Enhanced extracellular enzymatic peptide hydrolysis in the sea-surface microlayer

The accumulation of dissolved organic matter (DOM) at the air–sea interface is controlled by dynamic physical processes at the boundary between ocean and atmosphere. Much of the DOM concentrated in the surface microlayer is thought to be protein or glycoprotein. Enzymatic hydrolysis of these and other biopolymers is an important step in the microbial uptake of dissolved and particulate organic matter in many aquatic environments. We employed a sensitive fluorescence technique to investigate differences between extracellular enzymatic peptide hydrolysis in the sea surface microlayer and corresponding subsurface water from Stony Brook Harbor, NY. We separated the microlayer from its underlying water and thus measured hydrolysis potential rather than an in-situ process. Peptide turnover was always faster in the microlayer than in subsurface waters. This was confirmed by allowing a new surface film to form on subsurface water; hydrolysis was still faster in the new surface film. In a year-long study, we found the relative difference between turnover times in the surface film and subsurface waters to vary greatly with season. While rate constants of peptide hydrolysis were generally higher in both microlayer and bulk water samples in spring/summer than in fall/winter, the difference in activity between the two environments was greatest in winter. Enhanced hydrolysis in the sea surface microlayer is likely due to the greater concentrations of DOM in the microlayer. Seasonal changes in distribution of hydrolytic activity between surface film and subsurface water probably reflect seasonal variation in the mechanisms of DOM enrichment, which depend on water temperature, substance and energy fluxes across the water–air boundary, activity of aquatic organisms and other seasonal variables.     

Biogeochemistry of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in the surface microlayer and subsurface water of the western North Atlantic during spring

Sixteen surface microlayer samples and corresponding subsurface water samples were collected in the western North Atlantic during April–May 2003 to study the distribution and cycling of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) and the factors influencing them. In the surface microlayer, high concentrations of DMS appeared mostly in the samples containing high levels of chlorophyll a, and a significant correlation was found between DMS and chlorophyll a concentrations. In addition, microlayer DMS concentrations were correlated with microlayer DMSPd (dissolved) concentrations. DMSPd was found to be enriched in the microlayer with an average enrichment factor (EF) of 5.19. However, no microlayer enrichment of DMS was found for most samples collected. Interestingly, the DMS production rates in the microlayer were much higher than those in the subsurface water. Enhanced DMS production in the microlayer was likely due to the higher concentrations of DMSPd in the microlayer. A consistent pattern was observed in this study in which the concentrations of DMS, DMSPd, DMSPp (particulate) and chlorophyll a in the microlayer were closely related to their corresponding subsurface water concentrations, suggesting that these constituents in the microlayer were directly dependent on the transport from the bulk liquid below. Enhanced DMS production in the microlayer further reinforces the conclusion that the surface microlayer has greater biological activity relative to the underlying water.     

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.     

Biogeochemistry of Dimethylsulfoniopropionate (DMSP) in the Surface Microlayer and Subsurface Seawater of Funka Bay,Japan

Twenty-eight sea surface microlayer samples, along with subsurface bulk water samples were collected in Funka Bay, Japan during October 2000–March 2001 and analyzed for dimethylsulfoniopropionate, dissolved (DMSP_d) and particulate (DMSP_p), and chlorophyll a. The aim of the study was to examine the extent of enrichment of DMSP in the microlayer and its relationship to chlorophyll a, as well as the production rate of dimethylsulfide (DMS) from DMSP and the factors that influence this. The enrichment factor (EF) of DMSP_d in the surface microlayer ranged from 0.81 to 4.6 with a mean of 1.85. In contrast, EF of DMSP_p in the microlayer varied widely from 0.85–10.5 with an average of 3.21. Chlorophyll a also appeared to be enriched in the microlayer relative to the subsurface water. This may be seen as an important cause of the observed enrichment of DMSP in the microlayer. The concentrations of DMSP_p in the surface microlayer showed a strong temporal variation, basically following the change in chlorophyll a levels. Moreover, the microlayer concentrations of DMSP_p were, on average, 3-fold higher than the microlayer concentrations of DMSP_d and there was a significant correlation between them. Additionally, there was a great variability in the ratios of DMSP_p to chlorophyll a over the study period, reflecting seasonal variation in the proportion of DMSP producers in the total phytoplankton assemblage. It is interesting that the production rate of DMS was enhanced in the microlayer and this rate was closely correlated with the microlayer DMSP_d concentration. Microlayer enrichment of chlorophyll a and higher DMS production rate in the microlayer provide favorable evidence supporting the view that the sea surface microlayer has a greater biological activity than the underlying water.     

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).     

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.     

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.     

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.     

胶州湾及青岛近海微表层与次表层中二甲基硫(DMS)与二甲巯基丙酸(DMSP)的浓度分布

以胶州湾及青岛近海为研究区域,利用吹扫-捕集气相色谱法研究了二甲基硫(DMS)和二甲巯基丙酸(DMSP,分为溶解态DMSPd和颗粒态DMSPp)在微表层与次表层中的浓度以及它们在微表层中的富集行为。结果表明,DMS、DMSPd和DMSPp在微表层中的浓度高于次表层,它们在微表层中的富集因子分别为1.17、1.84和1.51。研究发现,DMS及DMSPp浓度与叶绿素a(Chl-a)浓度有很好的相关性,但它们的周日变化与Chl-a并不完全同步。DMS/Chl-a和DMSPp/Chl-a的比值在次表层和微表层分别为4.35、13.47mmol/g和3.99、15.88mmol/g。胶州湾及青岛近海生态环境受人为活动干扰严重,使本海域DMS含量较高,从而贡献出较大的DMS海-气通量。     

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.     

Spatial variations of dimethylsulfide and dimethylsulfoniopropionate in the surface microlayer and in the subsurface waters of the South China Sea during springtime

Spatial variations in dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) were surveyed in the surface microlayer and in the subsurface waters of the low productivity South China Sea in May 2005. Overall, average subsurface water concentrations of DMS and DMSP of dissolved (DMSPd) and particulate (DMSPp) fractions were 1.74 (1.00-2.50), 3.92 (2.21-6.54) and 6.06 (3.40-8.68) nM, respectively. No enrichment in DMS and DMSPp was observed in the microlayer. In contrast, the microlayer showed a DMSPd enrichment, with an average enrichment factor (EF, defined as the ratio of the microlayer concentration to subsurface water concentration) of 1.40. In the study area, none of the sulfur components were correlated with chlorophyll a. An important finding in this study was that DMS, DMSP and chlorophyll a concentrations in the surface microlayer were respectively correlated with those in the subsurface water, suggesting a close linkage between these two water bodies. The ratios of DMS:Chl-a and DMSPp:Chl-a showed a gradually increasing trend from North to South. This might be due to changes in the proportion of DMSP producers in the phytoplankton community with the increased surface seawater temperature. A clear diurnal variation in the DMS and DMSP concentrations was observed at an anchor station with the highest concentrations appearing during the day and the lowest concentrations during the night. The higher DMS and DMSP concentrations during daytime might be attributed to the light-induced increase in both algal synthesis and exudation of DMSP and biological production of DMS. The mean flux of DMS from the investigated area to the atmosphere was estimated to be 2.06 micromo lm(-2)d(-1). This low DMS emission flux, together with the low DMS surface concentrations was attributed to the low productivity in this sea.     

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.     

大亚湾海区微表层、次表层BOD和COD的研究

研究表明,大亚湾海区海--气界面微表层对BOD和COD均产生了富集,但富集概率有所差别,BOD为87.5%,COD为100%,平均富集因数,BOD为3.00,COD为3.28.BOD和COD与相应的营养盐和Chl·a的回归分析表明,其相关显著性水平,微、次表层优于表、底层.     

Bacteriological investigation of the neuston and plankton in the Fraser River estuary,British Columbia

Microbiological parameters were examined in the surface microlayer (150 μm) and the subsurface waters (1 m) of the Fraser River estuary (British Columbia) at salinities of 0, 15 and 25‰. Little difference was observed in the neustonic variables between these three stations. A comparison of the neuston with the plankton over the estuary as a whole revealed elevated detritus, particulate organic carbon and nitrogen but reduced ATP, heterotrophic activity and percentage respiration in the neuston. Enrichment of bacterial numbers or dissolved organic carbon was not observed in the surface microlayer.     

N,N-二烷基酰胺类物质的膜状态及其在水面溢油集油剂中的应用研究

合成了 5种 N,N-二烷基酰胺型表面活性剂 ,并对其所成膜的状态进行了测定。表明当N,N-二烷基酰胺类物质单独成膜时获得的集油膜为多层膜 ,而当选用合适的溶剂与其配制成溶液以后 ,所成的集油膜则为转变膜或液态凝聚膜。在 5种 N,N-二烷基酰胺类物质中 ,酰基碳链越长、氮烷基碳链越短则其集油能力越强。应用 N,N-二烷基酰胺类物质配制了 4个配方 ,均具备良好的集油能力 ,并且对原油的集油能力大于对柴油的集油能力     

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.     

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.     

南沙海区微表层的研究——pH、碱度、密度和表面张力的测定

对南沙海区部分站位微表层和次表层的ｐＨ、碱度、密度和表面张力进行了测定。结果表明：微表层的表面张力低于次表层的表面张力,并且表面张力与溶解有机碳（ＤＯＣ）相关;微表层的ｐＨ低于次表层的ｐＨ,并探讨了其原因;微表层的碱度和密度一般高于次表层,同时对其原因进行了探讨。     

Temporal changes in community composition of heterotrophic bacteria during in situ iron enrichment in the western subarctic Pacific (SEEDS-II)

Little is known about the effects of iron enrichment in high-nitrate low-chlorophyll (HNLC) waters on the community composition of heterotrophic bacteria, which are crucial to nutrient recycling and microbial food webs. Using denaturing gradient gel electrophoresis (DGGE) of 16S rDNA fragments, we investigated the heterotrophic eubacterial community composition in surface waters during an in situ iron-enrichment experiment (SEEDS-II) in the western subarctic Pacific in the summer of 2004. DGGE fingerprints representing the community composition of eubacteria differed inside and outside the iron-enriched patch. Sequencing of DGGE bands revealed that at least five phylotypes of α-proteobacteria including Roseobacter, Cytophaga-Flavobacteria-Bacteroides (CFB), γ-proteobacteria, and Actinobacteria occurred in almost all samples from the iron-enriched patch. Diatoms did not bloom during SEEDS-II, but the eubacterial composition in the iron-enriched patch was similar to that in diatom blooms observed previously. Although dissolved organic carbon (DOC) accumulation was not detected in surface waters during SEEDS-II, growth of the Roseobacter clade might have been particularly stimulated after iron additions. Two identified phylotypes of CFB were closely related to the genus Saprospira, whose algicidal activity might degrade the phytoplankton assemblages increased by iron enrichment. These results suggest that the responses of heterotrophic bacteria to iron enrichment could differ among phylotypes during SEEDS-II.     

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.