东海外陆架及钓鱼岛以北海域鱼类、底栖生物的痕量金属测定

从海洋生物生态学本身的研究,生物体常量,微量元素的测定,前人已作了很多的工作。随着国防、工业及海上交通运输不断高速发展,各种工业废物大量抛入海洋,海洋污染日趋严重。为此,许多海洋学者又从海洋环境保护出发,对各个海域里的生物成分进行了监测,特别对生物体痕量金属的测定已作了大量工作[3-6]。测定的范围是广范的,从大洋到极地,从深海到岸边,而对受污染严重的港湾及河口的生物毒物研究得更多。     

Determination of the apparent copper complexing capacity of seawater by anodic stripping voltammetry

A new experimental technique using differential pulse anodic stripping voltammetry with a thin-film mercury electrode and efficient mixing of the electrolyte for the apparent copper complexing capacity of seawater is proposed. The effects of some factors such as type of electrode and cell, pH of the solution, potential of deposition, time of equilibration, and influence of a non-ionic surface active agent on the measurements are examined. Experimental results for the apparent copper complexing capacity of seawater are calculated presuming 1:1 inert complex formation. By using EDTA as a model ligand, it is shown that the proposed procedure with efficient mixing of the solution excludes any appreciable kinetic influence upon the electroanalytical results.     

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.     

DIRECT AND SIMULTANEOUS DETERMINATION OF Zn, Cd, Pb, Cu and Bi IN SEAWATER BY DERIVATIVE-VOLTAMMETRY

This paper suggests direct and simultaneous determinations of the reducible species of Zn, Cd, Pb, Cu and Bi in seawater made by the derivative-differential pulse anodic stripping voltammetry with a hung mercury drop electrode. The influence of Cu on the determination of Zn in this experiment condition has been studied, of which both the accuracy and precision are satisfactory. The procedure of determination is so quick, simple and convenient that the background concentration of these five elements in coastal seawaters can be determined only by adjusting the acidity of seawater to pH 2.5 and by taking 10-minutes plating time. Actual measurement time of these five elements for every sample is approximately 25 min.     

黄海海洋生物中的痕量金属

本文对黄海海区二十几种甲壳动物、软体动物及个别鱼类体内的Zn,Cd,Pb,Cu进行了测定,并计算了其富集系数,同时对调查站的水质和沉积物进行了上述痕量金属的监测。通过实测资料,可以进一步了解该海域各类不同生物所含痕量金属的水平,对了解和评价黄海的环境质量有一定的参考作用。同时也为国家需要的环境背景值,提供科学数据。     

阳极溶出伏安法测定海水中低浓度镉

镉能积累于人体及生物体内造成慢性中毒,引起严重的“骨头病”[1],并与严重的心血管病有连带关系[2].海洋中镉的污染问题已引起人们极大的重视.目前,我国与世界其他国家一样,已将镉的污染列为国家海洋环境重点监测项目之一.     

动态式抽取、气相色谱法测定海水中的甲烷

本文报道了用动态（ｄｙｎａｍｉｃ）技术，经抽取、气相色谱法测定海水中溶存甲烷浓度的方法．详细论述了溶存甲烷经起泡、收集（吸附）、解吸和检测四步完成，并逐步讨论了起泡时间、起泡气体流速以及收集温度等有关因子对测定的影响。结果表明：该方法分析速度快、精密度好、灵敏度高，可广泛应用于海上现场测定海水中溶存的甲烷。     

DETERMINATION OF RESIDUAL MALATHION IN NATURAL WATER

A method for determination of malathion in natural water by cathodic stripping voltammetry using mercury film electrode is suggested in this paper. The method is based on the quantitativeformation of group generated by malathion as a result of elimination reaction inthe ethanol solution of sodium hydroxide. The group is similar to sulphide in electrochemical properties, and can be determined by cathodic stripping voltammetry. Interference from inorganic sulphide is prevented by the addition of Hg (NO3)2. This method has been applied to the determination of residual malathion in natural water (e. g. the sea, rivers, lakes, etc.). The waveheight is directly proportional to the malathion concentration within the range 5×10-9 - 1×10-7 mol/L. The method is simple and rapid, and the results of water sample determination is quite in accord with those of Gas Chromatograph.     

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.     

Studies in seawater and lake water on interactions of trace metals with humic substances isolated from marine and estuarine sediments: II. Voltammetric investigations on trace metal complex formation in the dissolved phase

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.     

Analysis of seawater for dissolved cadmium, copper and lead: An intercomparison of voltammetric and atomic absorption methods

An intercomparison study of voltammetric and atomic absorption spectrometric methods for determining cadmium, lead and copper in seawater samples was conducted. The voltammetric approach utilizes differential pulse anodic stripping voltammetry using a rotating, glassy carbon, mercury film electrode under conditions developed to minimize contamination sources and to enhance sensitivity for seawater matrices. The atomic absorption approach involves a concentration step using either an organic solvent extraction of metal dithiocarbamate chelates or a Chelex-100 column with detection by graphite furnace atomic absorption spectrometry. Similar and consistent results were obtained using both methods for the three trace metals studied on a wide range of natural seawater samples. Both methods are comparable in sensitivity for cadmium and copper, however the voltammetric method is better suited for the analysis of lead in seawater because of its enhanced sensitivity and low blank. An advantage of the voltammetric approach is its amenability towards real-time shipboard analysis.     

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.     

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.     

杂色鲍苗大规模脱落死亡的初步研究

研究了杂色鲍(Haliotis diversicolorReeve)鲍苗脱落死亡周期中水质、硅藻和细菌变化情况。结果显示,鲍苗脱落前各水质指标无明显变化,脱落前硅藻数量大幅度增加,以卵形藻(Cocconeisspp.)和舟形藻(Naviculaspp.)为主要种类。同时发现一株可疑致病菌,初步鉴定为溶藻弧菌(Vibrio alginolyticus)。实验表明水质等相关因子与鲍苗脱落无直接关系,而硅藻很可能是致病菌的“载体”,整个附着膜微环境与鲍苗存亡息息相关。     

The determination of sulfide in seawater by flow-analysis with voltammetric detection

Preliminary measurements of sulfide in seawater using cathodic stripping voltammetry and a hanging mercury drop electrode (HMDE) in batch-mode showed that the sulfide peak decreased rapidly with time. This decrease was not caused by O₂, H₂O₂ or IO₃⁻, and the sulfide peak was not stabilised by trace metal additions. A home-made flow-cell was constructed to enable the determination of sulfide in seawater using voltammetry with an HMDE. A stable sulfide peak was obtained by flow-analysis with voltammetric detection, with a precision of 2.8% and detection limit of 0.5 nM at a 60 s adsorption time. Several thiol compounds were found to produce a peak at, or very close to, the peak potential for sulfide. Their interference was evaluated by allowing the sulfide peak in conventional (batch) voltammetry to decay. Comparative experiments showed that waste metallic mercury is responsible for removal of sulfide in batch-mode analysis due to formation of insoluble mercuric sulfide salts causing the rapid decay of the sulfide peak. The problem is circumvented by using flow-analysis to determine sulfide.     

Preparation and Properties of Embeddable Ag/Ag Cl Gelling Reference Electrode for Rebars Corrosion Monitoring in Concrete

Reference electrodes are a key part for corrosion monitoring and measurement of rebars in concrete. A reference electrode that can be buried in concrete is fabricated by using Ag/Ag Cl electrode and methyl cellulose gelling electrolyte. The stability, repeatability and anti-polarization of the reference electrode are investigated; the influences of the inner electrolyte loss, exterior OH- contamination, and temperature on the potential of the reference electrode are also investigated in this paper. The results show that the reference electrode has good stability, repeatability, and antipolarization. The influences of inner electrolyte loss, exterior OH- contamination, and temperature on the potential of the reference electrode are minimal. Therefore, it can be used for corrosion monitoring and measurement of rebars in concrete.     

Preparation and Properties of Embeddable Ag/AgCl Gelling Reference Electrode for Rebars Corrosion Monitoring in Concrete

Reference electrodes are a key part for corrosion monitoring and measurement of rebars in concrete. A reference electrode that can be buried in concrete is fabricated by using Ag/AgCl electrode and methyl cellulose gelling electrolyte. The stability, repeatability and anti-polarization of the reference electrode are investigated; the influences of the inner electrolyte loss, exterior OH? contamination, and temperature on the potential of the reference electrode are also investigated in this paper. The results show that the reference electrode has good stability, repeatability, and anti- polarization. The influences of inner electrolyte loss, exterior OH? contamination, and temperature on the potential of the reference electrode are minimal. Therefore, it can be used for corrosion monitoring and measurement of rebars in concrete.     

Trace metal adsorption on inorganic solid phases under estuarine conditions

The adsorption of trace metals (Pb, Zn, Cu, Cd and Hg) on calcite, kaolinite and bentonite has been studied in Krka river water of various salinities (S = 3, 20 and 38‰).Model experiments were performed at pH 8 in natural water and in UV-irradiated water samples to determine the importance of natural soluble organic matter. Cold vapour atomic absorption spectrometry was used for the Hg determination, and a differential pulse anodic stripping voltammetry (DPASV) method for determination of other trace metals, using either a hanging mercury drop electrode or a mercury-coated glassy carbon working electrode. The following results have been obtained on calcite:

1. (1) a powerful absorption of Pb and Zn was observed for both natural and UV-irradiated waters at S=20‰;

2. (2) a strong adsorption of Hg was observed in natural water, and significantly lower adsorption in UV-irradiated water at all three salinities, particularly at low salinity;

3. (3) Cd adsorption was of medium intensity in both waters at S=20‰;

4. (4) Cu was practically not adsorbable in both waters at S=20‰ if the total Cu ion concentration was lower than the copper complexing capacity value;

5. (5) Cu adsorption was of a medium intensity at S=38‰. It has not influenced by the EDTA model ligand.

Trace metals Pb, Zn and Cu are adsorbable on kaolinite and bentonite at S=38‰, whereas Cd is practically not adsorbed. The Krka River is a calcareous river, which supplies the sea with calcite and aluminosilicates. In the light of our model experiments, we suggest that the self-purification of the Krka River is remarkable in respect to Pb, Zn and Hg; this occurs to a lesser extent for Cu, and is negligible in the case of Cd.