锑原位掺杂SiO2@PDA-Sb复合材料修饰电极用于海水中Zn离子检测

本研究提出了一种用于检测海水中锌离子(Zn²⁺)含量的电化学检测方法。该方法首先应用水热法合成SiO₂@PDA-Sb复合材料,然后将该复合材料修饰到玻碳电极上制备SiO₂@PDA-Sb-Nafion/GCE,利用差分脉冲阳极溶出伏安法(DPASV)对珠江口海水水样中Zn²⁺进行测定。研究结果表明,Zn²⁺在SiO₂@PDA-Sb-Nafion/GCE上具有较强的溶出峰。在最优条件下,SiO₂@PDA-Sb-Nafion/GCE对Zn²⁺浓度在1～1 000 nmol/L范围内可实现灵敏、准确的检测,Zn²⁺的检测出限为0.71 nmol/L。加标回收率实验显示Zn²⁺加标回收率为93.19%～100.12%,表明该方法可应用于现场海水样品Zn²⁺测定。本方法具有电极制作简单、稳定性和抗干扰性良好,能够提高现有测定方法的检测限和精确度,在现场海水检测...     

RESEARCH ON THE DETERMINATION OF Pb, Cd, Cu AND Zn IN SEAWATER BY STRIPPING VOLTAMMETRY

In this paper, a comparison viral made between the two results of determining Pb, Cd, Cu and Zn in seawater by direct current (tripping voltammetry (DCS) with rotating glass carbon electrode and by differential pulse stripping voltammetry (DPS) with hanging mercury drop electrode (HMDE). By DCS, the range of linear calibration curves obtained was 4×10-3 M-2×10-7M for Cu, Zn and Cd, and 4× 10-9M-2×10-3M for Pb. By using DPS, the range of linear calibration curve was as follows: Cu 0.65-1.9 ppb; Pb 1.0-10 ppb; Zn 0.65-2.0 ppb; Cd 0.02-0.14 ppb. It was found that DCS could be used for determining Pb, Cu, Zn in coastal waters, but it is necessary to add gallium ion to it to eliminate the interference of Cu-Zn inter-metallic compound for determining Zn. The DPS is better for determinig Cd.     

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.     

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.     

DIRECT DETERMINATION OP TRACE CADMIUM IN SEAWATER BY DERIVATIVE-VOLTAMMETRY

An analytical method is proposed for the direct determination of Cd in seawater by differential pulse anodic stripping voltammetry and the derivative technique with a hanging mercury drop electrode. The process of determination is quick, simple and convenient. The concentration of Cd in seawater is only determined by adjusting the acidity of seawater to pH 2 and by taking three minutes' plating time. Sensitivity of the method is about 1×10-10M, and accuracy of that satisfactory. Relative standard deviation is about 12% when the concentration of Cd in seawater is approximately 0.04 ppb. A good agreement was obtained by a standard curve and a standard addition technique respectively from determining Cd in the same seawater. Actual measurement time per sample is about 10 min.     

The influence of surfactants on the measurements of copper and cadmium speciation in model seawater by differential pulse anodic stripping voltammetry

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.     

Determination of the reduced sulfur species in the anoxic zone of the Black Sea: A comparison of the spectrophotometry and iodometry techniques

The report presents the results of the studies of the reduced sulfur species in the water of the anoxic zone of the Black Sea. The content of hydrogen sulfide was determined by means of spectrophotometry using dilution with oxygen-free distilled water. The detection limit of the H₂S amounted to 0.3 μM with the method’s precision below 3%. The accuracy of the spectrophotometric determination was verified by iodometry after the fixation of the hydrogen sulfide in zinc acetate under the distillation with argon from the acidified seawater sample.     

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.     

The influence of organics on the adsorption of copper (II) on γ-Al2O3 in seawater,model studies with EDTA

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.     

Apparent dissociation constants of hydrogen sulfide in chloride solutions

Spectrophotometric measurements are reported for the first apparent dissociation constant of hydrogen sulfide in seawater over the temperature range 7.5–25°C and 2–35.8‰ salinity. These data are described by the expression $\text{p}\text{K}{}_1\text{′ = 2.527 ? 0.169 Cl}{}^{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{+ 1359.96/T}$. The second apparent dissociation constant in potassium chloride solution was estimated potentiometrically using a sulfide specific ion electrode. A value of ～13.6 was found for pK₂′ at a KCl concentration of 0.67 M. It is suggested that explicit reference to the sulfide ion, S^2?, in describing equilibria in marine waters be dropped in favor of a formulation involving the bisulfide ion, HS^?.     

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3.5 mmol/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0.29 mg/L,线性相关系数r²=0.999 2,对SO₄^2-检出限为0.42 mg/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^-与SO₄^2-的准确测试。     

Calibration of a chalcogenide glass membrane ion-selective electrode for the determination of free Fe in seawater: I. Measurements in UV photooxidised seawater

Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe_2.5(Ge₂₈Sb₁₂Se₆₀)_97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe³⁺ concentrations ranging from 10⁻¹⁰ M to less than 10⁻²⁵ M Fe³⁺. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10⁻⁵ M Fe³⁺, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe³⁺] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10⁻⁵ M Fe³⁺ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10⁻² nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe³⁺ at concentrations typically found in natural seawater.     

Voltammetric study of adsorption of cu(II) species on solid particles added to seawater

The adsorption on solid particles of natural organic ligand in seawater of Cu(II) ions, and of the inert Cu(II) complexes has been studied. Model solids, γ-Al₂O₃, Na⁺-0.392-γ-Al₂O₃, ‘Aerosil 200’, chrysotile, northupite and CaCO₃ were added to seawater. It was observed that at pH 8 natural organic matter was strongly adsorbed on chrysotile and was not adsorbed on Na⁺ -0.392-γ-Al₂O₃; it was also adsorbed on γ-Al₂O₃ over the range of 3 < pH < 7. In this pH range, the complexing capacity and adsorption of Cu is at a minimum because Cu(II) is not adsorbed on γ-Al₂O₃ and natural organic matter is adsorbed. Inert CuL complexes were adsorbed at pH 8.0 on γ-Al₂O₃, ‘Aerosil 200’, CaCO₃, and chrysotile but they were not adsorbed on northupite. The voltammetric method can be recommended for use in natural waters for distinguishing between metal ionic and metal inert complex species which are adsorbed from solution onto various solid particles.     

海水ORP对3C钢腐蚀行为的影响

研究了氧化还原电位(Oxidation Reduction Potential, ORP)对海水中碳钢腐蚀电化学特征的影响,应用动电位极化曲线法探讨了 ORP 与碳钢腐蚀行为之间的关系。结果表明,海水的 ORP 参数对碳钢腐蚀行为具有较大的影响,其中 O2/OH?电对的作用占主导,其他电对如 Fe3+/Fe2+也有一定的影响。随着海水 ORP 的增大,其氧化能力越强,碳钢腐蚀电流增大,腐蚀速度加快。水质相对稳定的开放性大洋海水中,可以考虑海水氧化还原电位在碳钢腐蚀速度预测评估中的应用。     

Production and speciation of hydrogen sulfide in surface waters of the high latitude North Atlantic Ocean

During the August 1993 Intergovernmental Oceanographic Commission's Contaminant Baseline Survey cruise to the high latitude North Atlantic, determinations of total dissolved sulfide (TDS=free sulfide, H₂S_(g)+HS⁻+S²⁻, plus dissolved metal–sulfide complexes), free sulfide, and carbonyl sulfide (OCS) were made along a horizontal transect and at six vertical profile stations. Unlike data from lower latitudes, the distributions of OCS and TDS were remarkably uniform, with surface water OCS averaging 108 pmol/l and TDS averaging 58 pmol/l; free sulfide was below the detection limits of 5 pmol/l at all stations. The vertical profiles of both OCS and TDS show surface maxima and rapid decreases into the major thermocline. For OCS this is indicative of production via photolysis of dissolved organic sulfur compounds, while TDS may be produced from the hydrolysis of OCS. The concentrations of OCS are similar to those found in coastal waters, and suggests that these sub-polar regions may be large OCS sources to the troposphere during summer. However, it is unclear whether higher concentrations of OCS precursors, a long photo period during summer, or slow rates of removal by hydrolysis due to low temperatures are responsible for the elevated OCS levels. TDS concentrations are primarily controlled by the rate of OCS hydrolysis, production by phytoplankton, and oxidative loss by oxygen and iodate. Both of the losses are affected by trace metal complexation, and to examine this, freshly collected seawater was amended by hydrogen sulfide gas and trace metal additions, and the concentration of free sulfide monitored as a function of metal concentration. This allowed the determinations of conditional stability constants for metal sulfides, with the log K_cond of Cd(HS)⁺ being 8.0±0.5, 7.0±0.6 for Ni(HS)⁺, and 7.4±0.7 for Zn(HS)⁺; attempts at measuring the K_cond of Cu(HS)⁺ were thwarted by the apparent reduction of Cu(II) to Cu(I) by sulfide. Using these constants in an equilibrium speciation model indicates that on average about 75% of the measured TDS was free, with the remaining fraction complexed with Ni, Cd, and Zn (in order of decreasing percentages). While closer to the field observations than would be found with stability constants reported by other workers, these values are still at variance with the actual speciation (i.e., <30% free). This suggests that the stability constants for Cd, Ni, and Zn are somewhat higher than found, thus reducing the concentration of free sulfide. Nevertheless, these speciation data are important for balancing the TDS budget since the loss by iodate oxidation of free sulfide exceeds all production estimates.     

STUDY ON METABOLISM OF MERCURY IN Tilapia Mossambica

Using 203HgCl2 as a tracer, uptake and combination of inorganic mercury in Tilapia mossambica (petres) and its transfer between different tissues of the fish were studied. The results demonstrate that gill is the main tissue uptaking mercury directly from seawater and that the mercury in gill, skin, digestive tube and fin would be transferred to the other tissues. The result of gel chromatography with Sephadex G-75 shows that most of mercury in gill filaments, liver, and digestive tube are bound in high molecules (MW-70000) and not in metallothionein, but in kidney and bile mercury binding proteins are similar to metallothionein and are accounted for up to 60% and 46% respectively.     

Complexation of dimethylsulfide with mercuric ion in aqueous solutions

The tendency of dimethylsulfide (DMS) to form complexes with heavy metal ions in aqueous solutions and the factors that influence it have been investigated. Among five heavy metal ions examined (Cu²⁺, Cd²⁺, Zn²⁺, Pb²⁺ and Hg²⁺), only Hg²⁺ bound significantly with DMS in aqueous solutions in which Hg²⁺ concentration was increased to much higher levels than that of natural seawater. The complexation capacity of Hg²⁺ for DMS was influenced by pH and media. The affinity of Hg²⁺ for DMS was generally lower at high than at low pH, presumably due to the competition of hydroxide ion to form hydroxomercury species. In different solutions, the affinity of Hg²⁺ for DMS followed the following sequence: ultra-purified water > 35‰ NaCl solution > seawater. It seems apparent that chloride had a negative impact on the complexation of DMS by Hg²⁺, owing to the competition of chloride with DMS for complexing Hg²⁺. In addition, the affinity of Hg²⁺ for DMS in the bulk seawater appeared to be higher than that in the surface microlayer seawater. The tendency of Hg²⁺ to form complexes with DMS in aqueous solution can be reduced by the presence of 2 mM amino-acid such as glycine, alanine, serine and cysteine, as these ligands give stable mercury complexes. However, the presence of 2 mM acetate in experimental solutions had no significant effect on the complexation of Hg²⁺ with DMS, even though this ligand has a relatively strong complexing capacity for Hg²⁺. Although mercury ions appeared to have a strong affinity for DMS, the concentration of mercury in seawater is too low to produce a great effect on the distribution of DMS in oceans.     

Influence of water column dynamics on sulfide oxidation and other major biogeochemical processes in the chemocline of Mariager Fjord (Denmark)

Major electron donors (H₂S, NH₄⁺, Mn²⁺, Fe²⁺) and acceptors (O₂, NO₃⁻, Mn(IV), Fe(III)), process rates (³⁵SO₄²⁻ reduction, dark ¹⁴CO₂ fixation) and vertical fluxes were investigated to quantify the dominant biogeochemical processes at the chemocline of a shallow brackish fjord. Under steady-state conditions, the upward fluxes of reductants and downward fluxes of oxidants in the water column were balanced. However, changes in the hydrographical conditions caused a transient nonsteady-state at the chemocline and had a great impact on process rates and the distribution of chemical species. Maxima of S⁰ (17.8 μmol l⁻¹), thiosulfate (5.2 μmol l⁻¹) and sulfite (1.1 μmol l⁻¹) occurred at the chemocline, but were hardly detectable in the sulfidic deep water. The distribution of S⁰ suggested that the high concentration of S⁰ was (a) more likely due to a low turnover than a high formation rate and (b) was only transient, caused by chemocline perturbations. Kinetic calculations of chemical sulfide oxidation based on actual conditions in the chemocline revealed that under steady-state conditions with a narrow chemocline and low reactant concentrations, biological sulfide oxidation may account for more than 88% of the total sulfide oxidation. Under nonsteady-state conditions, where oxic and sulfidic water masses were recently mixed, resulting in an expanded chemocline, the proportion of chemical sulfide oxidation increased. The sulfide oxidation rate determined by incubation experiments was 0.216 μmol l⁻¹ min⁻¹, one of the highest reported for stratified basins and about 15 times faster than the initial rate for chemical oxidation. The conclusion of primarily biological sulfide oxidation was consistent with the observation of high rates of dark ¹⁴CO₂ fixation (10.4 mmol m⁻² day⁻¹) in the lower part of the chemocline. However, rates of dark ¹⁴CO₂ fixation were too high to be explained only by lithoautotrophic processes. CO₂ fixation by growing populations of heterotrophic microorganisms may have additionally contributed to the observed rates.     

Air-sea exchange of mercury in Tokyo Bay

In Tokyo Bay the concentrations of dissolved gaseous mercury (DGM) in the surface seawater and total gaseous mercury (TGM) over the sea were measured during December 2003, October 2004 and January 2005. Based on these data, the evasional fluxes of mercury from the sea surface were estimated using a gas exchange model. In addition, an automatic wet and dry deposition sampler was used to measure the wet and dry depositional fluxes of mercury from December 2003 to November 2004 at three locations in and near Tokyo Bay. The results indicate that the average DGM and TGM levels of seven locations are 52 ± 26 ng m⁻³ and 1.9 ± 0.6 ng m⁻³, respectively, which shows that the surface seawater in Tokyo Bay is supersaturated with gaseous mercury, leading to an average mercury evasional flux of 140 ± 120 ng m⁻²d⁻¹. On the other hand, the annual average wet and dry depositional fluxes of mercury at three locations were 19 ± 3 μg m⁻²yr⁻¹ and 20 ± 9 μg m⁻²yr⁻¹, respectively. These depositional fluxes correspond to the daily average total depositional flux of 110 ± 20 ng m⁻²d⁻¹. Thus, it is suggested that in Tokyo Bay, the evasional fluxes of mercury are comparable to the depositional fluxes.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, R² = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).