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.     

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.     

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.     

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.     

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.     

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.     

Estuarine transformation of organic matter: single coalescence events of estuarine surface active particles

Individual surface-active particles (SAP) in aqueous environmental samples can be characterized through their coalescence at a model hydrophobic interface. Each coalescence event is recorded as an electrical signal. As the electrical signal is a current transient (time on a millisecond scale), the sequence of fast processes leading to the formation of a condensed film can be studied from the moment of first attachment at the interface.In the stratified Krka Estuary, SAP are present in maximum concentrations (10⁷−5 × 10⁸ particles l⁻¹ min the size range > 1 μm) at the halocline (freshwater-seawater interface). This highly surface-active fraction of particulate organic matter can be viewed as oily droplets. SAP are fluid, and are readily transformed at interfaces to films of molecular thickness (surface area per particle is in the range 10⁻⁵–10⁻² cm²).Comparison of response of individual SAP with model particles, and the frequency of their appearance in estuarine samples, shows that a majority of estuarine SAP has, in terms of viscosity and film permeability, the properties of oleic acid. A significant fraction of SAP have more rigid structures, comparable to moleic acid + cholesterol model particles. A small fraction ( > 1%) behaves as phytoplankton cells with fluid outer membranes.We have also presented evidence for a strong interaction between elemental mercury and SAP, which is not sensitive to the molecular structure of the organic phase. The puzzling accumulation of mercury at the halocline of the Krka Estuary may be regarded as the result of interaction of elemental mercury with SAP.     

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.     

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.     

Estradiol-17β and o,p′-DDT stimulate gonadotropin release in Atlantic croaker

Xenobiotic estrogens have the potential to act at a variety of estrogen-responsive target tissues on the hypothalamic-pituitary-gonadal axis. However, to date most studies in fish have focused on stimulation of vitellogenin synthesis by the liver. In the present study the effects of the xenoestrogen o,p′-DDT and estradiol-17β on the neuroendocrine control of gonadotropin secretion were compared. Atlantic croaker (Micropogonias undulatus) were exposed to o,p′-DDT (0.02 and 0.1 μgg⁻¹ body weight day⁻¹) in the diet for 3 and 7 weeks during the gonadal recrudescence phase. The o,p′-DDT exposure elicited a significant increase in plasma gonadotropin levels after both 3 and 7 weeks of exposure. The stimulatory effect of o,p′-DDT on basal (spontaneous) gonadotropin release was accompanied by a slight increase in ovarian growth as evidenced by the increase in gonadosomatic index. It appears that the stimulation of gonadotropin release by o,p′-DDT during early-recrudescence phase results in enhanced ovarian growth. A comparable stimulatory effect was observed with estradiol-17β treatment during early- and late-recrudescence phases of the ovarian cycle using three injections on alternate days and slow release silastic implants (five days). The present study provides the first evidence for an estrogen-like action of o,p′-DDT on gonadotropin release in a teleost model.     

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.     

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (²²²Rn, ^{223,224,226,228}Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5 mg L^− 1) close to zero salinity and increased several-fold ( 18 mg L^− 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet.Surface water-column ²²²Rn activities were most elevated (> 28 dpm L^− 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (^{223,224,226,228}Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess ²²⁶Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 × 10⁵ m³ d^− 1 (20–74 L m^− 2 d^− 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH₄⁺ and PO₄^− 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5 μmol m^− 2 d^− 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates.     

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.     

Determination of adsorbed and absorbed polychlorinated biphenyls (PCBs) in seawater microorganisms

To distinguish between adsorbed and absorbed PCBs in seawater microorganisms, 2,2′,4,4′,5,5′-hexachlorobiphenyl (IUPAC #153; HCB) was added to a pure culture of Chrysochromulina apheles Moestrup et H.A. Thomsen. After the addition of the HCB, the cells were immediately harvested onto 2 μm polycarbonate filters and rinsed with a gradient of ethanol concentrations. Rinsing with 40% ethanol (v/v) was found to remove 80% of the HCB, which was loosely adsorbed to the cell surfaces, but did not extract the interior of the cells, as tested by chlorophyll a analysis. This method was used in a time course experiment which estimated PCBs adsorption and absorption to different groups of plankton organisms. Three different ¹⁴C-PCBs, 4-chlorobiphenyl (IUPAC #3; MCB), 2,2′,5,5′-tetrachlorobiphenyl (IUPAC #52; TCB), and 2,2′,4,4′,5,5′-hexachlorobiphenyl (IUPAC #153, HCB), were incubated in seawater from the northern Baltic Sea during a spring bloom. Samples were taken every third day and separated by filtration into three fractions; 0.2–2 μm (bacteria), 2–10 μm (flagellates), and >10 μm (microplankton; phytoplankton and protozoa). Two subsamples were retained from each size fraction. One of the subsamples was left untreated, to obtain adsorbed plus absorbed PCB, while the other subsample was rinsed with 40% of ethanol, to obtain the absorbed PCB. The sorption was found to vary depending on the hydrophobicity of the compounds, the structure of the cell membranes, and the lipid content and composition of the cells. The absorption increased for the TCB and the HCB in the largest size fraction over time, which coincided with an increase of the neutral and non-polar lipids.     

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.     

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.     

Seasonal and depth-related dynamics of prokaryotes and viruses in surface and deep waters of the northwestern Mediterranean Sea

The study site located in the northwestern Mediterranean Sea was visited nine times in 2005–2006 to collect water samples from the epi- (5 m), meso- (200, 600 m), and bathypelagic (1000, 2000 m) zone. Total abundance of prokaryotes and viruses was determined by flow cytometry (FCM). Prokaryotic abundance in the epi-, meso-, and bathypelagic varied between 0.9 and 15.9×10⁵, 0.6 and 2.1×10⁵, and 0.3 and 1.3×10⁵ ml⁻¹, respectively. Variation of viral abundance in the epi-, meso-, and bathypelagic was between 1.2 and 57.5×10⁶, 0.5 and 3.5×10⁶, and 0.4 and 1.3×10⁶ ml⁻¹, respectively. The fraction of low (LNA) and high (HNA) nucleic acid prokaryotes averaged 42.9% and 57.1% throughout the water column and did not differ between depth layers. Throughout the water column the fraction of low, medium, and high fluorescent viruses (Vir-LF, Vir-MF, Vir-HF) averaged 66.3%, 30.2%, and 3.5%. Vir-LF and Vir-MF did not differ between depth layers; however, Vir-HF showed a preference for surface waters. The fraction of LNA cells decreased in the epi- and increased in the bathypelagic with decreasing stratification. The fraction of Vir-LF viruses increased in the epipelagic and decreased in the bathypelagic with increasing prokaryotic abundance. Also, the relationship between viral abundance and the bacterial community was different in surface and deep waters. The data suggest that different mechanisms of interaction between viruses and their prokaryotic hosts prevail at the surface and in deep waters.     

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.     

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

Sources and biogeochemical cycling of particulate selenium in the San Francisco Bay estuary

As part of a study of estuarine selenium cycling, we measured the concentration, chemical form (speciation), and distribution of particulate selenium under various river flow conditions in the North San Francisco Bay (from the Golden Gate to the Sacramento and San Joaquin Rivers). We also conducted laboratory studies on the accumulation of selenium by phytoplankton, the critical first step in the transformation of dissolved to particulate selenium. Total particulate selenium concentration in the North SF Bay was relatively constant between high and low flow periods, ranging spatially from 0.05 to 0.35 nmol l⁻¹ and comprising between 5 and 12% of the total water column selenium inventory. Mean concentrations were generally highest in the Carquinez Strait–Suisun Bay region (salinity 0–17) and lowest in Central Bay. However, selenium content of suspended particles varied with river flow, with higher content during low flow (9.76 ± 4.17 nmol g⁻¹; mean ± sd; n = 67) compared to high flow (7.10 ± 4.24 nmol g⁻¹; n = 39). Speciation analyses showed that most particulate selenium is organic selenide (45 ± 27%), with a smaller proportion (typically <30%) of adsorbed selenite + selenate and a varying proportion (35 ± 28%) of elemental selenium. Based on the amount of elemental selenium in the seston (total suspended material), we calculate that resuspension of estuarine sediments could contribute 29–100% of particulate selenium in the water column. While selenium content of SF Bay seston (>0.4 μm) is relatively unenriched compared to phytoplankton (13.6–155 nmol g⁻¹ dry weight) on a mass basis, when normalized to carbon or nitrogen, seston contains a similar selenium concentration to SF Bay sediments or phytoplankton cultures. SF Bay seston is thus comprised of selenium-rich phytoplankton and phyto-detritus, but also inorganic clay mineral particles that effectively “dilute” total particulate selenium. Selenium concentrations in algal cultures (11 species) exposed to 90 nmol l⁻¹ selenite show relatively large differences in selenium accumulation, with the diatoms, chlorophytes and cryptophytes generally having lower selenium cell content (3.8 ± 2.7 × 10⁻⁹ nmol selenium cell⁻¹) compared to the dinoflagellates (193 ± 73 × 10⁻⁹ nmol selenium cell⁻¹). Because phytoplankton are such a rich (but variable) source of selenium, their dynamics could have a profound effect on the particulate selenium inventory in the North SF Bay.