On lipid surface films on the sea. I. A simple method for sampling and studies of composition

A method for collection of surface films on the sea has been developed and tested at various places along the Swedish West Coast. Considerable amounts of lipids on the sea surface were found even when no seaslicks were observed. Triglycerides, free fatty acids, and wax esters are the dominating constituents, and there are characteristic deviations in the fatty-acid patterns compared to the corresponding lipids dissolved in the sub-surface water. Organochlorine residues, phthalic acid esters and heavy metals also occur in considerable amounts.     

Variations of particulate proteins and dissolved amino acids in coastal seawater

The relationships existing between the protein-containing fraction of particulate matter and amino acids dissolved in seawater were studied in the Gulf of Marseille at different periods of the year. The concentration of particulate proteins was almost zero in February and attained maximum values during April and May, the average concentrations of dissolved amino acids (total) varied between 900 and 1200 nmole l^?1 but larger variations were encountered at the surface and in the vicinity of the sediment. The influence of meteorological conditions and the effect of the sediment on the distribution of nitrogenous substances were taken into account. Combined dissolved amino acids were more abundant than free dissolved amino acids in 90% of the cases. The concentrations of dissolved amino acids observed in a zone bordering the North Mediterranean are comparable to those found in other regions of the world.     

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

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.     

The decoupling of hydrocarbons and fatty acids in the dissolved and particulate water phases of a deltaic environment

Hydrocarbons and fatty acids have been analysed in the dissolved and particulate phases of a series of 46 water samples collected over a period of 16 months in different environments of the Ebro Delta (bays, channels and river-bed). Several qualitative and quantitative differences have regularly been observed between the particulate and the dissolved fractions, such as higher concentrations and spatial variability of lipids in the particulates, which are also enriched in unsaturated components. Furthermore, an apparent source-related decoupling between both phases has been detected by a cross-correlation study of the multivariate dataset resulting from the distributions of these components. In the dissolved fraction they have been classified into three groups. The largest, consisting mostly of hydrocarbons, reflects the anthropogenic (urban- and petroleumrelated) inputs. The second is composed of some C₁₅-C₂₀ fatty acids and represents the biogenic autochthonous inputs, especially those of algal origin. A third group is formed by the C₂₁-C₃₀ n-alkanoic acids and corresponds to the terrigenous distributions. However, the biogenic sources are better characterized in the particulate phase where groups of components reflecting algal, bacterial and terrestrial inputs have been observed.     

Evidence for the decoupling of dissolved, particulate and surface microlayer hydrocarbons in Northwestern Atlantic continental shelf waters

Detailed sampling of the water column and subsequent high-resolution gas chromatographic analyses of surface film, particulate and dissolved hydrocarbons from the Georges Bank region off the New England coast have revealed large spatial and temporal heterogeneity in the source of hydrocarbons. Dissolved hydrocarbons, largely of a petroleum-related origin, surface film hydrocarbon also of a petroleum-related origin but different from the dissolved fraction, and bulk-water particulate matter of a mixed biogenic and petrogenic origin are all decoupled with respect to source and quantity in the region.Surface film (microlayer) hydrocarbons are found in greater concentrations than the dissolved fraction, which in turn is greater than the particulate hydrocarbon quantities in the water column. Although the microlayer appears enriched in hydrocarbons relative to the bulk water, the nature of the hydrocarbons is quite different, indicating that the use of a microlayer enrichment factor may not be appropriate in these waters.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

Estuarine transformation of organic matter: single coalescence events of estuarine surface active particles

Individual surface-active particles (SAP) in aqueous environmental samples can be characterized through their coalescence at a model hydrophobic interface. Each coalescence event is recorded as an electrical signal. As the electrical signal is a current transient (time on a millisecond scale), the sequence of fast processes leading to the formation of a condensed film can be studied from the moment of first attachment at the interface.In the stratified Krka Estuary, SAP are present in maximum concentrations (10⁷−5 × 10⁸ particles l⁻¹ min the size range > 1 μm) at the halocline (freshwater-seawater interface). This highly surface-active fraction of particulate organic matter can be viewed as oily droplets. SAP are fluid, and are readily transformed at interfaces to films of molecular thickness (surface area per particle is in the range 10⁻⁵–10⁻² cm²).Comparison of response of individual SAP with model particles, and the frequency of their appearance in estuarine samples, shows that a majority of estuarine SAP has, in terms of viscosity and film permeability, the properties of oleic acid. A significant fraction of SAP have more rigid structures, comparable to moleic acid + cholesterol model particles. A small fraction ( > 1%) behaves as phytoplankton cells with fluid outer membranes.We have also presented evidence for a strong interaction between elemental mercury and SAP, which is not sensitive to the molecular structure of the organic phase. The puzzling accumulation of mercury at the halocline of the Krka Estuary may be regarded as the result of interaction of elemental mercury with SAP.     

The hydrophobic fraction of organic matter in the Krka River Estuary

Surface active substances have been studied in the Krka River Estuary using an a.c. polarography method and various fractionation procedures. Total surface substances (SA_T) were separated into (particulate) heterodispersed and dissolved fractions by filtration. The dissolved fraction was separated into hydrophobic basic and neutral components, hydrophobic acid and hydrophilic components by sorption on to XAD-8 resin.The content and the composition of SA_T varied seasonally, depending on the biological activities taking place in the Krka River Estuary. The accumulation of SA_T, with hydrophobic properties, occurred at the fresh/saline water interface along the vertical profile. Daily changes in the form of the surface active substances along the vertical profile were observed. The formation of the heterodispersed fraction, especially observable in the upper freshwater layer and at the halocline, resulted in the change of physico-chemical properties of surface active substances. Organic matter appeared mainly in a dissolved form in the deeper saline water layer, showing negligible oscillations.The electrochemical characterization of the fractionated SA_T indicated that strong hydrophobicity of the surface active substances under natural pH conditions could be attributed to the significant contribution of the heterodispersed fraction of the organic material, which is the most reactive part of the surface active substances in the Krka River Estuary.The dissolved fraction of the surface active substances, prevailing in the deeper saline water layer, exhibited either hydrophilic or conditionally hydrophobic properties, depending on pH and ionic strength of the medium.     

透明胞外聚合颗粒物碳输运新途径

目前大家普遍认为,透明胞外聚合颗粒物(Transparent Exopolymer Particles,TEP)因其独特的凝聚效应导致碳通量向海底输出。但是,近几年的研究表明TEP不仅影响了碳沉降途径,其本身能够悬浮甚至向海水表层迁移,导致其在海洋微表层(Surface Micro-layer, SML)积累,最终显著影响海洋表层碳通量。TEP和其他颗粒物聚集形成凝聚物后,其运动趋势则由凝聚物中TEP的含量占比,即最终颗粒物密度所决定。一个新的值得注意的现象是,密度低的TEP通过与其他微粒聚合形成表面活性物质(Surface-active Substances, SAS),会在海洋–大气界面形成薄膜,显著影响海–气CO₂交换通量,甚至对全球气候变化造成影响。     

Organic matter characterization and fate in the sub-arctic Norwegian fjords during the late spring/summer period

The organic matter (OM) pool has been studied in two sub-arctic north Norwegian fjords, Balsfjord and Ullsfjord, in July 2001 and June 2003. Besides general OM parameters such as dissolved organic carbon (DOC), particulate organic carbon and nitrogen (POC and PON), the distribution of specific compounds such as folic acid and surface active substances (SAS) was followed. The results are supported with data of salinity, temperature, and chlorophyll a (Chl a). This approach allowed assessment of the fate of the OM pool, and its distinct vertical, spatial, and seasonal variations. Fjord waters could be vertically divided into two layers: the upper mixed layer (UML), until 40 m depth, and the deep aphotic layer. Spatial variability between the two fjords is a consequence of different influences of shelf waters on the fjords. Significant enrichment of POC and PON concentrations (3–5 times), as well as those of particulate SAS and folic acid (up to 3.2 times) in the UML was recorded during the period of new production, in early June. Depletion of particulate OM in deep waters was ascribed to fast dissolution or remineralization in the UML or upper part of aphotic layer. OM in July 2001 was characterized with 15.9% higher DOC pool compared to June 2003, and had refractory properties, suggesting the fjords to be an important source of organic matter for the continental shelf ecosystem. The DOC pool in these subarctic fjords represents the major component of the OM pool. The DOC concentrations in fjords are lower than those in previously studied warmer seas (e.g. the Adriatic Sea), whereas the concentrations of folic acid and SAS are comparable to those in the Adriatic Sea.     

Possibilities of using optical spectral analysis to estimate characteristics of roughness in the presence of films on the sea surface

The possibility of using an optical spectrum analyzer (OSA) to determine the degree of short gravity-capillary wave damping by films of surface-active substances (SAS) is studied. Nonlinear mechanisms of optical surface imaging associated with a complex profile of sky brightness and long waves are analyzed. Using the model of free short gravity waves damping by the films, it is shown that the difference between the contrast of roughness and imaging in film-covered surface regions can be substantial and attributed to a variability of the damping degree within a specified wavelength range rather than to the wave-damping value. In addition, it is illustrated that Doppler shifts of the OSA space-time spectrum in regions covered with films can substantially increase due to nonlinear distortions of the surface images. This fact should be taken into account when obtaining additional information on the state of the surface and roughness based on the Doppler shift values.     

Seasonal variations in the production and consumption of amino acids by coastal microplankton

A seasonal study on coastal microplankton was conducted in surface waters near Boothbay Harbor, Maine. Phytoplankton biomass, particulate production and extracellular organic release were examined in conjunction with microheterotrophic biomass and the uptake and respiration of amino acids. In situ dissolved free amino acid (DFAA) concentrations were also determined. Several phytoplankton blooms occurred throughout the year, in mid-summer, late autumn and in mid-winter. Heterotrophic activity and biomass paralleled phytoplankton extracellular release more closely than either phytoplankton particulate production or biomass. DFAA concentrations were not wholly dependent on extracellular release. Heterotrophic uptake did not appear to be dependent on DFAA concentrations but rather on rates of production of DOC by phytoplankton.     

Vertical transport of organic materials in the northern North Pacific as determined by sediment trap experiment

Sediment traps were deployed at 5 depths of 100 through 5,250 m to collect suspended sediments in the northern North Pacific (47°51.1'N; 176°20.6'E, 5,300 m deep) in the summer of 1978. Fatty acid composition was determined in the samples of phytoplankton, particulate matter, trap sediment and bottom sediment.Fatty acid composition of the trap sediments revealed no significant vertical trend throughout the water column from depths of 100 to 5,250 m, and were also similar to those of the phytoplankton and the particulate matter from the euphotic layer. However, a marked difference in the fatty acid composition was observed between the trap sediments and the particulate matter from deep waters. Therefore, it can be concluded that the source of fatty acids in the trap sediments is the particulate matter from the euphotic layer but not from deep waters.Unsaturated fatty acids highly susceptible to biological agents were rather abundant in the trap sediments as well as in the phytoplankton and particulate matter from the euphotic layer, however no unsaturated fatty acid was found in the particulate matter from deep waters. From these findings, it is clear that the particulate matter of the euphotic layer is transported to deep waters very rapidly. As the sinking rate of fecal pellets produced by zooplankton is in the range of ten to hundreds of meters a day, fecal pellets are assumed to be the most likely carrier of rapid-transport of organic matter including fatty acids from the euphotic layer to deep waters.     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

Spectral radiometric measurements of the temperature and radiation capacity of a rough sea surface

The results of radiometric remote simultaneous field measurements of the temperature and radiation capacity of the upper layer of the sea-surface temperature film 0.2 mm thick are presented. The measurements were conducted in the presence of wind waves and were characterized by an increased accuracy, which was achieved owing to the use of measurements of the intensity of radio radiation from the surface illuminated by radiation of a specified varying power. In our experiment, this illumination was provided by the radio radiation of the atmosphere, whose radiance temperature varies significantly, depending on the frequency at the slope of the absorption band of molecular oxygen (52.5–56 GHz). As a result, the radiation capacity and temperature of the skin layer were determined from the correlation dependence between the radiance temperatures of the surface and atmosphere measured by a radiometer-spectrometer in a number of channels separated in frequency. The radiance temperatures of the sea and atmosphere were measured at four frequencies of the 5-mm spectral range (53–55 GHz) on a vertical polarization. For absolute measurements, a calibration method was developed on the basis of a blackbody disk and two reflecting mirrors with the same solid angles. The measured values of the radiation capacity are variable and substantially smaller than the theoretical values determined by the models accepted for the permittivity of water and sea roughness. A possible cause of this can be the change of the permittivity of water in a thin surface layer of the temperature film (0.2 mm) due to the concentration of gases dissolved in water and surface-active substances within this layer.     

Direct determination of surface active substances in natural waters

Advantages of direct determination of surface active substances without sample pretreatment, using the electrochemical method (a.c. polarography) based on the measurement of adsorption effects on the mercury electrode, are illustrated for a number of freshwater and marine samples and phytoplankton culture media. The effects of dilution, filtration and centrifugation of samples were investigated. A high loss of organic material through filtration was observed for selected sea surface microlayer samples and phytoplankton culture media. The samples were compared with different model surfactants and were found to possess similar adsorption characteristics to hydrophobic, fatty surfactants. The freshwater samples were found to be more stable during pretreatment than the marine samples. Humic substances are the predominant surface-active compounds in freshwater systems. The use of a calibration curve for humic material is proposed for the rapid and direct determination of surfactant activity values for freshwater samples.     

Organic chemistry of seawater particulates - concepts and developments

Organic chemistry of particulates has recently been developed with the increasing quality of analytical methods. Because of the low organic content in deep sea, most of the studies were dealing with the euphotic layer. So we have very little information about the purely detrital material. Particulate organic carbon range from about 100 μg/1 in the surface layer, to 5–30 μg/1 in deep sea. Total particulate organic carbon in the world ocean must be about 2 · 10¹⁶g.It is important to obtain more detailed information about this enormous quantity of organic matter, the relative stability of which suggests that it could be used as a geochemical tracer. The distribution of particulate organic carbon exhibits regional variations, especially in surface waters, and a sharp vertical gradient of limited extent down to 200–300 m.At this depth, the deep water situation is reached with a quite constant carbon concentration disrupted only by pronounced increases associated with particular water masses. Though particles are generally recovered by filtration on 0.45 μ pore size filters, many smaller particles are present in sea water. The dialysis of seawater demonstrated a recovery of non dialysable material of about six times the amount recovered by filtration. While we have to take into account the existence of soluble high molecular substances, it seems possible for a great part of them to be in the colloidal state. If we except the biological processes, most of the chemical reactions occurring in the sea must concern this fraction. The detritus are for the most part too inert to play an important role in chemical reactions, while the strictly dissolved compounds are rapidly degraded by organisms. This colloidal fraction is thus responsible for the metals fixation, aggregation and sedimentation processes. It has been proved that it plays a very important role in the fixation of pesticides and hydrocarbons and must be considered in all the studies dealing with pollution.Some works on the origin of suspensions, showed that they can be formed by bubbling. Large organic active molecules adsorb to bubbles and produce monomolecular film which may be aggregated into insoluble organic particles; the agitation results in a semi-stable colloidal suspension of organic materials.It is highly probable that most of the organic matter in the deep sea is in the form of heteropolycondensed molecules, containing important carbohydrates and protein chains. These molecules are in a colloidal state in the supposedly dissolved material, which can be adsorbed on, or aggregated with particles by physical or biological processes.     

Relationship between dissolved and particulate fatty acids and hydrocarbons, chlorophyll a and zooplankton biomass in Villefranche Bay, Mediterranean Sea

Dissolved, particulate, and plankton hydrocarbons and fatty acids have been analysed by gas chromatography and gas chromatography/mass spectrometry in samples taken during a 16-month period at two stations located in Villefranche Bay, Mediterranean Sea. The study has been conducted in connection with regular determinations of chlorophyll a, zooplankton biomass and species of net plankton samples. The n-alkanes show a regular distribution pattern of odd and even carbon numbered compounds between n-C₂₁ and n-C₃₆ with additional characteristics associated with biological phenomena: abundance of n-C₁₅ and n-C₁₇, predominance of pristane over n-C₁₇ in zooplankton-rich samples, predominance of even carbon numbered n-alkanes in the range C₁₈–C₂₀, generally associated with a mixture of higher molecular weight even carbon numbered n-alkanes, modifying the regular distribution of the n-alkanes. For the station located at the end of the bay, the correlation between particulate hydrocarbons, particulate n-alkanes and chlorophyll a contents ( 0.630) is significant — well below the 0.05 level. There is discussion of this correlation which indicates a possible direct contribution of phytoplankton to the hydrocarbons of seawater or other biochemical associations between plankton and dissolved organic matter. Polyunsaturated fatty acids such as C₂₀ and C₂₂ are more abundant in plankton and suspended matter than in seawater. Data relative to those components allow us to evaluate the percentage of living plankton in suspended matter. General trends indicate the existence of a relation between particulate fatty acid and zooplanktonic biomass concentrations in the bay water.     

Factors controlling the temporal variation of fatty acids in piculate matter during a phytoplankton bloom in a marine mesocosm

Fatty acids present in suspended particles were examined following the onset of a phytoplankton bloom in an experimental marine mesocosm set up in Patricia Bay, Saanich Inlet, British Columbia, Canada. The predominantly diatom bloom, triggered by the addition of nutrients at the commencement of the experiment, was succeeded by several other phytoplankton forms, which in turn led to changes in particulate chl a, and organic carbon, and nitrogen within the experimental enclosure. An examination of individual fatty acids indicated that the variation of individual fatty acids can be classified into three groups, although the variation pattern of individual fatty acids differed from one another. An attempt was made to establish the factors controlling particulate fatty acid concentrations by principal component analysis. After Varimax rotation, six factors were extracted, of which four factors contributed to 83% of the data matrix. These were mainly dependent on the source of the particles i.e., diatoms, dinoflagellates, and bacteria.Fatty acid concentrations obtained by analysis of different lipid class fractions indicated that the production of fatty acids was distinctly related to the growth stage of the phytoplankton bloom. Fatty acids in triglycerides peaked during stationary phase, whereas fatty acids in polar lipids were high during the stage of an increase of phytoplankton biomass. However, fatty acid composition in both lipid classes changed under the influence of species succession of the phytoplankton population. This strongly suggested that species succession of the phytoplankton exerted the most significant control on fatty acid composition of particulate matter.     

Seasonal trends in the abundance, composition and bioavailability of particulate and dissolved organic matter in the Chukchi/Beaufort Seas and western Canada Basin

The objectives of this study were to investigate the seasonality, abundance, sources and bioreactivity of organic matter in the water column of the western Arctic Ocean. The concentrations of particulate and dissolved amino acids and amino sugars, as well as bulk properties of particulate and dissolved organic matter (DOM), were measured in shelf, slope and basin waters collected during the spring and summer of 2002. Particulate organic matter concentrations in shelf waters increased by a factor of 10 between spring and summer. Dissolved organic carbon (DOC) and nitrogen (DON) concentrations exhibited only minor seasonal variations, whereas dissolved amino acid concentrations doubled between spring and summer, and dissolved amino sugars increased by 31% in shelf waters of the Chukchi and Beaufort Seas. Concentrations of DOC did not exhibit a significant seasonal change in surface waters of the Canada Basin, but dissolved amino acid concentrations increased by 45% between spring and summer. No significant seasonal differences were detected in the concentration or composition of DOM in waters below 100 m in depth. Concentrations of particulate and dissolved amino acids and amino sugars were strongly correlated with chlorophyll-a, indicating a plankton source of freshly produced organic matter. The amino acid and amino sugar compositions of freshly produced DOM indicated that a large portion of this material is bioavailable. While freshly produced DOM was found to be relatively bioreactive, preformed DOM in the Arctic appears to be less bioreactive but similar in degradation state to average DOM in the Atlantic and Pacific. These data demonstrate substantial summer production of POM and DOM on the Chukchi and Beaufort shelves that is available for utilization in shelf waters and export to the Canada Basin.