铝合金牺牲阳极材料的研究进展

论述了铝合金牺牲阳极材料的发展历程,阐述了适用于不用环境的铝合金牺牲阳极研发情况,综述了铝合金牺牲阳极的几种活化溶解理论,对影响阳极电化学性能的因素进行了探讨,分析了铝合金牺牲阳极材料技术目前存在的问题,并展望了铝合金牺牲阳极未来的发展方向。常规海水环境的牺牲阳极材料已发展得较为成熟,特殊工况环境的牺牲阳极尚有待进一步开发和完善。     

螯合剂对铜毒性的影响

研究了螯合剂EDTA和DTPA对海州香薷蓄铜能力和铜毒性的影响.结果显示,EDTA和DTPA能抑制植物的生长,使其生物量降低,叶绿素含量下降,同时降低了植物的根系活力.EDTA和DTPA都可引起植物SOD、POD活性上升,在与Cu²⁺共同作用下,EDTA对Cu²⁺毒性影响较小,表现在SOD、POD活性仍按Cu²⁺独立作用下的变化规律而变化,且数值上变化不大.而DTPA则降低了Cu²⁺作用下SOD、POD活性的变化.EDTA使海州香薷地上部分铜浓度增加,DTPA则明显降低了海州香薷的铜含量.     

不同浸提剂条件下生物炭溶解性有机物的浸出规律

生物炭广泛应用于环境污染修复、土壤改良和废物生物转化过程,但其中的可浸出物质可能在应用过程中释放,对反应体系和环境造成不利影响.以厌氧消化不同阶段的模拟溶液(蒸馏水、缓冲盐溶液、甲醇和腐殖酸溶液)为浸提剂,采用高分辨液质联用仪,研究了不同浸提剂条件下生物炭浸出液的溶解性有机物组成.生物炭各浸出液中共检测到536种有效物质,其中有100种物质与标准物质数据库高度匹配.结果表明,这100种物质的相对分子质量分布在109～458范围内,平均相对分子质量为290. 2,涵盖苯酚类、芳香酸类、芳香醛和酮类、脂肪酸类等物质.相比传统研究方法采用的蒸馏水,生物炭在厌氧培养常用缓冲盐溶液中多浸出了3种脂肪酸和4种芳香族物质;甲醇浸出液中的物质类别最丰富,共计71种,其中包括大量的酚类和有机酸类物质;腐殖酸溶液浸取过程中,部分腐殖酸,包括醇和脂肪酸类物质会被生物炭吸附,但腐殖酸同时促进了生物炭中酚类物质的浸出,总体可被检测出的有机物种类减少了41. 7%.     

Evaluation of N-acetylcysteine and glutathione as quenching agents for the analysis of halogenated disinfection by-products

Disinfection by-products (DBPs), formed from the reactions of disinfectants with natural organic matter and halides in drinking water, were considered to be cytotoxic and genotoxic, and might trigger various cancers. The relatively low concentration of DBPs in finished water (low µg/L or even ng/L levels) and the interference from water matrix inhibited in situ determination of DBPs. Moreover, the further formation and degradation of DBPs by disinfectants during the holding time (several hours to several days) from sample collection to analysis could adversely affect the determination of DBPs. To obtain accurate, precise and reliable data of DBP occurrence and formation, robust and reliable sample preservation is indispensable. However, the commonly used quenching agents (e.g., sodium sulfite, sodium thiosulfate, and ascorbic acid) for sample preservation can decompose reactive DBPs by reductive dehalogenation. This study evaluated the performance of N-acetylcysteine (NAC) and glutathione (GSH) as quenching agents for the analysis of halogenated DBPs by investigating the stoichiometry of the disinfectant-quenching agent reaction, the formation of DBPs during chlor(am)ination of NAC or GSH, and the effects of NAC or GSH on the stability of 18 individual DBPs and total organic halogen (TOX). Based on the results of this study, NAC and GSH were considered to be ideal quenching agents for the analysis of most DBPs and TOX, except halonitromethanes.     

Al-Zn-In系牺牲阳极在间浸环境中的性能研究

目的探究4种常用Al-Zn-In系牺牲阳极(Al-Zn-In、Al-Zn-In-Cd、Al-Zn-In-Mg-Ti、Al-Zn-In-Mg-Ga-Mn)在海水间浸环境中的电化学性能。方法采用恒电流法对4种阳极的开路电位、工作电位、实际电容量、电流效率及溶解形貌等进行研究,并结合电化学阻抗谱、动电位极化曲线等方法进行分析。结果在间浸环境中,Al-Zn-In、Al-Zn-In-Mg-Ti、Al-Zn-In-Mg-Ga-Mn的电流效率均在88.92%以上,3种阳极的工作电位在-0.96~-1.10 V波动,能满足碳钢在间浸环境中的保护需要。Al-Zn-In-Mg-Ga-Mn阳极溶解形貌均匀,Al-Zn-In和Al-Zn-In-Mg-Ti阳极溶解形貌略差。Al-Zn-In-Cd阳极电流效率仅为80.95%,工作电位在-0.93~-1.10 V波动,溶解形貌不均匀,电化学性能最差。研究发现,Al-Zn-In-Cd阳极表面附着的腐蚀产物多次在空气环境中脱水,并形成壳层,导致电位正移,阻碍阳极的进一步活化。结论在间浸环境中,4种阳极的电化学性能由好到差依次为Al-Zn-In-Mg-Ga-Mn阳极、Al-Zn-In阳极、Al-Zn-In-Mg-Ti阳极、Al-Zn-In-Cd阳极,前3种阳极适用于间浸环境中海洋结构物的阴极保护。     

淋洗剂在重金属污染土壤修复中的研究进展

针对镉/铅等一类重金属污染土壤、砷污染土壤,以及镉-铅-砷等复合污染土壤（三类不同重金属污染土壤）,就淋洗剂在污染土壤修复中的选用等问题进行综述.总的来看,对于镉/铅等一类重金属污染土壤,螯合剂的去除率较高.如GLDA（谷氨酸N,N-二乙酸）和柠檬酸等,不仅去除率高,而且环境较友好对于砷污染土壤,复合淋洗剂的去除效果比较显著,如NaOH-EDTA对As的去除率较高对于镉-铅-砷等复合污染土壤,复合淋洗剂则更能发挥其所含各类淋洗剂的优势.如NaOH-H₃PO₄与单一淋洗剂相比,对土壤中多种重金属的去除率均较高.笔者认为,同时对土壤中多种重金属均有较高去除率且二次污染较小的复合淋洗剂将是未来的研究重点.     

几种固化剂组配修复重金属污染土壤

选取沸石、硅藻土、海泡石、膨润土和石灰石等5种矿物材料,以6 g.kg-1的浓度分别添加到50 g供试土壤中,熟化两周后进行毒性浸出实验,研究各固化剂对土壤重金属的固化效果.实验表明石灰石对土壤重金属均有较好的固化作用,因此再将前4种固化剂与石灰石以不同质量比组配,并以同样方法研究各组配对土壤中重金属的固化效果,以期得到固化效果优于单一固化剂的组配固化剂.结果表明,几种组配中效果最好的是硅藻土与石灰石以质量比1∶2的组配,土壤浸提液中Pb、Cd、Cu、Zn浸出量较对照分别降低54.3%、100%、27.2%、63.8%.显然,1∶2的硅藻土+石灰石对土壤Pb、Cd、Zn均有较好的固化作用.     

螯合剂对小麦幼苗吸收金属以及土壤金属形态的效应

本文通过盆栽试验研究三种螯合剂（EDTA、[s,s】-EDDS、DTPA）对小麦幼苗吸收土壤中重金属及其它微量元素的效应,并且通过改进的BCR连续提取法分析了种植后土壤样品中金属元素的形态。结果表明：EDTA、DTPA的添加导致小麦幼苗地上部分生物量以及叶片叶绿素a含量显著下降。螯合剂的存在明显增加了Pb和Mn在幼苗根部和茎叶的富集,并增加其由根部向茎叶的传输．但对Fe和Ni的作用比较小。小麦幼苗收获时,除Zn之外,其它元素酸溶／可交换态金属含量与对照组相比均有非常显著的增加,而各元素的可还原态由于EDTA等螯合剂的添加而有明显下降。添加螯合剂的情况下,富集量与酸溶／可交换态含量之间的相关系数大大提高,且各处理组茎叶富集量与酸溶／可交换态之间呈显著（P〈0．05）或极显著相关（P〈0．01）。因此,三种螯合剂的添加主要影响的是生物可利用形态以及潜在的生物可利用形态,并且可能导致可还原态以及可氧化态向酸溶／可交换态转变,增加金属的生物可利用性,从而也增加潜在生态风险。     

Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

聚氨酯型固沙剂改性土室内试验研究

对自主研发的PUA、PUB和PUC 3种聚氨酯型固沙剂改性土的强度、抗冲刷性、抗风蚀性等性能进行了室内试验研究,并结合聚氨酯分子结构和功能对固沙剂改良原理进行了分析。试验结果表明:3种聚氨酯型固沙剂改性土的无侧限抗压强度、内聚力得到了提高,抗冲刷和抗风蚀性能得到了明显增强;3种固沙剂改性土的无侧限抗压强度和内聚力均随着固沙剂浓度的增加而增大;PUA、PUB和PUC浓度为3g/cm3的改性土试样的冲刷率分别只有4.4%、14.7%和0.6%,而参照样高达79.5%;PUA、PUB和PUC浓度达到1g/cm3以上的改性土风蚀后表面保持完整,没有风蚀破坏痕迹。因此,聚氨酯型固沙剂可以很好地增强土体粘聚力、促进表层固化、减少水土流失,可用于坡面防护、水土保持、防尘固沙、沙漠化治理等领域。