Determination of the complexing capacity and conditional stability constants of complexes of copper(II) with natural organic ligands in seawater by cathodic stripping voltammetry of copper-catechol complex ions

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.     

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

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.     

海水溶解色氨酸的荧光分析

本文初步建立了直接测定海水中溶解色氨酸的方法,并进行各种条件影响实验.在0～0.070mg/dm3浓度范围内色氨酸荧光强度与浓度之间线性关系良好.在最佳实验条件下,方法检测限为7.6×10-4mg/dm3,精密度小于3.1%,回收率86%～120%.     

Ultraviolet spectroscopic determination of the stability constants for copper carbonate and bicarbonate complexes up to the ionic strength of seawater

An ultraviolet spectroscopic study at 25°C is used to determine the stoichiometric stability constant of CuCO₃⁰ (β_CuCO3⁰) over a range of ionic strengths; extrapolation to zero ionic strength provides a thermodynamic constant (log β⁰_CuCO3⁰ = 6.89). At 0.69 m ionic strength, log β_CuCO3⁰) is 6.33.This study provides the first experimental evidence for the existence of CuHCO₃⁺. At 0.69 m ionic strength, log β_CuHCO3⁺ is 2.77.The ultraviolet molal absorptivity spectra for the two complexes are also determined. The spectrum for CuCO₃⁰ consists of a single band centered at 276.5 nm and was described well by a Gaussian function. The spectrum of CuHCO₃⁺ consists of at least two overlapping bands.Side reactions which might affect the data interpretation were included in the analysis of the results. The effects of the Cu(II) hydrolysis reactions were accounted for by using data from previous work, and possible effects due to copper-organic species were eliminated by a subtraction procedure.     

Determination of the chemical forms of dissolved cadmium, lead and copper in seawater

The chemical forms of Cd, Pb and Cu in seawater have been examined using a novel scheme which permits the quantification of up to seven different species of one metal. The concentration of each species was calculated from measurements using anodic stripping voltammetry of labile and total metal in samples which were (a) untreated, (b) UV irradiated, (c) passed through a chelating resin column, and (d) UV irradiated then passed through a chelating resin column. In the sample studied, the major proportion of Cd, Pb and Cu was found to be associated with organic and inorganic colloidal species. Less than half of the bound Pb and Cu was readily exchangeable with added ²¹⁰Pb and ⁶⁴Cu.     

Decomposition and alteration of organic compounds dissolved in seawater

The dissolved organic matter in seawater is grouped into two fractions which are defined as having greatly differing reactivities with respect to both chemical and biological decomposition. One fraction, which constitutes the bulk of the material, is extremely stable and inert and is only slowly degraded by either chemical or biological processes. The other fraction, which is composed of trace organic compounds derived from living organisms, contains components such as free amino acids which are rapidly degraded, probably by marine organisms which use these compounds as a food source. Conclusions about the cycle of organic compounds in seawater based on total organic carbon concentrations could thus be misleading, since pathways involving labile trace organic constituents would be completely obscured. Investigations of the distribution, concentration, and possible diagenetic reactions of specific organic compounds are necessary in order to elucidate the cycle of these compounds in the oceans.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

Sampling of dissolved organic material from seawater with reversed-phase techniques

Trichloro-n-octadecyl silanized porous glass is used to sample compounds of low polarity from natural seawater. Recoveries of some spike compounds were found to be semiquantitative. However, silanized porous glass is easy to keep free of contamination, has a comparatively high adsorption capacity, and permits the fractionated desorption of sampled compounds.     

Metaproteomic characterization of dissolved organic matter in coastal seawater

We performed a comprehensive metaproteomic analysis of the dissolved organic matter (DOM) in Japanese coastal waters using liquid chromatography–tandem mass spectrometry and demonstrated that these proteomes were characterized by proteins with various functions, including metabolic enzymes, membranes, and photosynthetic proteins. The protein sources included cyanobacteria, heterotrophic bacteria, and eukaryotic phytoplankton. Most of the components were similar among samples and also similar to pelagic components. We also observed differences in the compositions of the microbial communities of origin among the different dissolved protein samples and differences in the relative abundance of specific dissolved protein types (e.g., cytoskeletal proteins), possibly indicating potential dynamics in the coastal DOM pool.     

ICP-MS测定海水中溶解态痕量重金属——直接稀释法

海水水质监测是环境监测中的重要一环[1]。海水中痕量重金属元素地球化学研究现今仍面临两大挑战:一是痕量重金属元素有机和无机形态分析,二是海水中痕量重金属元素的含量测定[2]。海水的含盐量为35 g/dm3左右,基体中除了大量的NaCl外,还含有相当量的SO₄2-,Ca2+,Mg2+等离子及有机质。由于海水中溶解态重金属元素的含量基本上都在微克每立方分米量级或更低,在传统的分析方法中这部分元素含量的测定或受到严重的光谱干扰、或低于仪器检测限,定量分析相当困难。     

Binding of monomeric organic compounds to marcomolecular dissolved organic matter in seawater

Several monomeric organic compounds, including amino acids, sugars, and fatty acids, were found to bind abiologically to dissolved macromolecular materials in particle-free seawater at natural substrate concentrations. The binding primarily occurred in ocean surface waters, at rates slower than in situ biological utilization rates of most of the compounds. Seasonal patterns of binding in Gulf of Maine waters may have been related to seasonal variations in macroalgal exudation of polyphenolic materials. Enhanced reactivity of relatively hydrophobic monomers implicated hydrophobic effects as potentially important in marine organic condensations. The resultant condensates showed high particle reactivity, consistent with low concentrations of dissolved condensed materials in seawater.     

The stability of dissolved inorganic species of iodine in seawater

An oxidation state diagram was used to study the relative stability of inorganic iodine species in an aqueous system. It is shown that although iodate is the most stable form, iodide may exist as a metastable form in a basic solution. Molecular iodine may undergo disproportionation to form iodide and iodate. Results from laboratory studies suggest that molecular iodine is rapidly taken up by seawater, and hypoiodite is probably formed. Hypoiodite is also unstable in seawater, and may react with organic matter or undergo autodecomposition. Direct reactions between molecular iodine and organic matter were not observed.     

Measurement of manganese, zinc and cadmium complexation in seawater using Chelex ion exchange equilibria

Equilibria between Chelex 100* and manganese, zinc and cadmium ions were used to determine the complexation of these trace metals in 36‰ Gulf Stream seawater at 25°C and pH 8.2. The method utilized radiotracers (⁵⁴Mn, ⁶⁵Zn, and ¹⁰⁹Cd) to quantify trace metal adsorption from trace metal-amended seawater and from seawater containing a series of ethylenediaminetetracetate (EDTA)—metal ion buffers. Results were consistent with Chelex adsorption of both trace metal ions and trace metal—EDTA chelates. Equilibrium models fitted to the data were used to establish conditional stability constants for Chelex adsorption of manganese, zinc and cadmium ions and for adsorption of EDTA-chelates. These models also yielded ratios of free metal ions to total dissolved trace metal concentrations in seawater: 10^−0.1 for manganese, 10^−0.2 for zinc, and 10^−1.5 for cadmium. Independent measurements with a cadmium ion-selective electrode also yielded a free: total cadmium ratio of 10^−1.5.     

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.     

Analytical fractionation of dissolved copper, lead and cadmium in coastal seawater

The speciation of dissolved Cu, Pb and Cd in twelve seawater samples from the Inner Oslofjord, Norway, has been examined by an operational scheme which involves ultrafiltration followed by determination of labile, acid soluble and total Cu, Pb and Cd by differential pulse anodic stripping voltammetry (DPASV). The techniques employed are discussed and evaluated. It was found that Cd was present entirely in low molecular weight (LMW) labile species; Pb was mainly in non-labile LMW species, with half of the total Pb probably occurring in LMW organo-metallic compounds; Cu distribution was irregular, with extensive organic and colloidal association.     

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.     

海水中总溶解氮测定的高温燃烧法和湿化学氧化法的比较

对测量海水中总溶解氮(TDN)的两种常用方法——高温燃烧法和过硫酸钾氧化法进行了比较。结果表明,两种方法在空白、精密度和准确度实验中不存在显著差异。对不同化合物的回收率均在92%～107%之间,加标回收实验回归曲线的斜率分别为0.93和0.92。对于现场海水样品的测定结果,两个断面拟合的斜率分别为0.92和0.97。HTC法比PO法对实际海水样品的氧化效率略高,在操作上也更方便、快捷。因此,高温燃烧法更适合海水中总溶解氮(TDN)的测定。