城市地表汞含量及释放通量影响因素分析

测定了长春市不同类型地表汞含量及其释放通量，分析了地表汞释放通量的影响因素。研究结果表明，不同地表土样的汞含量存在很大的差异；煤炭堆放地和沥青地地表汞含量较高，应引起足够的重视。地表汞释放通量受地表汞含量、地表类型、降水、太阳辐射等因素的影响。降水期间或降水后期地表汞释放通量明显增加。可见，地表汞释放是一个动态过程，随时间和空间而变化。     

Seasonal variation of total dissolved arsenic and arsenic speciation in a polluted surface waterway

Seasonal differences in the dissolved arsenic concentration and speciation in a contaminated urban waterway in northwest England have been determined using a coupled ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) technique. Waters sampled in the vicinity of an industrial works during relatively dry conditions in April 2000 were found to contain total arsenic concentrations (As) of up to 132 g L^–1, more than an order magnitude greater than the 4 g L^–1 maximum found in December 2000. The difference in As between the April and December sampling periods is speculated to be largely due to the irregular anthropogenic supply of arsenic to the watercourse. For both sampling periods, the dissolved arsenic was exclusively inorganic in nature and had an As(V)/As ratio of between 0.6 and 0.8. Analysis of samples taken downstream of the industrial site, after the confluence with a relatively As-poor stream, revealed that As(III), As(V) and As concentrations were lower than would be expected from conservative mixing. The As(V)/As ratio was also observed to decrease markedly. The loss of arsenic from solution is thought to be due to adsorption on the iron oxyhydroxide-rich sediment observed to coat the riverbed downstream of the confluence. The reduction in the As(V)/As ratio is believed to be due to the more rapid adsorption of As(V) compared to that of As(III). Deviations from conservative behaviour were more marked during the relatively dry April 2000 sampling period and suggest the increased importance of adsorption processes controlling arsenic availability during this time.     

Lowest Effect Levels of Lead and Mercury on Decomposition of Mor Layer Samples in a Long-Term Experiment

Indications of possible negative effects of lead (Pb) and mercury(Hg) on microbial respiration in Southern Swedish forest humus layers led to experiments on dose-response relationships by additions of metal salts in the laboratory. Respiration rates andweight loss due to decomposition of organic material were measured. For relevance to field situations metal doses were low,the time span was long, 550 days including freeze storage, and microbial activity was kept up by plant litter additions. We looked for effects of Pb and Hg at levels moderately elevated above the Southern Swedish reference, as well as combined effectsof Pb + Hg. A reduction in respiration and decomposition of10% was found at about 225–245 g g^-1 of total Pb, i.e. ata Pb level elevated 3.5 times. Although small effects of Hg werefound even at the lowest dose level, 10% inhibition of microbialactivity appeared temporarily at about 2–3 g g^-1 of total Hg, i. e. at 6–8 times the reference level. There were nolong-term additive effects of Pb and Hg on decomposition. Type of anion had a strong influence on the test, chlorides of Pbbeing more toxic than nitrates. Long-term monitoring and maintenance of microbial activity during the experiment were prerequisites for the occurrence of effects at low metal levels.     

不同粒级的煤胶体对汞的吸附动力学

为了解煤胶体对汞的吸附动力学特性,采用沉降法和离心法提取由霍林河采集煤样中的煤胶体（0~2、2~5、5~10 μm）,采用批量实验对不同粒径和不同温度下,煤胶体对汞的吸附动力学特性进行了研究。结果表明：煤胶体对汞的吸附反应为吸热反应,以化学吸附为主,其吸附动力学过程可用准二级动力学方程和双室模型很好的描述。煤胶体对汞的平衡吸附量随粒径的减小和温度的升高而逐渐增大,不同粒径煤胶体受温度影响的大小关系为（5~10）μm > （2~5）μm > （0~2）μm。煤胶体对汞的吸附从初始阶段到达到表观平衡,快速吸附均占据优势。在表观平衡时,粒径越大,快速吸附的贡献率越小。煤胶体对汞的吸附反应速率随温度升高和粒径减小而增大。温度越高、粒径越小,快速吸附速率越大;而慢速吸附速率则随温度升高和粒径增大而增大。汞在0~2 μm和2~5 μm煤胶体上的吸附过程,粒内扩散是其主要控速步骤;而对于5~10 μm的煤胶体,膜扩散是主要控速步骤。     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).     

Investigation of the complexation of metal-ions by strong ligands in fresh and marine water

SCOPE: The detection and investigation of metal ions bound in strong complexes in natural waters is a difficult task, due to low concentration of the metal ions themselves, and also of the strong ligands, which, moreover, are often not of a well-defined composition. Here, a method is proposed for the investigation of the speciation of metal ions in natural waters. OBJECTIVE AND METHOD: It is based on the sorption of metal ions on strongly sorbing ion exchange resins, i.e. complexing resins. For this reason the method is called Resin Titration. It has been shown in previous investigations that the concentration of metal ion totally sorbed by a particular resin, and its reaction coefficient in the solution phase in the presence of the resin, can be determined from the sorption data using a simple relationship. Here, a data treatment (the Ruzic linearization method) is proposed for also determining the concentration of the ligands responsible for the complex in equilibrium with the resin. RESULTS: The method was applied to data obtained by Resin Titration of a freshwater and a seawater. Copper(II) and aluminium(III) were considered, using Chelex 100 as a titrant, due to its strong sorbing properties towards these metal ions. The results were: the total metal concentration in equilibrium with the resin, the side reaction coefficients, and the concentration of ligands. In all these cases the ligands forming very strong complexes were found to be at concentration lower than that of the metals. CONCLUSION: The Ruzic linearization method allows the determination of the concentration of the ligands forming very strong complexes in equilibrium with Chelex 100. The reaction coefficient was better determined by the calculation method previously proposed for RT. The ligands responsible for the strong complexes were found to be at low concentration, often lower than that of the metal ions considered. The metal in the original sample is partly bound to these ligands, since the complexes are very strong. Only a part of the metal is linked to weaker ligands, or free.     

氯化铜改性石墨相氮化碳吸附剂的脱汞性能

针对燃煤电厂汞污染物排放控制的问题, 以尿素为前驱体, 通过直接热聚合法制得绒毛状石墨相氮化碳(g-C₃N₄), 并用于低温条件下吸附脱除单质汞(Hg⁰)。利用透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附、X射线光电子能谱(XPS)等手段对吸附剂进行表征。结果表明:未改性g-C₃N₄具有良好的低温脱汞活性, 在120 ℃时其脱汞效率可达84.7%;CuCl₂改性可以有效提高g-C₃N₄的脱汞性能, 其脱汞效率在40~200 ℃范围内均可达到97%以上; 温度对吸附剂脱汞效率的影响较小。XPS表征测试结果表明, 铜离子和共价态氯原子均参与了单质汞的吸附脱除反应, Hg⁰被Cu²⁺离子和共价态Cl原子氧化成了Hg²⁺离子, 再吸附于g-C₃N₄表面而脱除。CO₂、SO₂和水蒸气对吸附剂脱汞效率影响较小, 但水蒸气可提高汞吸附量。     

纳米零价铁对铀尾矿库土壤中铀形态分布及固定效果的影响

针对纳米零价铁(nZVI)对铀尾矿库土壤中铀形态分布和U(Ⅵ)固定效果影响问题,采用逐级化学提取、毒性浸出(TCLP)和磁性分离实验,利用SEM-EDS和XRD对nZVI固定前后的铀尾矿土壤进行表征;研究了nZVI在不同投加量和pH条件下,对尾矿库土壤固定前后铀的形态分布和固定效果的影响,并对nZVI的固定机理进行了探讨。结果表明：当nZVI的投加量为8%、pH为5时,土壤中U(Ⅵ)的固定效果最好,固定后土壤中铀的毒性浸出值仅为13.98%;对经过nZVI处理后的铀尾矿土壤进行磁性分离发现,磁性和非磁性土壤重量占比分别为32.87%和67.13%,其铀含量分别达到55.05%和44.95%,说明nZVI对土壤中的U(Ⅵ)有较好的富集作用。nZVI对铀尾矿库土壤中的U(Ⅵ)有较好的原位固定和富集效果,并能减少土壤中铀的析出。     

Fenton氧化联合人工湿地处理污泥中的重金属

针对单独应用Fenton氧化技术处理污泥的不足以及人工湿地在处理污水污泥方面的优势,以污水处理厂污泥浓缩池中含重金属污泥为对象,研究其依次经过Fenton氧化和人工湿地处理后重金属的去除效果及形态变化,以及污泥pH、TN和TP的变化情况。结果表明,Fenton氧化提高了污泥重金属的生物有效性,并促进了人工湿地对重金属的去除。Fenton氧化污泥经人工湿地处理后,Cu、Zn、Ni和Mn的去除率分别为67.2%、79.7%、37.0%和17.0%,与对照相比重金属的平均去除率提高了27.5%。经人工湿地处理后Fenton氧化污泥和原污泥重金属的生物有效性均降低。Fenton氧化污泥pH为4.4～4.6,经人工湿地处理后为6.2～7.1。人工湿地对Fenton氧化污泥和原污泥中TN的影响较小,而对TP表现出较高的去除率,2系统TP的去除率分别为51.1%和45.5%。     

超声和无机酸浸提猪粪中的重金属

对比研究了无机酸及超声对猪粪中重金属Cu、Zn和Mn的去除效果,并对处理前后猪粪中重金属形态变化进行分析。结果表明:无机酸浸提优化条件下Cu、Zn和Mn的浸出率分别为43.24%、76.28%和78.91%;超声协同无机酸浸提优化条件下Cu、Zn和Mn的浸出率分别为39.6%、76.3%和79.9%;2种浸提方式均能显著降低猪粪中重金属有机结合态含量。