An investigation of the suitability of amberlite XAD-1 resin for studying trace metal speciation in seawater

Amberlite XAD-1 resin was examined to test its suitability for extracting organic complexes of copper, zinc and iron from seawater. At low flow rates and at loading capacities far below theoretical values, the adsorption of these metals is not reproducible and the results are reminiscent of the behaviour observed when the adsorption capacity is being exceeded or flow rates are too high. It is suggested that the resin also adsorbs small but significant amounts of inorganic ions from seawater and that this effect makes the resin unsuitable for quantitative measurements of trace metal speciation.     

东海泥质区表层沉积物中铜和铅的赋存形态研究

2007年11月在东海泥质区13个站点采集了表层沉积物样品,用连续提取法分离并测定了铜和铅的赋存形态。结果表明,铜主要赋存于易还原态(铁锰氧化物结合态),含量为1.2～5.1μg/g,平均值为3.3μg/g;铅主要赋存于碳酸盐结合态,含量为1.9～7.3μg/g,平均值为5.3μg/g。泥质区铜和铅的有机结合态和易还原铁锰氧化物结合态与水深之间的呈明显的相关关系,碳酸盐结合态则与水深不相关。铜和铅非残渣态总量与采样站点水深之间的关系受控于其主要赋存形态,反映了重金属形态分布受到陆源输入和在水体中迁移等因素的影响。济州岛西南泥质区表层沉积物中铁锰氧化物结合态的铜和铅含量高于其他海区表层沉积物,可能是由于沉积物再悬浮所致。     

基于PXRF的西南印度洋脊硫化物表层沉积物地球化学找矿研究

海底热液喷发形成的热液羽状流中富含成矿物质,并沉淀在距离热液喷口不等的范围内。对西南印度洋中脊热液喷口附近、距离喷口中等距离、远离喷口的六个表层沉积物样品开展了不同粒度沉积物的便携式XRF（PXRF）分析。结果表明,PXRF可以有效获得的洋中脊钙质沉积物中成矿元素的富集特征。>40目的沉积物样品具有较高的Cu、Zn、Fe、Mn等元素含量,40目以下沉积物中则相对稳定,可能与粗粒沉积物中玄武岩碎屑/玻璃含量较高有关,与镜下鉴定结果一致。以热液喷口为中心,表层沉积物中表现出Cu、Zn、As、Fe、Mn的元素分带,靠近喷口的沉积物中具有较高的成矿元素的含量,并具有较高的Cu/Fe、Zn/Fe比值或者Cu/Mn与Zn/Mn比值。上述结论表明,洋中脊沉积物中成矿元素的含量主要受与喷口的距离的影响,而与粒度的关系不大,洋中脊沉积物地球化学找矿应采用40目以下粒径沉积物作为分析样品。通过PXRF获得的Cu、Zn、As、Fe、Mn等元素含量及其比值特征可以作为海底多金属硫化物沉积物地球化学找矿的指标,该方法满足快速有效识别洋中脊沉积物中地球化学异常的要求。     

Seasonal metal remobilization in the sediments of Great Bay,New Hampshire

Concentrations of dissolved iron, manganese, molybdenum, copper, and organic carbon (DOC) were measured in the pore waters from surficial sediments of a temperate estuary to delineate seasonal metal remobilization from 1978 through 1980. Iron and DOC data were collected for 31 months and covaried inversely and exponentially. Iron dissolution occurred during the spring and during periods of active bioturbation with concentrations as high as 18 mg 1^?1. Iron values were low during winter due to oxidation to ferric oxides. The lack of active bioturbation during the summer of 1978 allowed for the nearly complete removal of iron as a monosulfide precipitate. However, bioturbation resumed during the summer of 1979 and 1980 and dissolved iron concentrations as high as 10 mg 1^?1 were observed at those times. The iron and DOC data were a qualitative measure of bioturbation activity. Dissolved manganese, molybdenum, and copper data were collected for 18 months during 1978 and 1979. All three metals displayed spring maxima covariate with iron, suggesting that they behaved chemically like iron and/or were associated with iron- or manganese-rich phases during this time of the year. In general, manganese and molybdenum varied temporally with iron while copper concentrations mimicked iron variations only during the spring.     

Trace metals (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) in feathers of Black-browed Albatross Thalassarche melanophrys attending the Patagonian Shelf

We investigated the concentrations of cadmium, chromium, copper, iron, nickel, lead and zinc among feather tissues in sexes of Black-browed Albatross Thalassarche melanophrys killed in longliners off Argentina in 2005. We found no different metal concentration with sex for cadmium, copper, iron, lead and zinc in feathers of adult birds, though there were significant body-size differences between sexes. However, the concentrations of trace metals differed significantly among the type of feather within individual bird. The mean concentrations of copper, iron, and zinc in breast feathers of T.?melanophrys were lower than those reported for the species from Georgias del Sur/South Georgia, the southern Indian Ocean and for other seabirds' worldwide. While cadmium fall within the known range of concentrations for bird feathers lead were not. Our results may be indicating that level of pollution in Patagonia may not be as negligible as previously thought at least for some trace metals.     

Trace metal concentrations in brown seaweeds, Cardigan Bay, Wales

Concentrations of zinc, cadmium, copper, manganese, iron, cobalt, nickel and molybdenum are examined in brown algae, Fucus serratus and F. vesiculosus, from Cardigan Bay, Irish Sea, Great Britain. In both species a seasonal variation in metal content was observed. Zinc, cadmium, copper, iron nickel and cobalt concentrations were highest in the spring and lowest in the autumn, probably reflecting levels of metabolic activity and climatic factors. All the studied elements, except nickel, reached highest concentrations in harbour specimens from Aberystwyth and Aberaeron where rivers draining mineralized areas enter the sea. Outside harbours, marked regional variations were observed in most of the studied elements. Zinc values were highest in the Aberystwyth area while copper and manganese were highest in the northeast part of the bay.Trace-element concentrations varied among different species from the same locality and also varied according to position on the shore.Marine algae may be used to monitor coastal-water trace-metal concentrations, provided a careful sampling procedure is adopted.     

Metal-organic complexes in seawater — An investigation of naturally occurring complexes of Cu,Zn, Fe,Mg, Ni,Cr, Mn and Cd using high-performance liquid chromatography with atomic fluorescence detection

Metal-organic complexes were isolated from coastal seawater by adsorption onto octadecyl-bonded silica (SEP-PAK cartridges) and injected into a high-performance liquid chromatograph. Trace metals were identified in the eluate by a four-channel non-dispersive atomic fluorescence detector. Organic complexes of copper, zinc, iron, magnesium, nickel and manganese were found to be present but no complexes of chromium or cadmium were detected. The complexes covered a wide range of polarities with no specific complexes being predominant. Interference from the stainless-steel chromatograph was negligible. The technique provides a minimum estimate of the amount of metal organics and it is suggested that a significant fraction of the metal organics present are too polar to be completely retained by the SEP-PAK cartridges. Typical values of the amounts of trace metal isolated by this technique corresponded to concentrations in the original seawater of >65 ngl^?1 (Cu), >27 ngl^?1 (Fe) and >41 ngl^?1 (Zn).     

黑鲷对Fe,Zn,Cu,Co和I的营养需求

作者在本刊的前一篇文章中报告了黑鯛对Ca,P,K,Mg和Mn的营养需求,本文将报告黑鲷对Fe,Cu,Zn,Co和I的营养需求的研究结果。     

无机胶体和铁、铜离子对中肋骨条藻生长的影响

选择无机胶体粒子Fe(OH) 3 胶体、伊利石胶体及其与金属铁和铜 ,对中肋骨条藻进行了培养实验。结果表明 :在培养介质中加入Fe(OH) 3 胶体后 ,在低添加量时可通过Fe(OH) 3 胶体提供满足微藻的生长所需的铁 ,从而提高其生长速度。但在较高添加量时 (>0 .5mg/L) ,由于胶体物质的吸附特性 ,微藻的生长受到抑制。Fe(OH) 3 对中肋骨条藻的最佳的添加量在 0 .2 5～ 0 .5 0mg/L之间。中肋骨条藻在加入伊利石胶体液时 ,微藻的生长均产生明显的抑制作用。通过伊利石胶体对培养介质中铁离子和铜离子浓度的调节控制作用 ,可直接影响到中肋骨条藻的生长。     

Lead, cadmium, copper, nickel and iron in limpets, mussels and snails from the coast of ras Beirut, Lebanon

Samples of Patella coerulea (Linnaeus), Brachydontes variabilis (Krauss), Monodonta turbinata (Born) and surface seawater were collected at eight locations along the coast of Ras Beirut, Lebanon, and analysed for lead, cadmium, copper, nickel and iron. With the exception of cadmium, the metal levels found in the three molluscs appear to be high in relation to levels reported by investigators from other coastal areas. The average values for lead, cadmium and nickel within these animals were quite similar. Concentrations of copper in P. coerulea were lower, but concentrations of iron were much higher than those found in both B. variabilis and M. turbinata. Further studies of metal levels in various other intertidal organisms from Ras Beirut, together with investigations into the possible effects of seasonal changes on metal concentration and distribution, are currently under way.     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

In vitro and in vivo inhibition of acetylcholinesterase and carboxylesterase by metals in zebrafish (Danio rerio)

Metals are natural components in ecosystems; however, if these elements are in excess, they can have adverse effects on living organisms. This study analyzes the interference of copper, lead, iron and cadmium in acetylcholinesterase (AChE) and carboxylesterase (CbE) activities in zebrafish. AChE was significantly inhibited in vitro by copper, iron, lead and cadmium at higher concentrations (10 and 20 mmol/L), whereas CbE was inhibited only at a concentration of 20 mmol/L. In vivo, only lead and cadmium were able to cause AChE inhibition at higher concentrations, while iron didn't cause any changes, and copper promoted an increase in AChE activity at a concentration of 0.06 mg/L. CbE activity did not change at any of the times (two and seven days) and concentrations tested, except in the case of copper exposure, which resulted in a decrease in CbE activity. Indeed, iodoacetamide treatment didn't changed AChE neither CbE activities, results which indicate that the metal inhibiting effect is probably not due to its biding to thiol groups close the active site of the enzyme. This outcome reveals that metals are important esterase inhibitors in zebrafish, and should be considered in environmental monitoring studies that use esterase inhibition as exposure biomarkers of organophosphate and carbamate pesticides.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, R² = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).     

Metal concentrations in the shell of Bathymodiolus azoricus from contrasting hydrothermal vent fields on the Mid-Atlantic Ridge

Specimens of Bathymodiolus azoricus were sampled along the Mid-Atlantic Ridge at the Menez Gwen, Lucky Strike and Rainbow hydrothermal fields. Individual shells (n = 51), through the weight range 0.62 to 15.70 g, were analyzed for their magnesium, strontium, iron, manganese, copper, zinc and cadmium concentrations. Amongst the marine molluscs the shell of B. azoricus is confirmed as being particularly impoverished in strontium (mean 943 microg g(-1)). Trace metal concentrations in the shells decreased in the order Fe> Mn> Zn> Cu> Cd. Despite originating from trace metal rich environments mean concentrations were low (37.9, 13.2, 10.7, 1.1 and 0.7 microg g(-1), respectively). Irrespective of geographical origin magnesium, strontium and copper concentrations were primarily dictated by shell weight. In contrast cadmium concentrations were elevated in shells from the Rainbow field and ambient seawater chemistry imparted site specific chemical fingerprints to the shells with respect to the iron to manganese ratio.     

The free amino acid composition of seawater obtained without desalting and preconcentration

A conventional amino acid analyzer was modified to allow detection of dissolved free amino acids in a direct injection of 0.5 to 2.0 ml of seawater. The amino acids were monitored fluorimetrically by reaction with o-phthaldialdehyde after column chromatography. The accuracies of two commonly employed desalting methods, cation exchange resin and copper Chelex, were determined by comparison with the direct injection method. After correcting the results of the desalting methods for the procedural blank and recovery rate for each individual amino acid, the amino acid compositions on a mole percent basis as determined by these methods resembled approximately the true composition determined by direct injection. However, on an absolute basis the cation resin method overestimates and the copper Chelex method underestimates the total amount of dissolved free amino acids. The reasons for these discrepancies are discussed. Using the direct injection method, the spectra of dissolved free amino acids in surface seawater samples from different locations were determined. As opposed to the relatively uniform patterns reported in most past investigations, the amino acid spectra found were highly variable. In a number of samples, the acidic amino acids dominated the spectra. Valine was also high in many samples. In a depth profile the deep samples were dominated by arginine. Application of the method to real-time shipboard analyses of dissolved free amino acids is discussed.     

岩藻黄素纳米复合物的制备及抗氧化、抗肿瘤活性研究

岩藻黄素是一种脂溶性类胡萝卜素,由于其水溶性差、环境敏感性强,使其应用受到限制。本研究采用有机溶剂浸提、大孔树脂纯化法,从裙带菜中提取高纯度岩藻黄素。通过复凝聚反应制备乳清分离蛋白-岩藻黄素-阿拉伯胶纳米复合物。通过透射电镜观察,纳米复合物呈光滑的球形,粒径约为44nm。红外光谱则表明,岩藻黄素与乳清分离蛋白、阿拉伯树胶发生相互作用,导致联烯键、乙酰基等特征吸收峰被遮蔽。与单一岩藻黄素相比,纳米包封的岩藻黄素具有较好的抗氧化活性稳定性。抗肿瘤实验表明,纳米复合物保留了岩藻黄素抑制HT29细胞增殖的生物活性。     

东海泥质区表层沉积物中锰、铁和铝的赋存形态及影响因素研究

2007年11月在东海泥质区采集了表层沉积物样品,用连续提取法对金属元素的赋存形态进行了分离,测定了各形态中锰、铁和铝的含量。结果表明,锰主要赋存于碳酸盐结合态,含量为0.04～0.19mg/g,平均0.13mg/g;铁主要赋存于易还原态(铁锰氧化物结合态),含量为1.1～2.3μg/g,平均1.5mg/g;大部分站点的铝主要赋存于易还原态,含量为0.4～1.1mg/g,平均0.7mg/g。沉积物主要成分对金属赋存形态产生影响,CARB态、ERO态Mn、Fe和Al分别随沉积物中碳酸钙、水合铁锰氧化物含量的升高而增加,且ERO态金属与水合铁锰氧化物的相关性显著;有机物的含量的对OSM态金属的影响则不明显。非残渣态Fe和Al的含量随水深增加而降低,主要是由于沉积物中ERO态Fe和Al受陆地径流输入和水体中清除作用的影响,导致近岸沉积物中有较多的活性Fe、Al;离岸距离增加则沉积物中活性Fe、Al含量减少。     

Sulfide control of cadmium and copper concentrations in anaerobic estuarine sediments

Equilibrium concentrations of the toxic trace metals copper and cadmium were calculated for the physico-chemical conditions characterizing pore waters of anaerobic estuarine sediments using available thermodynamic data and assuming simple sulfide minerals control solubilities. Polysulfide complexes are responsible for the solubility of copper in the cuprous (Cu(I)) oxidation state. Predicated copper concentrations, assuming covellite (CuS) is the controlling solid phase, are in reasonable agreement with copper analyses in a wide range of sulfidic waters and sediment pore waters. In the absence of thermodynamic data, no account could be taken of possible polysulfide complexes of cadmium. However, bisulfide complexes appear to account satisfactorily for observed solubilities assuming the existence of greenockite (CdS) as the controlling solid phase. Anaerobic estuarine sediments may act as a sink for copper and cadmium in the common situation in which free sulfide concentrations are controlled by the coexistence of iron sulfide and iron oxide minerals. However, where free sulfides reach high concentrations of 10^?3 M or more, the concomitant increase in concentration of bisulfide and polysulfide complexes may result in the sediments acting as a source of copper and cadmium.     

渤海莱州湾表层沉积物中金属元素分布及环境质量

利用X-射线荧光光谱仪、等离子质谱仪或原子荧光光度计测定了莱州湾表层沉积物中金属元素的含量,探讨了它们的分布特征、来源及污染程度,结果表明,沉积物中铜、锌、铅、镉、砷、镍、铬、钴、钒、钪、铁、锰的含量由近岸向湾内递减,莱州湾北部海域的含量大于南部的。银含量高的沉积物主要分布在莱州湾中部偏西南的环流中心区。沉积物中砷和镍含量超过ERL值,潜在生态风险较高。富集系数和主成分分析显示,沉积物中铁、铜、锌、镉、砷、铬、镍、钴、锰、钒和钪为无富集,砷为轻度富集,铅和银为中度富集。铁、铜、锌、镉、铬、镍、钴、锰、钒、砷和钪主要来源于自然源,铅既有岩石和土壤风化产物硅酸盐矿物等自然源的贡献,又受到了人为活动的影响,银主要受人为活动的影响。聚类分析表明,可把莱州湾沉积物分为4类,其中黄河口西北缘沉积物中砷和镍污染生态风险最高,其次是莱州湾中部和北部。     

The chemical composition and nickel,cobalt, copper,zinc and lead contents of Nanao Bay sediments

The contents of major and some of the minor elements, nickel, cobalt, copper, zinc and lead were studied on sediments collected from three inlets of Nanao Bay located at eastern side of Noto Peninsula. Little variation was found on the average contents of silicon, iron, titanium, aluminum, manganese, magnesium and potassium among the sediments of West, South and North Bays in Nanao Bay. Whereas significant difference was found on the contents of calcium, chlorine, sulfur and nitrogen among sediments of three bays.As to the minor elements, the average contents of nickel (20±5 ppm), cobalt (5±1 ppm), copper (18±5 ppm) and lead (17±8 ppm) are relatively low but zinc content is high in these sediments comparing with those of coastal deposit around Japan Island. From the results obtained here, it became clear that no environmental contamination of nickel, cobalt, copper and lead, and a little organic pollution were found in Nanao Bay sediments.