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

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).     

Benthic fluxes of copper,complexing ligands and thiol compounds in shallow lagoon waters

Benthic fluxes of copper, copper complexing ligands and thiol compounds in the shallow waters of Venice Lagoon (Italy) were determined using benthic chambers and compared to porewater concentrations to confirm their origin. Benthic copper fluxes were small due to small concentration differences between the porewaters and the overlying water, and the equilibrium concentration was the same at both sites, suggesting that the sediments acted to buffer the copper concentration. Thiol fluxes were ～10 × greater at 50–60 pmol cm^?2 h^?1, at the two sites. Porewater measurements demonstrated that the sediments were an important source of the thiols to the overlying waters. The overlying waters were found to contain at least two ligands, a strong one, L1 (log K′_CuL1 = 14.2) and a weaker one, L2 (log K′_CuL2 = 12.5). The concentration of L1 remained relatively constant during the incubation and similar to that of copper, whereas that of L2 was in great excess of copper, its concentration balanced by porewater releases and breakdown, probably due to uptake by microorganisms, similar to that of the thiol compounds. Similarity of the thiol and L2 concentrations and similar complex stability with copper suggest that L2 was dominated by the thiols. The free copper concentration ([Cu´]) in the Lagoon waters was lowered by a factor of 10⁵ as a result of the organic complexation.     

Chemical environment for red tides due toChattonella antiqua

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.     

Coincident application of a mass balance of radium and a hydrodynamic model for the seasonal quantification of groundwater flux into the Venice Lagoon, Italy

A mass balance of the naturally occurring short-lived radium isotopes (^223,224Ra) in the Venice Lagoon was conducted by an integrated approach combining the directly estimated individual Ra contributions and hydrodynamic model results. Hydrodynamic data allows for the calculation of the Ra mass balance in sub-sections of the Venice Lagoon (boxes), which are characterized by physically homogeneous properties, instead of investigating the entire lagoon. Utilizing this method, both the seasonal and the spatial variability of the submarine groundwater discharge in the Venice Lagoon have been estimated. Between 14–83 × 10⁹ L d^− 1 of water were calculated to flow across the sediment–sea interface, corresponding to 5–28 times the mean annual river input. The submarine groundwater discharge estimates were correlated with the residence time calculation to better understand spatial and seasonal variation.     

Use of shallow water habitats by fish assemblages in a Mediterranean coastal lagoon

The present study investigates the different uses and the functional roles of shallow habitats for fish fauna in the Venice Lagoon, by applying the functional guilds approach. Temporal (seasons) and spatial (location) changes within the lagoon show different habitat uses by fish assemblages, not influenced by local factors. Unvegetated mud habitats (salt marsh creeks and sub-tidal mud flats) and sparsely vegetated (seagrass) habitats show a common nursery role, especially for marine migrant fishes; but, contrary to other similar areas elsewhere shallow seagrass beds in the Venice Lagoon do not have a primary nursery role. This latter habitat has a more important role as a spawning ground for a resident, highly specialized component of the fish community. The habitat uses and their role to fish fauna illustrate the balance between predation risk and foraging profitability, as major factors structuring the fish assemblages. Spatial effects at a larger scale also highlight general characteristics of the fish assemblages in the Venice Lagoon. These indicate differences between the Northern sub-basin and the other two lagoon sub-basins, due to differences in the hydrodynamic regime, habitats distribution, and contributions from land and sea.     

Determination of copper complexation with natural organic ligands in seawater by equilibration with MnO2 II. Experimental procedures and application to surface seawater

The MnO₂ adsorption method combined with voltammetry is proposed for the direct determination of metal complexation in seawater of various salinities as a more satisfactory alternative to direct voltammetric measurements and bioassay methods. A small quantity of MnO₂ is equilibrated with copper ions in filtered seawater. Natural organic ligands in the seawater compete for copper with the MnO₂. Total dissolved copper is measured by differential pulse anodic stripping voltammetry after filtration and acidification of the sample. Preconcentration of natural water samples is unnecessary and measurement is performed at the natural equilibrium pH of the aerated sample. The analytical limit of detection of the method depends on contamination from the filtration step, and for copper complexation a ligand concentration of 5 × 10^?8 M was obtained. The sensitivity can be increased by use of radioisotopes as tracers. The method is very versatile in that complexation of various metals may be determined by any analytical method that measures total dissolved metal concentrations. Neither organic ligands nor their complexes with copper adsorb on the MnO₂ at pH8, but at pH 1.8 MnO₂ is an efficient scavenger for electroactive organic material.Samples of surface water from the Irish Sea and the Atlantic Ocean were found to contain ligand concentrations of 1.7 × 10^?7 and 1.1 × 10^?7 M, with conditional stability constants (log values) of 9.84 ± 0.13 and 9.86 ± 0.23, respectively, at pH 8.0.     

The behaviour of a Cu(II) ion selective electrode in seawater; copper consumption capacity and copper determinations

Determinations of copper consumption capacity (CuCs.C) and labile copper concentrations in surface coastal seawater, using a copper ion selective electrode (Cu-ISE) potentiometric method under predominantly diffusive conditions, are reported. For evaluation of the copper concentrations, the points of the endpoint contiguity zone of the CuCs.C titration curve were treated by an ISE multiple standard addition technique. The results were compared with those obtained by means of a Chelex-100 (calcic form) ‘batch’ procedure-potentiometric stripping analysis.The labile copper of the sample was determined at concentrations down to 10.70 nM with an average RSD of 12%, independent of the Cu-ISE employed. For adjacent subsamples, the mean CuCs.C values obtained for El Way seawater were equivalent to 81.05 and 48.00 nM copper, with an RSD of 4 and 7%, and for Isla Santa Maria seawater the value was equivalent to 70.27 nM copper, with an RSD of 7%. The theoretical approach of the electrode diffusive mechanism proposed, which would depend, fundamentally, on the adsorptive, complexing and reducing properties of the dissolved organic matter in the seawater sample, allows simultaneous analytical determination of CuCs.C and labile copper concentration in seawater.     

Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C₁₈ Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ? 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character.An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands.Studies of the exchange of ⁶⁴Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.     

Comparative yttrium and rare earth element chemistries in seawater

Comparisons of yttrium and rare earth stability constants for organic ligands indicate that Y(III)-organic complexation behavior most closely resembles, on average, the complexation characteristics of Sm(III). Yttrium organic complexation behavior distinctly differs from the behavior of Ho(III), whose ionic radius is most similar to that of yttrium. However, our stability constant comparisons demonstrate that the most reliable basis for predicting Y(III) organic stability constants are predictions based on the complexation behavior of Ho(III). Linear free energy relationships between Ho(III) and Y(III) exhibit better fits than those obtained for other rare earth elements, and much better fits than those obtained between Sm(III) and Y(III).The comparative abundances and distributions of yttrium and the rare earths in seawater are controlled by competitive equilibria between inorganic solution ligands and organic surface ligands. Due to yttrium solution complexation with hard inorganic ligands resembling that of Ho(III) and, yttrium surface complexation with soft organic ligands resembling that of light rare earth elements, the input normalized abundances of yttrium and the rare earths should be decoupled in seawater. In its seawater scavenging behavior, yttrium should act as a pseudolanthanide even heavier than the heaviest rare earth element, lutetium.     

Organic and inorganic speciation of copper in the Irish Sea

The metal complexing ability of surface water of the Irish Sea has been measured by the MnO₂ adsorption method. In all samples strong copper-chelating compounds are present at concentrations of 60–150 nM, with conditional stability constants (log values) of 10.0–10.4. The concentrations of Cu, Pb and Cd in the samples are 16–39 nM, 1–7 nM and 0.1–2 nM, respectively; much less than the ligand concentrations. The organic compounds form complexes with 94–98% of dissolved copper, and therefore constitute the major form of copper in surface water of the Irish Sea. Recalculation of speciation of the inorganic fraction of copper in seawater reveals that the major complex ion is that of CuCO₃⁰ (60%), followed by CuOH⁺ (16%) and Cu(OH)₂⁰ (16%). Complexes with borate ions form a small and rather insignificant fraction of 1%.     

Use of an ion exchange technique to measure copper complexing capacity on the continental shelf of the southeastern United States and in the Sargasso Sea

An ion exchange technique has been used to determine the copper complexing capacity (CuCC) of strong organic complexing agents at 21 stations across the continental shelf of the southeastern United States and in the western Sargasso Sea. The concentration of dissolved organic carbon (DOC) and total particulate materal (TPM), two pools of potential complexing agents, was also measured at each station. The CuCC ranged from 0.014 to 1.681 μM Cu dm⁻³ on the inner shelf, from 0.043 to 0.095 μM Cu dm⁻³ in mid and outer shelf waters, and from < 0.010 to 0.036 μM Cu dm⁻³ at the Sargasso Sea stations. The correlation between CuCC and both DOC and TPM is highly significant (α < 0.01). Two synoptic surveys of the distribution of DOC and TPM across the shelf showed that DOC ranges from > 3 mg C dm⁻³ nearshore to <1 mg C dm⁻³ offshore and that TPM ranges from > 50 mg dm⁻³ nearshore to <1 mg dm⁻³ offshore. Both TPM and DOC are most variable on the inner shelf. These data are consistent with CuCC data which indicate that the CuCC of inner shelf waters was relatively high and very heterogeneous. In contrast, DOC, TPM and copper complexing capacity are low and nearly invariant at the Sargasso Sea stations. We present a model of the distribution of complexing agents in different marine environments and hypothesize that the mechanisms underlying differences between environments relate to differences in the source(s) and nature of complexing agents in each system.     

Development and validation of a finite element morphological model for shallow water basins

Recognising the importance of understanding sediment dynamics to evaluate the status of a coastal lagoon environment, this work has been focused on the investigation of the hydrodynamic and sediment transport processes occurring in such basins. In order to describe the lagoon system, a modelling approach combining hydrodynamics, waves and sediment dynamics has been developed. The framework of the numerical model consists of a finite element hydrodynamic model, a third generation finite element spectral wave model and a sediment transport and morphodynamic model for both cohesive and non-cohesive sediments. The model adopts the finite element technique for spatial integration, which has the advantage to describe more accurately complicated bathymetry and irregular boundaries for shallow water areas. The developed model has been applied to test cases and to a very shallow tidal lagoon, the Venice Lagoon, Italy. Numerical results show good agreement with water level, waves and turbidity measurements collected in several monitoring stations inside the Lagoon of Venice. Such a model represents an indispensable tool in analysing coastal problems and assessing morphological impacts of human interference.     

Distribution of dissolved species and suspended particulate copper in an intertidal ecosystem affected by copper mine tailings in Northern Chile

The coastline near Chañaral in Northern Chile is one of the most highly Cu-contaminated zones in the world due to discharges from mining activities for more than 60 years. The speciation of Cu has been studied to determine the importance of organic complexation in highly contaminated areas, and to assess the likely physiological impacts of Cu on marine organisms. Dissolved Cu concentrations of up to 500 nM were measured, completely saturating organic ligands and leading to free Cu²⁺ concentrations in excess of 10^− 8 M. These values are higher than those reported in any other marine environment, and because they occur over an extensive area, provide a unique opportunity to study the effects of Cu on marine ecosystems and to see how Cu behaves when its speciation is predominantly inorganic. We found strong gradients in free Cu²⁺ between Chañaral and adjacent areas with lower Cu, where speciation is dominated by organic complexation. There is also a significant increase in the partitioning of Cu onto suspended particles in the contaminated areas, consistent with previous studies that showed that organic ligands stabilize Cu in the dissolved phase, whilst “excess” Cu is rapidly scavenged. Those high dissolved Cu concentrations persist in spite of solid phase partitioning and advective processes along this open-ocean coastline, suggesting that Cu inputs into the system are still very large. Measurements were made using anodic stripping voltammetry with a thin mercury film coated with Nafion, which previous workers have shown can mitigate ambiguity in the data arising from inadvertent reduction of organic complexes. Our findings suggest that this is a useful methodology for contaminated systems.     

Changes in Venice Lagoon dynamics due to construction of mobile barriers

The MoSE project (construction of mobile barrier to safeguard the Lagoon of Venice) entails changes to the structure of the lagoon's inlets. This could have consequences for the areas near the inlets and for the dynamics of the lagoon ecosystem as a whole. In order to predict the effects of the proposed alterations on the hydrodynamics of the lagoon, a well-tested hydrodynamic-dispersion model was applied. Simulations were carried out considering both idealised and realistic tide and wind scenarios.     

Voltammetric studies of the organic association of copper and lead in two canadian inlets

Anodic stripping voltammetry and gel filtration chromatography were used to examine the speciation and organic complexation of copper and lead in seawater. The extent of metal complexation in biologically different water types, the molecular weight ranges of the dissolved organic matter involved in metal-organic associations, and the metal uptake kinetics of these naturally occurring organic species were examined. Analyses of samples from Saanich and Narrows inlets, British Columbia, suggest organic complexation throughout the water column, including anoxic waters of Saanich Inlet. Several fractions of organic material from sedimentary interstitial water in the molecular weight range 500–10,000 were found to complex copper and lead, the concentration of complexing ligands decreasing with depth in the core. Rates of uptake of metals by organic material are slow, of the order of tens of minutes or longer.     

Dissolved and particulate heavy metals distribution in coastal lagoons. A case study from Mar Chiquita Lagoon,Argentina

Mar Chiquita Coastal Lagoon is located on the Atlantic coast of Argentina, and it has been declared a Biosphere Reserve under the UNESCO Man and Biosphere Programme (MAB). This coastal lagoon constitutes an estuarine environment with a very particular behaviour and it is ecologically important due to its biological diversity. The aim of the present study was to evaluate the distribution and geochemical behaviour of several heavy metals in this coastal system, focusing on their distribution in both the dissolved phase (<0.45 μm) and the suspended particulate matter. Therefore, the general hydrochemical parameters (salinity, temperature, turbidity, pH and dissolved oxygen) and concentration of total particulate and dissolved metals (Cd, Cu, Ni, Zn, Fe, Pb, Cr and Mn) were measured along 2 years (2004–2006) at two different sites. As regards their distribution, hydrological parameters did not present any evidence of deviation with respect to historical values. Suspended particulate matter showed no seasonal variation or any relationship with the tide, thus indicating that in this shallow coastal lagoon neither tides nor freshwater sources regulate the particulate matter input. Heavy metals behaviour, both in dissolved and particulate phases did not reveal any relationship with tide or seasons. Mar Chiquita Coastal Lagoon showed a large input of dissolved and particulate metals, which is probably due to intensive agriculture within the drainage basin of this system.     

Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.     

浙江西沪港重金属铜的配位容量和形态分析

根据2000年6月10～14日在浙江省西沪港采集的海水样品,利用AA-800石墨炉原子吸收分光光度技术和阳极溶出伏安法测定样品中重金属铜的含量,获得铜在海水中受不同的有机配体控制.不同粒级的铜表观配位容量表明西沪港海水过孔径1.00μm微孔膜的(ACuCC)较高,为144.4nmol/dm3;过0.40和0.20μm滤膜的(ACuCC)分别为103.0和102nmol/dm3;铜的有机配体条件稳定常数的对数值在7.25～9.14之间.铜的总量为21.72nmol/dm3.铜全部为稳定溶解态,其中pH2酸溶态占95.0%,强有机结合态占5.0%.溶解态铜中有机结合态占过滤海水中总铜的61.6%.     

Sequence stratigraphy based on high-resolution seismic profiles in the late Pleistocene and Holocene deposits of the Venice area

The sequence-stratigraphic investigation by Very High-Resolution (VHR) seismic profiles allowed recognition of the detailed architecture of the late Pleistocene and Holocene succession of the Venice area. In this way deposits previously known by the analyses of scattered cores, mainly taken along the lagoon margin and the littoral strips, have been correlated at regional scale including the near offshore sector and the result has pointed out the lateral variability of the stratal architecture. Late Pleistocene deposits consist of an aggrading floodplain and fluvial channel fills accumulated during decreasing eustatic sea level, and they are coeval with offlapping forced regressive marine wedges in the Central Adriatic basin. The Holocene sequence is composed of three main seismic units separated by major stratal surfaces. Unit 1 (up to 9 m thick) is formed by channelized deposits separated by areas showing sub-horizontal and hummocky reflectors, and is bounded at the base by a surface that records prolonged conditions of subaerial exposure and at the top by a flatter surface resulting from erosion by marine processes. Deposits of Unit 1 are interpreted as estuarine and distributary channel fills, and back-barrier strata. Unit 2 is well distinguishable from Unit 1 only in the offshore area and at the barrier island bounding the Venice Lagoon, and is composed of a prograding marine wedge (up to 10 m thick) that interacts laterally with ebb tidal deltas. Unit 3 consists of a tidal channel complex and inlet deposits, which testify the evolution of the lagoon area. Tidal channels are entrenched in the lagoon mud flat (coeval with Units 1–2) and cut the Pleistocene–Holocene boundary in several places.Following current sequence-stratigraphic concepts, the Holocene sequence is composed of a paralic transgressive systems tract (TST) (Unit 1) overlying a sequence boundary (the Pleistocene–Holocene boundary) and overlain by a marine highstand systems tract (HST) (Unit 2) in seaward locations and by highstand lagoonal deposits landwards. TST and HST are separated by a downlap surface that is amalgamated with a wave ravinement surface in several places. Unit 3 is coeval with the upper part of Unit 2, and its development has been favoured by human interventions, which led to a transgression limited to the lagoon area.Local factors during the deposition, i.e. subsidence, sediment supply, physiography, and current/wave regimes, led to a significant lateral variability in the architecture of the Holocene sequence, as evidenced by the extreme thickness variation of the TST along both depositional strike and dip. The HST, instead, shows less pronounced strike variations in the stratal architecture. Also, present data clearly evidence that the human impact has a great relevance in influencing the late Holocene sedimentation.     

Determination of copper complexation with natural organic ligands in seawater by equilibration with MnO2 I. Theory

The theory is discussed which describes the distribution of copper ions between a weak ion exchanger, as exemplified by MnO₂, and natural organic complexing material in seawater. Application of this theory and experimental procedures are outlined in part II of this series. It is apparent from the theory that titration with Cu²⁺ of one or more organic complexing ligands can be graphically represented by straight lines; slope and y-axis intercept provide information on the conditional stability constants and the ligand concentrations. Model calculations show that measurement of metal complexation at ligand concentrations higher than normally present in seawater may produce erroneous results because of possible changes in the metal to ligand ratio in the complexes. It is therefore advisable to measure metal complexation in the original, unaltered, water sample.