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.     

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

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

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.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, R² = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).     

Comparison of techniques for pre-concentrating radium from seawater

In the framework of the KEOPS project (KErguelen: compared study of the Ocean and the Plateau in Surface water), we aimed to provide information on the water mass pathways and vertical mixing on the Kerguelen Plateau, Southern Ocean, based on ²²⁸Ra profiles. Because ²²⁸Ra activities are extremely low in this area (~ 0.1 dpm/100 kg or ~ 2.10^− 18 g kg^− 1), the filtration of large volumes of seawater was required in order to be able to detect it with minimal uncertainty. This challenging study was an opportunity for us to test and compare methods aimed at removing efficiently radium isotopes from seawater. We used Mn-fiber that retains radium and that allows the measurement of all four radium isotopes (²²⁶Ra, ²²⁸Ra, ²²³Ra, ²²⁴Ra). First, we used Niskin bottles or the ship's seawater intake to collect large volumes of seawater that were passed onto Mn-fiber in the laboratory. Second, we filled cartridges with Mn-fiber that we placed in tandem on in situ pumps. Finally, we fixed nylon nets filled with Mn-fiber on the frame of in situ pumps to allow the passive filtration of seawater during the pump deployment.Yields of radium fixation on the cartridges filled with Mn-fiber and placed on in situ pumps are ca. 30% when combining the two cartridges. Because large volumes of seawater can be filtered with these pumps, this yields to effective volumes of 177–280 kg (that is, higher than that recovered from fourteen 12-l Niskin bottles). Finally, the effective volume of seawater that passed through Mn-fiber placed in nylon nets and deployed during 4 h ranged between 125 and 364 kg. Consequently, the two techniques that separate Ra isotopes in situ are good alternatives for pre-concentrating radium from seawater. They can save ship-time by avoiding repeated CTD casts to obtain the large volumes of seawater. This is especially true when in situ pumps are deployed to collect suspended particles. However, both methods only provide ²²⁸Ra/²²⁶Ra ratios. The determination of the ²²⁸Ra specific activity is obtained by multiplying this ratio by the ²²⁶Ra activity measured in a discrete sample collected at the same water depth.     

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.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

Measurement of manganese, zinc and cadmium complexation in seawater using Chelex ion exchange equilibria

Equilibria between Chelex 100* and manganese, zinc and cadmium ions were used to determine the complexation of these trace metals in 36‰ Gulf Stream seawater at 25°C and pH 8.2. The method utilized radiotracers (⁵⁴Mn, ⁶⁵Zn, and ¹⁰⁹Cd) to quantify trace metal adsorption from trace metal-amended seawater and from seawater containing a series of ethylenediaminetetracetate (EDTA)—metal ion buffers. Results were consistent with Chelex adsorption of both trace metal ions and trace metal—EDTA chelates. Equilibrium models fitted to the data were used to establish conditional stability constants for Chelex adsorption of manganese, zinc and cadmium ions and for adsorption of EDTA-chelates. These models also yielded ratios of free metal ions to total dissolved trace metal concentrations in seawater: 10^−0.1 for manganese, 10^−0.2 for zinc, and 10^−1.5 for cadmium. Independent measurements with a cadmium ion-selective electrode also yielded a free: total cadmium ratio of 10^−1.5.     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

The rate of oxidation of ferrous iron in seawater and the partition of elements between iron oxides and seawater

At the Minamichita Beach Land (Mihama-cho, Aichi, Japan), seawater is pumped up from underground and is supplied to aquaria. The underground seawater containsca. 2 ppm of Fe (II), 0.1 ppm of Mn (II) and a little dissolved oxygen. Iron oxide is formed in the seawater when aerated. The oxidation rate of Fe (II) was measured to be 1.4×10¹⁴ mol^–3 l ³ min^–1, which is comparable to the lowest values in the literature. The slow rate of Fe (II) oxidation obtained here can be attributed to the presence of organically bound iron in the seawater. The distribution coefficient of cations between seawater and iron oxide phase was in the order of Cu>Ni>Co>Cd>Mn, which is consistent with that predicted from their hydrolysis constants. The adsorption affinity sequence of oxyanions was phosphate >vanadate> molybdate. The difference in phosphate from the prediction of the adsorption theory was attributed to the formation of ferriphosphate on the oxide surface. On the basis of these data, the limitation and usefulness in the application of the distribution coefficients to marine environments were discussed.     

A sensitive and rapid method for analysis of dissolved mono- and polysaccharides in seawater

A spectrophotometric method is described for the determination of dissolved mono- and polysaccharides in seawater. It is based upon the well known alkaline ferricyanide reaction, but uses the reagent 2,4,6-tripyridyl-s-triazine (TPTZ) to give a strongly colored complex with the reduced iron. The method has been tested on model carbohydrates and other compounds, and also on natural samples of coastal and oceanic waters. Total carbohydrate content of the natural samples ranged from 5.2 to 25.1 μmol glucose-Cl⁻¹. The coefficient of variation was typically below 6% for values near 17 μmol Cl⁻¹ and approximately 10% for values near 3.5 μmol Cl⁻¹.     

Degradation of crude oils byPseudomonas sp. in enriched seawater medium

Microbial degradation of five crude oils such as Arabian light, Berri, Murban, Khafji and Minas crude oil by a pure bacterial strain,Pseudomonas sp. isolated from the sea water sampled at Kawasaki Harbor in Tokyo Bay, was studied experimentally in the enriched seawater medium.The degradation of crude oils was determined in total residual oil and in four fractions of saturated, aromatics, asphaltene and column residue by use of the column chromatography with activated alumina.The saturated fraction was shown to be most biodegradable. The aromatics followed for all five crude oils examined and the asphaltene was biodegradable to some extent. The column residue was not apparently degraded byPseudomonas sp. within 30 days. Each of Arabian light, Berri or Murban crude oil was degraded from 59 to 63.5 %, Khafji crude oil 49 % and Minas crude oil, solid at room temperature, only 33 %. Degradation rate of the five crude oils was determined to be in a range from 2.88 to 17.3 mg-oil 1^–1 hr^–1 or from 6.0×10^–12 to 1.56×10^–10 mg-oil cell^–1 hr^–1. Relative degradation ofn-paraffins of different carbon numbers in the saturated fraction was found to be similar regardless of carbon number for the five crude oils.     

Polycyclic aromatic hydrocarbons in surface seawater and in indigenous mussels (Mytilus galloprovincialis) from coastal areas of the Saronikos Gulf (Greece)

Polycyclic aromatic hydrocarbons (PAHs) were identified and measured in surface seawater and in the tissues (gills and mantle) of indigenous black mussels, Mytilus galloprovincialis, collected from three coastal sites of Saronikos Gulf (Greece), a gulf that exhibits high levels of pollution. The total PAHs measured by spectrofluorometry in the surface seawater were found in the range of 425–459 ng L⁻¹ at the most polluted sites 1 and 2 (Elefsis Bay–Salamis Island) and in the range of 103–124 ng L⁻¹ at site 3 (Aegina Island). PAHs' sources in seawater were identified by application of specific PAH ratios, such as phenanthrene/anthracene and fluoranthene/pyrene. Levels of PAHs in soft tissues (gills and mantle) of indigenous mussels were much higher than those reported for seawater. Total PAH concentrations in mantle tissues were in the range of 1300–1800 ng g⁻¹ dry weight (dw) tissue at sites 1 and 2 and approximately 380 ng g⁻¹ dw at site 3. In gill tissues total PAH concentrations were in the range of 1480–2400 ng g⁻¹ dw at sites 1 and 2 and approximately 430 ng g⁻¹ dw at site 3. PAHs composition was dominated by two-, three- and four-ring compounds in seawater, where 17 different PAH compounds were identified and measured in mussel tissues. Mussels can be used as sentinel organisms to monitoring PAHs' contamination, since they concentrate PAHs from the surrounding water media and therefore making the chemical analysis simpler and less prone to error than that for water. In surface seawater possible weathering and photodegradation due to hot climates contribute to reduced PAHs concentrations.     

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.     

ADSORPTION ACTION OF BASIC ZINC CARBONATE ADSORBENT ON URANIUM IN NATURAL SEAWATER

1. The adsorption action of basic zinc carbonate adsorbent on uranium in natural seawater can be expressed with the following formula of adsorption isotherm:C=k(U*)n = 8.51× 10-1(U*)0.49,where C is the concentration of uranium on adsorbent; U* is content of uranium in natural seawater employed.2. when the quantity of basic zinc carbonate adsorbent (T) is constant, with the increase of natural seawater quantity through the adsorption column (G), also increased are the adsorption content of uranium of the adsorbent (U), the concentration of uranium on the adsorbent (C) and the concentration of residual uranium (C0*) in natural seawater after adsorbing uranium, while the rate of recovery of uranium (R) is decreased. With the increase of (G) the coefficient of distribution (Kd) decreases to a certain value and then a little rises again.     

The effect of pressure on the solubility of amorphous silica in seawater at 0°C

The solubility of amorphous silica in seawater at 0°C and from 1 to 1,220 atm. was found to be a linear function of pressure above 270 atm., but to deviate from linearity below that pressure. Using a quadratic derivation of Planck's equation, ΔV for the dissolution was found to be −16.5 cm³mole⁻¹, and Δk was found to be −4.4 · 10⁻² cm³ mole⁻¹ atm⁻¹∂Δk/∂P was found to be 27.2 · 10⁻⁵ cm³ mole⁻¹ atm⁻² which is too significant a factor to allow the commonly made assumption that ∂Δk/∂P =0. North's (1973) model of hydration suggests that this non-zero ∂Δk/∂P may indicate that the silicic acid molecule is more extensively hydrated at lower pressures.If the pressure in an experiment is suddenly lowered to atmospheric pressure after equilibrium solubility had been attained at the higher pressure, the precipitation that occurs to reduce the resulting supersaturation is complete within one hour in the experimental system used in this study.     

Phytoplankton growth, microzooplankton herbivory and community structure in the southeast Bering Sea: insight into the formation and temporal persistence of an Emiliania huxleyi bloom

Using the seawater dilution technique, we measured phytoplankton growth and microzooplankton grazing rates within and outside of the 1999 Bering Sea coccolithophorid bloom. We found that reduced microzooplankton grazing mortality is a key component in the formation and temporal persistence of the Emiliania huxleyi bloom that continues to proliferate in the southeast Bering Sea. Total chlorophyll a (Chl a) at the study sites ranged from 0.40 to 4.45 μg C l⁻¹. Highest phytoplankton biomass was found within the bloom, which was a mixed assemblage of diatoms and E. huxleyi. Here, 75% of the Chl a came from cells >10 μm and was attributed primarily to the high abundance of the diatom Nitzschia spp. Nutrient-enhanced total phytoplankton growth rates averaged 0.53 d⁻¹ across all experimental stations. Average growth rates for >10 μm and <10 μm cells were nearly equal, while microzooplankton grazing varied among stations and size fractions. Grazing on phytoplankton cells >10 μm ranged from 0.19 to 1.14 d⁻¹. Grazing on cells <10 μm ranged from 0.02 to 1.07 d⁻¹, and was significantly higher at non-bloom (avg. 0.71 d⁻¹) than at bloom (avg. 0.14 d⁻¹) stations. Averaged across all stations, grazing by microzooplankton accounted for 110% and 81% of phytoplankton growth for >10 and <10 μm cells, respectively. These findings contradict the paradigm that microzooplankton are constrained to diets of nanophytoplankton and strongly suggests that their grazing capability extends beyond boundaries assumed by size-based models. Dinoflagellates and oligotrich ciliates dominated the microzooplankton community. Estimates of abundance and biomass for microzooplankton >10 μm were higher than previously reported for the region, ranging from 22,000 to 227,430 cells l⁻¹ and 18 to 164 μg C l⁻¹. Highest abundance and biomass occurred in the bloom and corresponded with increased abundance of the large ciliate Laboea, and the heterotrophic dinoflagellates Protoperidinium and Gyrodinium spp. Despite low grazing rates on phytoplankton <10 μm within the bloom, the abundance and biomass of small microzooplankton (<20 μm) capable of grazing E. huxleyi was relatively high at bloom stations. This body of evidence, coupled with observed high grazing rates on large phytoplankton cells, suggests the phytoplankton community composition was strongly regulated by herbivorous activity of microzooplankton. Because grazing behavior deviated from size-based model predictions and was not proportional to microzooplankton biomass, alternate mechanisms that dictate levels of grazing activity were in effect in the southeastern Bering Sea. We hypothesize that these mechanisms included morphological or chemical signaling between phytoplankton and micrograzers, which led to selective grazing pressure.     

Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Investigation of Cd, Cu, Ni and Th in the colloidal size range in the Gulf of Maine

Size-fractionated seawater samples were collected from the Gulf of Maine to determine the fraction (f_c/d) of total dissolved (< 1 μm) Cd, Cu, Ni and ²³⁴Th in the colloidal size range (1,000 nominal molecular weight, NMW, to 1 μm) using cross-flow filtration. Colloidal Cd, Cu and Ni represents < 1–7% of the total dissolved concentration in these shelf waters and increases with an increase in particle concentration. By comparison, results obtained for particle-reactive ²³⁴Th indicate that < 1–47% of total dissolved is associated with the colloidal size fraction. A revised relationship between the concentration of colloids (C_c) and suspended particles (C_p) is reported (log C_c = 0.66 log C_p −2.01 kg L⁻¹) and used to examine the dependence of f_c/d for these metals on the concentration of suspended particles for C_p = 0.01–100 mg L⁻¹. Results indicate that a significant fraction (˜ 10–30%) of Cd, Cu, Ni and ²³⁴Th in the traditionally defined ‘dissolved’ fraction may exist in the colloidal size range in regions characterized by high particle concentrations (C_p > 1–10 mg L⁻¹), such as in near-shore and estuarine waters.