氨三乙酸酐改性纤维素对Cd~(2+)的吸附性能

本实验采用氨三乙酸酐改性玉米秸秆纤维素和苎麻纤维素,制备了两种改性纤维素吸附剂NTAA-CS及NTAA-RF,并研究了这两种吸附剂对水中Cd2+的吸附性能.通过元素分析、FTIR及SEM分析发现,纤维材料表面成功引入了氨三乙酸分子中的酯键和氨基基团.在改性纤维素吸附剂投加量为2 g·L-1,Cd2+的初始浓度为200 mg·L-1,p H值为4.0时,NTAA-CS和NTAA-RF对Cd2+的去除率分别为82.6%和90.2%.吸附实验结果表明:改性纤维素吸附剂对Cd2+的吸附是一个快速过程,吸附的最佳p H范围为4.0~7.0.吸附等温线用Langmuir方程的拟合效果优于Freundlich方程.经过5次吸附再生,吸附剂仍可以保持较大的吸附容量.这些结果表明,NTAA-CS和NTAA-RF在去除重金属废水中有较大的应用前景.     

Formation of aerobic granules in the presence of a synthetic chelating agent

This paper examines the development of aerobic granular sludge in the presence of a synthetic chelating agent, nitrilotriacetic acid (NTA), in sequencing batch reactors (SBR). The growth of seed sludge at 0.26 mM, 0.52 mM and 1.05 mM of NTA was found to be significantly lower as compared to that in the absence of NTA. Aerobic granulation was significantly enhanced in the three SBRs (R2, R3 and R4), which were fed with 0.26 mM, 0.52 mM and 1.05 mM of NTA as a co-substrate, in comparison to the acetate-alone fed SBR (R1). After 2 months of operation, the mean diameter of the biomass stabilized at 0.35 mm in R1 (acetate alone), as compared to 2.18 mm in R4 (1.05 mM NTA+acetate). NTA degradation was established in SBRs, with almost complete removal during the SBR cycle. Batch experiments also showed efficient degradation of NTA by the aerobic granules.     

Polarographic investigations on the complexation of cadmium and zinc by thiol peptides

Complex formation of Cd²⁺ and Zn²⁺ with thiol derivatives has been investigated by differential pulse polarography. The binding of Cd²⁺ and Zn²⁺ with cysteine (CySH), glutathione (GSH) and the model peptide N‐acetyl‐cysteine‐methylamide (ASH) reveals different stoichiometry. Thus, Cd²⁺ forms 1:1 and 1:2 complexes with CySH while 1:2 and 1:4 complexes have been observed with GSH and ASH, respectively. Overall formation constants of Cd²⁺ with CySH (Iogβ ₂ 15.3) and with GSH (Iogβ5₂ 14.4) have been estimated using competitive complexation with nitrilotriacetic acid (NTA). Investigation of competition between Zn²⁺ and Cd²⁺ for the thiol complexation has underlined the role played by the amino group in CySH for the stabilization of Zn complexes in contrary to Cd complexes.     

烧结烟气氨-Fe(Ⅱ)NTA法同时脱硫脱硝

研究了烧结烟气氨-络合法同时脱硫脱硝。实验结果表明,氨-络合法可以实现烧结烟气同时脱硫脱硝,脱硫脱硝效率最高可达99%和40%。最佳运行条件为:Fe(NTA)浓度为0.075 mol/L,p H为5~6,停留时间为1.24 s(350 L/h的烟气流量)及55℃运行温度。     

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.     

NTA和DTPA对小麦幼苗对金属吸收的诱导效应

通过盆栽试验和化学提取实验研究了有机配体NTA和DTPA对小麦对沙土中外源重金属Cd,Cu,Pb和Zn的吸收的影响.研究表明,在所试验的土壤金属浓度下,有机配体NTA和DTPA的添加均明显导致小麦幼苗中金属Cu,Zn,Cd和Pb富集量的增加,且DTPA的作用效果高于NTA.10mmol·kg-1DTPA作用效果高于5mmol·kg-1DTPA,但提高程度有限.NTA处理组各金属14 d茎叶富集系数高于7 d茎叶富集系数.对于不同金属,DTPA的作用导致小麦幼苗茎叶富集系数随时间变化的规律不同.5mmol·kg-1NTA,5mmol·kg-1DTPA和10mmol·kg-1DTPA的添加明显导致土壤中4种外源金属的0.01 mol·L-1CaCl2提取态含量的增加.小麦茎叶重金属富集量与0.01mol·L-1CaCl2提取态金属含量具有较好的相关性,说明配体NTA和DTPA的添加导致小麦幼苗对4种金属的富集量的增加是与其导致0.01 mol·L-1CaCl2提取态含量的增加是密切相关的.     

NTA与EDTA联合施用对茼蒿富集土壤重金属的影响

为了解非生物螯合剂EDTA与生物螯合剂NTA协同施用对土壤重金属污染修复的效果,采用盆栽方法,研究不同配比螯合物EDTA和NTA施用下,茼蒿对土壤重金属(Pb、Cu和Cd)富集的程度;同时评估了螯合物对茼蒿叶绿素、维生素C含量以及土壤营养元素流失程度的影响。结果表明:处理(EDTA/NTA=2∶1)时,茼蒿根部重金属Pb、Cd含量均最高。处理(EDTA/NTA=1∶1)时,显著促进茼蒿植株对重金属Cu吸收和地上部转运,螯合剂用量最少,协同作用最好。不同配比的螯合剂处理均对茼蒿产生抑制作用,同时降低茼蒿生理指标叶绿素、维生素C含量。在处理(EDTA=1),叶绿素SPAD、维生素C含量分别达到最低值36 mg/100 g和38 mg/100 g。对于淋滤液中营养元素TN而言,处理(NTA=1、EDTA/NTA=1∶2)中TN随着时间推移逐渐减少,第十天均显著低于第一天淋滤液中浓度(p<0.05);第十五天TN流失量在处理(NTA=1)下降最多,达到51.6%,活化效果显著下降。淋滤液中营养元素TP,螯合剂活化效果高低依次为:处理(EDTA/NTA=1∶1)>处理(EDTA=1)>处理(EDTA/NTA=2∶1)>处理(EDTA/NTA=1∶2)>处理(NTA=1)。结合茼蒿生理指标、重金属提取效果以及氮磷流失量,推荐最佳的螯合剂施用配比为处理(EDTA/NTA=2∶1)。     

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.     

NTA对玉米体内Cu、Zn的积累及亚细胞分布的影响

通过向多金属复合污染土壤中加入螯合剂氨三乙酸(NTA)并运用差速离心法研究了NTA对玉米根、茎和叶中Cu、Zn亚细胞分布的影响.结果表明:Cu和Zn在玉米细胞内的分布特征与其吸收和富集重金属能力密切相关,NTA能显著促进Cu和Zn在玉米体内的吸收和积累并且影响重金属在细胞壁和液泡内的分布.在玉米细胞内,细胞壁是Cu的主要结合位点,其次为含液泡的细胞质部分,只有少量的Cu分布在叶绿体、线粒体、细胞核等细胞器组分中;Zn更趋向于分布在以液泡为主的细胞质中,并且在细胞器中也有较高的分布.在NTA诱导下,Cu和Zn在液泡内的分布呈强化趋势,有从细胞壁向细胞质转移的趋势,叶片中细胞器的重金属也部分向细胞质转移.     

Induction of gene mutations in salmonella and Drosophila by soluble Cr(Vi) compounds: Synergistic effects of nitrilotriacetic acid

The interaction between NTA and soluble Cr(VI) (K₂Cr₂O₇) was studied by the Ames test on S. typhimurium and the sex‐linked recessive lethal test on D. melanogaster. In both systems a synergistic effect of NTA on Cr(VI) mutagenicity took place at sub‐toxic doses of Cr(VI). The synergism could depend on the action of NTA on intracellular Cr(VI) reduction, as more Cr(VI) was reduced in vitro to Cr(III) by Salmonella and Drosophila protein extracts in the presence of NTA. A similar enhancement of soluble Cr(VI) mutagenicity was produced by low doses of EDTA.