ synchronized the bubble images and the surface temperature data. As the bubbles and their contact rings grew over the TFTC junction, correlations between bubble behavior and surface temperature changes were demonstrated. On the heaters with fused silica insulation layers, 1--2°C temperature drops on the order of 1 ms occurred as the contact ring moved over the TFTC junction during bubble growth and as the contact ring moved back over the TFTC junction during bubble departure. These temperature drops during bubble growth and departure were due to microlayer evaporation and liquid rewetting the heated surface, respectively. Microlayer evaporation was not distinguished as the primary method of heat removal from the surface. Heaters with sapphire insulation layers did not display the measurable temperature drops observed with the fused silica heaters. The large thermal diffusivity of the sapphire compared to the fused silica was determined as the reason for the absence of these temperature drops. These findings were confirmed by a comparison of temperature drops in a 2-D simulation of a bubble growing over the TFTC junction on both the sapphire and fused silica heater surfaces. When the fused silica heater produced a temperature drop of 1.4°C, the sapphire heater produced a drop of only 0.04°C under the same conditions. These results verified that the lack of temperature drops present in the sapphire data was due to the thermal properties of the sapphire layer. By observing the bubble departure frequency and site density on the heater, as well as the bubble departure diameter, the contribution of nucleate boiling to the overall heat removal from the surface could be calculated. These results showed that bubble vapor generation contributed to approximately 10% at 1 W/cm2, 23% at 1.75 W/cm2, and 35% at 2.9 W/cm 2 of the heat removed from a fused silica heater. Bubble growth and contact ring growth were observed and measured from images obtained with the high-speed camera. Bubble data recorded on a fused silica heater at 3 W/cm2, 4 W/cm2, and 5 W/cm 2 showed that bubble departure diameter and lifetime were negligibly affected by the increase in heat flux. Bubble and contact ring growth rates demonstrated significant differences when compared on the fused silica and sapphire heaters at 3 W/cm2. The bubble departure diameters were smaller, the bubble lifetimes were longer, and the bubble departure frequency was larger on the sapphire heater, while microlayer evaporation was faster on the fused silica heater. Additional considerations revealed that these differences may be due to surface conditions as well as differing thermal properties. Nucleate boiling curves were recorded on the fused silica and sapphire heaters by adjusting the heat flux input and monitoring the local surface temperature with the TFTCs. The resulting curves showed a temperature drop at the onset of nucleate boiling due to the increase in heat transfer coefficient associated with bubble nucleation. One of the TFTC locations on the sapphire heater frequently experienced a second temperature drop at a higher heat flux. When the heat flux was started from 1 W/cm2 instead of zero or returned to zero only momentarily, the temperature overshoot did not occur. In these cases sufficient vapor remained in the cavities to initiate boiling at a lower superheat.

Microlayered flow structure around an acoustically levitated droplet under a phase-change process

PubMed Central

Hasegawa, Koji; Abe, Yutaka; Goda, Atsushi

2016-01-01

The acoustic levitation method (ALM) has found extensive applications in the fields of materials science, analytical chemistry, and biomedicine. This paper describes an experimental investigation of a levitated droplet in a 19.4-kHz single-axis acoustic levitator. We used water, ethanol, water/ethanol mixture, and hexane as test samples to investigate the effect of saturated vapor pressure on the flow field and evaporation process using a high-speed camera. In the case of ethanol, water/ethanol mixtures with initial ethanol fractions of 50 and 70 wt%, and hexane droplets, microlayered toroidal vortexes are generated in the vicinity of the droplet interface. Experimental results indicate the presence of two stages in the evaporation process of ethanol and binary mixture droplets for ethanol content >10%. The internal and external flow fields of the acoustically levitated droplet of pure and binary mixtures are clearly observed. The binary mixture of the levitated droplet shows the interaction between the configurations of the internal and external flow fields of the droplet and the concentration of the volatile fluid. Our findings can contribute to the further development of existing theoretical prediction. PMID:28725723

Preliminary data on formaldehyde content in seawater samples from Terra Nova Bay (Ross Sea - Antarctica)

NASA Astrophysics Data System (ADS)

Largiuni, O.; Becagli, S.; Traversi, R.; Udisti, R.

2003-04-01

Formaldehyde is a key reactive intermediate in the methane oxidation chain. To date, only a few measurements of HCHO in surface seawater have been reported, suggesting a net flux of HCHO from the atmosphere to the ocean surface. Ocean is considered as a sink for atmospheric HCHO, but it cannot be excluded that marine areas characterized by high biogenic activity constitute a source of HCHO to atmosphere. Indeed, laboratory experiments carried out on seawater microlayer show HCHO production by photo-oxidation of dissolved organic matter. To date no measurements on deep seawater samples were performed. A sensitive method for the formaldehyde determination in aqueous sample by Flow Injection Analysis has been applied to seawater samples analysis. The method has a detection limit of 55 ng/l and a reproducibility of 2.5% at 1 ug/l level (5 % in sea water samples). The detector response is linear in the range 0.1 - 3000 ug/l. In the framework of the Italian Research Programme in Antarctica (PNRA), 20 samples were collected in two stations in the Gerlache Inlet (Terra Nova Bay, Western Ross Sea) during the 2001/2002 field campaign (November 2001 to February 2002). The samples were collected through a hole in the sea-ice, along the water column, using a Go-Flo type bottle. Usually, just sub-pack and 30 and 50 m depth fractions were collected. For each depth profile, temperature, salinity and chlorophyll fluorescence signal were measured. Formaldehyde concentrations range from 4.5 to 40 ppb. The relationship between HCHO content and other measured parameters is discussed. The sampling repetition in time at the same sites allowed evaluating the seasonal changes in the formaldehyde concentration/depth profiles.

Air-Sea exchange of biogenic volatile organic compounds and the impact on aerosol particle size distributions

NASA Astrophysics Data System (ADS)

Kim, Michelle J.; Novak, Gordon A.; Zoerb, Matthew C.; Yang, Mingxi; Blomquist, Byron W.; Huebert, Barry J.; Cappa, Christopher D.; Bertram, Timothy H.

2017-04-01

We report simultaneous, underway eddy covariance measurements of the vertical flux of isoprene, total monoterpenes, and dimethyl sulfide (DMS) over the Northern Atlantic Ocean during fall. Mean isoprene and monoterpene sea-to-air vertical fluxes were significantly lower than mean DMS fluxes. While rare, intense monoterpene sea-to-air fluxes were observed, coincident with elevated monoterpene mixing ratios. A statistically significant correlation between isoprene vertical flux and short wave radiation was not observed, suggesting that photochemical processes in the surface microlayer did not enhance isoprene emissions in this study region. Calculations of secondary organic aerosol production rates (PSOA) for mean isoprene and monoterpene emission rates sampled here indicate that PSOA is on average <0.1 μg m-3 d-1. Despite modest PSOA, low particle number concentrations permit a sizable role for condensational growth of monoterpene oxidation products in altering particle size distributions and the concentration of cloud condensation nuclei during episodic monoterpene emission events from the ocean.

Effect of temperature on the accumulation of marine biogenic gels in the surface microlayer near the outlet of nuclear power plants and adjacent areas in the Daya Bay, China.

PubMed

Yue, Wei-Zhong; Sun, Cui-Ci; Shi, Ping; Engel, Anja; Wang, You-Shao; He, Wei-Hong

2018-01-01

The surface microlayer (SML) in marine systems is often characterized by an enrichment of biogenic, gel-like particles, such as the polysaccharide-containing transparent exopolymer particles (TEP) and the protein-containing Coomassie stainable particles (CSP). This study investigated the distribution of TEP and CSP, in the SML and underlying water, as well as their bio-physical controlling factors in Daya Bay, an area impacted by warm discharge from two Nuclear power plants (Npp's) and aquaculture during a research cruise in July 2014. The SML had higher proportions of cyanobacteria and of pico-size Chl a contrast to the underlayer water, particularly at the nearest outlet station characterized by higher temperature. Diatoms, dinoflagellates and chlorophyll a were depleted in the SML. Both CSP and TEP abundance and total area were enriched in the SML relative to the underlying water, with enrichment factors (EFs) of 1.5-3.4 for CSP numbers and 1.32-3.2 for TEP numbers. Although TEP and CSP showed highest concentration in the region where high productivity and high nutrient concertation were observed, EFs of gels and of dissolved organic carbon (DOC) and dissolved acidic polysaccharide (> 1 kDa), exhibited higher values near the outlet of the Npp's than in the adjacent waters. The positive relation between EF's of gels and temperature and the enrichment of cyanobacteria in the SML may be indicative of future conditions in a warmer ocean, suggesting potential effects on adjusting phytoplankton community, biogenic element cycling and air-sea exchange processes.

The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles

PubMed Central

Wang, Xiaofei; Deane, Grant B.; Moore, Kathryn A.; Ryder, Olivia S.; Stokes, M. Dale; Beall, Charlotte M.; Santander, Mitchell V.; Burrows, Susannah M.; Sultana, Camille M.; Prather, Kimberly A.

2017-01-01

The oceans represent a significant global source of atmospheric aerosols. Sea spray aerosol (SSA) particles comprise sea salts and organic species in varying proportions. In addition to size, the overall composition of SSA particles determines how effectively they can form cloud droplets and ice crystals. Thus, understanding the factors controlling SSA composition is critical to predicting aerosol impacts on clouds and climate. It is often assumed that submicrometer SSAs are mainly formed by film drops produced from bursting bubble-cap films, which become enriched with hydrophobic organic species contained within the sea surface microlayer. In contrast, jet drops formed from the base of bursting bubbles are postulated to mainly produce larger supermicrometer particles from bulk seawater, which comprises largely salts and water-soluble organic species. However, here we demonstrate that jet drops produce up to 43% of total submicrometer SSA number concentrations, and that the fraction of SSA produced by jet drops can be modulated by marine biological activity. We show that the chemical composition, organic volume fraction, and ice nucleating ability of submicrometer particles from jet drops differ from those formed from film drops. Thus, the chemical composition of a substantial fraction of submicrometer particles will not be controlled by the composition of the sea surface microlayer, a major assumption in previous studies. This finding has significant ramifications for understanding the factors controlling the mixing state of submicrometer SSA particles and must be taken into consideration when predicting SSA impacts on clouds and climate. PMID:28630346

Gas and aerosol fluxes. [emphasizing sulfur, nitrogen, and carbon

NASA Technical Reports Server (NTRS)

Martens, C. S.

1980-01-01

The development of remote sensing techniques to address the global need for accurate distribution and flux determinations of both man made and natural materials which affect the chemical composition of the atmosphere, the heat budget of the Earth, and the depletion, of stratospheric ozone is considered. Specifically, trace gas fluxes, sea salt aerosol production, and the effect of sea surface microlayer on gas and aerosol fluxes are examined. Volatile sulfur, carbon, nitrogen, and halocarbon compounds are discussed including a statement of the problem associated with each compound or group of compounds, a brief summary of current understanding, and suggestions for needed research.

Impact of artificial monolayer application on stored water quality at the air-water interface.

PubMed

Pittaway, P; Martínez-Alvarez, V; Hancock, N; Gallego-Elvira, B

2015-01-01

Evaporation mitigation has the potential to significantly improve water use efficiency, with repeat applications of artificial monolayer formulations the most cost-effective strategy for large water storages. Field investigations of the impact of artificial monolayers on water quality have been limited by wind and wave turbulence, and beaching. Two suspended covers differing in permeability to wind and light were used to attenuate wind turbulence, to favour the maintenance of a condensed monolayer at the air/water interface of a 10 m diameter tank. An octadecanol formulation was applied twice-weekly to one of two covered tanks, while a third clean water tank remained uncovered for the 14-week duration of the trial. Microlayer and subsurface water samples were extracted once a week to distinguish impacts associated with the installation of covers, from the impact of prolonged monolayer application. The monolayer was selectively toxic to some phytoplankton, but the toxicity of hydrocarbons leaching from a replacement liner had a greater impact. Monolayer application did not increase water temperature, humified dissolved organic matter, or the biochemical oxygen demand, and did not reduce dissolved oxygen. The impact of an octadecanol monolayer on water quality and the microlayer may not be as detrimental as previously considered.

Diurnal variability of gas phase and surface water ethanol in southeastern North Carolina, USA

NASA Astrophysics Data System (ADS)

Kieber, R. J.; Powell, J. P.; Foley, L.; Mead, R. N.; Willey, J. D.; Avery, G. B.

2017-11-01

Diurnal variations in gas phase and surface water concentrations of ethanol and acetaldehyde were investigated at five locations in southeastern North Carolina, USA. There were distinct diurnal oscillations observed in gas phase concentrations with maxima occurring in late afternoon suggesting that photochemical production is an important process in the cycling of these analytes in the troposphere. The rapid decrease in concentrations after the mid day maximum suggests that there is also an atmospheric photochemical sink for both analytes most likely involving photo produced hydroxyl radicals with a half-life on the order of hours rather than days at ground level. Ethanol concentrations in the surface microlayer taken at the same time as gas phase samples had a very similar diurnal profile suggesting photochemical processes, in addition to atmospheric deposition, play a role in the aqueous phase cycling of both analytes. The concentration of ethanol and acetaldehyde increased significantly in flasks containing freshwater collected from the Cape Fear River exposed to simulated sunlight for 6 h underscoring the importance of in situ photochemical production. Results of this study are significant because they represent the first simultaneous analyses of the temporal variability of ethanol and acetaldehyde concentrations in the gas and aqueous phases. These measurements are essential in order to better define the processes involved in the global biogeochemical cycling of ethanol both now and in the future as our use of the biofuel continues to grow.

Variations of the Organic Matter Composition in the Sea Surface Microlayer: A Comparison between Open Ocean, Coastal, and Upwelling Sites Off the Peruvian Coast

PubMed Central

Zäncker, Birthe; Bracher, Astrid; Röttgers, Rüdiger; Engel, Anja

2017-01-01

The sea surface microlayer (SML) is the thin boundary layer between the ocean and the atmosphere, making it important for air-sea exchange processes. However, little is known about what controls organic matter composition in the SML. In particular, there are only few studies available on the differences of the SML of various oceanic systems. Here, we compared the organic matter and neuston species composition in the SML and the underlying water (ULW) at 11 stations with varying distance from the coast in the Peruvian upwelling regime, a system with high emissions of climate relevant trace gases, such as N2O and CO2. In the open ocean, organic carbon, and amino acids were highly enriched in the SML compared to the ULW. The enrichment decreased at the coastal stations and vanished in the upwelling regime. At the same time, the degradation of organic matter increased from the open ocean to the upwelling stations. This suggests that in the open ocean, upward transport processes or new production of organic matter within the SML are faster than degradation processes. Phytoplankton was generally not enriched in the SML, one group though, the Trichodesmium-like TrL (possibly containing Trichodesmium), were enriched in the open ocean but not in the upwelling region indicating that they find a favorable habitat in the open ocean SML. Our data show that the SML is a distinct habitat; its composition is more similar among different systems than between SML and ULW of a single station. Generally the enrichment of organic matter is assumed to be reduced when encountering low primary production and high wind speeds. However, our study shows the highest enrichments of organic matter in the open ocean which had the lowest primary production and the highest wind speeds. PMID:29375483

Variations of the Organic Matter Composition in the Sea Surface Microlayer: A Comparison between Open Ocean, Coastal, and Upwelling Sites Off the Peruvian Coast.

PubMed

Zäncker, Birthe; Bracher, Astrid; Röttgers, Rüdiger; Engel, Anja

2017-01-01

The sea surface microlayer (SML) is the thin boundary layer between the ocean and the atmosphere, making it important for air-sea exchange processes. However, little is known about what controls organic matter composition in the SML. In particular, there are only few studies available on the differences of the SML of various oceanic systems. Here, we compared the organic matter and neuston species composition in the SML and the underlying water (ULW) at 11 stations with varying distance from the coast in the Peruvian upwelling regime, a system with high emissions of climate relevant trace gases, such as N 2 O and CO 2 . In the open ocean, organic carbon, and amino acids were highly enriched in the SML compared to the ULW. The enrichment decreased at the coastal stations and vanished in the upwelling regime. At the same time, the degradation of organic matter increased from the open ocean to the upwelling stations. This suggests that in the open ocean, upward transport processes or new production of organic matter within the SML are faster than degradation processes. Phytoplankton was generally not enriched in the SML, one group though, the Trichodesmium -like TrL (possibly containing Trichodesmium ), were enriched in the open ocean but not in the upwelling region indicating that they find a favorable habitat in the open ocean SML. Our data show that the SML is a distinct habitat; its composition is more similar among different systems than between SML and ULW of a single station. Generally the enrichment of organic matter is assumed to be reduced when encountering low primary production and high wind speeds. However, our study shows the highest enrichments of organic matter in the open ocean which had the lowest primary production and the highest wind speeds.

ROS mediated high anti-bacterial efficacy of strain tolerant layered phase pure nano-calcium hydroxide.

PubMed

Samanta, Aniruddha; Podder, Soumik; Ghosh, Chandan Kumar; Bhattacharya, Manjima; Ghosh, Jiten; Mallik, Awadesh Kumar; Dey, Arjun; Mukhopadhyay, Anoop Kumar

2017-08-01

The present work provides the first ever report on extraordinarily high antibacterial efficacy of phase pure micro-layered calcium hydroxide nanoparticles (LCHNPs) even under dark condition. The LCHNPs synthesized especially in aqueous medium by a simple, inexpensive method show adequate mechanical properties along with the presence of a unique strain tolerant behaviour. The LCHNPs are characterized by FTIR, Raman spectroscopy, XRD, Rietveld analysis, FE-SEM, TEM, TG-DTA, surface area, particle size distribution, zeta potential analysis and nanoindentation techniques. The LCHNPs have 98.1% phase pure hexagonal Ca(OH) 2 as the major phase having micro-layered architecture made up of about ~100-200nm thick individual nano-layers. The nanomechanical properties e.g., nanohardness (H) and Young's modulus (E) of the LCHNPs are found to have a unique load independent behavior. The dielectric responses (e.g., dielectric constant and dielectric loss) and antibacterial properties are evaluated for such LCHNPs. Further, the LCHNPs show much better antibacterial potency against both gram-positive e.g., Staphylococcus aureus (S. aureus) and gram-negative e.g., Pseudomonas putida (P. putida) bacteria even in dark especially, with the lowest ever reported MIC value (e.g., 1 μg ml -1 ) against the P. putida bacterial strain and exhibit ROS mediated antibacterial proficiency. Finally, such LCHNPs has almost ~8-16% inhibition efficacy towards the development of biofilm of these microorganisms quantified by colorimetric detection process. So, such LCHNPs may find potential applications in the areas of healthcare industry and environmental engineering. Copyright © 2017 Elsevier Ltd. All rights reserved.

Biofilm-like properties of the sea surface and predicted effects on air-sea CO2 exchange

NASA Astrophysics Data System (ADS)

Wurl, Oliver; Stolle, Christian; Van Thuoc, Chu; The Thu, Pham; Mari, Xavier

2016-05-01

Because the sea surface controls various interactions between the ocean and the atmosphere, it has a profound function for marine biogeochemistry and climate regulation. The sea surface is the gateway for the exchange of climate-relevant gases, heat and particles. Thus, in order to determine how the ocean and the atmosphere interact and respond to environmental changes on a global scale, the characterization and understanding of the sea surface are essential. The uppermost part of the water column is defined as the sea-surface microlayer and experiences strong spatial and temporal dynamics, mainly due to meteorological forcing. Wave-damped areas at the sea surface are caused by the accumulation of surface-active organic material and are defined as slicks. Natural slicks are observed frequently but their biogeochemical properties are poorly understood. In the present study, we found up to 40 times more transparent exopolymer particles (TEP), the foundation of any biofilm, in slicks compared to the underlying bulk water at multiple stations in the North Pacific, South China Sea, and Baltic Sea. We found a significant lower enrichment of TEP (up to 6) in non-slick sea surfaces compared to its underlying bulk water. Moreover, slicks were characterized by a large microbial biomass, another shared feature with conventional biofilms on solid surfaces. Compared to non-slick samples (avg. pairwise similarity of 70%), the community composition of bacteria in slicks was increasingly (avg. pairwise similarity of 45%) different from bulk water communities, indicating that the TEP-matrix creates specific environments for its inhabitants. We, therefore, conclude that slicks can feature biofilm-like properties with the excessive accumulation of particles and microbes. We also assessed the potential distribution and frequency of slick-formation in coastal and oceanic regions, and their effect on air-sea CO2 exchange based on literature data. We estimate that slicks can reduce CO2 fluxes by up to 15%, and, therefore, play important local and regional roles in regulating air-sea interactions.

Skeletal growth phases of the cold-water coral Lophelia pertusa shown by scanning electron microscope and electron backscatter diffraction

NASA Astrophysics Data System (ADS)

Mouchi, Vincent; Vonlanthen, Pierre; Verrecchia, Eric P.; Crowley, Quentin G.

2016-04-01

Lophelia pertusa is a cold-water coral, which may form reefs by the association of multiple coralites within which a polyp lives. Each individual polyp builds an aragonite skeleton by an initial phase of early mineralization (traditionally referred to as centres of calcification) from which aragonite fibres grow in thickening deposits. The skeleton wall features successive optically opaque and translucent bands previously attributed to different regimes of growth as either uniform in crystal orientation (translucent bands) or with a chaotic organization (opaque bands). The processes involved in any organizational changes are still unknown. Microlayers in the coral wall, which represent separate periods of skeletal growth, have been recently identified and described. These growth patterns are readily visible under scanning electron microscope (SEM) after etching in dilute formic acid, but they do not necessarily form continuously visible structures. Here we present high quality SEM images and electron backscatter diffraction (EBSD) maps to study aragonite fibre orientation across the wall of L. pertusa. Both microlayers and opaque and translucent bands are compared to the crystallographic orientation of the aragonite fibres. EBSD maps and SEM images indicate that aragonite fibres do not exhibit a chaotic orientation, even in opaque bands. The absence of continuity of microlayers is partially explained by an association of multiple crystallographic preferred orientations of aragonite fibres. In the case of L. pertusa, careful textural characterisation is necessary prior to elemental or isotope analysis in order to select a skeletal transect representing a linear and continuous time period.

A Campaign Study of Sea Spray Aerosol Properties in the Bay of Aarhus

NASA Astrophysics Data System (ADS)

Nguyen, Quynh; Rasmussen, Berit; Kristensen, Kasper; Sloth Nielsen, Lærke; Bilde, Merete

2016-04-01

The oceans of the world are a dominant source of atmospheric aerosol. Together with mineral dust, sea spray aerosols (SSA) constitute the largest mass flux of particulate matter in the atmosphere (Andreae and Rosenfeld, 2008). Due to their effects on the global radiative budget - both directly as scatterers and absorbers of solar and terrestrial radiation, and indirectly as cloud condensation nuclei (CCN), SSA are considered an important component of the climate system. The sea-surface microlayer (SML) is an ultra-thin boundary layer between the ocean and the atmosphere. The high concentration of surface-active organic compounds in the SML, compared to that of the underlying water column, creates rigid film-like layer over the surface of the ocean. The SML is believed to play an important role in the formation and composition of SSA. However, current knowledge on the SML and its impacts on SSA remain limited. To characterize the SML of natural seawater and examine its impacts on aerosol properties, a field campaign was conducted in the bay of Aarhus, Denmark, during spring 2015. Bulk seawater was collected 1-2 times every week along with selective sampling of the SML. Characterization of the sea water and SML included a wide range of measurements, including surface tension, water activity, dissolved organic matter, and chemical composition analysis by liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). SSA was generated from sampled sea water by diffusion of air bubbles through a 10L seawater sample situated in a sea spray tank. Particle number concentration and CCN measurements were conducted along with measurements of the organic share in the aerosol phase as indicated by volatility measurements. To investigate the effect of the SML, spiking of the seawater samples with additional SML was performed and measurements repeated for comparison. Preliminary results show that the SML samples only displayed slightly lower surface tension compared to subsurface seawater. A number of overlapping masses were observed in dissolved organic matter extracted from SML and slick samples, which requires further identification. Spiking bulk seawater with SML seems to lead to a small increase in organic share in the aerosol phase as indicated by volatility measurements, while the trend is unclear in CCN measurements. Andreae, M. O., and Rosenfeld, D.: Aerosol-cloud-precipitation interactions. Part 1. The nature and sources of cloud-active aerosols, Earth-Sci Rev, 89, 13-41, 2008.

An adsorption model for the superheat at the critical heat flux

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reyes, R.; Wayner, P.C. Jr.

1995-08-01

The evaluation of the superheat at the critical heat flux (CHF) is a problem of considerable importance to the field of change-of-phase heat transfer. As demonstrated in the recent reviews by Katto and Bergles and in a descriptive paper by Unal et al., there has been extensive prior research on the CHF. In these studies, the following descriptive modeling terms affirm the complex transport processes occurring at CHF: macrolayer, microlayer, apparent contact angle, real contact angle, spreading, dry patch, instability, vapor mushrooms, and interfacial conditions. In order to simplify the analyses of these phenomena, we focus herein on a moremore » tractable model, which emphasizes a characteristic thickness in the contact line region at the vapor-liquid-solid junction, which would be present in the thinnest portion of an evaporating microlayer. A schematic drawing of this region is presented in Fig. 1 for a nonisothermal completely wetting system. This is the region where the substrate dries out in the hot spot hypothesis. The solid substrate is modeled as having an adsorbed ultrathin layer of liquid with a thickness {delta}, which is a function of the superheat and the interfacial force field. The characteristic thickness, {delta}{sub 0}, can (but does not have to) be of the order of a monolayer or less. Therefore, in the region x < 0, the film can be discontinuous and fill in {open_quotes}depressions{close_quotes} on a {open_quotes}rough{close_quotes} surface. Herein, a model of the physically indistinct contact line region, which varies spatially and fluctuates at the molecular level, is used to develop a predictive equation for the average value of the superheat that can be evaluated macroscopically. 9 refs., 2 figs., 1 tab.« less

Linking hygroscopicity and the surface microstructure of model inorganic salts, simple and complex carbohydrates, and authentic sea spray aerosol particles.

PubMed

Estillore, Armando D; Morris, Holly S; Or, Victor W; Lee, Hansol D; Alves, Michael R; Marciano, Meagan A; Laskina, Olga; Qin, Zhen; Tivanski, Alexei V; Grassian, Vicki H

2017-08-09

Individual airborne sea spray aerosol (SSA) particles show diversity in their morphologies and water uptake properties that are highly dependent on the biological, chemical, and physical processes within the sea subsurface and the sea surface microlayer. In this study, hygroscopicity data for model systems of organic compounds of marine origin mixed with NaCl are compared to data for authentic SSA samples collected in an ocean-atmosphere facility providing insights into the SSA particle growth, phase transitions and interactions with water vapor in the atmosphere. In particular, we combine single particle morphology analyses using atomic force microscopy (AFM) with hygroscopic growth measurements in order to provide important insights into particle hygroscopicity and the surface microstructure. For model systems, a range of simple and complex carbohydrates were studied including glucose, maltose, sucrose, laminarin, sodium alginate, and lipopolysaccharides. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM). It is shown here that the E-AIM model describes well the deliquescence transition and hygroscopic growth at low mass ratios but not as well for high ratios, most likely due to a high organic volume fraction. AFM imaging reveals that the equilibrium morphology of these single-component organic particles is amorphous. When NaCl is mixed with the organics, the particles adopt a core-shell morphology with a cubic NaCl core and the organics forming a shell similar to what is observed for the authentic SSA samples. The observation of such core-shell morphologies is found to be highly dependent on the salt to organic ratio and varies depending on the nature and solubility of the organic component. Additionally, single particle organic volume fraction AFM analysis of NaCl : glucose and NaCl : laminarin mixtures shows that the ratio of salt to organics in solution does not correspond exactly for individual particles - showing diversity within the ensemble of particles produced even for a simple two component system.

Biopolymers form a gelatinous microlayer at the air-sea interface when Arctic sea ice melts

PubMed Central

Galgani, Luisa; Piontek, Judith; Engel, Anja

2016-01-01

The interface layer between ocean and atmosphere is only a couple of micrometers thick but plays a critical role in climate relevant processes, including the air-sea exchange of gas and heat and the emission of primary organic aerosols (POA). Recent findings suggest that low-level cloud formation above the Arctic Ocean may be linked to organic polymers produced by marine microorganisms. Sea ice harbors high amounts of polymeric substances that are produced by cells growing within the sea-ice brine. Here, we report from a research cruise to the central Arctic Ocean in 2012. Our study shows that microbial polymers accumulate at the air-sea interface when the sea ice melts. Proteinaceous compounds represented the major fraction of polymers supporting the formation of a gelatinous interface microlayer and providing a hitherto unrecognized potential source of marine POA. Our study indicates a novel link between sea ice-ocean and atmosphere that may be sensitive to climate change. PMID:27435531

Ultra-thin clay layers facilitate seismic slip in carbonate faults.

PubMed

Smeraglia, Luca; Billi, Andrea; Carminati, Eugenio; Cavallo, Andrea; Di Toro, Giulio; Spagnuolo, Elena; Zorzi, Federico

2017-04-06

Many earthquakes propagate up to the Earth's surface producing surface ruptures. Seismic slip propagation is facilitated by along-fault low dynamic frictional resistance, which is controlled by a number of physico-chemical lubrication mechanisms. In particular, rotary shear experiments conducted at seismic slip rates (1 ms -1 ) show that phyllosilicates can facilitate co-seismic slip along faults during earthquakes. This evidence is crucial for hazard assessment along oceanic subduction zones, where pelagic clays participate in seismic slip propagation. Conversely, the reason why, in continental domains, co-seismic slip along faults can propagate up to the Earth's surface is still poorly understood. We document the occurrence of micrometer-thick phyllosilicate-bearing layers along a carbonate-hosted seismogenic extensional fault in the central Apennines, Italy. Using friction experiments, we demonstrate that, at seismic slip rates (1 ms -1 ), similar calcite gouges with pre-existing phyllosilicate-bearing (clay content ≤3 wt.%) micro-layers weaken faster than calcite gouges or mixed calcite-phyllosilicate gouges. We thus propose that, within calcite gouge, ultra-low clay content (≤3 wt.%) localized along micrometer-thick layers can facilitate seismic slip propagation during earthquakes in continental domains, possibly enhancing surface displacement.

Occurrence and distribution of bisphenol A and alkylphenols in the water of the Gulf of Gdansk (Southern Baltic).

PubMed

Staniszewska, Marta; Koniecko, Iga; Falkowska, Lucyna; Krzymyk, Ewelina

2015-02-15

In 2011-2012, the concentrations of bisphenol A (BPA), 4-tert-octylophenol (OP) and 4-nonylphenol (NP) in surface and near-bottom water of the Gulf of Gdansk, as well as inflowing rivers, were similar to those in other regions of Europe; BPA from <5.0 to 277.9 ng dm(-3), OP from <1.0 to 834.5 ng dm(-3), and NP from <4.0 to 228.6 ng dm(-3). The atmospheric transportation of phenol derivatives and their deposition into the water of the gulf was indicated by high enrichment factor values (EF) in the sea surface microlayer in relation to the sub-surface layer. The main route of BPA, OP and NP transportation into the waters of the Gulf of Gdansk is the River Vistula. In spring, significant amounts of bisphenol A and 4-nonylphenol were introduced to the coastal zone with meltwater. The main factors affecting the variability of BPA, OP and NP concentrations in surface and near-bottom water, particularly in summer, were increased tourism in the coastal region, water temperature and dissolved oxygen concentration. Copyright © 2014 Elsevier Ltd. All rights reserved.

Organic pollutants in the coastal environment off San Diego, California. 2: Petrogenic and biogenic sources of aliphatic hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tran, K.; Yu, C.C.; Zeng, E.Y.

1997-02-01

The results from the measurements of aliphatic hydrocarbons suggest that hydrocarbons suggest that hydrocarbons in the Point Loma Wastewater Treatment Plant (PLWTP) effluents are mainly petroleum derived; those in the Tijuana River runoff have largely originated from terrestrial plants with visible petroleum contamination; and those in the sea surface microlayer, sediment traps, and sediments at various coastal locations off San Diego have mostly resulted from biogenic contributions with enhanced microbial products in the summer season. Rainfall in the winter season appeared to amplify the inputs from terrestrial higher plants to the coastal areas. The PLWTP discharged approximately 3.85 metric tonsmore » of n-alkanes (C{sub 10}-C{sub 35}) in 1994, well below the level (136 metric tons) estimated in 1979. The input of aliphatic hydrocarbons from the Tijuana River was about 0.101 metric tons in 1994. Diffusion, solubilization, evaporation, and microbial degradation seemed partially responsible for the difference in the concentrations and compositions of aliphatic hydrocarbons in different sample media, although the relative importance of each mechanism cannot be readily discerned from the available data. The results from analyses of aliphatic hydrocarbon compositional indices are generally consistent with those of polycyclic aromatic hydrocarbons.« less

Atmospheric Aerosol Emissions Related to the Mediterranean Seawater Biogeochemistry

NASA Astrophysics Data System (ADS)

Sellegri, K.; Schwier, A.; Rose, C.; Gazeau, F. P. H.; Guieu, C.; D'anna, B.; Ebling, A. M.; Pey, J.; Marchand, N.; Charriere, B.; Sempéré, R.; Mas, S.

2016-02-01

Marine aerosols contribute significantly to the global aerosol load and consequently has an important impact on the Earth's climate. Different factors influence the way they are produced at the air/seawater interface. The sea state (whitecap coverage, temperature, etc. ) influence the size and concentration of primarily produced particles but also biogeochemical characteristics of the seawater influence both the physical and chemical primary fluxes to the atmosphere. An additional aerosol source of marine aerosol to the atmosphere is the formation of new particles by gaz-to-particle conversion, i.e. nucleation. How the seawater and surface microlayer biogeochemical compositions influences the aerosol emissions is still a large debate. In order to study marine emissions, one approach is to use semi-controlled environments such as mesocosms. Within the MedSea and SAM projects, we characterize the primary Sea Spray Aerosol (SSA) during mesocosms experiments performed during different seasons in the Mediteranean Sea. Mesocosms were either left unchanged as control or enriched by addition of nutriments in order to create different levels of phytoplanctonic activities. The mesocosms waters were daily analyzed for their chemical and biological composition (DOC, CDOM, TEP, Chl-a, virus, bacteria, phytoplankton and zooplankton concentrations). SSA production by bubble bursting was daily simulated in a dedicated set-up. The size segregated SSA number fluxes, cloud condensation nuclei (CCN) properties, and chemical composition were determined as a function of the seawater characteristics. We show that the SSA organic content was clearly correlated to the seawater Chl-a level, provided that the mesocosm was not enriched to create an artificial phytoplanctonic bloom. In our experiments, the enrichment of the seawater with natural surface microlayer did not impact the SSA organic content nor its CCN properties. At last, nucleation of secondary particles were observed to occur in the mesocosm headspace, without any connection to DMS emissions. The occurrence of nucleation of new particles in the open ocean atmosphere is still debated and these findings will be discussed in regard to observations performed in the ambient Mediterranean atmosphere during the MISTRAL/Charmex project.

Environmental Processing of Lipids Driven by Aqueous Photochemistry of α-Keto Acids

PubMed Central

2018-01-01

Sunlight can initiate photochemical reactions of organic molecules though direct photolysis, photosensitization, and indirect processes, often leading to complex radical chemistry that can increase molecular complexity in the environment. α-Keto acids act as photoinitiators for organic species that are not themselves photoactive. Here, we demonstrate this capability through the reaction of two α-keto acids, pyruvic acid and 2-oxooctanoic acid, with a series of fatty acids and fatty alcohols. We show for five different cases that a cross-product between the photoinitiated α-keto acid and non-photoactive species is formed during photolysis in aqueous solution. Fatty acids and alcohols are relatively unreactive species, which suggests that α-keto acids are able to act as radical initiators for many atmospherically relevant molecules found in the sea surface microlayer and on atmospheric aerosol particles. PMID:29806009

Sea spray as a source of ice nucleating particles - results from the AIDA Ocean03 campaign

NASA Astrophysics Data System (ADS)

Salter, M. E.; Ickes, L.; Adams, M.; Bierbauer, S.; Bilde, M.; Christiansen, S.; Ekman, A.; Gorokhova, E.; Höhler, K.; Kiselev, A. A.; Leck, C.; Mohr, C.; Mohler, O.; Murray, B. J.; Porter, G.; Ullrich, R.; Wagner, R.

2017-12-01

Clouds and their radiative effects are one of the major influences on the radiative fluxes in the atmosphere, but at the same time they remain the largest uncertainty in climate models. This lack of understanding is especially pronounced in the high Arctic. Summertime clouds can persist over long periods in this region, which is difficult to replicate in models based on our current understanding. The clouds most often encountered in the summertime high Arctic consist of a mixture of ice crystals and super-cooled water droplets, so-called mixed-phase clouds. This cloud type is sensitive to the availability of aerosol particles, which can act as cloud condensation nuclei and ice nuclei. However, since the high Arctic is a pristine region, aerosol particles are not very abundant, and the hypothesis of open leads in the Arctic as a potentially important source of cloud and ice nucleating particles via bubble bursting has emerged. In this context, we have conducted a series of experiments at the AIDA chamber at KIT, designed to investigate the mechanisms linking marine biology, seawater chemistry and aerosol physics/potential cloud impacts. During this campaign, two marine diatom species (Melosira arctica and Skeletonema marinoi) as well as sea surface microlayer samples collected during several Arctic Ocean research cruises were investigated. To aerosolize the samples, a variety of methods were used including a sea spray simulation chamber to mimic the process of bubble-bursting. The ice nucleating efficiency (mixed-phase cloud regime) of the samples was determined either directly in the AIDA chamber during adiabatic expansions, or using the INKA continuous flow diffusion chamber, or a cold stage. Results from the campaign along with the potential implications are presented.

Lipid and PCB compositions in water-striders from contaminated streams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Napolitano, G.E.; Richmond, J.E.; Klasson, K.T.

1995-12-31

In a study of hydrophobic substances in stream surface-waters, the authors investigated lipids and polychlorinated biphenyls (PCBs) of water-striders (Gerris remiges). Lipid class, fatty acid, and PCB congener compositions were analyzed in insects from four streams located downstream of the Department of Energy`s facilities near the city of Oak Ridge, Tennessee. Total lipid contents of water-striders varied seasonally, showing maximum concentrations in summer and fall ({approximately} 9.0% of wet weight), and minimum concentrations in winter and spring. Total PCB concentrations of water-striders varied between streams and appeared to parallel PCB concentrations reported for the aquatic fauna of each site. Fattymore » acids were used as chemical markers to detect differences in the food resources of water-striders. The triacylglycerol fatty acid composition was remarkably similar in all the streams and reflected to a large extent, that of a terrestrial insect. The PCB congener composition of water-striders varied significantly between streams, showing a relative enrichment of the less chlorinated congeners in the less contaminated samples. There was also a positive correlation between PCB burden and average molecular weights. Differences between the chlorine content of the dominant congeners suggest distinct sources of PCBs for the different streams. The apparent similarities in the food resources of the water-striders, as inferred from fatty acid markers, and their distinct PCB congener composition, suggest absorption or ingestion from the surface micro-layer, rather than diet, as a more likely route of uptake of lipophilic contaminants by water-striders.« less

Biomorphic microstructures of ferromanganese stromatolites

NASA Astrophysics Data System (ADS)

Avdonin, V. V.; Yeryomin, N. I.; Zhegallo, E. A.; Sergeyeva, N. E.

2016-11-01

It was found as a result of detailed study of ferromanganese stromatolites that columnar formations, i.e., fossilized stratified bacterial tufts with rhythmically alternating layers of glycocalyx, accumulations of filamentous bacteria, and lens-shaped two-layered (alternation of homogeneous microlayers with porous ones containing filamentous bacteria trichomes) packages, serve as the basis for stromatolite buildup.

Bacterial DNA of Ocean and Land on the Surface of the International Space Station.

NASA Astrophysics Data System (ADS)

Grebennikova, Tatiana

A.V. Syroeshkin2, T.V. Grebennikova1, E.V. Shubralova3, V.A. Shuvalov3, O.S. Tsygankov4, V.B. Lapshin2 1D. I. Ivanovsky Virology Institute, Moscow, Russia 2 Academician E. K. Fedorov Institute of Applied Geophysics, Moscow, Russia 3S.P. Korolev Rocket and Space Corporation «Energia» Korolev, Russia 4Central Research Institute of Machine Building, Korolev, Russia Existence of biological molecules as markers of microorganisms in the space environment has always attracted attention of researchers. There is great attention to the search for extraterrestrial life forms [Nicholson W.L. 2009, Kawaguchi Y. et al 2013], and as well as the coping mechanisms of living organisms in the interplanetary space [Hotchin J. et al 1965, Baranov V.M. 2009, Horneck G. et al 2010]. Experiments on American and Japanese segments of the International Space Station (ISS) over the different nature of resistance during prolonged stay in space were conducted [Scalzi G et al 2012, Wassmann M. et al 2012]. As a result of these experiments confirmed the possibility of preserving the viability of organisms in an open space for a long time. Consequence, became interested in the transfer of living matter from the stratosphere to near-Earth space [Smith D.J. 2013]. We hypothesized that viable forms, or at least, intact DNA can be transferred to the orbit of the ISS with the ascending branch of the global electric circuit. Samples of cosmic dust collected from the surface of the window of the ISS during the exit of an astronaut in space. Samples (washes with material of tampons and tampons) which were in vacuo, were analyzed for the presence of bacterial DNA by nested PCR using primers specific DNA genus Mycobacterium, the DNA of the strain of the genus Bacillus anthracis and DNA encoding the bacterial 16S ribosomal RNA after transportation of the samples to Earth. The results of amplification, followed by sequencing and phylogenetic analysis showed the presence in samples of cosmic dust DNA representatives bacteria of the genus Mycobacteria and extreme bacteria of the genus Delftia family Comamonadaceae order Burkholderiales. It is shown that the DNA sequence of one of the bacteria of the genus Mycobacteria genetically similar to that previously DNA sequence of bacteria observed in sea surface microlayer Barents Sea coast. The presence of representatives of the DNA of wild terrestrial and marine genera of bacteria on the surface of the ISS indicates their possible transfer from the stratosphere into the ionosphere with the ascending branch of the global electric circuit.

Natural Surfactant Enrichments in the Atlantic Ocean Between 50°N and 50°S: Data from the Atlantic Meridional Transect, Oct-Nov 2014

NASA Astrophysics Data System (ADS)

Sabbaghzadeh, B.; Upstill-Goddard, R. C.; Nightingale, P. D.; Beale, R.

2016-02-01

Surfactants that decrease air-sea gas exchange by suppressing the gas transfer velocity (kw) show variable enrichments in the sea surface microlayer (SML) relative to the underlying water. This reflects variability in the rates of surfactant production and consumption. Total surfactant activity (SA: equivalent to Triton-X-100, mgL -1) was determined daily between the UK and the Falkland Islands, during cruise 24 of the Atlantic Meridional Transect programme (AMT 24). Samples were simultaneously obtained from the SML (Garrett screen), from the ship's underway system (inlet at 7m) and in hydrocasts to 500m. SA analysis was by hanging mercury drop electrode polarography (Metrohm 797 VA Computrace). SA enrichment factors (EF: SML SA / underlying water SA) >1 were observed at most locations, showing the SML to be consistently SA-enriched along the entire cruise transect. The persistence of these enrichments up to wind speeds 12m s-¹ support previous conclusions regarding the stability of the SML under high winds. More specifically, SA in the SML was up to four-fold higher in the Atlantic Northern Hemisphere than in the Atlantic Southern Hemisphere. Even so, EF values were not significantly different between the two hemispheres (p >0.05). These various findings have potentially important implications for kw variability across ocean basin scales.

Biogeochemical linkage between atmosphere and ocean in the eastern equatorial Pacific Ocean: Results from the EqPOS research cruise

NASA Astrophysics Data System (ADS)

Furutani, H.; Inai, Y.; Aoki, S.; Honda, H.; Omori, Y.; Tanimoto, H.; Iwata, T.; Ueda, S.; Miura, K.; Uematsu, M.

2012-12-01

Eastern equatorial Pacific Ocean is a unique oceanic region from several biogeochemical points of view. It is a remote open ocean with relatively high marine biological activity, which would result in limited influence of human activity but enhanced effect of marine natural processes on atmospheric composition. It is also characterized as high nutrient low chlorophyll (HNLC) ocean, in which availability of trace metals such as iron and zinc limits marine primary production and thus atmospheric deposition of these trace elements to the ocean surface is expected to play an important role in regulating marine primary production and defining unique microbial community. High sea surface temperature in the region generates strong vertical air convection which efficiently brings tropospheric atmospheric composition into stratosphere. In this unique eastern equatorial Pacific Ocean, EqPOS (Equatorial Pacific Ocean and Stratospheric/Tropospheric Atmospheric Study) research cruise was organized as a part of SOLAS Japan activity to understand biogeochemical ocean-atmospheric interaction in the region. Coordinated atmospheric, oceanic, and marine biological observations including sampling/characterization of thin air-sea interfacial layer (sea surface microlayer: SML) and launching large stratospheric air sampling balloons were carried out on-board R/V Hakuho Maru starting from 29 January for 39 days. Biogeochemically important trace/long-lived gases such as CO2, dimethyl sulfide (DMS), and some volatile organic carbons (VOCs) both in the atmosphere and seawater were continuously monitored and their air-sea fluxes were also observed using gradient and eddy-covariance techniques. Atmospheric gas measurement of CO2, CH4, N2O, SF6, CO, H2, Ar and isotopic composition of selected gases were further extended to stratospheric air by balloon-born sampling in addition to a vertical profiling of O3, CO2, and H2O with sounding sondes. Physical and chemical properties of marine atmospheric aerosols such as size distribution, total and cloud condensation nuclei concentrations, particle morphology, bulk and single particle chemical composition were also continuously determined to find out potential link between biogenic VOCs emitted from the ocean and aerosol composition. Biological and biogeochemical characterizations of marine microorganisms, suspended particulate matter, dissolved nutrients in seawater and SML were also conducted. In the presentation, brief overview of the research activities during the EqPOS cruise and biogeochemical linkage atmosphere and ocean via atmospheric and oceanic gaseous and particulate matter from ocean surface to stratosphere observed during the cruise and unique importance of SML would be presented.

Size-resolved characterization of the polysaccharidic and proteinaceous components of sea spray aerosol

NASA Astrophysics Data System (ADS)

Aller, Josephine Y.; Radway, JoAnn C.; Kilthau, Wendy P.; Bothe, Dylan W.; Wilson, Theodore W.; Vaillancourt, Robert D.; Quinn, Patricia K.; Coffman, Derek J.; Murray, Benjamin J.; Knopf, Daniel A.

2017-04-01

Dissolved organic polymers released by phytoplankton and bacteria abiologically self-assemble in surface ocean waters into nano-to micro-sized gels containing polysaccharides, proteins, lipids and other components. These gels concentrate in the sea surface microlayer (SML), where they can potentially contribute to sea spray aerosol (SSA). Sea spray is a major source of atmospheric aerosol mass over much of the earth's surface, and knowledge of its properties (including the amount and nature of the organic content), size distributions and fluxes are fundamental for determining its role in atmospheric chemistry and climate. Using a cascade impactor, we collected size-fractionated aerosol particles from ambient air and from freshly generated Sea Sweep SSA in the western North Atlantic Ocean together with biological and chemical characterization of subsurface and SML waters. Spectrophotometric methods were applied to quantify the polysaccharide-containing transparent exopolymer (TEP) and protein-containing Coomassie stainable material (CSM) in these particles and waters. This study demonstrates that both TEP and CSM in surface ocean waters are aerosolized with sea spray with the greatest total TEP associated with particles <180 nm in diameter and >5 000 nm. The higher concentrations of TEP and CSM in particles >5 000 nm most likely reflects collection of microorganism cells and/or fragments. The greater concentration of CSM in larger size particles may also reflect greater stability of proteinaceous gels compared to polysaccharide-rich gels in surface waters and the SML. Both TEP and CSM were measured in the ambient marine air sample with concentrations of 2.1 ± 0.16 μg xanthan gum equivalents (XG eq.) m-3 and 14 ± 1.0 μg bovine serum albumin equivalents (BSA eq.) m-3. TEP in Sea Sweep SSA averaged 4.7 ± 3.1 μg XG eq. m-3 and CSM 8.6 ± 7.3 μg BSA eq. m-3. This work shows the transport of marine biogenic material across the air-sea interface through primary particle emission and the first demonstration of particle size discriminated TEP and CSM characterization of SSA and ambient aerosol under field conditions.

Tropical Archaea: Diversity associated with the surface microlayer of corals

USGS Publications Warehouse

Kellogg, C.A.

2004-01-01

Recent 16S rDNA studies have focused on detecting uncultivated bacteria associated with Caribbean reef corals in an effort to address the ecological roles of coral-associated microbes. Reports of Archaea associated with fishes and marine invertebrates raised the question of whether Archaea might also be part of the coral-associated microbial community. DNA analysis of mucus from 3 reef-building species of Caribbean corals, Montastraea annularis complex, Diploria strigosa and D. labyrinthiformis in the US Virgin Islands yielded 34 groups of archaeal 16S ribotypes (defined at the level of 97% similarity). The majority (75%) was most closely matched by BLAST searches to sequences derived from marine water column samples, whereas the remaining ribotypes were most similar to sequences isolated from anoxic environments (15%) and hydrothermal vents (9%). Unlike previous 16S studies of coral-associated Bacteria, the results do not suggest specific associations between particular archaeal sequences and individual coral species. Marine Archaea (Groups I, II and III) in addition to Thermoplasma-like, methanogen, and marine benthic crenarchaeote phylotypes, were detected in the mucus of tropical corals. The finding of sequences from coral-associated Archaea that are closely related to strict and facultative anaerobes, as well as to uncultivated Archaea from other types of anoxic environments, suggests that anaerobic micro-niches may exist in coral mucus layers. Archaea, with their unique biogeochemical capabilities, broaden the scope of possible interactions between corals and their associated microbial communities.

Glyoxal and methylglyoxal in Atlantic seawater and marine aerosol particles: method development and first application during the Polarstern cruise ANT XXVII/4

NASA Astrophysics Data System (ADS)

van Pinxteren, M.; Herrmann, H.

2013-06-01

An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol samples is presented. The method is based on derivatisation with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD <10%), sensitivity (detection limits in the low ng L-1 range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the POLARSTERN cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulkwater (BW) with average concentrations of 228 ng L-1 (GLY) and 196 ng L-1 (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng m-3) and MGLY (average concentration 0.15 ng m-3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosols could be a hint for interactions of especially GLY between seawater and the atmosphere.

Coupled DDD-FEM modeling on the mechanical behavior of microlayered metallic multilayer film at elevated temperature

NASA Astrophysics Data System (ADS)

Huang, Minsheng; Li, Zhenhuan

2015-12-01

To investigate the mechanical behavior of the microlayered metallic thin films (MMMFs) at elevated temperature, an enhanced discrete-continuous model (DCM), which couples rather than superposes the two-dimensional climb/glide-enabled discrete dislocation dynamics (2D-DDD) with the linearly elastic finite element method (FEM), is developed in this study. In the present coupling scheme, two especial treatments are made. One is to solve how the plastic strain captured by the DDD module is transferred properly to the FEM module as an eigen-strain; the other is to answer how the stress field computationally obtained by the FEM module is transferred accurately to the DDD module to drive those discrete dislocations moving correctly. With these two especial treatments, the interactions between adjacent dislocations and between dislocation pile-ups and inter-phase boundaries (IBs), which are crucial to the strengthening effect in MMMFs, are carefully taken into account. After verified by comparing the computationally predicted results with the theoretical solutions for a dislocation residing in a homogeneous material and nearby a bi-material interface, this 2D-DDD/FEM coupling scheme is used to model the tensile mechanical behaviors of MMMFs at elevated temperature. The strengthening mechanism of MMMFs and the layer thickness effect are studied in detail, with special attentions to the influence of dislocation climb on them.

The impact of marine surface organic enrichment on the measured hygroscopicity parameter of laboratory generated sea-spray aerosols

NASA Astrophysics Data System (ADS)

Schill, S.; Novak, G.; Zimmermann, K.; Bertram, T. H.

2014-12-01

The ocean serves as a major source for atmospheric aerosol particles, yet the chemicophysical properties of sea spray aerosol to date are not well characterized. Understanding the transfer of organic compounds, present in the sea surface microlayer (SSML), to sea-spray particles and their resulting impact on cloud formation is important for predicting aerosol impact on climate in remote marine environments. Here, we present a series of laboratory experiments designed to probe the fractionation of select organic molecules during wave breaking. We use a representative set of organic mimics (e.g. sterols, sugars, lipids, proteins, fatty acids) to test a recent physically based model of organic enrichment in sea-spray aerosol [Burrows et al., 2014] that is based on Langmuir absorption equilibria. Experiments were conducted in the UCSD Marine Aerosol Reference Tank (MART) permitting accurate representation of wave breaking processes in the laboratory. We report kappa values for the resulting sea-spray aerosols and compare them to a predictions made using Kappa-Köhler Theory driven by a linear combination of the pure component kappa values. Hygroscopicity determinations made using the model systems are discussed within the context of measurements of CCN activity made using natural, coastal water.

Dynamics of Vapour Bubbles in Nucleate Boiling. 2; Evolution of Thermally Controlled Bubbles

NASA Technical Reports Server (NTRS)

Buyevich, Yu A.; Webbon, Bruce W.; Callaway, Robert (Technical Monitor)

1995-01-01

The previously developed dynamic theory of growth and detachment of vapour bubbles under conditions of nucleate pool boiling is applied to study motion and deformation of a bubble evolving at a single nucleation site. The bubble growth is presumed to be thermally controlled, and two components of heat transfer to the bubble are accounted of: the one from the bulk of surrounding liquid and the one due to heat conduction across a liquid microlayer formed underneath the bubble. Bubble evolution is governed by the buoyancy and an effective surface tension force, both the forces making the bubble centre of mass move away from the wall and, thus, assisting its detachment. Buoyancy-controlled and surface-tension-controlled regimes are considered separately in a meticulous way. The duration of the whole process of bubble evolution till detachment, the rate of growth, and the bubble departure size are found as functions of time and physical and operating parameters. Some repeatedly observed phenomena, such as an influence of gravity on the growth rate, are explained. Inferences of the model agree qualitatively with available experimental evidence, and conclusions pertaining to the dependence on gravity of the bubble radius at detachment and the whole time of the bubble development when being attached to the wall are confirmed quantitatively.

Changes in optical characteristics of surface microlayers hint to photochemically and microbially mediated DOM turnover in the upwelling region off the coast of Peru

NASA Astrophysics Data System (ADS)

Galgani, Luisa; Engel, Anja

2016-04-01

The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4° S, and 82.0 to 77.5° W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation-emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 nm-1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15° S. By EEMs, we identified five fluorescent components (F1-5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m-1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air-sea gas exchange in this area.

Influence of PAHs among other coastal environmental variables on total and PAH-degrading bacterial communities.

PubMed

Sauret, Caroline; Tedetti, Marc; Guigue, Catherine; Dumas, Chloé; Lami, Raphaël; Pujo-Pay, Mireille; Conan, Pascal; Goutx, Madeleine; Ghiglione, Jean-François

2016-03-01

We evaluated the relative impact of anthropogenic polycyclic aromatic hydrocarbons (PAHs) among biogeochemical variables on total, metabolically active, and PAH bacterial communities in summer and winter in surface microlayer (SML) and subsurface seawaters (SSW) across short transects along the NW Mediterranean coast from three harbors, one wastewater effluent, and one nearshore observatory reference site. At both seasons, significant correlations were found between dissolved total PAH concentrations and PAH-degrading bacteria that formed a gradient from the shore to nearshore waters. Accumulation of PAH degraders was particularly high in the SML, where PAHs accumulated. Harbors and wastewater outfalls influenced drastically and in a different way the total and active bacterial community structure, but they only impacted the communities from the nearshore zone (<2 km from the shore). By using direct multivariate statistical analysis, we confirmed the significant effect of PAH concentrations on the spatial and temporal dynamic of total and active communities in this area, but this effect was putted in perspective by the importance of other biogeochemical variables.

Glyoxal and methylglyoxal in Atlantic seawater and marine aerosol particles: method development and first application during the Polarstern cruise ANT XXVII/4

NASA Astrophysics Data System (ADS)

van Pinxteren, M.; Herrmann, H.

2013-12-01

An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD < 10%), sensitivity (detection limits in the low ng L-1 range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng L-1 (GLY) and 196 ng L-1 (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng m-3) and MGLY (average concentration 0.15 ng m-3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere.

Molecular dynamics simulations reveal the assembly mechanism of polysaccharides in marine aerosols.

PubMed

Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

2014-12-21

The high Arctic marine environment has recently detected polymer gels in atmospheric aerosol particles and cloud water originating from the surface microlayer of the open leads within the pack ice area. These polysaccharide molecules are water insoluble but water solvated, highly surface-active and highly hydrated (99% water). In order to add to the understanding and to complement missing laboratory characterization of marine polymer gels we have in this work performed an atomistic study of the assembly process and interfacial properties of polysaccharides. Our study reveals a number of salient features of the microscopic process behind polysaccharide assembly into nanogels. With three- and four-repeating units the polysaccharides assemble into a cluster in 50 ns. The aggregates grow quicker by absorbing one or two polymers each time, depending on the unit length and the type of inter-bridging cation. Although both the hydrophobic and hydrophilic domains are contracted, the latter dominates distinctly upon the contraction of solvent accessible surface areas. The establishment of inter-chain hydrogen-bonds is the key to the assembly while ionic bridges can further promote aggregation. During the assembly of the more bent four-unit polymers, intra-chain hydrogen bonds are significantly diminished by Ca(2+). Meanwhile, the percentage of Ca(2+) acting as an ionic bridge is more eminent, highlighting the significance of Ca(2+) ions for longer-chain polysaccharides. The aggregates are able to enhance surface tension more in the presence of Ca(2+) than in the presence of Na(+) owing to their more compact structure. These conclusions all demonstrate that studies of the present kind provide insight into the self-assembly process and interfacial properties of marine gels. We hope this understanding will keep up the interest in the complex and the fascinating relationship between marine microbiology, atmospheric aerosols, clouds and climate.

The application of chemical and isotopic tracers to characterize aerosol sources and processing in marine air

NASA Astrophysics Data System (ADS)

Turekian, Vaughan Charles

2000-12-01

Aerosol production, transport, chemical and physical evolution and deposition impact the environment by influencing radiation budgets, altering the composition of the atmosphere, and delivering nutrients to marine and terrestrial ecosystems. The objective of this research was to combine high-resolution chemical measurements with stable isotopic analysis in order to characterize the sources and processing of carbon, nitrogen and sulfur bearing compounds, associated with sized aerosols on Bermuda, during spring. Chemical tracers combined with forward and backward trajectories demonstrated the transport of biomass burning products from North America to Bermuda. The size distributions of NH4+ from 1998 differed from those during spring, 1997, a year without the large-scale burning. These results suggest that transport of biomass burning products altered the pH of the aerosols. Marine and continentally derived carbon was associated with all aerosol size fractions. Supermicron radius sea- salt aerosol was enriched in marine derived carbon by 2 orders of magnitude compared to bulk surface seawater. Enrichments of oxalate relative to methanesulfonic acid (MSA) in supermicron radius aerosol suggested in situ formation of oxalate within the sea-salt solution, or direct injection from the organic rich surface microlayer. Compound specific isotope analysis of oxalic acid, indicated a marine source for all aerosol size fractions, indicating formation from in the gas phase for the submicron radius aerosol. Stable sulfur isotopes indicated that the biogenic non- sea-salt (nss) SO42-/MSA ratio varied with aerosol size indicating that MSA may not be a conservative tracer of biogenic nss SO4 2- in bulk aerosol sampling. The calculated biogenic nss SO 42-/MSA based on stable isotopes and sized aerosol sampling, was 3 times lower than previous estimates for Bermuda. Stable nitrogen isotope values for submicron and supermicron aerosol where significantly different, consistent with their different chemical compositions. Results suggested that HNO3 incorporation into supermicron aerosol was essentially unidirectional whereas submicron aerosol was both a source and a sink for NH3(g). Variable aerosol liquid water content over the relatively longer atmospheric lifetimes of submicron aerosol may lead to multiple NH3 phase changes. This study was the first to combine sized aerosol sampling, high-resolution chemical analysis and multiple stable isotopes to characterize both the sources and the processing of aerosols in marine air. The results of this study, therefore, provide crucial information for source apportionment of environmentally important atmospheric species in continentally impacted, marine air.

The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiaofei; Deane, Grant B.; Moore, Kathryn A.

Covering 71% of the Earth’s surface, oceans represent a significant global source of atmospheric aerosols. The size and composition of sea spray aerosols (SSA) affect their ability to serve as cloud seeds and thus understanding the factors controlling their composition is critical to predicting their impact on clouds and climate. SSA particles have been shown to be an external mixture of particles with different compositions. Film and jet drop production mechanisms ultimately determine the individual particle compositions which are comprised of an array of salt/organic mixtures ranging from pure sea salt to nearly pure organic particles. It is often assumedmore » that the majority of submicron SSA are formed by film drops produced from bursting hydrophobic organic-rich bubble film caps at the sea surface, and in contrast, jet drops are postulated to produce larger supermicron particles from underlying seawater comprised largely of salts and water soluble organic species. However, here we show that jet drops produced by bursting sub-100 m bubbles account for up to 40 % of all submicron particles. They have distinct chemical compositions, organic volume fractions and ice nucleating activities from submicron film drops. Thus a substantial fraction of submicron particles will not necessarily be controlled by the composition of the sea surface microlayer as has been assumed in many studies. This finding has significant ramifications for the size-resolved mixing states of SSA particles which must be taken into consideration when accessing SSA impacts on clouds.« less

The role of jet and film drops in controlling the mixing state of submicron sea spray aerosol particles

DOE PAGES

Wang, Xiaofei; Deane, Grant B.; Moore, Kathryn A.; ...

2017-06-19

Covering 71% of the Earth’s surface, oceans represent a significant global source of atmospheric aerosols. The size and composition of sea spray aerosols (SSA) affect their ability to serve as cloud seeds and thus understanding the factors controlling their composition is critical to predicting their impact on clouds and climate. SSA particles have been shown to be an external mixture of particles with different compositions. Film and jet drop production mechanisms ultimately determine the individual particle compositions which are comprised of an array of salt/organic mixtures ranging from pure sea salt to nearly pure organic particles. It is often assumedmore » that the majority of submicron SSA are formed by film drops produced from bursting hydrophobic organic-rich bubble film caps at the sea surface, and in contrast, jet drops are postulated to produce larger supermicron particles from underlying seawater comprised largely of salts and water soluble organic species. However, here we show that jet drops produced by bursting sub-100 m bubbles account for up to 40 % of all submicron particles. They have distinct chemical compositions, organic volume fractions and ice nucleating activities from submicron film drops. Thus a substantial fraction of submicron particles will not necessarily be controlled by the composition of the sea surface microlayer as has been assumed in many studies. This finding has significant ramifications for the size-resolved mixing states of SSA particles which must be taken into consideration when accessing SSA impacts on clouds.« less

Resistance of Marine Bacterioneuston to Solar Radiation

PubMed Central

Agogué, Hélène; Joux, Fabien; Obernosterer, Ingrid; Lebaron, Philippe

2005-01-01

A total of 90 bacterial strains were isolated from the sea surface microlayer (i.e., bacterioneuston) and underlying waters (i.e., bacterioplankton) from two sites of the northwestern Mediterranean Sea. The strains were identified by sequence analysis, and growth recovery was investigated after exposure to simulated solar radiation. Bacterioneuston and bacterioplankton isolates were subjected to six different exposure times, ranging from 0.5 to 7 h of simulated noontime solar radiation. Following exposure, the growth of each isolate was monitored, and different classes of resistance were determined according to the growth pattern. Large interspecific differences among the 90 marine isolates were observed. Medium and highly resistant strains accounted for 41% and 22% of the isolates, respectively, and only 16% were sensitive strains. Resistance to solar radiation was equally distributed within the bacterioneuston and bacterioplankton. Relative contributions to the highly resistant class were 43% for γ-proteobacteria and 14% and 8% for α-proteobacteria and the Cytophaga/Flavobacterium/Bacteroides (CFB) group, respectively. Within the γ-proteobacteria, the Pseudoalteromonas and Alteromonas genera appeared to be highly resistant to solar radiation. The majority of the CFB group (76%) had medium resistance. Our study further provides evidence that pigmented bacteria are not more resistant to solar radiation than nonpigmented bacteria. PMID:16151115

The Chemical Composition and Mixing State of Sea Spray Aerosol and Organic Aerosol in the Winter-Spring Arctic

NASA Astrophysics Data System (ADS)

Kirpes, R.; Bondy, A. L.; Bonanno, D.; Moffet, R.; Wang, B.; Laskin, A.; Ault, A. P.; Pratt, K.

2016-12-01

The Arctic region is undergoing rapid transformations and loss of sea ice due to climate change. With increased sea ice fracturing resulting in greater open ocean surface, winter emissions of sea spray aerosol (SSA) are expected to be increasing. Additionally, during the winter-spring transition, Arctic haze contributes to the Arctic aerosol budget. The magnitude of aerosol climate effects depends on the aerosol composition and mixing state (distribution of chemical species within and between particles). However, few studies of aerosol chemistry have been conducted in the winter Arctic, despite it being a time when aerosol impacts on clouds are expected to be significant. To study aerosol composition and mixing state in the winter Arctic, atmospheric particles were collected near Barrow, Alaska in January and February 2014 for off-line individual particle chemical analysis. SSA was the most prevalent particle type observed. Sulfate and nitrate were observed to be internally mixed with SSA and organic aerosol. Greater than 98% of observed SSA particles contained organic content, with 15-35% organic volume fraction on average for individual particles. The SSA organic compounds consisted of carbohydrates, lipids, and fatty acids found in the seawater surface microlayer. SSA was determined to be emitted from open leads, while transported sulfate and nitrate contributed to aging of SSA and organic aerosol. Determining the aerosol chemical composition and mixing state in the winter Arctic will further the understanding of how individual aerosol particles impact climate through radiative effects and cloud formation.

Conditions affecting the release of phosphorus from surface lake sediments.

PubMed

Christophoridis, Christophoros; Fytianos, Konstantinos

2006-01-01

Laboratory studies were conducted to determine the effect of pH and redox conditions, as well as the effect of Fe, Mn, Ca, Al, and organic matter, on the release of ortho-phosphates in lake sediments taken from Lakes Koronia and Volvi (Northern Greece). Results were evaluated in combination with experiments to determine P fractionation in the sediment. The study revealed the major effect of redox potential and pH on the release of P from lake sediments. Both lakes showed increased release rates under reductive conditions and high pH values. The fractionation experiments revealed increased mobility of the reductive P fraction as well as of the NaOH-P fraction, indicating participation of both fractions in the overall release of sediment-bound P, depending on the prevailing environmental conditions. The results were assessed in combination with the release patterns of Fe, Mn, Ca, Al, and organic matter, enabling the identification of more specific processes of P release for each lake. The basic release patterns included the redox induced reductive dissolution of P-bearing metal oxides and the competitive exchange of phosphate anions with OH- at high pH values. The formation of an oxidized surface microlayer under oxic conditions acted as a protective film, preventing further P release from the sediments of Lake Volvi, while sediments from Lake Koronia exhibited a continuous and increased tendency to release P under various physicochemical conditions, acting as a constant source of internal P loading.

Evidence for a Biological Control on Emissions of Marine Ice Nucleating Particles: Laboratory, Field and Modeling Results

NASA Astrophysics Data System (ADS)

McCluskey, Christina Song

Laboratory, field, and modeling studies were used to (1) confirm the hypothesized source of marine ice nucleating particle (INP) emissions associated with marine organic aerosol that arises from elevated oceanic biological productivity; (2) identify marine INP compositions and their activation temperatures; (3) determine the natural abundances and variability of the number concentrations of marine INPs (nINPs); and (4) evaluate the current best model estimates of marine INPs against new observations. Observations of seawater biology, aerosol composition and ice nucleation ability of bulk seawater, the sea surface microlayer (upper 50 mum of the ocean surface), and laboratory-generated sea spray aerosol (SSA) during simulated phytoplankton blooms revealed that emissions of INPs active at temperatures warmer than -22°C increased during the decay of two phytoplankton blooms. Enrichment of organic matter in the sea surface microlayer and its subsequent control on transferring organic material into the aerosol phase was found to be an important factor in the release of INPs from the ocean surface. Integration of all size and compositional analyses led to two proposed classes of marine INPs: (A) ice nucleation active molecules and (B) ice nucleation active intact or fragmented microbes (e.g., diatoms or bacteria). To investigate marine INPs present in nature, several field campaigns were carried out over oceans and at two remote coastal sites. Regarding their abundance and variability, the number concentrations of ice nucleating particles, nINPs, active at temperatures warmer than -30 °C, ranged over three or more orders of magnitude at any particular temperature for samples collected in the marine boundary layer during six research voyages over the Pacific Ocean, spanning 70°S to 60°N over various seasons. nINPs were greater and more variable in the Northern Hemisphere compared to the Southern Hemisphere. Factors that contributed to this variability were investigated in detail at a North Atlantic Ocean coastal site (Mace Head Research Station, MHD) and over the Southern Ocean (SO). At MHD, normalizing observations by aerosol surface area and limiting measurements to pristine marine air masses narrowed the variability in nINPs. That subset of data was used to develop a parameterization for INPs in pristine sea spray organic aerosol over the North Atlantic Ocean. Higher n INPs active at temperatures warmer than -22°C were observed in pristine SSA during a period that was influenced by organic aerosol arising from offshore biological activity. The INPs observed during this event comprised ice nucleation active microbes (marine INP class B), which were distinct from other marine organic INPs at MHD. These observations indicate that further research is required to incorporate the microbe INP type into parameterizations. Measurements of INPs in the SO marine boundary layer aerosol and in seawater samples were the first in this region in over four decades. Observed nINPs were a factor of 100 lower than those historical measurements. nINPs observed over the SO were less variable than MHD and INP composition included refractory, heat-stable organic (marine INP class A), and heat-labile materials (marine INP class B). These data serve as new observational constraints on nINPs and their sources and compositions that can be applied to evaluate numerical modeling studies. The database from this work was used in an exploratory study to evaluate current modeling approaches for predicting marine INPs. Simulations with the atmospheric component (CAM5) of the Department of Energy Community Earth System Model with implementation of a physically-based parameterization for sea spray organic aerosol were conducted for the MHD and SO study periods. Modeled aerosol mass, number and composition were used as input for two marine INP parameterizations that have been developed since the beginning of this work (circa 2014). Findings indicated that, for INPs active at -15°C during the MHD study period, observed nINPs were bounded by estimates derived from the two marine INP parameterizations. Periods with discrepancies between modeled estimates and observed nINPs were explained by observational evidence that different classes of marine INPs were present at MHD, further supporting the need for additional studies regarding the emissions of different marine INP classes. Different INP types (e.g., marine organic, mineral dust) are active at different temperatures and the observations from this work clearly indicate that organic aerosol is an important factor for determining marine nINPs. Thus, further evaluation of these parameterizations for INPs active at a range of temperatures (0 to -27°C) and against measurements over the Southern Ocean, where sea spray organic aerosol production may be quite different from other regions, will be conducted in the future with these simulations. This deeper analysis may reveal underlying limitations of the parameterizations and provide insights on how to further refine numerical representations of INPs. (Abstract shortened by ProQuest.).

The Impact of Organic Surfactants and Coatings in Regulating Heterogeneous N2O5 Reaction Kinetics on Nascent Marine Aerosol

NASA Astrophysics Data System (ADS)

Ryder, O. S.; Campbell, N.; Schill, S.; Pöhlker, C.; Andreae, M. O.; Bertram, T. H.

2013-12-01

The heterogeneous reaction of N2O5 on aerosol particles impacts both the lifetime of nitrogen oxides, and the production rate of chlorine radicals following the activation of particulate chloride to nitryl chloride in both coastal and continental regions. The extent to which N2O5 reactivity impacts oxidant loadings depends on the heterogeneous reaction rate, which is directly influenced by aerosol chemical composition, morphology, and physical phase state. In the marine environment, the chemical composition of aerosol particles produced via wave induced bubble bursting mechanisms varies greatly and is influenced by the composition of the sea surface microlayer . Here, we present direct measurements of N2O5 reaction kinetics determined using model sea-spray particles generated in a novel Marine Aerosol Reference Tank (MART), capable of generating accurate mimics of ambient sea spray particles, in a lab environment. Here, a synthetic sea salt ocean was sequentially doped with organic molecules chosen to mimic organic species present in natural sea water over the course of a phytoplankton bloom in the open ocean. These included sterol, galactose, lippolysaccharide, BSA protein, and 1,2-dipalmitoyl-sn-glycero-3-phosphate (DPPA). These observations permit discussion of the role of marine organics in regulating heterogeneous reaction kinetics, as well a re-evaluation of potential organic lab proxies for marine organics.

Does Marine Surface Tension Have Global Biogeography? Addition for the OCEANFILMS Package

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, Scott; Burrows, Susannah; Cameron-Smith, Philip

We apply principles of Gibbs phase plane chemistry across the entire ocean-atmosphere interface to investigate aerosol generation and geophysical transfer issues. Marine surface tension differences comprise a tangential pressure field controlling trace gas fluxes, primary organic inputs, and sea spray salt injections, in addition to heat and momentum fluxes. Mapping follows from the organic microlayer composition, now represented in ocean system models. Organic functional variations drive the microforcing, leading to (1) reduced turbulence and (by extension) laminar gas-energy diffusion; plus (2) altered bubble film mass emission into the boundary layer. Interfacial chemical behaviors are, therefore, closely reviewed as the background.more » We focus on phase transitions among two dimensional "solid, liquid, and gaseous" states serving as elasticity indicators. From the pool of dissolved organic carbon (DOC) only proteins and lipids appear to occupy significant atmospheric interfacial areas. The literature suggests albumin and stearic acid as the best proxies, and we distribute them through ecodynamic simulation. Consensus bulk distributions are obtained to control their adsorptive equilibria. We devise parameterizations for both the planar free energy and equation of state, relating excess coverage to the surface pressure and its modulus. Constant settings for the molecular surrogates are drawn from laboratory study and successfully reproduce surfactant solid-to-gas occurrence in compression experiments. Since DOC functionality measurements are rare, we group them into super-ecological province tables to verify aqueous concentration estimates. Outputs are then fed into a coverage, tension, elasticity code. The resulting two dimensional pressure contours cross a critical range for the regulation of precursor piston velocity, bubble breakage, and primary aerosol sources plus ripple damping. Concepts extend the water-air adsorption theory currently embodied in our OCEANFILMS aerosol emissions package, and the two approaches could be inserted into Earth System Models together. Uncertainties in the logic include kinetic and thermochemical factors operating at multiple scales.« less

Middle Adriatic Study of the Sea Surface Films as a Sink and Source of Trace Organics of Marine Aerosols

NASA Astrophysics Data System (ADS)

Frka Milosavljevic, S.; Cvitešić, A.; Kroflič, A.; Šala, M.; Ciglenečki, I.; Grgic, I.

2016-02-01

Properties, (trans)formation, and removal of organic particles remain the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Recently, organosulfur compounds (OS) have come into the focus of atmospheric research as significant reservoirs of S in the atmosphere, being potentially important components of gas-to-particle conversion and formation of secondary organic aerosol (SOA) especially in the oceanic region. Moreover, nitroaromatic compounds (NAC), as (methyl)nitrocatehols recently reported as potentially toxic constituents of aerosol water soluble organic matter (WSOM) and significant SOA tracers, have not been studied over marine atmosphere till now. A range of global exchange processes between the sea and the atmosphere is hindered by the sea surface microlayer (SML) generally enriched in surface active organics which form films and serve both as a sink and a source of marine OA. To better understand the role of surfactant films at the air-sea interface in global biogeochemistry as well as the sources and transport pathways of marine OA and to estimate their importance in global climate, it is necessary to study chemical composition and properties of trace organics, OS and NAC, in both the SML and marine aerosols as an integrated whole. We will present the first attempt to study marine aerosol WSOM as well as the SML collected in the Middle Adriatic with a special emphasis on its total S and OS content as well as on specific NAC. For that purpose a novel methodological approach capable of their quantification as well as determination of their surfactant nature is applied by combining liquid chromatography mass spectrometry, ion chromatography, inductively coupled plasma mass spectrometry, and electrochemistry. The obtained data are correlated with those for dissolved and particulate organic carbon, water soluble anions and cations, chlorophyll a, nutrients, and surfactants.

Ultraviolet radiation and the photobiology of earth's early oceans.

PubMed

Cockell, C S

2000-10-01

During the Archean era (3.9-2.5 Ga ago) the earth was dominated by an oceanic lithosphere. Thus, understanding how life arose and persisted in the Archean oceans constitutes a major challenge in understanding early life on earth. Using a radiative transfer model of the late Archean oceans, the photobiological environment of the photic zone and the surface microlayer is explored at the time before the formation of a significant ozone column. DNA damage rates might have been approximately three orders of magnitude higher in the surface layer of the Archean oceans than on the present-day oceans, but at 30 m depth, damage may have been similar to the surface of the present-day oceans. However at this depth the risk of being transported to surface waters in the mixed layer was high. The mixed layer may have been inhabited by a low diversity UV-resistant biota. But it could have been numerically abundant. Repair capabilities similar to Deinococcus radiodurans would be sufficient to survive in the mixed layer. Diversity may have been greater in the region below the mixed layer and above the light compensation point corresponding to today's 'deep chlorophyll maximum'. During much of the Archean the air-water interface was probably an uninhabitable extreme environment for neuston. The habitability of some regions of the photic zone is consistent with the evidence embodied in the geologic record, which suggests an oxygenated upper layer in the Archean oceans. During the early Proterozoic, as ozone concentrations increased to a column abundance above 1 x 10(17) cm-2, UV stress would have been reduced and possibly a greater diversity of organisms could have inhabited the mixed layer. However, nutrient upwelling from newly emergent continental crusts may have been more significant in increasing total planktonic abundance in the open oceans and coastal regions than photobiological factors. The phohobiological environment of the Archean oceans has implications for the potential cross-transfer of life between other water bodies of the early Solar System, possibly on early Mars or the water bodies of a wet, early Venus.

Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate variability in the North Pacific Rim

NASA Astrophysics Data System (ADS)

Pokhrel, A.; Kawamura, K.; Seki, O.; Ono, K.; Matoba, S.; Shiraiwa, T.

2015-12-01

180 m long ice core (ca. 343 years old) was drilled in the saddle of the Aurora Peak of Alaska, which is located southeast of Fairbanks (63.52°N; 146.54°W, elevation: 2,825 m). Samples were directly transported to the Institute of Low Temperature Science, Hokkaido University and have been analyzed for monoterpene- and isoprene-SOA tracers using gas chromatograph (GC; HP 6890) and mass spectrometry system (GC/MS; Agilent). Ice core collected from mountain glacier has not been explored for SOA yet. We found significantly high concentrations of these tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylrythritol), which show historical trends with good correlation with each other since 1665-2008. They show positive correlations with sugar compounds (e.g., mannitol, glucose, fructose, inositol, and sucrose), and anti-correlations with diacids (e.g., C9), w-oxocarboxylic (wC4-wC9), a-dicarbonyls and low molecular weight fatty acids (LFAs) (e.g., C18:1). LFAs show strong correlations with MSA- and nss-SO42- in the same ice core. These results suggest source regions of SOA tracers and ice core chemistry of Alaska. Concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) have increased in the ice core after the Great Pacific Climate Shift (late 1970's). They show positive correlations with a-dicarbonyls and LFAs (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the surface microlayer are recorded in the ice core. Photochemical oxidation processes for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations (e.g., North Pacific Index) and we can look at a whole range of environmental parameters in parallel with the robust reconstructed temperature changes in the Northern Hemisphere.

Diversity in UV sensitivity and recovery potential among bacterioneuston and bacterioplankton isolates.

PubMed

Santos, A L; Lopes, S; Baptista, I; Henriques, I; Gomes, N C M; Almeida, A; Correia, A; Cunha, A

2011-04-01

To assess the variability in UV-B (280-320 nm) sensitivity of selected bacterial isolates from the surface microlayer and underlying water of the Ria de Aveiro (Portugal) estuary and their ability to recover from previous UV-induced stress. Bacterial suspensions were exposed to UV-B radiation (3·3 W m⁻²). Effects on culturability and activity were assessed from colony counts and (3) H-leucine incorporation rates, respectively. Among the tested isolates, wide variability in UV-B-induced inhibition of culturability (37·4-99·3%) and activity (36·0-98·0%) was observed. Incubation of UV-B-irradiated suspensions under reactivating regimes (UV-A, 3·65 W m⁻²; photosynthetic active radiation, 40 W m⁻²; dark) also revealed diversity in the extent of recovery from UV-B stress. Trends of enhanced resistance of culturability (up to 15·0%) and enhanced recovery in activity (up to 52·0%) were observed in bacterioneuston isolates. Bacterioneuston isolates were less sensitive and recovered more rapidly from UV-B stress than bacterioplankton isolates, showing enhanced reduction in their metabolism during the irradiation period and decreased culturability during the recovery process compared to bacterioplankton. UV exposure can affect the diversity and activity of microbial communities by selecting UV-resistant strains and alter their metabolic activity towards protective strategies. © 2011 The Authors. Letters in Applied Microbiology © 2011 The Society for Applied Microbiology.

On the imprint of surfactant-driven stabilization of laboratory breaking wave foam with comparison to oceanic whitecaps

NASA Astrophysics Data System (ADS)

Callaghan, A. H.; Deane, G. B.; Stokes, M. D.

2017-08-01

Surfactants are ubiquitous in the global oceans: they help form the materially-distinct sea surface microlayer (SML) across which global ocean-atmosphere exchanges take place, and they reside on the surfaces of bubbles and whitecap foam cells prolonging their lifetime thus altering ocean albedo. Despite their importance, the occurrence, spatial distribution, and composition of surfactants within the upper ocean and the SML remains under-characterized during conditions of vigorous wave breaking when in-situ sampling methods are difficult to implement. Additionally, no quantitative framework exists to evaluate the importance of surfactant activity on ocean whitecap foam coverage estimates. Here we use individual laboratory breaking waves generated in filtered seawater and seawater with added soluble surfactant to identify the imprint of surfactant activity in whitecap foam evolution. The data show a distinct surfactant imprint in the decay phase of foam evolution. The area-time-integral of foam evolution is used to develop a time-varying stabilization function, ϕ>(t>) and a stabilization factor, Θ, which can be used to identify and quantify the extent of this surfactant imprint for individual breaking waves. The approach is then applied to wind-driven oceanic whitecaps, and the laboratory and ocean Θ distributions overlap. It is proposed that whitecap foam evolution may be used to determine the occurrence and extent of oceanic surfactant activity to complement traditional in-situ techniques and extend measurement capabilities to more severe sea states occurring at wind speeds in excess of about 10 m/s. The analysis procedure also provides a framework to assess surfactant-driven variability within and between whitecap coverage data sets.