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.     

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.     

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.     

Fine-scale Microbial Communities Associated with Manganese Nodules in Deep-sea Sediment of the Korea Deep Ocean Study Area in the Northeast Equatorial Pacific

Despite its potential significance for industrial utilization, any activities associated with the mining of manganese (Mn) nodules might have substantial impacts on benthic ecosystems. Because microorganisms respond quickly to changing environmental conditions, a study of microbial communities provides a relevant proxy to assess possible changes in benthic ecosystems associated with mining activities. We investigated fine-scale microbial community composition and diversity inside and on the surface of Mn nodules and in nearby deep-sea sediments in the Korea Deep Ocean Study (KODOS) area located in the Clarion-Clipperton Fracture Zone (CCFZ) of the northeast equatorial Pacific. Although microbial cell density was lower within nodules (3.21 × 10⁶ cells g^-1) than in sediment (2.14 × 10⁸ cells g^-1), nodules provided a unique habitat for microorganisms. Manganese-oxidizing bacteria including Hyphomicrobium and Aurantimonas in Alphaproteobacteria and Marinobacter in Gammaproteobacteria were abundant in nodules, which implied that these bacteria play a significant role in nodule formation. In contrast, Idiomarina in Gammaproteobacteria and Erythrobacter and Sulfitobacter in Alphaproteobacteria were abundant in sediments. Meanwhile, Thaumarchaeota, a phylum that consists of ammonia-oxidizing chemolithoautotrophs, were the predominant archaeal group both in nodules and sediment. Overall, microbial communities in Mn nodules were unique compared to those observed in sediments. Furthermore, the phylogenetic composition of microorganisms in the KODOS area was distinguishable from that in the nodule provinces claimed by China and Germany in the CCFZ and nodule fields in the central South Pacific Gyre, respectively.     

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.     

Evaluation of conditions along the grounding line of temperate marine glaciers: an example from Muir Inlet, Glacier Bay, Alaska

In the marine environment, stability of the glacier terminus and the location of subglacial streams are the dominant controls on the distribution of grounding-line deposits within morainal banks. A morainal bank complex in Muir Inlet, Glacier Bay, SE Alaska, is used to develop a model of terminus stability and location of subglacial streams along the grounding line of temperate marine glaciers. This model can be used to interpret former grounding-line conditions in other glacimarine settings from the facies architecture within morainal bank deposits.The Muir Inlet morainal bank complex was deposited between 1860 A.D. and 1899 A.D., and historical observations provide a record of terminus positions, glacial retreat rates and sedimentary sources. These data are used to reconstruct the depositional environment and to develop a correlation between sedimentary facies and conditions along the grounding line.Four seismic facies identified on the high-resolution seismic-reflection profiles are used to interpret sedimentary facies within the morainal bank complex. Terminus stability is interpreted from the distribution of sedimentary facies within three distinct submarine geomorphic features, a grounding-line fan, stratified ridges, and a field of push ridges. The grounding-line fan was deposited along a stable terminus and is represented on seismic-reflection profiles by two distinct seismic facies, a proximal and a distal fan facies. The proximal fan facies was deposited at the efflux of subglacial streams and indicates the location of former glacifluvial discharges into the sea. Stratified ridges formed as a result of the influence of a quasi-stable terminus on the distribution of sedimentary facies along the grounding line. A field of push ridges formed along the grounding line of an unstable terminus that completely reworked the grounding-line deposits through glacitectonic deformation.Between 1860 A.D. and 1899 A.D. (39 years),

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m³ of sediment were deposited within the Muir Inlet morainal bank complex at an average annual sediment accumulation rate of

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m³/a. This rate represents the annual sediment production capacity of the glacier when the Muir Inlet drainage basin is filled with glacial ice.     

Historical record of heavy metals in a highly contaminated Mediterranean deposit: The Besòs prodelta

The Besòs prodelta, located around a highly populated area, receives the discharge of the Besòs River, one of the most contaminated rivers discharging into the Mediterranean sea. The record of heavy metals accumulated in this prodelta is studied to assess the sedimentary behaviour and the history of the anthropogenic heavy metals in the area.

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dated sediments have allowed the identification of the sedimentation patterns and the elaboration of dated heavy metals and cenospheres profiles, which reflected the evolution of the anthropogenic impact in this marine environment. Sediments accumulated during the 18th and 19th centuries were already affected by a moderate heavy metal contamination. This contamination increased drastically in the sediments accumulated during the last decades. This data is well correlated with the increase in industrialisation, population and energy consumption in the Besòs drainage basin during the last century.     

The effect of temperature on carbon dioxide partial pressures in seawater

A correction formula is theoretically derived to evaluate the change in partial pressure of carbon dioxide in seawater upon heating. The constraints on the heating process are constant salinity, total alkalinity, and total carbon dioxide concentration. The result is

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. This equation fits δP_CO2/δt for open ocean seawater compositions to within approximately 9%. The almost constant 4.4%/°C effect is in agreement with that measured by Kanwisher (1960).     

A representation for the frequency spectrum of wind-generated waves

This paper proposes the following generalized representation for a wind-wave frequency spectrum:

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where E = ∫S(f)df is the variance of the surface displacement; f_m is the frequency of the spectral peak; and C_i's, i = 1,2,3, are dimensionless parameters that can be determined from the internal spectral parameters of a given spectrum.When applied to 234 sets of wave spectra recorded in the Great Lakes, this representation has been realistic, accurate, and capable of representing widely varied wave processes. The C_i's are clearly related to wave growth processes; they are large during early growth, decrease as waves grow, and reach approximate equilibrium when waves are fully developed.     

Regional maturity as determined by organic petrography and geochemistry of the Schei Point Group (Triassic) in the western Sverdrup Basin, Canadian Arctic Archipelago

Maturity and source rock potential of organic rich beds in the Triassic Schei Point Group in the Sverdrup Basin, Arctic Canada have been investigated using reflected light microscopy and the results are compared with other maturity parameters determined geochemically (i.e. Rock Eval, and biomarker maturation parameters). The samples evaluated belong to the Eden Bay Member of the Hoyle Bay Formation and contain a predominance of marine algal material, in the form of Tasmanales, and dinoflagellates, along with mixed terrestrial organics.The rock matrix is dominantly carbonate with some shaly input, indicating that the rocks were deposited in an iron-poor highly euxinic environment. With few exceptions there is good agreement between parameters,determined using microscopy; namely %R_o, λ_max and and geochemical parameters, T_max, HI,

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steranes, C₂₉ steranes. The ternary diagram showing the abundance of normalized C₂₇, C₂₈ and C₂₉ regular steranes indicates a mostly marine depositional environment for the Schei Point source rock. This is confirmed by the abundance of marine fauna and flora in these samples.Analytical results from several different techniques indicate that the source rocks become more mature from the margin towards the axis of the Sverdrup Basin. This is due, in part, to the increase in overburden of sediments in the axis of the basin. Also the high thermal conductivity of salt has strongly influenced the maturity of Schei Point source rocks over the crest of the salt cored structures, i.e. Well Hazen F-54, and the proximity of salt has enhanced maturation levels at Well Rock Point J-43. The sections investigated were also considered to have an excellent gas potential due to their higher than average TOC content.     

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:

Glass-electrode-Na+

Test solution (reference solution)

H+-glass-electrode

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8.

Tandem hydrofoil system     

Konstantin I. Matveev  Ivan Ivanovich Matveev 《Ocean Engineering》2001,28(2):963

     

9.

Field measurements of fairweather bottom boundary layer processes and sediment suspension on the Louisiana inner continental shelf   总被引：1，自引：0，他引：1  

L. D. Wright  C. R. Sherwood  R. W. Sternberg 《Marine Geology》1997,140(3-4):329-345

Field measurements of bottom boundary layer and sediment-transport processes were made on the Louisiana inner continental shelf in spring 1992 at a depth of 15.5 m, and in spring and summer 1993 at a depth of 20.5 m. Two different wave–current boundary layer/sediment-transport models were applied to the measured near-bed flows. In addition, the log-profile method was applied to estimate hydraulic roughness and bed stress. Consistent with the results of others, our measurements show that near-bed flows were very weak under non-storm conditions. Bed stresses were typically too low to resuspend bed sediments. However, the advection of high-turbidity layers or plumes past the instrumentation apparently caused a sustained period of high suspended sediment concentration throughout the log layer in spring 1993. In the absence of wave activity or high suspended sediment concentrations, boundary layer profiles showed the bed to have been hydraulically very smooth with

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cm. However, wave agitation, combined with increased suspended sediment concentration caused hydraulically rough conditions with

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cm.     

10.

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

Maurizio Pettine  Daniele Tonnina  Frank J. Millero 《Marine Chemistry》2006,99(1-4):31

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

Field measurements of fairweather bottom boundary layer processes and sediment suspension on the Louisiana inner continental shelf

Field measurements of bottom boundary layer and sediment-transport processes were made on the Louisiana inner continental shelf in spring 1992 at a depth of 15.5 m, and in spring and summer 1993 at a depth of 20.5 m. Two different wave–current boundary layer/sediment-transport models were applied to the measured near-bed flows. In addition, the log-profile method was applied to estimate hydraulic roughness and bed stress. Consistent with the results of others, our measurements show that near-bed flows were very weak under non-storm conditions. Bed stresses were typically too low to resuspend bed sediments. However, the advection of high-turbidity layers or plumes past the instrumentation apparently caused a sustained period of high suspended sediment concentration throughout the log layer in spring 1993. In the absence of wave activity or high suspended sediment concentrations, boundary layer profiles showed the bed to have been hydraulically very smooth with

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cm. However, wave agitation, combined with increased suspended sediment concentration caused hydraulically rough conditions with

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cm.     

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