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.     

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.     

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...     

STUDIES ON CATALYTIC WAVE OF CHROMIUM IN SEAWATER

In this paper, the polarographic catalytic wave of trace chromium in seawater and its mechanism are studied. In supporting electrolyte containing ethylene diamine-NaNO2-EDTA, a clear, sensitive and stable catalytic wave is obtained, and its largest peak potential in differential oscilloscopic pola-rogram is -1.7 V (S.C.E). The detection limit for Cr is 1.5 × 10-9 M. It is unnecessary for natural seawater samples to be separated and preconcentrated, and the samples can be directly detected. Variable coefficient is 5%, and the relative error of recovery efficiency, 10%. The wave is a kind of hydrogen catalytic one with absorbability.     

DETEMINATION OF TUNGSTEN AND MOLYBDENUM IN SEAWATER

Tungsten and molybdenum in seawater can be sensitively and accurately determined by the polaro-graphic catalytic wave. In a supporting electrolyte containing HCl-benzilic acid-Nad, tungsten has a clear and stable catalytic wave. Then, the peak current of molybdenum increases as KClO3 is added into the above medium. The sensitivity of the proposed method is 5×10-2 M for W and 6×10-10 M for Mo, respectively.This method is an extremely quick, sensitive one and is suitable for the analysis of various kinds of water.     

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.     

SEMIDIFFERENTIAL ELECTROCHEMICAL STRIPPING ANALYSIS FOR THE DETERMINATION OF TRACE HEAVY METALS IN SEAWATER

A new voltammetric technique has been described for the determination of trace Cu, Pb, Cd and Zn in seawater by semidifferential electrochemical stripping analysis, in which the semiderivative, e, of the stripping current, i, is measured as a function of electrode potential, at a rotating thin mercury film glassy carbon electrode formed in situ. The optimun conditions are reported. It is demonstrated that the technique has more merits than that of the ordinary linear sweep anodic stripping voltammetry, greatly enhances the sensitivity and resolution and shortens the time of pre-electrolysis.     

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.     

SIMULTANEOUS DETERMINATION OF TRACES OF URANIUM AND THORIUM IN SEAWATER BY ISOTOPE DILUTION MASS SPECTRO-METRIC ANALYSIS METHOD(IDMS)

The separation and simultaneous determination of the traces of U and Th in seawater by IDMS is described. The detection limits of this method are 2.4×10-9 g for Th and 1.1×10-8 g for U. The concentrations of U and Th in seawater nearby Xiamen were measured, which are 3.20 ppb and 7.73 ppt respectively. The precisions fo the method are ±1.7% for U and ±3.6% for Th respectively.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

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 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.     

吕宋海峡及周边海域湍流混合的时空分布特征研究

利用1992—2002年的温盐深数据与2012—2016年的Argo数据,基于细尺度参数化方法研究了吕宋海峡及周边海域(12°—30°N,115°—129°E)湍流混合的时空分布特征,并分析了地形粗糙度、内潮以及风输入的近惯性能通量对湍流混合的影响。结果表明,吕宋海峡和东海陆坡处具有强混合的特征,扩散率高达4×10~(-3) m~2/s,主要是由内潮产生导致的,其中吕宋海峡主要是M2、K1和O1内潮的贡献,而东海陆坡处主要是M_2内潮的贡献;南海北部也呈现较强的混合,且陆坡处的混合比海盆高1—2个量级;南海中央海盆和离岸的菲律宾海混合较弱,扩散率为O (10-5 m2/s)。此外,在研究区域内,湍流混合的年际变化和季节变化均不明显,且混合扩散率与风输入的近惯性能通量未表现出明显的季节相关。     

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 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.     

A simplified automated chelometric method for the determination of sulfate in interstitial water and seawater

A method is described for the determination of sulfate in interstitial water and seawater. After BaSO₄ precipitation, the Ba²⁺ excess is titrated with EDTA using an amalgated silver electrode for end-point detection. An accuracy better than 0.5% is obtained using this method.     

用Ag2S电极电位滴定法测定海水氯度

本文以Ag_2S银离子电极为指示电极,第二种离子选择电极为参比电极组成无液接测量系统,对海水中高含量氯的测定进行了研究。试验表朋,以氟电极或玻璃电极作参比电极,在酸性溶液中,电位突跃约为140mV,终点明显,尤其是氟电极作参比电极,电位较稳定。证明了在酸性溶液中,可以不加有机试剂直接测定海水中高含量氯。     

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.     

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.     

增殖放流影响下东海北部海域三疣梭子蟹(Portunus trituberculatus)最大可持续产量评估

当渔业资源出现衰退时,加强资源增殖放流以养护渔业资源、提高渔业产量对于渔业资源可持续利用具有重要意义;与此同时,增殖放流的实施会对基于资源开发与管理的评估的结果产生影响。基于2001~2015年间东海北部海域三疣梭子蟹(Portunus trituberculatus)渔业数据,采用增殖剩余产量模型,对东海北部海域三疣梭子蟹的最大可持续产量(MSY)及取得MSY时所需捕捞努力量(E_MSY)和原存生物量(B_MSY)进行了评估,并与传统Schaefer模型评估结果进行了比较。结果表明,当年增殖放流量约在3×10⁶~95×10⁶尾之间时,三疣梭子蟹年产量逐渐增加, MSY在14.2×10⁴ t和14.6×10⁴ t之间, E_MSY基本在15×10⁴吨位左右。增殖放流量增加,其对应的MSY也越高,能承受的E_MSY也越高(从15×10⁴~15.4×10⁴吨位之间),相反B_MSY则减小(从188.4×10⁴ t降至186.6×10⁴ t)。与传统的Schaefer模型评估结果相比,增殖剩余产量模型由于考虑了增殖放流生物量的因素,得到了MSY和E_MSY有所增加,而B_MSY有所下降的结论。研究结果有望为该研究海域三疣梭子蟹可持续地捕捞、放流与管理提供科学依据。