The sea-surface microlayer of puget sound: Part I. Toxic effects on fish eggs and larvae

The sea surface is an important habitat for the developmental stages (eggs and larvae) of many fish and invertebrates; it is also a concentration point for anthropogenic contaminants entering the sea. Studies were conducted to determine the extent to which the sea surface of Puget Sound was toxic to the early life history stages of fish. Three urban bays with suspected contamination, a rural reference bay, and a Central Sound site were compared. Surface-dwelling eggs and organisms (zooneuston) were collected with a surface-skimming neuston net and their densities enumerated. Sand sole (Psettichthys melanostictus) embryos were exposed in the field and laboratory to the sea-surface microlayer. To develop a useful year-round approach to monitoring sea-surface toxicity, larval development of anchovies, kelp bass, and sea urchins was also evaluated as an indication of sea-surface microlayer toxicity.During the spawning season (February and March), urban boys in Puget Sound had lower concentrations of sand sole eggs and neustonic organisms on the sea surface than did the rural bayor Central Sound reference sites. Compared to the reference sites, laboratory exposure to surface microlayer samples collected from urban bay sites generally resulted in more chromsomal aberrations in developing sole embryos, reduced hatching success of sole larvae, and reduced growth in trout cell cultures. In situ hatching success of sole eggs was reduced by half or more in urban bays compared to reference sites.Toxicity was associated with visible surface slicks and, in urban bays, increased with increasing surface pressure (dynes cm⁻¹). Results to be reported separately (Part II) indicate that toxicity is strongly correlated with the presence of high concentrations of polycyclic aromatic hydrocarbons and metals in the sea-surface microlayer. The toxicity of SMIC samples was similar when evaluated by sole, anchovy, kelp bass, or sea urchin tests. A sea-surface monitoring program could use sea urchin embryos to evaluate site-specific sea-surface toxicity throughout the year.     

Contaminant concentrations and toxicity of sea-surface microlayer near Los Angeles, California

Sea-surface microlayer samples were collected from six nearshore areas receiving different amounts of anthropogenic inputs. The samples were analyzed for selected trace metals, chlorinated hydrocarbons, and polycyclic aromatic hydrocarbons. The relative toxicities of the samples were determined with fish embryo bioassays.Contaminant concentrations generally increased from offshore to the inshore stations. Contaminant concentrations were several orders of magnitude higher in microlayer samples from the highly industrialized Los Angeles and Long Beach harbors compared to samples from a site 15km offshore. Microlayer samples from the inshore stations were significantly more toxic, and induced significantly more developmental abnormalities and chromosome aberrations, than samples from the offshore stations.     

Toxicity of sea-surface microlayer: Effects on herring and turbot embryos

Marine fish eggs, from herring (Clupea harengus) and turbot (Psetta maxima), were used to test the effects of the sea-surface microlayer on embryonic development. The eggs were exposed in static systems to full strength microlayer and 1,10,50% dilutions. Depending on the sampling site (Helgoland harbour, Kiel Förde, Travemünde marina, Elbe Hamburg Port) and time, microlayer contained varying amounts of Zn, Cd, Cu, Ni, Fe, Pb and Co, in concentrations 100 times above those found in subsurface bulk water. Chlorinated hydrocarbon pesticides were not found at concentrations elevated above bulk water, but considerable amounts of petroleum hydrocarbons and phthalate esters were detected. Microlayer displayed differential concentration-dependent toxicity for each species used in the experiments. Effects on hatching time as well as total hatch (%) and number of abnormal larvae were recorded. Herring eggs were most affected by Helgoland microlayer (suspected effect of high metal content) while turbot eggs were most sensitive to Travemünde and Elbe microlayer (suspected effect of high petroleum hydrocarbons). The usefulness of microlayer studies as a tool for environmental assessment is discussed. An impact of microlayer effects on recruitment in sensitive species is deemed possible.     

大亚湾微表层和次表层海水营养盐的研究

根据1998年秋季（10、11月）、1999年春、秋季（4、5、10月）5个航次对大亚湾海区微、次表层的调查结果，分析了微表层海水对氮、磷、硅营养盐的富集概况，讨论了营养盐与环境因子的关系。结果表明：大亚湾海区微表层海水对氮、磷、硅营养盐均有富集作用，因海况及季节不同，富集因数（EF）与其他海区的有所差别；无论夏季或秋季，大亚湾海区微表层海水中无机氮都以NH4－N为主要存在形态；其余水层则以NO3－N为主要存在形态。结果还表明，微表层、次表层海水中NH4－N与BOD5、COD测值都呈高度显著正相关，与PO4－P和SiO3-Si含量均无相关，说明大亚湾海区水中含氮有机物较含磷有机物丰富。     

Enrichment of organochlorine contaminants in the sea surface microlayer: An organic carbon-driven process

Over 50 seawater samples from two different sites—Barcelona (Spain) and Banyuls-sur-Mer (France)—were analyzed in order to study the extent and postulate the processes driving the enrichment of hydrophobic organic pollutants in the sea surface microlayer (SML). A number of individual polychlorinated biphenyl (PCB) congeners (41) were measured to study their partitioning between the particulate (fraction > 0.7 μm) and the dissolved + colloidal phases (fraction < 0.7 μm), with the latter being differentiated into estimated dissolved and colloidal phases. In addition, several organochlorine pesticides were also measured, namely, HCB, α-HCH, γ-HCH, 4,4′-DDE, 4,4′-DDD and 4,4′-DDT. The presence of PCB congener profiles found in the SML suggests a dynamic coupling with the atmosphere in Banyuls sampling site, whereas offshore Barcelona the presence of highly chlorinated congeners was due to persistent sediment resuspension. The average PCB concentration in the SML dissolved + colloidal phase were higher in Banyuls (7.8 ng L^{− 1}) than in Barcelona (3.6 ng L^{− 1}) samples, but in the particulate phase concentrations were higher in Barcelona (3.2 ng L^{− 1}) to that of Banyuls (1.4 ng L^{− 1}). However, PCB concentrations in the SML generally also showed large variability. Enrichment factors of PCBs and other organochlorine compounds in the SML with respect to the underlying water column ranged from 0.2 to 7.4. This may be explained for both the dissolved + colloidal and particulate phases by the enrichment in the SML of organic carbon (OC) as discerned from particle–water and colloid–water partitioning.     

Distribution of silver, mercury, lead, copper and cadmium in central puget sound sediments

Distributions of five of the more toxic heavy metals have been assessed for Puget Sound sediments. Twenty-one Kasten cores were collected for the study. Analysis by Zeeman-corrected graphite-furnace atomic absorption spectroscopy has made possible the accurate and precise determination of silver and cadmium in Puget Sound sediment cores for the first time. Data show that Puget Sound is moderately impacted by anthropogenic Ag, Hg, Pb and Cu. No enrichment of Cd was found. The study also indicates that Puget Sound is quite well mixed with respect to the residence time of particle-bound metals. Toxic metal accumulation sites in the central Sound are determined almost exclusively by grain size, rather than proximity to sources. Estimates are made of trace metal fluxes to the sediments as a function of sediment type and areal distribution.     

Municipal wastewater contamination in the Southern California Bight. Part II. Cytosolic distribution of contaminants and biochemical effects in fish livers

The objective of this study was to examine the cytosolic distribution of metals and oxygenated organic metabolites (MTBs), and biochemical effects, in livers of fish collected from both highly contaminated and less contaminated southern California coastal sites. Cytosolic extracts were separated by Sephadex G-75 column chromatography into high molecular weight (> 20 000 daltons) enzyme-containing (ENZ) pools, medium molecular weight (3000–20000 daltons) metallothionein- or metallothionein-like-containing (MT) pools, and low molecular weight (< 3000 daltons) glutathione-containing (GSH) pools.Concentrations of Cd, Cu and Zn were frequently lower in cytosolic pools of longspine combfish, yellowchin sculpin, and California tonguefish from highly contaminated Palos Verdes (PV) relative to those from less contaminated Santa Monica Bay (SMB) despite much higher concentrations of these metals in sediments at PV. Patterns of cytosolic metal distribution differed more between metals than between species or sampling locations. Most Cd, Cu and Zn occurred in the MT pools of these three species, with the exception of Zn in California tonguefish which occurred predominately in the ENZ pool. In all three species, ENZ-Cu showed positive slopes when regressed against total cytosolic Cu, while ENZ-Cd showed no significant slopes when regressed against total cytosolic Cd. Patterns for Zn were the least consistent among species, with higher ENZ-Zn slopes occurring in fish livers with lower cytosolic Zn concentrations.The largest portion of DDT and PCB oxygenated MTBs occurred in GSH pools of scorpionfish livers from PV or less contaminated Cortes Bank (CB). Concentrations of MTBs in ENZ- and MT-pools of CB scorpionfish livers showed positive slopes when regressed against total cytosolic- and GSH-MTBs.Positive slopes for regressions of ENZ-Cu, -Zn and -MTBs against total cytosolic concentrations are consistent with the model of an equilibrium-dependent exchange of these among cytosolic pools.The lower metal concentrations, higher glutathione concentrations, and higher catalase activities found in fish from PV relative to those from SMB are in accordance with effects known to result from exposure to organic contaminants.     

Seasonal variations of dimethylsul.de (DMS) and dimethylsulfoniopropionate (DMSP) in the sea-surface microlayer and subsurface water of Jiaozhou Bay and its adjacent area

The distributions of DMS and its precursor dimethylsulfoniopropionate, in both dissolved (DMSPd) and particulate fractions (DMSPp) were determined in the sea-surface microlayer and corresponding subsurface water of the Jiaozhou Bay, China and its adjacent area in May and August 2006. The concentrations of all these components showed a clear seasonal variation, with higher concentrations occurring in summer. This can be mainly attributed to the higher phytoplankton biomass observed in summer. Simultaneously, the enrichment extents of DMSPd and DMSPp in the microlayer also exhibited seasonal changes, with higher values in spring and lower ones in summer. Higher water temperature and stronger radiant intensity in summer can enhance their solubility and photochemical reaction in the microlayer water, reducing their enrichment factors (the ratio of concentration in the microlayer to that in the corresponding subsurface water). A statistically signi.cant relationship was found between the microlayer and subsurface water concentrations of DMS, DMSP and chlorophyll a, demonstrating that the biogenic materials in the microlayer come primarily from the underlying water. Moreover, our data show that the concentrations of DMSPp and DMS were signi.cantly correlated with the levels of chlorophyll a, indicating that phytoplankton biomass might play an important role in controlling the distributions of biogenic sulfurs in the study area. The ratios of DMS/chlorophyll a and DMSPp/chlorophyll a varied little from spring to summer, suggesting that there was no obvious change in the proportion of DMSP producers in the phytoplankton community. The mean sea-to-air .ux of DMS from the study area was estimated to be 5.70 μmol/(m2 ·d), which highlights the e.ects of human impacts on DMS emission.     

Chemical properties of colored dissolved organic matter in the sea-surface microlayer and subsurface water of Jiaozhou Bay, China in autumn and winter

The distribution and chemical properties of chromophoric dissolved organic matter (CDOM) in the Jiaozhou Bay, China were examined during four cruises in 2010-2011. The influence of freshwater and industrial and municipal sewage along the eastern coast of the bay was clearly evident as CDOM levels (defined as a 305 ), and dissolved organic carbon (DOC) concentrations were well correlated with salinity during all the cruises. Moreover, DOC concentrations were significantly correlated with chlorophyll a concentrations in the surface microlayer as well as in the subsurface water. The concentrations of DOC and CDOM displayed a gradually decreasing trend from the northwestern and eastern coast to the central bay, and the values and gradients of their concentrations on the eastern coast were generally higher than those on the western coast. In addition, CDOM and DOC levels were generally higher in the surface microlayer than in the subsurface water. In comparison with DOC, CDOM exhibited a greater extent of enrichment in the microlayer in each cruise, with average enrichment factor (E F ) values of 1.38 and 1.84, respectively. Four fluorescent components were identified from the surface microlayer and subsurface water samples and could be distinguished as peak A, peak T, peak B and peak M. For all the cruises, peak A levels were higher in the surface microlayer than in the subsurface water. This pattern of variation might be attributed to the terrestrial input.     

The sea surface microlayer: Biology, chemistry and anthropogenic enrichment

Recent studies increasingly point to the interface between the world's atmosphere and hydrosphere (the sea-surface microlayer) as an important biological habitat and a collection point for anthropogenic materials. Newly developed sampling techniques collect different qualitative and quantitative fractions of the upper sea surface from depths of less than one micron to several centimeters.The microlayer provides a habitat for a biota, including the larvae of many commercial fishery species, which are often highly enriched in density compared to subsurface water only a few cm below. Common enrichments for bacterioneuston, phytoneuston, and zooneuston are 10²−10⁴, 1−10², and 1−10, respectively. The trophic relationships or integrated functioning of these neustonic communities have not been examined.Surface tension forces provide a physically stable microlayer, but one which is subjected to greater environmental and climatic variation than the water column. A number of poorly understood physical processes control the movement and flux of materials within and through the microlayer. The microlayer is generally coated with a natural organic film of lipid and fatty acid material overlying a polysaccharide protein complex.The microlayer serves as both a source and a sink for materials in the atmosphere and the water column. Among these materials are large quantities of anthropogenic substances which frequently occur at concentrations 10²−10⁴ greater than these in the water column. These include plastics, tar lumps, polyaromatic hydrocarbons, chlorrinated hydrocarbons, and potentially toxic metals, such as, lead, copper, zinc, and nickel. How the unique processes occurring in the microlayer affect the fate of anthropogenic substances is not yet clear. Many important questions remain to be examined.     

Toxicity of sea-surface microlayer: Effects of hexane extract on baltic herring (Clupea harengus) and atlantic cod (Gadus morhua) embryos

This study was designed to determine whether contaminated sea-surface microlayer was toxic to marine fish embryos in its ntaive form and as a hexane extract. Developing embryos of Atlantic cod (Gadus morhua) and Baltic herring (Clupea harengus) were exposed to hexane extracts of sea-surface microlayer collected from five locations in the North Sea and Baltic Sea. Extracts from two of these locations produced significant embryos mortality as well as severe deformities in live hatched larvae. A control sample of bulk water collected from 20 cm under the surface and extracted in the same way produced no significant mortality or deformities. Significaant changes in timing of hatching were also observed in those samples which produced embryo toxic effects. A comparison of these data with those obtained from code embryos exposed to unextracted microlayer showed a similar biological effect with both unextracted samples and hexane extracts.Chemical analyses revealed the greatest biological effect in samples with petroleum hydrocarbon concentrations between 180 and > 200 μg liter⁻¹. The bulk water control had 1 μg liter⁻¹ while the three samples that showed no biological activity had 3 to 8 μg liter⁻¹ petroleum hydrocarbons. Phthalic acid esters were detected in four samples and chlorinated hydrocarbons in one, but could not be positively correlated with any of the toxic responses. No other chemical contaminants were detected in the five samples.The data presented here show that some sites contain sea-surface microlayer which can be toxic to marine fish embryos: that Baltic herring and Atlantic cod embryos respond similarly to the toxic effects of contaminated microlayer: and that unextracted microlayer and hexane extract of microlayer produce essentially the same toxic effect(s) if only organic contaminants are considered.     

The mesoscale variability in the Caribbean Sea. Part II: Energy sources

The processes which drive the production and the growth of the strong mesoscale eddy field in the Caribbean Sea are examined using a general circulation model. Diagnostics of the simulations suggest that:(1) The mean currents in the Caribbean Sea are intrinsically unstable. The nature of the instability and its strength vary spatially due to strong differences of current structure among basins.(2) The greatest and most energetic eddies of the Caribbean Sea originate in the Venezuela Basin by mixed barotropic-baroclinic instability of an intense jet, formed with waters mostly from the surface return flow of the Meridional Overturning Circulation and the North Equatorial Current which converge and accelerate through the Grenada Passage. The vertical shear of this inflow is enhanced by an eastward undercurrent, which flows along the south American Coast between 100 and 250 m depth. The shallow eddies (less than 200 m depth) formed in the vicinity of the Grenada Passage get rapidly deeper (down to 1000 m depth) and stronger by their interaction with the deep interior flow of the Subtropical Gyre, which enters through passages north of St. Lucia. These main eastern Caribbean inflows merge and form the southern Caribbean Current, whose baroclinic instability is responsible for the westward growth and strengthening of these eddies from the Venezuela to the Colombia Basin.(3) Eddies of lesser strength are produced in other regions of the Caribbean Sea. Their generation and growth is also linked with instability of the local currents. First, cyclones are formed in the cyclonic shear of the northern Caribbean Current, but appear to be rapidly dissipated or absorbed by the large anticyclones coming from the southern Caribbean. Second, eddies in the Cayman Sea, which impact the Yucatan region, are locally produced and enhanced by barotropic instability of the deep Cayman Current.(4) The role of the North Brazil Current (NBC) rings is mostly to act as a finite perturbation for the instability of the mean flow. Their presence near the Lesser Antilles is ubiquitous and they appear to be linked with most of the Caribbean eddies. There are some evidences that the frequency at which they form near the Grenada Passage is influenced by the frequency at which the NBC rings impinge the Lesser Antilles. But large Caribbean eddies also form without a close influence of any ring, and comparison between simulations shows that mean eddy kinetic energy and eddy population in the Caribbean Sea are not substantially different in absence or presence of NBC rings: their presence is not a necessary condition for the generation and growth of the Caribbean eddies.     

Seasonal variations of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in the sea-surface microlayer and subsurface water of Jiaozhou Bay and its adjacent area

The distributions of DMS and its precursor dimethylsulfoniopropionate, in both dissolved (DMSP_d) and particulate fractions (DMSP_p) were determined in the seasurface microlayer and corresponding subsurface water of the Jiaozhou Bay, China and its adjacent area in May and August 2006. The concentrations of all these components showed a clear seasonal variation, with higher concentrations occurring in summer. This can be mainly attributed to the higher phytoplankton biomass observed in summer. Simultaneously, the enrichment extents of DMSP_d and DMSP_p in the microlayer also exhibited seasonal changes, with higher values in spring and lower ones in summer. Higher water temperature and stronger radiant intensity in summer can enhance their solubility and photochemical reaction in the microlayer water, reducing their enrichment factors (the ratio of concentration in the microlayer to that in the corresponding subsurface water). A statistically significant relationship was found between the microlayer and subsurface water concentrations of DMS, DMSP and chlorophyll a, demonstrating that the biogenic materials in the microlayer come primarily from the underlying water. Moreover, our data show that the concentrations of DMSP_p and DMS were significantly correlated with the levels of chlorophyll a, indicating that phytoplankton biomass might play an important role in controlling the distributions of biogenic sulfurs in the study area. The ratios of DMS/chlorophyll a and DMSP_p/chlorophyll a varied little from spring to summer, suggesting that there was no obvious change in the proportion of DMSP producers in the phytoplankton community. The mean sea-to-air flux of DMS from the study area was estimated to be 5.70 μmol/(m²·d), which highlights the effects of human impacts on DMS emission.     

Diffusion of seawater ions. Part II. The role of activity coefficients and ion pairing

A theoretical evaluation of basic thermodynamic relationships reveals that variation of activity coefficients, ion pairing and electrical interactions must be considered when modelling ionic diffusion in seawater. The contributions of ion-pair formation and change in activity coefficient along the diffusion path were studied experimentally by conducting diffusion experiments in which solutions of KCl, NaCl, MgCl₂, Li₂SO₄, K₂SO₄, Na₂SO₄ and MgSO₄, at an ionic strength of 0.7, were allowed to diffuse into distilled water. The study reveals that the thermodynamic factor, required to correct for changes in the activity coefficient along the diffusion path, is significant for all the salts studied. Agreement between a simple diffusion model, which does not include ion pairing, and observed data was good for completely dissociated salts, but poor for salts which are known to form ion pairs at the concentration levels studied. The diffusion of MgSO₄, 0.425 of which is associated at I = 0.7, was successfully modelled by assuming that the diffusion coefficient of the MgSO₄⁰ ion pair is different from the diffusion coefficient of the dissociated salt. The diffusion coefficient of this ion pair is estimated to be 1.9 × 10⁻⁵ cm² s⁻¹ at 30°C, as compared to 0.49 × 10⁻⁵ cm² s⁻¹ for the dissociated salt. It is suggested that the high mobility of this ion pair could cause magnesium enrichment in pore water of sulfate depleted sediments.     

Hydrodynamics of an oscillating water column seawater pump. Part II: tuning to monochromatic waves

Flume experiments with a scale-model of a wave driven seawater pump in monochromatic waves are described. A tuning mechanism optimises the pump performance by keeping it at resonance with the waves. The pumping process itself was found to de-tune the system because of the reduced gravity restoring force due to spilling in the compression chamber. A perturbation analysis of the pump equations shows that performance of the system can be increased by optimising the shape of the pump intake to minimise losses due to vortex formation. An algorithm is derived, using a numerical model of the pump, which accurately determines the required volume of air in the compression chamber to induce resonance given variations in the wave frequency, the wave height and the tides. A sustainable development project to use a seawater pump to manage fisheries at a coastal lagoon in Mexico is described.     

Photo-oxidative behaviour of crude oils relative to sea pollution: Part II. Photo-induced phase separation

A phase separation appears during the photo-oxidation of a light crude oil (Zarzaitine from Algeria), an aromatic-rich petroleum distillate, and a model mixture. Analysis by steric exclusion chromatography shows that this phenomenon is due to the formation of high molecular weight species which are insoluble in the hydrocarbon mixture. The phenomenon is linked to the radical propagation of the oxidation reaction and mainly involves the aromatic fraction. Its mechanism is discussed on the basis of experimental results.     

Semipermeable membrane devices link site-specific contaminants to effects: Part 1 - Induction of CYP1A in rainbow trout from contaminants in Prince William Sound, Alaska

Extracts from semi-permeable membrane devices (SPMDs) deployed on beaches in Prince William Sound (PWS), Alaska, were used to evaluate if complex contaminant mixtures from different sources can be distinguished by the resulting cytochrome P450 1A (CYP1A) activity in exposed test animals. Deployment sites included canneries, salmon hatcheries, and beaches where lingering oil remains from discharges during the 1964 earthquake or the 1989 Exxon Valdez oil spill. Other sites were selected at random to evaluate region-wide contaminant inputs or were located in salmon streams to evaluate contaminants carried and released by migrating salmon carcasses following reproduction. Following standard deployments of approximately 28 d, an aliquot of the accumulated contaminants was intraperitoneally injected without cleanup into juvenile rainbow trout (Oncorhynchus mykiss). After 2 d and 7 d, the activity of CYP1A was measured by the ethoxyresorufin-o-deethylase (EROD) assay. Exposure to extracts from the oiled sites and one hatchery site with numerous creosote pilings elicited strong EROD responses, whereas fish exposed to salmon stream extracts elicited weak but significant responses during late summer compared to late spring. Responses from the other sites were not significant, indicating contaminants from these sources are unlikely to cause CYP1A induction in resident biota. Rather than simply assessing extant contaminants, this method evaluates the potency of the different sites for bringing about aryl hydrocarbon receptor responses in resident biota.     

Launch and impact of free-fall lifeboats. Part II. Implementation and applications

There is a great interest in a practical method of predicting the behaviour of a free-fall lifeboat, when dropped from an offshore platform or from a ship, in order to assess the risk of injury to the occupants. In particular, for those environmental conditions in which full-scale experiments are very difficult, one can benefit from numerical prediction. The hydrodynamic impact of the boat at water entry is a complex problem and makes the establishment of an analytical prediction method a challenging task.This paper is the second of two articles outlining a practical method for simulating the water entry of a free-fall lifeboat. The first article (Part I: impact theory) [Boef, W. J. C. (1992), Ocean Engng19, 119–138] reviewed the relevant literature on hydrodynamic impact and outlined the theoretical model for the water entry of a lifeboat. This paper discusses the implementation of the lifeboat launch model and a method for evaluating the effects of impacts on the occupants. The results of a comparison with full-scale tests and of a case study are also included.