共查询到20条相似文献，搜索用时 31 毫秒
1.
Damir Krznarić 《Marine Chemistry》1984,15(2):117-132
Model systems consisting of a heavy metal ion (Cu2+ or Cd2+), complexing ligand (EDTA or NTA), a surfactant (9,12-octadecadienoic acid, C18H32O2, i.e., linoleic acid), and a surfactant which is at the same time a complexing ligand (tert-octylphenol etoxylate, C8H17(C6H4)(OC2H4)9–10OH, i.e., Triton-X-100) in seawater and NaCl solution were used in order to investigate the influence of the surfactant adsorption (on the electrode surface) on the heavy metal speciation measurements. The samples were titrated with either the metal, complexing ligand or surfactant and were measured by differential pulse anodic stripping voltammetry. It was shown that the surfactant adsorption exerts a strong influence upon the overall metal redox process and, thus, changes considerably both the apparent complexing capacity and the conditional stability constant of the system. Considering the presence of high concentrations of surfactants in polluted seawaters, the danger of measuring the apparent complexing capacity with the anodic stripping voltammetry method, without a detailed knowledge of surfactant properties and influence upon the system, is discussed. 相似文献
2.
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. 相似文献
3.
Constant M. G. van den Berg Adri G. A. Merks Egbert K. Duursma 《Estuarine, Coastal and Shelf Science》1987,24(6)
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. 相似文献
4.
Dissolved electroactive concentrations of zinc, cadmium, lead and copper in river Rhine and North Sea samples have been measured at natural and lower pH values by differential pulsed anodic stripping voltammetry using a Kemula-type hanging mercury drop electrode. Average concentrations detected in North Sea samples at salinities and their range are (in μgl?1): 3.9 (2.0–7.5) for zinc, 0.23 (0.13–0.31) for cadmium, 0.3 (0.1–0.6) for lead and 0.3 (0.25–0.60) for copper (pH 8.1). The APDC-MIBK extracting/concentrating method, followed by AAS measurement applied to the same samples, resulted in 3.9 (2.0–7.5) for zinc, 0.11 (0.01–0.27) for cadmium, 0.5 (0.2–0.9) for lead and 1.6 (0.7–3.2) for copper. A fraction of the electroactive concentrations at pH 2.7 (6.1 for Zn) is electroactive at pH 8.1. The fractions are 100% for Cd, 20% for Cu, 13% for Pb and 40% for Zn. The remaining fractions are partly composed of organically bound species in solution. The low value for lead may be caused by the presence of particulate lead that is dissolved at low pH.Ionic copper and lead species, added separately to seawater at pH 8.1 are removed from the electroactive form, and taken up in (organic) complexes in the same ratio (at least for copper) as the species already present. Added ionic zinc is not removed within the time scale of the measurements (30 min). North Sea water at the natural pH has a complexing capacity, probably due to the presence of dissolved organic compounds, in a concentration equivalent to 3.10?7M copper. The complexing capacity is zero at pH 2.7. The usual method of standard addition for the determination of electroactive copper and lead concentrations may lead to erroneous results in samples where complexation of this type occurs. 相似文献
5.
《Marine Chemistry》2007,103(1-2):61-75
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. 相似文献
6.
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%. 相似文献
7.
Mortality of larval coon-stripe shrimp, Pandalus danae, was related to labile copper and the copper complexing capacity of sea water, as measured by differential pulse Anodic Stripping Voltammetry (ASV). In nominal treatments of control, 5 and 10μg/litre Cu which contained less than 1·0μg/litre ASV labile Cu, zoeal development was usually complete. In treatments of 20 and 50μg/litre Cu which contained more than 7·0μg/litre ASV labile Cu, most larvae died while in the first zoeal stage. ASV labile Cu was related to the copper complexing capacity of sea water. Copper toxicity at less than 1·0 μg/litre ASV labile Cu is indicated by moulting delay and apparent Cu accumulation in zoea of the 5 and 10μg/litre Cu nominal treatments. 相似文献
8.
Extractable organic copper using C18 Sep-Pak cartridges was investigated in seawater after laboratory experiment showed that the (C18 Sep-Pak) cartridges were reliable, in open and coastal waters with normal levels of dissolved organic carbon, for the separation of a specific fraction of organo-copper complexes.Given that the Sep-Pak cartridges retain the hydrophobic fraction of the dissolved organic matter, this extraction technique was applied for studying the characteristics of this particular hydrophobic dissolved organic copper fraction (hDOCu) in the north-western Mediterranean waters. Surface distribution of hDOC is influenced by organic matter input from the river Rhone and its estuary as well as the physical processes affecting the primary productivity such as coastal upwelling. By correlating hDOCu concentrations with total dissolved copper and other hydrochemical data such as salinity and dissolved organic carbon, it was possible to examine the behaviour of hDOCu in the water masses of different sources and ages.Marine organic matter has been shown to have high complexing capacity. Productive superficial and intermediate waters as well as deep waters showed relatively high and comparable complexing capacity indicating that old organic matter may have strong complexing sites. 相似文献
9.
The natural “complexing capacity” of aquatic systems was determined using titration with cupric ions. It was compared with “complexing capacity” determined in the presence of both EDTA, used as a model for organic substances, and of EDTA and γ-Al2O3. The γ-Al2O3 was used as a model for solid particles of hydrous oxide in natural waters. The adsorption isotherm of copper in seawater on γ-Al2O3 particles was determined with and without EDTA.For EDTA alone and for the Cu—EDTA complex, it was found that they are not adsorbed on γ-Al2O3 in the natural seawater. However, by adsorption on solid particles, the labile ionic Cu-complex can be removed from the seawater. 相似文献
10.
C.M.G. Van Den Berg 《Marine Chemistry》1982,11(4):307-322
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. 相似文献
11.
In seawater and lake water the complexation of several heavy metals, present in the dissolved state at relevant trace levels, with humic substances isolated from two marine and an estuarine sediment has been studied by differential pulse anodic stripping voltammetry (DPASV) at a hanging mercury drop electrode (HMDE). Taking Zn(II) as an example, the aim of this study was to gain direct information on the general level of importance of humic substances for the speciation of certain heavy metals in fresh and saline waters.In seawater humic acids originating from different sediments have very similar complexing properties for Zn(II), decreasing slightly in the order HAN > HAL > HAM. In lake water HAL is most efficient for complexing Zn(II), followed by HAN and HAM.In both types of natural waters, the sedimentary fulvic acid is less efficient in complexing Zn(II) than the respective humic acid from the same site. In general, the complexing efficiency decreases in the order EDTA > NTA > humic acids > fulvic acid.The problem of humic acid adsorption at the electrode, which somewhat limits the investigation of Pb(II) and Cd(II), and the impact of pH on the amount of complexed Zn(II) are also discussed.The findings provide further direct evidence for the conclusion previously drawn from existing complexation data that because of the rather low levels of dissolved humics in large parts of the oceans, the complexation efficiency of humics for Cd, Pb and Zn is too low to affect the speciation pattern of these three heavy metals. 相似文献
12.
《Marine Chemistry》1989,26(4)
The organic matter released by the marine phytoplankton species Dunaliella tertiolecta and its physico-chemical interaction with cadmium and copper ions were studied by electrochemical methods (differential pulse anodic stripping voltammetry (DPASV) and a.c. polarography). The interactions with cadmium and copper were studied at the model interface (mercury electrodesolution) and in the bulk phase by measuring the complexing ability of the released organic material.The axenic cultures were grown on different growth media, without and with trace metals and chelators. Culture media were analyzed 10 days after inoculation, containing 5 × 105−1.2 × 106 cells cm−3 when untreated or after separation of cells by gentle centrifugation.It was found that the content and type of the released surface-active material and complexing ligands depend on the initial composition of the growth media. In all cases, strong interaction of excreted organic substances with copper in the bulk phase and with cadmium at the model interface were observed.A rather high value of the complexing capacity, 9.5 × 10−7 mol Cu2+ dm−3, was found in the culture grown on medium without trace metals and chelators (medium I) whereas the surface activity of this culture was not high (0.2 mg dm−3 equivalent to Triton-X-100). Higher contents of surface-active material (0.8 and 1.0 mg dm−3) were found in cultures grown in media with trace metals and without chelators (II and III), accompanied by a high content of complexing ligands (5.8 × 10−7 and 9.5 × 10−7 mol Cu2+ dm−3). However, if the complexing capacity is calculated per cell the values obtained for cultures grown in media II and III (0.79 × 10−15 and 0.98 × 10−15 mol Cu2+ dm−3) are lower than for cultures grown on medium I (1.8 × 10−15 mol Cu2− dm−3). The exceptional adsorption effects and the copper complexing capacity for medium 1, and the presence of cells with degenerative symptoms can be ascribed to stressed growth conditions, and, particularly, to deficiency of metals. A qualitatively similar behaviour has been observed in natural samples of estuarine waters, indicating the existence of stressed conditions during the mixing of fresh and saline waters. 相似文献
13.
Constant M.G. van den Berg 《Marine Chemistry》1984,15(1):1-18
A new method is proposed for the determination of complexing capacities and conditional stability constants for complexes of copper(II) with dissolved organic ligands in seawater. This method is based on ligand competition by the added ligand catechol for free metal ions. The concentration of copper-catechol complex ions is measured with great sensitivity by cathodic stripping voltammetry. The concentration of the free copper ion is calculated from the concentration of copper-catechol complex ions. Ligand concentrations and conditional stability constants are obtained from a titration of the ligands with copper. Two techniques for treatment of the data are compared. A seawater sample, originating from open oceanic conditions, is analysed and two complexing ligands were detected, having concentrations of 1.1 × 10?8 and 3.3 × 10?8 M, and conditional stability constants (log K′CuL) of 12.2 and 10.2, respectively. 相似文献
14.
中国近岸部分海域海水中金属络合配位体浓度的研究 总被引：7，自引：0，他引：7
采用阳极溶出伏安法对黄河口、青岛近海、大亚湾和南海海域海水中的金属络合配位体的浓度进行了测定,同时探讨了其分布规律与相关参量的关系.结果发现:南海海域海水中的金属络合配体的浓度稍高于其他3个海域,且都明显高于大洋水的浓度;在微表层存在富集现象;在垂直分布上表层最大,然后随深度增加而降低,在底层有较大值;各海域配位体的性质呈复杂性;铜的络合配位体浓度大于镉和铅;总的来说与世界其他海域的分布规律是一致的.同时发现铜络合配位体浓度与BOD(生化需氧量)、COD(化学需氧量)、DOC(溶解有机碳)及黏度存在显著的正相关性. 相似文献
15.
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. 相似文献
16.
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. 相似文献
17.
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. 相似文献
18.
In batch cultures of the diatom Phaeodactylum tricornutum, organic materials capable of complexing ionic copper were released to the culture medium at all stages of growth; however, the largest proportion was released after the diatoms had reached the stationary phase. When the organisms were maintained in log phase growth in a cage culture turbidostat, a diurnal fluctuation in complexing capacity was found, similar to fluctuations measured in field populations. 相似文献
19.
Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans 总被引：1，自引：0，他引：1
Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19micromol site mg(-1) C, and a logK' of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu-FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC(50) of 58.9microgl(-1). However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC(50) ranging from 55.6microgl(-1) in the no-FA control to 137.4microgl(-1) in the 20mgl(-1) FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu-FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions. 相似文献
20.
Measurements have been made, by amperometric titration using anodic stripping voltammetry, of the zinc binding properties of organic material released by Skeletonema costatum in culture, after the stationary growth phase had been reached. Titration curves showed two inflection points, interpreted as indicating the presence of two analytically distinguishable ligand assemblages (L1 and L2). The complexing capacities of these assemblages increased with time and the associated conditional stability constants K1′ and K2′ decreased with time. This apparent reduction in stability constants could be accounted for by complex dissociation. Several methods for the calculation of complexing capacity and stability constant were employed and although the calculated concentrations of CL varied, each method showed similar trends.Size fractionation of the organic moieties revealed that CL, was composed of organic assemblages with apparent molecular weight greater than 3 × 104. The ligands L2 were of mixed size composition. 相似文献