THE EFFECT OF FOUR HEAVY METALS ON THE GROWTH RATE AND CHLOROPHYLL CONTENT OF Chaetoceros muelleri LEMMERMANN

Chaetoceros muelleri Lemmermann was cultured in solution of different concentrations of Cu2 , Pb2 , Zn2 and Cd2 , and in mixtures of any two of them. After 6 days the effect of these heavy metal cations on the growth rate and chlorophyll contents of the diatom were determined and an Opton microscope was used to observe the morphology and size of the cells.The experimental results show that the effects of toxicity of these four heavy metals on Chaetoceros muelleri are: Cu2 >Pb2 >Zn2 >Cd2 . However, the cells did not differ significantly in their morphology and size from the controled ones.In any of the mixed metals cultures, its growth rate came close to and was higher than that of the single metal culture of higher concentration.     

南海多金属结壳(核)铁锰矿物/海水界面效应与成矿元素的富集

海底铁锰结壳和结核是重要的海底矿产资源,蕴含着丰富的金属元素并且具有巨大的经济价值。本文主要以南海多金属结壳（核）为研究对象,采用X射线粉晶衍射（XRD）、激光拉曼光谱、红外光谱分析（FTIR）以及X射线光电子能谱对铁锰矿物的矿物学和谱学特征进行了系统的分析和研究。粉晶衍射和拉曼光谱分析结果表明,南海多金属结壳的矿物组成为水羟锰矿、石英和长石,结核的矿物组成为钡镁锰矿、水羟锰矿、石英和长石,铁相矿物均为无定形铁氧化物/氢氧化物,并且锰相矿物和铁相矿物的结晶程度均较差。红外光谱分析结果显示多金属结核和结壳中的铁锰矿物具有大量表面羟基,这些含质子表面羟基官能团,可为海水中各成矿元素的络合提供丰富的活性位点。XPS分析表明多金属结核和结壳中铁锰矿物表面以Fe、Mn和O元素为主,其中Fe呈正三价态,Mn以正四、正三价为主,可能还含有少部分正二价态。对比南海多金属结壳（核）与太平海山结壳,南海多金属结壳（核）具有更为显著的表面羟基氧（-OH）含量,而太平洋海山结壳则以晶格氧（O^2-）为主,表明太平洋海山结壳铁锰矿物结晶程度较南海多金属结壳（核）高。综合研究表明,在海底铁锰结壳和结核中（氢）氧化锰/铁矿物与海水之间界面效应对金属离子的富集机理主要有：（1）金属离子与矿物表面羟基进行络合反应,形成以配位键相连的羟基络合物,或与表面的质子交换生成稳定的内层络合物;（2）矿物的带电表面与金属离子通过静电作用形成双电层,生成外层络合物;（3）金属离子与矿物结构中的Mn、Fe离子同晶置换而成为结构阳离子。     

可口革囊星虫(Phascolosoma esculenta)重组铁蛋白富集Pb2+等重金属特性和功能研究

利用可口革囊星虫重组铁蛋白富集Pb²⁺、Fe³⁺、Cd²⁺、Cr³⁺、Cu²⁺、Mn²⁺、Sn²⁺和Zn²⁺等8 种重金属离子后, 通过透射显微镜和傅里叶红外光谱测定蛋白的超微结构变化和内部基团特性。以 天然的马脾铁蛋白为对照, 观察重组铁蛋白与天然铁蛋白的差别。结果显示, 重组铁蛋白富集Pb²⁺ 和其它7 种重金属离子后蛋白体积大小与重金属离子种类直接相关。重组铁蛋白相对天然铁蛋白来 说在富集不同种类重金属离子后, 除了非特异性酰胺特征峰和蛋白特征峰外, 还出现一些专门富集 某些重金属离子的特异基团, 如:-CH₃、-CH₂-、-CH-、-NH-、-SO₃-、-COOH、-S=S-和-C-S-C 等。 通过细胞实验进一步验证了铁结合蛋白能够通过富集重金属离子Pb²⁺来保护小鼠成骨前体细胞 MRC3T3-E1, 使细胞的死亡率明显降低(P<0.05).     

Regulation of Tilapia metallothionein gene expression by heavy metal ions

Tilapia is a common fish species inhabiting inland waters and estuarine regions in Hong Kong and Southeast Asia, and useful for bio-monitoring of metal pollution. Metallothionein (MT) gene expression in fish tissues has been useful to sub-lethal risk assessment as biomarker of exposure to metal ions in fishes inhabiting metal contaminated area. To investigate metal inductions of Tilapia MT gene expression in vivo, Tilapias were injected with different concentrations of heavy metals and tissues were then removed for quantitative PCR assay using mimic PCR methods. All of the metal ions tested (Cu²⁺, Cd²⁺, Hg²⁺, Ni²⁺, Pb²⁺ and Zn²⁺) were able to induce hepatic MT mRNA levels. Renal MT mRNA levels of Cd²⁺ and Zn²⁺ treated fish was not induced with significant fold induction, however MT mRNA levels in gills were sensitive to the administrations of these metal ions. These data indicated that Tilapia MT mRNA levels in gills and liver are sensitive biomarker of exposure to various metal ions.     

Basin-scale distribution of NH<Subscript>4</Subscript><Superscript>+</Superscript> and NO<Subscript>2</Subscript><Superscript>−</Superscript> in the Pacific Ocean

We used more than 25,000 nutrient samples to elucidate for the first time basin-scale distributions and seasonal changes of surface ammonium (NH₄ ⁺) and nitrite (NO₂ ^?) concentrations in the Pacific Ocean. The highest NH₄ ⁺, NO₂ ^?, and nitrate (NO₃ ^?) concentrations were observed north of 40°N, in the coastal upwelling region off the coast of Mexico, and in the Tasman Sea. NH₄ ⁺ concentrations were elevated during May–October in the western subarctic North Pacific, May–December in the eastern subarctic North Pacific, and June–September in the subtropical South Pacific. NO₂ ^? concentrations were highest in winter in both hemispheres. The seasonal cycle of NH₄ ⁺ was synchronous with NO₂ ^?, NO₃ ^?, and satellite chlorophyll a concentrations in the western subtropical South Pacific, whereas it was synchronous with chlorophyll-a but out of phase with NO₂ ^? and NO₃ ^? in the subarctic regions.     

Effects of heavy metals on phagocytosis by Molluscan hemocytes

The effects of ten heavy metal cations on phagocytosis of polystyrene latex spheres by hemocytes of the American oyster, Crassostreavirginica, were investigated. Exposure to 1 and 5 ppm Cd²⁺, 5 ppm Co²⁺, 1 ppm Cr³⁺, 1 ppm Cu²⁺, 0·5 ppm Fe³⁺, 0·05 ppm Hg²⁺, 1 and 5 ppm Mn²⁺, 1 and 5 ppm Pb²⁺, 1 ppm Sn²⁺, and 1 and 5 ppm Zn²⁺ resulted in no alteration of phagocytic ability. However, exposure to 1 ppm Co²⁺, 5 ppm Cu³⁺, 5 ppm Cu²⁺, 1 and 5 ppm Fe³⁺, 0·1 ppm Hg²⁺ and 5 ppm Sn²⁺ resulted in significantly enhanced uptake of polystyrene spheres. Finally, exposure to 0·5, 1 and 5 ppm Hg²⁺ resulted in inhibition of phagocytosis and increased cell death.     

Cd~(2+)对青蛤(Cyclina sinensis)的毒性及蓄积过程研究

利用水生动物急性毒性实验方法,在6个浓度下Cd2+对青蛤的急性毒性进行测定,经回归分析后,得到Cd2+对青蛤96h半致死浓度为20.09mg/L,安全浓度为0.201mg/L。分别对半致死浓度和安全浓度下Cd2+在青蛤体内不同组织的蓄积情况进行了分析。结果表明,在半致死浓度条件下,168h青蛤各组织Cd2+的含量依次为肌肉内脏团鳃;而在安全浓度下,其结果为内脏团鳃肌肉,内脏团对于Cd2+富集能力远高于肌肉。讨论了青蛤的养殖环境及产品检验等问题。     

Cd2+和Cu2+对泥蚶的急性毒性和联合毒性试验

为了解重金属Cd2+和Cu2+对泥蚶的毒害程度和泥蚶对重金属Cd2+和Cu2+的解毒能力,用毒理学实验方法研究了Cd2+和Cu2+对泥蚶(Tegillarca granosa)的急性毒性和联合毒性效应。结果表明:Cd2+、Cu2+对泥蚶的96 h半致死质量浓度分别为6.189、0.460 mg/L;安全质量浓度分别为0.062、0.005 mg/L;相对毒性Cu2+Cd2+。在1︰1毒性单位的联合作用下,Cd2+和Cu2+对泥蚶96 h的半致死质量浓度分别为1.984、0.147 mg/L;安全质量浓度分别为0.020、0.001 mg/L。2种重金属离子的联合毒性大于任一重金属离子的毒性,联合毒性表现为协同作用。     

Incorporation rate measurements of <Superscript>10</Superscript>Be, <Superscript>230</Superscript>Th, <Superscript>231</Superscript>Pa,and <Superscript>239,240</Superscript>Pu radionuclides in manganese crust in the Pacific Ocean: A search for extraterrestrial material

In order to estimate the deposition rate of extraterrestrial material onto a manganese crust in a search for supernova debris, we analyzed the contents of ¹⁰Be, ²³⁰Th, ²³¹Pa, and ^239,240Pu in a sample of manganese crust collected from the North Pacific Ocean. On the basis of the depth profile of ¹⁰Be, the growth rate of the manganese crust was determined to be 2.3 mm Myr⁻¹. The uptake rates of ¹⁰Be, ²³⁰Th, and ²³¹Pa onto the manganese crust were estimated to be 0.22–0.44%, 0.11–0.73%, and 1.4–4.5%, respectively, as compared to the deposition rates onto the deep-sea sediments near the sampling station, while that for ^239,240Pu was 0.14% as compared to the total inventory of seawater and sediment column. Assuming that sinking particles represent 0.11–4.5% of the uptake rates, the deposition rate of extraterrestrial material onto the manganese crust was estimated to be 2–800 μg cm⁻²Myr⁻¹ according to the uptake of ¹⁰Be onto the manganese crust. Further, our estimate is similar to the value of 9–90 μg cm^{− 2}Myr⁻¹ obtained using the integrated global production rate of ¹⁰Be and the deposition rate of ¹⁰Be onto the manganese crust.     

Chelation of divalent metal ions by brown algal polyphenols

High-molecular-weight, nondialyzable polyphloroglucinols from the marine brown algae Ascophyllum nodosum and Fucus vesiculosus (Phaeophyceae, Fucales) chelate the divalent metal ions Sr²⁺, Mg²⁺, Ca²⁺, Be²⁺, Mn²⁺, Cd²⁺, Co²⁺, Zn²⁺, Ni²⁺, Pb²⁺ and Cu²⁺ in weakly acidic aqueous solution. Values of the relative selectivity coefficients k have been calculated relative to Mn²⁺; the ionotropic series with the algal polyphenols are similar to those with catechol and pyrogallol. These studies may serve as a guide for the examination of metal chelation by brown algal polyphenols both in situ and after exudation into seawater.     

重金属Cu、Pb在泥鳅(Misgurnus anguillicaudatus)卵巢的蓄积特性及其对卵细胞发育的影响

采用静水法生物测试手段,研究了不同浓度梯度Cu、Pb(各0.00、0.10、0.25、0.50mg/L)随时间变化在泥鳅卵巢中的蓄积特性以及对卵细胞发育的影响。结果表明,泥鳅卵巢对Cu、Pb有较强的蓄积能力,在暴露期间20天内,蓄积量与时间呈线性关系,之后呈对数关系。其中,Cu的蓄积显著大于Pb(P0.01);卵巢中重金属的蓄积与水溶液中Cu、Pb的浓度梯度相关(P0.01),具有明显的时间效应和剂量效应。泥鳅卵巢中卵细胞的发育水平,亦与溶液重金属浓度的高低、暴露时间长短有关;在不同浓度重金属溶液中较长时间的暴露,将对卵巢及卵细胞的发育产生不可逆转的负效应。     

Adsorption of lead and cadmium ions on calcite in the Krka estuary

The adsorption of Pb²⁺ and of Cd²⁺ ions from calcareous Krka river water of various salinities (3, 14, 20 and 38 psu) on calcite (CaCO₃, Merck p.a.) was investigated. Simultaneous adsorption of Pb²⁺ and Cd²⁺ ions was studied as well. The results suggest that the two ions are adsorbed at different calcite surface sites; Pb²⁺ remained firmly bound to calcite at all salinities, whereas Cd²⁺ was firmly bound at low salinities and released at high salinities. Dissolved natural organic ligands at the freshwater-seawater interface (FSI; at 14 psu) promoted and below the FSI (at 20 psu) decreased the adsorption of Cd²⁺. The experiments were performed at metal concentrations of 8 × 10⁻⁸ mol l⁻¹ and at natural pH values around pH 8. Adsorbed amounts of trace metal ions were determined in filtered samples by differential pulse anodic stripping voltammetry (DPASV) with a three-electrode system, after 24 h of equilibration with calcite. Several adsorption models were tested, such as Freundlich's, Langmuir's and Schindler-Stumm's surface coordination model. Adsorption isotherms belong to S-1 class of empirical adsorption isotherms. None gave reasonable values of adsorption constants. The fractional partitioning of adsorbent to the solid phase when normalized to the quantity of adsorbent present (K_d) declined as solid concentration increased. It was found that the surface charge is not responsible for the observed effect. Instead, aggregate size increased, which effected a loss in surface area. This is a reasonable explanation for the observed S-shaped adsorption isotherms curves.     

Inhibitory effects of divalent metal ions on liver microsomal 7-ethoxyresorufin O-deethylase (EROD) activity of leaping mullet

The purpose of the present study was to elucidate in vitro effects of Hg²⁺, Zn²⁺, Ni²⁺ and Cd²⁺ on cytochrome P4501A1 (CYP1A1) dependent EROD activities in leaping mullet liver microsomes. Fish captured from the most polluted part of Izmir Bay, had highly elevated EROD activities, and induced CYP1A1 protein levels as determined by Western blotting. Although all of the metal ions caused inhibition of the initial velocity of the reaction, Hg²⁺ and Cd²⁺ exhibited much higher inhibitory effect at lower concentrations and they were evidently more potent inhibitors than others. The inhibitor concentration giving 50% inhibition (IC₅₀ values) of Zn²⁺, Ni²⁺, Cd²⁺ and Hg²⁺ of initial EROD activity were 107, 16, 1.3 and 0.15 micromolar, respectively. Glutathione (GSH) at 0.5 mM final concentration, completely reversed Ni²⁺ and Cd²⁺ inhibition of EROD activity indicating the protective action of GSH.     

<Superscript>234</Superscript>Th/<Superscript>238</Superscript>U disequilibrium and particulate organic carbon export in the northern South China Sea

We utilized ²³⁴Th, a naturally occurring radionuclide, to quantify the particulate organic carbon (POC) export rates in the northern South China Sea (SCS) based on data collected in July 2000 (summer), May 2001 (spring) and November 2002 (autumn). Th-234 deficit was enhanced with depth in the euphotic zone, reaching a subsurface maximum at the Chl-a maximum in most cases, as commonly observed in many oceanic regimes. Th-234 was in general in equilibrium with ²³⁸U at a depth of ∼100 m, the bottom of the euphotic zone. In this study the ²³⁴Th deficit appeared to be less significant in November than in July and May. A surface excess of ²³⁴Th relative to ²³⁸U was found in the summer over the shelf of the northern SCS, most likely due to the accumulation of suspended particles entrapped by a salinity front. Comparison of the ²³⁴Th fluxes from the upper 10 m water column between 2-D and traditional 1-D models revealed agreement within the errors of estimation, suggesting the applicability of the 1-D model to this particular shelf region. 1-D model-based ²³⁴Th fluxes were converted to POC export rates using the ratios of bottle POC to ²³⁴Th. The values ranged from 5.3 to 26.6 mmol C m⁻²d⁻¹ and were slightly higher than those in the southern SCS and other oligotrophic areas. POC export overall showed larger values in spring and summer than in autumn, the seasonality of which was, however, not significant. The highest POC export rate (26.6 mmol C m⁻²d⁻¹) appeared at the shelf break in spring (May), when Chl-a increased and the community structure changed from pico-phytoplankton (<2 μm) dominated to nano-phytoplankton (2–20 μm) and micro-phytoplankton (20–200 μm) dominated.     

Seasonal export fluxes of particulate organic carbon from <Superscript>234</Superscript>Th/<Superscript>238</Superscript>U disequilibrium measurements in the Ulleung Basin<Superscript>1</Superscript> (Tsushima Basin) of the East Sea<Superscript>1</Superscript> (Sea of Japan)

Export fluxes of particulate organic carbon (POC) were estimated from the ²³⁴Th/²³⁸U disequilibrium in the Ulleung Basin¹ (UB) of the East/Japan Sea¹ (EJS) over four seasons. The fluxes were calculated by multiplying the average POC/²³⁴Th ratio of sinking particles larger than 0.7 μm at 100- and 200-m water depths to ²³⁴Th fluxes by the integrated ²³⁴Th/²³⁸U disequilibrium from the surface to 100-m water depth. In spring, the ²³⁴Th profiles changed dramatically with sampling time, and hence a non-steady-state ²³⁴Th model was used to estimate the ²³⁴Th fluxes. The ²³⁴Th flux estimated from the non-steady-state model was an order of magnitude higher than that estimated from the steady-state model. The ²³⁴Th fluxes estimated using the steady-state model showed distinct seasonal variation, with high values in summer and winter and low values in autumn. In spring, the phytoplankton biomass had the highest value, and primary production was higher than in summer and autumn, but the ²³⁴Th fluxes were moderate. However, these values might have been significantly underestimated, as the ²³⁴Th fluxes were estimated using the steady-state model. The POC export fluxes estimated in autumn were about four times lower than those in other seasons when they were rather similar. The annually averaged POC flux was estimated to be 161 ± 76 mgC m⁻² day⁻¹, which was somewhat lower than that in highly productive coastal areas, and higher than that in oligotrophic regions. The export/primary production (ThE) ratios ranged from 7.0 to 56.1%, with higher values in spring and summer and lower values in autumn and winter. In summer, a high ThE ratio of 48.4 ± 7.0% was measured. This may be attributed to the mass diatom sinking event following nitrate depletion. In the UB¹, the annually averaged ThE ratio was estimated to be 34.4 ± 12.9%, much higher than that in oligotrophic oceans. The high ThE ratio may have contributed to the high organic carbon accumulation in the UB¹.     

Nearshore scavenging phenomenon elucidated by <Superscript>234</Superscript>th/<Superscript>238</Superscript>u disequilibrium in the coastal waters off Western Taiwan

Dissolved and particulate ²³⁴Th activities in surface seawater were determined at 27 stations along the coastline of western Taiwan during 19–23 November 2004. Contrasting scavenging settings were observed between the northern and southern regimes of the nearshore water off western Taiwan, separated by the Cho-Shui River. The northern regime is characterized by a large quantity of suspended load contributed by northward transport of a suspension plume from the Cho-Shui River, while the southern regime, low in suspended load and high in chlorophyll concentration, is a system controlled by biological activity. A scavenging model that takes account of the physical transport was used to estimate the ²³⁴Th budget in order to estimate the scavenging and removal rates from the nearshore water. The scavenging and removal rates ranged from 21 to 127 dpm m⁻³d⁻¹ and from 36 to 525 dpm m⁻³d⁻¹, for dissolved and particulate ²³⁴Th, respectively. The removal fluxes of particulate organic carbon (POC) and particulate organic nitrogen (PON) were estimated by multiplying the particulate ²³⁴Th removal flux to the organic carbon/²³⁴Th and nitrogen/²³⁴Th ratios in suspended particles, which ranged from 4.5 to 275.2 mmol-C m⁻²d⁻¹ and from 1.3 to 50.1 mmol-N m⁻²d⁻¹, respectively. These fluxes resulted in residence times of 1∼20 days for the POC in the surface water of nearshore water off western Taiwan.     

Complexation of dimethylsulfide with mercuric ion in aqueous solutions

The tendency of dimethylsulfide (DMS) to form complexes with heavy metal ions in aqueous solutions and the factors that influence it have been investigated. Among five heavy metal ions examined (Cu²⁺, Cd²⁺, Zn²⁺, Pb²⁺ and Hg²⁺), only Hg²⁺ bound significantly with DMS in aqueous solutions in which Hg²⁺ concentration was increased to much higher levels than that of natural seawater. The complexation capacity of Hg²⁺ for DMS was influenced by pH and media. The affinity of Hg²⁺ for DMS was generally lower at high than at low pH, presumably due to the competition of hydroxide ion to form hydroxomercury species. In different solutions, the affinity of Hg²⁺ for DMS followed the following sequence: ultra-purified water > 35‰ NaCl solution > seawater. It seems apparent that chloride had a negative impact on the complexation of DMS by Hg²⁺, owing to the competition of chloride with DMS for complexing Hg²⁺. In addition, the affinity of Hg²⁺ for DMS in the bulk seawater appeared to be higher than that in the surface microlayer seawater. The tendency of Hg²⁺ to form complexes with DMS in aqueous solution can be reduced by the presence of 2 mM amino-acid such as glycine, alanine, serine and cysteine, as these ligands give stable mercury complexes. However, the presence of 2 mM acetate in experimental solutions had no significant effect on the complexation of Hg²⁺ with DMS, even though this ligand has a relatively strong complexing capacity for Hg²⁺. Although mercury ions appeared to have a strong affinity for DMS, the concentration of mercury in seawater is too low to produce a great effect on the distribution of DMS in oceans.     

镉和汞两种重金属离子对四角蛤蜊的急性毒性

采用毒理学实验方法,比较研究了Cd~(2+)和Hg~(2+)对四角蛤蜊(Mactra veneriformis Reeve)急性毒性效应的差异,以期为进一步评价重金属离子对四角蛤蜊的毒性效应和作用机理等提供理论依据.死亡概率单位和实验液浓度对数的线性回归分析表明,Cd~(2+)对四角蛤蜊在24、48和96 h的半致死浓度(LC_(50))分别为15.961、5.149和2.383 mg/L,Hg~(2+)的LC_(50)分别为3.714、0.607和0.207 mg/L;Cd~(2+) 和Hg~(2+) 对四角蛤蜊的安全质量浓度分别为0.023 8 mg/L和0.002 1 mg/L,分别是我国渔业水质标准(GB11607-89)限定量的4.76倍和4.02倍.     

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.