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.     

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.     

离子交换—原子吸收光谱法测定海水中痕量铜、铅、锌、镉、铁、锰

本文介绍了用国产D401型螯合树脂分离富集海水中铜、铅、锌、镉、铁、锰等痕量元素,并用原子吸收光谱仪测定其含量的方法。讨论了各元素的分离条件选择及干扰元素的影响,并与溶剂萃取法的结果作了比较。各元素检测的定量下限为:铜0.5μg/L、铅0.1μg/L、锌1.0μg/L、镉0.01μg/L、铁2.0μg/L、锰2.0μg/L。方法精密度在4—8％之间,回收率为90—102％。     

Zn, Pb, Cu AND Cd IN PHASES OF SEDIMENTS IN ZHUJIANG ESTUARY

In this paper, the samples of sediments collected from five sampling-stations in the river-sea water mixing zone of the Zhujiang Estuary have been determined by the sequencial extraction procedure, anodic stripping voltammetry and atomic emission spectrometry etc. The contents of the heavy metals Zn, Cu, Pb and Cd in the various phases which are dissolvable, ion-exchangeable, combined with carbonates, easily-reducible, reducible, combined with organic matters and sulfides and residue in the sediments, have been obtained.     

FORM DISTRIBUTION OF Zn, Cd, Pb AND Cu IN WATERS OF THE NORTHWEST BOHAI GULF

The forms distribution of Zn, Cd, Pb and Cu in waters of the Northwest Bohai Gulf is investigated by inverse polarography of anti-adsorption physically coated mercury film electrode, the higher content of most forms of trace metals is in polluted estuary water, and unstable Zn and Pb are in anomalous distribution. The average concentrations read ΣZn 20.0μg/1 (14.5-36.6 μg/l, ΣCd 0.11pg/1 (0.080-0.14μg/1), ΣPb 1.0μg/1 (0.58-1.6 μg/1), and ΣCu 5.2μg/1) (2.37-8.43 μ/1) respectively.     

海水溶解氧测定方法的研究

溶解氧是海洋调查中化学要素部分的重要项目之一。“海洋调查规范”目前仍采用经典的Winkler修正法,由于此方法操作费时,劳动强度大,而且会引起主观误差,因此迫切要求改用仪器分析方法以提高海洋调查工作的质量。     

RESEARCH ON DETERMINATION OF DISSOLVED OXYGEN IN SEAWATER

Based on the principle of laminar flow-constant potential-chronocoulometry, this article presents a new method of determining the dissolved oxygen in seawater with considerable success. A new model of electrochemical sensor has been designed for this purpose.The sensor has the advantage of overcoming hysteresis and "outskirts effect", thus increasing its stability and prolonging its use to 1-2 years.In connection with this new method a new model SY-1 integrating microcoulorneter with digital display is designed.It is a fast (a sample/2 min) and accurate (±1 - 1.5%) method, suitable for use in the laboratory on board a ship.     

图们江口水中Zn,Cd,Pb,Cu的形式分析

本文用防吸附物理涂汞电极反问极谱对图们江口、东海及日本海水中Zn,Cd,Pb,Cu进行了形式分析,其不稳定态的平均浓度分别为5.9,0.071,0.039,0.69ug/L(占总量的15～27％),分布较为均匀,证实了痕量金属离子(自由离子及不稳定络离子的均匀分布规律。有机结合态Zn,Cd及Pb(10～30％)和颗粒态Zn,Cu和Cu(15～40％)的较高含量位于长江口、东海及图们江口。     

海洋沉积物中Cu、Zn、Pb、Ba的能量色散X射线荧光光谱测定

能量色散X射线荧光光谱仪是一种较为先进的化学分析仪器。我们应用此仪器,采用谱线背景作内标的方法对海洋沉积物中的Cu、Zn、Pb、Ba元素进行了测定,结果比较令人满意。本方法的准确度要优于重量法、比色法,与原子吸收法相比,本法不需要经过萃取分离处理样品,方法简便、快速。因此,本方法适用于大批量样品和多元素的快速测量。     

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.     

海水中溴离子气相色谱测定法的研究

研究了用气相色谱测定海水及天然水中溴离子含量的方法,确定了最佳条件。天然海水,稀释200倍后;取10ml稀释水样,用氯胺T为氧化剂,将Br-氧化为溴,在六次甲基四胺催化的条件下,溴与丁酮反应生成溴代丁酮;用环已烷萃取后,用ECD检测器测定。此方法简便快速,对溴离子含量较低的天然水尤为适用。方法与碘量法相对照,取得满意结果。     

渤海湾及其附近海域沉积物中Cu,Pb,Zn,Cd环境背景值的研究

根据渤海湾及其毗邻河口区10柱岩芯样细颗粒（＜0．063mm）（GF 1983－1985年采集）中重金属含量特点，结合^216Pb年代学编年资料，用未受人类影响沉积层中元素含量，藉统计学方法获得渤海湾岩芯样中Cu，Pb，Zn，Cd的分布类型，并根据各区重金属的含量水平，用t检验法获得了渤海湾Cu，Pb，Zn，Cd的环境背景值。     

THE BEHAVIOR AND SEDIMENTATION MECHANISM OF Pb, Cu AND Cd IN SEDWAENTARY PHASE OF THE CHANGJIANG ESTUARY

The authors have determined the distributions of Ph, Cu and Cd ia surface sediment, acid-soluble fraction and interstitial water of the Changjiang Estuary and analysed the relationship between them and some environmental parameters, finding that there exists a quasi-equilibrium between the interstitial water and the sediment. The distribution of Pb or Cu in both phases it controlled mainly by the adsorptioa-desorption and deposition-solution processes of HFO" and org." in the sediments, whereas Cd is mainly controlled by the depoahisn-Jolution process of CdS. The sedimentation mechanism of Ph, Cu and Cd in the Changjlang Estuary is preliminarily proposed.     

深圳福田白骨壤红树林Cu,Pb,Zn,Cd的累积及分布

于1994年3月，采用样方法分析、探讨深圳福田自然保护区车公庙林区白骨壤红树林重金属Cu，Ph，Zn，Cd元素的累积及分布。结果表明：该林地表层土壤（0—3cm深），Cu，Ph，Zn，Cd的含量分别为383．28．7，1140，0136×10－6，储量分别为5285.40，3960.60,15732.00,18.77mg／m2、植物体各部位Cu，Pb,Zn，Cd含量范围分别为1.81-13.8，0.402－3．51，3．42－69.5，0.013－0295×10-6对表层土壤加权平均富集系数为Cd＞Zn＞Cu＞Pb.该群落Cu，Pb，Zn，Cd现存累积量分别为53．70,19．27，187.89,0.72mg／m2；年净存留累积量分别为4063.91，1318.14，16358.62，60．21μg／m2；林地残留物相应元素的储量分别为2091.18，1958.66,5046.60,19.30μg／m2。该林区不同群落叶层Cu，Pb,Zn，Cd现存累积量为白骨壤林＞桐花树林＞秋茄林。     

基于电子鼻和HS-SPME-GC-MS方法研究 海水中七氯的快速检测技术

为了建立海水中有机氯农药的快速检测技术, 本文基于电子鼻和顶空固相微萃取气质联用法(HS-SPME-GC-MS)对海水中的七氯进行检测。结果表明, 电子鼻可以识别海水中的挥发性七氯成分及浓度, 最低检测限0.01mg/L。利用线性判别分析方法(LDA)的累计判别贡献率和欧氏距离、判别函数法、相关性对未知样品的识别率均达到了80%以上, 具有良好的区分效果; PLS模型预测七氯浓度跟实际值之间的相对误差在0.49%—16%之间。HS-SPME-GC-MS检测浓度小于0.10mg/L时, 相对误差在10%左右; 而大于此浓度时, 相对误差随之增大。检测到的主要挥发性物质基本呈现规律性的变化, 与电子鼻确认结果一致。对比两种检测技术, 发现电子鼻检测方法比HS-SPME-GC-MS更迅速、灵敏, 检测限更低, 相对误差也更小, 仪器便携、投资相对较小。     

SOLID-LIQUID INTERFACE PROCESS OF HEAVY METALS IN THE CHANGJIANG ESTUARYKINETICS OF ADSORPTION OF Pb, Cu AND Cd ON HFO

The adsorption kinetics of Pb, Cu and Cd on hydrous ferrk oxide (HFO) has been approached in tthe simulated environmental conditions of the Changjiang Estuary. The forward adsorption rate constants of different systems under different temperatures have been determined, and the activation energies of the adsorption for Pb and Cu evaluated (Pb=7 kcal/mol, Cu= 11 kcal/mol). The results show that Pb and Cu are strongly adsorbed by HFO; the order of their adsorption rate is found to be Pb≥Cu≥Cd, which follows thte order of their theonody-namic equilibrium constants. It has been demonstrated that the surface exchange-adsorption is the determining step of the solid-liquid interface process. The field investigation results are theoretically explained by the kinetic mechanism.     

海水中有机氯农药的气相色谱测定新方法的研究

海水样品用乙酸乙酯萃取后，萃取液加入乙酸和氧化铬，在１００℃下回流３０ｍｉｎ，再用正己烷萃取，干燥，浓缩，定容后进行色谱测定，方法简便易行，准确度高，该法已用于青岛胶州湾海水中有机氯农药残留量的测定进行验证。     

SOLID-LIQUID INTERFACE PROCESS OF HEAVY METAL IN THE CHANGJIANG ESTUARYADSORPTION THERMODYNAMIC MODEL OF Pb, Cu AND Cd BY HYDROUS FERRIC OXIDE

The adsorption of Pb, Cu and Cd on synthetic hydrous ferric oxide (HFO) has been performed under simulated environmental conditions of the Changjiang Estuary. An improved M2 - H exchange-adsorption model is proposed to explain the adsorption processes. The adsorption of these elements falls in the order: Pb ≥ Cu > Cd and has a good coincidence with the field results obtaimed from the Estuary. It has been concluded that the adsorption processes of Pb and Cu on HFO are mainly chemical actions, whereas static-electrical action dominates in the case of Cd.     

海水中三价与六价铬高效液相色谱-三重四级杆电感耦合等离子体质谱法(HPLC-TQ-ICP-MS)的联用测定

基于高效液相色谱(HPLC)与三重四级杆电感耦合等离子体质谱(TQ-ICP-MS)联用技术,构建海水中三价铬与六价铬在线分离与测定的检测方法。采用TQ-ICP-MS碰撞反应池(KED)技术消除³⁵Cl¹⁶O¹H⁺、⁴⁰Ar¹²C对⁵²Cr同位素测定可能存在的质谱干扰。选用Dionex IonPac AG 7 (4 mm×50 mm10μm)阴离子交换柱为分析柱,对流动相浓度及pH值进行优化,结果表明,当流动相浓度为0.08 mol/L NH₄NO₃、0.6 mmol/L EDTA,pH值7.5,流速1.0 mL/min时,仅需80 s就可以完成三价铬和六价铬的理想分离与测定。对络合剂EDTA的络合浓度、pH、温度及时间进行了深入研究,结果显示,当EDTA浓度为10 mmol/L、络合pH值7.5、络合温度50°C、络合时间2 h时,三价铬可以最大程度的被EDTA络合。在0.1～50.0μg/...