Zinc speciation in the Northeastern Atlantic Ocean     

Michael J. Ellwood  Constant M. G. Van den Berg 《Marine Chemistry》2000,68(4)

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.  相似文献   

Investigation of Cd, Cu, Ni and Th in the colloidal size range in the Gulf of Maine     

Jennifer M. Greenamoyer  S. Bradley Moran   《Marine Chemistry》1997,57(3-4)

Size-fractionated seawater samples were collected from the Gulf of Maine to determine the fraction (f_c/d) of total dissolved (< 1 μm) Cd, Cu, Ni and ²³⁴Th in the colloidal size range (1,000 nominal molecular weight, NMW, to 1 μm) using cross-flow filtration. Colloidal Cd, Cu and Ni represents < 1–7% of the total dissolved concentration in these shelf waters and increases with an increase in particle concentration. By comparison, results obtained for particle-reactive ²³⁴Th indicate that < 1–47% of total dissolved is associated with the colloidal size fraction. A revised relationship between the concentration of colloids (C_c) and suspended particles (C_p) is reported (log C_c = 0.66 log C_p −2.01 kg L⁻¹) and used to examine the dependence of f_c/d for these metals on the concentration of suspended particles for C_p = 0.01–100 mg L⁻¹. Results indicate that a significant fraction (˜ 10–30%) of Cd, Cu, Ni and ²³⁴Th in the traditionally defined ‘dissolved’ fraction may exist in the colloidal size range in regions characterized by high particle concentrations (C_p > 1–10 mg L⁻¹), such as in near-shore and estuarine waters.  相似文献   

Apparent copper complexation capacity and conditional stability constants in north atlantic waters     

Cees J.M Kramer 《Marine Chemistry》1986,18(2-4)

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) 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. CC_Cu 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). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu 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 k_f^′ 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 CC_Cu and higher K′ than those found for surface waters.  相似文献   

Molecular masses and chromophoric properties of dissolved organic ligands for copper(II) in oceanic water     

Takashi Midorikawa  Eiichiro Tanoue 《Marine Chemistry》1998,62(3-4)

The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log K_CuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log K_HL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.  相似文献   

Seasonal survey of copper-complexing ligands and thiol compounds in a heavily utilized, urban estuary: Elizabeth River, Virginia   总被引：1，自引：1，他引：0  

Christina L. Dryden  Andrew S. Gordon  John R. Donat   《Marine Chemistry》2007,103(3-4):276-288

Concentrations of thiol compounds, copper-complexing ligands, and total dissolved copper were followed over the course of 1 year (October 2002 until September 2003) in the Elizabeth River, Virginia to evaluate seasonality. Copper-complexing ligand concentrations were determined by competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE/ACSV). Thiol detection was carried out by high performance liquid chromatography (HPLC) and calibration using a suite of nine thiol compounds (cysteine, glutathione, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and monothioglycerol). Total dissolved copper concentrations reached a January low of 13.1 nM to a June high of 24.7 nM and were found to vary seasonally with higher concentrations occurring from June to September. With a low of 26 nM during April to a high of 56 nM in October, copper-complexing ligand (average log K′_CuL of 12.0 ± 0.2) concentrations displayed a similar seasonal pattern to that of total dissolved copper. Free cupric ion concentrations remained below 1.5 pM for a majority of the year except during March, April, and December when values reached pM levels greater than 1.5. Six of the nine thiol compounds surveyed were detected in the Elizabeth River samples and ranged in concentration from below detectable concentrations (< 5 nM) to individual highs ranging from 25.3 to168.5 nM. The thiol compound concentrations displayed a clear seasonality fluctuating at below detection limits during November to February then increasing with increasing surface water temperatures from March to July. CLE/ACSV was used to assess whether or not the suite of thiol compounds detected by HPLC could contribute to the copper-complexing ligand pool. Conditional stability constants for each one of six thiol standards (average log K′_CuL  12.1 ± 0.5) were found to be statistically equivalent to the naturally occurring copper-complexing ligands (average log K′_CuL  12.0 ± 0.2). This suggests that these thiol compounds could act as copper-complexing ligands in natural samples and could contribute to the copper-complexing ligand pool detected by CLE/ACSV. This study involving seasonality of copper-complexing ligands and thiols in an industrialized, urban estuary underscored several points that have to be substantiated in future research efforts including copper-complexing ligands sources and the role that thiol compounds as well as other unidentified organic compounds play in the copper-complexing ligand pool.  相似文献   

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation     

Pasquale Crea  Concetta De Stefano  Demetrio Milea  Silvio Sammartano   《Marine Chemistry》2008,112(3-4):142-148

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).  相似文献   

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)     

Yoann Louis  Cdric Garnier  Vronique Lenoble  Stphane Mounier  Neven Cukrov  Dario Omanovi&#x;  Ivanka Pieta 《Marine Chemistry》2009,114(3-4):110-119

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 (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 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 K₁^equ: 11.2–13.0, log K₂^equ: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 µM_C, i.e. 1 mg_CL^− 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   

Physico-chemical Speciation of Lead in South San Francisco Bay     

P.B. Kozelka  S. Sañudo-Wilhelmy  A.R. Flegal  K.W. Bruland 《Estuarine, Coastal and Shelf Science》1997,44(6):649-658

The speciation of lead at a site in the South San Francisco Bay was determined using a combination of physical size fractionation and electrochemical analyses. The ‘ total dissolvable ’ Pb was 8·1 nM from analysis of an acidified unfiltered sample. The ‘ dissolved ’ Pb was equal to 0·20 nM (41 ng l⁻¹), only 2·5% of the ‘ total dissolvable ’ Pb. The difference yielded the ‘ particulate ’ Pb equal to 7·9 nM (1·6 μg l⁻¹). Results from crossflow ultrafiltration indicated that almost all (0·19 nM) of the dissolved Pb was ‘ in solution ’ [<10K nominal molecular weight (MW)] and that colloidal Pb (10K MW to 0·2 μm)accounted for onlyc. 1% of the dissolved Pb at this station. This small concentration (0·01 nM) of colloidal Pb may be attributed to the low amount of organic carbon associated with colloid size fraction as determined by dissolved organic carbon analyses.The chemical speciation of lead was determined in the dissolved sample and ultrafiltered sub-sample. Differential pulse anodic stripping voltammetry (DPASV) on a thin mercury film (TMF) rotating glassy carbon disk electrode (RGCDE) was used to distinguish the kinetically labile inorganic species (Pb′) from the Pb-chelated by organic ligands (PbL_i). Lead titration results were similar for both samples revealing that Pb′, PbL_iand excess unbound ligands were present primarily in the ultrafiltrate, rather than in the colloidal phase. The titration data can be interpreted as dissolved Pb being influenced by two classes of Pb-binding ligands. In the dissolved sample, the concentration of the stronger class of ligands was [L₁]=0·89±0·35 nM, with a conditional stability constant ofK^cond_L1,Pb′=3±1×10¹⁰M⁻¹. The weaker class was [L₂]=12·8±1·9 nM, withK^cond_L1,Pb′=4±1×10⁸ M⁻¹. The presence of these ligands, in excess of the dissolved Pb, resulted in [Pb′]=7±2 pM and [Pb²⁺]=0·3 pM (62 pg l⁻¹). While less than 2·4% of the ambient Pb was ‘ in solution ’, it existed chiefly in the form of organic complexes with [PbL₁]=0·15 nM and [PbL₂]=0·03 nM. More significantly, there were large concentrations of unchelated Pb-binding ligands, (L_i′), available to buffer the free Pb²⁺concentration in the event of perturbations in dissolved Pb.  相似文献   

Seasonal variations of alkenones and U₃₇ in the Chesapeake Bay water column     

Jennifer L. Mercer  Meixun Zhao  Steven M. Colman   《Estuarine, Coastal and Shelf Science》2005,63(4):675-682

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.  相似文献   

A comparison of two voltammetric techniques for determining zinc speciation in Northeast Pacific Ocean waters     

John R. Donat  Kenneth W. Bruland 《Marine Chemistry》1990,28(4)

Two independent voltammetric techniques, differential pulse cathodic stripping voltammetry (DPCSV) and differential pulse anodic stripping voltammetry (DPASV), determined that 95% of the dissolved zinc is organically complexed at two depths (60 and 150 m) within the surface euphotic zone at an open ocean station in the Northeast Pacific. Average values for the concentrations of the natural zinc-complexing organic ligands (C_L) obtained from duplicate determinations at these two depths by DPCSV versus DPASV are in excellent agreement: 1.60 ± 0.01 versus 1.76 ± 0.03 nM at 60 m, and 2.14 (n=1) versus 2.22 ± 0.06 nM at 150 m. Average values for the conditional stability constants (with respect to free Zn²⁺) of the natural zinc-organic complexes (log K^′_ZnL) from duplicate determinations at both depths by DPCSV versus DPASV are 10.3 ± 0.2 versus 11.2 ± 0.2. Additional research is required to assess the significance of the difference in the conditional stability constants determined by these two techniques. These results confirm recent observations that strong zinc complexes formed with an organic ligand class existing at nanomolar concentrations dominates zinc speciation in the North Pacific.  相似文献   

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS     

Lutz Brügmann  Paul C. Bernard  Rene van Grieken 《Marine Chemistry》1992,38(3-4)

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 (K_d) 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   

Comparison of β-dimethylsulfoniopropionate (DMSP) levels in two mediterranean ecosystems with different trophic levels     

Natacha Jean  Grard Boge  Jean-Louis Jamet  Dominique Jamet 《Marine Chemistry》2006,101(3-4):190-202

β-dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) concentrations were recorded from September 1999 to September 2000 in two geographically close ecosystems, differently affected by eutrophication: the Little Bay of Toulon and the Niel Bay (N.W. Mediterranean Sea, France). Little Bay had higher nutrient levels ([NO₃⁻]_max. = 30.3 μM; [PO₄³⁻]_max. = 0.46 μM) and higher chlorophyll a concentrations ([chl a]_mean = 2.4 μg/L) compared to Niel Bay ([NO₃⁻]_max. = 19.7 μM; [PO₄³⁻]_max. = 0.17 μM; [chl a]_mean = 0.4 μg/L). In the two sites, we measured dissolved (DMSP_d < 0.2 μm) and particulate DMSP (DMSP_p > 0.2 μm) concentrations. The DMSP_p was particularly analysed in the 0.2–5, 5–90 and > 90 μm fractions. In the eutrophicated Little Bay, DMSP_d concentrations showed a clear seasonality with high values from January to March (124–148 nM). The temporal profile of the DMSP_p concentrations was similar, peaking in February–March (38–59 nM). In the less eutrophic Niel Bay, DMSP_p concentrations were much lower (6–9 nM in March–April), whereas DMSP_d concentrations were relatively high (110–92 nM in February–March). DMS concentrations were elevated from the end of the winter to the spring in Little Bay, ranging from 3 nM in October to 134 nM in March. In the less eutrophic Niel Bay, lower DMS levels were observed, generally not exceeding 20 nM. Each particulate fraction (0.2–5; 5–90; > 90 μm) contained less DMSP in Niel Bay than in Little Bay. At both sites, the 5–90 μm fraction made up most of the DMSP_p. This 5–90 μm fraction consisted of microphytoplankton, principally Dinophyceae and Bacillariophyceae. The 5–90 μm biomass calculated from cell biovolumes, was more abundant in Little Bay where the bloom at the end of the winter (165 μg/L in March) occurred at the same time as the DMSP peaks. The estimated DMSP_p to biomass ratio for the 5–90 μm fraction was always higher in Little Bay than in Niel Bay. This suggests that the high DMSP levels recorded in Little Bay were not only due to a large Dinophyceae presence in this ecosystem. Indeed, the peak of DMSP_p to biomass ratio obtained from cell biovolumes (0.23 nmol/μg in March) was consistent with the proliferation of Alexandrium minutum. This Dinophyceae species may account for between 50% (2894 cells/L) and 63% (4914 cells/L) of the total phytoplankton abundance in the Little Bay of Toulon.  相似文献   

Importance of organic Fe complexing ligands in the Mississippi River plume     

Rodney T. Powell  Amy Wilson-Finelli 《Estuarine, Coastal and Shelf Science》2003,58(4):757

As part of a larger program focused on understanding the biogeochemistry of large river plumes, we participated in two expeditions during 2000 to sample the Mississippi River plume. Surface water samples were collected using a trace metal clean towed fish and analyzed for total dissolved Fe, organic Fe complexing ligands and their associated conditional stability constants. The ligands in the river plume have conditional stability constants (log K′_FeL between 10.5 and 12.3 with an average of 11.2 and standard deviation of 0.6) very similar to ligands found in the open ocean. Comparison of high flow and low flow regimes indicates that variability in flow may be the main cause of the variability in Fe concentrations in the plume. The organic Fe complexing ligands are in greatest excess during a time of higher flow. These ligands are responsible for maintaining very high (5 nM) Fe concentrations throughout the plume. Due to complexation with these organic ligands, the concentration of Fe remains above the Fe-hydroxide solubility level until a salinity above 35 is reached where there appears to be a sink for Fe in the less productive waters. Therefore, Fe is transported a great distance from the river source and is available for biological utilization in the coastal zone.  相似文献   

Vertical flux of biogenic matter during a Lagrangian study off the NW Spanish continental margin     

Kalle Olli  Christian Wexels Riser  Paul Wassmann  Tatjana Ratkova  Elena Arashkevich  Anna Pasternak 《Progress in Oceanography》2001,51(2-4)

Lagrangian experiments with short-term, drifting sediment traps were conducted during a cruise on RRS Charles Darwin to the NW coast of Spain to study the vertical flux and composition of settling biogenic matter. The cruise was split into two legs corresponding to (i) a period of increased production following an upwelling event on the continental shelf (3–10 August 1998) and (ii) an evolution of a cold water filament originating from the upwelled water off the shelf (14–19 August). The export of particulate organic carbon (POC) from the upper layer (0–60m) on the shelf was 90–240mgC.m⁻².d⁻¹ and off the shelf was 60–180mgC.m⁻².d⁻¹. Off shelf the POC flux at 200m was 50–60mg.m⁻².d⁻¹. A modest sedimentation of diatoms (15–30mgC.m⁻².d⁻¹) after the upwelling was associated with increased vertical flux of chlorophyll a (1.8–2.1mg.m⁻².d⁻¹) and a decrease of the POC:PON molar ratio of the settled material from 9 to 6.4. Most of the pico-, nano-, and microplankton in the settled material were flagellates; diatoms were significant during the on shelf and dinoflagellates during the off shelf leg. Off shelf, the exponential attenuation of POC flux indicated a strong retention capacity of the plankton community between 40 and 75m. POC:PON ratio of the settled particulate matter decreased with depth and the relative portion of flagellates increased, suggesting a novel, flagellate and aggregate mediated particulate flux in these waters. Export of POC from the euphotic layer comprised 14–26% of the integrated primary production per day during the on shelf leg and 25–42% during the off shelf leg, which characterises the importance of sedimentation in the organic carbon budget of these waters.  相似文献   

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone     

F.J.G. Laurier  D. Cossa  C. Beucher  E. Brvire 《Marine Chemistry》2007,104(3-4):143-155

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 (HgT_D) 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 HgT_D 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 (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D 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 (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D 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   

Particle–water interactions of 2,2′,5,5′-tetrachlorobiphenyl under simulated estuarine conditions     

M. Carl Rawling  Andrew Turner  Andrew O. Tyler 《Marine Chemistry》1998,61(3-4)

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, K_D, 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   

Chemical environment for red tides due toChattonella antiqua     

Yasuo Nakamura 《Journal of Oceanography》1990,46(3):84-95

In order to assess the roles of Fe and Cu in outbreaks ofChattonella antiqua red tide, concentrations of these metals in the surface seawater were monitored around the Ie-shima Islands in the Seto Inland Sea during the summers of 1986–1988. Bioassay of the surface seawater with respect to Fe and Cu was also conducted using a cultured strain ofC. antiqua.Concentrations of Fe and Cu in the filtered seawater (Fe^F and Cu^F) were in the range of 3.9–10.0 and 9.3–11.2 nM, respectively. The bioassay with respect to Fe revealed that Fe at the surface layer was usually insufficient to support the maximum growth rate ofC. antiqua, except whenC. antiqua was dominant in the field. However, correlations between Fe^F and the growth rate of the control cultures (Fe, EDTA=not enriched; N, P, B₁₂=enriched at optimum levels) were not apparent, probably because Fe^F did not reflect the concentration of available Fe.The bioassay with respect to Cu was coupled with the Cu^F values obtained. The results indicated that Cu at the surface layer was detoxified by complexation with natural organic ligand(s), and that pCu (=minus log of cupric ion activity) was 11.5–11.7, optimum for the growth ofC. antiqua, throughout the survey period. It is suggested that Fe, but not Cu, is a potentially important factor in regulating the natural populations ofC. antiqua in the Seto Inland Sea.  相似文献   

Outflow of trace metals into the Laptev Sea by the Lena River     

Ccile Guieu  Wei Wen Huang  Jean-Marie Martin  Yoon Yi Yong 《Marine Chemistry》1996,53(3-4)

Freshwater concentrations confirm the pristine character of the Lena River environment as already pointed-out in a previous study with a limited set of data (Martin et al., 1993). Total dissolved concentrations of the freshwater are 13.8 ± 1.6 nM, Cu, 4.4 ± 0.1 nM, Ni, 0.054 ± 0.047 nM, Cd, 642 ± 208 nM, Fe, 0.2–0.3 nM Pb and 1.2 ± 1.0 nM, Zn. For Zn and Pb, a simple mixing of the Lena River waters with the Arctic waters is observed. Relationships with salinity suggest that for Cu, Ni and Cd, there is a mobilization of the dissolved fraction from the suspended matter, with an increase of the dissolved concentration of 1.5, 3 and 6 times, respectively. For Fe, the total dissolved concentrations follow an exponential decrease in the mixing zone and 80% of the total “dissolved” Fe is removed from the solution. For Cu, Ni, Cd and Fe, the riverine end-members are 20 nM, 12 nM, 0.3 nM and 47 nM, respectively. When considering the input of total dissolved metals to the Arctic Ocean, the fraction attributed to the freshwaters from the Arctic rivers appears to be small (4% of the input of dissolved metal to the Arctic Ocean for Cd, 27% for Cu, 11 % for Ni and 2% for Zn). Metal concentrations in the Laptev Sea and Arctic Ocean are very similar, indicating a generally homogeneous distribution in the areas sampled.  相似文献   

Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of pH and ionic strength   总被引：1，自引：0，他引：1  

Kelly A. Quinn  Robert H. Byrne  Johan Schijf 《Marine Chemistry》2006,99(1-4):128

The sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide at low ionic strength (0.01 M ≤ I ≤ 0.09 M) was investigated over a wide range of pH (3.9 ≤ pH ≤ 7.1). YREE distribution coefficients, defined as _iK_Fe = [MS_i]_T / (M_T[Fe³⁺]_S), where [MS_i]_T is the concentration of YREE sorbed by the precipitate, M_T is the total YREE concentration in solution, and [Fe³⁺]_S is the concentration of precipitated iron, are weakly dependent on ionic strength but strongly dependent on pH. For each YREE, the pH dependence of log _iK_Fe is highly linear over the investigated pH range. The slopes of log _iK_Fe versus pH regressions range between 1.43 ± 0.04 for La and 1.55 ± 0.03 for Lu. Distribution coefficients are well described by an equation of the form _iK_Fe = (_Sβ₁[H⁺]^− 1 + _Sβ₂[H⁺]^− 2) / (_SK₁[H⁺] + 1), where _Sβ_n are stability constants for YREE sorption by surface hydroxyl groups and _SK₁ is a ferric hydroxide surface protonation constant. Best-fit estimates of _Sβ_n for each YREE were obtained with log _SK₁ = 4.76. Distribution coefficient predictions, using this two-site surface complexation model, accurately describe the log _iK_Fe patterns obtained in the present study, as well as distribution coefficient patterns obtained in previous studies at near-neutral pH. Modeled log _iK_Fe results were used to predict YREE sorption patterns appropriate to the open ocean by accounting for YREE solution complexation with the major inorganic YREE ligands in seawater. The predicted log _iK_Fe′ pattern for seawater, while distinctly different from log _iK_Fe observations in synthetic solutions at low ionic strength, is in good agreement with results for natural seawater obtained by others.  相似文献   

Solubility of calcite in the ocean     

S. E. Ingle 《Marine Chemistry》1975,3(4):301-319

The apparent solubility product K′_sp 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 K′_sp 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(K′_sp ^P/K′_sp 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