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1.
We report radiocarbon measurements of dissolved inorganic carbon (DIC) in surface water samples collected daily during cruises to the central North Pacific, the Sargasso Sea and the Southern Ocean. The ranges of Δ14C measurements for each cruise (11–30‰) were larger than the total uncertainty (7.8‰, 2-sigma) of the measurements. The variability is attributed to changes in the upper water mass that took place at each site over a two to four week period. These results indicate that variability of surface Δ14C values is larger than the analytical precision, because of patchiness that exists in the DIC Δ14C signature of the surface ocean. This additional variability can affect estimates of geochemical parameters such as the air–sea CO2 exchange rate using radiocarbon. 相似文献
2.
Natural surface film experiments in inland waters and shallow offshore regions of the Baltic and Mediterranean Seas were carried out in the time period 1990–1999 under calm sea conditions using a novel device for sampling and force-area studies. The sampler-Langmuir trough-Wilhelmy filter paper plate system ‘cuts out’ an undisturbed film-covered sea area to perform π-A studies without any initial physico-chemical sample processing. The limiting specific area Alim (2.68–31.57 nm2/molecule) and mean molecular mass Mw (0.65–9.7 kDa) of microlayer surfactants were determined from the 2D virial equation of state applied to the isotherms. Enthalpy ΔH and entropy ΔSt of the 2D first-order phase transitions were evaluated using the Clausius-Clapeyron equation applied to the isotherms. Miscibility of film components and film structure evolution is expressed by the scaling exponent y adopting the 2D polymer film scaling theory. The stress-relaxation measurements revealed a two-step relaxation process at the interface with characteristic times τ1=1.1–2.8 and τ2=5.6–25.6 seconds suggesting the presence of diffusion-controlled and structural organisation relaxation phenomena. The obtained results suggest that natural films are a complex mixture of biomolecules covering a wide range of solubilities, surface activity and molecular masses with an apparent structural organisation exhibiting a spatial and temporal variability. 相似文献
3.
Tetsuo Yanagi 《Journal of Oceanography》1985,41(6):435-440
Prominent coastal upwelling and downwelling events due to Ekman transport were observed during the period from 14 to 18 August 1983 along the Misaki Peninsula in the Seto Inland Sea, Japan. The coastline of the Misaki Peninsula is aligned approximately in an ENE-WSW direction. When an ENE wind continued blowing for about two days, the warm water in the upper layer was pushed offshore and cold water in the lower layer upwelled along the peninsula. The estimated upwelling speed 3 m below the sea surface was 0.032 cm sec–1. On the other hand, when a WSW wind continued blowing for about two days the warm water in the upper layer sank into the lower layer along the peninsula. The estimated downwelling speed 3 m below the sea surface was 0.080 cm sec–1. The time lag between the variations of the alongshore wind and offshore current was about 0.5 days. 相似文献
4.
James N. Butler 《Marine Chemistry》1992,38(3-4)
Displaying “calculated minus observed” data for precise titrations of seawater with strong acid permits direct evaluation of important parameters and detection of systematic errors.At least two data sets from the GEOSECS (Geochemical Ocean Sections) program fit an equilibrium model (which includes carbonate, borate, sulfate, silicate, fluoride, and phosphate) within the most stringent experimental error, less than 2 μmol kg−1. The effect of various parameters on the fit of calculated to observed values depends strongly on pH. Although standard potential E0, total alkalinity At, total carbonate Ct, and first acidity constant of carbon dioxide pK1 are nearly independent, and can be determined for each data set, other parameters are strongly correlated. Within such groups, all but one parameter must be determined from data other than the titration curve.Adding an acid-base pair to the theoretical model (e.g. Cx=20 μmol kg−1, pKx=6.2) produces a deviation approaching 20 μmol kg−1 at constant Ct; however, adjustment of Ct by about −18 μmol kg−1 to produce a good fit leaves only ± 1.5 μmol kg−1 residual deviation from the reference values. Thus, at current standards of precision, an unidentified weak acid cannot be distinguished from carbonate purely on the basis of the titration curve shape.There are few full sets of numerical data published, and most show larger systematic errors (3–12 μmol l−1) than the above; one well-defined source is experiments performed in unsealed vessels. Total carbonate can be explicitly obtained as a function of pH by a rearrangement of the titration curve equation; this can reveal a systematic decrease in Ct in the pH range 5–6, as a result of CO2 gas loss from the titration vessel. Attempts to compensate for this by adjustment of At, Ct, or pK1 produce deviations which mimic those produced by an additional acid-base pair.Changing from the free H+ scale (for which [HSO4−] and [HF] are explicit terms in the alkalinity) to the seawater scale (SWS) (where those terms are part of a constant factor multiplying [H+]) requires modification of the titration curve equation as well as adjustment of acidity constants. Even with this change, however, omission of pH-dependent terms in [HSO4−] and [HF] produces small systematic errors at low pH.Shifts in liquid junction potential also introduce small systematic errors, but are significant only at pH <3. High-pH errors due to response of the glass electrode to Na+ as well as H+ can be adequately compensated to pH 9.5 by a linear selectivity expression. 相似文献
5.
Sea surface pCO2 was monitored during 49 cruises from February 1997 to December 1999 along a section perpendicular to the central California Coast. Continuous measurements of the ocean–atmosphere difference of pCO2 were made on a mooring in the same region from July 1997 to December 1999. The El Niño/La Niña cycle of 1997–1999 had a significant influence on local ocean–atmosphere CO2 transfer. During the warm anomaly associated with El Niño, upwelling was suppressed and average sea surface pCO2 was below atmospheric level. High rainfall and river runoff in the late winter and early spring of 1998 produced areas where pCO2 was depressed by as much as 100 μatm. A flux ranging from 0.3 to 0.7 mol C m−2 y−1 from the atmosphere into the ocean was estimated for the El Niño period from wind and ΔpCO2 data. Temperatures and upwelling returned to near normal in the summer of 1998, but a cold anomaly developed during autumn of that year. Temperature and pCO2 data indicate that upwelling continued throughout much of the 1998–1999 winter and intensified significantly in the spring of 1999. During strong upwelling events, the estimate of ocean to atmosphere flux approached rates of 50 mol C m−2 y−1. The estimate for the average CO2 flux from July 1998 to July 1999 was 1.5–2.2 mol C m−2 y−1 from the ocean to the atmosphere. While the flux estimate for the El Niño time period may be applicable to a larger area, the high ocean to atmosphere fluxes during La Niña might be the result of sampling near a zone of intense upwelling. 相似文献
6.
The wave transmission, reflection and energy dissipation characteristics of ‘’-type breakwaters were studied using physical models. Regular and random waves in a wide range of wave heights and periods and a constant water depth were used. Five different depths of immersion (two emerged, one surface flushing and two submerged conditions) of this breakwater were selected. The coefficient of transmission, Kt, and coefficient of reflection, Kr, were obtained from the measurements, and the coefficient of energy loss, Kl was calculated using the law of balance of energy. It was found that the wave transmission is significantly reduced with increased relative water depth, d/L, whether the vertical barrier of the breakwater is surface piercing or submerged, where ‘d’ is the water depth and ‘L’ is the wave length. The wave reflection decreases and energy loss increases with increased wave steepness, especially when the top tip of the vertical barrier of this breakwater is kept at still water level (SWL). For any incident wave climate (moderate or storm waves), the wave transmission consistently decreases and the reflection increases with increased relative depth of immersion, Δ/d from −0.142 to 0.142. Kt values less than 0.3 can be easily obtained for the case of Δ/d=+0.071 and 0.142, where Δ is the height of exposure (+ve) or depth of immersion (−ve) of the top tip of the vertical barrier. This breakwater is capable of dissipating wave energy to an extent of 50–80%. The overall performance of this breakwater was found to be better in the random wave fields than in the regular waves. A comparison of the hydrodynamic performance of ‘’-type and ‘T’-type shows that ‘T’-type breakwater is better than ‘’-type by about 20–30% under identical conditions. 相似文献
7.
An improved gas chromatographic system was constructed to analyze oceanic dissolved N2, Ar and O2 with a higher accuracy and shorter analytical time. To obtain a higher accuracy of N2, Ar and O2 measurements, the following was added to the system: (I) an air trapping system; (II) a N2–CO2 trapping system after the operation of the air trapping system; (III) an active carbon column system for separating N2 and CO2 completely and (IV) the introduction of automatic valves controlling most of the system. Compared to previous studies, the precision of the measurements of N2, Ar and O2 concentrations was higher at 0.04%, 0.05% and 0.02%, respectively, and our analytical time was shorter at 600 s. Using the improved analytical technique, concentrations of N2 (CN2, 561.69–611.81 μmol/kg) and Ar (CAr, 15.126–16.238 μmol/kg), saturation states of N2 (ΔN2, − 5.1–0.9%) and Ar (ΔAr, − 7.0 to − 1.1%) from 0 m to 3000 m depth in the western North Pacific were observed during March 2005. Based on these data, we propose a new concept for estimating the amount of bubble injection (B). The total error in calculating B was estimated to be about 20%. We estimated B from 12 to 43 μmol/kg in this region using the observational values of N2 and Ar. As each water mass had a significantly different value of B even with an error of 20%, it is possible to use it as an index of sea surface state for when each water mass is produced in the sea surface mixed layer. Moreover, based on our values of B, we estimated preformed dissolved oxygen (DO) (CpreDO, 309–332 μmol/kg) and the saturation state of CpreDO (ΔpreDO, − 7.0 to − 1.2%) in this region. Thus, the difference between CpreDO and DO content in the ocean interior may be a more useful index for biogenic organic decomposition in the ocean field compared to Apparent Oxygen Utilization (AOU). Until now, the estimation of oceanic uptake of anthropogenic CO2 has used AOU as a major parameter. Therefore, it may be necessary to re-evaluate the oceanic uptake of anthropogenic CO2 based on our new concept of B. 相似文献
8.
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 ΔHapp 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