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.     

Study on copper complexing ligand concentrations in several China’s coastal waters

Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows: Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer (SSL) in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complexing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China' s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.     

Study on copper complexing ligand concentrations in several China''s coastal waters

Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows： Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer （SSL） in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complex- ing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China＇s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

Dissolved copper and copper-organic complexes in the Narragansett Bay estuary

The geochemistry of dissolved copper-organic complexes was investigated in the estuarine waters of Narragansett Bay. A transect survey was conducted in August 1980, while one mid-bay station was monitored from March through August of that year. The transect data indicated that most of the copper-organic complexes enter the bay via sewage effluent which is discharged into the Providence River at the head of the bay. Organic copper concentrations in the estuary ranged from 0.12 to 2.30 μg kg^?1 and comprised from 14 to 70% of the total dissolved copper. The concentration of copper-organic complexes was not directly related to the amount of dissolved organic matter; and recently generated organic material from phytoplankton production within the bay had a negligible influence on the fraction of dissolved copper which was organically bound.The major source of total copper to the bay is anthropogenic inputs from sewage effluents. Particulate and dissolved copper concentrations ranged from 0.06 to 2.42 and 0.23 to 16.4 μg kg^?1, respectively, giving average values of about 40% particulate and 60% dissolved copper. Particulate copper concentrations decreased rapidly from the upper to the lower bay as a result of both removal and dilution. About 75% of the dissolved copper entering the bay is rapidly removed in the Providence River and upper bay, and the remaining portion (which is largely organic copper) follows conservative mixing in the mid to lower bay. The data suggest that copper binding by dissolved organic matter may be an important control on the riverine flux of dissolved copper through estuaries into coastal and oceanic waters.     

Dissolved trace metals in the Western Mediterranean Sea: total concentration and fraction isolated by C18 Sep-Pak technique

An investigation of trace metal distributions in the Western Mediterranean Sea was carried out during the RRS Discovery cruise (July 1993) in which a transect from the Strait of Gibraltar to the Strait of Sicily was conducted. Organically complexed dissolved trace metals and their total concentrations were measured to investigate the end-members and to predict the environmental capacity of the Mediterranean for potential toxic metals. The distribution of trace metals can be accounted for by the mixing of several end-members and by some atmospheric inputs to the surface water. For Pb and Fe, the effects of the atmospheric inputs are more pronounced than for the other metals. Due to the rapid exchange of water masses, the Western Mediterranean may have the ability to assimilate the increased external inputs for some trace metals such as Cu, Cd, Ni and Zn. But the external inputs for Pb and Fe exceed the removal capacity of the Western Mediterranean and these elements may accumulate in the water column of the western basin. The C18 Sep-Pak technique and direct determination by DPASV were used to determine the amount of trace metal–organic complexes. The C18 Sep-Pak column isolates only a small fraction of trace metals except for Cu. The maximum hydrophobic fractions for the studied trace metals, except for Cd and Pb, which are not detectable, were found in the subsurface layer at all stations. This maximum may well be linked to picoplankton activity and the picoplankton, prochlorophytes may have an important role in the speciation of dissolved Cu as well as Synechococcus. These organic ligands for Cu were produced at the maximum of biological activity in the Western Mediterranean basin and seem to be accumulated at halocline level by Mediterranean hydrodynamic characteristics. However, direct determination by DPASV showed that the major part of Cu, Cd and Pb, complexed by organic materials, was not isolated by C18 Sep-Pak technique.     

Organic carbon and nitrogen in the northern California current system: comparison of offshore, river plume, and coastally upwelled waters

During the first year of the Northeast Pacific GLOBEC program we examined the spatial distributions of dissolved and particulate organic carbon and nitrogen in the surface waters off the Oregon and Washington coasts of North America. Eleven east–west transects were sampled from nearshore waters to 190 km offshore. Hydrographic data and the distribution of inorganic nutrients were used to characterize three distinct water sources: oligotrophic offshore water, the Columbia River plume, and the coastal upwelling region inshore of the California Current. Warm, high salinity offshore water had very low levels of inorganic nutrients, particulate organic carbon (POC) and dissolved organic carbon (DOC). Warm, low salinity water in the Columbia River plume was relatively low in nitrate, but showed a strong negative correlation between salinity and silicate. The river plume water had the highest levels of total organic carbon (TOC) (up to 180 μM) and DOC (up to 150 μM) observed anywhere in the sampling area. Cold, high salinity coastal waters had high nutrient levels, moderate to high levels of POC and particulate organic nitrogen (PON), and low to moderate levels of DOC and dissolved organic nitrogen (DON). Each of these regions has characteristic C:N ratios for particulate and dissolved organic material. The results are compared to concentrations and partitioning of particulate and dissolved organic carbon and nitrogen in other regions of the North Pacific and North Atlantic Oceans.     

Seasonal variations in dissolved organic carbon concentrations and characteristics in a shallow coastal bay

Dissolved organic matter (DOM) composition and dynamics in temperate shallow coastal bays are not well described although these bays may be important as local sources of organic carbon to ocean waters and are often sites of economically-important fisheries and aquaculture. In this study surface water samples were collected on a monthly to bi-monthly basis over two years from a mid-Atlantic coastal bay (Chincoteague Bay, Virginia and Maryland, USA). Dissolved organic carbon (DOC) concentrations and light absorbance characteristics were measured on sterile-filtered water, and high-molecular weight (> 1 kDa) dissolved OM (DOM) was isolated to determine stable isotope composition and molecular-level characteristics. Our time series encompassed both a drought year (2002) and a year of above-average rainfall (2003). During the dry year, one of our sites developed a very intense bloom of the brown tide organism Aureococcus anophagefferens while during the wet year there were brown tide bloom events at both of our sampling sites. During early spring of the wet year, there were higher concentrations of > 1 kDa DOC; this fraction represented a larger proportion of overall DOC and appeared considerably more allochthonous. Based upon colored dissolved organic matter (CDOM) and high-molecular weight DOM analyses, the development of extensive phytoplankton blooms during our sampling period significantly altered the quality of the DOM. Throughout both years Chincoteague Bay had high DOC concentrations relative to values reported for the coastal ocean. This observation, in conjunction with the observed effects of phytoplankton blooms on DOM composition, indicates that Chincoteague Bay may be a significant local source of “recently-fixed” organic carbon to shelf waters. Estimating inputs of DOC from Chincoteague Bay to the Mid-Atlantic Bight suggests that shallow productive bays should be considered in studies of organic carbon on continental shelves.     

Contrasting complexing capacity of dissolved organic matter produced during the onset,development and decay of a simulated bloom of the marine diatom Skeletonema costatum

The capacity of natural dissolved organic matter (DOM) produced during the onset, development and decay of a simulated bloom of the marine diatom Skeletonema costatum to complex free copper has been followed for a 2 week period. Copper binding capacity of the culture was measured by anodic stripping voltammetry (ASV) with a hanging mercury drop electrode (HMDE). The concentration of dissolved organic carbon (DOC) and two fluorophores, M (humic-like, Ex/Em: 320 nm/410 nm) and T (protein-like, Ex/Em: 280 nm/350 nm), were followed during the course of the incubation. Models using DOC concentrations alone could not accurately predict the complexing capacity of the culture, especially at the end of the bloom, and better predictions were obtained when fluorescence measurements were considered. They were helpful in characterising two types of copper ligands produced in the culture. The first type, traced by the fluorescence of peak T, was related to labile DOC directly exuded by phytoplankton. The second type, traced by the fluorescence of peak M, was the refractory humic-like material presumably produced in situ as a by-product of the bacterial degradation of phytogenic materials. During the onset and development of the bloom (days 0 to 7), the fluorescence of peak T explains 60–80% of the total complexing capacity of the culture, suggesting that exuded “protein-like” compounds among other exuded complexing agents efficiently complexed free copper. On the contrary, during the decay (days 8 to 13), these ligands were replaced by humic substances as the complexing agent for copper.     

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.     

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.     

Wet-oxidation and automated colorimetry for simultaneous determination of organic carbon, nitrogen and phosphorus dissolved in seawater

We developed a simple and reliable method which allows simultaneous determination of organic forms of carbon (DOC), nitrogen (DON) and phosphorus (DOP) dissolved in seawater. Conversion of dissolved organic matter (DOM) to inorganic products (carbon dioxide, nitrate+nitrite and soluble reactive phosphate) is performed by a persulfate wet-oxidation in low alkaline condition. After oxidation, the concentration of the inorganic products dissolved in the sample was measured automatically by colorimetry using a 3-channel Technicon AutoAnalyzer system. A number of pure organic compounds were tested in the concentration range encountered in coastal and open ocean, indicating a high efficiency of the digestion procedure. The recovery range is similar to that obtained by other wet-oxidation procedures and by high-temperature catalytic oxidation techniques. Direct comparisons with usual methods used for separate determination of DOC, DON and DOP indicated a high efficiency of the procedure. Reproducibility tests demonstrated a very good precision (around 5%) for lagoonal and coastal waters, while precision was sometimes around 10–25% in oligotrophic oceanic waters, especially for DOP where values approached limits of detection for measuring phosphate. This method is highly suitable for routine analysis and especially appropriate for shipboard work.     

Nutrient (N,P and Si) and carbon partitioning in the stratified NW Mediterranean

The distribution of nutrients and carbon in the different pools present in the three functional layers (the upper, biogenic layer, the thermocline layer, and the deeper, biolythic layer) of the stratified NW Mediterranean Sea was examined. The stoichiometry between dissolved inorganic nutrients, which had low concentrations in the surface waters, indicated a deficiency in nitrogen, relative to phosphorus, and an excess nitrogen relative to phosphorus within the thermocline, as well as a general silicate deficiency relative to both N and P, even extending to the biolythic layer. The dissolved organic matter was highly depleted in N and, particularly, in P relative to C, with average DOC/DON ratios >60 and DOC/DOP ratios >1500 in all three layers. The particulate pool was also depleted in N and P relative to C, particularly in the biolythic layer. The concentration of biogenic silica was low relative to C, N and P, indicating that diatoms were unlikely to contribute a significant fraction of the seston biomass. Most (>80%) of the organic carbon was present as dissolved organic carbon. Total organic N and P comprised 50–80% of the N and P pool in the biogenic layer, and decreased with depth to represent 10–25% of these nutrient pools in the biolythic layer. The high total N:P ratios in all three depth layers (N/P ratio >20) indicated an overall phosphorus deficiency in the system. The high P depletion of the dissolved organic matter must derive from a very rapid recycling of the P-rich molecules within DOM, and the increasing C/N ratio of DOM with depth indicates that N is also recycled faster than C in the DOM. Because of the uniform depth distribution of the total dissolved nitrogen concentration, the increase in the percent inorganic N and the decline in the percent dissolved organic N with depth indicates that there must be biological transformations between these pools, with a dominance of DON production in surface waters and remineralisation in the underlying layers, from which dissolved inorganic nitrogen is supplied back to the biogenic layer. Downward fluxes of DON and DOC were estimated at 200–250 μmol N m⁻² d⁻¹ and 1.4–2.1 mmol C m⁻² d⁻¹, respectively, while there should be little or no export of P as dissolved organic matter. The downward DON flux exceeded the diffusive DIN supply of about 145 μmol N m⁻² d⁻¹ to the biogenic layer, suggesting that allochthonous N inputs must be important in the region.     

Isolation of dissolved organic matter and copper-organic complexes from estuarine waters using reverse-phase liquid chromatography

Reverse-phase liquid chromatography was used for the isolation of dissolved organic matter and dissolved copper-organic complexes from the estuarine waters of Narragansett Bay, Rhode Island. The procedure isolates 10–30% of the organic matter and up to 50% of the total dissolved copper from various bay samples. Chromatograms obtained by high-performance liquid chromatography of the isolated organic matter showed qualitative differences between sampling stations progressing from the Providence River in the upper bay to the lower bay.     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

Complexation of copper and nickel in the dissolved phase of marine sediment slurries

Speciation of copper and nickel in the water phase of incubated marine slurries under aerobic conditions was performed with MnO₂ and Sep—Pak C₁₈ cartridges. Changes in time during the incubations of concentrations of dissolved organic carbon (DOC), dissolved copper and nickel and inorganic nitrogen were followed. The influence of organic complexation on the dissolved concentrations of copper and nickel was investigated as well as competition between copper and nickel for dissolved organic ligands.Two pools of dissolved organic ligands could be distinguished. With the MnO₂ method a relatively strong ligand group was determined that was subjected to degradation. The conditional stability constant for copper with the relatively strong ligand was 10^11.1. The conditional stability constant for the relatively strong nickel ligand was difficult to determine due to saturation of the ligand sites; it was found to be around 10¹⁰. However, it could not be ascertained whether nickel was reversibly com-plexed with the organic ligands.With Sep—Pak a relatively weak Hgand group was detected that was probably more resistant to degradation. The conditional stability constant of the weaker ligand could not be estimated, an approximation revealed that it was weaker than the ligand group determined with the MnO₂ method. For copper the difference between binding strength of the ligand groups was at least 100, for nickel the difference was less.Competition between copper and nickel for the ligands could not be detected. Only during the first day of the experiment, when the system was not in equilibrium was competition suspected. However, the replacement of nickel by copper from the ligand sites was not straightforward and could not be accounted for by our model.The concentration of total dissolved copper during the first week of the experiment was found to be controlled on the one hand by release from the sediment of copper already associated with dissolved organic matter (DOM) and on the other hand by concentration of the strongest ligand. The calculated free copper concentration increased from 10⁻¹² to 10⁻⁹mol l⁻¹ due to the oxidation of the strongest ligand. After saturation of the strongest ligand the relatively weak ligand controlled the free copper concentration. A continuing release of copper from the sediment by degradation of particulate organic matter (POM) will not increase the free copper concentration until the ligand sites of the weaker ligands get saturated.The total dissolved nickel concentration seemed only to be determined by the sum of the concentrations of the organic ligands. A degradation of ligands resulted in a decrease of the total dissolved nickel concentration. The calculated free nickel concentration did not change with time.     

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.     

Stability and composition of terrestrially derived dissolved organic nitrogen in continental shelf surface waters

A linear decrease in dissolved organic carbon and nitrogen with increasing salinity offshore from the Georgia coast suggests that organic nitrogen compounds contributed to coastal waters by rivers are stable during the period (2–3 months) of their transfer over the continental shelf. While the C/N ratio decreased with distance from shore, total dissolved organic nitrogen (DON), total amino nitrogen, and primary amino nitrogen showed similar relative decreases, suggesting that nitrogen is associated with refractory organic compounds. Measured amino nitrogen accounted for about 20% of the total DON, leaving about 80% of the organic nitrogen undefined.     

Seasonal and spatial variations in the partial pressure of carbon dioxide in a eutrophic brackish lake,Lake Hamana,Japan

The dissolved inorganic carbon and total alkalinity in the surface brackish waters of Lake Hamana were investigated monthly from October 2017 to September 2019 at 14 stations. The partial pressure of carbon dioxide (pCO₂) in the surface water ranged from 29 to 1476 μatm and was undersaturated for atmospheric CO₂ during the observation periods, although most coastal waters were net source areas because of the large amount of terrestrial organic and inorganic carbon input. Since there was a strong negative correlation between pCO₂ and the dissolved oxygen, seasonal and temporal variations in pCO₂ were mainly derived from phytoplankton activity. The high phytoplankton activity induced by the effluents from sewage treatment plants, which was low in carbon and high in nitrogen. Therefore, in urbanized coastal waters with sewage treatment plants, such as the coastal waters of Japan, there is a possibility of shifting from weaker carbon dioxide source areas to sink areas. However, pCO₂ was oversaturated at the polluted river mouth, especially after high precipitation events due to the large carbon supply.

     

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%.