Sea-surface microlayer metals enrichments in an urban and rural bay

The sea-surface microlayer is an important interface between the atmosphere and ocean and a collection point for many anthropogenic materials including potentially toxic metals. We developed a glass plate sampler to collect the upper 30 to 55 micrometers of the sea surface. Samples of the microlayer and subsurface bulk water from an urban and rural bay were analysed for concentrations of Pb, Zn, Cu, Cd and Fe. Metal concentrations in both the microlayer and bulk water were generally 2 to 15 times greater in the urban than in the rural bay. Concentrations of metals in the microlayer of both bays averaged 6 to 65 times greater than those in the bulk water. In the urban bay, microlayer concentrations of Pb, Zn and Cu from 10 to > 100 μg 1^?1 were common. Measured microlayer metals concentrations agree well with those predicted from atmospheric deposition rates using a previously derived empirical model developed from laboratory microcosm studies. Further work will be required to determine whether or not these high microlayer metal concentrations contain significant biologically available fractions which could impact fisheries recruitment of larval icthyoneuston.     

Radiometric observations of sea temperature at 2.65 GHZ over the chesapeake bay

The present work describes the various corrections necessary in order to deduce ocean surface temperature fromS-band microwave radiometer measurements and applies these results to a series of data obtained with a high absolute accuracy radiometer. Measurements made with a 2.65 GHz radiometer from an aircraft flown over the Chesapeake Bay area are presented and compared in detail with accurately obtained sea truth data. For the calm sea, it was found that the observed brightness temperature agreed well with that calculated from the known sea surface and atmospheric properties over a fairly wide range of surface salinity values (0.2 per mille to 25 per mille). For cases where the surface wind speeds are of the order of 7 to 15 knots, an excess brightness temperature was observed which is attributable to surface roughness and microscale surface disturbances. The excess brightness temperature dependence on wind speed was found to correlate to a certain extent with the rms wave slope dependence on wind speed.     

胶州湾海域PAHs 污染与可培养半知菌的多样性

用5种不同的培养基对胶州湾近岸污染环境可培养半知菌进行选择性分离,共得到235株半知菌,其中YM培养基、MPDA培养基对半知菌的分离效果最好,分别占分离总量的26.4%和24.7%。试验选择的3个站位：石老人潮间带、海泊河入海口、李村河入海口PAHs含量存在显著性差异(P<0.05),其中石老人最低,平均为113.8 ng/g,海泊河 PAHs 为324.9 ng/g,介于中等水平,李村河含量最高为882.1 ng/g。可培养半知菌群体随PAHs含量的增加表现出先升高后降低的趋势。对各站位的半知菌进行统计发现,污染不同的站位,可培养半知菌优势种群不同,说明PAHs的污染可对半知菌的菌落结构组成产生影响。     

Processes affecting particulate trace metals in the sea surface microlayer

Concentrations of particulate Fe, Mn, Ni, Cu, Zn, Cd and Pb have been measured in surface microlayer and subsurface seawater samples collected in the North Sea adjacent to the East Anglian coast, in an area subject to a considerable fluvial input of clay minerals. The results are interpreted by estimating the magnitudes of different processes affecting particulate matter in the microlayer: atmospheric deposition, Brownian diffusion, gravitational settling, bubble flotation and mixing. Both Fe and Mn are strongly depleted in the microlayer, evidently as a result of gravitational settling of Fe- and Mn-bearing mineral particles out of the microlayer. These particles are mixed into the surface region from the water column beneath. Microlayer enrichment of Cu, Zn and Pb was also observed and probably results from flotation of particles attached to rising bubbles. In one set of samples, however, the marked enrichment of these elements, as well as Ni, may result instead from deposition of particles from the atmosphere directly onto the water surface.     

Dimethylsulfide enrichment in the surface microlayer of the South China Sea

A total of 22 sea surface microlayer samples collected from the Nansha Islands waters of the South China Sea were analyzed for dimethylsulfide (DMS), chlorophyll a and nutrients including nitrate, phosphate and silicate. The DMS concentrations in surface microlayer samples ranged from 82 to 280 ng S/l with a mean of 145 ng S/l. A significant correlation was found between DMS and chlorophyll a data both in the surface microlayer as well as in the subsurface water. However, no correlation was observed between DMS and nutrient concentrations in the surface microlayer. The DMS concentrations were higher in all surface microlayer samples, compared with subsurface samples. The enrichment factor (EF) of DMS in the surface microlayer varied from 1.21 to 3.08 with an average of 1.95. The EF of DMS was significantly correlated with that of chlorophyll a in the microlayer. The enrichment of DMS in the microlayer may be due to two factors, including the in situ production from phytoplankton and the transportation from the underlying seawater. The diel variations in DMS and chlorophyll a concentrations were studied at a fixed station. The highest concentrations of DMS in the surface microlayer and subsurface water were simultaneously observed in the late afternoon (1800 h), while the highest levels of chlorophyll a were simultaneously found at night (0200 h).     

Distribution and cycling of dimethylsulfide in surface microlayer and subsurface seawater

Laboratory experiments, along with in situ investigation in Funka Bay, Japan, were conducted to determine the enrichment factor (EF) of dimethylsulfide (DMS) in the sea surface microlayer, as well as its the production and consumption rates. The EF of DMS in the microlayer was largely affected by various factors including sampling methods, sampling thickness, temperature, salinity, and DMS concentration in bulk water. In all cases but the sealed system, a part of DMS in the microlayer was always unavoidably lost during sampling. High temperature, great wind speed, and slow sampling would increase the extent of loss of DMS due to volatilization. In the field, the screen-collected samples usually exhibited greater microlayer enrichment for DMS than the plate-collected samples, showing that the screen sampler might be more effective for collecting the in situ microlayer DMS. The production and consumption rates of DMS in the surface microlayer were higher than those in the bulk water and these two rates were significantly correlated with the microlayer DMS concentrations. Moreover, the EF of DMS appeared to be related to the microlayer production rate of DMS, providing evidence supporting the observed DMS enrichment in the microlayer. The DMS production and consumption rates were not directly related to its concentrations in the bulk water, suggesting that the processes of production and consumption of DMS were very complex. In the surface microlayer, the biological turnover time of DMS varied from 0.4 to 1.9 days, with an average of 0.9 days, which was about 540-fold greater than the mean DMS sea–air turnover time (2.4 min). Thus, the biological process occurring within the microlayer can be neglected when we consider the sea–air exchange of DMS. Considering the microlayer production rate of DMS (an average of 9.7 nM day⁻¹) to be too small to counteract the sea-to-air removal of DMS, the main source of DMS in the microlayer appears to be through vertical transport by turbulent diffusion from the underlying water.     

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.     

广西钦州湾外湾表层沉积硅藻分布特征

本文对钦州湾外湾54个表层沉积物中硅藻进行分析,鉴定出硅藻153种,分属50属。其中Thalassionema nitzschioides是本区域内最为丰富的硅藻种类。对应分析结果表明,钦州湾表层沉积硅藻分布主要受到海水盐度的影响,其中淡水硅藻Achnanthes delicatula、A.hauckiana、A.levanderi和Cocconeis disculus可以作为低盐度海水环境的指示种,半咸水种Cyclotella striata/C.stylorum、Paralia sulcata与海洋中硅藻Thalassionema frauenfeldii、T.nitzschioides则可以很好的指示高盐度环境。钦州湾外湾54个表层沉积站位可划分为3个硅藻分布区,分别对应高低不同的海水盐度,与实际站位地理分布基本一致。     

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.     

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.     

Raman scattering and fluorescence spectra of water from the sea surface microlayer

The Raman scattering and fluorescence spectra were first obtained for the water of sea surface microlayers (SML) of 1 and 0.2 mm thickness (sampled with a Garrett net and a Lapshin capillary sampler, respectively). For reference, samples of water below the SML (from the layer of 0.5 m) were also taken. Substantial differences were found for the values of the normalized intensity of the fluorescence (the number of photons from the volume unit in response to a unit of excitation) between the aqueous humic substances and, presumably, oil hydrocarbons and proteins. Some slight but analyzable differences in the shapes and location of spectral bands were also found. These latter allow one to determine the content of salts and the characteristics of complicated organic compounds in the SML and to compare them to those within the water volume.     

Comparison of sampling devices for the determination of polychlorinated biphenyls in the sea surface microlayer

Over 30 sea surface microlayer (SML) samples from two contrasting sites in the North Western Mediterranean -- Barcelona (Spain) and Banyuls-sur-Mer (France) -- were collected using three different sampling devices, namely, glass plate, metal screen (MS) and a surface slick sampler (SS), and compared with the corresponding underlying water (16 samples). The distributions of 41 polychlorinated biphenyl congeners (PCBs) were determined in the different phases: particulate (1.17-10.8 SigmaPCB ng L(-1)), truly dissolved (0.080-16.7 SigmaPCB ng L(-1)) and colloidal matter (1.17-43.0 SigmaPCB ng L(-1)), being the last two estimated from the analysis of the apparently dissolved phase. Concentrations of PCBs in the SML were higher than those in the underlying water (ULW), giving rise to enrichment factors (EF=[C](SML)/[C](ULW)) up to first-order of magnitude. The ANOVA statistical approach was used to assess differences of bulk data (e.g. dissolved organic carbon, DOC; particulate organic carbon, POC; suspended particulate matter, SPM) among sampling devices, whilst p-tailed t paired tests were used in order to compare the enrichments obtained for each sampling date. In this respect, no significantly different enrichment factors were found among sampling devices (p < 0.05), although the surface SS showed lower enrichments, probably due to the dilution of the SML with the ULW during sampling. The MS seemed to be the most suitable device for the determination of PCBs in the SML in terms of sampling efficiency under a variety of meteorological conditions.     

Determination of surfactant activity and anionic detergents in seawater and sea surface microlayer in the Mediterranean

The study of the physico-chemical properties and the determination of different classes of organic substances in the sea are of substantial interest and importance for understanding biogeochemical processes in the sea. The preferable method should be sensitive enough for direct measurement without pretreatment procedures in order to avoid changes in the composition of organic substances initially present in the sample.Surfactant activity data are presented here as measured by electrochemical methods during 1979, 1980 and 1981 in samples from open waters of the Western Mediterranean, and in a few characteristic coastal areas of the Adriatic Sea with different biological activity and different influence of man's activities. Data on sea surface microlayer samples collected during 1977, 1978 and 1981 at different locations and seasons in the Rijeka Bay, which is an integral part of the Adriatic Sea, are presented and discussed in more detail.It was found that the type and concentration of natural surface active material vary within different Mediterranean regions and along the depth profile of the water column.Petroleum hydrocarbons and detergents were found to be prevalent pollutants responsible for high surfactant activity values. Pollution effects are most pronounced in the sea surface microlayer.Electrochemical methods are proposed for research and monitoring of surface-active substances in the sea.     

Photochemical production of low-molecular-weight carbonyl compounds in seawater and surface microlayer and their air-sea exchange

Coastal and oceanic surface microlayer samples were collected using a stainless steel screen, along with subsurface bulk seawater, and were analyzed for low-molecular-weight (LMW) carbonyl compounds, including formaldehyde, acetaldehyde, propanal, glyoxal, methylglyoxal, glyoxylic acid and pyruvic acid. The enrichment factor in surface microlayer compared to corresponding subsurface seawater ranged from 1.2 to 21. A time-series measurement at a coastal site showed strong diurnal variations in concentrations of the LMW carbonyl compounds in the surface microlayer and in the enrichment factor, with maxima in the early afternoon and minima in the early morning. Exposure of samples to sunlight resulted in the higher yields of these compounds in the surface microlayer than in the bulk seawater, by a factor of 1.1–25, suggesting that the higher photoproduction rate of LMW carbonyl compounds in the surface microlayer accounts for the majority of the observed enrichment in these samples. Potential sinks include biological uptake and mixing. Air-sea exchange may be a source for soluble compounds and a sink for less soluble compounds. The enrichment of the LMW carbonyl in surface microlayer may alter their net air-sea exchange direction e.g., from the ocean as a potential sink to a source for atmospheric acetaldehyde and acetone. The residence times of the LMW carbonyl compounds in the microlayer were estimated to be on the order of tens of seconds to minutes using a modified two-layer model. However, to maintain the observed microlayer enrichment factor, the residence time should be on the order of ˜ 1 hour. This prolonged residence time may be due to organic enrichment in the surface microlayer (‘organic film’) which inhibited molecular transfer of carbonyl compounds into and out of the microlayer. The deviated behavior from model prediction may also be due to changes in the apparent partition coefficients of these species as a result of thier physical and chemical interactions with organic matrix in the surface microlayer.     

Transport and distribution of bacteria and diatoms in the aqueous surface microlayer of a salt marsh

The effects of tide and wind upon the distribution and transport of bacteria and diatoms in the aqueous surface microlayers of a Massachusetts and San Francisco Bay salt marsh were examined. The compression of the surface films by both tide and wind resulted in significant enrichments of bacterioneuston. At the San Francisco Bay site, significant numbers of diatoms were transported within the microlayer over a tidal cycle.     

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.     

Transport of no. 2 fuel oil between water column,surface microlayer and atmosphere in controlled ecosystems

No. 2 fuel oil hydrocarbons put into the bulk water columns of controlled estuarine ecosystems were found to accumulate in the surface microlayer at the air-water interface. The alkane hydrocarbons were disproportionately enriched in the microlayer compared with the aromatic hydrocarbons. A comparison of hydrocarbon boiling point distributions between bulk water, microlayer and air samples indicated that the oil hydrocarbons underwent extensive weathering by evaporation upon reaching the air-water interface. No evidence was found of increased biodegradation in the microlayer compared with that in the underlying water. A fraction of the high molecular weight alkanes, the least water soluble and least volatile constituents of the oil, appeared to be coated out from the microlayer onto the inner walls of the ecosystems.     

Effects of prudhoe bay crude oil contamination on sediment working rates of Abarenicola pacifica

Lugworms (Abarenicola pacifica) were exposed to sediment containing 250 to 1000 ppm Prudhoe Bay crude oil. At concentrations of 500 and 1000 ppm the rate of feeding, as measured by faecal production, was reduced by 70%. Smaller control animals turned over more sediment in proportion to their body size than larger ones. Exposure to oil at high levels abolished this difference by greater depression of the rate of faecal production by smaller individuals.     

Particulate matter at the estuarine salt marsh surface microlayer: Particle-size distributions and comparison to bulk suspension

Particle-size distributions have been measured for paired samples from the surface microlayer and bulk suspension in a South San Francisco Bay salt marsh. Comparison of size distributions reveals no consistent differences in surface microlayer and bulk particle populations; however, particle numbers were, at times, considerably enriched at the marsh microlayer. An empirical power curve was found to fit the particle-size distributions. The fitted exponents of particle size distributions indicate a slightly greater fraction of particle volume and a substantially greater fraction of particle surface area reside in small (colloidal) particle-size ranges.