Application of potentiometric method using a cell without liquid junction to underway pH measurements in surface seawater

This study evaluated a method to carry out underway pH measurements of surface seawater by means of a cell without liquid junction using glass electrodes for hydrogen and sodium ions as follows:

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

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

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.     

Temperature dependence of CO2 fugacity in seawater

Ideally, the correction of the measured CO₂ fugacity (fCO₂) at temperature T_m to fCO₂ at the in-situ temperature T_in should be made by using at least 2 known parameters (pH-A_T, C_T-A_T,…) and the reliable constants for carbonic acid. In practice however, a measured CO₂ property pair is not always available. When fCO₂ is measured alone, one must make an estimate of the effect of temperature on seawater fCO₂ from the accurate knowledge of seawater salinity and temperature and the approximate knowledge of the carbonate parameters. In this paper we present an empirical relationship that can be used to estimate the effect of temperature on fCO₂. The equation is of the form:

ƒCO_2[t] − ƒCO_2[20]=A + Bt + Ct² + Dt³ + Et⁴

where fCO_2[t] and fCO_2[20] represent fCO₂ at temperatures t°C and 20°C, respectively; the parameters A, B, etc. are functions of the ratio X = C_T/A_T:

E = e₀ + e₁X + e₂X²ln(X) + e₃exp(X) + e₄/ln(X)

where the parameters a_i, b_i, etc. are functions of salinity.The 25-parameter equation is fitted by the values of fCO₂ calculated using the constants of Goyet and Poisson (1989), when X varies from 0.8 to 1.0, t varies from −1dgC to 40°C, and S varies from 30 to 40. For T_m - T_in within ± 10°C, direct measurements of fCO₂ as a function of the temperature (from −I to 30°C verify this equation within less than ±5 μatm.     

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.     

Ecology of deep-sea meiobenthos in the western Pacific

I am deeply honored to have been awarded the 1988 Okada Prize of the Oceanographical Society of Japan. The present paper reviews my previous works regarding the ecology of deep-sea meiobenthos in the western Pacific area. The outline cen be summarized as follows:

Food web structure of two Mediterranean lagoons under varying degree of eutrophication

The food web structure and functioning of two north-western Mediterranean lagoons exhibiting contrasting degrees of eutrophication and marine influences were compared through δ¹³C and δ¹⁵N analysis of major potential food sources and consumers. The Lapalme Lagoon is well preserved and has kept a natural and temporary connection with the open sea. Conversely, the Canet Lagoon is heavily eutrophicated and its water exchange with the open sea has been artificially reduced. In Lapalme, all potential food sources and consumers exhibited δ¹⁵N values indicative of pristine coastal areas. Suspended particulate organic matter (POM) and sediment organic matter (SOM) pools seemed to constitute the main food sources of most primary consumers. Both primary producers and all consumers were much more ¹⁵N-enriched (by  10‰) and more ¹³C-depleted in Canet than in Lapalme. This reflected: (1) the assimilation of important amounts of anthropogenic nitrogen in the food web, and (2) a marked and uniform influence of ¹³C-depleted allochtonous sources of carbon. Based on the mean δ¹⁵N of primary consumers, we found rather similar food web lengths in both lagoons with top consumers at trophic levels 3.6 and 4.0 in Canet and Lapalme, respectively. However, the eutrophication of the Canet Lagoon resulted in a simplification of the food web structure (i.e., a single trophic pathway from a ¹⁵N-enriched fraction of the SOM pool to top predators) compared to what was observed in Lapalme Lagoon where additional ¹³C-enriched food sources played a significant trophic role. Moreover, some consumers of Canet tended to exploit primary producers to a larger extent (and thus to exhibit lower trophic levels) than in Lapalme.     

Physical dynamics and biological implications of Cyclone Noah in the lee of Hawaii during E-Flux I

Quasi-synoptic observations of the horizontal and vertical structure of a cold-core cyclonic mesoscale eddy feature (Cyclone Noah) were conducted in the lee of Hawai’i from November 4–22, 2004 as part of the E-Flux interdisciplinary collaborative research program. Cyclone Noah appears to have spun up to the southwest of the ‘Alenuihaha Channel (between Maui and Hawai’i) as a result of strong and persistent northeasterly trade winds through the channel. Shipboard hydrographic surveys 2.5 months later suggest that Noah weakened and was in a hypothesized spin-down phase of its life cycle. Although the initial surface expression of Noah was limited in scale to 40 km in diameter and, as evidenced by surface temperatures, 2–3 °C cooler than the surrounding waters, depth profiles revealed a fully developed semi-elliptical shallow feature (200 m), 144 km long and 90 km wide (based on sigma-t=23 kg m⁻³) with tangential speeds of 40–80 cm s⁻¹, and substantial isopycnal doming. Potential vorticity distribution of Noah suggests that radial horizontal flow of the core water was inhibited from the surface to depths of 75 m, with high vorticity confined above the sigma-t=23.5 kg m⁻³ isopycnal surface. Upward displacements of isopycnal surfaces in the eddy's center (50 m) were congruent with enhanced pigment concentrations (0.50 mg m⁻³). Comparisons of the results obtained for E-Flux I (Noah) and E-Flux III (Opal) suggest that translation characteristics of cyclonic Hawaiian lee eddies may be important in establishing the biogeochemical and biological responses of the oligotrophic ocean to cyclonic eddies.     

Geological interpretation of combined Seabeam,Gloria and seismic data from Anegada Passage (Virgin Islands,north Caribbean)

The Anegada Passage (sensu lato) includes several basins and ridges from Southeast of Puerto Rico to the corner of the Virgin Islands Platform. Seabeam (Seacarib I) and Gloria long-range sidescan sonar surveys were carried out in this area. These new data allow us to propose an interpretation of the Anegada Passage.Most of the features described are related to wrench faulting:

Uptake and metabolism of arsenate by anexic cultures of the microalgae Dunaliella tertiolecta and Phaeodactylum tricornutum

Axenic cultures of the microalgae species, Dunaliella tertiolecta and Phaeodactylum tricornutum were grown at arsenic (As) concentrations typically found in uncontaminated marine environments ( 2 µg L^− 1) under different phosphorus concentrations. D. tertiolecta accumulated higher arsenic concentrations (mean: 13.7 ± 0.7 µg g^− 1 dry mass) than P. tricornutum (mean: 1.9 ± 0.2 µg g−1 dry mass). Media phosphorus concentrations (0.6–3 mg/L) had little influence on microalgae growth rates or arsenic accumulation. Arsenic was present as lipid bound (29–38%; 4.2–9.5%), water-soluble (20–29%; 26–34%) and residue bound (41–45%; 57–69%) arsenic species in D. tertiolecta and P. tricornutum respectively. Hydrolysed lipids contained mostly glycerol arsenoribose (OH- ribose), dimethylarsinate (DMA) and inorganic arsenic (As(V)) moieties. Water-soluble species of microalgae were very different. D. tertiolecta contained inorganic arsenic (54–86%) with variable amounts of DMA (7.4–20%), arsenoriboses (5–25%) and traces of methylarsonate (MA) ( 1%). P. tricornutum contained mostly DMA (32–56%) and phosphate arsenoribose (PO₄-ribose, 23–49%) and small amounts of OH-ribose (3.8–6.5%) and As(V) (9–16%). Both microalgae contained an unknown cationic arsenic species. The residue fractions of both microalgae contained predominately inorganic arsenic (99–100%). These results show that at natural seawater arsenic concentrations, both algae take up substantial amounts of inorganic arsenic that is complexed with structural elements or sequestered in vacuoles as stable complexes. A significant portion is also incorporated into lipids. Arsenic is metabolised to simple methylated species and arsenoriboses.     

Oxidation of copper(I) in seawater at nanomolar levels

The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:

The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl₂⁻ species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations.     

Wave interaction with T-type breakwaters

The wave transmission, reflection and energy dissipation characteristics of partially submerged ‘T'-type breakwaters (Fig. 1) were studied using physical models. Regular and random waves, with wide ranges of wave heights and periods and a constant water depth were used. Five different depths of immersions of the ‘T'-type breakwater were selected. The coefficient of transmission, K_t, coefficient reflection, K_r, were obtained from the measurements and the coefficient of energy loss, K_l is calculated using the law of conservation of energy. It is found that the coefficient of transmission generally reduces with increased wave steepness and increased relative water depth, d/L. This breakwater is found to be effective closer to deep-water conditions. K_t values less than 0.35 is obtained for both normal and high input wave energy levels, when the horizontal barrier of the T type breakwater is immersed to about 7% of the water depth. This breakwater is also found to be very efficient in dissipating the incident wave energy to an extent of about 65% (i.e. K_l>0.8), especially for high input wave energy levels. The wave climate in front of the breakwater is also measured and studied.

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Fig. 1. Schematic view of the T-type breakwater.     

Isolation and characterization of low molecular weight carbohydrates dissolved in seawater

Chemical characterization and quantitative determination of dissolved low molecular weight carbohydrates in Mikawa Bay near Nagoya, Japan were conducted. The water samples were collected during the period of algal bloom of the dinoflagellate Prorocentrum minimum on 31 May 1980.Low molecular weight carbohydrates in seawater samples from depths of 1 and 6 m were first retained on a charcoal column and then eluted with aqueous ethanol. The carbohydrates obtained were permethylated and then isolated into each of the components by thin layer chromatography. The sugars isolated were characterized by gas chromatography (GC), combined gas chromatography and mass spectrometry (GC-MS), proton nuclear magnetic resonance spectroscopy (¹H-NMR) and some chemical analyses. Laminaribiose, laminaritriose, sucrose, raffinose,

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,

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were fully characterized and quantified with ranges from 2.3 to 27.7 μg l⁻¹ and from 0.5 to 17.8 μg l⁻¹.These low molecular weight carbohydrates were also identified, with some difference in their relative abundance, in particulate matter consisting mainly of dinoflagellate cells collected on the same occasion from this bay. These results indicate that low molecular weight carbohydrates dissolved in seawater are directly derived from those of phytoplankton through extracellular release or cell lysis.