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.     

A study on sample pretreatment of analysis of Cd, Pb and Zn in seawater by IDMS

Isotope dilution mass spectrometry (IDMS) and ultra-clean room approach are successfully used in the determination of Cd, Pb and Zn in seawater and the sample pretreatment of analysis. The precision in the determination of Cd, Pb and Zn in seawater is better than±3% and the limits of detection are 6×10-12, 6×10-11 and 2.4×10-10 respectively. The effects of sample pretreatment such as filtration and acidification on the results of determination of Cd- Pb and Zn in seawater are disscussed.     

海洋沉积物孔隙水中痕量金属元素的测试分析方法

孔隙水是沉积物-海水界面链接沉积物颗粒和上覆水体的一个重要过渡相态,针对其研究可更好地了解痕量金属在固-液界面的早期成岩过程。近年来,针对孔隙水中痕量元素研究的方法较为匮乏,为此建立了一种分析测定海洋沉积物孔隙水中7种痕量金属元素(Mn、Cu、Zn、Ni、Cd、Co、Pb)的方法,该方法使用Nobias PA1树脂进行富集分离,再使用电感耦合等离子体质谱(ICP-MS)进行测试,可针对孔隙水中的痕量金属元素进行准确分析。通过实验结果发现该方法最优实验条件为: Nobias PA1树脂富集时的pH值为5.5~6.0,洗脱酸浓度为1.3 mol/L硝酸,体积为1 mL。同时,样品需进行紫外消解4 h以上以分解有机络合物,该消解步骤对Cu和Co这两种元素尤其重要。该方法通过加标回收获得Mn、Cu、Ni、Co和Pb的回收率在92%~100%, Zn和Cd的回收率分别为72%和82%; Mn、Cu、Zn、Ni的方法检出限范围为0.03~0.53 nmol/L, Cd、Co、Pb的方法检出限范围为2.66×10^-3~8.60×10^-3 nmol/L,满足孔隙水中痕量金属浓度的测试需求。同时,根据检出限计算的结果显示,孔隙水样品只需1 mL,即可应用该方法进行测试。应用该方法测试了一根采集于北黄海中部沉积物短柱的孔隙水样品,测试结果显示其垂相分布合理、较符合早期成岩过程规律。此研究为分析海洋沉积物孔隙水中痕量金属元素提供了一种准确而简便的方法。     

Concentrations of suspended matter and particulate cadmium,copper, lead and zinc in the Indian sector of the antarctic ocean

The concentrations of suspended matter and particulate Cd, Cu, Pb and Zn were determined for 36 samples collected at 6 stations in the Antarctic Ocean during December, 1970 and January, 1971 using membrane filters. The concentration of suspended matter was determined gravimetrically and trace metal levels were determined using anodic stripping voltammetry. For waters deeper than 100 m the concentration of suspended matter was < 100 μg l^?1. Concentrations up to 542 μg l^?1 were recorded between surface and 100 m. Individual concentrations of the metals were scattered with depth. Average concentrations of particulate metals were: Cd, 3.5 ng l^?1; Cu, 100 ng l^?1; Pb, 35 ng l^?1; and Zn, 230 ng ;l^?1 These measurements represent non-steady state conditions of early Antarctic summer as the ice pack disintegrates and biological activity increases.     

Cd, Pb, Cu, Ni and Co distribution in the German Bight

Cd, Pb and Cu concentrations, dissolved and total, have been determined in the German Bight. In 1975, 1977, 1978, 1980 and 1983 water samples were collected at 215 sampling stations. In the 1983 mission samples were also analysed for Ni and Co. The samples were filtered and acidified immediately after collection. Analysis was performed by voltammetry.The analytical data indicate that a net portion of the Cd, the Weser being a distinct source for it, will cross the estuarine zone. Open sea Cd levels in the German Bight are about a factor 10 higher than North Atlantic values. Pb, being transported mainly with the suspended particulate phase (up to 99.5%), is better eliminated by sedimentation in the estuaries. Ni and Cu occur mainly in the dissolved phase. Pollution by Co is distinct in the Elbe, but the output is rapidly diluted to background contents below 10 ng kg⁻¹. An interpretation of the results from the different years yields a rather steady state situation in the German Bight.     

Behavior of Cu, Ni and Cd during nutrient depletion in a spring bloom in Funka Bay

The concentrations of Cu, Ni and Cd were determined in Funka Bay during a spring phytoplankton bloom, consisting of diatoms. Just after the bloom, both dissolved Cd and nutrients were removed in the euphotic zone. However, the removal ratio of Cd to phosphate was very different from that in seawater. The removal of Cd took place at a Cd/phosphate ratio of 0.07×10⁻³, which was lower than in seawater before the bloom (0.25×10⁻³), leading to an increase in this ratio in seawater exceeding 0.7×10⁻³ at the end of the bloom. Elevated concentrations of Cd and phosphate were observed in the deeper layer after the bloom due to the decomposition of detrital materials produced in the bloom. The ratio of Cd/phosphate in the regeneration step was 0.24×10⁻³ which was different from the removal ratio of 0.07×10⁻³. These observations suggest that the high Cd/phosphate ratio in the regeneration would reflect a relatively high regeneration rate of Cd than that of phosphate. No significant decrease in Cu and Ni concentrations was observed during the development of the bloom, suggesting that biological removal of these metals was not so significant during the spring bloom. The concentrations of Cd, Cu and silicate in surface waters increased after the bloom with decreasing salinity due to the influence of a spring thaw.     

Cadmium,lead, copper,and zinc in Elminius modestus Darwin (Crustacea,Cirripedia) from Waitemata and Manukau Harbours,Auckland, New Zealand

Abstract

Concentrations of cadmium (Cd), lead (Pb), copper (Cu), and zinc (Zn) were measured in adult barnacles (Elminius modestus Darwin) from Waitemata and Manukau Harbours in the Auckland area, New Zealand. As in studies on sediments reported in the literature, it was possible to identify areas of likely anthropogenic influence, e.g., around the Auckland Harbour Bridge for Pb, Cu, and Zn. Groups of individuals with highest concentrations for these metals showed 19.8–23.8 mg Pb kg^?1, 198–266 mg Cu kg^?1, and 4460–6530 mg Zn kg^?1 (95% confidence limits, dry weight basis). Cd concentrations found for all barnacles from the Auckland area ranged from 0.8 to 3.1 mg kg^?1. Two samples from Omaha Beach, 60 km north of Auckland, were used as a reference. Accordingly, groups of individuals with lowest concentrations for Pb, Cu, and Zn could be allocated to this site using the Student‐Newman‐Keuls Multiple Range Test (0.5–1.3 mg Pb kg^?1, 8–10 mg Cu kg^?1, and 144–214 mg Zn kg^?1 ; 95% confidence limits). Only Cd concentrations were highest at Omaha Beach (8.6–12.1 mg Cd kg^?1 ). This result may have arisen from “naturally” increased bio‐availabilities of certain metals in mangrove systems which are reported in the literature. Generally, metal concentrations in barnacles from the Auckland Harbour area and from Omaha Beach were within the wider range for E. modestus as well as other barnacle species reported in the international literature.     

Subcellular Distribution of Heavy Metals in Organs of BivalveModiolus Modiolus Living Along a Metal Contamination Gradient

Concentration and distribution of Fe, Zn, Cu, Cd, Mn, Pb, Ni among subcellular fractions (cellular membrane structures and cytosol) and Zn, Cu, Cd among cytoplasmic proteins in the kidney and digestive gland of musselModiolus modiolus living along a polymetallic concentration gradient were studied. It was found in the kidney ofM. modiolus from contaminated sites that the Fe percent increased in the “membrane” fraction, whereas Zn, Pb, Ni and Mn percent increased in the cytosol compared to the kidney of the control mussel. Note kidney cytosol ofM. modiolus from clean and contaminated sites sequestered major parts of Cu and Cd. In the digestive gland ofM. modiolus from contaminated sites Fe, Zn, Cd, Mn, Ni percent increased in the “membrane” fraction, whereas Cu, Pb percent increased in the cytosol compared to digestive gland of control mussel. Gel-filtration chromatography shows kidney ofM. modiolus contains increased metallothionein-like protein levels irrespective of ambient dissolved metal concentrations. It was shown that the metal detoxification system in the kidney and digestive gland ofM. modiolus was efficient under extremely high ambient metal levels. However, under complex environmental contamination in the kidney ofM. modiolus, the metal detoxification capacity of metallothionein-like proteins was damaged.     

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.     

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.     

Level and fate of heavy metals in the Changjiang estuary and its adjacent waters

Dissolved concentrations of Cu, Pb, Zn, and Cd were measured in the Changjiang estuary and its adjacent waters. The results indicate that the ranges of dissolved heavy metals in the studied waters are as follows: Cu = 1.0−6.9 μg/L, Pb = 0.10−0.39 μg/L, Zn = 3.2−9.1 μg/L, and Cd = 0.011−0.049 μg/L. The behavior of the dissolved Cu was essentially conservative, but a high scatter was observed for the high salinity samples, and it is the same with Zn and Pb. The overall concentrations of dissolved Cd increase with the salinity. There were no differences between the surface, middle, and bottom layer for Cu, Pb, Zn, and Cd. Seasonal changes of their averages were not obvious on the whole. River discharges, sedimentary dynamics, and biological processes might determine the profiles of heavy metals. The text was submitted by the authors in English.     

红海湾底质重金属分布与背景值探讨

红海湾表层沉积物中Zn,Cd,Cu,Pb含量呈湾顶高于湾中部和湾口的分布特征,在河口潮间带形成污染区。根据背景区沉积物重金属平均含量和2倍标准差,提出用红海湾表层沉积物中Zn,Cd,Cu,Pb,Ni,Cr的背景上限（分别为90,0.65,20,55,30,45mg·kg~-1干重）作为背景参考值。红海湾表层沉积物中Zn,Cd,Cu,Pb呈显著的正相关关系,推测四者具有相似的来源。     

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.     

Natural and anthropogenic sources of Hg,Cd, Pb,Cu and Zn in seawater and sediment of Mljet National Park,Croatia

Distributions of Hg, Cd, Pb, Cu and Zn in seawater and sediment from Mljet National Park, Adriatic Sea are presented for the first time. Natural and anthropogenic factors play an important role in determining resultant trace metals' concentrations in the region. We place particular emphasis on the saline “lakes” of Malo Jezero and Veliko Jezero, which have restricted flows of seawater. In Malo Jezero lake, fresh karstic spring water generated by flooding, and weathering of dolomites are the main sources of naturally elevated Cd, Pb and Zn concentrations (20.7 ± 1.6, 289 ± 19, 1260 ± 0.08 ng L^?1, respectively); anthropogenic input is negligible. In Veliko Jezero lake enhanced Cu and Zn contents originate from anthropogenic input (tourism and agriculture). Distributions of the Pb and Zn in the water columns of both lakes are influenced by natural aragonite precipitation and sedimentation. Exceptionally high total Hg concentrations of 24.2 and 33.7 ng L^?1 in the water column of Malo Jezero, sampled during periods of high rainfall associated with strong eastern winds, suggest an airborne input. Total Hg concentrations in waters of both lakes are elevated because of inefficient mixing. Two different metal distribution patterns exist in the sediment columns. First, Hg, Pb, Cu and Zn show elevated concentrations in recent sediments due to anthropogenic input. Second, Cd content increases with depth due to reprecipitation via a downward redox boundary shift.Described natural processes, as well as anthropogenic influence, enhance levels of trace metals. Careful study followed by suitable interpretation based on geochemical data were necessary to distinguish natural from anthropogenic sources.     

Simplified synthesis of an 8-hydroxyquinoline chelating resin and a study of trace metal profiles from Jellyfish Lake, Palau

We report a simplified synthesis, and some performance characteristics, for 8-hydroxyquinoline (8-HOQ) covalently bonded to a chemically resistant TosoHaas TSK vinyl polymer resin. The resin was used to concentrate trace metals from stored, acidified seawater samples collected from Jellyfish Lake, an anoxic marine lake in the Palau Islands. The Mn, Fe, and Zn profiles determined from the 8-HOQ resin extraction were similar to those determined using Chelex-100 resin. The Zn and Cd profiles did not exhibit removal by sulfide “stripping” in contrast to other anoxic marine basins. The profiles of Co and Ni also exhibited elevated concentrations in the anoxic hypolimnion. The solution speciation and saturation states for the metals were calculated using revised metal-bisulfide stability constants. The calculations suggest that the MS(HS)⁻ species dominates the solution speciation for Mn, Co, Ni, Zn, Cd, and Pb. Cu(I) is modeled as the CuS⁻ or Cu(HS)₂⁻ species, while Fe(II) behaves as the free Fe²⁺ cation. The Mn, Co, Ni, Cu and Cd concentrations appeared to be at least 10-fold undersaturated, while the Fe(II), Zn, and Pb concentrations were close to saturation with respect to their metal sulfides.     

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.     

Seasonal variability in the kinetics of Cu,Pb, Cd and Hg accumulation by macroalgae

Here it is demonstrated that both Porphyra spp. and Enteromorpha spp. of macro-algae display similar and very marked seasonal variations in their concentration factor (CF) of Cu, Pb, Cd and Hg in field conditions. The CF variations are specific for each metal and reproducible over several years. The way variations in the biological activity affect the equilibrium and kinetics of the interaction between trace metals and live algae was studied in vitro. Natural seawater was used as the culture medium. Voltammetry was used for the determination of natural organic ligands and trace metals except Hg, which was determined by mercury cold vapour after on-line pre-concentration. Titrations with the relevant metal demonstrated that the maximum binding capacity of the algae was not significantly dependent on the season for Pb (ca. 100 μmol g_{dry algae}⁻¹), Cd (ca. 50 μmol g⁻¹) and Hg (80–100 μmol g⁻¹). Marked seasonal variations were observed for Cu (ca. 40 μmol g⁻¹ in January; 70 μmol g⁻¹ in May; and 100 μmol g⁻¹ in August). The conditional stability constants of metal–algae complexation sites were seasonally independent and similar for both algae: logK_MS′=8.5±0.3 (Cu), 5.6±0.2 (Pb), 5.3±0.2 (Cd) and 18.0±0.3 (Hg). Exudates with a strong Cu complexing capacity (logK′_CuL=12.47±0.06) were determined in cultures with added Cu, Pb or Cd concentrations, and identified by cathodic stripping voltammetry (CSV) as cysteine or glutathione. All the tested metals promoted the liberation of exudates, both cysteine- and glutathione-like ligands were exuded in the presence of Cu, only cysteine-like ligands in the presence of Pb, and only glutathione-like ligands in the presence of Cd, the rise depending of the season of the year, particularly for Cu. Highest levels were produced in the presence of added Pb. When exposed to either 1- or 100-μM total dissolved metal concentrations, the metal uptake, and its rate, varied with the season and the algae.     

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.     

海水养殖池沉积物中重金属形态和生物酶活性的关系研究

以连云港市对虾养殖池表层沉积物为研究对象,采用Tessier连续萃取法,研究了表层沉积物中重金属(Cu、Zn、Pb、Cd、Cr、As、Mn)的赋存形态和酶(脲酶、碱性磷酸酶、过氧化氢酶、转化酶)活性的相关性。结果表明,重金属Cu和Zn以有机-硫化物结合态为主要的赋存形态,Pb以铁锰氧化物态为主要的赋存形态,Cd以可交换态(平均33.47%)和碳酸盐结合态(平均31.16%)为主要存在形态,Cr和As主要以残渣态存在,Mn的铁锰氧化物态比例最高。脲酶的活性范围为0.45—8.96mg/(g·24h),碱性磷酸酶活性范围为2.45—6.69mg/(g·24h),过氧化氢酶活性范围为0.14—2.36m L/(g·min),转化酶活性范围为0.45—10.45mg/(g·24h)。脲酶活性与Cd、As的可交换态、Cd的碳酸盐结合态、Cu、As的铁锰氧化物态、Zn、Pb、Cd、Mn的有机硫化物态之间显著相关;碱性磷酸酶活性与Zn、Cd的铁锰氧化物态显著相关;过氧化氢酶活性与Cd的可交换态、碳酸盐结合态及残渣态、Cu、Cd、As的铁锰氧化物态、Zn、Pb、Cd、Mn的有机硫结合态之间显著相关;转化酶活性与Cu、Cd、As的可交换态、Cd的碳酸盐结合态、Cu、Cd、As的铁锰氧化物态、Zn、Pb、Cd、Mn的有机硫化物态、Cd、As的残渣态之间显著相关。酶活性可以用来指示海水养殖池沉积物中重金属的形态转化过程。     

Concentrations of the elements Ag,Al, Ca,Cd, Cu,Fe, Mg,Mn, Pb and Zn,and the radionuclides 210Pb and 210Po in the digestive gland of the squid Nototodarus gouldi

Ag, Al, Ca, Cd, Cu, Fe, Mg, Mn, Pb and Zn concentrations and ²¹⁰Po and ²¹⁰Pb activities were measured in 26 specimens of the squid Nototodarus gouldi taken from the waters of Bass Strait in one jigging operation. All the elements show wide ranges in concentrations in specimens apparently subject to the same environmental conditions. Copper concentration was 27-1 200 μg/g, and ²¹⁰Po activity 4·8–24·2 Bq/g. The animal wet weights, the elements Ag, Al, Cd, Fe and Zn, and the radionuclide ²¹⁰Po have coefficients of variation in the range 40–60%; Ca, Mg and Mn show the smallest variability (CV = < 30%), and Cu the greatest (CV = 12%). Significant correlations (p < 0·001) were found between the following pairs of elements: Cd-Zn, Cd-Cu, Zn-Cu, Mg-Mn, Fe-Mn, Ca-Mg and Fe-²¹⁰Po.