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.     

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.     

Influence of water temperature and oxygenation on the aerobic metabolic scope of Atlantic cod (Gadus morhua)

Environmental influences (temperature and oxygenation) on cod metabolism and their impact on the ecology of this species were investigated. Limiting oxygen concentration curves (O₂ level ranging between 15 and 100% air saturation) were established at 2, 5 and 10°C. The standard metabolic rate (SMR), the maximum metabolic rate and the metabolic scope were then modelled as functions of temperature and/or oxygen saturation. The mean SMR at 2, 5 and 10°C were 19.8±4.9, 30.8±6.1 and 54.3±4.1 mg O₂ h⁻¹ kg⁻¹, respectively. Between 2 and 5°C, the active metabolic rate of cod almost doubled from 65 to 120 mg O₂ h⁻¹ kg⁻¹, to reach 177 mg O₂ h⁻¹ kg⁻¹ at 10°C. In terms of metabolic scope (MS), the temperature rise from 2 to 5°C resulted in a two-fold increase from 45 to 89 mg O₂ h⁻¹ kg⁻¹, with MS reaching 123 mg O₂ h⁻¹ kg⁻¹ at 10°C. Our proposed model describing the impact of temperature and oxygen level provides new insight into the energetic interactions which govern the relationship between Atlantic cod and its environment. We re-examined published experimental and field studies from the angle of the regulation of metabolic power. We suggest that, when faced with heterogeneous or unstable hydrological conditions, cod tend to behaviourally maximise their metabolic scope. Through this adaptive response, fish reduce energy budgeting conflicts and presumably increase the probability of routinely operating away from lethal boundaries.     

Diffusion coefficients of major ions in seawater

Self-diffusion coefficients of five major ions have been determined by a radioactive tracer method (capillary tube method) in seawater of salinity 34.86 at 25°C. Data are presented for Na⁺, Ca²⁺, Cl⁻, SO₄², and HCO₃⁻, which constitute about 95% by weight of sea salt. The influence of temperature and salinity on these coefficients has been studied for Na⁺ and Cl⁻ which are the major components of sea salt: self-diffusion coefficients of these two ions have been measured in seawater, at different temperatures for a salinity of 34.86 and at different salinities for a temperature of 25°C. Diffusion coefficients of the same ions have been determined at 25°C by using another radioactive tracer method (quasi-steady cell method). In this experiment, seawater ions were allowed to diffuse from natural seawater into dilute seawater. Data have been obtained at 25°C for Na⁺, Ca ²⁺, Cl⁻, SO₄²⁻ and HCO₃⁻, corresponding to different salinity gradients.     

Diffusion of seawater ions. Part II. The role of activity coefficients and ion pairing

A theoretical evaluation of basic thermodynamic relationships reveals that variation of activity coefficients, ion pairing and electrical interactions must be considered when modelling ionic diffusion in seawater. The contributions of ion-pair formation and change in activity coefficient along the diffusion path were studied experimentally by conducting diffusion experiments in which solutions of KCl, NaCl, MgCl₂, Li₂SO₄, K₂SO₄, Na₂SO₄ and MgSO₄, at an ionic strength of 0.7, were allowed to diffuse into distilled water. The study reveals that the thermodynamic factor, required to correct for changes in the activity coefficient along the diffusion path, is significant for all the salts studied. Agreement between a simple diffusion model, which does not include ion pairing, and observed data was good for completely dissociated salts, but poor for salts which are known to form ion pairs at the concentration levels studied. The diffusion of MgSO₄, 0.425 of which is associated at I = 0.7, was successfully modelled by assuming that the diffusion coefficient of the MgSO₄⁰ ion pair is different from the diffusion coefficient of the dissociated salt. The diffusion coefficient of this ion pair is estimated to be 1.9 × 10⁻⁵ cm² s⁻¹ at 30°C, as compared to 0.49 × 10⁻⁵ cm² s⁻¹ for the dissociated salt. It is suggested that the high mobility of this ion pair could cause magnesium enrichment in pore water of sulfate depleted sediments.     

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3 and SiO2(OH)2. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH⁻ was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H⁺] 11.7, respectively. Within these ranges the formation of SiO(OH)₃⁻ and SiO₂(OH)₂²⁻ with formation constants log β₋₁₁(Si(OH)₄ SiO(OH)₃⁻ + H⁺) = −9.472 ±0.002 and log β₋₂₁(Si(OH)₄ SiO₂(OH)₂²⁻ + 2H⁺) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H⁺] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Carbon and nitrogen primary productivity in three North Carolina estuaries

Uptake of inorganic carbon and ammonium by the plankton community of three North Carolina estuaries was measured using ¹⁴C and ¹⁵N isotope methods. At 0% light, C appeared to be lost via respiration, and at increasing light levels uptake of inorganic carbon increased linearly, saturated (mean I_k = 358±30 μEin m⁻² s⁻¹), and frequently showed inhibition at the highest light intensities. At 0% light NH₄⁺ uptake was significantly greater than zero and was frequently equivalent to uptake in the light (light independent); at increasing light levels NH₄⁺ uptake saturated (mean I_k = 172±44 μEin m⁻² s⁻¹) and frequently indicated strong inhibition. Light-saturated uptake rates of inorganic carbon and NH₄⁺ were a function of chlorophyll a (r² = 0·7−0·9); average assimilation numbers were 625 nmol CO₂ (μg chl. a)⁻¹ h⁻¹ and 12·9 nmol NH₄⁺ (μg chl. a)⁻¹ h⁻¹ and were positively correlated with temperature (r² = 0·3−0·7). The ratio of dark to light-saturated NH₄⁺ uptake tended to be near 1·0 for large algal populations at low NH₄⁺ concentrations, indicating near light independence of uptake; whereas the ratio was lower for the opposite conditions. These data are interpreted as indicative of nitrogen stress, and it is suggested that uptake of NH₄⁺ deep in the euphotic zone and at night are mechanisms for balancing the C:N of cellular pools. A 24-h study using summed short-term incubations confirmed this; the cumulative C:N of CO₂ and NH₄⁺ uptake during the daylight period was 10–20, whereas over the 24-h period the ratio was 6 due to dark NH₄⁺ uptake. Annual carbon and nitrogen primary productivity were respectively estimated as 24 and 4·0 mol m⁻² year⁻¹ for the South River estuary, 42 and 7·3 mol m⁻² year⁻¹ for the Neuse River estuary, and 9·6 and 1·6 mol m⁻² year⁻¹ for the Newport River estuary.     

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

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

On the form factor scale effect

Four geosim families, with fully available resistance test results, have been re-analyzed to check the possible scale effect on the form factor. The form factor determined by Prohaska's method, with exponent n=4 and ITTC'57 correlation line, increases with the model size in all four cases analyzed. Because of its high correlation coefficient, a linear variation of the form factor with the scale is assumed. It is possible to have a first estimation of the ship's form factor extrapolating for λ=1 in the regression line. Form factor Reynolds number dependency will always be associated with a friction line. Using the ITTC'57 correlation line, the following equation K_S−K_M=1.91·(λ−1)·10⁻³ can be used to estimate the scale effect on the form factor. Calculations carried out, for axisymetric bodies, with some CFD codes are in good agreement with the experimental findings.     

The speciation of Fe(II) and Fe(III) in natural waters

The interactions of Fe(II) and Fe(III) with the inorganic anions of natural waters have been examined using the specific interaction and ion pairing models. The specific interaction model as formulated by Pitzer is used to examine the interactions of the major components (Na⁺, Mg²⁺, Ca²⁺, K⁺, Sr²⁺, Cl⁻, SO₄⁻, HCO₃⁻, Br⁻, CO₃²⁻, B(OH)₄⁻, B(OH)₃ and CO₂) of seawater and the ion pairing model is used to account for the strong interaction of Fe(II) and Fe(III) with major and minor ligands (Cl⁻, SO₄²⁻, OH⁻, HCO₃⁻, CO₃²⁻ and HS⁻) in the waters. The model can be used to estimate the activity and speciation of iron in natural waters as a function of composition (major sea salts) and ionic strength (0 to 3 M). The measured stability constants (K_FeX^*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (K_FeX) and the activity coefficient of iron complexes (γ_FeX) with a number of inorganic ligands in NaClO₄ medium at various ionic strengths: In(K_FeX/γ_Feγ_X) = InK_FeX − In(γ_FeX) The activity coefficients for free ions (γ_Fe, γ_x) needed for this extrapolation have been estimated from the Pitzer equations. The activity coefficients of the ion pairs have been used to determine Pitzer parameters (B_FeX, B_FeX⁰, C_FeX^φ) for the iron complexes. These results make it possible to estimate the stability constants for the formation of Fe(II) and Fe(III) complexes over a wide range of ionic strengths and in different media. The model has been used to determine the solubility of Fe(III) in seawater as a function of pH. The results are in good agreement with the measurements of Byrne and Kester and Kuma et al. When the formation of Fe organic complexes is considered, the solubility of Fe(III) in seawater is increased by about 25%.     

Nitrogen dynamics within a wind-driven eddy

Wind-driven cyclonic eddies are hypothesized to relieve nutrient stress and enhance primary production by the upward displacement of nutrient-rich deep waters into the euphotic zone. In this study, we measured nitrate (NO₃⁻), particulate carbon (PC), particulate nitrogen (PN), their stable isotope compositions (δ¹⁵N-NO₃⁻, δ¹³C-PC and δ¹⁵N-PN, respectively), and dissolved organic nitrogen (DON) within Cyclone Opal, a mature wind-driven eddy generated in the lee of the Hawaiian Islands. Sampling occurred in March 2005 as part of the multi-disciplinary E-Flux study, approximately 4–6 weeks after eddy formation. Integrated NO₃⁻ concentrations above 110 m were 4.8 times greater inside the eddy (85.8±6.4 mmol N m⁻²) compared to the surrounding water column (17.8±7.8 mmol N m⁻²). Using N-isotope derived estimates of NO₃⁻ assimilation, we estimated that 213±59 mmol m⁻² of NO₃⁻ was initially injected into the upper 110 m Cyclone Opal formation, implying that NO₃⁻ was assimilated at a rate of 3.75±0.5 mmol N m⁻² d⁻¹. This injected NO₃⁻ supported 68±19% and 66±9% of the phytoplankton N demand and export production, respectively. N isotope data suggest that 32±6% of the initial NO₃⁻ remained unassimilated. Self-shading, inefficiency in the transfer of N from dissolved to particulate export, or depletion of a specific nutrient other than N may have led to a lack of complete NO₃⁻ assimilation. Using a salt budget approach, we estimate that dissolved organic nitrogen (DON) concentrations increased from eddy formation (3.8±0.4 mmol N m⁻²) to the time of sampling (4.0±0.09 mmol N m⁻²), implying that DON accumulated at rate of 0.83±1.3 mmol N m⁻² d⁻¹, and accounted for 22±15% of the injected NO₃⁻. Interestingly, no significant increase in suspended PN and PC, or export production was observed inside Cyclone Opal relative to the surrounding water column. A simple N budget shows that if 22±15% of the injected NO₃⁻ was shunted into the DON pool, and 32±6% is unassimilated, then 46±16% of the injected NO₃⁻ remains undocumented. Alternative loss processes within the eddy include lateral exchange of injected NO₃⁻ along isopycnal surfaces, remineralization of PN at depth, as well as microzooplankton grazing. A 9-day time series within Cyclone Opal revealed a temporal depletion in δ¹⁵N-PN, implying a rapid change in the N source. A change in NO₃⁻ assimilation, or a shift from NO₃⁻ fueled growth to assimilation of a ¹⁵N-deplete N source, may be responsible for such observations.     

Submarine hydrothermal brine seeps off Milos, Greece. Observations and geochemistry

A shallow hydrothermal brine seep located off the Greek island of Milos in the Aegean Sea was studied. The brine fluid outcropped as a pool of water in a seabed depression and was detected in the surrounding pore-waters of sediments colonised by the sulphur bacterium Achromatium volutans. The seep fluid was highly saline and sulphidic, depleted in Mg²⁺ and SO₄²⁻, but enriched over seawater in Na⁺, Ca²⁺, K⁺, Cl⁻, SiO₂, reduced species and dissolved gases. The high concentrations of Na⁺, Ca²⁺ and K⁺ were consistent with the Milos tectonic setting. Na-K and Na-K-Ca geothermometers predicted a reservoir temperature of 300–325 °C for the most concentrated seep samples. The deep geothermal reservoir within the metamorphic basement of Milos island has already been located and studied and may represent the source of the seep fluid. Faunal diversity was lowest in seep-influenced sediments, but a sulphide-intolerant species was found in areas of the bacterial mat where salinity and temperature were much lower. Pressure-induced variations in the vertical depth of the brine interface may be occurring in the sediment.     

The dissociation constants of carbonic acid in seawater at salinities 5 to 45 and temperatures 0 to 45°C

The pK₁^* and pK₂^* for the dissociation of carbonic acid in seawater have been determined from 0 to 45°C and S = 5 to 45. The values of pK₁^* have been determined from emf measurements for the cell:

Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag

where X is the mole fraction of CO₂ in the gas. The values of pK₂^* have been determined from emf measurements on the cell:

Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag

The results have been fitted to the equations:

lnK^*₁ = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S^0.5 + 0.08468345S − 0.00654208S¹

InK^*₂ = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S^0.5 + 0.1130822S − 0.00846934S^1.5

where T is the temperature in K, S is the salinity, and the standard deviations of the fits are σ = 0.0048 in lnK₁^* and σ = 0.0070 in lnK₂^*.Our new results are in good agreement at S = 35 (±0.002 in pK₁^*and ±0.005 in pK₂^*) from 0 to 45°C with the earlier results of Goyet and Poisson (1989). Since our measurements are more precise than the earlier measurements due to the use of the Pt, H₂|AgCl, Ag electrode system, we feel that our equations should be used to calculate the components of the carbonate system in seawater.     

Modelling of natural and synthetic polyelectrolyte interactions in natural waters by using SIT, Pitzer and Ion Pairing approaches

In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et₄NI and NaCl (for fulvic acid 0.1 < I /mol L^− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na⁺, K⁺, Mg²⁺, Ca²⁺) and anions (Cl⁻, SO₄²⁻) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments.     

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.     

Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of pH and ionic strength

The sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide at low ionic strength (0.01 M ≤ I ≤ 0.09 M) was investigated over a wide range of pH (3.9 ≤ pH ≤ 7.1). YREE distribution coefficients, defined as _iK_Fe = [MS_i]_T / (M_T[Fe³⁺]_S), where [MS_i]_T is the concentration of YREE sorbed by the precipitate, M_T is the total YREE concentration in solution, and [Fe³⁺]_S is the concentration of precipitated iron, are weakly dependent on ionic strength but strongly dependent on pH. For each YREE, the pH dependence of log _iK_Fe is highly linear over the investigated pH range. The slopes of log _iK_Fe versus pH regressions range between 1.43 ± 0.04 for La and 1.55 ± 0.03 for Lu. Distribution coefficients are well described by an equation of the form _iK_Fe = (_Sβ₁[H⁺]^− 1 + _Sβ₂[H⁺]^− 2) / (_SK₁[H⁺] + 1), where _Sβ_n are stability constants for YREE sorption by surface hydroxyl groups and _SK₁ is a ferric hydroxide surface protonation constant. Best-fit estimates of _Sβ_n for each YREE were obtained with log _SK₁ = 4.76. Distribution coefficient predictions, using this two-site surface complexation model, accurately describe the log _iK_Fe patterns obtained in the present study, as well as distribution coefficient patterns obtained in previous studies at near-neutral pH. Modeled log _iK_Fe results were used to predict YREE sorption patterns appropriate to the open ocean by accounting for YREE solution complexation with the major inorganic YREE ligands in seawater. The predicted log _iK_Fe′ pattern for seawater, while distinctly different from log _iK_Fe observations in synthetic solutions at low ionic strength, is in good agreement with results for natural seawater obtained by others.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²