首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
A liquid-liquid partition, ligand exchange procedure involving the formation of copper(II) complexes with acetylacetone is presented for the determination of stability constants and concentrations of copper chelators in seawater. Acetylacetone competes with natural ligands for copper, and the equilibrium concentration of the copper acetylacetonate complex is used in speciation calculations. The concentration of the complex is calculated by partitioning a fraction of it into an organic phase and determining the total Cu concentration in that phase by back extracting with acid, and analyzing by flameless atomic absorption spectroscopy. The concentration of Cu acetylacetonate in seawater in equilibrium with the organic phase is calculated from the partition coefficient. The simple, thermodynamically well characterized procedure offers several advantages over previous techniques. Studies using organic free seawater and model ligands show good agreement between experimental and calculated conditional stability constants. Studies from seawater in Biscayne Bay, Florida, indicate two ligand types are present; type 1, K1 = 1.2 × 1012, CL1 = 5.1 × 10−9 M; type 2, K2 = 2.8 × 1010, CL2 = 1.1 × 10−7 M. Speciation is dominated by ligand type 1. Depth profiles of [Cu(II)]free/[Cu(II)]total measured with the procedure at ambient copper concentrations show an increase from < 5 × 10−5 at 50–60 m to > 1 × 10−3 at the surface at two stations off the Florida coast.  相似文献   

2.
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   

3.
The present study extends the investigations of the hydrodynamic forces on a cylinder, laid on, or partly buried in the bed. They were determined by measuring the pressure distribution on the cylinder surface in the case of steady current, waves and coexisting flow. The pressure distribution around the cylinder was measured by using pressure transducers, which were replaced in the cylinder. Force coefficients were obtained for the ranges of Re=0.8×104–1.5×104, for steady current, low KC numbers (KC<5) for wave alone case and, for current-to-wave velocity RATIO=0, 3, 6 and infinity (current) for coexisting flow. The forces were also determined for the various burial-depth-to-diameter ratios between 0 and 0.7 values of the cylinder.  相似文献   

4.
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′PSPc = 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.  相似文献   

5.
Copper complexing capacity of cell exudates of Dunaliella salina in natural seawater culture medium was investigated in order to evaluate the influence of this organism on speciation of trace metals in seawater.Seawater samples were collected at 200 m and 2 miles off the coast and immediately filtered. Copper complexing capacity (CCCu) and stability constants (K′) of related cupric complexes were then measured. They were, respectively, 27.1 × 10−8 mol l−1 and 0.56 × 107 l mol−1 for the samples collected at 200 m and 12.8 × 10−8 mol l−1 and 6.10 × 107 l mol−1 for those collected 2 miles off the coast. A stock culture (20 ml, 106 cells ml−1) in log-phase was inoculated in 2 l of each sample of filtered natural seawater. The trend of cell influence was estimated on filtered culture medium by measuring CCCu and K′ after 1 h, 3 and 7 days. From the results it appears that CCCu increased with respect to time and this was related to the growth rate, indicating a certain relationship with cell metabolic activity.It can be concluded that a comparison between the culture referring to 200 m and 2 miles, respectively, shows that the former presents a CCCu two times higher than the latter while the K′ is ten times higher at 2 miles than that at 200 m.  相似文献   

6.
Concentrations of bacteria, chlorophyll a, and several dissolved organic compounds were determined during 11 tidal cycles throughout the year in a high and a low elevation marsh of a brackish tidal estuary. Mean bacterial concentrations were slightly higher in flooding (7·1 × 106 cells ml−1) than in ebbing waters (6·5 × 106 cells ml−1), and there were no differences between marshes. Mean chlorophyll a concentrations were 36·7 μg l−1 in the low marsh and 20·4 μg l−1 in the high marsh. Flux calculations, based on tidal records and measured concentrations, suggested a small net import of bacterial and algal biomass into both marshes. Over the course of individual tidal cycles, concentrations of all parameters were variable and not related to tidal stage. Heterotrophic activity measured by the uptake of 3H-thymidine, was found predominantly in the smallest particle size fractions (< 1·0 μm). Thymidine uptake was correlated with temperature (r = 0·48, P < 0·01), and bacterial productivity was estimated to be 7 to 42 μg Cl−1 day−1.  相似文献   

7.
In the spring of 1988, time series of microstructure and ADCP current profiles were collected at four locations in the North Main Basin of Puget Sound, Washington. Depth and time averages of diapycnal diffusivity at the four stations (1.8−67.0×10−4 m2 s−1) were one to three decades above typical open-ocean thermocline levels. The buoyancy frequency-squared N2 was near open-ocean levels, but unlike the open-ocean where N2S2, finescale shear-squared S2 was three to six times N2 over significant portions of the water column at two of the stations. The time and space mean of all measurements ( ) is close to inferred vertical eddy diffusivity from a primitive equation model for Puget Sound (Kz=3×10−3 m2 s−1) (J. Geophys. Res. 96 (1991) 16779). Large time and space variability of Kρ was found, with differences of inter-station, depth–time means over one decade. A simple scaling argument using the observed Kρ suggests significant exchange of mass between the layers of the subtidal flow over the basin's residence time. Additionally, measurements show that local mixing may be comparable to volume-weighted sill mixing in modifying the Main Basin's stratification. Both are contrary to the “advective reach” simplification of fjord dynamics. The mixing levels were dominated by the passage of a mid-depth, southward-flowing density intrusion and what we interpret as a strongly advected, non-linear internal tide. These mechanisms elevated profile-averaged Kρ by more than 10 times background levels, with sustained patches of Kρ≥1×10−2 m2 s−1. Critical 8-m gradient Richardson numbers (Ri8<0.25) matching regions of overturns (>20 m) and strong turbulence suggest that shear instabilities dominated the turbulence production, though there was support for double-diffusive convection in the warm core of the density intrusion.  相似文献   

8.
The organic matter released by the marine phytoplankton species Dunaliella tertiolecta and its physico-chemical interaction with cadmium and copper ions were studied by electrochemical methods (differential pulse anodic stripping voltammetry (DPASV) and a.c. polarography). The interactions with cadmium and copper were studied at the model interface (mercury electrodesolution) and in the bulk phase by measuring the complexing ability of the released organic material.The axenic cultures were grown on different growth media, without and with trace metals and chelators. Culture media were analyzed 10 days after inoculation, containing 5 × 105−1.2 × 106 cells cm−3 when untreated or after separation of cells by gentle centrifugation.It was found that the content and type of the released surface-active material and complexing ligands depend on the initial composition of the growth media. In all cases, strong interaction of excreted organic substances with copper in the bulk phase and with cadmium at the model interface were observed.A rather high value of the complexing capacity, 9.5 × 10−7 mol Cu2+ dm−3, was found in the culture grown on medium without trace metals and chelators (medium I) whereas the surface activity of this culture was not high (0.2 mg dm−3 equivalent to Triton-X-100). Higher contents of surface-active material (0.8 and 1.0 mg dm−3) were found in cultures grown in media with trace metals and without chelators (II and III), accompanied by a high content of complexing ligands (5.8 × 10−7 and 9.5 × 10−7 mol Cu2+ dm−3). However, if the complexing capacity is calculated per cell the values obtained for cultures grown in media II and III (0.79 × 10−15 and 0.98 × 10−15 mol Cu2+ dm−3) are lower than for cultures grown on medium I (1.8 × 10−15 mol Cu2− dm−3). The exceptional adsorption effects and the copper complexing capacity for medium 1, and the presence of cells with degenerative symptoms can be ascribed to stressed growth conditions, and, particularly, to deficiency of metals. A qualitatively similar behaviour has been observed in natural samples of estuarine waters, indicating the existence of stressed conditions during the mixing of fresh and saline waters.  相似文献   

9.
Using manganese-impregnated fiber extraction and high-efficiency gamma counting techniques, we measured the distribution of 228Ra and 226Ra in surface waters near the coast of Japan and in the western North Pacific. There is no evidence in our data that any significant amount of 228Ra is added to open ocean surface waters from the coastal waters around Tokyo Bay. High 228Ra concentrations (> 10 dpm/103 kg), were observed along the Kuroshio Current as compared to < 2.5 dpm/103 kg between 10° and 30°N of the central gyre, and hence the major source of 228Ra in the surface water is likely to be the East Asian continental shelf zones. A simple one-dimensional eddy diffusion and advection model is used to explain the observed decrease of 228Ra from coast to the open ocean. The model results indicate two mixing regimes across the Kuroshio Current System with apparent eddy diffusion coefficients of Ky = 4 × 105 cm2 s−1 at distance y < 200 km from the coast, and Ky = 4 × 107 cm2 s−1 at y > 200 km. Along 40°N where an eastward flow of the ‘Kuroshio Extension’ prevails, an advective flow of > 0.1 knot is consistent with the observation of nearly constant 228Ra along the track.The geographical distribution pattern of 228Ra is clearly different from that of atmospherically derived 210Pb. Thus the 228Ra in surface water serves as a useful tracer that accompanies fluvially and coastally derived elements during their subsequent lateral transport toward the central gyre.  相似文献   

10.
A batch sorption technique for the determination of particle–water interactions of hydrophobic organic micropollutants under simulated estuarine conditions is described. Results are presented for the behaviour of 2,2′,5,5′-tetrachlorobiphenyl (2,2′,5,5′-TCB) in river and sea waters, both in the presence and absence of estuarine suspended particles. Adsorption onto particles in sea water was enhanced compared with adsorption in river water owing to salting out of the compound, and possibly of the particulate organic matter, in the presence of high concentrations of dissolved ions. The particle–water distribution coefficient, KD, decreased from about 120×103 to 10×103 ml g−1, and from about 150×103 to 20×103 ml g−1, in river water and sea water, respectively, over a particle concentration range of 10–1000 mg l−1. Incomplete recovery of compound from the reactor walls is partly responsible for a particle concentration effect, while artefacts relating to inadequate sediment and water phase separation were ruled out following further experiments. The particle concentration effect, which is replicated in many field studies of hydrophobic organic micropollutants, including 2,2′,5,5′-TCB, is incorporated into a simple partitioning model and is discussed in the context of the likely estuarine behaviour of such compounds.  相似文献   

11.
The distribution and abundance of viable and non-viable (so-called resting eggs) embryos of the calanoid copepod Tortanus forcipatus were determined in the laboratory by the enumeration of nauplii that emerge from sediments collected in Victoria Harbor (Hong Kong). Sediment cores sliced down to a depth of 37 cm showed the highest number of viable resting eggs near the surface layer (0–5 cm). The number of viable eggs sharply decreased with sediment depth, particularly at the inner harbor stations, although diapause eggs remained viable as deep as 25 cm. 210Pb analyses of the sediments indicated that the mean egg age was 4.9 years. The egg mortality of T. forcipatus in the sediments was 0.135 year−1, or 78.22% annual egg survival, calculated by regressing ln (egg density) from sediment age. The range of horizontal distribution of viable resting eggs was 24.25 × 103–58.90 × 103 m−2, with a mean value of 36.8 × 103 m−2 over all stations. The accumulation of viable resting eggs that can persist for an extended period of time provided evidence for the existence of an egg bank of T. forcipatus in the sediments of Victoria Harbor.  相似文献   

12.
To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κq, for these quenchers were found to decrease in the order MV2+ (κq 1010M−1s−1) > I− (κq 2 × 109 M−1 s−1) >CH2CHCONH2 (κq 2 × 108 M−1 s−1) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.  相似文献   

13.
A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (Cp = 2.8 × 10− 5P + 3.4 × 10− 2 s nmol− 1, R2 = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (CΘ = 0.009e0.103Θ, R2 = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fea (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fea (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).  相似文献   

14.
  相似文献   

15.
The Great Belt, the Øresund and the Little Belt connect the central Baltic Sea and the Kattegat. A fixed station was moored in the contraction area in the Little Belt during the period 18–28 July 1995, measuring temperature, salinity and current in two levels, while discharge was measured by the RVDana. The composite Froude number calculated at the fixed station shows that the two layer flow through this area was most often supercritical. The discharges were satisfactorily related to the currents measured at the fixed station, and time-series of transports through the Little Belt were established. When compared to the transports through the Øresund the water transport ratio (Øresund:Little Belt) was found to be 4·4, while the salt transport ratio was found to be 3·0. The resistance of the Little Belt, when considering the differences in sea level from Gedser to Hornbæk, was 1839×10−12 s2 m−5. On the basis of water level and surface salinity measurements made during the period 1931–76, a net discharge of 2300 m3 s−1and a net salt transport of 36 tonnes s−1through the Little Belt from the central Baltic Sea were found.  相似文献   

16.
A new deep-sea laser Raman spectrometer (DORISS—Deep Ocean Raman In Situ Spectrometer) is used to observe the preferential dissolution of CO2 into seawater from a 50%–50% CO2–N2 gas mixture in a set of experiments that test a proposed method of CO2 sequestration in the deep ocean. In a first set of experiments performed at 300 m depth, an open-bottomed 1000 cm3 cube was used to contain the gas mixture; and in a second set of experiments a 2.5 cm3 funnel was used to hold a bubble of the gas mixture in front of the sampling optic. By observing the changing ratios of the CO2 and N2 Raman bands we were able to determine the gas flux and the mass transfer coefficient at 300 m depth and compare them to theoretical calculations for air–sea gas exchange. Although each experiment had a different configuration, comparable results were obtained. As expected, the ratio of CO2 to N2 drops off at an exponential rate as CO2 is preferentially dissolved in seawater. In fitting the data with theoretical gas flux calculations, the boundary layer thickness was determined to be  42 μm for the gas cube, and  165 μm for the gas funnel reflecting different boundary layer turbulence. The mass transfer coefficients for CO2 are kL = 2.82 × 10− 5 m/s for the gas cube experiment, and kL = 7.98 × 10− 6 m/s for the gas funnel experiment.  相似文献   

17.
Experiments were conducted to investigate the geometry of the scour hole and flow structure around short cylinders under the action of waves alone (WA) and combined flows (CF). The study is aimed at better understanding the dynamics of isolated objects on a sandy floor under oscillatory flows as occurs in shallow water regions in coastal areas. Flow velocities within the fluid core were recorded and 3D mapping of the bottom was performed with sub-aquatic acoustic sensors. Experiments were conducted for cylinder Reynolds wave number and Keulegan-Carpenter number within the ranges 104Re1.7×105 and 2KC71, respectively. The present experimental evidence shows that the geometric characteristics of the scour hole (length and width) depend primarily on the Keulegan-Carpenter number (KC) and the cylinder aspect ratio (ar=Lc/D). The effect of variation in the angle of attack of the flow with respect to the cylinder main axis was also investigated. Initial orientations of zero and ninety degrees were found to be stable while cylinders with intermediate initial orientations tended to orientate their main axes perpendicular to the flow direction. The final angle of orientation was found to be primarily a function of the Shields parameter, θ, and the initial angle of attack, αi.  相似文献   

18.
Climatological variability of picophytoplankton populations that consisted of >64% of total chlorophyll a concentrations was investigated in the equatorial Pacific. Flow cytometric analysis was conducted along the equator between 145°E and 160°W during three cruises in November–December 1999, January 2001, and January–February 2002. Those cruises were covering the La Niña (1999, 2001) and the pre-El Niño (2002) periods. According to the sea surface temperature (SST) and nitrate concentrations in the surface water, three regions were distinguished spatially, viz., the warm-water region with >28 °C SST and nitrate depletion (<0.1 μmol kg−1), the upwelling region with <28 °C SST and high nitrate (>4 μmol kg−1) water, and the in-between frontal zone with low nitrate (0.1–4 μmol kg−1). Picophytoplankton identified as the groups of Prochlorococcus, Synechococcus and picoeukaryotes showed a distinct spatial heterogeneity in abundance corresponding to the watermass distribution. Prochlorococcus was most abundant in the warm-water region, especially in the nitrate-depleted water with >150×103 cells ml−1, Synechococcus in the frontal zone with >15×103 cells ml−1, and picoeukaryotes in the upwelling region with >8×103 cells ml−1. The warm-water region extended eastward with eastward shift of the frontal zone and the upwelling region during the pre-El Niño period. On the contrary, these regions distributed westward during the La Niña period. These climatological fluctuations of the watermass significantly influenced the distribution of picophytoplankton populations. The most abundant area of Prochlorococcus and Synechococcus extended eastward and picoeukaryotes developed westward during the pre-El Niño period. The spatial heterogeneity of each picophytoplankton group is discussed here in association with spatial variations in nitrate supply, ambient ammonium concentration, and light field.  相似文献   

19.
Studies of mixing were done at the northern flank of Georges Bank in the summer and autumn of 1988. Two time-series of the evolution and intensity of microstructure were examined over a tidal period in the context of tidal forcing and the evolution of the density and velocity field at the site. From the CTD, ADCP and microstructure observations (EPSONDE) on Georges Bank, several interesting features of the mixing processes were found. High dissipation and diffusivity regions appear near the bottom of the Bank. Turbulence near the bottom is highest in intensity and reaches farthest from the bottom at peak tidal flow and diminishes in intensity and vertical extent as the flow decreases. The thickness of the bottom turbulent layer has its maximum value when the flow is strongest and the stratification is weakest. Characterization of the dissipation rate and turbulent diffusivities in respect to buoyancy frequency N, current shear S, Richardson Number Ri and ε/νN2 was done. Dissipation and χT showed little dependence on shear or N2 but decreased at larger Ri. χt was found to be higher in regions of higher N2 and increased as ε/νN2 increased. KT, K and Kν, were all highest near the bottom in excess of 10−2m2s−1 and decreased towards the surface. There was little suggestion of a dependence of mixing efficiency on S2, Ri or ε/νN2, but some indication that Γ decreases with decreasing N2.  相似文献   

20.
  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号