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.     

Measurements of biomass and activity of neustonic microorganisms

Microlayer samples from a coastal marine area near Marseilles (France) collected in 1979 and 1980 have been analysed for POC, PON, chlorophyll a, ATP, cell counts, carbon fixation and in some cases for heterotrophic activity. Comparison of microlayer data with those of underlying water showed in most cases enrichment of organic matter and microorganisms in the surface microlayer. Carbon fixation values were comparable to those observed at 0·50 m except in the slicks, where phytoneustonic activity was higher than that of the underlying phytoplankton. Though total heterotrophic activity was higher in the surface film, the turnover time was not significantly different in both microlayer and underlying water. Our data show that enrichment is highly dependent on sea conditions; whenever slicks are present, the surface film seems to function like an eutrophic system, including active living material, although detritus is regularly present in large amounts.     

Fatty acids in recent sediments in the St. Lawrence estuary

Surface sediments along the Rimouski section in the St. Lawrence estuary were sampled at the surface and at 10 cm depth. Fatty acids were extracted and analysed. Saturated and unsaturated fatty acid contents at the two depths vary with the nature of the sediments. The clay sediments rich in organic matter contain more fatty acids than the corresponding sand or gravel. Unsaturated fatty acids were more abundant in the surface sediments. Some iso- and anteiso-odd carbon fatty acids were detected in the sediments; these acids could indicate a microbial activity. Correlation is made with the fatty acid contents of the water column together with the surface microlayer of the estuarine water.     

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.     

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.     

A field evaluation of plate and screen microlayer sampling techniques

Field studies of surface microlayer sampling methods involving simultaneous use of glass plates and two depths of screens have been conducted. Intercomparisons of the two methods are based upon thicknesses of sample and amounts of dissolved organic carbon, dissolved UV-absorbing phenolic materials, chlorophyll a, ATP and particulate organic carbon and nitrogen collected. Plate samples are always thinnest, and are influenced by wave state and bulkwater temperature. Amounts of materials collected generally follow sample thicknesses. Biases toward fractions of microlayer materials are not evident in either method. It was concluded that intercomparisons of data collected separately by the two methods is inadvisable.     

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.     

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).     

Sampling and GC-FID,GC/MS analysis of petroleum hydrocarbons in the ocean surface microlayer off Richards Bay,South Africa

In view of the demonstrated concentration of hydrophobic pollutants at the air/water interface and their expected deleterious effects on the associated neuston, surface microlayer sampling with a Teflon disc was introduced as part of a coastal oil pollution survey. Differentiation of the petroleum assemblages comprising the samples is demonstrated, using gas chromatography with flame-ionization detection and GC/MS with computer-reconstructed mass fragmentograms. The former technique provides parameters such as the carbon-number preference index, which distinguishes biogenic from petrogenic n-alkanes, whilst the relative abundances of ions characteristic of steranes and triterpanes indicate similarities among samples, and give further evidence of the petrogenic origin of the hydrocarbon assemblages found. Levels of petroleum hydrocarbons found are uniformly higher (expressed as μg/m²) than those reported previously, where sampling techniques differed from the present one in taking a finite volume of surface water for analysis.     

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.     

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.     

Plankton distribution and vertical flux of biogenic matter during high summer stratification in the Krka estuary (Eastern Adriatic)

The aim of this study was to investigate phytoplankton abundance, composition and vertical export in the highly stratified Krka estuary, Croatia. The estuary is stratified throughout the year, and an interface between fresh- and brackish water plays an important role in production and degradation of biogenic matter. Vertical export of particulate organic carbon (POC), phytoplankton carbon (PPC) and faecal pellet carbon (FPC) was studied by deploying sediment traps in the middle and lower reach of the estuary and in the adjacent coastal zone. Zooplankton faecal pellet (FP) production experiments were conducted to provide additional information on the potential contribution of FP to the total carbon flux. High suspended concentrations of POC, chlorophyll a and phytoplankton was found in the lower reaches of the Krka estuary, adjacent to a source of anthropogenic eutrophication. The fraction of organic detritus to the total POC flux was 61–69% inside the estuary but only 7% at the marine station. This indicates that the primary producers in the surface layer of the Krka estuary are decomposed in and below the interface and then settle as detritus to the bottom. Low sedimentation rates in the coastal zone outside the estuary revealed that the eutrophication does not spread out of the estuary. Mesozooplankton played a modest role in vertical flux regulation, due to their low abundance and dominance of smaller forms as well as low faecal pellet production rates. It is concluded that processes taking place at the freshwater-seawater interface are of major importance for the vertical carbon flux in the investigated area.     

三峡截流后长江口秋季TSM、POC和PN的分布特征

基于2004年11—12月长江口56个站位的悬浮体调查资料,分析了长江口区悬浮体总量(TSM)、颗粒有机碳(POC)和颗粒氮(PN)质量浓度的平面分布特征,探讨该区TSM及颗粒有机质的物质来源和三峡截流对长江三角洲的影响。结果表明,表、底层TSM与POC、PN质量浓度之间存在显著的正线性相关关系并都呈现出南高北低的格局,说明了长江悬浮颗粒物入海后主要沿东南方向输运。POC、PN质量分数与POC、PN的质量浓度不同,它们与TSM质量浓度对数有负相关关系。由于河口区底质再悬浮作用显著,TSM和POC、PN质量浓度呈现表层低、底层高的特点。长江口悬浮体主要来自长江径流和底质沉积物的再悬浮。与三峡截流前数据的对比表明,截流对目前长江口区的TSM和POC尚未造成明显的影响。     

珠江口沉积物有机质特征、来源及其对碳存储的意义

河口沉积物作为承接陆海过程的重要载体, 是有机质赋存的主要形式之一。本文研究了珠江口沉积物总有机碳、总氮含量和沉积物可溶性有机物三维荧光特征, 以及其在口内区、混合区和口外区空间差异和影响因素, 并结合碳稳定同位素(δ¹³C)估算了珠江口各区域沉积物中不同来源有机质的贡献。结果显示: (1)沉积物总有机碳和总氮含量空间变化相似, 口内区和混合区域沉积有机质含量显著高于口外区; 主成分分析发现, 口内区沉积有机质含量主要受径流输入的影响, 口外区主要受Fe³⁺的影响; (2)MixSIAR稳定同位素混合模型结果显示, 口内区和混合区沉积有机质以陆源为主, 口外区则以海源为主; (3)珠江口沉积物新生有机质较多, 可快速被利用, 总体上不利于有机碳存储; 而陆源输入导致口内区和混合区沉积有机质腐殖化程度较高, 有机碳可存储性相对较高, 口外受海源有机质和铁氧化物—有机质复合体的影响, 有机碳可存储性相对较低。本研究可为深入认知河口区沉积有机质的生物地球化学过程及有机碳存储提供参考。     

珠江口及近海表层沉积有机质的特征和来源

测定了珠江口及近海表层沉积物中总有机碳(TOC), 总氮(TN)及稳定碳同位素组成和几类主要有机化合物(水解氨基酸THAA、糖类TCHO、脂类lipid、酸不溶有机物AIOC), 并分析了沉积有机质及化合物的特征和来源。结果表明珠江口表层沉积有机质主要为陆源和水生混合来源, 而近海有机质主要为当地水生来源。大量的陆源高等植物(含有较多的木质素、纤维素等)输入珠江口, 使得珠江口个别站位沉积物中糖类物质含量大幅高于近海样品; 而珠江口与近海沉积物中水生来源有机质的含量相当。氨基酸和糖类占TOC的份额在浮游生物和悬浮颗粒物中分别为56%和48%, 在表层沉积物中为19%, 说明珠江口和近海的有机质从水柱到达沉积物-水界面的过程中经历了较充分的降解。珠江口样品中活性组分氨基酸和糖类占TOC的份额低于近海, 可能说明珠江口沉积有机质的降解程度高于近海。     

Grain size, geochemistry, magnetic susceptibility: Proxies in identifying sources and factors controlling distribution of metals in a tropical estuary, India

The aim of this study is to understand the various sources and factors controlling the abundance and distribution of the metals through the analyses of selected metals (iron, manganese, chromium, copper, zinc and cobalt), sand, silt, clay, organic carbon and magnetic susceptibility of the surface sediments of Zuari estuary in three different seasons. Total suspended matter (TSM) concentration and salinity of near surface and bottom waters were also measured. The study undertaken for three seasons, based on 18 selected stations all along the estuary, indicated that the concentration of most of the metals were comparatively higher during pre-monsoon than in monsoon and post-monsoon seasons. Further, along the length of the estuary, high concentrations were observed at lower middle and lower estuary and also at few stations at the upstream end. Salinity, distribution of TSM, size of the sediment, organic matter, geomorphological setup, fresh water input from land and release of industrial waste within the estuary played a role in distribution and concentration of metals. Magnetic measurements indicated the dominance of haematite like minerals and helped in understanding the source and depositional processes.     

Preliminary study on the distribution of nutrients, organic matter, trace metals in sea surface microlayer in Xiamen Bay and Jiulong Estuary

-The enrichment of nutrients (NOa-, NOa-, PO43-), suspended particles, organic matter (POC, PON,DOC) , and trace metals (Cu, Ni, Cd) was determined in the sea surface microlayer of Xiamen Bay and Jiulong Estuary. The mean enrichment factors ([Xi]microlayer/[Xi ]15cm in depth) mostly ranged between 1 . 0 and 2. 0. The dissolved forms were the major forms of the components measured, the enrichment of dissolved organic matter and suspended particles could lead to the changes in the total amount and speciation of nutrients and trace metals. No correlation was observed between sample concentrations, speciation, enrichment factors and sample locations. However, some evidence shows that these parameters are correlated with sea state, indicating the complexity and dynamic nature of the sea surface microlayer.     

The carbonate system of the amur estuary and the adjacent marine aquatic areas

In July 2007, integrated studies of the Amur Estuary and the adjacent aquatic areas were performed on board R/V Professor Gagarinskii within the project of the Amur River basin exploration. On the basis of the data obtained during the cruise, the carbonate system of the Amur Estuary in the summer period was considered. It was shown that the distribution of the carbonate parameters in the Amur Estuary and the adjacent aquatic areas points to the high intensity of the bio-geochemical processes of production and mineralization of organic matter. It was found that the organic matter destruction is prevailing over the photosynthesis in the riverine part of the estuary. This aquatic area is a source of carbon dioxide for the atmosphere and rates as a heterotrophic basin. On the contrary, the surface waters at the outer boundaries of the estuary (the Gulf of Sakhalin and the Tatar Strait) act as a sink of the atmospheric carbon dioxide, which is caused by the intense photosynthesis in this area. This part of the estuary is treated as an autotrophic basin.     

The distribution and flux of particulate matter in the Bideford River Estuary,Prince Edward Island,Canada

The temporal and spatial distribution of total and organic particulate matter is investigated in the Bideford River estuary. Particulate matter is homogenously distributed in both the water column and the surface sediment, due to high rates of resuspension and lateral transport. The measured mean sedimentation rate for the estuary is 183·5 g of particulate matter m^?2 day^?1, of which more than half is due to resuspension.The surface sediment of the estuary is quantitatively the dominant reservoir of organic matter, with an average of 902·5 g of particulate organic carbon (POC) m^?2 and 119·5 g of particulate organic nitrogen (PON) m^?2. Per unit surface area, the sediment contains 450 times more POC and 400 times more PON than the water column. Terrestrial erosion contributes high levels of particulate matter, both organic and inorganic, to the estuary from the surrounding watershed. Low rates of sediment export from the estuary result in the accumulation of the terrigenous material. The allochthonous input of terrigenous organic matter masks any relationship between the indigenous plant biomass and the organic matter.In the water column, a direct correlation exists between the organic matter, i.e. POC and PON, concentration and the phytoplankton biomass as measured by the plant pigments. Resuspension is responsible for the residual organic matter in the water column unaccounted for by the phytoplankton biomass.The particulate content of the water column and the surface sediment of the estuary is compared to that of the adjacent bay. Water-borne particulate matter is exported from the estuary to the bay, so that no significant differences in concentration are noted. The estuarine sediment, however, is five to six times richer in organic and silt-clay content than the bay sediment. Since sediment flux out of the estuary is restricted, the allochthonous contribution of terrigenous particulate matter to the bay sediment is minor, and the organic content of the bay sediment is directly correlated to the autochthonous plant biomass.     

Aquatic surface microlayer contamination in chesapeake bay

The aquatic surface microlayer (SMIC), 50 μm thick, serves as a concentration point for metal and organic contaminants that have low water solubility or are associated with floatable particles. Also, the eggs and larvae of many fish and shellfish species float on, or come in contact with, the water surface throughout their early development. The objectives of this study were (1) to determine the present degree of aquatic surface microlayer pollution at selected sites in Chesapeake Bay, and (2) to provide a preliminary evaluation of sources contributing to any observed contamination.Twelve stations located in urban bays, major rivers, and the north central bay were sampled three times, each at 5-day intervals during May 1986. Samples of 1.4–4.1 each were collected from the upper 30–60-μm water surface (surface microlayer, SMIC) using a Teflon-coated rotating drum microlayer sampler. One sample of subsurface water was collected in the central bay.At all stations, concentrations of metals, alkanes, and aromatic hydrocarbons in the SMIC were high compared with one bulk-water sample and with typical concentrations in water of Chesapeake Bay and elsewhere. SMIC contamination varied greatly among the three sampling times, but high mean contaminant levels (total polycyclic aromatic hydrocarbons, 1.9–6.2 μg 1⁻¹; Pb, 4.9–24 μg 1⁻¹; Cu, 4–16 μg 1⁻¹; and Zn, 34–59 μg 1⁻¹) were found at the upper Potomac and northern bay sites. Three separate areas were identified on the basis of relative concentrations of different aromatic hydrocarbons in SMIC samples - the northern bay, the Potomac River, and the cleaner southern and eastern portions of the sampling area.Suspected sources of surface contamination include gasoline and diesel fuel combustion, coal combustion, and petroleum product releases. Concentrations of metals and hydrocarbons, at approximately half the stations sampled, are sufficient to pose a threat to the reproductive stages of some fish and shellfish. Sampling and analysis of the surface microlayer provides a sensitive tool for source identification and monitoring of potentially harmful aquatic pollution.