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.     

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.     

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。     

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.     

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.     

ECOLOGICAL DISTRIBUTION OF HYDROCARBON-DEGRADATION BACTERIA IN XIAMEN HARBOR

The ecology of hydrocarbon-degrading bacteria were investigated during five cruises in Xiamen Harbor. The results demonstrated that number of hydrocarbon-degrading bacteria were 2.1×102-7.5×106 cell/1 and 1.7×102-1.5×106 ceil/g dry and hetcrotrophic bacteria were 3.0× 104-5.9× 109 cell/1 and 2.53× 103-5.0× 103 cell/g dry in seawater and sediment respectively. The isolated strains which can degrade the petroleum belong to fifteen genera. Most, strains can only degsade one kind of hydro- carbon or petroleum. The results showed that the population and the species-composition of hydro carbon-degrading microorganisms were positively correlated with existing level of oil pollution and with water temperature, but independent of total microbtat count.     

黄渤海典型鳗草海草床重金属生态风险评估

为全面了解我国黄渤海鳗草(Zostera marina L.)床重金属污染水平, 本研究以大连林阳北海、葫芦岛兴城、唐山乐亭-曹妃甸和青岛湾四处鳗草床为研究对象。于夏季采集鳗草、海水和沉积物样品并分析其重金属(Cu、Zn、Pb和Cd)含量。以此分析海草的重金属富集特征, 并对比评估不同鳗草床重金属潜在生态风险。结果表明, 夏季四处鳗草床海水重金属含量由高到低依次为: Zn > Cu > Pb > Cd, 均低于国家一级水质标准; 对沉积物来说, 重金属含量由高到低依次为: Zn > Pb > Cu > Cd, 均低于国家一级沉积物质量标准。鳗草对重金属的富集因重金属种类和海草积累部位而异, 其地上组织对Cu、Zn、Cd的富集能力高于地下组织。研究区域海水中Cu、Zn、Pb和Cd潜在风险等级均处于低风险水平。而对沉积物而言, 葫芦岛兴城鳗草床Cd的潜在风险等级处于较高风险水平(E_i值为156.9)。唐山乐亭-曹妃甸和青岛湾鳗草床的地质累积指数(I_geo)由大到小依次为: Cd > Pb > Zn > Cu。综合所有元素的潜在生态风险指数(I_R), 葫芦岛兴城鳗草床的潜在生态风险值最高。     

Stoichiometry among bioactive trace metals in the Chukchi and Beaufort Seas

The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater was investigated in the Chukchi and Beaufort Seas of the western Arctic Ocean in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable metal (TDM) and dissolved metal (DM), respectively. The concentration of labile particulate metal (LPM) was estimated with the difference between that of TDM and DM. The concentrations of TDAl, TDMn, TDFe, TDCo and TDPb varied substantially in the study area. The high concentrations occurred at stations near the Bering Strait, in the Mackenzie delta, and above reductive sediments on the shelf and slope. These elements were mostly dominated by labile particulate species, such as Fe?CMn oxides and species adsorbed on terrestrial clay. DCo was correlated with DMn over the study area (r?=?0.78, n?=?135), and the slope of the regression line was 27 times higher at a pelagic station than at a shelf station. TDNi, TDCu, TDZn and TDCd showed relatively small variations and were generally dominated by dissolved species. There was a moderate correlation between DCd and phosphate for all samples (r?=?0.79), whereas there were no significant correlation between the other DMs and nutrients. TDNi and TDCu showed a remarkable linearity for most stations except those near the Bering Strait (R ²?=?0.95, n?=?126). These results suggest that biogeochemical cycling including uptake by phytoplankton and remineralization from settling particles has only minor control over the distribution of trace metals in this area. Using the present data, the annual input of bioactive trace metals form the Bering Strait and the Mackenzie River was estimated. Also, the trace metal compositions of major water masses were evaluated. The dissolved elemental ratio was P:Al:Mn:Fe:Co:Ni:Cu:Zn:Cd?=?1:1.2?×?10^?2:4.4?×?10^?4:1.4?×?10^?3:3.7?×?10^?5:3.7?×?10^?3:1.4?×?10^?3:4.5?×?10^?3:2.2?×?10^?4 for Canada Basin deep water (CBDW). This ratio was significantly different from that for Pacific deep water and Bering Sea water, suggesting substantial modification of the trace metal compositions of seawater in the study area.     

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.     

Chemical fractionation of zinc versus cadmium among other metals nickel, copper and lead in the northern North Sea

Concentrations of dissolved Ni, Cu, Zn, Cd and Pb were measured in water samples collected during a cruise with R.V Pelagia (29-6/14-7-1993) in the northern North Sea and N.E. Atlantic Ocean. At least six depths (0–90 m) were sampled with modified Go-Flo samplers from a rubber zodiac. In the study area, the first 25 m were well mixed and stratification occurred below this depth. The local bloom of Emiliania huxleyi hardly affected the trace metals concentration, except for some removal of Cd as seen from its correlation with nitrate. The mean dissolved concentrations were for Ni (3.66 nM), Cu (1.61 nM), Zn (4.5 nM), Cd (48 pM) and Pb (108 pM). These concentrations are among the lowest reported for the North Sea and are of similar magnitude to those found in the eastern North Atlantic at the same latitude. Zn was the only exception with values 10 times higher compared to those in the Atlantic Ocean, suggesting external inputs, mainly atmospheric and possibly from surrounding land masses. The observed ratio Zn:Cd in the North Sea and estuaries is in between the high ratio 600–900 for continental sources and the low ratio 5–10 for oceanic waters. Latter low ratio is consistent with the 21-fold stronger inorganic complexation of Cd in seawater which, in combination with the preferential biological uptake of Zn, may lead to the observed about hundredfold fractionation of Zn versus Cd in the marine system. Other processes may play a role but would need further investigation. The dissolved Pb values tend to be lower than found before in the North Sea, indicating decreasing inventories due to reduced anthropogenic emissions.     

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.     

2012年南海西北陆架冬季水文特征的观测分析

本文基于2012年12月南海西北部陆架海区的温盐和流速实测资料,分析了粤西和琼东陆架海区冬季三维温、盐结构和流场特征,给出沿陆架和跨陆架方向的水体和热盐通量。结果表明：（1）在50m以浅,粤西和琼东海区温度均由近岸向外海递增,深层则相反;冬季近岸海区混合层较深,外海密度跃层位于60—120m深度且层结较强,浮力频率大于10^–2/s;（2）海流大致沿等深线向西南流动,30m以深流速大小在0.03—0.40m/s之间,且随着深度增加而略有减小;琼东海区100m等深线附近在60m以浅水层观测到水体辐聚并有明显温度锋面存在;（3）沿陆架方向的水体和热盐输送均大于跨陆架方向,其中粤西单位面积沿/跨陆架水体通量平均值为0.13×10^–6/0.03×10^–6Sv/m²,低于琼东海区的0.91×10^–6/0.56×10^–6Sv/m²。     

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.     

海洋酸化对海水青鳉胚胎骨骼发育的影响

本文在实验室模拟近期海洋酸化水平,对海洋酸化对海水青鳉鱼(Oryzia melastigma)胚胎骨骼发育的影响进行了初步研究。实验中,通过往实验水体中充入一定浓度CO2气体酸化海水。对照组CO2分压为450×10-6,两个处理组CO2浓度分别为1 160×10-6和1 783×10-6,对应的水体pH值分别为8.14,7.85和7.67。将海水青鳉鱼受精卵放入实验水体中至仔鱼孵化出膜,对初孵仔鱼经骨骼染色、显微拍照,挑取了仔鱼头部、躯干及尾部骨骼染色清晰的28个骨骼参数的长度进行了显微软件测量及数据统计分析。结果发现,酸化处理对实验鱼所测量的骨骼长度影响均不显著。因此推测,未来100~200年间海洋酸化对海水青鳉鱼的胚胎及初孵仔鱼的骨骼发育没有显著影响。     

渤海中部沉积物铅来源的同位素示踪

本研究对渤海中部表层和柱状沉积物中Pb的含量和同位素进行了分析,研究了其时空分布规律,并探讨了其物质来源。结果表明,表层沉积物中Pb的含量为14.54×10-6~59.42×10-6,其含量在渤海湾近岸、黄河口附近、研究区的东北部较高,而在研究区的中部和渤海湾北部含量较低;Pb同位素207Pb/206Pb的值为0.8341~0.8489,208Pb/206Pb的值为2.0828~2.0980。岩心沉积物中Pb含量、同位素组成与表层沉积物相似,整体上较为稳定,但在1990s以来呈现增大的趋势。渤海中部沉积物中Pb以自然来源为主,黄河沉积物是其主要物质来源,但渤海湾北端则与滦河源物质或沿岸侵蚀相关;人类活动影响主要出现在1990s以后,与中国含Pb矿石的燃烧等工业活动相关,但影响微弱,仅在黄河口西北近岸海域、渤海湾等个别站位得到体现。     

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.     

多肽菌素在长牡蛎人工育苗生产中的应用

多肽菌素作为一类具有抗菌活性的生物短肽,是一种可以替代抗生素的生物肽。为了推广多肽菌素在水产养殖中的应用,本研究以长牡蛎(Crassostreagigas)人工育苗为基础,以添加2×10_(–6) mol/L青霉素钠为对照组,以添加5个不同浓度(2×10_(–6)、4×10_(–6)、6×10_(–6)、8×10_(–6)、10×10_(–6) mol/L)多肽菌素为实验组,研究多肽菌素在长牡蛎人工育苗生产中的应用。结果显示:(1)在长牡蛎种贝培育方面,培育前8天各组差异不显著(P 0.05),培育后期添加6×10_(–6) mol/L多肽菌素组存活率均最高,对照组最低,且培育至32天时该实验组均显著高于其他组(P0.05)。(2)在长牡蛎幼虫培育方面,幼虫壳高日增长量在添加6×10_(–6) mol/L多肽菌素组中最大,为11.57μm/d,而对照组仅为9.61μm/d;幼虫存活率方面对照组始终最低,而添加6×10_(–6) mol/L与8×10_(–6) mol/L多肽菌素组均保持较高存活率,显著高于对照组(P 0.05)。(3)在长牡蛎幼虫附着变态方面,添加6×10_(–6) mol/L多肽菌素组附着率最高、附着时间最短,且均与对照组差异显著(P0.05)。(4)在长牡蛎稚贝培育方面,稚贝壳长日增长量实验组均高于对照组,且随添加浓度的上升,日增长量也随之增加;稚贝存活率在添加6×10_(–6) mol/L多肽菌素组达到最高,与对照组差异显著(P0.05)。结果表明,使用多肽菌素与使用青霉素钠相比,多肽菌素显著提高了整个牡蛎培育过程中的存活率、生长速度、及附着变态率,这也为多肽菌素在贝类育苗生产中的推广提供了基础依据。     

Assessment of a Sr isotope vital effect (87Sr/86Sr) in marine taxa from Lee Stocking Island, Bahamas

 Data from Lee Stocking Island, Bahamas, confirms the hypothesis that there are no vital effects with the uptake of Sr isotopes (⁸⁷Sr/⁸⁶Sr) at the present mass spectrometer resolution [±2×10^-5 (2σ)]. Our data set contains analyses of 40 samples derived from 37 different calcareous taxa inhabiting a wide range of carbonate subenvironments (i.e., reefal, intertidal, supratidal, mangrove). The mean value of our analyses was 0.709179 with a standard deviation of 2.4×10^-5 (2σ) which was very close to the long-term uncertainty of the strontium isotope methodology [±2.0×10^-5 (2σ)] and to the widely reported ⁸⁷Sr/⁸⁶Sr value of seawater, which clusters around 0.709175. Received: 14 October 1997 / Revision received: 20 March 1998     

Experiments on the uptake of zinc and cadmium by manganese oxides

Experiments on the uptake of Zn and Cd by synthetic hydrous Mn oxides were carried out in an ionic medium at pH 3.5 and at pH 4. A slight preference for uptake of Cd²⁺ over Zn²⁺ was observed with both birnessite and nsutite, the Cd/Zn ratio being different for each mineral. Subsequently, the desorption of Zn and Cd from the obtained products in artificial seawater was studied. In this medium Cd is desorbed from the Mn oxides to a much higher extent than is Zn. The latter observations can be satisfactorily explained by the large difference of complex formation for the two metals in seawater, slightly counteracted by the preferential uptake of Cd²⁺ over Zn²⁺. The order of magnitude of the Zn/Cd ratio in natural manganese nodules is compatible with the ratio calculated on the basis of experimental results, taking fair estimates of the actual inorganic Zn/Cd ratio in seawater and of the pH of deep ocean water.