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Ideally, the correction of the measured CO2 fugacity (fCO2) at temperature Tm to fCO2 at the in-situ temperature Tin should be made by using at least 2 known parameters (pH-AT, CT-AT,…) 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: where fCO2[t] and fCO2[20] represent fCO2 at temperatures t°C and 20°C, respectively; the parameters A, B, etc. are functions of the ratio X = CT/AT: where the parameters ai, bi, 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 Tm - Tin 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. 相似文献
ƒCO2[t] − ƒCO2[20]=A + Bt + Ct2 + Dt3 + Et4
E = e0 + e1X + e2X2ln(X) + e3exp(X) + e4/ln(X)
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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. 相似文献
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P. R. Payne 《Ocean Engineering》1994,21(3)
The results of several recent isolated investigations in planing theory are consolidated in this paper, together with new insights generated by a recent numerical solution of the vertically impacting wedge problem by Zhao and Faltinsen [(1992), Water entry of two-dimensional bodies. J. Fluid Mech. 246, 593–612]. As a result, in contrast to some earlier studies, it is found that the “wetted width” associated with the added mass is not that of the intersection of the wedge with the undisturbed water surface, but the wetted width of the splashed-up water, as originally proposed by Wagner [(1932), Uber Stoss-und Gleitvorgange an der Oberflache von Flussig-Keiten, Zeitschrift für Angewandte Mathematik und Mechanik, Band 12, Heft 4 (August)]. However, the splash-up ratio is not the value of (π/2–1) which he proposed, but a value which decreases with increasing deadrise, originally proposed in the late-1940s by Pierson (“Pierson's hypothesis” in the paper). For 30° deadrise, for example, Pierson's splash-up ratio is two-thirds that of Wagner's.The new equations are employed to determine the increase in the “added mass” of prismatic hull sections due to chine immersion, using experimental data. If mo′ is the added amss of the hull section whose chines are just wetted, Payne [(1988), Design of High-speed Boats. Volume 1: Planing. Fishergate, Inc., Annapolis, Maryland, U.S.A.] postulated that the increase in added mass due to a chine submergence (zc) would be where b is the chine beam and k is a constant which Payne [(1988), Design of High-speed Boats. Volume 1: Planing. Fishergate, Inc., Annapolis, Maryland, U.S.A.] gave as
.The present analysis includes the “one-sided flow” correction introduced in Payne [(1990), Planing and impacting forces at large trim angels. Ocean Engng 17, 201–234]. Partly for that reason and partly because of the more precise analysis of the experimental data, the present paper revises the value to k = 2 for wetted length to beam ratios normally employed. For deadrise angles in excess of 40° and wetted keel to beam ratios in excess of 2.0, there is some evidence that k < 2.0.The revised theoretical formulation is compared with eight different sets of experimental data for flat plate and prismatic hull forms and is found to be in excellent agreement when the speed is high enough for “dynamic suction” (a loss of buoyancy at low speeds and low wetted lenghts) to be unimportant. This is true for “chines-dry” operation with deadrise angles up to 50° and chines-wet operation at length to beam ratios far in excess of the most extreme conventional practice.The research involved in performing this analysis led to the realization that different towing tanks measure different wetted chine lengths for the same hulls and test conditions. Some consistently measure more splash-up than “theory” (based on Pierson's splash-up hypothesis) predicts and others measure somewhat less than the theory. Some examples are given in Appendix B. The reason for this is not understood. 相似文献
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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 (KFeX*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (KFeX) and the activity coefficient of iron complexes (γFeX) with a number of inorganic ligands in NaClO4 medium at various ionic strengths: In(KFeX/γFeγX) = InKFeX − In(γFeX) The activity coefficients for free ions (γFe, γx) 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 (BFeX, BFeX0, CFeXφ) 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%. 相似文献
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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
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The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgTD) in the groundwater springs were 0.99 ± 0.15 ng l− 1 (n = 18) and 0.44 ± 0.17 ng l− 1 (n = 17) at Etretat and Yport respectively. High HgTD concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg− 1 (n = 16) and 0.16 ± 0.10 ng mg− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgRD/HgTD: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l− 1). The HgTD distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHgD) concentrations varied from 9.5 to 13.5 pg l− 1 (2 to 8% of the HgTD). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l−1; 6–12% of the HgTD). These groundwater karstic estuaries seem to be mostly characterized by the higher HgTD and HgRD concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels. 相似文献
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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
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Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, Kd, which varies from 0.67 × 105 to 3.38 × 106 ml g−1 for suspended particle concentrations of 2–64 mg l−1. The Kd values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for Kd values of 105, 106 and 107 ml g−1 with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with Kd value 107 ml g−1 and C0 values 16 × 10−6 mg ml−1 and 92 × 10−6 mg ml−1. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries. 相似文献
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Rabindra N Roy Lakshimi N Roy Kathleen M Vogel C Porter-Moore Tara Pearson Catherine E Good Frank J Millero Douglas M Campbell 《Marine Chemistry》1993,44(2-4)
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: where X is the mole fraction of CO2 in the gas. The values of pK2* have been determined from emf measurements on the cell: The results have been fitted to the equations: 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. 相似文献
Pt](1 − X)H2 + XCO2|NaHCO3, CO2 in synthetic seawater|AgC1; Ag
Pt, H2(g, 1 atm)|Na2CO3, NaHCO3 in synthethic seawater|AgC1; Ag
lnK*1 = 2.83655 − 2307.1266/T − 1.5529413 lnT + (−0.20760841 − 4.0484/T)S0.5 + 0.08468345S − 0.00654208S1
InK*2 = −9.226508 − 3351.6106/T− 0.2005743 lnT + (−0.106901773 − 23.9722/T)S0.5 + 0.1130822S − 0.00846934S1.5
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Abdirahman M. Omar Truls Johannessen Are Olsen Staffan Kaltin Francisco Rey 《Marine Chemistry》2007,104(3-4):203-213
The seasonal and interannual variability of the air–sea CO2 flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO2 (fCO2sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO2sw from phosphate (PO4), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO4 collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO2sw estimates were combined with data for the atmospheric mole fraction of CO2, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO2. The monthly mean uptake increases nearly monotonically from 0.101 mol C m− 2 in midwinter to 0.656 mol C m− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m− 2 month− 1. The variability is controlled mainly through combined variation of fCO2sw and wind speed. The annual mean uptake of atmospheric CO2 in the region was estimated to 4.27 ± 0.68 mol C m− 2. 相似文献
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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