重金属离子存在下腐植酸和芘之间的相互作用

建立并验证了腐植酸(HA)和芘结合常数(Koc)测定的荧光猝灭法,进而研究了重金属离子对HA和芘相互作用的影响,测定了重金属离子存在下HA和芘之间的Koc.结果表明:纯化后的HA是分子质量较小的部分,水溶性较高,具有羟基、羧基和碳氧键等极性基团;HA利用其分子中的羟基、羧基、碳氧键等基团和重金属离子产生络合作用,这种络合作用影响了HA的结构;随着重金属离子浓度的增大,Koc遵循先增大,再减小,最后趋于不变的趋势.     

不同分子量的腐殖酸存在下2种无机砷的生物毒性效应研究

水环境中天然有机质会与砷形成络合物,进而影响砷的迁移、转化和生物毒性。研究利用超滤方法将腐殖酸(humic acid, HA)分为5个不同分子量的组分,以大型溞为受试生物,探究了不同分子量HA存在下砷对大型溞的毒性效应。结果表明,不同分子量的HA均缓解了As(Ⅲ)和As(Ⅴ)对大型溞的氧化应激损伤和细胞膜损伤,并降低了砷对MT的诱导量。其中1～30 k Da的HA对砷的缓解效果最好,1 k Da的HA毒性缓解效果最差,可能的原因是HA与砷的络合增加溶液中络合态砷的含量,而络合态砷难以进入细胞并被生物利用。不同分子量的HA对砷毒性的缓解差异与其跟砷的络合比例不同有关。     

Ozonation as an efficient pretreatment method to alleviate reverse osmosis membrane fouling caused by complexes of humic acid and calcium ion

Humic acids (HA) didn’t cause obvious reverse osmosis (RO) membrane fouling in 45 h. Osmotic pressure (NaCl) affected slightly the RO membrane fouling behavior of HA. Ca²⁺ promoted aggregation of HA molecules and thus aggravated RO membrane fouling. Ozonation eliminated the effect of Ca²⁺ on the RO membrane fouling behavior of HA. The change of the structure of HA was related to its membrane fouling behavior. Humic acid has been considered as one of the most significant sources in feed water causing organic fouling of reverse osmosis (RO) membranes, but the relationship between the fouling behavior of humic acid and the change of its molecular structure has not been well developed yet. In this study, the RO membrane fouling behavior of humic acid was studied systematically with ozonation as a pretreatment method to control RO membrane fouling. Furthermore, the effect of ozone on the structure of humic acid was also explored to reveal the mechanisms. Humic acid alone (10–90 mg/L, in deionized water) was found not to cause obvious RO membrane fouling in 45-h operation. However, the presence of Ca²⁺ aggravated significantly the RO membrane fouling caused by humic acid, with significant flux reduction and denser fouling layer on RO membrane, as it was observed by scanning electron microscope (SEM) and atomic force microscope (AFM). However, after the pretreatment by ozone, the influence of Ca²⁺ was almost eliminated. Further analysis revealed that the addition of Ca²⁺ increased the particle size of humic acid solution significantly, while ozonation reduced the SUVA₂₅₄, particle size and molecular weight of the complexes of humic acid and Ca²⁺ (HA-Ca²⁺ complexes). According to these results and literature, the bridge effect of Ca²⁺ aggregating humic acid molecules and the cleavage effect of ozone breaking HA-Ca²⁺ complexes were summarized. The change of the structure of humic acid under the effect of Ca²⁺ and ozone is closely related to the change of its membrane fouling behavior.     

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.     

Evolution of humic substances in polymerization of polyphenol and amino acid based on non-destructive characterization

• Humification evolution was identified with non-destructive characterization method. • Humification process from precursors to fulvic and humic acid was confirmed. • MnO₂ alone had limited oxidation ability to form HA. • MnO₂ played a key role as a catalyst to transform FA to HA in the presence of O₂. • MnO₂ could affect the structure of the humification products. Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes. However, the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous. The aim of this study was to use non-destructive measurement methods to investigate the role of MnO₂ in the evolution of humic substances (HSs) during oxidative polymerization of polyphenol-amino acid. Our results suggested a synergistic effect between MnO₂ and O₂ in promoting the polymerization reaction and identified that MnO₂ alone had a limited ability in accelerating the transformation of fulvic acid (FA) to humic acid (HA), whereas O₂ was the key factor in the process. Two-dimensional correlation spectroscopy (2D-COS) showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process, indicating the formation of simple organic matter followed by FA and then HA. ¹³C nuclear magnetic resonance (¹³C NMR) analysis revealed that the products under both air and N₂ conditions in the presence of MnO₂ had greater amounts of aromatic-C than in the absence of MnO₂, demonstrating that MnO₂ affected the structure of the humification products. The results of this study provided new insights into the theory of abiotic humification.     

Effect of effluent organic matter on ozonation of bezafibrate

The influence of three effluent organic matter (EfOM) model compounds, humic acid (HA), bovine serum albumin (BSA), and sodium alginate (AGS), on the ozonation of bezafibrate (BF), a typical pharmaceutical and personal care product (PPCP), was investigated. The results show that ozonation efficiently removed BF from aqueous solution with removal efficiencies>95% within 8 min for all conditions. The reaction rate of BF decreased with increasing model compounds concentrations and the influence was more pronounced for HA and BSA, while less pronounced for AGS. Although BF concentration was significantly reduced, the degree of mineralization achieved was only approximately 11%. The addition of HA and BSA improved the mineralization of the solution, while the influence of AGS was minor. The acute toxicity of BF solution during ozonation was determined using the Luminescent bacteria test, and the toxicity exhibited an initial increase and a successive reduction. An overall decreased acute toxicity was observed with an increase of HA. The presence of BSA increased the formation rate of toxicity intermediates and resulted in inhibition peak forward.     

Abiotic association of phthalic acid esters with humic acid of a sludge landfill

The abiotic association between phthalic acid esters (PAEs) and humic substances (HS) in sludge landfill plays an important role in the fate and stability of PAEs. An equilibrium dialysis combined with ¹⁴C-labeling was used to study the abiotic association of two abundant PAEs (diethyl phthalate and di-n-butyl phthalate) with humic acid (HA) isolated from a sludge landfill with different stabilization times and different molecular weights. Elemental analysis and Fourier Transform Infrared Spectrophotometer (FTIR) suggested that high K _A value of HA was related to the high aromatic content and large molecular weight of HA. The results indicated that the association strength of PAEs with HA depended on both the properties of the PAEs and the characteristics of HA. The K _A values of the association were strongly dependent on solution pH, and decreased dramatically as the pH was increased from 3.0 to 9.0. The results suggested that nonspecific hydrophobic interaction between PAEs and HA was the main contributor to the association of the PAEs with HA. The interactive hydrogen-bonds between the HA and the PAEs molecules may also be involved in the association.     

Effects of water quality on the coagulation performances of humic acids irradiated with UV light

The presence of humic acid in drinking water treatment has received significant attention in recent years because of its adverse effects on the removal of many pollutants in coagulation. In this paper, the effects of water quality including pH, turbidity, alkalinity, and hardness on the removal of humic acid were investigated in a UV light hybridized coagulation process. Our results suggested that UV light radiation could effectively improve the removal rate of humic acid in coagulation under both neutral and basic conditions, and the variations of the selected water quality parameters had little adverse effect on the function of UV light. After UV light radiation, the removal rate of the nitro-humic acid (NHA) increased from 20% to 60% in coagulation, and increased further to 75% and 85% for the raw waters with 10.0 NTU kaolin and 100 mg·L^-1 hardness, respectively. In addition to NHA, the removal rates of the humic acid extracted from peat coal (PHA) and the humic acid provided by Japan metals and chemicals company (JHA) in coagulation were also improved, both in the range of 80%–90% after undergoing UV light radiation. By changing the radiation location from prior to coagulation to the flocculation process, similar experimental results were obtained. The formation of positive charged sites after UV light radiation was considered to be the primary factor that led to an enhanced removal of the humic acid in coagulation.     

环丙氨嗪在Aldrich胡敏酸中吸附-解吸特征的研究

采用批平衡法,研究了不同温度下环丙氨嗪在Aldrich胡敏酸中的吸附与解吸特征。结果表明：环丙氨嗪吸附和解吸过程都包含极快速、快速和缓慢阶段。伪二级动力学方程能较好地描述不同温度下环丙氨嗪的吸附动力学特性,表明吸附速率决定于胡敏酸表面吸附位点的可用度,而不是溶液中环丙氨嗪的浓度。环丙氨嗪在极快速吸附阶段的吸附速率随温度的升高而增大,但平衡时的吸附量却随温度的增加而降低。吸附等温线和解吸曲线符合Langmuir方程和Freundlich方程。环丙氨嗪在胡敏酸上的解吸速率小于吸附速率,表明存在滞后效应。吸附焓变、熵变和自由能都为负值,表明环丙氨嗪在胡敏酸上的吸附是一个自发、熵减小的放热过程。-Go〈40 kJ.mol^-1表明环丙氨嗪在胡敏酸表面以物理吸附为主。     

不同填埋年龄的矿化垃圾中胡敏酸的分子荧光光谱研究

对上海市老港填埋场封场6-10年矿化垃圾中的胡敏酸(HA)进行荧光光谱分析,结果表明,不同封场时间的矿化垃圾中HA的荧光光谱均为宽带峰型,pH值对HA荧光光谱的影响较小.而且随着矿化垃圾封场时间的加长,荧光特征峰波长缓慢增加.     

Comparative effects of different maize straw returning modes on soil humus composition and humic acid structural characteristics in Northeast China

In order to evaluate the effects of different maize straw returning modes on humus composition and humic acid (HA) structural, a field experiment was designed to have five treatments, i.e. Treatment CK (no straw returned), Treatment EIS (straw incorporated evenly into the soil using the crashing-ridging technique), Treatment SP (straw plowed into the soil), Treatment SM (straw returned as mulch) and Treatment SG (straw returned as pellets). Our results showed that Treatment EIS significantly increased the content of soil organic carbon (SOC), soil humus substances (HEC), soil humic acid carbon (HAC) and fulvic acid carbon (FAC) by 27.8%, 47.6%, 63.3% and 33.8%, respectively, as compared with CK. Among all the straw returning treatments, Treatment EIS was the most significant in effect of increasing the content of HEC, HAC and FAC. Moreover, Treatment EIS altered the composition of humus more significantly than all the other treatments, by increasing the proportion of alkyl C and the ratio of aliphatic C/aromatic C. These results suggest that straw returning accelerated the accumulation of soil organic C and various components of humus, significantly improved the structure of soil HA, with the practice of EIS in particular.     

Studies of Thermal Transformation of Humic and Fulvic Acids in Soils Ii. Thermogravimetry

The thermogravimetry and differential curves of the humic and fulvic acids in the soils from five areas of China were determined and the peaks of these curves were classified according to the results of infra-red (IR) spectra at high temperature and pyrolysis-mass spectra (Py/Ms). the kinetic parameters for heat-degradation of these humic and fulvic acids were calculated by the Coast-Redfern method. the initial temperatures, the final temperatures, and the peaks of DTG curves, the activation energies, the reaction orders and the percentages of weight loss at different reaction stages for these samples were analysed. Thus, the similarity of thermal transformation of humic and fulvic acids in the soils from different areas of China was demonstrated. in addition, the DTA curves of red earth HA and FA were determined.     

西湖沉积物有机质特征

分析了西湖沉积物腐殖质的组成及腐殖酸的红光谱特性,结果显示西湖沉积物腐殖质具有典型的湖泊沉积物腐质特征,腐殖化程度较高;结合形分析表明,腐殖质中：胡敏素〉胡敏酸〉富里酸〉脂类,钱塘江引水工程、水面种植荷花明显改变了沉积物有机质的构成,对西湖的碳和富营养化状况有显著影响。     

腐殖酸(HA)作用下纳米氧化锌对鲫鱼的毒性效应

通过静态模拟实验,研究不同浓度(0、1、1.5、2.5 mg L-1)腐殖酸(Humic acid,HA)对纳米ZnO(5 mg L–1)毒性效应的影响.将鲫鱼暴露于HA与纳米ZnO混合体系中7 d后,分析Zn在鲫鱼体内的富集分布,及对鲫鱼脑部和肝脏自由基含量、抗氧化系统等的影响.结果显示:随HA浓度的增加,鲫鱼鳃部和肌肉中Zn的含量增高,眼、脑和肝部Zn含量则随之下降.纳米ZnO诱导鲫鱼肝脏和脑产生羟基自由基,HA浓度增大诱导鲫鱼肝脏和脑中SOD活性升高,MDA、GSH含量增加.纳米ZnO胁迫导致鲫鱼肝脏和脑氧化损伤,HA的浓度增加会促进纳米ZnO对鲫鱼肝脏和脑部的氧化损伤.研究表明HA改变了纳米ZnO在环境中的生物效应,因此在关注纳米材料的水生态安全时,不能忽视环境因子的影响.     

Effect of wetland plant fermentation broth on nitrogen removal and bioenergy generation in constructed wetland-microbial fuel cells

● Fermentation broth facilitates N removal and energy yields in tertiary CW-MFC. ● Carbon sources are preferred for nitrogen removal over electricity generation. ● A mutual promotion relationship exists between acetic and humic acid in N removal. ● Humic acid boosts the abundances of functional genes relate to nitrogen metabolism. Constructed wetlands (CWs) are widely used as a tertiary treatment technology, and the addition of carbon sources can significantly improve advanced nitrogen removal. However, excessive carbon sources would lead to an increase in the effluent chemical oxygen demand in CWs, and microbial fuel cells (MFCs) can convert these into electricity. In this study, constructed wetland-microbial fuel cells (CW-MFCs) were built to achieve simultaneous nitrogen removal and electricity generation, using wetland plant litter fermentation broths as carbon sources. The total nitrogen removal in the groups with fermentation broth addition (FGs) reached 83.33%, which was 19.64% higher than that in the CG (group without fermentation broth), and the mean voltages in the FGs were at least 2.6 times higher than that of the CG. Furthermore, two main components of the fermentation broths, acetic acid (Ac) and humic acid (HA), were identified using a three-dimensional excitation emission matrix and gas chromatograph and added to CW-MFCs to explore the influence mechanism on the treatment performance. Denitrification and electrogenesis presented the same tendency: Ac&HA > Ac > CG’ (groups without Ac and HA). These results indicate that Ac and HA increased the abundance of functional genes associated with nitrogen metabolism and electron transfer. This study demonstrated that CW-MFC fermentation broth addition can be a potential strategy for the disposal of secondary effluent and bioelectricity generation.     

水环境中天然有机物对纳米颗粒吸附铅和镉的不同作用

为阐明天然有机物(NOM)在纳米颗粒(NPs)吸附重金属中的作用,研究了蛋白质(牛血清白蛋白,BSA)、碳水化合物(海藻酸钠,NaAlg)和腐殖酸(HA)对二氧化钛纳米颗粒(TNPs)和氧化铈纳米颗粒(CNPs)聚集沉降和吸附Cd²⁺和Pb²⁺的影响.结果表明,当Pb²⁺和Cd²⁺在20—120 mg·L-1范围内,HA和NaAlg显著促进了TNPs和CNPs对这些金属离子的吸附(P<0.05),而BSA对这些金属吸附的影响甚微.TNPs-HA和TNPs-NaAlg对Pb²⁺的吸附分别提高了14%—41%和16%—57%,对Cd²⁺的吸附分别提高了12%—112%和22%—143%.与CNPs相比,CNPs-HA和CNPs-NaAlg对Pb²⁺的吸附增加了21%—71%和23%—65%,对Cd²⁺的吸附增加了26%—45%和45%—91%.并且NPs和NPs-NOM对Pb²⁺和Cd²⁺的吸附符合Freundlich吸附模型.离子强度的增加抑制了NPs-HA/NaAlg和NPs对Pb²⁺和Cd²⁺的吸附,而pH的增加对NPs-HA/NaAlg和NPs吸附Pb²⁺和Cd²⁺起促进作用.     

Experimental study of chromium adsorption on minerals in the presence of phthalic and humic acids

The effect of phthalic acid (benzene 1,2 dicarboxylic acid), a surrogate compound for natural organic matter, and of humic acid, on the adsorption of chromium to the surface of minerals was observed. In ternary systems involving phthalic acid, chromium(III) adsorption decreases on clays, probably because of aqueous Cr(III)-phthalate complexation, preventing ionic-exchange. Phthalic acid was also found to reduce chromium(VI) adsorption onto alumina, because of a competitive effect. In ternary systems involving humic acid, Cr(III) adsorption is increased in the low pH range because of the formation of surface ternary complex S-L-Cr(III) and is decreased in the high pH range because of aqueous Cr(III)-humate complexation.     

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.     

Humic Acids from Endemic Arsenicosis Areas in Inner Mongolia and from the Blackfoot-Disease Areas in Taiwan: A Comparative Study

The physical and chemical properties of humic acids (HA) extracted from drinking waters from the endemic arsenicosis areas in Inner Mongolia and from the Blackfoot disease (BD) areas in Taiwan are studied by using AAS (atomic absorption spectrophotometry), ICP-MS (inductively coupled plasma emission-mass spectrometry), IR (Infrared spectroscopy), FR (fluorescence spectrometry) and TLS (total luminescence spectroscopy) in order to shed light on the pathogenesis of BD with the concern as to whether the disease may eventually occur in arsenicosis-affected areas in the Mainland of China. Ames test and lipid peroxidation experiments were also conducted on these HA samples. It is found that water samples from the two regions are high in arsenic (As) with strong fluorescence and apparent positive correlations between As content, fluorescence, pH and total dissolved solids (TDS). The water samples are similar in fluorescence spectra but differ somewhat in IR and TLS between the two regions. The difference may be a reflection of the difference in radicals and structure of the HA owing to different hydrogeological conditions, and may also be related to the difference in their biological effects, i.e., HA from Inner Mongolia have a stronger ability to cause lipid peroxidation while HA from Taiwan exhibits a more prominent effect of mutation with respect to TA98(±S9).     

溶解性有机碳的主要组成对青鳉鱼铜急性毒性的影响

为揭示溶解性有机碳(DOC)的组成对生物配体模型(BLM)预测铜的生物毒性准确性的影响,研究了不同浓度黄腐酸(FA)、腐殖酸(HA)和两者不同浓度比例混合物影响铜对青鳉急性毒性。结果表明:在相同水质条件下,黄腐酸或腐殖酸浓度增加时,铜对青鳉的LC50均增加;两者共存时,当腐殖酸质量百分比从10%增至90%时,铜对青鳉的LC50也增加。当天然水中DOC的组成不确定时,可假设HA和FA的组成比例为1∶1,此时BLM预测铜对青鳉的LC50的偏差最小。