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.     

海底沉积物保真采样技术研究进展

海底沉积物保真采样对于诸多海洋科学研究非常重要,各种研究目标的实现与沉积物样品的原位信息密切相关。本文论述了海底沉积物保真采样的目的和意义,提出了保真采样的定义,介绍了保真采样器的发展现状。论文重点讨论了保真采样器在采样过程中所涉及的共性关键技术。在此基础上,介绍了我国重力活塞式天然气水合物保真采样器的研究进展。最后,提出了关于发展我国保真采样技术的如下几点设想：1）重视沉积物低扰动技术研究,为相关海洋科学研究提供样品层次清晰、物质成分完备的沉积物样品。2）与HYACINTH计划类似,为适应不同海底地质条件,开发系列保真采样器。对松软的非岩性沉积物（从软泥、沙到砂砾）采样时,可采用重力驱动或震动冲击驱动保真采样装置;对硬质岩化的沉积物采样时,可采用回转式保真采样装置。3）重点开展沉积物样品无压降转移技术。实现实验室内的保真分析、存储和小段样品获取,开展原位压力条件下沉积物样品的地球物理学测试、地球化学、微生物、和石油物理学等研究分析。4）开展长柱状沉积物保真采样技术研究,为我国天然气水合物研究提供技术保障。     

Structural and thermodynamic signatures of marine microlayer surfactant films

Natural surface film experiments in inland waters and shallow offshore regions of the Baltic and Mediterranean Seas were carried out in the time period 1990–1999 under calm sea conditions using a novel device for sampling and force-area studies. The sampler-Langmuir trough-Wilhelmy filter paper plate system ‘cuts out’ an undisturbed film-covered sea area to perform π-A studies without any initial physico-chemical sample processing. The limiting specific area A_lim (2.68–31.57 nm²/molecule) and mean molecular mass M_w (0.65–9.7 kDa) of microlayer surfactants were determined from the 2D virial equation of state applied to the isotherms. Enthalpy ΔH and entropy ΔS_t of the 2D first-order phase transitions were evaluated using the Clausius-Clapeyron equation applied to the isotherms. Miscibility of film components and film structure evolution is expressed by the scaling exponent y adopting the 2D polymer film scaling theory. The stress-relaxation measurements revealed a two-step relaxation process at the interface with characteristic times τ₁=1.1–2.8 and τ₂=5.6–25.6 seconds suggesting the presence of diffusion-controlled and structural organisation relaxation phenomena. The obtained results suggest that natural films are a complex mixture of biomolecules covering a wide range of solubilities, surface activity and molecular masses with an apparent structural organisation exhibiting a spatial and temporal variability.     

Flow field analysis of submerged horizontal plate type breakwater

Submerged horizontal plate can be considered as a new concept breakwater. In order to reveal the wave elimination mechanism of this type breakwater, boundary element method is utilized to investigate the velocity field around plate carefully. The flow field analysis shows that the interaction between incident wave and reverse flow caused by submerged plate will lead to the formation of wave elimination area around both sides of the plate. The velocity magnitude of flow field has been reduced and this is the main reason of wave elimination.     

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.     

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

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

大亚湾微表层和次表层海水营养盐的研究

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

The wadic project: A comprehensive field evaluation of directional wave instrumentation

The results of a comprehensive field trial of nearly all commercially available directional wave measurement systems at the Edda field in the North Sea during winter 1985-86 are presented. The results summarize the accuracy of the principal engineering wave parameters from each system and the dependence on sea state. Limiting factors on system performance and operational problems are also included in the assessment. Overall experience has been good with systems utilizing widely different measurement principles returning consistent results.     

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

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

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.     

Tissue sampling from live blue mussels,Mytilus edulis. A field study from the Swedish west coast

Histological techniques are often used to study environmental effects on mussels, but since these techniques include killing of the individuals, rare or endangered populations cannot be studied using conventional tissue sampling. This study is an attempt to find a method that can be used repeatedly with the same mussel individual and which does not affect growth and survival. From 200 mussels, Mytilus edulis, tissue was sampled in different ways, such as drilling a hole in the shell or prising apart the shell valves. Two kind of instruments were used, an injection needle and surgery forceps. Some of the drilled mussels had their holes sealed again with cement.Drilling a hole in the shell, removing tissue sample with surgical forceps and then leaving the holes open did not seriously harm the mussels during the two months the experiment lasted. But if the holes were sealed with cement, both length and weight growth were negatively affected (35% lower length growth and 36% lower weight growth compared to the control mussels). Mortality was highest among the drilled and sealed mussels (80% higher than among the other treatments). The vulnerability of the population, the aim of the study and the duration of the experiment should decide what method to use for tissue sampling. For long-term experiments and repeated sampling, opening the mussels by prizing apart the valves is a better alternative than drilling holes in the shells, but depending on the morphology of the species it could be difficult to sample the anterior part of the mussel body. For a short experiment and to sample anterior parts, drilling the shells, leaving the holes open and using surgical forceps, seems to be an acceptable compromise between the different treatments used.     

海上气田排水采气工艺筛选

气井出水是气田开发生产中后期面临的主要问题,对气井生产有着极大的影响,而排水采气工艺是解决气井出水和井筒积液的有效手段。国内外排水采气工艺技术较多,不同工艺技术有其自身的适应范围。从海上气田生产特点出发,通过对国内外多种成熟的排水采气工艺技术的选井原则、适用条件和经济适用性进行对比分析,筛选了适合海上气田的排水采气工艺技术,并重点对优选管柱一气举复合工艺的实施方案进行了分析,对海上气田出水后的高效开发具有重要的指导意义。     

Development of indices for the evaluation of dune recovery techniques

Two effectiveness indices are proposed in this paper for evaluating dune recovery techniques: nourishment effectiveness (N_e) and sand fence effectiveness (F_e). Both indices were designed to be applied during monitoring programmes and were tested for Cacela Peninsula, Portugal. On this peninsula, a total volume of 480,000 m³ of sediments were dredged from the inner backbarrier channel and used for replenishment during the winter of 1996/1997. A 32% loss of material to the sea occurred due to superficial drainage during the spreading process. During the subsequent 25 months, 33% of the deposited material was eroded (50% due to wave action, 45% related to inlet displacement and 5% to lagoon processes).The determined nourishment life-time, based on monitoring data, was about 11 to 15 years, as compared to the designed life-time of 15 to 20 years. These values could be used as a guide for other re-nourishment projects. The value for the nourishment effectiveness index (N_e) obtained was about 75% to 76%, which corresponds to a reasonably effective protective scheme for this coastal dune.A set of fences was also installed and were effective sand traps in areas where the seaward nourishment bluff was small or absent. The sand fence effectiveness index (F_e) gave values increasing eastwards from 6% to 77%, corresponding to the longshore accumulation gradient related to the bluff height. This demonstrates that sand trap efficiency is very small when they are erected on top of obstacles (natural or artificial) to aeolian transport.For adequate dune recovery, in which the morphological, sedimentary and ecological characteristics are maintained, a combination of dune and upper beach nourishment and sand fencing is recommended. The effectiveness indices proposed here have the potential to be useful management tools but their use must be validated with the analysis of other monitored dune recovery cases.     

潮汐河口水沙资料整编原则探讨

本文分析了潮汐河口水沙资料的习用整编方法的合理性,指明其可能产生的误差与错误。提出了潮汐河口垂线平均流速与含沙量,单宽涨、落潮量与输沙量的统一整编原则及几个有关问题的处理方法,最后还提出了由实测流、沙资料估算断面涨、落潮量与输沙量的简易实用方法,并对其进行了初步的论证。     

深水油气田井场调查内容及方法技术研究

随着海洋油气资源开发的深入发展,我国的油气勘探开发已由浅海转向深水海域,深水井场调查是深水油气田勘探开发过程中的一个重要环节,但目前国内尚未开展此项工作,深水井场调查的内容和方法技术较浅水区相比有较大差异,难度较大。通过调研并结合以往浅水区井场调查经验,对深水井场工程地质及环境地质调查的内容和方法技术作了研究。针对深水海区地质环境条件和地质灾害因素复杂等特点,详细探讨了深水井场调查的技术难点和调查研究内容,重点介绍了深水井场调查的技术方法,特别是水下声学定位、深拖、水下机器人和深水地质取样等调查技术,以期为我国深水井场工程地质调查内容和技术方法的研究提供参考。     

Performance evaluation of fixed-station sampling design for a fishery-independent survey with multiple objectives

Fixed-station sampling design was widely used in fishery-independent surveys because of its characteristics of convenient sampling station setting, but the non-probabilistic(fixed) nature made it more uncertainty of drawing inferences on population. The performance of fixed-station sampling design for multispecies survey has not been evaluated, and we are uncertain if the design could detect the temporal trends of different populations in multispecies fishery-independent survey. In this study, s...     

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.