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1.
Over 50 seawater samples from two different sites—Barcelona (Spain) and Banyuls-sur-Mer (France)—were analyzed in order to study the extent and postulate the processes driving the enrichment of hydrophobic organic pollutants in the sea surface microlayer (SML). A number of individual polychlorinated biphenyl (PCB) congeners (41) were measured to study their partitioning between the particulate (fraction > 0.7 μm) and the dissolved + colloidal phases (fraction < 0.7 μm), with the latter being differentiated into estimated dissolved and colloidal phases. In addition, several organochlorine pesticides were also measured, namely, HCB, α-HCH, γ-HCH, 4,4′-DDE, 4,4′-DDD and 4,4′-DDT. The presence of PCB congener profiles found in the SML suggests a dynamic coupling with the atmosphere in Banyuls sampling site, whereas offshore Barcelona the presence of highly chlorinated congeners was due to persistent sediment resuspension. The average PCB concentration in the SML dissolved + colloidal phase were higher in Banyuls (7.8 ng L− 1) than in Barcelona (3.6 ng L− 1) samples, but in the particulate phase concentrations were higher in Barcelona (3.2 ng L− 1) to that of Banyuls (1.4 ng L− 1). However, PCB concentrations in the SML generally also showed large variability. Enrichment factors of PCBs and other organochlorine compounds in the SML with respect to the underlying water column ranged from 0.2 to 7.4. This may be explained for both the dissolved + colloidal and particulate phases by the enrichment in the SML of organic carbon (OC) as discerned from particle–water and colloid–water partitioning.  相似文献   

2.
Repeated measurements of depth profiles of 234Th (dissolved, 1–70 and >70 μm particulate) at three stations (Orca, Minke, Sei) in the Ross Sea have been used to estimate the export of Th and particulate organic carbon (POC) from the euphotic zone. Sampling was carried out on three JGOFS cruises covering the period from October 1996 (austral early spring) to April 1997 (austral fall). Deficiencies of 234Th relative to its parent 238U in the upper 100 m are small during the early spring cruise, increase to maximum values during the summer, and decrease over the course of the fall. Application of a non-steady-state model to the 234Th data shows that the flux of Th from the euphotic zone occurs principally during the summer cruise and in the interval between summer and fall. Station Minke in the southwestern Ross Sea appears to sustain significant 234Th removal for a longer period than is evident at Orca or Sei. Particulate 234Th activities and POC are greater in the 1–70 μm size fraction, except late in the summer cruise, when the >70 μm POC fraction exceeds that of the 1–70 μm fraction. The POC/234Th ratio in the >70 μm fraction exceeds that in the 1–70 μm fraction, likely due in part to the greater availability of surface sites for Th adsorption in the latter. Particulate 234Th fluxes are converted to POC fluxes by multiplying by the POC/234Th ratio of the >70 μm fraction (assumed to be representative of sinking particles). POC fluxes calculated from a steady-state Th scavenging model range from 7 to 91 mmol C m−2 d−1 during late January–early February, with the greatest flux observed at station Minke late in the cruise. Fluxes estimated with a non-steady-state Th model are 85 mmol C m−2 d−1 at Minke (1/13–2/1/97) and 50 mmol C m−2 d−1 at Orca (1/19–2/1/97). The decline in POC inventories (0–100 m) is most rapid in the southern Ross Sea during the austral summer cruise (Smith et al., 2000. The seasonal cycle of phytoplankton biomass and primary productivity in the Ross Sea, Antarctica. Deep-Sea Research II 47, 3119–3140. Gardner et al., 2000. Seasonal patterns of water column particulate organic carbon and fluxes in the Ross Sea, Antarctica. Deep-Sea Research II 47, 3423–3449), and the 234Th-derived POC fluxes indicate that the sinking flux of POC is 30–50% of the POC decrease, depending on whether steady-state or non-steady-state Th fluxes are used. Rate constants for particle POC aggregation and disaggregation rates are calculated at station Orca by coupling particulate 234Th data with 228Th data on the same samples. Late in the early spring cruise, as well as during the summer cruise, POC aggregation rates are highest in near-surface waters and decrease with depth. POC disaggregation rates during the same time generally increase to a maximum and are low at depth (>200 m). Subsurface aggregation rates increase to high values late in the summer, while disaggregation rates decrease. This trend helps explain higher values of POC in the >70 m fraction relative to the 1–70 m fraction late in the summer cruise. Increases in disaggregation rate below 100 m transfer POC from the large to small size fraction and may attenuate the flux of POC sinking out of the euphotic zone.  相似文献   

3.
Mesoscale eddies may enhance primary production (PP) in the open ocean by bringing nutrient-rich deep waters into the euphotic zone, potentially leading to increased transport of particles to depth. This hypothesis remains controversial, however, due to a paucity of direct particle export measurements. In this study, we investigated particle dynamics using 234Th–238U disequilibria within a mesoscale cold-core eddy, Cyclone Opal, which formed in the lee of the Hawaiian Islands. 234Th samples were collected along two transects across Cyclone Opal as well as during a time-series within the eddy core during a decaying diatom bloom. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO2) fluxes at 150 m varied spatially and temporally within the eddy and strongly depended on the 234Th model formulation used (e.g., steady state versus non-steady state, inclusion of upwelling, etc.). Particle fluxes estimated from a steady state model assuming an upwelling rate of 2 m day−1 yielded the best fit to sediment-trap data. These 234Th-derived particle fluxes ranged from 332±14 to 1719±53 μmol C m−2 day−1, 27±3 to 114±12 μmol N m−2 day−1, and 33±20 to 309±73 μmol Si m−2 day−1. Although PP rates within Cyclone Opal were elevated by a factor of 2–3, PC and PN fluxes were the same, within error, inside and outside of Cyclone Opal. The ratio of PC export to PP remained surprisingly low at <0.03 and similar to those measured in surrounding waters. In contrast, bSiO2 fluxes within the eddy core were three times higher. Detailed analyses of 234Th depth profiles consistently showed excess 234Th at 100–175 m, associated with the remineralization and possible accumulation of suspended and dissolved organic matter from the surface. We suggest that strong microzooplankton grazing facilitated particulate organic matter recycling and resulted in the export of empty diatom frustules. Thus, while eddies may increase PP, they do not necessarily increase PC and PN export to deep waters. This may be a general characteristic of wind-driven cyclonic eddies of the North Pacific Subtropical Gyre and suggests that eddies may preferentially act as a silica pump, thereby playing an important role in promoting silicic-acid limitation in the region.  相似文献   

4.
In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g−1), Cu (1330 μg g−1) and Cd (12 μg g−1) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (Kd) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.  相似文献   

5.
Dissolved Cd (CdD) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net CdD fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating CdD concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (CdD0), each representative of one distinct situation. The obtained CdD0 concentrations were relatively similar (201 ± 28 ng L−1) when freshwater discharge Q was >500 m3 s−1 (508 ≤ Q ≤ 2600 m3 s−1), but were highly variable (340 ± 80 ng L−1; 247–490 ng L−1) for low discharge situations (169 ≤ Q ≤ 368 m3 s−1). The respective daily CdD net fluxes were 5–39 kg day−1, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual CdD net fluxes, we proposed an empirical model, using representative CdD0 values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable CdD net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a−1 in 2005 and 6.0–7.2 t a−1 in 2004, depending on freshwater discharge. Comparing CdD net fluxes with the incoming CdD fluxes suggested that the annual net CdD addition in the Gironde Estuary ranged from 3.5 to 6.7 t a−1, without any clear temporal trend during the past seven years. The annual CdD net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual CdD net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.  相似文献   

6.
Radiolabelled experiments were carried out to measure necessary parameters in the development of a biodynamic ecotoxicological simulation model of Cd accumulation in the barnacle biomonitor Balanus amphitrite. The Cd uptake rate constant from the dissolved phase, the Cd assimilation efficiency (AE) from suspended particulate matter (SPM) and the efflux rate constant were obtained using 109Cd. A Cd uptake rate constant from the dissolved phase (ku) of 0.0072 L g−1 h−1 was determined for the barnacle under environmentally realistic dissolved Cd concentrations (maximum of 400 ng L−1). Cd AE from SPM was determined from the barnacle feeding on SPM with low and high chl a concentrations, resulting in AEs of 39.0% and 48.7%, respectively, and an efflux rate of 0.0072 d−1. The difference between the AEs resulted from differences in chl a:SPM ratios suggesting a general tendency of higher AE when SPM is enriched with chl a. These results reinforce that the accuracy of ecotoxicological models for metal accumulation in organisms depends on how representative the selected food items are of the organism’s natural diet.  相似文献   

7.
The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate 234Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (CL1=3–12 nM, log K1′=13.1–13.9) and (CL2=20–70 nM, log K2′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (CL1=8–23 nM, log K1′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r2=0.64), which improved when the dissolved ligands alone were considered (r2=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.  相似文献   

8.
Depth profiles of total 234Th (dissolved+particulate) were collected at Station ALOHA (22°45N, 158°00W) in the North Pacific Subtropical Gyre during 9 cruises from April 1999 to March 2000. Samples were collected and processed by a new 2 L technique that enables more detailed depth resolution then previous 234Th studies. Significant zones of particle export (234Th deficiency) and particle remineralization (234Th excess) were measured both temporally and with depth. 234Th derived particulate carbon (PC) and nitrogen (PN) fluxes were determined with steady-state and non-steady-state models and PC/234Th and PN/234Th ratios measured with both in situ pumps and free-drifting particle interceptor traps deployed at 150 m. 234Th based export estimates of 4.0±2.3 mmol C m−2 d−1 and 0.53±0.19 mmol N m−2 d−1, were approximately 60% higher than those measured in PIT style sediment traps from the same time period, 2.4±0.2 mmol C m−2 d−1 and 0.32±0.08 mmol N m−2 d−1. Most of this difference is attributable to two large export events that occurred during October and December 1999, when traps undercollected for 234Th by a factor of 2 to 4. 234Th export (ThE) ratios based on 234Th derived PC flux/14C based primary production ranged from 4% to 22% (average=8.8%). Our results confirm the recent estimates of C export by Emerson et al. (Nature 389 (1997) 951) and Sonnerup et al. (Deep-Sea Research I 46 (1999) 777) and indicate that C export from the oligotrophic ocean must be considered when discussing C sequestration in global climate change.  相似文献   

9.
The activity of234Th (t 1/2=24.1 days) in dissolved, particulate and sediment trap samples was determined in the water column off southwestern Taiwan during 2–4 October, 1993. Vertical234Th fluxes measured by the free-floating sediment traps ranged from 363 to 2290 dpm m–2 d–1 in the upper 450 m. Th-234 fluxes predicted from the irreversible scavenging model concur with those measured by the sediment traps. Comparison of the residence times of particulate234Th and particulate organic carbon showed that their respective values differ by a factor of approximately 23, which suggests organic carbon is preferentially recycled relative to234Th in the euphotic zone.  相似文献   

10.
Cadmium and copper in the dissolved and particulate phase and in zooplankton were determined in the Bahía Blanca estuary during six surveys from March to December 2005. Temperature, pH, salinity, dissolved oxygen, suspended particulate matter, particulate organic matter and chlorophyll-a were also considered. Dissolved Cd was below the detection limit (0.2 μg L−1) for almost the entire study period whereas Cu concentrations (0.5–2.4 μg L−1) indicated a continuous dissolved Cu input. Particulate Cd concentrations ranged from below the detection limit (<0.01) to 28.6 μg g−1 d.w. while particulate Cu ranged from below the detection limit (<0.04) to 53.5 μg g−1 d.w. Cd in mesozooplankton ranged from below the detection limit (<0.01) to 37.4 μg g−1 d.w. Some of the Cd levels were higher than those reported for other aquatic ecosystems. Cu in the mesozooplankton ranged from 1.3 to 89.3 μg g−1 d.w., values which were within the reported values or higher than other studies. The log of the partition coefficients (log (Kd)) of Cd was 0.04, while log (Kd) for Cu ranged from −0.39 to 2.79. These values were lower than both those calculated for other estuaries and the typical coefficients for marine environments. The log of the bioconcentration factor (log BCF) of Cd was 1.78, indicating that Cd concentration was higher in the zooplankton than in the dissolved phase. Log BCF of Cu ranged from 1.15 to 3. The logs of the biomagnification factors (log BMF) of Cd were low, with a range between −3.45 and 2.21 and those for Cu ranged from −0.1 to 3.35. Positive values indicate biomagnification while negative values indicate biodiminution. In general, no significant dissolved Cd concentration appeared to be present in the Bahía Blanca estuary and Cu values did not indicate a critical environmental status. The particulate phase seemed to be the major carrier for Cd and Cu and TPCu values were within the normal values for an anthropogenically stressed estuary but not for a strongly polluted system. This fraction was the most important metal source for the mesozooplankton. Moreover, the highest metal concentrations were in the mesozooplankton since most of the bioconcentration and biomagnification factors were positive, especially for Cu.  相似文献   

11.
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   

12.
In order to better understand the relationship between the natural radionuclide 234Th and particulate organic carbon (POC), marine particles were collected in the northwestern Mediterranean Sea (spring/summer, 2003 and 2005) by sediment traps that separated them according to their in situ settling velocities. Particles also were collected in time-series sediment traps. Particles settling at rates of >100 m d−1 carried 50% and 60% of the POC and 234Th fluxes, respectively, in both sampling years. The POC flux decreased with depth for all particle settling velocity intervals, with the greatest decrease (factor of 2.3) in the slowly settling intervals (0.68–49 m d−1) over trap depths of 524–1918 m, likely due to dissolution and decomposition of material. In contrast the flux of 234Th associated with the slowly settling particles remained constant with depth, while 234Th fluxes on the rapidly settling particles increased. Taking into account decay of 234Th on the settling particles, the patterns of 234Th flux with depth suggest that either both slow and fast settling particles scavenge additional 234Th during their descent or there is significant exchange between the particle classes. The observed changes in POC and 234Th flux produce a general decrease in POC/234Th of the settling particles with depth. There is no consistent trend in POC/234Th with settling velocity, such as might be expected from surface area and volume considerations. Good correlations are observed between 234Th and POC, lithogenic material and CaCO3 for all settling velocity intervals. Pseudo-Kds calculated for 234Th in the shallow traps (2005) are ranked as lithogenic material opal <calcium carbonate <organic carbon. Organic carbon contributes 33% to the bulk Kd, and for lithogenic material, opal and CaCO3, the fraction is 22% each. Decreases in POC/234Th with depth are accompanied by increases in the ratio of 234Th to lithogenic material and opal. No change in the relationship between 234Th and CaCO3 was evident with depth. These patterns are consistent with loss of POC through decomposition, opal through dissolution and additional scavenging of 234Th onto lithogenic material as the particles sink.  相似文献   

13.
Seabed distributions of 234Th excess (Thxs) were determined in the upper centimetres of 38 sediment cores from the north-western Iberian Margin, sampled from 41–44°N and from 9–12°E during five OMEX II cruises. Three main areas, a northern, and at 42°38 and 42°N, were investigated during representative seasons (winter, spring and summer). Low 234Thxs activities in summer 1998 (18–252 Bq per kg) were similar to those measured in summer 1997. In winter 234Th also showed moderate excess. The highest values were observed in spring with surface 234Thxs values up to 402 Bq kg−1. Maximum penetration depths of 234Thxs ranged from a few mm to 3 cm. 234Thxs activities always showed a smooth decrease with depth, without any evidence of non-local mixing. Thus particle mixing on a short time scale can be described as an eddy diffusive process, and bioturbation rates, calculated on this basis, range from 0.02 to 3.07 cm2 per year. Data (activities, inventories, bioturbation rates) are discussed in order to relate the observed surface and down-core variations to spatial and seasonal trends. Using 234Thxs data in sediment as a substitute for sediment trap estimates, particle fluxes were calculated from 234Thxs inventories. The range of 234Th-derived particle fluxes for the north-western Iberian Margin is 16–1418 mg.m−2.d−1. Mean values indicate a gradual decrease of mass fluxes from the shelf to the open ocean. On a 100-day scale, the northern area (43–44°N) represents a low sedimentation regime. Further south, around 42°–43°N, particle inputs are more important. On the middle slope, around 1000 to 2000 m depth, high inventories and bioturbation rates indicate enhanced, and probably organic-rich, particle fluxes to the seafloor, particularly in spring.  相似文献   

14.
Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O2/H2S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O2/H2S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.  相似文献   

15.
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   

16.
U–Th decay series isotopes, δ18O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ18O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. 234Th and 210Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l−1). 228Ra and 226Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, 210Pb and 210Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. 232Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.  相似文献   

17.
The distributions of the trace metals iron (Fe), copper (Cu) and cadmium (Cd) along with hydrological parameters (salinity, temperature and reactive phosphate) across the New Zealand continental shelf near Otago Peninsula have been studied. This is a region in which the Subtropical Convergence (STC), a major oceanic front separating subtropical and subantarctic waters, is uniquely located close to land, permitting an examination of the influence of terrestrial sources of Fe and Cu on oceanic waters containing excess micronutrients. Acid-soluble (110 nmol kg−1) and dissolved (6.3 nmol kg−1) Fe concentrations were highest over the central shelf, and decreased rapidly across the mixing zone of the STC to about 5 nmol kg−1 for both forms. The distribution of acid-soluble and dissolved Cu were similar to their counterparts for Fe. Depth-concentration profiles for acid-soluble Fe and Cu suggest resuspension of shelf sediments is the main source. The ratio of oxine-labile to acid-soluble Fe varied from 0.03 to 0.26, with the highest values found in the near surface waters. Oxine-labile Fe and Cu also decreased in concentration in a seawards direction, and with depth, indicating the influence of near surface processes on the reactivity of these elements. Cd concentrations across the continental shelf were very low (<200 pmol kg−1) and exhibited no clear spatial trend and no correlation with phosphate. Comparison of the Cd/P ratio across the shelf indicated that the waters in this region were strongly depleted in Cd relative to P. Phosphate concentrations were lowest in neritic water and increased in the seawards direction because of mixing with nutrient-rich Subantarctic Surface Water.  相似文献   

18.
Light attenuation (Kd) of photosynthetically active radiation (PAR) by chromophoric dissolved organic matter (CDOM), total suspended solids (TSS) and chlorophyll a (Chl a) were measured at nine stations along an estuarine gradient in the Swan River, Western Australia, over 15 months. There were strong spatial gradients associated with the marine-freshwater transition along the 32 km of estuary sampled, as well as seasonal gradients mainly associated with rainfall, 80% of which occurs between May and September. CDOM absorbances at 440 nm reached a maximum of 10.9 m−1 with the freshwater inflow but concentrations of suspended matter remained low throughout the sampling period (1.0–21.0 mg l−1) under the diurnal tides of the estuary. CDOM was the dominant constituent of Kd and a stepwise multiple regression showed that 66% (p < 0.0001) of the variation in Kd can be explained by CDOM and an additional 8% (p < 0.0001) by TSS. As a consequence of this result, analysis into the influence of river discharge rates on CDOM absorbance levels was examined for 2002 using data collected during this study, and for 2000 and 2001 using historical dissolved organic carbon (DOC) and river discharge data. The outcome of this analysis infers that greater river discharge rates result in increased CDOM absorbances in the Swan River estuary.  相似文献   

19.
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   

20.
During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fe addition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO43−, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20 m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 μg L−1) during developing phases of the bloom (<12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch hinted at an increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 μg L−1) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment.  相似文献   

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