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.     

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.     

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

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

Non-volatile Hydrocarbon Chemistry Studies Around a Production Platform on Australia's Northwest Shelf

In September 1994 and 1995, scientists from the Australian Institute of Marine Science (AIMS) and the Australian Geological Survey Organization (AGSO) conducted surveys aboard the RV Lady Basten to determine the dispersion, fates and effects of produced formation water (PFW) discharged from the ‘ Harriet A ’ oil production platform near the Montebello Islands. This report is one of four related papers and describes the non-volatile hydrocarbon chemistry studies. The dispersion of the PFW into dissolved and particulate fractions of seawater were measured using moored high volume water samplers, surface screen samplers and moored and drifting sediment traps. Bio-accumulation was studied using transplanted oysters, and dispersion measured into sediment with benthic grabs.Results showed enrichment in non-volatile hydrocarbons in surface microlayer samples to a distance of 1·8 km in the direction of tidal flow. Concentrations in surface microlayers near the platform varied by an order of magnitude and corresponded to when a surface slick was visible or not visible. Concentrations of oil in seawater ranged from 2·0 to 8·5 μg l⁻¹at near stations to 1·3 μg l⁻¹at 1·8 km. Water column samples showed the processes of desorption from particles for soluble components occur within the range of 1·8 km. Most particulate hydrocarbons drop out of suspension within c. 1 to 2 km from the platform. Fluxes of particulate hydrocarbons through the water column at c. 1 km, as estimated by moored sediment traps in 1995, were 138 to 148 ng cm⁻²day⁻¹. A decrease in sediment concentrations within c. 1 km of the platform was measured as 2·45±1·29 μg g⁻¹dry wt (n=15) in 1994 to 0·86±0·54 μg g⁻¹dry wt (n=21) in 1995, after the platform installed a centrifugal separator in the discharge treatment process. Thus the residence time of this relatively low molecular weight oil was estimated in the coarse aerobic sands surrounding the platform to be less than one year. Oysters suspended near the platform bio-accumulated hydrocarbons and other lipophilic organics in their tissues. Uptake rates and bio-concentration factors of hydrocarbons indicated potential toxicity at the near-field stations within c. 1 km radius.A mass balance was constructed to show the partitioning of the input of hydrocarbons from the PFW into the surrounding marine ecosystem. The rates of dissipation processes were estimated as follows: dilution from tidal currents>degradation in the water column>sedimentation>evaporation. The calculations based on maximum concentrations measured in the environmental samples accounted for 85% of the daily input suspended within a 1 km radius.It is estimated that the potential zone of toxic influence in the water column extends to a distance of approximately 1 km. Concentrations of oil in sediments were too low to indicate potential toxicity. By the collaborative application of oceanographic and geochemical techniques to marine environmental problems, we endeavour to provide effective feedback to the oil industry to gauge the effectiveness of their operational strategies in minimizing impact in these pristine regions.     

Sea-to-air flux of contaminants via bubbles bursting. An experimental approach for tributyltin

Although seawater concentration of tributyltin (TBT) should decrease when the direct inputs from ship hulls will cease after the incoming world ban of organotin-based antifouling paints in 2003 or later, the TBT environmental issue will still be present for decades as contaminated sediments in shallow waters will be acting as a long-lasting reservoir for TBT and its degradation products. The lost of TBT to the atmosphere by volatilization has already been proposed as a part of its molecular motion through the aquatic environment but most recent calculated values of water-to-air rate of exchange of TBT (from 20 to 510 nmol m⁻² year⁻¹) do not take into account the potential contribution of aerosols ejection to the atmosphere upon bubbles bursting, an important process for pollutants transport in the marine environment. In this work, an experimental approach to measure the seawater-to-air flux of TBT mediated by bubbles bursting is described, and the influence of phytoplankton cells and dissolved organic matter from exudates and culture weathering on flux rates was assessed. The results demonstrate that TBT can be transferred from water to air via the ejection of droplets from bubbles bursting and that cell density strongly affected the transfer. Under a bubbling regime, the water-to-air flux (pmol TBT cm⁻² min⁻¹ level) is estimated up to 1000-fold the flux measured for the molecular diffusion and volatilization under static quiescent conditions. The surface microlayer acted as a transient boundary between the water column and the atmosphere where the dynamic of TBT accumulation has the same trend as the dynamic of TBT ejection. This physical transfer mechanism might be of high significance in nearshore environments, harbors, and shallow channels where clouds of bubbles generated in the wake of large ships play an important role for the atmosphere/seawater chemical exchanges.     

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.     

Enrichment of organochlorine contaminants in the sea surface microlayer: An organic carbon-driven process

Over 50 seawater samples from two different sites—Barcelona (Spain) and Banyuls-sur-Mer (France)—were analyzed in order to study the extent and postulate the processes driving the enrichment of hydrophobic organic pollutants in the sea surface microlayer (SML). A number of individual polychlorinated biphenyl (PCB) congeners (41) were measured to study their partitioning between the particulate (fraction > 0.7 μm) and the dissolved + colloidal phases (fraction < 0.7 μm), with the latter being differentiated into estimated dissolved and colloidal phases. In addition, several organochlorine pesticides were also measured, namely, HCB, α-HCH, γ-HCH, 4,4′-DDE, 4,4′-DDD and 4,4′-DDT. The presence of PCB congener profiles found in the SML suggests a dynamic coupling with the atmosphere in Banyuls sampling site, whereas offshore Barcelona the presence of highly chlorinated congeners was due to persistent sediment resuspension. The average PCB concentration in the SML dissolved + colloidal phase were higher in Banyuls (7.8 ng L^{− 1}) than in Barcelona (3.6 ng L^{− 1}) samples, but in the particulate phase concentrations were higher in Barcelona (3.2 ng L^{− 1}) to that of Banyuls (1.4 ng L^{− 1}). However, PCB concentrations in the SML generally also showed large variability. Enrichment factors of PCBs and other organochlorine compounds in the SML with respect to the underlying water column ranged from 0.2 to 7.4. This may be explained for both the dissolved + colloidal and particulate phases by the enrichment in the SML of organic carbon (OC) as discerned from particle–water and colloid–water partitioning.     

The sea-surface microlayer of puget sound: Part II. Concentrations of contaminants and relation to toxicity

Many aquatic contaminants, because of low water solubility (hydrophobicity) or association with floatable particles, concentrate at the sea surface. Thirty-six samples of the sea-surface microlayer (SMIC), the upper 50 μm, were collected from sites in Puget Sound, Washington State. Sites included three urban bays, central Puget Sound, and a rural reference site. Exposure of floating fish eggs to approximately half of these samples resulted in sublethal and lethal toxic effects (Hardy et al., 1987c).Chemical analyses revealed high concentrations of contaminants in many of the samples. Major temporal and spatial differences in sea-surface chemistry occurred, but maximum (for all) and mean (for 1985) concentrations were aromatic hydrocarbons, 8030 (mean 132) μg liter⁻¹: saturate hydrocarbons, 2060 μg liter⁻¹: pesticides, 43·8 (mean 0·46) ng liter⁻¹; PCBs, 3890 (mean 631) ng liter⁻¹; and total metals, 4750 (mean 626) μg liter⁻¹. Stepwise multivariate regression indicated that the percentage of fish eggs developing to normal live larvae decreased with increasing concentrations of a complex mixture of contaminants. Principal component analysis demonstrated that the major types of contaminants did not differ greatly in their statistical contribution to the toxicity, i.e. no single chemical was responsible for the observed toxicity.The chemical composition of the SMIC samples suggested that contamination originated from a variety of sources including atmospheric deposition, terrestrial runoff of fossil fuel combustion products, and sewage disposal.     

A sulfur budget for the Black Sea anoxic zone

A budget for the sulfur cycle in the Black Sea is proposed which incorporates specific biogeochemical process rates. The average sulfide production in the water column is estimated to be 30–50 Tg yr⁻¹, occurring essentially in the layer between 500 and 2000 m. About 3.2–5.2 Tg sulfide yr⁻¹ form during sulfate reduction in surface sediments of the anoxic zone. Total sulfur burial in anoxic sediments of 1 Tg yr⁻¹ consists of 10–70% (ca. 40–50% is the average) water column formed (syngenetic) component, the rest being diagenetic pyrite. As a maximum, between 3 and 5 Tg yr⁻¹ contribute sulfide to the bottom water or diffuse downward in the sediment. About 20–50 Tg yr⁻¹ sulfide is oxidized mostly at the chemocline and about 10–20% of this amount (4.4–9.2 Tg yr⁻¹) below the chemocline by the oxygen of the Lower Bosphorus Current. A model simulating the vertical distribution of sulfide in the Black Sea water column shows net consumption in the upper layers down to ca. 500 m, essentially due to oxidation at the chemocline, and net production down to the bottom. On the basis of the calculated budget anoxic conditions in the Black Sea are sustained by the balance between sulfide production in the anoxic water column and oxidation at the chemocline. On average the residence time of sulfide in the anoxic zone is about 90–150 yr, comparable to the water exchange time between oxic and anoxic zones. Hydrophysical control on the sulfur cycle appears to be the main factor regulating the extent of anoxic conditions in the Black Sea water column, rather than rates of biogeochemical processes.     

Compositions and transport of lipid biomarkers through the water column and surficial sediments of the equatorial Pacific Ocean

A systematic investigation of fluxes and compositions of lipids through the water column and into sediments was conducted along the U.S. JGOFS EgPac transect from l2°N to l5°S at 140°W. Fluxes of lipids out of the euphotic zone varied spatially and temporally, ranging from ≈0.20 – 0.6 mmol lipid-C m⁻² day⁻¹. Lipid fluxes were greatly attenuated with increasing water column depth, dropping to 0.002-0.06 mmol lipid-C m⁻² day⁻¹ in deep-water sediment traps. Sediment accumulation rates for lipids were ≈ 0.0002 – 0.00003 mmol lipid-C m⁻² day⁻¹. Lipids comprised ≈ 11–23% of C_org in net-plankton, 10–30% in particles exiting the euphotic zone, 2–4% particles in the deep EgPac, and 0.1-1 % in sediments. Lipids were, in general, selectively lost due to their greater reactivity relative to bulk organic matter toward biogeochemical degradation in the water column and sediment. Qualitative changes in lipid compositions through the water column and into sediments are consistent with the reactive nature of lipids. Fatty acids were the most labile compounds, with polyunsaturated fatty acids (PUFAs) being quickly lost from particles. Branchedchain C₁₅ and C₁₇ fatty acids increased in relative abundance as particulate matter sank and was incorporated into the sediment, indicating inputs of organic matter from bacteria. Long-chain C₃₉ alkenones of marine origin and long-chain C₂₀-C₃₀ fatty acids, alcohols and hydrocarbons derived from land plants were selectively preserved in sediments. Compositional changes over time and space demonstrate the dynamic range of reactivities among individual biomarker compounds, and hence of organic matter as a whole. A thorough understanding of biogeochemical reprocessing of organic matter in the oceanic water column and sediments is, thus, essential for using the sediment record for reconstructing past oceanic environments.     

Factors controlling the timing of major spring bloom events in an UK south coast estuary

Factors controlling the timing of major (>10 mg chlorophyll a m⁻³) spring bloom events in the estuarine waters of the Solent, on the south coast of the UK, have been investigated. Winter to summer variations in chlorophyll a concentration together with relevant meteorological and hydrographical data have been analysed for 5 years (1988, 1992, 2001, 2002 and 2003). Mean water column irradiance is demonstrated to be the main factor controlling the timing of the first major spring bloom event, usually dominated by large chain-forming diatoms. When chlorophyll a concentration first exceeds 10 mg m⁻³ in spring (usually in May) the mean water column photosynthetic active radiation (PAR) averaged for one week prior to the sampling date was always >380 W h m⁻² d⁻¹. Prior to the main spring bloom event surface incident radiation and water turbidity combine to limit chlorophyll a concentration to levels <10 mg m⁻³. Chlorophyll a concentrations >10 mg m⁻³ do not occur in the Solent until almost the entire 10 m water column is within the euphotic zone (i.e. above 1% light level) and light extinction coefficient (k) is ca. ≤0.5 m⁻¹. Statistically, river flow explains the largest percentage of the variations in k and the delayed bloom in June 2002 is due to increased cloud cover and high levels of rainfall in May, which caused a reduction in surface incident irradiance and increased turbidity. Chlorophyll a peaks during these major bloom events generally occur on spring tides when increased mixing rates favour net growth of diatoms.     

The capacity of marine plankton, macrophytes and particulate matter to adsorb Cu in the presence of Mg

A complexometric titration technique was employed to measure the total capacity of a variety of marine organisms to adsorb Cu²⁺. Measured adsorption capacities were 0.22 meq g⁻¹ for phytoplankton, 0.3–1.0 meq g⁻¹ for macrophytes, 1.0–2.5 meq g⁻¹ for zooplankton and 0.3 meq g⁻¹ for suspended particulate matter. The capacity of these materials to adsorb Cu²⁺ was reduced significantly in the presence of Mg²⁺ at seawater concentrations. Competition between Mg^t2+ and Cu²⁺ for adsorption sites at pH 6 is described by an average conditional equilibrium constant of 10^3.7. This constant is such that very little Cu²⁺ may be adsorbed onto particulates and marine phytoplankton in the presence of Mg²⁺. Further, primary productivity data and estimates of the detrital carbon sedimentation in Long Island Sound suggest that the flux of particulate carbon is insufficient to remove significant amounts of Cu from the water column to sediments by adsorption mechanisms.     

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.     

Effect of changes in water salinity on ammonium, calcium, dissolved inorganic carbon and influence on water/sediment dynamics

The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH₄⁺-flux to the water and Ca-flux toward sediments increased (NH₄⁺-flux: 5000–3000 μmol m⁻² d⁻¹ in seawater and 600/250 μmol m⁻² d⁻¹ in brackish water; Ca-flux: −40/−76 meq m⁻² d⁻¹ at S=37 and −13/−10 meq m⁻² d⁻¹ at S=10); however, later NH₄⁺-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m⁻² d⁻¹), increased during the experiment at S=37 (from 30 mmol m⁻² d⁻¹ immediately after salinity increase to 60 mmol m⁻² d⁻¹ after 17 days).In brackish conditions, NH₄⁺ and Ca²⁺ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH₄⁺ production and a first-order reaction for Ca²⁺ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH₄⁺.The mass balance for 17 days indicated a higher retention of NH₄⁺ in porewater in the littoral station in seawater conditions (9.5 mmol m⁻² at S=37 and 1.6 mmol m⁻² at S=10) and a significant reduction in the water consumption at both sites (5 mmol m⁻² at S=37; 35/23 mmol m⁻² at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m⁻² at S=37; 50/90 meq m⁻² at S=10) and was linked to a higher efflux of CO₂ to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m⁻²). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.     

The distribution and abundance of pelagic gammarid amphipods on Georges Bank and Nantucket Shoals

In this study, long-term, broad-scale zooplankton survey data were used to estimate the temporal and spatial distribution and abundance of gammarid amphipods present in the water column on Georges Bank. Delta-mean abundances computed from 10 years of data showed that gammarid amphipod abundances peaked in summer and again in fall. The amphipods were also most numerous in water less than 50 m deep. The statistical tests employed revealed no conclusive evidence for diurnal vertical migration. Interannual delta-mean abundances fluctuated approximately 5-fold between 1977 and 1986, ranging from 217 to 1181 amphipods 100 m⁻³. Peak amphipod biomass occurred in July and was estimated to be 2.8 kcal m⁻². Using production-to-biomass ratios from the literature, mean annual production of amphipods in these samples was estimated to be between 1.6 and 9.8 kcal m⁻². Production in shallow areas was especially high, 22 kcal m⁻² year⁻¹.     

Effects of irradiance on benthic and water column processes in a Gulf of Mexico estuary: Pensacola Bay, Florida, USA

We examined the effect of light on water column and benthic fluxes in the Pensacola Bay estuary, a river-dominated system in the northeastern Gulf of Mexico. Measurements were made during the summers of 2003 and 2004 on 16 dates distributed along depth and salinity gradients. Dissolved oxygen fluxes were measured on replicate sediment and water column samples exposed to a gradient of photosynthetically active radiation. Sediment inorganic nutrient (NH₄⁺, NO₃⁻, PO₄³⁻) fluxes were measured. The response of dissolved oxygen fluxes to variation in light was fit to a photosynthesis–irradiance model and the parameter estimates were used to calculate daily integrated production in the water column and the benthos. The results suggest that shoal environments supported substantial benthic productivity, averaging 13.6 ± 4.7 mmol O₂ m⁻² d⁻¹, whereas channel environments supported low benthic productivity, averaging 0.5 ± 0.3 mmol O₂ m⁻² d⁻¹ (±SE). Estimates of baywide microphytobenthic productivity ranged from 8.1 to 16.5 mmol O₂ m⁻² d⁻¹, comprising about 16–32% of total system productivity. Benthic and water column dark respiration averaged 15.2 ± 3.2 and 33.6 ± 3.7 mmol O₂ m⁻² d⁻¹, respectively Inorganic nutrient fluxes were generally low compared to relevant estuarine literature values, and responded minimally to light exposure. Across all stations, nutrient fluxes from sediments to the water column averaged 1.11 ± 0.98 mmol m⁻² d⁻¹ for NH₄⁺, 0.58 ± 1.08 mmol m⁻² d⁻¹ for NO₃⁻, 0.01 ± 0.09 mmol m⁻² d⁻¹ for PO₄³⁻. The results of this study illustrate how light reaching the sediments is an important modulator of benthic nutrient and oxygen dynamics in shallow estuarine systems.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

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.     

The benthic silica cycle in the Northeast Atlantic: annual mass balance, seasonality, and importance of non-steady-state processes for the early diagenesis of biogenic opal in deep-sea sediments

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 μM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment–water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment–water interface and the annual DSi efflux was close to 0.057 mol Si m⁻² yr⁻¹. Biogenic silica accumulation was close to 0.008 mol Si m⁻² yr⁻¹ and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si m⁻² yr⁻¹. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si m⁻² yr⁻¹). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.     

Sorption model for dissolved and particulate aluminium in the Conway estuary, UK

Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, K_d, which varies from 0.67 × 10⁵ to 3.38 × 10⁶ ml g⁻¹ for suspended particle concentrations of 2–64 mg l⁻¹. The K_d values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for K_d values of 10⁵, 10⁶ and 10⁷ ml g⁻¹ with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with K_d value 10⁷ ml g⁻¹ and C₀ values 16 × 10⁻⁶ mg ml⁻¹ and 92 × 10⁻⁶ mg ml⁻¹. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.