乌江流域三个梯级水库氮磷形态的比较研究

为揭示河流梯级开发对生源要素氮磷输运的影响,本研究选择乌江流域的普定、乌江渡、思林作为上、中、下游梯级水库的代表,于2020年8月采集各水库水体剖面和沉积物柱样品,测定氮磷含量,并用SMT法提取沉积物磷形态。结果发现,受中下游人为污染输入影响,乌江渡水库水体总氮浓度最高,为3.92±0.50mg/L,总磷浓度在此坝前到下游急剧抬升为上游的2～3倍,达到0.04～0.06mg/L;坝前沉积物含有大量的高释放风险的铁铝活性磷(1310.3±1003.3mg/kg),可能成为下游的潜在污染源。中下游水库较高的生物量加快了氮磷的活化速度,提高了活性磷的浓度,反而减低了沉积物有机磷的生物拦截效率。除乌江渡水库外,其它水库沉积物中以钙结合态磷为主(占无机磷的60%以上)。梯级水库修建后,泥沙含量大幅降低,可能是下游水库沉积物钙结合态磷浓度降低的主要因素。总体上,梯级水库的累积效应使得水库对生源要素的“活化”效率增强、“拦截”效应减弱,增大了富营养化发生的风险。     

不同类型脱水药剂对底泥固化效果和理化性质的影响

为研究不同类型脱水药剂对疏浚底泥脱水固化等综合作用的效果,以太湖疏浚底泥为对象,选择了微生物类、聚合铁铝盐类、有机聚合物类、有机无机复合类和铝盐微生物复合类这5种类型的复合脱水药剂,以土工管袋固化的方式对疏浚底泥进行为期3个月的固化实验.结果表明,有机聚合物类和有机无机复合类药剂脱水效率较好,1个月后底泥含水率分别降至61.78%和63.26%, 3个月后分别降至40.56%和32.16%.与未固化底泥相比,经过有机无机复合类药剂固化后底泥总氮削减74.82%,达591 mg·kg^-1,主要以铵态氮的减少为主,固化底泥中的磷以铝结合态磷、钙结合态磷和铁结合态磷为主,其中有机无机复合类药剂对活性磷的削减量最大,活性磷含量降至64.3 mg·kg^-1.此外,研究发现有机聚合物类药剂对重金属的固化效果最好,重金属综合生态风险指数降低了51.3%,浸出毒性浓度均远低于标准阈值.有机聚合物类和有机无机复合类药剂对底泥的脱水固化综合效果较好,具有较好的应用前景.     

Cobalt speciation assay for human serum,Part I. Method for measuring large and small molecular cobalt and protein-binding capacity using size exclusion chromatography with inductively coupled plasma-mass spectroscopy detection

A method utilizing size exclusion liquid chromatography (SEC) was developed to separate and quantify large molecular cobalt (Co) (e.g., albumin-Co) from cyanocobalamin (vitamin B₁₂) and small molecular Co (e.g., glutathione-Co and free Co) in human serum. Highly selective and sensitive detection using inductively coupled plasma–mass spectrometry was coupled with SEC to provide a method with reliable accuracy, precision, recoveries, stability, and a detection limit of 0.037 μg/L in undiluted serum. Other divalent metal cations known to compete with Co(II) for serum albumin-binding sites (such as iron, zinc, manganese, cadmium, copper, nickel, and lead) did not significantly alter Co(II) quantification. Co–protein binding capacity determination of individual serum samples indicated that addition of 2500 μg Co/L to undiluted human serum resulted in approximately 90% distribution to the large molecular Co peak, consistent with Co binding to high-affinity divalent metal binding sites on albumin. Since serum albumin binding partially sequesters biologically active Co(II) ions, this method provides an important tool for better understanding the kinetics and toxicology of Co compounds. Thus, the proposed method might play an important role in establishing Co dose–response relationships that affect the equilibrium concentrations of free ionic Co(II).     

Induction of mercury‐binding peptide in whole cells and anucleated cells of Acetabularia calyculus

The present study reports the isolation and partial purification of a mercury‐binding polypeptide in whole and anucleated cells of Acetabularia calyculus. Sephadex G‐75 Gel filtration showed that cells exposed to Hg exhibit a major peak of protein(s) concomitant with both, a major peak of Hg (revealed by atomic absorption spectroscopy), and the major peak of mercury‐thiolate complex (based on a high 254 nm absorbance) accompanied by high content of SH groups. SDS‐Page electrophoresis showed that this peak contains one major polypeptide of apparent molecular weight 27.000 dalton. These results are in agreement with our previous finding of unusually high bioconcentration factor of Hg in Acetabularia related to the induction of a polypeptide in both, whole and anucleated cells of Acetabularia, in presence of Hg.     

槲皮素修饰玻碳电极(Qu/GCE)的制备及铜离子-牛血清白蛋白结合反应机制研究

通过滴涂法制备槲皮素修饰玻碳电极(Qu/GCE,Quercetin/Glassy Carbon Electrode),并对修饰电极进行电化学性能表征;利用槲皮素修饰电极研究了Cu2+离子与牛血清白蛋白(BSA,Bovine Serum Albumin)的结合反应机制.循环伏安法测试结果显示该修饰电极具有准可逆氧化还原反应;将槲皮素修饰电极应用于测试重金属离子-血清白蛋白的结合反应机制,在pH 5.0 HAc-NaAc缓冲溶液体系中,使用槲皮素修饰电极测定Cu2+-BSA相互作用,显示出良好的线性响应关系.根据文献报道结合实验数据,本文建议了结合参数计算理论方程,并利用建议的理论方程计算了Cu2+-BSA的结合常数及结合位点数,相关研究结果可为槲皮素修饰电极研究非共价相互作用提供有益参考.     

光谱法研究胞外聚合物与四溴双酚A的相互作用

利用三维荧光光谱和红外光谱研究污水处理厂活性污泥中萃取的胞外聚合物与四溴双酚A之间的相互作用.结果显示,活性污泥胞外聚合物中存在3个明显的荧光峰,分别为,E_x/E_m=230/300nm(峰A)、E_x/E_m=240/350nm(峰B)和E_x/E_m=270/370nm(峰C).荧光滴定结果表明,3个荧光峰随着四溴双酚A 的加入均发生不同程度的猝灭.修正的Stern-Volmer模型和Ryan-Weber非线性模型计算胞外聚合物与四溴双酚A之间的结合常数,二者间的结合常数值(lg K)在4.23~6.27之间.红外光谱和同步荧光结果显示,胞外聚合物与四溴双酚A 结合导致胞外聚合物原有的蛋白质结构发生变化.同时,考察了不同环境条件(pH值、电导率以及离子)对两者作用的影响.结果表明:pH值和离子变化对胞外聚合物与四溴双酚A结合强度有影响,但电导率的变化影响并不显著.     

文蛤谷胱甘肽抗氧化系统对北部湾沉积物中可提取态重金属的响应

为识别海洋双壳类谷胱甘肽抗氧化系统对滨海沉积物重金属可提取态和总量的响应特征差异,分析了北部湾潮间带沉积物中不同形态Cu、Pb、Zn、Cd、Cr的质量分数,文蛤(Meretrix meretrix)鳃组织中w(GSH)(GSH为还原型谷胱甘肽)、w(GSSG)(GSSG为氧化型谷胱甘肽)、GPx(谷胱甘肽过氧化物酶)和GST(谷胱甘肽硫转移酶)活性,并计算w(GSH)/w(GSSG)、tGSH(总谷胱甘肽)含量和OSI(氧化逆境指数). 结果表明:w(TE-Pb)(TE-Pb为可提取态Pb,下同)、w(TE-Cr)、w(TE-Cu)、w(TE-Zn)和w(TE-Cd)平均值分别为13.40、1.93、13.19、30.09和0.10mg/kg; w(TE-Cd)占w(T-Cd)(T-Cd为总Cd,下同)的60.2%~98.1%,并且主要为弱酸溶解态和有机物及硫化物结合态;部分采样点w(TE-Pb)和w(TE-Zn)较高,二者占w(T-Pb)和w(T-Zn)的平均值分别为44.6%和56.6%;Cr、Cu分别在全部或大多数采样点以残渣态为主,可提取态含量平均仅占总量的17.9%和36.5%. 重金属的可提取态质量分数与总量的空间分布基本一致(Cr除外). 文蛤鳃中w(GSH)、w(GSSG)分别为4.07~6.06、4.01~6.59mg/g. 抗氧化指标对沉积物中重金属总量和可提取态质量分数均有显著响应的为w(GSSG)与Cd,w(GSH)/w(GSSG)与Cr和Cd,OSI与Cr和Cd. 然而,w(GSH)/w(GSSG)和OSI只对w(T-Zn)有良好响应;GST只与w(TE-Cu)、w(TE-Zn)显著相关. 某些抗氧化指标对重金属总量和可提取态质量分数表现出不同程度的响应,因此,不能单独依据双壳类对重金属总量的生化响应特征来筛选用于沉积物综合毒性评价的生物标志物.      

Quantitative characterization of Cu binding potential of dissolved organic matter （DOM） in sediment from Taihu Lake using multiple techniques

Dissolved organic matter （DOM） plays an important role in heavy metal speciation and distribution in the aquatic environment especially for eutrophic lakes which have higher DOM concentration. Taihu Lake is the third largest freshwater and a high eutrophic lake in the downstream of the Yangtze River, China. In the lake, frequent breakout of algae blooms greatly increased the concentration of different organic matters in the lake sediment. In this study, sediment samples were collected from various part of Taihu Lake to explore the spatial difference in the binding potential of DOM with Cu. The titration experiment was adopted to quantitatively characterize the interaction between Cu（II） and DOM extracted from Taihu Lake sediments using ion selective electrode （ISE） and fluorescence quenching technology. The ISE results showed that the exogenous DOM had higher binding ability than endogenous DOM, and DOM derived from aquatic macrophytes had a higher binding ability than that derived from algae. The fluorescence quenching results indicated that humic substances played a key role in the complexation between DOM and Cu（II） in the lake. However, because of the frequent breakout of algae blooms, protein-like matters are also main component like hnmic matters in Taihu Lake. Therefore, the metals bound by protein-like substances should be caused concern as protein-like substances in DOM were unstable and they will release bound metal when decomposed.     

海岸带表层沉积物中磷的地球化学特征

通过连续提取法对莱州湾主要入海河流及近岸海域表层沉积物中5种形态磷进行了定量分析.结果表明,近海沉积物自生钙结合磷含量(45.6%)高于河流(37.3%),而铁结合磷(Fe-P)含量(18.2%)却低于河流(31.3%).在近海,可交换或弱结合磷含量和粉砂比例呈正相关,表明该形态磷主要吸附于细粒粉砂．河流沉积物Fe-P与Fe浓度呈显著正相关(P<0.01),表明河流沉积物Fe-P分布受沉积物活性铁含量的控制．河口处Fe-P普遍低于相应河流,这可能与海相泥沙输入及河口厌氧区硫酸盐还原或硫化物累积有关.近海沉积物总可提取态磷平均浓度总体呈现出由海洋向河口方向递减的趋势.     

香溪河流域富磷区土壤酶活性与无机磷形态相关性研究

陆源氮磷不断向水体输入已经成为水体富营养化的主要诱因。香溪河流域内分布着鄂西著名的磷矿区,该区域丰富的磷对香溪河水质产生严重影响。选取流域内磷矿区为研究对象,旨在探讨磷矿区土壤酶活性与无机磷形态之间的内在关系,进而探求用土壤酶系统表征土壤磷污染程度的可行性。结果表明:土壤酶活性与无机磷形态之间有着密切关系。其中,过氧化氢酶、蔗糖酶、脲酶活性与无机磷形态呈正相关关系,而多酚氧化酶和碱性磷酸酶活性与无机磷形态呈负相关关系。土壤过氧化氢酶、多酚氧化酶、蔗糖酶、脲酶及碱性磷酸酶活性均与无机磷形态之间呈现出不同程度的相关性,可作为反映磷矿区土壤磷污染状况的指示酶。