Effects of temperature and wave conditions on chemical dispersion efficacy of heavy fuel oil in an experimental flow-through wave tank

The effectiveness of chemical dispersants (Corexit 9500 and SPC 1000) on heavy fuel oil (IFO180 as test oil) has been evaluated under different wave conditions in a flow-through wave tank. The dispersant effectiveness was determined by measuring oil concentrations and droplet size distributions. An analysis of covariance (ANCOVA) model indicated that wave type and temperature significantly (p < 0.05) affected the dynamic dispersant effectiveness (DDE). At higher temperatures (16 °C), the test IFO180 was effectively dispersed under breaking waves with a DDE of 90% and 50% for Corexit 9500 and SPC 1000, respectively. The dispersion was ineffective under breaking waves at lower temperature (10 °C), and under regular wave conditions at all temperatures (10-17 °C), with DDE < 15%. Effective chemical dispersion was associated with formation of smaller droplets (with volumetric mean diameters or VMD ? 200 μm), whereas ineffective dispersion produced large oil droplets (with VMD ? 400 μm).     

Phytoplankton viability in ballast water from international commercial ships berthed at ports in Korea

We investigated the viability of phytoplankton from ballast water of international commercial ships berthed at the ports of Ulsan and Onsan, Korea. The incubation conditions used were temperatures of 13 °C to represent ambient water and 20 °C to represent the thermal optimum, as well as nutrients in ballast water, shipside water, and F/2 medium. Phytoplankton in new (∼7 days) and old (20 and 23 days) ballast water survived when incubated under the nutrients typical of shipside water and F/2 medium at 13 °C and 20 °C. Colonization process was mostly dominated by Skeletonema costatum, Cylindrotheca closterium and pennate diatoms (<10 μm in diameter). S. costatum and C. closterium were persistent during incubation time, whereas pennate diatoms dominated in the three types of media from doubling to last phase of growth. This study showed that bloom-forming and pennate diatoms appear to be the species most likely to become successfully established in the two ports.     

The seasonal variability of the northern Benguela undercurrent and its relation to the oxygen budget on the shelf

The seasonal variations in the advection and mixing of water masses in the northern Benguela were studied in relation to the oxygen minimum zone over the Namibian shelf. The used data set consists of hydrographic and current measurements from an oceanographic mooring 20 nm off Walvis Bay, monthly CTD transects from the Namibian 23°S monitoring line and recent large-scale hydrographic surveys. The current time series showed an intermittent southward continuation of the Angola Current (AC) through the Angola–Benguela frontal zone (ABFZ) into the northern Benguela, commonly known as poleward undercurrent. In austral summer hypoxic, nutrient rich South Atlantic central water (SACW) from the Angola Gyre is transported into the northern Benguela, whereas during the winter season the oxygen rich Eastern SACW (ESACW) spreads northward. The water mass analysis reveals a mixing between both water masses in the northern Benguela between the ABFZ and the Lüderitz upwelling cell (27°S). The oxygen balance over the Namibian shelf depends to a high extent on the water mass composition of the upper central water layer, controlled by the large scale and local circulation. The deviation of the measured oxygen concentration from its mixing concentration, calculated with the source water mass properties, was used to quantify the oxygen consumption. A new local definition SACW was derived to exclude biogeochemical processes, taking place in the Angola Gyre. The oxygen deficit in the northern Benguela central water amounted to about 60–80 μmol l⁻¹ at the shelf edge and increased up to 150 μmol l⁻¹ on the shelf, due to local oxygen consumption. In the austral summer anoxic bottom waters are observed at the central Namibian shelf, which correlate to an SACW fraction >55%. Periods with high SACW fraction in the water mass composition were congruent with hydrogen sulphide events detected by remote sensing.     

Sorption of heavy oil onto Jiaozhou Bay sediment

The sorption of heavy oil onto sediment collected from Jiaozhou Bay was studied in a series of kinetic and equilibrium experiments using NaCl solutions. The effects of temperature, salinity, and pH of the medium on sorption behavior were investigated.Sorption equilibrium of the heavy oil and sediment was established within 60 min. The process was shown to follow a pseudo-second-order kinetic rate model. The sorption rate decreased with increasing initial heavy oil concentration in the solution. Batch equilibrium experiments showed that the sorption isotherm could be described by the Freundlich model. The standard free energy change and enthalpy change at the temperatures studied (283, 288, 293, and 298 K) were negative. These findings indicated that the process was spontaneous and exothermic. Salinity, pH and temperature influenced sorption performance. Sorption was favored by higher concentrations of NaCl, by lower pH values and by lower temperatures.     

Recovery of interior brackish marshes seven years after the chalk point oil spill

Seven years after the April 2000 spill of 140,000 gallons of a mixture of No. 6 and No. 2 fuel oils in the Patuxent River, Maryland, heavily oiled brackish marshes showed continuing effects. Stem density and stem height were significantly lower in oiled versus unoiled sites for Spartina alterniflora but not Spartina cynosuroides habitats. In contrast, belowground biomass was significantly lower in S. cynosuroides habitats but not S. alterniflora habitats. Total PAH concentrations were up to 453 mg/kg in surficial soils (0-10 cm) and 2921 mg/kg with depth (10-20 cm). The oil had lost 22-76% of its initial PAH content after seven years, although the oil in marsh soils has undergone little to no additional weathering since Fall 2000. Based on amphipod acute toxicity tests and sediment quality guidelines, 25% of the soils in the marsh are expected to be toxic (ESB-TU_FCV values > 3.0; P_Max > 0.65).     

Evaluating crude oil chemical dispersion efficacy in a flow-through wave tank under regular non-breaking wave and breaking wave conditions

Testing dispersant effectiveness under conditions similar to that of the open environment is required for improvements in operational procedures and the formulation of regulatory guidelines. To this end, a novel wave tank facility was fabricated to study the dispersion of crude oil under regular non-breaking and irregular breaking wave conditions. This wave tank facility was designed for operation in a flow-through mode to simulate both wave- and current-driven hydrodynamic conditions. We report here an evaluation of the effectiveness of chemical dispersants (Corexit^® EC9500A and SPC 1000^™) on two crude oils (Medium South American [MESA] and Alaska North Slope [ANS]) under two different wave conditions (regular non-breaking and plunging breaking waves) in this wave tank. The dispersant effectiveness was assessed by measuring the water column oil concentration and dispersed oil droplet size distribution. In the absence of dispersants, nearly 8-19% of the test crude oils were dispersed and diluted under regular wave and breaking wave conditions. In the presence of dispersants, about 21-36% of the crude oils were dispersed and diluted under regular waves, and 42-62% under breaking waves. Consistently, physical dispersion under regular waves produced large oil droplets (volumetric mean diameter or VMD ? 300 μm), whereas chemical dispersion under breaking waves created small droplets (VMD ? 50 μm). The data can provide useful information for developing better operational guidelines for dispersant use and improved predictive models on dispersant effectiveness in the field.     

A laboratory study on the kinetics of the formation of oil-suspended particulate matter aggregates using the NIST-1941b sediment

The formation of oil-suspended particulate matter aggregates (OSAs) results from the heteroaggregation between dispersed oil droplets and suspended particulate matter present in coastal waters. This process has been recognized by the oil spill remediation community to enhance natural cleansing of oiled shorelines and oil dispersion in the water column. While several studies have been conducted on the formation and characteristics of OSAs, few studies have addressed the kinetics of OSA formation. Operationally, this has left decision-makers lacking information on the time scale of this process and its significance to oil dispersion in real spills. A laboratory study was conducted to investigate the kinetics of OSA formation as a function of mixing energy and the sediment-to-oil ratio using the standard reference material 1941b. Results showed that formation of OSAs increased exponentially with the mixing time and reached a maximum within 4 h. When the shaking rate increased from 2.0 to 2.3 Hz, the maximum oil trapping efficiency increased from 20% to 42% and the required shaking time decreased from 3.7 to 0.7 h.     

Detoxification of hazardous dust with marine sediment

Hazardous electric arc furnace dust containing dioxins/furans and heavy metals is blended with harbor sediment, fired at 950–1100 °C to prepare lightweight aggregates. Dust addition can lower the sintering temperature by about 100 °C, as compared to a typical industrial process. After firing at 950 °C and 1050 °C, more than 99.85% of dioxins/furans originally present in the dust have been removed and/or destructed in the mix containing a dust/sediment ratio of 50:100. The heavy metals leached from all fired mixes are far below Taiwan EPA legal limits. The particle density of the lightweight aggregates always decreases with increasing firing temperature. Greater addition of the dust results in a considerably lower particle density (mostly <2.0 g cm⁻³) fired at 1050 °C and 1100 °C. However, firing at temperatures lower than 1050 °C produces no successful bloating, leading to a denser particle density (>2.0 g cm⁻³) that is typical of bricks.     

Lab tests on the biodegradation of chemically dispersed oil should consider the rapid dilution that occurs at sea

Most crude oils spread on open water to an average thickness as low as 0.1 mm. The application of dispersants enhances the transport of oil as small droplets into the water column, and when combined with the turbulence of 1 m waves will quickly entrain oil into the top 1 m of the water column, where it rapidly dilutes to concentrations less than 100 ppm. In less than 24 h, the dispersed oil is expected to mix into the top 10 m of the water column and be diluted to concentrations well below 10 ppm, with dilution continuing as time proceeds. Over the multiple weeks that biodegradation takes place, dispersed oil concentrations are expected to be below 1 ppm. Measurements from spills and wave basin studies support these calculations. Published laboratory studies focused on the quantification of contaminant biodegradation rates have used concentrations orders of magnitude greater than this, as it was necessary to ensure the concentrations of hydrocarbons and other chemicals were higher than the detection limits of chemical analysis. However, current analytical methods can quantify individual alkanes and PAHs (and their alkyl homologues) at ppb and ppm levels. To simulate marine biodegradation of dispersed oil at dilute concentrations commonly encountered in the field, laboratory studies should be conducted at similarly low hydrocarbon concentrations.     

The magmatic feeding system of El Reventador volcano (Sub-Andean zone,Ecuador) constrained by texture,mineralogy and thermobarometry of the 2002 erupted products

After a 26 years long quiescence El Reventador, an active volcano of the rear-arc zone of Ecuador, entered a new eruptive cycle which lasted from 3 November to mid December 2002. The initial sub-Plinian activity (VEI 4 with andesite pyroclastic falls and flows) shifted on 6 and 21 November to an effusive stage characterized by the emission of two lava flows (andesite to low-silica andesite Lava-1 and basaltic andesite Lava-2) containing abundant gabbro cumulates. The erupted products are medium to high-K calc-alkaline and were investigated with respect to major element oxides, mineral chemistry, texture and thermobarometry. Inferred pre-eruptive magmatic processes are dominated by the intrusion of a high-T mafic magma (possibly up to 1165 ± 15 °C) into an andesite reservoir, acting as magma mixing and trigger for the eruption. Before this refilling, the andesite magma chamber was characterized by water content of 5.3 ± 1.0%, high oxygen fugacity (> NNO + 2) and temperatures, in the upper and lower part of the reservoir, of 850 and 952 ± 65 °C respectively. Accurate amphibole-based barometry constrains the magma chamber depth between 8.2 and 11.3 km (± 2.2 km). The 6 October 2002 seismic swarm (hypocenters from 10 to 11 km) preceding El Reventador eruption, supports the intrusion of magmas at these depths. The widespread occurrence of disequilibrium features in most of the andesites (e.g. complex mineral zoning and phase overgrowths) indicates that convective self-mixing have been operating together with fractional crystallization (inferred from the cognate gabbro cumulates) before the injection of the basic magma which then gave rise to basaltic andesite and low-silica andesite hybrid layers. Magma mixing in the shallow chamber is inferred from the anomalous SiO₂–Al₂O₃ whole-rock pattern and strong olivine disequilibria. Both lavas show three types of amphibole breakdown rims mainly due to heating (mixing processes) and/or relatively slow syn-eruptive ascent rate (decompression) of the magmas. The lack of any disequilibrium textures in the pumices of the 3 November fall deposit suggest that pre-eruptive mixing did not occur in the roof zone of the chamber. A model of the subvolcanic feeding system of El Reventador, consistent with the intrusion of a low-Al₂O₃ crystal-rich basic magma into an already self-mixed andesite shallow reservoir, is here proposed. It is also inferred that before entering the shallow chamber the “basaltic” magma underwent a polybaric crystallization at deeper crustal levels.     

Effects of alumina refinery wastewater and signature metal constituents at the upper thermal tolerance of: 1. The tropical diatom Nitzschia closterium

Ecotoxicological studies, using the tropical marine diatom, Nitzschia closterium (72-h growth rate), were undertaken to assess potential issues relating to the discharge from an alumina refinery in northern Australia. The studies assessed: (i) the species’ upper thermal tolerance; (ii) the effects of three signature metals, aluminium (Al), vanadium (V) and gallium (Ga) (at 32 °C); and (iii) the effects of wastewater (at 27 and 32 °C). The critical thermal maximum and median inhibition temperature for N. closterium were 32.7 °C and 33.1 °C, respectively. Single metal toxicity tests found that N. closterium was more sensitive to Al compared to Ga and V, with IC₅₀s (95% confidence limits) of 190 (140-280), 19,640 (11,600-25,200) and 42,000 (32,770-56,000) μg L⁻¹, respectively. The undiluted wastewater samples were of low toxicity to N. closterium (IC₅₀s > 100% wastewater). Environmental chemistry data suggested that the key metals and discharge are a very low risk to this species.     

Nitrogen and carbon cycling in the North Sea and exchange with the North Atlantic—A model study. Part I. Nitrogen budget and fluxes

The three-dimensional biogeochemical model ECOHAM was applied to the Northwest European Shelf (47°41′–63°53′N, 15°5′W–13°55′E) for the years 1993–1996. Nitrogen budgets were calculated for the years 1995 and 1996 for the inner shelf region, the North Sea (511,725 km²). Simulated temperatures as well as nitrate, oxygen, and chlorophyll concentrations are compared with observations.     

Effects of alumina refinery wastewater and signature metal constituents at the upper thermal tolerance of: 2. The early life stages of the coral Acropora tenuis

The success of early life history transitions of the coral Acropora tenuis were used as endpoints to evaluate thermal stress and the effects of wastewater discharged to a tropical marine environment. The studies assessed the effects of: (i) temperature; (ii) three signature metals of the wastewater, aluminium (Al), vanadium (V) and gallium (Ga); and (iii) the wastewater (at 27 °C and 32 °C) on fertilisation and larval metamorphosis. The median inhibition temperatures for fertilisation and metamorphosis were 32.8 °C and 33.0 °C, respectively. Fertilisation IC₅₀s for Al, V and Ga were 2997, 2884 and 3430 μg L⁻¹, respectively. Metamorphosis IC₅₀s for Al, V and Ga were 1945, 675 and 3566 μg L⁻¹, respectively. The wastewater only affected fertilisation and metamorphosis at moderate concentrations (IC₅₀s = 63% and 67%, v/v, respectively, at 27 °C), posing a low risk to this species in the field. The effects of wastewater and temperature on fertilisation and metamorphosis were additive.     

Isolation and characterization of a novel hydrocarbon-degrading bacterium Achromobacter sp. HZ01 from the crude oil-contaminated seawater at the Daya Bay,southern China

Microorganisms play an important role in the biodegradation of petroleum contaminants, which have attracted great concern due to their persistent toxicity and difficult biodegradation. In this paper, a novel hydrocarbon-degrading bacterium HZ01 was isolated from the crude oil-contaminated seawater at the Daya Bay, South China Sea, and identified as Achromobacter sp. Under the conditions of pH 7.0, NaCl 3% (w/v), temperature 28 °C and rotary speed 150 rpm, its degradability of the total n-alkanes reached up to 96.6% after 10 days of incubation for the evaporated diesel oil. Furthermore, Achromobacter sp. HZ01 could effectively utilize polycyclic aromatic hydrocarbons (PAHs) as its sole carbon source, and could remove anthracene, phenanthrene and pyrence about 29.8%, 50.6% and 38.4% respectively after 30 days of incubation. Therefore, Achromobacter sp. HZ01 may employed as an excellent degrader to develop one cost-effective and eco-friendly method for the bioremediation of marine environments polluted by crude oil.     

Frequency dependence of elastic wave speeds at high temperature: a direct experimental demonstration

At sufficiently high temperatures and/or long periods, the elastic behaviour of crystalline material gives way progressively to viscoelastic behaviour associated with the stress-induced migration of crystal defects. This transition is marked by the onset of appreciable strain energy dissipation accompanied by frequency dependence (dispersion) of the shear modulus and elastic wave speeds. Ultrasonic interferometry and torsional forced-oscillation techniques can be used to probe the low-amplitude stress-strain behaviour of fine-grained polycrystalline material in two very different frequency ranges, respectively 10-100 MHz and 1 mHz-1 Hz. Here we demonstrate and apply these two complementary methods in a study of the high-temperature mechanical behaviour of a fine-grained synthetic olivine polycrystal. At the high frequencies of ultrasonic interferometry, the shear wave speed varies linearly with temperature between room temperature and the highest experimentally accessible temperature (1300 °C) in close accord with expectations based on similarly high-frequency studies of the elastic behaviour of single-crystal olivine. However, at teleseismic frequencies (<1 Hz) and temperatures >900 °C, the shear wave speed becomes much more strongly temperature-sensitive reflecting markedly viscoelastic behaviour. Newly emerging laboratory-derived constraints on this viscoelastic enhancement of the temperature sensitivity of seismic wave speeds and its grain-size dependence will provide a more robust interpretation of seismological models for the variation of wave speeds and attenuation within the Earth's interior.     

Satellite observation of Brazil Current inshore thermal front in the SW South Atlantic: Space/time variability and sea surface temperatures

A data set of 199 sea surface temperature maps derived from the Advanced Very High Resolution Radiometer for the period 2000–2002 was processed to derive the position of the surface inshore thermal front of the Brazil Current (BCIF) in the SE Brazilian coastal and oceanic area. After the derivation of the position of the BC front for each image, the ensemble of digital frontal vectors was processed using the algorithm of frontal density (FD). For each 5′×5′ cell in the domain the calculated FD provided an index expressing the presence and persistence of the front in the area or the probability of finding the front in the region. In the paper we present the results of the FD analysis to get a better view of the space and time variability of the BC front in the region. The highest values of FD were in general observed close to or at the shelf break zone (between 200 and 1000 m isobaths). From 20°S to 23°S there is a tendency of BCIF to be positioned over the outer shelf, inshore of the 200 m isobaths. SE of Cape Sao Tome and S of Cape Frio it was observed a bimodal spatial distribution of highest FD caused by the presence of two semi-permanent frontal eddies. After moving offshore near Cape Frio, the BCIF tends to return to the shelf break zone south of 24°S probably due to a potential vorticity conservation mechanism. The position of the highest FD values calculated for different seasons confirms previous studies in that BCIF is closer to the coast during the summer and furthest offshore in the winter. Statistical analysis of the SST data gave for the BCIF an average SST gradient of 0.31°C km⁻¹ with a standard deviation of 0.15°C km⁻¹. A mean frontal width of 6 km was inferred from the average SST gradient and typical temperatures near the front at both sides, at outer shelf and in the BC itself. A Weibull probability density function can be fitted to describe the BCIF SST gradients with scale factor c=0.3460°C km⁻¹ and shape factor k=2.1737. The BCIF SST gradient showed a seasonal variability with the smallest gradients in summer (~0.24 °C km⁻¹) and the highest in autumn (~0.33 °C km⁻¹). Using a three harmonic Fourier fit for the SST field near the BCIF, at the outer shelf and at interior of BC, it was possible to derive an analytical model for the time variability of the SST gradient of BCIF.     

A high-resolution satellite-derived sea surface temperature climatology for the western North Atlantic Ocean

Long-term and high-resolution (∼1.2 km) satellite-derived sea surface temperature (SST) fields of a monthly mean time series for the 1985–1999 period, and a daily climatology have been calculated for the North West Atlantic Ocean. The SST fields extend from 78°W to 41°W in longitude, and 30°N to 56°N in latitude, encompassing the region off Cape Hatteras, North Carolina, to the southern Labrador Sea. The monthly mean time series, consists of 180 cloud-masked monthly mean SST fields, derived from a full-resolution NOAA/NASA Pathfinder SST data set for the 1985–1999 period. The satellite-derived monthly mean SST fields, as compared with in situ monthly mean near-surface ocean temperatures from buoys located in the western North Atlantic, yield an overall RMS difference of 1.15 °C. The daily climatology, which consists of 365 fields, was derived by applying a least-squares harmonic regression technique on the monthly mean SST time series for the full study period. The monthly mean and daily climatological SST fields will be useful for studying inter-annual variability related to climate variability of SST over the study domain.     

A continental shelf scale examination of the Leeuwin Current off Western Australia during the austral autumn-winter

A continental shelf scale survey from 22°S to 34°S along the Western Australia coast provides the first detailed synoptic examination of the structure, circulation and modification of the southward flowing Leeuwin Current (LC) during the late austral autumn-early winter (May-June 2007). At lower latitudes (22°S-25°S), the LC was masked within a broad expanse of warm ambient surface water, which extended across the shelf and offshore before becoming constrained at the shelf break and attaining its maximum velocity of ∼1.0 m s⁻¹ at 28°S. The temperature and salinity signature of the LC experienced substantial modification as it flowed poleward; surface temperature of the LC decreased by ∼5.25 °C while surface salinity increased by ∼0.72, consistent with climatology estimates and smaller (larger) for temperature (salinity) than those found during summer. Subsequently, LC water was denser by ∼2σ_T in the south compared to the north, and the surface mixed layer of the LC revealed only a small deepening trend along its poleward trajectory. Modification of the LC resulted from a combination of mixing due to geostrophic inflow and entrainment of cooler, more saline surrounding subtropical waters, and convective mixing driven by large heat loss to the atmosphere. Air-sea heat fluxes accounted for 50% of the heat lost from the LC in the south, whilst only accounting for 25% in the north, where large geostrophic inflow occurred and the LC displayed its maximum flow. The onshore transport was characterised by distinct jet-like structures, enhanced in the upper 200 m of the water column, and the presence of eddies in the vicinity of the shelf break generated offshore transport.     

The Luingo caldera: The south-easternmost collapse caldera in the Altiplano–Puna plateau,NW Argentina

This article identifies the Pucarilla–Cerro Tipillas Volcanic Complex and its major eruptive source, the Luingo caldera (26° 10′S–66° 40′W). Detailed geological mapping, stratigraphic sections, facies analysis and correlations, including the identification of typical caldera components, allow us to infer the position of a collapse caldera, elongated at N65° and with a diameter of 19 km × 13 km, which is responsible for an eruption of 135 km³ (DRE) of magma. The high-crystal contents of the associated ignimbrites, combined with its tectonic setting, indicate that regional and local tectonic structures played a crucial role in the formation of the caldera.     

Oil viscosity limitation on dispersibility of crude oil under simulated at-sea conditions in a large wave tank

This study determined the limiting oil viscosity for chemical dispersion of oil spills under simulated sea conditions in the large outdoor wave tank at the US National Oil Spill Response Test Facility in New Jersey. Dispersant effectiveness tests were completed using crude oils with viscosities ranging from 67 to 40,100 cP at test temperature. Tests produced an effectiveness-viscosity curve with three phases when oil was treated with Corexit 9500 at a dispersant-to-oil ratio of 1:20. The oil viscosity that limited chemical dispersion under simulated at-sea conditions was in the range of 18,690 cP to 33,400 cP. Visual observations and measurements of oil concentrations and droplet size distributions in the water under treated and control slicks correlated well with direct measurements of effectiveness. The dispersant effectiveness versus oil viscosity relationship under simulated at sea conditions at Ohmsett was most similar to those from similar tests made using the Institut Francais du Pétrole and Exxon Dispersant Effectiveness (EXDET) test methods.