Surface boundary-layer variability off Northern California, USA, during upwelling

A five-element mooring array is used to study surface boundary-layer transport over the Northern California shelf from May to August 2001. In this region, upwelling favorable winds increase in strength offshore, leading to a strong positive wind stress curl. We examine the cross-shelf variation in surface Ekman transport calculated from the wind stress and the actual surface boundary-layer transport estimated from oceanic observations. The two quantities are highly correlated with a regression slope near one. Both the Ekman transport and surface boundary layer transport imply curl-driven upwelling rates of about 3×10⁻⁴ m s⁻¹ between the 40 and 90 m isobaths (1.5 and 11.0 km from the coast, respectively) and curl-driven upwelling rates about 1.5×10⁻⁴m s⁻¹ between the 90 and 130 m isobaths (11.0 and 28.4 km from the coast, respectively). Thus curl-driven upwelling extends to at least 25 km from the coast. In contrast, upwelling driven by the adjustment to the coastal boundary condition occurs primarily inshore of the 40-m isobath. The upwelling rates implied by the differentiating the 40-m transport observations with the coastal boundary condition are up to 8×10⁻⁴ m s⁻¹. The estimated upwelling rates and the temperature–nitrate relationship imply curl-driven vertical nitrate flux divergences are about half of those driven by coastal boundary upwelling.     

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.     

Association of picophytoplankton distribution with ENSO events in the equatorial Pacific between 145°E and 160°W

Climatological variability of picophytoplankton populations that consisted of >64% of total chlorophyll a concentrations was investigated in the equatorial Pacific. Flow cytometric analysis was conducted along the equator between 145°E and 160°W during three cruises in November–December 1999, January 2001, and January–February 2002. Those cruises were covering the La Niña (1999, 2001) and the pre-El Niño (2002) periods. According to the sea surface temperature (SST) and nitrate concentrations in the surface water, three regions were distinguished spatially, viz., the warm-water region with >28 °C SST and nitrate depletion (<0.1 μmol kg⁻¹), the upwelling region with <28 °C SST and high nitrate (>4 μmol kg⁻¹) water, and the in-between frontal zone with low nitrate (0.1–4 μmol kg⁻¹). Picophytoplankton identified as the groups of Prochlorococcus, Synechococcus and picoeukaryotes showed a distinct spatial heterogeneity in abundance corresponding to the watermass distribution. Prochlorococcus was most abundant in the warm-water region, especially in the nitrate-depleted water with >150×10³ cells ml⁻¹, Synechococcus in the frontal zone with >15×10³ cells ml⁻¹, and picoeukaryotes in the upwelling region with >8×10³ cells ml⁻¹. The warm-water region extended eastward with eastward shift of the frontal zone and the upwelling region during the pre-El Niño period. On the contrary, these regions distributed westward during the La Niña period. These climatological fluctuations of the watermass significantly influenced the distribution of picophytoplankton populations. The most abundant area of Prochlorococcus and Synechococcus extended eastward and picoeukaryotes developed westward during the pre-El Niño period. The spatial heterogeneity of each picophytoplankton group is discussed here in association with spatial variations in nitrate supply, ambient ammonium concentration, and light field.     

Interaction of cadmium and copper with surface-active organic matter and complexing ligands released by marine phytoplankton

The organic matter released by the marine phytoplankton species Dunaliella tertiolecta and its physico-chemical interaction with cadmium and copper ions were studied by electrochemical methods (differential pulse anodic stripping voltammetry (DPASV) and a.c. polarography). The interactions with cadmium and copper were studied at the model interface (mercury electrodesolution) and in the bulk phase by measuring the complexing ability of the released organic material.The axenic cultures were grown on different growth media, without and with trace metals and chelators. Culture media were analyzed 10 days after inoculation, containing 5 × 10⁵−1.2 × 10⁶ cells cm⁻³ when untreated or after separation of cells by gentle centrifugation.It was found that the content and type of the released surface-active material and complexing ligands depend on the initial composition of the growth media. In all cases, strong interaction of excreted organic substances with copper in the bulk phase and with cadmium at the model interface were observed.A rather high value of the complexing capacity, 9.5 × 10⁻⁷ mol Cu²⁺ dm⁻³, was found in the culture grown on medium without trace metals and chelators (medium I) whereas the surface activity of this culture was not high (0.2 mg dm⁻³ equivalent to Triton-X-100). Higher contents of surface-active material (0.8 and 1.0 mg dm⁻³) were found in cultures grown in media with trace metals and without chelators (II and III), accompanied by a high content of complexing ligands (5.8 × 10⁻⁷ and 9.5 × 10⁻⁷ mol Cu²⁺ dm⁻³). However, if the complexing capacity is calculated per cell the values obtained for cultures grown in media II and III (0.79 × 10⁻¹⁵ and 0.98 × 10⁻¹⁵ mol Cu²⁺ dm⁻³) are lower than for cultures grown on medium I (1.8 × 10⁻¹⁵ mol Cu²⁻ dm⁻³). The exceptional adsorption effects and the copper complexing capacity for medium 1, and the presence of cells with degenerative symptoms can be ascribed to stressed growth conditions, and, particularly, to deficiency of metals. A qualitatively similar behaviour has been observed in natural samples of estuarine waters, indicating the existence of stressed conditions during the mixing of fresh and saline waters.     

Modelling the manganese cycling in two stratified fjords

This paper presents a parameterized model for the particulate and dissolved manganese profiles in two stratified fjords. Rates of oxidation and reduction of manganese are of the order of 1.0 × 10⁻¹⁵ mol cm⁻³ s⁻¹. Oxidation of manganese is probably not promoted by an inorganic surface-catalyzed reaction. Cycling of manganese in the redoxcline is extensive (10–100 cycles) and is related to the input of manganese to the fjords. Calibration of the model against sediment-trap-data allow instantaneous eddy diffusion coefficients to be estimated. These are of the order of 0.01 and 1.0 × 10⁻⁴ cm² s⁻¹.     

Copper complexing capacity of phytoplanktonic cell exudates

Copper complexing capacity of cell exudates of Dunaliella salina in natural seawater culture medium was investigated in order to evaluate the influence of this organism on speciation of trace metals in seawater.Seawater samples were collected at 200 m and 2 miles off the coast and immediately filtered. Copper complexing capacity (CC_Cu) and stability constants (K′) of related cupric complexes were then measured. They were, respectively, 27.1 × 10⁻⁸ mol l⁻¹ and 0.56 × 10⁷ l mol⁻¹ for the samples collected at 200 m and 12.8 × 10⁻⁸ mol l⁻¹ and 6.10 × 10⁷ l mol⁻¹ for those collected 2 miles off the coast. A stock culture (20 ml, 10⁶ cells ml⁻¹) in log-phase was inoculated in 2 l of each sample of filtered natural seawater. The trend of cell influence was estimated on filtered culture medium by measuring CC_Cu and K′ after 1 h, 3 and 7 days. From the results it appears that CC_Cu increased with respect to time and this was related to the growth rate, indicating a certain relationship with cell metabolic activity.It can be concluded that a comparison between the culture referring to 200 m and 2 miles, respectively, shows that the former presents a CC_Cu two times higher than the latter while the K′ is ten times higher at 2 miles than that at 200 m.     

Solvent extraction of copper acetylacetonate in studies of copper(II) speciation in seawater

A liquid-liquid partition, ligand exchange procedure involving the formation of copper(II) complexes with acetylacetone is presented for the determination of stability constants and concentrations of copper chelators in seawater. Acetylacetone competes with natural ligands for copper, and the equilibrium concentration of the copper acetylacetonate complex is used in speciation calculations. The concentration of the complex is calculated by partitioning a fraction of it into an organic phase and determining the total Cu concentration in that phase by back extracting with acid, and analyzing by flameless atomic absorption spectroscopy. The concentration of Cu acetylacetonate in seawater in equilibrium with the organic phase is calculated from the partition coefficient. The simple, thermodynamically well characterized procedure offers several advantages over previous techniques. Studies using organic free seawater and model ligands show good agreement between experimental and calculated conditional stability constants. Studies from seawater in Biscayne Bay, Florida, indicate two ligand types are present; type 1, K₁ = 1.2 × 10¹², C_L1 = 5.1 × 10⁻⁹ M; type 2, K₂ = 2.8 × 10¹⁰, C_L2 = 1.1 × 10⁻⁷ M. Speciation is dominated by ligand type 1. Depth profiles of [Cu(II)]_free/[Cu(II)]_total measured with the procedure at ambient copper concentrations show an increase from < 5 × 10⁻⁵ at 50–60 m to > 1 × 10⁻³ at the surface at two stations off the Florida coast.     

The solubility of CaCO3 in seawater at 2°C based upon in-situ sampled pore water composition

Analyses of the concentration product (Ca²⁺) × (CO₃²⁻) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′_SPc) and aragonite (K′_SPa) in seawater. Regression of the data gives the relation In K′^P_SPc = 1.94 × 10⁻³ δP − 14.59 The 2°C, 1 atm value of K′_SPc is, then, 4.61 × 10⁻⁷ mol² l⁻². The pressure coefficient yields a at 2°C of −43.8 cm³ atm⁻¹. A single station where aragonite is present in the sediments gives a value of K′_SPa = 9.2 × 10⁻⁷ (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′_SPc at 2°C and 1 atm. The calculated is also indistinguishable from the experimental results of Ingle (1975) if is assumed to be independent of pressure.     

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.     

Particle–water interactions of 2,2′,5,5′-tetrachlorobiphenyl under simulated estuarine conditions

A batch sorption technique for the determination of particle–water interactions of hydrophobic organic micropollutants under simulated estuarine conditions is described. Results are presented for the behaviour of 2,2′,5,5′-tetrachlorobiphenyl (2,2′,5,5′-TCB) in river and sea waters, both in the presence and absence of estuarine suspended particles. Adsorption onto particles in sea water was enhanced compared with adsorption in river water owing to salting out of the compound, and possibly of the particulate organic matter, in the presence of high concentrations of dissolved ions. The particle–water distribution coefficient, K_D, decreased from about 120×10³ to 10×10³ ml g⁻¹, and from about 150×10³ to 20×10³ ml g⁻¹, in river water and sea water, respectively, over a particle concentration range of 10–1000 mg l⁻¹. Incomplete recovery of compound from the reactor walls is partly responsible for a particle concentration effect, while artefacts relating to inadequate sediment and water phase separation were ruled out following further experiments. The particle concentration effect, which is replicated in many field studies of hydrophobic organic micropollutants, including 2,2′,5,5′-TCB, is incorporated into a simple partitioning model and is discussed in the context of the likely estuarine behaviour of such compounds.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

Resting stages of Tortanus forcipatus (Crustacea, Calanoida) in sediments of Victoria Harbor, Hong Kong

The distribution and abundance of viable and non-viable (so-called resting eggs) embryos of the calanoid copepod Tortanus forcipatus were determined in the laboratory by the enumeration of nauplii that emerge from sediments collected in Victoria Harbor (Hong Kong). Sediment cores sliced down to a depth of 37 cm showed the highest number of viable resting eggs near the surface layer (0–5 cm). The number of viable eggs sharply decreased with sediment depth, particularly at the inner harbor stations, although diapause eggs remained viable as deep as 25 cm. ²¹⁰Pb analyses of the sediments indicated that the mean egg age was 4.9 years. The egg mortality of T. forcipatus in the sediments was 0.135 year⁻¹, or 78.22% annual egg survival, calculated by regressing ln (egg density) from sediment age. The range of horizontal distribution of viable resting eggs was 24.25 × 10³–58.90 × 10³ m⁻², with a mean value of 36.8 × 10³ m⁻² over all stations. The accumulation of viable resting eggs that can persist for an extended period of time provided evidence for the existence of an egg bank of T. forcipatus in the sediments of Victoria Harbor.     

Transport Through the Contraction Area in the Little Belt

The Great Belt, the Øresund and the Little Belt connect the central Baltic Sea and the Kattegat. A fixed station was moored in the contraction area in the Little Belt during the period 18–28 July 1995, measuring temperature, salinity and current in two levels, while discharge was measured by the RVDana. The composite Froude number calculated at the fixed station shows that the two layer flow through this area was most often supercritical. The discharges were satisfactorily related to the currents measured at the fixed station, and time-series of transports through the Little Belt were established. When compared to the transports through the Øresund the water transport ratio (Øresund:Little Belt) was found to be 4·4, while the salt transport ratio was found to be 3·0. The resistance of the Little Belt, when considering the differences in sea level from Gedser to Hornbæk, was 1839×10⁻¹² s² m⁻⁵. On the basis of water level and surface salinity measurements made during the period 1931–76, a net discharge of 2300 m³ s⁻¹and a net salt transport of 36 tonnes s⁻¹through the Little Belt from the central Baltic Sea were found.     

Benthic Denitrification in the Gulf of Bothnia

Denitrification was measured over an 8-month period in the Bothnian Bay and the Bothnian Sea, the two northernmost basins of the Baltic Sea. The recorded rates varied between 0 and 0·94 mmol N m⁻²day⁻¹. In the Bothnian Sea, a seasonal pattern could be discerned with high rates in spring, no rate in summer and a moderate rate in winter. In the Bothnian Bay, no such seasonality was observed. It is suggested that denitrification in the Gulf of Bothnia is regulated by sediment nitrification. Calculation of annual mean rates of denitrification gave that the amount of nitrogen consumed by denitrification corresponded to 1·45×10⁴tons N year⁻¹for the Bothnian Bay and 3·45×10⁴tons N year⁻¹for the Bothnian Sea. A comparison with total N input (river runoff, point sources and atmospheric deposition) to the two basins showed that the proportion of N removed through denitrification amounted to 23% for the Bothnian Bay and 31% for the Bothnian Sea.     

Total organic carbon distribution and budget through the Strait of Gibraltar in April 1998

In order to investigate total organic carbon (TOC) exchange through the Strait of Gibraltar, samples were taken along two sections from the western (Gulf of Cádiz) and eastern (Western Alboran Sea) entrances of the Strait and at the middle of the Strait in April 1998. TOC was measured by using a high-temperature catalytic oxidation method. The results referenced here are based on a three-layer model of water mass exchange through the Strait, which includes the Atlantic inflow, Mediterranean outflow and an interface layer in between. All layers were characterised by a decrease of TOC concentrations from the Gulf of Cádiz to the Western Alboran Sea: from 60–79 to 59–66 μM C in the Atlantic inflow and from 40–60 to 38–52 μM C in the Mediterranean waters, respectively. TOC concentrations in the modified North Atlantic Central Water varied from 43 to 55 μM C. Intermediate TOC values were measured in the interface layer (43–60 μM C). TOC concentrations increased from the middle of the Strait towards continents indicating a contribution of organic carbon of photosynthetic origin along Spain and Morocco coasts or TOC accumulation due to upwelling in the northeastern part of the Strait. Our results indicate that the short-term variability caused by the tide greatly impacts the TOC distribution, particularly in the Gulf of Cádiz. The TOC input from the Atlantic Ocean to the Mediterranean Sea through the Strait of Gibraltar varies from 0.9×10⁴ to 1.0×10⁴ mol C s⁻¹ (or 0.28×10¹² to 0.35×10¹² mol C year⁻¹, respectively). This estimate suggests that the TOC inflow and outflow through the Strait of Gibraltar are two and three orders of magnitude higher than reported via the Turkish Straits and Mediterranean River inputs.     

Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium

A program of long-term observation of suspended solids (TSS), particulate organic carbon (POC) and cadmium transported into the Gironde estuary (France) by its major tributaries has been carried out between 1990 and 1999. This decade included contrasting hydrologic cycles and appears representative of a much longer period (1959–1999). The Garonne and the Dordogne river systems are the main tributaries of the Gironde estuary and derive their waters from drainage basins with different geological, industrial and agricultural features. To better understand their respective contributions, they have been observed separately and compared. Water and TSS fluxes of the Garonne River show greater temporal variations and discharge is more related to the hydrology of the drainage basin (e.g. wet/dry years, local flood events etc.). As POC and particulate Cd concentrations in suspended matter are much less variable than turbidity, their fluxes are mainly controlled by the TSS transport. A major part of annual fluxes of TSS and associated pollutants may occur within few flood days (depending on various parameters, e.g. intensity, duration, season, etc.), and also the succession of dry and wet years has an important influence on annual fluxes. The presented data allow calculating fluvial inputs into the Gironde as the sum of fluxes transported by its major tributaries, the Garonne and the Dordogne river systems. Mean annual fluxes into the Gironde observed in 1990–1999 are about 34×10⁹ m³ year⁻¹ for river water, 3.24×10⁶ t year⁻¹ for suspended solids (TSS) and 9.88×10⁹ mol year⁻¹ for particulate organic carbon (POC). Generally, these fluxes are dominated by the contributions of the Garonne River. However, in dry years, the mean contribution of the Dordogne river system (including Dronne and Isle rivers) to the POC input into the estuary exceeded that of the Garonne. This reflects significant differences in vegetation and soil due to natural properties and land management of the basins. Mean Cd fluxes into the estuary are about 110×10³ mol year⁻¹ of which 19.6×10³ mol year⁻¹ are transported in the dissolved and 90.8×10³ mol year⁻¹ in the particulate phases, respectively. In 1991 (dry year), the net (dissolved) Cd flux towards the ocean exceeded the gross fluvial input of total Cd, suggesting the release of Cd from an important stock in the maximum turbidity zone (MTZ) or the fluid mud of the Gironde estuary.     

Shear and Richardson number in a mode-water eddy

Measurements of stratification and shear were carried out as part of the EDDIES tracer release experiment in mode-water eddy A4 during the summer of 2005. These measurements were accomplished using both shipboard instrumentation and a drifting mooring. A strong relationship between shear intensity and distance from the center of the eddy A4 was observed with the shipboard ADCP. Diapycnal diffusivity at the SF₆ tracer isopycnal prior to and during the release was estimated from the drifting mooring to be 2.9×10⁻⁶ m² s⁻¹. Diffusivity increased by an order of magnitude to 3.2×10⁻⁵ m² s⁻¹ during the period of the final tracer survey in early September, which was similar to the value estimated from the tracer analysis for the whole experiment (3.5×10⁻⁵ m² s⁻¹, [Ledwell, J.R., McGillicuddy Jr., D.J., Anderson, L.A., 2008. Nutrient flux into an intense deep chlorophyll layer in a mode-water eddy. Deep-Sea Research II, this issue [doi:10.1016/j.dsr2.2008.02.005]].     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

The solubility of calcite in seawater at atmospheric pressure and 35%permil; salinity

The apparent (stoichiometric) solubility product of calcite in artificial seawater of salinity 35‰ was measured by a saturometer technique. The value of the apparent solubility product was found to be (4·59 ± 0·05) × 10⁻⁷ moles/(kilogram of seawater)² at 25°C with a temperature coefficient of −0·0108 × 10⁻⁷/°C between 2 and 25°C. These values are significantly smaller than those found by MacIntyre (1965) and other workers. The effect of these results on the saturation of the oceans with respect to calcite is examined.