The effect of estrogen on cadmium distribution in rainbow trout (Oncorhynchus mykiss)

The effects of injections of 17β-estradiol (E2) and Cd, on the distribution of Cd and the induction of metallothionein (MT) mRNA and vitellogenin mRNA was investigated. Bone and liver were the main organs accumulating Cd. However, E2 redirected the metal accumulation from the bone and liver to the gill, gut and muscle upon exposure to E2. Cd did not induce the hepatic MT mRNA levels in animals treated with E2. The VTG mRNA levels were also reduced following co-injection of E2 and Cd. However, the kidney responded to Cd exposure by upregulating MT mRNA even in the presence of E2 treatment. In the liver the reduced MT mRNA induction led to a redistribution of CD from MT to non-MT proteins. The toxicological significance of these alterations in Cd handling remains to be determined.     

The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

Cd2+与Zn2+的联合效应对马氏珠母贝(Pinctada martensii)受精率的影响

采用中心组合设计和响应曲面法在实验室条件下研究了Cd2+与Zn2+对马氏珠母贝受精率的影响。Cd2+、Zn2+的浓度范围分别为0.030—20mg/L、0.100—20mg/L。结果表明:Cd2+与Zn2+两因子对马氏珠母贝受精率的一次效应极显著(P<0.01);Cd2+与Zn2+两因子一次互作效应极显著(P<0.01)。经响应曲面法分析,随着Cd2+与Zn2+浓度的增加受精率呈下降趋势,当Zn2+浓度在最低浓度(0.100mg/L)时,受精率随着Cd2+浓度的上升而下降;当Cd2+浓度在最低浓度(0.030mg/L)时,受精率随Zn2+浓度的上升而先下降后升高。本实验建立了马氏珠母贝受精率与Cd2+、Zn2+间关系的模型方程(R2=0.996,Adj.R2=0.987,Pred.R2=0.887,P<0.01)并可用于预测Cd2+、Zn2+对马氏珠母贝受精率的影响。     

Kinetics of Cd accumulation and elimination in tissues of juvenile rockfish (Sebastes schlegeli) exposed to dietary Cd

Cadmium (Cd) accumulation and elimination were investigated in the tissues (gill, intestine, kidney, lever and muscle) of juvenile rockfish, Sebastes schlegeli, after sub-chronic dietary Cd exposure (0, 0.5, 5, 25 and 125 mg/kg). No mortality occurred during the sub-chronic exposure to dietary Cd. Specific growth rates of the rockfish estimated by weight and length were significantly different from those of the control, and a significant inverse relationship was observed between weight gain and the exposure concentration of dietary Cd at 25, 125 mg/kg. Cd accumulation in the tissues increased with exposure periods and concentrations for the 60 days of dietary Cd exposure. Cd accumulation in the intestine of rockfish was higher than other tissues, and the order of Cd accumulation in tissues were intestine>kidney approximately liver>gill>muscle. Accumulation factors showed an increase with the exposure period and an inverse relationship between the accumulation factor and the exposure concentrations in the gill, intestine, liver and muscle, but not in kidney. Cd elimination in tissues of rockfish decreased during the 30 days of depuration except kidney and muscle. Intestine showed the fastest elimination rates of Cd at all concentrations compared with other tissues.     

浙江三门湾表层沉积物重金属含量分布、赋存形态及生态风险评价

以三门湾表层沉积物为研究对象,对5种重金属(Zn、Cr、Cd、Cu、Pb)的含量分布、赋存形态进行分析,并运用潜在生态危害指数法、Risk Assessment Code(RAC)法、次生相与原生相比值法对重金属生态风险进行了评价。结果表明:三门湾表层沉积物重金属的含量分布整体表现为湾内高于湾外海域,人类活动是主要影响因素。运用BCR法对沉积物中重金属进行分级提取,结果显示 Zn、Cd、Cr、Cu均以残渣态为主要赋存形态(Zn:79.20%~84.25%、Cr:93.24%~96.16%、Cd:34.71%~57.58%、Cu:66.06%~79.51%),而Pb以可还原态为主(56.58%~76.44%)。评价结果中,潜在生态危害指数法和次生相与原生相比值法均显示湾内的重金属污染比湾外严重,而RAC法指出Pb污染为湾外高于湾内海域;潜在生态危害指数法和RAC均指出Cd是主要污染元素;在次生相与原生相比值法中Pb则是主要危害元素,Cd次之。     

Speciation of dissolved copper and cadmium in the Loire estuary and over the North Biscay continental shelf in spring

Dissolved cadmium and copper species were measured in the Loire estuary and the North Biscay Bay continental shelf (France) in spring 2002. Metal behaviours along the salinity gradient, metal fluxes from the Loire system and surface distributions on the continental shelf were described and compared with the ones obtained at a period of higher discharge (i.e., winter 2001). Vertical distributions at different stations were also examined with the aim to assess whether the Loire inputs affect the Cu and Cd speciation over the continental shelf. In the Loire estuary, different metal behaviours were observed from winter. Cu and its various species mostly followed a theoretical dilution line whereas a Cd addition composed of chloro- and organic complexes was observed. According to our estimations, the Cu flux was composed, as in winter, of 40% hydrophobic organic complexes. On the other hand, Cd organic complexes accounted for less in the total dissolved metal flux than they did in winter (55 and 78% for spring and winter, respectively). On the continental shelf, a C₁₈Cu-to-TDCu ratio of 40% was observed in the stratified area under Loire influence. For Cd, the organic fraction was relatively important in the surface waters near the mouth of the estuary and decreased deeper and seaward. Thus, the Cu and Cd speciation on the North Biscay Bay continental shelf are firstly determined by the extent of the estuarine plume. Beyond the estuarine influence, biological processes appeared to be the origin of the observed variations.     

中国黄、渤海海水中溶解镉的形态研究

黄、渤海是我国重要的海洋经济渔业开发区域,海水中痕量金属的含量及其存在形态会对海洋环境、海洋渔业产生重要影响。随着近年我国痕量金属采集与分析测试技术的发展,数据的准确性有了新的提升。2016-06—07采集黄、渤海40个站位的海水样品,测定其溶解态金属Cd的总浓度,并应用电化学方法(阳极溶出伏安法)分析Cd存在形态。结果表明,渤海海水中的总溶解态Cd浓度是南黄海海水中的2~3倍,这可能与渤海海水停留时间较长,水深较浅,周边较多河流输入有关。20%~92%以上的溶解态Cd是以有机络合物形态存在,以自由离子态存在的Cd浓度不超过100 pmol/L,低于Cd对浮游生物的毒性阈值。渤海比黄海的金属配体浓度高出2倍以上,高值出现在黄河口周围海域,表明黄河水携带较多有机配体输入。推测我国近海有机配体来源可能包括陆源输入、沉积物再悬浮的解析过程以及藻类分泌。研究还表明,黄、渤海海水中溶解态Cd的有机配体络合常数较其他海域的稍高,这与我国近海废、污水排放的有机络合配体类型有关。     

四种金属离子对中国对虾无节幼体生长的毒性影响

对虾工厂化育苗在我国沿海已经普及,对虾人工养殖也在沿海地区蓬勃发展,到1992年养殖面积已达200多万亩,人工育苗场全国约有上千个。养殖对虾已成为我国水产业中规模最大、经济效益最高的水产品。但近几年来沿海地区的工业飞速发展,沿岸海水均受到了不同程度的污染,各对虾育苗场卵孵化率普遍下降。今年我国养殖对虾又出现了大面积暴发性死亡,原因是复杂的,但作者认为,治虾病之本应是治水质。众所周知,一切生物的幼体阶段都是最敏感的时期,海水中的金属离子对对虾幼体生长的影响已有报道(吴彰宽等,1988; Lawrence et al.,1981),但其实验环境、方法及条件各有不同。作者于1992年5月至1993年4月在海阳育苗场作了现场实验,本文根据实验结果分析和研究了Zn、Cd、Pb、Cu金属离子对中国对虾受精卵及无节幼体生物毒性的影响;不同pH值海水加入不同浓度的混合金属离子,对无节幼体生长的毒性影响;不同盐度的海水加入不同浓度的混合金属离子对无节幼体生长毒性的影响。     

Analytical fractionation of dissolved copper, lead and cadmium in coastal seawater

The speciation of dissolved Cu, Pb and Cd in twelve seawater samples from the Inner Oslofjord, Norway, has been examined by an operational scheme which involves ultrafiltration followed by determination of labile, acid soluble and total Cu, Pb and Cd by differential pulse anodic stripping voltammetry (DPASV). The techniques employed are discussed and evaluated. It was found that Cd was present entirely in low molecular weight (LMW) labile species; Pb was mainly in non-labile LMW species, with half of the total Pb probably occurring in LMW organo-metallic compounds; Cu distribution was irregular, with extensive organic and colloidal association.     

Studies in seawater and lake water on interactions of trace metals with humic substances isolated from marine and estuarine sediments: II. Voltammetric investigations on trace metal complex formation in the dissolved phase

In seawater and lake water the complexation of several heavy metals, present in the dissolved state at relevant trace levels, with humic substances isolated from two marine and an estuarine sediment has been studied by differential pulse anodic stripping voltammetry (DPASV) at a hanging mercury drop electrode (HMDE). Taking Zn(II) as an example, the aim of this study was to gain direct information on the general level of importance of humic substances for the speciation of certain heavy metals in fresh and saline waters.In seawater humic acids originating from different sediments have very similar complexing properties for Zn(II), decreasing slightly in the order HAN > HAL > HAM. In lake water HAL is most efficient for complexing Zn(II), followed by HAN and HAM.In both types of natural waters, the sedimentary fulvic acid is less efficient in complexing Zn(II) than the respective humic acid from the same site. In general, the complexing efficiency decreases in the order EDTA > NTA > humic acids > fulvic acid.The problem of humic acid adsorption at the electrode, which somewhat limits the investigation of Pb(II) and Cd(II), and the impact of pH on the amount of complexed Zn(II) are also discussed.The findings provide further direct evidence for the conclusion previously drawn from existing complexation data that because of the rather low levels of dissolved humics in large parts of the oceans, the complexation efficiency of humics for Cd, Pb and Zn is too low to affect the speciation pattern of these three heavy metals.     

镉对共培养赤潮微藻的急性毒性效应研究——基于流式细胞术的研究探讨

在实验条件下,利用流式细胞术探讨了重金属镉对赤潮异弯藻和微小原甲藻的种群增长和种间竞争的影响,实验结果如下:(1)共培养的条件下,Cd2+胁迫前后2种微藻的细胞体积和细胞内容物复杂程度没有一致的变化规律,但叶绿素a含量和存活率均呈下降趋势;(3)叶绿素a荧光值和存活率可以考虑作为Cd2+胁迫增强的微藻生物标志物系统的指标。     

镉对中华绒螯蟹(Eriocheir sinensis)抗氧化酶活性的影响

将中华绒螯蟹(河蟹Eriocheir sinensis)浸泡在2．Omg/L氯化镉(CdCl2)溶液中，分别于第0、6、12、24、48、72、96小时提取河蟹的肝胰腺，测定抗氧化酶：超氧化物歧化酶(Superoxicle dismutase，SOD)、过氧化氢酶(Catalase，CAT)、谷胱甘肽过氧化物酶(Glutathione Peroxiclase．GPx)的活性，探讨了镉(Cd^2 )对河蟹肝胰腺抗氧化酶活性的影响。结果显示，在低浓度Cd^2 环境下，河蟹肝胰腺的抗氧化酶活性随时间发生规律性变化。暴露于Cd^2 后，河蟹肝胰脏SOD活性降低，随时间的延长，在暴露72h后，SOD活性恢复并超过未染毒时22．3％。表明Cd^2 中毒导致细胞内氧自由基大量积累从而诱导酶活性升高；CAT活性先下降后增高，随后减少，最后以低于对照的水平趋于平衡；肝胰腺中GPx酶活性的变化规律与SOD相似，在解除氧自由基毒性方面有一定的协调性。实验表明河蟹抗氧化系统酶对Cd^2 很敏感。而酶活性在短时间内的变化规律可以为镉对河蟹早期的毒性研究提供参考。     

Study on the Adsorption of Metal Ions by Immobilized Marine Algae with the Existence of Clay

The process of adsorption of metal ions by immobilized marine algae with the existence of clay was investigated. It can be noted from the results that, after mixing with clay, the adsorption rate increases rapidly with the increasing amount of the marine algae. When pH=5, the best ratio between the clay and the marine algae is 1：4 for Pb^2＋. The result of in situ handling of the waste water containing heavy metals shows that the average adsorption rates of heavy metal irons Cu^2＋, Cd^2＋, Pb^2＋ and Ni^2＋ are all over 70 %.     

Metallothioneins and cytosolic metals in Neomysis integer exposed to cadmium at different salinities

In the present study the induction of metallothioneins (MTs) and its relation to cytosolic metal concentrations (Zn, Cu and Cd) in the euryhaline crustacean Neomysis integer exposed to Cd at different salinities was studied. N. integer was exposed to the same free cadmium ion activity of 5.74 x 10(-9) mol l(-1) (i.e. 1/5 of the 96 h LC(50) value expressed as cadmium activity) in hypo-osmotic (5 psu), isosmotic (16 psu) and hyper-osmotic media (25 psu) for 7 days. In this way, the effect of salinity on cadmium speciation was eliminated and therefore the physiological effect of salinity on Cd accumulation and MT induction could be studied. The accumulation of cytosolic Cd in N. integer changed with salinity from 1.11+/-0.05 micromol l(-1) at 5 psu up to 1.43+/-0.17 micromol l(-1) at 25 psu. This could indicate that the physiological response of euryhaline estuarine invertebrates like N. integer to salinity changes can influence the rate of trace metal uptake from solution. While the salinity changes did not cause significant differences in cytosolic Zn concentrations (mean value of all tested salinities: 34.4+/-2.8 micromol l(-1)), an inverse relationship between salinity and cytosolic Cu concentration was observed. The highest concentration of 15.7+/-2.3 micromol Cul(-1) was determined at 5 psu and the lowest 10.9+/-1.4 micromol Cul(-1) at 25 psu. This could point to a possible relationship between the copper concentration and the hemocyanin metabolism in N. integer. This is the first time that differential pulse voltammetry method was applied to MT assays with N. integer. Although the exposure to Cd resulted in a higher Cd cytosolic concentration, no subsequent MT increase was detected. The significant positive correlation between MT levels and cytosolic Cu concentrations (Spearman correlation coefficient r(s)=0.356, p=0.009) implies a strong relationship between MT and Cu in N. integer.     

Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.     

Organic and inorganic speciation of copper in the Irish Sea

The metal complexing ability of surface water of the Irish Sea has been measured by the MnO₂ adsorption method. In all samples strong copper-chelating compounds are present at concentrations of 60–150 nM, with conditional stability constants (log values) of 10.0–10.4. The concentrations of Cu, Pb and Cd in the samples are 16–39 nM, 1–7 nM and 0.1–2 nM, respectively; much less than the ligand concentrations. The organic compounds form complexes with 94–98% of dissolved copper, and therefore constitute the major form of copper in surface water of the Irish Sea. Recalculation of speciation of the inorganic fraction of copper in seawater reveals that the major complex ion is that of CuCO₃⁰ (60%), followed by CuOH⁺ (16%) and Cu(OH)₂⁰ (16%). Complexes with borate ions form a small and rather insignificant fraction of 1%.     

重金属Cd2+、Cu2+对文蛤的急性毒性

用静态急性毒性试验的方法,研究24h、48h和96h内重金属离子Cd2+、Cr+对文蛤的毒性影响.结果表明:Cd2+对文蛤的24h、48h、96h LC50和安全浓度分别为197.35mg/L、40.47mg/L、13.18mg/L和0.13mg/L;Cu2+的24h、48h、96h LC50和安全浓度分别为1.66m...     

Effects of an environmental estrogen, 17alpha-ethinyl-estradiol,on the maternal-fetal trophic relationship in the eelpout Zoarces viviparus (L)

In the present experiment pregnant eelpout Zoarces viviparus females were exposed to 0, 5, 10, 50, 500 ng/l of the synthetic estrogen ethinylestradiol (EE2) and to 500 ng/l estradiol-17beta (E2) under flow-through conditions during 3 weeks and the maternal-fetal trophic response was investigated. The circulating yolk-precursor protein vitellogenin, measured by ELISA, increased from a mean control value of 0.017-36 mg/ml in the plasma of the motherfish exposed to the highest concentration of EE2 This increase in vitellogenin was also depicted by a 288% increase in circulating calcium levels. During pregnancy the ovary represents a new route of calcium loss from the maternal blood for the growth of the embryos. However, a significant decrease (120% in the group exposed to the highest concentration of EE2) in the calcium level in the ambient medium of the embryos, the ovarian fluid, was observed concomitant with the increase in maternal plasma calcium in the EE2-exposed females. In contrast, the level of circulating amino acids decreased in the maternal blood, with a slight concomitant increase in the ovarian fluid of the exposed fish. These and other metabolic observations indicate that exposure to different doses of EE2 and to estradiol-17beta affects the maternal-fetal trophic relationship.     

Hepatic metallothionein as a biomaker for metal contamination: age effects and seasonal variation in European flounders (Pleuronectes flesus) from the Severn Estuary and Bristol Channel

Hepatic concentrations of metallothionein [MT] and three metals (Cu, Zn, Cd) were determined in 242 European flounders (Pleuronectes flesus) collected from power stations at Oldbury-upon-Severn and Hinkley Point, located in Severn Estuary and Bristol Channel, UK, respectively, between March 1996 and February 1998. A model involving three-factor analysis of variance (ANOVA) was used to examine variation in MT and metal concentrations with respect to season, year and site; with age-class included as a covariate in the analysis. Hepatic concentrations of MT and Cd (and to some degree, Cu, but not Zn) increased significantly with age. The model explained 38, 25, 17 and 26% of the variation in MT, Cu, Zn and Cd, respectively, with significant effects due to season, and to a lesser extent, to year. Site was only a significant factor for Cd which was higher in fish from Hinkley. Correlation between the individual concentration of MT and each metal alone, or in combination, was poor, and explained only an additional 3.0% of the residual variation in MT, most of which was attributable to Cu (2.7%). Compared to other industrialised estuaries, Cd concentrations were high (>20 micro g-1 in some individuals). The study emphasises the importance of seasonal variation and other factors in biomonitoring programmes and highlights the limitations of using [MT] as a biomarker for metal contamination in flounders from the Severn Estuary.     

Production and speciation of hydrogen sulfide in surface waters of the high latitude North Atlantic Ocean

During the August 1993 Intergovernmental Oceanographic Commission's Contaminant Baseline Survey cruise to the high latitude North Atlantic, determinations of total dissolved sulfide (TDS=free sulfide, H₂S_(g)+HS⁻+S²⁻, plus dissolved metal–sulfide complexes), free sulfide, and carbonyl sulfide (OCS) were made along a horizontal transect and at six vertical profile stations. Unlike data from lower latitudes, the distributions of OCS and TDS were remarkably uniform, with surface water OCS averaging 108 pmol/l and TDS averaging 58 pmol/l; free sulfide was below the detection limits of 5 pmol/l at all stations. The vertical profiles of both OCS and TDS show surface maxima and rapid decreases into the major thermocline. For OCS this is indicative of production via photolysis of dissolved organic sulfur compounds, while TDS may be produced from the hydrolysis of OCS. The concentrations of OCS are similar to those found in coastal waters, and suggests that these sub-polar regions may be large OCS sources to the troposphere during summer. However, it is unclear whether higher concentrations of OCS precursors, a long photo period during summer, or slow rates of removal by hydrolysis due to low temperatures are responsible for the elevated OCS levels. TDS concentrations are primarily controlled by the rate of OCS hydrolysis, production by phytoplankton, and oxidative loss by oxygen and iodate. Both of the losses are affected by trace metal complexation, and to examine this, freshly collected seawater was amended by hydrogen sulfide gas and trace metal additions, and the concentration of free sulfide monitored as a function of metal concentration. This allowed the determinations of conditional stability constants for metal sulfides, with the log K_cond of Cd(HS)⁺ being 8.0±0.5, 7.0±0.6 for Ni(HS)⁺, and 7.4±0.7 for Zn(HS)⁺; attempts at measuring the K_cond of Cu(HS)⁺ were thwarted by the apparent reduction of Cu(II) to Cu(I) by sulfide. Using these constants in an equilibrium speciation model indicates that on average about 75% of the measured TDS was free, with the remaining fraction complexed with Ni, Cd, and Zn (in order of decreasing percentages). While closer to the field observations than would be found with stability constants reported by other workers, these values are still at variance with the actual speciation (i.e., <30% free). This suggests that the stability constants for Cd, Ni, and Zn are somewhat higher than found, thus reducing the concentration of free sulfide. Nevertheless, these speciation data are important for balancing the TDS budget since the loss by iodate oxidation of free sulfide exceeds all production estimates.