The relationship between the copper complexing capacity of sea water and copper toxicity in shrimp zoeae

Mortality of larval coon-stripe shrimp, Pandalus danae, was related to labile copper and the copper complexing capacity of sea water, as measured by differential pulse Anodic Stripping Voltammetry (ASV). In nominal treatments of control, 5 and 10μg/litre Cu which contained less than 1·0μg/litre ASV labile Cu, zoeal development was usually complete. In treatments of 20 and 50μg/litre Cu which contained more than 7·0μg/litre ASV labile Cu, most larvae died while in the first zoeal stage. ASV labile Cu was related to the copper complexing capacity of sea water. Copper toxicity at less than 1·0 μg/litre ASV labile Cu is indicated by moulting delay and apparent Cu accumulation in zoea of the 5 and 10μg/litre Cu nominal treatments.     

海水中氨基酸对Cu(Ⅱ)—蒙脱石、SiO_2之间离子交换的影响

本文研究了海水中组氨酸、天冬氨酸、丙氨酸对Cu(Ⅱ)—蒙脱石、SiO_2之间离子交换率(%)—pH曲线的影响。结果表明,低浓度氨基酸促进Cu(Ⅱ)—蒙脱石之间离子交换,而高浓度则起抑制作用;但低浓度氨基酸对Cu(Ⅱ)—SiO_2离子交换没有影响,而高浓度起抑制作用。分析表明,氨基酸的促进效应与表面三元络合物相关,而抑制效应与液相中Cu(Ⅱ)—氨基酸络合反应相关。     

Cu complexation by organic ligands in the sub-arctic NW Pacific and Bering Sea

Cu speciation was characterized at three stations in the sub arctic NW Pacific and Bering Sea using cathodic stripping voltammetry with the competing ligands benzoylacetone and salicylaldoxime. A single ligand model was fit to the titration data, yielding concentrations throughout the water column of ∼3–4 nM, and conditional stability constants ranging from 10^12.7 to 10^14.1, this range being partly due to the choice of competing ligand. Free Cu²⁺ in surface waters was 2–4×10⁻¹⁴ M, in close agreement with values reported by previous workers in the NE Pacific using anodic stripping voltammetry (ASV). However, those results showed that complexation by strong organic ligands becomes unimportant below 200–300 m, while our data indicated Cu is strongly complexed to depths as great as 3000 m. Free Cu²⁺ concentrations in surface waters reported here and in previous work are close to the threshold value where Cu can limit the acquisition of Fe by phytoplankton.     

The distribution of total and electrochemically available copper in the northwestern atlantic ocean

Copper in a series of samples from the northwestern Atlantic has been determined by anodic stripping voltammetry (ASV) and atomic absorption spectrometry after preconcentration by cobalt—APDC coprecipitation. Samples from a transect across the continental shelf directly off the New York Bight showed a linear relationship between total copper and salinity (31–34‰) and less than 5% of the total copper was detectable by ASV. A slope water station showed less than 9% of the total copper to be ASV detectable in the upper 780m, below which the ASV detectable copper increased to 70% at 3000 m. The Sargasso Sea profiles showed less than 7% ASV detectable copper in the upper 150 m; the fraction of the total copper detected by ASV increased to about 80% of the total copper at greater depths. The reduced availability of copper to the ASV measurement in coastal waters and open ocean surface waters appears to be related to recent contact with waters where biological productivity occurs.     

自动表面船用于岛礁水深测绘

岛礁具有重要的地位,然而对其附近水深的调查手段却不充分。比较了几种水深测绘手段的优缺点,设计了一种小型自动表面船用于岛礁水深测绘。该表面船底部安装声学测深仪,具备自动定位、导航与运动功能;其尾部安装两个电动推进器提供动力,通过独立控制两个推进器的转速,可实现船体的前进、后退和转向;利用无线电与岸基单元进行数据通讯。根据不同水深测绘条件,该船可以用三种控制方式进行水深测量:直接控制、间接控制和自主控制。测量数据实时传输到岸基单元,并自动存储于船载存储单元。初步试验结果表明,设计的自动表面船测量系统具有可行性。     

海水中氨基酸对Cu（Ⅱ）在r—MnOOH上吸附的影响

实验测定了海水中氨基酸存在下Ｃｕ（Ⅱ）在ｒ－ＭｎＯＯＨ上吸附的等温线、Ｃｕ（Ⅱ）％－－ｐＨ曲线和Ｃｕ（Ⅱ）％－氨基酸深度曲线。结果表明，较低浓度氨基酸对Ｃｕ（Ⅱ）在ｒ－ＭｎＯＯＨ上吸附没有影响，而较高浓度氨基酸却起抑制作用，这主要是由于海水中Ｃｕ（Ⅱ）－氨基酸络合反应与ｒ－ＭｎＯＯＨ竞争Ｃｕ（Ⅱ）所致。此外，海水中较高浓度氨基酸只使Ｃｕ（Ⅱ）在ｒ－ＭｎＯＯＨ上吸附的表面分级离子交换稳定常数Ｋｉ（ｉ     

Potentiometric determination of calcium and magnesium in seawater

Methods are described for the complexometric determination of calcium and magnesium in seawater, using an amalgamated silver electrode for end-point detection. In the presence of a small amount of mercury(II)-chelonate, the amalgamated silver electrode serves as a pM indicator during the complexometric titration, the Hg complex being stronger than Ca, Mg and Sr complexes. Calcium is determined by titration with EGTA, calcium+magnesium+strontium by titration with EDTA and magnesium is obtained by difference. Average values of 0.02120 (standard deviation 0.00004) for Ca:Cl‰ and 0.06671 (standard deviation 0.00014) for Mg:Cl‰ were obtained for samples from tropical North Atlantic Ocean.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

A Small Autonomous Surface Vehicle for Ocean Color Remote Sensing

This paper provides a study on the development and the use of a small autonomous surface vehicle (ASV) that automatically follows programmed mission transects, while measuring sensor outputs along the tracks. It discusses the mechanical construction of the ASV, the distributed architecture of controller area network (CAN)-based nodes for science and vehicle payloads, high-speed radio-frequency (RF) communications, the performance of the heading autopilot, global positioning system (GPS)-based guidance algorithm, and the mission programming technique. The field trials of the ASV, performed off the coast of Goa, India, are focused on retrieving the 2-D spatial distribution of surface chlorophyll, which is one of the useful parameters in characterizing the nature of calibration-validation (CALVAL) sites for ocean remote sensing needs. A further benefit of ASVs is that they can be built at a low cost and used in monitoring applications of diverse coastal ecosystems.     

Apparent copper complexation capacity and conditional stability constants in north atlantic waters

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CC_Cu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that k_f^′ is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 10⁴s⁻¹M⁻¹ Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CC_Cu and higher K′ than those found for surface waters.     

Oxidation of copper(I) in seawater at nanomolar levels

The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:

The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl₂⁻ species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations.     

Complexation of calcium and copper with carbohydrates: Implications for seawater speciation

The extent of complexation of calcium(II) and copper(II) with 33 carbohydrates found in seawater has been determined potentiometrically using calcium and copper ion-selective electrodes. The measurements were performed in an essentially neutral aqueous medium at 25°C in 0.70 M KNO₃.Neutral sugars form very weak 1:1 complexes with Ca(II) and Cu(II) ions. Sugars with carboxylate groups from much stronger complexes. K′_Cu(II) >K′_Ca(II)) for a given sugar. The extent of complexation is dependent on the conformation of the sugar ligand.     

Oxidation kinetics of Cu(I) in seawater: implications for its existence in the marine environment

A variety of photochemical and thermochemical processes may lead to the formation of Cu(I) in the upper water column. A thermodynamic model based on measured steady state levels of H₂O₂ in the photic zone indicates that a significant proportion of total dissolved Cu is present as Cu(I).The oxidation kinetics of Cu(I) in seawater have been studied to assess the potential for Cu(I) to accumulate at significant steady state levels when it is generated by non-equilibrium processes.     

低盐度海水中重金属标准物质研制

本文介绍了低盐度海水中5种重金属元素混合溶液标准物质的研究和制备过程。以稀释的大洋海水为基体,用容量法以加标方式制备了低盐度海水中重金属标准物质。各元素统计结果表明样品的均匀性和稳定性良好。经9家具有中国计量认定(CMA)资质的实验室分别采用原子吸收分光光度法、电感耦合等离子体质谱法和阳极溶出伏安法对标准溶液进行分析定值,并用国家标准物质作量值溯源,以分析结果的总平均值作为标准值,标准值及不确定度的结果分别为铜15.2±0.7 μg/L、铅15.3±0.7 μg/L、锌98.9±4.7 μg/L、镉2.02±0.10 μg/L以及铬15.3±0.6 μg/L。该标准物质可用于近岸、河口区低盐度海水重金属分析过程的量值传递和质量控制。     

Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans

Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19 μmol site mg⁻¹ C, and a log K′ of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu–FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC₅₀ of 58.9 μg l⁻¹. However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC₅₀ ranging from 55.6 μg l⁻¹ in the no-FA control to 137.4 μg l⁻¹ in the 20 mg l⁻¹ FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu–FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.     

Speciation of metals in the oceans. I. Inorganic complexes in seawater,and influence of added chelating agents

The speciation of the metal ions in the surface waters of the open ocean has been computed by using critical stability constants describing all of the inorganic complexes that can be formed by the metal ions and inorganic ligands present. The stability constants used were adjusted to change the literature values from 0.10 M ionic strength to the 0.70 M ionic strength of seawater by using a new empirical technique involving experimentally observed variations of stability constants with ionic strength for complexes of similar charge types. For stability constants not listed in Critical Stability Constant compilations, values were estimated by using known trends of stability constants of similar complexes. The speciation determinations made include equilibria with suspended solid phases such as hydroxides, carbonates, and basic carbonates of the metal ions present. Perturbation of metal speciation resulting from the addition of some common chelating agents is determined and the results obtained are discussed in terms of the effects on seawater by the introduction of these chelating agents into the environment. In the 10⁻⁹ to 10⁻⁷ range of added chelant, EDTA (ethylenediaminetetraacetate), NTA (nitrilotriacetate), TPP (tripolyphosphate) and CIT (citrate) exist in the ocean primarily as their Ca(II) and Mg(II) chelates. EDTA and NTA are the dominant ligands for Cu(II) and Ni(II), while TPP is extensively complexed to Fe(III). CIT strongly influences Cu(II) speciation, while SSA (sulfosalicylate, a well-known Fe(III) reagent) has no influence on any of these metal ions or their complexes.     

塞曼石墨炉原子吸收法直接测定海水中的铜

本文选择酒石酸消除海水基体对铜信号的干扰,用塞曼石墨炉原子吸收法直接测定海水中的铜。从Cu的原子化曲线可知,加入酒石酸后,背景值减小,Cu原子吸收信号增强,且出现时间提前,表明酒石酸是有效的海水基体改进剂。用P.E.Z3030光谱仪测得双蒸水及海水中的元素Cu的特征质量(m。)分别为12.5pg及12.7pg;检测限分别为0.18μg/L和0.19μg/L,表明基体效应已消除,符合海洋监测要求。可用纯Cu标准溶液作校正曲线,以国家海洋局的两个标准海水样品中的Cu评定本法的准确度,相对偏差为0及-4.6%,与经典的经富集后的FAAS法的结果相比,相对偏差在3.0—6.5％范围内。用不同类型的光谱仪测定了30个海水样品,回收率在89—104％范围内。本法操作简便、快速。     

13C NMR spectra and Cu(II) formation constants for humic acids from fluvial,estuarine and marine sediments

Humic acids extracted from fluvial, estuarine and marine sediments from the eastern coast of Florida were studied by CP/MAS ¹³C nuclear magnetic resonance. The freshwater humic acid contained a large percentage of lignin-derived aromatic carbon whereas the offshore marine samples contained large amounts of aliphatic carbon. The aliphatic carbon of the marine humic acids was more highly branched than that found for freshwater and estuarine sediments. Despite significant differences in the relative amounts and types of carbon present, conditional formation constants for Cu(II)-humic acid were very similar.     

Molecular masses and chromophoric properties of dissolved organic ligands for copper(II) in oceanic water

The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log K_CuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log K_HL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.     

Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans

Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19micromol site mg(-1) C, and a logK' of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu-FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC(50) of 58.9microgl(-1). However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC(50) ranging from 55.6microgl(-1) in the no-FA control to 137.4microgl(-1) in the 20mgl(-1) FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu-FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.