珠江口水体中铜与悬浮颗粒物相互作用的研究

使用无机离子交换法研究珠江口水体中铜与悬浮颗粒物的相互作用，测出钢与悬浮颗粒物相互作用的ｐＨ曲线呈Ｓ形，其分级离子交换等温线是一种新的“台阶”型；从分级离子交换理论求得分级平衡常数Ｋ１为５．０，Ｋ２为７８．１，珠江口水体中铜的表观络合容量为０．９２μｍ及其条件稳定常数为３．５×１０７。     

壳聚糖/纳米铜复合微球的制备及其对刚果红染料的脱色性能

以壳聚糖和CuCl₂·2H₂O为原料,分别采用直接负载法和吸附法成功制备了壳聚糖/纳米铜复合微球,运用傅里叶变换红外光谱(FT-IR)、X-射线衍射(XDR)和扫描电镜(SEM)对催化剂结构进行了表征。以刚果红(CR)染料为目标污染物,评价了催化剂的制备方法、制备条件及氢转移催化反应条件对其催化性能的影响。结果表明,由直接负载法(CS/CuNPs)和吸附法(CS/CuNPs-X)制备的壳聚糖/纳米铜复合微球在CR染料浓度为100 mg/L,催化剂投加量为0.05 g,供氢体浓度为0.05 mol/L的氢转移催化反应条件下,催化反应进行180和60 min时CR脱色率可分别达95.8%和96.8%。CS/CuNPs-X比CS/CuNPs表现了更高的对CR氢转移催化反应的催化速率。两种催化剂催化还原CR染料的反应均符合准一级动力学模型。在连续循环使用10次后,CS/CuNPs和CS/CuNPs-X对CR的脱色率分别为93.9%和89.4%,表明催化剂具有良好的重复使用性能。     

Accumulation of Cu and Zn in discarded antifouling paint particles by the marine gastropod, Littorina littorea

The short-term (5 day) accumulation of Cu and Zn in different tissues of the marine gastropod, Littorina littorea, has been studied in the presence of 10 mg l⁻¹ of antifouling paint particles and pre- or simultaneously contaminated algal food (Ulva lactuca). Accumulation of Cu was observed in the head–foot, digestive gland–gonad complex and gills to extents dependent on how and when food was contaminated and administered. However, retention of Zn was only observed in the gills and only when L. littorea and U. lactuca were simultaneously exposed to paint particles. Relative to the alga, faecal material was highly enriched in Zn, suggesting that the animal is able to rapidly eliminate this metal, most likely through the formation and egestion of insoluble phosphate granules. Thus, L. littorea is a useful biomonitor of marine contamination by antifouling applications in respect of Cu but not Zn.     

LMWOA (low molecular weight organic acid) exudation by salt marsh plants: Natural variation and response to Cu contamination

This work aimed to evaluate, in vitro, the capability of roots of two salt marsh plants to release low molecular weight organic acids (LMWOAs) and to ascertain whether Cu contamination would stimulate or not organic acids exudation. The sea rush Juncus maritimus and the sea-club rush Scirpus maritimus, both from the lower Douro river estuary (NW Portugal), were used. Plants were collected seasonally, four times a year in 2004, during low tide. After sampling, plant roots were washed for removal of adherent particles and immersed for 2 h in a solution that matched salinity (3) and pH (7.5) of the pore water from the same location to obtain plant exudates. In one of the seasons, similar experiments were carried out but spiking the solution with different amounts of Cu in order to embrace the range between 0 and 1600 nM. In the final solutions as well as in sediment pore water LMWOAs were determined by high performance liquid chromatography. Plants were able to release, in a short period of time, relatively high amounts of LMWOAs (oxalate, citrate, malate, malonate, and succinate). In the sediment pore water oxalate, succinate and acetate were also detected. Therefore, plant roots probably contributed to the presence of some of these organic compounds in pore water. Exudation differed between the plant species and also showed some seasonally variation, particularly for S. maritimus. The release of oxalate by J. maritimus increased with Cu increase in the media. However, exudation of the other LMWOAs did not seem to be stimulated by Cu contamination in the media. This fact is compatible with the existence of alternative internal mechanisms for Cu detoxification, as denoted by the fact that in media contaminated with Cu both plant species accumulated relatively high amounts (29–83%) of the initially dissolved Cu. This study expands our knowledge on the contribution of globally dominant salt marsh plants to the release of LMWOAs into the environment.     

Study on copper complexing ligand concentrations in several China’s coastal waters

Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows: Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer (SSL) in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complexing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China' s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.     

Distribution of dissolved species and suspended particulate copper in an intertidal ecosystem affected by copper mine tailings in Northern Chile

The coastline near Chañaral in Northern Chile is one of the most highly Cu-contaminated zones in the world due to discharges from mining activities for more than 60 years. The speciation of Cu has been studied to determine the importance of organic complexation in highly contaminated areas, and to assess the likely physiological impacts of Cu on marine organisms. Dissolved Cu concentrations of up to 500 nM were measured, completely saturating organic ligands and leading to free Cu²⁺ concentrations in excess of 10^− 8 M. These values are higher than those reported in any other marine environment, and because they occur over an extensive area, provide a unique opportunity to study the effects of Cu on marine ecosystems and to see how Cu behaves when its speciation is predominantly inorganic. We found strong gradients in free Cu²⁺ between Chañaral and adjacent areas with lower Cu, where speciation is dominated by organic complexation. There is also a significant increase in the partitioning of Cu onto suspended particles in the contaminated areas, consistent with previous studies that showed that organic ligands stabilize Cu in the dissolved phase, whilst “excess” Cu is rapidly scavenged. Those high dissolved Cu concentrations persist in spite of solid phase partitioning and advective processes along this open-ocean coastline, suggesting that Cu inputs into the system are still very large. Measurements were made using anodic stripping voltammetry with a thin mercury film coated with Nafion, which previous workers have shown can mitigate ambiguity in the data arising from inadvertent reduction of organic complexes. Our findings suggest that this is a useful methodology for contaminated systems.     

饲料中铜离子对斑节对虾血细胞组成、活性和免疫功能的影响

以不同铜离子添加量(0, 10, 25, 40, 55 和110 mg/kg)的饲料喂养斑节对虾(Penaeus monodon)8 周,测定对虾的血细胞总数(THC), 并应用流式细胞术测定血细胞中含颗粒细胞(小颗粒细胞和大颗粒细胞)的比例、血细胞凋亡率、活性氧(ROS)含量和酯酶活性。结果显示, 当铜添加量为10～55 mg/kg 时, 与对照组相比, 对虾的THC、血细胞凋亡率、ROS 含量和酯酶活性均没有显著的变化(P>0.05); 铜添加量为25～110 mg/kg 时, 含颗粒细胞的比例显著提高(P<0.05); 铜添加量为110 mg/kg 时, ROS 含量显著高于其他组(P<0.05), 血细胞凋亡率高于25 和55 mg/kg 组(P<0.05), THC 低于55 mg/kg 组(P<0.05), 酯酶活性低于25mg/kg 组(P<0.05)。这些结果表明, 适宜的饲料铜含量有利于两类颗粒细胞的生成; 铜添加过量(110 mg/kg)会诱导血细胞ROS 的产生, 造成氧化损伤, 从而导致凋亡率上升和THC 下降。综上所述, 在本实验日粮条件下, 针对斑节对虾的血细胞功能, 其饲料中铜适宜添加含量范围为25～55mg/kg。     

Copper,chromium, and lead in Manukau Harbour sediments

A limited survey was undertaken to determine the concentrations of copper, lead, and chromium in sediments of the upper Manukau Harbour, New Zealand. The concentrations of copper and chromium (33–70 and 70–107 μg g^‐1 respectively) were of the same order of magnitude as those reported for other New Zealand harbours. However, lead concentrations (98–247 μg g^‐1) were higher than those found for the other harbours. This may be a consequence of higher traffic densities in the surrounding area.     

吡啶硫酮类防污剂对华美盘管虫早期不同发育阶段的毒性效应研究

以中国南海常见的多毛类——华美盘管虫(Hydroides elegans)作为受试生物,分别研究了吡啶硫酮铜和吡啶硫酮锌对早期不同发育阶段的华美盘管虫的急性毒理效应。发现暴露于吡啶硫酮铜的华美盘管虫精子和卵子的受精半数抑制浓度(IC50)分别为19.49μg/L和88.44μg/L,担轮幼虫24 h半数致死浓度(24h-LC50)和48 h半数致死浓度(48h-LC50)分别为7.35μg/L和5.00μg/L,后担轮幼虫24h-LC50和48h-LC50分别为8.57μg/L和5.87μg/L;暴露于吡啶硫酮锌的华美盘管虫精子和卵子的受精IC50分别为36.74μg/L和159.59μg/L,担轮幼虫24 h-LC50和48 h-LC50分别为8.57μg/L和6.67μg/L,后担轮幼虫24 h-LC50和48 h-LC50分别为12.03μg/L和8.07μg/L。表明华美盘管虫早期发育的不同阶段对吡啶硫酮铜和吡啶硫酮锌的敏感性表现出一定差异,与配子受精率和后担轮幼虫的毒性反应相比,担轮幼虫对吡啶硫酮铜和吡啶硫酮锌的毒性表现出较高的敏感性;而且,对吡啶硫酮铜的敏感性普遍高于吡啶硫酮锌。     

斑岩Cu-(Mo-Au)矿床的成矿构造环境及勘查意义

斑岩矿床是重要的矿床勘查目标。斑岩矿床的成矿构造环境研究有助于确定斑岩矿床的战略勘查方向。斑岩矿床形成的成矿构造环境包括板块汇聚边缘、大陆转换板块边界、陆内造山环境和非造山环境。本文重点对斑岩矿床在汇聚边缘和大陆转换板块边界的成矿构造环境及其勘查意义进行初步总结。构造变化对斑岩矿床的形成起到触发作用。微弱和中等程度的转换挤压应力最有利于岩浆的集聚、上升和就位。岩浆侵入可以是在广阔的转换挤压断层带内或在其周围局部呈引张的地区集中出现。对于斑岩矿床战略勘查方向而言,应注意研究区域走滑断层与侵入体的关系,加强对地表浅部喷气蚀变的识别。在我国西南地区已勘查发现的5个斑岩成矿带中,应注意沿区域走滑断裂构造方向开展找矿。从成矿构造环境与哀牢山-红河构造带对比来看,鲜水河-小江断裂带可能是西南地区新的斑岩矿床勘查区。