不同性质天然有机物对水中颗粒稳定性影响的机理研究

以不同来源天然有机物(NOM)及其各分离组份和模型颗粒Al(OH)₃为研究对象,考察了pH值、二价金属离子Ca²⁺以及NOM的特性等因素对Al(OH)₃颗粒稳定性的影响,并通过研究几种NOM吸附性能和吸附前后的特性变化,进一步探讨了NOM对颗粒稳定性的影响机理.结果表明,Al(OH)₃颗粒的等电点pH_iep出现在pH5～6之间,吸附态有机物是造成颗粒稳定性提高的主要原因,溶液中自由态Ca²⁺离子能够起到压缩双电层的作用,降低吸附态NOM之间的静电斥力,减小表面负电性,增加pH_iep;吸附络合态Ca²⁺离子对颗粒表面负电性影响较小,但能够强化NOM在颗粒表面的吸附.NOM作为聚合态阴离子,在颗粒表面的吸附行为不符合Langmuir吸附模型,最大吸附发生在pH 4左右,吸附作用能够去除几种NOM中分子量较大的部分,并减小其羧基官能团的相对含量,NOM中大分子量、芳香性高的成分是造成水中颗粒稳定性提高的主要原因.     

Complexing agents in waste waters of finnish electrolytic and chemical surface treatment plants

Goal, Scope and Background  Complexing agents are one of the major environmental concerns in electrolytic and chemical surface treatment (ECST) industry; e.g. the EU reference document on the best available technology (BREF) pays special attention to the usage of EDTA. However, no comprehensive studies are available on usage of EDTA or other complexing agents or their load to the receiving waters from ECST industry. In this study, the concentrations of complexing agents were analyzed to get an overview of their usage and load and also to recognize their relevance in the environmental permitting and compliance monitoring of such facilities. Methods  Complexing agent concentrations of treated waste water samples of 23 ECST plants with vat volume exceeding 30 m³ was studied. HPLC and GC-MS were used to analyze and identify complexing agent concentrations, ICP-AES to analyze metals, and TOC to analyse the organic load. The number of the plants in this study equals around 50% of such installations in Finland subject to environmental permit as the IPPC directive provides. Results  EDTA, DTPA, and NTA were found in 11 samples out of 23 mainly in rather small concentrations. Their annual load to the receiving waters may be estimated to be 0.3 tons and the total load from Finnish ECST industry can be extrapolated to be up to 1 ton. Compared to the estimated use of 5–10 tons in the industry this finding is rather low, even though in Finland cast-off treatment baths are typically delivered to the hazardous waste treatment plants. Discussion  Since the load of complexing agents is rather low, the chemical waste water treatment seems to be either capable of reducing complexing agent concentrations to some extent or their usage is lower than expected. On the other hand, it is possible that not all complexing agents were identified from the samples. The metal concentrations and TOC were well hand in hand with concentrations found in the Finnish environmental database, which proves that the samples were of average quality of the waste water from the facilities. Conclusions  According to the results, complexing agents cannot be considered as an environmental risk in the ECST industry in Finland; EDTA concentrations are clearly below PNEC_aqua (2.2 mg/l) and the total discharge is very marginal compared to the discharge from the pulp and paper industry. However, DPTA seems to be as commonly used as EDTA, but also biodegradable NTA was found. Recommendations and Perspectives  Since EDTA has gained plenty of attention in the BREF, DTPA and other, poorly biodegradable complexing agents should also be taken into account when the BREF is updated within a few years. Also an EU risk assessment report especially for DTPA should be supplied, since its use is obviously increasing.     

The use of poplar during a two-year induced phytoextraction of metals from contaminated agricultural soils

The efficiency of poplar (Populus nigra L.xPopulus maximowiczii Henry.) was assessed during a two-year chemically enhanced phytoextraction of metals from contaminated soils. The tested metal mobilizing agents were EDTA (ethylenediaminetetraacetic acid) and NH4Cl. EDTA was more efficient than chlorides in solubilizing metals (especially Pb) from the soil matrix. The application of chlorides only increased the solubility of Cd and Zn. However, the increased uptake of metals after the application of higher concentrations of mobilizing agents was associated with low biomass yields of the poplar plants and the extraction efficiencies after the two vegetation periods were thus comparable to the untreated plants. Additionally, the application of mobilizing agents led to phytotoxicity effects and increased mobility of metals. Higher phytoextraction efficiencies were observed for Cd and Zn compared to Pb and Cu. Poplars are therefore not suitable for chemically enhanced phytoextraction of metals from severely contaminated agricultural soils.     

Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.     

EDTA和铁对铜绿微囊藻和四尾栅藻生长和竞争的影响

铁限制不但会影响浮游植物的种群密度,而且会影响浮游植物的群落结构.为了探讨有机配体和铁的作用对湖泊中浮游植物的种群竞争,采用批量培养的方法,研究了不同EDTA及Fe浓度下,太湖蓝藻铜绿微囊藻和绿藻四尾栅藻的生长和竞争.结果表明,较高浓度的EDTA（≥13 .5 μmol/L）可以抑制铜绿微囊藻的生长,但不抑制四尾栅藻,因而有利于四尾栅藻占据优势;铁的浓度由3 μmol/L增大至18 μmol/L时,可缓解较高浓度EDTA（13 .5～27 μmol/L）对铜绿微囊藻的抑制作用,而增大其它微量元素浓度（B、Mn、Zn、Cu、Mo等）则无此作用;说明高浓度EDTA与铁的螯合作用能抑制铜绿微囊藻而不抑制四尾栅藻.高浓度EDTA对2种藻具有不同影响的原因可能是2种藻对铁的吸收机制不同.     

EDTA对4种花卉富集Cd、Pb的效应

植物提取修复技术(Phytoremediation)是一种环境友好的重金属污染土壤原位修复技术,但是修复植物的提取效率经常受到目标金属的低植物有效性所限制。通过盆栽试验研究了乙二胺四乙酸(ethylenedi-aminetetraacetic acid,EDTA)对4种花卉富集Cd、Pb效应的影响。结果表明:施加EDTA溶液(3mmol/kg)7d后,矮牵牛、万寿菊、彩叶草叶部Cd含量显著增加(P<0.05);所选4种花卉叶部Pb的含量均极显著增高(p<0.01)。施加EDTA后万寿菊对Cd和孔雀草对Pb的富集系数和转移系数均达到了1以上,这表明这两种植物可用于螯合辅助植物提取方式的污染土壤修复。     

EDTA及有机酸对污染土壤中Pb去除效应的研究

研究EDTA及柠檬酸、酒石酸、草酸3种低相对分子质量有机酸对棕壤、潮土、褐土中Pb(含量为1 000 mg/kg)的去除效应.结果表明,EDTA及3种低相对分子质量有机酸对棕壤中Pb的去除能力依次为EDTA＞柠檬酸＞酒石酸＞草酸,去除效率分别为83%、5.4%、3.4%和0.5%;对潮土和褐土中Pb的去除能力依次为EDTA＞柠檬酸＞草酸＞酒石酸,EDTA对Pb的去除效率分别为81%和90%,柠檬酸对Pb的去除效率分别为2.7%和2.5%,草酸和酒石酸对Pb没有明显去除效应.研究表明,EDTA和柠檬酸对Pb的去除率基本随着自身浓度的增加而增大,且柠檬酸对棕壤中Pb的去除效果明显好于潮土和褐土.     

亚临界锅炉的化学清洗

针对灞桥热电厂300MW超临界机组的特点、安装进度及环保要求,制定了相应的化学清洗方案并进行了炉前热力系统和锅炉本体除油清洗,以及中高压给水系统和炉本体的EDTA清洗。实践表明,灞桥热电厂化学清洗范围、清洗工艺和清洗系统的设计是合理的。     

Degradation of chelating agents in aqueous solution using advanced oxidation process (AOP)

This article presents an overview with critical analysis of technical applicability of advanced oxidation process (AOP) in removing chelating agents from aqueous solution. Apart from the effect of metals for chelating agents as a major influencing factor, selected information such as pH, oxidant’s dose, concentrations of pollutants and treatment performance is presented. The performance of individual AOP is compared. It is evident from our literature survey that photocatalysis with UV irradiation alone or coupled with TiO₂, ozonation and Fenton’s oxidation are frequently applied to mineralize target pollutants. Overall, the selection of the most suitable AOP depends on the characteristics of effluents, technical applicability, discharge standard, regulatory requirements and environmental impacts.     

活性炭吸附处理电镀废水中的EDTA

采用颗粒活性炭对模拟废水中EDTA进行批式吸附实验,在实验中考察了恒温振荡器的振荡速度、温度、pH值等因素对吸附的影响,同时探讨了吸附等温线模型和吸附动力学模型。实验结果表明,在25％时活性炭对EDTA的吸附平衡时间为40h。在pH值为5．0、温度为25℃、振荡器振荡速度为200r／min、活性炭粒径为1～2mm、活性炭加入量为10g／L的情况下,EDTA的浓度在48h内由368．8mg／L降低至76．34mg／L,对应的COD值从305．9mg／L降低为67．21mg／L,去除率达到了79．3％。活性炭对EDTA的吸附符合Langmuir吸附等温线模型,其吸附行为可以用准二级吸附动力学模型来描述。