Retention of arsenic and phosphorus in iron-rich concretions of Tagus salt marshes

Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O₂ takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O₂ and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g⁻¹ and 3.1 μmol g⁻¹, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g⁻¹), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g⁻¹ and 1.6 mmol g⁻¹, respectively) and of cracks (5.1 μmol g⁻¹ and 0.47 mmol g⁻¹). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.     

Benthic microalgal biomass in sediments of Onslow Bay, North Carolina

Sediment samples were collected at stations along cross-shelf transects in Onslow Bay, North Carolina, during two cruises in 1984 and 1985. Station depths ranged from 11 to 285 m. Sediment chlorophyll a concentrations ranged from 0·06 to 1·87 μg g⁻¹ sediment (mean, 0·55), or 2·6–62·0 mg m². Areal sediment chlorophyll a exceeded water column chlorophyll a a at 16 of 17 stations, especially at inshore and mid-shelf stations. Sediment ATP concentrations ranged from 0 to 0·67 μg g⁻¹ sediment (mean, 0·28). Values for both biomass indicators were lowest in the depth range including the shelf break (50–99 m). Organic carbon contents of the sediments were uniformly low across the shelf, averaging 0·159% by weight. Photography of the sediments revealed extensive patches of microalgae on the sediment surface.Our data suggest that viable benthic microalgae occur across the North Carolina continental shelf. The distribution of benthic macroflora on the North Carolina shelf indicates that sufficient light and nutrients are available to support primary production out to the shelf break. Frequent storm-induced perturbations do not favour settling of phytoplankton, an alternative explanation for the presence of microalgal pigments in the sediments. Therefore, we propose that a distinct, productive benthic microflora exists across the North Carolina continental shelf.     

Influence of Particle Mixing on Vertical Profiles of Chlorophyll a and Bacterial Biomass in Sediments of the German Bight, Oyster Ground and Dogger Bank (North Sea)

In May and September 1999 11 stations were sampled in the southern and central North Sea, located in the German Bight, eastern Oyster Ground and Dogger Bank. The study focused on the influence of particle mixing on transport of chlorophyll a to deeper sediment layers and vertical bacterial distribution (max. DEPTH=10 cm). The sampling stations were chosen to reflect a gradient in environmental conditions in the North Sea. The sampling stations differed in respect to redox potential (eH up to −243 mV in the German Bight and up to 274 mV in the offshore regions), silt content (up to 54% in the German Bight and 0·34% at the northern Dogger Bank) and different proportion of fresh organic material on total organic matter content (C/N ratios ranging from 9·27 in the German Bight up to 1·72 in the offshore sediments). Although bacterial densities (8·55×10⁹ g⁻¹in the German Bight up to 0·35×10⁹ g⁻¹in offshore sediments) were significantly correlated to chlorophyll a content in the sediment (P<0·01), inconsistencies in the temporal pattern of both variables in the surficial sediment layer suggested, that the dynamics of bacterial densities is generally controlled by food supply but also by other variables. The chlorophyll a content in the surficial sediments of the German Bight (up to 1·84 μg g⁻¹) was significantly higher than in the Oyster Ground (up to 0·58 μg g⁻¹) and the Dogger Bank area (up to 0·68 μg g⁻¹). With increasing chlorophyll a input to the benthic realm a subsequent enhanced burial of this compound into deeper sediment layers was expected either by biological (bioturbation) or by physical sediment mixing. However, the vertical profile of chlorophyll a decreased steeply in the sediments of the German Bight. Contrary, subsurface peaks were measured in the offshore areas. It was concluded from these results, that the vertical distribution of organic matter in sediments is less limited by the quantitative input from the water column but concomitant with particle mixing itself. The extent and possible mechanisms of particle mixing in the different study areas in relation to specific environmental factors is discussed.     

Distribution of Organic Matter, Iron, Mangenese in SurfaceSediments in the Nansha Islands Sea Area, South China Sea

Concentrations of organic matter, iron and manganese in the deep sea surface sediments in the Nansha Islands sea area, South China Sea are measured, Horizontal and vertical distributions of iron and manganese are discussed. The vertical distribution of iron and manganese in the sediments results from reduction, diffusion, and redeposition of manganese (or iron) oxide and hydroxide in the sediment. There are the maxima of iron and manganese in solid phase in the top of the sediment, which is caused by the penetration of O2 and the upward flux of Mn^2 ( or Fe^2 ). Manganese bacteria play a very important role in the cycle of solid-phase iron and manganese in the ocean environment. Manganese bacteria oxidize Mn^2 ( or Fe^2 ) in dissolved state to Mn^4 ( or Fe^3 ) in oxidized state under the aerobic condition, whereas they reduce iron and manganese in anaerobic conditions.     

Nitrogen cycling in deep-sea sediments of the Porcupine Abyssal Plain, NE Atlantic

Rates of transformation, recycling and burial of nitrogen and their temporal and spatial variability were investigated in deep-sea sediments of the Porcupine Abyssal Plain (PAP), NE Atlantic during eight cruises from 1996 to 2000. Benthic fluxes of ammonium (NH₄) and nitrate (NO₃) were measured in situ using a benthic lander. Fluxes of dissolved organic nitrogen (DON) and denitrification rates were calculated from pore water profiles of DON and NO₃, respectively. Burial of nitrogen was calculated from down core profiles of nitrogen in the solid phase together with ¹⁴C-based sediment accumulation rates and dry bulk density. Average NH₄ and NO₃-effluxes were 7.4 ± 19 μmol m⁻² d⁻¹ (n = 7) and 52 ± 30 μmol m⁻² d⁻¹ (n = 14), respectively, during the period 1996–2000. During the same period, the DON-flux was 11 ± 5.6 μmol m⁻² d⁻¹ (n = 5) and the denitrification rate was 5.1 ± 3.0 μmol m⁻² d⁻¹ (n = 22). Temporal and spatial variations were only found in the benthic NO₃ fluxes. The average burial rate was 4.6 ± 0.9 μmol m⁻² d⁻¹. On average over the sampling period, the recycling efficiency of the PON input to the sediment was 94% and the burial efficiency hence 6%. The DON flux constituted 14% of the nitrogen recycled, and it was of similar magnitude as the sum of burial and denitrification. By assuming the PAP is representative of all deep-sea areas, rates of denitrification, burial and DON efflux were extrapolated to the total area of the deep-sea floor (>2000 m) and integrated values of denitrification and burial of 8 ± 5 and 7 ± 1 Tg N year⁻¹, respectively, were obtained. This value of total deep-sea sediment denitrification corresponds to 3–12% of the global ocean benthic denitrification. Burial in deep-sea sediments makes up at least 25% of the global ocean nitrogen burial. The integrated DON flux from the deep-sea floor is comparable in magnitude to a reported global riverine input of DON suggesting that deep-sea sediments constitute an important source of DON to the world ocean.     

Bioavailability and effects of sediment-bound TBT in deposit-feeding clams, Scrobicularia plana

Concentrations of tributyltin (TBT), dibutyltin (DBT), inorganic and total tin have been measured in water, sediments and deposit feeding clams, Scrobicularia plana, from 25 estuarine locations in England and Wales, in order to compare the bioavailability of different forms of the element. Abnormally high tin values in Scrobicularia from harbours and areas of high boating activity testify to the high bioaccumulation potential of organotins, notably TBT derived from anti-fouling paints, relative to inorganic tin.Infaunal deposit-feeding bivalves consistently contain higher concentrations of TBT than other benthic organisms indicating that sediments may be an important route for uptake. Significant correlations between sediment TBT values and residues in clams such as S. plana (r = 0·81, p < 0·001) support this hypothesis. Direct evidence of the bioaccumulation of sediment-bound TBT is provided from laboratory experiments in which Scrobicularia were exposed to TBT in water and in sediments, either separately or in combination. The results of these experiments clearly demonstrate a predominantly particulate component for TBT uptake in clams.The kinetics of TBT accumulation and elimination were studied in Scrobicularia exposed to sediments containing 0·3 and 1·0 μg/g TBT (as tin). Equilibrium concentrations in tissue are approached after 40 days.Sediments containing 10 μg/g TBT are acutely toxic to S. plana, although such concentrations are only likely to occur close to dockyards and large marinas. Preliminary laboratory and field observations suggest however, that clam populations could be affected at TBT concentrations in sediments of 0·3 μg/g and possibly lower.     

Manganese and iron distributions off central California influenced by upwelling and shelf width

In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L⁻¹ and dissolved manganese reached 25 nmol L⁻¹. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L⁻¹ and dissolved manganese concentrations were less than 5 nmol L⁻¹. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L⁻¹, and dissolvable iron concentrations of 12–20 nmol L⁻¹ in the upper 100 m in the north, compared to 3.5–2 nmol L⁻¹ Mn and 0.6 nmol L⁻¹ Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf.These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling.Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L⁻¹ dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L⁻¹ dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.     

Relationships between macroalgal biomass and nutrient concentrations in a hypertrophic area of the Venice Lagoon

Macroalgae biomass and concentrations of nitrogen, phosphorus and chlorophyll a were determined weekly or biweekly in water and sediments, during the spring-summer of 1985 in a hypertrophic area of the lagoon of Venice. Remarkable biomass production (up to 286 g m⁻² day⁻¹, wet weight), was interrupted during three periods of anoxia, when macroalgal decomposition (rate: up to 1000 g m⁻² day⁻¹) released extraordinary amounts of nutrients. Depending on the macroalgae distribution in the water column, the nutrients released in water varied from 3·3 to 19·1 μg-at litre⁻¹ for total inorganic nitrogen and from 1·8 to 2·7 μg-at litre⁻¹ for reactive phosphorus. Most nutrients, however, accumulated in the surficial sediment (up to 0·640 and to 3·06 mg g⁻¹ for P and N respectively) redoubling the amounts already stored under aerobic conditions, Phytoplankton, systematically below 5 mg m⁻³ as Chl. a, sharply increased up to 100 mg m⁻³ only after the release of nutrients in water by anaerobic macroalgal decomposition. During the algal growth periods, the N:P atomic ratio in water decreased to 0·7, suggesting that nitrogen is a growth-limiting factor. This ratio for surficial sediment was between 6·6 and 13·1, similar to that of macroalgae (8·6–12·0).     

Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Nondetrital and total metal distribution in core sediments from the U-Tapao Canal, Songkhla, Thailand

The U-Tapao Canal is the main source of freshwater draining into the outer part of Songkhla Lake, which is the most important estuarine lagoon in Thailand. Songkhla Lake is located in southern Thailand between latitudes 7°08' and 7°50' N and longitudes 100°07' and 100°37' E. Acetic acid (HOAc)-soluble Cu, Fe, Mn, Pb, and Zn and the total concentration of these metals along with Al concentration, organic carbon, carbonate, sand, silt, and clay contents were determined in 4 sediment cores obtained at selected intervals from the mouth of the canal to 12 km upstream. Readily oxidizable organic matter in the cores varies from 1.52% to 7.30% and is generally found to decrease seaward. Total concentrations of Al (61.7–99.0 g kg⁻¹; 2.29–3.67 mol kg⁻¹), Cu (12.4–28.2 mg kg⁻¹; 195–444 μmol kg⁻¹), Fe (25.2–42.0 g kg⁻¹; 451–752 mmol kg⁻¹), Mn (0.22–0.49 g kg⁻¹; 4.0–8.9 mmol kg⁻¹), Pb (16.7–43.1 mg kg⁻¹; 80.6–208 μmol kg⁻¹), and Zn (48.6–122.7 mg kg⁻¹; 0.74–1.88 mmol kg⁻¹) vary to a certain extent vertically and seaward in the U-Tapao Canal core sediments. These concentrations are at or near natural levels and show no indication of anthropogenic contamination.Overall, the data show that total metal concentrations in the surface and near surface core sediments are enriched in varying degrees relative to Al in the order of Zn>Mn>Pb>Fe>Cu. Chemical partitioning shows that the enrichment in the surface and near surface sediments is related to the relatively high proportion of the total metal concentrations (Mn>Zn>Fe>Cu>Pb) that occur in the acetic acid-soluble (nondetrital) fraction, and they generally decrease with depth. Nondetrital Cu, Pb, and Zn likely derive from those metals held in ion exchange positions, certain carbonates, and from easily soluble amorphous compounds of Mn and perhaps those of Fe. Diagenetic processes involving Mn and to a lesser extent, Fe compounds, as well as the vertical changes in the oxidizing/reducing boundaries, appear to be the most important factors controlling the behavior of the metals in these cores. Organic matter and the aluminosilicate minerals, however, appear to be less important carriers of the metals studied.     

Microbial biogeochemistry and bioturbation in the sediments of Great Bay, New Hampshire

The influence of bioturbation on certain aspects of the biogeochemistry of sulfur and iron was examined in shallow-water sediments of Great Bay Estuary, New Hampshire. A bioturbated (JEL) and non-bioturbated (SQUAM) site were compared. Annual sulfate reduction measured with ³⁵S, was 4·5 times more rapid at JEL. A significant portion of this difference was attributed to rapid rates which occurred throughout the upper 12 cm of sediment at JEL due to infaunal reworking activities. Sulfate reduction decreased rapidly with depth at SQUAM. FeS in the upper 2 cm at JEL increased in concentration from 3 to 45 μmol ml⁻¹ from early May to late July while only increasing from 3 to 8 μmol ml⁻¹ at SQUAM. Infaunal irrigation and reworking activities caused rapid and continous subsurface cycling of iron and sulfur at JEL. This maintained dissolved iron concentrations at 160–170 μM throughout the summer despite rapid sulfide production. Therefore, dissolved sulfide never accumulated in JEL pore waters. Although dissolved organic carbon (DOC) was generated during sulfate reduction, bioturbation during summer caused a net removal of DOC from JEL pore waters. Sulfate reduction rates, decomposition stoichiometry and nutrient concentrations were used to calculate turnover times of nutrients in pore waters. Nutrient turnover varied temporally and increased three-to five-fold during bioturbation. A secondary maximum in the abundance of recoverable sulfate-reducing bacteria occurred at 10 cm in JEL sediments only during periods of active bioturbation, demonstrating the influence of macrofaunal activities on bacterial distributions.     

Bacterial iron oxide reduction in a terrigenous sediment-impacted tropical shallow marine carbonate system, north Jamaica

Discovery Bay, a carbonate-dominated embayment in north Jamaica, has been subject to inputs for 40 years of iron-rich bauxite sediment associated with the local mining and transport of processed bauxite. As such, this site is an ideal natural laboratory to study the records and impacts of iron oxide inputs upon geochemical, diagenetic, and microbial processes in tropical carbonate sediments.Total Fe contents in sites in the bay not receiving bauxite inputs are negligible and porewater Ca²⁺, SO₄²⁻ and Cl⁻ indicate that bacterial sulphate reduction is an important process. In contrast, surface sediments receiving bauxite inputs contain significant total Fe, from 44 μmol/g in shallow (5 m water depth) sites to 110 μmol/g in deeper (20 m water depth) sites. Up-core increases in total Fe record increased temporal inputs into the bay. Within these Fe-rich sediments porewater data shows the presence of Fe^II released by bacterial Fe^III reduction. There is no direct evidence for significant bacterial sulphate reduction in these sediments. Iron oxides within all bauxite-impacted sediments display a high potential reducibility, from 40% to 80% of the total Fe present as dithionite-extractable Fe^III. Experimental analysis of the potential susceptibility to, and rates of, bacterial Fe^III reduction, utilising Discovery Bay sediment and Shewanella putrefaciens CN32 (a known Fe^III-reducer) has confirmed the high bacterial reducibility of iron oxides within the sediment. Up to 75% of initial dithionite-extractable Fe^III in the sediments was reduced over 15 days.The presence of iron oxides within the Discovery Bay shallow marine carbonate systems has markedly altered the chemical diagenetic processes taking place, with a shift from apparent dominance of bacterial sulphate reduction at non-impacted (Fe-poor) sites, to highly significant bacterial Fe^III reduction in Fe-rich bauxite-impacted sediments. Given the perceived global increases in terrigenoclastic sediment inputs into tropical carbonate systems as a result of land-use and climate changes, coupled with the documented role that iron oxide reduction plays in nutrient and contaminant cycling in sediment systems, more research into the perturbation of early diagenesis by iron oxide inputs is required.     

Settleable and Non-Settleable Suspended Sediments in the Ogeechee River Estuary, Georgia, U.S.A.

Suspended particle dynamics were investigated in the Ogeechee River Estuary during neap tide in July 1996. Samples were operationally separated into ‘ truly suspended ’ (settling velocity <0·006 cm s⁻¹) and ‘ settleable ’ (settling velocity >0·006 cm s⁻¹) fractions over the course of a tidal cycle to determine whether these two fractions were comprised of particles with differing biological and chemical characteristics. Total suspended sediment, organic carbon and nitrogen, chlorophyll a and phaeopigment concentrations were measured in each fraction, as well as rates of bacterial hydrolytic enzyme activity [β-1,4-glucosidase (βGase) and β-xylosidase (βXase)]. The majority of the suspended sediment (by weight) was in the truly suspended fraction; all measured parameters were largely associated with this fraction as well. When compared to the settleable material, the truly suspended material was significantly higher in % POC (5·7±0·6 vs. 3·9±1·8), % chlorophyll (0·07±0·02 vs. 0·03±0·01), % phaeopigment (0·030±0·006 vs. 0·018±0·012), and weight-specific maximal uptake rates (V_maxper mg suspended sediment) of both enzymes (1·8±0·4 vs. 0·7± 0·2 nmol mg⁻¹ h⁻¹βGase and 1·1±0·3vs . 0·3±0·2 nmol mg⁻¹ h⁻¹βXase), providing clear evidence for a qualitative distinction between the two fractions. These results are interpreted to mean that the more organic-rich, biologically active material associated with the suspended fraction is likely to have a different fate in this Estuary, as ‘ truly suspended ’ sediments will be readily transported whereas ‘ settleable ’ sediments will settle and be resuspended with each tide. These types of qualitative differences should be incorporated into models of particle dynamics in estuaries.     

N2O Production, Nitrification and Denitrification in an Estuarine Sediment

The mechanisms regulating N₂O production in an estuarine sediment (Tama Estuary, Japan) were studied by comparing the change in N₂O production with those in nitrification and denitrification using an experimental continuous-flow sediment–water system with¹⁵N tracer (¹⁵N-NO−3 addition). From Feburary to May, both nitrification and denitrification in the sediment increased (246 to 716 μmol N m⁻² h⁻¹and 214 to 1260 μmol N m⁻² h⁻¹, respectively), while benthic N₂O evolution decreased slightly (1560 to 1250 nmol N m⁻² h⁻¹). Apparent diffusion coefficients of inorganic nitrogen compounds and O₂at the sediment–water interface, calculated from the respective concentration gradients and benthic fluxes, were close to the molecular diffusion coefficients (0·68–2·0 times) in February. However, they increased to 8·8–52 times in May except for that of NO−2, suggesting that the enhanced NO−3 and O₂supply from the overlying water by benthic irrigation likely stimulated nitrification and denitrification. Since the progress of anoxic condition by the rise of temperature from February to May (9 to 16 °C) presumably accelerated N₂O production through nitrification, the observed decrease in sedimentary N₂O production seems to be attributed to the decrease in N₂O production/occurrence of its consumption by denitrification. In addition to the activities of both nitrification and denitrification, the change in N₂O metabolism during denitrification by the balance between total demand of the electron acceptor and supply of NO−3+NO−2 can be an important factor regulating N₂O production in nearshore sediments.     

The influence of dissolved petroleum hydrocarbon residues on natural phytoplankton biomass

The effect of dissolved petroleum hydrocarbons in the environment on phytoplankton biomass measured as chlorophyll a was studied near the oil tanker route in the southern Bay of Bengal. In the transect from 5° N, 77° E to 5° N, 87° E the concentrations of dissolved petroleum hydrocarbons were negatively correlated with phytoplankton biomass, whereas in the 0° N, 87° E to 1° N, 79° E transect they were positively correlated with phytoplankton biomass. The mean petroleum hydrocarbon concentrations in the two transects were 12·12 ± 4·67 μg litre⁻¹ and 11·23 ± 4·5 μg litre⁻¹, respectively.It is surmised that the effect of dissolved petroleum hydrocarbons on phytoplankton biomass varies depending on the nature rather than the quantity of petroleum hydrocarbons present. Culture studies with unialgal Nitzschia sp. in seawater collected from selected stations in the study area as well as in artificial seawater spiked with the water-soluble petroleum hydrocarbon fraction of light Arabian Crude support this.     

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.     

Nutrient flux in the Rhode River: Tidal transport of microorganisms in brackish marshes

Concentrations of bacteria, chlorophyll a, and several dissolved organic compounds were determined during 11 tidal cycles throughout the year in a high and a low elevation marsh of a brackish tidal estuary. Mean bacterial concentrations were slightly higher in flooding (7·1 × 10⁶ cells ml⁻¹) than in ebbing waters (6·5 × 10⁶ cells ml⁻¹), and there were no differences between marshes. Mean chlorophyll a concentrations were 36·7 μg l⁻¹ in the low marsh and 20·4 μg l⁻¹ in the high marsh. Flux calculations, based on tidal records and measured concentrations, suggested a small net import of bacterial and algal biomass into both marshes. Over the course of individual tidal cycles, concentrations of all parameters were variable and not related to tidal stage. Heterotrophic activity measured by the uptake of ³H-thymidine, was found predominantly in the smallest particle size fractions (< 1·0 μm). Thymidine uptake was correlated with temperature (r = 0·48, P < 0·01), and bacterial productivity was estimated to be 7 to 42 μg Cl⁻¹ day⁻¹.     

Sublethal effects of hydrogen sulfide in sediments on the Urchin Lytechinus pictus

Laboratory exposures of the urchin Lytechinus pictus to sediment dosed with varying concentrations of hydrogen sulfide (H₂S), but without elevated organic material, were conducted. Changes in mortality, behavior, growth and gonad production were measured during 49 days' flow through exposures. Hydrogen sulfide concentrations of 165·8 μ liter⁻¹ in pore water caused significant changes in all parameters measured. Concentrations as low as 32·9 μ liter⁻¹ caused significant decreases in wet weight and male gonad production. A concentration of 91·8 μ liter⁻¹ caused the mortality rate to increase 100-fold over control exposures (0·63 μ liter⁻¹). Sublethal effects on growth and gonad production could have been caused by either direct biochemical inhibition by H₂S or secondarily through behavioral modifications. Hydrogen sulfide concentrations above 165·8 μ liter⁻¹ are common near sewage outfalls and could contribute to changes in species composition and sediment toxicity that occur there.     

Reproductive success, xenobiotic contaminants and hepatic mixed-function oxidase (MFO) activity in Platichthys stellatus populations from San Francisco Bay

To identify some specific effects of organic contaminants on fisheries in an urbanized estuary we compared the reproductive success of starry flounder from San Francisco Bay with concentrations of tissue contaminants and hepatic mixed-function oxidase (MFO) activity. We found significantly lower (P < 0·05) sediment concentrations of total identified polynuclear aromatic hydrocarbons (PAHs) in the less urbanized San Pablo Bay (SP) area (Fig. 1) than in the more urbanized central bay (CB) stations (Table 1). For flounder in early gametogenesis (August and September) the SP fish (n = 20) had significantly lower (P < 0·01) liver concentrations of Aroclor 1260 (0·34 ± 0·14 μg/g) than those at the CB stations: Berkeley (BK, n = 20, 1·6 ± 1·6 μg/g); Oakland (OK, n = 16, 2·3 ± 2·8 μg/g); and Alameda (AL, n = 4, 2·2 ± 1 μg/g). A similar pattern existed for DDT concentrations: SP = 0·2 ± 0·16 μg/g; BK = 0·1 ± 0·34 μg/g; OK = 0·4 ± 0·53 μg/g; and AL = 0·4 ± 0·33 μg/g. Total PAHs in livers were as follows: SP = 0·14 μg/g; BK = 2·6 μg/g; OK = 1·4 μg/g; and AL = 14 μg/g. Although gonad index, liver index, and presence of fin rot are inversely related to aryl hydrocarbon hydroxylase (AHH) activity, healthy fish in a similar reproductive state have lower AHH activities in the SP area. For example, in August and September, 1984, mean AHH activities were as follows: SP = 203 ± 89, and CB = 355 ± 200 pmol 3-OH-B[a]P mg microsomal protein min. We found a log-linear relationship for AHH activity and its percent inhibition by 7,8-benzoflavone (10⁻⁴m) and only a few fish from SP showed enhanced AHH activity after addition of 7,8-benzoflavone. This suggests that most of the starry flounder in San Francisco Bay are induced.     

Assessing Trends in Nutrient Concentrations in Coastal Shelf Seas: a Case Study in the Irish Sea

Single point time-series data collected in the Irish Sea since 1954 by Allen et al. (1998) have been re-evaluated using more recent data and areal winter surveys of the Celtic and Irish Seas. Survey data illustrate the heterogeneity of nutrient distributions with N (≈28 μM) and P (2·0 μM) enrichment of the eastern Irish Sea relative to the western Irish Sea (7–8 μM N and 0·7 μM P). Salinity nutrient relationships demonstrate distinct regional differences throughout the two seas. Trends in the Isle of Man time-series are unlikely to have resulted from changes in analytical procedures and personnel. Concerns over data quality cannot be resolved and there are no independent data to validate the time-series. Including more recent data shows P has declined since the late 1980s and N concentrations have remained stable since the mid 1970s. The absence of a Si trend is consistent with limited anthropogenic influence on riverine Si concentrations. Trends in N and P are consistent with changes in riverine concentrations of these two nutrients and the biogeochemical processes controlling their cycling in shelf waters. Denitrification is the most likely reason for offshore Irish Sea concentrations of N being lower than expected.