Behaviour of no. 2 fuel oil in the water column of controlled ecosystems

Four experiments were carried out to determine the effect of different temperatures, light levels and biological activities on the residence times of petroleum hydrocarbons. No. 2 fuel oil was added as a seawater dispersion to give an initial concentration of 150 to 300 μg/litre in the water columns of large, outdoor marine microcosms. Hydrocarbons in water samples fractionated on passage through glass fibre filters (0·3 μm pore size) according to the solubilities, so that 80–90 % of the aromatics entered the filtrate while all of the saturates were trapped by the filter. The removal of oil compounds from the water columns was exponential, with rates which appeared to be determined chiefly by the temperature. The half life of total hydrocarbons varied from more than 10 days in March to ～30 h in July and September. Volatilisation was hypothesised to be an important removal mechanism for the 40–60% of the saturates which were not sedimented with suspended particulate matter. In warm water, the residence times of normal alkanes were increased up to 50 % by poisoning the water column, but no similar increase was noted for the bulk of the F₁ hydrocarbons. Aromatic (F₂) hydrocarbons appeared to be removed slowly volatilisation from cold water ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{> 200 h}$) and rapidly by biodegradation from warm water ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 40 h}$).     

Response of benthic communities in merl experimental ecosystems to low level, chronic additions of No. 2 fuel oil

The macrofauna and meiofauna of three oiled and three control experimental ecosystems at the Marine Ecosystems Research Laboratory (MERL) were followed for 25 weeks of semi-continuous additions of an oil-water dispersion of No. 2 fuel oil. Water column hydrocarbon levels were maintained at about 190 ppb, and after 20 weeks 109 sm/g dry weight fuel oil hydrocarbons were recorded in the top 2 cm of sediment.This simulated chronic oil pollution resulted in a highly significant decline in the number of macrofaunal and meiofaunal individuals in the experimental tanks compared with the controls. The effect was apparent on the numbers of individual macrofaunal species and on all metazoan meiofaunal groups.     

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.     

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.     

The effect of low, chronic levels of no. 2 fuel oil on natural phytoplankton assemblages in microcosms: 1. Species composition and seasonal succession

No. 2 fuel oil-sea water dispersions were added to three large scale (13 m³) microcosms twice weekly for a period in 1977 and a 4 month period in 1978. Water column concentration of total hydrocarbons averaged 190 μg litre⁻¹ in 1977 and 93 μg litre⁻¹ in 1978. Several responses of t the phytoplankton community in the oiled microcosms, relative to control microcosms, were similar during both periods of oil addition: total phytoplankton abundance and chlorophyll concentration were elevated, species diversity was higher and diatoms represented a greater proportion of the total p phytoplankton abundance than flagellates during 4 months of oil addition in 1977 and the entire period of oil addition in 1978. Phytoplankton species composition in the oiled microcosms was similar to the source water, Narragansett Bay, but the microcosm assemblages were numerically dominated by populations of the diatom Chaetoceros spp. and nanoflagellates in 1977 and several Chaetoceros spp. in 1978. Reduced predation pressure and altered herbivore feeding behaviour combined with the low level, non-lethal (to the majority of phytoplankton populations), concentrations of No. 2 fuel oil in the water column are postulated as mechanisms that can account for the elevated phytoplankton abundance in the oiled microcosms relative to the controls.     

Chronic sublethal effects of the water soluble fractions of no. 2 fuel oils on the marine isopod, Sphaeroma quadridentatum

Two series of experiments were carried out to assess the long-term effects of the water soluble fractions (WSF) of fuel oils on the marine isopod, Sphaeroma quadridentatum. In one experiment, juvenile isopods (one month old) were exposed to sublethal concentrations (0·1% to 15% WSF) of a fuel oil (Baytown, Exxon) at room temperatures of 24 ± 1–6°C for nine months. These isopods survived to maturity and reproduced. However, growth rate was adversely affected at concentration ≥ 3% WSF and fecundity was depressed at concentrations ≥ 1% WSF. Survival of offspring in clean seawater was dependent to a large extent on the history of the previous generation. Offspring from groups exposed to ≥ 1% WSF experienced high mortality (> 70% within five weeks) even in clean seawater. This may imply that a population of Sphaeroma exposed to WSF as low as 0·2 ppm may eventually disappear, although animals can grow to maturity and reproduce at concentrations < 3 ppm.In another experiment, adult Sphaeroma (three months old) were subjected to the WSFs of four fuel oils (Baton Rouge, Baytown, Montana and New Jersey) for one month. Fecundity was depressed at a concentration > 15% WSF, regardless of the kind of fuel oil. On the other hand, the number of young produced bythe surviving females varied with the type of fuel oil for the same level of WSF. This may be attributed to different relative amounts of toxic components present in the WSF.     

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.     

Organic sedimentation in the water column in the Arabian Sea: Relationship between the lipid composition of small and large-size,surface and deep particles

Small and large-size particulates (>50 μm) have been collected during the ORGON IV cruise in the Arabian Sea (North-western Indian Ocean), using conventional metallic bottles and vertical near-surface (200-0 m) and deep (below 1000 m) plankton nets. This area presents remarkable conditions for studying organic sedimentation: a high superficial productivity, low oxygen content of seawater and low terrigenous inputs.Lipids have been quantified and analysed by gas-liquid chromatography and gas-liquid chromatography/mass spectrometry for fatty acids, saturated hydrocarbons and sterols. The distribution of biological species, size range and biological nature have been determined through microscopic examination.Principal results are presented in a geochemical context: small and large-size particles belong to two different reservoirs both for concentrations and chemical compositions.The comparison between the size range of particles and chemical characteristics observed through analyses of net and bottle samples emphasizes the importance of large-size particles in the geochemical process of material transfer between surface and sediment. For various lipids, this transfer concerns freshly biosynthesized molecules such as long-chain polyunsaturated fatty acids, pristane and sterols, compounds which are of high metabolic value for abyssal and pelagic organisms.The lipid fluxes, determined from in situ concentrations, and settling velocity estimated from the size range of deep particulate material, are compared to those reported by different authors using other sampling procedures for deep settling matter.     

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.     

Effects of high pressure,hot water shore cleaning after oil spills on shore ecosystems in the Northern Baltic proper

The use of high pressure, hot water hosing techniques in oil spill clean-up operations on rocky and stony-gravelly shores drastically reduces the shore vegetation and macrofauna. The negative effects are more substantial than on oiled shores cleaned by raking and scraping. After one year the hot water cleaned shores were not restored completely.On rocky shores the high pressure, hot water technique is very efficient in terms of freeing the rocks from oil. However, due to its detrimental effects on shore organisms this type of oil spill clean-up operation can only be recommended for bird or wildlife protection areas. The cleanup method is inefficient on stony-gravelly shores due to penetration of oil into the ground and sediment and direct killing of shore organisms. The method should be avoided on these types of shores.     

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.     

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.     

Ground-based measurements of total column of hydrogen chloride in the atmosphere near St. Petersburg

We present ground-based spectroscopic measurements of the total hydrogen chloride in the atmosphere of Peterhof near St. Petersburg from April 2009 to March 2012. The well-known computer code SFIT-2 (Zephyr-2) was used to interpret the spectra of the solar IR radiation. The random and systematic errors of total column (TC) HCl measurements did not exceed 3.8 and 4.5%. The seasonal behavior of TC HCl in Peterhof is characterized by the presence of a maximum in March–April and a minimum in October–November. There are also extremely small TC HCl values in January–February. The time behavior obtained for Peterhof agrees well with data from nearest stations in the NDACC international network. The ground-based measurements of the TC HCl were compared with satellite measurements with the help of ACE-FTS and MLS instruments. The direct comparisons of coincident (within a day) and collocated (within 500 km) satellite and ground-based measurements showed a correspondence of results within their total errors.     

Interplay between top-down, bottom-up, and wasp-waist control in marine ecosystems

In October 2004, the North Pacific Marine Science Organization (PICES) sponsored a symposium to consider “Mechanisms that regulate North Pacific ecosystems: Bottom up, top down, or something else?” It sought to examine how marine populations, particularly the upper-trophic-level species, are regulated and to understand how energy flows through marine ecosystems. This introductory essay examines aspects of control mechanisms in pelagic marine ecosystems and some of the issues discussed during the symposium and in the 11 papers that were selected for this special issue. At global scales, the greatest biomass of fishes, seabirds and marine mammals tends to occur in regions of the world ocean with high primary production, e.g., the sub-arctic seas and up-welling regions of continental shelves. These large-scale animal distribution patterns are driven by food availability, not the absence of predators. At regional scales however, it is likely that current predation or past predation events have shaped local distributions, at least in marine birds and pinnipeds. Wasp-waist control occurs when one of the intermediate trophic levels is dominated by a single species, as occurs with small pelagic fishes of the world’s up-welling zones. Processes in these ecosystems may have features that result in a switch from bottom-up to top-down control.     

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.     

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.     

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.     

Measurement of water column primary production using photosynthesis-irradiance relations for surface phytoplankton,the vertical chlorophyll profile,and underwater light intensity

A method has been developed to measure water column integrated primary production (PP_int) in the water column using photosynthesis-irradiance relations for surface phytoplankton, the vertical profile of chlorophyll a concentration, and the underwater light intensity. Good correlation has been found for the results calculated with this method and light dependences in situ. The advantages of this method are the independence of PP_int calculation from CTD profiling and water sampling, and thus optimization (reduction) of the station working time.     

南沙海域初级生产力与水柱垂直稳定度的关系

海洋中浮游植物利用光能吸收水体中的CO₂和营养盐合成有机物,不但为海洋食物链的运行提供物质和能量基础,而且还通过海一气界面气体交换影响着大气CO₂浓度.水柱垂直稳定度对海洋初级生产力有重要影响,对此人们早已认识,但通过实测数据分析两者定量关系的文章至今仍极为罕见.此外,南沙海域是世界最大的边缘海之一,然而有关该海域的初级生产力仅见报道过两个测站的实测数据[1].     

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.