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.     

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.     

Determination of thorium isotopes in seawater by moored MnO2-fiber method

A method is described for the determination of Th isotopes (²³²Th,²³⁰Th,²²⁸Th and²²⁷Th) in seawater through analysis of Th adsorbed on MnO₂-impregnated fiber that has been moored in the deep sea for up to 10 months. Since the MnO₂-fiber adsorbs Th from seawater at a constant rate, natural²³⁴Th can be used as a yield monitor by making a correction for its decay during the period of deployment. The results obtained by the method showed good reproducibility and accuracy. The method has the advantage over the chemical coprecipitation method that the time and labor for sampling and processing a large-volume of seawater is reduced.     

Cu complexation by organic ligands in the sub-arctic NW Pacific and Bering Sea

Cu speciation was characterized at three stations in the sub arctic NW Pacific and Bering Sea using cathodic stripping voltammetry with the competing ligands benzoylacetone and salicylaldoxime. A single ligand model was fit to the titration data, yielding concentrations throughout the water column of ∼3–4 nM, and conditional stability constants ranging from 10^12.7 to 10^14.1, this range being partly due to the choice of competing ligand. Free Cu²⁺ in surface waters was 2–4×10⁻¹⁴ M, in close agreement with values reported by previous workers in the NE Pacific using anodic stripping voltammetry (ASV). However, those results showed that complexation by strong organic ligands becomes unimportant below 200–300 m, while our data indicated Cu is strongly complexed to depths as great as 3000 m. Free Cu²⁺ concentrations in surface waters reported here and in previous work are close to the threshold value where Cu can limit the acquisition of Fe by phytoplankton.     

Determination of conditional stability constants of organic copper and zinc complexes dissolved in seawater using ligand exchange method with EDTA

To clarify the nature of organic metal complexes dissolved in seawater, a ligand exchange reaction between ligands of natural origin and an aminopolycarboxylic acid (EDTA) was used to determine the conditional stability constants of organic metal complexes. The results indicate that more than two organic molecules complexed with copper and zinc exist in surface seawater. It is found that the conditional stability constants of these naturally-occurring organic metal complexes are 1–3 orders of magnitude higher than those of EDTA-Cu and EDTA-Zn complexes. These estimates of the conditional stability constants for the dominant species of organic copper and zinc complexes are 10^11.8 and 10^9.3, respectively, at pH 8.1. The results indicate that these naturally-occurring organic metal complexes are stable species and not easily dissociated or displaced with others in the marine environment.     

Determination of cadmium(II), copper(II), manganese(II) and nickel(II) species in Antarctic seawater with complexing resins

The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log α_M(I) = 11.6 at pH = 7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 10²⁰ M^− 1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log α_M(I) = 5.5 and 6.5 at pH = 7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite CG-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations.     

Interaction of cadmium and copper with surface-active organic matter and complexing ligands released by marine phytoplankton

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.     

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

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

The association of copper,mercury and lead with surface-active organic matter in coastal seawater

Significant fractions of copper (6–30%), lead (3–12%) and mercury (4–50%) were associated with surface-active dissolved or colloidal organic matter isolated from the water column of a controlled experimental ecosystem. Changes in the concentration of surface-active forms of these metals were attributed to release of surface-active metal-binding organic matter during the collapse of a phytoplankton bloom and early diagenesis of settled detritus. Naturally occurring surface-active organic matter can be expected to significantly influence the chemical speciation and transfer of metals across air-water and solid-water interfaces in the marine environment.     

海水中丙烯酸的高效液相色谱法建立及应用

建立了一种测定海水介质中丙烯酸的高效液相色谱法。采用耐纯水相和较低pH的Agilent SB-Aq-C18柱(100 mm×4.6 mm i.d.,5 μm), 0.35%磷酸溶液(pH=2)为流动相,使用紫外检测器,检测波长为210 nm,外标法定量测定。丙烯酸的保留时间在14.2~ 14.9 min,方法的检出限为4 nmol/dm3(S/N=3),在0.01~10 μmol/dm3的范围内均有良好的线性关系,相关系数可达0.999 6,加标回收率为95.4%~98.1%,相对标准偏差为1.3%~1.6%(1.04~2.32 μmol/dm3)。采用0.2 μm滤膜重力过滤冷藏的办法来保存海水丙烯酸样品。检测出2011年5月份青岛近海海水中丙烯酸的平均浓度为(0.101±0.069) μmol/dm3;海洋微藻球形棕囊藻在整个生长周期内培养体系中丙烯酸的浓度为0.339~2.219 μmol/dm3。     

Analytical procedures to classify organic pollutants in natural waters, sediments, and benthic organisms

Procedures are described to extract, fractionate and analyze organic pollutants in environmental samples. The methods are based on organic solvent extraction to isolate the pollutants, liquid-solid adsorption chromatography to separate the various pollutants into four fractions, and analyses of the fractions using glass capillary gas-chromatography. Based on a number of considerations, the procedures were found suitable for the analyses of trace level organic pollutants in a variety of sample types. The data from these studies has provided important information on the biogeochemistry of organic pollutants in the aquatic environment.     

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.     

Growth stimulation and inhibition of natural phytoplankton communities by model organic ligands in the western subarctic Pacific

The influence of organic ligands on natural phytoplankton growth was investigated in high-nitrate low-chlorophyll (HNLC) waters and during a phytoplankton bloom induced by a mesoscale iron enrichment experiment (SEEDS II) in the western subarctic Pacific. The growth responses of the phytoplankton in the treatments with iron complexed with model ligand were compared with those with inorganic iron or a control. Desferrioxamine B and protoporphyrin IX were used as models for hydroxamate-type siderophore and tetrapyrrole-type cell breakdown ligand, respectively. In the HNLC water, iron associated with protoporphyrin IX especially stimulated smaller phytoplankton (<10 μm) growth, 1.5-fold more than did inorganic iron. Surprisingly, only the addition of protoporphyrin IX stimulated small phytoplankton growth, suggesting that these cell breakdown ligands might be more bioavailable for them. The protoporphyrin IX’s stimulatory effect on small phytoplankton was not observed during bloom decline phase. The growth of phytoplankton was inhibited in the treatment with desferrioxamine B-complexed iron, suggesting its low bioavailability for the natural phytoplankton community. Its inhibitory effects were particularly pronounced in pico-eukaryotic phytoplankton. During the iron-induced bloom, the phytoplankton’s iron-stress response gradually increased with the desferrioxamine B concentration, suggesting that the competition for iron complexation between natural ligands and desferrioxamine B affected phytoplankton growth. However, the pico-eukaryotes did seem better able to utilize the desferrioxamine B-complexed iron during the bloom-developing phase. These results indicate that the iron bioavailability for phytoplankton differs between bloom-developing and bloom-decline phases.     

The interaction of manganese(II) with the surface of calcite in dilute solutions and seawater

The interaction of Mn²⁺ with the surface of calcite in aqueous solutions is complex. In dilute solutions the Mn²⁺ is rapidly absorbed, MnCO3₃ nucleates on the calcite surface and then grows by a first order reaction with respect to the initial Mn²⁺ concentration. At higher ionic strengths in NaCl solutions, the rate of these processes is slower, but the same general pattern persists. In solutions containing Mg²⁺, at the concentration of seawater and in seawater, the nucleation phase of the uptake process does not appear to occur. The long-term uptake rate of Mn²⁺ on the surface of calcite in seawater is first order with respect to the dissolved Mn²⁺ concentration. The rate constant is over three orders of magnitude smaller than that found in dilute Mg²⁺-free solutions. A probable explanation for the slower growth rate in seawater is that MnCO₃ is not nucleated on the calcite surface due to the presence of high Mg²⁺ concentrations. The Mg²⁺, through site competition, prevents enough Mn²⁺ from being adsorbed to reach a critical concentration for MnCO₃ nucleation. This behavior is similar to that found for orthophosphate with calcite surfaces in dilute solutions and seawater. It indicates that rhodochrosite cannot nucleate in carbonate-rich recent sediments unless the Mg²⁺ concentration is lowered below that of seawater.Measurements of the solubility of rhodochrosite in seawater gave results from an undersaturation approach to equilibrium in excellent agreement with those found in previous studies in dilute solutions. When equilibrium was approached from supersaturation, approximately fifty times more calcium was precipitated than Mn²⁺. The measured solubility was over twice that determined from undersaturation. It is possible that a Mn—calcite containing 25 to 30 mol% MnCO₃ formed on the rhodochrosite from the supersaturated solutions. Consequently, it is doubtful that pure rhodochrosite controls the concentration of Mn²⁺ even in calcium carbonate-poor marine environments.     

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.     

Determination of surfactant activity and anionic detergents in seawater and sea surface microlayer in the Mediterranean

The study of the physico-chemical properties and the determination of different classes of organic substances in the sea are of substantial interest and importance for understanding biogeochemical processes in the sea. The preferable method should be sensitive enough for direct measurement without pretreatment procedures in order to avoid changes in the composition of organic substances initially present in the sample.Surfactant activity data are presented here as measured by electrochemical methods during 1979, 1980 and 1981 in samples from open waters of the Western Mediterranean, and in a few characteristic coastal areas of the Adriatic Sea with different biological activity and different influence of man's activities. Data on sea surface microlayer samples collected during 1977, 1978 and 1981 at different locations and seasons in the Rijeka Bay, which is an integral part of the Adriatic Sea, are presented and discussed in more detail.It was found that the type and concentration of natural surface active material vary within different Mediterranean regions and along the depth profile of the water column.Petroleum hydrocarbons and detergents were found to be prevalent pollutants responsible for high surfactant activity values. Pollution effects are most pronounced in the sea surface microlayer.Electrochemical methods are proposed for research and monitoring of surface-active substances in the sea.     

Marine sampling by scuba diving. 3. Sampling procedures for measurement of mercury concentrations in estuarine waters and seawater

A method for sampling estuarine waters and seawater by scuba diving is described. Samples taken from the Krka River Estuary on the eastern Adriatic coast were analysed for mercury content using cold vapour atomic absorption spectrometry (CVAAS). Mercury levels as low as 1 ng dm⁻³ were determined and these are among the lowest values reported to date. A simple contamination free procedure for the preconditioning of sample containers in the sea was applied. Sampling of water by divers is particularly useful when the intermediate layer in an estuary has to be identified and sampled, as well as for obtaining detailed vertical concentration profiles for mercury and other trace elements.     

White-light promoted degradation of leucopterin and related pteridines dissolved in seawater, with evidence for involvement of complexation from major divalent cations of seawater

The photochemical instability of several related pteridines in seawater was investigated by aseptic incubation of solutions at 20–22°C under illumination from cool-white light of intensity 6 kerg cm⁻² sec⁻¹, and the chemical changes were spectrophotometrically monitored. All the pteridines showed markedly accelerated degradation from this illumination relative to their behaviour in total darkness.Pterin and lumazine were degraded very slowly with zero-order reaction kinetics, while the other pteridines photolysed rapidly (according to first-order kinetics) with decomposition rates increasing in the order dioxylumazine (2,4,6,7-tetrahydroxypteridine) < leucopterin < isoxanthopterin < xanthopterin < oxylumazine (2,4,6-trihydroxypteridine). Excepting leucopterin and dioxylumazine, the photolysis rates were attributable to the pH of seawater and not its salt content; this was also the case with oxylumazine which required the salt content of seawater for decomposition in darkness. Leucopterin and dioxylumazine (both 6,7-dihydroxylated pteridines) gave evidence of complexation with the major divalent cations (Ca²⁺, Mg²⁺) of seawater, by virtue of which their photolytic degradation rates were enhanced to magnitudes obtained in pH-10 buffer without seawater. It is proposed that such complexation produces structural forms of these pteridines analogous to their normal ionic forms at pH 10–12.The photolysis of the 6-hydroxylated pteridines (xanthopterin, oxylumazine) proceeded via intermediate formation of their corresponding 7-hydroxylated derivatives (leucopterin, dioxylumazine).     

离子色谱法测定海水中氯离子和硫酸根离子

氯离子和硫酸根离子是海水中重要的无机阴离子,在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多,但缺少相应的测试方法。本文对测定海水中Cl^–,SO₄^2–的离子色谱方法进行了优化,选用IonPacAS14碳酸盐选择性离子色谱柱,以3.5mmol/L Na₂CO₃+1 mmol/L NaHCO₃为流动相,可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl^–检出限为0.29mg/L,线性相关系数r²=0.999 2,对SO₄^2–检出限为0.42mg/L,线性相关系数r²=0.997 9。样品的加标回收率在95%～102%,Cl^–和SO₄^2–的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高,可满足批量海水样品中Cl<...     

国产沸石的改性处理及其在海水硝酸盐氮同位素预处理中的应用

使用多种改性方法对几种国产天然沸石进行改性处理,提高其铵氮吸附率,制备符合海水硝酸盐氮同位素预处理要求的沸石。发现重力筛选可提高沸石铵氮吸附率16%以上,钠改性及酸改性后钠改性可提高沸石铵氮吸附率80%以上,微波改性和超声波改性均可进一步提高沸石铵氮吸附率。改性处理后,几种沸石在酸性条件下对低浓度铵氮吸附率达90%以上,其氮同位素分馏较美国UOP沸石分馏系数更小,且更稳定。改性后的国产沸石更适于海水硝酸盐氮同位素预处理。应用改性后沸石对长江口海域硝酸盐水样进行了分析,结果表明,改性后沸石可以应用于海水中溶解态硝酸盐的氮同位素分析,为海水中溶解态氮的来源问题及循环机理研究等提供了有效信息。