环糊精对腐植酸-芘、蒽相互作用影响初探

利用吸收光谱、荧光猝灭法、圆二色谱法及芘荧光探针法,探讨了环糊精(CDs)对腐植酸(HA)与以芘为代表的多环芳烃(PAHs)相互作用的影响.β-CD与HA的吸收光谱和荧光光谱测定结果表明:β-CD能够包络HA的芳环部分;荧光猝灭法和圆二色谱法测定结果表明:HA能够与被β-CD空腔包络的芘分子发生相互作用,CDs和HA之间存在与芘相互作用的竞争;用荧光猝灭法测定了四种不同CDs存在下HA和芘的结合常数,并用芘为荧光探针进行测定,结果表明:CDs浓度较低时,HA对芘的作用占优势;反之,CDs占优势.与其它三种CDs不同,γ-CD存在下HA与芘的结合常数随其浓度的升高一直增大.     

土壤中抗生素的吸附行为与机理研究进展

抗生素进入土壤后会发生一系列环境行为,造成环境污染。该文梳理了土壤中抗生素的来源、污染现状和环境行为,系统总结抗生素的官能团和分子结构以及土壤的类型、pH、共存离子和有机质影响抗生素在土壤中吸附的基本规律以及作用机制。土壤中抗生素主要来源于畜牧和医疗产生的废弃物;主要有四环素类、磺胺类、大环内酯类和喹诺酮类;通过生物蓄积和吸附作用残留在土壤中,诱导抗性基因产生或与其他污染物交叉污染造成生态风险。具有羟基、羧基、胺基等可电离基团和不同分子结构的抗生素,存在不同酸解离常数,通过H键作用、π–π相互作用、金属离子络合作用、去质子化作用和阳离子交换等机制被土壤吸附;颗粒细小,质地细腻,具有较大比表面积和孔隙体积的土壤会暴露更多吸附位点,更容易吸附抗生素;土壤存在可变电荷,土壤电荷与抗生素的价态相同会抑制抗生素吸附,反之则促进;有机质通过羟基、羧基等官能团增强抗生素吸附,或与抗生素竞争土壤吸附位点抑制抗生素吸附;Al³⁺、Fe³⁺等酸性金属离子,作为抗生素与土壤颗粒联结的桥梁促进抗生素吸附;K⁺、Na⁺、Ca...     

松花江腐殖酸的提取、表征及与重金属的络合作用

本文提得了第二松花江水及底泥中的黄腐酸(FA)和棕腐酸(HA),测定了总酸性基、羧基、醌基等官能团并进行了元素分析,研究了红外、紫外及荧光光谱,与一般水体腐殖酸的特征相同。 选用凝胶过滤法研究了腐殖酸与汞、镉、锌的络合作用,测定了水及底泥的FA和HA对Zn、Cd、Hg的络合容量,其趋势为Hg>Cd>Zn,计算了条件稳定常数,logA值显示出汞与腐殖酸的稳定性高于汞与水体中除S~(2-)及SH-外的其它配位络合物,合成了腐殖酸汞固体络合物,用红外光谱确定其络合作用,测定了腐殖酸汞在水中的溶解度。     

生活垃圾填埋富里酸电子转移能力与影响因素

为了研究生活垃圾填埋过程中富里酸(fulvic acids,FA)电子转移特征及其影响因素,通过紫外-可见吸收、荧光和红外光谱手段表征FA结构,使用电化学方法测定FA的电子供给能力(electron donating capacity,EDC)和电子接受能力(electron accepting capacity,EAC).结果表明,填埋初期(1—3年)FA分子量和芳香性随填埋深度增加而减小,而填埋中后期(3年)FA分子量和芳香性随填埋深度增加而增加.随着填埋深度的增加FA中羟基和羧基含量先增加后减少,碳水化合物含量持续减少.填埋初期,FA的EAC随着填埋深度的增加而增加,EDC变化趋势不明显;填埋中后期FA的EDC和EAC随填埋深度呈现先增加后减小的趋势.表层填埋垃圾中FA给电子基团起主导作用,而深层填埋垃圾中FA接受电子基团起主导作用.相关性分析显示FA分子量越小、碳水化合物含量越低、羟基含量越高,越利于FA给出电子;而FA分子量越大、羧基含量越高、碳水化合物和脂肪族含量越低,越利于FA得到电子.     

苯并[a]芘和1-羟基芘诱导人胚胎干细胞分化心肌细胞ROS、CYP基因表达和DNA损伤

多环芳烃(PAHs)化合物中的苯并[a]芘和PAHs暴露检测标志物1-羟基芘与心脏功能障碍有关,但其生物学机制尚不清楚。为研究苯并[a]芘和1-羟基芘对心脏的毒性作用,基于人胚胎干细胞分化心肌细胞(hESC-CM)研究了苯并[a]芘和1-羟基芘对心肌细胞活性氧(ROS)生成、CYP基因表达和DNA损伤等的影响。结果表明,苯并[a]芘和1-羟基芘对h ESC-CM活性无影响,但能显著增强细胞ROS水平,诱导DNA损伤。此外,苯并[a]芘还能诱导细胞线粒体促凋亡基因的表达。研究表明,苯并[a]芘和1-羟基芘能通过诱导氧化应激和DNA损伤事件导致h ESC-CM损伤,在一定程度上解释了多环芳烃暴露导致心脏疾病的分子机制。     

草炭溶解态有机物质与Cu2+、Cd2+络合稳定性的研究

研究了由草炭提取的胡敏酸(HA)、富里酸(FA)、水溶解态有机物质(WSOM)的基团特征,分子量分布及其与Cu2+、Cd2+两种金属离子之间的络合稳定性。对HA、FA及WSOM的红外光谱研究显示三者的官能团组成相似,只是含量略有不同。固态13C-NMR对HA、FA及WSOM结构特征的描述以及水相凝胶色谱法对三种有机质样品的分子量及分子量分布的测定结果显示HA分子最大且含有大量的长链烷烃,而FA分子小得多,结构以碳水化合物及多糖为主,WSOM的分子量略低于FA,结构与FA相近。离子交换平衡法对三种有机质样品与Cu2+、Cd2+的络合配位数和稳定常数的测定结果显示两种介质条件下络合配位数(x)、络合稳定常数(logk)的次序均为:Cu2+>Cd2+;同一介质条件下,对不同有机质而言均满足:M-HA>M-FA>M-WSOM。     

二级出水典型污染物超滤膜污染行为的分子动力学模拟研究

以6-羧基葡萄糖、半胱氨酸和水杨酸分别代表二级出水的3种典型污染物多糖(SA)、蛋白质(BSA)和腐殖酸(HA)的分子组成,通过分子动力学(MD)技术,模拟了二级出水典型污染物,与醋酸纤维素(CA)、聚醚砜(PES)、聚偏氟乙烯(PVDF)等3种主流商业膜材料之间的结合能(ΔE),作为对具有特征污染物性质的二级出水,在不同的膜材料上产生膜污染行为的判断依据.MD数据显示:PVDF结构单元与6-羧基葡萄糖和水杨酸分子间的ΔE高于半胱氨酸,而PES结构单元与半胱氨酸分子间的ΔE值高于其它分子间的组合.3种污染物在超滤膜上的过滤通量衰减及膜污染指数,证实了MD对PVDF膜上SA和HA污染性更高,而BSA在PES膜上更易产生膜污染的预测结论;分别对6-羧基葡萄糖、水杨酸、半胱氨酸与3种聚合物结构单元间的ΔE值,与SA、HA、BSA的超滤操作初始通量衰减率间进行了线性拟合,得到的拟合系数分别为0.9981、0.9555、0.7186,说明半胱氨酸作为蛋白质类代表物进行分子模拟尚有一定的不足.     

腐殖酸对巯基功能化离子印迹聚合物吸附Cd~(2+)的增效作用

复合污染条件下共存的有机物可能对水溶液中重金属的吸附去除产生抑制作用,作为天然水体中有机物的代表,腐殖酸(Humic acid,HA)对水体中重金属的迁移转化等具有极其重要的影响.采用表面印迹法合成了巯基功能化离子印迹聚合物IIP-MPTS/SiO_2,利用扫描电镜(SEM)、X射线能谱仪(EDS)、傅里叶红外光谱仪(FT-IR)、X射线衍射仪(XRD)等方法对其进行了表征.以HA作为共存有机物,以IIP-MPTS/SiO_2作为吸附剂,研究HA对IIP-MPTS/SiO_2吸附去除水体中Cd~(2+)的影响.HA与Cd~(2+)相互作用的紫外吸收光谱表明,基于Cd~(2+)浓度的HA分子聚合增强作用,增大了分子体系的共轭程度,使紫外光谱吸收峰红移;溶液离子强度的增大也促进紫外光谱吸收带的红移和吸收强度的增大.吸附实验表明,Cd~(2+)在IIP-MPTS/SiO_2上的吸附容量随溶液pH值(2.00—8.00)的升高而逐渐增大;共存HA对Cd~(2+)在IIP-MPTS/SiO_2上的吸附具有增效作用,但降低了吸附反应速率;吸附行为符合拟二级动力学模型,吸附等温线可以用Langmuir模型描述;吸附过程为自发吸热反应,HA的存在增大了吸附反应的自发程度,吸附能垒降低.结合XPS分析结果,推断共存HA促进Cd~(2+)吸附的原因是,HA作为配位体桥梁而形成IIP-MPTS/SiO_2-HA-Cd~(2+)稳定的三元配位化合物,通过富集而促进Cd~(2+)的吸附.     

环境条件对渗滤液中溶解性有机物分子构型的影响

采用同步荧光光谱,结合移动窗口二维相关光谱技术,研究了垃圾渗滤液中溶解性有机物(DOM)在外界干扰下的分子构型变化.结果显示,填埋垃圾渗滤液DOM含有类蛋白、类富里酸和类胡敏酸物质,它们均含有羧基和酚羟基官能团,填埋3—5年垃圾渗滤液DOM酚羟基含量较高,且主要分布在类蛋白组分上,而填埋10年以上渗滤液DOM中羧基含量较高,但主要分布在类富里酸组分上.p H升高引起DOM分子构型改变不受Hg(Ⅱ)存在的影响,填埋3—5年垃圾渗滤液DOM在p H 3和p H 8—10时分别由于羧基和酚羟基解离分子构型发生了剧烈改变,而填埋10年以上垃圾渗滤液DOM仅在p H 3—4时由于羧基解离分子构型发生了变化.在Hg(Ⅱ)对DOM分子构型的影响上,填埋3—5年垃圾渗滤液DOM分子构型在溶液Hg(Ⅱ)浓度升至5μmol·L~(-1)和20—25μmol·L~(-1)时发生了两次剧烈改变,而填埋10年以上垃圾渗滤液DOM在体系Hg(Ⅱ)浓度为10—25μmol·L~(-1)发生了一次缓慢的改变.同步荧光光谱结合移动窗口二维相关光谱技术可以有效识别环境条件改变时DOM分子构型的变化及成因.     

腐殖酸对As(V)在覆铁砂介质中吸附行为的影响

对腐殖酸(HA)进行了成分分析及红外表征,并从HA浓度、pH值、As(Ⅴ)初始浓度等方面,研究了HA对As(Ⅴ)在覆铁砂介质中吸附行为的影响.结果表明,随着HA浓度的升高,总砷去除率逐渐降低.当HA浓度增加到25mg.l-1时,与不存在HA条件下相比,总砷去除率降低了12%左右.溶液pH值影响As(Ⅴ)的去除,pH值从6升高到8时,总砷去除率从52.1%降到了39%.其中的作用机理主要是HA与As(Ⅴ)在覆铁砂表面形成竞争吸附,HA争夺了As(Ⅴ)的吸附点位.此外,HA与Fe(Ⅲ)的络合作用也是导致覆铁砂对砷的去除率降低的一个重要原因.     

荧光猝灭法测定菲、苊、芘与腐殖酸的结合常数

用荧光猝灭法测定了胡敏酸（Fluka）与苊、菲和芘相互作用的结合常数（KDOC），其lgKDOC值分别为4．4，4．48和4．89．用同样方法测得长江水生FA以及黑龙江水生FA和HA的KDOC之间有显著差别．HA的KDODC一般高于FA．黑龙江水生FA的KDOC高于长江．对同一来源的腐殖酸，三种多环芳烃的KDOC与KOW呈线性相关．     

五氯苯酚与腐殖酸作用的荧光猝灭效应研究

通过对五氯苯酚与腐殖酸作用的荧光猝灭效应研究,探讨了五氯苯酚与腐殖酸之间的相互作用机理.结果表明,五氯苯酚可以有规律地猝灭腐殖酸的内源荧光,其猝灭机理可认为是五氯苯酚和腐殖酸形成复合物的静态猝灭,五氯苯酚与腐殖酸的结合常数较大,说明腐殖酸能够有效吸附五氯苯酚分子,形成复合物;并获得了不同温度下,五氯苯酚与腐殖酸作用的结合常数和热力学参数.根据所得结果可推断五氯苯酚与腐殖酸的主要作用力为氢键和范德华力.     

Application and mechanism of polysaccharide extracted from Enteromorpha to remove nano-ZnO and humic acid in coagulation process

Green source Ep was extracted from marine alga waste. The molecule model structure of Ep was studied and constructed. PAC-Ep coagulation system improves the efficiency of removal efficiency. Synergistic effects between NPs and HA make a big difference to enhance efficiency. Mechanism is charge neutralization, hydrogen bonding and adsorbing-complexing Enteromorpha polysaccharide (Ep) extracted from alga a novel green coagulant aid for nanoparticles (NPs) and heavy metal ions removal and the structure of EP was intensively studied in this study. The integration of Ep with polyaluminum chloride (PAC-Ep) coagulants exhibited higher coagulation performance than that of the polyaluminum chloride (PAC) because of the negatively charged NPs suspension and humic aid (HA) solution. Significant high removal efficiencies of dissolved organic matter (94.1%), turbidity (99.3%) and Zn ions (69.3%) were achieved by the PAC-Ep coagulants. The dual-coagulation properties of PAC-Ep for different pollutants was based on multiple mechanisms, including (i) Al³⁺ charge neutralization; (ii) hydroxy aluminum hydroxyl bridging formed polynuclearhydroxy complexes bridge and sweep colloidal particles; (iii) adsorption and bridging of Ep chain for the NPs and heavy metal ions. Results indicated that the destabilization of colloid was induced by the coexisting HA and higher removal was achieved as ions adsorption was enhance in the presence of HA complexation. On the basis of that, the extraction of polysaccharide is a promising candidate for its high coagulation performance in water treatment.     

Cadmium removal mechanistic comparison of three Fe-based nanomaterials: Water-chemistry and roles of Fe dissolution

● nZVI, S-nZVI, and nFeS were systematically compared for Cd(II) removal. ● Cd(II) removal by nZVI involved coprecipitation, complexation, and reduction. ● The predominant reaction for Cd(II) removal by S-nZVI and nFeS was replacement. ● A simple pseudo-second-order kinetic can adequately fit Fe(II) dissolution. Cadmium (Cd) is a common toxic heavy metal in the environment. Taking Cd(II) as a target contaminant, we systematically compared the performances of three Fe-based nanomaterials (nano zero valent iron, nZVI; sulfidated nZVI, S-nZVI; and nano FeS, nFeS) for Cd immobilization under anaerobic conditions. Effects of nanomaterials doses, initial pH, co-existing ions, and humic acid (HA) were examined. Under identical conditions, at varied doses or initial pH, Cd(II) removal by three materials followed the order of S-nZVI > nFeS > nZVI. At pH 6, the Cd(II) removal within 24 hours for S-nZVI, nFeS, and nZVI (dose of 20 mg/L) were 93.50%, 89.12% and 4.10%, respectively. The fast initial reaction rate of nZVI did not lead to a high removal capacity. The Cd removal was slightly impacted or even improved with co-existing ions (at 50 mg/L or 200 mg/L) or HA (at 2 mg/L or 20 mg/L). Characterization results revealed that nZVI immobilized Cd through coprecipitation, surface complexation, and reduction, whereas the mechanisms for sulfidated materials involved replacement, coprecipitation, and surface complexation, with replacement as the predominant reaction. A strong linear correlation between Cd(II) removal and Fe(II) dissolution was observed, and we proposed a novel pseudo-second-order kinetic model to simulate Fe(II) dissolution.     

腐殖酸存在下镉和铅对土壤脱氢酶活性的影响

采用室内培养试验研究Cd和Pb污染红壤添加不同组分腐殖酸后,其脱氢酶活性的变化,结果表明,红壤遭受镉和铅污染后,脱氢酶活性显著降低,然而腐殖酸特别是胡敏酸的存在能够使脱氢酶活性得到显著回升,说明腐殖酸与重金属的相互作用对重金属污染土壤微生物活性的改善和修复功能,对土壤有一定的去污降毒作用.不同腐殖酸组分的效应大小为:灰色胡敏酸(GHA)>棕色胡敏酸(BHA)>富里酸(FA),表明分子量愈大、芳构化程度愈高的腐殖酸组分,其对重金属的钝化愈强,从而解除土壤重金属对生物毒害的能力愈强.     

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.     

Interaction between Humic Acid and p-Arsanilic Acid Using Fluorescence Quenching Approach

P-arsanilic acid(p-ASA),as a kind of organoarsenic feed additive,has been widely used in poultry and swine breeding.However,it has caused the arsenic pollution around the farm.Currently data shows humic acid(HA)is closely to the migration and transformation of p-ASA.Therefore,the interaction between p-ASA and HA was investigated by using the method of fluorescence quenching titration.The association constant changed from2.74 to 4.88 L·mol-1at a p H varying from 5 to 9 and reached the maximum at p H 7.In addition,log K varied from4.15 to 5.02 L·mol-1when the temperature increased from 15℃to 35℃.The log K increased with an increase in the concentration of HA.The dominant mechanism between p-ASA and HA is static quenching.The primary interaction force was likely the hydrogen bond,and the binding behavior occurred on the As-O stretch of p-ASA and the carboxylic acid C=O stretch of HA.The results showed that dissolved organic matters could affect the fate and biogeochemical cycling of organoarsenic pharmaceuticals in aquatic ecosystems.     

Interaction between peat, humic acid and aqueous metal ions

Analysis of peat samples from four regions of the British Isles indicates that the concentrations of Al, Pb and common transition metals tend, as expected, to be higher in regions subject to industrial pollution, but that the concentrations of the nontransition metals Na, K, Mg, Ca and Zn tend to be higher in regions remote from industrial pollution. Humic acids were extracted from the most polluted and least polluted of the peat samples and some characteristics of these acids were compared with those of two commercial acids. Values for stability constants of complexes formed between humic acids extracted from peat and Cu²⁺, Zn²⁺ or Pb²⁺ have been obtained by an ionexchange equilibrium method. Of the three metal ions examined, Pb²⁺ was found to form the most stable humic acid complexes, followed by Cu²⁺: this order agrees with the findings of Irving and Williams and of Bunzl. Implications to the binding of actinide and other heavy metal ions in aqueous humic acid are discussed.     

Preparation and characterization of calcium alginate-based composite adsorbents for the removal of Cd,Hg, and Pb ions from aqueous solution

Composite adsorbent materials containing calcium alginate, clinoptilolite, and coal-derived humic acid were prepared. Humic acid (HA), clinoptilolite (CL), alginate (AL), alginate-entrapped humic acid (AL/HA), clinoptilolite (AL/CL), and humic acid/clinoptilolite (AL/HA/CL) samples were characterized. The effectiveness of the samples as adsorbents for the removal of cadmium (Cd), mercury (Hg), and lead (Pb) were studied in a series of batch-adsorption experiments. For the AL, AL/HA, AL/CL, and AL/HA/CL adsorbents, uptake versus time data were evaluated using two kinetic models, a linear and a non-linear pseudo-first-order and a pseudo-second-order model. The data for each metal ion on all adsorbents showed good correspondence with the pseudo-second-order kinetic model. The equilibrium data were fitted to Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models. The results show that a non-linear method seems more appropriate for obtaining isotherm parameters. The non-linear Freundlich and Langmuir models for Pb and Hg produced a best fit with high R ² value (0.99). For HA adsorbent, the equilibrium data for Cd removal better fit to the non-linear Dubinin–Radushkevich isotherm.     

Eco-friendly approach for leaching out heavy metals from sewage sludge

Sewage sludge contains rich organic matter and nutrients essential for the growth of plants but the presence of toxic heavy metals restricts its land application. To overcome this, the study aims an eco-friendly approach for leaching out heavy metals. Sewage sludge from sewage treatment plant, Chennai, India was characterised. The analysis of total heavy metal concentration was done by digesting in nitric acid and different forms were extracted by community bureau of reference sequential method. Heavy metals: As, Cd, Cr, Cr, Ni, Pb and Zn were determined using inductively coupled plasma optical emission spectrometry Perkin Elmer Optima 5300 DV. The experimental set-up for heavy metal leaching was held for five consecutive days at different concentrations of humic acid (0.1%, 0.5% and 1%) at varied pH (5–9). Results revealed that at the end of fifth day at pH 8, 1% humic acid is capable of leaching out 75.5% cadmium, 66.0% nickel, 52.0% lead, 51.2% zinc, 31.2% copper and 8.5% cadmium from sewage sludge. Statistically positive correlation (0.7088) existed between the percentage of heavy metals leached out and the sum of soluble and reducible fractions. Thus, from ecological point of view, humic acid can be used to leach out heavy metals from sewage sludge serving the need in restoration of soil fertility upon land application.