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1.
Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CCCu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CCCu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CCCu and K′ were found to differ between these waters. The range of values for CCCu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that kf is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 104s−1M−1 Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CCCu and higher K′ than those found for surface waters.  相似文献   

2.
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   

3.
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 (KSPc) and aragonite (KSPa) in seawater. Regression of the data gives the relation In KPSPc = 1.94 × 10−3 δP − 14.59 The 2°C, 1 atm value of KSPc 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 KSPa = 9.2 × 10−7 (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for KSPc 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   

4.
The apparent solubility product Ksp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of Ksp at 25°C was 4.59·10−7 mole2/(kg seawater)2 at 35‰S, 5.34·10−7 at 43‰S, and 3.24·10−7 at 27‰S. The apparent partial molal volume was found to be −34.4 cm3 at 25°C and −42.3 cm3 at 2°C from a linear fit of log(Ksp P/Ksp 1). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.  相似文献   

5.
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   

6.
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+q 1010M−1s−1) > Iq 2 × 109 M−1 s−1) >CH2CHCONH2q 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   

7.
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   

8.
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   

9.
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   

10.
We have investigated the chemical forms, reactivities and transformation kinetics of Fe(III) species present in coastal water with ion exchange and filtration methods. To simulate coastal water system, a mixture of ferric iron and fulvic acid was added to filtered seawater and incubated for a minute to a week. At each incubation time, the seawater sample was acidified with hydrochloric acid and then applied to anion exchange resin (AER) to separate negatively charged species (such as fulvic acid, its complexes with iron and iron oxyhydroxide coated with fulvic acid) from positively charged inorganic ferric iron (Fe(III)′). By monitoring the acid-induced Fe(III)′ over an hour, it was found that iron complexed by fulvic acid dissociated rapidly to a large extent (86–92% at pH 2), whereas amorphous ferric oxyhydroxide particles associated with fulvic acid (AFO-L) dissociated very slowly with the first-order dissociation rate constants ranging from 6.1 × 10− 5 for pH 3 to 2.7 × 10− 4 s− 1 for pH 2. Therefore, a brief acidification followed by the AER treatment (acidification/AER method) was likely to be able to determine fulvic acid complexes and thus differentiate the complexes from the AFO-L particles (the dissolution of AFO-L was insignificant during the brief acidification). The acidification/AER method coupled with a simple filtration technique suggested that the iron–fulvic acid complexes exist in both the < 0.02 μm and 0.02–0.45 μm size fractions in our coastal water system. The truly dissolved iron (< 0.02 μm) was relatively long-lived with a life-time of 14 days, probably due to the complexation by strong ligands. Such an acid-labile iron may be an important source of bioavailable iron in coastal environments, as a significant relationship between the chemical lability and bioavailability of iron has been well recognised.  相似文献   

11.
12.
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   

13.
14.
The apparent (stoichiometric) solubility product of calcite in artificial seawater of salinity 35‰ was measured by a saturometer technique. The value of the apparent solubility product was found to be (4·59 ± 0·05) × 10−7 moles/(kilogram of seawater)2 at 25°C with a temperature coefficient of −0·0108 × 10−7/°C between 2 and 25°C. These values are significantly smaller than those found by MacIntyre (1965) and other workers. The effect of these results on the saturation of the oceans with respect to calcite is examined.  相似文献   

15.
A theoretical evaluation of basic thermodynamic relationships reveals that variation of activity coefficients, ion pairing and electrical interactions must be considered when modelling ionic diffusion in seawater. The contributions of ion-pair formation and change in activity coefficient along the diffusion path were studied experimentally by conducting diffusion experiments in which solutions of KCl, NaCl, MgCl2, Li2SO4, K2SO4, Na2SO4 and MgSO4, at an ionic strength of 0.7, were allowed to diffuse into distilled water. The study reveals that the thermodynamic factor, required to correct for changes in the activity coefficient along the diffusion path, is significant for all the salts studied. Agreement between a simple diffusion model, which does not include ion pairing, and observed data was good for completely dissociated salts, but poor for salts which are known to form ion pairs at the concentration levels studied. The diffusion of MgSO4, 0.425 of which is associated at I = 0.7, was successfully modelled by assuming that the diffusion coefficient of the MgSO40 ion pair is different from the diffusion coefficient of the dissociated salt. The diffusion coefficient of this ion pair is estimated to be 1.9 × 10−5 cm2 s−1 at 30°C, as compared to 0.49 × 10−5 cm2 s−1 for the dissociated salt. It is suggested that the high mobility of this ion pair could cause magnesium enrichment in pore water of sulfate depleted sediments.  相似文献   

16.
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   

17.
An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (Kiequ), total ligands concentration (LiT) and association/dissociation rate constants (ki1,ki- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K1equ: 11.2–13.0, log K2equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k11:6.1–20 × 103 (M s)− 1, k21: 1.3–6.3 × 103 (M s)− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µMC, i.e. 1 mgCL− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).  相似文献   

18.
The natural human female hormones oestrone and 17β-oestradiol have been implicated in the disruption of endocrine systems in some wildlife adjacent to sewage effluents. The sorption behaviour of these two compounds under estuarine conditions was studied by spiking either 2.55 μg of oestrone or 2.65 μg of 17β-oestradiol in kinetic experiments. In equilibrium experiments, 3 ng of oestrone or 3.2 ng of 17β-oestradiol was added in each of the centrifuge tubes. Sorption onto sediment particles was relatively slow, with sorption equilibrium being reached in about 70 and 170 h for oestrone and 17β-oestradiol, respectively. The effects of a variety of environmental parameters on sorption were studied including salinity, sediment concentration (SC), the presence of a third phase, particle size and, also, surfactant concentrations. Results show that although salinity did not induce any statistically significant effect on the sorption of 17β-oestradiol, it did statistically enhance the sorption of oestrone, and a salting constant of 0.3 l mol−1 was derived. The partition coefficient for both compounds decreased with increasing sediment concentration, a phenomenon that has been widely reported and attributed to the presence of colloids (which could enhance dissolved concentrations). In this paper, the true partition coefficients for sediment particles (Kptrue) and colloidal particles (Kctrue) have been calculated, and a Kptrue value of 141 and 102 ml g−1 was obtained for oestrone and 17β-oestradiol, respectively. In addition, Kctrue values for oestrone (222×102 ml g−1) and 17β-oestradiol (135×102 ml g−1) were two orders of magnitude higher than their respective Kptrue values, suggesting that the colloidal particles are significantly stronger sorbents for natural oestrogens than sediment particles. Particles of different sizes were found to have different partition coefficients due to the strong relationships between partition coefficients for the two compounds and particulate organic carbon (POC) contents and specific surface areas (SSAs). The presence of a surfactant was shown to reduce the partition coefficients for the two compounds, although its concentrations being used were higher than those normally found in the natural environment.  相似文献   

19.
The uptake of atmospheric carbon dioxide in the water transported over the Bering–Chukchi shelves has been assessed from the change in carbon-related chemical constituents. The calculated uptake of atmospheric CO2 from the time that the water enters the Bering Sea shelf until it reaches the northern Chukchi Sea shelf slope (1 year) was estimated to be 86±22 g C m−2 in the upper 100 m. Combining the average uptake per m3 with a volume flow of 0.83×106 m3 s−1 through the Bering Strait yields a flux of 22×1012 g C year−1. We have also estimated the relative contribution from cooling, biology, freshening, CaCO3 dissolution, and denitrification for the modification of the seawater pCO2 over the shelf. The latter three had negligible impact on pCO2 compared to biology and cooling. Biology was found to be almost twice as important as cooling for lowering the pCO2 in the water on the Bering–Chukchi shelves. Those results were compared with earlier surveys made in the Barents Sea, where the uptake of atmospheric CO2 was about half that estimated in the Bering–Chukchi Seas. Cooling and biology were of nearly equal significance in the Barents Sea in driving the flux of CO2 into the ocean. The differences between the two regions are discussed. The loss of inorganic carbon due to primary production was estimated from the change in phosphate concentration in the water column. A larger loss of nitrate relative to phosphate compared to the classical ΔN/ΔP ratio of 16 was found. This excess loss was about 30% of the initial nitrate concentration and could possibly be explained by denitrification in the sediment of the Bering and Chukchi Seas.  相似文献   

20.
The incidence of a large scale Trichodesmium erythraeum bloom along the southwest coast of India (Arabian Sea) observed in May 2005 is reported. Around 4802 filaments of T. erythraeum ml−1 seawater was observed and a colony consisted of 3.6 × 105 cells. The bloom was predominant off Suratkal (12° 59′N and 74° 31′E) with a depth of about 47 m, covering an area of 7 km in length and 2 km width. The concentrations of Zinc, Cadmium, Lead, Copper, Nickel and Cobalt were determined in samples collected from the bloom and non-bloom sites using stripping voltammetry. The observed hydrographical and meteorological parameters were found to be favorable for the bloom. The concentrations of Zinc, Cadmium and Nickel were found to be higher at bloom stations, while the concentrations of Lead, Copper and Cobalt were found to be very low at bloom stations. Elevated concentrations of Cadmium and Cobalt were observed at Valappad mainly due to the decomposition of detrital material produced in the bloom. Statistically significant differences (P > 0.01) in metal concentrations between the bloom and non-bloom stations were not observed except for Copper. Metals such as Lead, Copper and Cobalt were removed from the seawater at all places where bloom was observed. Cadmium was found to be slowly released during the decaying process of the bloom.  相似文献   

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